The synthesis of 2-methyl butanal by reaction of n-butyl isocyanide with secondary-butylcadmium
bromide, pt. 1 : a study of the reactions between carbon monoxide and the sodium salt of nitroethane,
pt. 2
by John M Bruce Jr
A THESIS Submitted to the Graduate Committee in partial fulfillment of the requirements for the
degree of Master of Science in Chemsitry at Montana State College
Montana State University
© Copyright by John M Bruce Jr (1949)
Abstract:
Part I.
2-methyl butanal was prepared by the following sequence of reactions: [Formulas not Captured by
OCR] A light yellow liquid was obtained as product. Confirmatory tests were run using small portions
of the final product, and close agreement was found to exist between these results and the actual data
pertaining to 2-methyl butanal. The 2,4-dinitrophenylhydrazone derivative was prepared from the final
product, and its melting point determined.
Experimental details of the above procedure ere presented, along with an explanation of the
experimental results.
Part II A reaction mixture consisting of the sodium salt of nitroethane and nickel carbonyl in a solvent
of cyclohexane, was subjected to high pressures of carbon monoxide. This reaction mixture yielded,
upon hydrolysis, a substance possessing a solubility which could not readily be accounted for. This
substance is not obtained in the absence of nickel carbonyl, or when cyclohexane itself is subjected to
carbon monoxide under pressure in the presence of nickel carbonyl. The unidentified substance is
decomposed by steam distillation, simple distillation, and vacuum distillation, and cannot be
crystallised satisfactorily even at low temperatures. Positive Schiff's and Tollen's tests were obtained by
use of the appropriate reagent and the unknown substance. Derivatization of the unidentified material
has not been possible.
Additional investigation of the unidentified substance is being conducted. Part
I,
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sutize op m gaoE m A m i.
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',JOBS M> BvBGOB,'
A fHBSlS
submit
• ’ ;’
to the Graduate Oomslttea
,.
p a r tia l fulfillm ent- Of the requirements
for the decree of
Master o f Science in Chemistry
at
Montana State. College
Approyedt
"'I'WWjIlO.' HI.U'
Head o f M ajor D epartm ent
Chairman, Examining Committee
ife a n ^ G -H ^ d u a te ^ ris io ft
Bozeman, M ontana
June 1949
- 2 -
TABLE Of CONTENTS
Sgim
I-
I.
ABSTRACT ...........................
4
II.
INTRODUCTION ..................
5
III.
theoretical d iscu ssio n
7
..................
10
IV.
experimental
S il v e r c y e n ld e . . ...........................
10
n -B u ty l le o c y s n td e ..........................
10
Secondsry-butylm s»nee Ium bromide
11
Secondsry-butylcedm lum brom ide.
12
S y n th e s is o f 2-m ethyl b n te n e l .
13
T e s ts o f c o n firm a tio n ..................
14
P r e p e r e tlo n of th e d e r iv a tiv e ,
16
V.
DISCUSSION OP EXPERIMENTAL RESULTS
18
VI.
SUMMARY.........................................................
20
PART H .
I.
ABSTRACT......................................................................
21
II.
INTRODUCTION......................................................................................................
22
III.
THEORETICAL DISCUSSION................................................................................
23
EXPERIMENTAL
................................................................................
2?
A p p p r e tu s ............................................................................................ .
27
P r e p p r e tlo n o f th e sodium s a l t o f n i t roe t h e n # ..................
28
!ty p ica l p ro c e d u re f o r e x p e rim e n ta l r u n s .................................
29
IV.
8 9 3 "3
(T able
o f C o n ten ts )
A.
C.
V.
31
(1 )
E e e t ..............................................................................................................31
(2)
O m ission o f N ic k el C arb o n y l.........................................................31
(3 )
O m ission o f S a l t ......................................................... ....
(b )
Use o f S a lt c o n ta in in g m ethyl a lc o h o l........................................ 31
( 5)
In p re se n c e o f hydro .............................................................................32
(6)
H y d ro ly sis o f run p re v io u s to p re s s u rin g w ith
carb o n m o n o x i d e ..................................
