Halogen Exchange Between Alkyl Halides and Halogen Atoms

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HALOGEN EXCHANGE BJ&TWKKN ALKYL HALILLS AND HALOGEN ATOMS

by e N o rris G,^ Wheeler

A t h e s i s su b m itted in p a r t ia l f u l f i l l m e n t o f th e r e q u ir e ­ m ents fo r th e degree o f D octor o f P h ilo so p h y , in th e departm ent o f C hem istry, in th e Graduate C o lle g e o f th e S ta te U n iv e r s ity o f Iowa August , 1950

ProQuest Number: 10666186

All rights reserved INFORMATION TO ALL USERS The quality of this reproduction is d e p e n d e n t upon th e quality of th e co p y subm itted. In th e unlikely e v en t th a t th e author did not send a c o m p lete manuscript an d th ere are missing p ag es, th ese will b e noted. Also, if material h ad to b e rem oved, a n o te will indicate th e deletion.

uest ProQuest 10666186 Published by ProQuest LLC (2017). Copyright of th e Dissertation is held by th e Author. All rights reserved. This work is p ro te cted 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

T ii

V O SC o^ fs tip

ACKNOWLEDGSr1SNT

The au th or w ish e s to e x p re ss h i s s in c e r e a p p r e c i­ a t io n t o Dr. Robert £ . B uckles fo r h i s many h e lp f u l s u g g e s t io n s , encouragement and gu idan ce g iv e n through­ ou t t h i s in v e s t ig a t io n . Thanks are a ls o due t o Dr. A lexander Popov f o r

c

Yv

su p p ly in g bromine a b so rp tio n data*

iii

TABLE OF CONTENTS Page INTRODUCTION,

1

DISCUSSION,. . . EXPERIMENTAL .J(,>3 O » OQV&Oa 3 rt fr {a-x){Br2 )

dx/{a-x) = k3(2I0/k2 )^Keq4(Br2 )dt 2.3 log a/(a-x) - k(I0 ) h B r 2 )t 2.3 log 1/(1-X) = k{I0 ) h B r 2 )t

Such an in flu e n c e o f bromine m o lecu les in a id in g is o m e r iz a tio n a s shown in the two p o s s i b i l i t i e s

th e

above i s

n o t u n lik e ly in such co n cen tra ted bromine s o lu t io n s . The s lo p e s o f the cu rv es were s e t equal to k d ^ ^ B r g ) and th e eq u a tio n was so lv e d fo r wkff.

The c a lc u la te d wkw

v a lu e fo r th e cu rve shown in f ig u r e 4 was 3 . 6 .

The valu e

o b ta in ed fo r the run u sin g 0 .9 7 5 4 m olar bromine was 2 .6 aid f o r 0 .2 4 3 6 m olar bromine was 6 . 1 .

The v a lu e ob tain ed

when th e l i g h t i n t e n s i t y was reduced was 4 .1 . In a d d itio n t o the two p o s s i b i l i t i e s shown above o f bromine m o le c u le s a id in g th e iso m e r iz a tio n i t i s a ls o quit® p o s s ib le th a t a com bination o f s e v e r a l d if f e r e n t s t e p s compete in th e r e a c t io n .

I f the dependence o f th e

20

s p e c i f i c r e a c t io n - r a t e c o n sta n t on th e square ro o t o f th e bromine c o n c e n tr a tio n i s c a lc u la t e d i t i s found th a t th e v a lu e s o b ta in ed fo r "krl a re equal w ith in exp erim en tal error *

The s lo p e s o f th e cu rv es were s e t equal t o

h (I^ )^ (B rg )^ and t h e eq u a tio n was so lv e d fo r ttk*.

The

c a lc u la t e d "k*1 v a lu e fo r the curve shown in fig u r e 4 was 2 .5 .

The c a lc u la t e d "k" v a lu e f o r th e run u sin g 0 .9 7 5 4

m olar bromine was 2 .5 and for 0 . 243& m olar bromine was 3 .0 .

The v a lu e o b ta in ed when th e lig h t in t e n s it y was

reduced was 2 . S .

Thus th e iso m e r iz a tio n r e a c tio n was

found to be a p p a r en tly one h a lf ord er w ith r e sp e c t t o brom ine• The ex p erim en ta l d ata ob ta in ed a t 35

was in no way

c o n s is t e n t w ith the r e s u l t s ob tain ed in the o th er e x p e r i­ m ental ru n s and i t is f e l t th a t the work a t 35° should be re p e a te d and a d d itio n a l work done b e fo r e any in te r p r e ta ­ t io n i s a ttem p ted . There i s e v id e n t ly a s li g h t amount o f s id e r e a c tio n o cc u r in g in a d d itio n t o th e is o m e r iz a tio n r e a c tio n .

Hydro­

gen bromide g a s was g iv e n o f f in sm all amounts and a s l i g h t q u a n tity o f an o i l was form ed.

The rubber sleev©

on th e s t i r r i n g apparatus was c o n sid e r a b ly decomposed d uring th e r e a c t io n .

This was probably due t o the e f f e c t

o f bromine and u l t r a v i o l e t l i g h t .

The hydrogen bromide

21

g a s and th e o i l w hich were formed a re p o s s ib ly th e r e s u lt of th e d eco m p o sitio n o f th e ru b ber. I t was o r i g i n a l l y in ten d ed t o in v e s t ig a t e th e in v e r ­ s io n ty p e mechanism by u sin g halogen atoms and o p t i c a l l y a c t iv e a lk y l h a lid e s .

I t was planned t o d is s o lv e an

o p t i c a l l y a c t iv e a lk y l bromide or io d id e in carbon t e t r a ­ c h lo r id e and t r e a t th e s o lu t io n w ith bromine or io d in e . The change in r o t a t io n was th en t o be o b serv ed , and th e e f f e c t o f c o n c e n tr a tio n , tem perature and l i g h t in t e n s it y ob serv ed . The o r i g in a l is o m e r iz a tio n r e a c tio n was observed w ith d l - s t i l b e n e d ib rom id e, which c o n ta in s two s im ila r asymme­ t r i c carbon atom s.

. I t was t h e r e f o r d e s ir e d to o b ta in an

o p t i c a l l y a c t iv e a lk y l bromide s im ila r in s tr u c tu r e t o s t ilb e n e dibrom ide but cant a in in g o n ly one asymmetric carbon atom*

1 , 2 -D ip h en y l e t h y l a lc o h o l was prepared by

a Grignard r e a c tio n u sin g benzaldehyde and benzylmagnesium c h lo r id e .

