A comparison of the electron donor properties of 1,3- and 1,4-dioxane

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Content COMPARISON OP THE ELECTRON DONOR PROPERTIES OF 1 , 3 - AND 1,4-DIOXANE A T h e s is P r e s e n t e d t o t h e F a c u l t y o f t h e D e p a rtm e n t o f C h e m is try The U n i v e r s i t y o f S o u t h e r n C a l i f o r n i a 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 ir e m e n ts f o r t h e D e g re e M a s te r o f S c i e n c e by V i n c e n t P e r r y G uinn Ju n e 1941 UMI Number: EP41536 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. UMT ' ■ ' O tesw laticft pBblisMng UMI EP41536 Published by ProQuest LLC (2014). Copyright in the Dissertation held by the Author. Microform Edition © ProQuest LLC. All rights reserved. This work is protected against unauthorized copying under T itle 17, United States Code ProQuest LLC. 789 East Eisenhower Parkway P.O. Box 1346 Ann Arbor, Ml 48106- 1346 This thesis, written by V I N P M ? ...? ™ X .'.M I H N ......................... under the direction of h..%3Faculty Committee, and a p p ro ved by all its members, has been presented to and accepted by the Council on Graduate Study and Research in partial fulfill ment of the requirements for the degree of .MS.TER...QJL..aCJEN!3E Secretary D ate... Faculty Com m ittee Chairman S ' f/o - P & fc c s TABLE OP CONTENTS CHAPTER PAGE I . DISCUSSION OP THE PROBLEM............................................................. 1 Types and m echanism s o f v a l e n c e • • • • • •• . 1 E l e c t r o n d o n o r - a c c e p t o r a d d i t i o n compounds • • 1 The d io x a n e s a s e l e c t r o n d o n o rs • • • • • • • • 2 B o ro n t r i f l u o r i d e a s an e l e c t r o n a c c e p t o r • • • 3 P o s s i b l e a d d i t i o n compounds o f b o r o n t r i f l u o r i d e an d t h e d io x a n e s • • • • • • • • 3 I I . PERTINENT INFORMATION PROM THE LITERATURE . . . . 6 1 .3 - D io x a n e • • • • • • • • • • • • • • • • • • 6 P h y s i c a l p r o p e r t i e s • • • • • • • • • • • • • 6 M ethods o f p r e p a r a t i o n • • • . . • • • • • • 7 C h e m ic a l p r o p e r t i e s • • • • • • • • • • • • • 7 A d d i t i o n compounds • • • • • • • • • • • • • 7 1 .4 - D io x a n e • • • • • • • • • • • • • • • • • • 8 P h y s i c a l p r o p e r t i e s • • • • • • • • • • • • • 8 M ethods o f p r e p a r a t i o n • • • • • • • • • • • 9 C h e m ic a l p r o p e r t i e s • • • • • • • • • • • • • 9 A d d i t i o n compounds • • • » • • • • • • • ♦ • 10 B oron t r i f l u o r i d e • « • • • • • . • • • • • • • 20 P h y s i c a l p r o p e r t i e s .......................................... 20 M ethods o f p r e p a r a t i o n .......................... 20 C h em ical p r o p e r t i e s • • • • • • • • • • • • • 21 A d d i t i o n compounds • • • • • • • • • • • • • 21 iii CHAPTER PAGE I I I . PREPARATION AND PURIFICATION OF REAGENTS . . . . 22 1 .3 - D io x a n e . ............................ • • • • • • • • • • 22 1 .4 - D i o x a n e • • • • • • • • • • • . • • • • • 24 B o ro n t r i f l u o r i d e • • • • . • • • • • • • • • 28 C h lo ro fo rm • • • • • • • ...................... . . . . . . 29 C arb o n t e t r a c h l o r i d e • • • • • . • • • • • • • 29 IV. APPARATUS, PROCEDURES, DATA, GRAPHS, CALCULATED VALUES ................................................. 30 P r e l i m i n a r y w ork • • • • • • • • • • • • • • • 30 B o ro n t r i f l u o r i d e — 1 , 3 - d i o x a n e a d d i t i o n • • 30 The M e n z ie s - S m ith a p p a r a t u s ••• ••• •• 33 H igh-vacuum w ork • • • • • • • • • • • • • • • 37 The v a p o r t e n s i o n s o f 1 , 3 - d i o x a n e • • • • • 37 A d d i t i o n compounds o f 1 , 3 - d i o x a n e and h o r o n f l u o r i d e • • • • • • • • • • • • • • 42 A d d i t i o n compounds o f 1 , 4 - d i o x a n e and b o r o n f l u o r i d e • • • • • • • • • • • • • • 48 V. DISCUSSION ............................................................................................. 58 V I. SUMMARY.............................................•.......................................................... 62 BIBLIOGRAPHY ....................................................................................................... 63 LIST OP TABLES TABLE PAGE I . A d d i t i o n Compounds o f 1 ,4 - D i o x a n e • • • • • • • • 11 I I . I n d i c a t e d A d d i t i o n Compounds o f 1 , 4 - D i o x a n e • • • 17 I I I . P r e p a r a t i o n o f t h e 1 ,3 - D io x a n e . . . . . . . . . 23 IV . The V apor T e n s io n s o f 1 ,4 - D i o x a n e . . . . . . . . 25 V. F o r m a tio n o f t h e 1 : 1 Complex o f 1 ,3 - D io x a n e and B oron T r i f l u o r i d e i n t h e P r e l i m i n a r y Work • • • • • ........................................................... 32 V I. The V apor T e n s io n s o f 1 , 3 - D i o x a n e b y t h e M e n z ie s - S m ith Method 37 V I I . The V apor T e n s io n s o f 1 , 3 - D i o x a n e b y t h e H igh-vacuum Method • • • • • • • • • • • . • • 40 V I I I . F o r m a tio n o f t h e 1 : 1 Complex o f 1 ,3 - D io x a n e and B oron T r i f l u o r i d e i n t h e H igh-vacuum W o r k ............................................................................................................ 43 IX. D i s s o c i a t i o n D ata o f t h e 1 : 1 B o ro n T r i f l u o r i d e — 1 ,3 - D i o x a n e Complex 44 X. D i s s o c i a t i o n D ata o f t h e 1 : 1 B oron T r i f l u o r i d e — 1 ,4 - D io x a n e Complex . • • . • • • • • . . . • 49 X I. D i s s o c i a t i o n D ata o f t h e 2 : 1 B o ro n T r i f l u o r i d e - - 1 , 4 - D i o x a n e Complex • • • • . • • • • • • • • 55 LIST OF FIGURES FIGURE PAGE 1 . The V apor T e n s io n s o f 1 ,4 - D i o x a n e .................................. 27 2 . D ia g ra m o f t h e A p p a r a tu s Used i n t h e P r e l i m i n a r y Work on t h e B o ro n T r i f l u o r i d e - - 1 . 3 - D i o x a n e A d d i t i o n • • • • • • • • • • • • • 31 3 . D iag ram of th e M e n z ie s - S m ith A p p a r a tu s • . • • • 34 4 . D iag ram of th e B u lb Used i n t h e H igh-vacuum Work on V a p o r . T e n s io n s and D i s s o c i a t i o n P r e s s u r e s 38 5 . The V apor T e n s io n s o f 1 ,3 - D i o x a n e • • • • • • • • 41 6 . The D i s s o c i a t i o n P r e s s u r e s o f t h e 1 : 1 B o ro n T r i f l u o r i d e — 1 ,3 - D i o x a n e Complex • • • • • • • 45 7 . The E q u i l i b r i u m C o n s t a n t s o f t h e D i s s o c i a t i o n R e a c t i o n o f t h e 1 : 1 B o ro n T r i f l u o r i d e - - 1 .3 - D io x a n e Complex . . ................................. • • • • • 47 8 . The D i s s o c i a t i o n P r e s s u r e s o f t h e 1 : 1 B o ro n T r i f l u o r i d e — 1 ,4 - D i o x a n e Complex • • • • • • • 50 9 . The E q u i l i b r i u m C o n s t a n t s o f t h e D i s s o c i a t i o n R e a c t i o n o f t h e 1 : 1 B o ro n T r i f l u o r i d e — 1 .4 - D io x a n e Complex • • • • • • • • • . . . • • 52 1 0 , The D i s s o c i a t i o n P r e s s u r e s o f t h e 2 : 1 B oron T r i f I u o r i d e - - l , 4 - D i o x a n e Complex • • • • • • • 54 1 1 . The E q u i l i b r i u m C o n s t a n t s o f t h e D i s s o c i a t i o n R e a c t i o n o f t h e 2 : 1 B o ro n T r i f l u o r i d e — 1 .4 - D i o x a n e Complex • • • • • • • • • • • • • • 57 CHAPTER I DISCUSSION OP THE PROBLEM The s t u d y o f t h e f o r c e s w h ic h h in d a to m s , m o l e c u l e s , r a d i c a l s and i o n s t o one a n o t h e r i s a v e r y i m p o r t a n t an d f u n d a m e n ta l c h e m ic a l s t u d y . Much i s known o f t h e v a r i o u s t y p e s of t h e s e s o - c a l l e d " v a l e n c e " f o r c e s , h u t much m ore r e m a in s y e t t o b e d i s c o v e r e d . T h is t h e s i s r e p r e s e n t s t h e r e s u l t s o f a n i n v e s t i g a t i o n i n t o a few c a s e s o f one ty p e o f v a l e n c e i n a n e f f o r t t o d e t e r m i n e t h e n a t u r e an d e x t e n t o f t h e i n t e r a c t i o n o f ato m s d i f f e r e n t l y p l a c e d i n two i s o m e r s . I . TYPES AND MECHANISMS OF VALENCE V a le n c e f o r c e s a r e u s u a l l y c l a s s i f i e d i n t o t h r e e m ain c a t e g o r i e s : (1 ) e l e c t r o v a l e n t , (2 ) c o v a l e n t and (3 ) c o o r d i n a t e c o v a l e n t . The m ean in g o f t h e s e te rm s i s common know l e d g e among c h e m is ts and n eed n o t h e d i s c u s s e d h e r e . I n a d d i t i o n t o t h e s e t h r e e ty p e s o f c o m b in in g f o r c e s io n s a n d m o le c u le s o f t e n com bine b e c a u s e o f h y d ro g e n b o n d i n g , c o o r d i n a t i o n num ber o r c r y s t a l l a t t i c e f o r c e s . I I . ELECTRON DONOR-ACCEPTOR ADDITION COMPOUNDS I n t h e p r e s e n t s t u d y t h e f o r m a t i o n o f m o l e c u l a r com pounds b y a d d i t i o n s i n v o l v i n g c o o r d i n a t e c o v a l e n c e was t h e s u b j e c t o f I n t e r e s t . C o o r d i n a t e c o v a l e n c e e n t a i l s t h e b o n d in g o f m o le c u le s b y t h e s h a r i n g o f p a i r s o f e l e c t r o n s i n 2 w h ic h one o f t h e two m o le c u le s f u r n i s h e s b o t h e l e c t r o n s of t h e b o n d in g p a i r . I n t h i s m anner t h e e l e c t r o n a c c e p t o r m o le c u l e u s u a l l y com ple^-tes o r te n d s t o c o m p le te a v a l e n c e o c t e t o f e l e c t r o n s . The c o n n e c t i n g p a i r o f e l e c t r o n s i s so m etim es sp o k e n o f a s t h e d a t i v e b o n d . A s im p l e exam ple of t h e f o r m a t i o n o f a m o l e c u l a r com pound b y c o o r d i n a t e c o v a l e n t f o r c e s i s t h e c o m b in a tio n o f ammonia an d b o r o n t r i f l u o r i d e t o fo rm t h e m ono-am m inate of 1 b o r o n f l u o r i d e : H : F : H .'F* •» .• .. •• H*N: + B :F : H-*N:B*F: •• * • * * It * 4 * H *F: H :F : I I I . THE DIOXANES AS ELECTRON DONORS The s t r u c t u r e o f th e m o l e c u l e s o f 1 , 3 - and 1 , 4 - d i o x a n e i m m e d ia te ly s u g g e s t s t h e l i k e l i h o o d o f e l e c t r o n d o n o r a c t i v i t y on t h e i r p a r t . The two compounds a r e h e r e w i t h r e p r e s e n t e d b y s im p le e l e c t r o n - b o n d i n g p i c t u r e s : *'o‘ ' o ’ H - •* .. H H .. •• •* .. H H:C C:H H:C C:H HtC o ! 1 , 3 - d i o x a n e H:C C.-H 1 , 4 - d i o x a n e H ** •• •. * H * ' .• •. * ' H .C.. . 0 . H H P r e p a r e d b y S i r Humphrey D avy. 3 S in c e e a c h m o l e c u l e c o n t a i n s two o x y g en a to m s , an d e a c h o f th e oxygen ato m s p o s s e s s e s f o u r u n s h a r e d e l e c t r o n s , i t was c o n c lu d e d t h a t b o t h compounds m ig h t p o s s i b l y fo rm a d d i t i o n compounds i n w h ic h t h e d i o x a n e s w ould a c t a s e l e c t r o n d o n o r s . I t i s known t h a t e t h y l e t h e r a c t u a l l y d o e s b in d b o r o n f l u o r i d e . IV. BORON TRIFLUORIDE AS AN ELECTRON ACCEPTOR An e x p e r i m e n t a l s t u d y o f t h e e l e c t r o n d o n o r a c t i o n o f t h e d io x a n e s r e q u i r e d t h e s e l e c t i o n o f a s u i t a b l e e l e c t r o n a c c e p t o r compound. B o ro n f l u o r i d e was c h o s e n b e c a u s e o f i t s v e r y p o w e r f u l t e n d e n c y t o a c c e p t a p a i r o f e l e c t r o n s ( t o c o m p le te t h e b o r o n o c t e t ) , i t s e a s e o f f o r m a t i o n , and th e f a c t t h a t i t i s a g as a t room t e m p e r a t u r e . V. POSSIBLE ADDITION COMPOUNDS OF BORON TRIFLUORIDE AND THE DIOXANES B o th s p a t i a l and e l e c t r o n - d r i f t c o n s i d e r a t i o n s te n d to r u l e o u t t h e p o s s i b i l i t y o f two e l e c t r o n a c c e p t o r m o le c u l e s a t t a c h i n g t o t h e same oxygen a to m i n e i t h e r o f t h e d i o x a n e s . H en ce, m o l e c u l a r r a t i o s o f 2 b o r o n f l u o r i d e t o 1 d i o x a n e and 1 b o r o n f l u o r i d e t o 1 d i o x a n e w ould a p p e a r t o b e t h e o n ly ones l i k e l y to b e d e t e c t e d , a c c o r d i n g to t h i s r a t h e r s i m p l i f i e d t r e a t m e n t . The q u e s t i o n o f t h e r e l a t i v e s t a b i l i t i e s o f t h e 1 : 1 compound an d t h e c o r r e s p o n d i n g 2 : 1 com pound, i f b o t h e x i s t e d , 4 i s n e x t t o tie t r e a t e d on t h e o r e t i c a l g r o u n d s . A g a in , a s im p le e l e c t r o n - d r i f t c o n c e p t i o n g i v e s a q u a l i t a t i v e a n s w e r to t h e q u e s t i o n . I f e i t h e r o f t h e d io x a n e s w e re to fo rm a 1 : 1 a d d i t i o n compound w i t h b o r o n f l u o r i d e , a " d r i f t ” o f e l e c t r o n s to w a rd t h e oxygen ato m i n v o l v e d s h o u ld o c c u r , t h e r e b y b i n d i n g t h e e l e c t r o n - p a i r s o f th e o t h e r oxy g en a to m m ore t i g h t l y t o t h e oxygen a to m . T h is i n c r e a s e d b i n d i n g would d e c r e a s e t h e t e n d e n c y o f t h e s e c o n d oxygen ato m to s h a r e i t s e l e c t r o n - p a i r w i t h a se c o n d b o r o n f l u o r i d e m o le c u l e . I n o t h e r w o rd s , t h e s e c o n s i d e r a t i o n s l e d to t h e c o n c l u s i o n t h a t t h e 1 : 1 com plex s h o u ld b e more s t a b l e t h a n t h e c o r r e s p o n d i n g 2 : 1 c o m p lex . The w o rd , " s t a b l e " , i s h e r e i n t e n d e d to mean t h a t t h e compound e x h i b i t s o n ly a r e l a t i v e l y s l i g h t te n d e n c y t o d i s s o c i a t e i n t o t h e o r i g i n a l c o m p o n e n ts. I n t h i s t h e s i s t h e t e r m s , " c o m p le x " , " c o m p le x com pound", " a d d i t i o n compound" and " m o l e c u l a r compound" a r e u s e d i n t e r c h a n g e a b l y . A s i m i l a r t r e a t m e n t l e a d s one t o e x p e c t t h a t t h e b o r o n f l u o r i d e — 1 , 4 - d i o x a n e compounds s h o u ld b e m ore s t a b l e t h a n t h e c o r r e s p o n d i n g 1 , 3 - d i o x a n e com pounds, s i n c e t h e d i s t a n c e b e tw e e n t h e two oxygen ato m s i s l e s s i n th e c a s e o f t h e 1 , 3 - d i o x a n e and s i n c e oxy g en i s c o n s i d e r a b l y m ore e l e c t r o n e g a t i v e t h a n c a r b o n . T h e se two f a c t o r s c a u s e t h e two oxygen ato m s i n 1 , 3 - d i o x a n e t o h o ld t h e i r e l e c t r o n s m ore f i r m l y t h a n do t h e two oxygen atom s i n 1 , 4 - d i o x a n e , r e s u l t in g i n a d e c r e a s e d t e n d e n c y f o r t h e 1 , 3 - d i o x a n e t o fo rm 5 m o l e c u l a r compounds o f t h e s im p le e l e c t r o n d o n o r - a c c e p t o r t y p e . I t was th e p u r p o s e o f t h e p r e s e n t s t u d y to t e s t e x p e r i m e n t a l l y t h e h y p o t h e s e s h e r e d e v e l o p e d . The r e m a in d e r o f t h i s t h e s i s i s t a k e n up w i t h a d i s c u s s i o n o f t h e l i t e r a t u r e b a c k g ro u n d o f t h e p r o b le m , t h e p r e p a r a t i o n and p u r i f i c a t i o n o f t h e r e a g e n t s , t h e e x p e r i m e n t a l w o rk , t h e c o n c l u s i o n s draw n and a summary o f t h e r e s u l t s . CHAPTER II PERTINENT INFORMATION FROM THE LITERATURE I . 