31
32
V a ria tio n s in p r e s s u r e ..................................................................33
A ttem pts a t P u r i f i c a t i o n o f Layer B . . . . . . . . . . .
.
33
(1 )
D i s t i l l a t i o n a t o rd in a ry p r e s s u r e ...........................................
33
(2 )
Vacuum d i s t i l l a t i o n . . . . . . .
.......................................
3^
(3 )
Steam d i s t i l l a t i o n ..........................................................................
3^
(h )
C r y s t a l l i z a t i o n a t Low T e m p e ra tu re .............................................35
A ttem pts to I d e n tif y Layer B and P rep a re D e r iv a tiv e s . . . .
(1 )
S c h i f f *s end T o lle n 1s T e s t .......................... ..............................35
(2 )
2 , U -dInltro p h e n y Ih y d raz In e and sem lcarb azld e hydro­
c h lo rid e ..................................
35
35
(3)
S c h i f f 1s Base F o rm atio n . .................................................................. 36
(b )
A c e ta l fo rm atio n ....................................................................................3&
•(5)
O x id a tio n ....................................................
36
R e d u c t i o n ..................................
38
(6 )
D.
JaS-
E f f e c t o f V a ria tio n s In P ro ced u re on Y ield o f P ro d u c t . . .
(? )
B.
- 3 -
A R e a c tio n In v o lv in g th e S a lt o f 2 -N itro p ro p e n e ...........................38
DISCUSSION Of EXPERIMENTAL RESULTS...............................................
40
VI.
SUMMARY.......................................................................................................................... 42
V II.
ACKNOWLEDGMENT.............................................................................................................4-3
V III.
LITERATURE CITED AND CONSULTED......................................................................44
— ^4- —
I*
abstract
£zrk I.
2- methy I b u te n e I wee p re p sre d by th e fo llo w in g sequence o f r e e c tlo n e :
CH1CH2CH2CH2N=C + CH1CH2-IJHCdBr
H
Br
H
H
A l i g h t yellow l i q u i d was o b ta in e d se p ro d u c t.
C o n firm ato ry t e s t s
were ru n u s in g em ail p o r tio n s o f th e f i n a l p ro d u c t, end c lo s e agreem ent
wee found to e x i s t betw een th e se r e s u l t s end the a c tu a l d a ta p e r ta in in g
to 2-m ethyl b u ta n e I .
The 2 f b -d in itro p h e n y lh y d re zone d e r iv a tiv e was p re ­
p a re d from th e f i n a l p ro d u c t, and I t s m e ltin g p o in t d e term in e d .
E x p erim en tal d e t a i l s o f th e above p ro ced u re a re p re s e n te d , along w ith
an e x p la n a tio n o f th e e x p e rim e n ta l r e s u l t s .
- 5 -
JI.
INTRODUCTION
The ie o c y p n ld e s, o r c erb y lem ln ee, RNC, e x i s t me c o lo r le s s liq u id s ,
w hich pre in s o lu b le In w e te r, end hpve a pp r t l c u l f r l y d is a g re e a b le odor.
The v ap o rs a re v e ry to x ic , cap a b le o f c au sin g d iz z in e s s end v o m itin g I f in ­
h a le d o v e r a s u f f i c i e n t p e rio d o f tim e.
The cerbylem lnes a re v ery r e a c tiv e compounds.
Some g e n e r a l r e a c tio n s
in v o lv in g I so cyan id ee and o th e r m o lecu les a re l i s t e d by Nef^
and C o h e n ^ ^ .
Oilmen^ ^ ,
I t h a s been d em o n strated th a t th e I socyanide group e n te r s
in to an a d d itio n r e a c tio n w ith th e O rig n erd r e a g e n t; i t e ls e e n te r s in to
r e a c tio n s w ith s u l f u r and c h lo rin e a t te m p e ra tu re s above IOO0 C1 w ith th e
fo rm a tio n o f HNCS and ENCtCljg, r e s p e c tiv e ly .
F u rth erm o re, i t adds a c id
c h lo r id e s to g ive a lk y llm ld o c h lo r id e s , HNiC(Cl)COR.