The a lc o h o l was r e so lv e d and used t o prepare

th e o p t i c a l l y a c t iv e 1 , 2 -d ip h e n y l e th y l bromide.

When

th e o p t i c a l l y a c t iv e bromide was p laced in a brominecarbon t e t r a c h lo r id e s o lu t io n and, l e f t in th e dark fu r th e r b rom lnatlon occured and hydrogen bromide was ev o lv e d , Brom ination was a l s o found to occur when 2-brom o-octane was s u b je c te d to the same c o n d itio n s .

I t was then

22

d ecid e d n o t to attem p t t o us© o p t i c a l l y a c t iv e bromides* The co u rse o f stud y was then d ir e c te d toward o b ta in * in g an o p t i c a l l y a c t iv e io d id e so th a t th e r e a c tio n o f th e io d id e and io d in e could be stu d ied *

O ctanol-2 was

r e s o lv e d to g iv e an o p t i c a l l y a c t iv e a lco h o l*

A ll a ttem p ts

by th e u se o f hydrogen io d id e gas t o o b ta in an o p t i c a l l y a c t iv e io d id e o f o c ta n o l-2 were u n s u c c e s s fu l, a s w e ll a s s im ila r a ttem p ts t o o b ta in an io d id e o f s e c - b u ty l a lco h o l* B ecause o f i n a b i l i t y to o b ta in an o p t i c a l l y a c t iv e io d id e t h a t method o f stu d y was tem p o r a rily dropped*

However

work i s now in p ro g re ss t o o b ta in an o p t i c a l l y a c t iv e io d id e fo r t h i s stu d y by th e r e a c t io n o f phosphorus and io d in e and an o p t i c a l l y a c t iv e a lc o h o l in an e x tr a c tio n v e s s e l*

The o p t i c a l l y a c t iv e io d id e b eing prepared I s

s e c - b u t y l io d id e*

The io d id e w i l l be tr e a te d w ith io d in e

in carbon t e t r a c h lo r id e and th e r a te o f ra cem isa tio n w i l l be s t u d ie d .

The r e a c tio n o f d l- s e c - b u t y l io d id e

w ith r a d io a c t iv e io d in e w i l l then be stu d ie d under th e same c o n d it io n s .

The r a t e o f exchange o f n o n -r a d io a c tiv e

io d in e in th e a lk y l io d id e w ith r a d io a c tiv e io d in e w i l l be c a lc u la t e d .

I f i t can be shown th a t th e s p e c i f i c

r e a c tio n -r a t® c o n sta n t of th e exchange r e a c tio n i s i d e n t i c a l w ith t h a t o f th e racem issation r e a c tio n then every d isp la cem en t i s accompanied by in v e r s io n and I t can then

23

be proved th a t th e isom eri& ation r e a c tio n ta k e s p la c e by w alden in v e r sio n *

24

E X E B K E M E IIT A L

P r e p a r a t io n o f I s o (C ls) S tilb e n e C i s - s t ilb e n e was prepared by the method o f T aylor and C raw ford^ c a r b o x y la tio n o f

I t was o b ta in ed in 72 % y ie ld by th e de­ -p h en ylcin n am ic a cid and had a

b o i l i n g p o in t o f 1 3 4 ° a t 10 mm. P re p a r a tio n of C ia -g ftlb e n e Dibromide C i s - s t i l b e n e dibrom ide ( d l) was prepared in $2$ y ie ld by th e method o f W isltcen u s^ 0 .

I t was prepared by the

a d d it io n o f bromine to c is - s t ilb e n © in carbon d is u lf i d e in th e c o ld and in darkness and had a m eltin g p o in t o f

111

0

*

P u r if ic a t io n o f Carbon T e tr a c h lo r id e ^ Two and one h a l f l i t e r s o f carbon t e t r a c h lo r id e were r e flu x e d w ith a lk a lin e p otassiu m permanganate fo r s i x h o u r s.

I t was th e n washed once w ith w a ter, d ried o v er-

n l # i t w ith calciu m c h lo r id e , d i s t i l l e d from dri@rit@# d r ie d w ith d r i e r l t e o v e r -n ig h t, d i s t i l l e d from phosphorus p en to x id e and b o t t le d . P u r if ic a t io n o f Bromine^ One pound o f C. P. bromine was re flu x e d w ith 200 g . o f p otassiu m brom ide, d i s t i l l e d from i t , r e flu x e d fo r

25 fo u r h ou rs o v e r 100 g . o f barium o x id e md d i s t i l l e d from It.

I t was d i s t i l l e d once more from barium o x id e and

p la ce d in a g la s s -s t o p p e r e d b o t t le * P re p a r a tio n o f Uranvl O xalate Uranyl o x a la t e was prepared by the method o f Forbes 12 and H eld t * I t was prepared b y m ixing hot s o lu t io n s o f U ranyl n i t r a t e (7 5 .3 g .

0*1$ M* in $0 ml*

o f w a ter) and reagen t grade o x a lic a c id (19 g * , 0*15 M.t In 200 ml* o f w a te r ).

The y e llo w p r e c ip it a t e

o f u ra n y l o x a la t e was th o ro u g h ly washed w ith w a ter, d ried o v e r -n ig h t in a vacuum d e s ic c a to r and th en d rie d in a ir a t 110® fo r th r e e h o u rs. P rep a ra tio n o f a S ta b le Hydrate o f Uranyl O xalate The u ra n y l oxalat© o b ta in ed a f t e r drying a t 110° f o r t h r e e hours was found t o absorb w ater from th e a ir when p la c e d on a b a la n ce pan and a co n sta n t w eig h t cou ld not be o b ta in e d .

The u ran yl o x a la te was th en r e c r y s t a lliz e d

from w ater and d r ie d in th e a ir a t room tem perature to o b ta in a s t a b le h y d r a te .

0 .6 $ 1 7 g . and 0 .6 2 0 4 g* o f tllie

r e c r y s t a l l i z e d product req u ired r e s p e c t iv e ly , 3 4 .9 and 33*5 m l. o f 0 .1 1 6 7 N. p otassiu m permanganate*

The average

m o lecu la r w eight a s determ ined by the potassium perman­ g a n a te t i t r a t i o n was 411*9 a s compared to 4 1 2 .1 4 which i s th e c a lc u la te d m o lecu la r w eigh t o f 1102020^*3^20*

26

The c a lc u la t e d m olecu lar w eigh t o f th e d i-h y d r a te i s 394*12* . S o l u b i l i t y o f DL- and M eso-St11bene Dibromide in Carbon T e tr a c h lo r id e At 30° Two hundred ml* o f b o ilin g carbon t e t r a c h lo r id e was s a tu r a te d w ith r a e s o -s tilb e n e dibrom ide.