1,3-DIOXANE (META DIOXANE) P h y s i c a l p r o p e r t i e s . 1 ,3 - D i o x a n e i s a c o l o r l e s s l i q u i d w i t h a n a g r e e a b l e , a c e t a l - l i k e o d o r . I t s b o i l i n g o 2 o p o i n t h as b e e n r e p o r t e d a s 105 C. a t 755 mm. and 106 C. 3 a t 760 mm. L i k e w i s e , two d i f f e r e n t v a l u e s f o r t h e f r e e z in g p o i n t o f 1 , 3 - d i o x a n e a r e i n t h e l i t e r a t u r e , n a m e ly , 0 4 o 5 -4 5 C. and -4 2 C. I t s s p e c i f i c g r a v i t y , a s com pared w i t h o 6 o ? w a t e r a t 4 C ., i s 1 .0 3 9 8 7 a t 15 C. an d 1 .0 3 4 2 2 a t 20 C. I t i s m i s c i b l e w i t h w a t e r , a l c o h o l , e t h e r and m o st o r g a n i c l i q u i d s . ^ Hans T. C l a r k e , " R e l a t i o n b e tw e e n R e s i d u a l A f f i n i t y and C h em ical C o n s t i t u t i o n . I I I . Some H e t e r o c y c l i c Compounds'*, J o u r n a l o f t h e C hem ical S o c i e t y , 1 0 1 :1 7 8 8 - 1 8 0 9 . (C h e m ic a l A b s t r a c t s , 7 :5 9 3 ( 1 9 1 3 ) ) . L o u is H enry and A ug. D e w a e l, " O b s e r v a t i o n s o f t h e A c t i o n o f A l c o h o l s on E s t e r s " , C h em isch es Z e n t r a l b l a t t , 9 2 8 - 30 ( 1 9 0 2 ) . 4 W ils o n B a k e r and F r e d e r i c k B. F i e l d , " C y c l i c E s t e r s o f S u l f u r i c A c id . I I . C o n s t i t u t i o n o f M e th y le n e and G ly o x a l S u l f a t e s an d t h e R e a c t i o n o f M e th y le n e S u l f a t e w i t h T e r t i a r y B a s e s ” , J o u r n a l o f t h e C h e m ic a l S o c i e t y , 8 6 -9 1 ( 1 9 3 2 ) . ( C h em ical A b s t r a c t s , 2 6 : 2 1 6 7 ( 1 9 3 2 ) ) . H enry and D e w a e l, o p . c i t . , p . 928* , ® L o c . c i t . 7 L o c. c i t . 7 M ethods o f p r e p a r a t i o n . Two m e th o d s o f p r e p a r i n g 1 . 3 - d i o x a n e a r e g i v e n i n t h e l i t e r a t u r e : (1 ) a m eth o d c o v - 8 e r e d b y a B r i t i s h p a t e n t i n w h ic h h e x a m e th y le n e t e t r a m i n e i s t r e a t e d w i t h v a r i o u s mono- o r d i - h y d r i c a l c o h o l s i n th e p r e s e n c e o f a c i d s s u c h a s h y d r o c h l o r i c o r s u l f u r i c , and (2) t h e m ethod by w h ic h 1 , 3 - d i o x a n e was f i r s t p r e p a r e d , by H enry 9 an d D ew ael i n 1 902, n a m e ly , t h e c o n d e n s a t i o n o f t r i m e t h y l en e g l y c o l and trio x y w e th y le n e i n t h e p r e s e n c e o f o r t h o p h o s - p h o r i c a c i d a s a d e h y d r a t i n g a g e n t# C h e m ic a l p r o p e r t i e s . L i t t l e i s known c o n c e r n i n g t h e c h e m ic a l p r o p e r t i e s o f 1 , 3 - d i o x a n e , a l t h o u g h a num ber o f o r g a n i c d e r i v a t i v e s o f i t a r e d e s c r i b e d i n t h e l i t e r a t u r e # 1 .3 - D i o x a n e i s much more s u s c e p t i b l e t o d e c o m p o s it i o n t h a n i s i t s 1 , 4 - iso m er# A d d i t i o n compounds # Only two a d d i t i o n compounds o f 1 . 3 - d i o x a n e h av e b e e n r e p o r t e d , a n d n e i t h e r o f t h e s e i s o f t h e s im p l e e l e c t r o n d o n o r - a c c e p t o r t y p e . They a r e a w h i t e c r y s t a l l i n e m e r c u r i c h l o r i d e w h ic h s i n t e r s a n d decom poses a t o 10 a b o u t 126 C ., and a p a l e y e l l o w , c r y s t a l l i n e p i c r a t e w h ic h ® T. B i r c h a l l and S . C o f f e y , " M e th y le n e E t h e r s ” , ( B r i t i s h P a t e n t 3 3 8 ,6 2 4 , A u g u s t 3 0 , 1 9 2 9 , t o I m p e r i a l Chem i c a l I n d u s t r i e s , L t d . ) # ( C h e m ic a l A b s t r a c t s , 2 5 :2 4 3 7 ( 1 9 3 1 ) ) . ® H enry and D ew ael, 0£ . c i t . , p . 9 2 8 . ^ C l a r k e , ojd. c i t . , p p . 1 7 8 8 -1 8 0 9 . 0 11 m e l t s i n d i s t i n c t l y a t 57 C. S m a ll s a m p le s o f e a c h o f t h e s e a d d i t i o n compounds w e re p r e p a r e d by t h e a u t h o r a s a c h e c k on t h e b e h a v i o u r o f t h e 1 , 3 - d i o x a n e p r e p a r e d . I I . 1,4-DIOXANE (PARA DIOXANE) P h y s i c a l p r o p e r t i e s . C o n s i d e r a b l y m ore d a t a a r e a v a i l a b l e on t h e 1 , 4 - d i o x a n e t h a n on i t s 1 , 3 - i s o m e r . The b o i l i n g p o i n t o f 1 , 4 - d i o x a n e h as b e e n v a r i o u s l y r e p o r t e d i n e 12 t h e l i t e r a t u r e , t h e v a l u e , 1 0 1 .3 1 C* a t 760 mm., a p p a r e n t l y b e i n g t h e m o s t a c c u r a t e . The b e s t f r e e z i n g p o i n t d a t a o 13 0 14 g i v e 1 1 .7 C. and 1 1 .8 C. a s t h e f r e e z i n g p o i n t . The s p e c i f i c g r a v i t y o f 1 , 4 - d i o x a n e , a s com pared w i t h w a t e r a t o o 1 5 o 1 6 4 C . , i s 1 .0 3 4 8 4 a t 15 C. an d 1 .0 3 0 3 4 a t 20 C. I t i s m i s c i b l e w i t h w a t e r an d m o st o r g a n i c l i q u i d s . I t i s a c o l o r l e s s l i q u i d p o s s e s s i n g a s t r o n g , p l e a s a n t o d o r . The e a r l y w ork on t h e p h y s i c a l c o n s t a n t s o f 1 , 4 - d i o x a n e i s su m m a riz e d , H L o c . c i t . ^ K u r t H ess an d Hermann Frahm , " P r e p a r a t i o n and P r o p e r t i e s o f P u re D io x a n e " , B e r i c h t e d e r D e u ts c h e n C hem isehen G e s e l l s c h a f t , 7 1 B :2 6 2 7 -3 6 ( 1 9 3 8 ) . ( C h em ical A b s t r a c t s , 3 3 : 1663 ( 1 9 3 9 ) ) . 13 F . H. G etm an, " F r e e z i n g P o i n t s o f t h e S y stem p - D i o x a n e - T e r t i a r y - B u t a n o l " , R e c u e i l d e s t r a v a u x c h im iq u e s , 5 6 :9 2 7 - 3 0 ( 1 9 3 7 ) . ( C h e m ic a l A b s t r a c t s . 3 2 :2 0 1 2 ( 1 9 3 8 ) ) . 14 Hess and F rahm , £ £ . c i t . , p p . 2 6 2 6 - 3 6 . 15 C l a r k e , 0£ . c i t . , p p . 1 7 8 8 -1 8 0 9 . 1® L o c . c i t . 9 and t h e o r i g i n a l r e f e r e n c e s n o t e d i n B e i l s t e i n f3 H andbuch d e r 17 O r g a n is c h e n C hem ie. M ethods o f p r e p a r a t i o n . 1 ,4 - D i o x a n e i s p r e p a r e d 18 c o m m e r c ia lly by c a t a l y t i c d e h y d r a t i o n o f d i e t h y l e n e g l y c o l . 19 O th e r m e th o d s o f p r e p a r a t i o n a r e : (1 ) h e a t i n g e t h y l e n e b ro m id e w i t h e t h y l e n e g l y c o l , (2 ) c o m b in in g e t h y l e n e o x id e w i t h e t h y l e n e c h l o r o h y d r i n , (3 ) h e a t i n g BB’ - d i c h l o r o d i e t h y l e t h e r w i t h so d iu m h y d r o x id e o r w i t h m e r c u r i c o x i d e , plum bous o x i d e , s i l v e r o x id e o r c u p r i c o x i d e , (4 ) d e h y d r a t i n g e t h y l ene g l y c o l , e . g . w i t h p h o s p h o r i c a c i d a n d (5 ) h e a t i n g e t h y l ene o x id e w i t h so d iu m h y d r o x i d e . 20 C h e m ic a l p r o p e r t i e s . 1 ,4 - D i o x a n e i s t o x i c , an d ca n 21 fo rm e x p l o s i v e m i x t u r e s w i t h a i r . I t i s a n e x c e l l e n t s o l v e n t f o r many s u b s t a n c e s , i n c l u d i n g c e l l u l o s e a c e t a t e , r e s i n s , ^ B e i l s t e i n ’ s Handbuch d e r O r g a n is c h e n Chemie ( B e r l i n : J u l i u s S p r i n g e r , 1934). 1 9 :3 ( 4 t h E d i t i o n , up to 1 9 1 0 ) ; 1 9 :6 0 9 ( 4 t h E d i t i o n , 1 9 1 0 - 1 9 1 9 ) . H enry D r e y f u s , " C y c l i c E t h e r s " , ( U n ite d S t a t e s P a t e n t 2 , 0 7 2 , 1 0 1 , M arch 2 , 1 9 3 7 ) . (C h e m ic a l A b s t r a c t s , 3 1 :2 6 1 3 ( 1 9 3 7 ) ) . C a r l e t o n E l l i s , The C h e m is tr y of P e t r o l e u m D e r i v a t i v e s , Volume _I (New Y o rk : The C h e m ic a l C a t a l o g Company, I n c . , 1934)'", p . 5 5 5 . C. L. M. Brown, " C o n s t i t u t i o n a n d T o x i c i t y o f t h e G l y c o l s " , P h a r m a c e u t i c a l J o u r n a l , 1 4 0 :4 9 ( 1 9 3 8 ) . ( C h e m ic a l A b s t r a c t s , 5 2 : 5554 (1938) T» ^ G. W. J o n e s , H. Seaman a n d R. E . K ennedy, " E x p l o s i v e P r o p e r t i e s o f D i o x a n - a i r M i x t u r e s ” , I n d u s t r i a l and E n g i n e e r i n g C h e m is tr y , 2 5 :1 2 8 3 - 6 ( 1 9 3 3 ) . (C h e m ic a l A b s t r a c t s , 2 8 :3 2 5 ( 1 9 3 4 ) ) . 10 22 o gum s, f a t s and o i l s . On h e a t i n g t o 4 5 9 -5 3 4 C ., 1 , 4 - d i o x a n e 23 decom poses e s s e n t i a l l y a s f o l l o w s : C4 H8°2 2 CO + Hg + C2 H6 . C om m ercial 1 , 4 - d i o x a n e c o n t a i n s s e v e r a l i m p u r i t i e s : a 24 25 p e r o x i d e , a c e t a l , g l y c o l a c e t a l , a c e t i c a c i d , a n d w a t e r . 26 D io x a n e o x i d i z e s i o d i d e s t o f r e e i o d i n e . A d d i t i o n com pounds. A lth o u g h a l a r g e num ber o f a d d i t i o n compounds o f 1 , 4 - d i o x a n e h a v e b e e n p r e p a r e d , o n ly two a r e o f t h e c l e a r - c u t e l e c t r o n d o n o r - a c c e p t o r t y p e , 27 n a m e ly , t h e com pounds, C^HgOg^SOg and C^H gO g^SO ^. I t w ould a p p e a r t h a t i n t h e l a t t e r c a s e b o t h oxy g en atom s o f t h e d io x a n e m o le c u le a r e s h a r i n g e l e c t r o n s w i t h s u l f u r t r i o x i d e m o l e c u l e s . 2 2 E l l i s , 0£ . . c i t . , p . 5 5 5 . 23 P h . G ro ss and H. S u e s a , " T h e rm a l D e c o m p o s itio n o f D io x a n e " , M o n a t s h a f t e , 6 8 :2 0 7 - 1 4 ( 1 9 3 6 ) . (C h e m ic a l A b s t r a c t s , 3 0 :7 9 8 9 ( 1 9 3 6 ) ) . ^ E r n s t E i g e n b e r g e r , " O c c u r r e n c e o f P e r o x i d e i n C rude D io x a n e " , J o u r n a l f u r p r a k t i s c h e C hem ie, 1 3 0 : 7 5 - 8 ( 1 9 3 1 ) . ( C h e m ic a l A b s t r a c t s , 2 5 :3 3 1 5 ( 1 9 3 1 ) ) • ^ Hess and Frahm , ojs. c i t . , p p . 2 6 2 7 - 3 6 . Abraham S a i f e r an d James H u g h es, " D io x a n e a s a R e a g e n t f o r t h e D e t e c t i o n a n d D e t e r m i n a t i o n o f S m a ll Amounts o f I o d i d e . I t s A p p l i c a t i o n t o t h e D e t e c t i o n o f I o d i d e i n I o d i z e d S a l t " , J o u r n a l o f B i o l o g i c a l C h e m is tr y , 1 1 8 :2 4 1 - 5 ( 1 9 3 7 ) . ( C h e m ic a l A b s t r a c t s , 3 1 :3 9 5 3 ' ( 1 9 3 7 ) ) . ^ C. M. S u t e r , P . B. Evans a n d James M. K i e f e r , " D io x a n e S u l f o t r i o x i d e , a New S u l f a t i n g an d S u l f o n a t i n g A g e n t" , J o u r n a l o f t h e A m e ric a n C h e m ic a l S o c i e t y , 6 0 :5 3 8 - 4 0 ( 1 9 3 8 ) . ( C h e m ic a l A b s t r a c t s , 3 2 :3 4 0 5 ( 1 9 3 8 ) ) . © 11 T a b le I l i s t s e v e r y m o l e c u l a r compound of 1 , 4 - d i o x a n e w h ic h t h e w r i t e r h a s b e e n a b l e t o d i s c o v e r m e n tio n o f i n t h e l i t e r a t u r e , w i t h t h e C h e m ic a l A b s t r a c t s r e f e r e n c e an d t h e o r i g i n a l r e f e r e n c e i n e a c h c a s e . I n c e r t a i n c a s e s B e i l s t e i n * s H andbuch i s r e f e r r e d t o i n s t e a d o f C h e m ic a l A b s t r a c t s . TABLE I ADDITION COMPOUNDS OP 1,4-DIOXANE F o rm u la C h e m ic a l A b s t r a c t s O r i g i n a l r e f e r e n c e r e f e r e n c e D«SO, D*2S03 2D*InBr-: D*(C0C1)2 D'HgClg D• HgBrg D*HgIg 2D*HgClg 3 2 :3 4 0 5 (1 9 3 8 ) 3 2 :3 4 0 5 (1 9 3 8 ) 3 2 :2 9 1 3 (1 9 3 8 ) 3 2 :2 1 3 0 (1 9 3 8 ) (S e e B e i l s t e i n 1s H a n d b u ch , 1 9 :3 ) " ' 3 3 :6 9 (1939) 3 1 :6 6 1 5 (1 9 3 7 ) 3 3 :6 9 (1 9 3 9 ) 3 1 :6 6 1 5 (1 9 3 7 ) 3 3 :6 9 (1939) 3 1 :2 1 2 (1 9 3 7 ) J o u r n a l o f t h e A m e ri c a n C h e m ic a l S o c i e t y , 6 0 :5 3 8 - 4 0 (1 9 3 8 ) L o c . c i t . J o u r n a l o f t h e A m e ri- c a n C h e m ic a l S o c i e t y , 6 0 :3 0 6 - 8 (1 9 3 8 ) B e r i c h t e d e r D e u ts c h e n C hem isch en G e s e l l - s c h a f t , 7 1 B :3 2 -4 (1 9 3 8 ) A t t i d e l l a R e a le A cca- dem ia d e l L i n c e i ( R en- d i e o n t i ) , ('5)', 16 1 :8 9 See a l s o : J o u r n a l o f t h e A m e ric a n C h e m ic a l S o c i e t y , 6 0 :2 3 0 8 - 1 1 “ (1 9 3 8 ) See a l s o : J o u r n a l f u r p r a k t i s c h e C hem ie, 1 4 9 :3 0 -5 4 (1 9 3 7 ) J o u r n a l o f t h e A m e ri- ca n C h e m ic a l S o c i e t y , 6 0 :2 3 0 8 -1 1 (1 9 3 8 ) L o c . c i t . (B o th a r t i c l e s ) P h a r m a z e u t i a c h e Z e n t - r a l h a l l e f u r D e u ts c h - l a n d , 7 7 : 5 9 1 - 3 (1 9 3 6 ) 12 TABLE I (Continued) 2D*HgBr? 2D*HgIo 2D*Hg(CN). 3 1 :2 1 2 3 1 :2 1 2 3 1 :2 1 2 3 1 :2 1 2 (1937) (1 9 3 7 ) (1937) (1 9 3 7 ) D-HCIO^H^O 3 1 :1 8 1 5 (1937) 12D*Ni(C104 )2 «6H2 0 12D*Co (C1 0 J ) 2 «6H2 0 12D«Mn(C104 )2 «6Ho0 12D*Cu(C10a )2 »6H20 D *LiCl 3 1 :1 8 1 5 3 1 :1 8 1 5 3 1 :1 8 1 5 3 1 :1 8 1 5 3 1 :4 3 2 1 (1937) (1937) (1937) (1937) (1937) D*LiBr 2 D * L iI 3D»lTaI D*KI 2D*NH4 I D«CaCI2 3 1 :4 3 2 1 3 1 :4 3 2 1 3 1 :4 3 2 1 3 1 :4 3 2 1 3 1 :4 3 2 1 3 1 :6 6 1 5 (1937) (1937) (1937) (1 9 3 7 ) (1937) (1 9 3 7 ) 3 5 :1 7 1 7 (1941) D*CdCl2 3 1 :6 6 1 5 (1937) L o c . c i t . L o c . c i t . L o c . c i t . L o c . c i t . Na t u u r w e t e n s c h a p p e l i .1k T i . i d s c h r i f t , 1 9 : 1 2 - 5 (1 9 3 7 ) L o c . c i t . L o c . c i t . L o c . c i t . L o c . c i t . J o u r n a l f u r p r a k t i s c h e C h em ie. 1 4 8 :8 1 - 7 (1 9 3 7 ) L o c . c i t . Lo c . c i t . L o c . c i t . L o c . c i t . L o c . c i t .