Sachs and L o e v y ^ ? ) g ive th e com plete p ro ced u re f o r th e p re p a ra tio n o f
benzaldehyde by a r e a c tio n in v o lv in g phenylm agnesiua brom ide and methyl Ie o c y a n ld e .
method.
No o th e r ald eh y d es a re re p o rte d to have been s y n th e s iz e d by t h i s
On th e b a e is o f the r e s u l t s o b ta in e d from a tte m p ted in te r a c t io n
betw een phenylm agneslum bromide end v a rio u s a la p h a tic and aro m a tic Iso c y a n id e s . Oilmen and H eck ert
(o)
concluded t h a t o n ly m ethyl lso cy an id e wee
o f s u f f i c i e n t r e a c t i v i t y to combine w ith th e O rignard r e a g e n t.
The d e s i r a b i l i t y o f d e v e lo p in g . th e method o f Sachs and Loevy in to a
good aldehyde s y n th e s is i s a p p a re n t, s in c e ald eh y d es a re th e s t a r t i n g
m a te r ia ls from which a la rg e number o f im p o rtan t compounds may be made.
The s e le c tio n o f th e orgenocedmlum compound as sn a l t e r n a t i v e o rg sn o m e ta llie compound was prom pted by th e c o n c lu sio n s drawn from th e e x p e ri­
m ental work o f Oilman and Nelson^
and de B o n n e v i l l e ^ .
These w orkers
found th a t th e r e l a t i v e l y low er r e a c t i v i t y o f th e orgpnocadmium compounds
caused th e a r r e s t i n g o f subsequent harm fu l i n t e r a c t i o n betw een th e p ro d u c ts
formed d u rin g an i n i t i a l s ta g e .
Inasmuch as organom e ta llic compounds
d i f f e r g e n e r a lly in deg ree o r r a te o f r e a c tio n , r a t h e r th an in k in d , i t
was assumed th a t th e organocadm lua compound would add to th e ieo cy an ld e
group in a manner s im ila r to t h a t o f the G rignard re a g e n t.
I t was hoped
t h a t a s in g le a d d itio n p ro d u c t would r e s u l t from the r e a c tio n between th e
eerbylam ine and th e organocadmium compound.
Oilman and M e ls o n ^ ^ have t r e a t e d th e s u b je c t o f o rg a n o m e ta llic
compound p r e p a r a tio n q u ite e x te n s iv e ly ; how ever, some d isag ree m e n t e x is t s
(<)
betw een th e se men and Cason J
w ith re g a rd to the s t a b i l i t y o f organo­
cadmium compounds e t e le v a te d te m p e ra tu re s .
A ccording to th e l e t t e r , th e
organocadmium compounds can be p re p a re d a t room tem p eratu re w ith o u t decom­
p o s i t i o n o f th e p ro d u c t, w h ile Gilman and N elson s t a t e t h a t a cooled
r e a c tio n m ixture i s n e c e s sa ry to p re v e n t d eco m p o sitio n .
C a so n 's procedure
was th e one used in th e p r e p a r a tio n o f th e organocadmium compounds in th le
w ork.
n -B u ty l is o c y a n id e was s e le c te d in s te a d o f m ethyl iso c y a n id e as a
s u ita b le eerbylam ine because o f th e g r e a t e r convenience in h a n d lin g , and
a ls o to check G ilm an 's o b s e rv a tio n on th e u n s u i t a b i l i t y o f th e h ig h e r
m o le c u la r w eight is o c y a n id e s .
P a r t I in c lu d e s th e s y n th e s is o f 2-m ethyl b u ta n e ! from a re a c tio n be­
tw een n -b u ty l iso cy a n id e end secondery-butylce& m ium brom ide.
-
III.
? -
T ^ O IS tTIOL DISCUSSION
/ g r e a t d e e l o f work h as been, done In o rd e r to a s c e r t a i n th e e le c tr o n i c
c o n f ig u r a tio n o f the leo cy en id e g ro u p .
Two s t r u c tu r e s e re now reg ard ed es
most n e a r ly re p re s e n tin g th e c o n f ig u r a tio n .
