A study of the reactions of carbon monoxide with B-Dicarbonyl compounds and their derivatives [and]
the synthesis of aldehydes by the reaction of formyl fluoride with organocadmium bromides
by Jack R Gaines
A THESIS Submitted to the Graduate Committee in partial fulfillment of the requirements for the
degree of Master of Science in Chemistry
Montana State University
© Copyright by Jack R Gaines (1950)
Abstract:
The reactions between carbon monoxide and the metal enolates of β -di-carbonyl compounds have
been investigated. The catalysts used were nickel tetracarbonyl and dicobalt octacarbonyl. Hydrogen
was used, in many cases, in addition to the carbon monoxide. Reactions were also run with the free β
-dicarbonyl compounds.
No apparent reaction was found to take place between carbon monoxide and these compounds under
the conditions which were used. The reaction of O-acetylacetoacetic ester with carbon monoxide and
hydrogen in the presence of dicobalt octacarbonyl, however, led to the synthesis of an aldehyde. The
identity of this aldehyde has not yet been determined.
Experimental details are given on the preparation of formyl fluoride and the synthesis of
2-methyl-l-butanal by the reaction of formyl fluoride with secondary-butylcadmium bromide. The
synthesis of other aldehydes by using formyl fluoride and organocadmium compounds is mentioned. A STbW OP
RiSAOTIOKg OIF OARBOR 'M DRGIim R IT g
/J-DIOARBQIiIL COSSFOUHDg M B TliElS D:%I7ATI7ES*
T m . G W m g i s o r ALDEmmEg m T m E m c T s m o ?
mam, mmmm -,smi oRcmocAiamm BRo&EDEg,
Jack E, Caines
. A TRBSIg -
,
-Sabmitted to the Graduate Committee
in
partial AlfilIment of the reqhiremente
for the degree of
laster of Science, in Chemistry .
at
Montana. State College
Approved;
Boaemanj Montana
,Tular
1950
Q-ILs
C f-f3, Zj
—2 —
TABLIj OF CONTENTS
I .
ABSTRACT..........................................................................................................
4
II.
INTRODUCTION ................................................................................................
5
III.
THEORETICAL DISCUSSION ........................................................................
7
IV .
EXPERIMENTAL................................................................................................
11
M a t e r i a l s ...........................................................................................
11
A p p a r a tu s ...........................................................................................
11
D i c o b a l t o c t a c a r b o n y l ..............................................................
11
Sodium a c e t o a c e t i c e s t e r
.....................................................
12
. ..........................................................
13
Sodium a c e t y l a c e t o n e
C opper a c e to a c e tic e s t e r
.....................................................
13
..............................................................
13
...................................................................
14
O - A c e t y l a c e t o a c e t i c e s t e r .....................................................
14
R e a c ti o n o f a c e t o a c e t i c e s t e r v d th c a rb o n m onoxide
a n d h y d ro g e n
. . . .
............................................................
15
R e a c ti o n o f a c e t y l a c e t o n e w i t h c a rb o n m onoxide
15
R e a c ti o n o f a c e t y l a c e t o n e w ith c a rb o n m onoxide
a n d h y d r o g e n ..................................................................................
15
R e a c tio n o f so d iu m a c e t o a c e t i c e s t e r w ith c a rb o n
m onoxide
...........................................................................................
15
R e a c tio n o f so d iu m a c e t y l a c e t o n e w i t h c a rb o n
m o n o x i d e ..................................................... .... .................................
17
R e a c tio n o f z i n c a n d c o p p e r a c e t y l a c e t o n e w ith
c a rb o n m o n o x id e a n d h y d ro g e n ................................................
17
R e a c ti o n o f O - a c e t y l a c e t o a c e t i c e s t e r w ith
c a rb o n m o n o x id e an d h y d ro g e n ...........................................
17
C opper a c e ty la c e to n e
Z in c a c e t y l a c e t o n e
Jfw
-T
CM
94725
(T a b le o f C o n te n ts )
P r e p a r a t i o n o f f o rm y l f l u o r i d e
PKt
. . . . .
.......................................
19
S e o o n d a ry -b u ty lm : £ae slum b ro m id e .........................................................
20
S ec o n d a ry -b u ty lc a d iid u m b ro m id e ..............................................................
20
S y n t h e s i s o f S - m e t h y l b u t a n a l - l ..............................................................
21
R e a c tio n s o f fori«iyl f l u o r i d e w i t n o t h e r
organoeadm ium b ro m id e s .................................................................................
22
V.
DISCUSSION OF EXPERIMENTAL RESULTS..................................................................
.. ;
V I.
SU K LU R Y ................................................................................................................................
24
V II.
ACKNOWLEDGMENT.................................................................................................................
25
V III.
LITERATURE CITED AND CONSULTED...........................................................................
26
-
I
l
4
-
ABSTRACT
The r e a c t i o n s b e tw e e n c a rb o n m o n o x id e a n d t h e m e t a l e n o l a t e s o f - d i ­
c a r b o n y l com pounds h a v e b e e n i n v e s t i g a t e d .
t e tr a c a r b o n y l and d i c o b a lt o c ta c a rb o n y l.
i n a d d i t i o n t o t h e c a rb o n m o n o x id e .
The c a t a l y s t s u s e d w ere n i c k e l
H ydrogen was u s e d , i n many c a s e s ,
R e a c ti o n s w e re a l s o r u n w ith t h e f r e e
/6 - d i c a r b o n y l com pounds.
No a p p a r e n t r e a c t i o n w as fo u n d t o t a k e p l a c e b e tw e e n c a rb o n m onoxide
a n d t h e s e com pounds u n d e r t h e c o n d i t i o n s w h ic h w ere u s e d .
T he r e a c t i o n o f
O - a c e t y l a c e t o a c e t i c e s t e r w i t h c a rb o n m o n o x id e an d h y d ro g e n i n t h e p r e ­
s e n c e o f d i c o b a l t o c t a c a r b o n y l , h o w e v e r, l e d t o t h e s y n t h e s i s o f an a l d e ­
hyde.
The i d e n t i t y o f t h i s a ld e h y d e h a s n o t y e t b e e n d e te r m i n e d .
E x p e r im e n ta l d e t a i l s a r e g iv e n on t h e p r e p a r a t i o n o f f o r m y l f l u o r i d e
and t h e s y n th e s is o f 2- m e t h y l- l- b u ta n a l b y th e r e a c tio n o f fo rm y l f lu o r id e
w i t h s e c o n d a ry -b u ty lc a d m iu m b r o m id e .
The s y n t h e s i s o f o t h e r a ld e h y d e s b y
u s in g f o r m y l f l u o r i d e a n d o r g a n ocadmium com pounds i s m e n tio n e d .
I
I
.
I N
T
H
: - D T in T ia N
The u s e o f c a rb o n m onoxide a s a n a d d i t i o n r e a g e n t i n o r g a n i c s y n t h e s e s
h a s become o f g r e a t t e c h n i c a l i m p o r ta n c e .
The num ber o f t y p e s o f com pounds
w h ic h may b e s y n t h e s i z e d b y t h e u s e o f c a r b o n m onoxide h a v e b een g r e a t l y
i n c r e a s e d w i t h i n t h e p a s t few y e a r s .
The s y n t h e s i s o f m e th y l a l c o h o l a n d h i g h e r a l c o h o l s fro m c a rb o n mon­
o x id e a n d h y d ro g e n
^ ^
i s c a r r i e d o u t on a c o m m e rc ia l s c a l e .
B oth l a b ­
o r a t o r y a n d i n d u s t r i a l r e a c t i o n s a r e knovn f o r t h e p r e p a r a t i o n o f a l d e h y d e s ,
a li p h a ti c and s u b s titu te d a li p h a ti c a c id s .
a c e t i c a c id and i t s
The c o m m e rc ia l p r o d u c t i o n o f
h i g h e r hom ologs by E . I . du P o n t d e Nem ours ^
Is
a c c o m p lis h e d by t h e f o l l o w i n g r e a c t i o n :
CH3OH + CO
BP3 +• H2O
75 a tm s . , 1 2 5 -1 8 0 * 0 ^
CH5COOH
A s i m i l a r r e a c t i o n b e tw e e n e t h y l e n e a n d c a rb o n m onoxide y i e l d s p r o p io n i c
a c i d C5 2 ) .