^ J o u r n a l f u r p r a k t i s c h e Chem ie. 1 4 9 :3 0 - 5 4 (19371 S ee a l s o :__ ________________ o f t h e K e n tu c k y Academy o f S c i e n c e , 7 : 8 5 - 9 119381 J J o u r n a l f u r p r a k t i s c h e C h em ie. 1 4 9 :3 0 -5 4 (1 9 3 7 ) See a l s o : J o u r n a l o f t h e A m e ric a n C h e m ic a l T r a n s a c t i o n s 3 1 :6 6 1 5 (1 9 3 7 ) S o c i e t y , 6 2 :3 5 2 2 (1940) D*CdBr2 L oc. l e s ) c i t . (B o th a r t i c - D»CdI2 3 1 :6 6 1 5 (1937) L o c . l e s ) c i t . (B o th a r t i c - D*CoC12 3 1 :6 6 1 5 (1 9 3 7 ) L o c . l e s ) c i t . ( B o th a r t i c - 2D*ZnClg 3 1 :6 6 1 5 (1937) Loc * l e s ) c i t . ( B o th a r t i c - 2D*ZnBr2 3 1 :6 6 1 5 (1937) Loc • l e s ) c i t . (B o th a r t i c - 2D*ZnI2 3 1 :6 6 1 5 (1 9 3 7 ) L o c . l e s ) c i t . (B o th a r t i c - 2D .CoBr2 3 1 :6 6 1 5 (1937) L oc. l e s ) c i t . ( B o th a r t i c - 13 TABLE I (Continued) 2D *N iI2 2D*CoI0 2D«CaBiv 2D*CaI2 2 D * S rI0 2D* Bair D*Hg(CNS)g D*Cu C12 D*CuBr2 D*SnBr2 D*MnCl2 2D *SrBr2 2D*MgCl2 2D*MgBr2 2D*MgI2 2D*Hg(CN)2 2D*MnBr2 2D*MnI2 2 D .P e C l2 2D*FeBr2 2D *FeI2 2D*NiCl2 2D*NiBrp D*Hg(CN)2 4D*CoI 2 D*SnCl2 3D*2AsClg 3 1 :6 6 1 5 (1 9 3 7 ) Loc* " 1 Q Q \ c i t . (B o th a r t i c - 3 1 :6 6 1 5 (1 9 3 7 ) Xuo / Loc* c i t . ( B o th a r t i c - 3 1 :6 6 1 5 (1937) JL OO ) J o u r n a l f u r p r a k t i s c h e C hem ie, 1 4 9 :3 0 - 5 4 (1 9 3 7 ) 3 5 :1 7 1 7 (1 9 4 1 ) See a l s o : T r a n s a c t i o n s o f t h e K en tu ck y Academy o f S c i e n c e , 7 : 8 5 - 9 119 3 8 ) 3 1 :6 6 1 5 (1 9 3 7 ) Loc* c i t . (B o th a r t i c - 3 5 :1717 (1 9 4 1 ) l e s ) 3 1 :6 6 1 5 (1 9 3 7 ) L o c. c i t . (B o th a r t i c - 3 5 :1 7 1 7 (1 9 4 1 ) l e s ) 3 1 :6 6 1 5 (1 9 3 7 ) L o c. c i t . (B o th a r t i e - 3 5 :1 7 1 7 (1 9 4 1 ) l e s ) 3 1 :6 6 1 5 (1 9 3 7 ) J o u r n a l f u r p r a k t i s c h e Chem ie, 1 4 9 :3 0 - 5 4 (1 9 3 7 ) 3 1 :6 6 1 5 (1 9 3 7 ) L o c. c i t . 3 1 :6 6 1 5 (1937) L oc. e x t . 3 1 :6 6 1 5 (1937) Loc • c i t . 3 1 :6 6 1 5 (1937) L o c . c i t . 3 1 :6 6 1 5 (1937) L oc. c i t . 3 1 :6 6 1 5 (1937) L o c . c i t . 3 1 :6 6 1 5 (1 9 3 7 ) Loc* c i t . 3 1 :6 6 1 5 (1 9 3 7 ) Loc* c i t . 3 1 :6 6 1 5 (1 9 3 7 ) L oc. c i t . 3 1 :6 6 1 5 (1 9 3 7 ) L oc. c i t . 3 1 :6 6 1 5 (1 9 3 7 ) L o c . c i t . 3 1 :6 6 1 5 (1 9 3 7 ) L o c. c i t . 3 1 :6 6 1 5 (1937) L o c . c i t . 3 1 :6 6 1 5 (1 9 3 7 ) L oc. c i t . 3 1 :6 6 1 5 (1 9 3 7 ) L o c . c i t . 3 1 :6 6 1 5 (1937) L o c. c i t . 3 1 :6 6 1 5 (1937) L o c . c i t . 3 1 :6 6 1 5 (1 9 3 7 ) L o c . c i t . 31:66X 5 (1 9 3 7 ) L oc. c i t . 2 8 :2 5 9 9 (1934) See a l s o : J o u r n a l o f P h y s i c a l C h e m i s t r y , 3 8 : 1 5 3 - 60 (1 9 3 4 ) 2 9 :2 5 3 9 (1 9 3 5 ) J o u r n a l o f t h e A m e ric a n P h a r m a c e u t i c a l A s s o c i a t i o n , 2 3 : 5 4 1 - 3 (1 9 3 4 ) 14 TABLE I (Continued) D*BF3 *2H20 2 7 :5 0 5 3 (1 9 3 3 ) d *c h i3 2 6 :3 4 8 1 (1 9 3 2 ) D*CoI2 d *c4h n i4 D«2SbCl5 2D«SnCl4 2 6 :3 4 8 1 2 6 :3 4 8 1 2 6 :3 4 8 1 2 6 :3 4 8 1 2 5 :2 6 9 1 (1 9 3 2 ) (1 9 3 2 ) (1 9 3 2 ) (1 9 3 2 ) (1 9 3 1 ) 2D*SnBr4 2D‘ S n I 4 2 5 :2 6 9 1 2 5 :2 6 9 1 (1 9 3 1 ) (1 9 3 1 ) B e r i c h t e d e r D e u ta c h e n C h em isch en G e s e l l s c h a f t , D»Brf D-Ig (S e e B e i l a t e i n 1a H andbuch, 1 9 :5 ) B e i l a t e i n , 1 9 :3 B e i l a t e i n , 1 9 :3 B e i l a t e i n , 1 9 :3 B e i l a t e i n , 1 9 :3 B e i l s t e i n , 1 9 :3 2 5 :2 6 9 1 (1931) (S ee B e i l s t e i n | a H an d b u ch , 19:5)" B e i l a t e i n , 1 9 :3 2 5 :2 6 9 1 (1 9 3 1 ) 6 6 6 :4 1 1 -4 ,,( 1 9 3 3 ) J o u r n a l f u r p r a k t i s c h e C h em ie, 1 3 3 :2 8 4 - 8 (1 9 3 2 ) L o c . c i t . L o c . c i t . L o c . c i t . L o c . c i t . J o u r n a l f u r p r a k t i s c h e C hem ie, 1 2 9 :2 6 8 -7 2 (1 9 3 1 ) L o c . c i t . L o c . c i t . A n n a le a d e c h im ie e t de p h y s i q u e , ( 3 ) , 6 9 :3 2 1 See a l s o : L i e b i g 1s A n n a le n d e r Chem ie, 1 2 2 :3 5 4 See a l s o : R u s s i s c h e n J o u r n a l d e r c h e m is c h e n 3 8 :7 4 7 See a l s o : P h y s i k a l i s c h - G e s e l l s c h a f t , C hem isches Z e n t r a l b l a t t , 16 See a l s o : A t t i R e a le (1907 I ) : d e l l a ______ A ccadem ia d e i L i n c e i ( R e n d i c o n t i ) , ( 5 ) , 16 1 :8 8 See a l s o : G a z z e t t a C him ica I t a l i a n a , 37 1 :1 0 7 See a l s o : J o u r n a l f u r p r a k t i s c h e Chem ie, 1 2 9 :2 7 3 - 7 (1 9 3 1 ) A t t i d e l l a R e a le A ccad emia d e i L i n c e i c o n t i ) , (5 )', See a l s o : (R e n d i- 1 6 1 :8 8 J o u r n a l d e r R u s s i s c h e n c h e m is c h e n 3 8 :7 4 7 See a l s o : p r a k t i s c h e 2 7 3 -7 P h y s i k a l i s c h - G e s e l l s c h a f t , J o u r n a l f u r C hem ie, 129: (1 9 3 1 ’) 15 TABLE I (Continued) D -IC1 D *lB r D*Au C13 D *PtCl, D*LiCl*HgO 2D*2LiBr.HgO 2D*LiI*2H20 2D -U aI.2H g0 D*CuClg.2Hg0 D*MnCl2 *2HgO D*CoClg.2H20 D *N iC lg.2H 20 D*CaClg.H20 3D*ZnClg*2H20 D«ZnBrg*2HgO 2D *2Z nIg.E 20 D«AuCl3 .Hg0 D * P tC l4 .2H20 2D«SnCl4 .2Hg0 3D*4HN03 D*ZnClg D*2CdClg 3D*CoIo D«C ol2.2H 2 0 D 'C o Ig ^ H g O D»NiCl2 D- D« N iB rg S rB rg 2D*CuCl2 2D*CuBrg D»CgH5*SbClg D*3((NH3 )3 CrClgO CHgCHpOCrClo ( nh3 )S) 3 5 :1 7 1 7 (1 9 4 1 ) 3 5 :1 7 1 7 (1941) 3 5 :1 7 1 7 (1 9 4 1 ) 3 4 :2 3 2 7 (1 9 4 0 ) 3 4 :2 3 3 0 (1 9 4 0 ) 25 {2691 (1 9 3 1 ) L oc. c i t . 25 {2691 (1 9 3 1 ) Loc. c i t . 27 :653 (1 9 3 3 ) Z e i t s c h r i f t g a n i s c h e und C hem ie, 2 0 8 : (1932) 27 653 (1 9 3 3 ) L oc. c i t . 27 653 (1 9 3 3 ) L oc. c i t . 27 653 (1 9 3 3 ) L o c. c i t . 27 653 (1 9 3 3 ) L o c . c i t . 27 653 (1 9 3 3 ) L o c . c i t . 27 653 (1 9 3 3 ) Loc. c i t . 27 653 (1 9 3 3 ) L oc. c i t . 27 653 (1 9 3 3 ) Loc. c i t . 27 653 (1 9 3 3 ) L oc. c i t . 27 653 (1 9 3 3 ) L oc. c i t . 27 653 (1 9 3 3 ) L o c . c i t . 27 653 (1 9 3 3 ) Loc. c i t . 27 653 (1 9 3 3 ) L oc. c i t . 27 653 (1 9 3 3 ) Hoe". c i t . 27 653 (1933) L o c . c i t . 27 653 (1 9 3 3 ) Loc . c i t . 25 75 (1 9 3 1 ) R e c u e i l d es f u r a n o r - a l l s e m e i n e c h im iq u e a , (1 9 3 0 ) J o u r n a l o f t r a v a u x 4 9 :1 0 4 0 - 4 t h e A m e ric a n 6 2 : C h e m ic a l S o c i e t y , T 1 9 4 0 ) c i t » c i t . c i t . c i t . c i t . c i t . T r a n s a c t i o n s o f t h e K e n tu c k y Academy o f S c i e n c e , 7 : 8 5 - 9 (1 9 3 8 ) L o c . c i t . L o c . c i t . J o u r n a l f u r Loc . L oc. L oc. L oc. L o c . L o c . Chem ie, (1 9 3 9 ) J o u r n a l C hem ie, (1 9 4 0 ) 154 p r a k t i s c h e 8 3 -1 5 6 f u r p r a k t i s c h e 1 5 4 :2 8 5 -3 0 8 16 TABLE I (Continued) D*NH2«((NH3)3CrBr2 OCHo CHp 0CrBr2 D*Br2*HBr D*H2S 04 D^CgHgOyNg 2 D * o - p h e n y le n e - d i a r s i n e t e t r a c h l o r i d e 3 4 :2 3 3 0 (1940) (S e e B e i l a t e i n ^ H an d b u ch , 19:3") B e i l s t e i n , 1 9 :3 B e i l a t e i n , 1 9 :3 B e i l a t e i n , 1 9 :3 B e i l a t e i n , 1 9 :3 B e i l s t e i n , 1 9 :3 3 3 :5 3 7 7 (1 9 3 9 ) L o c . c i t . A n n a le a d e c h im ie e t d e p h y s i q u e , ( 3 ) , 6 9 :3 2 1 See a l s o : L i e b i g 13 A n n a le n d e r Chem ie, 1 2 2 :3 5 4 See a l s o : H e l v e t i c a C him ica A c t a , 7 :9 9 3 "(1924) A t t i d e l l a R e a le A c c a d - em ia d e i L i n c e i ( R e n d i- c o n t i T 7 ~ ( 5 ) , 16 1 :8 8 See a l s o : J o u r n a l d e r R u s s i a c h e n P h y s i k a l i s c h - c h e m is c h e n G e s e l l s c h a f t , 3 8 :7 4 7 L o c . c i t . J o u r n a l o f t h e C h e m ic a l S o c i e t y , 6 1 0 -5 (1 9 3 9 ) N o te s : I n t h i s t a b l e , D r e p r e s e n t s 1 , 4 - d i o x a n e . A l l r e f e r e n c e s t o B e i l s t e i n i n t h i s t a b l e r e f e r t o t h e s e r i e s w h ic h c o v e r s t h e l i t e r a t u r e u p t o 1 9 1 0 . O th e r p o s s i b l e a d d i t i o n compounds w hose e x i s t e n c e h as b e e n i n d i c a t e d , b u t n o t d e f i n i t e l y p r o v e d , a r e l i s t e d i n T a b le I I . A g a in , t h e C h e m ic a l A b s t r a c t s r e f e r e n c e and t h e o r i g i n a l j o u r n a l r e f e r e n c e a r e b o t h g i v e n . 17 TABLE II INDICATED ADDITION COMPOUNDS OF 1,4-DIOXANE I n d i c a t e d compound C h e m ic a l A b s t r a c t s O r i g i n a l r e f e r e n c e r e f e r e n c e Compounds o f D and v a r i o u s a l i p h a t i c and a r o m a t i c a l c o h o l s , i n v o l v i n g h y d ro g e n b o n d s . A d e u te r iu m - b o n d e d d e u t e r i u m o x i d e - D co m p lex . A zo b en zen e -D and a z ob enz en e - t r i - n i t r o p h e n o l- D c o m p le x e s . A d e u t e r i u m m e th y l a l c o h o l - D com plex i n v o l v i n g d e u t e r ium b o n d s . A w a te r - D com plex fo rm ed b y h y d r o g e n b o n d s . A m e th y l a l c o h o l - D com p lex i n v o l v i n g h y d ro g e n b o n d s . A d i o x a n a t e o f mag n e s iu m d i m e t h y l . A t r i c h l o r o a c e t i c a c i d - D co m p le x . A h y d ro g e n c h l o r - id e - D c o m p le x . 3 2 :6 1 1 5 (1 9 3 8 ) 3 2 :5 6 7 4 (1 9 3 8 ) 3 2 :5 6 8 3 (1 9 3 8 ) 3 2 :4 8 7 7 (1 9 3 8 ) 3 2 :7 3 1 9 (1 9 3 8 ) 3 3 :2 3 9 6 (1 9 3 9 ) 3 3 :4 5 2 1 (1 9 3 9 ) 2 8 :9 4 5 (1 9 3 4 ) 3 3 :4 5 2 1 (1 9 3 9 ) 3 3 :6 2 6 3 (1 9 3 9 ) 3 0 :1 2 8 5 (1936) 2 8 :2 5 9 9 (1 9 3 4 ) T r a n s a c t i o n s o f F a r a d a y S o c i e t y , 7 2 8 -4 2 (1938) See a l s o : J o u r n a l t h e C h e m ic a l o f S o c i e t y , 4 6 0 -4 (1938) See a l s o : R e c u e i l d e s t r a v a u x c h i m i q u e s , 5 6 : 1 0 2 5 -3 3 (1 9 3 7 ) J o u r n a l o f t h e A m e ric a n C h e m ic a l S o c i e t y , 6 0 : 6 0 5 - 1 2 ( 1 9 3 8 ) B e r i c h t e d e r D e u ts c h e n C hem ischen G e s e l l s c h a f t , 7 I B :1 4 1 5 -2 1 (1938) J o u r n a l o f C h em ical P h y s i c s , 7 : 9 3 - 9 (1 9 3 9 ) B u l l e t i n d e s a c a d a m ie d e s s c i e n c e , 3 7 3 -8 2 119381---------- See a l s o : J o u r n a l o f t h e A m e ric a n C h e m ic a l S o c i e t y , 5 5 :4 8 3 2 -7 (1 9 3 3 ) B u l l e t i n d e s a c a d a m ie d e s s c i e n c e , 3 7 3 -8 2 119381 J o u r n a l o f t h e A m e ric a n C h e m ic a l S o c i e t y , 61: 1 1 5 2 -6 (19391 J o u r n a l o f t h e C h e m ic a l S o c i e t y , 1 4 3 2 -5 (1 9 3 5 ) J o u r n a 1 o f P h y s i c a l C h e m is tr y , 3 8 : 1 5 3 - 6 0 T T o f lT TABLE II (Continued) A c y l c h l o r i d e - and b e n z y l c h l o r i d e - D c o m p le x e s . An a r s e n i c t r i - ----------------------------------------- c h l o r i d e - D com p l e x , m e l t i n g a t 6 6 -8 C. (May b e t h e 3D»2AsCl-z com p l e x r e p o r t e d i n T a b le I ) . A q u i n o l - D com plex 2 4 :4 7 7 2 (1 9 3 0 ) m e l t i n g a t 9 3 -1 0 0 °C D.CHClg, D.2CHC13 , 3 0 :4 7 3 6 (1936) D*CC14 and D«2CC14 ( r e p o r t e d on t h e b a s i s o f p o l a r i z a t i o n d a t a o n l y — n o t i s o l a t e d ) . N o te : I n t h i s t a b l e , D r e p r e s e n t s 1 , 4 - d i o x a n e , S in c e t h e two s u l f u r t r i o x i d e — 1 , 4 - d i o x a n e com p lex es 28 p r e p a r e d b y S u t e r , Evans an d K i e f e r a r e a p p a r e n t l y o f t h e same t y p e a s t h e b o r o n f l u o r i d e — 1 , 4 - d i o x a n e co m p lex es whose p r e p a r a t i o n was a t t e m p t e d i n t h i s w o rk , some d i s c u s s i o n o f t h e i r w ork i s a p p r o p r i a t e . They r e p o r t t h a t s u l f u r t r i o x i d e d i r e c t l y a d d e d t o 1 , 4 - d i o x a n e a t room t e m p e r a t u r e p r o d u c e s c h a r r i n g , b u t t h a t when P r a k t i k a Akad A th e n o n , 1 3 : 4 2 - 4 (1 9 3 8 ) ( S u m m a r iz e d ,in Chem- i s c h e s Z e n t r a l b l a t t , 1 1 9 3 8 I I ) :1 3 9 4 -5 ) J o u r n a l o f G e n e r a l C h e m is tr y ( T J .S .S .R .) , 1 0 : 1 2 0 2 T l 9 4 0 F J o u r n a l o f t h e A m e ric a n C h e m ic a l S o c i e t y , 5 2 : 3 2 0 4 -6 (1 9 3 0 ] J o u r n a l o f t h e C h e m ic a l S o c i e t y , 1 7 2 0 -3 (1935) 28 S u t e r , Evans a n d K i e f e r , 0£ . c i t , , p p , 5 3 8 - 4 0 , 19 t h e s u l f u r t r i o x i d e i s ad d e d t o a s o l u t i o n o f t h e d i o x a n e i n c a r b o n t e t r a c h l o r i d e o r e t h y l e n e c h l o r i d e , t h e a d d i t i o n com pounds s e p a r a t e o u t i n w h i t e f l a k e s o r c r u s t s . The s o l u t i o n o f d i o x a n e i n e t h y l e n e c h l o r i d e was c h i l l e d and s t i r r e d m ech a n i c a l l y w h i l e s u l f u r t r i o x i d e was d i s t i l l e d i n t o i t fro m 60 p e r c e n t o leu m . The s o l u t i o n c o u ld b e p r e s e r v e d u n c h a n g e d f o r s e v e r a l d a y s i n t h e i c e b o x . I f t h e d i o x a n e i s i n e x c e s s , t h e m o n o s u l f o t r i o x i d e i s f o rm e d , w h e re a s e x c e s s s u l f u r t r i o x i d e p r o d u c e s t h e d i s u l f o t r i o x i d e . The a d d i t i o n o f 1 , 4 - d i o x a n e t o a s u s p e n s i o n o f t h e d i s u l f o t r i o x i d e compound i n c a r b o n t e t r a c h l o r i d e p r o d u c e s h e a t an d t h e m o n o s u l f o t r i o x i d e co m p le x . U nder a n h y d ro u s c o n d i t i o n s b o t h compounds a r e s t a b l e a t room O t e m p e r a t u r e , b u t upo n h e a t i n g t o 75 C. i n c a r b o n t e t r a c h l o r i d e , d e c o m p o s it i o n e n s u e s w i t h t h e f o r m a t i o n o f w a t e r - s o l u b l e p r o d u c t s . B o th compounds r e a c t w i t h w a t e r i n s t a n t l y to g i v e s u l f u r i c a c i d and r e g e n e r a t e d i o x a n e . I t i s i m p o r t a n t to n o t e t h a t fro m t h e e v i d e n c e o f s u l f a t i n g and s u l f o n a t i n g a c t i o n o f t h e com pounds, no d i f f e r e n c e i n r e a c t i v i t y c o u ld b e d e t e c t e d . A lth o u g h t h e a u t h o r s r e p o r t t h e r a t i o s o f 1 : 1 an d 2 : 1 , t h e y do n o t g i v e a n y a n a l y t i c a l d a t a i n s u p p o r t o f t h e s e c o m p o s i t i o n s . U n f o r t u n a t e l y , no d i s s o c i a t i o n p r e s s u r e d a t a a r e g i v e n . I t i s o f c o n s i d e r a b l e i n t e r e s t t h a t t h e c o r r e s p o n d i n g s u l f u r t r i o x i d e — t h i o x a n e a d d i t i o n compounds h a v e b e e n p r e - 29 p a r e d , and th e m eth o d s o f p r e p a r a t i o n p a t e n t e d . T h io x a n e 29 P a u l N aw iasky and G e rh a rd E . S p r e n g e r ( t o G e n e r a l A n i l i n e and F ilm C o r p o r a t i o n ) , " T h io x a n e S u l f u r T r i o x i d e Ad d i t i o n Com pounds", U n ite d S t a t e s P a t e n t 2 , 2 1 9 , 7 4 8 , O c to b e r 2 9 , 1 9 4 0 . ( C h e m ic a l A b s t r a c t s , 3 5 :1 0 6 7 (1941)). 