The Reactions of Fluoroacetyl Chloride with Organocadmium Compounds

Citation preview

THE REACTIONS OF FLUOROACETYL CHLORIDE WITH ORGANOCADMIUM COÎJIPOUNDS

A T h e sis S u b m itte d t o th e F a c u lty of P urdue U n iv e r s ity

by C e c il E« O lson

I n P a r t i a l F u lf il lm e n t o f th e R eq u irem en ts f o r th e D egree of M a ste r o f S c ie n c e F e b r u a ry , 1950

ProQuest Number: 27714102

All rights reserved INFORMATION TO ALL USERS The quality of this reproduction is d e p e n d e n t upon the quality of the copy subm itted. In the unlikely e v e n t that the a u thor did not send a c o m p le te m anuscript and there are missing pages, these will be noted. Also, if m aterial had to be rem oved, a n o te will ind ica te the deletion.

uest ProQuest 27714102 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

ACKNOWLEDGMENT S in c e r e a p p r e c i a t i o n i s e x p re s s e d b y th e a u th o r t o D r. W illiam E . Truce f o r th e i n t e r e s t and i n s i g h t shown a lo n g w ith th e many h e l p f u l s u g g e s tio n s and in v a lu a b le d i r e c t i o n g iv e n d u rin g th e p r o g r e s s o f th e work*

TABLE OF CONTENTS

P age ABSTRACT ...................................................................................................................

i

INTRODUCTION..........................................................................................................

1

DISCUSSION ..............................................................................................................

2

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

4

P r e p a r a t i o n o f F lu o r o a c e ty l C h lo r id e

............... *

4

R e a c tio n o f F lu o r o a c e ty l C h lo rid e w ith P h en y lcad m iu ü u ...................

4

R e a c tio n o f F lu o r o a c e ty l C h lo rid e w ith n«Butylcadm ium

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

7

SUMMARY.....................................................................................................................

9

BIBLIOGRAPHY.........................................................................................................

10

[ c o n t r i b u t i o n from th e D ep artm ent o f C h e m istry , P urdue U n iv e r s ity ] The R e a c tio n o f F lu o r o a c e tv l C h lo rid e w ith Organocadmium Compounds1 By W illia m E . T ruce and C e c il E . O lson

(1 )

Taken from Mr. O lson*s m a s te r* s t h e s i s .

The r e a c t i o n o f alkylcadm ium r e a g e n ts w ith a c y l c h l o r id e s h a s b ee n a p p lie d w ith m oderate s u c c e s s t o th e p r e p a r a tio n o f o c -c h io r o k eto n e s^ »3 »&.

T h is p a p e r r e p o r t s on th e u se o f t h i s method

(2 )

B u n n e tt and T a r b e l l , THIS JOURNAL, 6%, 1944 (1 9 4 5 ).

(3 )

C ason, i b i d / , 6 8 , 2078 (1 9 4 6 ).

(4 )

C ason, Chemu R e v ., ^O, 15 (1 9 4 7 ).

w ith f l u o r o a c e ty l c h l o r i d e . P h e n a c y l f l u o r i d e and l - f l u o r o - 2-hexanone w ere o b ta in e d i n a p p ro x im a te ly 30% y i e l d s from diphenylcadm ium and d i-n -b u ty lc a d m iu m re s p e c tiv e ly .

I n th e fo rm er p r e p a r a t i o n , d eso x y b en zo in was s u r p r i s i n g ­

l y th e p r i n c i p l e r e a c t i o n p r o d u c t.

The r a t i o o f p h en acy l f l u o r i d e t o

d e so x y b e n z o in was n o t a p p r e c ia b ly a l t e r e d by th e mode o f m ixing th e re a c ta n ts •

ii r e y p erim en tfll.

P h en a cy l F l u o r i d e . - F lu o r o a c e ty l c h lo r id e was p re p a re d a c c o rd in g t o d i r e c t i o n s i n th e l i t e r a t u r e 5* b . p . 69-71°# y i e l d 66% o f th e o r y .

