The Preparation of Certain Organic Fluorides

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P U R D U E U N IV ERSITY

T H IS IS TO C E R T IF Y T H A T T H E T H E S IS P R E P A R E D U N D E R MY S U P E R V IS I O N

Anthony Truchan

E N T IT L E D

THE PREPARATION OF CERTAIK ORGANIC FLUORIDES

C O M P L IE S W IT H T H E U N IV E R S IT Y R E G U L A T IO N S O N G R A D U A T IO N T H E S E S

A N D I S A P P R O V E D B Y M E A S F U L F IL L IN G T H IS P A R T O F T H E R E Q U IR E M E N T S

FOR THE D EG REE OF

D octor o f P h ilo so p h y

19

TO T H E L IB R A R IA N :---r IS —* T H IS T H E S IS I S N O T TO B E R E G A R D E D A S C O N F ID E N T IA L .

GRAD. SCHOOL FORM 9—3 - 4 9 — 1M

THE PREPARATION OF CERTAIN ORGANIC FLUORIDES A T h e sis S u b m itted to th e F a c u lty of P urdue U n iv e r s ity by Anthony Truchan I n P a r t i a l F u l f i l l m e n t of th e R eq u irem en ts f o r th e D egree of D o cto r o f P h ilo so p h y Ju n e , 1950

ProQuest Number: 27714164

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uest ProQuest 27714164 Published by ProQuest LLC (2019). C opyright 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 M icroform Edition © ProQuest LLC. ProQuest LLC. 789 East Eisenhower Parkway P.O. Box 1346 Ann Arbor, Ml 48106 - 1346

ACKNd/LEDCMhT

The a u th o r i s g r e a t l y in d e b te d t o P r o f e s s o r E* T* McBee, TNho h as b e e n i n d i r e c t c h a rg e o f t h i s r e s e a r c h , f o r h i s v a lu a b le s u g g e s tio n s and a s s i s ta n c e d u r in g th e c o u rs e o f t h i s i n v e s t ig a tio n * A g r e a t d e a l i s owed t o my f e llo w r e s e a r c h w o rk e rs . D o c to rs C. F . B aran au ck as and Yf. R* Rausch and many o th e r s f o r t h e i r f r i e n d l y s p i r i t o f c o o p e r a tio n and encouragem ent *

S p e c ia l

acknow ledgm ent i s made o f t h e v a lu a b le a id o f D o cto r Z. D. W elch. Much i s owed to th e e x p e r t h e lp of M e ssrs. Yf. E. F is h , J . V. H e ssio n , and C. S . S i l v e r t h c r n f o r t h e i r e f f o r t s i n con­ s t r u c t i n g t h e equipm ent and to Mr. I . F . M e r r it and h i s s t a f f f o r t h e i r a i d i n p ro c u rin g equipm ent and s u p p l i e s . T h is work was sp o n so red b y th e M a llin c k r o f t Chem ical Yforks, S t . L o u is , M is s o u ri, a s a Purdue R e se a rc h F o u n d a tio n F e llo w s h ip .

TABIE OF CONTENTS

Page ABSTRACT..................................................................................................... .......

i

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

1

INTRODUCTION

H ISTO R IC A L............................................................................................

3

D ISC U SSIO N ............................................................................................

U

EXPERIMENTAL.......................................................................................... 13 A. B.

F lu o rin a tio n of 1 ,1 ,l- T r ic h lo r o - 3 , 3 , B - tr if lu o r o p ro p an e w ith Anhydrous Rydrogen F lu o r id e . . . .

13

F lu o r in a tio n o f 1 , 1 , 1 - T r i c h l o r 0 -3 ^ 3 ,3 - t r i f l u o r o p ro p an e w i t h Antim ony( I I I ) F lu o r id e . . . . . . .

13

C.

F lu o r in a tio n o f 1 ,1 , 2 -T ric h L o ro -3 , 3 , 3 - t r i f l u o r o p r o p a n e .......................................................................................... 13

D.

S y n th e s is of 1 , 1 , 3 , 3 , 3 -P e n t a f lu o r opr op e n e ................ 1?

E.

F lu o r in a tio n o f 1 , 1 , 3 , 3 , 3 -P e n ta flu o ro p ro p e n e . . . .

F.

S y n th e s is o f 1 , 1 , 1 , 2 - T e tr a c h lo r o - 3 , 3 , 3 - t r i f l u o r o p ro p an e ............................................................................................18

G.

F lu o r in a tio n o f 1 , 1 , 1 , 2 - T e tr a c .h lo r o - 3 ,3 ,3 ................................................................ 18 t r i f l u o r opr opane

H.

S y n th e s is o f 1 , 2 -D ib ro m o -l, 1 , 3 , 3 , 3 - p e n ta f lu o r o p ro p an e and 2-B r o n o - l, 1 , 3 , 3 , 3 - p e n ta f l u o r o p ro p en e ............................................................................................19

I.

F l u o r i n a t i o n o f 1 , 2 -D ib ro m o -1 ,1 -d ic KLo ro p ro p an e

J.

F l u o r i n a t i o n o f 2-B r omo-1- c h lo r o - l , 1 - d i f l u or o p ro p an e ............................................................... . . . . . .

.

K.

F l u o r i n a t i o n o f 2 - C hlor o - l , 2-dibrom opropane

L.

F l u o r i n a t i o n o f 1 , 2 , 2 , 3-T etrabrom opropane

M.

S y n th e s is o f 1 -C h lo ro p ro p en e and 2- C hloroprop a ie . .

N.

S y n th e s is o f 1 - C hlor o - l , 2-dibrom opropane

18

• 19 21

. . . .

21

. . . . .

22 22

..........................2h

Page 0.

F l u o r in a tio n o f 1 -C h lo ro -l,2 -d ib ro m o p ro p a n e

. .

29

P.

C h lo r in a tio n o f 1 , 1 , 1 - T r i f lu o r o p r o p a n e .............................

29

Q.

S y n th e s is o f 3 , 3 , 3 - T r i f lu o r o - l - p r o p a n o l

26

R.

S y n th e s is o f U ,It,U -T riflu o ro b u ta n o ic A c i d ................ 2?

S.

Therm al B ro m in atio n of 1 , 1 , 1 - T r if lu o r o e th a n e . . . .

REACTION SmitARI

.

«

28

.......................................................................... 31

B IB I10G R A P H Ï..................................................................................... VITA

.

. . .

3h

LISTS OF TABLES AMD FIGURES

Page

l i s t o f T a b le s 1.