By u s i n g v a r i o u s s t a r t i n g m a t e r i a l s , h y d r o x y -a c id ::
a m in o - a c id s ^
P o n t.
and p o ly c a r b o x y lic -a c id s
G a tte rm a m i a n d Koch ^
,
' h a v e b e e n p ro d u c e d by du
- h a v e shown t h a t a r o m a tic a ld e h y d e s c a n be
p r e p a r e d by t h e r e a c t i o n o f a r o m a tic h y d r o c a r b o n s with c a r b o n m onoxide
a n d d r y h y d ro g e n c h l o r i d e i n t h e p r e s e n c e o f a n h y d ro u s alum inum c h l o r i d e
a n d a s m a l l am ount o f c u p r o u s c h l o r i d e .
G u tiik e ^ ,A)' h a s r e p o r t e d t h e
s y n t h e s i s o f b e n z a ld e h y d e by t h e r e a c t i o n o f ben zen e an d c a r b o n m onoxide
i n t h e p r e s e n c e o f a n h y d ro u s alum inum c h l o r i d e and t i t a n i u m tetrachloride
a t h ig h p r e s s u r e s .
B o th i n o r g a n i c ^ v' ' a n d o r g a n ic b a s e s
^ w ill
r e a c t w i t h c a rb o n m o n o x id e , u n d e r p r e s s u r e , t o y i e l d f o r m a te s o r o t h e r
a d d i t i o n com pounds.
Two s u c h r e a c t i o n s a r e :
-
KOH ( a q . ) + CO
6
-
----- I^O 0Ct---- ^
20 a tm .
CH3 OH + CO
HCOOK
(9 8 > )
HCOOCH3
200-400 a tm ?
7 0-100°C .
A ld e h y d e s h a v e b e e n s y n t h e s i z e d i n d u s t r i a l l y by r e a c t i o n s b e tw e e n c a rb o n
m o n o x id e , h y d ro g e n an d o l e f i n s i n t h e p r e s e n c e o f c o b a l t c a t a l y s t s and
tin d e r c o n d i t i o n s o f h ig h p r e s s u r e ^
"oxo" p r o c e s s .
(3 1 ^
T h is p r o c e s s i s known a s t h e
A d k in s a n d K rs e k (Z ) ( 3 ) h a v e s t u d i e d l a b o r a t o r y c o n d i t i o n s
u n d e r w hich c e r t a i n u n s a t u r a t e d com pounds w i l l add c a rb o n m o n o x id e an d
h y d ro g e n i n t h e p r e s e n c e o f d i c o b a l t o c t a c a r b o n y l .
T hese r e a c tio n s
y i e l d , i n n e a r l y a l l c a s e s , a h ig h p e r c e n t a g e o f a s i n g l e a d d i t i o n p r o ­
d u c t.
An i l l u s t r a t i v e ex am p le i s g iv e n w i t h a l l y l a c e t a t e :
Ch2=Chch2 OOcch3 + co + h2
g o w - lo o ^ ^ /^ s .i^
110-125°c!
Ch3 Cooch2 Ch2 Ch2 Cho
The i n c r e a s i n g im p o r ta n c e o f c a rb o n m o n o x id e a s a n a d d i t i o n r e a g e n t
i n o r g a n i c s y n t h e s e s w as one o f t h e r e a s o n s f o r t h e i n v e s t i g a t i o n s con­
s id e re d in t h i s p a p e r.
One o f t h e o r i g i n a l p u r p o s e s o f t h i s i n v e s t i g a t i o n
w as t h e s y n t h e s i s o f a ld e h y d e s th r o u g h t h e r e a c t i o n o f c a rb o n m onoxide
an d h y d ro g e n w ith
- d i c a r b o n y l com pounds o r t h e i r d e r i v a t i v e s .
F o rm y l f l u o r i d e ( Z l) i s t h e o n ly a c i d h a l i d e d e r i v a t i v e o f fo rm ic
a c i d w h ich h a s b e e n i s o l a t e d .
I t h a s b e e n p o s t u l a t e d t h a t t h e hypo­
t h e t i c a l f o rm y l c h l o r i d e i s fo rm e d a s a n i n t e r m e d i a t e i n t h e G a tte rm a n n Koch s y n t h e s i s o f a r o m a ti c a ld e h y d e s ( H ) .
G ilm an a n d N e ls o n ( 1 3 J h a v e shown t h a t organocadm ium com pounds w i l l
r e a c t w ith a c i d c h l o r i d e s t o form k e t o n e s .
Ihus e x p e r im e n ts w e re c a r r i e d
-
7
-
o u t t o d e te r m in e t h e p o s s i b i l i t y o f p r e p a r i n g a ld e h y d e s t h r o u g h t h e
r e a c t i o n o f f o r m y l f l u o r i d e w i t h organocadm ium com pounds.
I I I . THEORETICAL DISCUSSION
No w o rk , up t o t h e p r e s e n t t i m e , h a s b e e n r e p o r t e d i n v o l v i n g r e a c t i o n s
o f c a rb o n m onoxide an d /S - d i c a r b o n y l c o n fo u n d s o r t h e i r m e t a l e n o l a t e s .
M ost o f t h e w ork d e a l i n g w i t h t h e r e a c t i o n o f a n o r g a n i c s a l t o f a n y ty p e
w i t h c a rb o n m o n o x id e , i s t h a t o f sodium e t h o x i d e and c a rb o n m o n o x id e .
S t a b l e r (2 6 ) ^ a s r e p o r t e d t h a t a l c o h o l f r e e sodium e t h o x i d e w i l l r e a c t
w ith c a rb o n m o n o x id e a t h i g h p r e s s u r e s t o fo rm t h e a d d i t i o n p r o d u c t
NaCOOC2H ^.
S c h e i b l e r a n d F r i k e l l ( ^ J j h o w e v e r, r e p o r t t h e f o r m a tio n o f
a b e v a l e n t c a rb o n d e r i v a t i v e C(ONa)OC2 H5 , u s i n g t h e same c o n d i t i o n s .
A d ie k e s , S im son a n d P e c k e l h o f f ( ^
s t a t e t h a t b o th t h e c a rb o n m onoxide
a n d t h e sodium e th o x i d e u s e d b y S c h e i b l e r a n d F r i c k e l l w ere im p u r e , and
t h a t t h e r e i s n o r e a c t i o n b e tw e e n p u r e c a rb o n m onoxide an d p u r e sodium
e t h o x i d e , e v e n a f t e r 86 h o u r s .
T hus t h e r e i s no s u b s t a n t i a l p r o o f t h a t
a n a d d i t i o n p r o d u c t o f a n y k in d i s fo rm e d when sodium e t h o x i d e i s
t r e a t e d w ith c a rb o n m onoxide a t h ig h p r e s s u r e s .
I t h a s , h o w e v e r, b e e n
d e f i n i t e l y shown b y B u r r e l l (° ^ and o t h e r i n v e s t i g a t o r s ( ^ )
t h a t a s m a ll
am ount o f sodium o r so d iu m e th o x i d e w i l l c a t a l y z e t h e r e a c t i o n b etw een
e t h y l a l c o h o l an d c a rb o n m o n o x id e .
T he r e a c t i o n r e s u l t s i n t h e form a­
t i o n o f e t h y l f o r m a te i n a n e a r l y q u a n t i t a t i v e y i e l d .
T h i s w ould
i n d i c a t e t h a t t h e a d d i t i o n o f t h e c a rb o n m o n o x id e p r o c e e d s t h r o u g h an
i o n i c m ec h a n ism , q u i t e p o s s i b l y i n v o l v i n g t h e e th o x i d e i o n .
The a d d i t i o n o f c a r b o n m onoxide t o a c a r b a n io n w o u ld r e q u i r e t h a t
t h e c a rb o n atom i n t h e c a rb o n m onoxide m o le c u le c a r r y a p o s i t i v e c h a r g e .
From t h e w ork o f P a u lin g a n d S h e ra a n ( 2 2 ) ( 2 3 ) i t h a s b e e n c o n c lu d e d t h a t t h e
- 8 c a rb o n m onoxide m o le c u le c o n s i s t s o f t h r e e r e s o n a t i n g s t r u c t u r e s :
/
~
-----
:c:o:
:c::o:
I
/
-
:c:::9:
ii
in
A l l t h r e e s t r u c t u r e s m ake a b o u t e q u a l c o n t r i b u t i o n s t o t h e s t a b i l i t y o f
t h e m o le c u le .