The hot s o lu tio n

was th e n c o o le d in a w ater bath at 3O0 fo r th r e e hours and t h e s o lu t io n was th en f i l t e r e d *

Three 50 ml* p o r tio n s

o f the s a tu r a te d s o lu t io n were then evaporated to dryness and th e f o llo w in g w e ig h ts were o b ta in ed ; 0*0900 g l* and Q.0&95 g*

0*0901 g * t

T herefor 10 ml* o f carbon t e t r a ­

c h lo r id e a t 3 0 ° w i l l d is s o lv e 0*01$ g . o f m e so -stilb e n e d i bromide* Ten ml* o f carbon t e t r a c h lo r id e a t 30° was found t o d is s o lv e more th an 2 g* o f d l - s t i l b e n e dibromide* Ho c o - p r e c ip it a t io n was observed when m e so -s tilb e n e dibrom ide was p r e c ip it a t e d from s o lu t io n s co n ta in in g d is s o lv e d d l - s t i l b e n e dibromide* D e s c r ip tio n o f Apparatus and Equipment A F is h e r u n it is e d bath was used as a co n sta n t tempera­ tu r e w ater bath* A r e a c t io n v e s s e l was c o n stru cted o f Pyrex g la ss * F la t windows o f Pyrex g l a s s were s e a le d t o a

cm* le n g th

o f 3 cm* g l a s s tu b in g to which a 15 cm* len g th o f 1 cm*

27

g l a s s tu b in g had been s e a le d a s a s id e arm so th a t the v e s s e l co u ld be f i l l e d and a g la s s s t i r r e r in s e r t e d •

The

s id e ana ended in a 1 4 /2 0 standard ta p e r f i t t i n g so t h a t a sta n d a rd ta p e r b ea rin g equipped w ith a rubber s le e v e ecu Id be used w ith the s t i r r i n g rod*

Corning G la ss l i g h t

f i l t e r © were th en fa s te n e d to th e fr o n t window o f the r e a c t io n v e s s e l and th e rem ainder o f the o u ts id e o f th e v e s s e l ex c ep t th e upper h a l f ©f th e s id e arm was p ain ted b la ck w ith an under ch at o f o p t ic a l b la ck p a in t and an o u te r c o a t o f asphaltum v a r n ish t o make the b lack co a tin g w a ter r e s ista n t®

The g la s s s t i r r i n g rod was so a d ju sted

th at i t would n o t p rotru de in t o th e p o rtio n o f th e s o lu t io n which was b ein g illu m in a te d but would s t i r the s o lu t io n in the low er p art o f th e s id e a m .

A sm a ll c o n tr o lle d e l e c ­

t r i c m otor was used t o o p era te the s t i r r i n g rod* The g l a s s f i l t e r s s e a le d to t h e fr o n t window o f the r e a c t io n v e s s e l w ere a y ello w Corning G lass N ovlol A f i l ­ t e r and a b lu e C om ing G lass f i l t e r .

The per cen t lig h t

tr a n sm is sio n v e r s u s wave le n g th cu rves fo r th e two f i l t e r s were o b ta in ed by mea ns o f a Coleman electro p h o to m eter and the f i l t e r s w ere found to be s u it a b le fo r i s o l a t i o n o f th e 4 3 A® l i n e o f m ercury, which i s the wave len g th o f maximum a b so rp tio n o f bromine in carbon te tr a c h lo r id e *

2d

A G eneral E l e c t r i c SH4 mercury arc f lo o d ligjh t was u se d a s a lig h t source*

A two second exposure o f th e 100

w a tt mercury a r c , u sin g a Ian®-W ells sp ectro p h o to m eter, showed th e 435$ A® l i n e of mercury and s e v e r a l mercury l i n e s In the v i c i n i t y o f 5*500 A® to be o f stro n g i n t e n s i t y . The apparatus was assem bled in a dark room and was mounted on a s o l i d work bench*

The apparatus was assem bled

so th a t a l l equipment would be in th e same p o s it io n fo r a l l t h e ex p er im en ta l runs*

The lig h t sou rce was clamped

in a r i g i d p o s it io n so a s to be alw ays a c o n sta n t d ista n c e from th e tem perature bath*

The r e a c tio n v e s s e l was always

clamped so a s t o be in the. same p o s it io n in th e tem perature bath*

In a l l ex p erim en ta l runs th e lig h t source was turned

on for 30 m in u tes so th a t th e lig h t would reach maximum in t e n s i t y b efo re th e s o lu t io n t o b e illu m in a te d was p laced in the li^ h t path . C a lib r a tio n o f th e Llffhfc Source The number o f quanta o f l i g h t energy from th e mercury arc l i g h t sou rce s t r ik in g the s o lu t io n per second was $ found by th e method o f L eigh ton and Forbes by means o f a u ra n y l o x a la t e * o x a lic a cid a ctin o m e te r . A s t o c k o x a la t e s o lu t io n was prepared by d is s o lv in g 1 .0 5 8 g . o f U02C2 0^»3H20 and 1 .6 0 g , o f H2C20^*2H20 in 200 m l. o f w a te r.

The s o lu t io n was k ep t in a g la s s

29

sto p p er ed b o t t l e which was p a in ted b la ck w ith o p t i c a l b la c k p a in t ,

18 ml* o f th e sto c k o x a la te s o lu t io n was

m easured from a b u r e t te , in a darkened room, in t o a 125 m l, erlenm eyer f l a s k with b lack en ed s i d e s ,

A s o lu t io n

o f 2 m l, o f co n cen tra ted s u lf u r ic a c id in 10 m l, o f w ater was then added to the o x a la te so lu tio n *

The a c id ic o x a la te

s o lu t io n was then h ea ted t o 80® on a h o t p la t e and t i t r a ­ t e d w ith p otassiu m permanganate.

The s o lu t io n was found

to r e q u ir e 23*35 ml# o f 0 ,1 1 8 ? tf. p otassiu m permanganate# 1$ m l, o f th e sto c k o x a la te s o lu t io n was then measured from a b u r e tte in t o th e r e a c tio n v e s s e l which was equipped w ith th e y e llo w C om ing G la ss K oviol A and b lu e Corning G la ss f i l t e r #

The r e a c tio n v e s s e l was th e n p laced in th e

c o n s ta n t tem perature bath and illu m in a te d w ith th e mercury arc a t 30® fo r 13 h o u rs.