20 i s a s u l f u r a n a l o g u e o f 1 , 4 - d i o x a n e , h a v in g t h e f o r m u l a , C.HoOS. 1 , 4 - T h io x a n e a l s o fo rm s o x o n iu m -ty p e com pounds, e .g * 4 p 30 a m e r c u r l c h l o r i d e w h ic h m e l t s a t 171 C* The o t h e r a n a l o g u e o f 1 , 4 - d i o x a n e , 1 , 4 - d i t h i a n e , fo rm s 31 s e v e r a l o x o n iu m -ty p e a d d i t i o n com pounds, e . g . C4H8Sg*H gl2 > 3C4HgSg»4AgN0;5, C4H8Sg»2AuCl2, C4H8Sg.HgClg, ^HgSg^HgBrg, 2C4H8 S2 .3H gClg and C4H8 S g . P t C l 4 . I t s h o u ld b e n o te d t h a t t h e b o r o n f l u o r i d e — 1 , 4 - d i o x a n e 32 com plex r e p o r t e d b y M eerw ein ( s e e T a b le I ) a l s o c o n t a i n s w a t e r . The p r e s e n c e o f w a t e r i n t h e m o l e c u l e v e r y l i k e l y c h a n g e s t h e t y p e o f b o n d in g c o n s i d e r a b l y fro m t h e t y p e i n v o lv e d i n t h e a n h y d ro u s co m p lex es w hose p r e p a r a t i o n was a t te m p te d i n t h e p r e s e n t w o rk . I I I . BORON TRIFLUORIDE P h y s i c a l p r o p e r t i e s . B o ro n t r i f l u o r i d e i s a c o l o r l e s s O g a s a t room te m p e r a t u r e * I t m e l t s a t -1 2 8 C ., an d b o l l s a t o 33 - 9 9 . 9 C. M ethods o f p r e p a r a t i o n . B o ro n f l u o r i d e i s p r e p a r e d m o st c o n v e n i e n t l y b y t h e r e a c t i o n o f ammonium f l u o b o r a t e , 3 ^ B e i l s t e i n , o p . c i t . , 1 9 :6 0 9 (1 9 1 0 -1 9 1 9 s e r i e s ) . 31 I b i d . , 1 9 :3 ( s e r i e s up t o 1 9 1 0 ) . 32 Hans M eerw ein , "B o ro n F l u o r i d e Com plexes and t h e Use o f B o ro n F l u o r i d e f o r S y n t h e s e s . P r e l i m i n a r y Communica t i o n " , B e r i c h t e d e r D e u ts c h e n C hem isch en G e s e l l s c h a f t , 66B: 4 1 1 -4 ( 1 9 3 3 ) . ( C h e m ic a l A b s t r a c t s . 2 7 :5 0 5 3 ( 1 9 3 3 ) ) . 33 E . P o h la n d and W. H a r l o s , " N o n - m e t a l l i c H a lo g e n Com p o u n d s . I I I . S a t u r a t i o n P r e s s u r e s o f B o ro n T r i f l u o r i d e " , Z e i t s c h r i f t f u r a n o r g a n i s c h e und a l l g e m e i n e C hem ie, 2 0 7 : 2 4 2 - 5 ( 1 9 3 2 ) . (“ C h e m ic a l A b s t r a c t s , 2 6 :5 4 7 0 ( 1 9 3 2 ) 7 T ^ 21 34 b o r i c o x id e and c o n c e n t r a t e d s u l f u r i c a c i d : 6NH4BP4 4- B2 03 + 6HgS04 ---- >» 8BF3 4- 6NH4 HS04 -I- 3 1 ^ 0 . C h em ical p r o p e r t i e s . B o ro n f l u o r i d e i s q u i t e r e a c t i v e to w ard w a t e r , f o rm in g f l u o b o r i c a c i d and b o r i c a c i d . I t d o e s n o t a t t a c k m e r c u ry n o r e t c h g l a s s ( b u t d o e s e t c h g l a s s i f n o t u n d e r a n h y d ro u s c o n d i t i o n s ) . I t a t t a c k s r u b b e r and s t o p c o c k g r e a s e , b u t n o t n e o p r e n e , a p i e z o n g r e a s e o r p i c e i n c e m e n t. A d d i t i o n com pounds. B o ro n t r i f l u o r i d e e x h i b i t s s t r o n g e l e c t r o n a c c e p t o r p o w e r, f o rm in g num erous m o l e c u l a r compounds i n w h ic h i t b e h a v e s a s a n e l e c t r o n - p a i r a c c e p t o r . A few e x - 35 am p les a r e t h e compound, PH3 «BF3 and t h e b o r o n f l u o r i d e — 36 h e x a m e th y le n e t e t r a m i n e c o m p le x e s . L a r g e l y b e c a u s e o f i t s te n d e n c y t o fo rm m o l e c u l a r c o m p le x e s , b o r o n f l u o r i d e i s em p lo y e d v e r y e x t e n s i v e l y a s a n i n d u s t r i a l c a t a l y s t f o r o r g a n i c r e a c t i o n s • ^ H a ro ld Simmons B o o th , I n o r g a n i c S y n t h e s e s , Volume I (New Y o rk : M cG raw -H ill Book Company, I n c . , 1 9 3 9 ) . p p . 2 1 - 4 . Egon W ib erg and U l r i c h Heubaum, "The A c t i o n o f P h o s - p h i n e on B oron F l u o r i d e ( 2 . W ith R e f e r e n c e t o t h e Q u e s t i o n o f t h e E x i s t e n c e o f B oron H a l i d e A d d i t i o n Compounds o f Anomolous C o m p o s i t i o n ) " , Z e i t s c h r i f t f u r a n o r g a n i s c h e und a l l g e m e i n e Chem ie, 2 2 5 :2 7 0 - 2 ( 1 9 3 5 ) . ( C h e m ic a l A b s t r a c t s , 3 0 :2 5 1 3 ( 1 9 3 6 ) ) . M a r t i n , M.A. t h e s i s , The U n i v e r s i t y o f S o u t h e r n C a l i f o r n i a L i b r a r i e s , 1 9 4 0 . CHAPTER III PREPARATION AND PURIFICATION OF REAGENTS I . 1,3-DIOXANE S i n c e 1 , 3 - d i o x a n e i s n o t c o m m e r c ia lly a v a i l a b l e , i t had t o b e s y n t h e s i z e d i n t h e l a b o r a t o r y . The m ethod o f p r e p - 37 a r a t i o n was t h a t o f H enry and D ew ael: H3 P04 C3H6 (0H )2 -t- HCHO ■ ■ ~ g - C4H8 0g ( 1 , 3 - ) + ■ HgO . 100 C , The d e t a i l s o f t h e s y n t h e s i s a r e w e l l s t a t e d by Hans T. 38 C l a r k e , Due t o a l a c k o f s u f f i c i e n t l y l a r g e e q u ip m e n t t h r e e p r e p a r a t i o n s o f t h e 1 , 3 - d i o x a n e had t o b e made f o r t h e p r e s e n t s t u d y . T r i m e t h y l e n e g l y c o l , t r i o x y m e t h y l e n e and 85 p e r c e n t p h o s p h o r i c a c i d w e re h e a t e d i n a P y r e x bomb tu b e i n a O f u r n a c e , a t 100 C ., f o r one o r m ore d a y s . The m i x t u r e was t h e n c o o l e d , r e n d e r e d f a i n t l y a l k a l i n e w i t h 6 n o rm a l so d iu m h y d r o x id e s o l u t i o n , and d i s t i l l e d . The f r a c t i o n b o i l i n g w i t h i n t h e 9 0 -1 1 0 ° C , r a n g e was s a t u r a t e d w i t h s o l i d p o t a s siu m h y d r o x i d e , and t h e s e p a r a t e d l i q u i d d r i e d by r e f l u x i n g 3 7 L o u is H enry a n d Aug, D e w a e l, 1 1 O b s e r v a t i o n s o f t h e A c t i o n o f A lc o h o ls on E s t e r s ” , C h em isch es Z e n t r a l b l a t t , 9 2 8 -3 0 ( 1 9 0 2 ) , 3 ® Hans T, C l a r k e , " R e l a t i o n b e tw e e n R e s i d u a l A f f i n i t y and C h e m ic a l C o n s t i t u t i o n , I I I . Some H e t e r o c y c l i c Com p o u n d s ” , J o u r n a l o f t h e C h e m ic a l S o c i e t y , 1 0 1 :1 7 8 8 - 1 8 0 9 , ( C h e m ic a l A b s t r a c t s , 7 :5 9 3 (1913)T » 23 w i t h s o l i d p o t a s s i u m h y d r o x id e f o r two t o t h r e e h o u r s . The d r i e d l i q u i d was t h e n d i s t i l l e d t w i c e o v e r f r e s h l y - c u t m e t a l l i c so d iu m i n h o t - a i r - d r i e d a p p a r a t u s , an d c o l l e c t e d i n a t h o r o u g h ly d r i e d , g l a s s - s t o p p e r e d d a r k b o t t l e i n t h e a b s e n c e of m o i s t u r e . The d e t a i l s o f t h e t h r e e s e p a r a t e p r e p a r a t i o n s a r e sum m arized i n T a b le I I I . TABLE I I I PREPARATION OP THE 1,3-DIOXANE W eig h t W eig h t W e ig h t Time I n T h e o r e t - A c t u a l P e r c e n t o f t r i - o f t r i - o f 85 bomb i c a l y i e l d y i e l d m e th y l - oxym eth - p e r c e n t tu b e y i e l d ene y l e n e p h o s p h o r g l y c o l i c a c i d gram s gram s gram s h o u r s gram s gram s p e r c e n t 30 15 1 7 . 5 24 35 13 37 59 30 3 5 . 5 48 69 39 56 50 25 3 0 . 0 66 58 ->30 52 ■*This sa m p le was p l a c e d i n a d r i e d a m p o u le , s e a l e d and g i v e n t o D r. C h a r le s ; S. C o p e la n d , o f The U n i v e r s i t y o f S o u t h e r n C a l i f o r n i a , f o r u s e i n a s t u d y o f t h e d i e l e c t r i c c o n s t a n t and d i p o l e moment o f 1 , 3 - d i o x a n e , n e i t h e r o f w h ic h h a s b e e n r e p o r t e d i n t h e l i t e r a t u r e . The t r i m e t h y l e n e g l y c o l u s e d was t h e E a stm an Kodak Com p an y ’’P r a c t i c a l " g r a d e , r e d i s t i l l e d u n t i l a l m o s t c o l o r l e s s . The t r i o x y m e t h y l e n e ( p o ly o x y m e th y le n e o r p a r a f o r m a l d e h y d e ) was t h e " P r a c t i c a l " g r a d e , and t h e 85 p e r c e n t o r t h o p h o s p h o r i c 24 a c i d was o f " C .P ." q u a l i t y ( B a k e r ’ s A n a l y z e d ) . The p u r i f i e d 1 , 3 - d i o x a n e b o i l e d a t 1 0 4 -5 ° C . a t 7 5 8 - 6 0 nun. and f r o z e a t o a b o u t -4 0 C. I t was c o l o r l e s s w i t h a p u n g e n t o d o r l i k e a c e t a l . F o r u s e i n t h e h ig h -v a c u u m w o rk , t h i s p u r i f i e d 1 , 3 - 39 d i o x a n e was d r i e d o v e r a n h y d ro u s c a l c i u m s u l f a t e and t h e n O f r a c t i o n a l l y d i s t i l l e d u n d e r h ig h -v a c u u m , r e f l u x i n g a t 21 C ., o t h e r e f l u x i n g j a c k e t b e i n g h e l d a t 0 C. an d t h e r e c e i v i n g O tu b e a t -3 C. A l l t h r e e f r a c t i o n s w e re k e p t f o r u s e , s i n c e t h e i r v a p o r t e n s i o n s w ere p r a c t i c a l l y i d e n t i c a l . I I . 1,4-DIOXANE C o m m ercial 1 , 4 - d i o x a n e was a llo w e d t o s t a n d o v e r a n h y d r o u s c a l c i u m c h l o r i d e f o r t w e lv e h o u r s , r e f l u x e d o v e r f r e s h l y - c u t m e t a l l i c so d iu m f o r t h r e e h o u r s , and f i n a l l y d i s t i l l e d i n h o t - a i r - d r i e d a p p a r a t u s , t h e d i s t i l l a t e b e i n g c o l l e c t e d i n a t h o r o u g h l y d r i e d , g l a s s - s t o p p e r e d d a r k b o t t l e i n t h e a b s e n c e O o f m o i s t u r e . The f i n a l p r o d u c t m e l t e d a t 12 C. ( a p p r o x i m a t e l y ) an d b o i l e d a t 1 0 0 -2 ° C . a t 7 5 8 -6 0 mm. I t was a c o l o r l e s s l i q u i d w i t h a s t r o n g , b u t n o t d i s p l e a s i n g o d o r . I n o r d e r to b e d o u b l y s u r e o f t h e p u r i t y o f t h e 1 , 4 - d io x a n e th u s o b t a i n e d and t o c h e c k t h e M e n z ie s - S m ith a p p a r a t u s c o n s t r u c t e d , t h e v a p o r t e n s i o n s o f a sa m p le o f t h e s u b s t a n c e w e re d e t e r m in e d a t a s e r i e s o f t e m p e r a t u r e s by t h e W. A. Hammond and James R. W ith ro w , " S o l u b l e Anhy d r i t e a s a D e s i c c a t i n g A g e n t" , J o u r n a l o f I n d u s t r i a l a n d E n g i n e e r i n g C h e m is tr y , 2 5 :6 5 3 - 9 ( 1 9 3 3 ) . ("Chemical A b s t r a c t s , 2 7 :3 5 6 2 ( 1 9 3 3 ) ) . 25 40 M e n z ie s - S m ith m ethod* The v a l u e s o b t a i n e d a r e l i s t e d i n T a b le IV a l o n g w i t h v a l u e s c a l c u l a t e d fro m t h e f o r m u l a , lo glO ^C 1 ™1*) ” 8*0588 - 1 9 3 3 * 8 /T , g i v e n by H o v o rk a , S c h a e f e r 41 and D r e is b a c h * TABLE IV THE VAPOR TENSIONS OF 1,4-DIOXANE E x p e r i m e n t a l v a l u e s C a l c u l a t e d v a l u e s T e m p e ra tu r e V apor t e n s i o n T e m p e ra tu re V apor t e n s i o n o o • mm. *c. mm. 2 1 .7 27 15 2 2 .2 2 3 .6 31 2 0 2 8 . 8 2 6 . 4 35 25 3 7 . 1 2 8 . 1 40 30 4 7 . 4 3 0 .1 44 35 6 0 .5 3 1 .7 48 40 7 6 . 0 4 9 .4 112 45 9 5 . 1 5 2 .1 127 50 1 1 8 . 5 5 .1 146 55 1 4 6 . 5 7 .7 163 60 1 7 8 . 6 2 .9 197 65 2 1 8 . 6 6 .7 231 70 2 6 4 . 7 2 . 4 287- 75 3 1 8 . 7 6 . 8 335 80 3 8 2 . 8 1 .2 394 85 4 5 5 . 8 5 .3 452 90 5 3 9 . 8 9 .0 510 95 6 3 7 . 40 A le x a n d e r S m ith and A la n W, C. M e n z ie s , " S t u d i e s i n V apor P r e s s u r e : I I . A S im p le Dynam ic M ethod, A p p l i c a b l e to B o th S o l i d s and L i q u i d s , f o r D e t e r m i n in g V a p o r P r e s s u r e s , and A ls o B o i l i n g P o i n t s a t S ta n d a r d P r e s s u r e s " , J o u r n a l o f t h e A m e ric a n C h e m ic a l S o c i e t y , 3 2 : 9 0 7 - 1 4 ( 1 9 1 0 ) . ( C h e m ic a l A b s t r a c t s , 4 :2 5 9 5 ( 1 9 1 0 ) ) . F r a n k H o v o rk a , R a lp h A. S c h a e f e r an d D a le D r e i s b a c h , "The S y ste m D io x a n e and W a te r " , J o u r n a l o f t h e A m e ric a n C h e m ic a l S o c i e t y , 5 8 :2 2 6 4 -7 ( 1 9 3 6 ) . ( C h em ical A b s t r a c t s , 3 1 :9 3 5 ( 1 9 3 7 ) ) . 26 I n F i g u r e 1 t h e s e e x p e r i m e n t a l d a t a a r e p l o t t e d a l o n g w i t h t h e v a l u e s com puted fro m t h e H o v o rk a, S c h a e f e r , D r e i s b a c h 42 f o r m u l a . I t i s a p p a r e n t t h a t t h e c h e c k i s f a i r l y c l o s e , t h e f a c t t h a t t h e e x p e r i m e n t a l v a l u e s a r e c o n s i s t e n t l y s l i g h t l y l e s s t h a n t h e com puted ones a t t h e lo w e r t e m p e r a t u r e s p r o b a b l y b e i n g due t o a s l i g h t s o l u b i l i t y o f t h e d i o x a n e v a p o r i n t h e l i g h t l i q u i d p e t r o l a t u m u s e d a s t h e s u r r o u n d i n g l i q u i d . Temp t s e r a t u r e s w e re r e a d on a c a l i b r a t e d 110 C. th e r m o m e te r and s te m c o r r e c t i o n s made a c c o r d i n g t o t h e f o r m u l a , c o r r e c t i o n t - t 1) 0 .0 0 0 1 5 4 . The t e m p e r a t u r e s l i s t e d i n T a b le IV a r e c o r r e c t e d O and a r e p r o b a b l y a c c u r a t e t o ± 0 . 