Preparation and Properties of Certain Organic Compounds Containing Nitrogen and Fluorine

Citation preview

P U R D U E U N IV E R SIT Y

THIS IS TO CERTIFY THAT THE T H ESIS PREPARED U N D E R MY SU PER V ISIO N

b

y

e n title d

K eith Mar T aylor

PREPARATION AND PROPERTIES OF CERTAIN ORGANIC COMPOUNDS CONTAINING NITROGEN AND FLUORINE

COMPLIES WITH THE UNIVERSITY REGULATIONS O N GRADUATION T H E SE S

AND IS APPROVED BY ME A S FULFILLING THIS PART O F THE REQUIREM ENTS

FOR THE D EG REE OF

D octor o f P hilosophy

^

— —P

—H

r o f e sso r

ea d

o f

S

in

C

h a r g e

c h o o l

o r

D

o f

T

h e s is

epa r t m e n t

TO THE LIBRARIAN

«■— ; THIS T H E SIS IS NOT TO BE REGARDED A S CONFIDENTIAL.

PROFESSOR m

GRAD, SCHOOL FORM 9—3 - 4 9 — 1M

CHARGE

PREPARATION AND PROPERTIES OF CERTAIN ORGANIC COMPOUNDS CONTAINING NITROGEN AND FLUORINE

A T h e sis S u b m itted t o th e F a c u lty of Purdue U n iv e rs ity

by

K e ith Mar T ay lo r

I n P a r t i a l F u lf illm e n t o f th e R equirem ents f o r th e Degree

of D octor o f P h ilo so p h y Ju n e, 19^0

ProQuest Number: 27714157

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 27714157 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

The a u th o r w ishes to e x p re ss h i s g r a t i tu d e to D r. E. T. McBee, who was i n d i r e c t charge o f t h i s work.

He w ishes a ls o to e x p re ss

h is th an k s to th e E. I . duPont de Nemours and Company and to th e Purdue R esearch Foundation f o r f i n a l c i n g t h i s work.

No acknowledg­

ment would be com plete w ith o u t m entioning th e many o th e r s who have o f f e r e d in v a lu a b le a s s is ta n c e th ro u g h o u t th e co u rse o f t h i s work. An in co m p lete l i s t o f th e s e p eo p le would in c lu d e D r. Z. D. Welch, Dr. 0 . R. P ie r c e , John Barone, Henry R akoff and James H ig g in s.

TABLE OF CONTENTS Page ABSTRACT PERFLUORINATED ACIDS

PART Is

HYDRAZIDES AND AZIDES........................

i

ABSTRACT PREPARATION AND PROPERTIES OF CERTAIN FLUORINATED AI/ŒNES.................. x i i i PART I s PERFLUORIMATED ACIDS PART I :

HYDRAZIDES AND AZIDES

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

1

EXPERIMENTAL AND DISCUSSION .......................................................................................

6

T riflu o ro a c e th y d ra z id e ....................................................................................... M in eral a c id s a l t s ................................................................................................ R eactio n w ith a c e tic anhydride ...................................................................... B ib e n z a lh y d ra z ide ........................................................................................ R eactio n w ith p h e n y lis o th io c y a n a te ............................................................. Sodium tr if lu o r o a c e th y d r a z id e ........................................................................ Disodium b i s ( t r i f l u o r o a c e t ) h y d ra z id e ......................................................... B is ( t r i f l u o r o a c e t ) h y d raz id e ................................................................... I d e n t i f i c a t i o n o f b i s ( t r if l u o r o a c e t ) h y d r a z i d e ..................................... A c id ity o f b i s ( t r i f l u o r o a c e t ) h y d ra z id e ..................................................... N itro u s a c id i n m e th a n o l................................................................................... N itro u s a c id from amyl n i t r i t e I n e th a n o l .............................................. O x id atio n o f tr if lu o r o a c e th y d r a z id e w ith io d in e .......................... O x id atio n o f tr if lu o r o a c e th y d r a z id e w ith brom ine ..................... O x id a tio n o f tr if lu o r o a c e th y d r a z id e w ith m erc u ric o x i d e • H e x a flu o ro g lu ta ry l a z id e ................................................................................... D iflu o ro ac etam id e .................................................................................................. T e tr a f lu o ro s u c c in ic a c i d ................................................................................... O c ta flu o ro a d ip y l a z id e ....................................................................................... T r if lu o r o a c e ty l a z id e ......................................................................................... Chemical I d e n t i f i c a t i o n o f t r i f l u o r o a c e t y l a z id e ............................... O c ta flu o ro a d ip y l c h lo rid e ................................................................................. H e x a flu o ro g lu ta ry l c h lo rid e ............................................................................ T r if lu o r o a c e ty l brom ide ......................................................................... T r if lu o r o a c e ty l io d id e ..............................................................

6 6 7 7 8 8 9 10 11 12 13 lU 15 15 16 16 18 19 21 21 22 25 25 26 26

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

27

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

28

Page PART I I .

PREPARATION AND PROPERTIES OFCERTAIN FLUORINATED AMINES.

EXPERIMENTAL AND DISCUSSION.....................................................................................

29 33

F lu o r in a tio n o f b e n z o n i t r i l e ...................................................................... 33 F l u o r i n a t i on o f n-Va! e r o n i t r i l e .................................................................. 3h 36 A ttem pted f l u o r i n a tio n o f n -b u ta y l am ine.................................. F lu o ri n a tio n o f a c è t o n i t r i l e ........................................................................ 36 38 F lu o ri n a tio n o f t r i f l u o r o a c e t o n i t r i l e ..................................................... 38 A ttem pted f l u o r i n a tio n o f a c e t o n i t r i l e .................................... A ttem pted f l u o r i n a tio n o f t r i f l u o r o a c e t o n i t r i l e ............................... 39 T riflu o ro a c e ta m id e ............................ IjO T r i f l u o r o a c e t o n i t r i l e ............................. ......................................................... J4O R e ac tio n o f t r i f l u o r o a c e t o n i t r i l e w ith hydrogen f l u o r i d e Uo 1 , 1 , 2 , 2 - t e t r a f l u o r o - l , 2 -d i n i t r o e th a n e ..................................................... i;6 R eduction o f 1 , 1 , 2 , 2 - t e t r a f l u o r o - l ,2 - d i n i t r o e t h a n e w ith i r o n and h y d ro c h lo ric a c i d ................................ k7 R eduction o f 1 , 1 , 2 , 2 - t e t r a f l u o r o - 1 , 2 - d in itr o e th a n e w ith stannous c h lo r i d e .................................... h9 A ttem pted r e a c t i o n o f p o tassiu m p h th a lim id e w ith 1 , 1 , 2 , 2 - t e t r a f lu o r o - 1 , 2- d iio d o e th a n e ................ ... ............ .............. ....................... 50 SUMMARY..............................................................................................................................

51

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

52

VITA

AN ABSTRACT D epartm ent o f C hem istry and Purdue R esearch F oundation Purdue U n iv e rs ity , L a f a y e tte , In d ia n a PERFLUORINATED ACIDS PART I :

HYDRAZIDES AND AZIDES1

By E. T. McBee and K. M, T ay lo r

1.

C o n tain s m a te r ia l from Mr. T a y lo r 's d o c to r a l t h e s i s .

As a p a r t o f th e g e n e ra l program o f e lu c id a tin g th e c h e m istry o f o rg an ic compounds c o n ta in in g f l u o r i n e , a stu d y o f some o f th e d e r iv a tiv e s o f f l u o r in a te d a c id s was u n d e rta k e n . 2 C u rtiu s and Franzen r e p o r t th e p r e p a r a tio n o f a c id h y d ra z id e s by

2.

C u rtiu s and F ranzen, B er. 35, 32U0 (1 9 0 2 ).

h e a tin g th e h y d ra z id e s a l t s .

T h is p r e p a r a tio n in v o lv e s th e i s o l a t i o n o f

th e h y d ra z id e s a l t and th e n s e v e r a l days o f h e a tin g to c o n v e rt i t to th e a c id h y d ra z id e .

I n t h i s i n v e s t i g a t i o n , tr if lu o r o a c e th y d r a z id e was r e a d i­

l y p re p a re d from t r i f l u o r o a c e t ! c a c id by t r e a t i n g i t w ith h y d ra z in e hy­ d ra te .

The t r i f l u o r o a c e ti c a c id -h y d ra z in e m ix tu re was h e a te d to about

110° to remove w a te r and e x cess h y d ra z in e and th e rem aining m a te r ia l was vacuum d i s t i l l e d to g iv e tr if lu o r o a c e th y d r a z id e i n y i e l d s exceeding 90 %. T riflu o ro a c e th y d ra z id e , l i k e o th e r a c id h y d ra z id e s , forms s a l t s w ith m in e ra l a c id s .

When a w a ter s o lu tio n o f tr if lu o r o a c e th y d r a z id e was

t r e a t e d w ith a c e ti c an h y d rid e by a common a c e ty l a t i n g p ro c e d u re ^ .

i i

3*

S h r in e r , R* L* and Fuson, R. C*, "The S y stem atic I d e n t i f i c a t i o n o f O rganic C o m p o u n d s T h ird E d itio n , John WLley and Sons, I n c . , New York.

b i s ( tr if lu o r o a c e t) h y d r a z id e was o b ta in e d i n good y i e l d .

T h is p ro d u c t

p ro b ab ly r e s u l t e d from a c é ty l a t i o n o f tr if lu o r o a c e th y d r a z id e by th e mixed anhydride form ed fo llo w in g th e h y d ro ly s is o f some h y d ra z id e to t r i f l u o r o a c e t i c a c id and h y d ra z in e . Aldehydes and k e to n es form c o lo re d s o lu tio n s when h e a te d w ith t r i ­ f lu o ro a c e th y d ra z id e .

A rom atic aldehydes and k e to n e s form s o l i d d isu b ­

s t i t u t e d h y d ra z id e s w ith th e e lim in a tio n o f t r i f l u o r o a c e t i c a c id .

A

s o l i d , nup. 251°, was form ed a f t e r tr if lu o r o a c e th y d r a z id e was b o ile d f o r s ix te e n h o u rs w ith more th a n equim olar amounts o f e th y l a c e to a c e t a t e . E lem ental a n a ly s is in d ic a te s th e form ula o f t h i s s o l i d to be C ^R ^N ^O . O ther a l i p h a t i c carb o n y l compounds r e a c te d to form complex p ro d u c ts which f a i l e d t o y i e l d c r y s t a l l i n e d e r i v a t i v e s .

P h e n y lis o th io c y a n a te

and tr if lu o r o a c e th y d r a z id e form , by c o n d e n sa tio n , a d d itio n and e lim in a ­ t i o n o r s o lv o ly s is a su b sta n c e b e lie v e d to be 1 , 6 - d i p h e n y l - 5 - th i o - l , 3 ,it, 6 te tr a z a h e x a - 1 , 2 -d ie n e .

P h en y li so cy an ate gave in s e p a ra b le p ro d u c ts be­

cause o f th e w a te r e lim in a te d i n th e co n d en sa tio n form ing c a r b a n i ü d e . B en rath ^ and Struve'* r e p o r t th e fo rm a tio n o f m e ta l d e r iv a tiv e s o f

I*.

B enrath e t a l . , J . P r a k t. Chem. 107, 211 (192k) ♦



S tru v e , J . P r a k t. Chem. 50, 29$ (1Ô9U)•

b en zo h y d razide and b is(b e n z o )h y d ra z id e , b u t no re fe re n c e was found to th e fo rm atio n o f m etal s a l t s by a c e th y d r a z id e .

B enzohydrazi de form s a

i i i

sodium d e r iv a tiv e when r e flu x e d "with sodium i n to lu e n e o r when t r e a t e d w ith sodium e th o x id e i n e th a n o lic s o lu tio n * from th e e th a n o l by a d d itio n o f e t h e r .

T his s a l t i s p r e c i p i t a t e d

B is (benzo) h y d ra z ide form ed a

monosodium s a l t when t r e a t e d w ith sodium e th o x id e i n e th a n o l and form ed a disodium s a l t when r e flu x e d w ith sodium i n to lu e n e .

No m ention i s

made o f th e chem ical r e a c tio n s o f th e s e sodium s a l t s .

T r if lu o r o a c e t­

h y d raz id e form ed a monosodium s a l t which was in s o lu b le i n e th a n o l. B is ( t r if lu o r o a c e t) h y d r a z id e showed no tendency to form a monosodium s a l t b u t r e a d i ly form ed an in s o lu b le d i sodium s a l t when t r e a t e d w ith sodium e th o x id e .

These s a l t s a re w h ite i n c o n tr a s t to th e y e llo w c o lo r

o f th e b en zo hydrazide s a l t s .

They undergo n u c le o p h ilic r e a c tio n s w ith

a lk y l h a lid e s * T riflu o ro a c e th y d ra z id e was c o n v e rte d to b i s ( t r i f l u o r o a c e t ) h y d ra z id e by th e a c tio n o f o x id iz in g a g e n ts .

H y d ro ly sis o f b i s ( t r i f l u o r o a c e t ) -

h y d razid e form ed t r i f l u o r o a c e t i c a c id and h y d ra z in e which were i d e n t i f i e d by t h e i r c o n v ersio n to tr if lu o r o a c e ta m id e , m .p. 7U°> and h y d ra z in e d i h y d ro c h lo rid e , m .p. 1 9 8 °.

Q u a n tita tiv e s tu d ie s showed th e p re se n c e o f

two m olecules o f t r i f l u o r o a c e t i c a c id f o r each m olecule o f h y d ra z in e . These r e s u l t s in d ic a te d th e n a tu re o f th e m a te r ia l and were v e r i f i e d by a n a ly s is .

No p o s i t iv e p ro o f i s a v a ila b le as to w hether th e compound i s

o f , ot o r

>/& d i s u b s ti t u t e d h y d ra z in e , b u t from th e methods o f p r e ­

p a r a tio n and analogous r e a c tio n s , i t i s assumed to be th e sym m etrical form .

B is ( t r i f l u o r o a c e t ) h y d raz id e i s a w hite c r y s t a l l i n e s o l i d , s o lu b le

i n a lc o h o ls , a c e to n e , e th e r and w a te r and in s o lu b le i n benzene and o th e r aro m atic h y d ro ca rb o n s. a c id ic to litm u s*

I t d is s o lv e s i n w a te r to form a s o lu tio n which i s

These r e a c tio n s and p r o p e r t i e s show th e e le c t r o n w ithdraw ing e f f e c t o f th e tr if lu o r o m e th y l group by making th e s e h y d ra z id e s more a c id ic th a n o th e r a c id h y d ra z id e s and more s u s c e p tib le t o s o lv o ly s is by weakening th e n itro g e n — hydrogen and c a rb o n -n itro g e n bonds* O rganic a c id a z id e s a re u s u a lly p re p a re d by th e r e a c t i o n betw een th e a c id c h lo rid e and sodium a z id e o r by th e a c tio n o f n i tr o u s a c id on th e a c id h y d razid e* ^

6*

A cid a z id e s u s u a lly undergo rea rran g e m en t t o th e

"O rganic R e a c tio n s” V o l. I l l , John W iley and Sons, I n c . , New York,

19U6. is o c y a n a te , when h e a te d , acconqoanied by l o s s o f n itr o g e n .

When th e

g e n e ra l d e g ra d a tio n r e a c tio n s o f Schm idt and Hofman^ were c a r r i e d o u t V 8 on p e r f lu o r in a te d a c id s , th e r e a c tio n e i t h e r f a i l e d * , o r l e d to th e

7.

Gilman, H. and Jo n es, R. G., J . Am. Chem. Soc. 65, 2037 (1943) •

8.

Rhodehamel, H ., U npublished r e s u l t s , Purdue U n iv e rs ity , 191+6.

fo rm atio n o f u nexpected p ro d u c ts .



o

H e x a flu o ro g lu ta ry l a z id e was h e a te d

G ryszkiew icz-T rochinow ski, S p o rz y n sk i, and Wnuk, Rec. T rav . Chim. 6 6 , 719 (191+7).

w ith w a te r, form ing t e t r a f l u o r o s u c c i n i c and d i f lu o r o a c e ti c a c i d s .

The

u su a l p ro d u c t o f th e C u rtiu s r e a c tio n would have been 1 , 3 -(h e x a flu o r o propane)diam ine which a p p a re n tly lo s e s hydrogen f l u o r i d e , accom panied by h y d ro ly s is t o form d iflu o ro m a lo n ic a c id which d e c a rb o x y la te s spontaneous­ l y a t room te m p e ra tu re to form d i f lu o r o a c e ti c acid*

When p a r t i a l h y d ro ly ­

s i s o c c u rre d b e fo re rearran g em en t, such t h a t th e d e g ra d a tio n o c c u rre d o n ly

V

a t one c arb o x y l group i n th e m olecule, t e t r a f l u o r o s u c c i n i c a c id was th e p r o d u c t.

Mien t r i f l u o r o a c e t y l a z id e was h e a te d t o e f f e c t i t s re a r ra n g e ­

ment to tid .flu o ro m e th y lis o c y a n a te , i t decomposed e x p lo s iv e ly *

E ffo rts

to i s o l a t e t r i f l u o r o a c e t y l a z id e from th e r e a c t i o n betw een t r i f l u o r o ­ a c e th y d ra z id e and n i tr o u s a c id were u n s u c c e s s f u l.

B is (triflu o ro a c e t)-

h y d raz id e and t r i f l u o r o a c e t i c a c id o r i t s e s t e r s , depending on th e s o l ­ v e n t u se d , were th e p ro d u c ts o f th e r e a c t i o n , i n d ic a t i n g th e fo rm a tio n o f t r i f l u o r o a c e t y l a z id e which th e n r e a c te d w ith th e s o lv e n t o r t r i ­ flu o ro a c e th y d ra z id e to form th e observed p r o d u c ts .



EXPERIMENTAL T r if lu o r o a c e th y d r a z id e > T r if l u o r o a c e t i c a c id (28 g . , 0*2^ mole) was t r e a t e d w ith h y d raz in e h y d ra te (llj.«6 g #> 0 .2 5 mole) w ith c o n tin u o u s ta p -w a te r c o o lin g .

The r e s u l t i n g s o lu tio n was d i s t i l l e d t o a tem pera­

tu r e o f 110° and th e rem aining m a te r ia l was vacuum d i s t i l l e d .

T r if lu o r o ­

a c e th y d ra z id e d i s t i l l e d i n q u a n ti t a t iv e y i e l d and c o n v e rsio n (32 g .) a t 78-814° u n d e r 6 -8 ram. p r e s s u r e .

The h y d ra z id e d i s t i l l e d a s a c o lo r le s s

s ir u p which s o l i d i f i e d to a w h ite s o l i d , m .p. llli.»50> on c o o lin g .

No

s u i t a b l e c r y s t a l l i z a t i o n s o lv e n t was fo u n d . A nal:

C alc»d. f o r C ^ F ^ O :

N, 21.88%; F, UU.5%

Found:

N, 22.18%; F , U2.9%

T r iflu o ro a c e th y d ra z id e may be e a s i l y p re p a re d by u s in g e th y l t r i f lu o r o a c e ta te r a t h e r th a n th e f r e e a c id i n t h i s r e a c t i o n .

The r e a c t a n ts

may be mixed more r a p i d l y , b u t a p e rio d o f r e f l u x o f one to th r e e h ours i s n e c e s s a ry .

The y i e l d s by t h i s method a re above 90%.

C ondensations o f t r if lu o r o a c e th y d r a z id e w ith carb o n y l compounds. T riflu o ro a c e th y d ra z id e ( 0 .5 g*) was t r e a t e d w ith benzaldehyde (2 m l.) and th e m ix tu re was b o ile d f o r one m in u te .

The m e lt c r y s t a l l i z e d when

co o led and th e s o l i d was r e c r y s t a l l i z e d s e v e r a l tim e s from d i l u t e e th a n o l, form ing y e llo w p l a t e s , m .p. 93°•

T r if lu o r o a c e tic a c id was

i s o l a t e d from th e m a te r ia l d i s t i l l e d w h ile th e m ix tu re was b e in g h e a te d . A n a ly sis showed th e s o l i d to be d ib e n z a lh y d ra z in e • ^

10.

C u r tiu s , J . , J . P r a k t. Chem. 39, UU (1 8 8 9 ).

A s i m il a r r e a c tio n p ro ced u re was u se d f o r r e a c tio n s w ith benzophenone and acetophenone, and s im ila r r e s u l t s were o b ta in e d . A n a ly sis

C arbonyl compound

Analyzed as

m .p.

Ac etophenone

Cl 6 Hl 6 N2

123°

C, 81.3%

H, 6.77%

C, 81.0%

H, 6.79%

Benzophenone

C26H20N2

16U°

C, 86.7%

H, 5.6%

C, 86.1j5%

H, 6.0%

c a l c 'd .

Found

TMhile th e benzaldehyde and acetophenone c o n d e n sa tio n p ro d u c ts were y e llo w , th e benzophenone p ro d u c t was w h ite .

When i n s o lu tio n o r m elted ,

th e l a t t e r p ro d u c t was y e llo w , b u t i t tu rn e d w h ite when s o l i d i f i e d o r when c r y s t a l l i z e d from th e s o l u t io n . R e ac tio n o f tr if lu o r o a c e th y d r a z id e w ith p h e n y lis o th io c y a n a te .

T r i­

flu o ro a c e th y d ra z id e (1 g .) was mixed w ith 1 m l. o f p h e n y lis o th io c y a n a te and th e m ix tu re was fu s e d .

Hydrogen s u l f i d e was evolved and was t e s t e d

f o r by means o f le a d a c e ta te p a p e r.

The m elt s o l i d i f i e d on c o o lin g , and

th e s o l i d was p u lv e riz e d and washed w ith p etro leu m e th e r and $ 0% aqueous e th a n o l.

The rem aining s o l i d was c r y s t a l l i z e d s e v e ra l tim e s from d i l u t e

e th a n o l, form ing w h ite p l a t e s , m .p. 2U7°*

Q u a lita tiv e a n a ly s is confirm ed

th e p re se n c e o f n itr o g e n and s u l f u r i n t h i s compound.

A n a ly sis showed

t h i s m a te r ia l to be 1 , 6 - d ip h e n y l- 5 - th io - 1 ,3>It>6-te tr a z a h e x a - 1 , 2 -d ie n e . A nal:

C a lc 'd . f o r C ^ H ^ N ^ S : Found:

Sodium tr if l u o r o a c e t h y d r a z i d e .

C, 62.7%;

H, U-55%

C, 62.95%; H, U»56% T riflu o ro a c e th y d ra z id e ( 6 . 1; g . ,

0 .0 5 m ole) was d is s o lv e d i n 20 m l. o f a b s o lu te e th a n o l and t r e a t e d w ith an e th a n o lic s o lu tio n o f sodium (1 .1 5 g»> 0 .0 5 m o le).

The s o lu tio n was

th e n h e a te d , and p r e c i p i t a t i o n o f sodium tr if lu o r o a c e th y d r a z id e began im m ed iately .

The p r e c i p i t a t i o n was com plete w ith in f i f t e e n m in u te s.

The s u p e rn a ta n t l i q u i d was poured th ro u g h a f i l t e r and th e r e s id u a l s a l t

was washed tw ic e w ith e th e r , and th e n c o ll e c t e d on th e f i l t e r .

Four grams

(0 .2 6 mole) o f w h ite powdery s a l t , re p r e s e n tin g a y i e l d o f 53%, was ob­ ta i n e d .

T h is m a te r ia l decomposed on b e in g h e a te d , le a v in g a r e s id u e o f

sodium f l u o r i d e . A nal:

C a lc 'd . f o r CgHgF^NgONa: Found:

B is ( t r i f l u o r o a c e t ) h y d ra z id e .

C, 16.0%; H, 1.33%; Na, 15-30% C, 16.15%, H, l.U7%J Na, 15.15%

T r if lu o r o a c e th y d r a z ide (5 g», O.Oli

mole) was d is s o lv e d i n a m ix tu re o f 15 m l. o f w a te r and 5 m l. o f conc. h y d ro c h lo ric a c id , and th e r e s u l t i n g s o lu tio n was co o le d i n i c e and covered w ith 25 m l. o f d ie th y l e t h e r .

A s o lu tio n o f 3 .5 g . o f sodium

n i t r i t e i n 20 m l. o f w a ter was added slow ly to th e w e ll s t i r r e d c o ld s o l u t io n .

The e th e r l a y e r was s e p a ra te d and th e aqueous l a y e r was ex­

t r a c t e d tw ic e w ith 10 m l. p o r tio n s o f e t h e r .

The combined e th e r ex­

t r a c t s were d r ie d o v e r anhydrous sodium s u l f a t e , a f t e r which th e e th e r was removed by r a p i d e v a p o ra tio n i n v acuo.