(5 )

A s o l u t i o n o f diphenylcadm ium i n benzene was p re p a re d

T ru c e , THIS JOURNAL, 7 0 , 2828 (1 9 4 8 ).

i n th e u s u a l manner^ from 90 g . ( .5 7 m .) o f brom obenzene, 14 g . ( .5 2 m .) o f magnesium and 56 g . ( .3 0 m .) o f cadmium c h l o r i d e .

To t h i s s o lu t i o n

t h e r e was added d u rin g two h o u rs a m ix tu re o f 39 g . ( .4 0 m .) o f f l u o r o a c e t y l c h lo r id e and 50 m l. o f b e n z e n e . f o r a n o th e r h o u r .

S t i r r i n g was c o n tin u e d

The b r i g h t y e llo w m a te r ia l was h y d ro ly z e d w ith a

m ix tu re o f ic e and d i l u t e s u l f u r i c a c i d .

The benzene l a y e r was washed

w ith 5% sodium c a rb o n a te s o l u t i o n fo llo w e d by w a t e r . o v e r sodium c a r b o n a te , th e m a t e r ia l was d i s t i l l e d .

A f te r d r y in g The y i e l d o f

p h en a c y l f lu o r i d e ^ was 1 6 .6 g . (30%), b . p . 102- 104° (12 mm.); 2 , 4- d in itr o p h e n y lh y d r a z o n e , m .p . 185- 186° •

(6 )

G ry sz k iew ic z and Wnuk,

t r a v , ych£jnî , 6 6 . 419 (1 9 4 8 ).

^Anal. C alcd f o r CgH^OF:

C, 69*6;

H, 5 .0 7 .

Found C, 7 0 .2 ;

H, 5 .1 9 . The y i e l d o f d eso x y b en zo in was 2 0 .3 g . (47% ), b . p . 1 7 4 -1 7 5 ° (12 m m .), m .p. 54- 56° ; m e ltin g p o in ts o f th e 2 , 4-d in itr o p h e n y lh y d ra z o n e and th e oxime ag re e d w ith l i t e r a t u r e v a l u e s . ^Anal^ C a lc d . f o r G]jH-)p0: C, 8 5 .8 ;

H, 6 .2 8 .

C, 8 5 .7 ;

H, 6 .1 8 .

Found

ill l-F lu o ro -2 -h e x a n o p e * - A m ix tu re o f 38 g* («44 m .) o f f l u o r o a c e t y l c h lo r id e and 50 m l. o f benzene was added d u rin g two h o u rs t o a s o l u t i o n o f b en zene and d i-n -b u ty lc a d m iu m prepared-^ from 80 g* ( .5 8 m .) o f n - b u ty l b ro m id e, 14. g . (.5 2 m .) o f m agnesium , and 56 g . ( .3 m .) o f cadmium c h l o r id e .

T his was s t i r r e d f o r a n o th e r h o u r

and h y d ro ly z e d i n an i c e and d i l u t e s u l f u r i c a c id m ix tu re •

The

b enzene l a y e r was washed w ith 5% sodium c a rb o n a te s o lu t i o n fo llo w e d by w a te r . d is tille d . b .p .

The m a t e r ia l was d r ie d o v er sodium c a rb o n a te and th e n The y i e l d o f l- f lu o r o -2 - h e x a n o n e was 14*2 g .

(3 0 * 6 ^ ),

7 0 ° (68 mm. ) 5 2 ,4 d in itro p h e n y lh y d re rz o n e , m .p. 56- 58° . C a lc d .

C, 5 9 .4 ;

f o r C^H-j j OFî

C, 6 0 .1 ;

H, 9*35*

Found;

H, 9 .5 1 * Summary P h e n a c y l f l u o r i d e and 1- f lu o r o - 2-h e x an o n e, a new compound,

have b een p re p a re d from f l u o r o a c e t y l c h lo r id e and th e c o rre s p o n d in g organocadmium r e a g e n t s .