2 C. P r e s s u r e s w e re r e a d o n ly t o t h e n e a r e s t m i l l i m e t e r on a m e r c u ry m an o m eter e q u ip p e d w i t h a n a t t a c h e d m e t e r s t i c k . The r e a d i n g s a r e p r o b a b l y o n l y a c c u r a t e t o i 1 mm. The v a l u e s com puted fro m t h e p r e v i o u s l y m e n tio n e d f o r - 43 m ula c h e c k c l o s e l y w i t h t h o s e com puted fro m t h e f o r m u l a , l o g 2 _QP(mm.) sa 7 .8 6 4 2 - 1 8 6 6 .7 / T , g i v e n b y G a l l a u g h e r and 44 H i b b e r t . F o r u s e i n t h e h ig h -v a c u u m w ork t h e p u r i f i e d 1 , 4 - d i o x a n e was f r a c t i o n a l l y d i s t i l l e d u n d e r h ig h -v a c u u m . The ^ k o c . c i t . 43 L o c. c i t . 44 A. F . G a l l a u g h e r an d H. H i b b e r t , " R e a c t i o n s R e l a t i n g t o C a r b o h y d r a te s an d P o l y s a c c h a r i d e s . LV. V apor P r e s s u r e s o f t h e P o l y e t h y l e n e G ly c o ls a n d T h e i r D e r i v a t i v e s " , J o u r n a l o f t h e A m e ric a n C h e m ic a l S o c i e t y , 5 9 :2 5 1 4 - 2 1 ( 1 9 3 7 ) . (C h e m ic a l A b s t r a c t s , 3 2 :9 1 4 (193877^ V apor T e n s io n (mm.) 1000 900 800 700 500 390 20 0 1 0 0 80 F I guy a LI____ i __ _ i f a p a r Ttenalono C a l c n l £ t e 4 va^Lue The so 30 3.7 3.3 a.s d i o x a n e was r e f l u x e d fro m a b a t h a t 30 C ., t h e r e f l u x i n g o O j a c k e t b e i n g h e l d a t 15 C ., and t h e r e c e i v i n g tu b e a t 0 C. The f i r s t f r a c t i o n showed a n e a r l y a c c e p t a b l e v a p o r t e n s i o n o o f 3 5 . 5 mm. a t 2 3 .3 C ., b u t was d i s c a r d e d t o b e d o u b l y s u r e o f p u r i t y . The m id d le f r a c t i o n showed a v a p o r t e n s i o n o f o 3 4 . 0 mm. a t 2 3 . 3 C ., and was k e p t f o r u s e . The end f r a c t i o n was r e j e c t e d w i t h o u t e v e n c h e c k in g i t s v a p o r t e n s i o n . I I I . BORON TRIFLUORIDE The b o r o n t r i f l u o r i d e u s e d I n t h e p r e l i m i n a r y w ork was p r e p a r e d by t h e r e a c t i o n d i s c u s s e d on p a g e 21 o f t h i s t h e s i s , n a m e ly , t h e r e a c t i o n o f ammonium f l u o b o r a t e , b o r i c o x id e an 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 . " R e a g e n t" q u a l i t y ammonium f l u o b o r a t e an d b o r i c o x i d e w e re u s e d , and " C .P ." s u l f u r i c a c i d . The m i x t u r e was warmed w i t h a n o p en f la m e u n d e r a p r e s s u r e o f a b o u t 20 mm. ( w a t e r a s p i r a t o r w i t h d r y i n g t u b e b e tw e e n t h e a p p a r a t u s and t h e a s p i r a t o r ) i n h o t - a i r - d r i e d a p p a r a t u s , t h e f i r s t p o r t i o n o f b o r o n f l u o r i d e e v o lv e d b e i n g u s e d t o sw eep o u t t h e s m a l l am ount o f a i r r e m a i n i n g i n t h e s y s te m . The b o r o n f l u o r i d e was p a s s e d t h r o u g h a w a t e r - j a c k e t e d c o n d e n s e r an d th e n a d r y - i c e j a c k e t t o t r a p a n y m o i s t u r e i n t h e e v o lv e d g a s , and a l s o a n y s u l f u r i c a c i d o r f l u o b o r i c a c i d . 29 The b o r o n t r i f l u o r i d e u s e d i n t h e h ig h -v a c u u m w o rk was 45 p r e p a r e d b y t h e same m ethod b y D r. A n to n B. B u rg , a t The U n i v e r s i t y o f S o u t h e r n C a l i f o r n i a , an d was s t o r e d i n a o n e - l i t e r c a p a c i t y b u l b a t t a c h e d t o t h e vacuum a p p a r a t u s b y means o f a m e r c u r y - f l o a t e d , g r o u n d - g l a s s v a lv e * IV. CHLOROFORM The c h l o r o f o r m u s e d i n t h e p r e l i m i n a r y w ork was a com m e r c i a l g r a d e o f h i g h p u r i t y . I t was d r i e d o v e r a n h y d ro u s c a l c i u m c h l o r i d e f o r two h o u r s an d t h e n o v e r f r e s h l y - c u t m e t a l l i c so d iu m f o r one h o u r b e f o r e u se * V. CARBON TETRACHLORIDE The c a r b o n t e t r a c h l o r i d e u s e d i n t h e p r e l i m i n a r y w ork was a c o m m e rc ia l g r a d e o f h i g h p u r i t y , and was d r i e d o v e r a n h y d ro u s c a l c i u m c h l o r i d e and f r e s h l y - c u t m e t a l l i c so d iu m a s i n t h e p u r i f i c a t i o n o f t h e c h l o r o f o r m ( d e s c r i b e d a b o v e )* B o o th , £ £ . c i t *, p . 2 1 . CHAPTER IV APPARATUS, PROCEDURES, DATA, GRAPHS, CALCULATED VALUES I . PRELIMINARY WORK B o ro n t r i f l u o r i d e - - 1 , 5 - d i o x a n e a d d i t i o n . The a p p a r a t u s u s e d i n t h e p r e l i m i n a r y s t u d y i s i l l u s t r a t e d i n F i g u r e 2 . I t was d r i e d i n a c u r r e n t o f warm a i r a n d t h e n s t r o n g l y h e a t e d w i t h a n op en f la m e w h i l e b e i n g e v a c u a t e d b y a w a t e r a s p i r a t o r ( s e p a r a t e d fro m t h e s y s te m b y a d r y i n g tu b e p a c k e d w i t h a n h y d ro u s c a l c i u m c h l o r i d e and a s c a r i t e ) . A f t e r a p r e l i m i n a r y c h e c k r e v e a l e d t h a t b o r o n f l u o r i d e d i d n o t r e a c t w i t h o r d i s s o l v e i n e i t h e r c a r b o n t e t r a c h l o r i d e o r c h l o r o f o r m , a sa m p le o f 1 , 3 - d i o x a n e was p i p e t t e d i n t o a m i x t u r e o f 35 c c . c h l o r o f o r m and 10 c c . c a r b o n t e t r a c h l o r i d e ( t h e m i x t u r e was u s e d i n o r d e r t o o b t a i n a s o l v e n t w i t h a low f r e e z i n g p o i n t ) , i n w h ic h t h e d i o x a n e d i s s o l v e d . An am ount o f b o r o n f l u o r i d e g a s i n e x c e s s o f t h e volum e n e e d e d f o r a 1 : 1 a d d i t i o n was a d d e d , i n s e v e r a l s m a l l a m o u n ts , b y b u b b l i n g i t s l o w l y t h r o u g h t h e c h l o r o f o r m - c a r b o n t e t r a c h l o r i d e - 1 , 3 - d io x a n e s o l u t i o n , t h e s o l u t i o n b e i n g c o o le d t o -4 0 ° C . Any b o r o n f l u o r i d e n o t t a k e n up b y t h e 1 , 3 - d i o x a n e was a b s o r b e d i n a w e ig h e d a b s o r p t i o n t u b e f i l l e d w i t h p e l l e t s o f p o t a s s i u m h y d r o x i d e . The d a t a fro m t h e two s e p a r a t e e x p e r i m e n t s a r e shown i n T a b le V. ASPIRATOR DRf ICE u A M a r it e KQ H ETMERjORt ICE ASPjRAfTO R f t «< FI6URE Z d ia ^ f w o f t h e a p p a r a t u s u s e d in t h e p r e l im in a r y w ork 0 4 THE b o r o n TMFUJORIDE — 1,3-D lO M N E ADDITION 32 TABLE V FORMATION OF THE' 1 : 1 COMPLEX OF 1,3-DIOXANE AND BORON TRIFLUORIDE IN THE PRELIMINARY WORK W e ig h t o f 1 , 3 - d i o x a n e T o t a l w e i g h t o f BFg u s e d Y feight o f BF3 n o t a b s o r b e d W eig h t o f BFg a b s o r b ed M oles o f BFg a b s o r b ed Moles o f 1 , 3 - d i o x a n e u s e d Mole c o m b in i n g r a t i o P e r c e n t - d e v i a t i o n fro m 1:1 gram s gram s grams gram s m o le s m o le s p e r c e n t 0 .8 8 0 .8 2 6 0 .2 0 7 0 .6 1 9 0 .0 0 9 1 0 0.0100 0 .9 1 0 8 .9 6 1 .7 6 1 .5 6 3 0*375 1 .1 8 8 0*0175 0.0200 0 .8 7 5 1 2 .5 The p r i n c i p a l e r r o r s i n v o l v e d i n t h e m ethod w ere t h e m e a su re m e n t o f t h e v o lu m es o f b o r o n f l u o r i d e and t h e l a c k o f i n t i m a t e m ix in g o f t h e b o r o n f l u o r i d e w i t h t h e d i o x a n e when t h e f o rm e r was b u b b le d t h r o u g h t h e s o l u t i o n o f t h e l a t t e r . S i n c e t h e e r r o r i n v o l v e d i n e a c h volum e m e a s u re m e n t was o n l y a b o u t 2 p e r c e n t , an d s i n c e t h e e r r o r s l a r g e l y te n d e d t o c a n c e l one a n o t h e r , t h e p r i n c i p a l s o u r c e o f e r r o r seems t o b e t h e se c o n d one m e n t i o n e d . T h is w ould a c c o u n t f o r t h e s l i g h t l y low com b i n i n g r a t i o s * The a d d i t i o n compound a p p a r e n t l y c r y s t a l l i z e d fro m t h e o m i x t u r e a s w h i t e n e e d l e s ' a t - 4 0 C. An a t t e m p t t o f i l t e r o u t t h e c r y s t a l s by r a p i d s u c t i o n f i l t r a t i o n f a i l e d , a s was f e a r e d i n a d v a n c e , b e c a u s e o f t h e im m e d ia te d e c o m p o s i t i o n o f t h e com p l e x b y a t m o s p h e r i c m o i s t u r e . 55 A n o th e r a t t e m p t t o e v a p o r a t e aw ay t h e c h l o r o f o r m and c a r b o n t e t r a c h l o r i d e a t 2 5 °C . t o 5 0 #C. u s i n g t h e w a t e r a s p i r a t o r f a i l e d b e c a u s e t h e com plex decom posed t o a b ro w n , v i s c o u s , a l m o s t n o n - v o l a t i l e l i q u i d b e f o r e a l l of t h e s o l v e n t had e v a p - o ra t ed • The s m a l l p o r t i o n o f t h e com plex w h ic h was s u c c e s s f u l l y s e p a r a t e d fro m t h e s o l u t i o n r e m a in e d f o r s e v e r a l h o u rs i n d r y a i r a s l o n g , w h i t e , n e e d l e - l i k e c r y s t a l s . I t i s p r o b a b l e , h o w e v e r, t h a t t h e s e c r y s t a l s c o n t a i n e d some c h l o r o f o r m o f s o l v a t i o n . I t was a t t h i s p o i n t t h a t t h e a d v a n t a g e a n d n e a r n e c e s s i t y o f a h ig h -v a c u u m a p p r o a c h t o t h e p ro b le m was d e f i n i t e l y r e c o g n i z e d • The M e n z ie s - S m ith a p p a r a t u s . A t t h e s t a r t o f t h e work i t was assum ed t h a t t h e d i s s o c i a t i o n p r e s s u r e , t e m p e r a t u r e r e l a t i o n s h i p s o f a n y o f t h e p r o p o s e d a d d i t i o n compounds c o u ld 46 b e s t u d i e d c o n v e n i e n t l y b y means o f t h e M e n z ie s - S m ith m ethod* A d ia g r a m o f t h e a p p a r a t u s c o n s t r u c t e d f o r t h i s p u r p o s e i s shown i n F i g u r e 5 . F o r d e t a i l s o f t h e e x p e r i m e n t a l t e c h n i q u e i n v o l v e d i n th e m a n i p u l a t i o n o f t h e a p p a r a t u s t h e r e a d e r i s r e f e r r e d t o t h e o r i g i n a l a r t i c l e b y M enzies and 46 A le x a n d e r S m ith and A la n W. C. M e n z ie s , " S t u d i e s i n V ap o r P r e s s u r e s I I * A S im p le Dynamic M eth o d , A p p l i c a b l e t o B o th S o l i d s an d L i q u i d s , f o r D e te r m in in g V ap o r P r e s s u r e s , and A ls o B o i l i n g P o i n t s a t S t a n d a r d P r e s s u r e s " , J o u r n a l o f t h e A m e ric a n C h e m ic a l S o c i e t y , 5 2 : 9 0 7 - 1 4 ( 1 9 1 0 ) . fC h e m ic a l A b s t r a c t s , 4 :2 5 9 5 ( 1 9 1 0 ) J . to snivavddv miws-saizNaw aw i jo wvaovw e 3 f c r i 9 U 47 S m ith . B e f o r e a t t e m p t i n g t o d e t e r m i n e t h e v a p o r t e n s i o n c u r v e o f t h e 1 , 3 - d i o x a n e o r t h e d i s s o c i a t i o n p r e s s u r e c u r v e s o f a n y a d d i t i o n compounds p r e p a r e d , i t was deemed a d v i s a b l e t o c h e c k t h e e f f i c a c y o f t h e a p p a r a t u s , t h e m ethod a n d t h e a u t h o r ’s t e c h n i q u e b y d e t e r m i n i n g t h e v a p o r t e n s i o n c u r v e o f 1 , 4 - d i o x a n e an d c o m p a rin g t h e d a t a w i t h t h o s e r e p o r t e d i n th e 4 8 ,4 9 l i t e r a t u r e . The r e s u l t s , a l r e a d y d i s c u s s e d on p a g e 2 5 , a r e l i s t e d i n T a b le IV an d p l o t t e d , t o g e t h e r w i t h t h e c a l c u l a t e d v a l u e s , i n F i g u r e 1 . The r e s u l t s a r e s a t i s f a c t o r y . When t h e a t t e m p t was made t o o b t a i n t h e v a p o r t e n s i o n c u r v e o f t h e 1 , 3 - d i o x a n e , w h ic h i s n o t g i v e n i n t h e l i t e r a t u r e an d w h ic h was n e c e s s a r y f o r t h e i n t e r p r e t a t i o n of a n y d i s s o c i a t i o n p r e s s u r e d a t a o b t a i n e d i n t h e s t u d y o f t h e c o m p le x e s , a s t r a i g h t l i n e c u r v e was o b t a i n e d when log-j^ P was p l o t t e d a g a i n s t l / T , b u t a l a t e r , and d e f i n i t e l y m ore a c c u r a t e , s t u d y e m p lo y in g t h e h ig h -v a c u u m s y s te m r e v e a l e d t h a t t h e p r e s s u r e s o b t a i n e d by t h e M e n z ie s - S m ith t e c h n i q u e 47 L o c . c i t . A. F . G a l l a u g h e r and H. H i b b e r t , ’’R e a c t i o n s R e l a t i n g t o C a r b o h y d r a t e s an d P o l y s a c c h a r i d e s . LV. V apor P r e s s u r e s o f t h e P o l y e t h y l e n e G l y c o l s and T h e i r D e r i v a t i v e s ” , J o u r n a l o f t h e A m e ric a n C h e m ic a l S o c i e t y , 5 9 :2 5 1 4 - 2 1 ( 1 9 3 7 ) . {c fie m ic a l A b s t r a c t s , 3 2 :9 1 4 (1 9 3 8 7 T ; 49 F r a n k H o v o rk a , R a lp h A. S c h a e f e r and D a le D r e i s b a c h , ’’The S y stem D io x a n e and W a t e r " , J o u r n a l o f t h e A m e ric a n C h e m ic a l S o c i e t y , 5 8 :2 2 6 4 (1936)T ( C h e m ic a l A b s t r a c t s , 31T935 Tl937TTi» 36 w e re c o n s i s t e n t l y and m a r k e d ly to o h i g h a t t h e lo w e r tem p e r a t u r e s . No p l a u s i b l e e x p l a n a t i o n o f t h i s d e v i a t i o n c o u ld b e r e c o g n i z e d . Q u a l i t a t i v e l y , a p r e l i m i n a r y c h e c k had shown no a p p a r e n t s o l u b i l i t y o f e i t h e r o f t h e d i o x a n e s i n t h e l i q u i d p e t r o l a t u m , e i t h e r d i o x a n e i m m e d i a t e l y s e p a r a t i n g fro m t h e p e t r o l a t u m a s a d i s t i n c t l a y e r a f t e r i t was s h a k e n v i g o r o u s l y w i t h t h e p e t r o l a t u m . A lth o u g h a n o t h e r f a i r l y n o n - v o l a t i l e l i q u i d , i n w h ic h t h e 1 , 3 - d i o x a n e was i n s o l u b l e , p r o b a b l y c o u ld h a v e b e e n fo u n d a f t e r s e v e r a l a t t e m p t s , i t was c o n s i d e r e d m ore e f f i c i e n t t o a b a n d o n t h e u s e o f t h e M e n z ie s - S m ith m eth o d and u s e t h e h ig h -v a c u u m a p p a r a t u s f o r t h e w o rk . Even th o u g h t h e s e d a t a f o r 1 , 3 - d i o x a n e , o b t a i n e d by t h e M e n z ie s - S m ith m e th o d , a r e u n d o u b t e d l y ' i n a c c u r a t e , t h e y a r e h e r e l i s t e d i n T a b le V I . As i n t h e d a t a f o r t h e 1 , 4 - d i o x a n e , t h e t e m p e r a t u r e s l i s t e d i n t h e t a b l e a r e c o r r e c t e d O and a r e a c c u r a t e t o t 0 . 