T hus, i t
seem s l o g i c a l t h a t t h e t y p e o f s t r u c t u r e t a k i n g
p a r t i n a n a d d i t i o n r e a c t i o n d e p e n d s upon t h e c h a rg e o f t h e i o n t o w hich
t h e a d d i t i o n i s b e in g made a n d t o t h e s t a b i l i t y o f t h e p r o d u c t .
W hitm ore ^ 7 ) h a s p o s t u l a t e d t h a t o l e f i n s e x i s t i n an a c t i v a t e d s t a t e
u n d er c e r ta in c o n d itio n s .
F o rm u la s IV a n d V r e p r e s e n t t h e n o rm a l and
a c t i v a t e d e th y l e n e m o le c u le r e s p e c t i v e l y :
H
H
H
h:c: : c:h
h:c
H
:
c :h
T he e x i s t a n c e o f t h e a c t i v a t e d fo rm V h a s b e e n f a i r l y w e ll v e r i f i e d by
t h e w ork o f n u m ero u s i n v e s t i g a t o r s .
As p r e v i o u s l y m e n tio n e d , c a rb o n
m o n o x id e an d h y d ro g e n h a v e b e e n fo u n d t o a d d t o u n s a t u r a t e d com pounds i n
th e p re s e n c e o f d ic o b a lt o c ta c a rb o n y l
(3 ).
A lly l a c e ta te ,
e th y l
c r o t o n a t e , e t h y l a c r y l a t e , an d a l l y l a l c o h o l a r e f o u r com pounds w hich
w e re fo u n d t o u n d e rg o t h i s r e a c t i o n .
A p ro b a b le p o la r iz e d o r a c tiv a te d
fo rm o f e a c h compound i s g iv e n b e lo w .
/
-
-
H2 C-C h CH2 OOCCH3
/
CH3 CH2 OOCCH-CliCH3
VI
V II
-
/
Ch3 CH2 UOCCH-CH2
V III
/
-
H2 C-CHCH2 OH
H
The r e s p e c t i v e p r o d u c t s o b t a i n e d b y A d k in s a n d K rsek w e re y - a c e t o x y -
-
9
-
b u t y r a l d e h y d e , e t h y l / ^ - f o r m y l b u t y r a t e , f t - c a r b e th o x y p r o p ic m a ld e h y d e , a n d
7 - h y d r o x y D u ty r a ld e h y d e .
p o la riz e d
o ie c u le s , i t i s
I f t h e p r o d u c t s a r e com pared w ith t h e p ro p o se d
s e e n t h a t t h e a d d i t i o n o f t h e c a rb o n m onoxide
t a x e s p l a c e on t h e c a rb o n ato m c a r r y i n g t h e p a r t i a l p o s i t i v e c h a r g e .
/ 3- d i c a r b o n y I co m pounds( ^
ROGHpCRi
.
e x i b i t t a u tu m o rism :
RC=CHCF'
x
RG' H=CF'
XI
X II
The m o n o v a le n t s a l t s o f y S - d i c a r b o n y i com pounds
^ p o s s e s s a re s o n a tin g
s tru c tu re :
*r
RCCHrCR'
4
L
X IlI
RC=CHCR'
6_ %
XIV
M+
XV
A d iv a le n t s a l t , such a s copper a c e ty ! a c e t o n e \
e x i s t s in s c h e la te
rin g :
x
CH5C=O'
z
'OrCCH,
XVI
S t r u c t u r e s X I I I , XIV, an d XV e r e t r u e a n i o n s , w h i l e V I, V I I , V I I I ,
a n d IX p o s s e s s o n ly p a r t i a l p o s i t i v e an d n e g a t i v e c h a r g e s .
A lth o u g h I t
a p p e a r s t h a t t h e p r e f e r e n t i a l a d d i t i o n o f c a rb o n m onoxide t o u n s a t u r a t e d
com pounds i s on t h e c a rb o n atom c a r r y i n g a p a r t i a l p o s i t i v e c h a r g e , i t
i s s t i l l l i k e l y , due t o t h e r e a s o n a n c e s t r u c t u r e o f c a rb o n m o n o x id e,
th a t
n a d d i t i o n t o t h e a n io n XIV i s p o s s i b l e .
The s t r u c t u r e o f t h e d i v a l e n t
s a l t s s u c h a s XVI an d t h e s t r u c t u r e o f t h e e n d s X and X II r e s e m b le t h e
e t h y l e n i c s t r u c t u r e o f t h e u n s a t u r a t e d com pounds m ore s c t h a n t h e
-
,o n o v a le n t s a l t s .
10
-
The ^ s a t u r a t i o n i n XVI i s ,
to a c e r t a i n d e g r e e , f i x e d
due t o th e p re s e n c e o f c h e l a t i o n .
0- a c e t y l a c e t o a c e t i c e s t e r i s a t r u e e t i y l e n i c com pound, i t s a c t i v a t e d
fo rm i s p o s t u l a t e d a s :
+ Oh s O-OHOOOO2 H5
OOCCH5
XVIII
T ills d e r i v a t i v e o f a c e t o a e c t i c e s t e r s h o u ld fo rm t h e f o l l o w i n g a d d i t i o n com­
pound w i t h c a r b o n m onoxide a n d h y d r o g e n :
CHO
GH5C:CH2C00C2 H5
vOOCCH5
XIX
G ilm an a n d N e ls o n
h a v e shov.n t h a t a c i d c h l o r i d e s w i l l r e a c t w i t h
o r g a n o c a d a iu n com pounds t o fo rm good y i e l d s o f k e t o n e s .
Two s u c h r e a c t i o n s
a re :
C2 H5 CdC2 H5 +
CHf COCl
CHsCH2CH2CH2CdBr + CHf COCl
------
CH5COC2 H5
(46:.:)
CH5COC4 H9
(74 )
G r ig n a r d r e a g e n t s , on t h e o t h e r h a n d , fo rm a l c o h o l s w i t h a c i d c h l o r i d e ! ' ^ .
The f o r m a ti o n o f t h e k e to n e s w ith t h e organocadm ium com pounds i s a t t r i b u t e d
t o t h e slo w r a t e o f r e a c t i o n o f t h e s e com pounds w ith t h e c a r b o n y l g r o u p \
I t i s l o g i c a l , t h e r e f o r e , t o assum e t h a t f o r m y l f l u o r i d e s h o u ld r e a c t w i t h
organocadm ium com pounds t o fo rm a ld e h y d e s .
The p ro p o s e d r e a c t i o n o f
s e c o n d a r y - d u ty !cad m iu m b ro m id e w ith f o rm y l f l u o r i d e i s ;
C4 Hg CdBr + HCOF -------*- C4 E9CHO
-
11
-
IV . iilXHLRIMXMTAL
M a te ria ls
The a c e t o a c e t i c e s t e r and a c e t y l a c e t o n e w e re iilastm an' s p u r e o r p r a c t i ­
c a l g rad e .
use.
T h ey w e re p r o p e r l y d r i e d (when n e c e s s a r y ) a n d d i s t i l l e d b e f o r e
The i n o r g a n i c and o t h e r o r g a n i c r e a g e n t s w ere o f C .P . g r a d e and w ere
u s e d , i n m o st c a s e s , w i t h o u t f u r t h e r p u r i f i c a t i o n .
The n i c k e l c a r b o n y l,
c a rb o n m o n o x id e , a n d h y d ro g e n w ere p u r c h a s e d from t h e M a th e so n Co. and
w e re u se d w i t h o u t f u r t h e r p u r i f i c a t i o n .
A p p a r a tu s
N e a r ly a l l o f t h e h i g h p r e s s u r e r e a c t i o n s w ere c a r r i e d o u t i n a
s t a i n l e s s s t e e l , m ic r o r e a c t i o n v e s s e l , m a n u f a c tu r e d by t h e A m erican I n ­
s tr u m e n t Co.
The bomb h a d a t o t a l volum e o f 183 m l.
h e n l a r g e r v o lu m es
o f r e a c t a n t s w ere u s e d , a 500 m l P a r r bomb w as e m p lo y e d .
K ach bomb w as
p r o v id e d w i t h a h e a t i n g j a c k e t w hich w as m o u n ted i n a n o s c i l l a t i n g m ech­
a n is m .
The o s c i l l a t i n g m echanism w as pow ered b y a 1 / 6 H .P . g e a r e d h e a d
m o to r , w h ich r a n t h e c o n t e n t s o f t h e bomb fro m end t o en d a t t h e r a t e o f
36 c y c l e s p e r m in u t e .