New F lu o r in a te d D e r iv a tiv e s o f E th a n e , P ro p an e, and B u t a n e ........................................................... . . . . 11

2.

F r a c tio n s I s o l a t e d fro m th e F l u o r i n a t i o n o f 1 , 1 , 2 -T ric h L o ro -3 ^ 3> 3 - tr if lu o r o p r o p e n e • .

. • 16

l i s t o f F ig u re s !♦

2.

D iagram m atic R e a c tio n Summary of S y n th e s is o f F lu o r in a te d D e r iv a tiv e s o f E th a n e , Bropane and B utane ..................................................... R e c t i f i c a t i o n Curve of F lu o r in a te d 1 , 1 ,2 T r i c h l o r o - 3 , 3* 3 - tr i f lu o r o p r o p e n e . . . . . . .

.

12 15

3.

R e c t i f i c a t i o n Curve f o r th e F l u o r i n a t i o n o f 2 - C h lo ro -1 ,2 -d ib ro m o p ro p an e .......................................... 23

U*

A p p aratu s f o r th e Therm al B ro m in a tio n o f 1 , 1 ,1 - T r i f l u o r o e t h a n e .......................

29

( C o n tr ib u tio n from th e D epartm ent o f C h em istry and Purdue R e se a rc h F o u n d a tio n , Purdue U n iv e r s ity )

SOME FLUORINATED DERIVATIVES OF ETHANE, PROPANE, AND BUTANE1

(1 )

P r e s e n te d i n p a r t b e f o r e th e Symposium on F lu o r in e C h em istry as p a p e r 2it, D iv is io n o f I n d u s t r i a l and E n g in e e rin g C h em istry , 1 1 2 th M eetin g of t h e A m erican C hem ical S o c ie ty , Mew Y ork, New Y ork, Taken i n p a r t from th e d o c t o r a l t h e s i s s u b m itte d by Anthony T ru ch an t o t h e f a c u l t y o f P urdue U n iv e r s ity i n p a r t i a l f u l f i l l m e n t o f re q u ire m e n ts f o r t h e d e g re e o f D o cto r o f P h ilo s o p h y .

By E . T. McBee and Anthony T ruchan

AN ABSTRACT T h is p a p e r i s one o f a s e r i e s ^ d e s c r i b i n g th e s y n th e s is

(2 )

E. T. McBee and c o -w o rk e rs. T his J o u r n a l, 6 2 , 33UO-33lil (19U0),

(3 )

E . T. McBee and c o -w o rk e rs . T h is J o u r n a l, 6 9 , 9I1J4.- 9 U7 (19U 7).

(U)

E. T. McBee and c o -w o rk e rs . I n d . Eng. Chem., 39, U09, lîl8 , k20 (1 9 lt7 ).

o f d e r i v a t i v e s o f f lu o r o a l k a n e s .

I t o f f e r s a n im proved s y n th e s is

o f CF^CHgCF^, t h e p r e p a r a t i o n of a G rig n ard r e a g e n t fro m CF-^CHgCHgCl, and d e s c r i b e s new f l u o r i n a t e d d e r i v a tiv e s o f e th a n e , p ro p a n e , and b u ta n e . Hexac h l o r oprop ene was s u b je c te d t o t h e sequence CCl^CCl^GClg ^ * 3 ) CFjCCl=CClg-j ■■

CF3CH2CF3

.

> CF3 CHC1CC1F2

Zn/ C2H501^

CF3CH=CF2 J E —)

il

(5 )

A. L , Henne, A. M. Whaley and J . K. S te v e n so n , T h is J o u r n a l, 6 3 , 3U78-3U79 (19U1)*

(6)

A» L» Henne and T. P . W aalkes, T h is J o u r n a l, 6 8 , U96-li.97 (19U 6).

No a d d i t i o n o f hydrogen f l u o r i d e a c ro s s t h e d o u b le bond o r h a li d e re p la c e m e n t o c c u rre d when CF^CCl^CClg was h e a te d w ith anhydrous l^rdrogen f l u o r i d e a t 2 U0 ° i n a p r e s s u r e v e s s e l , b u t i t was shown b y McBee and B o lt^ t h a t i n t h e p re s e n c e o f antim ony(V ) h a li d e s

(7 )

E . T. McBee and R. 0 . B o lt , In d . Eng. Chem., 39, U12-1Û5 (19U 7).

r e a c t i o n d id o c c u r.

The i d e n t i f i c a t i o n of t h e r e a c t i o n p ro d u c ts

have now b een s tu d i e d .

R e c t i f i c a t i o n of t h e p ro d u c t showed t h a t

CF3 CC1=CC12, CF3 CIIC1CC12F , CF3 CHCICCIF2 , CF3 CHC1CF3 , CF^CClgCClgF and CF3 CCI2 CCIF2 w ere p r e s e n t . Two in d e p e n d e n t r e a c t i o n s may b e view ed as ta k in g p l a c e , ( a ) a d d i t i o n o f hydrogen f l u o r i d e t o t h e d o u b le bond fo llo w e d by h a lo g e n exchange and (b ) a d d itio n of c h lo r in e (from antim ony(V ) c h l o r o f l u o r i d e s ) t o t h e d o u b le bond fo llo w e d by h a lo g e n ex ch an g e. CF^CHClCClgF was form ed b u t i t could n o t b e r e c t i f i e d from u n r e a c te d CF3 CC1"CC12 b e c a u s e th e d if f e r e n c e i n b o i l i n g p o i n t s i s o n ly one d e g ree.

F or p h y s ic a l c o n s ta n ts , CF^CHCICC^F was in d e p e n d e n tly

p r e p a re d by f l u o r i n a t i o n o f CF^CHCICGI^, o b ta in e d by a d d i tio n o f c h l o r in e t o CF^CB^CClg*

The s t r u c t u r e o f CF3 CHCICCIF2 was e s ta b lis h e d

by d e c h l o r i n a t io n t o CF^CB^CFg CF,CCl=GFg

and d e h y d r o c h lo r in a tio n to

The r a t i o o f CF3 CHCICCIF2 t o CF3 CHCICF3 was c o n t r o ll e d b y v a r y in g t h e amount o f hydrogen f l u o r i d e u s e d .

The u s e o f a 100

p e r c e n t e x c e ss of hydrogen f l u o r i d e gave h ig h y i e l d s o f CF3 CHCICF3 w ith a c o rre s p o n d in g d e c re a s e i n th e y i e l d o f CF^CHOlCClFg.