2 C . , and t h e p r e s s u r e r e a d i n g s w ere made t o t h e n e a r e s t m i l l i m e t e r . P a r t o f t h e s e d a t a a r e com p a r e d w i t h t h e m ore a c c u r a t e d a t a , o b t a i n e d b y u s e o f t h e h ig h -v a c u u m a p p a r a t u s , i n F i g u r e 5* 37 TABLE VI THE VAPOR TENSIONS OF 1,3-DIOXANE BY THE MENZIES-SMITH METHOD T e m p e ra tu r e V apor ( l / T ) 1 0 3 T e m p e ra tu r e V ap o r ( l / T ) 1 0 3 t e n s i o n t e n s i o n ° C . mm. l / ° A . ° c . mm. l / ° A . 2 6 .7 38 3 .3 3 6 7 3 .3 293 2 .8 8 7 2 9 . 6 43 3 .3 0 4 7 5 . 2 . 313 2 .8 7 1 3 1 . 3 47 3 .2 8 5 7 7 . 4 338 2 .8 5 3 4 9 . 4 111 3 .1 0 1 7 9 . 5 363 2 . 8 3 6 5 1 .2 122 3 .0 8 4 8 1 .3 386 2 .8 2 2 5 2 .8 131 3 .0 6 8 8 3 .3 406 2 .8 0 6 5 5 . 1 143 3 .0 4 7 8 5 .4 434 2 .7 8 9 5 7 .2 157 3 .0 2 8 8 7 .6 461 2 .7 7 2 5 9 .2 170 3 .0 0 9 8 9 .2 488 2 .7 6 0 6 1 .0 182 2 .9 9 3 9 1 . 4 517 2 .7 4 3 6 3 .3 198 2 .9 7 3 9 2 .2 526 2 .7 3 8 6 5 .0 216 2 .9 5 8 9 3 .2 539 2 .7 3 0 6 7 .2 232 2 .9 3 9 9 4 .2 552 2 .7 2 3 6 9 .4 249 2 .9 2 0 9 5 .1 560 2 .7 1 6 7 1 .3 271 2 .9 0 4 I I . HIGH-VACUUM WORK The v a p o r t e n s i o n s o f 1 , 3 - d i o x a n e . The v a p o r t e n s i o n c u r v e o f 1 , 3 - d i o x a n e was d e t e r m i n e d i n t h e b u l b show n, w i t h I t s a t t a c h e d a c c e s s o r i e s , I n F i g u r e 4 . The b u l b i s c o n s t r u c t e d so t h a t t h e m e r c u r y l e v e l can b e d ra w n down b e lo w t h e p o i n t m arked !IAH i n F i g u r e 4 , i n o r d e r t h a t s u b s t a n c e s c a n b e c o n d e n s e d i n t o o r d i s t i l l e d o u t o f t h e b u l b p r o p e r . When t h e m e r c u r y r e s e r v o i r i s c o n n e c te d 38 m m m r m P i a u R E 4* DlftQRAM OF THE BULB « S tO m ^ H ) S H - V « U W WORK ON VftPORTEHSIOWS mo DISSOCIATION PRESSURES 39 w i t h t h e a t m o s p h e r e b y t u r n i n g t h e t h r e e - w a y s t o p c o c k m arked " B " , an d t h e g r o u n d - g l a s s ro d HC” l i f t e d , m e r c u r y may b e f o r c e d up i n t o t h e m an o m eter s p a c e a s t h e p r e s s u r e w i t h i n t h e b u l b i n c r e a s e s . I f t h e p r e s s u r e w i t h i n t h e b u l b i s d e c r e a s i n g , t h e m e r c u r y l e v e l s may b e lo w e re d b y t u r n i n g s t o p c o c k ,rB” so t h a t t h e m e r c u ry r e s e r v o i r i s c o n n e c t e d w i t h t h e w a t e r a s p i r a t o r . The l e f t - h a n d s i d e o f t h e m an o m eter i s c o n n e c te d t o t h e m a in p a r t o f t h e h ig h -v a c u u m a p p a r a t u s . The p r e s s u r e i n t h e m a in a p p a r a t u s was c o n s t a n t l y c h e c k e d b y a McLeod g a u g e and was k e p t w i t h i n t h e l i m i t s , 10 ram. — 5 and 10 mm. A l a r g e sa m p le o f t h e p u r i f i e d 1 , 3 - d i o x a n e was c o n - Q d e n s e d i n t o t h e b u l b by a d r y - i c e - e t h e r b a t h ( - 8 0 C .) and v a p o r t e n s i o n r e a d i n g s made b y means o f a c a t h e t o m e t e r , a c c u r a t e t o £ 0 . 0 5 mm., a t v a r i o u s t e m p e r a t u r e s . F o r a h e a t in g b a t h a t w o - l i t e r b e a k e r , w h ic h s u r r o u n d e d b o t h t h e b u lb and m e r c u ry r e s e r v o i r , was u s e d . The b e a k e r was f i l l e d w i t h enough w a t e r t o come a t l e a s t two i n c h e s a b o v e t h e to p o f t h e e n c l o s e d b u l b , warmed w i t h a g a s b u r n e r , and t h e w a t e r s t i r r e d w i t h a s t i r r i n g r o d b y h a n d . T e m p e ra tu r e s w e re h e l d O c o n s t a n t w i t h i n 0 . 1 C, f o r fro m two t o f i v e m i n u t e s f o r e a c h r e a d i n g , and w e re r e a d t o t h e n e a r e s t 0 .1 ° C . on a c a l i b r a t e d o 20 0 C. th e r m o m e te r . The t e m p e r a t u r e r e a d i n g s w e re c o r r e c t e d o f o r ex p o se d s te m and a r e p r o b a b l y a c c u r a t e t o ± 0 . 1 C. f o r t e m p e r a t u r e s up t o a b o u t 7 5 °C . an d t o ± 0 . 2 ° C . fro m 7 5 °C . t o 1 0 0 °C . 40 The d a t a a r e g i v e n i n T a b le V II and t h e lo g -j^ P , l / T c u r v e g i v e n i n F i g u r e 5* The p r e v i o u s d a t a on t h e v a p o r t e n s i o n s o f 1 , 3 - d i o x a n e , d e t e r m i n e d b y t h e M e n z ie s - S m ith m eth o d ( s e e p a g e , 3 7 , T a b le V I ) , a r e a l s o p l o t t e d i n F i g u r e 5* TABLE V II THE VAPOR TENSIONS OF 1,3-DIOXANE BY THE HIGH-VACUUM METHOD T e m p e ra tu r e V apor t e n s i o n ( l / T ) 1 0 5 E x p T tl . C a l c . ° c . mm. mm. l / ° A . 3 7 . 9 4 4 .1 3 .2 1 5 4 0 .2 5 0 .9 -------- 3 .1 9 2 4 2 .8 5 8 .3 -------- 3 .1 6 6 4 4 .9 66.1 -------- 3 .1 4 5 4 7 .7 7 5 . 8 -------- 3 .1 1 7 5 0 .3 88.2 88.1 3 .0 9 2 5 2 .8 9 8 .6 9 9 .1 3 .0 6 8 5 5 .0 1 1 0 .5 1 0 9 .6 3 .0 4 8 5 8 .0 1 2 5 .4 1 2 6 .2 3 .0 2 0 6 2 .0 1 5 1 .2 1 5 1 .0 2 .9 8 4 The d a t a do n o t q u i t e f a l l on a s t r a i g h t l i n e when l o g P i s p l o t t e d v e r s u s l / T , b u t r e v e a l a s l i g h t c o n v e x n e s s . S i n c e t h e f i v e d a t a a t t h e h i g h e s t t e m p e r a t u r e s a r e m o st i n a c c o r d w i t h t h e o b s e r v e d and l i t e r a t u r e v a l u e s f o r t h e b o i l i n g p o i n t o f 1 , 3 - d i o x a n e , o n ly t h e s e f i v e w e re u s e d i n t h e compu t a t i o n o f t h e v a p o r t e n s i o n e q u a t i o n . ( N o te : a l l m a th e m a t i c a l e q u a t i o n s p r e s e n t e d i n t h i s t h e s i s w e re c a l c u l a t e d fro m V apor T e n s io n (mm*) 41 7500 600 SOQ 400 300 200 100 80 60 50 P l g i m q E ' _______ TJ-ie Vapoi*- Tene-£-<»*& ■- o f l,3-j«DiPJcan!i C ) “ H i g j i ^ r a c t t t n i P a t t e n 0 = P r o 1 fttjina < 3a turn So IQ 3.4 3.5 3.1 3.0 2.9 42 t h e d a t a b y t h e m ethod o f l e a s t s q u a r e s ) . T h ese f i v e d a t a g i v e t h e r e l a t i o n s h i p , l o g 10P(inm.) =• 8 .6 5 2 - 2 1 6 9 /T . Prom t h i s e q u a t i o n t h e n o rm a l b o i l i n g p o i n t o o f 1 , 3- d i o x a n e i s c a l c u l a t e d t o b e 1 0 2 .7 C. an d t h e l a t e n t h e a t o f v a p o r i z a t i o n t o b e 9920 * 4 0 g r a m - c a l o r i e s p e r m o le . The T r o u to n c o n s t a n t i s th e n 2 6 . 4 g r a m - c a l o r i e s p e r d e g r e e p e r m o le , a r a t h e r h i g h v a l u e ( t h e T r o u to n c o n s t a n t f o r 1 , 4 - d i o x a n e i s 2 3 . 7 ) . A d d i t i o n compounds o f 1 , 3 - d i o x a n e a n d b o r o n f l u o r i d e . The f i r s t h ig h -v a c u u m w ork do n e b y t h e a u t h o r i n a n a t t e m p t t o form b o t h a 1:1 and a 2:1 a d d i t i o n compound r e v e a l e d two i m p o r t a n t f a c t s : ( 1 ) t h a t b o r o n f l u o r i d e i s e v i d e n t l y s o l u b l e i n t h e l i q u i d o b t a i n e d b y t h e a c t i o n o f b o r o n f l u o r i d e on 1 , 3 - d i o x a n e , and (2 ) t h a t b o r o n f l u o r i d e e v i d e n t l y d i s r u p t s t h e 1 , 3 - d i o x a n e m o l e c u l e on s t a n d i n g w i t h t h e l a t t e r f o r s e v e r a l h o u r s , w i t h t h e f o r m a t i o n o f a n a l m o s t n o n v o l a t i l e , v i s c o u s brow n l i q u i d , and p o s s i b l e o t h e r n o n v o l a t i l e p r o d u c t s . The d e c o m p o s i t i o n o f 1 , 3 - d i o x a n e b y b o r o n f l u o r i d e to fo rm t h e brow n l i q u i d had b e e n p r e v i o u s l y n o t e d i n t h e p r e l i m i n a r y w o rk ( s e e p a g e 3 3 ) . As a r e s u l t o f t h e s e two c o m p l i c a t i o n s , s a m p le s w h ic h w e re w orked w i t h a t f i r s t g a v e a p p a r e n t c o m b in in g r a t i o s o f 1 . 4 3 : 1 and 1 . 8 8 : 1 . H ow ever, t h r e e o t h e r s a m p le s w h ic h w ere h a n d le d m ore r a p i d l y p ro d u c e d d a t a w h ic h d e f i n i t e l y e s t a b l i s h t h e 1 : 1 r a t i o . T h e se d a t a a r e l i s t e d i n T a b le V I I I . ' (N o te : fro m t h i s p o i n t o n , a l l volum es r e p o r t e d a r e u n d e r s t o o d t o b e 43 g a s e o u s v o lu m es a t s t a n d a r d t e m p e r a t u r e an d p r e s s u r e ) , TABLE V I I I FORMATION OF THE 1 : 1 COMPLEX OF 1,3-DIOXANE AND BORON TRIFLUORIDE IN THE HIGH-VACUUM WORK E x p e rim e n t num ber 1 2 3 O r i g i n a l volum e o f b f 3 11.8 c c . 2 .0 7 c c . 3 5 . 8 c c . O r i g i n a l volum e o f 1 , 3 - d i o x a n e 3 . 6 7 cc * 3 . 6 1 c c . 1 4 .1 c c . Volume o f BF3 a b s o r b e d 4 . 02 c c , 2 .0 7 cc • 1 4 .9 c c . Volume o f 1 , 3 - d i o x a n e a b s o r b e d 3 . 6 7 c c . 1 .7 6 c c . 1 4 .1 c c . Mole c o m b in in g r a t i o 1 . 10:1 1 . 1 8 :1 1 . 0 6 : 1 P e r c e n t a g e d e v i a t i o n fro m 1:1 • o H 1 8 . % 6.0 % S i n c e e v e n l a r g e e x c e s s e s o f b o r o n f l u o r i d e f a i l e d t o p r o d u c e a c o m b in in g r a t i o g r e a t e r t h a n 1:1 ( e x c e p t on d e c o m p o s in g ) , w i t h i n t h e l i m i t s o f e x p e r i m e n t a l e r r o r , t h e e x i s t e n c e o f a n y 2:1 com p lex i s d i s p r o v e d , a t l e a s t f o r t h e c o n d i t i o n s em ployed i n t h i s w o rk . A v e r a g in g t h e t h r e e m o le co m b in in g r a t i o s g i v e n i n T a b le V I I I and t h e two g i v e n i n T a b le V p r o d u c e s a n a v e r a g e r a t i o o f 1 . 0 2 : 1 , 44 The sa m p le i n w h ic h 2 . 0 7 c c . o f b o r o n f l u o r i d e a b s o r b e d 1 .7 6 c c . o f 1 , 3 - d i o x a n e was s t u d i e d i n a n e f f o r t t o o b t a i n t h e d i s s o c i a t i o n p r e s s u r e c u r v e o f t h e 1:1 c o m p le x . The d a t a o b t a i n e d a r e l i s t e d i n T a b le IX and t h e d i s s o c i a t i o n p r e s s u r e c u r v e p l o t t e d i n F i g u r e 6 . The c u r v a t u r e o f t h e lo w e r p o r t i o n o f t h e c u r v e may i n d i c a t e t h e r e l e a s e o f b o r o n f l u o r i d e d i s s o l v e d b y t h e 1 : 1 c o m p le x . On t h e o t h e r h a n d , t h e s t e e p e r s l o p e o f t h e u p p e r p o r t i o n o f t h e c u r v e may i n d i c a t e i r r e v e r s i b l e d e c o m p o s i t i o n o f t h e c o m p le x . The d e c o m p o s i t i o n o f t h e com p lex o b s e r v e d i n b o t h t h e p r e l i m i n a r y an d t h e h ig h -v a c u u m w o rk l e n d s w e i g h t t o t h e s e c o n d a l t e r n a t i v e . TABLE IX DISSOCIATION DATA OF THE 1,3-DIOXANE 1 : 1 BORON COMPLEX TRIFLUORIDE— T e m p e r a tu r e T o t a l d i s s o c i a t i o n p r e s s u r e ( l / T ) 1 0 3 Ka t m . x l° 5 . o o mm. l / ° A . a t m .^ 3 6 . 5 5 .2 3 .2 3 0 1.2 5 0 .4 6 . 4 3 .0 9 1 1.8 6 0 .0 8 . 4 3 .0 0 2 3 . 0 7 0 . 5 12.0 2 .9 1 0 6 .2 3 8 0 .6 1 8 .0 2 .8 2 7 1 4 .0 8 3 .0 1 9 .8 2 .8 0 8 1 7 .0 D i s s o c i a t i o n P r e s s u r e (rtcie) 1 0 0 do so 4Q z o rP h .© : D i s s o c i a t i o n t P n e s s u r s s ©f tiib l s l Bb"On T.cifiuo:<:-i^O' 1 . 5-'D:iokano C otto los e _ 3.4 3.Z 3.3 3 . 0 46 The d i s s o c i a t i o n p r e s s u r e m e a s u re m e n ts w e re t a k e n w i t h t h e b u l b i l l u s t r a t e d i n F i g u r e 4 . The v o lu m e o f t h e b u l b i s 165*6 c c . m in u s 0 . 7 tim e s t h e d i s t a n c e i n c e n t i m e t e r s fro m t h e to p o f t h e r i g h t - h a n d m e r c u ry colum n t o t h e p o i n t m arked "A1 1 i n t h e d i a g r a m . S i n c e a t o t a l o f 3 . 8 3 c c , o f g a s a t S . T . P . ( 2 .0 7 c c . b o r o n f l u o r i d e p l u s 1 . 7 6 c c . 1 , 3 - d i o x a n e ) was u s e d t o fo rm t h e a d d i t i o n com pound, a c o m p u t a t i o n shows t h a t i f t h e com plex w e re c o m p l e t e l y v a p o r i z e d and c o m p l e t e l y O d i s s o c i a t e d a t 8 3 .0 C ., t h e o b s e rv e d p r e s s u r e s h o u ld b e 2 3 . 2 o mm. The p r e s s u r e a c t u a l l y o b s e rv e d a t 83*0 C. was 19*8 mm. ( s e e T a b le I X ), a d e v i a t i o n o f 15 p e r c e n t . I f t h e s e d a t a a r e v a l i d , i t w ould a p p e a r t h a t t h e co m p lex i s a t l e a s t a l m o s t e n t i r e l y d i s s o c i a t e d i n t h e v a p o r s t a t e . U n f o r t u n a t e l y , a l a c k o f tim e p r e v e n t e d t h e d a t a fro m b e i n g e x t e n d e d u p w ards o t o a b o u t 100 C. ( d e c o m p o s i t i o n o c c u r r e d s o o n a f t e r t h e 8 3 .0 C. r e a d i n g was t a k e n ) . I f t h i s had b e e n d o n e , t h e c u r v e i n F i g u r e 6 m ig h t h a v e shown a s h a r p d e c r e a s e i n s l o p e a t t h e t o p , t h e r e b y d e f i n i t e l y e s t a b l i s h i n g t h e c o m p le te d i s s o c i a t i o n o f t h e v a p o r . L i k e w is e , i t w ould h a v e b e e n h i g h l y v a l u a b l e t o o b t a i n d a t a a s t h e t e m p e r a t u r e was d e c r e a s i n g , so a s t o t e l l w h e t h e r t h e r e a c t i o n i n v o l v e d was r e a l l y a r e v e r s i b l e d i s s o c i a t i o n o r m e r e l y a n i r r e v e r s i b l e d e c o m p o s i t i o n . The v a l i d i t y o f n e i t h e r p o r t i o n o f t h e c u r v e i n F i g u r e 6 i s c e r t a i n , and e i t h e r o n e g i v e s a v a l u e f o r t h e t e m p e r a t u r e a t w h ic h t h e d i s s o c i a t i o n p r e s s u r e e q u a l s 380 mm. h i g h e r t h a n M 5 -r # 0 0 c i ) * ■ o . ( l/T 48 t h a t f o r t h e 1 , 4 - d i o x a n e a n a l o g u e . H ence, i t seems l i k e l y t h a t n e i t h e r o f t h e s e p o r t i o n s o f t h e c u r v e r e p r e s e n t s t h e r e v e r s i b l e d i s s o c i a t i o n o f t h e 1 , 3 - d i o x a n e — b o r o n f l u o r i d e c o m p le x . A d d i t i o n compounds o f 1 , 4 - d i o x a n e and b o r o n f l u o r i d e . The f i r s t h ig h -v a c u u m w o rk a t t e m p t e d w i t h t h e a d d i t i o n o f e x c e s s b o r o n f l u o r i d e t o 1 , 4 - d i o x a n e r e v e a l e d t h a t e i t h e r a 2:1 com plex fo rm e d s l o w l y fro m a 1:1 c o m p le x , o r e l s e t h e 1 , 4 - d i o x a n e was b e i n g decom posed by t h e b o r o n f l u o r i d e . The f a c t t h a t no e v i d e n c e o f d e c o m p o s i t i o n c o u ld b e d e t e c t e d an d t h a t t h e p r o d u c t was w h i t e , c r y s t a l l i n e , and r e a d i l y s u b lim e d c a u s e d t h e se c o n d h y p o t h e s i s t o b e d i s c a r d e d . E v i d e n t l y b o t h a 1:1 a n d a 2:1 com p lex w e re b e i n g f o rm e d . An a t t e m p t t o fo rm t h e 1 : 1 com p lex i n t h e p u r e fo rm was m ade, u s i n g e x c e s s d i o x a n e . 