W ith diphenylcadm ium , a good y i e l d o f

d e so x y b e n z o in was o b ta in e d i n a d d itio n t o p h en acy l f l u o r i d e .

1 the reactions of fluoroacetyl chloride

WITH ORGANOCADMIUM COMPOUNDS INTRODUCTION I n 1 9 3 6 , G ilman and N elson (5 ) su g g e ste d th e u se o f organocadm ium compounds w ith a c id c h lo r id e s f o r th e p r e p a r a tio n o f k e to n e s *

R e c e n t work by Cason ( 2 ,3 ) h as shown t h i s t o be a g e n e r a l

and u s e f u l s y n t h e t i c p ro ce d u re*

The p u rp o se o f t h i s r e s e a r c h was

t o d e te rm in e w h e th e r t h i s method co u ld be u sed t o p re p a re

«c-fluoro*»

k e to n e s from f l u o r o a c e t y l c h lo rid e * P h e n a c y l f l u o r i d e and 1- f lu o r o - 2-h ex an o n e, a new compound, were p re p a re d i n t h i s way.

The fo rm er had been p r e v io u s ly made by

th e F r i e d e l - C r a f t s method ( 6 ,9 ) •

2 DISCUSSION The g e n e r a l p la n f o r p r e p a rin g k e to n e s (3 ) in v o lv e s th e f o llo w in g s t e p s :

fo rm a tio n o f th e organomagnesium b ro m id e, c o n v er­

s i o n o f th e G rig n a rd r e a g e n t t o th e c o rre s p o n d in g organocadmium compound, and f i n a l l y r e a c t i o n o f th e organocadmium compound w ith t h e a c id c h l o r i d e . RBr 4- Mg ----------------- v RMgBr 4- CdCl2

RMgBr » RCdCl 4- MgBrCl

RCdGl 4- R, C 0C 1-----------►RCOR1 4- CdCl2 T hese r e a c t i o n s a r e c a r r i e d o u t i n one c o n tin u o u s o p e r a tio n w ith o u t i s o l a t i o n o f th e i n t e r m e d ia t e s . i n th e f i r s t two s t e p s .

A nhydrous e t h e r i s used a s s o lv e n t

Benzene i s used i n th e l a t t e r r e a c t i o n t o

a v o id e t h e r c le a v a g e (1 ) . I n th e r e a c t i o n u s in g an a ro m a tic h a l i d e , i . e . , phenyl b ro m id e , i t was found t h a t th e c o rre s p o n d in g f l u o r o k e to n e , p h en acy l f l u o r i d e , c o u ld be p re p a re d i n y i e l d s up t o 30%, b u t t h a t th e m ain p r o d u c t was d e so x y b e n z o in .

T h is may in v o lv e a r e a c t i o n o f th e

f l u o r oke to n e w ith th e organocadmium compound. < ~ > -C 0 C H ?F +

C > C d C l

►< = > C0CH2

A t f i r s t , i t was th o u g h t t h a t t h i s r e a c t i o n was o c c u r rin g b e c a u se o f t h e method o f a d d i t i o n i n th e l a s t s t e p .

F lu o r o a c e ty l c h lo r id e had

b een slo w ly added t o l a r g e q u a n t i t i e s o f th e phenylcadm ium compound.

3 t h e r e b y k e e p in g th e l a t t e r i n e x c e s s .

A d d itio n a l e x p e rim e n ts , employ­

in g th e r e v e r s e method o f a d d i t i o n , were p erfo rm ed •

The p ro d u c ts

i s o l a t e d w ere s t i l l th e same w it h in th r e e p e r c e n t. A nalogous r e s u l t s w ere o b ta in e d u s in g butylcadraium w ith f l u o r o a c e t y l c h lo r id e *

4 EXPERIMENTAL P r e p a r a t i o n o f F lu o r o a c e ty l C h lo rid e * The a c id c h lo r id e was p re p a re d as o u tlin e d by Truce (9 ) * A f i v e - l i t e r , ro u n d -b o tto m f l a s k was used co n n ected th ro u g h a g o o se­ neck to an o r d in a r y W est co ndenser*

The r e c e i v e r was t i g h t l y jo in e d

t o th e c o n d e n se r and open t o th e atm osphere th ro u g h a d r y in g t u b e . To p r e v e n t l o s s o f th e v e ry v o l a t i l e p r o d u c t, th e r e c e i v e r was c o o le d i n a n ic e b a t h .