The

amount o f CF3 CC12 CC12F and CF3 C012 C01F2 v a r ie d w ith th e amount o f a n tim o n y (v ) c h l o r id e u s e d . Brom ine was added to CF3 CI?5CF2 u n d e r p r e s s u r e i n C a riu s tu b e s a t II4.O0 t o g iv e CF3 CEBrCBrF2 .

I^rdrogen b ro m id e was e lim in a te d

r e a d i l y from t h e l a t t e r compound to give CF3 CBr= CF2 . G rig n a rd r e a g e n ts c o n ta in in g f l u o r i n e o f f e r p o s s i b i l i t i e s f o r t h e p r e p a r a t i o n o f many i n t e r e s t i n g f l u o r o compounds.

Numerous

a tte m p ts have b e e n made t o p r e p a re G rig n ard r e a g e n ts fro m p o ly f lu o r o a l k y l c h l o r i d e s , b rom ides and io d id e s b u t w ith l i t t l e s u c c e s s in th e p a s t.

H e n n e t r e a t e d s e v e r a l f lu o r i n e - c o n t a i n i n g a l i p h a t i c

( 8)

A. L. Henne, T h is J o u r n a l, 60, 2275 (1 9 3 8 ).

(9 )

A. L. Henne and A. M. W haley, T his J o u r n a l, Q±} 1157 (19U2)•

h a l i d e s w ith magnesium i n e th e r s o lu t i o n and i n each in s ta n c e e i t h e r r e a c t i o n f a i l e d to o c c u r o r an o l e f i n r e s u l t e d th ro u g h th e l o s s o f t h e h a lo g e n s on a d ja c e n t carb o n atom s.

Thus f a r , t h e r e i s no e v id e n c e

t h a t a G rig n a rd “ a lp h a ” t o a f lu o r i n a t e d group has b e e n p r e p a re d ex ­ c e p t i n one

(1 0 )

in s ta n c e -^ ,

f o r w hich t h e a r t a s y e t d i s c l o s e s no c o r r o b o r a tio n .

T. J . B r ic e , W. H. P e a rls o n and J . H. Sim ons, T h is J o u r n a l, 6 8 , 968 ( 19 U6 ) .

iv

I t h a s now b e en fo u n d t h a t CF3 CH2 CH2 CI r e a c t s i n a n e th e r s o l u t i o n w ith magnesium t o fo rm th e G rig n a rd r e a g e n t 5 CF^GHgCHgMgCl. The s u c c e s s o f th e r e a c t i o n i s d ep en d en t upon anhydrous c o n d i t i o n s . The CF3 CH2 CH2 CI may b e d r ie d s a t i s f a c t o r i l y o v er D r i e r i t e o r T^y d i s t i l l a t i o n from p h o sp h o ru s(V ) o x id e .

A n a ly ti c a l g rad e d i e t h y l

e t h e r was s u c c e s s f u l l y u sed a s s o lv e n t f o r t h e r e a c t i o n .

A c ry s ta l

o f io d in e o r m e th y l io d i d e was em ployed i n th e u s u a l way t o i n i t i a t e th e r e a c tio n .

The G rig n a rd r e a g e n t, GF^C^Cf^MgCl, was c o n v e rte d

to CF3 CH2 CH3 by h y d r o ly s i s , t o CF3 CH2 CH2 OH by oxygen and h y d r o ly s is , and t o CF3 CH2 CH2 CO2H by c a rb o n d io x id e and h y d r o ly s i s .

The a lc o h o l

was fo u n d t o b e i d e n t i c a l t o th e one p re p a re d by Scherer*^* f o llo w in g

(1 1 )

S c h e re r, O ff. Pub. Bd. R ep o rt PB 7U3* 19Ule

a n o th e r p ro c e d u re . The CF3 CH2 CH2 C I, u se d i n t h e p r e p a r a tio n of th e G rig n a rd r e a g e n t , was p r e p a re d b y th e v a p o r p h ase c h l o r i n a t i o n o f CF^CHgCH^ f o llo w in g an im proved s y n th e s is w hich g iv e s a p re p o n d e ra n c e o f m o n o c h lo rid e s . F l u o r i n a t i o n o f CHgBrCB^CI^Br w ith antimonyClQ). f l u o r i d e y i e l d e d CI^BrCF2 CH2B r ♦

The f l u o r i n a t i o n p ro c e e d s b e s t when th e

f l u o r i n a t i n g a g e n t, a n tim o n y C n i)flu o rid e , c o n ta in s f r e e brom ine up t o 50 p e r c e n t o f t h e a n tim o n y (II3 )flu o rid e on a mole b a s i s . T rea tm e n t o f CHBrClCHBrC^ w ith m e r c u ry ( II ) f l u o r i d e ( p re p a r e d i n s i t u ) by t h e a c tio n o f anhydrous hydrogen f l u o r i d e

V

upon r e d m e r c u r y ( I I ) o x id e ^ ) p ro d u ced t h r e e new compounds, t o w hich t h e f o llo w in g s t r u c t u r e s w ere a s s ig n e d :

CHClFCHBrCH3 > CHFgCHBrCH^

and CHCIFCHFCH3 . The p h y s ic a l c o n s ta n ts o f a l l new compounds a r e summ arized i n T a b le I . E x p e rim e n ta l S ta r tin g M a te ria ls .

-

The CF3 CCI-CCI2 was p r e p a re d by

th e m ethod o f Herme^ from hexac h l o r o p r opene ( Hooker E le c tro c h e m ic a l Company).

J . T. B a k e r, C .p . antim ony(V ) c h lo r id e and anhydrous

hydrogen f l u o r i d e (p rim e com m ercial g rad e from Harshaw) w ere u sed f o r th e f lu o r in a tio n s . F lu o r in a ti o n o f CF^CCl- O C l^

-

A 2 - l i t e r , n ic k e l-lin e d

a u to c la v e was assem bled, evacuated and th en c h i l l e d to

0°.

CF^CCl-CClg (3*25 m o le s ), antimony(V) c h lo r id e ( 0 .3 m ole) and hydrogen f lu o r id e ( l 8 .lt m o les) were sucked in t o th e a u to c la v e i n th e order M entioned through th e n eed le valve*

The charged

a u to c la v e was h ea ted in a s ta tio n a r y , v e r t i c a l p o s it io n f o r one hundred hours a t 2 5 0 °.

