Part I: A Study of the Addition of Bromine to Olefins in Carbon-Tetrachloride Solution. Part II: Preparation and Reactions of Mercurials Derived from Olefins

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Part I: A Study of the Addition of Bromine to Olefins in Carbon-Tetrachloride Solution. Part II: Preparation and Reactions of Mercurials Derived from Olefins

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PART I A 3TUDX OF THE ADDITION OF BROliXNE TO 0LSFIH 8

in carbon wirachloribe solution

PART I I PREPARATION AN© REACTIONS OF MERCURIALS SBBtTOD FROM OLEFINS

fey Robert Johnson Smith

A d issertatio n submitted in p a r tia l fulfillm ent of the requirement® for the degree of Dootor of Philosophy in the Department of Chemistry in the Graduate College of the State University of Iowa August 1950

ProQuest Number: 10666183

All rights reserved INFORMATION TO ALL USERS The quality o f this reproduction is d e p en d en t upon th e quality o f the cop y submitted. In th e unlikely ev en t that the author did not send a co m p lete manuscript and there are missing p ages, th ese will b e noted. Also, if material had to b e rem oved, a n ote will indicate the deletion.

uest ProQuest 10666183 Published by ProQuest LLC (2017). Copyright of the Dissertation is held by the Author. All rights reserved. This work is protected against unauthorized copying under Title 17, United States C o d e Microform Edition © ProQuest LLC. ProQuest LLC. 789 East Eisenhower Parkway P.O. Box 1346 Ann Arbor, Ml 48106 - 1346

C o ti

A C K N O W L K D C r ilE N T

'; The author wishes to express M s ap p reciatio n to Dr* Robert 8. Buckles, under whose d ire c tio n th i s In v e s ti­ g ation was e a rn e d out, fo r h is I n te r e s t, h elp , and encouragement.

I t has been a p riv ile g e and a pleasure to

work with hi© and to know hi© as a research d ire c to r, teacher, and frie n d .

11

TABLE OF CONTENTS

PART I .

A 3TUOT OF THE ADDITION OF BROMINE TO OLEFINS IN (JARBON TETRACHLORIDE SOLUTION page

I II

INTRODUCTION............................................... DISCUSSION, .......................................... . ......... . ................. 3 Development of Sampling and A nalysis Techniques , , ............ . . . . . . . . . ........... . ..................3 The A ddition of Bromine to T lgllo and Angelic Acid® In Carbon T etrachloride Solution, without Gat&lyet.................................. © The Addition of Bromine to T lgllo Acid in the Presence of Hydrogen Bromide as a .13 C a ta ly st................ . . . . ............ . . . . . . .............. Complex Formed by Reaction of T etrabutylammonium Bromide with Bromine.......... ................ 21 The Addition of Bromine to G ls-stilb en e and Trans-etilben© In Carbon T etrachloride Solution............................. 22

III

EXPERIMENTAL. . . ...... . ..........................................................2© P u rific a tio n of Reagent®. ........... .2© A n alytical Methods ................. .26 Addition of Bromine to T lgllo and Angelic Acid®. ................. .2? Attempt to Prepare Angelic Dlbroml&e.............28 Hydrogen Bromide as a C atalyst In the Addition o f Bromine to T lgllo and Angelic A cids.................... ........... . . . . . . . . . . . . . . . . . . . 6..2 8 P reparation of a Bromine Complex by Reaction of Tetrabutylammaniurn Bromide wl th Bromine ......... 29 A, In Carbon T etrachloride S o lu tio n .. . . . , 2 9 B. In Vapor P h ase. ................. .30 Addition of Bromine to Ois-stllben© and T rans-atllbene in Carbon T etrachloride S olution............. .31 111

.1

page IV

.....................................................................................33

V APPENDIX............ , . ..................................................................38 VI

BIBUOORAPHX

PAM XI.

.................................

48

PREPARATION AND REACTIONS OF MERCURIALS DERIVED FROM OLEFINS

I

INTRODUCTION........................................................................ 49

II

DISCUSSION............................................. ............................... 52

III

EXPERIMENTAL...........................

5?

P rep aratio n of dl-M ercurio M andelate............... 5? P rep aratio n of l-M andeloxymercuri-2methoxycyclohexane . . ........... . . ......... *................ . . 57 P rep aratio n o f X-Bromomerourl-2methoxycyclohexan©............................................. . . .67 P rep aratio n o f Trans*-l-bromo«-2~ methoxyoyolohexane......................... . . . . . . ..............58 Attempt to Prepare Trang-l«brorao-2methoxy cyclohexane from l~Bromofflerourt-*2~ .......... 58 raethoxyeyolohexane ............... 59 R esolution o f dl-M andelio A cid P rep aratio n o f d-M ercuric Mand e la te ................... 60 P rep aratio n of d«X-4!&nd©loxyraerGurl-2~ methoxyoyolohexane................... ...............................60 F ra c tio n a l C ry s ta lliz a tio n o f &-1Mandeloxyme rourl-2-m ethoxycyclohexane............. 61 iv

sm m n x .

.................................