B is ( t r i f l u o r o a c e t ) h y d ra z id e

(3*5 g . , 0.016 mole) rem ained a s a powdery w h ite s o l i d i n 82% y i e l d . B is ( tr if lu o r o a c e t) h y d r a z id e , c r y s t a l l i z e d from a lc o h o l-b e n ze n e and e th e r-b e n z e n e mixed s o lv e n ts and from to lu e n e , m elted a t 17U°. A nal:

C a lc 'd . f o r C ^2^6^2^2"

°*

H> 0.89%; F, 50.9%;

N, 12.50%; Mol. Wt. 22^. Found:

C, 2 1 .U% ; H, 0.88%; F, 53.9%;

N, 12.95%; Mol. Wt. ( E a s t) , 228. T r if lu o ro a c e th y d ra z id e was a ls o c o n v e rte d to b i s ( t r i f l u o r o a c e t ) h y d ra z id e by th e a c tio n o f brom ine, io d in e , and m ercu ric oxide on i t s aqueous s o l u t i o n s . A c id ity o f b i s ( t r i f l u o r o a c e t ) h y d r a z i d e .

B is (triflu o ro a c e t)-

h y d ra z id e (0.0570 g .) was d is s o lv e d i n w a te r and t i t r a t e d to a

p h e n o lp h th a le in end p o in t w ith 0.1025 N. sodium h ydroxide s o l u t io n .

Two

and s i x - t e n t h s m i l l i l i t e r s o f b a se was re q u ir e d f o r th e n e u t r a l i z a t i o n . C a lc u la tin g th e m o le cu la r w eig h t on th e assum ption t h a t b i s ( t r i f l u o r o a c e t ) h y d ra z id e has one a c id ic hydrogen p e r m olecule g iv e s an e x p e rim e n ta l v a lu e o f 2Hj..

T his shows t h a t b i s ( t r i f l u o r o a c e t ) h y d ra z id e behaves as a mono­

b a s ic a c id u nder th e s e c o n d itio n s . Disodium b i s ( t r if l u o r o a c e t ) h y d r a z i d e .

B is ( tr if lu o r o a c e t) h y d r a z id e

(0 .5 g«, 0.002 mole) was d is s o lv e d i n 10 m l. o f a b s o lu te e th a n o l and added t o a s o lu tio n o f sodium (0 .0 9 2 g . , O.OOli mole) i n 10 m l. o f ab­ s o lu te e th a n o l, and th e m ix tu re was h e a te d . h y d ra z id e s e p a ra te d a s a s o l i d .

Di sodium b i s ( t r i f l u o r o a c e t ) -

The s u p e rn a ta n t l i q u i d was d ecan ted

th ro u g h a f i l t e r and th e r e s i d u a l p r e c i p i t a t e was washed tw ice w ith e th e r and th e n c o ll e c t e d on th e f i l t e r a s a w h ite pow der.

A y i e l d o f 81$ (0 .5 g

0.0018 mole) o f d i sodium b i s ( t r i f l u o r o a c e t ) h y d ra z id e was o b ta in e d .

TVhen

t h i s s a l t was a c i d i f i e d w ith d i l u t e m in e ra l a c id s , b i s ( t r i f l u o r o a c e t ) h y d ra z id e was a g a in form ed. A nal:

C a lc 'd . f o r C^NgOgN ag: c > 17.85%; Na, 17.17% Found: C, 17.65%; Na, 17*10%

O c ta flu o ro a d ip y l c h lo r i d e .

F in e ly powdered o c ta flu o r o a d ip ic a c id

(29 g . , 0 .1 mole) was p la c e d i n a 200 m l. round bottom f l a s k f i t t e d w ith a r e t u r n co n d en ser. f l a s k was warmed.

An ex cess o f th io n y l c h lo rid e was added and th e The te m p e ra tu re was in c r e a s e d slo w ly over a th r e e day

p e rio d from 1*0° to 8 0 °. vacuum.

The e x ce ss th io n y l c h lo r id e was removed under

O c ta flu o ro a d ip y l c h lo r id e , a s o l i d a p p e a rin g l i k e f in e sand,

m .p. 120°, rem ained i n th e f l a s k . A nal:

C a lc 'd . f o r C^Cl^F^O^:

C, 21.88%

Found:

C, 21.95%

X

H e x a flu o ro g lu ta ry l c h lo r id e was p re p a re d i n a s i m ila r m anner. H e x a flu o ro g lu ta ry l a z id e .

Sodium a z id e (25

0 .3 5 mole) was

added to th e a c id c h lo r id e o f h e x a f lu o r o g lu ta r ic a c id p re p a re d from ij.2 g . (0 .1 7 mole) o f th e a c id .

Benzene was added f o r f l u i d i t y and th e

m ix tu re was h e a te d u n d er r e f l u x w h ile b e in g s t i r r e d . th e m ix tu re s e t to a s t i c k y m ass.

A fte r tw elve h o u rs

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

c i p i t a t i n g th e a z id e from e th a n o lic s o lu tio n by th e a d d itio n o f p etro leu m e th e r .

The a z id e o b ta in e d i n t h i s manner m elted w ith decom position a t

170-17U°«

Two grams o f th e h e x a flu o ro g lu ta ry l a z id e was b o ile d w ith

w a te r f o r tw enty m in u te s.

Some h y d ro ly s is o c c u rre d a s was evidenced

by q u a l i t a t i v e t e s t s f o r th e a z id e io n d u rin g th e h e a tin g .

The s o lu ­

t i o n was a c i d i f i e d w ith s u l f u r i c a c id and e x tr a c te d c o n tin u o u sly w ith d ie th y l e th e r f o r two d a y s.

E v ap o ratio n o f th e e th e r l e f t t e t r a f l u o r o ­

s u c c in ic a c id , m .p. 86°, which was p u r i f i e d by r e c r y s t a l l i z a t i o n from benzene.

The a c id was t r e a t e d w ith ammonium hydroxide to form th e

ammonium s a l t f o r a n a l y s i s .

D iflu o ro a c e tic a c id was i s o l a t e d as d i ­

flu o ro a c e ta m id e , m .p. 51°• A nal:

C a lc 'd . f o r C^HgF^NgOg:

N, 12.50%; C, 21.1*3%; H, 3.57%

Found:

N, 12.80%; C, 21.78%; H, 3.1*2%

T r if lu o r o a c e ty l a z id e .

Sodium a z id e (35 g . , 0.51* m ole) was

p la c e d i n a 500-m l. , th re e -n e c k e d , round bottom f l a s k f i t t e d w ith a m ercury s e a le d H ershberg s t i r r e r , a gas i n l e t tu b e and a d ry ic e c o ld f i n g e r r e f l u x c o n d en se r.

The t r i f l u o r o a c e t y l brom ide p re p a re d by th e

a c tio n o f phosphorous trib ro m id e on t r i f l u o r o a c e t i c a c id (75 g*, 0 .6 l mole) was p a sse d i n t o th e f l a s k through th e gas i n l e t tu b e .

The gaseous

a c id brom ide, b .p . 6 -8 ° , was condensed by th e r e t u r n condenser and

dropped on to th e s o l i d sodium a z id e .

No s o lv e n t was u se d and s t i r r i n g

was m ain tain ed th ro u g h o u t th e r e a c t i o n .

As th e r e a c tio n p ro g re s se d ,

th e f l a s k became warm and a q u a n tity o f l i q u i d , b .p . 1*5°, c o lle c te d i n th e f l a s k .

A ttem pts to cause th e rearran g em en t o f t h i s t r i f l u o r o a c e t y l

a z id e t o th e is o c y a n a te , by h e a tin g , r e s u l te d i n i t s e x p lo s iv e decom­ p o s itio n . T r if lu o r o a c e ty l a z id e was a ls o p re p a re d by th e a c tio n o f t r i f l u o r o ­ a c e ty l c h lo r id e on an e th e r su sp en sio n o f sodium a z id e .

A bsolute e th a n o l

(30 m l.) was t r e a t e d w ith 50 m l. o f e th e r e a l s o lu tio n o f t r i f l u o r o a c e t y l a z id e and th e r e s u l t i n g s o lu tio n was r e c t i f i e d .

I n a d d itio n to d ie th y l

e th e r and e th a n o l, a f r a c t i o n , b .p . 1*5-U6°, was o b ta in e d .

T h is m a te r ia l

r e a c te d r a p i d l y w ith sodium, form ing a w h ite s o l i d which exploded when h e a te d .

Q u a lita tiv e t e s t s showed t h i s r e a c tio n to be due to th e p re se n c e

o f h y d r a z o ic a c id i n t h i s f r a c t i o n .

The hydr a z o ic a c id was removed by a

thorough w ashing w ith p o tassiu m c a rb o n ate s o lu tio n , and th e rem aining m a te r ia l was d i s t i l l e d , y ie ld in g d ie th y l e th e r , b .p . 35°* and e th y l t r i ­ flu o r o a c e ta te , b .p . 6 2 °. T r if lu o r o a c e ty l i o d id e .

Red phosphorous ( l6 g . , 0 .5 mole) was

added to t r i f l u o r o a c e ti c a c id (57 g«, 0 .5 mole) and th e m ix tu re was c o o le d i n i c e .

Io d in e (190 g . , 1 .5 gram atoms) was added to th e c o ld

m ix tu re and th e r e s u l t i n g m ix tu re was allow ed to warm to room tem pera­ tu r e o v e rn ig h t.

The m ix tu re was b o ile d u n d er r e f l u x f o r f i v e to s i x

h o u rs and th e n d i s t i l l e d .

The d i s t i l l a t e was r e c t i f i e d , y ie ld in g t r i ­

f lu o r o a c e ty l io d id e , b .p . 59-61°•

The t r i f l u o r o a c e t y l io d id e was id e n ­

t i f i e d by i t s c o n v ersio n to tr iflu o ro a c e ta m id e by th e a c tio n o f ammonia. Acknowledgement The a u th o rs w ish t o e x p re ss t h e i r th an k s to th e E. I . duPont de

Nemours and Company and to th e Purdue R esearch Foundation f o r fin a n c in g th is rese a rc h . Summary T riflu o ro a c e th y d ra z id e was p re p a re d by th e r e a c tio n betw een hydra­ z in e h y d ra te and e i t h e r e th y l t r i f l u o r o a c e t a t e o r t r i f l u o r o a c e t i c a c id . T r if lu o ro a c e th y d ra z id e form s s a l t s w ith m in e ra l a c id s and r e a c t s w ith aro m atic carb o n y l compounds to form s o l i d d e r iv a tiv e s o f h y d ra z in e . I t r e a c te d w ith p h e n y lis o th io c y a n a te to form 1 , 5 - d ip h e n y l- l, 5 - t h i o 1 ,3 , h 96 - t e t r azahexa-1, 2 -d ie n e • T riflu o ro a c e th y d ra z id e i s c o n v e rte d t o b i s ( t r i f l u o r o a c e t ­ h y d razid e by th e a c tio n o f n i tr o u s a c id , brom ine, io d in e , m ercu ric o x id e, o r a m ix tu re o f a c e ti c anhydride and sodium a c e ta te .

T riflu o ro a c e th y d ra z id e

forms a monosodium s a l t w hile b i s ( t r i f l u o r o a c e t ) h y d razid e forms a d i­ sodium s a l t .

Both s a l t s undergo n u c le o p h ilic r e a c t i o n s .

The b i s -

( tr if lu o r o a c e t) h y d r a z id e i s a c id ic t o l itm u s . H e x a flu o ro g lu ta ry l a z id e , formed by th e a c tio n o f sodium a z id e on th e a c id c h lo r id e , decomposed when h e a te d w ith w a ter t o form t e t r a ­ f lu o r o s u c c in ic and d if lu o r o a c e tic a c id s .

T r if lu o r o a c e ty l a z id e decom­

p osed e x p lo s iv e ly when h e a te d . T r if lu o r o a c e ty l brom ide and io d id e were p re p a re d by th e a c tio n o f th e p ro p e r phosphorous t r i h a l i d e on t r i f l u o r o a c e t i c a c id .

H exafluoro­

g l u ta r y l c h lo r id e and o c ta flu o ro a d ip y l c h lo rid e were p re p a re d by th e a c tio n o f th io n y l c h lo rid e on th e a c id .

AN ABSTRACT D epartm ent o f C hem istry and Purdue R esearch F oundation Purdue U n iv e rs ity , L a f a y e tte , In d ia n a

PREPARATION AND PROPERTIES OF CERTAIN FLUORINATED AMINES1 By E. T. McBee and K. M. T ay lo r

1.

C o n tain s m a te r ia l from Mr. T a y lo r 's d o c to ra l t h e s i s .

I n c o n n ec tio n Trith th e g e n e ra l stu d y o f th e o rg an ic c h e m istry o f f lu o r in e a t Purdue U n iv e rs ity , r e a c tio n s le a d in g to th e p r e p a r a tio n o f p e r f lu o r in a te d amines and N,Nf - d if lu o r o — p e r f lu o r in a te d amines were s tu d ie d .

P re p a ra tio n o f p e r f lu o r in a te d t e r t i a r y amines by th e M innesota

Mining and M anufacturing Company and th e fo rm atio n o f N, N‘ - d i f lu o r o ( tr if lu o r o m e th y l) amine by R uff and co-w orkers^ by d i r e c t f l u o r in a ti o n

2.

R u ff, 0 . , F is c h e r, J . , and L u f t, F ., A. Anorg. Chem. 172, 1*17 (1 9 2 8 ).

o f s i l v e r cyanide and th e p r e p a r a tio n o f f l u o r i n a te d p ip e r id in e s by Simons^ and B i t t l e s ^ a re th e o n ly re p o rte d examples o f th e s e ty p e s o f

3.

Simons, J . H ., U .S. P a te n t 2, 14.90, 098.

I4.

B i t t l e s , J . , PhD T h e s is , Purdue U n iv e rs ity , 191*7.

compounds.

The d e g ra d a tio n r e a c tio n s o f Hofman, C u rtiu s and Schm idt,

when a p p lie d to p e r f lu o r in a te d a c id s o r t h e i r d e r iv a tiv e s , e i t h e r f a i l to re a c t'* , y i e l d unexpected p ro d u c ts ^ , o r y i e l d on ly th e low er a c id in



Gilman, H ., and Jo n es, R. G*> J • Am. Chem. Soc* 6g, 1U58 (19U3) •

6.

Grys zkiew ic z-T rochinow ski, S p o rz y n sk i, and Wnuk, Rec. T rav . Chim. 66, 719 (19U7).

th e homologous s e r i e s . ^

7.

The amine p ro d u c ts u s u a lly i s o l a b l e i n th e s e

T ay lo r, K. M., PhD. T h e s is , Purdue U n iv e rs ity , 1950.

r e a c tio n s a re n o t found i n th e r e a c tio n s in v o lv in g th e p e r f lu o r in a te d a c id s . S lu o r in a tio n o f n i t r i l e s , u sin g a c tiv e m e ta llic f lu o r id e s a t tem­ p e r a tu r e s betw een 100° and 300° produced N, N1-d iflu o ro -p e rflu o ro a m in e s . N, N* - d i f l u o r o ( trid e c a flu o ro c y c lo h e x y lm e th y l) amine and N, N1- d i f l u o r o (u n d e c a flu o ro -n -a n y l) amine were produced by f l u o r in a ti o n o f benzoni­ t r i l e and n - v a l e r o n i t r i l e w ith s i l v e r d i f l u o r i de o r le a d t e t r a f l u o r i d e . When s h o r t exposure tim es were u se d , a p p re c ia b le q u a n ti t ie s o f s t a r t i n g m a te r ia ls were re c o v e re d w h ile c le av a g e p ro d u c ts and p a r t i a l l y f l u o r i n ­ a t ed p ro d u c ts w ere form ed i n a l l c a s e s .

Evidence was found f o r f l u o r i n ­

a tio n o f o n ly th e n i t r i l e u n i t when a c e t o n i t r i l e was f lu o r in a te d , u s in g s i l v e r d i f lu o r i d e a t 1£>0°.

These p ro d u c ts were i d e n t i f i e d by a n a ly s is

o r m o le cu la r w e ig h ts and t h e i r i n e r tn e s s to chem ical a t t a c k . N, N* - d i f lu o r o ( t r i d e c aflu o ro c y clo h ex y lm eth y l) amine was r e flu x e d f o r f i f t y h o u rs w ith 20 % sodium hydroxide s o lu tio n w ith o u t showing any n o tic e a b le r e a c tio n w h ile N, N1- d i f l u o r o (

,o 6 -d iflu o ro e th y l) amine showed no r e ­

a c tio n when b ubbled th ro u g h b o ilin g $0% sodium hydroxide s o lu tio n o r con­ c e n tr a te d s u l f u r i c a c id a t 3 0 °.

These tre a tm e n ts show th e s t a b i l i t y o f

th e n i tr o g e n - f lu o r in e bond to chem ical a t t a c k .

These f l u o r in a te d amines

XV

bu rn ed -when h e ld i n a flam e, b u t would n o t b u rn when n o t i n th e d i r e c t flam e.

T h e ir s o l u b i l i t y c h a r a c t e r i s t i c s a re s i m il a r to th o s e o f f l u o r o -

c a rb o n s• P e r f lu o r in a te d n i t r i l e s add hydrogen h a lid e s to form l i q u i d and Q

s o l i d p ro d u c ts o f m oderate s t a b i l i t y .

8.

These p ro d u c ts were found to be

W illiam son, A. H ., PhD. T h e sis, Purdue U n iv e rs ity , 19U9-

n i t r i l e s a l t s o f th e ty p e p o s tu la te d by H antzsch.^

9-

H antzsch, A», B er. 6LB, 667 (1931)•

R eduction o f 1 , 1 , 2 , 2 - t e t r a f l u o r o - l ,2 - d i n i t r o e t h a n e w ith ir o n and h y d ro c h lo ric a c id , o r stannous c h lo rid e and hydrogen c h lo r id e , produced o n ly ammonia, o x a lic a c id , and h y d ro flu o ric a c id .

While re d u c tio n does

o c c u r, th e re d u c tio n p ro d u c ts form ed a re u n s ta b le , le a d in g to th e f o r ­ m ation o f h y d r o ly tic p ro d u c ts . A ttem pts t o c a r r y o u t a r e a c tio n betw een 1 , 1 , 2 , 2 - t e t r a f l u o r o - l , 2 d iio d o e th a n e and p o tassiu m p h th a lim id e were u n s u c c e s s f u l. A ttem pts to f l u o r i n a t e n -b u ty lam in e u s in g a c tiv e m e ta llic f lu o r id e s as f l u o r in a ti n g a g e n ts were u n s u c c e s s fu l. E xperim ental N ,N1- D iflu o ro ( trid e c a flu o ro c y c lo h e x y lm e th y l)a m in e .

B e n z o n itr ile

(100 g . , 1 .0 mole) was p a sse d th ro u g h a s e r i e s o f f o u r s i l v e r d i f lu o r id e o

r e a c t o r s , w ith each r e a c t o r c o n ta in in g f i v e moles o f s a l t s a t a tem pera­ t u r e o f 200-220°.

Two o n e - l i t e r n ic k e l t r a p s , one immersed i n an i c e

b a th and th e o th e r i n a d ry i c e b a th were connected to th e o u t l e t w ith

xvi

3 /8 in c h o .d . copper tu b in g .

The n i t r i l e was p a sse d i n t o th e r e a c t o r s

o v er a p e r io d o f two h o u rs a f t e r which th e system was purged f o r t h r e e h o u rs w ith a slow stream o f n itr o g e n . i n th e i c e t r a p .

The o rg a n ic p ro d u c t was tra p p e d

The p ro d u c t was poured o v er crack ed i c e , and th e r e ­

s u l t in g m ix tu re was made a lk a lin e w ith aqueous sodium h y d ro x id e, and th e n steam d i s t i l l e d .

The o rg a n ic p ro d u c t was re c y c le d th ro u g h f r e s h l y

charged r e a c t o r s a t te m p e ra tu re s ra n g in g from 220° to 280°.

The p ro d u c t

was a g a in t r e a t e d w ith i c e , n e u tr a liz e d w ith sodium h y d ro x id e s o lu tio n and steam d i s t i l l e d .

The o rg a n ic p ro d u c t was d r ie d over anhydrous sodium

s u l f a t e and r e c t i f i e d .

A 3 m l. f r a c t i o n was o b ta in e d , b .p . l $ 0y i n d i ­

c a tin g some f l u o r i n o l y s i s to p e rflu o ro m e th y lc y c lo h e x a n e . tio n was o b ta in e d , b .p . 91°•

A 7 g* f r a c ­

A n a ly sis in d ic a te d t h i s m a te r ia l to be

N, N1- d i f lu o r o ( trid e c a flu o ro c y c lo h e x y lm e th y l) am ine. A nal:

C alc*d. f o r C^F^N :

N, 3.66$

Found:

N, 3*^0$

A sample o f h ig h e r b o ilin g m a te ria l was found to c o n ta in a h ig h e r p e rc e n ta g e o f n itr o g e n , i n d ic a tin g i t to be in c o m p le te ly f l u o r in a te d . The s t a b i l i t y o f th e p ro d u c t to chem ical a tt a c k i n d ic a te d d e f i n i t e ­ l y t h a t th e n i t r i l e u n i t was f l u o r in a te d .

When f l u o r in a te d n i t r i l e s ,

such a s o c ta f lu o r o a d ip o n i t r il e , a re t r e a t e d w ith aqueous a l k a l i , th e h y d ro ly s is r e a c tio n i s spontaneous and v ig o ro u s .

A sample o f C^F-^N

was b o ile d f o r f i f t y h o u rs w ith 20$ aqueous sodium h ydroxide w ith no n o tic e a b le e f f e c t .

Cold c o n c e n tra te d s u l f u r i c a c id and h y d ro c h lo ric

a c id d id n o t a f f e c t t h i s m a t e r i a l.

I t burned when h e ld i n a flam e, b u t

would n o t c o n tin u e to b u rn when removed from th e fla m e . v e n t found f o r t h i s compound was p e r f lu o ro - n -h e p ta n e .

The o n ly s o l ­

The in d e x o f r e f r a c t i o n o f C^F^N was to o low t o be d e te rm in e d w ith an Abbe r e f r a c to m e te r .

- 2.09U*

N,N1-D iflu o ro (u n d e c a flu o ro -n -a m y l) am ine.

n - V a l e r o n i t r i l e (138 g . ,

1*6U m oles) was p a sse d through a s e r i e s o f fo u r s i l v e r d i f l u o r i d e r e a c t o r s , each c o n ta in in g f iv e m oles o f s i l v e r s a l t s a t an i n i t i a l te m p e ra tu re o f 1 5 0 °.

Two o n e - l i t e r n ic k e l t r a p s , one immersed i n an i c e b a th and th e

o th e r i n a d ry i c e b a th were a tta c h e d t o th e o u t l e t by means o f 3 /8 in c h o .d . copper tu b in g .

The n i t r i l e was p a sse d th ro u g h th e r e a c t o r s over a

p e rio d o f f o r t y - f i v e m inutes d u rin g which tim e th e h e a t o f th e r e a c tio n r a is e d th e te m p e ra tu re o f th e r e a c t o r s to 200°.

The r e a c t o r s were flu s h e d

w ith a slow stream o f n itr o g e n f o r th r e e h o u rs .

The p ro d u c t was poured

o v er crack ed ic e and n e u tr a liz e d w ith sodium h y d ro x id e .

The o rg a n ic

l a y e r was washed w ith d i l u t e a l k a l i , d r ie d o v e r anhydrous sodium s u l ­ f a t e , and r e c t i f i e d .

R e c t if i c a t io n y ie ld e d an 8 g . f r a c t i o n , b .p . 6 9 °,

a sm all amount o f m a te r ia l b o ilin g o v er th e ran g e 70-135°, and a la r g e amount o f s t a r t i n g m a te r ia l, b .p . 135-138°.

The f r a c t i o n b o ilin g a t 69°

was N, N1- d i f lu o r o ( unde c a flu o ro -n -a m y l ) am ine. A nal:

C a lc 'd . f o r C^F^N:

N, U»36$

Found:

N, U»U5%

The chem ical and p h y s ic a l c h a r a c t e r i s t i c s o f t h i s compound were s imi l a r t o th o se o f N,N* —d if lu o ro (trid e c a flu o ro c y c lo h e x y lm e th y l)a m in e . C a re fu l r e c t i f i c a t i o n o f th e f l u o r in a te d p ro d u c ts f a i l e d to show any f r a c t i o n i n which o n ly th e n i t r i l e u n i t was f l u o r in a te d . The in d ex o f r e f r a c t i o n o f C^F^N was to o low to be d eterm ined w ith an Abbe r e f r a c to m e te r .