A fte r c o o lin g t o l 5 0 ° , th e c o n te n ts were

r e le a s e d through t h e n e e d le v a lv e in to a reco v ery t r a in c o n s is t in g o f a g a llo n b o t t l e th r e e -fo u r th s f u l l of w a ter, a calcium c h lo r id e drying tow er and, f i n a l l y , a r e c e iv e r co o led w ith s o li d carbon d io x id e .

No a l k a l i was used i n th e w ater scrubber b ecau se

CF3 CHCICCIF2 i s e a s i l y d eh yd roch lorin ated to CF3 CC1 =CF2 *

The

o rg a n ic p ro d u c t was steam d i s t i l l e d , d r ie d and r e c t i f i e d i n a column o f a b o u t 25 t h e o r e t i c a l p l a t e s '^ .

(1 2 )

The p ro d u c ts from t h r e e

H. S . Lecky and R. H. E w e ll, I n d . Eng* Chem., A n a l. E d ., 12 5HU (19U 0).

s im i l a r r u n s w ere com bined f o r r e c t i f i c a t i o n .

P u r i f i c a t i o n of th e

compounds f o r ch em ic al a n a l y s is and d e te r m in a tio n o f p h y s ic a l p r o p e r t i e s was acco m p lish e d b y w ashing w ith w a te r , d r y in g and re -re c tify in g .

The r e c o v e ry o f CF^CCl^CClg p lu s an unknown

amount o f OF^OHClCClgF was 21%.

The c o n v e rs io n s to CF3 CHCICF3 ,

CF^CHClCClFg, CF3 CCI2 CCI2F , and CF3 CCI2 CCIF2 w ere 16%, 50%, 2%, and 2% r e s p e c t i v e l y . I n a n o th e r e x p e rim e n t, a 2 - l i t e r , m onel l i n e d a u to c la v e was ch a rg e d w ith CF3 CCI-CCI2 ( 3 .3 m o les) and anhydrous hydrogen f l u o r i d e (12 m o le s) and h e a te d a t 2 I4.O0 f o r s ix ty - s e v e n h o u r s . o f 1225 l b . / s q . i n . was o b se rv e d . u s u a l manner and r e c t i f i e d .

A p re ssu re

The p ro d u c t was i s o l a t e d i n th e

T hree m oles o f t h e s t a r t i n g m a t e r i a l ,

CF3 CCl=CCl2 , was r e c o v e re d , i n d i c a t i n g t h a t s u b s t a n t i a l l y no f l u o r i n a t i o n h as o c c u rre d . S y n th e s is o f CF3 CB=CF2 and CF3 CH2 CF3 .

-

A 5 - l i t e r , 3 -n eck ed

f l a s k was f i t t e d w ith a d ro p p in g f u n n e l, a m ercu ry s e a le d s t i r r e r and a r e f l u x co n d en ser th ro u g h w hich i c e c o ld w a te r was c i r c u l a t e d . A r e c e i v e r c o o le d b y s o l i d c arb o n d io x id e was c o n n e c te d i n s e r i e s w ith t h e c o n d e n s e r.

The f l a s k was ch a rg e d w ith z in c d u s t (7 m o le s)

and a b s o lu te e th a n o l (1500 m l . ) .

T h is m ix tu re was h e a te d to t h e

te m p e ra tu re o f r e f l u x i n g a lc o h o l and CF^CHClCClFg (5*8 m o le s ) was added d r o p m s e t o th e z in c - a lc o h o l s u s p e n s io n o v er a p e r io d of s ix h o u rs.

Upon r e c t i f i c a t i o n of th e p r o d u c t c o l l e c t e d i n th e

co ld t r a p , CF3 CIFCF2 ( 5 .0 m o les) and CF^CHClCClFg ( 0 ,6 m ole) w ere o b ta in e d r e p r e s e n t i n g a c o n v e rsio n o f Q6% and a y i e l d o f 96% to CF^CE^CFg*

CF3 CIFCF2 was c o n v e rte d to CF-^CHgCF^ by th e a d d i t i o n o f

hydrogen f l u o r i d e ^ , % m th e s is o f CF^CHClCClj.

-

A C a riu s tu b e was c h a rg e d •vd.th

CF^CîFCGl2 (O.U m o le ), l i q u i d c h lo r in e (0 .7 5 m ole) and an tim o n y (7 ) c h l o r id e (O.OU m o le) and t h e m ix tu re was h e a te d a t lU 0o f o r tw e n ty fo u r h o u rs.

The p r o d u c t was washed w ith aqueous a l k a l i , d r ie d and

p u rifie d by r e c tif ic a tio n .

F i f t y grams o f CF^CHCICCI^ (0 .2 1 m ole)

was o b ta in e d r e p r e s e n t i n g a y i e l d and c o n v e rs io n o f 53 $» S y n th e s is of CF^CHClOClgF.

-

A m ix tu re of CF3 CHCICCI3

( 0 .1 8 m o le ), antim ony( I I I ) f l u o r i d e ( 0 .1 3 m ole) and antim ony( 7 ) c h lo r id e (0 .0 6 m ole) was r e f l u x e d f o r one h o u r. steam d i s t i l l e d and p u r i f i e d t y r e c t i f i c a t i o n .

The p r o d u c t was One t e n t h mole o f

CF^CHCICC^F was o b ta in e d r e p r e s e n t in g a y i e l d and c o n v e rs io n o f 56$. S y n th e s is o f CF^CHBrCBrFg and CFjCB^CFg*

** Two C a riu s

tu b e s w ere c h arg e d w ith CF^CH^CFg ( 0 .7 m ole) and brom ine ( 0 .7 2 m o le) and h e a te d a t II4.O0 f o r tw e n ty -fo u r h o u rs .

The p r o d u c ts w ere com­

b in e d , w ashed f r e e o f brom ine w ith aqueous sodium s u l f i t e , d r ie d and re c tifie d .

Two t e n t h s mole o f CFjCBr=CF2 311(1 0 .7 m ole of CF^CHBrCBrFg

w ere o b ta in e d .

Del^rd ro b ro m in a tio n o f CF^ CHBr CBrF g d u rin g t h e

w ashing s te p cau sed t h e f o rm a tio n o f CF^CBr-CFg* C h lo r in a tio n o f CF3 CH2 CH3 .

-

C h lo r in a tio n s were c a r r i e d

o u t a t 1 1 0 ° i n a 2- l i t e r ro u n d -b o tto m f l a s k s u rro u n d e d b y t h r e e 2 0 0 -w a tt in c a n d e s c e n t la m p s.

