A STUDY OF HTHEEIFICAT 10K BY AH A2EQTK0PIC METHOD By John D a n i e l D raper T h e s i s s u b m i t t e d t o t h e F a c u l t y o f t h e G ra d u a te S c h o o l o f t h e U n i v e r s i t y o f M aryland i n p a r t i a l f u l f i l l m e n t o f t h e r e q u i r e m e n t s f o r t h e d e g r e e of D o c t o r o f P h i l o s o p h y 1 9 4 8 UMI Number: DP70320 All rights reserved INFORMATION TO ALL USERS The quality of this reproduction is dependent upon the quality of the copy submitted. In the unlikely event that the author did not send a complete manuscript and there are missing pages, these will be noted. Also, if material had to be removed, a note will indicate the deletion. Dissociation Publishing UMI DP70320 Published by ProQuest LLC (2015). Copyright in the Dissertation held by the Author. Microform Edition © ProQuest LLC. All rights reserved. This work is protected against unauthorized copying under Title 17, United States Code ProQuest LLC. 789 East Eisenhower Parkway P.O. Box 1346 Ann Arbor, Ml 48106- 1346 AC KN 0 WL EDO Mil MT The a u t h o r o f f e r s M s s i n c e r e a p p r e c i a t i o n t o Dr. E r n e s t F . P r a t t who s u g g e s t e d t h i s p r o b le m and u n t i r i n g l y d i r e c t e d i t t o I t s c o n c l u s i o n . The h e l p f u l a d v i c e o f D r . //I 111 am J • S v l r b e l y on t h e k i n e t i c I n t e r ­ p r e t a t i o n s o f t h e I n v e s t i g a t i o n i s a l s o a p p r e c i a t e d * TABLE OF CONTENTS Page HISTORICAL INTRODUCT ION.................................................. . . . . 1 DISCUSSION DHVKLOPMENT OF A METHOD FOR DETERMINING HATES OF ETHERIFICATION . . . . . . . ........................................... . . . . . . ................... 11 SCOPE AND LIMITATIONS OF THE AZ EOT HO PIC METHOD* . . . . . . . 15 THE EFFECT OF VARIATIONS IN THE CHAIN LENGTH OF ROB*.. 26 THE EFFECT OF VARIATIONS IN THE NUMB® OF PHENYL GROUPS ON I HE ALPHA CARBON OF R*OH................ 32 THE ALKYL AT ION OF BENZENE BY BENZYL ALCOHOL AND BENZYL ETHER....................................................... 37 THE EFFECTS OF VARIATIONS IN CATALYST CONCENTRATION ON THE RATE AND ORDER OF ETHERIFICATION REACTIONS 44 THE EFFECT OF VARIATION IN CATALYST CONCENTRATION ON THE COURSE OF THE REACTION OF TBIPHENYL CARBINOL WITH DIPHENYL CARBINOL....................... 4 9 THE EFFECT OF VARIATION IN THE HUMBER OP PHENYL GROUPS OH THE ALPHA CARBON OF ROH............... 55 TRANSET HEEX FIG AT I ON REACTIONS..................... 66 THE DETERMINATION OF THE EFFECT OF THE NUMBER OF ALPHA PHENYL GROUPS OH THE BASICITY OF THE ALCOHOL.. .. 77 EXPERT MENTAL DEVELOPMENT OF A MET HDD FOR DETERMINING RATES OF FT HER IF IC AT 10 N ....................... 85 SCOPE AND LIMITATIONS OF THE AZEOTROPIC METHOD.. . . . . . . 90 THE EFFECT OF VARIATIONS IN THE CHAIN LENGTH OF ROIL **102 THE EFFECT OF VARIATIONS IN T HE NUMBER OF PHENYL GROUPS ON THE ALPHA CARBON OF R'OH............................................. . . 1 0 6 THE ALKYLATIQN OF BENZENE BY BENZYL ALCOHOL AND BENZYL MT HER ..................... .................................................................... . . 1 0 8 THE EFFECTS OF VARIATIONS IN CATALYST CONCENTRATION ON THE HATE AND OBD :B OF ET HER IF IC AT ION REACTIONS............ 1 1 0 THE EFFECT OF VARIATION IN CATALYST CONCENTRATION ON THE COURSE OF THE REACTION OF TRI PHENYL C ARBINOL WITH DIPHENYL QARBINOL.................... . . . . . . . . ........................................I l l THE EFFECT OP VARIATION IN THE NUMBER OP PHENYL GROUPS ON THE A LPHA CARBON OF RGH* . . . . . . . . ............................113 TRANS El REIFICATION REACTIONS. . ........... * .................. 1 15 THE DETERMINATION OF TIE EFFECT OF THE NUMBER OF ALPHA PHENYL GROUPS ON THE BASICITY OF THE ALCOHOL . . . . 1 1 8 SUMMARY.................. 121 BIBLIOGRAPHY............................ 12 3 HISTORICAL INTRODUCTION The o b j e c t i v e s o f t h i s I n v e s t i g a t i o n w e re t h r e e f o l d : ( 1 ) t o d e t e r m i n e t h e e f f e c t o f v a r i a t i o n s In s t r u c t u r e o f a l c o h o l s upon t h e e a s e w i t h w h i c h t h e y e f c h e r i f y * ( 2 ) t o i n ­ v e s t i g a t e t h e mechanism o f e t h e r l f l c a t l o n w i t h a v ie w t o c o r r o b ­ o r a t in g : or d i s p r o v i n g Hammett f s m ec h a n ism ,^ * ( 1 ) ( 2 ) ( 3 ) (4 ) H ’ :*5j n * k* z m m ^ V St ^ 4}'» H* s o : H I*1 * R 80: H r >Ip * i o * r 4% R * tO j H i : !*0i H ' * K* • • and ( 3 ) t o a p p l y t h e r e s u l t s o b t a i n e d t o t h e im provem ent o f t h e s y n t h e s i s o f e t h e r s # I t i s a p p a r e n t t h a t when a m o l e c u l e o f an u n s y m m e t r i c a l e t h e r , B.’ OH, I s fo rm ed f r o m a m o l e c u l e o f e a c h o f two a l c o h o l s t h e n e t e f f e c t , r e g a r d l e s s o f -mechanism, i s t h a t o n e a l c o h o l m o l e c u l e f u r n i s h e s an n ’ ( o r R) g r o u p w h i l e t h e o t h e r a l c o h o l m o l e c u l e s u p p l i e s t h e OR ( o r OR’ ) p o r t i o n o f t h e e t h e r mo 1©~ c u l e # For t h e p u r p o s e s o f s i m p l l f y l n g t h i s d i s c u s s i o n , t h e f o r m e r a l c o h o l w i l l b e c a l l e d t h e R ’OJ! a l c o h o l w h i l e t h e o t h e r a l c o h o l w i l l be c a l l e d t h e HdH a l c o h o l * As t h e d i s c u s s i o n p r o ­ c e e d s , I t w i l l b e .found t h a t f o r t h e u n a y m m e t r lc a l e t h e r s c o n ­ s i d e r e d her© I t I s u s u a l l y a p p a r e n t w h i c h I s t b s R * OH a l c o h o l and w h ic h I s t h e RuB a l c o h o l # A s t u d y o f t h e l i t e r a t u r e shows t h a t In g e n e r a l t h e BOil a l c o h o l i a u n im p o r ta n t In d e t e r m i n i n g t h e e a s e o f e t h e r i f I c a t I o n , hut a c t i v a t e d a l c o h o l s a r e n e e d e d f o r t h e a l c o h o l I f t h e r e ­ a c t i o n I s t o o c c u r e a s i l y * T h i s a c t i v a t i o n I s u s u a l l y s u p p l i e d by an a r o m a t i c o r o l e f i n i c bond on t h e c a r b o n atom a d j a c e n t t o t h e o n e h o l d i n g t h e h y d r o x y l g r o u p o r by an a tom w i t h an u n s h a r e d e l e c t r o n p a i r a t t a c h e d t o t h e carb on h o l d i n g t h e h y d r o x y l group* In o r d e r t o s i m p l i f y t h e e x p e r i m e n t a l p r o c e d u r e , t h e s t u d y was l i m i t e d t o t h o s e e t h e r s w h i c h fo r m r e a d i l y * The d e s c r i p t i o n o f a w i d e v a r i e t y o f s u c h e t h e r s I s a v a i l a b l e In t h e l i t e r a t u r e * One l a r g e g r o u p o f a c t i v a t e d R ’OH a l c o h o l s i s t h e p h e n y l c a r h l n o l s • B e n z y l a l c o h o l I s t h e s i m p l e s t member o f t h i s group* I t h a s r e c e i v e d a t t e n t i o n f r o m many I n v e s t i g a t o r s f o r s y n t h e s e s o f b o t h s y m m e t r i c a l and u n sv m m e tr ic& l e t h e r s * S e n d e r e n s I n v e s t i g a t e d b e n z y l § l c o h o l e x t e n s i v e l y . By r e ­ a c t i n g f i f t y p a r t s b e n z y l a l c o h o l w i t h on© p a r t s u l f u r i c a c i d t r i h y d r a t e a t 125 t o 1 4 0 In an a p p a r a t u s w h i c h a l lo w e d , t h e w a t e r t o be d i s t i l l e d o f f a s I t f o r m e d , h e was a b l e t o c o l l e c t t h e t h e o r e t i c a l amount o f w a t e r f o r e t h e r i f i c a t I o n In o n e - h a l f 76hour* At room t e m p e r a t u r e tw o p a r t s b e n z y l a l c o h o l i n t h e p r e s e n c e o f on© p a r t s u l f u r i c a c i d t r i h y d r a t e r e a c t e d i n e i g h t 78d a y s to. tiI v e a 70% y i e l d o f d i b e n z y l . e t h e r * The c o r r e s p o n d ­ i n g r e a c t i o n w i t h a two t o o n e r a t i o o f a c i d t o a l c o h o l went i n a f e w h o u r s t o g i v e a h i g h y i e l d o f y e l l o w r e s i n * A m i x t u r e o f on e p a r t c a t a l y s t w i t h f i v e p a r t s b e n z y l a l c o h o l and f i v e p a r t s I s o a m y l a l c o h o l r e a c t e d i n o n e - h a l f h o u r a t 1 2 0 U t o g i v e a p p r o x i m a t e l y e q u a l p r o p o r t i o n s o f a l l ' , t h r e e p o s s i b l e e t h e r s W ith b u t a n o l , p r o p a n o l , e t h a n o l , i s o p r o p y l or I s o b u t y l a l c o h o l p r e s e n t i n p l a c e o f i s o a m y l a l c o h o l a t t h e same a c i d c o n c e n ­ t r a t i o n , o n l y t h e s y m m e t r i c a ! and u n s y m m e t r i c a l b e n z y l e t h e r s w e re o b t a i n e d * Sodium a c i d s u l f a t e was l a t e r e m p lo y e d b y S e n d e r e n s a s a c a t a l y s t f o r making s y m m e t r i c a l o r m ixed e t h e r s fro m b e n z y l 79a l c o h o l * Ten p a r t s b e n z y l a l c o h o l and t e n p a r t s n - b u t a n o l , o r i s o - b u t y l , or i s o - a m y l a l c o h o l h e a t e d w i t h one p a r t o f c a t a l y s t a t 12 5 t o 1 3 0 ° y i e l d e d t h e s y m m e t r i c a l and m ixed b e n z y l e t h e r s , b u t n e v e r t h e s y m m e t r i c a l a l i p h a t i c e t h e r * One p a r t c a t a l y s t h e a t e d t o 1 3 5 ° w i t h t w e n t y p a r t s c y c l o h e x a n o l and t w e n t y p a r t s b e n z y l a l c o h o l y i e l d e d b o t h t h e s y m m e t r i c a l and u n s y r m e t r i c a i b e n z y l e t h e r s , 'but a t h i g h e r t e m p e r a t u r e s c y c l o h e x e r t e was p r o d u ce d * D i b e n z y l e t h e r was p r e p a r e d i n ‘6 6 $ y i e l d w i t h o u t c a t a l y s t by h e a t i n g b e n z y l a l c o h o l i n a s e a l e d t u b e f o r f i v e d a y s a t 2 1 0 t o 2 1 5 7 An i n t e r e s t i n g s y n t h e s i s o f d i b e n z y l e t h e r i s o n e In w h ic h t e n p a r t s b e n z y l a l c o h o l w e r e h e a t e d t o XB0'J f o r R4 «tw o h o u r s w i t h o n e p a r t s u l f u r * ”" A 2 0 # y i e l d o f e t h e r was oh t a in ©d • S e c o n d a r y a r o m a t i c a l c o h o l s r e q u i r e d l e s s a c i d f o r e t h e r - 78i f l c a t i o n and d e h y d r a t i o n t h a n d i d t h e p r im a r y a l c o h o l s * At room t e m p e r a t u r e , a m i x t u r e o f one p a r t s u l f u r i c a c i d t r i - h y d r a t e to t h r e e o f m e t h y l p h e n y l carto irjo l g a v e an 84,1 y i e l d o f t h e s y m m e t r i c a l e t h e r i n t w e n t y h o u rs* I f t h i s same e a r - b i n o l i s , ' b o i l e d w i t h d i l u t e h y d r o c h l o r i c a c i d f o r e i g h t h o u r s , a 5 0 # y i e l d o f - ^ - c l i p h e n y l d i e t h y l e t h e r i s o b ta in ed *® ® m -H ydroxyben z y l a l c o h o l h a s been c o n v e r t e d t o t h e c o r r e s ­ p o n d i n g m e t h y l or e t h y l b e n z y l e t h e r by m e r e l y warming i n e i t h e r e t h a n o l o r m e t h a n o l w i t h o u t c a t a l y s t . The p h e n o l i c h y d r o x y l w ss a n a f f a c t e d . A n o th e r compound o f t h e b e n z y l a l c o h o l t y p e w h i c h e t h e r - 1 f i o s r e a d i l y i s b e n z o i n , t o l l F i s c h e r d i s s o l v e d i t In f i f t e e n p a r t s m e t h a n o l o r e t h a n o l s a t u r a t e d w ith , h y d r o g e n c h l o r i d e a t o40" and a f t e r a l l o w i n g t h e m i x t u r e t o s t a n d f o r one day I s o l a t e d , t h e m e t h y l o r e t h y l e t h e r In q u a n t i t a t i v e y i e l d , ^ C l o s e l y r e l a t e d t o b e n z y l a l c o h o l In s t r u c t u r e and I n ­ t e r e s t I s p - p h e n y l e t h a n o l , S e h r o e t e r f i r s t c o n v e r t e d I t t o t h e s y m m e t r i c a l e t h e r In 5 9 $ y i e l d by h e a t i n g i t w i t h a s m a l l amount o f m e t h l o n l c d l c h l o r l d e f o r s e v e n h o u r s a t 1 6 5 ° ,^ ® Some s t y r e n e was p r o d u ce d a l s o . S e n d e r e n s a l s o worked, w i t h t i l l s a l c o h o l , r e p o r t i n g t h a t I t e t h e r i f l e d l e s s r e a d i l y u n d e r 7*3 M s c o n d i t i o n s than d i d b e n z y l a l c o h o l . ' I f o n e p a r t so d iu m a c i d s u l f a t e and t e n p a r t s o f t h e a l c o h o l w ere h e a t e d f o r two h o u r s a t 1 8 0 t o 1 7 0 ° t h e e t h e r was form ed i n g o o d y i e l d . C o n c e n t r a t e d s u l f u r i c a c i d a t 1 7 0 J c o n v e r t e d b o t h t h e a l c o h o l 7« and th e s y m m e t r i c a l e t h e r t o s t y r e n e , ■ ^ .D ib e n z y l m e t h y l c a r - h i n o l a p p e a r s t o e t h e r i f y m ore r e a d i l y t h a n t h e r e l a t e d (3- p h e n y l ­ e t h a n o l « I t w a s r e f l u x e d In m e t h a n o l w5 t h 4 $ s u l f u r i c a c i d f o r t h i r t y m i n u t e s t o g i v e a 4 0 $ y i e l d o f t be m e t h y l e t h e r ,® ® l a n z h y d r o l i s t h e most i m p o r t a n t e x a m p le o f t h e d i p h e n y l c a r t i n o l t y p e o f p h e n y l c a r b l n o l s , I t fo r m s t h e s y m m e t r i c a l e t h e r In a b o u t 5 0 $ y i e l d when h e a t e d many h o u r s a t t h e b o i l i n g a £~ k n /> *2 n p : p o i n t w i t h o u t c a t a l y s t . * 9 * l a r d h a s u s e d d i l u t e h y d r o ­ c h l o r i c a c i d a t 100® t o g i v e an 82^ y i e l d ‘o f th© e t h e r ,® ® Th© f o r m a t i o n i n g o a l y i e l d o f t h e m e t h y l o r e t h y l e t h e r o f h e n z - h y d i o l ny d i s s o l v i n g I t In m e t h a n o l i c o r e t h a n o l 1 c h y d r o c h l o r i c ^ ? 51o r s u l f u r i c 1 a c i d a t room t e m p e r a t u r e h a s b e e n r e p o r t e d * In t h i s work a p p a r e n t l y n on e o f th© s y m m e t r i c a l d i b e n s h y d r y l e t h e r was i s o l a t e d , 'but Ward, on t r e a t i n g b e n s h y d r o 1 w i t h a d i l u t e a l c o h o l i c h y d r o c h l o r i c a c i d s o l u t i o n , o b t a i n e d b o t h th© s y m m e t r i c a l b e n z h y & r y l © th er and t he h e n a h y d r y l e t h y l e t h e r When a b e n z e n e s o l u t i o n o f two m o le s b e n z h y d r o l end on© mol© o x a l y l . c h l o r i d e w as r e f l u x e d f o r on© h o u r a 30w y i e l d o f d i ~ b e n a h y d r y l © th e r was o b t a i n e d * ^ In 1 92 4 Z i e g l e r r e p o r t e d some e t h e r i f I c a t I o n w ork w i t h v a r i o u s d i p h e n y l c a r b l n o l s . He r e a c t e d th e p h e n y l c a r b l n o l s w i t h e x c e s s m e t h a n o l a t room t e m p e r a t u r e f o r f r o m o n e t o t w e n t y - f i v e h o u r s w i t h s u l f u r i c a c i d a t a c o n c e n t r a t i o n o f 2;T a s c a t a l ­ y s t * In th© s h o r t e r p e r i o d o f t i m e t h e m e t h y l e t h e r s o f e t h y l d i p h e n y l c a r b l n o l and o f b e n z y l d i p h e n y l c s r h i n o i form ed i n 00 t o 90,1 y i e l d s * C y c l o h e x y l d i p h e n y l c s r h i n o i e t h e r ! f l e d m e th a n o l t o t h e e x t e n t o f IB% In t w e n t y - f i v e h o u r s * The t r l p h e n y l c a r b l n o l s , o f w h i c h t r i p h e n y l c a r b l n o l i t ­ s e l f l a t h e o n l y o n e c o n s i d e r e d h e r e , r e a d i l y form e t h e r s * Th© e t h y l © t h e r o f t r i p h e n y l c a r b l n o l I s p r e p a r e d by d i s s o l v i n g th© c a r b l n o l In a l c o h o l c o n t a i n i n g 5;% o f h y d ro g e n c h l o r i d e * 4 ® Th© p r o p y l e t h e r h a s b e e n made I n g o o d y i e l d by a p p l i c a t i o n o f g e n t l e b e a t t o a m i x t u r e o f t en p a r t s c o n c e n t r a t e d s u l f u r i c a na c i d , t a n p a r t s t r l p h e n y l c a r b l n o l and s e v e n p a r t s n - p r o p a n o l * Th© a l l y l a l c o h o l s fo rm a l a r g e c l a s s o f a c t i v a t e d a l c o ­ h o l s w h i c h a r e c l o s e l y r e l a t e d to th© p h e n y l c a r b l n o l s * As a g ro u n t h e y should, be r e a c t i v e e n o u g h t o e t h e r ! f y e a s i l y i f c o n ­ d i t i o n s a r c s e l e c t e d w h i c h © v o id t r o u b l e s o m e s i d e r e a c t i o n s * By t r e a t m e n t w i t h l i q u i d h y d rog en c h l o r i d e , a l l y l a l c o h o l h a s - 6 - b e e n c o n v e r t e d i n e x c e l l e n t y i e l d s t o d l a l l y l e t h e r s S e n d e r e n s c a r r i e d o u t th© same t r a n s f o r m a t i o n w i t h e q u a l \ e a s e by e m p l o y in g on© p a r t . s u l f u r ! c a c i d t r i h y d r a t e w i t h f i v e p a r t s a l l y l a l c o h o l a t 1 0 8 u . O th er m eth ods g i v e p o o r e r y i e l d s . A l l y l a l c o h o l v a p o r s p a s s e d o v e r c a l c i n e d a lum c a t a l ­ y s t a t 185 t o 190^ g i v e a 3 0 a y i e l d o f a l l y l e t h e r . 0 ^ A t t e m p t s t o make t h e m ix ed a l l y l e t h e r s o f m e t h a n o l , e t h a n o l , p r o p a n o l , i s o h u t . y l and I s o a m y l a l c o h o l by m i x in g t h e i r v a p o r s w i t h a l l y l a l c o h o l and p a s s i n g them to t h o v e r t h e c a t a l y s t g i v e a t b e s t o n l y a 10> y i e l d . c < , Y - D l m e t h a l l y l a l c o h o l I s c o n v e r t e d to t h e s y m m e t r i c a l o ^ , Y - d i m e t h y a l l y l e t h e r i n a b o u t 6 7 a y i e l d a t room t e m p e r a t u r e i n t w e l v e h o u r s by t h e a d d i t i o n o f a f e w d r o p s o f c o n c e n t r a t e d s u l f u r i c a c i d . ^ CInnamyl a l c o h o l e t h e r ! f l e s i t s e l f in g o o d y i e l d In a m a t t e r o f m i n u t e s a t 1 1 S W In t h e p r e s e n c e o f a s m a l l 7Ramount o f s u l f u r i c a c i d . I t h a s a l s o b e e n p o i n t e d o u t t h a t d l a l l y l a l c o h o l s o f t h e t y p e o b t a i n e d by t h e r e d u c t i o n o f th© k e t o g r o u p o f d l b e n s a l a c e t o n e a r e © s p e c i a l l y s u s c e p t i b l e t o Q%e t h e r f o r m a t i o n . ^ O f ten mere r e c r y s t a l l i s a t I o n o f t h e u n s a t - u ra t© d c a r b l n o l from an a l c o h o l I s s u f f i c i e n t t o g i v e t h e e t h e r o f th© s o l v e n t ' a l c o h o l * In c o n s i d e r i n g t h e p h e n o l l c t y p e o f Kf0H a l c o h o l , a s t u d y o f t h e e t h e r I f l e n t ton o f p h e n o l s , naphtfcto ls , an throls and p h e n - a n t h r o I s o f f e r s c o n t r a s t s due to v a r i a t i o n s In t h e a r o m a t i c c h a r a c t e r o f t h e v a r i o u s m o l e c u l e s . T h e s e compounds may be c o n s i d e r e d t o b e b o t h v i n y l and a l l y l a l c o h o l s o f a s p e c i a l t y p e * hamborger f i r s t i n d i c a t e d t h a t I t w as th® n o n - a r o m a t i c c h a r a c t e r o f n a p h t h o l s t h a t a l l o w e d th e m t o fo rm e t h e r s w i t h a l c o h o l s i n - 7- t h e p r e s e n c e o f s m a l l am ounts o f a c i d c a t a l y s t w h i l e p h e n o l w ou ld n o t r e a c t * 0 The p r e s e n c e o f a c t i v a t i n g g r o u p s c a n , how­ e v e r , r e n d e r a p h e n o l i c compound s u c h a s p h l o r o g l u c i n o l r e a d i l y CO c a p a b l e o f e t h e r i f i c a t i o n # T h i s compound was d i s s o l v e d i n s i x p a r t s m e t h a n o l , h y d r o g e n c h l o r i d e was p a s s e d i n , and t h e s o l u t i o n was r e f l u x e d f o r t h r e e h o u r s t o g i v e a 70,2 y i e l d , o f t h e d i m e t h y l e t h e r and a 12 .5 )2 y i e l d o f t h e m onom ethyl © t h e r . In g e n e r a l , t h o u g h , i t i s t r u e t h a t more d r a s t i c m ethods must be u s e d I f t h e p h e n o l and t h e a l c o h o l a r e t o be r e a c t e d d i r e c t - l y . T h e s e m ethods a p p r o a c h t h o s e u s e d f o r o r d i n a r y u n a c t i v a t e d R 1 O’- a l c o h o l s and w i l l n o t be c o n s i d e r e d h e r e . A l t h o u g h u n s u b s t i t u t e d p - n a p h t h o l i s e a s i l y e t h e r i f l e d w i t h an a l c o h o l i n t h e p r e s e n c e o f an a c i d c a t a l y s t . D a v i s ^ e a r l y fo u n d t h a t t h i s r e a c t i o n i s b l o c k e d by a h a l o g e n atom o r n i t r o g r o u p i n t h e a d j a c e n t ^ p o s i t i o n and P l e s e r and L o t h - rop^® fo u n d t h a t a l k y l g r o u p s i n t h i s p o s i t i o n h a v e a s i m i l a r e f f e c t . They r e a c t e d tw o -g r a m p o r t i o n s o f v a r i o u s n a p h t h o l s f o r s e v e n t e e n h o u r s a t 1 0 0 ° i n a s e a l e d tub© w i t h t e n m i l l i ­ l i t e r s o f a b o u t a 5% s o l u t i o n o f p - t o l u © n e s u l f o n i c a c i d In m e t h a n o l . 2 - N a p h t h o l i t s e l f g a v e a 51% y i e l d , 1 - e t h y l o r 1 - b e n z y l n & p h t h o l g a v e no r e a c t i o n and 1 - c h l o r o - o r 1 , 6 - d i br omo- g a v e a 2% y i e l d o f t h e m e t h y l © t h e r . I t seem ed t h a t g r o u p s f a c i l i t a t i n g o r d i n a r y a r o m a t i c s u b s t i t u t i o n pro m o ted t h e r e ­ a c t i o n when t h e y were l o c a t e d a t c e r t a i n p o s i t i o n s o t h e r th a n t h e a d j a c e n t y i e l d o f t r i p h e n y l - m e t h y l m e t h y l e t h e r was I s o l a t e d . When t h e p h o s p h o r i c a c i d was r e p l a c e d by on© p a r t p - t o l u e n e s u l f o n i c a c i d m o n o h y d r a t e , a 75:1 y i e l d o f t h e sam© © t h e r was r e c o v e r e d # On t h e b a s i s o f t h e s e r e s u l t s t h e p r o p e r c o m b i n a t i o n s o f a l c o h o l s c o u ld b© s e l e c t e d f o r t e s t i n g t h e p r o p o s e d m eth ods o f f o l l o w i n g t h e e t h e r i f i c a t i o n r e a c t i o n s . T h e s e r e a c t i o n s ar© I n h e r e n t l y d i f f i c u l t t o f o l l o w by- s t a n d a r d m e th o d s f o r n e i t h e r a l c o h o l s nor e t h e r s ar© e a s y t o d e t e r m i n e q u a n t i t a t i v e l y . Some method o f m e a s u r i n g t h e w a t e r form ed a © r e a r e d t o be t h e most p r o m i s i n g p r o c e d u r e . At f i r s t an a b s o r p t i o n t r a i n was s e t up i n c o n n e c t i o n w i t h t h e r e a c t i o n f l a s k . As t h e e t h e r i f i e a t i o n p r o c e e d e d and on© m o l e c u l e o f w a t e r w a s produced, f o r © very m o l e c u l e o f e t h e r fo r m e d , ( 5 ) H» 0 H + H O H -------------- > B* 0 B + BE 0 B a d r y a i r s t r e a m drawn t h r o u g h t h e s y s t e m s w e p t th© m o i s t u r e I n t o a s e r i e s o f a b s o r p t i o n t u b e s , w h e r e i t c o u l d b e w e i ghed . A m i n e r a l o i l t r a p p l a c e d b e tw e e n t h e r e a c t i o n f l a s k , and th© anhyd.rone a b s o r p t i o n t u b e s d i d n o t r e t a i n a l l t h e o r g a n i c r e ­ a c t a n t s w h ic h had a t e n d e n c y t o b e sw e p t o u t o f t h e f l a s k and some o f t h o s e w e r e a l s o drawn i n t o t h e t u b e s . As a r e s u l t , t h e g a i n - I n w e i g h t o f t h e a b s o r p t i o n t u b e s d i d n o t r e p r e s e n t w a t e r a l o n e , s o t h e method was a b an don ed * N ext an a t t e m p t was mad© t o m ea sure t h e w a t e r w h ic h was d i s t i l l e d d i r e c t l y fro m t h e r e a c t i o n m i x t u r e a s t h e e t h e r i - f i e a t i o n p r o g r e s s e d . T h i s was in e f f e c t an adaptation t o r a t e s t u d i o s o f S e n d e r e n s ’ p r e p a r a t i v e method f o r b e n z y l © t h e r s . 76 - 15- when t e n p a r t s o f b e n z y l a l c o h o l -were r e a c t e d w i t h f i f t e e n p a r t s p h e n o l i n t h e p r e s e n c e o f on© p a r t a n h y d r o u s p h o s p h o r i c a c i d c a t a l y s t a t 1 5 0 ° , 70% o f t h e t h e o r e t i c a l amount o f w a t e r was d i s c h a r g e d i n f i v e h o u r s * Wo © t h e r was f o u n d , h u t a 48^S y i e l d o f p - b e n z y l p h e n o l was I s o l a t e d * C o n c u r r e n t work on an a z e o t r o p i c p r o c e d u r e , d e s c r i b e d b e l o w , i n d i c a t e d t h a t i t w o u ld g i v e more n e a r l y q u a n t i t a t i v e r e s u l t s , e s p e c i a l l y on a s m a l l s c a l e , so th© method o f d i r e c t d i s t i l l a t i o n o f w a t e r from t h e s y s t e m was abandoned* The a z e o t r o p i c method I s based, upon t h e w e l l known f a c t t h a t b e n z e n e and t o l u e n e , as w e l l a s a number o f o t h e r com­ p o u n d s , form low b o i l i n g a z e o t r o p e s w i t h w a t e r * In F i g u r e I i s shown t h e a p p a r a t u s u s e d . The b e n z e n e or t o l u e n e s o l v e n t was p l a c e d In t h e f l a s k t o g e t h e r w i t h t h e a l c o h o l o r a l c o h o l s t o be e t h e r i f l ed * As t h e r e a c t i o n m i x t u r e was r e f l u x e d on© m o l e c u l e o f w a t e r was c a r r i e d I n t o th© w a t e r s e p a r a t o r f o r e a c h m o l e c u l e o f e t h e r fo r m e d ( e q u a t i o n 5 ) . From r e a d i n g s o f th© vo lum e o f w a t e r p r e s e n t a t v a r i o u s t i m e s t h e r a t© o f r e ­ a c t i o n c o u l d b e m easured* In a t y p i c a l r e a c t i o n o n e - f o u r t h m ole o f n - h u t a n o l and o n e - f o u r t h m ole o f t r i p h e n y l c a r b l n o l w ere d i s s o l v e d In f i v e h u nd red m i l l i l i t e r s o f b e n z e n e w i t h 0 . 