1 .4 7 c c . o f b o r o n f l u o r i d e w e re c o n d e n s e d w i t h 4 . 5 3 c c . o f 1 , 4 - d i o x a n e i n t h e b u l b shown i n F i g u r e 4 b y means o f a Dewar f l a s k f i l l e d w i t h l i q u i d a i r . A f t e r t h e m i x t u r e had b e e n warmed t o room t e m p e r a t u r e a n d r e - c o n d e n s e d w i t h l i q u i d a i r s e v e r a l t i m e s , i t showed r e p r o d u c i b l e p r e s s u r e s . The e x c e s s v a p o r was e v i d e n t l y 1 , 4 - d i o x a n e , o s i n c e i t s o l i d i f i e d i m m e d i a t e l y a t 0 C . , d e c r e a s i n g t h e p r e s s u r e t o l e s s t h a n 1 mm. C o m p u ta tio n showed t h a t of t h e 4 . 5 3 c c . o f 1 , 4 - d i o x a n e u s e d , o n l y 1 .5 6 c c . had r e a c t e d w i t h t h e b o r o n f l u o r i d e . T h is g i v e s a v a l u e o f 0 . 9 4 2 : 1 f o r t h e m o le c o m b in in g r a t i o o f b o r o n f l u o r i d e t o 1 , 4 - d i o x a n e , a d e v i a t i o n o f o n l y 5 . 8 p e r c e n t fro m t h e t h e o r e t i c a l 1 : 1 r a t i o . 49 The d i s s o c i a t i o n p r e s s u r e d a t a o f t h e 1 : 1 com plex a r e l i s t e d i n T a b le X an d a r e p l o t t e d i n F i g u r e 8 , TABLE X DISSOCIATION DATA OF THE 1 : 1 BORON TRIFLUORIDE— 1,4-DIOXANE COMPLEX T e m p e ra tu r e T o t a l d i s s o c i a t i o n p r e s s u r e ( l / T ) 1 0 3 ^ a tm . x lO 5 Exp* t l . C a l c . E x p f t l . C a l c . ° c . mm. mm. l / ° A . a t m .^ a t m .^ 5 6 .7 5 . 2 5 .2 3 .0 3 2 1.2 1.2 6 5 .7 8 . 3 8 . 4 2 .9 5 2 3 . 0 3 . 1 7 1 . 0 1 1 .3 11.1 2 .9 0 6 5 .5 3 5 .3 1 7 8 .6 1 4 .9 mm mm 2 .8 4 3 — ~ 9 2 . 0 1 7 .7 — . 2 .7 3 9 — — 8 1 .6 1 6 .2 — 2 .8 1 9 •M M — 7 5 . 5 1 3 . 8 1 3 .9 2 .8 6 9 8 .2 4 8 . 2 8 The com p lex e x i s t e d i n t h e fo rm o f w h i t e , n e e d l e - l i k e c r y s t a l s w h ic h m e l t e d a t a p p r o x i m a t e l y 5 0 ° C ., a l t h o u g h t h e m e l t i n g p o i n t was o n l y r o u g h l y e s t i m a t e d * S i n c e a t o t a l o f 3*0 3 c c . o f v a p o r was u s e d ( 1 .4 7 c c , o f b o r o n f l u o r i d e p l u s 1 . 5 6 c c . o f 1 , 4 - d i o x a n e ) , t h e t h e o - O r e t i c a l d i s s o c i a t i o n p r e s s u r e a t 9 2 . 0 C . , a s s u m in g c o m p le te v a p o r i z a t i o n and c o m p le te d i s s o c i a t i o n o f t h e com plex i s o 1 8 .7 ram. The p r e s s u r e o b s e r v e d a t 9 2 . 0 C. was 1 7 .7 mm. ( s e e T a b le X ), a d i f f e r e n c e o f o n l y 5 . 3 p e r c e n t . I t i s p o s s i b l e , 109 90 d o 51 h o w e v e r, t h a t t h e d i s s o c i a t i o n i s n o t a c t u a l l y 100 p e r c e n t , s i n c e a t t h e p o i n t w h e re t h e s h a r p b r e a k o c c u r s i n F i g u r e 8 (P = 1 4 .4 mm., l / T = 0 . 0 0 2 8 6 8 / ° A . ) a c a l c u l a t i o n shows t h e d i s s o c i a t i o n p r e s s u r e t o b e o n ly 8 0 .5 p e r c e n t o f t h e t h e o r e t i c a l , w h e re a s a t a h i g h e r t e m p e r a t u r e (P = 1 8 .2 mm., l / T ** 0 . 0 0 2 7 2 5 / ° A . ) t h e d i s s o c i a t i o n p r e s s u r e h a s becom e 9 6 .7 p e r c e n t o f t h e t h e o r e t i c a l . I t w ould t h u s a p p e a r t h a t t h e s h a r p b r e a k i n t h e c u r v e i n F i g u r e 8 d e n o t e s t h e p o i n t a t w h ic h t h e com plex was c o m p l e t e l y v a p o r i z e d , an d t h a t a b o v e t h i s te m p e r a t u r e t h e v a p o r i z e d com p lex g r a d u a l l y becam e m ore c o m p l e t e l y d i s s o c i a t e d . H ow ever, s i n c e t h e a p p a r e n t d i s s o c i a t i o n s a r e s o n e a r 100 p e r c e n t , th e y c o u ld e a s i l y b e c a u s e d b y a s y s te m a t i c e x p e r i m e n t a l e r r o r o r by v a n d e r W aals f o r c e s , h e n c e t h e lo w e r p o r t i o n o f t h e c u r v e i n F i g u r e 8 i s c o n s i d e r e d t o r e p r e s e n t t h e e q u i l i b r i u m b e tw e e n l i q u i d c o m p lex and g a s e o u s b o r o n f l u o r i d e and 1 , 4 - d i o x a n e . The lo w e r p o r t i o n o f t h e c u r v e i n F i g u r e 8 may b e r e p r e s e n t e d b y t h e e q u a t i o n , l o g ^ P (mm*) =* 8.666 - 2 6 2 2 /T . Ac c o r d i n g t o t h i s e q u a t i o n , t h e com plex h a s a d i s s o c i a t i o n p r e s s u r e o f 760 mm. a t 1 8 0 °C . AH f o r t h e r e a c t i o n , l , 4-C4HQ0g*BF3 ( >■ l^ - C ^ H g O g (Q) + ■ BF3 ( q ) , i s 2 3 >500±500 g r a m - c a l o r i e s p e r m o le , a s c a l c u l a t e d fro m t h e e q u a t i o n , l ° S i o ^ a t m = - 5 1 4 6 /T ( s e e F i g u r e 9 ) , w h ere K ^ . = pc4H802 x PBF3 • A F ggs e9u a l s 9 0 0 0 i2 0 0 g r a m - c a l o r i e s p e r m o le . loo 90 7 0 C L Q 5 0 4Q |® P e _ 9 !Uie C o n s t a n t s a t h e t>£i i a a c i a t i c m B ea cation a t h s ' 1 .;B oron| ^±flu<j>ricl ex 3-p^rl>i-OXane Comp' 3.10 2.90 2.80 3. 00 3.05 53 I n a n e f f o r t to p r e p a r e a sa m p le o f t h e i n d i c a t e d 2:1 co m p le x , t h e sa m p le j u s t d i s c u s s e d o f t h e 1:1 com p lex was t r e a t e d w i t h m ore b o r o n f l u o r i d e . Of t h e 6 .9 9 c c . o f a d d i t i o n a l b o r o n f l u o r i d e o n l y 1 .8 1 c c . was a b s o r b e d a t -8 0 ° C . , m ak in g t h e c o m b in in g r a t i o now 2 . 0 9 : 1 , s i n c e t h e t o t a l volum e o f b o r o n f l u o r i d e a d d e d t o t h e 1 , 5 6 c c . o f 1 , 4 - d i o x a n e was 1 .4 7 c c . p l u s 1 .8 1 c c . , o r 3 . 2 8 c c . T h is r a t i o d i f f e r s b y o n l y 4 . 5 p e r c e n t fro m t h e t h e o r e t i c a l 2 : 1 r a t i o . The co m p lex was i n t h e fo rm o f w h i t e , r o d - l i k e c r y s t a l s w h ic h r e a d i l y s u b l i m e d . The c r y s t a l s m e l t e d a t a b o u t 71° C. The d i s s o c i a t i o n p r e s s u r e d a t a of t h e 2 : 1 com p lex a r e l i s t e d i n T a b le X I, an d r e p r e s e n t e d g r a p h i c a l l y i n F i g u r e 1 0 . E v i d e n t l y t h e d i s s o c i a t i o n o f t h e com plex i s r e a d i l y r e v e r e - s i b l e , s i n c e t h e t e m p e r a t u r e s a r e l i s t e d i n T a b le XI i n t h e same o r d e r i n w h ic h t h e m e a s u re m e n ts w ere t a k e n . A s l i g h t t e m p e r a t u r e l a g i s i n d i c a t e d b y t h e d a t a . I f t h e com plex w e re c o m p l e t e l y v a p o r i z e d an d d i s s o c i - O a t e d a t 9 6 . 5 C . , t h e d i s s o c i a t i o n p r e s s u r e s h o u ld b e 3 0 . 3 mm. The d i s s o c i a t i o n p r e s s u r e a c t u a l l y o b s e r v e d a t 9 6 .5 ° C . was 2 6 . 9 mm. ( s e e T a b le X I ) . T h is v a l u e d i f f e r s by 11 p e r c e n t fro m t h e t h e o r e t i c a l 3 0 . 3 mm. The c o m p le te d i s s o c i a t i o n o f t h e v a p o r i s , h o w e v e r, n o t c o m p l e t e l y c e r t a i n , s i n c e a t t h e s h a r p b r e a k i n t h e c u r v e i n F i g u r e 10 (P 2 4 . 7 mm., l / T as 0 .0 0 2 8 0 5 ) t h e p r e s s u r e i s D i s s o c i a t i o n P r e s s u r e (ran®) 54 lOP 9 0 80 60 5 0 4 - Q 30 - XQ TH aO oeia tiO rt P r o s Our on f 2 : t Boron* T rix lu ip rl'd o <k»aple5£ os Z.S5 ( l / T ° A . ) x !0‘ 3.00 55 o n l y 84*5 p e r c e n t o f w h a t i t w ould b e f o r c o m p le te d i s s o c i a t i o n , w h i l e a t a h i g h e r t e m p e r a t u r e (P as 2 7 . 0 mm., l / T — 0 .0 0 2 7 0 0 ) t h e p r e s s u r e o b s e r v e d i s 8 8 . 8 p e r c e n t o f t h e t h e o r e t i c a l * TABLE XI DISSOCIATION DATA OP THE 2 : 1 BORON TRIFLUORIDE— 1,4-DIOXANE COMPLEX T e m p e ra tu r e T o t a l d i s s o c i a t i o n p r e s s u r e ( l / T ) 1 0 3 a tm . x lO 7 E x p ’ t l * C a l c . E x p 1t l . C a l c . ° c . mm* mm* l / ° A . a tm . ^ a t m .^ 6 0 .4 5 . 0 5 .3 2 .9 9 8 0 .4 2 0 . 5 1 7 0 . 7 1 0 .4 1 0 .8 2 .9 0 9 3 . 7 8 4 . 2 7 7 5 .7 1 5 . 0 1 5 .0 2 .8 6 7 1 1 .4 1 1 .4 8 1 . 0 2 1 .3 2 1 .0 2 .8 2 4 3 2 . 6 3 1 . 3 8 6 .3 2 4 . 9 — 2 .7 8 2 — — 90*6 2 5 .9 — 2 . 7 5 0 — 9 6 . 5 2 6 .9 — 2 .7 0 6 mt mm 0m mm 8 5 .2 2 4 .9 - - 2 .7 9 1 — — 8 0 .7 2 1 . 0 2 0 .7 2 .8 2 6 3 1 . 2 2 9 . 6 7 6 . 3 1 5 .7 1 5 .6 2 .8 6 2 1 3 . 0 1 2 .8 7 0 . 7 1 0 .9 1 0 .8 2 .9 0 9 4 . 3 6 4 . 2 7 6 5 .7 7 .7 7 . 7 2 .9 5 2 1 . 5 1 . 5 6 0 .7 5 . 6 5 . 5 2 .9 9 6 0 .5 9 0 . 5 5 5 5 .7 4 . 0 3 . 8 3 .0 4 1 0 .2 2 0 .1 9 T h e se d i s c r e p a n c i e s e x i s t i n g b e tw e e n t h e o b s e r v e d d i s s o c i a t i o n p r e s s u r e s an d t h o s e c a l c u l a t e d f o r 100 p e r c e n t d i s s o c i a t i o n o f t h e v a p o r may b e d u e t o e x p e r i m e n t a l e r r o r o r t o v a n d e r W aals f o r c e s . C e r t a i n l y t h e v a p o r s may b e c o n s i d e r e d 56 t o b e h a v e e s s e n t i a l l y a s i d e a l g a s e s , h o w e v e r, a t s u c h low p r e s s u r e s , e v e n th o u g h t h e t e m p e r a t u r e s a r e n o t p a r t i c u l a r l y h ig h * A d e f i n i t e p o s s i b i l i t y i s t h a t a s m a l l p o r t i o n o f t h e 2 : 1 co m p lex d i s s o c i a t e s i n t o t h e 1 : 1 co m p le x an d b o r o n f l u o r i d e r a t h e r t h a n i n t o d i o x a n e a n d b o r o n f l u o r i d e . N e v e r t h e l e s s , i t seem s r e a s o n a b l y w e l l e s t a b l i s h e d t h a t t h e ' l o w e r p o r t i o n o f t h e c u r v e i n F i g u r e 10 r e p r e s e n t s t h e e q u i l i b r i u m b e tw e e n s o l i d a n d l i q u i d 2 : 1 co m p lex ( t h e h e a t o f f u s i o n o f t h e co m p lex i s e v i d e n t l y v e r y s m a l l , a s t h e c u r v e shows no c h a n g e i n s l o p e i n t h e n e ig h b o r h o o d o f t h e m e l t i n g p o i n t of t h e co m p lex ) an d d i o x a n e an d b o r o n f l u o r i d e v a p o r* The u p p e r p o r t i o n o f t h e c u r v e r e p r e s e n t s m e r e l y t h e t h e r m a l e x p a n s i o n o f t h e v a p o r s . The lo w e r p o r t i o n o f t h e c u r v e i n F i g u r e 10 may b e r e p r e s e n t e d b y t h e e q u a t i o n , log-j^P (mm.) =■ 1 0 .9 5 9 - 3412/ t * O T h is e q u a t i o n g i v e s 149 C. a s t h e t e m p e r a t u r e a t w h ic h t h e d i s s o c i a t i o n p r e s s u r e o f t h e com plex becom es e q u a l to 760 o mm., o r 159 C. a s t h e t e m p e r a t u r e a t w h ic h t h e p a r t i a l p r e s s u r e o f 1 , 4 - d i o x a n e e q u a l s 380 mm. AH f o r t h e r e a c t i o n , 1 ,4 - C 4Hq02*2BF3 ( s , l ) 1 #4 " C4H8 °2 ( G) 2 BF3 (G) * i s 4 7 ,0 0 0 * 3 0 0 0 g r a m - c a l o r i e s p e r m o le , a s c a l c u l a t e d fro m t h e e q u a t i o n , l o S ^ K ^ ^ * = ■ 2 3 ,3 7 4 - 10226/ t ( s e e F i g u r e 1 1 ) , w h ere ^atra. = PC4H802 x PbF3 • AP29 8 “ 1 5 ,0 0 0 * 1 0 0 0 g r a m - c a l o r i e s p e r m ole* Katm*xlu‘ 70 60 5 0 40 h : ^ =^*r — 3o£53t: ZPL ■ < ffl !H,ea-<u; j,on ^ t l ^ i x r c n d i d f e : 10 3.10 3.05 3.00 2.80 CHAPTER V DISCUSSION The r e s u l t s o b t a i n e d i n t h i s i n v e s t i g a t i o n seem t o i n d i c a t e t h a t t h e 1 : 1 a n d 2 : 1 co m p lex es o f b o r o n f l u o r i d e and 1 , 4 - d i o x a n e a r e o f s i m i l a r s t a b i l i t y , a s i n t h e c a s e o f 50 t h e s u l f o t r i o x i d e c o m p lex es d i s c u s s e d on p a g e 1 8 . H ow ever, t h e 2 : 1 com plex i s d e f i n i t e l y , th o u g h s l i g h t l y , l e s s s t a b l e t h a n t h e 1 : 1 co m p lex , t h e l a t t e r p r o d u c i n g a d i o x a n e p a r t i a l p r e s s u r e o f 380 mm. a t 1 8 0 ° C ., t h e f o r m e r a t 159 C. T h is r e s u l t i s q u a l i t a t i v e l y i n a c c o r d w i t h p r e v i o u s e x p e c t a t i o n s . The f a c t t h a t t h e h e a t o f d i s s o c i a t i o n o f t h e 2 : 1 com p l e x i s j u s t t w i c e t h a t o f t h e 1 : 1 com plex a l s o i n d i c a t e s t h a t t h e B -0 bond e n e r g y i s p r a c t i c a l l y t h e same i n t h e two com p o u n d s . T h is i s o n ly a ro u g h c h e c k , s i n c e b o t h AH v a l u e s a r e s u b j e c t t o r a t h e r l a r g e u n c e r t a i n t i e s an d s i n c e h e a t s o f v a p o r i z a t i o n o f t h e co m p le x e s w e re n o t c o n s i d e r e d . S i n c e t h e 2 : 1 com plex i s s l i g h t l y l e s s s t a b l e t h a n t h e 1 : 1 c o m p le x , i t seem s l i k e l y t h a t t h e h e a t o f v a p o r i z a t i o n o f t h e 2 : 1 compound i s g r e a t e r t h a n t h a t o f t h e 1 : 1 com pound. The f a c t t h a t t h e 2 : 1 compound h a s a h i g h e r m e l t i n g p o i n t t h a n h a s t h e 1 : 1 compound i s i n a c c o r d w i t h t h i s r o u g h d e d u c t i o n . 50 C. M. S u t e r , P . B . Evans a n d James M. K i e f e r , " D io x a n e S u l f o t r i o x i d e , a New S u l f a t i n g a n d S u l f o n a t i n g A g e n t” , J o u r n a l of t h e A m e ric a n C h e m ic a l S o c i e t y , 6 0 :5 3 8 - 4 0 ( 1 9 3 8 ) . ~ ( C h e m ic a l A b s t r a c t s , 3 2 :3 4 0 5 1 1 9 3 8 ) ) . 59 The b e h a v i o r o f t h e 1 : 1 a d d i t i o n compound o f 1 , 3 - d i o x a n e was in d e e d p u z z l i n g . The c o m b in in g r a t i o i s d e f i n i t e l y e s t a b l i s h e d , s i n c e f i v e s a m p le s o f t h e compound w e re p r e p a r e d , t h e a v e r a g e d e v i a t i o n fro m t h e 1 : 1 r a t i o b e i n g 11 p e r c e n t ( t h e a v e r a g e v a l u e o f t h e r a t i o was 1 . 