The r e a c t i o n t e m p e r a t u r e was c o n t r o l l e d by m eans
o f a Brown m i l l i v o l t m e t e r p y r o m e te r .
T he th e m o c o u p le w as i n s e r t e d
t h r o u g h t h e e n d o f t h e h e a t i n g j a c k e t i n t o t h e r e a r p o r t i o n o f t h e bomb.
T he h i g h p r e s s u r e s , n e c e s s a r y f o r t h e r e a c t i o n s , w ere o b t a i n e d b y m eans o f
a n Am inco g a s b o o s t e r pump.
The b o o s t e r pump g i v e s a maximum c o ld p r e s s u r e
o f 6000 p . s . i .
D i c o b a l t O c ta c a r b o n y l C a t a l y s t
The p r e p a r a t i o n o f t h e a c t i v e R aney c o b a l t w as c a r r i e d o u t a c c o r d in g
t o t h e p r o c e d u r e g iv e n by P a v l i c a n d A d k in s
fo r th e p re p a ra tio n of
—
R aney n i c k e l .
12
—
The "R aney C o b a lt Aluminum C a t a l y s t Pow der" w as p u r c h a s e d
fro m t h e G ilm an P a i n t a n d V a r n is h Co.
The p r o c e d u r e f o llo w e d f o r t h e p r e (
2)
p a r a t i o n o f d i c o b a l t o c t a c a r b o n y l , was t h a t g iv e n by A d k in s a n d K rse k ' ' .
A bout 6 g o f R aney c o b a l t w as p l a c e d i n 120 m l o f e t h e r a n d p r e s s u r e d
w i t h c a rb o n m o n o x id e t o 3 4 0 0 p . s . i .
f o r 6 h o u r s a t 1 5 0 °C .
The m ix t u r e was h e a te d w i t h s h a k in g
A f t e r t h e bomb h a d c o o le d t o room t e m p e r a t u r e , t h e
p r e s s u r e was 2 6 0 0 p . s . i . ,
a d ro p o f 800 p . s . i .
The d a r k r e d d i s h brown
c l e a r s o l u t i o n w as s e p a r a t e d fro m u n r e a c t e d c o b a l t by c e n t r i f u g a t i o n and
d e c a n ta tio n .
T he c a r b o n y l w as a lw a y s u s e d i n s o l u t i o n .
I t w as fo u n d
t h a t t h e u s e o f c y c lo h e x a n e a s t h e s o l v e n t , r e s u l t e d i n a n i n c r e a s e d
f o r m a ti o n o f t h e c o b a l t c a r b o n y l .
Sodium A c e t o a c e t i c b s t e r
A o n e - l i t e r t h r e e - n e c k e d f l a s k was m o u n te d i n an i c e b a t h and f i t t e d
w ith a r e f l u x c o n d e n se r, a s e p a r a to r y f u n n e l, and a m e rc u ry -s e a le d s t i r r e r .
300 m l o f a b s o l u t e e t h y l a l c o h o l was p o u r e d i n t o t h e f l a s k a n d t o t h i s was
ad d e d 23 g ( I m o le ) o f so d iu m w i r e .
As t h e r a t e o f t h e r e a c t i o n becam e
s lo w e r , t h e i c e b a t h w as r e p l a c e d w i t h a ste a m b a t h .
A fte r th e re a c tio n
w as c o m p le te , t h e s o l u t i o n w as c o o le d t o r o a n te m p e r a t u r e w i t h c o n s ta n t
s tirrin g .
130 m l ( I m o le ) o f e t h y l a c e t o a c e t a t e w as s lo w ly a d d e d th r o u g h
t h e s e p a r a t o r y f u n n e l ( a b o u t .5 o f a n h o u r ) .
The r e f l u x c o n d e n s e r was
t h e n r e p l a c e d b y a s h o r t s t i l l h e a d , a n d t h e a l c o h o l w as rem oved by d i s ­
t i l l a t i o n a t 3 5 - 4 0 ° C ., u n d e r t h e p a r t i a l vacuum p r o v id e d b y a n a s p i r a t o r .
When m o st o f t h e a l c o h o l h a d b e e n re m o v e d , t h e p r e s s u r e was r e d u c e d ( 1 -
2 mm) a n d t h e r e m a in d e r o f t h e a l c o h o l w as d r iv e n o f f w i t h a ste a m b a t h .
T he f l a s k w as a llo w e d t o c o o l t o room t e m p e r a t u r e u n d e r t h e r e d u c e d p r e s ­
13
-
su re .
-
The y i e l d was 150 g o r 96%.
S o d iu n A c e t y la c e t o n e
A 500 m l, t h r e e - n e c k e d f l a s k w as m o u n ted i n an i c e b a th a n d f i t t e d
w ith a r e f l u x c o n d e n s e r , a g l a s s s t o p p e r , an d a m e r c p r y - s e a l e d s t i r r e r .
I n t h e f l a s k w as p l a c e d 1 5 0 m l o f a b s o l u t e e t h y l a l c o h o l a n d t o t h i s was
a d d e d 1 2 .5 g ( 0 . 5 m o le ) o f sodium w i r e .
As t h e r e a c t i o n b e g a n t o slo w
down, t h e i c e b a th was r e p l a c e d w i t h a ste a m b a t h .
A f t e r t h e r e a c t i o n was
c o m p le te , t h e sodium e th o x i d e s o l u t i o n w as c o o le d t o room t e m p e r a t u r e an d
5 0 .0 g ( 0 .5 m o le ) o f a c e t y a c e t o n e was s lo w ly a d d e d th r o u g h a s e p a r a t o r y
fu n n e l.
The p r e c i p i t a t e d e n o l a t e w as rem oved by s u c t i o n f i l t r a t i o n an d
a llo w e d t o a i r d r y f o r 2 4 h o u r s .
C o p p er A c e t o a c e t i c E s t e r
The y i e l d was 58 g o r 9 5 ^ .
(3 8 )
A s o l u t i o n o f 130 g ( I m o le ) o f a c e t o a c e t i c e s t e r , d i s s o l v e d i n
300 m l o f e t h e r , w as t h o r o u g h l y s h a k e n w i t h a s o l u t i o n o f 9 9 .8 g ( 0 .5 m o le )
o f c o p p e r a c e t a t e m o n o h y d ra te d i s s o l v e d i n 800 m l o f d i s t i l l e d w a t e r .
s a l t w h ic h p r e c i p i t a t e d o u t was f i l t e r e d
o ff.
The
The f i l t r a t e w as n e u t r a l i z e d
w ith d i l u t e sodium h y d r o x id e s o l u t i o n u n t i l i t was o n ly s l i g h t l y a c i d . The
a d d i t i o n a l p r e c i p i t a t e w h ich form ed was f i l t e r e d o f f a n d a d d e d t o t h e
f i r s t b a tc h .
T he s a l t w as w ashed u n t i l t h e f i l t r a t e g a v e n o a c i d r e a c t i o n .
The y i e l d w as H O g o r 6 8 $ .
C o p p e r A c e t y la c e t o n e (^ )
4 9 .9 g ( 0 .2 5 m o le ) o f c o p p e r a c e t a t e m o n o h y d ra te w as d i s s o l v e d i n
4 0 0 m l o f d i s t i l l e d w a t e r , h e a te d t o a b o u t 8 0 ° C ., an d f i l t e r e d .
A s o lu ­
t i o n o f 5 0 .0 g ( 0 .5 m o le ) o f a c e t y ! a c e t o n e d i s s o l v e d i n 100 m l o f w a t e r a t
8 0 °C . was a d d e d w ith s t i r r i n g t o t h e c o p p e r a c e t a t e s o l u t i o n .
w h ic h fo rm e d , w as rem oved by f i l t r a t i o n .
The s a l t
The f i l t r a t e w as t r e a t e d w ith
—
d ilu te
14
—
sodium h y d r o x id e u n t i l i t w as j u s t a c i d .
The a d d i t i o n a l p r e c i p i ­
t a t e w hich fo rm e d was f i l t e r e d o f f and a d d e d t o t h e f i r s t b a t c h .
Tne com­
b i n e d s a l t w as w ashed w i t h w a t e r u n t i l t h e f i l t r a t e no l o n g e r g a v e a n a c i d
r e a c t i o n an d t h e n d r i e d f o r 12 h o u r s a t 8 0 -8 5 ° C .