0 5 mol© o f a n h y d r o u s p h o s p h o r i c a c i d c a t a l y s t * The r e a c t i o n ran a t r e f l u x t e m p e r a ­ t u r e f o r t h r e e h o u r s u n t i l 90-iS o f th© w a t e r c o r r e s p o n d i n g t o co m n le t© e t h e r ! f i e a t i o n had c o l l e c t e d * The p r o d u c t was I s o ­ l a t e d i n o v e r B5% y i e l d * Ahen o n e - t e n t h a s much c a t a l y s t was e m p lo y ed In th© s y s t e m a b o v e , t h e r e a c t i o n was 90.1 c o m p l e t e In f o u r h o u r s * p - T o l u e n e s u l f o n i c a c i d was a l s o an e f f e c t i v e 1 4 - D R YIN 6 T U B E C O N D E N S E R W A T E R S E P A R A T O R S O L V E N T W A T E R R E A C T I O N S O L U T I 0 N G L A S C O L H E A T I N G M A N T L E F i g u r e I * The s t a n d a r d a z e o t r o p i c a p p a r a t u s - 15- c a t a l y s t f o r t h e s y n t h e s i s &£' t r l p h e n y l m e t h y l b u t y l e t h e r • T h e r e was no e t h e r form ed b e t w e e n t r i p h e n y l c a r b l n o l and n - b u t y l a l c o h o l i n t h e a b s e n c e o f any c a t a l y s t . T h e s e r e ­ s u l t s i n d i c a t e d t h a t t h i s a z e o t r o p i c d i s t i l l a t i o n method was t h e b e s t b o t h fro m t h e s t a n d p o i n t o f r a t e s t u d y and o f a c t u a l s y n t h e s i s . SCOPE AKD LIMITATIONS OF THE AZEOTROPIC METHOD A f t e r I t was p r o v e n t h a t t h e a z e o t r o p i c method was a p p l i ­ c a b l e , i t n e x t becam e o f i n t e r e s t t o d e t e r m i n e t h e s c o p e o f t h e m e t h o d . A s t u d y o f v a r i o u s p o s s i b l e R f OH a l c o h o l s w a s , t he r © f o r e , made . A t o l u e n e s o l u t i o n o f b e n z y l a l c o h o l and n - b u t y l a l c o h o l w i t h 0.1'Jj a n h y d r o u s p h o s p h o r i c a c i d a s a c a t a l y s t was r e - of l u x e d a t 113 f o r t h r e e d a y s In t h e a z e o t r o p i c a p p a r a t u s w i t h ­ o u t t h e a p p e a r a n c e o f w a t e r . No e t h e r c o u l d b e I s o l a t e d . When a b e n z e n e s o l u t i o n o f b e n z y l a l c o h o l and n - d e c y l a l c o h o l w i t h 1*2% a n h y d r o u s p h o s p h o r i c a c i d was r e a c t e d f o r two d a y s , t h e s o l v e n t w a s s l o w l y a l k y l a t e d by t h e b e n z y l a l c o h o l t o t h e e x ­ t e n t o f &Q%. In t h e same w a y , a l k y l a t i o n o f t h e s o l v e n t t o o k p l a c e t o t h e e x t e n t o f 48/1 when a t o l u e n e s o l u t i o n o f b e n z y l a l c o h o l and n - h e p t y l a l c o h o l was r e f l u x e d w i t h 2% a n h y d r o u s p h o s p h o r i c a c i d s ( 6 ) CL Br CBL ♦ C H CH OH > C I* CH0 Cr H.,CH_ * H0K6 5 3 6 5 2 6 5 2 6 4 3 A l t h o u g h t h e s e r e s u l t s w i t h b e n z y l a l c o h o l w e r e e n t i r e l y n e g a ­ t i v e f r o m th © s t a n d p o i n t o f e t h e r i f i e a t i o n , t h e y p o i n t e d t o an e n t i r e l y new a p p l i c a t i o n o f th© m ethod I n a I k y l a t i o n s t u d i e s . T h i s I s d i s c u s s e d i n t h e s e c t i o n on a l k y l a t i o n • - 16- S u b a t l t u t e d b e n z y l a l c o h o l s w e r e tr5 ed n e x t * When b e n z o i n and. n - b u t y l a l c o h o l w e r e r e f l u x e d in a b e n z e n e s o l u t i o n w i t h 0 . 1 $ ' s o l i d p h o s p h o r i c a c i d c a t a l y s t , w a t e r was p r o d u c e d s l o w l y t o t h e e x t e n t o f 7 8 $ o f t h e o r y f o r e t h e r i f i e a t i o n . At t h e same c o n c e n t r a t i o n s o f r e a c t a n t s and c a t a l y s t , h o?;ever , m e t h y l p h e n y l c a r b l n o l and b u t a n o l w e re u n r o a e t i v e . On d o u b l i n g t h e a c i d c o n ­ c e n t r a t i o n th© c a r b l n o l d e h y d r a t e d a l m o s t q u a n t i t a t i v e l y t o s t y ­ r e n e in t e n h o u r s . D i p h e n y l c a r b l n o l p r o v e d to h e much more r e a c t i v e th a n th© m on o p h en y l c a r b i n o l s . Two r u n s w e r e made w i t h b e n z h y d r o l and n - b u t a n o l . One was c a r r i e d o u t In t h e p r e s e n c e o f 0 . 1 $ a n h y ­ d r o u s p h o s p h o r i c a c i d and th© o t h e r i n t h e p r e s e n c e o f a n e q u a l amount o f p - t o l u e n e s u l f o n i c a c i d . The y i e l d s o f p r o d u c t w ere o v e r 90% i n e a c h c a s e . I t h a s b e e n p o i n t e d out in th© p r e c e d i n g s e c t i o n t h a t t r i ­ p h e n y l c a r b l n o l r e a d i l y a t h e r i f i @ s b u t a n o l in t h e p r e s e n c e o f p h o s p h o r i c o r p - t o l u e n e s u l f o n i c a c i d . T r i p h e n y l c a r b l n o l a l s o r e a d i l y e t h e r i f i e s ^ - p h e n y l e t h a n o l o r - p h e n y l p r o p a n o l In t h e p r e s e n c e o f G*01$ p - t o l u e n e s u l f o n i c a c i d m o n o h y d r a t e . A n e a r ­ l y q u a n t i t a t i v e y i e l d o f e a c h o f t h e t r i p h e n y l m e t h y l e t h e r s was i s o l a t e d . Then m o le f o r mol© q u a n t i t i e s o f t r i p h e n y l c a r b l n o l and e t h a n o l w a re r e a c t e d In b e n z e n e s o l u t i o n , an a q u e o u s l a y e r s e t t l e d o u t i n t h e s e p a r a t o r , but i n t h i s c a s e t h e vo lum e o f a q u e o u s l a y e r was g r e a t e r t h a n t h e o r y . I t I s a p p a r e n t t h a t e t h a n o l d i s t i l l e d o v e r i n t o t h e s e p a r a t o r and d i s s o l v e d i n th© w a t e r f o r m e d . The ©mount o f e t h a n o l In t h e a q u e o u s l a y e r was c a l c u l a t e d from d e n s i t y and r e f r a c t i v e i n d e x m e a s u r e m e n t s . The c o r r e c t e d v o lu m e o f w a t e r c o r r e s p o n d e d t o 9 3 $ o f th© amount - 17- c a l c u l a t e d f o r t o t a l e t h e r I f i c a t i o n * The a l l y l i c t y p e a l c o h o l s w e r e n e x t c o n s i d e r e d * Th© a z e o t r o p i c m ethod p r o v e d u n s a t i s f a c t o r y when a t o l u e n e s o l u ­ t i o n o f a l l y l a l c o h o l and p h o s p h o r i c a c i d c a t a l y s t was r e ­ f l u x e d * A f t e r t h r e e h o u r s a l m o s t t w i c e t h e t h e o r e t i c a l amount o f w a t e r f o r o t h e r ! f i c a t I o n had been d i s c h a r g e d . Ho d i a l l y l e t h e r was I s o l a t e d and e x t e n s i v e p o l y m e r i z a t i o n had t a k e n p l a c e . R e s u l t s o f r u n s w i t h c in n a r a y l a l c o h o l and b u t a n o l and w i t h cam- phena c a r b l n o l and b u t a n o l ware f a r more s a t i s f a c t o r y . In e a c h c a s e a b e n z e n e s o l u t i o n o f b u t a n o l and t h e p a r t i c u l a r a l l y l a l ­ c o h o l was r © f l u x e d w i t h 0 , 1 f p h o s p h o r i c a c i d c a t a l y s t * The t h e o r e t i c a l voluma o f w a t e r was produ ced In two d a y s i n t h e c in n a m y l a l c o h o l run w h i l e o n l y e i g h t e e n h o u r s w ere r e q u i r e d i n t h e camphene c a r b i n a l r u n . P r o d u c t s w ere i s o l a t e d i n 88^ and GOT y i e l d s , r e s p e c t i v e l y , w h ic h d i s t i l l e d a t t h e e x p e c t e d t e m p e r a t u r e s f o r t h e e t h e r s , b u t t h e y w e r e n o t f u r t h e r i n d e n t i - f l e d . From a c o n s i d e r a t i o n o f w o r k r e p o r t e d i n t h e h i s t o r l e a l i n t r o d u c t i o n i t was hoped t h a t t h e a p p l i c a t i o n o f t h e a z e o - t r o o i c p r o c e d u r e t o t h e © t h e r l f i e a t i o n o f ^ - n a p h t h o i w o u ld f u r n i s h soma i n t e r e s t i n g r e s u l t s * T h i s hope was n o t r e a l i z e d . In an a t t e m p t t o make t h e d i - ^ - n a p h t h y l e t h e r , d e s c r i b e d by Oraebe,®*' a ben s a n e s o l u t i o n o f ^ - n a p h t h o l was r e f l u x e d w i t h 1 T o f p h o s p h o r i c a c i d a s a c a t a l y s t b u t no r e a c t i o n t o o k p l a c e . S i m i l a r a t t e m p t s t o make ^ - n a p h t h y l b u t y l e t h e r w e re a l s o u n ­ s u c c e s s f u l ♦ Even a t e n f o l d e x c e s s o f b u t a n o l would n o t fo r e © t h e e t h e r I f l e a l i o n a t t h e r e f l u x t e m p e r a t u r e o f b e n z e n e . A t t e m p t s t o e t h e r i f y n - b u t y l a l c o h o l w i t h i t s e l f w e r e u n - s u c c e s s f u l * S o l u t i o n s o f n - b u t a n o l i n t o l u e n e w ere r e f l u x e d w i t h b o t h p h o s p h o r i c a c i d and p - t o l u e n e s u l f o n i c a c i d w i t h n e g a t i v e r e s u l t s . R e f l u x i n g , o f a one m olar s o l u t i o n o f n - h u t - anoJT i n b e n z e n e o r d1 c h i o r o e t h a n e w i t h b o r o n t r l f l u o r i d e y i e l d ­ ed no © t h e r . Aluminum c h l o r i d e and aluminum brom ide w e re t e s t e d i n b e n z e n e s o l u t i o n w i t h o u t s u c c e s s . At t h e c o n c l u s i o n o f t h i s p r e l i m i n a r y work on t h e scop© o f t h e a z e o t r o p i c method s e v e r a l p o i n t s w e re c l e a r . b e n z e n e a p p e a r e d t o b e t h e most n e a r l y i d e a l s o l v e n t f o r t h e a z e o t r o p i c r e m o v a l o f w a t e r from, t h e s y s t e m . T o l u e n e , w h i l e p e r m i t t i n g a h i g h e r r e f l u x t e m p e r s ! u r e , s u f f e r e d th© d i s a d v a n ­ t a g e o f b e i n g more s u s c e p t i b l e t o a l t e y l a t i o n * H e a v i e r t h a n w a t e r s o l v e n t s , s u c h a s d i c h l o r o © t h a n e , w e re u n s a t i s f a c t o r y b e c a u s e no s u i t a b l e t y p e o f w a t e r s e p a r a t o r was a v a i l a b l e f o r a c c u r a t e l y m ea su r in g t h e w a t e r v o l u m e . The c h o i c e o f th© b e s t c a t a l y s t was a c o m p le x p r o b le m . Van Alphen g i v e s a v e r y c o m p l e t e d i s c u s s i o n o f c a t a l y s t s t h a t w i l l p rom ote th© e t h e r 1 f i c a t i o n o f a l c o h o l s u n d e r © v a r i e t y o f 87 onc o n d i t i o n s . The i n o r g a n i c a c i d s i nc lutis h y d r o c h l o r i c , h y d r o - 76 4Pf l u o r i c , h y d r c h r o m i c , h y d r x o d i c , s u l f u r i c and p h o s p h o r i c . 15 piThe o r g a n i c a c i d s I n c l u d e p - t o l u e n e s u l f o n i c , m e t h i o n i c , m ono- , d i - , and t r i c h l o r o a c e t i c , p i c r i c and m a l e i c . The i n ­ o r g a n 1 c h a l i d e s most f r e q u e n t l y u s e d a r e boron t r i f l u o r i d e and t h e c h l o r i d e s o f p e n t a v a l e n t a n t i m o n y , t e t r a v a l e n t t i n , t r i v e ­ t'sl e n t i r o n and d i v a l e n t z i n c , n i c k e l and cadmium. Among th© i n o r g a n i c s u l f a t e s o f t e n em p loy ed a r e t h o s e o f z i n c , n i c k e l , c o b a l t , c o p p e r , cadmium, a luminum and t r i v a l e n t i r o n . Sodium pa h y d r o g e n s u l f a t e ~ h a s a l s o been u s e d w i t h s u c c e s s . On t h e o t h e r hand p o t a s s i u m , so d iu m , ammonium and c a l c i u m s u l f a t e s , p o t a s s i u m h y d r o x i d e , a luminum c h l o r i d e , a r s e n i c c h l o r i d e and s i l i c o n t e t r a f l u o r l d © g a v e no e t h e r s . A f t e r n n k i n t the r u n s w i t h p - t o l u e n e s u l f o n i c a c i d mono- h y d r a t e , a n h y d r o u s p h o s p h o r i c a c i d , b o r o n t r i f l u o r i d e , a l u m i ­ num b r o m id e and alum inum c h l o r i d e d e s c r i b e d i n t h e p r e l i m i n a r y a z e o t r o p i c w o r k , a n d a f t e r c o n s i d e r i n g o t h e r c a t a l y s t s n o t a c t u a l l y t e s t e d e x p e r t r e n t a l l y , i t was d e c i d e d t o us© p - t o l u e n e s u l f o n i c a c i d a s t h e s t a n d a r d c a t a l y s t i n s u b s e q u e n t work* p - T o l u e n e s u l f o n i c a c i d was c h o s e n b e c a u s e i t i s a s t r o n g a c i d , s o l u b l e In b e n z e n e and c a p a b l e o f c a t a l y z i n g a w i d e v a r i e t y o f a t h e r i f i c a t i o n s a t t h e c o m p a r a t i v e l y low r e f l u x t e m p e r a t u r e o f 7 0b e n z e n e . I t i s s t a b l e a s a m o n o h y d r a te and e a s i l y w e ig h e d o u t m d I n t r o d u c e d i n t o a r e f l u x i n g b e n z e n e s o l u t i o n o f t h e r e a c t a n t s a t t h e a p p r o p r i a t e moment, t h u s i n s u r i n g an a c c u r a t e z e r o t i m e f o r b e g i n n i n g t h e w a t e r vo lum e and t i m e r e a d i n g s * I f n e e d e d , s u c c e s s i v e p o r t i o n s c a n be a d d e d , a f t e r t h e r e a c t i o n h a s s t a r t e d , i n t h e same c o n v e n i e n t way* T h i s a c i d d o e s n o t p ro m o te s u l f o r a t i o n , c h a r r i n g o r o t h e r s i d e r e a c t i o n s t o t h e 95e x t e n t t h a t a n h y d r o u s s u l f u r i c a c i d d o e s * Th© w a t e r o f c r y s t a l l i z a t i o n from t h e m o n o h y d r a te b e c o m e s s i g n i f i c a n t o n l y when u n u s u a l l y 3b r g e am ounts o f c a t a l y s t a r e u s e d a n d , i f n e e d b e , t h e a c i d can b e e a s i l y d e h y d r a t e d by a z e o t r o p i c r e m o v a l o f t h e w a t e r w i t h b e n z e n e b e f o r e t h e a l c o h o l i c r e a c t a n t s ar© added p-O'oluene s u l f o n i c a c i d i s n o t v o l a t i l e a s i s h y d r o c h l o r i c a c i d h y d r o b r o m ic a c i d and o t h e r s , so t h a t a c o n s t a n t c a t a l y s t c o n ­ c e n t r a t i o n ca n b e m a i n t a i n e d e a s i l y In an open r e f l u x i n g b e n ­ z e n e s o l u t i o n * The b e n z e n e s o l u t i o n o f p - t o l u e n e s u l f o n i c a c i d - 2 0 - l a a l w a y s hom ogeneous In c o n t r a s t t o p h o s p h o r i c a c i d s o l u t i o n s w h ic h t e n d e d t o s e p a r a t e I n t o tw o l a y e r s tow a rd t h e end o f t h e r e a c t i o n * P h o s p h o r i c a c i d s u f f e r s f r o m t h e a d d i t i o n a l d i s a d ­ v a n t a g e t h a t I t I s d i f f i c u l t t o w e i g h o u t a c c u r a t e l y i n an a n ­ h y d r o u s c o n d i t i o n * On t h e b a s i s o f t h i s e a r l y work t h e a p p a r a t u s and p r o ­ c e d u r e w e r e s t a n d a r d i z e d f o r maximum a c c u r a c y * T h i s s t a n d a r d s e t - u p and p r o c e d u r e was u s e d i n a l l s u b s e q u e n t I n v e s t i g a t i o n s o f t h e e t h e r l f i e a t i o n o f th© p h e n y l c a r b l n o l s u n l e s s o t h e r w i s e n o t e d . The a p p a r a t u s i s d ia g r a m e d i n F i g u r e I . The w a t e r s e p a r a t o r was c a l i b r a t e d f o r © f i v e m i l l i l i t e r v o lu m e . In t h e s t a n d a r d run o n e - e i g h t h m o le o f e a c h a l c o h o l , E ’QH and KQH, was d i s s o l v e d i n s u f f i c i e n t b e n z e n e t o b r i n g th© t o t a l volum e t o f i v e hundred m i l l i l i t e r s * The amount o f c a t a l y s t was v a r i e d f r o m e x p e r i m e n t t o e x p e r i m e n t a c c o r d i n g t o t h e r e q u i r e ­ m en ts o f t h e p a r t i c u l a r R 1 OH b e i n g s t u d i e d . O r d i n a r i l y an e f f o r t was .made t o a d j u s t th© c a t a l y s t c o n c e n t r a t i o n t o g i v e a. c o m p l e t e r e a c t i o n ra t© c u r v e In f o u r t o e i g h t h o u r s . Th© c o n c e n t r a t i o n o f c a t a l y s t w as v a r i e d In d e f i n i t e a m o u n t s . I t was i n c r e a s e d from t h e l o w e s t c o n c e n t r a t i o n , 0 . 0 0 0 2 5 m o l a r , a c c o r d i n g t o t h e f o l l o w i n g p r o g r e s s i o n , 0 . 0 0 0 5 , 0 * 0 0 1 , 0 . 0 0 2 , 0 . 0 0 4 , e t c . , t o t h e h i g h e s t one u s e d , 0 . 2 5 8 m o l a r . A l l a l c o h o l i c r e a c t a n t s w e re c a r e f u l l y p u r i f i e d u n t i l t h e m e l t i n g p o i n t s , r e f r a c t i v e I n d i c e s , o r d e n s i t i e s c h e c k e d v a l u e s g i v e n In t h e l i t e r a t u r e . T h i s p u r i f i c a t i o n was don© on q u a n ­ t i t i e s l a r g e e n o u g h s o t h a t a s u f f i c i e n t s u p p l y o f u n i f o r m s t a r t ­ i n g m a t e r i a l from, t h e same s o u r c e was on hand f o r ©11 e x p e r i m e n t s i n v o l v i n g th© s a n e r e a c t a n t s w h ere r a t e s w e r e t o be c o m p a r e d . To - 21- i n s u r e u n i f o r m i t y o f s o l v e n t , t h e b e n z e n e was a z e o t r o p i c a l l y d r i e d In l o t s o f t w e n t y - f i v e l i t e r s . At t h e s t a r t o f a r u n , t h e b e n z e n e s o l u t i o n o f R 1 OH and ROM w i t h o u t a n y c a t a l y s t p r e s e n t was b r o u g h t t o r e f l u x In th© s t a n d a r d a p p a r a t u s . Th© c a t a l y s t i n a o n e m i l l i l i t e r b e a k e r was t h e n added t h r o u g h th© s i d e n e c k o f th e f l a s k . I f c o n c e n ­ t r a t i o n s o f c a t a l y s t l a r g e r t h a n 0 . 0 0 2 m o la r were r e q u i r e d th© w a t e r o f c r y s t a l l i z a t i o n a s s o c i a t e d w i t h t h e a c i d was r e m o v ed a z e o t r o p i c a l l y f r o m a b e n z e n e s o l u t i o n o f t h e c a t a l y s t b e f o r e t h e a l c o h o l i c r e a c t a n t s w e re a d d e d . As th© r e a c t i o n p r o c e e d e d f r e q u e n t r e a d i n g s o f th© v o lu m e o f w a t e r w ere t a k e n a l o n g w i t h n o t a t i o n s o f t e m p e r a t u r e . From t h e w a t e r v o lu m e d a t a t h e p e r ­ c e n t a g e c o m p l e t i o n o f t h e r e a c t i o n was c a l c u l a t e d . T h e s e p e r ­ c e n t a g e v a l u e s were p l o t t e d a g a i n s t t im e and when t h e c u r v e became h o r i z o n t a l , t h e r e a c t i o n was s t o p p e d . The b e n z e n e s o l u ­ t i o n was t h e n n e u t r a l i z e d w i t h d i l u t e a q u e o u s so d iu m b i c a r b o n ­ a t e and th© p r o d u c t was I s o l a t e d by e x t r a c t i o n and d i s t i l l a t i o n o r c r y s t a l l i z a t i o n p r o c e d u r e s . In th© u s e o f t h e a z e o t r o p l c method o f e t h s r i f I c a t I o n c e r t a i n l i m i t a t i o n s and p o s s i b l e s o u r c e s o f e r r o r m ust b e k e p t i n m in d . A f a c t o r o f g r e a t I m p o r t a n c e i s t h e c o n s t a n c y and r e p r o d u c i b i l i t y o f t h e r e a c t i o n t e m p e r a t u r e * In a g i v e n e x p e r i ­ ment t h e t e m p e r a t u r e d i d n o t v a r y more t h a n + 0 . 2 ° f o r t h e f i r s t 90;I? o f t h e r e a c t i o n . Among v a r i o u s e x p e r i m e n t s t h e t e m p e r a t u r e a l w a y s r e m a in e d w i t h i n 1 Q o f 8 2 . S'-' and In t h e m a j o r i t y o f t h e e x o e r i r e n t s t h e t e m p e r a t u r e was S 2 . 5 ;) + 0 . 5 ° t h r o u g h o u t th© r e ­ a c t i o n . B a r o m e t r i c p r e s s u r e s h av e b e e n n o t e d r e g u l a r l y d u r i n g a l l r u n s ; i n g e n e r a l , v a r i a t i o n s o f r e f l u x t e m p e r a t u r e due t o p r e s s u r e f l u c t u a t i o n s w ere n o t s i g n i f i c a n t . - 22- The r e m o v a l o f w a t e r from t h i s a z e o t r o p i c s y s t e m must n o t o n l y b e q u a n t i t a t i v e but t h e w a t e r m ust b e rem oved a s f a s t a s formed# In o r d e r t o i n s u r e prompt r e m o v a l o f w a t e r , t h e p r o p e r v o l t a g e s e t t i n g o f th© g l a s c o l b e a t i n g m a n t l e was d e t e r m i n e d # By a s e r i e s o f t r i a l s i t was fo u n d t h a t w i t h o n © - e i g h t h m ole t r i p h e n y l c a r b i n c l , o n e - e i g h t h mole n - b u t a n o l and 0 . 0 0 0 2 5 m o le s p - t o l u e n e s u l f o n i c a c i d d i l u t e d w i t h b e n z e n e t o a t o t a l vo lu m e o f f i v e h u nd red m i l l i l i t e r s a s e v e n t y v o l t s e t t i n g o f th© v a r i a c c a u s e d t h e w a t e r t o b e removed a s f a s t a s I t was fo r m e d ( s e e F i g u r e I I # ) T h ree I d e n t i c a l r u n s e x c e p t f o r t h e v o l t a g e s , w h i c h w e r e s e t a t s i x t y , s e v e n t y and s e v e n t y - f i v e , g a v e e s s e n t i a l l y i d e n t i c a l c u r v e s when v o lu m e s o f w a t e r c o l l e c t e d w e r e p l o t t e d a g a i n s t t i m e . I t f o l l o w e d t h a t a s e v e n t y v o l t s e t t i n g would rem ove w a t e r a s f a s t a s fo r m e d from any r e a c t i o n w h i c h d i d n o t go f a s t e r t h a n t h i s p a r t i c u l a r one and c a r e was t a k e n t o k e e p r e a c t i o n r a t e s b e l o w t h i s v a l u e b? p r o p e r a d j u s t m e n t o f t h e c a t a l y s t c o n c e n t r a t i o n w here p o s s i b l e * T h i s was f e a s i b l e In a l l b u t two c a s e s # ISven t h e s e c a s e s a r e b e l i e v e d t o b@ a c c u r a t e f o r r e a s o n s g i v e n i n t h e e x p e r i m e n t a l s e c t i o n # C e r t a i n a l c o h o l s form a q u eo u s a z e o t r o p e s w h ic h d i s t i l l o u t o f th © r e a c t i o n f l a s k . I f , h o w e v e r , th© a l c o h o l s a r e s o l u b l e In w a t e r t o o n l y a s m a l l d e g r e e t h e y ar© c a r r i e d b a ck i n t o t h e r e a c t i o n f l a s k w i t h t h e r e t u r n i n g b e n z e n e a s th© r © f l u x i n g p r o ­ c e e d s # A m ea s u r e o f t h e d e n s i t y o f th© w a t e r In t h e s e p a r a t o r I n d i c a t e d t h a t o n l y n e g l i g i b l e a m ou n ts o f a l c o h o l i c r e a c ta n tes# e v en t h o s e a s v o l a t i l e and s o l u b l e a s b u t a n o l , w ere f o u n d I n t h e w a t e r l a y e r # T h ere i s no s i g n i f i c a n t e r r o r t h a n In t h e method due t o t h e s o l u b i l i t y o f b u t a n o l o r a n y h i g h e r a l c o h o l * As m e n t io n e d b e f o r e , e t h a n o l d o e s a p p e a r i n th© w a t e r l a y e r and t h e amount o f i t p r e s e n t can b e c a l c u l a t e d from d e n s i t y o r r e f r a c t i v e i n d e x d e t e r m i n a t i o n s . A n o t h e r p o s s i b l e s o u r c e o f i n a c c u r a c y i s t h e d e s t r u c t i o n o r i n a c t i v a t i o n o f t h e c a t a l y s t due t o some s i d e r e a c t i o n . A p o s s i b l e r e a c t i o n i n w h i c h i t c o u ld b e consum ed would be t h e O Qs u l f o n a t i o n o f t h e b e n z e n e s o l v e n t t o & s u l f o n e . fro m th© r e s u l t s o f pH d e t e r m i n e t i o n s i t seem s u n l i k e l y t h a t t h i s r e ­ a c t i o n t a k e s p l a c e t o a d e t e c t a b l e e x t e n t . I t was f o u n d t h a t d u r i n g th© c o u r s e o f r u n s a t c a t a l y s t c o n c e n t r a t i o n s o f 0 . 0 0 0 2 5 m o la r and a b o v e , t h e r e was no s i g n i f i c a n t c h a n g e i n t h e c o n c e n ­ t r a t i o n o f t h e c a t a l y s t . As some I n d i c a t i o n o f t h e d e g r e e o f i o n i z a t i o n o f a q u e o u s p - t o l u e n © s u l f o n i c a c i d , i t can b e s t a t e d t h a t © 0 * 0 0 0 0 5 m o la r s o l u t i o n h a s a pH o f 4 . 7 6 a s d e t e r m i n e d on t h e pH m e t e r and a c a l c u l a t e d pH o f 4 . 3 0 . Th© r e m o v a l o f w a t e r by a z e o t r o p i c d i s t i l l a t i o n w i t h b e n ­ z e n e i s a w e l l known m eth od f o r d e t e r m i n i n g w a t e r i n v a r i o u s s o l u t i o n s . T h i s method h a s been foun d t o b e o f s a t i s f a c t o r y a c c u r a c y f o r q u a n t i t a t i v e w o r k . S i m i l a r a c c u r a c y w ou ld b e e x ­ p e c t e d t o be a t t a i n e d i n t h e a z e o t r o p i c m ethod o f f o l l o w i n g r e ­ a c t i o n s and t h e l a r g e number o f c a s e s i n w h ic h a l m o s t e x a c t l y t h e t h e o r e t i c a l amount o f w a t e r was o b t a i n e d shows t h a t h i g h a c c u r a c y i s a t t a i n e d . 