V BIBLIOGRAPHY........................... VI

BIOGRAPHY...............

.62

.63 64

ir

fkBhM OF FXOUB&S

page 1.

Apparatus fo r use In Hate D eterm inations . . .............. . . . . . .............. 4

2.

A ddition of Bromine to T lg llo and Angelic Acids without a C a ta ly s t.. . . . . . . 7

3.

A ddition of Bromine to T lg llo and Angelic Acid® using Hydrogen Bromide .......... a s a C a ta ly s t.

.16

E ffect of Product and Bromide Ion upon the Hate of Addition o f Bromine to T lg llo Acid.............

19

4. 0.

A ddition of Bromine to Q ls-stilb en e and T ran s-stilb en e without a C a ta ly s t...23

ir

TABLE OF TABLES page T able 1 ......................................................................................35 T able I I

. . .................................................................36 ............................

T able I I I .

T able IV .............................................. T able V............................

37 33 .3 9

T able V J . . . ...........

40

T able V I I . . . . ........................................................................41 T able V I I I . . ................................................................... . . . 4 2 T able IX ................

43

T able X............................

.4 4

T able X I ................................................................................... 45 T able X I I ............................ T able X I I I

46

................................................................ 47

vl

i PART I A 8T O OF t88 ADDITION OF BROMINE TO OLEFINS IN 0AHBON TETRACHLORIDE SOLUTION I INTRODUCTION In previous work in th is Laboratory (1) the a d d itio n re a c tio n s o f t l g l l o and angelio a c id s with bromine have been found to be e sp e c ia lly s e n s itiv e to l i g h t .

Consequently, I t

was found necessary to carry out determ inations o f the ra te s o f re a c tio n in ab so lu te darkness.

With ra te determ inations

c a rrie d out In the absence o f a c a ta ly s t and In the presence o f the normal amount o f oxygen found In the re a c tio n fla s k , in d u ctio n p erio d s o f about t h i r t y hours were c o n siste n tly observed (1 ).

Following the induction p eriod a ty p ic a l

second ord er ra te law was observed.

Under the same conditions,

when anhydrous hydrogen bromide was present as a c a ta ly s t, no in duction period was observed.

The re a c tio n proceeded

ra p id ly a t f i r s t , but then slowed considerably, as would be expected i f the ac tio n of the c a ta ly s t, bromine o r both, was In h ib ite d by the product of th© re a c tio n ( ! ) . The p resen t study was undertaken to c la r if y fu rth e r the mechanism fo r the ad d itio n o f bromine to t i g l i c and an g elic a c id s, to devise a method and apparatus to obtain d ata In a more q u a n tita tiv e fashion in extending the study

2

on the e f fe c t of hydrogen bromide as a c a ta ly s t In the ad d itio n re a c tio n s, and to in v e s tig a te fu rth e r the ra te of ad d itio n of bromine to o is -s tilb e n e and tr& ns-atilbene in carbon te tra c h lo rid e so lu tio n under conditions of constant tem perature and absolute darkness. The exact co n figuration of t l g l i e and angelic acids i s not known a t the p resent tim e.

P hysical measurements, how­

ever, in d ic a te th a t the following configurations are believed to be presents t l g l l o acid

an&ello acid

C ^ -C II C ^ -C -c o o H

CHj-c /( HOoC - C, - Ctfj

3 n

PI3O00SXOH A,

D evelopm ent o f Sam pling and A nalysis Techniques

I n previous work (1) on %ho a d d itio n o f bromine to t l g l l o and an g elic acld e, the samples to be t i t r a t e d a t re g u la r in te rv a le , in order to determine the bromine co n ten t, were o b tain ed by opening the re a c tio n fla sk and p ip e ttin g out the d e sire d q u a n tity ,

gtoall amounts o f hydrogen bromide were

l o s t each time the re a c tio n fla s k was opened, and the contents of the fla s k were exposed to the surrounding m oist atmosphere. I n the p re se n t work two methods o f obtaining a sample from the re a c tio n fla s k were used.

By means o f an a l l- g la s s

apparatus, shown in Figure 1, a sample of about 10 ml, was obtained by fo rcin g a stream o f dry a i r in to the re a c tio n fla s k ,

the sample was d eliv ered under w ater in a ta re d re ­

ceiving f la s k .

I n th e second method, used e s p e c ia lly to

minimize lo s s o f hydrogen bromide from the re a c tio n m ixtures, a serum sto p p le was used to stopper the re a c tio n fla s k and the sample was obtained with a syringe by in s e rtin g the needle through the sto p p le. In o rd er to check on the constancy of the concentra­ tio n of hydrogen bromide throughout the course o f a re a c tio n , an a n a ly sis technique was developed so th a t the bromine content and the hydrogen ion co ncentration could be determined fo r

4

Af7»/VD*. I OtnL. CA-^lCfT

OfKYtAtt IRAtft

^------ RfCbl 'Jffi(r Fi./*SK

l

F ig u re X A p p a r a t u s f o r U se i n R a te D e t e r m i n a t i o n s

a e a c h sam ple w ithdraw n.