The lam ps s e rv e d a d u a l p u rp o se o f

f u r n i s h in g l i g h t f o r t h e p h o to c h e m ic a l r e a c t i o n and h e a t t o m a in ta in t h e te m p e r a tu r e .

C h lo rin e and t r i f l u o r o p r opane w ere in tr o d u c e d

a t p re d e te rm in e d r a t e s th ro u g h c a l i b r a t e d flo w m e te r s .

The p r o d u c ts

w ere l e d from t h e r e a c t i o n f l a s k t o t h e b o tto m o f a c o u n te r c u r r e n t w a te r s c ru b b e r t o remove hydrogen c h l o r id e .

Gases le a v in g th e

s c ru b b e r w ere d r ie d w ith anhydrous calciu m c h l o r id e and c o l l e c t e d i n a r e c e i v e r co o le d w ith s o l i d c a rb o n d io x id e . I n a t y p i c a l e x p e rim e n t, CF3 CH2 CH2 and c h lo r in e w ere i n t r o ­ duced i n t o t h e r e a c t o r a t a r a t e o f li5 l . / h r . and 1 1 .5 l . / h r . re s p e c tiv e ly .

A f te r 1U.7 m oles o f CF3 CH2 CH3 had b een in tr o d u c e d ,

th e system was p u rg e d w ith a i r and th e p ro d u c t was r e c t i f i e d t o s t r i p o u t u n r e a c te d CF3 CH2 CH3 f o r r e c y c l i n g . c o n tin u e d u n t i l 1 0 .U m oles h ad r e a c t e d .

T his p ro c e d u re was

Upon r e c t i f i c a t i o n o f th e

f i n a l p r o d u c t, t h e r e was o b ta in e d 2 .2 m oles o f CF3 CHCICH3 , 5 .8 m oles o f CF3 CH2 CH2 C I, and 1 .7 m oles o f CF3 CB2 CHCI2 o r a t o t a l y i e l d o f c h l o r in a te d p r o d u c t o f 93$.

T h is i s a d i f f e r e n t r a t i o of

p r o d u c ts th a n t h a t o b ta in e d by Henne u s in g a d i f f e r e n t te c h n iq u e ^ , a lth o u g h t h e p r e f e r e n t i a l p a th o f c h l o r in a ti o n i s s t i l l s u b s t i ­ t u t i o n o f a hydrogen b e t a t o t h e tr i f l u o r o m e t h y l g ro u p .

S y n th e s is o f CF^CHgCHgOH.

-

A 1 - l i t e r , 3 -n eck ed f l a s k

was eq u ip p ed w ith a m e rc u ry -s e a le d s t i r r e r , a d ro p p in g f u n n e l and a r e f l u x c o n d e n se r t h e to p o f which was capped w ith a c a lc iu m c h l o r id e tu b e .

Magnesium t u r n in g s ( 0 .8 m ole) was p la c e d i n th e

f l a s k and t h e system was f lu s h e d w ith d ry n i t r o g e n .

A s o lu t i o n o f

CF^CHgCHgCl ( 0 .8 m ole) i n d r y e t h y l e t h e r (3 0 0 m l .) was added from th e d ro p p in g f u n n e l .

The r e a c t i o n was slow i n s t a r t i n g and had to

b e c a ta ly z e d w ith a c r y s t a l o f i o d i n e . was v e ry v ig o ro u s u n t i l c o m p le te d .

Dry oxygen was in tr o d u c e d i n t o

t h e f l a s k u n t i l no more was a b s o rb e d . s u l f u r i c a c id was a d d e d .

Once s t a r t e d , t h e r e a c t i o n

Then 200 m l. o f 25$ aqueous

The w a te r p h a se was c o n tin u o u s ly e x tr a c te d

w ith e t h e r f o r f i v e h o u r s .

The e th e r e x t r a c t was d r ie d o v e r

D r i e r i t e and th e n r e c t i f i e d t o g iv e 36 g . o f CF^CHgCHgOH. S y n th e s is o f OF^CHgCHgOOgH.

-

The G rig n ard r e a g e n t was

p r e p a re d a s b e f o r e s t a r t i n g w ith O.U m ole o f CF^CHgOHgCl.

S n a il

lum ps o f s o l i d c arb o n d io x id e w ere d ro p p ed i n t o t h e e th e r s o l u t i o n . The r e s u l t i n g m ix tu re was th e n t r e a t e d w ith 100 m l. o f d i l u t e s u l f u r i c a c id .

The l a y e r s w ere s e p a r a te d and th e aqueous l a y e r

was e x t r a c t e d s e v e r a l tim e s w i th f r e s h p o r ti o n s o f e t h e r .

The

com bined e t h e r l a y e r s w ere d r ie d o v e r anhydrous c a lc iu m c h lo r id e and th e e t h e r was b o i l e d away.

The r e s id u e was t r a n s f e r e d t o a

5O-m l. s id e arm d i s t i l l i n g f l a s k f i t t e d w ith an a i r c o n d e n s e r. f r a c t i o n b o i l i n g i n t h e r a n g e 162 - 1 7 6 ° was c o l l e c t e d as cru d e CF^CI^CE^COgH (2li. g . ) .

The cru d e OF^GH^OH^OO^B was d is s o lv e d i n

The

X

(3 0 -6 0 ° ) p e tro le u m e t h e r , d e c o lo r iz e d w ith N o r ite and r e c r y s t a l l i z e d tw ic e t o g iv e a w h ite s o l i d (m .p . 3 3 .2 ° , t u p . 1 6 6 .6 ° ) h a v in g an odor s im ila r t o t h a t o f b u ty ric a c id . fo r

1U 2.1.

Found:

I l 4l . l 1..

P r e p a r a tio n o f CHgBrCFgCHgBr. r e a c t i o n s was u se d :

N e u tr a l e q u iv a le n t c a l c d .

-

The f o llo w in g s e r i e s o f

CHgBrCHBrCN^Br—— —

CBr CHgBr — ------ ^ 2 - ^

lli SbFo ON^BrOBr^ON^Br-------------3—

CHgBrCFgCHgBr.

(1 3 )

«O rganic S y n th e s is "

C o ll. V ol. 1 , 209-211 (19U 1).

(lU )

C. D. H urd, R. N. M e in e rt and L. U. S pence, T h is J o u r n a l, 5 2 , 1138-111:6 (1 9 3 0 ).

T hree m oles o f

CH^BrCBrgCHgBr, 3 m oles o f b rom ine and U m oles o f a n tim o n y ( I I I ) f l u o r i d e w ere p la c e d i n a 5 - l i t e r , 3 -n eck ed f l a s k f i t t e d w ith a s t i r r e r and a c o n d e n s e r.