1 6 c-*4The a z e o t r o p i c *' m ethod o f c a r r y i n g o u t r e a c t i o n s o f f e r s a number o f a d v a n t a g e s . I t 1ms b e e n u s e d f o r s e v e r a l d i f f e r e n t t y p e s o f s y n t h e s e s and d e t e r m i n a t i o n s . * ^ To o u r k n o w l e d g e , how­ e v e r , I t h a s n e v e r p r e v i o u s l y b e e n u s e d f o r k i n e t i c s t u d i e s . The method h a s b e e n u s e d in t h e p r e p a r a t i o n o f k e t a l s , - 24 - 75 27 95a c e t a l s 9 and e s t e r s • The r e m o v a l o f w a t e r p r o d u c e d In t h e r e a c t i o n s f o r c e d th© r e a c t i o n s t o c o m p l e t i o n * M ix t u r e s o f f o r m a ld e h y d e , h e x a m e t h y l e n e t e t r a m i n e and v a r i o u s a l c o h o l s h a v e b e e n r e a c t e d i n b e n z e n e or t o l u e n e s o l u t i o n and t h e w a t e r p r o d u c e d h a s been a z e o t r o p i c a l l y rem oved t o h a s t e n t h e f o r m a - t l o r , o f {ROCHg) c o m p o u n d s . ^ E t h y l c y a n o a c e t a t a and k e t o n e s h a v e been c o n d e n s e d In t h e p r e s e n c e o f ammonium a c e t a t e and g l a c i a l a c e t i c a c i d by t h e a z e o t r o p i c r e m o v a l o f w a t e r w i t h 12b e n z e n e . «Vith t h e same c a t a l y s t s , t h i s method h a s been u sed i n d e t e r m i n i n g t h e t i m e f o r t o t a l r e a c t i o n b e tw e e n m a l o n o n i - 62t r i l e and. v a r i o u s l y s u b s t i t u t e d a c e t o p h e n o n e s . The v o lu m e s o f t h e a q u e o u s l a y e r s w ere in e x c e s s o f t h e o r y by a b o u t 20% i n e v e r y c a s e b e c a u s e o f t h e s i d e r e a c t i o n i n w h i c h ammonium a c e t a t e d e c o m p o se d t o t . i v e a c e t a m i d e and w a t e r and b e c a u s e o f t h e d i s t i l l a t i o n o f a c e t i c a c i d and i t s s o l u t i o n i n t h e w a t e r * 72Hi c a r d h a s p a t e n t e d a c o n t i n u o u s p r o c e s s f o r th© m a n u f a c t u r e o f s h o r t c h a i n s y m m e t r ic a l a l i p h a t i c e t h e r s i n w h ic h a ^ w i t h ­ d r a w i n g b o d y ” s u c h a s g a s o l i n e o r b e n z e n e i s a dd ed t o a m i x t u r e o f t h e a l c o h o l and s u l f u r i c a c i d . T h i s s o l v e n t i s d i s t i l l e d o f f c a r r y i n g th® w a t e r w i t h i t . He e m p lo y e d r e a c t i o n m edia w i t h s u l f u r i c a c i d c o n c e n t r a t i o n s o f 4 0 t o 50% and b e n z e n e o r g a s o l i n e c o n c e n t r a t i o n s o f 3 t o 5%. H is p r o c e s s i s e s s e n t i a l l y a m ethod o f a v o i d i n g d e a c t i v a t i o n o f t h e c a t a l y s t by t h e w a t e r form ed i n t h e c l a s s i c a l s u l f u r i c a c i d p r o c e s s f o r e t h e r s y n ­ t h e s i s . The t e c h n i q u e a s d e v e l o p e d in t h i s s t u d y h a s b een fo u n d t o h a v e w i d e a p p l i c a t i o n i n t h e s y n t h e s i s o f e t h e r s and i n r e ­ a c t i o n r a t e d e t e r m i n a t i o n s o f e t h e r i f l c a t i o n s and t r a n s e t h e r i - f l c a t i o n s * I t has a l s o b e e n shown t o b e a p p l i c a b l e t o c e r t a i n a l k y l a t i o n s and a l c o h o l d e h y d r a t i o n s and i t c a n b e u s e d f o r a s t u d y o f t h e r e l a t i v e b a s i c i t y o f v a r i o u s a l c o h o l s * o t h e r a p p l i c a t i o n s a r e be ing , i n v e s t i g a t e d In t h e s e l a b o r a t o r i e s * The a z e o t r o p i c rem ova l o f w a t e r from t h e r e a c t i o n m i x t u r e s i m p l i f i e s t h e k i n e t i c s o f t h e s y s t e m by p r e v e n t i n g t h e r e v e r s e r e a c t i o n . I t a l s o g i v e s h i £ h y i e l d s , o f t e n e s s e n t i a l l y q u a n t i ­ t a t i v e , when u s e d f o r s y n t h e s i s s i n c e r e m o v a l o f t h e w a t e r f o r c e s t h e r e a c t i o n t o c o m p l e t i o n * The a p r o t i c b e n z e n e s o l u - rj t i o n i s k i n e t i c a l l y s i m p l e . S i n c e t h e w a t e r i s rem oved a s f a s t a s I t i s form ed , t h e c a t a l y s t l a n o t d e a c t i v a t e d by I t . In a d d i t i o n , t h e o n e p h a s e r e f l u x i n g b e n z e n e s o l u t i o n a f f o r d s a d e q u a t e m i x i n g f o r k i n e t i c s t u d i e s . The ra t© a t w h ic h t h e w a t e r I s a s e o t r o p i c a l l y d i s c h a r g e d and c o l l e c t e d i s d i r e c t l y d e t e r m i n e d by r e a d i n g t h e v o lu m e in t h e s e p a r a t o r . Each r e a d i n g i s a c t u a l l y a q u a n t i t a t i v e d e t e r ­ m i n a t i o n o f t h e m o le s o f p r o d u c t p r e s e n t a t t h a t t i m e s i n c e one m ole o f w a t e r i s p r o d u c e d f o r e v e r y mole o f e t h e r f o r m e d . The s i m p l i c i t y h e r e c a n b e c o n t r a s t e d w i t h t h e u s u a l p r o c e d u r e o f w i t h d r a w i n g s a m p le s from th© r e a c t i o n m i x t u r e and r u n n i n g numerous a n a l y s e s . An added a d v a n t a g e i s t h a t t h e p o r t i o n o f a l c o h o l s y e t r e m a i n i n g t o b e e t h e r i f l e d i s l e f t u n d i s t u r b e d . The p r o c e d u r e o f a d d i n g t h e c a t a l y s t t o t h e m i x t u r e o f a l c o h o l s In s o l u t i o n a f t e r t h e y h a v e b e e n b r o u g h t t o r e a c t i o n t e m p e r a t u r e i s a b e t t e r w a y o f e s t a b l i s h i n g z e r o r e a c t i o n t i m e t h a n t h a t u sed i n many k i n e t i c m eth o d s* Th© method h a s t h e a d v a n t a g e t h a t o n l y two r u n s a r e r e ­ q u i r e d f o r an a c c u r a t e p l o t o f t h e r e a c t i o n r a t © . In t h e f i r s t - 2 6 - r u n , s t a r t i n g w i t h a t r a c e o f c a t a l y s t , a d d i t i o n a l p o r t i o n s can be add ed u n t i l t h e amount n e c e s s a r y f o r r e a c t i o n i s i n ­ d i c a t e d b y t h e d i s c h a r g e o f w a t e r i n t o t h e s e p a r a t o r a t a c o n v e n i e n t r a t e * A n o t h e r run can t h e n b e made s t a r t i n g a t t h i s I n i t i a l c o n c e n t r a t i o n g i v i n g a r e l i a b l e c u r v e . O f te n t h e p r o d u c t need n o t be i s o l a t e d t o d e t e r m i n e what I s t a k i n g p l a c e , and I f t h e r e a c t i o n d o e s n o t go t o an a p p r e c i a b l e e x ­ t e n t , t h i s f a c t I s i m m e d i a t e l y e v i d e n t . At t h i s p o i n t i t was d e c i d e d t o l i m i t f u r t h e r I n v e s t i g a ­ t i o n c h i e f l y t o th© m o n o - , d i - , and t r l p h e n y l c a r b l n o l s • I t was deemed a d v i s a b l e t o make a r a t h e r broad s u r v e y o f t h e g e n ­ e r a l a p p l i c a t i o n s o f t h e a z e o t r o p i c m ethod to th© e t h e r i f I c a t i o n and r e l a t e d r e a c t i o n s o f t h e s e c a r b l n o l s . I t was p la n n e d t h a t more c o m p l e t e s t u d i e s o f t h e m ost i m p o r t a n t a p p l i c a t i o n s w ou ld t h e n b e c a r r i e d , o u t by o t h e r I n v e s t i g a t o r s in t h e s e l a b o r a t o r i e s * THE EFFECT OF VAT l'ATIOKS IN THE CHAIN LENGTH OF ROB. T he f i r s t o b j e c t i v e o f t h e i n v e s t i g a t i o n o f t h e p h e n y l c a r b l n o l s was t o d e t e r m i n e w h e t h e r th© r a t e o f e t h e r ! f l c a t io n o f t r i p h e n y l car lo3 n o l v a r i e d a s t h e c h a i n l e n g t h o f t h e RGH a l c o h o l w as v a r i e d . F i v e h u n d r e d m i l l i l i t e r s o f a b e n z e n e s o l u t i o n , w h ic h was 0 . 2 5 m o la r i n t r i p h e n y l c a r b i n o l and 0 . 2 5 m o la r i n n - b u t a n o l , was b r o u g h t t o r e f l u x i n th© s t a n d a r d a p p a r a t u s ( F i g u r e I ) . S u f f i c i e n t p - t o l u e n e s u l f o n i c a c i d m o n o h y d r a te was t h e n added t o g i v e a 0 . 0 0 0 5 m o la r s o l u t i o n . F r e q u e n t r e a d i n g s o f t h e v o l um© o f w a t e r p r o d u c e d were t a k e n . Th© d a t a a r e g r a p h e d In F i g u r e I I i n t e r m s o f p e r c e n t c o m p l e t i o n v e r s u s t i m e . P er ce nt re ac ti on co m p le te 100 50 100 150 Minutes F ig u r e I I . Rate o f e t h e r i f i c a t i o n o f t r i p h e n y l c a r b i n o l and 1 - b u t a n o l # # # , t - h e p t a n o l €)C C , and 1 d e c a n o l O O O * A l l c a t a l y s t c o n c e n t r a t i o n s are 0 -0 0 0 5 molar . -L % - Th© e x p e r i m e n t was c a r r i e d o u t t w i c e more w i t h n » h e p t y l a l c o h o l , a ml n - d e c y l a l c o h o l i n p l a c e o f t h e n - b u t v l a l c o h o l * F i g u r e XI g i v e s th© r e s u l t s o f t h e s e r u n s a l s o * I t I s a p p a r e n t t h a t t h e method h a s s y n t h e t i c v a l u e i n t h e p r e p a r a t i o n o f e t h e r s fro m t r i p h e n y l c a r b i n o l and norm al p r im a ry a l i p h a t i c a l c o h o l s a b o v e m e t h a n o l* W ell o v e r 9 0 $ o f t h e d e s i r e d p r o d u c t was i s o l a t e d from e a c h o f t h e a b o v e t h r e e r e a c t i o n m ix ­ ture®-* S i n c e , amon*, o t h e r s , t h e e t h y l , p r o p y l , c e t y l and © t h y - qr l o n e c l ye. o 1 e t h e r s o f t r i p h e n y l c a r b i n o l a r e c r y s t a l l i n e s o l i d s , *“ t h i s method s h o u l d be a p p l i c a b l e t o t h e p r e p a r a t i o n o f d e r i v a ­ t i v e s o f t h e s e a l c o h o l s * 0The r e l a t i v e l y low r e a c t i o n t e m p e r a t u r e o f 82 i s a d e f i n ­ i t e a d v a n t a g e i n t h e s y n t h e s i s o f t h e s e t r i p h e n y l m e t h y l e t h e r s f o r a t more e l e v a t e d t e m p e r a t u r e s t h e y w i l l r e a d i l y u n d e r g o p y r o - l y s i s , y i e l d i n g t h e a l d e h y d e o f ROH and t r i p h e n y l m ethane* In c o n t r a s t , d i b e n s y l e t h e r d o e s n o t d e c o m p o s e e x c e p t in t h e p r e s e n c e o f a luminum o x i d e * * A p l o t ( F i g u r e I I I ) o f t h e l o g a r i t h m o f t h e t r i p h e n y l c a r b i n o l c o n c e n t r a t i o n v e r s u s t i m e g a v e c l o s e a g r e e m e n t t o a f i r s t o r d e r m echan ism up to a b o u t 9 0 $ c o m p l e t i o n f o r t h e r e a c t i o n t a k i n g p l a c e whan e a c h o f t h e s e t h r e e a l c o h o l s was r e f l u x e d w ith , t h i s p a r t i c u l a r p h e n y l c a r b i n o l . The c a l c u l a t i o n o f a s p e c i f i c r a t e c o n s t a n t from t h e p l o t In F i g u r e I I I g i v e s a v a l u e o f 0 . 0 5 6 r e c i p r o c a l m in u te s * S ec o n d o r d e r p l o t s w e r e m a r k e d ly c u r v e d In a l l t h r e e c a s e s * Tim© was a v a i l a b l e f o r o n l y a p r e l i m i n a r y s t u d y o f t h e e f f e c t o f c h a n g e s In c o n c e n t r a t i o n o f t h e a l c o h o l s . I t was f o u n d , h o w e v e r , t h a t good f i r s t o r d e r p l o t s w e r e o b t a i n e d f o r a run made w i t h a t w o f o l d e x c e s s o f t r i o h e n y l c a r b i n o l and f o r a run made Lo g of co nc . of tr ip he ny l ca rb in ol - 29- - 1.0 ■ 1 .5 Oc R E A C T I O N 9 0 % C O M P L E T E ■2.0 1 L_ 10050 M in u t e s F i g u r e I I I . F i r s t o r d e r p l o t from d a t a i n F i g u r e I I . - 30- w l t h a t h r e e f o l d e x c e s s o f n - b u t a n o l • The r a t© d a t a f o r t h e s e r u n s a r e g i v e n i n t h e E x p e r i m e n t a l . I t I s * o f c o u r s e , r e c o g n i z e d t h a t a d d i t i o n a l i n f o r m a t i o n must h e o b t a i n e d b e f o r e an a d e q u a t e t h e o r e t i c a l i n t e r p r e t a t i o n o f many o f t h e e x p e r i m e n t a l r e s u l t s r e p o r t e d h e r e can h e made. I t s e e m s , n e v e r t h e l e s s , t h a t w h ere r e a s o n a b l e t h e o r e t i c a l e x ­ p l a n a t i o n s ca n he g i v e n a t t h i s t im e i t w i l l b e h e l p f u l t o do s o i f i t i s k e p t in mind t h a t many o f t h e s e e x p l a n a t i o n s a r e a s y e t o f a t e n t a t i v e n a t u r e . T h i s p l a n w i l l be f o l l o w e d i n t h i s and t h e s u b s e q u e n t s e c t i o n s o f t h i s t h e s i s . As p r e v i o u s l y s t a t e d , a c c o r d i n g t o H ammett’ s t h e o r y , ^ t h e m ec h a n ism o f e t h e r i f i c a t io n i s : ( 1 ) R' : 0 : B + H + -------.* T 1 -------- * B* s t f : B , .H+ (2 ) R 1 sds B ^-------------• • <:------------- — ^ R f + + B* ( 3 ) R l+ + R s*0*: H -?— * • «--- ----------» R ’ s t f s E———— . * R + ( 4 ) R * s o : h p -----------------• . ^ ------------- -— --------> H i p ’s R* S i n c e t h e s e r e a c t i o n s w e r e f o l l o w e d b y m e a s u r i n g th© r a t e a t w h i c h w a t e r was fo rm e d th© ra t© o f o n l y s t e p s ( 1 ) and ( 2 ) was m ea su r ed d i r e c t l y . In t h e work d e s c r i b e d j u s t a b o v e , how­ e v e r , i t was f o u n d t h a t I n c r e a s i n g th© c o n c e n t r a t i o n o f R ’ OH ( t r i p h e n y l c a r b i n o l ) g r e a t l y I n c r e a s e d t h e r a t e o f r e a c t i o n w h i l e i n c r e a s i n g th© c o n c e n t r a t i o n o f BOH ( n - b u t a n o l ) had l i t t l e e f f e c t on t h e r a t e . I t a p p e a r s , t h e r e f o r e , t h a t s t e p ( 3 ) , In w h i c h th© BO FI i s f i r s t i n v o l v e d , g o e s t o o f a s t t o b e r a t e c o n t r o l l i n g . T h i s w o u ld n o t be u n e x p e c t e d s i n c e carboniura I o n s i n g e n e r a l a r e h i g h l y r e a c t i v e . S t e p ( 4 ) n e e d n o t be c o n s i d e r e d s i n c e I t s r a t e i s n o t m e a s u r e d by t i l l s a z e o t r o p i c m ethod and s i n e © t h e p r o c e s s i t d e n o t e s i s n o t i m p o r t a n t t o t h e main o b j e c t i v e o f t h e p r e s e n t d i s c u s s i o n . I t may b© c o n c l u d e d , t h e n , t h a t e i t h e r s t e p ( 1 ) o r s t e p { 2 ) i s th© most l i k e l y r a t e c o n ­ t r o l l i n g s t e p and t h e r a t e c o n t r o l l i n g s t e p f o l l o w s a f i r s t o r d e r m echanism * From t h e s t a n d p o i n t o f o r g a n i c c h e m i s t r y t h e most p r o b a b l e r a t© c o n t r o l l i n g s t e p m ig h t be i n t e r p r e t e d a s be ing, s t e p ( 2 ) • A d e f i n i t e c h o i c e b e t w e e n s t e p ( 1 ) and ( 2 ) i s d i f f i c u l t and c a n n o t be made on th© b a s i s o f t h e e v i d e n c e a v a i l a b l e a t p r e s e n t * S i n c e t h e p r o t o n c o n c e n t r a t i o n may o r d i n a r i l y b e c o n s i d e r e d t o rem a in c o n s t a n t , s t e p ( 1 } m ig h t b e e x p e c t e d to b e f i r s t o r d e r ami o f c o u r s e s t e p ( 2 ) r e p r e s e n t s a f i r s t o r d e r p r o c e s s * S t e p ( 1 ) i s an a c i d - b a s e r e a c t i o n w h ic h wou ld o r d i n a r i l y b e e x p e c t ­ ed t o p r o c e e d r a p i d l y and h e n c e n o t c o n t r o l t h e r a t e , j u s t a s p r o t o n s In t h e p r e s e n c e o f w a t e r a r e r a p i d l y c o n v e r t e d t o th© h v d ro n iu m i o n . S t e p ( 2 ) , f u r t h e r m o r e , p r o d u c e s t h e carboniura Ion w h ic h g e n e r a l l y r e q u i r e s h i g h e n e r g y i n p u t and h e n c e m ig h t be e x p e c t e d t o p r o c e e d s l o w l y and c o n t r o l t h e r a t e . Some c o n ­ t r a r y e v i d e n c e , h o w e v e r , w h i c h a p p e a r s t o f a v o r s t e p ( 1 ) a s t h e r a t e c o n t r o l l i n g s t e p , I s g i v e n in t h e s e c t i o n on t h e v a r i a ­ t i o n o f c a t a l y s t c o n c e n t r a t i o n . No m a t t e r w h i c h o f t h e s e s t e p s I 3 r a t e c o n t r o l l i n g t h e c h a i n l e n g t h o f HOB w ou ld n o t be e x p e c t ­ ed t o a f f e c t t h e r a t e . T h i s d i s c u s s i o n o f t h e mechanism has b e e n g e n e r a l and s h o u l d , t h e r e f o r e , a p p l y t o o t h e r e t h e r i f I c a t i o n s w h i c h a r e shown i n l a t e r s e c t i o n s o f t h i s p a p e r t o b© f i r s t o r d e r a s w e l l a s t h e © t h e r l f i c a t i o n s d i s c u s s e d I n t h i s s e c t i o n . ■32- THE EFFECT OF VARIATIONS IK THE NUMBER OF PHENYL GROUPS OH THE ALPHA CART-OH OF H1 OH The n e x t o b j e c t i v e was t h e d e t e r m i n a t i o n o f t h e r e l a t i v e e f f e c t s o n t h e e a s e o f e t h e r ! f I c a t i o n o f o n e , two o r t h r e e p h e n y l g r o u p s on t h e c a r b o n o f t h e R*0I1 a l c o h o l . The r a t a o f e t h e r i f I c a t i o n o f t r i p h e n y l c a r b i n o l by n - b u t y l a l c o h o l i n t h e p r e s e n c e o f a 0 . 0 0 0 5 m o la r s o l u t i o n o f t h e c a t a l ­ y s t was d e s c r i b e d i n p r e c e d i n g s e c t i o n . S i m i l a r r u n s w e r e made i n w h ic h t h e t r i p h e n y l c a r b i n o l was r e p l a c e d by b e n z h y d r o 1 a t s i x t e e n t i m e s t h e a b o v e c a t a l y s t c o n c e n t r a t i o n and by b e n z y l a l c o h o l a t s i x t e e n t i m e s t h e c a t a l y s t c o n c e n t r a t i o n u s e d w i t h t he h e n z h y d r o 1 • Under t h e s e c o n d i t i o n s t h e r a t e s o f e t h e r i f I c a t i o n o f b e n - z h v d r o l and t r i p h e n y l c a r b i n o l a r e p r a c t i c a l l y i d e n t i c a l ( F i g u r e I V ) . S i n c e t h e s h a p e s o f t h e c u r v e s a g r e e so c l o s e l y , t h e p r e ­ c e d i n g d i s c u s s i o n o f t h e o r d e r and m echan ism o f t h e t r i p h e n y l c a r b i n o l r e a c t i o n s h o u l d a l s o a p p l y t o t h e b e n z h y d r o l r e a c t i o n . The r e a c t i o n r a t e c o n s t a n t c a l c u l a t e d from t h e f i r s t o r d e r p l o t f o r t h e b e n z h y d r o l r e a c t i o n I s 0 . 0 3 8 r e c i p r o c a l m i n u t e s * (The o r d e r p l o t f o r b e n z h y d r o l I s g i v e n i n F i g u r e X.) The b e n z h y d r o l b u t y l e t h e r was a l s o i s o l a t e d i n n e a r l y q u a n t i t a t i v e y i e l d . The g r e a t d i f f e r e n c e i n r e a c t i v i t y o f t r i p h e n y l c a r b i n o l and b e n ­ z h y d r o l can b e e m p h a s iz e d b y r e f e r r i n g t o t h e s e c t i o n on th© e f f e c t s o f v a r i a t i o n s i n c a t a l y s t c o n c e n t r a t i o n on t h e ra t© and o r d e r o f e t h e r i f i c a t i o n , w h ere i t i s shown t h a t by o n l y d o u b l i n g t h e a c i d c o n c e n t r a t i o n o f 0 . 0 0 0 5 m o la r u sed f o r t h e r e a c t i o n w i t h t r i p h e n y l c a r b i n o l t h e h a l f r e a c t i o n t i m e i s d e ­ c r e a s e d from t w e n t y - s i x m i n u t e s t o t w e l v e m i n u t e s ( F i g u r e V I ) . P er ce nt re ac ti on co m p le te 100 ~ioo” i_ 15050 M inutes F ig u r e IV. Hate o f e t h e r i f i c a t i o n o f t r i p h e n y l c a r b i n o l and n - b u t a n o l 'with 0 .0 0 0 5 molar c a t a l y s t # # 0 , benzhyd ro l and n - b u t a n o l w i t h 0 . 0 0 3 molar c a t a l y s t 0 0 0 , and b e n z y l a l c o h o l and n - b i i t a n o l w i t h 0 . 1 2 3 molar c a t a l y s t O O O * i w 03I Th© c u r v e f o r t h e r e a c t i o n w i t h b e n z y l a l c o h o l i s ^ i v o n a l s o i n F ig u r e IV# (A more n e a r l y c o m p l e t e c u r v e i s g i v e n In F i g u r e V o f t h e n e x t s e c t i o n . ) Upon i s o l a t i o n o f th© p r o d u c t s t h e r e was o b t a i n e d a 5 3 . 2 h y i e l d o f d i p h e n y l m e th a n e i n a d d i ­ t i o n t o o n l y a 4 0 * 4 > y i e l d o f b e n z y l b u t y l e t h e r . A g e n e r a l d i s c u s s i o n o f a l k y l a t i o n work b y t h i s m eth od w i l l be g i v e n In t h e n e x t s e c t i o n . A l t h o u g h b o t h a l k y l a t i o n and e t h e r I f I c a t i o n w e re - o c c u r r in g i n t h e r e a c t i o n i n v o l v i n g b e n z y l a l c o h o l , on t h e b a s i s o f e v i d e n c e t o b e p r e s e n t e d l a t e r , i t i s b e l i e v e d t h a t o t h e r ! f i c a t i o n p r e d o m i n a t e s d u r i n g t h e e a r l y s t a g e s o f t h e r e ­ a c t i o n . C o n s e q u e n t l y a r o u g h c o m p a r i s o n o f r a t e s o f e t h e r ! f l ­ o a t I on d u r i n g th© f i r s t p a r t o f a l l t h r e e r e a c t i o n s h a s some j u s t i f i c a t i o n . In a n y c a s e , t h e t r u e c u r v e f o r e t h e r i f I c a t I o n o f b e n z y l a l c o h o l w o u ld b e b e l o w r a t h e r t h a n a b o v e t h a t one g i v e n i n F i g u r e IV . The d i f f e r e n c e s i n r a t e s o f e t h e r i f i c a t I o n o f t h e t h r e e I t1 OK a l c o h o l s s t u d i e d her© a r e o f a h i g h e r o r d e r o f m a g n i t u d e t h a n d i f f e r e n c e s w h i c h m ig h t r e s u l t from t h e i r d i f f e r e n t b a s i c i ­ t i e s a s d i s c u s s e d i n t h e s e c t i o n on t h e d e t e r m i n a t i o n o f t h e e f f e c t o f t h e number o f a l p h a p h e n y l g r o u p s on t h e b a s i c i t y o f t h e a l c o h o l . T h i s method o f d e t e c t i n g d i f f e r e n c e s i n th© e a s e o f e t h a r - 5 f I c a t i o n o f a c t i v a t e d a l c o h o l i c h y d r o x y l s may p r o v e u s e f u l In c h o o s i n g b e tw e e n a l t e r n a t i v e p o s i t i o n s f o r an h y d r o x y l grou p In compounds o f unknown s t r u c t u r e . In v i e w o f t h e Hammett mechanism,*5^ i t a p p e a r s t h a t th© s i x t e e n - f o l d I n c r e a s e In th© c a t a l y s t c o n c e n t r a t i o n r e q u i r e d t o e t h e r i f y b e n z h y d r o l a t th© same ra t© a s t r i p h e n y l c a r b i n o l - 35- w i t h n - b u t a n o l i s n o t u n r e a s o n a b l e . The f a c t t h a t b e n z y l a l c o h o l r e q u i r e s a two h u nd red and f i f t y - s i x f o l d i n c r e a s e i n t h e c o n c e n t r a t i o n o f p - t o l u e n e s u l f o n i c a c i d t o e t h e r i f y b u t a ­ n o l a t an a p p r e c i a b l e b u t much s l o w e r r a t e i s a l s o i n a g r e e m e n t w i t h t h i s m e c h a n ism . From t h e p r e l i m i n a r y w ork, i t was s e e n t h a t b u t a n o l had l i t t l e d i s p o s i t i o n t o a c t a s t h e R 1 OH a l c o h o l i n t h e p r e s e n c e o f any o f a v a r i e t y o f c a t a l y s t s . T h e s e r e ­ s u l t s w o u ld c a u s e u s t o a r r a n g e t h e c a r b l n o l s i n an o r d e r o f i n c r e a s i n g a c t i v i t y from n - p r o p y l t o m o n o p h e n y l t o d i p h e n y l t o t r i p h e n y l c a r b i n o l . T h i s i s t h e same o r d e r o f a c t i v i t y shown by t h e c h l o r i d e s o f t h e s e a l c o h o l s to w a r d s i l v e r n i t r a t e , f o r e x a m p l e , and by t h e s e a l c o h o l s , t h e m s e l v e s , t o w a r d s h y d r o ­ g e n h a l i d e s . B o th e l e c t r o n a t t r a c t i n g and e l e c t r o n r e p e l l i n g p r o p e r t i e s 53a r e g e n e r a l l y a s s o c i a t e d w i t h t h e p h e n y l g r o u p . ^ I f t h e e l e c t - t r o n r e p e l l i n g p r o p e r t i e s o f t h e p h e n y l group p r e d o m i n a t e h e r e o n e p h e n y l gro u p on t h e *< c a rb o n w o u ld h a v e a c e r t a i n t e n d e n c y t o p u t a n e g a t i v e c h a r g e on t h a t c a r b o n atom w h i c h w o u ld r e p e l l t h e n e g a t i v e h y d r o x y l a t t a c h e d t h e r e t o and a s a r e s u l t f a c i l i ­ t a t e e t h e r i f I c a t i o n ( e q u a t i o n s i and 2 ) . Two p h e n y l g r o u p s w ou ld h a v e a g r e a t e r e f f e c t i n t h e same d i s p l a c e m e n t o f h y d r o x y l and i n t r i p h e n y l c a r b i n o l t h e e f f e c t w i l l b e g r e a t e s t I n weak­ e n i n g t h e c a r b o n t o o x y g e n bon d . In t h e l a s t s e c t i o n , h o w e v e r , e x p e r i m e n t s on t h e r e l a t i v e b a s i c i t y o f b u t a n o l and t h e p h e n y l c a r b l n o l s c a n b e s t b e I n t e r ­ p r e t e d i n t e r m s o f t h e e l e c t r o n a t t r a c t i n g power o f t h e p h e n y l g r o u p . I t ap e a r s , t h e r e f o r e , t h a t t h e b e t t e r e x p l a n a t i o n o f t h e r e l a t i v e r e a c t i v i t i e s o f t h e t h r e e p h e n y l c a r b l n o l s I s I n •36 t e r m s o f t h e s t a b i l i s a t i o n by r e s o n a n c e o f t h e i r r e s p e c t i v e c a rb o n iu m i o n s , Bergman and l a r a e l a a h v i l i h a v e p o i n t e d o u t t h a t when d i a r y l c a r b l n o l s r e a c t w i t h e l e c t r o p h l l i c r e a g e n t s , t h e c h a r g e on t h e r e s u l t i n g c a r b o n 5 urn Ion can b© d i s t r i b u t e d o v e r a l l a v a i l a b l e o r t h o a fid p a ra . p o s i t i o n s . They s t a t e t h a t "th© a c c u m u l a t i o n o f p h e n y l r a d i c a l s i n c r e a s e s t h e p r o b a b i l i t y o f t h e i r p a r t i c i p a t i o n i n t h e r e s o n a n c e o f th© carbon!urn io n #n^ E e m lc k , i n t h e sama w a y , h a s i n d i c a t e d t h a t th© s t a b i l i t y o f t r i p h e n y l carbon!urn i o n c a n be a t t r i b u t e d t o r e s o n a n c e s t a f c l l t - 71s a t l o n o f t h e s o r t : T h e r e a r e ten p o s s i b l e fo rm s h e r e # The i n t e n s e y e l l o w c o l o r p ro d u ced when a c i d i s added t o t r i p h e n y l c a r b i n o l may v e r y d e f i n i t e l y be r e l a t e d ' t o t h i s l a b i l i t y o f e l e c t r o n s i n t h e t r l p h e n y l m e t h y l r a d i c a l . W ith b e n z h y d r o l , s t a b i l i z a t i o n o f t h e c a r b o n ! urn i o n w i l l b e r e d u c e d s i n c e t h e r e a r e o n l y two a r o m a t i c n u c l e i and s e v e n p o s s i b l e form s# In t h e c a s e o f b e n z y l a l c o h o l , t h e number o f form s c o n t r i b u t i n g t o t h e r e s o n a n c e h y b r i d i s e v e n f u r t h e r r e ­ d u c e d t o f o u r b e c a u s e o f th© p r e s e n c e o f o n l y o n e p h e n y l g r o u p on th© X c a r b o n atom# Of c o u r s e w i t h n - f e u t a n o l no s u c h s t a b i l i ­ z a t i o n i s p o s s i b l e # - 37- TE.E ALKYLATION OP BBNZENE BY BENZYL ALCOHOL AND BENZYL ETHER As m e n t io n e d In t h e p r e c e d i n g s e c t i o n t h e a t t e m p t e d e t h e r l f i c a t i o n o f b e n z y l a l c o h o l by n - b u t y l a l c o h o l g a v e a l ­ most a s l a r g e a y i e l d o f b e n z y l b e n z e n e a s I t d i d o f b e n z y l b u t y l e t h e r . Most o f t h e d a t a a r e foi v a n In Curve I , F i g u r e Y. when an a t t e m p t e d s e l f - e t h e r i f ’I c a t I on r e a c t i o n o f b e n z y l a l c o h o l a t t h e same c a t a l y s t c o n c e n t r a t i o n o f 0 . 