The o x a la te s o lu t io n was th en

poured from th e r e a c tio n v e s s e l in to a 125 ml# e r le n a e y e r f l a s k w ith blackened s i d e s ,

A s o lu t io n o f 2 m l. o f

c o n c e n tr a te d s u lf u r ic a cid and 10 ml# o f w ater was used t o r in s e the r e a c tio n v e s s e l and was added t o th e e r le n m eyer.

The s o lu t io n was then h eated to 80® and when

t i t r a t e d was found to req u ire 2 2 .5 0 ml# o f 0 .1 1 8 ? N. p o ta ssiu m permanganate.

By compering th e amount o f

p otassiu m permanganate req u ired fo r eq u a l volumes o f illu m in a te d and

n o n - illu m in a te d

o x a la te s o lu t io n s i t was

30

found t h a t 2 3 .3 5 - 2 2 .5 0 ©r 0 .8 5 m l. o f 0 .1 1 8 7 N. p o ta ssiu m perm anganate was e q u iv a le n t to th e amount o f o x a la t e used up d u rin g 13 h ours o f illu m in a t io n . L eigh ton and Forbes^ have shown th a t th e f o llo w in g eq u a tio n may b e u sed t o c a l c u la t e the number of l i g h t quanta s t r ik in g a s o lu t io n s T 6 .0 6 X 1023 X m ° s "/ i t X $ where l*0 g iv e s th e a verage number o f quanta par secon d o v e r the in t e r f a c e betw een the fr o n t window and th e s o lu t io n , and ® i s th e number o f m oles o f o x a la t e decomposed in A t se c o n d s.

0 i s th e quantum y i e l d .

t o 0.5® fo r t h i s r e a c t io n . o f 2 .5 cm .,

w hich t h i s

At 4358 A0 0 i s eq u al

The s o lu t io n

in a t h ic k n e s s

r e a c t io n v e s s e l w a s,

tr a n s m its

0 . 5 0 o f L0 a t 4358 A®. When the v a lu e s o b ta in e d fo r the 13 hour illu m in a t io n p eriod were u sed the fo llo w in g e x p r e s s io n was o b ta in e d :

L°

6 .0 6 X IQ23 X 0 .0 0 0 0 5 0 5

,

t in l5

O TYTorroT58— = 1,127 * 10

* - / __

^ aata/s®0.

However s in c e 50$ o f th e lig h t i s not absorbed in th e r e a c t io n the v a lu e o f L0 % 2 .2 5 4 X 10^5 quanta p er second i s o b ta in ed for the t o t a l amount o f lig h t th e r e a c t io n v e s s e l .

p a ssin g in t o

n k second illu m in a t io n was accomplished in a s im ila r manner u sin g the s to c k o x a la t e s o l u t i o n , e x c e p t th e i ll u m i­ n a tio n was fo r 24 hours#

When t h i s s o lu t io n was t i t r a t e d

w ith p o ta ssiu m p®rwis$i*n&te and compared w ith t h a t r e t i r e d t o t i t r a t e a similar volume o f o o n ^ iilu m in a te d o x a la t e I t was found t h a t 1 ,5 $ m l, o f 0*1137 H, p otassium permanganate was e q u iv a le n t t© th e amount o f o x a la te used up d u r in g ,24 h ours o f illu m in a tio n #

When the v a lu e s o b ta in ed from t h e

24 hour illu m in a t io n p erio d were s u b s t it u t e d in t o t h e e q u a tio n i t was fou n d t h a t th e v a lu e o f 2 ,2 6 4 1 10*5 quanta per secon d was o b ta in e d , A t h ir d I llu m in a tio n o f th e o x a la t e s o lu t io n was a cco m p lish ed under the i d e n t i c a l c o n d it io n s o f th e first two e x c e p t th e illu m in a t io n p erio d was for 1§ h o u r s.

When

t h e standard

o f d l - s t i l b e n e dibrom ide was accou n ted f o r , o r an e r r o r o f about 4% was o b ta in ed * A s im ila r d e te r m in a tio n a s th e p r e v io u s one was run e x c e p t th e a n a ly s is was f o r m e so -c tilb e n © d ib ro m id e*

0*16 g*

o f a 50% m ixture o f d l* and m eso -stilb en © dibromid© was t r e a t e d a s in th e p rev io u s d eterm in a tio n *

A fte r th® 10 ml*

o f s o lu t io n was a llo w ed t o sta n d f o r 3 h ou rs a t 30® th© s o lu t io n w as d eca n ted from th e p r e c ip it a t e d ra eso -stilb en © dibrom ide*

The s o l i d was washed w ith one h a l f ml* o f

carbon t e t r a c h lo r id e th en d r ie d and w eig h ed .

The product

w eighed 0*0592 g . and when the s o l u b i l i t y f a c t o r o f 0 .0 1 # g* was in c lu d e d , accounted f o r 0*0772 g* o f th e t h e o r e t i c a l 0 .0 # g . , o r an e r r o r o f about 3*5 p a r ts per hundred. P relim in a ry d e te r m in a tio n s in which th e bromine was removed from the s o lu t io n by h e a tin g in th e p resen ce o f a copper w ir e gave c o n f l i c t i n g r e s u l t s and th e method was d is c a r d e d ,

A 1 g , ©ample o f d l - s t i l b e n e dibromid© was

p la ce d in the r e a c t io n v e s s e l and 1# ml* o f Q.4&77 m olar bromine in carbon t e t r a c h lo r id e was added.

Both l i g h t

f i l t e r s were used and th® r e a c tio n was run a t 3 0 ° f o r an illu m in a t io n p e r io d o f 20 h o u rs.

In a run where th© bro­

mine was removed by the copper w ire method o n ly 0*057 g .

39

o f the d l - s t i l b e n e dibrom ide was r e c o v e r e d .