The y i e l d w as 55 g o r
85%.
Z in c A c e t v la c e t o n e (^ 8 )
To a m ix t u r e o f 1 5 .7 g ( 0 .1 2 5 m o le ) o f z i n c c a r b o n a te a n d 2 5 .0 g
( 0 .2 5 m o le ) o f a c e t y l a c e t o n e , i n a 300 m l e rle n m e y e r f l a s k , w as a d d e d
200 m l o f d i s t i l l e d w a te r.
T he m ix t u r e w as s t i r r e d f o r one h o u r and was
a llo w e d t o s t a n d f o r 12 h o u r s .
d r i e d a t 90°C .
T he s a l t w as rem oved by f i l t r a t i o n an d
T he y i e l d w as 25 g o r 75%.
O -A c e ty la c e to a c e tic A s te r
°)
130 g ( 1 .0 m o le ) o f a c e t o a c e t i c e s t e r was m ix ed w i t h 158 g ( 2 .0 m o le s )
o f p y r i d i n e a n d 170 g ( 1 .5 m o le s) o f a c e t y l c h l o r i d e w as s lo w ly added
th r o u g h a d r o p p in g f u n n e l .
( The a c e t o a c e t i c e s t e r was d r i e d o v e r c a lc iu m
s u l f a t e a n d d i s t i l l e d ; t h e p y r i d i n e was d r i e d o v e r sodium h y d r o x id e a n d
d i s t i l l e d ; t h e a c e t y l c h l o r i d e w as f r e s h l y d i s t i l l e d b e f o r e u s i n g . )
m ix t u r e was v i g o r o u s l y s t i r r e d th r o u g h o u t t h e a d d i t i o n .
a d d i t i o n , t h e s o l u t i o n becam e n e a r l y s o l i d .
e d and a llo w e d t o s i t f o r 2 d a y s .
The
At t h e end o f t h e
The f l a s k w as t i g h t l y s t o p p e r ­
300 m l o f e t h e r w as a d d ed a n d t h e
p y r i d i n e h y d r o c h l o r i d e w as f i l t e r e d o f f an d w ashed s e v e r a l t i m e s w ith e t h e r .
The f i l t r a t e
a n d e t h e r w a s h in g s w e re c o o le d t o O0G. a n d w ashed w ith a
c o ld ( 0 . 5 C . ) I-N s o l u t i o n o f sodium h y d r o x id e u n t i l t h e e t h e r l a y e r
n o l o n g e r g a v e an e n o l t e s t w ith f e r r i c c h l o r i d e .
The e t h e r s o l u t i o n w as
t h e n s h a k e n w ith c o ld w a t e r , t h e n w ith c o l d d i l u t e s u l f u r i c a c i d , and
f i n a l l y w ith c o ld w a t e r .
A f t e r d r y in g o v e r c a lc iu m c h l o r i d e , t h e e t h e r
-
15
-
w as rem oved b y d i s t i l l a t i o n a n d t h e r e m a in in g o i l w as f r a c t i o n a t e d u n d e r
red u ced p r e s s u r e .
C. a t 9 mm.
T he a c e t y l a c e t o a c e t i c e s t e r d i s t i l l e d o v e r a t 1 0 0 -1 0 2 °
The a v e r a g e y i e l d o b t a i n e d w as 1 0 0 -1 1 0 g o r 58-64/8.
R e a c ti o n o f A c s t o a c e t i c d s t e r w ith C arbon M onoxide a n d H ydrogen
1 3 .0 g ( 0 .1 m o le ) o f a c e t o a c e t i c e s t e r , 50 m l o f b e n z e n e a n d 2 g o f
R aney c o b a l t w e re p l a c e d i n t h e bomb and p r e s s u r e d t o 1630 p . s . i . w ith
h y d ro g e n a n d t h e n t o 3 7 3 0 p . s . i . w ith c a rb o n m o n o x id e .
a g i t a t e d f o r 4 h o u r s a t 1 5 0 °C .
ta in e d .
The m ix tu r e was
A p r e s s u r e d r o p o f 310 p . s . i . was ob­
The r e s u l t i n g m i x t u r e c o n ta i n e d b e n z e n e , a c e t o a c e t i c e s t e r , d i ­
c o b a l t o c t a c a r b o n y l , a n d some u n c h a n g ed c o b a l t .
R e a c tio n o f A c e ty a c e to n e w i t h C a rb o n M onoxide
1 0 .0 g ( 0 .1 m o le ) o f a c e t y l a c e t o n e , 30 m l o f e t h e r an d 15 m l o f t h e
d i c o b a l t o c ta c a r b o n y 1 - e t h e r s o l u t i o n w e re p l a c e d i n t h e bomb an d p r e s ­
s u r e d t o 3830 p . s . i . w ith c a rb o n m o n o x id e .
p . s . i . , a d r o p o f 610 p . s . i .
h o u rs.
The f i n a l p r e s s u r e was 3220
The m ix t u r e w as a g i t a t e d a t 1 0 0 °C . f o r 3
The r e s u l t i n g m ix t u r e c o n ta i n e d e t h e r , a c e t y l a c e t o n e a n d c o b a l t
a c e ty la c e to n e .
R e a c ti o n o f A c e t y la c e t o n e w ith C arbon M onoxide and H ydrogen
2 0 .0 g ( 0 .2 m o le ) o f a c e t y l a c e t o n e , 28 m l o f e t h e r a n d 15 m l o f t h e
d i c o b a l t o c t a c a r b o n y l - e t h e r s o l u t i o n w e re p r e s s u r e d t o 1980 p . s . i . w ith
h y d ro g e n and t h e n t o 4 2 0 0 p . s . i . w i t h c a rb o n m o n o x id e .
a g i t a t e d f o r 2 h o u r s a t° 1 5 0 C.
The m ix tu r e w as
2 0 .0 g o f a c e t y l a c e t o n e was r e c o v e r e d .
R e a c ti o n o f Sodium A c e t o a c e t i c A s t e r w ith C arbon M onoxide
1 5 .2 g ( 0 .1 m o le ) o f t h e s a l t , I m l o f n i c k e l t e t r a c a r b o n y l an d 40 m l
o f c y c lo h e x a n e w ere p l a c e d i n t h e bomb l i n e r .
T he bomb was p r e s s u r e d t o
-
5290 p * s . i . w ith c a rb o n
h o u rs.
m o n o x id e .
16
-
The r e a c t i o n was r u n a t IBO0 C. f o r tw o
The f i n a l p r e s s u r e was :C?70 p . e . i . , a d ro p o f 520 p . s . i .
The s o l i d
was rem oved by f i l t r a t i o n , w ashed w i t h e t h e r and a llo w e d t o a i r d r y .
s o lid
(4 g ) was r e d d is h - b r o w n i n c o l o r .
The
Vacuum a i s t i - l a t i o n o f t h e f i l t r a t e
y i e l d e d a n a d d i t i o n a l 6 g o f t h e brow n s o l i d .
A r u n u s i n g 0 .0 5 m ole o f s a l t g a v e a p r e s s u r e d ro p o f 4 5 0 p . s . i . j
m ole o f s a l t g a v e 610 p . s . i . d r o p .
0 ,1 5
B o th r u n s h ad a n I n i t i a l p r e s s u r e o f
5280 p . s . i . a n d w e re c a r r i e d o u t a t IbO 0 C. f o r two h o u r s .
7 .8 g o f t h e brow n s o l i d was r e f l u x e d f o r 5 h o u r s w i t h 100 ml o f I-N
so d iu m h y d r o x id e s o l u t i o n .
The s o l u t i o n was a c i d i f i e d w i t h d i l u t e h y d ro ­
c h lo r i c a c id and f r a c t i o n a t e d .
The f r a c t i o n c o l l e c t e d u n d e r 6 0 ° U. was
l d e n l t i f l e d a s a c e t o n e by t h e f o r m a tio n o f i t s
d e riv tiv e
(m .p . 1 2 5 °C .
2, 4 -d in ltro p h e n y ltp d ra a ln e
- i^ ) .
A s u s p e n s io n o f 2 1 ,5 g o f t h e brow n s o l i u i n 150
e t h e r , was p l a c e d i n a 200 m l t h r e e - n e c k e d f l a s k .
m l o f a n h y d ro u s
The f l a s k was p r o v id e d
w ith a n i n l e t t u b e , a m e c h a n ic a l s t i r r e r a n d a c o n a e n a e r - o u t i e t tu b e com­
b in a tio n .