1 2 8 m o la r was run t o c o m p l e t i o n , t w i c e th© t h e o r e t i c a l amount o f w a t e r f o r e t h e r I f i c a t i o n was e v o l v e d . The e x p e r i m e n t was run t w i c e and t h e d a t a In Curve I I , F i g u r e V r e p r e s e n t t h e a v e r a g e . The o r d i ­ n a t e v a l u e s o f t h e s e p a r a t e c u r v e s d i d n o t d i f f e r from t h i s a v e r ­ a g e c u r v e by more t h a n o n e u n i t a t any p o i n t . S i n c e a l l t h e o xy g e n o f th© b e n z y l a l c o h o l had b e e n d i s c h a r g e d a s w a t e r I t was n o t s u r p r i s i n g t o f i n d no e t h e r In t h e p r o d u c t s . A 6 6 . 4 $ y i e l d o f d i p h e n y l m eth ane and a 1 7 $ y i e l d o f m - d i b e n z y l b e n ­ z e n e w ere i s o l a t e d . The most I n t e r e s t i n g f e a t u r e o f th© p e r c e n t r e a c t i o n com­ p l e t e d v e r s u s t i m e c u r v e was t h e I n f l e c t i o n p o i n t n e a r th© h a l f ­ way p o i n t o f t h e r e a c t i o n . The r e a c t i o n r a t e from t h e b e g i n n i n g t o t h a t p o i n t g r a d u a l l y d e c r e a s e d and t h e n I t i n c r e a s e d u n t i l t h e f i n a l f l a t t e n i n g to t h e h o r i z o n t a l {Curva I I , F i g u r e V ) . In a l l p r e v i o u s c u r v e s f o r e t h e r i f i c a t i o n t h e s l o p e o f t h e c u r v e d e c r e a s e d fro m b e g i n n i n g t o e n d , i . e . t h e r a t© n e v e r I n c r e a s e d a s h e r e . As w i l l be d i s c u s s e d l a t e r , I t h a s been shown t h a t a l c o h o l s e x e r t v a r y i n g d e a c t i v a t i n g e f f e c t s on t h e c a t a l y s t t h r o u g h t h e c o o r d i n a t i n g power o f th© f r e e e l e c t r o n s on t h e o x y g e n a to m . E t h e r s p o s s e s s t h i s same b a s i c p r o p e r t y b u t t h i s d e a c t i v a t i n g : e f f e c t c a n n o t e x i s t w i t h h y d r o c a r b o n p r o d u c t s . 100 - —r>— ~D=^=- Hours F igu re V. Rate o f ( l ) e t h e r i f i c a t i o n o f b e n z y l a l c o h o l and n b u t a n o l , ( l l ) a l k y l a t i o n , 9? o f benzene w i t h b e n z y l a l c o h o l and ( I I I ) a l k y l a t i o n o f benzene w i t h d i b e n z y l e t h e r . i A l l c a t a l y s t c o n c e n t r a t i o n s are 0 . 1 2 3 m o la r . - 3 9 - C o n s e q u e n t l y a s t h e a l k y l a t i o n r e a c t i o n p r o c e e d s t h e e f f e c t i v e a c i d c o n c e n t r a t i o n becom es g r e a t e r d u e t o t h e p r e s e n c e o f l e s s o x y g e n a to m s f o r c o o r d i n a t i o n w i t h th© c a t a l y s t and th e r a t e i n c r e a s e s In s p i t e o f th© f a c t t h a t th© c o n c e n t r a t i o n o f th© a l c o h o l r e a c t a n t i s d e c r e a s i n g . In e t h e r i f i c a t i o n t h e r a t e d o e s n o t I n c r e a s e s i n c e h e r e t h e e t h e r p r o d u c e d i s s t i l l an o xy g e n compound t h a t can d e a c t i v a t e t h e a c i d t h r o u g h c o o r d i n a ­ t i o n and t h e e f f e c t i v e a c i d c o n c e n t r a t i o n n e v e r i n c r e a s e s o r a t l e a s t I t d o e s n o t i n c r e a s e s u f f i c i e n t l y t o c o m p e n s a t e f o r th© d e c r e a s e In r a t© due t o d e c r e a s e in c o n c e n t r a t i o n o f R ’QH, The f a c t t h a t In t h e f i r s t h a l f o f t h e r e a c t i o n t h i s c u r v e showed a d e f i n i t e t e n d e n c y t o w a r d a d e c r e a s i n g rat© a s In e t h e r ­ i f i c a t i o n and t h a t a f t e r w a r d t h e r a t e I n c r e a s e d s u g g e s t e d t h a t p e r h a p s b e n z y l a l c o h o l a l k y l a t e d b e n z e n e a t l e a s t p a r t l y t h r o u g h t h e I n t e r m e d i a t e f o r m a t i o n o f d i b e n z y l e t h e r * To e s t a b l i s h t h i s p o i n t more c l e a r l y , a b e n z e n e s o l u t i o n 1 , 2 5 m o la r I n b e n z y l a l c o h o l and 0 , 1 2 8 m o la r i n p - t o l u e n e s u l ­ f o n i c a c i d was r e f l u x e d • When o n e - f i f t h o f t h e amount o f w a t e r r e p r e s e n t i n g 1 0 0 $ e t h e r i f i c a t i o n had b e e n c o l l e c t e d , t h e r e ­ a c t i o n was s t o p p e d In o r d e r t o h a v e more f a v o r a b l e c o n d i t i o n s f o r t h e i s o l a t i o n o f any © t h e r , A 4 8 $ y i e l d o f d i b e n z y l e t h e r was I s o l a t e d b a s e d on th© o n e - s i x t e e n t h mol© w a t e r d i s c h a r g e d . D i p h e n y l m eth a n e a m o u n t in g t o n e a r l y h a l f th© w e i g h t o f d l b e n z y l e t h e r was a l s o r e c o v e r e d * In th© p r e v i o u s a l k y l a t i o n run t o 1 0 0 $ c o m p l e t i o n no e t h e r was r e c o v e r e d , I t w i l l b e rem em b ered . T h i s r e s u l t sh o w s t h a t t h © 1 © t h e r form ed e a r l y In t h e p r o c e s s was l a t e r c o n v e r t e d t o d i p h e n y l m e t h a n e . The n e x t s t e p was t o d e t e r m i n e w h e t h e r d i b e n z y l © th e r c o u l d be u s e d d i r e c t l y a s t h e a l k y l a t i n g a g e n t * A b e n z e n e s o l u t i o n 0 . 1 2 5 m o la r i n d i b e n z y l e t h e r and. 0 . 1 2 8 m o la r i n c a t a l y s t was r e a c t e d u n t i l t h e t o t a l w a t e r f o r c o m p l e t e a l k y l a t i o n bad b e e n c o l l e c t e d (C urve I I I , F i g u r e V ) . B i g h t y - t h r e e p e r c e n t d i p h e n y l m eth a n e and 1% d i b e n z y l b e n z e n e w e re I s o l a t e d * I t I s a p p a r e n t , t h e r e f o r e , t h a t u n d e r t h e s e c o n d i t i o n s a l a r g e p a r t o f t h e a l k y ­ l a t i o n o f b e n z e n e by b e n z y l a l c o h o l p r o c e e d s t h r o u g h t h e i n t a r - 56m e d i a t e f o r m a t i o n o f b e n z y l e t h e r . A r e a s o n a b l e m echan ism I s : The b e n z y l a l c o h o l fo r m e d oy t h e s p l i t t i n g o f th© e t h e r In e q u a t i o n ( 1 1 ) w ou ld r e a c t j u s t a s t h e o r i g i n a l a l c o h o l . A c t u a l l y , t h e r e a p p e a r s t o b e c o m p e t i t i o n f o r t h e b e n z y l carbon!ura i o n b? t h e two © l e c t r o d o t i c r e a g e n t s , b e n z y l a l c o h o l and b e n z e n e ( e q u a t i o n s 9 and 1 2 ) * A f t e r a l l t h e b e n z y l a l c o h o l h a s b e e n u s e d up In f o r m i n g b e n z y l © th e r and d i p h e n y l m e t h a n e , th© e t h e r u n d e r g o e s t h e f u r t h e r r e a c t i o n s shown In e q u a t i o n s ( 10 ) , ( 1 1 ) , ( 12 } and ( 13 } t o a l k y l a t e b e n z e n e . In t h e c a s e o f t h e r e a c t i o n b e t w e e n n - b u t a n o l and b e n z y l a l c o h o l m e n t i o n e d i n t h e p r e c e d i n g s e c t i o n , a s i t u a t i o n o f t h e same s o r t w ou ld e x i s t e x c e p t t h a t a f t e r t h e b e n z y l b u t y l © th er ( 8 ) CgHgCHgOH + H+ > CgHgCHg* + HOH (: d i ) 2 6 5 ^ C II CH + + 0 K CH 016 5 2 6 5 2 -41 I s form ed I t d o e s n o t a g a i n s p l i t a s i n e q u a t i o n s ( 10 ) and ( 1 1 ) t o g i v e b e n z y l carboniurn i o n and f a r t h e r a l k y l a t i o n o f th© b e n z e n e d o e s n o t o c c u r * I t w i l l be r e c a l l e d t h a t when t h i s r e a c t i o n was run t o c o m p l e t i o n ( Curve I , F i g u r e V) a 4 0 * 4 ^ y i e l d o f b e n z y l b u t y l e t h e r in a d d i t i o n t o a 33*2j» y i e l d o f d i p h e n y l m eth an e was o b t a i n e d * T h i s I s I n marked c o n t r a s t t o t h e t o t a l a l k y l a t i o n w h i c h r e s u l t e d when b e n z y l a l c o h o l was u s e d a l o n e * On© r e a s o n why d i b e n z y l © th er s p l i t s t o a l k y l a t e b e n z e n e w h i l e b e n z y l b u t y l e t h e r d o e s n o t I s v e r y p r o b a b l y t h a t th© r e - ■ m o v a l o f th© w a t e r d i s p l a c e s th© e q u i l i b r i u m i n th© f o r m e r c a s e , b u t s i n c e no w a t e r I s form ed i n t h e l a t t e r t h e r e i s n o t h i n g t o f o r c e t h e r e a c t i o n t o t h e r i g h t : The c a t a l y s t c o n c e n t r a t i o n l a n o t s u f f i c i e n t l y h i g h t o a l l o w t h e b u t y l a l c o h o l t o a l k y l a t e b e n z e n e o r t o e t h e r i f y I t s e l f * A n o t h e r s i g n i f i c a n t p o i n t i s t h a t a l t h o u g h t h e t o t a l c a t ­ a l y s t c o n c e n t r a t i o n was th© same I n t h e two c a s e s th© b u t y l a l c o h o l a p p e a r s t o d e a c t i v a t e t h e c a t a l y s t more t h a n t h e b e n z y l a l c o h o l d o e s * ( S e e s e c t i o n on th© d e t e r m i n a t i o n o f t h e e f f e c t o f t h e number o f a l p h a p h e n y l g r o u p s on th© b a s i c i t y o f th© a l ­ c o h o l *) A t h i r d p o i n t w h i c h s h o u l d b e c o n s i d e r e d i s t h a t s i n c e b u t y l a l c o h o l a p p e a r s t o b e more b a s i c t h a n b e n z y l , i t can com­ p e t e w i t h b e n z e n e more s u c c e s s f u l l y f o r t h e b e n z y l c a r b o n iu m i o n th a n can t h e b e n z y l a l c o h o l * Compare e q u a t i o n ( 16 ) b e lo w w i t h e q u a t i o n s ( 9 ) , ( 12 ) and ( 13 ) a b o v e . ( 1 4 ) c 6 h5c b 2 o c h 2c 6 h5 ♦ 2 c 6 h6 2c RC,H c H + H0IJ6 5 2 6 5 ( 1 5 ) C6 H5CH2 C6 H5 + C4 H9 ° H ( 1 6 ) C6 HBCHg + Luder and Z u f f a n t I f r e e l y e a l l b e n z e n e a b a s e i n i t s r e a c t i o n In t h e r e a c t i o n o f b e n z y l a l c o h o l , b u t y l a l c o h o l and b e n ­ z e n e d i s c u s s e d a b o v e , b o t h b e n z y l b u t y l © th er and b e n z y l b e n z e n e w e re f o r m e d . T h is f a c t i s n o t u n r e a s o n a b l e s i n c e t h e same p r o ­ p o r t i o n o f w a t e r i s form ed i n e a c h r e a c t i o n . B e n z en e was p r e s e n t , f u r t h e r m o r e , In a b o u t f o r t y t i n e s t h e c o n c e n t r a t i o n o f b u t y l a l ­ c o h o l so i t c o u l d c o m p e te s u c c e s s f u l l y w i t h t h e b u t y l a l c o h o l f o r t h e b e n z y l carbon!urn Ion even t h o u g h t h e b e n z e n e I s much l e s s b a s i c th a n b u t y l a l c o h o l . T h i s a p p e a r s to be t h e f i r s t t i m e t h a t i t h a s been shown o r p o s t u l a t e d t h a t th© © t h e r can b e an i m p o r t a n t i n t e r m e d i a t e i n a l k y l a t i o n w i t h b e n z y l a l c o h o l . B enzen e h a s b e e n a l k y l a t e d w i t h a l c o h o l s and b or o n t r i f l u o r i d e c a t a l y s t i n t h e p r e s e n c e o f s u c h a s s i s t a n t s a s p h o s p h o r o u s p e n t o x i d e , s u l f u r i c a c i d and b e n - 86z e n e s u l f o n i c a c i d . The m ech a n ism h a s b e e n e x p l a i n e d on th© b a s i s o f a d e h y d r a t i o n o f t h e a l c o h o l t o an o l e f i n and th© s u b ­ s e q u e n t c o o r d i n a t i o n o f boron t r i f l u o r i d e w i t h th© o l e f i n t o g i v e t T h is com pound, a s t r o n g a c i d , c o u l d f o r c e b e n z e n e t o a c t a s a baa©. O k y l a t l o n wou ld f o l l o w i n a s i m i l a r f a s h i o n t o t h a t shown i n e q u a t i o n s ( 12 ) and { 15 ) . S im ons and A r c h e r , how­ e v e r , a l k y l a t e d b e n z e n e w i t h b e n z y l a l c o h o l a t room t e m p e r a t u r e 5 0 w i t h t h e a c i d carboniuxn Ion i n a l k y l a t l o n s • 5H - 43- w i t h h y d r o g e n f l u o r i d e t o g i v e a 65% y i e l d o f d i p h e n y l m e t h a n e # Luder and L u f f a n t i s t a t e t h a t s i n c e i t i s d i f f i c u l t t o s e e how b e n z y l a l c o h o l c o u l d form an o l e f i n a t a n y t e m p e r a t u r e , n o t t o m e n t io n room t e m p e r a t u r e , an o l e f i n i n t e r m e d i a t e seem s v e r y u n l i k e l y . They s u g g e s t i n s t e a d t h a t t h e a l c o h o l r e a c t s w i t h t h e c a t a l y s t t o fo rm a compound t h a t i s c a p a b l e o f i o n i z i n g t o a c a r b o n iu m i o n . 5 ® T h i s i o n w i l l t h e n r e a c t w ith , t h e a r o m a t i c h y d r o c a r b o n t o g i v e t h e a l k y l a t e d p r o d u c t . T h e s e r e a c t i o n s a r e shown In e q u a t i o n s ( B 5, ( 12 ) and ( 1 5 ) a b o v e . In a l k y l a t l o n s w h e r e an e t h e r i s t h e a l k y l a t i n g ; a g e n t , t h e f o r m a t i o n o f t h e c a r b o n iu m i o n I n a f a s h i o n s i m i l a r t o t h a t from 57a l c o h o l s I s p o s t u l a t e d :' n3 ( 1 7 ) R iT)’i R • + B F „ —------ ?» R {O s R ’* • O •• n3 ( 1 8 ) R * H * V ? R '*• F ( 1 9 ) R SO : R* ~ ^ R + +#. It s 0 : 3 F * • * o R * : 0*: B F „ 3 The r e a c t i o n s a r e t h e same t y p e a s t h o s e i n e q u a t i o n s C 1 0 ) and ( 11 ) a b o v e . In t h e a l k y l a t i o n o f b e n z e n e w i t h d i b e n z y l e t h e r a h i g h e r y i e l d o f d i p h e n y l m eth ane ( 83% ) was o b t a i n e d t h a n when b e n z y l a l c o h o l was t h e a l k y l a t i n g a g e n t ( 6 6 . 4% )• T h i s r e s u l t was in 41c o n t r a s t t o t h e work o f H uston and F r ie d e m a n n • A l s o In c o n ­ t r a s t t o t h e i r f i n d i n g s was t h e f a c t t h a t r a - d i b e n z y l b e n z e n e was t h e o n l y d i - s u b s t i t u t e d b e n z e n e i s o l a t e d i n a l l t h e s e a l k y - l a t i o n s I n v o l v i n g e i t h e r t h e a l o e h o i o r e t h e r . They a l k y l a t e d b e n z e n e w i t h b e n z y l a l c o h o l and a luminum c h l o r i d e c a t a l y s t t o - 44 - g e t a 30% y i e l d o f d i p h e n y l m eth ane and Q% p - d i b e n z y l b e n z e n e , w h i l e t h e same a l k y l a t i o n u s i n g b e n z y l e t h y l e t h e r a s t h e a l k y ­ l a t i n g a g e n t g a v e t h e same p r o d u c t s , b u t i n l o w e r y i e l d * The o c c u r a n c e o f th© meta I s o m e r i n a l k y l a t i o n p r o d u c t s 69h a s b e e n e x p l a i n e d by P r i c e * B enzen e can be a l k y l a t e d t o t h e 1 , 2 , 4 - t r i a l k y l d e r i v a t i v e . The l o s s o f t h e a l k y l g r o u p In t h e one p o s i t i o n t h e n a c c o u n t s f o r t h e met a p r o d u c t i s o l a t e d * The a l k y l a t i o n o f b e n z e n e a s c a r r i e d o u t her© i s o f c o n ­ s i d e r a b l e v a l u e from t h e s y n t h e t i c s t a n d p o i n t * Th© y i e l d s w i t h d i b e n z y l e t h e r a r e a b o u t 1 5 # b e t t e r t h a n t h e b e s t r e p o r t e d p r e - D p v i o u s l y , w h ic h w ere o b t a i n e d w i t h h y d r o g e n f l u o r i d e * ^ The m e o - t r o p i c method i s m o r e o v e r much s a f e r and s i m p l e r t h a n a n y method w h i c h I n v o l v e d h a n d l i n g h y d r o g e n f l u o r i d e * Th© r e a c t i o n m i x t u r e her© i s e x t r e m e l y c l e a n i n c o n t r a s t t o a lum inum c h l o r i d e c o n ­ d e n s e ! i o n s and t h e y i e l d s a r e more t h a n t w i c e t h o s e o b t a i n e d from t h e o l d e r p r o c e d u r e * The s c o p e and m echan ism o f a l k y l a t i o n h r t h i s method i s b e i n g i n v e s t i g a t e d by o t h e r s i n t h e s e l a b o r a ­ t o r i e s • THE EFFECTS OF VARIATIONS IN CATALYST CONCENTRATION ON TEE RATE AND ORDER OF EFEERIFICATICN The e f f e c t o f c h a n g e s i n a c i d c o n c e n t r a t i o n on t h e r a t e and o r d e r o f e t h e r i f i c a t Ion was n e x t s t u d i e d * B en z en e s o l u t i o n s 0*2 5 m o la r In t r i p h e n y l c a r b i n o l and 0 * 2 5 m o la r In n - b u t a n o l w e re r e a c t e d a t a c i d c o n c e n t r a t i o n s o f 0 . 0 0 0 2 5 m o l a r , 0 . 0 0 0 5 m o la r and 0 . 0 0 1 m o l a r . In e a c h c a s e an I n c r e a s e In a c i d c o n ­ c e n t r a t i o n I n c r e a s e d t h e r e a c t i o n r a t e . The h a l f r e a c t i o n t i m e s d e c r e a s e d from f i f t y - n i n e m i n u t e s t o t w e n t y - s i x m i n u t e s t o t w e l v e m i n u t e s a s t h e c a t a l y s t c o n c e n t r a t i o n was I n c r e a s e d ( F i g u r e VI ) . - 4 5 - In t h e o r d e r p l o t s f o r t h e r e a c t i o n o f t r i p h e n y l c a r ­ b i n o l and n - b u t a n o l ( F ig u r e V l i ) t h e r e i s a d e f i n i t e t e n d e n c y away f r o m a f i r s t o r d e r m echanism t o w a r d s a h i g h e r o r d e r a s t h e c a t a l y s t c o n c e n t r a t i o n I s i n c r e a s e d * As h a s b e e n p r e v i o u s l y p o i n t e d o u t t h e p l o t o f t h e l o g a r i t h m o f th© c o n c e n t r a t i o n o f t r i p h e n y l c a r b i n o l v e r s u s t im e a t a c a t a l y s t c o n c e n t r a t i o n o f o f 0 , 0 0 0 2 5 m o lar I s d e f i n l t © l y Aa f i r s t o r d e r r e a c t i o n t o 87,0 com­ p l e t i o n I f th© f i r s t f i v e m i n u t e s a r e o m i t t e d ( Curve I , F i g u r e V II )» The same i s t r u e f o r th© r e a c t i o n a t a c a t a l y s t c o n c e n ­ t r a t i o n o f 0 . 0 0 0 5 m o la r { Curve I I , F i g u r e V I I )* At a c a t a l y s t c o n c e n t r a t i o n o f 0 . 0 0 1 m o l a r , h o w e v e r , th© r e a c t i o n d e f i n i t e l y s h i f t s away fro m a f i r s t o r d e r m echanism * Somewhat s u r p r i s ­ i n g l y t h i s d a t a was fo u n d to f i t a s e c o n d o r d e r p l o t v e r y w e l l ( F i g u r e V I I I )* A d u p l i c a t e run a t 0 . 0 0 1 m o la r a c i d c o n c e n ­ t r a t i o n a g r e e d v e r y s a t i s f a c t o r i l y * The d a t a p l o t t e d i n F i g u r e s V I, V II and V I I I a r e a c t u a l l y a v e r a g e s o f th© two r u n s . The o r d i n a t e v a l u e s o f t h e s e p a r a t e c u r v e s d i f f e r e d by no more th a n o n e u n i t a t any p o i n t . In t h e s e c t i o n on t h e e f f e c t o f v a r i a t i o n s i n t h e c h a i n l e n g t h o f BOH Hammett’ s median i s m r * was c, i v e n and i t was p o i n t e d o u t t h a t e i t h e r s t e p ( 1 ) o r s t e p ( 2 ) o f t h i s m echan ism I s r a t e c o n t r o l l i n g . I t i s a p p a r e n t t h a t t h e I n c r e a s i n g , r a t e w i t h I n c r e a s i n g c a t a l y s t c o n c e n t r a t i o n d o e s n o t a i d us In c h o o s i n g b e t w e e n t h e s e s t e p s f o r su c h an e f f e c t w o u ld be e x p e c t e d f o r e i t h e r s t e p . Th© s h i f t t o w a r d a s e c o n d o r d e r r e a c t i o n w i t h i n c r e a s i n g c a t a l y s t c o n c e n t r a t i o n t e n d s t o f a v o r s t e p ( \ } a s - t h e r a t© c o n t r o l l i n g p r o c e s s o v e r s t e p ( 2 } . A s i m i l a r s h i f t to w a r d 50 100 150 Minutes F ig u re VI . Rate o f e t h e r i f i c a t i o n o f t r i p h e n y l c a r b i n o l and n - b u t a n o l w i t h ( i ) 0 .0 0 0 2 5 molar c a t a l y s t , ( I I ) 0 . 0 0 0 5 molar c a t a l y s t and ( I I I ) 0 . 0 0 1 molar c a t a l y s t . Lo g of co ne , of tr ip h en yl ea rb in o l - m R E A C T I O N 67 % COMPLET E 15010050 Minutes F ig u r e V I I . F i r s t o r d e r p l o t s from d ata i n F ig u r e VI. -L f- R ec ip ro ca l of co nc . of tr ip he ny l ca rb in ol -48 100 50 50 100 M in u t e s F i g u r e V I I I . S e c o n d o r d e r p l o t from d a t a o f Curve I I I , F i g ­ u r e V I . • 4 9 * a h i g h e r o r d e r , a l t h o u g h t h e s i m i l a r i t y m a y h e o n l y s u p e r ­ f i c i a l , h a s b e e n n o t e d I n t h e a d d c a t a l y s e d i n v e r s i o n o f s u c r o s e * H a m m e t t e x p l a i n s t h e p o s s i b i l i t y o f s u c h a s h i f t 3 6o n a m a t h e m a t i c a l b a s i s * A n a d e q u a t e e x p l a n a t i o n o f t h e c a u s e o f t h e s h i f t i n o r d e r m u s t b e l e f t t o s u b s e q u e n t w o r k e r s * R e a c t i o n s s i m i l a r t o t h o s e j u s t d e s c r i b e d f o r t r i p h e n y l c a r b l n o l a n d b u t a n o l w e r e a l s o c a r r i e d o u t w i t h b e n & h y d r o l a n d b u t a n o l * I n t h i s c a s e c a t a l y s t c o n c e n t r a t i o n s o f 0 * 0 0 2 a n d 0 * 0 0 8 m o l a r w e r e u s e d * T h e h a l f - r e a c t l o n t i m e s w e r e t h r e e h u n d r e d f i f t e e n m i n u t e s a n d t w e n t y - s e v e n m i n u t e s r e s p e c t i v e l y * D a t a f o r t h e r u n a t 0 * 0 0 2 m o l a r a r e p l o t t e d I n C u r v e I , F i g u r e X I ? a n d d a t a f o r t h e r u n a t 0 * 0 0 8 m o l a r a r e p l o t t e d i n F i g u r e I V * I n b o t h c a s e s t h e r e a c t i o n s f i t t e d f i r s t o r d e r p l o t s q u i t e s a t i s f a c t o r i l y { F i g u r e s I X a n d X ) * No t e n d e n c y t o w a r d a s h i f t t o a h i g h e r o r d e r I s a p p a r e n t * S u c h a t e n d e n c y m i g h t a p p e a r a t a n e v e n h i g h e r c o n c e n t r a t i o n o f c a t a l y s t * T H E E F F E C T OF V AH I AT I O N I N C A TAL YST CO N C E N T R A T IO N ON T H E C O U R S E O F T H E R E A C T I O N O F T R I P H E N Y L C A R B IN O L W IT H D I P H E N Y L C A R B IN O L I n t h e r e a c t i o n o f t r l p h e n y l c a r b l n o l w i t h b e n z h y d r o l a t a p - t o l u e n e s u l f o n i c a c i d c a t a l y s t c o n c e n t r a t i o n o f 0 . 0 0 0 2 5 m o l a r I t w a s f o u n d t h a t a f t e r t w e n t y - e i g h t h o u r s o n l y o f t h e t h e o r e t i c a l a m o u n t o f w a t e r f o r e t h e r i f 1 c a t i o n h a d b e e n c o l l e c t e d ( C u r v e I , F i g u r e X I ) a n d t h e r e a c t i o n h a d s t o p p e d * A 55% y i e l d o f t h e e x p e c t e d u n s y m m e t r i c a l e t h e r w a s I s o l a t e d a s w h i t e s h a r p m e l t i n g c r y s t a l s * O n r e p e t i t i o n o f t h e r u n a t 0 * 0 0 2 m o l a r c a t a l y s t c o n c e n ­ t r a t i o n , t h e w a t e r v o l u m e h a d b e c o m e c o n s t a n t i n t h r e e h o u r s Lo g of co ne , of be n& hy dr ol - 50- 10 BO H ours F i g u r e I X . F i r s t o r d e r p l o t o f e t h e r i f i c a t i o u o f b e n ^ h y d r o l and n - b u t a n o l w i t h 0 . 0 0 S aaoiar c a t a l y s t . ( F or r a t e d a t a s e e C urve I , F i g u r e X I V . ) Lo g of co ne , of be nz hy dr ol - 51- - 2 . 0 h- 9 5% COMPLETE 1 2 3 H ours F i g u r e X. F i r s t o r d e r p l o t o f e t h e r i f i c a t i o n o f b e n z h y d r o l and n - b u t a n o l w i t h 0 . 