Whereas in

an i d e n t i c a l run ex c ep t t h a t th e bromine was removed by e v a p o r a tio n in d a rk n e ss, in s t e a d o f by the cop p er w ire m ethod, not s u f f i c i e n t d l- s t ilb e n © dibromid© was iso m er Iz e d to d e t e c t by th© s o l u b i l i t y method u se d . The E f f e c t o f Cuprous and Cupric Bromide As Isom©rjgin& A gents A ft e r comparing th e two runs j u s t m entioned i t was d e s ir e d to i n v e s t i g a t e th e e f f e c t o f cuprous and cu p r ic bromide a s I s o m e r is in g a g e n ts . 0*5 g* o f d l - s t i l b e n e dibromid® and 0 .0 3 0 6 g . o f c u p r ic bromide were added to 10 m l. o f carbon t e t r a ­ c h lo r id e and b o ile d for 40 m inu tes in th e d a rk n ess. Carbon t e t r a c h lo r id e was added from tim e to tim e to main­ t a in th e volum e.

Upon c o o lin g a t 3 0 ° o n ly a v ery few

sm a ll c r y s t a l s were o b ser v ed .

One fo u r th m l. o f bromine

was then added a id th© s o lu t io n again b o ile d f o r 40 m in u tes.

Again upon c o o lin g a t 3 0° o n ly a v ery few

sm a ll c r y s t a l s were o b serv ed .

About 6 in c h e s o f fin©

copper w ire was then p la ced in the form o f a c o i l in th© s o lu t io n and one fo u r th ml. o f bromine was added. s o lu t io n was b o ile d for 40 m inutes*

The

Upon c o o lin g a t 30®

a c o n s id e r a b le q u a n tity o f c r y s t a ls were o b serv ed .

Th®

s o lu t io n was f i l t e r e d and th e c l e a r f i l t r a t e evap orated

40

t o dryness#

th e r e s id u e o b ta in e d w eighed 0.4X 01 g , o f

which 0.0X 3 g , was m e s o -s tilb e n e d ib rom id e; so 0 .3 9 2 1 g . o f d l- s t ll b e n © dibrom ide rem ained o f th© o r i g i n a l 0 .5 g . 0 .5 g# o f d l « s t i l b e n e dibrom ide and 0 .0 3 5 g* o f cuprous bromide w ere added to 10 m l. o f carbon t e t r a ­ c h lo r id e and b o ile d fo r 40 m in u tes in the d ark ,

th e

volume was m a in ta in ed by adding carbon t e t r a c h lo r id e . Upon c o o lin g a t 3 0 ° fo r t h r e e hours no p r e c i p i t a t e o f m e s o -s tilb e n e dibrom ide was o b se r v e d .

One fo u r th ml* o f

bromine was th e n added and th e s o lu t io n a g a in b o ile d f o r 40 m in u te s.

The volume was m a in ta in ed a t 10 m l. and

c o o le d a t 3 0 ° fo r t h r e e h o u r s.

The s o lu t io n was th en

f i l t e r e d to remove th e copper bromide and th e c o n s id e r ­ a b le q u a n tity o f m e s o - s t ilb e n e dibrom ide which had p r e c ip it a t e d .

The f i l t r a t e was evap orated to d ry n ess

and th e r e s id u e o b ta in ed w eighed 0*2725 o f w hich 0.01& g . was m e s o -s tilb e n e d ibrom ide.

T h erefo r 0 .2 5 4 5 g* o f d l -

stllb e n ® dibromid© was reco v ered o f th e o r i g in a l 0 .5 g# Experiment a l D eterm in ation A ccom plished One gram o f d l - s t i l b e n e dibrom ide was d is s o lv e d in 1# m l. o f G.4&77 m olar bromine in carbon t e t r a c h lo r id e and was illu m in a te d at 30° fo r 120 h o u rs. f i l t e r s were u sed .

Both lig h t

Ho m e s o -stI lb e n e dibrom ide was o b ta in ed

so l e s s than 0 .0 1 3 g . o f d l - s t i l b e n e dibrom ide was iso m e r iz e d .

41

One graffi o f d l- s t llb e n © dibrom ide was d is s o lv e d in 18 m l. o f 0 .4 8 7 7 m olar bromine and was illu m in a te d a t 3 0 ° u s in g th© N o v io l A f i l t e r f o r 75 h o u r s. dibrom ide o b ta in e d w eighed 0 .0 9 4 6 g .

The m e s o - s t ilb e n e

Th© s o lu t io n c o n t a in ­

in g th e u n iso m erized d l - s t i l b e n e dibrom ide was ev a p o ra ted to d r y n ess and a p roduct w eig h in g 1 .0 8 2 8 g . o f w hich 0 .0 1 8 g . was m e s o - s t ilb e n e dibrom ide w as o b ta in e d .

T h is c r y s t a l ­

l i n e p roduct c o n ta in e d a s l i g h t amount o f y e llo w o i l . As some hydrogen bromide was g iv e n o f f d u rin g each run and a sm a ll amount o f o i l was o b ta in ed i t was d e s ir e d to d eterm in e how much bromine was u sed up. d l-s tilb e n e

One gram o f

dibrom ide was d is s o lv e d in 18 m l. o f 0 .4 8 7 7

m olar bromine and was illu m in a te d a t 3 0 ° u s in g th e N o v io l A i i I t e r fo r 70 h o u r s.

Ten m l. o f the r e a c t io n m ixtu re

was th e n t i t r a t e d and found to r e q u ir e 1 6 .1 m l. o f 0 .4 8 7 9 N, sodium t h i o s u l f a t e .

The r e a c t io n m ix tu re was 0 .3 9 2 7

m olar w ith r e s p e c t to brom ine.

The 0 .4 8 7 7 m olar bromine

s o lu t io n was t i t r a t e d a t th a t tim e and th e c o n c e n tr a tio n was found t o be unchanged. One gram o f d l - s t i l b e n e dibrom ide was d is s o lv e d in 18 ail. o f 0 ,4 8 7 7 m olar bromine and was illu m in a te d at 30° u s in g th e M oviol A f i l t e r fo r 95 h o u rs. dibromid© o b ta in e d w eighed 0 ,1 3 2 2 g»

The m © so~ stilb en e

42

One gram o f d l - s t i l b e n e dibrom ide was d is s o lv e d in 16 m l. o f 0 .4 6 7 7 m olar bromine and was illu m in a te d a t 3 0 ° u s in g th e N o v io l A f i l t e r f o r 116 h o u r s .