Sodium f l u o r o a c e t a t e , 44-0 g . (4*4 m oles) was added

t o p h o sp h o ru s p e n t a c h l o r i d e , 1000 g . (4*81 m o le s ).

The two s o l i d s

w ere mixed w e ll and th e p ro d u c t was d i s t i l l e d by h e a tin g th e r e a c t i o n f l a s k w ith a steam c o n e .

The p ro d u c t was p u r i f i e d by r e c t i f i c a t i o n

th ro u g h a 100 cm ., h e lix -p a c k e d column a t a tm o sp h e ric p r e s s u r e , b .p # 6 9 -7 1 0 * F lu o r o a c e ty l c h lo r id e was o b ta in e d i n good y i e l d s , 274 g* ( 2 .9 m o le s );

66% o f th e o r y .

R e a c tio n o f F lu o r o a c e tv l C h lo rid e w ith Phenvlcadm ium . The a p p a ra tu s u sed i n th e fo llo w in g e x p e rim e n ts c o n s is te d o f a o n e - l i t e r , th r e e - n e c k , ro u n d -b o tto m f la s k eq u ip p ed w ith a s e p a r a to r y f u n n e l, a H e rsh b e rg e r m e rc u ry -se a le d s t i r r e r and a W est r e f l u x c o n d e n s e r.

C o n s ta n t s t i r r i n g was m a in ta in e d th ro u g h o u t th e

e x p e rim e n t and th e system was k e p t under an atm osphere o f d ry n i t r o g e n . Phenylm agnesium brom ide was p re p a re d a s d i r e c t e d i n O rg an ic S y n th e s e s ( 7 ) .

The a p p a ra tu s was h e a te d and f lu s h e d w ith d ry n i t r o g e n .

A m ix tu re o f 90 g . ( .5 7 mole) bromobenzene and 100 m l. o f anhydrous e t h e r were added v e ry s lo w ly t o 14 g • (*52 m ole) o f magnesium t u r n i n g s

5 i n th e r e a c t i o n f l a s k w ith 150 m l. o f e t h e r •

The r e a c t i o n s t a r t e d

im m e d ia te ly and th e m ix tu re was k e p t a t low r e f l u x te m p e ra tu re d u r in g th e a d d i t i o n o f th e bromobenzene*

S t i r r i n g was c o n tin u e d f o r an

a d d i t i o n a l h o u r. The c o n v e rs io n o f th e G rig n ard r e a g e n t t o th e organocadmium compound was made by c o o lin g th e r e a c t i o n f l a s k i n an ic e b a th f o llo w ­ ed by t h e a d d i t i o n o f 56 g* (*30 m ole) o f anhydrous cadmium c h l o r i d e . The a d d i t i o n was made i n t h r e e m in u te s.

The ic e b a th was r e p la c e d

by a steam cone and th e g ra y p a s ty mass was s t i r r e d f o r an h o u r u n d er g e n t l e r e f lu x *

The Gilm an t e s t (4 ) f o r G rig n a rd r e a g e n t was made and

fo u n d t o be n e g a tiv e * The e t h e r (3) was removed by a r ra n g in g th e r e f l u x c o n d e n se r f o r d i s t i l l a t i o n , h e a tin g th e r e a c t i o n f l a s k w ith steam and p a s s in g n i t r o g e n th ro u g h th e sy ste m .

HThen most o f th e e t h e r had b een rem oved,

th e g ra y m ass became to o t h i c k f o r th e s t i r r e r , so some benzene was added t o f a c i l i t a t e s t i r r i n g .