0 0 8 m o l a r c a t a l y s t . ( F o r r a t e d a t a s e e F i g u r e I V . ) a t a b o u t 8 6 /S o f t h e t h e o r e t i c a l amount f o r t o t a l e t h e r ! f i c a t l o n { Curve I I I , F i g u r e XI ) • At 0 . 0 0 0 5 m o la r a c i d c a t a l y s t , t h e run was f i n i s h e d In a b o u t e l e v e n h o u r s w i t h 76/S w a t e r c o l l e c t e d i Curve I I , F i g u r e XI )» I t i s a p p a r e n t t h a t i n c r e a s e d c a t a l y s t c o n c e n t r a t i o n I n c r e a s e d t h e r e a c t i o n r a t e and a l s o d e c r e a s e d t h e t o t a l amount o f w a t e r c o l l e c t e d . The h a l f - r e a c t i o n t i m e s a t 0 , 0 0 0 2 5 m o l a r , 0 . 0 0 0 5 m o la r a nd 0 , 0 0 2 m o la r a c i d c o n c e n t r a t i o n s w e r e two h u n d r e d t w e n t y - t w o m i n u t e s , o n e hundred t e n m i n u t e s and f o r t y - e i g h t m i n u t e s . When t r i p h e n y l c a r b l n o l and b e n z h y d r o l w e r e r e a c t e d In t h i s s y s t e m w i t h t h e c a t a l y s t , a s i t u a t i o n e x i s t e d w h ere e i t h e r a l ­ c o h o l m ig h t r e l a t i v e l y e a s i l y s e r v e a s R*0H. T h i s s i t u a t i o n me&nt t h a t a c o m p e t i t i v e r e a c t i o n t o t h e fo r m a t i o n o f t h e u n - s y m m e t r l c a l e t h e r was t h e f o r m a t i o n o f d l b e n z h y d r y l e t h e r . Data i n t h e s e c t i o n f o l l o w i n g on t h e e f f e c t o f v a r i a t i o n i n t h e number o f p h e n y l g r o u p s on t h e alpha, ca rb o n o f ROB show t h a t t r l p t e e n y i c a r b l n o l h a s l i t t l e t e n d e n c y t o e t h e r i f y I t s e l f p o s s i b l y b e c a u s e o f s t e r i c h i n d r a n c e . A ccord ing , t o c a l c u l a ­ t i o n s b a s e d on th© a s s u m p t io n t h a t a l l t h e b e n z h y d r o l h a s been u sed up e i t h e r In th® f o r m a t i o n o f s y m m e t r i c a l o r u n s y m m e t r i c a l e t h e r , t h e f o l l o w i n g y i e l d s o f u n s y m m e t r l e a l e t h e r w e r e p r o ­ d u c e d a s t h e c a t a l y s t c o n c e n t r a t i o n was i n c r e a s e d : 63 .2 /C, 53*8/5 and 3 2 .8 : ^ . The f o l l o w i n g p e r c e n t a g e s o f d i b e n e h y d r y l e t h e r w e r e o b t a i n e d : 3 6 . 8 $ , 4 6 . 4 > and 6 7 . 2 / 5 . The p e r c e n t a g e s o f th© o r i g i n a l t r i p h e n y l c a r b l n o l l e f t u n r e a c t e d w e re t h e same a s o f d ibensshy& ryl e t h e r p r o d u c e d . The i n c r e a s e in amount o f c a t a l y s t , o v e r minimum am ounts f o r t h e t r i p h e n y l c a r b l n o l t o r e a c t , a p p a r e n t l y s p e e d s up t h e f o r m a t i o n o f t h e s y m m e t r i c a l e t h e r more t h a n i t s p e e d s up th© f o r m a t i o n o f t h e u n s y m m e t r i c a l P er ce n t re ac ti on co m p le te 1 0 0 - Hours F ig u r e XI . 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I d e n t i f i a b l e c o n s t i t u e n t s w e r e u n s u c c e s s f u l * T h e i s o l a t i o n o f t r i p h e n y l m e t h a n e w a s n o t t o o s u r p r i s i n g s i n c e t r i p h e n y l c a r b ­ l n o l h a s b e e n c o n v e r t e d t o t r i p h e n y l m e t h a n e b y h e a t i n g w i t h r e d u c i n g a g e n t s a s m i l d a s a l c o h o l i c s i n e c h l o r i d e o r a l c o h o l i c h y d r o g e n c h l o r i d e # 4 ^ T h e r e a c t i o n i n v o l v i n g b e n z y l a l c o h o l a n d t r i p h e n y l c a r b ­ l n o l p r o c e e d e d a c c o r d i n g t o a f i r s t o r d e r m e c h a n i s m ( F i g u r e X I I I ) j u s t a s d i d t h e r e a c t i o n i n v o l v i n g n - b u t y l a l c o h o l a n d t r i p h e n y l c a r b i n o l a t t h i s s a m e a c i d c o n c e n t r a t i o n ( F i g u r e V I I ) * T h e r e a c t i o n i n v o l v i n g b e n z y l a l c o h o l w a s r u n i n d u p l i c a t e * T h e t w o r u n s a g r e e d w i t h e a c h o t h e r v e r y c l o s e l y * T h e a v e r a g e o f t h e t w o I s p l o t t e d * I n n o c a s e d i d a s i n g l e o r d i n a t e v a l u e v a r y f r o m t h e a v e r a g e b y m o r e t h a n 1 * 5 u n i t s * T h e r e s p e c t i v e s p e c i f i c r a t e c o n s t a n t s f o r t h e r e a c t i o n s e m p l o y i n g b e n z y l a l c o h o l a n d b u t a n o l w e r e 0 * 0 4 1 a n d 0 . 0 1 2 r e c i p r o c a l m i n u t e s a n d t h e h a l f r e a c t i o n rc en t re ac ti on co m p le te 1 0 0 - 50----- 100 200 300 M inutes F ig u r e X I I . Rate o f e t h e r i f i c a t i o n o f t r i p h e n y l c a r b i n o l and ( l ) b e n z y l a l c o h o l , ( I I ) n - b u t a n o l and ( I I I ) b e n z h y d r o l . A l l c a t a l y s t c o n c e n t r a t i o n s are 0 .0 0 0 2 5 molar i Oi i t i m e s w e r e n i n e t e e n m i n u t e s e n d s i x t y m i n u t e s * B e n z h y d r o l w & s r e a c t e d i n a s i m i l a r w a y w i t h b u t y l a l ­ c o h o l , b e n z y l a l c o h o l a n d t r i p h e n y l c a r b l n o l * ' T h e c a t a l y s t c o n c e n t r a t i o n w a s 0 * 0 0 2 m o l a r I n e a c h c a s e w h i l e t h e c o n c e n ­ t r a t i o n s o f t h e B ’ OB a n d B O B a l c o h o l s w e r e e a c h 0 * 2 5 m o l a r * W i t h b e n z h y d r o l a s B f G B # t h e h a l f r e a c t i o n t i m e d e c r e a s e d i n g o i n g f r o m b u t a n o l t o b e n z y l a l c o h o l f r o m t h r e e h u n d r e d t w e n t y - f i v e m i n u t e s t o s e v e n t y - t h r e e m i n u t e s ( F i g u r e X I V ) * T h e s e r e a c t i o n s g i v e g o o d f i r s t o r d e r p l o t s * T h e f i r s t o r d e r p l o t f o r n - b u t y l a l c o h o l w a s g i v e n i n F i g u r e I X , a n d t h e c o r r e s p o n d ­ i n g p l o t f o r b e n z y l a l c o h o l i s s h o w n I n F i g u r e XV* T h e s p e c i f 1 r a t e c o n s t a n t s w e r e c a l c u l a t e d t o b e G * Q 0 g 5 a n d 0 * 0 1 1 r e c i p r o ­ c a l m i n u t e s * B y w a y o f s u m m a r y i t m a y b e p o i n t e d o u t t h a t t h e r e a c t i o n s f o r t h © f o r m a t i o n o f f o u r o f t b s m i x p o s s i b l e u n s y m m e t r i c a l e t h e r s w h i c h i t I s p o s s i b l e t o m a k e f r o m b u t y l a l c o h o l a n d f r o m m o n o - , d i - , a n d t r l p h e n y l c a r b l n o l s h a v e b e e n s h o w n t o f o l l o w f i r s t o r d e r k i n e t i c s * T h e e x c e p t i o n s a r e b e n z y l b u t y l e t h e r > w h i c h w a s d i s c u s s e d I n t h © s e c t i o n o n t h e a l k y l a t i o n o f b e n z e n e b y b e n z y l a l c o h o l a n d b e n z y l e t h e r a n d d i p h e n y l m e t h y l t r l p h e n y l m e t h y l e t h e r , w h i c h w a s d i s c u s s e d I n t h © s e c t i o n o n t h e e f f e c t o f v a r i a t i o n i n c a t a l y s t c o n c e n t r a t i o n o n t h e c o u r s e o f t h e r e a c t i o n o f t r l p h e n y l c a r b l n o l w i t h d i p h e n y l c a r b i n o l * I t w i l l b e n o t e d t h a t F i g u r e X I V i n c l u d e s C u r v e I I I f o r t h e s e l f - e t h e r i f I c a t i o n o f b e n z h y d r o l * A 0 * 2 5 m o l a r c o n c e n t r a ­ t i o n o f b e n z h y d r o l w a s u s e d h e r e * S i n c e t h © c o n c e n t r a t i o n o f R f QH h a s a g r e a t e r e f f e c t o n t h e r a t e t h a n t h e c o n c e n t r a t i o n o f H O B , t h e b e s t c o m p a r i s o n w i t h t h e o t h e r e x p e r i m e n t s c o u l d b e Lo g of co ne , of tr ip he ny l ca rb in ol - 1.0 - 1 - 2 .0 50 100 M in u t e s F i g u r e X I I I . F i r s t o r d e r p l o t from d a t a o f Curve 1 , F i g u r e X I I . P er ce n t re ac ti on co m p le te 5C- 15 Hours F igu re XIV, Hate o f e t h e r i f i c a t i o n o f benzhydro l and ( i ) n - b u t a n o l , ( I I ) b e n z y l a l c o h o l , ( i l l ) b e n z h y d ro l and ( IV ) t r i p h e n y l c a r b i n o l . A l l c a t a l y s t c o n c e n t r a t i o n s are 0 .0 0 2 m olar . -0 9 - Lo g of co nc . of b en zh yd ro l REACTION 84% L 1 _ I__ 15050 100 M inutes F ig u r e XV. F i r s t order p l o t f o r e t h e r i f i c a t i o n o f benzhydro l and benzyl a l c o h o l w i t h 0 .0 0 2 molar c a t a l y s t . ( For r a t e d a ta s e e Curve I I , F ig u r e XIV.) -T 9' - 62 - m a d © b y m a i n t a i n i n g t h © ©am© I n i t i a l H * O H c o n c e n t r a t i o n i n a l l c a s e s * D a t a i n t h ® s e c t i o n o n t h © d e t e r m i n a t i o n o f t h e e f f e c t o f t h © n u m b e r o f a l p h a p h e n y l g r o u p s o n t h e b a s i c i t y o f t h e a l c o h o l i n d i c a t e t h a t a n y d e a c t i v a t i o n o f t h e c a t a l y s t b y b e n z h y d r o l w o u l d b e s l i g h t # I t i s a p p a r e n t ( F i g u r e X I V ) t h a t u n d e r t h e s e c o n d i t i o n s t h i s r e a c t i o n c u r v e f a l l s i n t o p l a c e a b o v e t h © c u r v e w h e r e t h e BOH i s b e n z y l a l c o h o l a n d s t i l l f a r t h e r a b o v e t h e c u r v e w h e r e BOH i s b u t y l a l c o h o l # F i g u r e X V I s h o w s t h a t t h e f i r s t o r d e r p l o t f o r t h i s r e a c t i o n g i v e s a s t r a i g h t l i n e w i t h a s p e c i f i c r e a c t i o n c o n s t a n t o f 0 # 0 2 6 r e c i p r o c a l m i n u t e s . W h e n t h e e x p e r i m e n t w a s r e p e a t e d u s i n g t w i c e t h e c o n c e n t r a t i o n o f b e n z h y d r o l t h e r e a c t i o n w e n t a l m o s t e x a c t l y t w i c e a s f a s t # T h u s w h e n p e r c e n t c o m p l e t i o n v e r s u s t i m e w a s p l o t t e d t h e c u r v e w a s a l m o s t a n e x a c t d u p l i c a t e o f t h e c u r v e I n F i g u r e X V I # C u r v e I V # F i g u r e X I V f o r t h e f o r m a t i o n o f d l p h e n y l m e t h y l t r i p h e n y l m e t h y l e t h e r I s I n c l u d e d f o r t h e p u r p o s e o f r o u g h c o m ­ p a r i s o n o n l y . A s p o i n t e d o u t i n t h e p r e c e d i n g s e c t i o n t h © s y m ­ m e t r i c a l d i b e n z h y d r y l e t h e r i s f o r i t e d h e r e a t t h ® s a m e t i m e a s t h e u n s y m m e t r i c a l e t h e r # I f I t w e r e p o s s i b l e t o d e t e r m i n e t b s c u r v e f o r t h e f o r m a t i o n o f t h e u n s y m m e t r i c a l e t h e r o n l y I t w o u l d f a l l c o n s i d e r a b l y b e l o w C u r v e I V # W i t h t r i p h e n y l c a r b l n o l a s t h e K * O H a l c o h o l t h e r a t e o f e t h e r i f 1 c a t I o n I n c r e a s e d w h e n b e n z y l a l c o h o l w a s s u b s t i t u t e d f o r b u t y l a l c o h o l # b u t t h e r a t © f e l l s h a r p l y w h e n b e n z h y d r o l w a s s u b s t i t u t e d f o r t h e b e n z y l a l c o h o l # I t w a s p o i n t e d o u t a b o v e t h a t w i t h t r l p h e n y l c a r b i n o l a s t h e BOH a l c o h o l m u c h h i g h e r c a t a l y s t c o n c e n t r a t i o n s w e r e n e e d e d f o r r e a c t i o n a n d t h e n n o e t h e r w a s I s o l a t e d . I t a p p e a r s # t h e r e f o r e # t h a t o n e co n e. of be nz hy d ro l - 63- - 1.0 R E A C T I O N 9 0 % C O M P L E T E -2 1____ i__ 50 100 M in u t e s F i g u r e XVI. F i r s t o r d e r p l o t f o r s e l f - e t h e r i f i c a t i o n o f 0 . 2 5 0 m o l a r b e n z h y d r o l I n t h e p r e s e n c e o f 0 . 0 0 2 m o l a r c a t a l y s t . ( F o r r a t e d a t a s e e Curve I I I , F i g u r e X I V . ) - 6 4 - p h e n y l g r o u p on t h e R CHn :* r f i th b e n z y l a l c o h o l , th© e l e c t r o n a t t r a c t i v e power o f t h e p h e n y l g r o u p m ig h t b e e x p e c t e d t o p u l l th© e l e c t r o n s away from th© m e t h y l o l c a r b o n w h ic h i n t u r n would a t t r a c t e l e c t r o n s away from t h e o x y g e n so t h a t t h e y a r e l e s s a b l e t o c o o r d i n a t e w i t h th© p r o t o n t h a n i n t h e c a s e o f b u t a n o l . Her©, t h e n t h e e q u i l i ­ br ium w o u ld b e l e s s t o t h e r i g h t t h e n w i t h n - b u t a n o l * In t h e c a s e o f b e n z h y d r o l o r t r l p h e n y l c a r b i n o l , t h e m u l ­ t i p l e p h e n y l g r o u p s w ould b e e x p e c t e d t o h a v e g r e a t e r e l e c t r o n a t t r a c t i n g power s o t h a t t h e e q u i l i b r i a w i l l b e s h i f t e d e v en f a r t h e r t o t h e l e f t * Even i f th© e q u i l i b r i a i n a l l t h e s e c a s e s ar© d i s p l a c e d a l m o s t c o m p l e t e l y t o th© r i g h t i n e q u a t i o n ( 26 ) , t h e c a t a l y s t a c t i v i t i e s w ou ld s t i l l v a r y In t h e same manner* Under t h e s e c o n d i t i o n s t h e c a t a l y s t c o u l d be c o n s i d e r e d t o b e t h e c o m p l e x e s H* H+ CV H2CH2CB2 0 < f i , C h g O S , e t c • i n s t e a d o f t h e free p r o t o n • In th© f o r m a t i o n o f a e a r b o n iu m io n fro m b e n z h y d r o l , f o r e x a m p l e , r e a c t i o n ( 27 ) wou ld b e e x p e c t e d t o p r o c e e d l e s s r e a d i l y t h a n r e a c t i o n ( 2 8 ) s i n c e n - b u t s n o l would h o l d th© p r o t o n w i t h a g r e a t e r f o r c e t h a n t h e b e n z y l a l c o h o l . - 6 6 - + ( 2 7 ) (C H_ )_CHQH + C .B , , : 0 : H z ± ( C . I L L C H + C fl OH + H 06 5 2 4 y •• ^ o o 2 4 9 2 ( 2 8 ) (CgHg)gCHOH + Cg Hg CH H ( c 6 a 5 ) 2 CH+ + C6 H5 GH2 0H + H The s e c o n d f a c t o r , I . e . t h e one w h ic h c a u s e s t h e r a t e o f e t h e r i f 1 c a t I o n t o d e c r e a s e a s t h e number o f p h e n y l g r o u p s i n t h e KGH a l c o h o l e x c e e d s a c e r t a i n v a l u e , may "be s t e r i c h i n d r a n c e . I t seem s n o t u n r e a s o n a b l e t h a t s t e r i c h i n d r a n c e m ight s lo w up b o t h o f t h e f o l l o w i n g r e a c t i o n s : H+ ( 2 9 ) (C6 H5 ) 3 C+ ♦ (C6 U6 ) 8 CH0H ^ 2 CHUH + C4 fi9° H^ ((V V 2 C3 h E9 + H0H ( 3 2 ) ( C 6 H5 ) 2 CHCH ♦ C6 H5 ) 2 C H O H ^ ( C 6 ^ ) 2 ( HOC»(C6 Hs ) g ♦ HOE ( 3 3 ) (C4 Ka0H ♦ C4 Hq 0 H <-------_ > C4 H9 OG4 H9 ♦ HQH £34) (C6 H5 ) 2CH0CH(C6 H5 ) 2 * 2 h V 1^ 2 lC 6 H5 ) 2 CH0C4 H9 + HCH ( 3 5 ) C H 0 0 H + 2 (C H ) C H O B (C _ H ) CHOC H + HOH4 9 4 9 6 5 c * 6 5 2 4 9 R e a c t i o n s ( 3 3 ) and { 3 5 ) c a n n o t o c c u r a t t h e low c a t a l y s t c o n c e n t r a t i o n s u s e d * At t h e © t a r t o f th© p r o c e s s r e a c t i o n s ( 3 1 ) and ( 3 2 ) o c c u r . I f b u t a n o l a n d b e n z h y d r o l a r e p r e s e n t In e q u i v a l e n t am ounts a t t h e s t a r t , u n r e a c t e d b u t a n o l w i l l be l e f t when r e a c t i o n s ( 31 ) and ( 3 2 } h a v e u s e d up a l l t h e b e n z ­ h y d r o l * As soon as some o f t h e s y m m e t r i c a l e t h e r I s f o r m e d i n r e a c t i o n ( 3 2 ) h o w e v e r , i t can r e a c t a s In e q u a t i o n ( 3 4 ) • T h e s K e o t r o p i c r e m o v a l o f w a t e r f o r c e s r e a c t i o n ( 3 4 ) t o com­ p l e t i o n and s i n c e t h e P r o d u c t s o f t h i s r e a c t i o n a r e t h e same a s • 6 9 - t h o s e from r e a c t i o n ( 31 ) , a q u a n t i t a t i v e y i e l d o f t h e b u t y l d i p h e n y l r a e t h y l e t h e r i s o b t a i n e d * T h i s I n t e r p r e t a t i o n e m p h a s i z e s a f u r t h e r a d v a n t a g e o f t h e a z e o t r o p i c method f o r h e r e t h e f o r c i n g o f t h e e q u i l i b r i a c o n ­ v e r t s a m i x t u r e o f p r o d u c t s t o a s i n g l e p r o d u c t . In t r a n s e t h e r i - f i c a t l o n s th© a z e o t r o p i c method would u s u a l l y b e p r e f e r r e d , w here a p p l i c a b l e , s i n c e an e x c e s s o f t h e a l c o h o l i s n o t n ee d e d in o r d e r t o o b t a i n h i g h y i e l d s * Ther© a r e t e n e t h e r s p o s s i b l e f r o m b u t y l a l c o h o l and m o n o - , d l - , and t r l p h e n y l e a r b l n o l s • They a r e l i s t e d In t h e l e f t hand column o f T a b l e I* Th© r e m a i n d e r o f t h e t a b l e I n d i c a t e s th© p r o b a b i l i t y o f t h e s e e t h e r s t r & n s e f c b e r i f y i n g w i t h e a c h o f t h e f o u r a l c o h o l s . T r a n s e t h e I f l e e t i o n s c a n n o t b© c o n s i d e r e d to b© t a k i n g p l a c e i n t h o s e i n s t a n c e s w h ere th© t r a n s o t h e r i f y i n g a l c o h o l and b o t h e l e m e n t s o f t h e e t h e r a r e th© sam e, e , g * A - l , B - 5 , € - 8 , and D-10* The sarrt© i s a l s o t r u e i f t h e a l c o h o l i c r e a c t a n t and on© a l c o h o l i c e l e m e n t o f t h e e t h e r a r e th© sam e, e . g . A - 2 , A - 3 , A- 4 , B - 2 , B—6 , B - 7 , C - 3 , 0 - 6 , C - 9 , D - 4 , D-7 and D-9* I f com­ p l e t e t r a n s e t h e r l f i c a t i o n o c c u r r e d In any o f t h e s e c a s e s th© p r o d u c t s w o u ld b e th© same a s i f th© a l c o h o l e t he r i f l e d i t s e l f . A l l t h e s e p o s s i b i l i t i e s In t h e T a b l e I h a v e b e e n marked w i t h an X. In th© r e m a i n i n g c a s e s , A-S and A - 7 , w h er e b u t a n o l i s r e ­ a c t e d w i t h a. mixed b e n z y l e t h e r , e v en th o u g h th e r © may h e a t e n d e n c y to w a r d t r a n s e t h e r l f i c a t i o n w i t h t h e o r i g i n a l e t h e r s u p p l y i n g t h e F 1 o f t h e r e s u l t i n g R f 0 CHgCHgC KgCII ^ th er© w i l l a c t u a l l y b e no n e t d i s c h a r g e o f w a t e r s o th© p r o c e s s i s n o t - 7 0 - a d a p t e d t o s t u d y by t h i s a s e o t r o p l c method# F o r e x a m p le w i t h b u t a n o l and d i p h e n y l m e t h y l b e n z y l e t h e r th e r © w ou ld be t h e f o l l o w i n g e q u i l i b r i a : ( 3 6 ) (C6 H5 ) 2 CH0CV :6 H5 ♦ ♦ 1 / 2 ( C 6 i;5 ) g C i I 0 C : l ( ( - 6 Hs ) 2 + 1 / 2 T h i s I s n o t t h e same t y p e t r a n s e t h e r i f i c a t i o n a s g i v e n i n e q u a t i o n ( 24 ) a t t h e b e g i n n i n g o f t h i s s e c t i o n s i n c e o n l y o n e - h a l f a s much w a t e r w o u ld b e d i s c h a r g e d p e r m o l e c u l e o f o r i g i n a l - 73- e t h e r . U n l i k e t h e t y p i c a l t r a n s e t h e r i f I c a t I o n , h e r e t h e a l c o ­ h o l r e a c t i n g w i t h t h e e t h e r wou ld be an R fQH a l c o h o l i n s t e a d o f IvOfj• A c c o r d i n g l y , D-3 and D- 6 a r e marked M o d i f i e d t r a n a - e t Tie r 1 f 1c a 1 1 o n * The c h a n c e s o f r e a c t i o n In D - 8 , marked S t a r l c h i n d r a n c e * a r e not good s i n c e In t h e s e c t i o n p r e c e d i n g I t w as f o u n d t h a t t r i p h e n y l c a r b l n o l r e m a in e d u n r e a c t e d I n t h e p r e s e n c e o f t h e s y m m e t r i c a l d i b e n z h y d r y l e t h e r * I h e r e m a i n i n g p o s s i b l e r e a c t i o n s , A - 8 , A- 9 , A-1Q, B - 8 , B-9 and B - 1 0 , seem l i k e l y and, a r e marked T r a n a e t h e r 1 f l o a t Ion * In o r d e r t o t e s t t h e p r e d i c t i o n s o u t l i n e d In t h e t a b l e i t was d e c i d e d to work w i t h t h e s y m m e t r i c a l t y p e e t h e r f i r s t b e ­ c a u s e o n l y on© e t h e r p r o d u c t would be formed b y I t s r e a c t i o n w i t h e a c h a l c o h o l * D i b e n z h y d r y l e t h e r was s e l e c t e d b e c a u s e i t was t h e s y m m e t r i c a l ether* e a s i e s t t o p r e p a r e . F i r s t t h e t r a n s - e t h e r l f I c a t l o n w i t h b u t a n o l w as r e p e a t e d ( A- 8 i n T a b l e I ) . The t o t a l amount o f c a t a l y s t was a dd ed a t t h e s t a r t i n s t e a d o f b e i n g added In i n c r e m e n t s * A b e n z e n e s o l u t i o n 0 . 1 2 5 m o la r i n d i b e n z - h y d r y l e t h e r and 0 * 2 5 m olar i n b u t a n o l was r e f l u x e d w i t h 0*004 m o la r p - t o l u e n © s u l f o n i c a c i d c a t a l y s t * A t h e o r e t i c a l y i e l d o f h e n z h y d r y l b u t y l e t h e r was i s o l a t e d . The e x p e r i m e n t was r e p e a t e d w i t h b e n z y l a l c o h o l In p l a c e o f b u t a n o l (B -3 In T a b le I I ) and t h e u n s y r a m e t r ic a l b e n z h y d r y 1 e t h e r was a g a i n i s o l a t e d q u a n t i t a t i v e ­ l y . B o th s e t s o f d a t a a r e p l o t t e d i n F i g u r e X V II . T he t i m e s f o r 50;l r e a c t i o n w ere n i n e and f o u r - t e n t h h o u r s when b u t a n o l was u s e d and two h o u r s when b e n z y l a l c o h o l was u s e d . I t I s I n t e r e s t i n g t o not© t h a t t h e same r e l a t i v e r e a c t i o n r a t e d i f f e r e n c e i s In e v i ­ d e n c e h e r e a s was found i n th© d i r e c t e t h e r l f i c a t I o n r e a c t i o n s w i t h 5 10 15 Hours F ig u r e XVII. Rate o f t r a n s e t h e r i f i c a t i o n o f d i b e n z h y d r y l e t h e r w i t h ( l ) n - b u t a n o l and ( I I } b e n z y l a l c o h o l bo th a t a c a t a l y s t c o n c e n t r a t i o n o f 0 . 0 0 4 molar and o f d i b e n z y l e t h e r w i th ( I I I ) n - b u t a n o l a t a c a t a l y s t c o n c e n t r a t i o n o f Q.256 m olar . - 7 5 - b e n z h y d r o l In t h e p r e c e d i n g s e c t i o n . Aga in t h i s f a c t a p p e a r s t o be due t o t h e c a t a l y s t d e a c t i v a t i o n . An a t t e m p t t o t r a n a e t h e r I f y d i b e n z h y d r y l e t h e r w i t h t r i - p h e n y l c a r b l n o l (D-B In T a b l e I ) a t a c o n c e n t r a t i o n o f c a t a l y s t o f 0 * 0 0 4 m o la r a n d 0 . 0 0 8 m o la r was u n s u c c e s s f u l * T h e r e was l i t t l e I f any r e a c t i o n even a f t e r tw o d a y s . T h i s r e s u l t i s pro v i s t o n a l l y a s c r i b e d t o a t e r i c h i n d r a n c e . Other p o s s i b i l i t i e s must n o t be d i s r e g a r d e d , h o w e v e r . I f t h e m echan ism i s l i k e t h e s t a n d a r d t r a n s e t h e r I f I c a t i o n p r o c e s s : (C6 W 0 f H(C5Hs h + - (C6H5 )2CH+ + (C6V eCH0K( 3 9 ) (40) (C6 H5 ) 2 CH+ + (C H ) COH ^ (C^JgCHOCtCgHjj) ♦ H+ 6 5 3 I t i s p r o b a b l e t h a t t h e r e v e r s e o f r e a c t i o n ( 39 } w ou ld o c c u r in p r e f e r e n c e t o r e a c t i o n { 40 ) s i n c e b e n z h y d r o l a p p e a r s t o be more b a s i c th a n t r i p h e n y l c a r b l n o l * The r e s u l t w o u ld be no a p p a r ­ e n t r e a c t i o n . I f th e p r o c e s s t e n d e d t o p r o c e e d v i a r e a c t i o n s { 3 9 ) and < 41 ) , ( 4 1 ) p h o s p h o r i c a c i d ( 0 . 0 0 4 mol© o r 0 . 4 g • } and 130 m l . d i e t h y l c a r h l t o l s o l v e n t w ere l i k e w i s e u n s u c c e s s f u l . S o l v e n t f r e e r e a c t i o n o f p h e n o l and b e n z y l a l c o h o l • Pheno 1 , B a k e r f s C, P., was d i s t i l l e d In a von f a u n f l a s k a t 25 - 26 mm. and t h e f r a c t i o n b o i l i n g a t 90 - 9 1 u was c o l l e c t e d . B e n z y l a l ­ c o h o l ( 0 . 5 m ole o r 54 g . ) , p h e n o l ( 0 . 7 5 m o le s o r 7 0 . 5 g* ) and a n h y d r o u s p h o s p h o r i c a c i d ( 0 . 0 5 mole or 4 . 9 g . ) w e r e p l a c e d In a two n e c k 5 0 0 m l . s t a n d a r d t a p e r f l a s k w i t h s t i l l h ea d and c o n ­ d e n s e r a t t a c h e d . The r e a c t i o n m i x t u r e was s t i r r e d m e c h a n i c a l l y t h r o u g h t h e s e c o n d n e c k o f t h e f l a s k . The o i l b a t h was t a k e n t o 1 5 0 “" and 6 . 6 m l . o f w a t e r d i s t i l l e d f ro m t h e m i x t u r e a t a v a p o r 0t e m p e r a t u r e o f 1 0 0 - 1 0 0 . 5 V i n 5 . 5 h o u r s . The m i x t u r e was e x ­ t r a c t e d t w i c e w i t h 1 0 0 m l . v o l u m e s o f 2 0 $ sod ium h y d r o x i d e s o l u ­ t i o n . The s o d i u m h y d r o x i d e s o l u t i o n was a c i d i f i e d w i t h d i l u t e - 8 9 - h y d r o e h l o r l c a c i d a n d e x t r a c t e d w i t h e t h e r * The e t h e r s o l u t i o n was d i s t i l l e d t h r o u g h a s h o r t column a t 3 - 4 ram* P h e n o l ( 1 2 . 5 g . ) d i s t i l l e d a t 5 9 - 6 2 ° • A s e c o n d f r a c t i o n c o n s i s t i n g o f p - h e n z y l p h e n o l ( 4 5 g . o r 4 8 $ ) d i s t i l l e d a t 150 - 1 5 2 ° • When c r y s t a l l I z e d t w i c e from 3 0 - 60" p e t r o l e u m e t h e r , I t m e l t e d a t 32 - 33 ^• The l i t e r a t u r e v a l u e I s 8 4 ° . Two l a t e r f r a c t i o n s , o n e o f 6 g • , o . p . 