0 2 : 1 ) . H ow ever, when t h e a t t e m p t was made t o o b t a i n d i s s o c i a t i o n d a t a w i t h th e co m p le x , a s i n g l e s t r a i g h t - l i n e l o g P— l / T c u r v e ( s e e F i g u r e 6) d i d n o t r e s u l t fro m t h e d a t a . N e i t h e r o f t h e two p o r t i o n s o f t h e c u r v e i s known t o b e t h e one r e p r e s e n t i n g t h e r e v e r s i b l e d i s s o c i a t i o n o f t h e com p lex i n t o 1 , 3 - d i o x a n e and b o r o n f l u o r i d e . B o th s o l u b i l i t y an d d e c o m p o s i t i o n e f f e c t s a p p e a r t o i n t e r f e r e w i t h t h i s s t u d y . T h e r e f o r e , no c o m p a r is o n o f t h e r e l a t i v e s t a b i l i t i e s o f t h e 1 : 1 co m p lex es o f b o r o n f l u o r i d e w i t h t h e two d i o x a n e s c a n b e made u n t i l f u r t h e r d a t a a r e o b t a i n e d . A p p a r e n t l y t h e 2 : 1 com plex o f 1 , 3 - d i o x a n e i s n o n e x i s t e n t , a t l e a s t u n d e r t h e c o n d i t i o n s em ployed i n t h i s w o rk . T h is i s i n a c c o r d w i t h t h e o r i g i n a l p r e d i c t i o n t h a t t h e 2 : 1 co m p le x e s s h o u ld b e l e s s s t a b l e t h a n t h e i r c o r r e s p o n d i n g 1 : 1 com pounds. L i k e w i s e , a s p r e d i c t e d , t h e te n d e n c y f o r t h e f o r m a t i o n o f a 2 : 1 com plex i s l e s s w i t h 1 , 3 - d i o x a n e t h a n w i t h 1 , 4 - d i o x a n e , d u e t o t h e p r o x i m i t y o f t h e two o x y g en atom s i n t h e f o rm e r c a s e . The u n c e r t a i n t y c o n n e c te d w i t h t h e d i s s o c i a t i o n d a t a o f t h e 1 , 3 - d i o x a n e 1 : 1 com plex u n f o r t u n a t e l y p r e v e n t s one fro m f u l l y s o l v i n g t h e m a jo r p r o b le m o f t h i s t h e s i s , n a m e ly , 60 t h e n a t u r e an d e x t e n t o f t h e i n t e r a c t i o n o f t h e two o x y g en ato m s i n e a c h o f t h e d i o x a n e m o l e c u l e s .. T h a t t h e f o r m a t i o n o f a 1 : 1 co m p lex t e n d s t o make t h e o t h e r o x y g en ato m l e s s a b l e t o s h a r e a n e l e c t r o n - p a i r f o l l o w s fro m t h e d a t a . A t l e a s t i n t h e c a s e o f t h e 1 , 4 - d i o x a n e c o m p le x , h o w e v e r, t h i s i n t e r a c t i o n i s n o t v e r y g r e a t . A c o n s i d e r a b l e am ount o f a d d i t i o n a l w o rk c o u ld b e p u t i n t o t h e s t u d y o f t h i s p r o b le m , i n t h e a u t h o r ’s o p i n i o n , w i t h w o r t h w h i le r e s u l t s . M ost i m p o r t a n t o f a l l w ould b e a d d i t i o n a l w o rk on t h e d i s s o c i a t i o n o f t h e 1 , 3 - d i o x a n e 1 : 1 c o m p le x , i n a n e f f o r t to c l e a r up t h e d o u b t c o n n e c te d w i t h t h e p r e s e n t d a t a • A lth o u g h i t i s q u e s t i o n a b l e w h e t h e r b o r o n c h l o r i d e , b o r o n b r o m id e , m e th y l b o r o n d i b r o m i d e o r d i m e t h y l b o r o n brom i d e w ould fo rm e l e c t r o n d o n o r - a c c e p t o r m o le c x ila r compounds w i t h e i t h e r o f t h e d i o x a n e s , w o rk w i t h t h e s e compounds w ould b e m o st i n t e r e s t i n g a n d m ig h t p r o d u c e d a t a v a l u a b l e f o r f u r t h e r c o m p a r i s o n s . An a t t e m p t i n t h e p r e l i m i n a r y p a r t o f t h i s s t u d y t o fo rm a m o l e c u l a r compound o f s u l f u r d i o x i d e and 1 , 3 - d i o x a n e d i d n o t r e v e a l t h e e x i s t e n c e o f a n y c o m p le x , b u t t h e w o rk was n o t a t a l l e x h a u s t i v e ( s u l f u r d i o x i d e g a s was b u b b l e d s l o w l y th r o u g h a sa m p le o f 1 , 3 - d i o x a n e k e p t a t 0 ° C . ) . An a t t e m p t t o fo rm t h e s u l f o t r i o x i d e co m p lex es o f 1 , 3 - d i o x a n e s h o u ld b e m ade, s i n c e t h e r e s u l t s o b t a i n e d c o u ld t h e n b e com pared w i t h t h o s e a l r e a d y d e s c r i b e d i n t h e l i t e r a t u r e f o r t h e c o r r e s p o n d i n g 61 51 1 , 4 - d i o x a n e com pounds. The two l , 4 - d i o x a n e - - s u l f o t r i o x i d e c o m p lex es s h o u ld b e s t u d i e d m ore c r i t i c a l l y , s i n c e d i s s o c i a t i o n p r e s s u r e d a t a f o r them i s l a c k i n g . 5 1 L o c . c i t . CHAPTER VI SUMMARY The v a p o r t e n s i o n c u r v e o f 1 , 3 - d i o x a n e was d e t e r m i n e d , an d fo u n d t o f o l l o w t h e f o r m u l a , l o g ^ P (mm.) ® 8 .6 5 2 - 2 1 6 9 /T . The 1 : 1 a d d i t i o n o f b o r o n f l u o r i d e t o 1 , 3 - d i o x a n e was s u c c e s s f u l l y a c c o m p l i s h e d . The com plex was a p p a r e n t l y l i q u i d a t room t e m p e r a t u r e , b u t c r y s t a l l i z e d fro m c h l o r o f o r m - c a r b o n t e t r a c h l o r i d e s o l u t i o n a t -4 0 ° C . a s l o n g w h i t e n e e d l e s ( p r o b a b l y a com plex a l s o c o n t a i n i n g c h l o r o f o r m ) . The 1 : 1 com plex i s q u i t e l a b i l e , d e c o m p o s in g u n d e r vacuum t o a b ro w n , v i s c o u s , o n l y s l i g h t l y v o l a t i l e l i q u i d on s t a n d i n g f o r s e v e r a l h o u r s o r i m m e d i a t e l y on w arm ing even g e n t l y w i t h a n o p e n f l a m e . S a t i s f a c t o r y d i s s o c i a t i o n d a t a c o u ld n o t b e o b t a i n e d . A tte m p ts t o f o rm a 2 : 1 com plex w i t h 1 , 3 - d i o x a n e g a v e no e v i d e n c e o f t h e e x i s t e n c e o f a n y s u c h s e c o n d a r y a d d i t i o n . The 1 : 1 co m p lex o f 1 , 4 - d i o x a n e was p r e p a r e d and s t u d i e d . I t fo rm s s m a l l w h i t e n e e d l e - l i k e c r y s t a l s w h ic h m e l t a t a b o u t 50 C. a n d s u b lim e r e a d i l y . The d i s s o c i a t i o n o f t h e com p lex i n t o d i o x a n e an d b o r o n f l u o r i d e was s t u d i e d . The 2 : 1 com p lex o f 1 , 4 - d i o x a n e was a l s o p r e p a r e d and s t u d i e d . I t fo rm s s m a l l w h i t e r o d - l i k e c r y s t a l s w h ic h m e l t a t 71 C. The d i s s o c i a t i o n of t h e com p lex i n t o d io x a n e and b o r o n f l u o r i d e was s t u d i e d . The 2 : 1 com plex i s l e s s s t a b l e to w a rd d i s s o c i a t i o n t h a n i s t h e 1 : 1 c o m p le x . BIBLIOGRAPHY NOTE: Books an d j o u r n a l a r t i c l e s c i t e d i n T a b le s I and I I a r e n o t i n c l u d e d I n t h i s b i b l i o g r a p h y . A. BOOKS B e i l s t e i n , B e i l s t e i n t s H andbuch d e r O r g a n ! s c h e n C hem ie, Volume XIX. B e r l i n : J u l i u s S p r i n g e r , 1 9 3 4 . ( 4 t h E d i t i o n , l i t e r a t u r e up t o 1 9 1 0 ) . 466 p p . B e i l s t e i n , B e i l s t e i n f s H andbuch d e r O r g a n ! s c h e n C hem ie, Volume XIX. B e r l i n : J u l i u s S p r i n g e r , 1 9 3 4 . ( 4 t h E d i t i o n , l i t e r a t u r e fro m 1910 to 1 9 1 9 ) . 232 p p . B o o th , H a ro ld Sim m ons, I n o r g a n i c S y n t h e s e s , Volume 1 . New Y o rk : M cG raw -H ill Book Company, I n c . , 1 9 3 9 . 197 p p . E l l i s , C a r l e t o n , The C h e m is tr y o f P e t r o l e u m D e r i v a t i v e s , Volume 1 . New Y o rk : The C h e m ic a l C a t a l o g Company, I n c . , 1 9 3 4 . 1153 p p . B. PERIODICAL ARTICLES B a k e r , W ils o n an d F r e d e r i c k B. F i e l d , " C y c l i c E s t e r s o f S u l f u r i c A c i d . I I . C o n s t i t u t i o n o f M e th y le n e an d G ly - o x a l S u l f a t e s an d t h e R e a c t i o n o f M e th y le n e S u l f a t e w i t h T e r t i a r y B a s e s " , J o u r n a l o f t h e C h e m ic a l S o c i e t y , 8 6 -9 1 ( 1 9 3 2 ) . Brown, C. L. M ., " C o n s t i t u t i o n and T o x i c i t y o f t h e G l y c o l s " , y r m a c e u t i c a l J o u r n a l , 1 4 0 :4 9 ( 1 9 3 8 ) . C l a r k e , Hans T . , " R e l a t i o n b e tw e e n R e s i d u a l A f f i n i t y and C h e m ic a l C o n s t i t u t i o n . I I I . Some H e t e r o c y c l i c Com pounds", J o u r n a l o f t h e C h e m ic a l S o c i e t y , 1 0 1 :1 7 8 8 - 1 8 0 9 . D e w a e l, A ug. a n d L o u is H e n ry , " O b s e r v a t i o n s o f t h e A c t i o n o f A l c o h o l s on E s t e r s " , C h em isch es Z e n t r a l b l a t t , 9 2 8 -3 0 ( 1 9 0 2 ) . D r e i s b a c h , D a l e , F r a n k H ovorka and R a lp h A. S c h a e f e r , "The S y ste m D io x a n e an d W a t e r " , J o u r n a l o f t h e A m e ric a n C h e m ic a l S o c i e t y , 5 8 :2 2 6 4 - 7 ( 1 9 3 6 ) • 64 E i g e n b e r g e r , E r n s t , " O c c u r r e n c e o f P e r o x i d e i n C rude D i o x a n e " , J o u r n a l f u r p r a k t i a c h e C h em ie, 1 3 0 : 7 5 - 8 ( 1 9 3 1 ) , E v a n s , P . B . , James M. K i e f e r an d C. M. S u t e r , " D io x a n e S u l f o t r i o x i d e , a New S u l f a t i n g and S u l f o n a t i n g A g e n t " , J o u r n a l o f t h e A m e ric a n C h e m ic a l S o c i e t y , 6 0 : 5 3 8 - 4 0 ( 1 9 3 8 ) , F rahm , Hermann an d K u r t H e s s , " P r e p a r a t i o n an d P r o p e r t i e s o f P u r e D io x a n e " , B e r i e h t e d e r D e u ts c h e n C h em isch en G e s e l l s c h a f t , 7 1 B :2 6 2 7 -3 6 (1938*H " G a l l a u g h e r , A. F , an d H. H i b b e r t , " R e a c t i o n s R e l a t i n g t o C a r b o h y d r a t e s and P o l y s a c c h a r i d e s . LV. V apor P r e s s u r e s o f t h e P o l y e t h y l e n e G l y c o l s and T h e i r D e r i v a t i v e s " , J o u r n a l o f t h e A m e ric a n C h e m ic a l S o c i e t y , 5 9 :2 5 1 4 - 2 1 ( 1 9 3 7 ) . G etm an, F . H . , " F r e e z i n g P o i n t s o f t h e S y stem p - D io x a n e - T e r t i a r y - B u t a n o l " , R e c u e i l d e s t r a v a u x c h i m i q u e s , 56 : 9 2 7 -3 0 ( 1 9 3 7 ) . G r o s s , P h . a n d H. S u e s s , " T h e rm a l D e c o m p o s itio n o f D io x a n e " , M o n a t s h a f t e , 6 8 : 2 0 7 - 1 4 ( 1 9 3 6 ) . Hammond, W. A. an d James R. W ith ro w , " S o l u b l e A n h y d r i t e a s a D e s i c c a t i n g A g e n t " , J o u r n a l o f I n d u s t r i a l and E n g i n e e r in g Chemis t r y , 2 5 : 6 5 3 - 9 Cl933T^ H a r l o s , W. an d E . P o h l a n d , " N o n - m e t a l l i c H a lo g e n Com pounds. I I I . S a t u r a t i o n P r e s s u r e s o f B o ro n T r i f l u o r i d e " , Z e i t s c h r i f t f u r a n o r g a n i s c h e und a l l g e m e i n e C h em ie, 2 0 7 : 2 4 2 - 5 ( 1 9 3 2 ) . Heubaum, U l r i c h a n d Egon W ib e rg , "T h e A c t i o n o f P h o s p h in e on B o ro n F l u o r i d e ( 2 . W ith R e f e r e n c e to t h e Q u e s t i o n o f t h e E x i s t e n c e o f B o ro n H a l i d e - A d d i t i o n Compounds o f Anomolous C o m p o s i t i o n ) " , Z e i t s c h r i f t f u r a n o r g a n i s c h e un d a l l g e m e i n e C hem ie, 2 2 5 : 2 7 0 - 2 ( 1 9 3 5 ) . H u g h es, James a n d Abral^pi S a i f e r , " D io x a n e a s a R e a g e n t f o r t h e D e t e c t i o n an d D e t e r m i n a t i o n o f S m a ll Amounts o f I o d i d e . I t s A p p l i c a t i o n t o t h e D e t e c t i o n o f I o d i d e i n I o d i z e d S a l t " , J o u r n a l o f B i o l o g i c a l C h e m i s t r y , 1 1 8 :2 4 1 - 5 ( 1 9 3 7 ) . J o n e s , G. W ., R. E . K ennedy a n d H. Seam an, " E x p l o s i v e P r o p e r t i e s o f D i o x a n - a i r M i x t u r e s " , J o u r n a l o f I n d u s t r i a l an d E n g i n e e r i n g C h e m i s t r y , 2 5 : 1 2 8 3 - 6 ( 1 9 3 3 ) • 65 M e e rw e in , H ans, "B o ro n F l u o r i d e C om plexes an d t h e Use o f B o ro n F l u o r i d e f o r S y n t h e s e s . P r e l i m i n a r y C o m m u n ic a tio n " , B e r i c h t e d e r D e u t s c h e n C h em isch en G e s e l l s c h a f t , 66B: 4 1 1 -4 (1 9 3 3 7 . M e n z ie s , A la n W. C. an d A l e x a n d e r S m ith , " S t u d i e s i n V apor P r e s s u r e : I I . A S im p le Dynamic M eth o d , A p p l i c a b l e to B o th S o l i d s and L i q u i d s , f o r D e t e r m i n i n g V apor P r e s s u r e s , and A ls o B o i l i n g P o i n t s a t S t a n d a r d P r e s s u r e s " , J o u r n a l o f t h e A m e ric a n C h e m ic a l S o c i e t y , 3 2 : 9 0 7 - 1 4 ( 1 9 1 0 ) • C. PATENTS B i r c h a l l , T. an d S . C o f f e y , " M e th y le n e E t h e r s " , B r i t i s h P a t e n t 3 3 8 , 6 2 4 , A u g u s t 3 0 , 1 9 2 9 , t o I m p e r i a l C h e m ic a l I n d u s t r i e s , L t d . D r e y f u s , H e n ry , " C y c l i c E t h e r s " , U n i t e d S t a t e s P a t e n t 2 , 0 7 2 , 1 0 1 , M arch 2 , 1 9 3 7 . N a w ia s k y , P a u l and G e rh a rd E . S p r e n g e r , " T h io x a n e S u l f u r T r i o x i d e A d d i t i o n C om pounds", U n ite d S t a t e s P a t e n t 2 , 2 1 9 , 7 4 8 , O c to b e r 2 9 , 1 9 4 0 , t o G e n e r a l A n i l i n e a n d F ilm C o r p o r a t i o n . D. THESES M a r t i n , M.A. t h e s i s , The U n i v e r s i t y o f S o u t h e r n C a l i f o r n i a L i b r a r i e s , 1 9 4 0 .

Asset Metadata

Creator Guinn, V. P (author)

Core Title A comparison of the electron donor properties of 1,3- and 1,4-dioxane

Contributor Digitized by ProQuest (provenance)

Degree Master of Science

Degree Program Chemistry

Publisher University of Southern California (original), University of Southern California. Libraries (digital)

Tag chemistry, organic,OAI-PMH Harvest

Language English

Advisor Burg, Anton B. (committee chair), Copeland, Charles S. (committee member), Vollrath, Richard E. (committee member)

Permanent Link (DOI) https://doi.org/10.25549/usctheses-c17-790547

Unique identifier UC11348425

Identifier EP41536.pdf (filename),usctheses-c17-790547 (legacy record id)

Legacy Identifier EP41536.pdf

Dmrecord 790547

Document Type Thesis

Rights Guinn, V. P.

Type texts

Source University of Southern California (contributing entity), University of Southern California Dissertations and Theses (collection)

Access Conditions The author retains rights to his/her dissertation, thesis or other graduate work according to U.S. copyright law. Electronic access is being provided by the USC Libraries in agreement with the au...

Repository Name University of Southern California Digital Library

Repository Location USC Digital Library, University of Southern California, University Park Campus, Los Angeles, California 90089, USA