The m e s o - s t i l ­

bene dibrom ide o b ta in e d w eighed 0 .1 6 1 0 g . One gram o f d l - s t i l b e n e dibrom ide was d is s o lv e d in 16 m l. o f 0*4677 m olar bromine and was I llu m in a te d a t 3 0 ° u sin g th e N o v io l A f i l t e r fo r 60 hours*

The m e s o - s t i l ­

bene dibrom ide o b ta in e d w eighed 0 .0 7 0 3 g . One gram o f d l- s t ilb e n © dibrom ide was d is s o lv e d in 16 m l. o f 0 .4 6 7 7 m olar bromine and was illu m in a te d a t 30® u s in g t h e N o v io l A f i l t e r fo r 50 h o u r s.

The r a e s o - s t li­

feen© d ibrom ide o b ta in e d w eighed 0 .0 5 7 0 g . One gram o f d l - s t i l b e n e dibromid© was d is s o lv e d in 16 m l. ©f 0 .4 6 7 7 m olar bromine arid was illu m in a te d a t 3 0° u s in g th e N o v io l A f i l t e r f o r 30 h o u r s.

The m e s o - s t i l ­

bene dibrom ide o b ta in ed w eighed 0 .0 2 9 0 g . One gram o f d l - s t i l b e n e dibromid© was d is s o lv e d in 16 m l. o f 0 .2 4 3 6 m olar bromine and was illu m in a te d a t 30® u s in g the N o v io l A f i l t e r fo r 57 h o u rs.

Th© m e s o - s t i l ­

bene dibrom ide o b ta in ed w eighed 0 .0 5 3 3 g* On© gran o f d l - s t i l b e n e dibrom ide was d is s o lv e d in 16 m l. o f 0 .2 4 3 6 molar bromine and was illu m in a te d a t 30° u s in g the N o v io l A f i l t e r fo r 70 h o u rs. ben© dibrom ide o b ta in ed weighed 0 .0 7 3 4 g*

The n & s o -s til*

43

One gram o f d l - s t i l b e n e dibromid© was d is s o lv e d in 15 m l. o f 0 .9 7 5 4 molar bromine said was illu m in a te d a t o 30 u s in g th e N o v io l A f i l t e r f o r 40 h o u rs. The m esos t i l b e n e dibrom ide o b ta in e d w eighed 0 ,0 5 8 1 g . On© gram o f d l - s t l l b e n e dibrom ide was d is s o lv e d in 1$ m l. o f 0 .9 7 5 4 m olar bromine and was illu m in a te d a t 3 0 ° u s in g th e N o v io l A f i l t e r fo r 70 h o u rs.

The m eso-

stilb e n © dibrom ide o b ta in ed weighed 0 .1 2 6 2 g . One gram o f d l - s t i l b e n e dibrom ide was d is s o lv e d in Id m l. o f 0 .4 8 7 ? m olar bromine and was illu m in a te d a t o 30 u sin g th e N o v io l A f i l t e r fo r 50 h o u rs. A 20 gauge w ire sc r e e n was p laced over the l i g h t source to reduce the l i g h t i n t e n s i t y .

The m e s o -s tilb e n e dibromid© o b ta in ed

we ighedl 0 .0 3 3 7 g . One gram o f d l - s t i l b e n e dibrom ide was d is s o lv e d in 15 m l. o f 0*4877 molar bromine and was illu m in a te d a t 30® u s in g th e N o v io l A f i l t e r f$ r SO h o u rs.

A 20 gauge w ire

sc ree n was p la ce d over th e l i g h t sou rce t o reduce th e l i $ i t in te n s ity .

The m e s o -s tilb e n e dibromid© o b ta in ed

w eighed 0 .0 7 1 5 g* One gram o f d l- s t ll b o n e dibrom ide was d ie so lv ed in 13 m l. o f 0 .4 S 7 7 m olar bromine and was illu m in a te d a t 35° u s in g the N o v io l A f i l t e r for AO h o u rs. dibrom ide o b ta in e d w eighed 0 ,0 5 5 $ g .

The a e s o - s t ilb e n e

44

On© gram o f d l - s t i l b e n e dibrom ide was d is s o lv e d in

IB m l. o f 0 .4 # 7 7 m olar bromine and was illu m in a te d a t 3 5 ° u s in g th e H o v io l A f i l t e r f o r 70 h o u r s.

The m e s o - s t ilb s n e

d ibrom ide o b ta in ed w eighed 0 .0 9 4 2 g . C a lc u la tio n o f Quantum Y ie ld I t was found When the 435# A° l i n e o f mercury was u sed th a t 2 .2 5 X 10^5 quanta per second en tered th e r e a c t io n v e s s e l .

During 120 hours 2 .2 5 X 1 0 ^ quanta

p er secon d were found t o iso m e r iz e l e s s th an 0 .0 1 # g . o f d l - s t i l b e n e d ib rom id e.

T h erefor a t l e a s t 3 0 ,3 quanta

a re re q u ir ed fo r ev ery m o lecu le iso m eriz^ d . ( S y n th e s is and R e so lu tio n o f P h en y lb en zy lca rb in o l P h e n y lb e n z y lc a r b in o l was prepared a cco rd in g to th e method o f Gerrard and K enyon ^ ,

Benzaldehyde was added

to b en zy l magnesium c h lo r id e and th e a d d itio n product was decomposed w ith ammonium c h lo r id e to g iv e phenyl­ b e n z y lc a r b in o l (m .p. 67°* b .p . 177°/l5m m .} . The p h e n y lb e n z y lc a r b in o l was r e s o lv e d by form ing th e h a l f e s t e r of p h th a lic a c id and then c r y s t a l l i z i n g th e q u in in e s a l t o f th e h a lf e s t e r from a c e to n e . a lc o h o l gave a r o t a t io n of

The r e so lv e d

C«]0 i 5 3 .5 ° .

S y n th e sis of l~ 1 .2 ~ I3 ip h en v l flth y l Bromide Four grains o f d - l f 2 -d ip h e n y l e th y l a lc o h o l were d is s o lv e d in 50 ml, o f benzene and the s o lu t io n liras

45

sa tu r a te d w ith hydrogen bromid© g a s fo r one h ou r.

The

s o lu t io n was washed w ith w a ter t o remove hydrogen bromide and th e benzene was removed oh a steam bath under reduced p ressu re.

The 1 - 1 , 2 -d ip h e n y l e t h y l bromide was o b ta in ed

was a y e llo w o i l which gave a s p e c i f i c r o t a t io n o f -2 5 ,3 ® (G « 2 ,2 9 3 $ g« in 25 ml* o f carbon t e t r a c h l o r i d e ) .