170 - 1 7 8 ° , and o n e o f 16 g * , b .p * 2 2 6 - 2 3 2 ° , w ere u n i d e n t I f 1 e d . F i r s t a z e o t r o p l c e x p e r i m e n t s * A l l hen sen© s o l v e n t , s u p p l i e d by J o n e s and L a u g h l i n in 55 g a l * drums, was d r i e d b; a z e o t r o p i c d i s t i l l a t i o n . The f i r s t 1 5 $ w a t e r and b e n z e n e m i x t u r e was d i s ­ c a r d e d , t h e n e x t 70/S o f t h e d i s t i l l a t e was c o l l e c t e d f o r u s e and l a s t 1 5 $ was d i s c a r d e d . The n - b u t a n o l , from Com m ercia l S o l v e n t s , was f r a c t i o n a t e d t h r o u g h a t w o - f o o t co lum n p a c k e d w i t h g l a s s h e l i c e s * The co lum n was e l e c t r i c a l l y h e a t e d . The m a t e r i a l 0 2 0 c o l l e c t e d d i s t i l l e d a t 1 1 8 - 1 1 8 . 5 a t a t m o s p h e r i c p r e s s u r e , 2 0 1 . 3 9 8 0 ( l i t . 1 . 3 9 9 9 ) .D T r i p h e n y l c a r b l n o l ( 0 . 2 5 m o le s o r 6 5 g . ) , n - b u t a n o l ( 0 . 2 5 m o l e s o r 9*25 g . ) and 1 0 0 $ p h o s p h o r i c a c i d ( 0 . 0 5 m o l e s or 4 . 9 g . ) w e re d i s s o l v e d i n 500 m l . b e n z e n e In an a z e o t r o p l e a p p a r a t u s s i m i l a r to t h e on© shown In F i g u r e I . The r e a c t i o n was r e f l u x e d Of o r 3 h o u r s a t 8 2 - 8 3 “ u n t i l 4 ml* o f w a t e r was c o l l e c t e d . A s m a l l d a r k s e c o n d l a y e r s e p a r a t e d on t h e b o t t o m o f t h e f l a s k . The r e ­ a c t i o n m i x t u r e w as s h a k e n t w i c e w i t h 5 00 m l . p o r t i o n s o f so d iu m b i c a r b o n a t e s o l u t i o n and t w i c e w i t h 5 0 0 m l . p o r t i o n s o f w a t e r . A f t e r t h e b e n z e n e had b een rem oved t h r o u g h a s h o r t column a t w a t e r pump p r e s s u r e o f 1 0 mm., the p r o d u c t , w h ic h d i s t i l l e d a t 2 - 2 . 5 mm. and 1 7 5 - 1 7 7 ° , w e ig h e d 60 g . ( 36$ ) . A r e s i d u e o f 5 g . r e m a i n e d . The ab o ve s y n t h e s i s was r e p e a t e d w i t h 0 , 0 0 5 m o le s o r 0 . 4 9 g . c a t a l y s t * In t h i s c a s e t h e m i x t u r e was r e f l u x e d f o r 4 h o u r s t o y i e l d 4 ml* o f w a t e r . An 8 Q;i y i e l d o f p r o d u c t was o b t a i n e d . T r i p h e n y l c a r b l n o l { 0 . 1 1 5 m o le s o r 30 g . ) , n - b u t a n o l ( 0 . 1 1 5 m o le s o r 8 . 5 g* ) and p - t o l u e n e s u l f o n i c acid , m o n oh y d ra te ( 0 . 0 0 0 0 2 5 m o le s or 0 . 0 0 4 7 g . ) w e r e r e a c t e d f o r 22 h o u r s a t 83 - 3 3 . 5 ^ t o y i e l d 90% o f t h e t h e o r e t i c a l amount o f w a t e r f o r t o t a l e t h e r l f i - c a t io n • An 85% y i e l d or 35 g . o f t h e p r o d u c t was i s o l a t e d . T h i s 38p r o d u c t was i d e n t i f i e d by a t r a n s e t h e r i f I c & t i o n r e a c t i o n . Two grams o f t h e t r i p h e n y l m e t h y l b u t y l e t h e r and 1 6 0 m l . o f 0 . 1 % m e t h a n o l l e h y d r o c h l o r i c a c i d w e r e s t o p p e r e d and l e f t s t a n d i n g f o r 4 d a y s a t room t e m p e r a t u r e . The c a t a l y s t w a s t h e n n e u t r a l ­ i s e d w i t h s o l i d so d iu m b i c a r b o n a t e and t h e s o l u t i o n was f i l t e r e d . The m e t h a n o l was c o n c e n t r a t e d and t r i p h e n y l m e t h y l m e t h y l e t h e r ( 1 . 5 g . ) c r y s t a l l i z e d , m .p . 8 2 - 8 3 ° ( l i t , m .p . 8 2 u ) . Tri p h e n y l c a r b l n o l ( 0 . 2 5 mol© o r 65 g . ) and n - b u t a n o l ( 0 . 2 5 m ole o r 9 . 2 5 g . ) w ere d i s s o l v e d i n 500 m l . b e n z e n e s o l u t i o n and r e f l u x e d w i t h o u t c a t a l y s t In t h e a z e o t r o p i c a p p a r a t u s f o r 24 h o u r s . Wo w a t e r was fo r m e d . SCOPE AND LIMITATIONS OF TIE A&KOTROPIC LET HOP A tte m p te d p r e p a r a t i o n o f b e n z y l e t h e r s . The c o m m e r c ia l t o l u e n e was a z e o t r o p i c a l l y d r i e d by e x a c t l y t h e same p r o c e d u r e as w as d e s c r i b e d f o r b e n z e n e . B e n z y l a l c o h o l ( 0 , 2 5 m ole o r 27 g • } , n - b u t & n o l ( 0 . 2 5 m o le o r I S . 5 g . ) and 100% p h o s p h o r i c a c i d ( 0 . 0 0 5 mole o r 0 . 4 9 g . ) w e r e d i s s o l v e d i n t o l u e n e t o g i v e 5 0 0 m l . o f s o l u ­ t i o n w h ic h was r e f l u x e d a t 1 1 2 - 1 1 3 ° f o r 3 d a y s . No w a t e r c o l l e c t e d i n t h e s e p a r a t o r . A f t e r n e u t r a l i s i n g t h e s o l u t i o n and r e m o v in g t h e s o l v e n t , 85% o f t h e b e n z y l a l c o h o l was r e c o v e r e d bv d i s t i l l a t i o n . - 9 1 - The n - d e c a n o l u s e d In a n o t h e r e x p e r i m e n t w a s East-man p r a c t i c a l No* P 5 7 0 . I t was d i s t i l l e d t h r o u g h a t w o - f o o t d'idmer column a t 2 3 - 2 4 mm. and t h e f r a c t i o n b o i l i n g a t 1 2 8 - 1 2 8 . 5 ^ was c o l l e c t e d . The a b o v e r e a c t i o n was r e p e a t e d In b e n z e n e s o l v e n t w i t h 0*05 m ole o r 4 . 9 g . a c i d c a t a l y s t and n - d e c a n a l { 0 . 2 5 m o le o r 39*5 g . ) In p l a c e o f n - b u t a n o l . The s o l u t i o n was r e f l u x e d f o r 48 h o u r s and t h e v o lu m e o f w a t e r c o l l e c t e d was 2 . 6 2 ml * On d i s ­ t i l l a t i o n o f t h e p r o d u c t a t 1 . 3 mm* t h r o u g h a f o u r - i n c h c o lu m n , a f t e r r e m o v a l o f t h e s o l v e n t , 2 2 g . ( 52% ) o f d i p h e n y l m e t h a n e 0was o b t a i n e d , b . p . 7 3 - 7 5 • T h r e e grams o f m a t e r i a l , b . p . 1 0 5 - 0108 , made up a s e c o n d f r a c t i o n . No b e n z y l e t h e r was I s o l a t e d . A 5 0 0 m l . t o l u e n e s o l u t i o n o f b e n z y l a l c o h o l ( 0*5 m ole or 54 g . ) , n - h e p t y l a l c o h o l ( 0 . 6 1 m ole o r 71 g . ) and lOOg p h o s ­ p h o r i c a c i d ( 0 . 0 5 mol© o r 4 . 9 0 g . ) was r e f 1 uxed a t 1 1 2 - 1 1 3 u f o r 24 h o u r s . The w a t e r c o l l e c t e d was 0 . 8 0 ml* The c a t a l y s t c o n c e n ­ t r a t i o n was d o l l e d and 70 h o u r s l a t e r 8 . 2 m l . o f w a t e r had c o l l e c t ­ e d . A f t e r n e u t r a l i z a t i o n o f th e r e a c t i o n m i x t u r e and r e m o v a l o f s o l v e n t , t h e p r o d u c t s w ere d i s t i l l e d t h r o u g h a m o d i f i e d C l a i a e n f l a s k w i t h s i x - i n c h colum n under 1 1 mm. p r e s s u r e . A main f r a c t i o n 0o f 45 g . w a s c o l l e c t e d a t 1 4 8 - 1 5 0 • T h i s r e p r e s e n t e d a 4 6 * 4 # 2 0 2 0 1 4 . 7 y i e l d o f p - b e n z y l t o l u e n e , 1 . 5 5 4 5 , 0 . 9 9 5 8 ( l i t . 1 . 5 6 9 2 , 20 d 4 0 . 9 9 4 ) . E t h e r i f l c a t i o n o f B e n s o i n ♦ The b e n z o i n , Eastman w h i t e l a b e l No. 3 0 2 , m .p . 1 3 5 - 1 3 6 ° , was not r e c r y s t a l l i z e d . B e n z o in ( 0 . 2 5 mole o r 53 g . ) , n - b u t a n o l ( 0 . 2 5 mol© o r 1 8 . 5 g . ) and 100;! p h o s p h o r i c a c i d ( 0 . 0 0 5 m ole or 0 . 4 9 g . ) w ere d i s s o l v e d I n e n o u g h b e n z e n e t o g i v e 500 m l . s o l u t i o n . When t h i s was r e f l u x e d f o r 6 d a y s , 78;! o f t h e t h e o r e t i c a l amount o f w a t e r f o r t o t a l e t h e r ! f i c a t I o n w as f o r m e d . - 92- The s o l u t i o n was n o t w orked up t o i s o l a t e t h e p r o d u c t s * A t te m p te d p r e p a r a t i o n o f - p h e n y l e t h y l b u t y l e t h e r * The p h e n y l m e t h y l c a r b l n o l was u n d i s t i l l e d Eastman w h i t e l a b e l l lo , 7 9 6 . P h e n y lm e t h y l c a r b l n o l ( 0 , 2 5 mole o r 5 0 * 5 g* ) , n - b u t a n o l ( o #2 5 mole o r 19*5 g . ) and 100;S p h o s p h o r i c a e i d ( 0 . 0 0 5 m ole o r 0 . 4 9 g . ) , d i s s o l v e d in e n o u g h b e n z e n e t o &1 ve 5 0 0 m l . o f s o l u t i o n , w e r e r e f l u x e d a t 8 3 - 0 4 ° f o r 26 h o u r s . ho w a t e r c o l l e c t e d . The c a t a l y s t was i n c r e a s e d t o 0 . 0 5 m o l e s and In t h e n e x t 10 h o u r s 0 . 2 5 mole w a t e r was c o l l e c t e d . T h e r e was a 0 . 5 m l . s e c o n d l a y e r on t h e b o t t o m o f t h e f l a s k . A f t e r t h e n o r m a l p r o c e d u r e f o r n e u ­ t r a l i z a t i o n , w a s h i n g and s o l v e n t rem ov a l had b e e n c a r r i e d o u t , . a 92% y i e l d { 2 5 . 9 g . ) o f s t y r e n e was d i s t i l l e d t h r o u g h a f o u r - i n c h 0 2 0column u n d e r a t m o s p h e r i c p r e s s u r e a t 1 4 4 - 1 4 6 , n^ 1 . 5 5 0 0 ( l i t . , n ® ° 1 . 5 4 6 2 ) .D B e n z h y d r o l b u t y l e t h e r . The b e n z h y d r o l was u n r e c r y s t a l l i z e d Bastman w h i t e l a b e l No. 1 4 3 2 , m.p* 6 7 - 6 8 ° . B e n z h y d r o l ( 0 . 2 5 mole or 46 £ * ) , n - b u t a n o l ( 0 . 2 5 mol© or 1 8 . 5 g . ) and 1 0 0 b p h o s p h o r i c a c i d ( 0 . 0 0 5 mole or 0 . 4 9 g . ) w ere d i s s o l v e d In b e n z e n e a s a b o v e and when t h e m i x t u r e had r e f l u x e d f o r 2 . 7 5 h o u r s a t 8 3 - 8 3 , 5 U, 4 . 2 8 m l , w a t e r had b e e n d i s c h a r g e d * The s o l u t i o n , c o n t a i n i n g a b o u t 1 m l . o f a s e c o n d p h a s e , was n e u t r a l i z e d and w ashed and t h e s o l v e n t was rem oved t h r o u g h a s h o r t column a t 10 mm. The p r o d u c t ( 55 g . o r 92%) d i s t i l l e d a t 5 - 5 . 5 mm. t h r o u g h a f o u r - i n c h v i g r e u x colum n 0a t 1 4 2 - 1 4 4 • The b e n z h y d r o l b u t y l e t h e r was r e d i s t i l l e d t h r o u g h 0t h e same a p p a r a t u s a t 5 mm* a t 1 4 0 - 1 4 1 • From a r u n w i t h 0 . 1 2 5 e q u i m o l a r q u a n t i t i e s o f t h e tw o a l c o h o l s In 5 0 0 m l . b e n z e n e s o l u ­ t i o n and w i t h p - t o l u e n e s u l f o n i c a c i d c a t a l y s t ( 0 . 0 0 2 5 m o l e s o r 0 . 4 7 5 g . ) , 2 7 g . ( 9 0 $ ) p r o d u c t w as I s o l a t e d . T r i p h e n y l m e t h y l | g - p h © n y l e t h y l e t h e r * ^ - P h e n y l e t h a n o l , Paragon Wo, 2 4 7 8 , was d i s t i l l e d t h r o u g h t h e Wldraer column a t 1 2 , 5 mm* and t h a t f r a c t i o n b o l l l n a t 1 1 1 - 1 1 1 . 5 ^ was c o l l e c t e d , TO n n rip ' 1 * 5 2 8 0 ( l i t * , n j 1 * 5 2 6 7 ) . A 5 0 0 m l . b e n z e n e s o l u t i o n o f t r i p h e n y l c a r b l n o l ( 0 . 1 2 5 m o le or 3 2 . 5 £ • } , ^ - p h e n y l e t h a n o l ( 0 * 1 2 5 mole or 1 5 . 2 5 g . ) and p - t o l u e n © s u l f o n i c a c i d m ono h ydra te ( 0 * 0 0 0 2 5 mol© or 0 * 0 4 7 5 g . ) was r e f l u x e d in t h e u s u a l manner* A l t h o u g h t h e r a t e was somewhat f a s t e r t h a n t h a t l a t e r e s t a b l i s h e d f o r t h e s t a n d a r d run a t 70 v o l t s v ar i& c s e t t i n g , t h e d a t a g a v e a good f i r s t o r d e r c u r v e t o o v e r 8 0$ c o m p l e t i o n o f t h e r e a c t i o n and a re g i v e n i n T a b le I I . T a b l e I I Tim© © l a p s e d ( ralru ) Volume o f w a t e r ( ml* ) 2 0 . 1 0 4 0 . 2 0 6 0 . 5 0 7 0 . 6 0 8 0 . 7 0 9 0 . 8 0 1 0 0 . 9 0 1 1 1 . 0 0 1 2 1 . 1 0 13 1 . 1 9 14 1 . 2 4 16 1 . 3 8 17 1 . 4 1 18 1 . 4 9 19 1 . 5 2 2 0 1 . 5 8 23 1 . 7 0 27 1 . 8 0 3 0 1 . 8 5 33 1 . 9 0 41 1 . 9 9 51 2 . 0 4 74 2 . 1 0 92 2 . 1 1 1 0 1 2 . 1 2 131 2 *1 7 165 2 . 1 8 205 2 . 1 8 A f t e r n e u t r a l i z a t i o n o f t h e s o l u t i o n and c o n e e n t r a t i o n o f t It© s o l v e n t i n t h e u s u a l w ay , 41 g . { 9 0 $ ) o f e t h e r c r y s t a l l i z e d f ro m t h e b e n z e n e # One r e c r y s t a l l i z a t i o n f r o m d i e t h y l e t h e r ^ a v e a a p r o d u c t , m .p . 6 6 - 3 7 ° ( l i t . m .p . 8 7 . 1 - 3 7 . 8 ° ) . The f i r s t o r d e r r e a c t i o n c u r v e m e n t i o n e d a b o v e was o b t a i n e d , a s in a l l s u c c e e d i n g c a s e s , by p l o t t i n g t h e l o g a r i t h m o f t h e c o n ­ c e n t r a t i o n o f t r i p h e n y l c a r b l n o l ( H f 0 ' ; ) a g a i n s t t i m e . The s p e c i f i c r e a c t i o n rat© c o n s t a n t i s r e a d i l y a v a i l a b l e i n r e c i p r o c a l m i n u t e s from, t h i s p l o t to;- m u l t i p l y i n g t h e n e g a t i v e o f t h e s lo p © by 2 * 3 0 3 . I f t h e o r i g i n a l t i m e I n t e r v a l s w e r e In h o u r s , t h e y were c o n v e r t e d t o m i n u t e s in c a l c u l a t i n g ” k n . T r i p h e n y l m e t h y l Y - p h e n y l p r o p y l e t h e r * Y - P h e n y l p r o p a n o l , Para {-.on No* 24 8 4 , was d i s t i l l e d th r o u g h t h e Wldmer column a t 21 mm. O 20and t h a t f r a c t i o n b o i l i n g a t 1 2 9 - 1 2 9 .5 " was c o l l e c t e d , 1 . 5 3 8 0 20 ( l i t . n^ 1 * 5 3 5 7 ) . T r i p h e n y l c a r b l n o l ( 0 . 1 2 5 mol© or 3 2 . 5 £ * ) , V -p h en y l p r o p a n o l ( 0 . 1 2 5 mole o r 17 g . ) and p - t o l u e n e s u l f o n i c a c i d m o n oh y d ra te ( 0 . 0 0 0 2 5 mole or 0 . 0 4 7 5 g* ) w ere d i s s o l v e d i n b e n z e n e a s a b o v e and t h e s o l u t i o n w a s r e f l u x e d . A ga in t h e r a t e was somewhat f a s t e r than t h a t f o r t h e s t a n d a r d run a t 70 v o l t s v a r l a c s e t t i n g , b u t d a t a g i v e n In T a b l e I I I g a v e a g oo d f i r s t o r d e r c u r v e t o o v e r 8 0 $ c o m p l e t i o n o f r e a c t i o n . Prom t h e b e n z e n e s o l u t i o n 4 2 g . ( 8 9 $ ) s o l i d was i s o l a t e d i n t h e u s u a l w ay . One r e c r y s t & l l - i z a t l o n o f a s m a l l p o r t i o n f r o m 6 0 - 8 0 ° p e t r o l e u m o t h e r g a v e m a t e r - l a l m e l t i n g a t 7 8 - 7 9 ° . A n a l , c a l c ' d . f o r C H ° i C, 8 8 . 8 9 ; H, 6 . 8 7*50 © Found : C, 9 £ 4 7 i E, 6 . ? ? 9 5 - T a b l© I I I Tim© e l a p s e d ( m ln . ) Vo I ume o f w a t e r ( m l * ) 2 0 * 1 0 5 0 . 2 9 7 0*44 9 0 . 6 2 1 1 0 . 8 8 13 1 . 0 2 15 1 . 1 7 17 1 . 3 0 19 1 . 4 0 2 1 1 . 5 1 23 1 . 6 1 27 1 . 7 2 29 1 . 7 5 33 1 . 8 3 3 9 1 . 9 3 46 2 . 0 0 54 2 . 0 3 62 2 . 0 7 71 2 . 1 0 1 30 2 . 1 7 155 2 . 2 0 183 2 . 2 1 2 0 1 2 . 2 1 T r i p h e n y l m e t h y l e t h y l e t h e r * C om m erc ia l a n h y d r o u s e t h a n o l 1 7was f u r t h e r d r i e d o v e r m a g n es iu m t u r n i n g s * I t was d i s t i l l e d t h o u g h an e i g h t - I n c h v l g r e u x column and t h e p o r t i o n b o i l i n g a t 7 7 - 7 7 . 4 ° was c o l l e c t e d * The a b o v e r e a c t i o n was r e p e a t e d u s i n g 0 . 1 2 5 mol© e t h a n o l i n p l a c e o f ^ - p h e n y l e t h a n o l • The r e a c t i o n m i x t u r e was r e f l u x e d f o r 3 h o u r s a t 8 2 * 5 - 8 3 ° . The v o lu m e o f a q u e o u s l a y e r c o l l e c t e d was 2 . 7 1 m l . The t h e o r e t i c a l amount o f w a t o r i s o n l y 2 * 2 5 m l . The w a t e r l a y e r had a d e n s i t y a t 2 5 u o f 0 * 9 6 4 7 . T h i s c o r r e s p o n d e d t o 2 3 $ e t h a n o l p r e s e n t by w e i g h t . The c o r r e c t e d w a t e r vo lum e w o u ld b e 2 . 0 9 m l . , w h ic h I s 9 3 $ o f t h e t h e o ­ r e t i c a l v a l u e f o r c o m p l e t e e t h e r l f I c a t i o n . T he t r i p h e n y l m e t h y l e t h y l e t h e r was not I s o l a t e d . A t t e m p t e d e t h e r l f i c a t i o n o f a l l y l a l c o h o l . The a l l y l a l c o h o l was Pastman w h i t e l a b e l No * 5 1 8 . A l l y l a l c o h o l ( 1 mol© o r 58 g . ) and 1 0 0 $ p h o s p h o r i c a c i d ( 0 *15 mol© o r 1 4 . 7 g . ) w e r e d i s s o l v e d i n en o u g h t o l u e n e t o g i v e 1 0 0 0 ml* o f s o l u t i o n w h ic h was r e f l u x e d f o r 3 h o u r s . A t o t a l o f 1 3 . 3 m l . o f w a t e r c o l l e c t e d . The r e ­ a c t i o n m i x t u r e was v e r y dark and a brown l a y e r o f s e v e r a l m i l l i ­ t e r s s e t t l e d on t h e b o t t o m o f t h e f l a s k . The s o l u t i o n y i e l d e d no r e a d i l y i d e n t i f i a b l e p r o d u c t on b e i n g worked up . T h e r e was an a b u n d a n ce o f p o l y m e r i c m a t e r i a l * B t h e r l f i c a t l o n o f camphene c a r b i n o l and c ln n a m y l a l c o h o l . Camphene c & r b i n o l was p r e p a r e d by t h e c o n d e n s a t i o n o f t r i o x y - 49m e t h y l e n e w i t h camphene i n t h e p r e s e n c e o f a c e t i c a c i d . Cam­ phene c a r b i n o l ( 0 . 2 5 mole o r 4 1 . 5 g . ) , n - b u t a n o l ( 0 . 2 5 m ole or 1 8 . 5 g . ) and 1 0 0 $ p h o s p h o r i c a c i d ( 0 . 0 0 5 mole or 0 . 4 9 g . ) w e re r e f l u x e d w i t h 5 0 0 m l . b e n z e n e f o r 1 8 h o u r s t o y i e l d t h e t h e o r e t i c a l amount o f w a t e r f o r 1 0 0 $ e t h e r i f i c a t I o n • A f t e r r e ­ moval of t h e s o l v e n t t h e p r o d u c t was d i s t i l l e d from a von hraun f l a s k a t 8 mm* a t 1 3 3 - 1 3 5 u . I t w e ig h e d 33 g* ( 60 $ } and was w a t e r w h i t e . T h er e was an und 1 s t l l l e d r e s i d u e o f 13 g . The a b o v e e x p e r i m e n t was r e p e a t e d w i t h c ln n a m y l a l c o h o l { 0 . 2 5 m ole or 3 3 . 5 g . ) In p l a c e o f camphene c a r b i n o l . C lnnam yl a l c o h o l , Eastman p r a c t i c a l Ho. P 7 8 , w as d i s t i l l e d t h r o u g h t h e ot w o - f o o t Widmer colum n and t h e f r a c t i o n b o i l i n g a t 1 4 3 - 1 4 4 a t 1 4 - 1 5 mm. was c o l l e c t e d . The r e a c t i o n r e q u i r e d 2 d a y s t o y i e l d t h e t h e o r e t i c a l amount o f w a t e r . On f r a c t i o n a t i o n o f t h e p r o d u c t , 4 6 g . ( 8 8 $ ) o f m a t e r i a l d i s t i l l e d a t 1 1 5 - 1 1 8 ^ and 3 mm. p r e s s u r e t h r o u g h a s h o r t c o lu m n . T h i s m a t e r i a l was n o t p o s i t i v e l y i d e n ­ t i f i e d a s t h e e t h e r . Thar© was a 2 g . r e s i d u e . A t t e m p t e d p r e p a r a t i o n o f f j - n a p h t h y l e t h e r s . - Ha p lit ho 1 ( 0 . 5 mole o r 72 g . ) and 1 0 0 $ p h o s p h o r i c a c i d { 0 , 0 0 5 m ole o r - 9 7 - 0 . 4 9 g . ) w e re r e f l u x e d w i t h 5 0 0 ml* b e n z e n e a t 8 3 - 3 3 • 5 ' “' Tor 12 h o u r s . The c a t a l y s t was i n c r e a s e d t o 0 . 0 5 mole and r e - f l u x i n g c o n t i n u e d f o r 1 2 h o u r s b u t s t i l l no w a t e r was e v o l v e d . The s t a r t i n g m a t e r i a l was q u a n t i t a t i v e l y r e c o v e r e d . ^ - N & p h th o l ( 0 . 2 5 m ole o r 36 g . ) and n - h u t a n o l ( 0 . 2 5 m ole o r 13*5 g . ) w ere r e f l u x e d . In 5 0 0 m l . b e n z e n e w i t h p h o s p h o r i c a c i d ( 0 . 0 0 5 m o le o r 0 . 4 9 g . ) f o r 48 h o u r s a t 8 3 - 8 3 . 5 ^ • Mo r e a c t i o n was n o t e d s o t h e c a t a l y s t was i n c r e a s e d t o 0 * 05 mole and r © f l u x ­ ing, c o n t i n u e d f o r 24 h o u r s . No e t h e r i f i c a t i o n t o o k p l a c e . ^ - N a p h - t h o l was a g a i n r e c o v e r e d i n q u a n t i t a t i v e a m o u n t s . ^ - N a p h t h o l ( 0 . 0 9 m ole or 1 2 . 9 6 g . ) and r s - b u t a n o l ( 0 . 9 mol© o r 6 6 * 6 g . ) w e re r e f l u x e d i n 990 m l . o f b e n z e n e w i t h 10Q;S p h o s ­ p h o r i c a c i d ( 0 . 0 1 mole or 0 . 9 8 g . ) f o r 20 h o u r s a t 8 2 . 5 - 8 3 ^ . No w a t e r formed# The c a t a l y s t was i n c r e a s e d t o 0 . 1 m o le and t h e r e f l u x i n g c o n t i n u e d f o r 4 8 h o u r s , but no r e a c t i o n t o o k p l a c e . The t o t a l amount o f ^ - n a p h t h o l was r e c o v e r e d . A t t e m p t e d p r e p a r a t i o n o f d i b u t y l e t h e r , n - B u t a n o l { 0 . 5 0 m ole o r 3 7 g . ) and p h o s p h o r i c a c i d ( 0 . 0 0 5 m o le or 0 . 4 9 g . ) w e r e r e f l u x e d i n 5 0 0 m l . t o l u e n e a t 1 0 5 - 1 0 8 u f o r 19 hour s . p - T o l u e n e s u l f o n i c a c i d m onoh ydra te ( 0 , 0 0 5 mole o r 0 . 9 5 g . ) was added and t h e amount w a s i n c r e a s e d 4 h o u r s l a t e r t o 0 . 0 5 mole b u t s t i l l no e t h e r i f I e a t i o n t o o k p l a c e d u r i n g 4 8 h o u r s . In a n o t h e r e x p e r i m e n t , g a s e o u s bo ro n t r i f l u o r i d e ( 0 . 0 5 m ole o r 3 . 4 g . ) was p a s s e d i n t o 5 2 1 . 5 g . o f d i c h l o r o e t b a n e c o o l e d i n a d r y I c e a c e t o n e b a t h . Fuming o f t h e boron t r i f l u o r i d e s t o p p e d when t h e n - b u t & n o l ( 0 . 5 mol© o r 37 g . ) was a d d e d . A l i q u i d s e p ­ a r a t o r w h ic h r e t u r n e d s o l v e n t s h e a v i e r t h a n w a t e r t o t h e r e a c t i o n m i x t u r e was u s e d . R e f l u x i n g was c o n t i n u e d a t 8 5 - 8 6 ^ f o r 3 h o u r s - 9 8 - and t h e s o l u t i o n became v e r y d a r k i n c o l o r . Ho w a t e r l a y e r a p p e a r e d * A w h i t e s o l i d o f unknown i d e n t i t y w h ic h m e l t e d o v e r 2 0 0 u c o l l e c t e d In t h e c o n d e n s e r . The a b o v e e x p e r i m e n t w i t h b o r o n t r i f l u o r i d e was r e p e a t e d u s i n g b e n z e n e a s t h e s o l v e n t . The c a t a l y s t was d i s s o l v e d i n 8 5 0 m l , b e n z e n e s o l u t i o n and a 2 5 0 m l , b e n z e n e s o l u t i o n c o n t a i n ­ i n g t h e b u t a n o l was a d d e d . The s o l u t i o n was r e f l u x e d f o r 24 h o u rs but no w a t e r a p p e a r e d . B u t a n o l ( 0 . 5 m ole o r 37 g . ) and p - t o l u e n e s u l f o n i c a c i d { 0 , 0 5 mole o r 9 . 5 g . ) w ere r © f l u x e d w i t h 500 m l . b e n z e n e f o r 24 h o u r s w i t h o u t r e a c t i o n . The same amount o f b u t a n o l and a luminum b ro m id e ( 0 , 0 0 5 m o le or 1 . 3 g , ) w ere r e f l u x e d i n 5 0 0 m l . b e n z e n e f o r 4 8 h o u r s w i t h o u t r e a c t i o n . The c a t a l y s t was i n c r e a s e d t o 0 , 0 5 m o le and r e f l u x c o n t i n u e d f o r 4 8 more h o u r s . Ho w a t e r a p p e a r e d i n t h e s e p a r a t o r . Aluminum c h l o r i d e ( 0 . 0 0 5 mole o r 0 . 6 6 g • ) was added and t h e r e a c t i o n m i x t u r e r e f l u x e d f o r a n o t h e r 4 8 h ou rs* No w a t e r was c o l l e c t e d * S t a n d a r d a z e o t r o p l c p r o c e d u r e . The s t a n d a r d a p p a r a t u s i s shown i n F i g u r e I . A 1 0 0 0 m l , two n eck s t a n d a r d t a p e r f l a s k was u s e d . The w a t e r s e p a r a t o r was a s t a n d a r d m ode l made bv Ac© G l a s s Co. w h ic h was c a l i b r a t e d t o m e a s u r e 5 m l , o f w a t e r . The c a l i b r a ­ t i o n s w e r e c h e c k e d b v t h e method o f w e i g h i n g m ercu ry and w e r e f o u n d a c c u r a t e t o w i t h i n e x p e r i m e n t a l e r r o r s o f r e a d i n g . The West c o n ­ d e n s e r , w i t h a c c o m p a n y in g c a l c i u m c h l o r i d e t u b e , was u s e d i n a l l e x p e r i m e n t s . Both t h e c o n d e n s e r and s e p a r a t o r w e r e c l e a n e d b e ­ f o r e e a c h run w i t h f r e s h c h rom ic a c i d c l e a n i n g s o l u t i o n . A h e m i ­ s p h e r i c a l g l a s c o l m a n t l e s u p p l i e d t h e h e a t f o r r e f l u x i n g . I t was a t t a c h e d t o a v a r l a c s e t f o r 70 v o l t s * The v a r i a c was c a l i b r a t e d by a v o l t m e t e r * In t h e s t a n d a r d run 0 * 1 2 5 m o l e s e a c h o f t h e Hf 0 E and RQH a l c a h o I s w e r e d i s s o l v e d i n s u f f i c i e n t b e n z e n e t o b r in g t h e v o l ­ ume t o 5 0 0 ml* The a l c o h o l s w e r e p u r i f i e d a s l a d e s c r i b e d f o r e a c h e x p e r i m e n t . The c a t a l y s t was Eastman w h i t e l a b e l No. 984 p - t o l u e n e s u l f o n i c a c i d m o n o h y d r a t e . I t s n e u t r a l e q u i v a l e n t was 1 9 2 . 1 ( c a l c d . 1 90 ) . The e x a c t amount o f c a t a l y s t was d e t e r ­ m ined by s u c c e s s i v e a d d i t i o n s i n a p r e v i o u s run* U n l e s s o t h e r ­ w i s e i n d i c a t e d , t h e amount o f c a t a l y s t p r e s e n t was i n c r e a s e d s t e p w i s e a s shown In T a b le IV* T a b l e IV h o l e s c a t a l y s t Grama Grama w a t e r In t h e c a t a l y s t 0 . 0 0 0 1 2 5 0 . 0 2 3 7 5 0 . 0 0 2 2 5 0 . 0 0 0 2 5 0 0 . 0 4 7 5 0 . 0 0 4 5 0 . 0 0 0 5 0 . 0 9 5 0 . 0 0 9 0 . 0 0 1 0 * 19 0 . 0 1 8 0 . 0 0 2 0 . 3 8 0 . 0 3 6 0 . 0 0 4 0 . 7 6 0 . 0 7 2 0 . 0 0 8 1 . 5 2 0 . 1 4 4 0 . 0 1 6 3 • 04 0 . 2 8 8 0 . 0 3 2 6 . 0 8 0 . 5 7 6 0 . 0 6 4 1 2 . 1 6 1 . 1 5 2 0 . 1 2 8 , 2 4 . 3 2 2 . 3 0 4 At t h e s t a r t o f a n y r e a c t i o n , t h e a l c o h o l i c r e a c t a n t s w e re put i n t o t h e r e a c t i o n f l a s k w i t h t h e s o l v e n t , b u t w i t h o u t t h e c a t a l y s t , and t h e s e p a r a t o r , c o n d e n s e r , d r y i n g t u b e and t h e r ­ mometer w e l l w ere put i n p l a c e . M in e r a l o i l was used i n t h e t h e r ­ mometer w e l l . About 0 . 