* 1 .3 8 1 .

A ttem pts to p re p a re s i m il a r compounds by f l u o r i n a t i o n o f amines fa ile d .

No p ro d u c ts could be o b ta in e d from th e r e a c t o r .

x v iii

N,N1- D iflu o ro (o ^ 3o C -d iflu o ro e th y l)a m in é . 3 m oles) was p a sse d , d u rin g a p e rio d o f

two h o u rs , i n t o a s i l v e r d i -

f l u o r id e r e a c t o r c o n ta in in g tw enty m oles o f t u r e o f 220°.

A c e t o n i t r i l e (123 g . ,

s i l v e r s a l t s a t a tem pera­

A t r a i n c o n s is tin g o f an ammonium h y d ro x id e wash b o t t l e ,

a t h r e e - f o o t d ry in g column, d ry i c e and l i q u i d a i r t r a p s was connected to th e o u t l e t .

A fte r a l l o f th e n i t r i l e had b een p a s s e d i n t o th e r e a c t ­

o r , th e system was pu rg ed w ith a slow stre am o f n itr o g e n f o r t h r e e h o u rs . A c o lo r le s s l i q u i d i n th e d ry i c e t r a p and a w h ite s o l i d i n th e l i q u i d a i r t r a p c o n s t it u t e d th e p ro d u c ts o f th e r e a c t i o n .

They were s e p a r a te ly

v a p o riz e d and p a sse d thro u g h aqueous sodium h ydroxide and a d ry in g to w er, and recondensed i n th e t r a p s .

Ifflhen m elted and b o ile d , th e p ro d u c t i n

th e l i q u i d a i r t r a p b o ile d a t -8 0 ° .

Ane s tim a tio n

w eight by Dumas' method gave a v a lu e o f

o f i t s m o le cu la r

29. These v a lu e s i n d ic a t e t h a t

t h i s m a te r ia l m ight have been m ethyl f l u o r i d e , b .p . - 7 8 .5 ° , m ol. w t. 3lt« The p ro d u c t caught i n th e d ry i c e t r a p was r e c t i f i e d thro u g h a f o u r - f o o t Stedman column.

A fte r rem oving 15 m l. o f m a te r ia l, b .p .

-7 0 ° to -3 1 °, a 20 m l. f r a c t i o n o f m a te r ia l, b .p . -30° was o b ta in e d . The rem aining 15» m l. o f m a te r ia l d i s t i l l e d o v e r th e range -2 9 ° to 1 5 °. M o lecu lar w eight d e te rm in a tio n s by Dumas' method on th e f r a c t i o n b .p . -3 0 ° gave v a lu e s o f 100 and 105•

Assuming th e G-C-N c h a in to be

i n t a c t , t h i s would i n d ic a te t h a t th r e e o r fo u r f l u o r in e atoms had been in tro d u c e d i n t o th e m o lecu le.

The o n ly l o g i c a l p ro d u c t c o n ta in in g th r e e

f lu o r in e atoms would be t r i f l u o r o a c e t o n i t r i l e , b .p . -61*°, e lim in a tin g th e p o s s i b i l i t y o f th e in tr o d u c tio n o f th r e e f lu o r in e atom s.

No r e ­

a c tio n o c c u rre d when th e o rg a n ic p ro d u c t was p a sse d i n t o b o ilin g 50$ sodium hydroxide o r c o n c e n tra te d s u l f u r i c a c id a t 3 0 °.

T his in d ic a te s

t h a t th e m olecule no lo n g e r c o n ta in e d a n i t r i l e g roup, and le a d s to th e b e l i e f t h a t th e n i t r i l e was f l u o r in a te d , form ing N, N1—d iflu o ro (o C ,cC— d i f lu o r o e th y l ) amine • N itrile s a l t s .

The chem ical b e h a v io r o f th e l i q u i d p ro d u c t form ed

by th e a c tio n o f anhydrous hydrogen f l u o r id e on t r i f l u o r o a c e t o n i t r i l e was s tu d ie d .

On b e in g h e a te d , t h i s m a te r ia l c y c l i zed t o th e t id a z i n e ,

2, U > 6 -tris ( tr if lu o r o m e th y l) - 1 ,3 , 5 - t r i a z i n e •

T reatm ent w ith su b sta n c e s

which r e a c t w ith hydrogen f l u o r i d e , such as s i l i c a , calcium c a rb o n a te , o r anhydrous p o tassiu m f l u o r id e , re g e n e ra te d th e n i t r i l e .

T reatm ent

w ith a h y d ro ly z in g medium, such a s a c id s o l u t io n s , formed ammonia, t r i f lu o r o a c e tic a c id , and h y d ro flu o ric a c id .

The r e a c tio n p ro d u c t would

n o t undergo r e a c tio n s c h a r a c t e r i s t i c o f an amine o r im in o f lu o r id e .

The

q u a n tity o f p ro d u c t o b ta in e d i n th e r e a c tio n in d ic a te d th e p re se n c e o f more hydrogen f l u o r id e th a n would be acco u n ted f o r by th e a d d itio n o f th r e e moles o f hydrogen f lu o r id e to each mole o f n i t r i l e . Acknowledgment The a u th o rs w ish to e x p re ss t h e i r th a n k s to th e E. I . duPont de Nemours and Company and to th e Purdue R esearch F oundation f o r fin a n c in g th is re se a rc h . Summary F lu o ri n a t i on o f n i t r i l e s u sin g s i l v e r d i f l u o r id e a t te m p e ra tu re s above 100° form ed N,N' - d if lu o r o p e r f lu o r in a te d am ines.

N, N1- d i f l u o r o -

( trid e c a flu o ro c y c lo h e x y lm e th y l ) amine and N, N1- d if lu o r o (u n d e c a flu o ro -n an y l) amine were p re p a re d by f l u o r in a ti o n o f b e n z o n i tr i l e and n - v a le r o — n itrile .

N, N1- d if lu o r o ( o ( ,o £ -d iflu o ro e th y l) amine was p re p a re d by

flu o rin a tio n o f a c e to n itr ile .

These N, N1—d if lu o r o p e r f lu o r o amines were

XX

v ezy s t a b l e to a l l u s u a l chem ical a g e n ts .

A ttem pts to f l u o r i n a t e amines

were n o t s u c c e s s f u l. A ttem pts to add f lu o r in e to n i t r i l e bonds by th e u se o f le a d t e t r a f l u o r id e were u n s u c c e s s f u l. F lu o r in a te d n i t r i l e s r e a c t w ith anhydrous hydrogen h a lid e s t o form n itr ile s a lts . R eduction o f 1 ,1 , 2 , 2 - t e t r a f l u o r o - l ,2 - d i n i t r o e t h a n e fo m e d o x a lic a c id , h y d ro f lu o ric a c id and ammonia. A ttem pts to c a r r y o u t a G a b rie l s y n th e s is u s in g 1 , 1 , 2 , 2 - t e t r a f lu o r o -1 ,2 - d iio d o e th a n e were u n s u c c e s s f u l.

PREPARATION AND PROPERTIES OF CERTAIN ORGANIC COMPOUNDS CONTAINING NITROGEN AND FLUORINE PART I PERFLUORINATED ACIDS HYDRAZIDES AND AZIDES

INTRODUCTION As a p a r t o f th e g e n e ra l stu d y o f th e o rg a n ic c h e m istry o f f lu o r in e a stu d y o f some o f th e r e a c tio n s o f f lu o r in a te d a c id d e r iv a tiv e s was u n d e rta k e n . A cid h y d ra z id e s a re u s u a lly p re p a re d by th e r e a c tio n betw een hydra­ z in e and th e e th y l e s t e r o f th e a c id .

They may a ls o be p re p a re d by th e 2 r e a c tio n o f a c y l h a lid e s w ith h y d ra z in e . C u rtiu s and Franzen r e p o r t th e p r e p a r a tio n o f a c id h y d ra z id e s by h e a tin g th e h y d ra z id e s a l t s o f th e a c id s .

In t h e i r p re p a ra tio n s o f h y d ra z id e s th e y f i r s t i s o l a t e d th e

h y d ra z id e s a l t s o f th e a c id s as c r y s t a l l i n e s o l i d s , and th en c o n v erted them to th e a c id h y d ra z id e s by s e v e ra l d a y s' h e a tin g under r e f l u x .

T ri-

flu o r o ac e th y d ra z i de was r e a d i ly p re p a re d by th e r e a c tio n betw een e th y l t r i f l u o r o a c e t a t e and h y d raz in e h y d r a te .

T r if lu o r o a c e th y d r a z ide c o u ld be

as e a s i l y p re p a re d from t r i f l u o r o a c e t i c a c id by t r e a t i n g i t w ith h y d ra­ z in e h y d ra te , d i s t i l l i n g th e m ix tu re to a te m p e ra tu re above 110°C. , and th en vacuum d i s t i l l i n g th e rem aining m a t e r i a l.

No i s o l a t i o n o f th e

h y d ra z id e s a l t was n e c e s s a ry , and th e sim ple a p p a ra tu s and s h o r t p ré p a ra t i o n tim e make t h i s a d e s ir a b le method o f p re p a rin g tr if lu o r o a c e t h y d r a z id e .

The y i e l d s o f t r i f l u o r o ac e th y d r a z i de were g e n e r a lly above 90%

when i t was p re p a re d i n t h i s way.

2

T riflu o ro a c e th y d ra z id e c o n ta in s th r e e c e n te r s f o r chem ical a t t a c k • These a r e th e amino group ■which undergoes c e r t a i n norm al amine r e a c t i o n s > th e im ino group which undergoes some a c id -ty p e r e a c t i o n s , p ro b a b ly due to e n o liz a tio n , and th e c a rb o n y l-n itro g e n lin k a g e which undergoes s o l v o l y ti c r e a c t i o n s . T r if lu o ro a c e th y d r a z ide form s s a l t s w ith m in e ra l a c id s as do o th e r a c id h y d razid es* Hïhen a w a te r s o lu tio n o f t r i f l u o r o a c e th y d r a z i de was t r e a t e d w ith a c e tic a n h y d rid e and sodium a c e ta te , a common a c e ty la tin g p ro c e d u re , b i s ( t r i f l u o r o a c e t )h y d ra z id e was o b ta in e d i n good y i e l d .

9

T his p ro d u c t

may be th e r e s u l t a n t o f an exchange r e a c t i o n . C arbonyl compounds form c o lo re d s o lu tio n s when h e a te d w ith t r i ­ flu o ro a c e th y d r a z i d e .

T rifL u o ro a c e th y d ra z id e r e a c t s w ith aro m atic c a r­

bonyl compounds to form s o l i d d e r iv a tiv e s . These d é r iv â te s a re formed by th e c o n d e n sa tio n o f two m olecules o f c arb o n y l compound w ith each m olecule o f h y d ra z id e , accompanied by e x p u lsio n o f t r i f l u o r o a c e t i c a c id , form ing th e d i s u b s ti t u t e d h y d ra z id e .

A s o l i d d e r iv a tiv e was formed by

lo n g r e f lu x in g o f e th y l a c e to a c e ta te w ith t r i f l u o r o a c e t h y d r a z i d e .

O ther

a l i p h a t i c carb o n y l compounds r e a c te d w ith tr if lu o r o a c e th y d r a z id e to form complex p ro d u c ts which f a i l e d to y i e l d c r y s t a l l i n e d e r iv a tiv e s # T r if lu o ro a c e th y d ra z id e r e a c te d w ith p h e n y lis o th io c y a n a te by conden­ s a tio n , a d d itio n and e lim in a tio n o r s o lv o ly s is to form 1 , 6 -d ip h e n y l-^ t h i o - 1 ,3 , i t,6 - t e t r a z a h e x a - l , 2 -d ie n e .

A s i m ila r r e a c tio n w ith p h e n y lis o -

cy an ate gave in s e p a r a b le p ro d u c ts because o f th e w a te r e lim in a te d i n th e c o n d en sa tio n r e a c t i o n r e a c tin g w ith th e p h e n y liso c y a n a te to form c a rb a n ilid e . B en rath^ and S t r u v e ^ r e p o r t th e fo rm a tio n o f m etal d e r iv a tiv e s o f

3

b en zo h y d razide and b is (b e n z o )h y d ra z id e , b u t C u rtiu s and Hofman^ make no m ention o f th e fo rm a tio n o f m etal d e r iv a tiv e s o f ac e th y d r a z i d e.

Benzo­

h y d ra z id e forms a sodium d e r iv a tiv e -when re flu x e d -with sodium i n to lu e n e , o r -when t r e a t e d -with sodium e th o x id e i n e th a n o lic s o lu tio n .

T his s a l t

i s p r e c i p i t a t e d from th e e th a n o l s o lu tio n by th e a d d itio n o f e th e r . B is (benzo) h y d ra z id e form s a mono sodium s a l t -when t r e a t e d w ith sodium e th ­ o xid e i n e th a n o l, and form s a d i sodium s a l t when re flu x e d w ith sodium i n to lu e n e w ith a t r a c e o f e th a n o l added as a c a t a l y s t . y e llo w c o lo re d , a s a re t h e i r e th a n o lic s o lu tio n s .

These s a l t s a re

S a l ts were form ed o f

th e s e h y d ra z id e s u sin g a wide ran g e o f m etal a lc o h o la te s , w ith th e m etals u sed in c lu d in g mono, d i , and t r i v a le n t m e ta ls . chem ical r e a c tio n s o f th e s e m e ta llic s a l t s .

No m ention i s made o f th e

TWhen t r e a t e d w ith sodium

e th o x id e i n e th a n o l, tr if lu o r o a c e th y d r a z id e r e a d i ly formed a monosodium s a l t which was in s o lu b le i n e th a n o l.

B is ( t r i f l u o r o a c e t) h y d raz id e r e a d i­

l y form ed an in s o lu b le disodium s a l t when t r e a t e d w ith sodium e th o x id e i n e th a n o l.

B is ( tr if lu o r o a c e t) h y d r a z id e showed no ten d en cy to form a

monosodium s a l t a s d id th e o th e r d i s u b s ti t u t e d h y d ra z id e s .

These s a l t s

were w h ite and were in s o lu b le i n e th a n o l as c o n tr a s te d to th e s o l u b i l i t y and y e llo w c o lo r o f th e benzohydrazide s a l t s .

These s a l t s underw ent

n u c le o p h ilic r e a c tio n s w ith a lk y l and a c y l h a li d e s . T riflu o ro a c e th y d ra z id e was c o n v e rte d to b is ( t r if l u o r o a c e t ) h y d r a z i d e when i t s aqueous s o lu tio n s were t r e a t e d w ith such o x id iz in g a g e n ts as brom ine, io d in e , and m ercu ric o x id e . Bi s ( t r i flu o ro a c e t ) h y d ra z id e i s a w h ite c r y s t a l l i n e s o l i d , so lu b le i n a lc o h o ls , a c e to n e , e th e r and w a te r and in s o lu b le i n b enzene.

B is -

( t r i f l u o r o a c e t ) h y d ra z id e d is s o lv e d i n w a te r to form an a c id ic s o lu tio n w ith a pH o f ap p ro x im ately 3*

T his s o lu tio n , when t i t r a t e d to a

u

p h e n o lp h th a le in end p o in t w ith sodium hydroxide s o lu tio n , showed th e p re se n c e o f one a c id ic hydrogen p e r m o lecu le.

No m ention has been

found i n th e l i t e r a t u r e o f o th e r d i s u b s t i t u t e d h y d ra z id e s e x h ib itin g such a c id ic p r o p e r t i e s . These r e a c tio n s and p r o p e r tie s show th e e f f e c t o f th e t r i f l u o r o ­ m ethyl group i n making th e h y d ra z id e s more a c id ic in n a tu re th a n o th e r sym m etrical d i s u b s ti t u t e d h y d ra z id e s .

T his i s p ro b ab ly due to th e

in d u c tiv e e f f e c t o f th e trif lu o r o m e th y l group weakening th e n itr o g e n hydrogen bond to such a degree t h a t th e hydrogen i s a c t u a l l y a c i d ic . O rganic a c id a z id e s a re u s u a lly p re p a re d by th e r e a c t i o n betw een th e a c id c h lo r id e and sodium a z id e o r by th e a c t io n o f n i tr o u s a c id on 6,8 th e a c id h y d ra z id e . TShen tr if lu o r o a c e th y d r a z id e was t r e a t e d w ith n i tr o u s a c id i n aqueous s o lu tio n , b i s ( t r i f l u o r o a c e t ) h y d ra z id e was formed i n 82% y i e l d .

A sm all amount o f t r i f l u o r o a c e t i c a c id was a ls o form ed.

TNhen a lc o h o ls were u sed as s o lv e n ts i n t h i s r e a c tio n , e s t e r s and t r i ­ f lu o r o a c e tic a c id were th e p ro d u c ts .

These p ro d u c ts in d ic a t e t h a t t r i -

f lu o r o a c e ty l a z id e may have been form ed, i n i t i a l l y , b u t r e a c te d r a p id ly w ith th e s o lv e n t o r u n re a c te d tr if lu o r o a c e th y d r a z id e to form th e observed p ro d u c ts .

"When Rhodehamel^ a ttem p ted t o p re p a re h e x a f lu o ro g lu ta r y l a z id e

by t r e a t i n g h e x a f lu o r o g lu ta r y l h y d ra z id e w ith n i tr o u s a c id , he found on ly h e x a f lu o r o g lu ta r ic a c id and u n re a c te d s t a r t i n g m a te r ia l.

Treatm ent o f

p e r f lu o r in a te d a c id h a lid e s w ith sodium a z id e was found to be a s a t i s ­ f a c to r y method o f p re p a rin g th e a z id e s .

"When a c id a z id e s a re h e a te d ,

th e y u s u a lly undergo rea rran g e m en t, accompanied by l o s s o f n itro g e n , to form th e c o rre sp o n d in g is o c y a n a te .

A ttem pts have been made by o th e r

w orkers to p re p a re f l u o r in a te d is o c y a n a te s o r t h e i r r e a c tio n p ro d u c ts by means o f th e Hofman *

and Schmidt

r e a c tio n s , b u t w ith o u t s u c c e s s .

5

G ryszk±ew icz-T rochinow ski5 Sporzynski and Vfcmk^ r e p o r t th e i s o l a t i o n o f h e x a flu o ro e th a n e "when a Hofman d e g ra d a tio n was c a r r i e d o u t on t r i f l u o r o — acetaim d e, itiiile Gilman and Jones^ r e p o r t t h a t no ex p ected p ro d u c ts were form ed when a Schmidt r e a c tio n was attem p ted on t r i f l u o r o a c e t i c a c id . H e x a flu o ro g lu ta ry l a z id e when b o ile d w ith w a ter formed t e t r a f l u o r o s u c c i n i c a c id and d if lu o r o a c e tic a c id .

The p ro d u c ts i n d ic a t e t h a t a p a r t i a l hy­

d r o ly s is o c c u rre d such t h a t th e a c tu a l d e g ra d a tio n , i n p a r t , o c c u rre d on o n ly one carb o x y l group i n th e m o lecu le.

None o f th e n itro g e n c o n ta in in g

p ro d u c ts u s u a lly i s o l a b l e i n C u rtiu s r e a c tio n s were found i n t h i s i n ­ s ta n c e .

VUhen tr if L u o r o a c e ty l a z id e was h e a te d to e f f e c t i t s re a rra n g e ­

ment, i t decomposed e x p lo s iv e ly .

T r if lu o r o a c e ty l a z id e was a r e a c tiv e

compound r e a d i l y form ing e s t e r s when t r e a t e d w ith a lc o h o ls . T r if lu o r o a c e ty l brom ide and io d id e and h e x a flu o ro g lu ta ry l and o c ta fL u o ro ad ip y l c h lo r id e s were p re p a re d i n th e course o f t h i s i n v e s ti g a t i o n .

EXPERIMENTAL AND DISCUSSION T r if lu o ro a c e th y d ra z id e .

E th y l t r i f l u o r o a c e t a t e (28.1* g ., 0 .2 mole)

was d is s o lv e d i n 100 m l. o f a b so lu te e th a n o l, and h y d razin e h y d ra te (26 g . , 0 .£ mole) was added slo w ly . c o o lin g d u rin g th e a d d itio n .

Heat was evolved, n e c e s s i t a t i n g

The s o lu tio n was h e a te d un d er r e f lu x f o r

th r e e h o u rs, a f t e r which th e excess a lc o h o l was removed by d i s t i l l a t i o n , and th e rem aining m a te r ia l was th e n vacuum d i s t i l l e d .

The t r i f l u o r o ­

a c e th y d ra z id e d i s t i l l e d a t 75>°C • under 5 mm. p r e s s u r e . was c o lo r l e s s and s o l i d i f i e d to a pure and c o n v e rsio n were

99•2%.

The d i s t i l l a t e

w hite mass on c o o lin g . They i e l d

The amount o f p ro d u ct o b ta in e d was 2$.l* g.

A ttem pts to c r y s t a l l i z e th e h y d raz id e r a t h e r th a n use d i s t i l l a t i o n met w ith f a i l u r e . A nal:

C a lc 'd . f o r C ^ F - ^ O :

N,

21.38%; F, 1*1*.5%

Found:

N,

22.18%; F, 1*2.9%

T r if lu o r o a c e th y d r a z id e .

T r if lu o r o a c e tic a c id (28 g . , 0 .2 5 mole) was

t r e a t e d w ith h y d ra z in e h y d ra te (ll*.6 g ., 0 .2 5 m ole). s a ry d u rin g th e r e a c t i o n .

C ooling was n eces­

The r e s u l ti n g s o lu tio n was d i s t i l l e d to a

te m p e ra tu re o f 110°C. and th e n vacuum d i s t i l l e d .

T riflu o ro a c e th y d ra z id e

d i s t i l l e d i n q u a n ti t a t iv e y i e l d and co n v ersio n o f 32 g . a t 78-81*°C. u n d er 6 -8 mm. p r e s s u r e . T riflu o ro a c e th y d ra z id e was found to be to o s e n s i t iv e to h y d ro ly s is and a lc o h o ly s is to a llo w c r y s t a l l i z a t i o n from s o lv e n ts c o n ta in in g w a te r o r a lc o h o ls .

I t was p u re w h ite i n c o lo r and r a t h e r w a x -lik e i n n a tu r e .

I t m elted a t Hi*°C. M in eral a c id s a l t s .

Two drops o f c o n c e n tra te d m in e ral a c id was

added to an a ceto n e s o lu tio n o f o n e -h a lf gram o f tr if lu o r o a c e th y d r a z id e .

7

P r e c i p i t a t e s formed im m ediately -which were f i l t e r e d , washed w ith e th e r and d r ie d i n a vacuum d e s ic c a to r . determ in ed by q u a l i t a t i v e t e s t s .

The components o f th e s e s a l t s were S a l ts were r e a d i l y form ed w ith s u l ­

f u r i c and h y d ro c h lo ric a c id s , b u t on ly a cloudy s o lu tio n was produced when th e aceto n e s o lu tio n was t r e a t e d w ith c o n c e n tra te d n i t r i c a c id . R e actio n w ith a c e tic a n h y d rid e .

A w ater s o lu tio n o f 1 g. o f t r i ­

flu o ro a c e th y d ra z id e was t r e a t e d w ith 5 m l. o f a c e tic a n h y d rid e, and a s o lu tio n o f 5 g* o f sodium a c e ta te i n 20 m l. o f w a te r was added a t o nce. A f te r th e m ix tu re was allow ed to sta n d f o r f iv e m inutes i t was thorough­ l y e x tr a c te d w ith e th e r .

Treatm ent o f th e e th e r s o lu tio n w ith benzene

form ed a p r e c i p i t a t e which was so lu b le i n th e mixed s o lv e n t when i t was h o t.

T his s o l i d was c r y s t a l l i z e d from th e mixed so lv e n t and was found

to be b i s ( t r i f l u o r o a c e t ) h y d ra z id e , m .p. 17U°* B ib en z a lh y d ra z id e (D ib e n z a la z in e ).

O ne-half gram o f t r i f l u o r o a c e t ­

h y d ra z id e was mixed w ith 1 m l. o f benzaldehyde, and th e m ix tu re was h e a te d f o r a few m inutes u n t i l a uniform s o lu tio n was form ed.

The s o lu ­

t i o n s o l i d i f i e d when i t c o o le d , and th e s o lid was c r y s t a l l i z e d from aqueous a lc o h o l.

B ib en z alh y d raz id e, m .p. 93°y was form ed.

S im ila r r e ­

s u l t s were o b ta in e d w ith acetophenone and benzophenone. C arbonyl compound Benzaldehyde Acetophenone Benzophenone

A nalyzed as

A n aly sis m .p.