The f l a s k was c o o le d i n a n i c e b a t h and d r y h y d ro g e n c h l o r i d e
was s lo w ly p a s s e d i n t o t h e s t i r r e d s u s p e n s i o n f o r 5 h o u r s .
draw n t h r o u g h t h e i n l e t t u b e f o r a b o u t one h o u r ,
and f r a c t i o n a t e d u n d e r re d u c e d p r e s s u r e .
o b t a i n e d a t 7 2 -7 2 °C . (1 2 -1 5 mm).
D r; a i r
a s th e n
Tne m ix t u r e was f i l t e r e d
6 . 9 g o f a c o l o r l e s s o i l was
B e ils te in l i s t s th e b o ilin g p o in t o f
a c e t o a c e t i c e s t e r a t 1 2 .5 mm a s 7 1 °C.
0 .7 8 g (0 .0 0 6
m o le , b a s e d on t h e
m o le c u la r w e ig h t o f a c e t o a c e t i c e s t e r ) o f t n e o i l a n d 0 .6 2 g (0 ,0 0 6 m o le )
o f p h e n y lh y d r a z in e w ere m ixed i n a s m a ll b e a k e r and a llo w e d t o s ta n d o v e r
n i g h t on a s te a m p l a t e .
The r e s u l t i n g v i s c o u s o i l was s t i r r e d w ith e t h e r ;
- 17 t h i s r e s u l t e d i n t h e f o r m a ti o n o f a w h ite c r y s t a l l i n e s o l i d .
The s o l i d
was rem oved b y f i l t r a t i o n , w ashed w i t h e t h e r a n d d r i e d a t IOO 0 C.
r e c r y s t a l l i z a t i o n from a l c o h o l , i t m e l te d a t 1 2 7 0C.
A fte r
U s in g t h e same p r o ­
c e d u r e , e t h y l a c e t o a c e t a t e fo rm s 3 - m e t h y l - l - p h e n y l - 5- p y r a z o l o n e ( 1 7 ) ( 2 7 ) i
w h ic h h a s a m e l t i n g p o i n t o f 127 C.
By u s in g a n e x c e s s o f p h e n y l-
h y d r a z i n e , b o th t h e o i l an d a c e t o a c e t i c e s t e r '-*-7) xl ^ ) y i e l d a h
in s o lu b le w h ite s o l i d .
s itin g ,
The o i l w a s, t h e r e f o r e , a c e t o a c e t i c e s t e r .
R e a c ti o n o f Sodium A c e t y la c e to n e w i t h C arb o n M onoxide
1 2 .2 g ( 0 .1 m o le ) o f t h e s a l t , 25 m l o f e t h e r a n d 15 m l o f t h e d i c o b a l t
o c ta c a r b o n y 1 - e t h e r s o l u t i o n w e re p l a c e d i n t h e bomb a n d p r e s s u r e d t o 3730
p . s . i . w ith c a rb o n m o n o x id e .
C.
Uhe m ix t u r e w as a g i t a t e d f o r 2 h o u r s a t 1 5 0 °
A d ro p o f 360 p . s . i . w as o b t a i n e d .
t i o n a n d w ashed t w i c e w ith e t h e r .
m l o f d i s t i l l e d w a t e r f o r one h o u r .
upon d i s t i l l a t i o n .
T h e s o l i d was rem oved b y f i l t r a ­
7 .2 g o f t h e s o l i d was r e f l u x e d w i t h 200
A bout one m l o f a c e t o n e was o b t a i n e d
The r e s i d u e c o n s i s t e d o f a r e s i n o u s m a t e r i a l w h ich
c o u ld n o t b e i d e n t i f i e d .
7 .2 g o f t h e o r i g i n a l s a l t g a v e 2 . 5 m l o f a c e t o n e
when r e f u l x e d f o r I h o u r w ith 100 m l o f d i s t i l l e d w a t e r ,
a
d r o p o f 350 p . s . i .
w as o b t a i n e d when 40 m l o f e t h e r w as s u b j e c t e d t o t h e same c o n d i t i o n s .
R e a c ti o n s o f Z in c and C o p p er ^ c e t y l a c e t o n e w ith C arbon M onoxide and H ydro g en
T y p i c a l r u n s i n t h e p r e s e n c e o f b o th n i c k e l t e t r a c a r b o n y l and d i c o b a l t
o c t a c a r b o n y l r e s u l t e d i n t h e r e d u c t i o n o f t h e c o p p e r compound t o m e t a l l i c
c o p p e r and a c e t y la c e to n e .
The z i n c s a l t , u n d e r t h e sam e c o n d i t i o n s was
r e c o v e r e d u n c h a n g e d a t t h e end o f t h e r e a c t i o n s .
R e a c ti o n o f O - A c e t y l a c e t o a c e t i c Z s t e r w ith C arbon M onoxide a n d H ydrogen
A d e s c r i p ti o n o f a t y p i c a l ru n i s g iv e n a s fo llo w s :
3 4 .4 g ( 0 .2 m o le )
—
18
—
o f a c e t y l a c e t o a c e t i c e s t e r , 4 0 m l o f b e n z e n e and 2 g o f H aney c o b a l t c a t a ­
l y s t w ere p l a c e d i n t h e bomb.
The m ix tu r e was p r e s s u r e d t o 1 5 0 0 p . s . i . and
3400 p . s . i . w ith h y d ro g e n a n d c a rb o n m o n o x id e r e s p e c t i v e l y .
was a g i t a t e d f o r 4 h o u r s a t 1 5 0 °C .
ta in e d .
T he m ix tu r e
A p r e s s u r e d ro p o f 1750 p . s . i . was ob­
F r a c t i o n a t i o n o f t h e p r o d u c t y i e l d e d t h e f o llo w in g f r a c t i o n s :
1.
B enzene.
2.
16 m l o f a c l e a r , low b o i l i n g l i q u i d .
3.
17 m l o f a c o l o r l e s s o i l ( 5 0 - 8 0 ° C ., 12 mm).
4.
17 m l o f a c o l o r l e s s o i l ( 8 5 - 1 0 0 ° C ., 12 mm).
5.
23 m l o f a h i g h b o i l i n g r e s i d u e .
F r a c t i o n 2 c o n ta i n e d 3 . 4 g o f a c e t i c a c i d , t h e r e m a in d e r b e in g b e n z e n e .
F r a c t i o n s 3 a n d 4 w e re r e d i s t i l l e d t o g i v e 15 g o f a c o l o r l e s s o i l , X
( b . p . 8 8 -9 0 ° C . a t 11 mm), 4 . 1 g o f a c e t i c a c i d , and some h i g h e r b o i l i n g
m a te ria l.
I d e n t i f i c a t io n o f U il X
T he o i l w as i n s o l u b l e i n w a t e r an d % NaHCOg s o l u t i o n ;
NaOH, c o n c e n t r a t e d HgSO^ a n d 85$ H^PO/^.
y e llo w c o l o r e d s o l u t i o n .
s o l u b l e i n 5/»
W ith t h e s u l f u r i c a c i d i t g a v e a
A s m a ll am ount o f
p ro d u c e d a b ro w n ish
p re c ip ita te .
I t s r e a c t i o n w ith l i t m u s was a c i d .
I t g a v e a s i l v e r m i r r o r w ith
T o l l e n 1s r e a g e n t a n d a n im m e d ia te d e e p p u r p l e c o l o r w i t h b a i l i f f ' s r e a g e n t .
I t s 2 , 4 - d i n i t r o p h e n y ! h y d r a z i n e d e r i v a t i v e m e lte d a t 4 9 -5 0 ° C .
A s e ra i-
c a r b a z o n e d e r i v a t i v e c o u ld n o t be o b t a i n e d .
6 m l o f t h e o i l was r e f l u x e d f o r 24 h o u r s w ith 100 m l o f 20$ HNO-^.
The s o l u t i o n was e v a p o r a te d t o d r y n e s s on a steam b a t h , w i t h r e p e a te d a d ­
d i t i o n s o f d i s t i l l e d w a t e r t o rem ove t h e l a s t t r a c e s o f n i t r i c a c i d .