When

a p o r tio n o f t h e y e llo w o i l was d i s t i l l e d a t 1 3 0 -1 3 5 ° a t 2 mm, a q u a n tity o f white n e e d le s m e ltin g a t 1 1 9 ° were o b ta in ed w hich gave no d e p r e ssio n when m elted w ith tr a n s s tilb e n e .

The d i s t i l l a t e from w hich the t r a n s -s tilb e n ®

was se p a r a te d was o p t i c a l l y in a c t iv e . R ea c tio n o f 1 - 1 ,2 -D ip h en y l 'Ethyl Bromide With Bromine In Carbon T e tr a c h lo r id e In the Dark, Two grams o f 1 - 1 , 2 -d ip h e n y l e t h y l bromide were d i s ­ s o lv e d in 20 m l, o f carbon t e t r a c h lo r id e and i m l, o f bromine was added and the s o lu t io n th en p la ced in th® d ark ,

Hydx*ogen bromide was g iv en o f f and w h ite c r y s t a ls

m e ltin g a t 2 27° sep a ra ted from th e s o lu t io n .

The c r y s­

t a l l i n e compound was i d e n t i f i e d a s m e s o -s tilb e n e d ib r o ­ mide and gave no d e p r e ssio n when m elted with an a u th e n tic sample * R e a c tio n o f 1 -1 ^ 2 -D iphenyl E th yl Bromide With Io d in e in D if fu s e Liafct Two grams o f 1 - 1 ,2 -d ip h e n y l e t h y l bromide wore d i s ­ s o lv e d in 25 m l, o f carbon t e t r a c h lo r id e and a few c r y s t a ls

46

o f io d in e were added and th e s o lu t io n th en p la ce d in d i f ­ fu s e lig h t f o r 4& hours*

The s o lu t io n was washed w ith

sodium t h i o s u l f a t e and w a ter and th e r e s u lt i n g s o lu t io n showed no change in o p t i c a l r o t a t io n . lleactio ja o f 1 - 1 .2 -D ip h e n y l K thvl Bromide With U lt r a v io le t

Msbl Two grams o f 1 - 1 ,2 -d ip h e n y l e t h y l bromide were d i s ­ so lv e d in 25 ml* o f carbon t e t r a c h lo r id e and su b je c te d to u l t r a v i o l e t l i g h t fo r 24 hours*

No change in o p t ic a l

r o t a t io n was observed* R ea ctio n o f 1 - 1 * 2 - D iphenyl B th y l Bromide With Io d in e in the P resen ce o f U lt r a v io le t L ight Two grams o f 1 - 1 p2 -d ip h e n y l e th y l bromide was d i s ­ so lv e d in 25 ini. o f carbon t e t r a c h lo r id e and a few c r y s ­ t a l s o f io d in e were added and the s o lu t io n was p la ced in u l t r a v i o l e t l i g h t fo r th r e e days*

At the end o f th e

f i r s t day a w h ite s o l i d s e t t l e d out*

A fter th e comple­

t io n o f th e illu m in a t io n th e s o l i d was f i l t e r e d o f f . A fte r s e v e r a l r e c - r y s t a liiz a t io n s from benzene th e s o lid m elted a t 2 25° and no d e p r e s sio n was observed when th e compound was m eltad w ith m e s o -s tilb e n e dibrom ide. The f i l t r a t e of the r e a c t io n m ixture was washed w ith sodium t h i o s u l f a t e and w a ter and th e r e s u lt in g carbon t e t r a c h lo r id e s o lu t io n was o p t i c a l l y i n a c t i v e .

47

He s o lu t io n o f Q e ta n o l-2 ^ Q cta n o l-2 was r e s o lv e d by form ing s e c - o c t y l hydro­ gen p h th a la te and c r y s t a l l i z i n g the b ru cin e s a l t o f th e h a lf e s t e r from a c e to n e .

Upon h y d r o ly s is o f th e b ru cin e

s a l t d - and l - o c t a n o l - 2 w ere o b ta in ed which gave r o ta ­ t i o n s o f 4*7*1° and - 6 .7 5 ° r e s p e c t iv e ly . R ea ctio n o f l- S e c - O c t y l A lco h o l With Hydrogen Io d id e Gas 35 m l. o f 1 - s e c - o c t y l a lc o h o l were sa tu r a te d w ith hydrogen io d id e ga s a t 0 ° and kept a t th a t tem perature fo r 24 h o u r s.

The r e a c tio n m ixture was then e x tr a c te d

w ith e t h e r , washed w ith w a te r , d ilu t e sodium b ic a r b o n a te , sodium b i s u l f i t e and w a te r , and d rie d over anhydrous sodium s u l f a t e .

The eth er was then removed and the liq u id

r e s id u e d i s t i l l e d .

Ho a lk y l io d id e was o b ta in e d .

I - S e c - o c t y l a lc o h o l was sa tu r a te d w ith hydrogen io d id e g a s a t 0 ° and s e a le d in an ampule aid a llo w ed to come t o room tem p eratu re and a llo w ed to stand fo r 4 d a y s. The product was th e n worked up a s in th e above r e a c t io n . No a lk y l io d id e was o b ta in e d . R ea ctio n o f d l-S e c -B u t v l A lco h o l With Hydrogen J M ide_G as S e c -b u ty l a lc o h o l was sa tu r a te d with hydrogen io d id e gas a t 0 ° in one t r i a l end again at room tem perature in another t r i a l .

Each tim e the r e a c t io n m ixtu re was worked

up in a manner s im ila r to th e o c t y l a lc o h o l r e a c t io n . s e c - b u t y l io d id e was o b ta in e d .

No

4$

P r e p a r a tio n o f S e c -B u ty l Io d id e S e c -b u ty l io d id e xves prepared by th e e x t r a c t io n method d e s c r ib e d in O rganic S y n t h e s e s ^ *

The r e a c t io n

v e s s e l was m o d ifie d in th a t a l l j o i n t s were sta n d a rd ta p e r g la s s .

$0 ml* ( 4 0 .5 g . ) o f s e c » b u ty l a lc o h o l

was p la c e d in th e pot o f th e r e a c t io n v e s s e l and 5* 65 g. o f red phosphorus and 75 ml* o f ch lo ro fo rm were added* 69*5 g® o f p u lv e r iz e d io d in e c r y s t a l s were p la ced in th e e x t r a c t io n chamber*

The pot was h ea ted by moans o f a

m an tel u n t i l th e ch loroform r e flu x e d s u f f i c i e n t l y t o g iv e s te a d y e x t r a c t io n o f th e io d in e . th e e x t r a c t io n was c o m p le te .