The r e a c t i o n m ix tu re was h e a te d a t 150°

and CH^BrCF^CH^Br d i s t i l l e d th e r e fr o m a s r a p i d ly a s fo rm e d .

The

y i e l d a n d c o n v e rs io n w ere ]&%• F l u o r i n a t i o n o f CHBrClCHBrCH^.

-

The s t a r t i n g m a t e r i a l was

p r e p a re d by d e h y d r o c h lo r in a tio n o f CH^OlCHClCH^ w ith c o ld a lc o h o lic p o ta ss iu m H ydroxide a c c o rd in g t o t h e m ethod o f R eboul

(1 5 )

15

.

R e c tifi-

H. R eb o u l, Ann. ch in u p h y s ., ( 8 ) , l i t , I4.6 U (1 9 0 7 ).

c a t i o n o f t h e p ro d u c t gave CHCl-CHCH^ to w hich b ro m in e was added to g iv e CHBrClCHBrCH^.

F or t h e f l u o r i n a t i o n , a m ix tu re o f 2 .1 m oles

o f m e r c u r y ( ll) o x id e was p la c e d i n t h e a u to c la v e and h e a te d a t Wi°

f o r s ix t e e n h o u rs •

The p ro d u c t c o n s is te d o f CHClFCHBrCH3 ( 13^

y i e l d ) , CHFgCHBrCH^ ( 10 % y i e l d ) and CHCIFCHFCH3 ( 6 % y i e l d ) .

Aclmowledgment.

-

The a u th o r s w ish t o acknow ledge t h e

f i n a n c i a l a s s i s t a n c e o f M a llin c k ro d t Chem ical Works w h ich made th is re se a rc h p o s s ib le .

Summary A new s e r i e s o f r e a c t i o n s f o r t h e p r e p a r a ti o n o f CF3CH2CF3 i s d e s c r ib e d .

The f l u o r i n a t i o n o f CF^CCl-CCl^ w ith anhydrous

hydrogen f l u o r i d e and antim ony(V ) c h l o r id e gave CF^CHClCClgF, CF3CHCICCIF2, CF3CHCICF3, CF3CCI2CCI2F and CF3CCI2CCIF2. A G rig n a rd r e a g e n t c o n ta in in g f l u o r i n e was o b ta in e d b y t r e a t i n g CF3CH2CH2CI i n d i e t h y l e th e r w ith magnesium tu r n in g s to g iv e CF3CH2CH2MgCl.

The l a t t e r v/as c o n v e rte d t o CF3CH2CH3,

CF3CH2CH2OH and CF3CH2CH2CO2H by r e a c t i o n s common to G rig n ard re a g e n ts . F l u o r i n a t i o n o f C i^B rC B ^C ï^B r w ith a n t im o n y ( lll ) f l u o r i d e gave CH2BrCF2CH2Br. F l u o r i n a t i o n o f CHBrClCHBrCH3 w ith m e r c u r i c ( I I ) o x id e and hyd ro g en f l u o r i d e gave t h r e e new compounds CHClFCHBrC^, CHF2 CHBrCH3 and CHCIFCHFCH3 .

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rCA O H y o CA P=< O

0 ° , t h e c o n te n ts w ere r e l e a s e d by means o f t h e n e e d le v a lv e i n t o t h e re c o v e ry t r a i n c o n s is tin g o f a 1 g a llo n b o t t l e t h r e e f o u r t h s f u l l o f w a te r , fo llo w e d by a d ry in g to w er f i l l e d w ith c a lc iu m c h l o r id e , and, f i n a l l y , a r e c e i v e r c o o le d w i t h s o l i d c a rb o n d io x id e *

No a l k a l i was u sed i n th e w a te r s c ru b b in g

b o t t l e "because 1 , 2- d i c h l o r o - l , 1 , 3 , 3 , 3 - p e n t a f lu o ro p ro p a n e i s e a s i l y dehydro c h l o r in a te d t o 2 - c h lo r o - l , l , 3 , 3 , 3 - p e n ta f lu o r o p r o p en e.

The

o r g a n ic p ro d u c t was steam d i s t i l l e d , d r ie d over calc iu m c h l o r i d e , and r e c t i f i e d *

P u r i f i c a t i o n o f t h e compounds f o r c h em ical a n a l y s is

and p h y s ic a l p r o p e r t i e s was accom plished by w ashing w ith w a te r , d r y in g , and r e - r e c t i f y i n g . T h ree b a tc h e s o f 1 , 1 , 2 - t r i c h l o r o - 3 , 3 , 3 - t r i f lu o ro p r opene w ere f l u o r i n a t e d as f o llo w s : 1

2

3

CF^CCl^CClgj m oles

U.8 6

3.2 5

3.2 5

S bC l^, m oles

0 .5

0 .3

0 .3

1 5 .7

1 2 .7

Run No.

HF, m oles

18.U

The p r o d u c ts from th e t h r e e ru n s w ere combined f o r r e c t i f i c a t i o n , th e d a t a from w hich a r e shown g r a p h ic a lly i n F ig u re 2 . l i s t s t h e f r a c t i o n s i s o la te d *

T a b le 2

The re c o v e ry o f 1 , 1 , 2 - t r i c h l o r o -

3 , 3 , 3 - t r i f lu o ro p ro p e n e ( f r a c t i o n No* 7 , T ab le 2) p lu s a n unknown

15

z O O Tf

8

ÛC H t cO

oc 3 O

z

o H

S YO LU

o

û c: m V9

«o

o Q . 'i - N I O j

vS 9N m og

2b

c i s 1 -c h lo ro p ro p e n e a t 3 2 e 8 ° 5 and t r a n s 1 - c h lo ro p ro p e n e a t 3 7 . h ° • H ence, i t sh o u ld b e p o s s i b l e t o s e p a r a te such a m ix tu re b y r e c t i f i ­ c a tio n *

I t was fo u n d t h a t a 2b in c h L ecky-E w ell ty p e c o lu m n ^

d e v e lo p in g a b o u t 5 0 t h e o r e t i c a l p l a t e s could b e u s e d to g iv e t h e d e s ir e d s e p a ra tio n * A 5 - l i t e r , 3 -n eck ed f l a s k was equipped w ith a m e r c u ry - s e a le d s t i r r e r , a d ro p p in g f u n n e l , and a r e f l u x condenser th ro u g h w h ic h i c e c o ld w a te r was c i r c u l a t e d .