C a lc 'd . »

Found

Cl l A 2 N2

93°

c , 80.8% ; H, 5-77%; C, 80.8% ; H, 6.02%

Cl 6 Hl 6 N2

123°

c . 81.3% ; H, 6.77%; C, 81.0% ; H, 6.79%

C26H20N2

16U°

C, 86.70%; H, 5.6% ; C, 86.45%; H, 6.0%

T riflu o ro a c e th y d ra z id e was h e a te d w ith n -b u ty ra ld e h y d e , n -h e p ta ld e hyde, m onochloroacetone, form aldehyde s o lu tio n , g lu co se, c h lo r a l , a c r o le in and a c e to n e , b u t i t d id n o t form a s o l i d d e r iv a tiv e w ith any o f th e s e

Ô

m a te r ia ls •

A ll o f them formed c o lo re d s o lu tio n s which were a p p a re n tly

complex p r o d u c ts . R e ac tio n w ith p h en y li s o th io c y a n a te .

One gram o f t r i f l u o r o a c e t ­

h y d ra z id e was mixed w ith 1 ml* o f p h e n y li s o th io c y a n a te and th e m ix tu re was

fu s e d . Hydrogen s u l f i d e was evolved and was t e s t e d

le a d a c e ta te p a p e r.

f o r b y means

of

Q u a lita tiv e a n a ly s is showed th e p resen c e o f n i t r o ­

gen and s u l f u r and th e absence o f f lu o r in e i n th e m o le cu le .

The m elt

s o l i d i f i e d on b e in g cooled, and th e s o lid was p u lv e riz e d and washed w ith p etro leu m e th e r and $0% aqueous e th a n o l •

The rem aining s o l i d was th e n

c r y s t a l l i z e d s e v e ra l tim es from d i lu t e e th a n o l, fo ra in g w h ite p l a t e s , m .p. 2V7°C.

A n aly sis showed t h i s m a te ria l to be th e p ro d u c t formed by

b o th c o n d en sa tio n w ith th e th io group and th e a d d itio n o f th e o th e r end o f th e condensed h y d razin e m olecule to a n o th e r is o th io c y a n a te u n i t to form th e th io u r e a , l >6 - d ip h e n y l- 5 - th io - l, 3>U > 6 -te tra z a h e x a -l,2 -d ie n e . A nal:

C a lc 'd . f o r cli;H12N^S: Found:

c > 6 2 .6 %

H,

C, 6 2 .9 % H,

A s i m il a r r e a c tio n was u n d ertak en w ith p h e n y li so c y an a te , b u t w h ile a r e a c t i o n does o c c u r, th e p ro d u c ts a re in s e p a r a b le .

In th e r e a c tio n

w ith p h e n y li so th io c y a n a te th e co n d en satio n occurs w ith th e e lim in a tio n o f hydrogen s u l f i d e which i s d riv e n o u t by th e tem p era tu re o f th e r e ­ a c tio n w ith o u t c a u sin g any co m p licatin g r e a c t i o n s .

The co rresp o n d in g

r e a c tio n w ith p h e n y li socyanate i s com plicated by th e w a ter which i s formed i n th e c o n d en sa tio n r e a c tio n f u r t h e r r e a c tin g w ith p h e n y li so­ c y an ate to form d ip h e n y lu re a .

No method o f s e p a ra tio n was found f o r

th e p ro d u c ts o f t h i s r e a c tio n . Sodium tr if lu o r o a c e th y d r a z id e .

T riflu o ro a c e th y d ra z id e (3 .2 g . ,

0 .0 2 5 mole) was d is s o lv e d i n a b so lu te e th a n o l and t h i s s o lu tio n was

Ô

m a t e r i a ls .

A ll o f them form ed c o lo re d s o lu tio n s which were a p p a re n tly

complex p r o d u c ts . R e a c tio n w ith p h e n y li s o th io c y a n a te .

One gram o f t r i f l u o r o a c e t ­

h y d ra z id e was mixed w ith 1 m l. o f p h e n y li s o th io c y a n a te and th e m ix tu re was fu s e d .

Hydrogen s u l f i d e was evolved and was t e s t e d f o r by means o f

le a d a c e ta te p a p e r .

Q u a lita tiv e a n a ly s is showed th e p re se n c e o f n i t r o ­

gen and s u l f u r and th e absence o f f lu o r in e i n th e m o lecu le. s o l i d i f i e d on b e in g c o o le d , and th e s o l i d was p u lv e riz e d p etro leu m e th e r and £0$ aqueous e th a n o l •

The m elt

and washed w ith

The rem aining s o l i d

wasth e n

c r y s t a l l i z e d s e v e ra l tim e s from d i l u t e e th a n o l, form ing w h ite p l a t e s , m .p. 2lt7°C.

A n a ly sis showed t h i s m a te r ia l to be th e p ro d u c t formed by

bo th c o n d en sa tio n w ith th e t h io group and th e a d d itio n o f th e o th e r end o f th e condensed h y d raz in e m olecule to a n o th e r is o th io c y a n a te u n i t to form th e th io u r e a , 1 ,6 - d i p h e n y l - ^ - t h i o - l ,3 ,b ,6 - t e t r a z a h e x a - l ,2 - d i e n e . Anal:

C a lc 'd .

fo r

c > & 2 .6 % H> Found:

C, 6 2 . 9 %

H, k . # #

A s i m ila r r e a c tio n was u n d e rta k e n w ith p h e n y li so c y a n a te , b u t w h ile a r e a c tio n does o c c u r, th e p ro d u c ts a re i n s e p a r a b le .

In th e r e a c tio n

w ith p h e n y li s o th io c y a n a te th e c o n d e n sa tio n o ccu rs w ith th e e lim in a tio n o f hydrogen s u l f i d e which i s d riv e n o u t by th e te m p e ra tu re o f th e r e ­ a c tio n w ith o u t c au sin g any c o m p lic a tin g r e a c t i o n s .

The co rre sp o n d in g

r e a c tio n w ith p h e n y li so cy an ate i s co m p licated by th e w a te r which i s formed i n th e c o n d en sa tio n r e a c tio n f u r t h e r r e a c tin g w ith p h e n y lis o — cy an ate to form d ip h en y lu re a .

No method o f s e p a r a tio n was found f o r

th e p ro d u c ts o f t h i s r e a c t i o n . Sodium t r if lu o r o a c e th y d r a z id e .

T riflu o ro a c e th y d ra z id e (3 .2 g . ,

0*025 mole) was d is s o lv e d i n a b s o lu te e th a n o l and t h i s s o lu tio n was

9

added to a s o lu tio n o f sodium (0*575 g** 0 .2 5 mole) i n a b s o lu te e th a n o l, and th e m ix tu re was h e a te d to a te m p e ra tu re n e a r i t s b o i li n g p o in t f o r f iv e m in u te s.

A "white s o l i d s e p a ra te d and s e t t l e d a f t e r th e s o lu tio n

was allo w ed to sta n d f o r 0 .5 h o u r.

The su p e rn a ta n t l i q u i d was d e ca n te d

through a f i l t e r , and th e re s id u e was washed tw ic e w ith 15 ml* p o r tio n s o f e th e r which were a ls o poured th ro u g h th e f i l t e r . was c o lle c te d on th e f i l t e r as a p u re w h ite s o l i d . h ig h te m p e ra tu re (above 200°) w ith o u t m e ltin g .

The r e s i d u a l s a l t I t decomposed a t

T his s a l t was sodium

t r if lu o r o a c e th y d r a z id e • A nal:

C a lc 'd . f o r C ^ F y ^ O N a :

C, 1 6 .0 # ;

H, 1 .3 3 # , Na, 15-30#

Found: C, 16.15#5

H, 1.U7#, Na, 15-U5#

Disodium b i s ( t r i f l u o r o a c e t ) h y d r a z i d e .

B is ( t r i f l u o r o a c e t )h y d ra z id e

(0 .5 g ., 0*002 mole) was d is s o lv e d i n 10 m l. o f a b s o lu te e th a n o l and added to a s o lu tio n o f sodium (0 .092 g . , 0.00U mole) i n 10 m l. o f ab­ s o lu te e th a n o l, and th e m ix tu re was h e a te d to a te m p e ra tu re n e a r th e b o ilin g p o in t f o r f i v e m in u te s.

A f te r th e s o lu tio n had co o led and th e

s a l t had s e t t l e d , th e su p e rn a ta n t l i q u i d was d ecan ted th ro u g h a f i l t e r . The r e s id u a l s a l t was washed tw ic e w ith 10 m l. p o r tio n s o f e th e r which were d e can ted thro u g h th e f i l t e r .

The s a l t was th e n c o lle c te d and d r ie d .

I t was a powdery w h ite s o l i d which decomposed w ith o u t m e ltin g when i t was h e a te d .

A n a ly sis showed t h i s m a te r ia l to be d i so diurn b i s ( t r i f l u o r o —

a c e t) h y d r a z id e . A nal:

C a lc 'd . f o r c^

N2°2Na2!

C’ 17*85#; Na> 17*17#

Found: C, 17*65#; Na, 17.10# A c id if ic a tio n o f th e sodium s a l t w ith d i l u t e m in e ra l a c id s reg en ­ e ra te d th e b i s ( t r if l u o r o a c e t ) h y d r a z i d e , showing th e r e a c t i o n to be r e v e r s a b le and o f f e r in g more evidence f o r th e s t r u c t u r e o f th e sodium s a lt.

10

When th e s e sodium s a l t s were h e a te d w ith e x ce ss a lk y l h a l i d e , t e t r a — a lk y l h y d ra z in e s were form ed.

T e tra b e n z y l h y d ra z in e , m .p. 136°C, was

i s o l a t e d from th e r e a c tio n betw een disodium b i s ( t r i f l u o r o a c e t) h y d ra z id e and b en zy l brom ide. A nal;

C a lc 'd . f o r Found:

C, 8^.70%;

H, 7.32%, N, 7.32%

C, 85.35%;

H, 7.22%; N, 7-U3%

The fo rm a tio n o f th e t e t r a a l k y l h y d ra z in e s r a t h e r th a n th e mono­ a lk y l h y d ra z in e may be due to c o n ta c t o f r e a c t a n t s .

S in ce sodium t r i ­

flu o ro a c e th y d ra z id e i s e s s e n t i a l l y in s o lu b le i n a b s o lu te e th a n o l, th e f i r s t r e a c tio n to form th e m o n o su b stitu te d h y d ra z id e would be slow . m o n o su b stitu te d h y d ra z id e would be s o lu b le i n

The

th e s o lu tio n so t h a t th e

r e a c tio n betw een th e m o n o su b stitu te d h y d ra z id e and th e a lk y l h a lid e would o ccu r much more r a p id ly th a n th e r e a c t i o n betw een th e sodium s a l t and th e a lk y l h a li d e .

T his would le a d to th e c o n v ersio n o f th e mono­

s u b s ti t u t e d h y d ra z id e s to t e t r a s u b s t i t u t e d h y d ra z in e s i n p re fe re n c e to th e fo rm a tio n o f more o f th e m o n o su b stitu te d h y d ra z id e . B is ( t r i flu o r o a c e t) h y d ra z id e .

T riflu o ro a c e th y d ra z id e (5 g«, 0.039

mole) was d is s o lv e d i n a m ix tu re o f 15 m l. o f w a te r and 5 m l. o f conc. h y d ro c h lo ric a c id , and th e r e s u l t i n g s o lu tio n was co o led i n i c e and covered w ith 25 m l. o f e t h e r .

A s o lu tio n o f 3 .5 g. o f sodium n i t r i t e

in 20 m l. o f w a ter was added slow ly w ith s t i r r i n g to th e c o ld s o l u t io n . When th e a d d itio n o f th e sodium n i t r i t e s o lu tio n was com p lete, th e e th e r l a y e r was removed and th e aqueous la y e r was e x tr a c te d tw ic e w ith 10 m l. p o r tio n s o f e t h e r .

The combined e th e r e x tr a c t s were d r ie d o v er anhydrous

sodium s u l f a t e , a f t e r which th e e th e r was removed by r a p id e v a p o ra tio n i n v acu o .

B i s ( t r i f l u o r o a c e t ) h y d raz id e (3 .6 g. c ru d e, 0.016 mole) i n 82%

y i e l d rem ained as a powdery w h ite s o l i d .

T his powder c o u ld be

11

c r y s t a l l i z e d Arom e i t h e r an a lc o h o l— benzene mixed s o lv e n t, an e t h e r — benzene mixed s o lv e n t, o r to lu e n e -

The im p u r itie s seemed to be t r i ­

f l u o r o a c e t ic a c id and t r if l u o r o a c e t h y d r a z i d e . c a r r i e d o u t by vacuum s u b lim a tio n •

F in a l p u r i f i c a t i o n was

The p u re m a te r ia l m elted a t 17U°*

I d e n t i f i c a t i o n o f b i s ( t r i f lu o r o a c e t) h y d ra z id e .

A s e r i e s o f chemi­

c a l r e a c tio n s se rv e d to i d e n t i f y t h i s m a te r ia l and i t s i d e n t i t y was v e r i f i e d by a n a l y s i s .

I t r a p id ly d e c o lo riz e d brom ine w a te r and d i l u t e

aqueous perm anganate, w ith a gas b e in g evolved d u rin g th e r e a c t i o n . s im ila r r e a c t i o n was n o te d w ith e e r ie n i t r a t e r e a g e n t.

A

A p o s i t iv e r e ­

a c tio n was n o ted w ith T o lle n s r e a g e n t, b u t th e m a te r ia l showed no r e ­ a c tio n w ith p h e n y lh y d ra z in e .

A sample o f two grams was h e a te d w ith

conc. h y d ro c h lo ric a c id s o lu tio n i n a sm all d i s t i l l i n g f l a s k .

The s id e

arm was connected to a b u b b le r c o n ta in in g aqueous sodium h y d ro x id e . A fte r th e h e a tin g had been c o n tin u e d f o r te n m in u te s, th e sodium hydro­ x id e t r a p was examined f o r th e p re se n c e o f c a rb o n a te io n , b u t none was fou n d .

The r e s id u a l s o lu tio n was t r e a t e d w ith e th a n o l, form ing a w hite

p re c ip ita te .

T h is p r e c i p i t a t e was f i l t e r e d and d r ie d and i t s m eltin g

p o in t was d eterm in ed .

I t m elted a t 198°C. and was r e a d i l y o x id iz e d by

such o x id iz in g a g e n ts a s brom ine w a ter and n i t r i c a c id , w ith th e l i b e r ­ a tio n o f n itr o g e n , which in d ic a te d th e m a te r ia l to be h y d ra z in e d ih y d ro ­ c h lo r id e . A sample o f th e o r i g i n a l m a te r ia l was h e a te d u n d er r e f l u x w ith siru p y p h o sp h o ric a c id and th e n d i s t i l l e d .

The aqueous d i s t i l l a t e was

n e u tr a liz e d w ith aqueous sodium hydroxide and th e r e s u l t i n g s o lu tio n was e v ap o rate d to d ry n e s s .

The d ry s a l t th u s o b ta in e d was t r e a t e d w ith

conc. s u l f u r i c a c id and d i s t i l l e d , y ie ld in g 5 m l. o f c o lo r le s s l i q u i d w ith a s tro n g v in e g a r - lik e o d o r.

T his l i q u i d , b ein g s tr o n g ly a c i d ic .

12

was n e u tr a li z e d w ith conc* ammonium h ydroxide s o lu tio n and th e n vacuum d is tille d .

A w h ite c r y s t a l l i n e s o l i d d i s t i l l e d whose m e ltin g p o in t was

7b*6°C ., i n d ic a t i n g i t to be t r i f l u o r o a c e t am ide.

S in ce no m a te r ia ls

o th e r th a n t r i f l u o r o a c e t i c a c id and h y d ra z in e were i s o l a t e d from th e m a te r ia l, i t was s tr o n g ly su sp e c te d o f b e in g b i s ( t r i f l u o r o a c e t ) h y d r a z i d e . M o lecu lar w eight d e te rm in a tio n s and a n a ly s is i n d i c a t e t h i s to be th e case. A nal: C a lc ’d . f o r

C, 2 1 .1 ^ 5 H, 0.89^3 F, 50.9#?

N, 1 2 .5 0 # ; m ol. w t. 22U» Found: C, 2 1 .it# ? H, 0.88#? F, 53.9#? N, 12,95#? m ol. w t. (H a s t) , 228. No a tte m p t h as been made to determ ine i f o r c(

s u b s t i t u t i o n p r o d u c t.

th e compound i s th e

o(, o(,

From analagous r e a c tio n s i t i s assumed

to be th e sym m etrical p ro d u c t. A c id ity o f b i s ( t r i f l u o r o a c e t ) h y d r a z i d e .

B is ( t r i f lu o ro a c e t) h y d ra ­

z id e d is s o lv e d i n w a te r to form an a c id ic s o lu tio n w ith a pH o f approx­ im a te ly 3 .

T i t r a t i o n o f t h i s s o lu tio n gave evidence o f th e a c id ic

n a tu re o f b i s ( t r i f l u o r o a c e t ) h y d ra z id e .

B is ( tr if lu o r o a c e t) h y d r a z id e

(0.0570 g .) was d is s o lv e d i n w a te r, and th e s o lu tio n wast i t r a t e d p h e n o lp h th a l e in end p o in t w ith aqueous sodium

to a

h y d ro x id e. Twoand s i x -

te n th s m i l l i l i t e r s o f 0.1025 norm al sodium h ydroxide s o lu tio n was r e ­ q u ire d f o r th e t i t r a t i o n .

C a lc u la tin g th e m o lecu lar w eig h t o f b i s ( t r i ­

f lu o r o a c e t) h y d ra z id e from t h i s t i t r a t i o n on th e assum ption t h a t i t con­ t a i n s one a c id ic p ro to n g iv e s a v a lu e o f 211i f o r th e ex p erim e n tal mole­ c u la r w eig h t as a g a in s t 22U f o r th e c a lc u la te d m o le cu la r w e ig h t.

This

b e a rs o u t th e assum ption t h a t b i s ( t r i f l u o r o a c e t) h y d ra z id e i s a monobasic a c id w ith r e s p e c t to a n e u tr a l s o lu tio n .

13

"While th e u re a o r th e a z id e was th e p ro d u c t ex p ected from th e r e ­ a c tio n betw een n i tr o u s a c id and tr if lu o r o a c e th y d r a z id e , i t i s a p p a re n t t h a t th e a z id e which was p ro b a b ly form ed was more a c tiv e i n undergoing a c id h a lid e ty p e r e a c tio n s r a t h e r th a n rearran g em en t t o th e is o c y a n a te . Such r e a c tio n s a re n o t uncommon f o r a z i d e s . p e c te d i n t h i s r e a c tio n :

Two p ro d u c ts would be ex­

one when th e r e a c tio n o c c u rre d betw een th e

a z id e and w a te r to form h y d raz o ic a c id and t r i f l u o r o a c e t i c a c id , and th e second when th e r e a c tio n o c c u rre d betw een an u n re a c te d m olecule o f t r i ­ flu o ro a c e th y d ra z id e and th e a z id e , form ing h y d raz o ic a c id and b i s ( t r i ­ f lu o r o a c e t) h y d ra z id e .

Form ation o f th e d i s u b s ti t u t e d h y d ra z id e a p p a re n t­

l y p re v e n ts f u r t h e r r e a c tio n w ith th e n i tr o u s a c id .

The r e l a t i v e l y h ig h

y i e l d o f b i s ( t r if l u o r o a c e t ) h y d r a z i d e (&2%) in d ic a te s t h a t th e r e a c tio n o f th e a c id a z id e w ith tr if lu o r o a c e th y d r a z id e was th e p r e f e r r e d r e a c t i o n . The odor o f t r i f l u o r o a c e t i c a c id was c l e a r l y e v id e n t on th e crude p ro ­ d u c t, i n d ic a t i n g t h a t th e h y d r o ly tic r e a c tio n d id o ccur to a lim ite d e x te n t.

The p r e f e r e n t i a l r e a c tio n w ith tr if lu o r o a c e th y d r a z id e i s f u r ­

t h e r in d ic a te d by th e mole r a t i o o f w a te r to t r if lu o r o a c e th y d r a z id e , 1 to 0 .0 3 9 . I n view o f th e f a i l u r e o f th e tre a tm e n t o f tr if lu o r o a c e th y d r a z id e w ith n i tr o u s a c id i n aqueous s o lu tio n to y i e l d th e is o c y a n a te , th e r e ­ a c tio n was a tte m p te d u nder v a ry in g c o n d itio n s , b u t i n no c ase was e i t h e r a z id e n o r is o c y a n a te i s o l a t e d .

The u s u a l p ro d u c ts were h y d ro c h lo rid e s

o f h y d ra z in e , h y d ra z o ic a c id , t r i f l u o r o a c e t i c a c id and e s t e r s , depending on th e s o lv e n t u s e d .

T y p ical experim ents a re l i s t e d .

N itro u s a c id i n m eth an o l.

T riflu o ro a c e th y d ra z id e (5> g . , 0.039 mole)

was powdered and d is s o lv e d i n 20 m l. o f anhydrous m ethanol, sodium n i t r i t e (3*5 g*) was added, and th e m ix tu re was co o led i n an i c e b a th .

Ik

Concentrâted hydrochloric acid solution (5 ml.) was added slowly to the well stirred solution.

When the addition of the hydrochloric acid solu­

tion was complete> the sodium chloride formed in the reaction was filter­ ed off and the methanol solution was rectified.

Several milliliters of

material boiling at 101-10$°C. was found in addition to methanol and methyl trifluoroacetate. azeotrope.

This fraction irasa trifluoroacetic acid-water

A solid remaining in the pot was recrystalli zed from methanol

and its melting point was determined.

It was hydrazine monohydrochloride.

N itro u s a c id from amyl n i t r i t e i n e th a n o l.

T riflu o ro a c e th y d ra z id e

(5 g»> 0.039 m ole) was d is s o lv e d i n 29 m l. o f a b s o lu te e th a n o l i n a th r e e necked round bottom f l a s k f i t t e d w ith a m ercury s e a le d s t i r r e r , a gas i n l e t tu b e and a r e f l u x condenser p r o te c te d w ith a calcium c h lo r id e d ry in g tu b e .

Amyl n i t r i t e (7 g . , 0 .0 6 mole) was added and th e r e s u l t i n g

s o lu tio n was c o o le d i n i c e .

Diy hydrogen c h lo rid e g e n e ra te d by dropping

8 m l. o f conc. h y d ro c h lo ric a c id i n t o conc. s u l f u r i c a c id was p a sse d i n t o th e w e l l - s t i r r e d m ix tu re .

“When a l l o f th e hydrogen c h lo rid e had

been p a sse d i n t o th e s o lu tio n , th e m ix tu re was allow ed to warm to room te m p e ra tu re , and a w h ite s o l i d was f i l t e r e d o f f .

P u r i f i c a t i o n and exami­

n a tio n o f th e s o l i d showed i t to be h y d ra z in e d ih y d ro c h lo rid e .

R e c ti­

f i c a t i o n o f th e f i l t r a t e gave a f r a c t i o n b o ilin g a t ii5-U7°C. i n a d d itio n to e th a n o l. manner:

T his f r a c t i o n was shown to be an a z e o tro p e i n th e fo llo w in g

Mien t r e a t e d w ith 1% aqueous f e r r i c c h lo rid e s o lu tio n , a deep

b lo o d r e d c o lo r was formed by t h i s m a t e r i a l .

T his c o lo r was d e stro y e d

by th e a c tio n o f conc. m in e ra l a c id s , o r by h e a tin g .

Mien th e o r i g i n a l

s o lu tio n was t r e a t e d w ith aqueous s i l v e r n i t r a t e , a w h ite p r e c i p i t a t e which was r e a d i l y s o lu b le i n n i t r i c a c id was form ed.

These a re q u a li­

t a t i v e t e s t s f o r th e a z id e io n , in d ic a tin g th e p re se n c e o f h y d raz o ic

15

acid *

T h is a c id was removed by w ashing w ith aqueous p o tassiu m c a rb o n a te

s o l u t io n .

The p re se n c e o f e th y l t r i f l u o r o a c e t a t e was i n d ic a t e d by b o th

d i s t i l l a t i o n te m p e ra tu re and odor*

A s i m il a r r e a c t i o n w ith th e o u t l e t

tu b e a tta c h e d to a d ry i c e t r a p was c a r r i e d o u t. y e llo w l i q u i d was tra p p e d i n th e d ry i c e t r a p .

Two m i l l i l i t e r s o f E xam ination o f t h i s

l i q u i d f a i l e d to e s t a b l i s h i t s i d e n t i t y b u t showed t h a t i t was n e it h e r a z id e n o r is o c y a n a te . O x id a tio n o f tr if lu o r o a c e th y d r a z id e w ith i o d i n e .