A fte r I B hours

The s o lu t io n was f i l t e r e d

to remove th e phosphorus and then washed w ith sodium b i­ s u l f i t e and w a ter and d r ie d over n ig h t w ith sodium s u l­ fa te .

The ch loroform was d i s t i l l e d o f f and th e s o lu t io n

was then f r a c t i o n a l l y d i s t i l l e d y ie ld in g 64 £• (64%) o f s e c - b u t y l io d id e , b o ilin g at 117-119°®

49

SMEARY

1»

A k i n e t i c stu d y was made o f th e is o m e r iz a tio n

o f d l - s t i l b e n e dibrom ide in to m eso-qstilb e no dibrom ide by th e a c t io n o f bromine in carbon t e t r a c h lo r id e in th e p r e se n c e o f lig h t • 2.

The e f f e c t s o f bromine c o n c e n t r a t i o n , l i g h t

i n t e n s i t y and t e m p e r a t u r e were s t u d ie d . 3.

The r e a c t i o n was found t o be f i r s t o r d e r w ith

r e s p e c t t o d l - s t i l b e n e dibroinide c o n c e n t r a t i o n and t o be one h a l f o r d e r w i t h r e s p e c t t o l i g h t i n t e n s i t y .

The r a t e

c o n s t a n t a ls o v a r i e d d i r e c t l y a s t h e s q u a r e r o o t o f th e bromine c o n c e n t r a t i o n , 4.

S in c e t h e r a t e o f t h e i s o m e r i z a t i o n v a r i e d d i r ­

e c t l y w ith t h e s q u a r e r o o t o f th e l i g h t i n t e n s i t y a f r e e r a d i c a l mechanism i s most l i k e l y i n v o l v e d . 5.

The d a t a o b t a i n e d s u p p o r t s th e o r i g i n a l proposed

mechanism t h a t a bromine f r e e r a d i c a l i s formed by th e incom ing l i g h t e n e r g y , which noa t l i k e l y makes a rearward a tta c k on one o f th e ca rb o n atoms and b r i n g s about an in v e r s io n a t t h e c a rb o n atom,

f v i d e n e e was a l s o o o ta in ed

that bromine m o l e c u l e s in some manrter a i d t h e bromine f r e e r a d ic a l in the 6.

in v e r s io n o f t h e c a rb o n atom,

The e f f i c i e n c y o f th e p h o to c h e m i c a l r e a c tio n was

in v e s t ig a t e d by a d eterm in a tio n o f the u p p e r li m i t o f th e

50

quantum y i e l d a t 435$ A@.

I t was found t h a t a t l e a s t

30*3 quanta o f l ig h t are req u ired fo r t h e is o m e r iz a tio n o f one m o lecu le o f d l - s t i l b e n e d ib rom id e. 7*

A method o f a n a ly s is based on s o l u b i l i t y was

d e v e lo p e d 9 so th a t th e amount o f e i t h e r isom er could be determ ined in th e p resen ce o f the o th e r isom er. F u rth er work u s in g o p t i c a l l y a c t iv e io d id e s i s su g g e ste d to show th a t the is o m e r iz a tio n r e a c tio n in v o l­ v e s Walden in v e r sio n *

51

BIBLIOGRAPHY

1* B u t l e r w , A nn., 1 1 1 . 242 (1 6 9 5 ); Z. Chem., j>, 276 (1 6 6 9 ) 2 . N oyes, J . A. Chem. S o c ., 2 2 , 2614 (1 9 4 6 ) 3 . P r ic e , " R e a c tio n s a t Carbon-Carbon Double Bonds", I n t e r s c ie n c e P u b lis h e r s , I n c . , New York, N .Y ., Chap* 3 , 1946 4 . B u c k le s , S te in m e tz and W heeler, J . Am. Chem. S o c .. 2 2 , 2496 (1 9 5 0 ) 5. B u c k le s , Hausman and W h eeler, J . Am. Chem. S o c ., 7 2 , 2494 (1 9 5 0 ) ~ 6 . A rcu s, Campbell and W illia m s, J. Chem. S o c ., 5 6 , (3 ) 2363 I 1934) — 7 . S te in m e tz , Ph. D. T h e s is , S .U .I .

(1949)

6.

L eig h to n and F o rb es, J . Am. Chem. S o c ., j>2, 3139

9.

T a y lo r and Crawford, J . Chem. S o c .,

(1 9 3 0)

(2 ) 1130 (1934)

1 0 . W is lic e n u s , C ., 1 9 0 1 . (1 ) 464 11.

Mock, Ph. D. T h e s is , S . U . I . , (1949)

12.

F orb es and H e id t, J . Am. Chem. S o c ., j>6,

(3 ) 2362

(1934)

1 3 . Gerrard and Kenyon, J . Chem* S o c ., (2) 256 4 -7 (1926) 1 4 . Kenyon, "Organic S y n th e se s " , C o l. V ol. I , Sec* L d ., Page 4 1 6 , John W iley and S on s, 1941

1 5 * K in e, "Organic S y n th e se s " , C ol. V o l. I I , Page 399 John W iley arid S on s, 1943

52

BIOGRAPHY

N o r r is G. W heeler was born in B ethany, M is s o u r i, on March 7 , 1 9 2 0 ,

He r e c e iv e d h i s elem en ta ry e d u c a tio n in

t h e Bethany and King C it y , M is s o u r i, p u b lic s c h o o l sy ste m s and was g ra d u a ted from Iowa C it y High S c h o o l, Iowa C it y , Iow a, in 1 9 3 $ .

In th e T a li o f 193$ he e n te r e d th© U n iv er­

s i t y o f Iow a, from w hich he r e c e iv e d th e d e g r e e o f B. S . in C hem istry in June 1 9 4 2 .

He c o n tin u e d h i s s t u d i e s in

th e Graduate C o lle g e o f the U n iv e r s it y .

In November 1942

he e n te r e d the U n ited S t a t e s Army A ir Corps and se r v e d f o r t h r e e y e a r s and sev en m onths.

He a g a in e n te r e d th e

G raduate C o lle g e o f th e S ta te U n iv e r s it y o f Iowa and r e c e iv e d th e d eg re e o f M. S . in O rganic C hem istry In June 194$.

He h e ld th e du Pont f e llo w s h ip in c h e m istr y

from 1949 * 1 9 5 0 . He i s a member o f th e American C hem ical S o c ie t y , Alpha Chi Sigma, Phi Lambda U p silo n and Sigma X i.