A
— 19 —
w h i t e , c r y s t a l l i n e s o l i d was fo rm e d ,
i t w as i d e n t i f i e d a s s u c c i n i c a c i d
t h r o u g h i t s n e u t r a l i z a t i o n e q u i v a l e n t ( o b t a i n e d , 5 9 .1 2 ; c a l c u l a t e d , 5 9 .0 5 )
a n d i t s p - t o l u i d i n e d e r i v a t i v e (rn .p . o b t a i n e d , 2 6 0 ° C .; l i t e r a t u r e v a l u e ^
2 6 0 ° C .) .
The m o le c u la r w e ig h t o f t h e o i l was d e te r m in e d b y t h e f r e e z i n g p o i n t
m e th o d , t h e s o l v e n t u s e d w as b e n z e n e .
t o i n f i n i t e d i l u t i o n w as 1 4 7 .
The v a l u e o b ta in e d by e x t r a p o l a t i o n
I n v e s t ig a t io n re g a rd in g th e i d e n t i t y o f t h i s
compound i s b e in g c o n t i n u e d .
P r e p a r a t i o n o f F orm yl F l u o r i d e
T he a p p a r a t u s w hich was u s e d c o n s i s t e d o f a 200 m l ro u n d b o tto m f l a s k
f i t t e d w ith an e f f i c i e n t r e f l u x c o n d e n se r.
The t o p o f t h e c o n d e n s e r was
c o n n e c te d t o a s e r i e s o f tw o l a r g e U - t u b e s , 2 5 -3 0 cm i n h e i g h t .
The o u t l e t
o f t h e se c o n d U -tu b e w as c o n n e c te d t o two c a lc iu m c h l o r i d e t u b e s , t h e
f i r s t c o n ta i n e d sodium h y d r o x id e p e l l e t s a n d t h e se co n d c o n ta i n e d f u s e d
c a lc iu m c h l o r i d e .
T he a p p a r a t u s w a s f l u s h e d w ith h o t , d r y n i t r o g e n f o r 2
h o u r s im m e d ia te ly b e f o r e u s i n g .
The a n h y d ro u s fo rm ic a c i d , u s e d i n t h e p r e ­
p a r a t i o n , w as p r e p a r e d b y r e f l u x i n g c o m m e rc ia l 98 - 100,0 f o rm ic a c i d w ith
p h t h a l i c a n h y d r id e f o r 2 - 3 h o u r s a n d t h e n d i s t i l l i n g t h e m i x t u r e .
19 m l ( 0 .5 m o le) o f a n h y d ro u s f o rm ic a c i d , 57 m l ( 0 .5 m o le ) o f b e n ­
z o y l c h l o r i d e and 2 1 g ( 0 .5 m o le) o f sodium f l u o r i d e w e re p l a c e d i n t h e
ro u n d b o tto m f l a s k .
The f l a s k w as t h e n c o n n e c te d t o t h e c o n d e n s e r , t h e
t e m p e r a t u r e o f w hich w as h e l d a t 1 0 -1 5 ° C .
The f i r s t U -tu b e w as s u r ­
ro u n d e d by a n i c e - s a l t b a t h a n d t h e s e c o n d U -tu b e was s u r r o u n d e d by a d r y
ic e - a c e to n e b a th ( - 8 0 ° C .) .
u n t i l th e r e a c tio n b eg an .
The r e a c t i o n f l a s k was h e a te d on a steam b a th
The r e a c t i o n p ro c e e d e d so r a p i d l y a t t im e s .
-Z O t h a t i t was n e c e s s a r y t o rem ove t h e ste a m b a t h and c o o l t h e f l a s k w ith
c o ld w a t e r .
As t h e r a t e o f r e a c t i o n b e c a n t o d e c r e a s e , t h e ste a m b a th
w as r e p l a c e d a n d h e a t i n g was c o n tin u e d f o r 30 m in u t e s ,
i'he a v e r a g e y i e l d
o f f o r m y l f l u o r i d e , w h ic h c o l l e c t e d i n t h e se co n d U - tu b e , w as 7 -8 g o r
2 9 -3 4 $ .
S e c o n d a ry - B u tv h n a ^ n e slum B rom ide
T he g e n e r a l p r o c e d u r e f o r t h e p r e p a r a t i o n o f a G r i g n a r d r e a g e n t i s
g i v e n b y G ilm a n , Z o e l l n e r a n d D ic k e y
.
I n a t h r e e - n e c k e d f l a s k f i t t e d w ith a r e f l u x c o n d e n s e r , a m e rc u ry s e a l s t i r r e r , a n d a d r o p f u n n e l w ere p l a c e d 3 g ( 0 .1 2 5 m o le ) o f d r y mag­
n e siu m t u r n i n g s , 25 m l o f a b s o l u t e e t h e r , a n d a s m a ll c r y s t a l o f i o d i n e .
17 g ( 0 .1 2 5 m o le ) o f s e c o n d a r y - b u t y l b ro m id e was p l a c e d i n t h e d ro p f u n n e l
an d a f t e r 10 d r o p s o f t h i s h a l i d e h a d b e e n ad d ed t o t h e r e a c t i o n f l a s k ,
75 m l o f a b s o l u t e e t h e r w as ad d e d t o t h e d ro p f u n n e l .
s t a r t e d by m eans o f g e n t l e h e a t i n g .
The r e a c t i o n was
Once t h e r e a c t i o n h ad b e g u n , t h e mo­
t o r d r i v e n s t i r r e r w as s t a r t e d and t h e s e c o n d a r y - b u t y l b r o m i d e - e th e r s o l ­
u t i o n w as a llo w e d t o f lo w i n t o t h e f l a s k a t a r a t e o f 1 -2 d r o p s p e r s e c o n d .
The s t i r r i n g w as c o n tin u e d f o r an a d d i t i o n a l 30 m in u te s a f t e r t h e c o n t e n t s
o f t h e d ro p f u n n e l h a d b e e n a d d e d t o t h e f l a s k .
The e t h e r s o l u t i o n o l t h e
s e c o n d a ry -b u ty lm a g n e s iu m b ro m id e w as u s e d imr e d i a t e l y t o p r e p a r e t h e cad ­
mium com pound.
S e c o n d a ry -G u t y l cadmium B rom ide
T he p r o c e d u r e s u g g e s te d by C ason
(7 )
w as f o llo w e d f o r t h e p r e p a r a t i o n
o f t h i s com pound.
An a d d i t i o n a l 50 m l o f a b s o l u t e e t h e r was ad d ed t o t h e G rig n a r d r e -
-
21
a g e n t p re p a re d by th e above p ro c e d u re .
-
The d r o p f u n n e l w as r e p l a c e d by a
l a r g e t e s t t u b e c o n t a i n i n g 2 2 .9 g ( 0 .1 2 5 m o le ) o f a n h y d ro u s cadmium c h l o r i d e .
The c o n n e c t io n b e tw e e n t h e f l a s k a n d t h e t e s t t u b e w as a s h o r t p i e c e o f
Tygon t u b i n g .
The cadmium c h l o r i d e w as a d d e d t o t h e s e c o n d a r y - b u ty lm a g n e s -
ium b ro m id e —e t h e r s o l u t i o n d u r in g a p e r i o d o f 15—20 m i n u t e s .
The s o l u t i o n
w as v i g o r o u s l y s t i r r e d th r o u g h o u t t h e a d d i t i o n an d f o r a p e r i o d oi 30 m in­
u t e s f o ll o w i n g t h e a d d i t i o n .
S y n t h e s i s o f 2 - I - ie t h .y l- l- b u t a n a l
The f o r m y l f l u o r i d e w h ic h w a s c o l l e c t e d i n t h e se c o n d U - tu b e , was
d i s t i l l e d i n t o a g l a s s j a c k e t e d d ro p f u n n e l c o n t a i n i n g 30 m l o f a b s o l u t e
e th e r.
The d ro p f u n n e l j a c k e t w as f i l l e d w i t h a d r y i c e - a c e t o n e m ix t u r e .
The l a r g e t e s t t u b e c o n n e c te d t o t h e f l a s k c o n t a i n i n g t h e organocadm ium
compound was r e p l a c e d by t h i s d r o p f u n n e l .
T he organocadm ium b ro m id e -
e t h e r s o l u t i o n was c o o le d w ith a d r y i c e —a c e to n e b a th a n d t h e fo rm y l
f l u o r i d e - e t h e r s o l u t i o n w as a d d ed o v e r a p e r i o d o f one m i n u t e .