The r e s t o f th e e t h e r was removed and

r e p la c e d by b e n z e n e . The organocadmium compound was th e n t r e a t e d w ith f l u o r o a c e t y l c h lo r id e .

A m ix tu re o f 50 m l. o f d ry benzene and 39 g* ( .4 0 m ole) o f

f l u o r o a c e t y l c h lo r id e was added dropw ise t o th e r e a c t i o n f la s k *

The

mass tu rn e d o liv e g re e n and f i n a l l y b r i g h t y e llo w w ith th e e v o lu tio n o f much h e a t .

A d d itio n o f th e a c id c h lo r id e r e q u ir e d two h o u rs and

s t i r r i n g was c o n tin u e d f o r a n o th e r h o u r. The b r i g h t y e llo w mass was h y d ro ly z e d by p o u rin g i t i n t o a m ix tu re o f ic e and d i l u t e s u l f u r i c a c i d .

The benzene l a y e r was

6 s e p a r a te d and w ashed w ith a 5% sodium c a rb o n a te s o l u t i o n and th e n w ith w a te r •

A f t e r s ta n d in g o v er d r i e r i t e f o r a day th e benzene was removed

u n d e r vacuum d i s t i l l a t i o n .

The r e s id u e was d r ie d o v er anhydrous

sodium c a rb o n a te i n e t h e r s o lu tio n f o r a n o th e r d a y .

The e t h e r was

f la s h e d o f f and th e p ro d u c ts were d i s t i l l e d u n d er vacuum. f r a c t i o n b o i l e d a t 1 0 2 -1 0 4 ° (12 m m.).

The f i r s t

I t gave a s o l i d 2 , 4 - d i n i t r o ­

p h en y lh y d razo n e (8 ) w ith a m e ltin g p o in t o f 1 8 5 -8 6 °.

The y i e l d o f

p h e n ac y l f l u o r i d e was 1 6 .6 g . o r 29*8# o f th e o r y . A n a l.

C a lc d . f o r CgH^OFs

C, 6 9 .6 ;

H, 5 .0 7 .

Found:

0 ,7 0 .2 ; H, 5 .1 9 .

A second compound was i s o l a t e d , b . p . 174 -7 5 ° (12 mm.).

It

was a w h ite , c r y s t a l l i n e m a te r ia l and was i d e n t i f i e d a s d eso x y b en zo in by th e fo llo w in g p r o p e r t i e s .

A y i e l d o f 2 0 .3 g . was o b ta in e d ;

47% o f t h e o r y . E x p e rim e n ta l M e ltin g p o i n t

5 4 -6 °

B o ilin g p o i n t

L ite ra tu re 60° (5 5 -6 0 °)

174-76° (12 mm.) 322° (760 mm.)

D e riv a tiv e s — 2 ,4 -D in itro p h en y lh y d ra zo n e Oxime A n a l.

1 9 7-99°

202-04°

9 6 -9 7 ° C a lc d .

H, 6 .2 8 .

fo r C y^^O s

C, 8 5 .7 ;

98° H, 6 .1 8 .

Found:

C, 8 5 .8 ;

7 R e a c tio n o f F lu o r o a c e ty l C h lo rid e w ith n -B u ty l cadmium* The same a p p a ra tu s was u sed a s i n th e p re v io u s ex p erim en t# The f l a s k was d r ie d and 14 g . (.5 2 m ole) o f magnesium tu r n in g s w ith 100 m l. o f anhydrous e t h e r were p la c e d i n i t .

A m ix tu re o f 100 m l.

o f e t h e r and 80 g . ( .5 8 m ole) o f d ry n - b u ty l brom ide was added s lo w ly . The r e a c t i o n s t a r t e d im m ed ia tely and was com pleted in two h o u r s . The f l a s k was c o o le d i n an ic e b a th and 55 g • ( .3 m ole) o f anh y d ro u s cadmium c h lo r id e was added a t once*