T r if lu o r o a c e t­

h y d ra z id e (6.1; g . , 0 .0 £ mole) was d is s o lv e d i n w a te r and th e s o lu tio n was h e a te d to a te m p e ra tu re o f 60°C.

Io d in e was added u n t i l th e ev o lu ­

t i o n o f n itr o g e n cea sed and a y e llo w c o lo r p e r s i s t e d .

The s o lu tio n was

c o o le d and th e e x ce ss io d in e was d e stro y e d by th e a d d itio n o f sodium b i ­ s u lfite .

The aqueous s o lu tio n was e x tr a c te d w ith th r e e 15 m l. p o r tio n s

of e th e r.

The e th e r s o lu tio n was t r e a t e d w ith enough benzene to cause

th e fo rm a tio n o f a p r e c i p i t a t e which was c r y s t a l l i z e d from th e h o t s o lu ­ tio n .

Four grams o f b i s ( t r i f lu o r o a c e t ) h y d ra z id e , r e p r e s e n tin g a y i e l d

o f 36$, was o b ta in e d . O x id atio n o f tr if lu o r o a c e th y d r a z id e w ith brom ine.

T r if lu o r o a c e t­

h y d ra z id e (6.1; g . , 0 .0 5 mole) was d is s o lv e d i n w a te r and brom ine (16 g . , 0 .1 mole) was added slo w ly .

C o n sid e rab le h e a t was evolved d u rin g th e

r e a c tio n and a g as was g iv en o f f .

The c o o le d s o lu tio n was e x tr a c te d

w ith e th e r , and b i s ( t r i f l u o r o a c e t ) h y d ra z id e was p r e c i p i t a t e d from th e e th e r s o lu tio n by th e a d d itio n o f b en zen e. was form ed i n 18$ y i e l d .

B is ( t r i f l u o r o a c e t ) h y d ra z id e

T r if lu o r o a c e tic a c id was a ls o form ed e i t h e r

by f u r t h e r a c tio n o f brom ine on b i s ( t r i f l u o r o a c e t ) h y d ra z id e o r by hy­ d ro ly s is .

16

O x id a tio n o f tr if lu o r o a c e th y d r a z id e w ith m erc u ric o x id e .

T r i­

flu o ro a c e th y d ra z id e (6.U g.» 0.05> mole) was d is s o lv e d i n w a te r and mer­ c u r ic o x id e (1 0 .8 g . , 0 .0 5 mole) was added and th e m ix tu re was h e a te d to a te m p e ra tu re n e a r th e b o i li n g p o in t f o r t e n m in u te s. d ark g ray m ix tu re was co o led and e x tr a c te d w ith e th e r .

The r e s u l t i n g B is ( t r i f l u o r o ­

a c e t) h y d ra z id e was i s o l a t e d from th e e th e r s o lu tio n by tre a tm e n t w ith benzene as b e f o r e •

Five and f o u r - te n th s gram s, re p re s e n tin g a y i e l d o f

lj.8$, was o b ta in e d . H e x a flu o ro g lu ta ry l a z id e .

Sodium a z id e (25 g-> 0*35 mole) was

added to th e a c id c h lo rid e o f h e x a flu o ro g lu t a r i e a c id p re p a re d from 0 .1 7 mole o f h e x a flu o r o g lu t a r t c a c id , benzene was added f o r f l u i d i t y , and th e m ix tu re was h e a te d u n d er r e f l u x w ith s t i r r i n g .

H eating was

m ain ta in e d o v e rn ig h t d u rin g which tim e th e m ix tu re s e t to a s t i c k y m ass. The benzene was poured o f f , and th e mass was t r e a t e d w ith a c e to n e .

A

g e la tin o u s su b sta n c e seemed to form f i r s t and was th e n d is s o lv e d i n th e * a c e to n e .

A d ark am ber-colored s o lu tio n was fo m e d .

f i l t e r e d o f f and examined.

A w h ite s o l i d was

Q u a lita tiv e t e s t s showed th e p re se n c e o f

sodium io n , a z id e io n , and c h lo r id e io n , showing i t to be a m ix tu re o f sodium c h lo r id e and sodium a z id e . The a c e to n e s o lu tio n was b o ile d w ith d e c o lo riz in g c h a rc o a l and filte re d .

A l i g h t y e llo w c o lo re d s o lu tio n r e s u l t e d .

w ith d e c o lo riz in g c h a rc o a l seemed to have no e f f e c t .

F u rth e r tre a tm e n t E v ap o ra tio n o f th e

a ceto n e from th e s o lu tio n l e f t a v isc o u s y e llo w ish s ir u p which s o l i d i f i e d a f t e r sta n d in g f o r s e v e ra l d ay s.

The p resen c e o f n itro g e n and f lu o r in e

i n t h i s s o l i d was in d ic a te d by means o f a sodium f u s io n and subseq u en t te s ts .

The s o l i d was s o lu b le i n w a te r, e th a n o l, a ceto n e and dioxan

and ^ a s in s o lu b le i n benzene and p etro leu m e t h e r .

A ttem pts to f in d a

17

r e c r y s t a l l i z a t i o n s o lv e n t were u n s u c c e s s f u l. e th a n o l.

The s o l i d was d is s o lv e d i n

T reatm ent o f th e e th a n o l s o lu tio n w ith p e tro le u m e th e r caused

th e s e p a r a tio n o f an o i l which s o l i d i f i e d a f t e r s ta n d in g f o r f o u r o r f iv e d a y s.

T his s o l i d m e lte d w ith d ecom position a t 170-17li°C.

At h ig h ­

e r te m p e ra tu re s th e decom position o c c u rre d more r a p i d l y , le a v in g a r e s i ­ due.

A w a te r s o lu tio n o f t h i s r e s id u e was n e u tr a l to litm u s p a p e r.

Q u a lita tiv e t e s t s showed th e p re se n c e o f f lu o r in e and sodium in h ig h c o n c e n tr a tio n , and so t h i s r e s id u e was c o n sid e re d to be c h ie f ly sodium flu o rid e .

The o r i g i n a l m a te r ia l d id n o t d e c o lo riz e brom ine w a te r b u t

slo w ly d e c o lo riz e d n e u tr a l aqueous perm anganate s o l u t io n .

An aqueous

s o lu tio n o f th e m a te r ia l was n e u tr a l to litm u s p a p e r, and q u a l i t a t i v e t e s t s showed th e p re se n c e o f f l u o r id e io n i n s o l u t io n . A sample o f two grams o f t h i s s o l i d was t r e a t e d w ith

s u lfu ric

a c id s o lu tio n , and th e r e s u l t i n g s o lu tio n was d i s t i l l e d i n t o a s o lu tio n o f ammonium h y d ro x id e . tio n .

Only ammonium s u l f a t e was found i n t h i s s o lu ­

The r e s i d u a l s u l f u r i c a c id s o lu tio n was n e u tr a liz e d and made

s tr o n g ly a lk a li n e w ith e x ce ss aqueous sodium h y d ro x id e . ammonia was v e ry s tr o n g .

T his s o lu tio n was d i s t i l l e d i n t o a d i l u t e

s o lu tio n o f h y d ro c h lo ric a c id . from t h i s r e a c t i o n .

An odor o f

Only ammonium c h lo rid e was i s o l a t e d

The i s o l a t i o n o f ammonium c h lo rid e i n d ic a te d t h a t

a p o s i t i v e r e a c tio n had been o b ta in e d a s i s shown by th e s e r i e s o f e q u a tio n s : R-CF2-C0C1 —^ 3 ^ * R-CF2-N-C02H

r~CF2-C/-Nj

> - R-CF2-NH2

R-CF2-N=C=0

?2°_^

R-C=m ---- -2 ° —>- R-COgH 4- NH3

Such a s e r i e s o f r e a c tio n s a s p o s tu la te d would i n d ic a t e n o t o n ly th e

18

p re se n c e o f ammonia, b u t a ls o th e p re se n c e o f f l u o r id e io n i n th e r e s i ­ d u a l s o l u t io n .

C onfirm ation o f i t s p re se n c e added f u r t h e r evidence f o r

th e c o r r e c tn e s s o f th e s e e q u a tio n s . A sample o f 2 g . o f t h i s s o l i d was h e a te d w ith 10 m l. o f w a te r con­ t a i n i n g a low c o n c e n tra tio n o f f e r r i c io n ( ta p w a ter) w ith fre q u e n t c o o lin g s d u rin g th e p r o c e s s . grew i n i n t e n s i t y .

A re d c o lo r developed i n th e s o lu tio n and

T his re d c o lo r ap p eared o nly a s th e s o lu tio n was

c o o le d and d isa p p e a re d when th e s o lu tio n was h e a te d . d e stro y e d by th e a c tio n o f s tro n g m in e ra l a c id s .

The re d c o lo r was

These q u a l i t a t i v e t e s t s

i n d ic a te d t h a t a c o n c e n tra tio n o f a z id e io n was b e in g b u i l t up i n th e aqueous s o lu tio n .

T his in d ic a te d t h a t th e o r i g in a l s o l i d was an a z id e

and t h a t th e a z id e io n was b e in g formed by h y d ro ly s is o f th e o r i g in a l p ro d u c t.

When th e s o lu tio n was t r e a t e d w ith conc. h y d ro c h lo ric a c id

s o lu tio n , a s o l i d se p a ra te d which was i s o l a t e d and i d e n t i f i e d a s sodium c h lo r id e . D iflu o ro ac etam id e * I t was found t h a t h e x a flu o r o g lu ta ry l a z id e r e ­ duced a lk a lin e p o tassiu m perm anganate s o lu tio n .

A sam ple o f 2 g. was

t r e a t e d w ith e x cess a lk a lin e perm anganate, and th e r e s u l t i n g s o lu tio n was b o ile d f o r te n m in u te s.

The s o lu tio n was th e n a c i d i f i e d w ith

s u l f u r i c a c id , d e c o lo riz e d by th e a d d itio n o f sodium b i s u l f i t e , and e x tr a c te d w ith d ie th y l e th e r f o r f o r t y - e i g h t h o u rs i n a co n tin u o u s e x tr a c tio n a p p a ra tu s .

The e th e r s o lu tio n was s tr o n g ly a c id ic to litm u s

and was d r ie d o v er anhydrous sodium s u l f a t e and e v a p o ra te d .

The concen­

t r a t e d s o lu tio n was t r e a t e d w ith ammonium hydroxide s o lu tio n and eva­ p o ra te d f u r t h e r . t i c s o f an am ide.

A s o l i d formed which had th e s o l u b i l i t y c h a r a c t e r i s ­ I t was r e c r y s t a l l i z e d from a w a te r-e th a n o l s o lv e n t

and found to m elt a t 5 l°C •, in d ic a tin g i t to be

19

d iflu o ro a c e ta m id e , m«p•

An exam inaliion o f "bhe r é a c tio n s in v o lv e d

i n d ic a t e t h a t th e fo rm a tio n o f diflu.oroacetanD .de o r d if lu o r o a c e ti c a c id i s a d is tin c t p o s s ib ility : 0

coci

H

(ÇF2) 3

c-n3 (ÇF2) 3

COCI

C-Nq

^

n=c=o (ÇF2) 3

n -c o 2h

H2 V

(ÇF2 ) 3

N-C-0

K-COpH

0

H

F C=NH

m 2

C02H

( c f 2 ) 3 — HF- ^ - C F 2 — h 2 ° -* - CF2

jm.

Or:

9=HH F F C=NH

— HoO _

CF2 C-NH F

Or:

_____

o =co2 ^

h c f ? - co 2 h

_ J ® 3 ^ hcf2 - c-

nh ,

COgH P C-NH9 CF2 *

0

//

— -CO — 2

HCF2-C-MH2

COgH

MHo (CF2 ) 3 *

C=N OF, i ^

C-HH, (°) >■ CF„ u _n i c

NHo

C5N

H2°

C=N

H?°

3-

C-MH0 '/__ CF„ — rC02 ^HGF 2 -C-NH2 i 2 co2h

c o 2h

ço 2h

(CF2) 2 —^ co 2h

NH3 +

HF

The fo rm a tio n o f b o th t e t r a f l u o r o s u c c i n i c and d iflu o ro m a lo n ic a c id s i n t h i s r e a c t i o n a ff o r d s no problem o f s e p a r a tio n .

The

21

d iflu o ro m a lo n ic a c id d e c a rb o x y la te s a t room te m p e ra tu re to form d i f lu o r o a c e t i c a c id o r i t s d e r i v a ti v e s .

The d e r iv a tiv e s a re h y d ro ly ze d by th e

s u l f u r i c a c id s o lu tio n to f o r a th e f r e e a c id which i s r e a d i l y s e p a ra te d d u rin g th e r e c r y s t a l l i z a t i o n o f th e t e t r a f l u o r o s u c c i n i c a c id from benzene, o r th e y may be s e p a ra te d by r e c t i f i c a t i o n . A two gram sample o f th e o r i g i n a l a z id e was h e a te d w ith d i l u t e s u l ­ f u r i c a c id s o lu tio n f o r te n m inutes and th e n was e x tr a c te d w ith d ie th y l e th e r f o r tw e n ty -fo u r hours i n a c o n tin u o u s e x tr a c tio n a p p a ra tu s .

The

e th e r e x t r a c t was c o n c e n tra te d somewhat and th e n n e u tr a liz e d w ith excess ammonium h y d ro x id e .

Benzene was added and th e m ix tu re was h e a te d to

steam d i s t i l l o u t th e w a te r.

During t h i s h e a tin g p ro c e s s , th e m a te r ia l

exploded w ith s u f f i c i e n t f o rc e to b rea k th e f l a s k .

A p p aren tly a q u a n tity

o f th e f r e e a z id e was e x tr a c te d and i t was t h i s which ex ploded.

No such

r e s u l t was encountered as lo n g a s th e m a te ria l was h e a te d w ith a lk a lin e perm anganate s o lu tio n .

The perm anganate s o lu tio n must have a id e d i n th e

decom position o f th e a z id e . O c ta flu o ro a d ip y l a z id e .

Sodium a z id e (13 g . , 0 .2 mole) was mixed

w ith th e a c id c h lo rid e o f o c ta f lu o r o a d ip ic a c id p re p a re d from 0 .1 mole o f o c ta f lu o r o a d ip ic a c id , and n itro m eth a n e (100 m l.) was added a s a s o lv e n t. h o u rs .

The m ix tu re was h e a te d un d er r e f l u x w ith s t i r r i n g f o r s ix te e n L i t t l e o r no r e a c tio n o c c u rre d , p ro b ab ly due to th e p oor c o n ta c t

betw een th e two s o l i d r e a c t a n t s . T r if lu o r o a c e ty l a z id e .

Sodium a z id e (6j> g . , 1 mole) was p la c e d i n

a 25>0-ml. th re e necked round bottom f l a s k which was f i t t e d w ith a gas i n l e t tu b e , a m ercury s e a le d H ershberg s t i r r e r , and a d ry i c e c o ld f i n ­ g e r r e t u r n co n d en ser.

The a z id e was covered w ith 100 m l. o f p u r i f i e d

d ie th y l e th e r and th e t r i f l u o r o a c e t y l c h lo r id e , p re p a re d by th e a c tio n

22

o f phosphorous p e n ta c h lo rid e on one mole o f sodium t r i f l u o r o a c e t a t e , was b u b b led th ro u g h th e w e ll s t i r r e d a z id e su sp e n sio n .

A r e a c t i o n seemed

to o c cu r f o r a c e r t a i n r e f l u x r a t e co u ld n o t be exceeded and no a c id c h lo r id e p a sse d th ro u g h th e r e t u r n co n d en ser.

When a l l o f th e t r i f l u o r o ­

a c e ty l c h lo r id e had been p a sse d i n t o th e s o lu tio n , th e s t i r r i n g was con­ tin u e d f o r one h o u r, a f t e r which th e m ix tu re was f i l t e r e d . a w a te r c l e a r , c o lo r le s s l i q u i d , was s to r e d i n d ry i c e .

The f i l t r a t e ,

The p r e c i p i t a t e

was examined and found to c o n ta in b o th sodium c h lo rid e and sodium a z id e , i n d i c a t i n g t h a t a r e a c tio n had o c c u rre d . S in ce no d a ta on t r i f l u o r o a c e t y l a z id e were known, i t was d ecid ed to a tte m p t th e rearran g em en t o f th e a z id e to th e is o c y a n a te and r e a c tio n o f th e is o c y a n a te by h e a tin g th e a z id e w ith v a rio u s a lc o h o ls .

The u r e ­

th a n e s which sh o u ld be no rm ally s ta b le l iq u i d s a s opposed to th e r e a c tiv e a z id e sh o u ld be more e a s i l y i s o l a t e d . Chemical I d e n t i f i c a t i o n o f t r i f l u o r o a c e t y l a z id e .

A bsolute e th a n o l

(30 m l.) was t r e a t e d w ith 5>0 m l. o f th e e th e r e a l s o lu tio n o f t r i f l u o r o ­ a c e ty l a z id e , and th e r e s u l t i n g s o lu tio n was r e c t i f i e d .

I n a d d itio n to

d ie t h y l e th e r and e th a n o l, a f r a c t i o n was o b ta in e d b o ilin g a t Uf>-l|60C. T his f r a c t i o n gave a p o s i t iv e iodoform t e s t when t r e a t e d w ith a l k a l i and io d in e .

I t r e a c te d r a p id ly w ith sodium, form ing a w h ite s o l i d which

exploded when h e a te d .

When th e l i q u i d was t r e a t e d w ith 1% aqueous

f e r r i c c h lo r id e s o l u t io n , a deep blood re d c o lo r was form ed which was d e s tro y e d by tre a tm e n t w ith m in e ral a c id o r by h e a tin g .

T reatm ent w ith

aqueous s i l v e r n i t r a t e fo m e d a w h ite p r e c i p i t a t e which was d is s o lv e d by tre a tm e n t w ith n i t r i c a c id .

These q u a l i t a t i v e t e s t s i n d ic a t e th e p re ­

sence o f h y d ra z o ic a c id ; so a h y d raz o ic a c i d - e t h e r - e th y l t r i f l u o r o a c e t a t e a z e o tro p e was su s p e c te d .

The m a te r ia l was washed th o ro u g h ly w ith

23

p o tassiu m c a rb o n a te s o lu tio n , d r ie d o v er anhydrous sodium s u l f a t e and th e n d i s t i l l e d . 35>-60°C.

The l i q u i d , l e s s th a n 5> m l., d i s t i l l e d o v er a range o f

The f i r s t p o r tio n was undoubtedly d ie th y l e t h e r , and th e l a s t

p a r t to d i s t i l l sm elled vezy much l i k e e th y l t r i f l u o r o a c e t a t e . F i f t y m i l l i l i t e r s o f n -b u ta n o l was t r e a t e d w ith £0 m l. o f th e e th e r e a l s o lu tio n o f t z i f lu o r o a c e t y l a z id e , and th e r e s u l t i n g s o lu tio n was r e c t i f i e d .

F ra c tio n s were o b ta in e d a t 1*5>-U6°C. and 99°C.

The f r a c ­

t i o n d i s t i l l i n g a t 99°C. was shown to be a b u ty l t i i f l u o r o a c e t a t e b u ta n o l a z e o tro p e sin c e i t had e x a c tly th e same r e f r a c t i v e in d e x as a b u ty l t ii f l u o r o a c e t a t e - b u t a n o l aze o tro p e o b ta in e d by th e a c tio n o f b u ta n o l on t r i f l u o r o a c e t i c a c id , n ^ = 1.3U87. S in ce no f r e e t r i f l u o r o a e e t y l c h lo rid e was p r e s e n t i n th e o r i g i n a l e th e r e a l s o lu tio n , th e e s t e r s formed in th e two p re c e d in g experim ents were assumed to be formed by a lc o h o ly s is o f th e a z id e i n th e same manner i n which b i s (t r i f l u o r o a c e t ) h y d raz id e was form ed.

These r e s u l t s i n d ic a t e

t h a t any a tte m p ts to re a rra n g e t r i f l u o r o a e e t y l a z id e i n a r e a c tiv e s o l ­ v e n t w i l l f a i l because o f th e a c t i v i t y o f th e a z id e i n a manner c o rr e s ­ ponding to a c id h a li d e s .

I n o rd e r to p re p a re th e d e s ire d is o c y a n a te s ,

i t m ust be n e c e ssa ry to i s o l a t e th e a z id e and cause i t s rearran g em en t i n th e p re se n c e o f an i n e r t so lv e n t o r w ith o u t s o lv e n t.

S c h ro e te r^ r e ­

p o rte d th e p r e p a r a tio n o f m ethyl is o c y a n a te by t r e a t i n g sodium a z id e w ith a c e ty l c h lo r id e i n th e absence o f any s o lv e n t.

The r e s u l t i n g mix­

tu r e o f sodium c h lo rid e and a c e ty l azid e was h e a te d , c a u sin g th e o r d e r ly rearran g em en t o f th e a z id e and th e d i s t i l l a t i o n o f th e m ethyl is o c y a n a te fo ra e d by th e r e a c t i o n .

S im ila r r e a c tio n s were re p o rte d f o r m ono-chloro

and t r i c h l o r o a c e t i c a c id s .

T his method o f p r e p a r a tio n was a tte m p te d f o r

th e p r e p a r a tio n o f trif lu o r o m e th y lis o c y a n a te .

An a ttem p ted r e a c tio n

2h

u s in g t r i f l u o r o a e e t y l c h lo r id e on an e th e r e a l su sp en sio n o f sodium a z id e was a tte m p te d much a s i n th e p re v io u s r e a c tio n b u t met w ith f a i l u r e .

The

t r i f l u o r o a e e t y l c h lo rid e d i s t i l l e d from th e m ix tu re and was condensed i n a d ry i c e t r a p .

P re p a ra tio n o f t r i f l u o r o a e e t y l brom ide and t i i f l u o r o -

a c e ty l io d id e was c a r r i e d out b ecause th e s e re a g e n ts sh o u ld be more r e ­ a c tiv e i n t h i s r e a c t i o n . T r if lu o r o a e e ty l a z id e .

Sodium a z id e (35> g ., 0.5U mole) was p la c e d

i n a SOO-ml. th r e e necked round bottom f l a s k f i t t e d w ith a m ercury s e a le d H ershberg s t i r r e r , a gas i n l e t tu b e and a d ry i c e c o ld f in g e r r e f l u x con­ d e n s e r.

The t r i f l u o r o a e e t y l brom ide p re p a re d from f i v e - t e n t h s mole o f

t r i f l u o r o a c e t i c a c id was p a sse d i n t o th e f l a s k through th e gas i n l e t tu b e . The gaseous a c id brom ide, b .p . li.-80C ., was condensed by th e r e t u r n con­ d e n se r and dropped on th e s o l i d sodium a z id e .

No s o lv e n t was u se d and

s t i r r i n g was m ain tain ed th ro u g h o u t th e r e a c tio n .

As th e r e a c tio n p ro ­

g re s se d , th e f l a s k became warm and a q u a n tity o f l i q u i d , b o i li n g above room te m p e ra tu re , c o lle c te d i n th e f l a s k .

"When a l l o f th e a c id brom ide

had been p a sse d i n t o th e f l a s k , th e m ix tu re i n th e f l a s k gave th e ap p ear­ ance o f la r g e c u b ic c r y s t a l s o f s a l t (p ro b ab ly sodium brom ide) mixed i n a liq u id .

A b u b b le r a tta c h e d to th e o u t l e t from th e d ry i c e condenser

was u se d to check f o r decom position and re a rran g e m en t.

S in ce n itro g e n

i s form ed by th e rea rran g e m en t, th e decom position can be e a s i l y fo llo w ed by n o tin g th e e v o lu tio n o f n itr o g e n .

No rearran g em en t seemed to be

o ccu rin g as no gaseous m a te r ia l was b e in g e v o lv e d . h e a te d to r e f l u x a t a p o t te m p e ra tu re o f U5°C.

The l i q u i d was th e n

No rea rran g e m en t ap peared

to o ccu r a t th e r e f l u x te m p e ra tu re , i n d ic a t i n g t h a t t r i f l u o r o a e e t y l a z id e m ight be s ta b le enough f o r i s o l a t i o n .

I n view o f t h i s , i t was d e cid ed

to d i s t i l l th e a z id e from th e r e a c tio n f l a s k .

The f l a s k and i t s c o n te n ts

25

were c o o le d below r e f l u x tem p era tu re as rep lacem en t o f th e r e t u r n con­ d e n se r was n e c e ssa ry along w ith rea lig n m e n t o f th e f l a s k .