2 m l . o f w a t e r was p l a c e d i n t h e s e p a r a t o r a t t h e b e g i n n i n g i n o r d e r t o p r o v i d e a more a c c u r a t e s t a r t i n g p o i n t f o r t h e w a t e r v o l u m e r e a d i n g s . The g l a s c o l was p l a c e d u n d e r t h e f l a s k and t h e s o l u t i o n was h e a t e d to r e f l u x . B o l l i n g c h i p s w ere u s e d t o p r e v e n t b u m p in g . When t h e s o l u t i o n was r e f l u x i n g r e g u l a r l y - 1 0 0 - and t h e r e was no s u p e r h e a t i n g a s i n d i c a t e d by t h e c o n s t a n t s t a n d a r d r e a c t i o n t e m p e r a t u r e o f 8 2 . 5 ° * l u ( u s u a l l y 82 . 5 V m o . 5 v }> a on e ml* b e a k e r c o n t a i n i n g t h e c a t a l y s t was p l a c e d i n t h e r e a c t i o n m i x t u r e t h r o u g h t h e s i d e n e c k o f t h e f l a s k . The t h e r m o m e t e r w e l l was r e p l a c e d and t h e f l a s k w h i l e s t i l l s i t t i n g i n the g l a s c o l was s w i r l e d f o r on© m in u te t o i n s u r e p r o p e r m i x i n g b e f o r e r e a d i n g s w ere s t a r t e d . The t h e r m o m e t e r u s e d was c a l i b r a t e d a g a i n s t a Bu­ r e a u o f S t a n d a r d s c a l i b r a t e d A n sc h u tz t h e r m o m e t e r . I f t h e t h e r ­ mometer w as o f f more t h a n 1 u i n t h e v i c i n i t y o f 8 0 , t h e c a l i ­ b r a t i o n p o i n t , i t was d i s c a r d e d f o r a n o t h e r on©. I f l a r g e r am ounts o f c a t a l y s t than 0 . 0 0 1 mol© w e r e r e q u i r e d , t h e w a t e r in t h e c a t a l y s t w as 'removed a Z e o t r o p i c a l l y f r o m a b e n ­ z e n e s o l u t i o n o f t h e a c i d b e f o r e t h e a l c o h o l i c r e a c t a n t s w e r e a d d e d . In s u c h c a s e s t h e c a t a l y s t w as usually d i s s o l v e d i n 4 5 0 m l . o f b e n z e n e s o l u t i o n a n d t h e m a t e r i a l was r e f l u x e d u n t i l i t was d e h y d r a t e d . The a l c o h o l i c r e a c t a n t s , d i s s o l v e d in b e n z e n e t o g i v e a t o t a l vo lum e o f 5 0 m l . , w ere t h e n added b r i n g i n g th e t o t a l vo lum e t o 50 0 m l . The 5 0 m l . o f s o l u t i o n was warmed on a h o t p l a t e and added warm t o t h e r e f l u x i n g m i x t u r e . A f t e r one m in u te o f s w i r l i n g , v o lu m e and t e m p e r a t u r e r e a d i n g s w ere b e g u n . B arom eter r e a d i n g s w ere t a k e n , tw o or t h r e e t i m e s a d a y . D u r in g t h e c o u r s e of r u n s a t a c a t a l y s t c o n c e n t r a t i o n o f 0 . 0 0 0 2 5 m o la r and a b o v e t h e r e was no s i g n i f i c a n t , c h a n g e i n t h e c o n c e n t r a t i o n o f t h e c a t a l y s t . In on© run o f t r i p h e n y l c a r b i n o l w i t h n - b u t a n o l i n t h e p r e s e n c e o f 0 * 0 0 0 2 5 m ole c a t a l y s t p e r 5 0 0 m l . b e n z e n e , 1 0 0 ml* p o r t i o n s o f t h e r e a c t i o n m i x t u r e w e re p i p e t t e d o u t e v e r y 15 m i n u t e s and e a c h p o r t i o n was s h a k e n 5 m i n u t e s w i t h an e q u a l v o lum e o f w a t e r and t h e pH o f t h e w a t e r s o l u t i o n was t a k e n - 1 0 1 - on a Beckmann pH m eter* The s o l u t i o n was a l s o t i t r a t e d w i t h s t a n d a r d a l k a l i * In a s i m i l a r e x p e r i m e n t u s i n g o n e - h a l f t h i s a c i d c o n c e n t r a t i o n , 5 0 ml* p o r t i o n s w ere p l p e r t e d f r o m t h e r e - f l u x i n g s o l u t i o n . T h e s e w ere shaken w i t h e q u a l v o lu m e s o f w a t e r f o r o n e - h a l f h o u r In a m e c h a n i c a l s h a k e r and t h e pH o f t h e a q u e o u s l a y e r was d e t e r m i n e d * The d a t a o b t a i n e d a r e r e c o r d e d In T a b le V. T a b le V wfoles c a t a l y s t H r s . e l a p s e d pH by- piI by m e t e r t i t r a 0 . 0 3 . 6 9 3 * 5 1 0 . 2 5 3 . 7 1 3 . 5 5 0 . 5 0 3 * 7 9 3 . 5 3 0 . 0 0 0 2 5 0 . 7 5 3 . 8 2 5 . 5 2 1 . 0 0 3 . 8 2 5 . 5 1 1 . 2 5 3 . 8 8 3 . 5 1 1 . 5 3 . 8 7 3 . 5 2 0 . 0 4 . 1 8 0 . 5 4 . 2 0 1 . 5 4 . 3 0 0 . 0 0 0 1 2 5 2 . 5 4 . 2 5 3 . 5 4 . 2 0 4 . 5 4 . 2 0 6 . 5 4 . 1 0 The w a f e r vo lu m e d a t a w ere t r a n s p o s e d t o g i v e t h e p e r c e n t a g e c o m p l e t i o n o f t h e r e a c t i o n . T h e s e p e r c e n t a g e v a l u e s w e re p l o t t e d a g a i n s t t i m e * When t h i s c u r v e became h o r i z o n t a l , th© r e a c t i o n was assum ed c o m p l e t e and i t was s t o p p e d * The s o l u t i o n was a lw a y s o n e p h a s e , a l t h o u g h on c o o l i n g ; , some of th© a c i d c a t a l y s t did, a t t i r e s c r y s t a l l i z e o u t i f o n e o f t h e l a r g e r am ounts had b e e n em­ p l o y e d . The s o l u t i o n w as u s u a l l y l i g h t s t r a w c o l o r , e x c e p t w i t h t r i p h e n y l c a r b i n o l , when i t becam e g o l d e n y e l l o w * The r e a c t i o n m i x t u r e , a f t e r r e f T a x in g was s t o p p e d , was c o o l e d and washed t w i c e w i t h e q u a l v o lu m e s o f a q u e o u s s o d iu m b i c a r b o n a t e -102- s o l u t I o n and t h e n w a sh e d t w i c e w i t h w a t e r * The n e u t r a l b e n z e n e s o l u t i o n was f i r s t d r i e d o v e r c a l c i u m c h l o r i d e o n l y I f some p r o d u c t was p r e s e n t w h ic h w o u ld s t e a m d i s t i l l . O t h e r w i s e , th e s o l v e n t was rem oved i m m e d i a t e l y t h r o u g h an e i ^ h t - i n c h v l g r e u x column und e r w a t e r pump p r e s s u r e a t 1 5 - 2 0 mm. up t o a b a t h t emp- pe r a t u r e o f 110" • 'when t h e p r o d u ct was a s o l i d , th© s o l u t i o n w a s c o n c e n t r a t e d u n t i l th© e t h e r c r y s t a l l i s e d o u t on c o o l i n g * In c a s e s w h ere l i q u i d e t h e r s w e re o b t a i n e d , t h e compounds w e r e d i s ­ t i l l e d un d er vacuum a t a p p r o p r i a t e p r e s s u r e s down t o 0 . 0 5 mm. o r w ere m o l e e u l a r l y d i s t i l l e d , a f t e r a l l t h e s o l v e n t had b e e n r e ­ m oved. I f t h e l a t t e r p r o c e d u r e was f o l l o w e d , a Hickman m o l e c u l a r s t i l l was em p loy ed i n t o w h ic h was i n t r o d u c e d a s m a l l m a g n e t i c s t i r r e r t o p r e v e n t bumping and t o h a s t e n v o l a t i l i s a t i o n . TKit! L3PFKC! OF VARIATIONS IN T!:K CHAIN LENOI/r OF NO5! f r l ph en y l ,m eth y l b u t y l e t h e r . T r l p h e n y l c a r b i n o l end n - b u t ­ a n o l w ere e i h e r i f l e d by t h e s t a n d a r d p r o c e d u r e ; t h e amount o f c a t a l y s t u s e d was 0 . 0 0 0 2 5 m o le s ( 0 . 0 4 7 5 g . ) The r e a c t i o n m i x - ot u r o s was r e f l u x e d 3 h o u r s a t 8 2 . 5 ' a t w h ic h t i m e t h e vo lum e o f w a t e r was c o n s t a n t a t t h e t h e o r e t i c a l a m o u n t , 2 . 2 5 ml* The r e ­ a c t i o n r a t e d a t a are p l o t t e d In F i g u r e I I and t h e f i r s t o r d e r p l o t I s g i v e n i n F i g u r e I I I . A f t e r t h e s t a n d a r d method o f n e u t r a l i s a ­ t i o n and r em o v a l o f s o l v e n t had b e e n c a r r i e d o u t , th© p r o d u c t was d i s t i l l e d t h r o u g h a s t i l l head w i t h o u t co lum n a t 0 . 1 nm. p r e s s u r e 0and 1 3 7 . 8 - 1 4 0 • Two grams o f l i g h t t a n r e s i d u e r e m a i n e d . H ie y i e l d o f c r u d e e t h e r was 3 6 . 8 g . ( 9 5 $ ) • The c r u d e e t h e r was 0m o l e e u l a r l y d i s t i l l e d a t 0 * 0 1 0 5 mm. a t 1 3 8 - 1 3 9 and f o u r e q u a l f r a c t i o n s w e re c o l l e c t e d . T h ere was no r e s i d u e . The t h i r d f r a c t i o n f r o m th® m o l e c u l a r d i s t i l l a t i o n was f r a c t i o n a t e d a t 0 * 2 8 mm. t h r o u g h a f o u r - i n c h v i g r e u x c o l u m n • 2 . 5 g* was s e t a s i d e . The se c o n d f r a c t i o n o f v i s c o u s y e l l o w o i l 25was a n a l y z e d , 1 . 5 3 3 9 5 . T r l p h e n y l m e t h y l h e p t y l e t h e r . The n - h e p t a n o l was p u r i f i e d 25 25 25a s p r e v i o u s l y d e s c r i b e d , 1 . 4 1 8 5 and d^ 0 . 8 1 9 0 ( l i t . njj w ere e t h e r ! f l e d by t h e s t a n d a r d p r o c e d u r e In t h e p r e s e n c e o f 0 . 0 0 0 2 5 m o l e s ( 0 . 0 4 7 5 g . ) o f c a t a l y s t . A f t e r 4 h o u r s 2 . 2 0 m l . w a t e r had s e p a r a t e d . The r e a c t i o n r a t e d a t a and f i r s t o r d e r p l o t a r e g i v e n In F i g u r e s I I and I I I , r e s p e c t i v e l y * F o l l o w i n g n e u t r a l i z a t i o n and s o l v e n t r e m o v a l , th© h e p t y l © t h e r was d i s t i l l e d fro m a von Craun f l a s k a t 0 . 1 0 mm. and t h e f r a c t i o n b o i l i n g a t 1 5 2 - 1 5 6 was c o l l e c t e d . The y i e l d was 41 g . ( 9 1 $ ) • T h e r e was 1 g . o f r e s i d u e . Upon m o l e c u l a r d i s t i l l a t i o n o f t h i s c r u d e p r o d u c t f o u r e q u a l f r a c t i o n s w e r e c o l l e c t e d . The d i s t i l l a t i o n was c a r r i e d o u t na t 0 . 0 0 7 5 mm. and 1 4 3 - 1 4 5 ^ • T h ere was no r e s i d u e . The f o u r t h f r a c t i o n was d i s t i l l e d a t 0.2 mm. t h r o u g h a s t i l l he ad on iy . a 2 .5 g* f i r s t f r a c t i o n was c o l l e c t e d a t 150-154^ and a s e c o n d f r a c t i o n o f 3 . 5 g . came o v e r a t 164-165J • Two grams o f r e s i d u e were d i s c a r d e d . The s e c o n d f r a c t i o n was a l i g h t y e l l o w The f i r s t f r a c t i o n ( 3 g . ) came o v e r a t 1 6 6 - 1 6 7 and t h e s e c o n d p o r t i o n ( 2*9 g . ) d i s t i l l e d a t 1 7 0 ° a t C .3 0 mm. The r e s i d u e o f A n a l , c a l c 1 d . f o r c 2 3 ^2 4 ° Found C, 8 7 . 3 4 ; B, 7 . 5 9 0 , 8 7 . 4 8 ; H, 7 . 9 2 0 . 8 1 8 2 ) • T r i p h e n y l c a r b i n o l and n - h e p t a n o l o i l , n g 5 1 . 5 6 6 5 . -104- T r i p h e n y l m e th y l d e c y l e t h e r . The n - d @ c a n o l , p u r i f i e d a s 2 1 O Q p r e v i o u s l y d e s c r i b e d had n D 1 * 4 5 4 7 and 0 * 8 2 4 6 . Th© l i t e r a - p n 20 t u r a v a l u e s a r e n^ 1 *4 3 7 2 and 0 . 8 2 9 7 . T r i p h e n y l c a r b i n o l and n - d e c a n o l were e t h e r i f l e d by t h e p r o c e d u r e j u s t d e s c r i b e d . A f t e r r e f l a t i n g 4 h o u r s 2 * 2 4 m l . o f w a t e r had c o l l e c t e d * The r a t e d a t a a r e p l o t t e d i n F i g u r e I I and t h e f i r s t o r d e r p l o t o f t h i s d a t a i s g i v e n In F i g u r e I I I . The s o l u t i o n w as n e u t r a l i s e d and t h e s o l v e n t rem oved In th© u s u a l m a n n er . The d e c y l e t h e r was d i s t i l l e d t h r o u g h t h e s t i l l head w i t h o u t a co lu m n a t 0 . 0 8 mm. and 174 - 1 7 6 . 5 The p r o d u c t w e i g h e d 4 5 . 6 g . ( 91,T ) . Th® r e s i d u e was 1 gram . The c r u d e e t h e r was m o l e c u l a r l v d i s t i l l e d a t 0 . 0 0 8 mm. and 1 6 3 - 1 6 4 ^ and f o u r ©qua! f r a c t i o n s wer© c o l l e c t e d . To © v o id d e - 67c o m p o s i t i o n , no f u r t h e r d i s t i l l a t i o n was a t t e m p t e d . The f o u r t h f r a c t i o n from t h e m o l e c u l a r d i s t i l l a t i o n was a v e r y l i g h t y e l l o w o i l , n?.° 1 . 5 5 3 'i.u A n a l , c a l c *d. f o r Cg 9 l! 0* C, 87 .00- , H, 9 . 0 0 Found : C, 8 7 . 1 1 ;H, 9 . 4 0 E t h e r i f l e a t i o n o f n - b u t a n o l w i t h e x c e s s t r i p h e n y l c a r b i n o l . T r i p h e n y l c a r b i n o l ( 0 *25 mol© o r 6 5 g . ) and n - b u t a n o l ( 0 . 1 2 5 m ole o r 9 . 2 5 g . ) w ere r e a c t e d In t h e u s u a l way w i t h 0 . 0 0 0 1 2 5 mole ( 0 . 0 2 3 5 0 g . ) c a t a l y s t . The p ro d u ct In t h i s c a s e was n o t I s o l a t e d * A l t h o u g h t h e r a t e was much more r a p i d t h a n u n d e r s t a n d a r d c o n d i ­ t i o n s a t a 7 0 v o l t v a r l a c s e t t i n g , th© d a t a g a v e a go od f i r s t r e ­ a c t i o n p l o t up t o a b o u t 9 0$ r e a c t i o n c o m p l e t i o n . T h i s d a t a a r e r e c o r d e d i n T a b l e VI* -loa­ d a b le VI e l a p s e d ( m i n . ) V o l u m e o f w a t e r < m l * ) 2 0 . 1 0 3 0 * 1 9 4 0 * 2 5 5 0 * 3 0 6 0 * 3 8 7 0 . 4 2 8 0 * 4 9 9 0 . 5 3 1 0 0 * 6 0 1 1 0 . 6 7 1 2 0 . 7 5 1 3 0 . 8 0 1 4 0 . 8 9 1 5 0 * 9 3 1 6 1 . 0 0 1 7 1 . 0 5 1 8 1 . 1 0 2 2 1 * 3 9 2 3 1 . 4 6 2 4 1 . 5 0 2 5 1 * 5 8 2 6 1 * 6 2 2 7 1 . 7 0 2 8 1 . 7 6 3 0 1 . 8 6 3 2 1 . 9 3 3 4 2 . 0 0 3 6 2 . 0 7 3 8 2 * 1 0 4 0 2 . 1 1 4 8 2 . 1 6 5 6 2 . 1 8 6 7 2 . 1 9 1 2 0 2 . 1 9 B t h e r l f l e c t i o n of t r l p h a n y l c a r b i n o l w i t h e x c e s s n - b u t a n o l . T r l p h e n y l c a r b i n o l ( 0 * 1 2 5 m o l e o r 3 2 * 5 g . ) a n d n - b u t a n o l ( 0 * 3 7 5 m o l e o r 2 7 * 7 5 g . ) w e r e r e a c t e d I n t h e u s u a l w a y w i t h 0 * 0 0 0 1 2 5 m o l e s ( 0 * 0 2 3 5 0 g . ) c a t a l y s t * T h e p r o d u c t w a s n o t I s o l a t e d * T h e d a t a g i v e n I n T a b l e V I I g a v e a g o o d f i r s t o r d e r p l o t t o a b o u t 9 0 $ r e a c t i o n c o m p l e t i o n * —100 T a b le V II Time e l a p s e d ( m ln . / Volume o f w a t e r ( m l , ) 6 0 . 1 2 11 0 . 2 2 19 0 . 3 7 2 9 0 . 5 7 42 0 . 8 0 54 1 . 0 0 64 1 . 1 4 75 1 . 2 7 8 8 1 . 4 2 101 1 . 5 2 111 1 . 6 2 121 1 . 6 7 136 1 . 7 7 143 1 . 8 2 1 63 1 . 9 0 1 85 1 . 9 7 193 2 . 0 1 2 36 2 . 1 1 2 7 6 2 . 1 5 2 9 9 2 . 2 0 341 2 . 2 2 THE EFFECT OF VARIATIONS IN THE NUMBER OF PHENYL GROUPS ON THE ALPHA CARBON OF R * O H D l p h e n y l m e t h y l b u t y l e t h e r * Th© b e n s h y d r o ! u s e d h e r e was 92 op r e p a r e d from b e n z o p h e n o n e . I t m e l t e d a t 6 7 - 6 7 , 5 • The l i t - r \ e r a t u r e v a l u e i s 6 7 . 5 - 6 8 v . D i p h e n y l c a r b i n o l was © t h e r l f i e d w i t h b u t a n o l b y th© s t a n d a r d p r o c e d u r e ? 0 , 0 0 4 mol© ( 0 * 7 6 g . ) c a t a l y s t was u s e d , Th© r e a c t i o n ra t© d a t a are p l o t t e d in F i g u r e IV and t h e f i r s t o r d e r p l o t I s g i v e n In F i g u r e X. A f t e r n e u t r a l i s a t i o n o f th© s o l u t i o n and s o l v e n t r e m o v a l , th© p r o d u c t , a w h i t e o i l , was d i s ­ t i l l e d t h r o u g h a f o u r - i n c h v i g r e u x co lum n a t 0 * 5 mm. A f r a c t i o n o f 20 g *. { 9 3 % ) was c o l l e c t e d a t 1 1 6 - 1 1 7 ^ . One and o n e - h a l f grama o f d a r k r e s i d u e r e m a i n e d . A n a l . C a l c *d. f o r 5 C, 8 5 , 0 0 ; K, 8.55 Pound t C, < gS.l£* H, ff.22. R e a c t i o n o f b e n z y l a l c o h o l and b u t y l a l c o h o l * The b e n z y l a l c o h o l , Paragon ?lo. 2 7 5 5 , was d i s t i l l e d t h r o u g h a t w o - f o o t n 2 0Wldraer column a t 1 0 4 . 5 - 1 0 5 u and 2 3 - 2 4 mm., 1 * 5 4 0 2 ( l i t . o a n g 1 * 5 3 9 5 5 ) . The s t a n d a r d s e t up was u s e d w i t h o u t m o d i f i c a t i o n . p-T o lu en © s u l f o n i c a c i d m o n o h y d r a te ( 0 . 0 6 4 m o l e s o r 1 2 . 1 6 g . ) was d i s s o l v e d In 4 5 0 m l . b e n z e n e s o l u t i o n and was d e h y d r a t e d In one h o u r by r © f l u x i n g * At t h i s t i m e a b e n z e n e s o l u t i o n { 50 m l . ) c o n t a i n i n g b e n z y l a l c o h o l ( 0 . 1 2 5 m o le o r 1 3 * 5 g * ) and n - b u t a n c l ( 0 . 1 2 5 m o le o r 9 . 2 5 g . ) was added t o t h e r © f l u x i n g s o l u t i o n . The r e a c t i o n p r o c e e d e d s l o w l y f o r 7 7 . 6 h o u r s a t 8 2 ° . The r e a c t i o n r a t e c u r v e I s g i v e n a s Curve I , F i g u r e V. A f t e r n e u t r a l i z a t i o n o f t h e s o l u t i o n and s o l v e n t r e m o v a l , t h e p r o d u c t was d i s t i l l e d f i r s t t h r o u g h a s t i l l h e a d w i t h o u t c o lu m n . Th© f i r s t f r a c t i o n ( 1 5 . 5 g . ) d i s t i l l e d a t 6 5 - 7 6 ° a t 0 . 8 mm., n£ 5 1 . 5 2 5 7 . The s e c o n d f r a c t i o n { 1 . 6 g . ) d i s t i l l e d a t 0 . 1 5 mm. a t 7 6 - 9 0 u , n 1 . 5 5 8 0 . The t h i r d f r a c t i o n { 1 g . ) d i s t i l l e d a t 0 . 1 0 mm. Aa t 109-120'-' and w as y e l l o w In c o l o r . The f i r s t two f r a c t i o n s w ere w a t e r w h i t e . The r e s i d u e was n e g l i g i b l e . In o r d e r t o g e t some f r a c t i o n a t i o n t h e v a r i o u s c u t s o f th© p r e v i o u s d i s t i l l a t i o n were r u n t h r o u g h th© f o u r - i n c h v l g r e u x c o lu m n . The f i r s t f r a c t i o n ( 5*6 g * ) was c o l l e c t e d a t 22 mm. a t 1 1 3 - 1 1 3 . 5 U, 1 . 4 8 9 2 . For an a n a l y t i c a l s a m p le o f b e n z y l b u t y l e t h e r from a n o t h e r run ng was 1 . 4 8 9 1 . A n a l , c a l c fd . f o r c x 4 H1 4 0 : °* 8 0 »5 0 J 9 *76 Found s 0 , 8 0 . 8 4 ; 11 ,1 0 .01 To t h e d i s t i l l a t i o n pot was t h e n add ed t h e s e c o n d f r a c t i o n o f th© f i r s t d i s t i l l a t i o n and a f r a c t i o n { 3 . 0 5 g . ) d i s t i l l e d a t 20 mm. a t 1 0 8 * 5 - 1 0 9 , 1 . 5 0 3 0 , r e p r e s e n t i n g a m i x t u r e o f d i p h e n y l m ethane and b e n z y l b u t y l e t h e r . The p u r e d i p h e n y l m ethane f r a c t i o n ( 5 . 7 g . ) d i s t i l l e d n e x t a t 1 3 2 - 1 3 3 . 5 ° a t 20 mm, n ^ 1 . 5 7 0 0 ; t h e f r e e z i n g p o i n t was 2 3 ° . The l i t e r a t u r e v a l u e i s 2 4 - 2 5 ° . A f o u r t h f r a c t i o n i 1 . 6 5 g . ) was c o l l e c t e d a t 10 mm. a t 1 4 1 - 1 4 3 ° , 1 . 5 6 6 0 . A y e l l o w r e s i d u e o f 1 . 5 g . , 1 . 5 4 7 3 , r e m a i n e d . The t h i r d and f o u r t h f r a c t i o n s a b o v e w e re r e c o m b in e d and d i s t i l l e d t h r o u g h t h e f o u r - i n c h v i g r e u x . c o lu m n . Th© f i r s t f r a c t i o n ( 1 . 0 2 g . ) r e p r e s e n t e d a d ip h e n y lm e t h a n © and b e n z y l b u t y l e t h e r n m i x t u r e and d i s t i l l e d a t 1 2 8 a t 1 5 mm., 1 . 5 6 3 7 . The pure d ip h e n y lm e th a n © f r a c t i o n ( 4 . 5 6 g . ) d i s t i l l e d a t 1 3 2 - 1 3 3 ° a t 15 p r^ mm., 1 . 5 7 2 1 . The f r e e z i n g p o i n t w as 2 5 . S . A r e s i d u e ( 1 . 5 5 g . ) o f d i p h e n y l m e t h a n e , n** 1 . 5 6 8 0 , was a l s o f o u n d . A c a l c u l a t i o n o f y i e l d s from b o t h t h e pu re f r a c t i o n s and t h e I n t e r m e d i a t e m i x t u r e g a v e a 4 0 . 4 $ y i e l d o f b e n z y l b u t y l e t h e r and a 3 3 m2% y i e l d o f d i p h e n y l m e t h a n e . ?:TK ALKYL AT I OK' OF BEK'SLYE BY I1BK2YL AL OOKCL ANY BENZYL FT HER A l k y l a t i o n o f b e n z e n e w i t h b e n z y l a l c o h o l . p - T o l u e n e s u l ­ f o n i c a c i d m o n o h y d r a te { 0 . 0 6 4 m ole o r 1 2 * 1 6 g . ) was d e h y d r a t e d In t h e u s u a l manner in t h e s z e o t r o p i e a p p a r a t u s and 50 m l . o f a b e n z e n e s o l u t i o n o f b e n z y l a l c o h o l ( 0 . 2 5 0 mole or 27 g . ) was added t o t h e f l a s k . R e f l u x l n g was c o n t i n u e d a t 32 f o r 13 h o u r s d u r i n g w h i c h t i m e 4 . 4 5 m l . w a t e r ( 9 8 . 9 $ a l k y l a t i o n ) had b e e n c o l l e c t e d . T h i s run was made i n d u p l i c a t e and t h e r e a c t i o n ra t© d a t a a r e p l o t t e d i n Curve I I , F i g u r e V* The d a r k amber s o l u t i o n was n e u t r a l i z e d and washed and t h e s o l v e n t was r e m o v e d . The p r o d u c t was d i s t i l l e d t h r o u g h a s t i l l h e a d w i t h o u t column a t 0 . 2 5 mm. A f i r s t f r a c t i o n o f d i p h e n y l m e t h a n e { 2 8 g • o r 6 6 * 4 ^ ) , A b . p . 6 3 - 7 1 / was w a t e r w h i t © . A s e c o n d f r a c t i o n o f r a - d i b o n z y l - b e n z e n e ( 5 . 5 g . o r 1 7 ,1 ) , b . p . 1 4 7 - 1 5 0 was a l s o c o l l e c t e d . T h e r e was a r e s i d u e o f 1*5 g* The d i p h e n y lm e t h a n e f r a c t i o n was r e d i s t i l l e d t h r o u g h th© f o u r - I n c h v i g r e u x column a t 15 mm. a t 1 5 2 - 1 3 2 *5U* The f r e e z i n g p o i n t w a s £ 5 - 2 5 . 2 ° ( l i t . f r e e z i n g p o i n t 2 4 - 2 5 ^ } . The m - d i b e n z y l b e n z e n e was c r y s t a l l i z e d t w i c e from m e t h a n o l t o g i v e a w h i t e c r y s t a l l i n e s o l i d , m .p . 5 8 - 5 8 .5 '^ ( l i t . i?up* 5 8 -5 9 ' f o r m e t a - , m . p . 7 8 ° f o r o r t h o - , and m .p . 8 6 ° f o r p a r a - ) Anal* C a l c 1 d . f o r Cg0 H1 8 s C, 9 3 , 0 0 ; B, 7 . 0 0 Pound s C, 9 3 . 1 9 ; B, 7 . 3 0 P i b e n z y l e t h e r * p - T c l u e n e s u l f o n i c a c i d ( 0 . 0 6 4 m o l e s o r 1 2 * 1 6 g . ) was d e h y d r a t e d a s a b o v e i n 4:00 m l . b e n z e n e and 100 ml* o f a b e n z e n e s o l u t i o n o f b e n z y l a l c o h o l ( 0 * 6 2 5 m o le o r 6 7 . 5 g . ) was a d d e d . The m i x t u r e was r e f l u x e d a t 8 2 .5 ® f o r 4 . 5 h o u r s un ­ t i l 1 . 1 3 m l . w a t e r , o n e - f i f t h t h e t h e o r e t i c a l amount f o r © t h e r i - f i c a t i o n , had b e e n c o l l e c t e d * A f t e r n e u t r a l i z a t i o n and r e m o v a l o f t h e s o l v e n t , t h e r e s i d u e was d i s t i l l e d t h r o u g h a s t i l l h e a d . A 41 g . f r a c t i o n o f b e n z y l a l c o h o l was c o l l e c t e d a t 8 0 - 6 5 ° a t 0 . 8 mm. A s e c o n d f r a c t i o n o f d i p h e n y l m e t h a n e ( 2 . 5 g . ) d i s t i l l e d a t 69 -69 .5 ' - ' a t 0 . 3 ram. A t h i r d f r a c t i o n ( 9 . 3 g . ) , c h i e f l y d i - 0 b e n z y l e t h e r , d i s t i l l e d a t 9 1 - 1 0 4 a t 0 . 3 ram. A 6 g . r e s i d u e r e ­ m a in e d . The b e n z y l e t h e r f r a c t i o n was r e d i s t i l l e d t h r o u g h t h e f o u r - i n c h v i g r e u x column a t 9 8 - 9 9 r~ a t 0 . 1 0 ram. and y i e l d e d 6 g . -H O - 25 p r o d u c t , 1 * 5 5 9 2 . Known d i b e n z y l e t h e r was p r e p a r e d fro m b e n z y l a l c o h o l and b e n z y l c h l o r i d e In t h e p r e s e n c e o f p o t a s s i u m h y d r o x i d e , 1 . 5 5 9 7 . ^ A l k y l a t i o n o f b e n z e n e w i t h d i b e n z y l e t h e r * The d i b e n z y l a 2 0 *> e t h e r , b . p . 1 5 9 - 1 6 0 ( IX mm. ) , d^ 1 . 0 4 1 6 ( l i t . b . p . 1 6 0 u , PQ x . Q d 1 • 0 4 2 3 } , was p r e p a r e d a s j u s t d e s c r i b e d . D i b e n z y l e t h e r ( 0 . 0 6 2 5 m ole o r 1 2 . 4 g . ) and p - t o l u e n e s u l f o n i c a c i d { 0 . 0 6 4 mole or 1 2 . 1 6 g . ) were r e f l u x e d w i t h s u f f i c i e n t b e n z e n e t o g i v e 5 0 0 m l . o f s o l u t i o n a t 02^ f o r 5 . 5 h o u r s * The r e a c t i o n r a t a d a t a a r e p l o t t e d i n Curve I I I , F ig u r e V. The p r o d u c t s w ere i s o l a t e d i n e x a c t l y t h e same way a s i n t h e p r e v i o u s a l k y l a t i o n o f b e n z e n e w i t h b e n z y l a l c o h o l . D ip h e n y lm e t h a n e ( 1 7 . 4 g . o r 83 ^ ) and r a - d i b e n z y l b e n z e n e ( 1 g . o r 7,1 5 w e r e r e c o v e r e d . TBK EFFECTS OF VARIATION IN CATALYST CONCENTRATION ON T H E HATE AND ORDiF! up ETHERIF1C AT ION REACTIONS Et h e r i f I c a t i o n o f t r l p h e n y l c a r b i n o l w i t h n - b u t a n o l • T r i p h - e n y l m e l h y l b u t y l e t h e r was p r e p a r e d a t v a r i o u s a c i d c o n c e n t r a t i o n s i n a d d i t i o n t o t h e 0 . 0 0 0 2 5 m ole c o n c e n t r a t i o n d e s c r i b e d i n t h e t h i r d s e c t i o n . T r i p h e n y l c a r b i n o l ( 0 . 1 2 5 mole o r 3 2 . 5 g . ) and n-buta .ncT ( 0 . 1 2 5 mol© or 9 . 2 5 g . ) w ere r e a c t e d w i t h p - t o l u e n e s u l f o n i c a c i d in e a c h c a s e . S ta n d a r d r u n s w e r e made u s i n g 0 . 0 0 0 1 2 5 and 0 . 0 0 0 5 mol© c a t a l y s t . Th© l a t t e r run was made i n d u p l i c a t e . In th3 s c a s e , In ordar t o i n s u r e prompt r e m o v a l o f t h e w a t e r as i t w as formed a t t h e f a s t e r r a t a , t h e column o f t h e s e p a r a t o r was wrapped and a s p i r a l c o n d e n s e r was u s e d In p l a c e o f t h e West c o n d e n s e r . The v a r l a c s e t t i n g was 86 v o l t s . E e a e t l o n r a t e d a t a and f i r s t o r d e r c u r v e s a r e p l o t t e d f o r b o t h acid, c o n c e n t r a t i o n s In F i g u r e s VI and V I I , r e s p e c t i v e l y . The d a t a p l o t t e d f o r t h e 0 . 0 0 0 5 mole ru n a r e a v e r a g e v a l u e s * The -111- a v e r a g e s e c o n d o r d e r p l o t f o r t h e 0 . 