The brom ine c o n te n t was d eterm in ed

i n th e u s u a l manner by t i t r a t i n g I o d in e 11 h e r e t e d f r o is po­

In

ta ss iu m io d id e ! p r e s e n t th lo s u lfa te so lu tio n .

e x c e s s , w ith sta n d a r d sodium

P o ta ssiu m l o d a t e s o l u t i o n was th en

added! and th e l i b e r a t e d I o d in e was t i t r a t e d a g a in w ith s ta n ­ dard sodium t h l o s u l f a t e s o l u t i o n .

The method was b ased on

th e f a c t t h a t l o d a t e io n w i l l n o t r e a c t w ith e i t h e r io d id e Io n o r t h l o s u l f a t e io n i n a b sen ce o f an a c id , and th a t lo d a t e i o n , io d id e io n , and hydrogen io n w i l l r e a c t q u a n t i t a t i v e l y w ith each o t h e r t o form io d in e u n t i l th e io n p r e s e n t i n th e l e a s t amount i s c o m p le te ly u sed up .

A b la n k , u s in g an i d e n t i ­

c a l r e a c t i o n m ix tu re w ith th e e x c e p t io n o f hyd rogen brom ide, was run to •determ ine t h e hydrogen i o n due t o s o u r c e s o t h e r th a n hyd rogen bromide added.

I t was fou n d t h a t th e hyd rogen

io n c o n te n t rem ained c o n s ta n t w it h in th e l i m i t s o f e x p e r i­ m en ta l e r r o r th ro u g h o u t th e c o u r se o f th e r e a c t i o n s stu d ie d * B.

Ttie A d d itio n o f Bromine to T jjt.ilc and A n g e lic A c id s i n

Carbon T e tr a c h lo r id e S o lu t io n , w ith o u t C a t a ly s t B ein g I s o m e r ic a c id s , t l g l l o and a n g e l ic a c id s sh o u ld have d i f f e r e n t r a t e s o f a d d it io n , a n g e l ic a c id b e in g f a s t e r th a n t l g l l o a c i d .

W right ( 2 ) foun d t h a t c l e -m e th y l

olnnam ate was m ercu rated much f a s t e r than tr a n s-m e th y l cin n a m a te, and th a t o l s - s t l l b e n e was raercurated t d iile t r a n s e t i l b e n e was n o t, presum ably due to e t e r i c e f f e c t s ,

lo o k (1 )

foun d t h a t i n th e v e r y slo w a d d it io n o f brom ine t o t l g l l o and

a n g e l i c a c ld a i n carb on t e t r a c h l o r i d e i n th e d a rk , v e r y l i t t l e d i f f e r e n c e I n r a t e s b etw een t l g l l o and a n g e l i c a c i d s e x i s t e d , and c a l c u l a t e d th e s p e c i f i c r e a c t i o n . r a t e s f o r t i g l i o and a n g e l i c a c i d s t o be 3 .1 x 10*® and 2 . 6 x 10*® l i t e r / m o l e s se c o n d s r e s p e c t i v e l y *

C a l c u l a t io n o f th e s p e c i f i c r e a c t i o n

r a t e s f o r t i g l i o and a n g e l i c a c i d s from th e slo p e ® o f th e s t r a i g h t l i n e s I n F ig u r e 2 g a v e S .? x 10"® and 3 . 0 x 10*® lite r /m o le s -s e o o n d s r e s p e o t iv e ly . A s shown i n F ig u r e 2 a d e f i n i t e i n d u c t io n p e r io d o f tw e n ty t o f o r t y h o u r s e x is t ® In th e a b se n c e o f h yd rogen b ro m id e.

A f t e r t h i s p e r io d , brom ine was added s lo w ly ' to th e

d o u b le bond*

I n th e a b s e n c e o f oxygen i t was fo u n d t h a t th e

a d d i t io n o f brom ine i n th e dark r e q u ir e d a p p r o x im a te ly fo u r h ou rs.

The i n h i b i t o r y e f f e c t o f o x y g e n m ig h t be e x p la in e d

by th e s u g g e s t io n o f P aul el® and W illa r d ( 3 ) t h a t when la r g e am ounts o f o x y g e n w ere p r e s e n t In th e p h o to c h e m ic a l a d d i t io n o f brom ine t o t e t r a c h l o r o e t h y l e n e , th e r a t e o f a d d it io n a p p ro a ch ed s e r e , p r o b a b ly on a c c o u n t o f a com p etin g brom ine p h o to s e n s itiz e d o x id a tio n .

E xp erim ent ( 1 ) h a s shown t h a t

a n g e l i c and t l g l l o a c i d s i n th e a b se n c e o f oxy g en add brom ine i n a p p r o x im a te ly t h r e e m in u te s i n th e p r e s e n c e o f l i g h t . S o l u t io n s o f t h e s e acid ® c o n t a in in g oxygen and brom ine r e q u ir e d a t l e a s t two d a y s to become d e c o lo r iz e d In th e p r e s e n c e o f lig h t* The e f f e c t o f th e p ro d u ct o f th e r e a c t i o n upon th e

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