The s t i r r i n g

was sto p p ed and th e clamps h o ld in g th e f l a s k were lo o se n e d to p e rm it changing o f th e p o s i t io n o f th e f l a s k when th e c o n te n ts exploded w ith g r e a t v io le n c e •

C o nsidering th e n a tu r e and f o rc e o f th e e x p lo s io n , f u r ­

t h e r e x p e rim e n ta tio n in v o lv in g th e fo rm atio n o f t r i f l u o r o a e e t y l a z id e was d is c o n tin u e d • O ctafL uoroadipyl c h lo r id e .

O c ta flu o ro a d ip ic a c id (29 g . , 0 .1 mole)

was ground t o a f in e powder i n a m o rta r and p la c e d i n a 200-m l. th r e e necked round bottom fla s k *

Excess th io n y l c h lo rid e was added and th e

f l a s k was warmed w ith a h e a tin g m an tle. c h lo r id e in d ic a te d a r e a c t i o n .

The e v o lu tio n o f hydrogen

The te m p e ra tu re was in c r e a s e d slow ly

o v er a th r e e day p e rio d from l;0-80OC.

The e v o lu tio n o f hydrogen c h lo r id e

had ceased by t h a t tim e and th e excess th io n y l c h lo rid e was removed i n vacu o .

O c ta flu o ro a d ip y l c h lo rid e , a s o l i d a p p ea rin g l i k e f i n e sand,

rem ained i n th e f l a s k . A nal:

C a lc 'd . f o r C^Cl^FgOg:

C, 21.88$

Found:

C, 21.95%

H e x a flu o ro g lu ta ry l c h lo r id e .

H e x a flu o ro g lu ta ric a c id (1|2 g .,

0 .1 7 mole) was t r e a t e d w ith ex cess th io n y l c h lo rid e (166 g . , 1.1; m oles) i n a 500-m l. th r e e necked round bottom f l a s k f i t t e d w ith an a i r d riv e n s t i r r e r and a r e t u r n condenser.

The m ix tu re was m ain ta in e d a t a tem­

p e r a tu r e o f U0°C. f o r one day and th en slow ly in c re a s e d to 70°C. over a p e rio d o f two d ay s, a t which tim e th e e v o lu tio n o f hydrogen c h lo r id e had c e a se d .

The e x cess th io n y l c h lo rid e was removed i n vacuo.

am b er-co lo red v isc o u s l i q u i d rem ained.

A dark

T his l i q u i d was h e x a flu o ro ­

g l u ta r y l c h lo rid e as was shown by i t s chem ical b e h a v io r.

26

T r if lu o r o a e e ty l brom ide» T r if lu o r o a c e tic a c id (75

, 0*6l mole)

and phosphorous trib ro m id e (100 g . , 0 .3 7 mole) were mixed i n a 500-m l. round bottom f l a s k f i t t e d w ith a r e tu r n condenser a rra n g e d so t h a t v a p o rs p a ssin g thro u g h th e condenser were caught i n a d ry i c e t r a p .

The

m ix tu re was re f lu x e d u n t i l th e t r i f l u o r o a c e t i c a c id d isa p p e a re d and o n ly p h o sp h o ric a c id rem ained i n th e f l a s k , (fo u r to f i v e h o u rs) .

The p ro ­

d u c t, b .p . 6 -8 C ., was p u r i f i e d by d i s t i l l a t i o n from one t e s t tu b e to a n o th e r i n a d ry i c e b a th . TOien a m ix tu re o f t r i f l u o r o a c e t i c a c id and phosphorous trib ro m id e w a s h e a te d i n a r e g u la r d i s t i l l a t i o n a p p a ra tu s , th e y c o - d i s t i l l e d w ith ­ out re a c tin g . T r if lu o r o a e e ty l i o d id e .

Bed phosphorous (17 g ., 0 .5 mole) was

added to t r i f l u o r o a c e t i c a c id (57 g.> 0 .5 mole) and th e m ix tu re was co o led i n ice *

Io d in e (190 g . , 1 .5 gram-atoms) was added to th e c o ld

m ix tu re , and th e r e s u l t i n g m ix tu re was allow ed to warm to room tem pera­ tu r e o v e rn ig h t.

The m ixture was th e n h e a te d under r e f l u x f o r a p p ro x i­

m ately s i x h o u rs, and th e n d i s t i l l e d .

The d i s t i l l a t e was r e c t i f i e d ,

y ie ld in g t r i f l u o r o a e e t y l io d id e , b .p . 5 9 -6 l°C . Trifluoroaeetyl iodide was also prepared by passing trifluoroaeetyl chloride into an acetone solution of sodium iodide. The trifluoroaeetyl halides were identified by their reaction with ammonium hydroxide to form trifluoroacetamide and the corresponding hydrogen halide acid.

SUMMARY T r if lu o r o a c e th y d r a z ide was p re p a re d by th e r e a c tio n betw een h y d ra­ z in e h y d ra te and e i t h e r e th y l t r i f l u o r o a c e t a t e o r t r i f l u o r o a c e t i c a c id . T riflu o ro a c e th y d ra z id e form s s a l t s w ith m in eral a c id s .

I t re a c ts

w ith aro m a tic carb o n y l compounds to form s o l i d d e riv a tiv e s #

I t formed

a s o l i d d e r iv a tiv e when re flu x e d w ith e th y l a c e to a c e ta te , b u t form ed complex p ro d u c ts w ith a l l o th e r a li p h a t i c carbonyl compounds t r i e d . T riflu o ro a c e th y d ra z id e r e a c te d w ith p h e n y liso th io c y a n a te by con­ d e n s a tio n , a d d itio n and e lim in a tio n to form 1 , 5-d ip h e n y l-5- t h i o - l , 3, L, 6te tr a z a h e x a - 1 , 2- d i e n e . T riflu o ro a c e th y d ra z id e i s c o n v erted to b is ( t r i f l u o r o a c e t ) h y d raz id e by th e a c tio n o f n i tr o u s a c id , brom ine, io d in e , m ercuric o x id e , and a m ix tu re o f a c e t i c anhydride and sodium a c e ta te . T r if lu o ro a c e th y d ra z id e form s a monosodium s a l t w h ile b i s ( t r i ­ f lu o r o a c e t) h y d ra z id e forms a disodium s a l t .

These s a l t s undergo n u c le o -

p h ilic re a c tio n s . B is ( t r i f l u o r o a c e t ) h y d razid e i s an a c id . H e x a flu o ro g lu ta ry l a z id e , formed by th e a c tio n o f sodium a z id e on th e a c id c h lo r id e , decomposed when h e a te d w ith w a te r to form t e t r a f lu o r o s u c c in ic and d if lu o r o a c e tic a c id s . T r if lu o r o a e e ty l a z id e underw ent d isp lacem en t r e a c tio n s to form e s t e r s , b u t decomposed e x p lo s iv e ly when h e a te d . T z if lu o r o a c e ty l brom ide and io d id e were p re p a re d by th e a c tio n o f th e p ro p e r phosphorous t z i h a l i d e on t i i f l u o r o a c e t i c a c id . H e x a flu o ro g lu ta ry l c h lo rid e and o c ta flu o ro a d ip y l c h lo r id e were p r e ­ p a re d by th e a c tio n o f th io n y l c h lo rid e on th e a c id .

BIBLIOGRAPHY 1#

B en rath e t a l , J . P r a k t. Chem. 107* 211 (l92lj.) •

2.

C u rtin s and Firanzen, B er. 35, 32U0 (1902) •

3* C u rtin s and Hofman, J . P r a k t. Chem. 53, 52it (1897) • k*

Gilman, J . , and Jo n e s, R. G ., J . Am. Chem. Soc. 65, 2037 (19U5) •

5*

G iyszkiew icz-T rochinow ski, S p o rzy n sk i, and Wnuk, Rec. T rav. Chim. 6 6, 719 (19U 7).

6.

"O rganic R e a c tio n s" , V ol. I l l , John 1/fâ.ley and Sons, I n c . , New York, (19U 6).

7.

Rhodehamel, H. W., U npublished r e s u l t s , Purdue U n iv e rs ity ,

19U6.

8 . S c h r o e te r , G ., B er. U2, 3356 (1909)• 9» S h rin e r , R. L . and Fuson, R. C ., "The S y stem atic I d e n t i f i c a t i o n o f O rganic Compounds", T h ird E d itio n , John M le y and Sons, I n c . , New York, 19U71 0. S tru v e , J . P r a k t. Chem. 50, 295 (1Ô9U)•

PART H PREPARATION AND PROPERTIES OF CERTAIN FLUORINATED AMINES I n c o n n e c tio n w ith th e g e n e ra l stu d y o f th e o rg a n ic c h e m istry o f f l u o r in e a t Purdue U n iv e rs ity , r e a c tio n s le a d in g to th e p r e p a r a tio n o f p e r f l u o r i n a t e d amines and N ,N * -d iflu o ro p e rflu o rin a te d amines were s tu d ie d .

P r e p a r a tio n o f p e r f lu o r in a te d t e r t i a r y amines by th e Minne­

s o ta M ining and M anufacturing Company, th e fo rm atio n o f N ,N » -d iflu o ro ( tr if lu o r o m e th y l) amine by R uff and Co-workers

by d i r e c t f l u o r in a ti o n

o f s i l v e r cyanide and th e p r e p a r a tio n o f f l u o r in a te d p ip e r id in e s by Simons^" and B it t i e s ’*" and th e o n ly known examples o f th e s e ty p e s o f compounds.

The d e g ra d a tio n r e a c tio n s o f Hofman, C u rtin s and Schm idt,

when a p p lie d t o p e r f lu o r in a te d a c id s o r t h e i r d e r iv a tiv e s e i t h e r f a i l to r e a c t ^ , y i e l d u nexpected products*4" o r y i e l d only th e low er a c id i n th e homologous s e r i e s .

The amine p ro d u c ts u s u a lly i s o l a b l e i n th e s e

r e a c tio n s a re n o t found i n th e r e a c tio n s in v o lv in g th e p e r f lu o r in a te d a c id s . The s t a b i l i t y o f th e n i tr o g e n - f lu o r in e bond as ex p erien c ed i n n i t r o ­ gen t r i f l u o r i d e , N, N1-d iflu o ro triflu o r o m e th y la m in e , and N -flu o ro d ec aflu o ro p ip e rL d in e i n d ic a t e t h a t compounds o f th e g e n e ra l type RCF^NF^, where R i s any o rg a n ic r a d i c a l which would n o t cause th e i n s t a b i l i t y o f th e -CFg- u n i t , sh o u ld be s t a b l e .

The fo rm a tio n o f such compounds could

be e a s i l y accom plished i f f lu o r in e co u ld be added to th e n i t r i l e u n i t . With r e s p e c t to th e p r e p a r a tio n o f compounds o f t h i s ty p e , f l u o r in a ti o n o f n i t r i l e s was c a r r i e d o u t, and th e a d d itio n o f f l u o r in e to n i t r i l e bonds to p re p a re N, N1- d i ü u o r o - o£, o C -d ifiu o ro compounds was in v e s tig a te d #

30

Two g e n e ra l methods o f adding f lu o r in e to m u ltip le bonds a re a v a i l ­ a b le .

Both methods in v o lv e th e u se o f le a d t e t r a f l u o r i d e , b u t i n d i f f e r —

r e n t form s.

The r e a c tio n to p re p a re one o f th e s e le a d t e t r a f l u o r i d e

r e a g e n t s ^ i s c a r r ie d o u t by p a s s in g e le m e n ta l f lu o r in e o ver anhydrous le a d s a l t s , u s u a lly th e c h lo r id e , c o n ta in e d i n a n ic k e l can a p p ro x im ate ly s i x by e ig h t in ch e s i n c ro s s s e c tio n and s ix f e e t lo n g .

The in tr o d u c tio n

o f e le m e n tal f lu o r in e i n to th e system i s begun w ith th e r e a c t o r a t room te m p e ra tu re and th e s a l t s a re s a tu r a te d w ith f lu o r in e b e fo re th e tem­ p e r a tu r e i s in c re a s e d .

The c o n d itio n o f s a t u r a t io n i s determ ined by

o c c a s io n a lly i n s e r t i n g a wooden s p l i n t i n to th e ex h au st g a s e s .

"When

s u f f i c i e n t f lu o r in e i s p re s e n t i n th e ex h au st to i g n i t e th e s p l i n t , th e s a l t i s c o n sid e re d s a tu r a te d .

The flow o f ele m e n tal f lu o r in e i s con­

tin u e d w h ile th e tem p eratu re i s r a is e d to 330-U00°C. and th e n c o n tin u e d u n t i l th e ex h au st gas w i l l a g a in i g n i t e a wooden s p l i n t .

The r e a c t o r i s

p urged f o r a p e rio d o f o n e -h a lf hour im m ediately b e fo re u se w ith a stream o f n itr o g e n to remove excess elem en tal f l u o r in e . th e s a l t i s c o n v erted to th e t e t r a f l u o r i d e .

About f i f t y p e r c e n t o f

The o th e r method o f u sin g

le a d t e t r a f l u o r i d e in v o lv e s th e g e n e ra tio n o f th e re a g e n t " in s i t u " by th e r e a c tio n betw een le a d p ero x id e and hydrogen f l u o r id e .^ I n th e p o ly m e riz a tio n o f n i t r i l e s to t r i a z i n e s , l i q u i d and s o l i d p ro d u c ts , a p p a re n tly in te rm e d ia te s i n th e t r i a z i n e fo rm atio n , were p ro ­ d u c e d .^

When th e s e m a te ria ls were h e a te d , t h e i r c y c liz a tio n to t r i ­

a z in e s was com pleted.

When t r e a t e d w ith aqueous a l k a l i , th e s e sub­

s ta n c e s decomposed, re g e n e ra tin g th e o r ig in a l n i t r i l e s .

The p h y s ic a l

c o n s ta n ts o f th e s e m a te r ia ls in d ic a te d t h a t th e y m ight be amines o r 7

im ines r a t h e r th a n s a l t s o f th e type r e p o rte d by H a n ts z c h .

A n a ly sis

on th e m a te r ia ls formed when hydrogen c h lo rid e was u se d a s th e

31

c y c l iz a t i o n c a t a l y s t appeared to b e a r o u t t h i s assum ption a lth o u g h th e compounds formed were to o u n s ta b le f o r v e iy a c c u ra te r e s u l t s .

The

g r e a t e r s t a b i l i t y o f f lu o r in e compounds le d to th e b e l i e f t h a t th e p ro ­ d u c ts form ed when hydrogen f lu o r id e was u sed as th e c y c liz in g c a t a l y s t m ight form p e r f lu o r in a te d amines o f g r e a t enough s t a b i l i t y to p e rm it th e fo rm a tio n o f s ta b le d e r i v a ti v e s .

The l i q u i d p ro d u c t form ed by th e

a c tio n o f anhydrous hydrogen f lu o r id e on t r i f l u o r o a c e t o n i t r i l e ^ was examined and found to be a n i t r i l e s a l t o f th e ty p e p o s tu la te d by H ants zch'*. Two r e a c tio n s which u s u a lly le a d to th e p r e p a r a tio n o f amines were i n v e s ti g a t e d to see i f p e r f lu o r in a te d amines co u ld be p re p a re d . S tro n g red u c in g re a g e n ts r e a d i ly reduce most n i t r o compounds to am ines.

Weaker red u c in g a g e n ts may g iv e r i s e to a v a r i e t y o f i n t e r ­

m ediate p ro d u c ts a s w e ll as c e r t a i n secondary p ro d u c ts , depending on th e c o n d itio n s o f th e r e a c tio n . The f i r s t problem en co u n tered i n t h i s method o f p r e p a r a tio n o f f lu o r in a te d amines i s th e p r e p a r a tio n o f th e p e r f lu o r in a te d n i t r o com­ pounds.

There a re no p r e p a ra tio n s o f p e r f lu o r in a te d m ononitro compounds

known which would be f e a s i b l e .

1 ,2 - D in itr o compounds can be p re p a re d by

a d d itio n o f d in itr o g e n te t r o x id e , ^ 0^ , to p e r f lu o r in a te d o l e f i n s ^ » T his r e a c tio n i s q u ite g e n e ra l and th e y ie ld s and c o n v ersio n s a re high enough to make th e r e a c tio n a s u ita b le s y n th e tic t o o l .

Many methods o f

re d u c tio n o f n i t r o compounds to amines may be employed so t h a t a wide range o f c o n d itio n s can be u se d .

A ll methods o f re d u c tio n u se d on

1 , 1 , 2, 2- t e t r a f l u o r o - l , 2- d in itr o e th a n e le d to th e fo rm atio n o f o x a lic a c id , h y d ro flu o ric a c id , and ammonia.

32

The G a b rie l s y n th e s is i s a p rim ary amine p r e p a r a tio n i n which two o f th e p o s i t io n s on th e n itr o g e n a re te m p o ra rily b lo ck ed to p re v e n t th e i n ­ tr o d u c tio n o f more th a n one a lk y l group. P h th a lim id e i s a c y c lic im ide which does n o t r e a c t d i r e c t l y w ith a lk y l h a li d e s .

The im ide group, b e in g doubly a c tiv a te d by th e two c a r ­

bonyl g ro u p s, i s a c id ic enough to r e a c t w ith p o tassiu m hydroxide to form th e p o tassiu m s a l t .

T his p o tassiu m s a l t behaves l i k e a t y p ic a l n u c le o -

p h i l i c re a g e n t and g e n e ra lly r e a c t s sm oothly w ith a lk y l h a li d e s .

The

a lk y la te d p h th a lim id e may th en be h y drolyzed w ith a l k a l i , and th e amine removed by steam d i s t i l l a t i o n # P r e p a r a tio n o f f l u o r in a te d compounds to a tte m p t t h i s method o f p re ­ p a r a tio n i s n o t d i f f i c u l t .

While a flu o ro c a rb o n would n o t be ex p ected

to undergo such a r e a c t i o n , th e c h lo r id e , bromide o r io d id e o f a p e r ­ f l u o r in a te d compound may do so and th e s e compounds may be r e a d i ly p r e o p a re d by adding th e halogen to a p e r f lu o r in a te d o l e f i n . Such r e a c tio n s g e n e r a lly go i n good y i e l d s .

EXPERIMENTAL AND DISCUSSION F lu o ri n a tio n o f b e n z o n i t r i l c .

B e n z o n itrile (100 g . , 1 .0 mole) was

p a sse d th ro u g h a s e r i e s o f fo u r s i l v e r d if lu o r id e r e a c to r s ^ w ith each u n i t c o n ta in in g f iv e m oles o f s a l t s . was m a in ta in e d .

A r e a c tio n te m p e ra tu re o f 200-220oC

Two o n e - l i t e r n ic k e l t r a p s , one immersed i n an i c e b a th

and th e o th e r i n a d ry i c e b a th , were connected to th e o u t l e t w ith 3 /8 in c h o .d . copper tu b in g .

The n i t r i l e was p a sse d i n t o th e r e a c t o r s o v er

a p e rio d o f two h o u rs, a f t e r which th e system was purged f o r t h r e e hours w ith a slow stream o f n itr o g e n . ic e tra p .

The o rg an ic p ro d u c t was cau g h t i n th e

The c o n te n t o f th e t r a p was poured o v er i c e and th e r e s u l t i n g

m ix tu re was n e u tr a liz e d w ith sodium hydroxide s o lu tio n .

The m ix tu re was

steam d i s t i l l e d and th e o rg an ic l a y e r was se p a ra te d and re c y c le d th ro u g h th e s i l v e r d i f lu o r i d e r e a c t o r s .

R eactio n te m p e ra tu re ranged from 220-

280°C. and th e same s e r i e s o f t r a p s as was u se d i n th e f i r s t run was u se d a g a in .

The p ro d u c t was a g a in t r e a t e d w ith i c e , n e u tr a liz e d w ith

sodium hydroxide s o lu tio n and steam d i s t i l l e d . s e p a ra te d and d r ie d o v er sodium s u l f a t e .

The o rg a n ic p ro d u c t was

T his p ro d u c t was a w a te r c l e a r ,

c o lo r l e s s l i q u i d o f d e n s ity g r e a t e r th a n w a te r.

I t was r e c t i f i e d through

a sm all g la s s h e li c e packed column ( p l a t e v a lu e approx. 8) .

A 3 m l. f r a c

t i o n was o b ta in e d , b .p . 75°> i n d ic a tin g some f l u o r i n o l y s i s to p e r f lu o r o m eth y lcy clo h ex an e.

A 7 g« f r a c t i o n was o b ta in e d , b .p . 9 1 °.

A n a ly sis

in d ic a te d t h i s m a te r ia l to be N, N1- d if lu o r o ( t r i d e c a flu o ro c y c lo h e x y lm ethyl) am ine. A nal:

D ^ = 2.09U

C a lc 1d . f o r C^F^N :

N, 3*66#

Found:

N, 3*50#

3h

A sample o f h ig h e r b o ilin g m a te ria l was found to c o n ta in a h ig h e r p e rc e n ta g e o f n itr o g e n , i n d ic a t i n g i t to be in c o m p le te ly f l u o r i n a t e d . The i n e r t n e s s o f t h i s m a te r ia l t o chem ical a c tio n in d ic a t e s d e f i ­ n i t e l y t h a t th e n i t r i l e u n i t was f l u o r in a te d .

When f l u o r in a te d n i t r i l e s ,

such a s o c ta f lu o r o a d ip o n i t r il e , a re t r e a t e d w ith aqueous sodium h y d ro x id e , th e h y d ro ly s is r e a c tio n i s spontaneous and v e iy v ig o ro u s .

A sample o f

N, N1-d iflu o ro trid e e a flu o ro c y c lo h e x y lm e th y la m in e was b o ile d w ith 20% aqueous sodium hydroxide f o r a p e rio d o f f i f t y h o u rs .

At th e end o f

t h i s tim e , th e o rg a n ic m a te r ia l was steam d i s t i l l e d from th e m ix tu re un­ changed*

T reatm ent w ith c o n c e n tra te d s u l f u r i c and h y d ro c h lo ric a c id s

a t room te m p e ra tu re f a i l e d to have any e f f e c t on t h i s m a te r ia l.

It

proved to be in s o lu b le i n a l l s o lv e n ts t e s t e d w ith th e e x c e p tio n o f p e rf lu o r o - n - h e p ta n e .

I t burned when h e ld i n a flam e, b u t would n o t

c o n tin u e to b u m when removed from th e flam e. F lu o r in a tio n o f n - V a l e r o n i t r i l e .

n - V a le r o n i tr i l e (138 g . , 1*61*

m oles) was p a sse d through a s e r i e s o f 1* s i l v e r d if lu o r id e r e a c t o r s , each c o n ta in in g

m oles o f s i l v e r s a l t s .

Two o n e - l i t e r n ic k e l t r a p s ,

one immersed i n an i c e b a th and th e o th e r i n a d ry i c e b a th were a tta c h e d to th e r e a c t o r o u t l e t by means o f 3 /8 in c h o .d . copper tu b in g . t i a l te m p e ra tu re o f th e r e a c to r s was l50°C .

The i n i ­

The te m p e ra tu re was r a i s e d

by th e h e a t o f th e r e a c tio n to 200°C. as th e r e a c tio n p ro ce ed e d .

The

n i t r i l e was p a sse d thro u g h th e r e a c to r s over a p e rio d o f f o r t y - f i v e min­ u te s a f t e r which th e r e a c to r s were f lu s h e d w ith a slow stream o f n i t r o ­ gen f o r a p e rio d o f th r e e h o u rs to remove a l l t r a c e s o f p ro d u c t.

The

r a t e o f flo w o f th e n itro g e n was k e p t slow enough so t h a t no p ro d u c t would be c a r r i e d th ro u g h th e r e c e i v e r s .

The p ro d u c t was t r e a t e d w ith

i c e , n e u tr a li z e d w ith aqueous sodium hydroxide s o lu tio n , and th e o rg a n ic

3f>

la y e r was s e p a r a te d .

T his la y e r was th o ro u g h ly washed to remove th e

l a s t t r a c e s o f hydrogen

f l u o r id e ,

d r ie d o v er anhydrous sodium s u l f a t e

and r e c t i f i e d th ro u g h a

fo u r—fo o t

c o n c e n tric tu b e column ( p l a t e v a lu e

10) •

g . was o b ta in e d a t 69°C. , w ith m ost o f th e

A f r a c t i o n o f 6 -7

m a te r ia l b ein g s t a r t i n g

m a te r ia l,

b .p . 135-138°C. Thef r a c t i o n b o ilin g

a t 69°C. was su b m itte d f o r a n a ly s is and found to be N,N * -d iflu o ro u n d e ca flu o ro -n -a m y l am ine. A nal:

C alc*d. f o r C^F^N:

N, U-36%

Found:

N, k»h5%

The in d ex o f r e f r a c t i o n o f t h i s m a te ria l was too low to be d e te r ­ mined w ith an Abbe r e f r a c to m e te r .