»lef
(19)
, an e a r l y I n v e s tig a to r ,
su g g este d th e s tr u c tu r e I which would in v o lv e a s e x te t o f e le c tr o n s on th e
carbon atom .
Langmuir, in 1919, p ro p o sed form I I .
.Actual measurements o f
(1 3 ), ( 1*0
d ip o le moments c a r r ie d o u t by Hammich, Sedgwick, New and S u tto n
ten d to confirm th e v a l i d i t y o f form I I .
A d d itio n a l su p p o rt o f form I I is
( 18)
g iv en by th e p a ra c h o r v a lu e s o b ta in e d by Llademann and W iegrebe
KS * Cr
BH * Cr
I
II
S tr u c tu r e I I is th e sem ip o lar form gnd th e s ta b le c o n fig u ra tio n , w h ile
I , th e s e x te t s t r u c t u r e , i s reg ard ed es the a c tiv e form .
The c o n fig u ra tio n s
p re s e n te d can e a s i l y account f o r such a d d itio n p ro d u c ts a s a lk y lim in o c srb o n y l c h lo rid e and a lk y l I so th io c y a n a te from a r e a c tio n betw een an is o cyanide end c h lo rin e end s u lf u r r e s p e c tiv e ly .
R r N t r C r
+
. . . .
. Cl :
: Cl r Cl r -------» R t N r r C
. . . .
"
- 'c i;
R r Nr r Cr
+
S r -------- > R r N r t C t r S r
The c o n c lu sio n s drawn from th e e x p e rim e n ta l work o f Q -Illile n d end B la n (7)
c h e rd w on th e r e a c tio n s betw een carbon monoxide a s n ic k e l carb o n y l and
phenylmagnesium brom ide a re p re s e n te d h e re so t h a t an analogy may be made
betw een t h e i r work end th e mechanism o f th e a d d itio n o f an orgenocedmlum
compound to an is o c y e n id e .
- 8 -
G i l l i l n a d pad B leach erd pos t a l e t e d t h r t in th e r e a c tio n between
n ic k e l carbonyl end an ex cess o f th e G rignnrd re a g e n t, phenylmpgneslam
brom ide, the r e a c tio n s shown below took p la c e .
They assamed th a t cleav ag e
o f th e n ic k e l c a rb o n y l mole c a le to o k p la c e sim u lts n e o n s ly w ith th e a d d itio n
o f th e G rlgnard re a g e n t; th a e , we h av e;
= C=O
+
CgH^MgBr -
0
C^EjCMgBr * C^HjMgBr
—
> C^,Hj — C — MgBr
=6h 5
/ X
c6a 5
MgBr
CzH
6^5.
N
Z
C^H5
' 0
x
f
r,
MgBr
MgBr
%
C ^ M g B r --------» C^H^j—- C - MgBr + BrMgOMgBr
MgBr
III
c6H5
H y d ro ly sis o f the f i n a l p ro d u c t y ie ld e d an abundance o f trip h e n y Imeth a n e ,
w hich ten d s to s u b s ta n tia te th e mechanism p roposed above.
I t i s to be n o te d
t h a t in s te p I , th e pheny!magnesium bromide added to the carb o n atom.
T h is,
o f c o u rs e , is c o n tra ry to th e g e n e r a l mode of a d d itio n , a c c o rd in g to which
RMgX adds a s two fra g m e n ts, R end MgX, to two d i f f e r e n t atom s.
A d d itio n a l ev id en ce o f the a d d itio n o f th e G rignard re a g e n t to a s in g le
atom is fu rn is h e d from the work o f Sachs and Loevyv ^ .
These men o b ta in e d
b e n sa ldehyde from th e h y d ro ly s is o f th e r e a c tio n m ixture o f m ethyl is o cyanide end phenylmagneslum brom ide.
They re p re s e n te d th e I n i t i a l s te p o f
th e fo re g o in g r e a c tio n as th e mono-atom a d d itio n p ro d u c t.