A f te r s t i r r i n g th e

m ix tu re f o r t h i r t y m in u te s, th e Gilman t e s t f o r th e p re se n c e o f a G rig n a rd r e a g e n t was n e g a t i v e . The e t h e r was r e p la c e d by benzene and a m ix tu re o f 4-0 m l. o f d ry benzene and 38 g . (*44 m ole) o f f lu o r o a c e t y l c h lo r id e was added a t su ch a r a t e a s t o k eep th e benzene r e f lu x in g g e n t l y . s t i r r e d f o r one h our a f t e r th e a d d itio n was com pleted*

I t was

The heavy

mass tu rn e d from a l i g h t g re e n c o lo r t o a b r i g h t c a n a ry y e llo w . H y d ro ly sis was c a r r i e d o u t w ith a m ix tu re o f ic e and d i l u t e s u l f u r i c a c id *

The benzene l a y e r was s e p a ra te d and washed w ith 5%

sodium c a rb o n a te s o lu t i o n fo llo w e d by w ater* an h y d ro u s sodium c a rb o n a te f o r a d a y . p ro d u c t was d i s t i l l e d u n d er vacuum.

T h is was d r ie d o v e r

The s o lv e n t was removed and th e The f i r s t f r a c t i o n , b . p . 7 0 ° (68 mm.),

was c o l o r l e s s , had a v e ry p le a s a n t odor and gave a s o l i d 2 , 4 - d i n i t r o ­ p h en y lh y d razo n e w ith a m e ltin g p o in t o f 5 6 -5 8 °.

T his k e to n e was

o b ta in e d i n 30.6% y i e l d o f th e o r y , w eig h t 14*2 g . A n a l.

C a lc d .

H, 9 .5 1 .

f o r C^PnOFs

C, 6 0 .1 ;

H, 9.35*

Found:

0,59*45

8 A second f r a c t i o n was c o l l e c t e d a t 5 0 ° (17 mm.), b u t t h i s p ro d u c t was v e ry u n s ta b le and changed t o a deep re d and th e n t o a b la c k l i q u i d i n a v e ry s h o r t tim e when exposed t o th e atm osphere •

9 SUMMARY The r e a c t i o n o f f l u o r o a c e t y l c h lo r id e w ith organocadmium compounds gave th e c o rre s p o n d in g

oc‘- f lu o r oke to n e s •

The y i e l d o f

th e s e k e to n e s was low , p resum ably becau se o f t h e i r a b i l i t y t o r e a c t w ith organocadmium compounds •

I n th e r e a c t i o n o f phenylcadmium and

f l u o r o a c e t y l c h l o r i d e , d eso x y b en zo in was o b ta in e d i n good y i e l d s a lo n g w ith p h e n a c y l f l u o r i d e . A new compound, 1 - f lu o r o -2 -h e x a n o n e , h a s been p re p a re d and i t s p h y s ic a l c o n s ta n ts d e te rm in e d •

10 BIBLIOGRAPHY 1*

C ason, J e

Jgn* Ghem# S o c», 6 4 , 1106 (1 9 4 2 )•

2*

Cason, J .

Çhem# S o c » > 6 8 » 2078 (194-6)•

3*

C ason, Chem» Review s » 4.0»15 (194-7) #

4-*

G ilm an, J» Am. Chem. S o c», 4 7 . 2002 (1 925)•



Gilman and N e lso n , R ec. t r a v . chim . . 55. 518 (1 9 3 6 ).

6*

G ryszk iew icz and Wnuk, R ec. t r a y . chim . . 6 6 . 419 (194-8)•

7*

” O rganic S y n th e se s 1*, V o l. 2 1 , p . 7 9 , New Y ork, Jo h n W iley and S o n s, I n c . , 1941 •

8.

S h r in e r and F uson, nI d e n t i f i c a t i o n o f O rganic Compounds**, 3 rd e d . , p . 1 7 1 , New Y ork, John W iley and S o n s, I n c . , 194-8*

9* 10*

T ru ce, J .

J^n. Chem. S o c. . 70 . 2828 (1948)•

T ruce and S a ck , J . JUn. Chem. S o c*. 7 0 . 3959 (1 9 4 8 ).