DgQ = 1 .3 8 1 .

The chem ical b e h a v io r and s o l u b i l i t y c h a r a c t e r i s t i c s o f t h i s com­ pound were found to be s im ila r to th o se which were found f o r N, N1d i f lu o r o ( t r i d e ca flu o ro c y clo h exylm ethyl ) am ine. I t was hoped t h a t th e u se o f low te m p e ra tu re i n th e f l u o r in a ti o n r e a c tio n , coupled w ith th e s h o r t exposure tim e b ro u g h t about by th e r a p id a d d itio n o f th e n i t r i l e i n t o th e r e a c t o r , would g iv e r i s e t o a p ro d u c t w ith o n ly th e n i t r i l e bonds f l u o r in a te d .

R e c t if i c a t io n o f th e

r e a c tio n p ro d u c ts seemed to i n d i c a t e d e f i n i t e l y t h a t none o f t h i s p ro ­ d u c t was form ed.

The o n ly f r a c t io n s found were th e p e r f lu o r in a te d p ro ­

d u c t, b .p . 69°C ., and s t a r t i n g m a te r ia l, b .p . 135>-138°C.

T his would

seem to i n d i c a t e t h a t th e hydrogen atoms a re re p la c e d more e a s i l y th a n th e n i t r i l e group i s f lu o r in a te d . S e v e ra l f l u o r in a ti o n s o f n - v a le ro z ri.trile were c a r r i e d o u t a t v a rio u s r a t e s o f a d d itio n o f n i t r i l e i n t o th e r e a c t o r s and a t d i f f e r e n t te m p e ra tu re s, b u t i n a l l c a s e s , th e co n v ersio n s were low , u s u a lly ran g ­ in g betw een one and te n p e r c e n t.

36

I t was th o u g h t t h a t f l u o r in a ti o n o f amines would y i e l d th e same p ro ­ d u c ts and t h a t t h i s would be a d e s ir e d method o f p r e p a r a tio n o f th e s e compounds i n view o f th e a v a i l a b i l i t y o f amines and th e u n a v a i l a b i l i t y of n itrile s .

I n th e r e a c tio n w ith amines i t was assumed t h a t th e most

a c tiv e hydrogens, th o se a tta c h e d to th e n itr o g e n , would be re p la c e d firs t.

The N,N* —d iflu o ro am in e form ed i n t h i s way would p ro b a b ly lo s e

hydrogen f l u o r id e , form ing th e n i t r i l e , which would th e n be f l u o r in a te d i n th e u s u a l m anner. A ttem pted f l u o r in a ti o n o f n -b u ty la m in e .

n-B utylam ine (73 g . , 1*0

mole) was p a sse d i n t o a s i l v e r d if lu o r id e r e a c t o r c o n ta in in g U0 moles of s ilv e r s a lts .

The r e a c t o r was m ain tain ed a t a te m p era tu re o f 220°C .,

and th e u s u a l two n ic k e l tr a p s i n i c e and d ry i c e b a th s were connected to th e o u t l e t by means o f l / 2 in c h o .d . copper tu b in g .

The amine was

p a sse d i n t o th e r e a c t o r over a p e rio d o f two hours a f t e r which th e r e a c t o r was flu s h e d w ith a slow stream o f n itr o g e n f o r th r e e h o u rs.

No

p ro d u c t o f any k in d was found i n th e t r a p s a t th e end o f t h i s tim e .

The

t r a p s were a g ain connected and th e n itro g e n purge was c o n tin u e d f o r tw e n ty -fo u r h o u rs, b u t w ith o u t e f f e c t . o b ta in e d from t h i s a tte m p t.

No p ro d u ct o f any s o r t was e v e r

I t may be t h a t th e amine forms a s a l t - l i k e

a d d itio n p ro d u c t w ith th e s i l v e r d i f lu o r i d e , com parable to many s t a b le b iv a le n t s i l v e r complexes and w hich, i n t h i s c a s e , m ight be s t a b le and r e l a t i v e l y n o n v o la tile .

T his would remove th e amine from th e p o s s i b i l ­

i t y o f r e a c tin g and so no p ro d u ct would be fo rth co m in g .

The amine would

rem ain i n th e r e a c t o r i n th e form o f a s a l t - l i k e s o l i d . F lu o r in a tio n o f a c e t o n i t r i l e .

A c e t o n i tr i l e (123 g . , 3 m oles) was

p a sse d i n t o a s i l v e r d i f lu o r id e r e a c to r c o n ta in in g 20 m oles o f s i l v e r s a l t s a t a te m p era tu re o f 220°C.

The a c e to n i t r i l e was p a sse d th ro u g h

37

th e r e a c t o r over a p e rio d o f two h o u rs .

A t r a i n c o n s is tin g o f an ammon­

ium h y d ro x id e sc ru b b e r, d ry in g column 3 f e e t i n le n g th , d iy i c e and l i q u i d a i r t r a p s was a tta c h e d to th e o u t l e t .

A fte r a l l o f th e n i t r i l e

had been p a sse d i n t o th e r e a c t o r , th e system was purged w ith a stream o f n itr o g e n f o r t h r e e h o u rs.

A c o lo r le s s l i q u i d i n th e d ry i c e t r a p and a

w h ite s o l i d i n th e l i q u i d a i r tr a p c o n s titu te d th e p r o d u c ts .

They were

re c y c le d th rough aqueous sodium hydroxide and th e d ry in g tow er and r e ­ condensed.

The m a te r ia l i n th e l i q u i d a i r t r a p b o ile d a t -80°C .

An

e s tim a tio n o f i t s m o lecu lar w eight by Dumas1 method gave v a lu e s o f 28— 30 .

These v a lu e s in d ic a te t h a t t h i s m a te r ia l m ight have been m ethyl

f l u o r i d e , b .p . -78.5°C *, m o lecu lar w eight 3U»

The p ro d u c t i n th e d ry -

i c e t r a p was r e c t i f i e d through a vacuum ja c k e te d f o u r - f o o t Stedman column.

A f te r a p re -ru n o f 10 m l., b .p . -60 to -3 1 °C ., was removed, a

f r a c t i o n o f 20 m l., b .p . -30°G. was o b ta in e d .

The rem ainder o f th e

m a te r ia l, ap p ro x im ately an equal q u a n tity , d i s t i l l e d o v er a range from -29 to 15°C. w ith o u t showing any f r a c t i o n s .

M olecular w eight d e te r ­

m in a tio n s by Dumas1 method on th e -30°C . f r a c t i o n gave v a lu e s o f 100 and 105.

Assuming th e C-C-N c h ain to be i n t a c t , t h i s would i n d ic a t e

t h a t th r e e o r fo u r f lu o r in e atoms had been in tro d u c e d i n t o th e m o lecu le. The o n ly l o g i c a l p ro d u c t c o n ta in in g th r e e f lu o r in e atoms would be t r i ­ flu o r o a c e to n i t r i l e , b .p . - 6U°C. , e lim in a tin g th e p o s s i b i l i t y o f th e in tr o d u c tio n o f th r e e f lu o r in e atom s.

No r e a c tio n o c c u rre d when t h i s

m a te r ia l was p a sse d i n t o b o ilin g 50% sodium hydroxide o r c o n c e n tra te d s u l f u r i c a c id a t room te m p e ra tu re .

T his in d ic a t e s t h a t th e m olecule

no lo n g e r c o n ta in e d a n i t r i l e group, and le a d s to th e b e l i e f t h a t th e n i t r i l e u n i t was f l u o r in a te d , form ing N, N1-d iflu o ro -o f,o C - d i f l u o r o e t h y l am ine.

S in ce a n a ly s is o f gaseous m a te r ia ls was n o t a v a i la b l e , no f u r t h e r

38

•work was done on t h i s m a te ria l* F lu o r in a tio n o f t r i f l u o r o a e e t o n i t r i l e * T r i f l u o r o a c e t o n i t r i l e (37 g . , 0 .3 9 mole) was p a sse d i n t o a le a d f l u o r id e r e a c to r which was a t a te m p e ra tu re o f 230°C.

Dry i c e and l i q u i d a i r t r a p s were connected

i n s e r i e s to th e r e a c t o r e x i t .

The n i t r i l e was p a sse d i n t o th e system

i n two h o u rs a f t e r which a stream o f n itro g e n was p a sse d th ro u g h th e system to c a r r y th ro u g h th e l a s t t r a c e s o f p ro d u c t.

The p ro d u c ts , a l l

gaseous a t room te m p e ra tu re , were b u b b led through a sodium hydroxide s o lu tio n to remove t r a c e s o f hydrogen f l u o r id e , th e n p a sse d th ro u g h a 3- f o o t d ry in g tu b e packed w ith sodium hydroxide p e l l e t s and s o l i d c a l ­ cium c h lo r id e and a g a in condensed i n d r y - ic e and l i q u i d a i r t r a p s .

Two

f r a c t i o n s r e s u l t e d , a y e llo w l i q u i d i n th e d ry i c e t r a p and a w h ite s o l i d i n th e l i q u i d a i r t r a p .

A ttem pts to r e c t i f y th e s e p ro d u c ts were unsuc­

c e s s f u l b ecause th e q u a n ti t ie s were to o sm a ll.

The s o l i d i n th e l i q u i d

a i r t r a p m elted a t -129°C . and b o ile d a t - 80°C.

The y e llo w l i q u i d i n

th e d ry i c e t r a p b o ile d a t -39°C . A ttem pted f l u o r i n a t i o n o f a c e to n i t r i l e .

Lead p e ro x id e (bSh g . >

1 .9 m oles) and a c e t o n i t r i l e (60 g . , 1 . 1*6 m oles) were p la c e d i n a onel i t e r n ic k e l l in e d a u to c la v e and th e a u to c la v e head, f i t t e d w ith an i n ­ l e t v a lv e , was se cu re d i n p l a c e .

The a u to c la v e was th e n coo led i n a

d ry i c e b a th , and anhydrous hydrogen f lu o r id e ( 1*10 g . , 20.5 m oles) was b le d i n t o th e a u to c la v e thro u g h th e v a lv e .

The a u to c la v e was p la c e d i n

a ro c k e r and allow ed to warm to room te m p era tu re w h ile b ein g ro ck e d . The ro c k in g was co n tin u ed f o r two d a y s.

A s e r i e s o f t r a p s c o n s is tin g

o f wash s o lu tio n s o f w ater and aqueous a l k a l i and d ry i c e t r a p s was co n n ected t o th e o u t l e t , and th e v a lv e was opened.

Only a sm all amount

o f gas escap ed , p ro b a b ly due to a i r i n i t i a l l y p r e s e n t i n th e a u to c la v e .

39

The c o n te n t o f th e a u to c la v e was h y d rolyzed w ith i c e and th e m ix tu re was examined f o r p r o d u c ts .

Only ac e t amide and a c e ti c a c id were found.

A ttem pted f l u o r i n a t i o n o f t r i f l u o r o a e e t o n i t r i l e .

Lead p e ro x id e

g . > 1*9 m oles) was p la c e d i n a o n e - l i t e r n ic k e l l in e d a u to c la v e and th e a u to c la v e h ead, f i t t e d w ith an i n l e t v a lv e , was se c u re d i n p lace* The a u to c la v e was c o o le d i n a d ry i c e b a th , and anhydrous hydrogen f lu o ­ r i d e (f>75> g . , 29 m oles) and t r i f l u o r o a e e t o n i t r i l e (UO g . , 0 . 2:2 mole) were b le d i n th ro u g h th e i n l e t v a lv e i n t o th e a u to c la v e .

The a u to c la v e was

p la c e d i n a ro c k e r and allow ed to warm to room te m p era tu re w h ile b e in g ro c k e d .

Aqueous sodium hydroxide and w a ter wash b o t t l e s , fo llo w ed by a

d ry i c e t r a p , were th e n connected to th e a u to c la v e o u t l e t .

Only a sm all

amount o f gaseous m a te r ia l escaped when th e v a lv e was opened.

The con­

t e n t o f th e a u to c la v e was hyd ro ly zed w ith i c e and examined f o r p ro d u c t. Only t r i f l u o r o a c e t i c a c id was found. F a ilu r e to f in d f l u o r in a te d p ro d u c ts from th e s e r e a c tio n s would n o t a t f i r s t seem to i n d ic a t e f a i l u r e o f th e r e a c t i o n , because such p o s tu ­ l a t e d p ro d u c ts a s CH^CFgMFg s is .

CF^CFgRFg

n° t be s t a b le to h y d ro ly ­

I f h y d ro ly s is o f th e s e m a te r ia ls d id o c c u r, th e a c id o r th e amide

would be th e expected p ro d u c ts .

P re v io u s experim ents have shown, how ever,

t h a t th e -CFg-NFg s t r u c tu r e i s s t a b le to h y d r o ly s is .

T h is f a c t in d ic a t e s

t h a t no a d d itio n o f f l u o r in e to th e n i t r i l e u n i t o c c u rre d . t h a t n i t r i l e s form s a l t s w ith hydrogen h a lid e a c id s ^ .

I t i s known

I t may be t h a t

th e n i t r i l e s i n th e s e c a se s form s a l t s w ith anhydrous hydrogen f l u o r id e , and t h a t th e s a l t m o d ific a tio n s a re n o t a tta c k e d by th e le a d t e t r a f l u o ­ r i d e which i s g e n e ra te d on ly when th e a u to c la v e and i t s c o n te n ts warm u p . T r i f l u o r o a e e t o n i t r i l e was p re p a re d i n th e c o n v e n tio n a l manner by ammonolysis o f e th y l t r i f l u o r o a c e t a t e , fo llo w ed by d e h y d ra tio n o f th e

ko

amide form ed^.

The t r i f l u o r o a e e t o n i t r i l e th u s form ed was condensed i n a

s t e e l c y lin d e r co o led i n d iy i c e .

An e x cess o f anhydrous hydrogen f l u o r ­

id e was b le d i n t o a n ic k e l a u to c la v e f i t t e d w ith a n e ed le v a lv e .

The

t r i f l u o r o a e e t o n i t r i l e was th e n b le d i n to th e a u to c la v e th ro u g h th e n e ed le v a lv e w ith th e d r iv in g fo rc e b e in g o n ly th e p re s s u re d if f e r e n c e . method was found to be e n t i r e l y s a t i s f a c t o r y .

This

The fo llo w in g ex p erim en ts

a re t y p i c a l : T riflu o ro a c e ta m id e .

E th y l t r i f l u o r o a c e t a t e ( l 60 g . , 1 .1 3 m oles)

was d is s o lv e d i n p u r i f i e d d ie th y l e th e r (100 m l.) and th e s o lu tio n was co o led i n i c e to a te m p e ra tu re o f 0-5°C .

Anhydrous ammonia was p a sse d

i n t o th e c o ld s o lu tio n f o r s ix te e n h o u rs.

The e th a n o l- e th e r s o lv e n t

was removed by d i s t i l l a t i o n w ith th e f i n a l t r a c e s b e in g removed u n d er vacuum w ith o u t h e a tin g when c r y s t a l l i z a t i o n o f th e amide began. flu o ro a c e ta m id e (121 g . , 1 .0 7 m oles) was o b ta in e d .

T r i­

This was a y i e l d

and co n v ersio n o f T riflu o ro a e e to n itrile .

T riflu o ro a c e ta m id e (121 g . , 1 .0 ? m oles) was

mixed w ith phosphorous p e n to x id e (200 g . , 1 *U m oles) and th e m ix tu re was h e a te d w ith a m antle u n t i l no more gaseous p ro d u ct was e v o lv ed .

The g as­

eous p ro d u c ts were p a sse d thro u g h a t r a p i n an i c e b a th and th e n i n to a c y lin d e r c o o le d i n a d ry i c e b a th .

S e v e n ty -fiv e grams o f t r i f l u o r o -

ac e to n i t r i l e > r e p re s e n tin g a y i e l d and c o n v ersio n o f 7U%> was o b ta in e d . R e ac tio n o f t r i f l u o r o a e e t o n i t r i l e w ith hydrogen f l u o r i d e .

Anhydrous

hydrogen f lu o r id e (225 g . , 11 m oles) and t r i f l u o r o a e e t o n i t r i l e (120 g . , 1 .2 6 m oles) were b le d i n t o a 1 .5 l i t e r n ic k e l lin e d a u to c la v e and shaken a t room te m p e ra tu re f o r f o r t y h o u rs .

The a u to c la v e was b le d th ro u g h a

s e r i e s o f s u i t a b l e t r a p s to remove th e ex ce ss hydrogen f l u o r i d e .

No.

la o th e r gaseous p ro d u c ts were evolved*

The l i q u i d c o n te n t, 230 g* o f

l i q u i d , was p la c e d i n a c e r e s in wax b o t t l e f o r s to r a g e . The l i q u i d p ro d u c t o b ta in e d was a f l u i d , amber c o lo re d l i q u i d which fumed c o p io u s ly on c o n ta c t w ith a i r and had an o dor s i m il a r to t h a t o f a c id h a li d e s .

The amount o f t h i s l i q u i d o b ta in e d was alw ays i n e x cess

o f t h a t p r e d ic te d by th e sim ple re a c tio n s CFjCN + 3HF

CF3CF2NH2 *HF

T his i n d ic a t e d th e p re se n c e o f an e x ce ss o f hydrogen f l u o r id e o v e r th e t h e o r e t i c a l amount.

T his e x ce ss hydrogen f l u o r id e was th o u g h t to be

p r e s e n t a s a s o lu tio n i n th e norm al p ro d u c t.

I n i t i a l s t u d i e s o f th e

l i q u i d were done i n th e p re s e n c e o f t h i s ex ce ss hydrogen f l u o r i d e , and a tte m p ts were l a t e r made to remove i t .

A number o f r e a c tio n s were

attem p ted to p re p a re d e r iv a tiv e s o f t h i s l i q u i d and to i d e n t i f y i t chem­ ic a lly .

These r e a c tio n s w i l l be re p o rte d and d is c u s s e d i n th e fo llo w in g

p ag es. A t e s t tu b e c o n ta in in g $ m l. o f th e l i q u i d p ro d u c t was immersed i n a d r y - ic e - tr ic h lo r o e th y le n e b a th .

The m a te r ia l d id n o t s o l i d i f y .

Twenty m i l l i l i t e r s o f th e l i q u i d p ro d u c t was mixed w ith an e q u al volume o f c o ld w a te r, and th e m ix tu re was allow ed to sta n d a t room tem­ p e r a tu r e .

I n l e s s th a n h a l f an hour w hite c r y s t a l s ap p eared .

Ammonia,

h y d r o f lu o ric a c id and t r i f l u o r o a c e t i c a c id were i s o l a t e d from th e s e c ry s ­ ta ls .

T his in d ic a t e s th e ease o f h y d ro ly s is o f th e l i q u i d to ammonium

s a l t s o f t r i f l u o r o a c e t i c and h y d ro flu o ric a c id s as w e ll as th e f r e e a c id s . A 20 m l. sam ple o f th e l i q u i d was p la c e d u n d er a s p i r a t o r vacuum f o r o n e -h a lf h o u r i n an a tte m p t to draw o f f th e d is s o lv e d hydrogen flu o rid e .

The l i q u i d r e s id u e was th e n tak e n up i n d ie th y l e th e r and

U2

d is tille d *

There was c o n s id e ra b le e tc h in g o f th e a p p a ra tu s and th e o n ly

p ro d u c t found was 10 m l. o f 2, I*, 6- t r i s ( t r i f l u o r om ethyl ) - 1 ,3 >5- tr L a z in e , b*p. 98-100°C.

T his in d ic a te s t h a t r e a c tio n s o r s e p a r a tio n s in v o lv in g

h e a tin g w i l l p ro b a b ly form th e t r i a z i n e . C o n cen trated h y d ro c h lo ric a c id s o lu tio n (100 m l.) was c o o le d i n ic e and 25 m l. o f th e l i q u i d p ro d u c t was added to i t . s o lu tio n r e s u l t e d .

A deep p u rp le -r e d

T his s o lu tio n was t r e a t e d w ith d ie th y l e th e r (100 m l . ) ,

form ing a w h ite p r e c i p i t a t e which was im m ediately f i l t e r e d , washed w ith e th e r and d r ie d .

The f i l t r a t e r e ta in e d th e p u rp le c o lo r , b u t a f t e r

s ta n d in g a few h o u rs, t h i s c o lo r reduced to a few sm all s p o ts o f s t i c k y m a te r ia l which was n o t w orkable.

The w h ite p r e c i p i t a t e gave a p o s itiv e

c h lo r id e io n t e s t , b u t a poor f lu o r id e io n t e s t .

A sodium fu s io n on th e

m a te r ia l, fo llo w ed by subsequent t e s t s , in d ic a te d th e p re se n c e o f n i t r o ­ gen, f lu o r in e and c h lo r in e .

Halogen a n a ly s is showed 28.8$ C l, 3h*h% F,

which does n o t co rresp o n d to any known p o s s ib le compound.

T his m ate­

r i a l r e a d i l y evolved amnonia when t r e a t e d w ith base and a c te d as an i n ­ o rg a n ic compound contam inated w ith some o rg an ic m a te r ia l. p u r i f i c a t i o n was found. te m p e ra tu re s .

No rea d y

S u b lim atio n was v e ry slow and o n ly a t high

No r e c i y s t a l ü z a tio n so lv e n t could be found.

A ttem pts

were made to d ia z o tiz e any amine which m ight be p r e s e n t and cou p le i t w ith / ^ - n a p h th o l.

I n i t i a l experim ents seemed to i n d ic a t e p o s itiv e

r e s u l t s , b u t a f u r t h e r exam ination showed t h a t t h i s was n o t th e c a s e . F ive m i l l i l i t e r s o f th e l i q u i d p ro d u c t was mixed w ith te n m l. o f a c e ty l c h lo rid e i n a t e s t tu b e .

C o n sid erab le e tc h in g o f th e t e s t tube

o c c u rre d and c o n s id e ra b le h e a t was e v o lv ed .

HShen w a ter was added, no

acetam ide s e p a ra te d and ammonia, hydrogen f l u o r id e and t r i f l u o r o a c e t i c a c id were a g a in form ed i n a d d itio n to a q u a n tity o f s i l i c a .

k3

A sa n p le o f th e l i q u i d p ro d u c t, -when p la c e d i n a t e s t tu b e , r e a c te d v i o l e n t l y w ith th e g la s s and much h e a t was ev o lv ed .

The m a te r ia l was

co m p letely decomposed, le a v in g o n ly s i l i c a i n th e b a d ly e tc h e d tu b e . R eactio n s were a tte m p te d w ith a c e tic a n h y d rid e and benzoyl c h lo r id e , b u t n e it h e r form ed th e amide. T hree m i l l i l i t e r s o f th e l i q u i d p ro d u c t was h e a te d w ith 5 m l. o f m ethyl io d id e .

No r e a c tio n o c c u rre d .

f i f t e e n m i l l i l i t e r s o f th e l i q u i d p ro d u c t was t r e a t e d w ith s o l i d calciu m c a rb o n a te .

I t was hoped t h a t th e calcium c a rb o n a te , b e in g a

weak b a s e , would remove on ly th e ex cess hydrogen f l u o r i d e , b u t i t be­ haved as d id a l k a l i , l i b e r a t i n g th e o r i g in a l n i t r i l e . F iv e m i l l i l i t e r s o f th e l i q u i d p ro d u c t was t r e a t e d w ith 3 m l. o f phenyl is o c y a n a te b u t th e re was no r e a c tio n .

A s im ila r a tte m p t u sin g

p h e n y li so t h i ocyanate a ls o f a i l e d to r e a c t . Ten m i l l i l i t e r s o f th e l i q u i d p ro d u c t was h e a te d u n d er r e f l u x w ith 3 grams o f p -n itro b e n z o y l c h lo r id e .

C y c liz a tio n to th e t r i a z i n e was

th e o n ly r e a c tio n which o c c u rre d , w ith no amine d e r iv a tiv e b e in g form ed. Twenty m i l l i l i t e r s o f th e l i q u i d p ro d u c t was t r e a t e d w ith s o l i d calciu m c a rb o n a te . e v o lv e d .

The m ix tu re e ffe rv e s c e d s tro n g ly and much h e a t was

The ex cess calcium c a rb o n a te was d e stro y e d by adding conc.

h y d ro c h lo ric a c id s o lu tio n , a t which tim e a v h i te p r e c i p i t a t e formed and was f i l t e r e d and d r ie d .