0 0 0 5 m ole run i s g i v e n i n F i g u r e V I I I . E t h e r i f l e a t i o n o f b en & h yd ro l w i t h n - b u t a n o l a t a r e d u c e d c a t a l y s t c o n c e n t r a t i o n . In a d d i t i o n t o t h e e t h e r I f i c a t io n of b e n z h y d r o l w i t h n - b u t a n o l a l r e a d y d e s c r i b e d i n an e a r l y s e c t i o n , a n o t h e r s t a n d a r d e t h e r i f l c a t i o n was c a r r i e d o u t u s i n g 0 . 0 0 1 mol© { 0 . 1 9 g . ) c a t a l y s t . The r e a c t i o n r a t e d a t a a r e p l o t t e d i n F i g u r e XIV and t h e f i r s t o r d e r p l o t i s g i v e n i n F i g u r e IX . THE EFFECT OF VARIATION IN CATALYST CON'GENERATION OR THIS COURSE OF THE REACTION OF TRIPHENYL CARBINOL WITH DIPHENYL CARBINOL E t h e r i f I c a t I o n o f t r l p h e n y l c a r b i n o l w i t h b e n z h y d r o l a t v a r i o u s c a t a l y s t c o n c e n t r a t i o n s . T r l p h e n y l c a r b i n o l ( 0 . 1 2 5 mo l ie o r 3 2 . 5 g . ) and b e n z h y d r o l ( 0 . 1 2 5 m ole o r 23 g . ) w e r e r e a c t e d i n t h e s t a n d a r d manner w i t h p - t o l u e n © s u l f o n i c ac id , c a t a l y s t ( 0 . 0 0 0 1 2 5 m o le or 0 . 0 2 3 7 5 g • ) . A f t e r 27 h o u r s 1 . 8 3 m l . w a t e r had b e e n c o l l e c t e d . The r e a c t i o n m i x t u r e was th e n d i v i d e d i n t o tw o e q u a l p o r t i o n s . R e f l u x l n g was c o n t i n u e d w i t h one p o r t i o n and th e c a t a l y s t was f i n a l l y I n c r e a s e d t o 0 . 0 0 8 mol© p e r 2 5 0 m l . s o l u t i o n , b u t no a d d i t i o n a l w a t e r c o l l e c t e d o v e r a p e r i o d o f 3 d a y s . The d a t a ©re g r a p h e d In Curve I , F I , u r e X I . T r l p h e n y l m e t h y l d i p h e n y l m e t h y l e t h e r ( 14 g . o r 5 5 1) was i s o l a t e d from t h e s e c o n d 250 m l . f r a c t i o n in t h e u s u a l manner . T h i s w h i t e s o l i d was r e c r y s t a l l i z e d f r o m a c e t o n e t h r e e 0 t i m e s t o g i v e a p r o d u c t m e l t i n g a t 1 5 2 - 1 5 3 . A n a l , c a l c fd • from s C, 9 0 . 1 4 ; H, 6 . 1 0 Found : C, 3 0 . ( 9 } H, 6 2 7 Th© a b o v e e x p e r i m e n t was c a r r i e d o u t w i t h same c o n c e n t r a t i o n -1 1 2 - o f a l c o h o l s hu t w i t h 0*0 01 m ole ( G .1 9 g # ) c a t a l y s t * A f t e r 4 h o u r s 1 * 4 9 ml* w a t e r ( 66%) had b e e n d i s c h a r g e d * The d a t a a r e p l o t t e d In Curve I I I , F i g u r e XI* F i f t y grams o f a m i x t u r e o f c r y s t a l l i n e compounds, p r o b a b l y t r i p h e n y l c a r b i n o l , d i b e n z - h y d r y l e t h e r and t r i p h e n y l m e th y l d i p h e n y l m e t h y l e t h e r was I s o ­ l a t e d on e v a p o r a t i n g th© b e n z e n e s o l u t i o n t o d r y n e s s * T h i s m a t e r ­ i a l was r e d i s s o l v e d t o g i v e 4 5 0 ml* b e n z e n e s o l u t i o n . The s o l u t i o n was b r o u g h t t o r e f l u x in t h e s t a n d a r d a p p a r a t u s , 50 ml* o f a b e n ­ z e n e s o l u t i o n o f b u t a n o l ( 0 . 3 7 5 m ole o f 2 7 * 7 5 g . ) w as a dd ed and 5 m i n u t e s l a t e r 0 * 0 0 2 m ole { 0 * 3 8 g * ) c a t a l y s t w as a d d e d . R e - f l u x l n g w as c o n t i n u e d a t 8 3 u f o r 30 h o u r s and 4 * 3 7 m l . o f w a t e r was c o l l e c t e d * A f t e r n e u t r a l i z a t i o n and r e m o v a l o f t h e s o l v e n t s t h e m ix t u r e was d i s t i l l e d t h r o u g h a s t i l l head w i t h o u t column a t 1 . 4 - 1 . 5 mm. B e n z h y d r y l b u t y l e t h e r ( 2 5 . 2 g . or 90yJ) d i s t i l l e d a t 1 3 0 - 1 3 2 ° and t r i p h e n y l m e t h y l b u t y l e t h e r ( 3 4 . 6 g . o r &Q% ) d i s t i l l e d a t 1 3 0 - 1 8 2 ° * T h e r e w as a 1 g • r e s i d u e . The r e a c t i o n was run a t h i r d t i m e w i t h 0 . 0 0 0 2 5 mole ( 0 . 0 4 7 5 g . ) c a t a l y s t . Th© 5 0 0 m l . o f b e n z e n e s o l u t i o n was r e f l u x e d f o r 11 h o u rs a t 3 5 . 5 ° t o g i v e 1 . 7 3 m l . o f w a t e r ( 7 6 .9 ,1 ) . The d a t a a r e p l o t t e d i n Curve XI, F i g u r e XI* W ithou t i s o l a t i o n o f t h e p r o d u c t , n - b u t - a n o l ( 0 . 3 7 5 mole o r 2 7 . 7 5 t • ) was added a f t e r 23 h o u r s and r e ­ f l u x was c o n t i n u e d . A f t e r 4 6 * 5 h o u r s , 2 * 7 3 m l . had b e e n g i v e n o f f and th© c a t a l y s t was I n c r e a s e d t o 0 . 0 0 0 5 m o l e . (T heory f o r t h e r e a c t i o n o f t h e t r i p h e n y l c a r b i n o l i s 2 . 7 6 m l . ) A f t e r 4 9 h o u r s t h e w a t e r v o lu m e was s t i l l c o n s t a n t s o t h e c a t a l y s t was a g a i n d o u b l e d b r i n g i n g th© t o t a l p - t o l u e n © s u l f o n i c a c i d mono- h y d r a t e t o 0 . 0 0 1 m o l e s . The r e a c t i o n p r o c e e d e d t o y i e l d 4 . 4 3 m l . w a t e r a f t e r 1 50 h o u r s . The t h e o r e t i c a l vo lum e o f w a t e r f o r com- p l e t e c o n v e r s i o n t o b u t y l e t h e r s i s 4 . 5 0 m l . The r e a c t i o n m i x t u r e was worked up i n e x a c t l y t h e same way a s b e f o r e t o g i v e b e n z h y d r y l b u t y l e t h e r ( 26 g . o r 9 3 $ ) and t r i p h e n y 1 m e t h y l b u t y l e t h e r ( 3 6 . 5 g* o r 9 2 $ ) . THE EFFECT OF VARIATION I N THE NUMBER OF PHENYL GROUPS ON THE ALPHA CARBON OF ROB E t h e r i f i c a t i o n o f t r i p h e n y l c a r b i n o l w i t h b e n z y l a l c o h o l . T r i p h e n y l c a r b i n o l was e t h e r l f i e d w i t h b e n z y l a l c o h o l w i t h 0 . 0 0 0 1 2 5 m o le ( 0 . 0 2 3 7 5 g . ) c a t a l y s t p e r 5 0 0 ml* b e n z e n e in t h e u s u a l manner* T h i s run was made In d u p l i c a t e and t h e a v e r a g e r e a c t i o n r a t e d a t a a r e p l o t t e d i n Curve I , F i g u r e X I I . The f i r s t o r d e r c u r v e i s g i v e n In F i g u r e X I I I . The r e a c t i o n m i x t u r e w as n e u t r a l ­ i z e d and t h e v o lu m e was r e d u c e d t o 75 m l . W h ite c r y s t a l s m e l t i n g 0a t 9 9 - 1 0 2 came o u t o f s o l u t i o n . The f i l t r a t e was f u r t h e r e v a p ­ o r a t e d on a s t e a m c o n e un d er an a i r s t r e a m t o g i v e a d d i t i o n a l p r o d u c t w i t h t h e same m e l t i n g p o i n t . The t o t a l amount o f e t h e r was 3 9 . 5 g . { 9 0 $ ) . A f t e r f i v e c r y s t a l l i z a t i o n s f r o m d i e t h y l 0 n 67 ^ 0 B3 e t h e r t h e m .p . was 1 0 5 . 5 - 1 0 6 ( l i t . m .p . 1 0 3 - 1 0 4 , 1 0 6 - 1 0 7 ) . A ttem p t t o e t h e r i f y t r i p h e n y l c a r b i n o l w i t h i t s e l f . In much t h e same way a s t r i p h e n y l c a r b i n o l was e t h e r l f i e d w i t h n - b u t a n o l , w i t h b e n z y l a l c o h o l and w i t h b e n z h y d r o l , an a t t e m p t e d e t h e r l f i c a - t i o n o f t r i p h e n y l c a r b i n o l w i t h i t s e l f was c a r r i e d o u t . p - T o l u e n e s u l f o n i c a c i d m on o h y d r a te ( 0 . 0 3 2 mole o r 6 . 0 8 g . ) was d e h y d r a t e d In t h e u s u a l manner i n 2 5 0 m l . o f b e n z e n e in t h e s t a n d a r d a p p a r a ­ t u s . The 2 5 0 m l . o f a b e n z e n e s o l u t i o n o f t r i p h e n y l c a r b i n o l ( 0 . 1 2 5 mole or 3 2 . 5 g* ) was a d d ed to t h e 2 5 0 m l . p o r t i o n c o n - ot a i n i n g t h e c a t a l y s t and th© t o t a l s o l u t i o n w as r e f l u x e d a t 83 f o r 1 8 h o u r s t o g i v e 2 . 2 5 m l . o f w a t e r . The r e a c t i o n r a t e d a t a a r e g i v e n In T a b le V I I I . T a b l e V I H Time e l a p s e d { h o u r s ) Volume o f w a t e r ( m l . ) 0 . 3 3 0 . 2 5 0 . 5 3 0 . 3 1 0.-73 0 . 4 0 1*0 0 . 5 0 1 . 2 0 . 5 9 1 . 4 8 0 . 7 2 1*8 2 0 . 8 0 2 . 1 8 0 . 9 0 2 . 9 1 1 . 1 0 3 . 6 1 . 2 5 3 . 7 3 1 . 3 0 4 . 4 1 . 4 0 5 . 0 7 1 . 5 6 6 . 4 7 1 . 6 2 7 . 6 8 1 . 9 0 8 . 3 8 2 . 0 1 8 . So 2 . 0 4 9 . 6 2 . 1 0 1 4 . 0 2 . 2 3 1 7 . 5 2 . 2 5 On n e u t r a l i s a t i o n and c o n c e n t r a t i o n o f t h e s o l v e n t t o 1 0 0 m l* , t fc lp h en y lm eth a n © ( 9*75 g . o r 3 2 > ) was o b t a i n e d * A f t e r f o u r s u c c e s s i v e r e c r y s t a l l i s a t i o n s from b e n z e n e i t m e l t e d a t 9 3 - 9 3 *5U ( l i t * m*p. 9 3 * 4 ° ) • A m ixed m e l t i n g p o i n t o f 9 2 . 8 - 9 3 ^ was o b ­ t a i n e d w i t h a known s a m p le o f t r i p h e n y l m e t h a n e • On f u r t h e r e v a p o r a t i o n o f t h e f i l t r a t e t o rem ove a l l t h e b e n z e n e , 3 0 g . o f v i s c o u s m a t e r i a l was o b t a i n e d w h ic h was c r y s ­ t a l l i s e d from an e t h a n o l - a c e t o n © m i x t u r e t o y i e l d 25 g , o f a y e l l o w s o l i d * On s i x r e c r y s t a l l i z a t i o n s fro m a c e t o n e - e t h a n o l m i x t u r e and s i x r © c r y s t a l l i z a t i o n s fro m an a c e t o n © - p e t r o l e u m m ixed s o l v e n t , a w h i t e u n i d e n t i f i a b l e m a t e r i a l was o b t a i n e d 0w h ic h de c o m p o se d around 2 6 0 • B e n z h y d r y l b e n z y l e t h e r * B e n z h y d r o l and b e n z y l a l c o h o l w e r e e t h e r l f i e d In t h e s t a n d a r d way w i t h 0 * 0 0 1 m ole ( 0*19 g . ) p - t o l - u e n e s u l f o n i c a c i d m o n o h yd ra te c a t a l y s t * Th© r e a c t i o n rat© d a t a -115- a r e p l o t t e d i n Curve I I , F i g u r e XIV and t h e f i r s t o r d e r p l o t I s g i ven In F i g u r e XV* The n e u t r a l i z e d s o l u t i o n was r e d u c e d t o 1 0 0 m l , v o lu m e and a f i r s t f r a c t i o n ( 2 6* 7 g . ) p r e c i p i t a t e d * A s e c o n d c r o p ( 6 . 5 g . ) was c r y s t a l l i z e d from a y e l l o ? j o i l w i t h t h e a i d o f e t h a n o l * A 9 6 . 3 T y i e l d o f t h e e t h e r was t h u s o b t a i n e d * T h r e e c r y s t a l l i z a t i o n s fro m e t h a n o l y i e l d e d a p r o d u c t w i t h a m e l t ­ i n g p o i n t o f 6 0 * 0 - 5 0 *2U• Anal* c a l e fd* f o r c2oH18°2 C> 37*59 > H* 6 «57 Found : C, 87-f>£ • h , £. S & D l b e nz h y d r y 1 e t h e r * B e n z h y d r o l ( 0 * 1 2 5 mole or 2 3 g . } was d i s s o l v e d In b e n z e n e t o g i v e 500 m l . o f s o l u t i o n and b r o u g h t t o r e f l u x a t 8 2 *5'J i n th© s t a n d a r d a p p a r a t u s * The c a t a l y s t ( 0 . 0 0 1 mol© or 0 * 1 9 g * ) was added and r e f l u x c o n t i n u e d f o r s i x h o u r s . The r e a c t i o n r a t e d a t a a r e p l o t t e d i n Curve I I I , F i g u r e XIV and t h e f i r s t o r d e r p l o t i s g iv e r s i n F i g u r e XVI* A f t e r n e u t r a l i z a ­ t i o n and c o n c e n t r a t i o n o f t h e s o l u t i o n t o 1 0 0 m l . , a w h i t e s o l i d c r y s t a l l i z e d from, th© g o l d e n y e l l o w b e n z e n e s o l u t i o n . The m e l t ­ ing: p o i n t was 1 0 2 - 1 0 3 J u n c o r r e c t e d . Boon c o n c e n t r a t i o n o f t h e f i l t r a t e more e t h e r , ©bout o n e - t e n t h a s much ©s t h e f i r s t c r o p , came o u t s o l u t i o n , g i v i n g a t o t a l y i e l d o f 2 0 * 7 g* { 9 5 * 2 ^ ) . A f t e r one c r y s t a l l i z a t i o n f r o m b e n z e n e a n d on e f ro m e t h a n o l , t h e m e l t i n g p o i n t was 1 0 7 - 1 0 7 . 5 U { l i t * m.p* 1 0 7 * 6 - 1 0 8 u )*^ A run s i m i l a r to t h e a b o v e e x c e p t t h a t 0 . 2 5 0 ® o le b e n z ­ h y d r o l was u s e d was run t o 97 .5)1 c o m p l e t i o n In 4 h o u r s * TRANS FT HER IPIC AT 10 ?•! REACTIONS T r a n a e t h e r l ^ l c a t I o n o f d l b e n z h y d r y l e t h e r * The d l b e n z h y - d r y l e t h e r was p r e p a r e d a z e o t r o p i c a l l y ©s d e s c r i b e d i n a p r e v i o u s s e c t i o n . 0 1 b e n z h y d r o l e t h e r ( 0 . 0 6 2 5 mole o r 2 1 . 9 g . ) and n - b u t a n o l ( 0 . 1 2 5 m ole o r 9 . 2 5 g . ) w are d i s s o l v e d i n e n o u g h b e n ­ z e n e t o g i v e 5 00 m l . s o l u t i o n and r e f l u x e d w i t h 0 . 0 0 2 mole ( 0 . 5 8 g . ) o f p - t o l u e n e s u l f o n i c a c i d c a t & l y s t a t 8 3 v f o r t w e n t y h o u r s . The d a t a a r e p l o t t e d i n Curve I , F i g u r e XVI1 . (A p r e v i o u run had been made i n w h ic h t h e c a t a l y s t c o n c e n t r a t i o n was I n ­ c r e a s e d fro m 0 . 0 0 1 t o 0 . 0 0 2 t o 0 . 0 0 4 m o l e s p e r 5 0 0 m l . ) The r e ­ a c t i o n m i x t u r e w as w orked up e x a c t l y a s i n t h e c a s e o f t h e e t h e r I f i c a t l o n o f b e n z h y d r o l w i t h n - b u t a n o l . An B ( 2 6 . 3 g . ) y i e l d o f b e n z h y d r y l b u t y l e t h e r , b . p . 1 1 6 - 1 1 7 ° { 0 . 5 mm.), was o b t a i n e d . The a b o v e r e a c t i o n w as r e p e a t e d w i t h 0 . 1 2 5 m ole ( 1 3 . 5 g . ) o f b e n z y l a l c o h o l i n p l a c e o f t h e n - b u t a n o l • The r e a c t i o n r a t e d a t a f o r t h i s run a r e p l o t t e d i n Curve I I , F i g u r e X V II . The s o l u t i o n was worked up a s In t h e c a s e o f t h e r e a c t i o n o f b e n z ­ h y d r o l and b e n z y l a l c o h o l . A y i e l d o f 2 9 g . ( 8 5^ ) h e n z h y d r y l b e n z y l e t h e r , m .p . 5 0 . 0 - 5 0 . 2 ^ , was i s o l a t e d . 0 1 b e n z h y d r y l e t h e r { 0 . 0 6 2 5 m ole or £ 1 . 9 g . ) and t r i p h e n y l c a r b i n o l ( 0 . 1 2 5 m o le o r 3 2 . 5 g . ) w e r e r e f l u x e d w i t h p - t o l u e n e s u l f o n i c a c i d c a t a l y s t ( 0 . 0 0 4 m o le o r 0 . 7 6 g . ) i n b e n z e n e In t h e u s u a l way f o r 4 8 b o o r s huit no r e a c t i o n t o o k p l a c e . T r a n s e t h e r ! f i c a t io n o f t r l p h e n y l m e t h y l d l p h e n y l m e t h y l e t h e r . Ths t r l p h e n y l m e t h y l d i p h e n y l m e t h y l e t h e r w as o b t a i n e d b y t h e method d e s c r i b e d p r e v i o u s l y . T r l p h e n y l m e t h y l d i p h e n y l m e t h y l e t h e r ( 0 . 0 6 2 5 m ole or 2 6 . 6 2 g . ) and n - b u t a n o l ( 0 . 1 2 5 m ole or 9 . 2 5 g . ) w ere r e f l u x e d In b e n z e n e w i t h p - t o l u e n e s u l f o n i c a c i d ( 0 . 0 0 0 2 5 m o le o r 0 . 0 4 7 5 g . ) f o r 2 h o u r s a t 8 3 . Su t o g i v e 1 . 1 2 m l . w a t e r r e p r e s e n t i n g 100;£ t r a n s e t h e r i f I c a t Ion • The r e a c t i o n d a t a a r e p l o t t e d i n T a b l e IX . - 1 1 7 - T a b l e IX. Time e l a p s e d ( a i n . ) Volume o f w a t e r ( m l . ) 6 0 . 0 7 7 0 . 1 0 8 0 . 1 6 9 0 . 1 8 11 0 . 2 5 14 0 . 3 9 17 0 . 4 8 20 0 . 5 7 22 0 . 6 3 24 0 . 6 9 27 0 . 7 6 32 0 . 8 5 35 0 . 9 0 37 0 . 9 3 42 1 . 0 0 47 1 . 0 5 70 1 . 1 2 10 0 1 . 1 2 A f t e r n e u t r a l i z a t i o n o f t h e s o l u t i o n and r e m o v a l o f t h e s o l v e n t , t h e tw o e t h e r s w ere d i s t i l l e d t h r o u g h a s t i l l hea d w i t h o u t column a t 1 . 5 mm. B e n z h y d r y l b u t y l e t h e r ( 1 3 . 5 g . or 90:1) d i s t i l l e d a t 1 3 2 - 1 3 3 " and t r l p h e n y l m e t h y l b u t y l e t h e r ( 18 g . o r 92% ) 0 d i s t i l l e d a t 1 8 1 - 1 8 2 . 5 ' ' . T h ere was a n e g l i g i b l e r e s i d u e . T r a n a e t h e r l f i c a t i o n o f d l b e n a y I e t h e r . p -T o lu en © s u l f o n i c ■ .11—1 nw i . hwiiiii n—.m — w iMWi.w u w ii iwiiriwia ummMt r tai.i.n a c i d m o n o h y d r a te ( 0 * 1 2 3 m o l e s or 2 4 . 3 g . 5 was d i s s o l v e d i n 4 5 0 m l . b e n z e n e a n d d e h y d r a t e d i n t h e s t a n d a r d a p p a r a t u s In t h e u s u a l w a y . F i f t y m i l l i l i t e r s o f a warm b e n z e n e s o l u t i o n o f c i b e n z y l e t h e r ( 0 . 0 6 2 5 m o le s o r 1 2 . 4 g . ) and n - b u t a n o l ( 0 . 1 2 5 m o l e s o r 9 . 2 5 g . ) was added t o t h e a c i d s o l u t i o n . The r © f l u x i n g was c o n ­ t i n u e d a t 8 3 w t o g i v e 1 . 1 2 m l . w a t e r , 100% f o r t r a n s e t h e r ! f l o a t i o n • T h e r e a c t i o n r a t© d a t a a r e p l o t t e d i n Curve I I I , F i g u r e X V II . A f t e r n e u t r a l i z a t i o n o f t h e s o l u t i o n and r e m o v a l o f t h e s o l v e n t , a f i r s t f r a c t i o n o f b e n z y l b u t y l e t h e r ( 1 0 g . o r 48%) d i s t i l l e d yv th r o u gh t h e f o u r - i n c h v i g r e u x a t 2 0 mm. a t 1 1 3 - 1 1 4 ° . A s e c o n d f r a c t i o n o f d I p h e n y lr a e th a n e ( 6 g . or 28 .8% j was c o l l e c t e d a t 1 3 8 - 1 3 9 ° . -lie­ 'll HE DETERMINATION OF THE EFFECT OF THE NUMBER. OP ALPHA PHENYL GROUPS ON THE BASICITY OF THE ALCOHOL D e h y d r a t i o n o f t e r t - b u t y l a l c o h o l i n t h e p r e s e n c e o f a s e c o n d a l c o h o l # T r i p h e n y l c a r b i n o l ( 0 . 1 2 5 m o le o r 5 2 . 5 g . ) , t e r t - b u t y l a l c o h o l ( 0 . 1 2 5 m ole or 9 . 2 5 g . } and p - t o l u e n © s u l ­ f o n i c a c i d ( 0 . 0 0 0 1 2 5 mole or 0 . 0 2 3 7 g . ) w ere d i s s o l v e d in e n o u g h b e n z e n e t o g i v e 5 0 0 m l . o f s o l u t i o n w h ic h was r e f l u x e d a t 8 2 . 5 ^ • The s t a n d a r d a z e o t r o p i c a p p a r a t u s was u sed w i t h t h e m o d i f i c a t i o n t h a t a t u b e l e d from t h e t o p o f t h e c o n d e n s e r t o a d r y 1 c e a c e ­ t o n e t r a p w h ere a n y i s o b u t y l e n © form ed In t h e r e f l u x l n g m i x t u r e would Id© c o l l e c t e d . A f t e r 1*5 h o u r s no w a t e r had c o l l e c t e d * The c a t a l y s t w a s i n c r e a s e d s t e p w i s e t o a t o t a l amount o f 0 . 0 0 4 m o l e s . At t h i s c o n c e n t r a t i o n d e h y d r a t i o n o f th© t e r t - b u t y l a l c o h o l b e g a n . I t was 90,4 c o m p l e t e i n IS h o u r s and i s o b u t y l e n © ( 6 g* o r 85,1 ) was c o l l e c t e d In t h e t r a p . D u p l i c a t e d e h y d r a t i o n s were t h e n c a r r i e d o u t i n t h i s same s y s t e m a t 0 . 0 0 8 m ole ( 1 . 5 2 g . } c a t a l y s t . In e a c h c a s e 97^1 i s o b u t y l e n e ( 6 . 8 g . ) was I s o l a t e d . The a v e r a g e d a t a f o r t h e s e runs a r e p l o t t e d i n Curve IV, F i g u r e X V I I I . In t h e n e x t run b e n z y l a l c o h o l ( 0 . 1 2 5 m ole o r 1 3 . 5 g . ) , t e r t - b u t y l a l c o h o l ( 0 . 1 2 5 mol® or 9 . 2 5 g* ) and p - t o l u e n © s u l ­ f o n i c a c i d c a t a l y s t ( 0 . 0 0 0 2 5 mole o r 0 . 0 4 7 5 g* ) w ere d i s s o l v e d In b e n z e n e t o g i v e 500 ml* o f s o l u t i o n w h ic h w as r e f l u x e d a t S 2 U. I t was n e c e s s a r y a g a i n t o i n c r e a s e t h e a c i d c o n c e n t r a t i o n t o 0 . 0 0 4 m o le s per 5 0 0 m l . s o l u t i o n b e f o r e w a t e r a p p e a r e d a t an a p p r e c i a b l e r a t e In th© s e p a r a t o r . Th© a l c o h o l was t o t a l l y d e h y d r a t e d i n t h r e e d a y s and i s o b u t y l e n © ( 6 . 4 g . o r 91,4 ) was c o l l e c t e d In t h e t r a p . On d u p l i c a t e r u n s w i t h t h e same s y s t e m a t 0 . 0 0 8 mol© ( 1 . 5 2 g . ) c a t a l y s t , t h e d e h y d r a t i o n was c o m p l e t e i n 12 h o u r s and 6 . 7 g . - 1 1 9 - { 96/C ) I s o b u t y l e n © w ere r e c o v e r e d * The a v e r a g e r e a c t i o n r a t© d a t a a r e p l o t t e d i n Curve I I I , F i g u r e X V I I I . When n - b u t y l a l c o h o l ( 0 . 1 2 5 mol© o r 9*25 g . } was s u b s t i ­ t u t e d i n th© a b o v e s y s t e m f o r b e n z y l a l c o h o l and t h e c a t a l y s t was k e p t a t 0 . 0 0 8 m o le ( 1 . 5 2 g . ) , t h e d e h y d r a t i o n o f t h e t e r t - b u t y l a l c o h o l w as n o t c o m p l e t e u n t i l a l m o s t two d a y s . T h i s run was r e p e a t e d a s a c h e c k and t h e a v e r a g e d a t a o f t h e two r u n s a r e p l o t t e d In Curve I I , F i g u r e X V I I I . I s o b u t y l e n © ( 6 . 5 g . o r 90,1 ) w as c o l l e c t e d * A s i m i l a r run w h ere n - d e c y l a l c o h o l ( 0 . 1 2 5 m ole o r 1 9 . 7 5 g . } s e r v e d a s th© s e c o n d a l c o h o l y i e l d e d i s o b u t y l e n © { 6 . 4 g . o r 9 1 # ) a t a r a t e o n l y s l i g h t l y g r e a t e r than t h a t i n t h e run i n w h ic h n - b u t a n o l was p r e s e n t . The d a t a a r e g i v e n i n T a b l e X. T a b l e X. Time © l a p s e d ( h o u r s ) Volum© o f w a t e r ( m l . ) 0 . 7 5 0 . 1 9 1 . 2 5 0 . 2 4 1 . 7 5 0 . 2 7 7 . 2 5 0 . 7 0 1 7 . 2 5 1 . 5 1 1 8 . 0 1 . 5 5 1 9 . 2 5 1 . 6 7 2 1 . 0 1 . 8 3 2 3 . 5 2 . 0 0 2 5 . 0 2 . 1 0 2 6 . 0 2 . 1 5 2 6 . 6 2 . 1 9 2 9 . 6 2 . 2 5 4 1 . 6 2 . 2 5 D e h y d r a t io n o f t © r t - b u t y l a l c o h o l a l o n e . T e r t - b u t a n o l ( 0 . 1 2 5 mol© or 9 . 2 5 g . ) and p - t o l u e n e s u l f o n i c a c i d ( 0 . 0 0 4 mole o r 0 . 7 6 g . w ere d i s s o l v e d I n e n o u g h b e n z e n e t o g i v e 5 0 0 m l . o f s o l u t i o n w h ic h was r e f l u x e d a t 8 2 . 5 • A f t e r 33 h o u r s t h e d e h y d r a t i o n was c o m p l e t e a s i s shown by t h e d a t a p l o t t e d i n Curve V, F i g u r e X V I I I . I s o b u t y ­ l e n e { 6*65 g . o r 9 5 $ ) was c o l l e c t e d In t h e t r a p * T h i s run was r e p e a t e d i n d u p l i c a t e w i t h 0 * 0 0 8 mole ( 1 . 6 2 g . ) c a t a l y s t and t h e a v e r a g e d a t a a r e p l o t t e d i n Curve I , F i g u r e XVIII* The I s o t u t y l e n e I s o l a t e d h e r e was 6 . 8 g . ( 9 7 $ )* SUMMARY An a z e o t r o p l c method o f © t h e r l f i c a t 1 on em ploying , an a c i d c a t a l y s t i n b e n z e n e s o l u t i o n h a s b e e n d e v e l o p e d . By t h i s method n e a r l y q u a n t i t a t i v e y i e l d s o f a number o f e t h e r s o f t r l p h e n y l c a r b i n o l , o f b e n z h y d r o l , and o f c e r t a i n o t h e r a c t i v a t e d a l c o h o l s c a n b e e a s i l y o b t a i n e d * E t h e r s o f b e n z y l a l c o h o l a r e o b t a i n e d In y i e l d s o f a b o u t 5 0 y . A number o f new e t h e r s h a v e b e e n p r e ­ pared# I t h a s been fo u n d t h a t t r a n s e t h e r l f I c a t i o n s can a l s o b e c a r r i e d ou t i n h i g h y i e l d by a s l r r l l a r a z e o t r o o l c m e th o d . The s c o n e o f t r a n s e t h e r I f 1 c a t Ion by t h i s p r o c e s s h a s b een I n v e s t i ­ g a t e d . The a z e o t r o p l c method h a s b e e n shown t o be a p p l i c a b l e to t h e d e t e r m i n a t i o n o f r a t e s o f e t h e r l f i c a t I o n w i t h s a t i s f a c t o r y p r e c i s i o n . A number o f e t h e r l f i c a t i o n s h a v e b e e n shown t o f o l l o w f i r s t o r d e r k i n e t i c s . A c o n s i d e r a b l e amount o f a d d i t i o n a l I n ­ f o r m a t i o n on t h e c o u r s e ©nd m echanism o f e t h e r i f l e e t i o n h a s b e e n o b t a i n e d . T h e s e r e s u l t s can i n g e n e r a l b e e x p l a i n e d i n t e r m s o f a m echan ism o f e t h e r I f i c a t I o n p r o p o s e d by Hammett• B enzen e h a s b e e n a l k y l a t e d In good y i e l d s w i t h b e n z y l a l c o ­ h o l and w i t h d i b e n z y l e t h e r by an a z e o t r o p i c m e t h o d . T h i s p r o c e s s a p p e a r s t o h a v e c o n s i d e r a b l e s y n t h e t i c v a l u e and b o t h t h e s y n ­ t h e t i c and t h e o r e t i c a l a s p e c t s a r e b e i n g f u r t h e r s t u d i e d In t h e s e l a b o r a t o r i e s . I t h a s b e e n shown t h a t , c o n t r a r y t o t h e most w i d e l y a c c e p t e d m ech a n ism , d i b e n z y l e t h e r I s , u n d er t h e c o n d i t i o n s u s e d h e r e , an I m p o r t a n t I n t e r m e d i a t e In t h e a l k y l a t l o n o f b e n z e n e by - 1 2 2 - b e n z y l a l c o h o l * T h e a z e o t r o p l c m e t h o d h a s b e e n a p p l i e d t o f o l l o w i n g t h e d e h y d r a t i o n o f t e r t - b u t y l a l c o h o l * I t h a s b e e n s h o w n t h a t t h i s r e a c t i o n m a y b e u s e d a s a n I n d i c a t o r t o d e t e r m i n e t h e r e l a t i v e b a s i c i t i e s o f b u t y l a l c o h o l , b e n z y l a l c o h o l , a n d t r i p h e n y l c a r b i ­ n o l * T h e r e s u l t s o f t h i s d e t e r m i n a t i o n a r e u s e f u l i n e x p l a i n i n g d i f f e r e n c e s I n r a t e s o f c e r t a i n e t h e r l f l c a t i o n r e a c t i o n s * A t t e m p t s w i l l b e m a d e I n t h e s e l a b o r a t o r i e s t o a p p l y t h e m e t h o d t o t h e d e ­ t e r m i n e t l o n o f t h e r e l a t i v e b a s i c i t i e s o f w e a k b a s e s I n g e n e r a l * - 1 2 3 - BIBLIQGRAPHY 1* Adams, R. and Weeks, L . 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