The m ix­
t u r e was s t i r r e d d u r in g t h e a d d i t i o n a n d f o r t h r e e h o u r s t h e r e a f t e r .
Tne
m ix tu r e was a ll o w e d t o come t o room t e m p e r a t u r e by s t a n d i n g o v e r n i , n t .
The m ix t u r e w as h y d r o l i z e d w i t h 30 m l o f d i l u t e s u l f u r i c a c id and t h e
e t h e r l a y e r w as s e p a r a t e d .
50 m l o f e t h e r .
T h e a q u e o u s s o l u t i o n w as e x t r a c t e d t w i c e w ith
The e t h e r s o l u t i o n s w e re co m b in e d , d r i e d o v e r c a lc iu m
c h l o r i d e , and f r a c t i o n a t e d .
A f t e r t h e e t h e r had b e e n re m o v e d , 3 m l o f a
c o l o r l e s s l i q u i d ( b . p , 85—90 °C . , 640 ram) w as o b t a i n e d .
T h i s l i q u i d g a v e a p o s i t i v e T o l l e n 1s a n d b c h i f f 1s t e s t .
d i n i t r o p h e n y lh y d r a z in e d e r i v a t i v e m e lte d a t 120 C.
I t s 2 ,4 -
h u n t r e s s and
-
K u llik e n
2 2
-
g iv e t h e b o i l i n g p o i n t o f 2 - m e t h y l - l - b u t a n a l a n d t h e m e l t i n g
p o i n t o f i t s 2 , 4 - d i n i t r o p h e n y lh y d r a z o n e d e r i v a t i v e a s 9 2 - 9 3 ° C . (7 6 0 mm)
and 1 2 0 . 5°C . r e s p e c t i v e l y .
The y i e l d o f 2 - m e t h y l - l - b u t a n a l w as 28% o f
th e o re tic a l.
R e a c tio n o f F o n ity l F l u o r i d e w ith O th e r Organocadm ium B ro m id e s
By u s i n g t h e same p r o c e d u r e , ph en y lcad m iu m b ro m id e g a v e a 4-6% y i e l d
o f b e n z a ld e h y d e .
I t w as i d e n t i f i e d b y i t s 2 , 4 - d i n i t ro p h e n y I h y d r a z one
d e r i v a t i v e ( n . p . o b t a i n e d , 2 3 5 ° 0 . ; l i t e r a t u r e v a lu e ^ 6 ) ^ 2 3 5 - 2 3 7 ° C .) .
N o rm a l-b u ty lc a d m iu m b ro m id e g a v e a v e r y s m a ll y i e l d o f an u n i d e n t i f i e d
a ld e h y d e , p r o b a b l y n o r m a l - v a l e r a l d e h y d e .
- 23 V.
DISCUSSION QF E.v '^KlM^NTAL RESULTS
T he f a c t t h a t no d e f i n i t e r e a c t i o n r e s u l t e d b e tw e en t h e
-d ic a rb o n y l
com pounds o r t h e i r m e t a l e n o l a t e s and c a rb o n m onoxide i n d i c a t e s t h a t t h e s e
com pounds do n o t p o s s e s s t h e n e c e s s a r y s t r u c t u r e f o r s u c h a n a d d i t i o n .
A lth o u g h t h e
- d i c a r b o n y l com pounds a n d t h e i r m e ta l e n o l a t e s a r e a c t i v a t e d
by r e s o n a n c e , i t a p p e a r s t h a t t h e i r a c t i v a t e d form b e a r s n o s i m i l a r i t y t o
t h e a c t i v a t e d form o f u n s a t u r a t e d com pounds.
I t w ould seem l o g i c a l , t h e r e -
f o r e , t h a t i f a compound w as i n c a p a b l e o f fo rm in g a n a c t i v a t e d m o le c u le
c o n t a i n i n g a p o s i t i v e l y c h a rg e d c a rb o n a to m , no a d d i t i o n u n d e r t h e con­
d i t i o n s u s e d w o u ld o c c u r .
The r e a c t i o n o f O - a c e t y l a c e t o a c e t i c e s t e r w ith c a rb o n m onoxide an d
h y d ro g e n i n t h e p r e s e n c e o f d i c o b a l t o c t a c a r b o n y l s u p p o r t s t h e t h e o r y o f
a d d i t i o n g iv e n a b o v e .
Compound XIX e v i d e n t l y l o s e s a m o le c u le o f a c e t i c
a c i d a n d t h e u n s a t u r a t e d compound fo rm e d i s f u r t h e r h y d r o g e n a te d , i n t h e
p r e s e n c e o f t h e d i c o b a l t o c ta c a r b o n y l
t o form e t h y l / 3 - io r r a y I b u t y r a t e .
T he e v id e n c e t h u s f a r o b t a i n e d , i n d i c a t e s t h a t t h e u n i d e n t i f i e d o i l X i s
e t h y l /3 - f o r a y ! b u t y r a t e .
The f o r m a ti o n o f s u c c i n i c a c i d by t h e o x i d a t i o n
o f o i l X c a n n o t b e a c c o u n te d f o r .
The s y n t h e s i s o f a ld e h y d e s by t h e r e a c t i o n o f f o rm y l f l u o r i d e w ith
organocadm ium com pounds h a s d e f i n i t e l y b e e n shown t o b e p o s s i b l e .
Trie
h ig h s u s c e p t i b i l i t y o f fo rm y l f l u o r i d e t o t r a c e s o f m o i s t u r e i s one o f t h e
f a c t o r s w h ic h c a u s e s t h e lo w y i e l d s w h ich w e re o b t a i n e d .
f o rm y l f l u o r i d e r e p o r t e d b y Nesm eyanov a n d Kahn ^2 1 ^was W
T he y i e l d o f
of th e o re tic a l.
T he i n c r e a s e d y i e l d w h ich w as o b t a i n e d i s a t t r i b u t e d t o t h e u s e o f sodium
f l u o r i d e i n p l a c e o f p o ta s s iu m f l u o r i d e w h ic h was u s e d b y N esm eyanov and
K ahn.
^
—
24
—
V I . SUMMARY
1.
I t h a s b e e n shown t h a t no d e f i n i t e r e a c t i o n o c c u r s b e tw e e n / 9 - d i c a r -
b o n y l com pounds o r t h e i r m e t a l e n o l a t e s a n d c a rb o n m o n o x id e o r c a rb o n
m on o x id e a n d h y d ro g e n a t h i g h p r e s s u r e s a n d i n t h e p r e s e n c e o f e i t h e r
d ic o b a lt o c ta c a rb o n y l o r n ic k e l t e t r a c a r b o n y l .
2.
A r e a c t i o n h a s b e e n shown t o t a k e p l a c e b e tw e en c a rb o n m o n o x id e , h y d r o ­
gen and O - a c e ty la c e to a c e tic e s t e r in th e p re se n c e o f d i c o b a lt o c ta c a rb o n y l.
A m o d e ra te y i e l d o f a n u n i d e n t i f i e d a ld e h y d e w as o b t a i n e d .
3.
T he s y n t h e s i s o f 2 - m e t h y l - l - b u t a n a l b y t h e r e a c t i o n o f f o r a y l f l u o r i d e
w ith s e c o n d a r y - b u ty lc a d n iu m b ro m id e i s g i v e n .
4.
The s y n t h e s i s o f o t h e r a ld e h y d e s th r o u g h t h e u s e o f f o r m y l f l u o r i d e
and organocadm ium h a l i d e s i s m e n tio n e d .
-
V II.
25
-
ACKNOWLEDGMENT
T he a u t h o r w is h e s t o t a k e t h i s o p p o r t u n i t y t o e x p r e s s h i s s i n c e r e
a p p r e c i a t i o n a n d t h a n k s t o D r. L a u re n c e 0 . B in d e r , J r .
f o r h is p e rso n a l
g u id a n c e a n d i n s p i r a t i o n d u r in g t h i s r e s e a r c h , and t o t h e s t a f f o f t h e
C h e m is try D e p a rtm e n t f o r t h e i r many h e l p f u l s u g g e s t i o n s .
t o th a n k th e O ffic e o f N aval
He a l s o w is h e s
R e s e a rc h o f t h e D e p a rtm e n t o f N avy f o r t h e
g r a n t w h ic h m ade t h i s i n v e s t i g a t i o n p o s s i b l e .
- 26 V III.
LITERA Tim CITED AND CONSULTED
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-
27
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