The p r e c i p i t a t e was a p u re w h ite powder and

alth o u g h i t c o n ta in e d n itro g e n , c h lo rin e and f l u o r in e , i t behaved a s an in o rg a n ic s a l t . Twenty m i l l i l i t e r s o f th e l i q u i d p ro d u c t was mixed w ith 7^ m l. o f d ry b en zen e.

I t was hoped t h a t i f th e amine were formed any f r e e amine

would be d is s o lv e d o u t i n th e benzene and would be s ta b le i n th e absence

to

o f -water o r o th e r h y d ro ly zin g s u b s ta n c e s . from th e r e s i d u a l l i q u i d p ro d u c t.

The benzene was s e p a ra te d

Five m i l l i l i t e r s o f t h i s benzene s o lu ­

t i o n was t r e a t e d w ith 3 m l. o f p h e n y lis o th io c y a n a te and th e m ix tu re was h e a te d .

There was no evidence o f a r e a c t i o n .

A fte r th e m ix tu re had

s to o d f o r f i v e h o u rs, a w hite p r e c i p i t a t e s e t t l e d .

T his p r e c i p i t a t e was

i s o l a t e d and i d e n t i f i e d as d ip h e n y lu re a , formed by th e a c tio n o f t r a c e s o f w a te r on th e p h e n y li so c y a n a te . Twenty m i l l i l i t e r s o f th e l i q u i d p ro d u c t was mixed w ith 80 g . o f anhydrous p o tassiu m f lu o r id e on th e p o s s i b i l i t y t h a t th e p o tassiu m f l u o r id e would t i e up th e excess hydrogen f lu o r id e and le a v e any amine which m ight have been form ed.

A v i o le n t r e a c tio n ensued and th e m ix tu re

s e t to a s o l i d c ak e.

T his cake was p u lv e r iz e d and th o ro u g h ly e x tr a c te d

w ith anhydrous e th e r •

T his e th e r s o lu tio n was t r e a t e d w ith p h e n y li so­

c y an ate a s was th e benzene s o lu tio n .

D iphenylurea was th e o n ly p ro d u c t

i n t h i s c a se a ls o . I f o n ly one m olecule o f hydrogen f lu o r id e had added a c ro ss th e n i t r i l e bond, th e im in o flu o rid e would have been formed a s shown i n th e e q u a tio n : CF^GN + HF

CF^CF=m

Such a compound m ight be ex p ected to behave l i k e an a c id c h lo r id e .

On

t h i s b a s i s , r e a c tio n o f th e l i q u i d p ro d u c t w ith m ethanol and e th a n o l was a tte m p te d , b u t no r e a c tio n o c c u rre d . A ll o f th e fo re g o in g r e a c tio n s have been conducted on th e assump­ t i o n t h a t a d d itio n o f hydrogen f lu o r id e to th e n i t r i l e bond o c c u rre d w ith th e hydrogen going to th e n itro g e n and th e f lu o r in e going to th e c arb o n . T his seems l o g i c a l i f we examine th e r e l a t i v e e le c t r o n e g a t i v i t i e s o f th e carb o n and n itr o g e n atom s, as w e ll as th e hydrogen and f lu o r in e atom s.

ItS S in ce th e n itro g e n atom i s more e le c tr o n e g a tiv e th a n th e carbon atom, i t m rnld be expected to p r e f e r e n t i a l l y u n i te w ith th e more p o s i t i v e p o r tio n o f th e hydrogen f l u o r id e .

The e f f e c t o f th e tr if lu o r o m e th y l group must

a ls o be examined i n o rd e r t o p r e s e n t a com plete p ic tu r e *

S in ce th e t r i ­

flu o ro m eth y l group i s s tr o n g ly e le c tr o n e g a tiv e , i t m ight be

e x p ected by

means o f i t s e le c tr o n a t t r a c t i n g q u a l i t i e s to re n d e r th e carbon atom o f th e n i t r i l e u n i t even more p o s i t i v e , a c o n d itio n which would le a d to th e method o f a d d itio n a lre a d y p o s tu la te d , i f th e a d d itio n d id o c c u r. The 1 9 11 s t a b i l i t y o f th e n itr o g e n - f lu o r in e bond * 9 may a f f e c t th e s e f a c t o r s however, le a d in g to th e re v e rs e method o f a d d itio n .

I f t h i s re v e rs e

a d d itio n d id o ccu r to form th e N, N1- d if lu o r o compound, a l l p re v io u s a tte m p ts to i s o l a t e th e p ro d u c t would have f a i l e d s in c e th e y a l l de­ pended on th e p resen ce o f th e amino group and i t s r e a c t i o n s .

The i n ­

s t a b i l i t y o f th e p ro d u ct formed would c a s t doubts on t h i s ty p e o f a d d itio n . I f such a compound were form ed, th e m ethylene group so form ed would be a c tiv a te d by th e two h ig h ly e le c tr o n e g a tiv e groups a tta c h e d to i t and m ight be a c tiv e enough to undergo co n d en sa tio n s w ith c arb o n y l compounds.

I f such a c o n d en satio n d id o ccu r, i t would n o t be c o n c lu siv e

as to th e ty p e o f a d d itio n because amines r e a c t w ith many c arb o n y l com­ pounds to form th e so c a lle d f,S c h i f f 1s B ases” .

Due to th e u n r e a c t i v i t y

o f th e p ro d u c t tow ard r e g u la r amine re a g e n ts such a r e a c tio n would be in d ic a tiv e .

C ondensations were attem p ted w ith a ceto n e and b e n z a ld e -

hyde, b u t no r e a c tio n o c c u rre d . From th e numerous a tte m p ts to p re p a re amine d e r iv a tiv e s o f th e l i q u i d p ro d u c t, i t appears t h a t no amine i s form ed.

I f th e amine were

form ed, th e n from i t s f a i l u r e to form a d e r iv a tiv e w ith any ty p e o f

1*6

amine r e a g e n t, i t m ast be e s p e c i a l l y u n r e a c tiv e .

Such a compound sh o u ld

be s t a b le enough f o r i s o l a t i o n i n th e f r e e s t a t e , and s in c e t h i s a ls o co u ld n o t be accom plished, th e amine must n o t have been form ed.

The

read y decom position o f th e p ro d u c t by such weak b a se s as calcium c a r­ b o n ate o r s i l i c a i n d ic a t e s t h a t th e hydrogen f l u o r id e i s v e iy r e a d i l y lo s t.

No re a g e n t c o u ld be found which was weakly b a s ic enough to r e ­

move o n ly p a r t o f th e hydrogen f lu o r id e , i n d ic a t i n g t h a t i t may a l l be removed w ith e q u al f a c i l i t y . I t i s r e p o rte d t h a t amines form p o ly (h alo g en a c id ) s a l t s i n which from one to fo u r o r more m olecules o f h alogen a c id a re u n ite d w ith each m olecule o f a m in e^ *

These a re r a t h e r i n d e f i n i t e compounds whose com­

p o s i t i o n depends on th e tem p eratu re and c o n c e n tra tio n o f halogen a c id p r e s e n t.

I t i s e n t i r e l y p o s s ib le t h a t a s im ila r s e r i e s o f compounds

e x i s t s i n n i t r i l e s a l t s as re p o rte d by H antzsch i n which th e number o f m olecules o f h alo g en a c id a tta c h e d to each m olecule o f n i t r i l e i s de­ p en d en t o n ly on th e tem p era tu re and c o n c e n tra tio n o f h alo g en a c id p re ­ s e n t.

Such a c o n d itio n would r e a d i ly account f o r th e e ase o f decomposi­

t i o n by tre a tm e n t w ith weak b a s e s . and r e a d i l y h y d ro ly ze d .

Such s a l t s would be w a ter s o lu b le

Any tre a tm e n t under no n -h y d ro ly zin g c o n d itio n s

would e a s i l y remove th e hydrogen f lu o r id e and re g e n e ra te th e n i t r i l e . Such a u n io n would a ls o be i n e r t to a l l amine r e a g e n ts .

These conclu­

s io n s a re c o m p letely i n agreem ent w ith th o se drawn by H antzsch i n h i s stu d y o f th e n i t r i l e s a l t s ^ . 1 , 1 , 2 , 2 - t e t r a f l u o r o - l , 2 - d in itr o e th a n e .

A two l i t e r n ic k e l l in e d

a u to c la v e was c o o le d i n dry i c e to a te m p e ra tu re below 0 °C ., and d i ­ n itr o g e n t e t r o x id e (550 g . , 60 m oles) d is s o lv e d i n carbon t e t r a c h l o r i d e (250 m l.) was p la c e d i n th e a u to c la v e .

The a u to c la v e head, f i t t e d w ith

hi

a s a f e t y d i s c , b le e d e r v a lv e and p re s s u re gauge was se c u re d i n p la c e . The a u to c la v e was th e n co o led to d iy i c e te m p era tu re and 1 , 1 , 2, 2- t e t r a f lu o r o e th y le n e (I4I4.O g . , I4..J+ m oles) was b le d i n to th e a u to c la v e thro u g h th e v a lv e .

The a u to c la v e was allow ed to warm to room te m p e ra tu re and

a f t e r s i t t i n g f o r f o u r days, was b le d through a w a te r wash b o t t l e and a d ry i c e t r a p .

The l i q u i d p ro d u c t i n th e a u to c la v e was poured over i c e .

The lo w er heavy l a y e r was washed w ith sodium hydroxide s o lu tio n to r e ­ move th e b lu e c o lo r , d r ie d over calcium c h lo rid e and r e c t i f i e d .

One

hundred and s i x t y grams (0 .8 3 mole) o f 1, 1 , 2, 2- t e t r a f l u o r o - l , 2- d i n i t r o e th a n e , b . p . 57-5Ô c . under 750 mm. p re s s u re , was o b ta in e d .

T his i s a

c o n v ersio n o f 19 %* The f i r s t method o f r e d u c tio n o f t h i s compound a tte m p te d was w ith 7

i r o n and h y d ro c h lo ric a c id s o lu tio n •

The g e n e ra l method i s a s fo llo w s :

R eduction o f 1 , 1 , 2 , 2 - t e t r a f l u o r o - l , 2—d in itr o e th a n e w ith i r o n and h y d ro c h lo ric a c i d .

Ten m i l l i l i t e r s o f c o n c e n tra te d h y d ro c h lo ric a c id

s o lu tio n was added to 35 g . o f I4.O mesh i r o n f i l i n g s i n 75 m l. o f w ater i n a 300-inl. th r e e necked round bottom f l a s k f i t t e d w ith a m ercury s e a le d H ershberg s t i r r e r , a r e f l u x condenser and a dropping fu n n e l. A fte r th e e v o lu tio n o f hydrogen had ceased , 1 , 1 , 2 , 2 - t e t r a f l u o r o - l , 2 d in itr o e th a n e (16 g . , 0 .5 mole) was added dropw ise w ith v ig o ro u s s t i r ­ rin g .

A te m p e ra tu re o f 60°C. was m ain tain ed and th e s t i r r i n g was con­

tin u e d f o r two h o u rs . The g e n e ra l p ro ce d u re i s to add sodium hydroxide s o lu tio n a t t h i s s ta g e o f th e r e a c tio n and steam d i s t i l l th e amine o u t o f th e r e a c t i o n m ix tu re .

I n t h i s p a r t i c u l a r in s ta n c e , th e n e u tr a l m ix tu re was steam

d i s t i l l e d on th e p o s s i b i l i t y t h a t i f th e amine had been form ed, i t m ight be a c id ic enough, due to th e in f lu e n c e o f th e f lu o r in e atom s, t h a t

U8

i t would steam d i s t i l l r a t h e r th a n form a s a l t .

The r e s id u a l s o lu tio n

was th e n made a lk a lin e w ith aqueous sodium hydroxide and a g a in steam d is tille d .

The p ro d u c ts o f th e d i s t i l l a t i o n s were t r e a t e d w ith conc.

h y d ro c h lo ric a c id s o lu tio n and ev ap o rate d to d ry n ess when s e p a r a tio n o f th e p ro d u c ts by d i s t i l l a t i o n f a i l e d .

The s o lid s form ed by th e evapora­

t io n s were e x tr a c te d w ith b o ilin g e th a n o l.

TBhite c r y s t a l l i n e p r e c i p i ­

t a t e s were i s o l a t e d from th e e th a n o l and were shown by a n a ly s is to be ammonium c h lo r id e . Some e tc h in g o c cu rred i n th e r e a c tio n f l a s k , showing t h a t f r e e h y d r o f lu o ric a c id was formed i n th e r e a c tio n .

The r e a c tio n re s id u e

was f i l t e r e d , and th e f i l t r a t e was t r e a t e d w ith a s a tu r a te d s o lu tio n o f calcium c h lo r id e .

A w h ite p r e c i p i t a t e was form ed.

t a t e showed no ev id en ce o f f lu o r id e io n .

T his p r e c i p i ­

I t f a i l e d to e tc h g la s s when

t r e a t e d w ith conc. s u l f u r i c a c id on a g la s s p l a t e and warmed. t i o n o f th e p r e c i p i t a t e was d is s o lv e d i n d i l u t e

A p o r­

s u l f u r i c a c id s o lu tio n

and was found t o d e c o lo riz e d i l u t e perm anganate s o lu tio n in d ic a tin g t h a t i t i s p ro b a b ly calcium o x a la te . These r e s u l t s i n d ic a t e t h a t , w h ile th e n i t r o groups were com plete­ l y red u ced u n d er th e c o n d itio n s u se d , th e in te rm e d ia te o r f i n a l p ro ­ d u c ts were u n s t a b le .

Loss o f hydrogen f lu o r id e from t e t r a f l u o r o e t h y l -

enediam ine, i f i t were form ed, would y i e l d th e im in o flu o rid e o f o x a lic a c id o r cyanogen.

E ith e r o f th e s e m a te r ia ls would h y d ro ly ze to form

o x a lic a c id and ammonia. ene diam in e.

R eduction o f th e cyanogen would y i e l d e th y l­

The p o s s i b i l i t y o f both re d u c tio n and h y d ro ly s is o c c u rrin g

sim u lta n e o u sly on th e same m olecule su g g ested th e p o s s ib le fo rm a tio n o f g ly c in e .

The f i l t r a t e o f th e re s id u e was h e a te d w ith copper oxide b u t

no b lu e c o lo r was form ed, showing t h a t no g ly c in e was form ed.

S in ce i t became a p p a re n t t h a t h y d ro ly tic c o n d itio n s would le a d to th e fo rm a tio n o f o x a lic a c id and ammonia, d i f f e r e n t c o n d itio n s were so u g h t f o r th e r e a c t i o n .

Stannous c h lo rid e d is s o lv e d i n h y d ro c h lo ric

a c id s o lu tio n i s an e f f e c t i v e a g en t f o r red u c in g n i t r o compounds to amines and has been w id ely u se d .

In such r e a c tio n s , th e r e i s u s u a lly

a ten d en cy f o r complex fo rm atio n in v o lv in g th e o x id iz e d form o f th e t i n These complexes a re u s u a lly o f th e form R^SnCl^ where R i s one m olecule 2 o f amine • These complexes a re f r e q u e n tly o n ly s l i g h t l y s o lu b le and c r y s t a l l i z e o u t o f th e r e a c tio n s o lu tio n when i t i s c o o le d . be a good method o f i s o l a t i n g th e amine.

T his may

I n such circ u m sta n ce s th e t i n

i s removed by p r e c i p i t a t i n g i t from s o lu tio n by th e u se o f hydrogen sul­ fid e .

The p r e c i p i t a t e o f t i n s u l f i d e i s f i l t e r e d o f f , and th e amine

rem ains i n s o lu tio n as th e h y d ro c h lo rid e s a l t . R ed u ction o f 1 , 1 , 2 , 2 - t e t r a f l u o r o - l , 2 - d in itr o e th a n e w ith stannous c h lo r i d e .

G la c ia l a c e tic a c id (100 m l.) and 1 , 1 , 2 , 2 - t e t r a f l u o r o - l , 2 -

d in itr o e th a n e (19 g . , 0 .1 mole) were mixed i n a 500-m l. th r e e necked round bottom f l a s k equipped w ith a dropping fu n n e l, m ercury s e a le d g la s s s t i r r e r , and a r e f l u x condenser.

The s o lu tio n was h e a te d to r e ­

f lu x te m p e ra tu re w ith a h e a tin g m an tle, and stannous c h lo rid e (175 g»> 0 .9 mole) d is s o lv e d i n conc. h y d ro c h lo ric a c id s o lu tio n (100 m l.) was added d ro p w ise.

When th e a d d itio n o f th e red u cin g a g en t was com plete,

th e m ix tu re was h e a te d to a tem p eratu re o f 95 C. f o r o n e -h a lf hour and th e n allo w ed to co o l o v e rn ig h t. d u rin g t h i s tim e .

A w h ite c r y s t a l l i n e p r e c i p i t a t e formed

The m ix tu re was cooled i n ic e and f i l t e r e d th ro u g h a

c o a rse s i n t e r e d g la s s fu n n e l.

The p r e c i p i t a t e c o n s is tin g o f c o lo r le s s

o c ta h e d ra l c r y s t a l s was washed w ith a lc o h o l, th e n e th e r , and f i n a l l y d r ie d i n a vacuum d e s s ic a to r .

5o

A sam ple o f th e s e c r y s t a l s was d is s o lv e d i n h y d ro c h lo ric a c id s o lu tio n , and hydrogen s u l f i d e was bubbled thro u g h th e s o lu tio n u n t i l no more p r e c i p i t a t e form ed. f i l t r a t e was e v a p o ra te d .

The t i n s u l f i d e was f i l t e r e d o f f and th e

Ammonium c h lo rid e rem ained.

The r e s u l t s o f th e s e re d u c tio n s in d ic a te t h a t th e d e s ir e d p e r flu o ro am in e s a re u n s ta b le and a tte m p ts to p re p a re them w i l l p ro b a b ly y i e l d deco m position p r o d u c ts .

I n o rd e r to a tte m p t to determ ine i f t h i s

deco m p o sitio n o ccu rs through th e f i n a l p ro d u c t o r th ro u g h one o f th e in te r m e d ia te s in v o lv e d i n th e r e a c tio n s , th e p r e p a r a tio n o f N,Nt d i s u b s t i t u t e d in te r m e d ia te s was attem pted by th e G a b rie l sy n th e sis* A ttem pted r e a c tio n o f potassium p h th alim id e w ith 1 , 1 , 2 , 2 - t e t r a f l u o r o - 1 , 2 -d iio d o e th a n e .

Potassium p h th alim id e (75 g*> 0 .2 8 mole) was

t r e a t e d w ith 1 , 1 , 2 , 2 - t e t r a f l u o r o - l , 2 -d iio d o e th a n e (^0 g . , 0.11 mole) . B ecause o f th e h ig h d e n s ity o f th e d iio d o compound as c o n tra s te d to th e l i g h t , c o tt o n - li k e n a tu re o f th e p otassium p h th a lim id e , th e h a lo g e n a te d was ab so rb ed so co m p letely t h a t th e r e was no v is u a l evidence o f i t s p re se n c e .

The m ix tu re was h e a te d to a tem p era tu re o f ap p ro x im ately

100°C. f o r two h o u rs and th en cooled and t r e a t e d w ith w a te r .

T his r e ­

s u l t e d i n th e s e p a r a tio n o f th e d iio d o compound which was i s o l a t e d un­ changed.

Only u n re a c te d p h th a lim id e was i s o l a t e d from th e r e s t o f th e

m ix tu re . A ttem pted r e a c tio n o f potassium p h th a lim id e w ith 1 , 1 , 2 , 2 - t e t r a f lu o r o - 1 ,2 - d iio d o e th a n e .

Potassium p h th a lim id e (25 g . , 0.09 mole) and

1 , 1 , 2 , 2 - te tr a f lu o r o - l,2 - d iio d o e th a n e (20 g . , 0.055 mole) were m ixed. The r e s u l t i n g m ix tu re was t r e a te d w ith enough dioxan to form a t h in p a s te and th e n h e a te d on a steam b a th .

As th e m ix tu re warmed up, th e

d iio d o compound decomposed, ev o lv in g t e t r a f l u o r o e t h y l e n e .

SUMMARY F lu o r in a tio n o f n i t r i l e s u sin g s i l v e r d i f lu o r i d e a t te m p e ra tu re s above 150 C. form ed N,N1- d if lu o r o p e r f lu o r in a te d am ines.

N,N1—d if lu o r o —

( t r i d e c a flu o ro c y clo h ex y lm eth y l) amine and N, N1- d if lu o r o (undec a f lu o r o - n amyl ) amine were p re p a re d by f l u o r i n a t i on o f b e n z o n i tr i l e and n - v a le r o n itrile .

These N, N1-d iflu o ro p e rflu o ro a m in e s were v e ry s ta b le to a l l

u s u a l chem ical a g e n ts . ELuo r i n a tio n o f a c e t o n i t r i l e w ith s i l v e r d i f l u o r id e a t l50°C . form ed N,Nl -d iflu o ro (o C ,o C -d iflu o ro e th y l)a n iin e .

N ,N *-difluoro(oC ,oC -

d iflu o ro e th y l)a m in e was s ta b le to a c id s and b a s e s . A ttem pts to f l u o r in a te p rim ary amines u s in g s i l v e r d i f lu o r id e were n o t s u c c e s s f u l. A ttem pts to add f lu o r in e to n i t r i l e bonds by th e u se o f le a d t e t r a f l u o r i d e were u n s u c c e s s fu l. E L uorinated n i t r i l e s r e a c t w ith anhydrous hydrogen h a lid e s to form n i t r i l e s a l t s .

*

R eduction o f 1 , 1 , 2 , 2 - t e t r a f l u o r o - l , 2 - d in i tro e th a n e formed o x a lic a c id , h y d ro flu o ric a c id and ammonia. A ttem pts to c a r r y o u t a G a b rie l s y n th e s is u sin g 1 , 1 , 2 , 2 - t e t r a f lu o r o - 1 ,2 -d iio d o e th a n e were u n s u c c e s s fu l.

BIBLIOGRAPHY I#

B i t t l e s , J e , PhD. T h e s is , Purdue U n iv e rs ity , 19U7»

2.

E in h o rn , A. and U h lf e ld e r, E ., Ann 371, 131 (1909)*

3.

Gilman, H. and Jo n e s, R. G., J . Am. Chem. Soc. 6 ^, 1U58 (19U3)*

U*

G ryszklew icz-T rochinow ski, S p o rzy n sk i, and Wnuk, Rec. T rav . Chim. 66, 719 (19U7).

3*

H antszch. A ., B er. 6bB, 667 (1931)*

6.

Henne, A. L . , J . Am. Chem. Soc. 67, 1639 (19U 5)•



Johnson, K ., PhD. T h e sis, Purdue U n iv e rs ity , 1937*

8.

Raasch, M. S ., U .S. P a te n t 2,li2l|.,666.

9*

R u ff, 0 . , F is c h e r, J . , and L u ft, F ., Z. Anorg. Chem. 172, 1+17 (1 9 2 8 ).

10.

Sidgw ick, N. V ., "The O rganic C hem istry o f N itro g e n ”, Oxford a t th e C larendon P re ss (1937)•

11.

Simons, J . H ., U .S. P a te n t 2,1+90,098.

12.

M iitta k e r , A. C. and H ass, H. B ., U .S. P a te n t 2,1+1+7,501+.

13*

‘W illiam son, A. H ., PhD. T h e sis, Purdue U n iv e rs ity , 191+9*

VITA

K e ith Mar T ay lo r was b o rn a t T h atch er, A rizo n a, on November 15, 1922.

He a tte n d e d p u b lic sc h o o ls a t T h atch e r,

b e in g g ra d u a te d from T hatcher High School i n May, 1939*

He

a tte n d e d th e G ila J u n io r C o lle g e, a ls o a t T h atch er, A rizo n a, and was awarded a C e r t i f i c a t e i n S cien ce i n May, 191+1*

He

e n te r e d th e Brigham Young U n iv e rs ity a t Provo, U tah, Septem ber, 191+1, b u t l e f t school to a c c e p t employment i n Ja n u ary , 191+2. I n Septem ber, 191+3, he e n te re d th e U n iv e rs ity o f A rizona a t Tucson, A rizona, and was awarded th e degree o f B achelor o f S cien ce i n C hem istry i n June, 191+5, and th e degree o f M aster o f S cience i n C hem istry i n June, 191+7*

He e n te re d Purdue

U n iv e rs ity i n Septem ber, 191+7, and was awarded th e degree o f D octor o f P h ilo so p h y on June 18, 1950. Mr. T aylor i s a member o f Phi Lambda U p silon and The S o c ie ty o f Sigma X i.

He was awarded th e duPont fe llo w s h ip f o r

re s e a rc h i n ch em istry w hile a t Purdue U n iv e rs ity .