The f l a s k was c h a rg e d w ith 15 m oles

o f te c h n ic a l g ra d e p o ta ssiu m h y d ro x id e d is s o lv e d i n t h r e e l i t e r s o f a b s o lu te e th a n o l. tr o u g h .

T h is s o lu t i o n was k e p t a t 15° by a c o ld w a te r

T e c h n ic a l g rad e 1 , 2 - d ic h lo ro p ro p a n e , lU*5 m o le s , was

added from t h e d ro p p in g f u n n e l over a p e r io d o f tw o h o u rs .

At th e

end o f t e n h o u r s , th e m ix tu re was ste a m d i s t i l l e d t o renove t h e c h lo r opr o p e n e s .

The d i s t i l l a t e was w ashed once w ith c o ld w a te r and

d r ie d o v e r c a lc iu m c h l o r i d e .

The p ro d u c t was r e c t i f i e d on a 2b

in c h L eck y -E w ell ty p e colum n to g iv e l . U m oles o f 2 -c h lo ro p ro p e n e , b . p . 2 2 . 0- 2 3 . 0 ° ( y ie ld and c o n v e rsio n w ere 1 6 and 1 0 p e r c e n t r e s p e c t i v e l y ) and U*0 m oles of a m ix tu re o f c i s and t r a n s 1 - c h l o r o p ro p e n e s , b o i l i n g ra n g e 3 2 . 0 - 3 7 *0 ° ( y i e l d a n d c o n v e rs io n w ere bb and 28 p e r c e n t r e s p e c t i v e l y ) . was 5*U m oles*

The re c o v e ry of 1 , 2 -d ic h lo ro p ro p a n e

No a tte m p t was made to s e p a r a te t h e c i s and tr a n s

1 - c h lo r o p r o p e n e s •

S y n th e s is o f 1 -C h lo ro -l* 2 -d ib ro m o p ro p a n e .

-

A m ix tu re of

c i s and t r a n s 1- c h lo r o p r o p e n e s , b o i l i n g ra n g e 31 - 37 ° (U *6 m o les) was r e a c t e d w ith brom ine (lj.,6 m o les) a t 0 ° .

The p ro d u c t was

25

p u r i f i e d by re d u c e d p r e s s u r e d i s t i l l a t i o n fro m a C la is e n f l a s k . The m a t e r ia l b o i l i n g a t 69° a t 12 mm. Hg o r 93-95° a t 53 mm. Hg was c o l l e c t e d a s p u re 1 - c h lo r- l,2 - d ib ro m o p r o p a n e .

The y i e l d was

91 p e r c e n t .

F l u o r i n a t i o n o f l-C h lo ro - l,2 - d ib ro m o p r o p a n e .

-

A 1 -lite r.,

c o p p e r - lin e d a u to c la v e was c h i l l e d to - 70 ° w ith a m ix tu re o f s o li d c arb o n d io x id e and t r i c h i o r o e t h y l e n e and th e n ch arg e d w ith 2 . 1 m oles o f 1 - c h l o r o - l , 2 -d ib ro m o p ro p a n e, 7 moles o f anhydrous h y d ro g en f l u o r i d e and 2 .1 m oles o f r e d m e r c u r y ( I I ) o x id e i n t h e o rd e r named. The m e r c u r y ( I I ) o x id e was added i n sm a ll p o r tio n s w ith th o r o u ^ i s t i r r i n g a f t e r each a d d itio n a c c o rd in g t o t h e p ro c e d u re d ev elo p ed b y T o la n d ^ *

The a u to c la v e was e l e c t r i c a l l y h e a te d a t UU° f o r 16

h o u rs a f t e r w hich i t was c o o le d to 0 ° .

The c o n te n ts w ere s c ra p e d

o u t i n t o a U l i t e r b e a k e r c o n ta in in g c ra c k e d i c e and 1 l i t e r o f 3 m o lar sodium h y d ro x id e .

The m ix tu re was steam d i s t i l l e d y i e l d in g

16? g . o f a w et o rg a n ic p r o d u c t.

A second b a tc h of 1 - c h l o r o - l , 2-

dibrom opropane was f l u o r i n a t e d a s b e f o r e y i e l d i n g 188 g . o f a w et p r o d u c t.

The combined p r o d u c ts w ere d r ie d over calciu m c h lo r id e

and r e c t i f i e d on a 2 lt-in c h L ecky-E w ell ty p e colum n. compounds w ere i s o l a t e d .

T h ree new

The y i e l d o f 1 - c h l o r o - l , 2 - d if lu o r o p ro p a n e

was 60 m l. o r 15 p e r c e n t .

The y i e l d o f 2 - b r om o-l, 1 - d i f lu o r o p r opane

was 50 m l. o r 12 p e r c e n t .

The y i e l d o f 2 - b r o m o - l- c h lo r o - l- f lu o r o ­

p r opane was 60 m l. o r l l; p e r c e n t. C h lo r in a tio n o f 1 . 1 , 1-T r i f lu o r opr o p a n e .

-

Chi o r i n a tio n s

w ere co n d u cted a t 11 0° i n a 2 - l i t e r , ro u n d -b o tto m f l a s k su rro u n d ed

26

by 3 , 200 - w a t t in c a n d e s c e n t lam ps.

The lam ps se rv e d a d u a l

p u rp o se o f f u r n i s h in g l i g h t f o r t h e p h o to c h e m ic a l r e a c t i o n and h e a t t o m a in ta in th e te m p e r a tu re .

C h lo rin e and t r if l u o r o p r o p a n e

w ere in tr o d u c e d a t p re d e te rm in e d r a t e s th ro u g h c a l i b r a t e d flo w m e te r s .

The p r o d u c ts w ere l e d from th e r e a c t i o n f l a s k to th e

b o tto m o f a c o u n te r c u r r e n t w a te r s c ru b b e r t o remove h y d ro g en c h lo r id e . Gases l e a v i n g t h e s c ru b b e r w ere d r ie d w ith anhydrous c a lc iu m c h lo r id e and condensed i n a r e c e i v e r c o o le d w ith s o li d c a rb o n d io x id e . I n a t y p i c a l e x p erim e n t, 1 , 1 , 1 - t r i f lu o ro p ro p a n e and c h lo r in e w ere in tr o d u c e d i n t o th e r e a c t o r a t a r a t e o f U5 l i t e r s p e r hour and H . 5 l i t e r s p e r h o u r r e s p e c tiv e ly *

A f te r l i t . 7 m oles of 1 , 1 ,1 -

t r i f lu o ro p ro p a n e had b ee n in tr o d u c e d , th e sy stem was purged w ith a i r and t h e p ro d u c t was r e c t i f i e d t o remove u n r e a c te d 1 , 1 , 1t r i f l u o r opropane f o r r e c y c l i n g . u n t i l 1 0 .it m oles had r e a c t e d .

T his p ro c e d u re was c o n tin u e d Upon r e c t i f i c a t i o n of th e f i n a l

p r o d u c t, t h e r e w ere o b ta in e d 2 .2 m oles o f 2 - c h l o r o - l , 1 , 1 - t r i f l u o r o ­ p ro p a n e , 5*8 m oles o f 3- c h l o r o - l , 1 , 1 - t r i f lu o r opropane and 1 . 7 m oles o f 3*3 - d i c h i o r o - l , 1 , 1 - t r i f l u o r o p r o p a n e .

T his i s a d i f f e r e n t r a t i o

o f p r o d u c t th a n t h a t o b ta in e d by H e n n e ^ u s in g a n o th e r te c h n iq u e a lth o u g h t h e p r e f e r e n t i a l p a th o f c h l o r in a ti o n i s s t i l l s u b s t i t u t i o n o f a h y d ro g en b e t a t o t h e t r i f lu o r orae t h y l g ro u p . S y n th e s is o f 3,3 -)Kf CF3 CIFCF2

Y ie ld , 96$

Conv. , 86 $ .

130 ° 5.

CF3 CH=CF2 + HF CF3 CH2 CF3

Y ie ld and c o n v e rs io n , 88 $ .

32

6.

CF3 CÎPCCI2 + Cl 2

11*0°

CF3 CHCICCI3 *

Y ie ld and c o n v e rs io n , 53/oSbCl5

7.

CF3 CHCICCI3 + SbFj CF3 CHC1CC12F-K

8.

CF3CIFCF2 f B r2

■ÎHÎ-

-

Y ie ld and c o n v e rs io n , 56 /3.

11*0 °

CF3 CHBr CBrF 2^

Y ie ld , 50^.

CF3 CB1CCF2*

Y i e ld , lh%. Br,

9.

10.

CBrCl2 CHBrCH3 + ^ 3 CFoCHBrCHo

Y ie ld ,

CClF2CHBrCH3

Y ie ld , 30%.

CF3 CHBrCH3

11,

13.

Br, Y ie ld and c o n v e r s io n , 5 6 $ .

CH2BrCBr2CH2Br f SbF3 CHgBrCF2 CH2Br CH2 C1CHC1CH3 f KOH

■xx

Y ie ld an d c o n v e r s io n , 80$.

CB2BrOBrO1CB3 + SbF3 CH2BrCF2 CH3

12.

SbCl^

CClF2 CHBrCH3 + BbF^

■ÎHf

Br, ------------- >

-x->

Y ie ld an d c o n v e rs io n , U5$. EtOH 15°

lU,

CHC1=CHCH3

Y ie ld , Uk%

C onv., 28$,

CH2=CC1 CH3

Y ie ld , 16$

C onv., 10$,

CHC1=CH2 CH3 + B r 2~~ CHBrGlCHBrCH-3

Y ie ld a n d c o n v e r s io n , 91$.

33

15.

16.

17.

CHBrClCHBrCEj + HgO + H F

—>

CHF2CHBrCH3*

Y ie ld , 12$.

CHClFCHBrCH3^

Y ie ld , l l $ .

CHClFCHFCHy*

Y ie ld , 15%.

CF3CH2CH3 + C l2

h»

->CM.

CF3CHC1CH3

Y ie ld , 21$.

OF3 OH2 OH2Ol

Y ie ld , 56$.

CF3 GH2 CHCl2

Y ie ld , 16$.

GF3OH2OH2Ol t Mg

EtpO ** ----> CF3CH2CH2MgCH "

CF3CH2CH2MgGl t 0 2 OF3OH2GH2OH 18.

OF3OH2OH2MgOl + C02 CF3CH2CH2COgH'îf1

19.

CF3CH3 + B r2

Y ie ld and c o n v e rs io n , 39$/o. ■ÎHfr Y ie ld and c o n v e r s io n , 1+2$.

625°

CF3CH2Br

Y ie ld , 29$.

C onv., 17$.

CF3CHBr2

Y ie ld , 33$.

C onv., 19$.

CF3 CBr3*

Y ie ld , 16 $ .

Coiwv,

9$.

3U

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VITA

A nthony Truchan was born O ctober 8 , I 91 I4.5 i n F l i n t , M ich ig an . He a tte n d e d F l i n t J u n io r C o lle g e , F l i n t , M ichigan, d u rin g th e y e a r s 1935-1936 and 1936-1937 •

He, th e n , t r a n s f e re d to th e U n iv e r s ity of

M ichigan i n S eptem ber, 1938, and g ra d u a te d w ith t h e B. S . d e g re e i n C h em istiy i n Ju n e, I 9I4I , and th e M. S . d e g re e i n C h o n is tiy i n May, 19U2.

He e n te r e d t h e G raduate S chool o f Purdue U n iv e r s ity i n

J a n u a ry , IpUU, a s a r e s e a r c h f e llo w i n th e D epartm ent o f C h em istry . He g ra d u a te d w ith th e d e g re e of D o cto r o f P h ilo so p h y i n Ju n e , 1 9 5 0 . He i s a member o f P h i Lambda U p silo n and The S o c ie ty o f Sigma X i. He i s a c o -a u th o r o f th e f o llo w in g p u b l i c a t i o n s : 1.

R apid P h o to m e tric D eterm in atio n , of I ro n and Copper i n Red P h o sp h o ru s, J . A. B ra sb so n , 0 . A. S c h a e f f e r , Anthony T ruchan, and LaVem D e a l, I n d . Eng. Chem., A n a l.E d ., 18, 55U -556 (19U 6).

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F lu o r in a te d D e r iv a tiv e s of P ro p an e, E. T. McBee, H. B. H ass, R. M. Thomas, W. G. T o lan d , J r . , and Anthony T ru ch an , J . Am. Chan. S o c ., 6 9 , 9UU-9U7 (1 9 l;7 ).

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D i r e c t B ro m in atio n o f F lu o r in a te d A lk an es, E . T. McBee, H. B. H ass, W. G. T o la n d , J r . , and Anthony T ruchan, I n d . Eng. Chem., 3 9 , U20-U21 (191+7).

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