/ C6S$
CH3-H=C 4- C6H5MgBr---------- CH3-H=Cx ^
- 9 -
The hydr o l y s Ie o f the a d d itio n p ro d u c t formed from e r e a c tio n o f the
Irl= ^ ie rd re e g e n t end r cerh o n y l c o n tp ln ln g compound, ceuees th e cleev»»e
o f th e MgX end I t s sim u ltan eo u s rep lacem en t by e hydrogen =tom.
I t wee,
th e r e f o r e , Reeumed th » t » s im ila r r e a c tio n would r e s u l t from th e h y d ro ly s is
o f th e F d d ltto n p ro d u c t betw een en a lk y l leo cy p n ld e end en orgenomegneslum
compound w ith the fo rm atio n o f a S c h lf f 1s b a s e .
zMgX
R-N=C
R
+- HOH ---- B-N=Cn
H
+
/H
Mg
R
zX
OH
A ccording to O ilm e n ^ th e h y d ro ly s is o f s S c h l f f s b a se o ccu rs w ith
th e fo rm a tio n o f an aldehyde as one o f th e p ro d u c ts .
On t h i s b a s is , th e
s y n th e s is o f benealdehyde by th e method employed by Sachs and Loevy can
l o g i c a l l y be e x p la in e d .
Due to th e s i m i l a r i t y e x i s t i n g betw een th e mode o f r e a c tio n o f o rg an o magneslum compounds end organocadmlum compounds. I t was b e lie v e d th » t an
aldehyde would r e s u l t from a s e r i e s o f r e a c tio n s em ploying orgenocadmlum
compounds In p la c e o f th e organoraagneslum compounds.
- 10 -
IV.
KXPgHITg1TT^L
The COrHpmmdF1 b o th ia te r m e d tr te end f i n a l , which were need in t h i s
i n v e s t ig a ti o n , were p re p a re d a c c o rd in g to s ta n d a rd p ro c e d u re s .
S ilv e r c y a n id e t
One hundred and t h i r t y g ran s (.8/4-5 mole) o f s i l v e r
n i t r a t e was r e a c te d w ith 55 5 (.8 4 5 mole) p o ta ssiu m cyanide in an aqueous
medium, whereupon th e in s o lu b le s i l v e r cy an id e p r e c ip ita te d from th e s o lu ­
ti o n .
AgSO3 + KCS--------> AaCS + KSO3
The p r e c i p i t a t e d s i l v e r cyan id e was f i l t e r e d by s u c tio n and washed
w ith s e v e r a l p o r tio n s o f w a te r, end then th o ro u g h ly d r ie d in th e d ark .
( I f the r e a c tio n i s c a r r ie d o u t in the p re se n c e o f w h ite l i g h t , the p ro d u c t
w i l l be g ra y -b la c k in c o lo r in s te a d o f w h i t e . )
Y ie ld s as la r g e a s 9*5-98 p e rc e n t o f th e t h e o r e t i c a l were o b ta in e d from
th e fo re g o in g r e a c t i o n .
The pure s a l t has a m o lecu lar w e ig h t o f 133*90 and
e x i s t s as w h ite hexagonal c r y s t a l s which decompose a t 320°C,
I t is o n ly
s l i g h t l y so lu b le in w e te r, b u t i s s o lu b le in p o tassiu m cy an id e end ammonium
h y d ro x id e .
n -B u tv l Is o c v a n ld e :
The p ro ced u re fo llo w e d wee th a t g iv e n by C slm els
One hundred grams o f n -b u ty l io d id e and I 50 g o f d ry s i l v e r cyanide were
p la c e d in a round bottom f l a s k w hich wee f i t t e d w ith a r e f l u x condenser,
and t h i s r e a c tio n m ix tu re was h e a te d to 130 C on an o i l b a th f o r one end
o n e -h a lf h o u rs .
The o p e ra tio n was th en in te r r u p te d , as th e e x tr a c tio n o f
th e I socyanide i s e a s i e r i f th e c o n te n ts o f th e f la s k do n o t become too
d a rk in c o lo r .
W ater and p o ta ssiu m cyanide were added to th e double s a l t ,
CijHgNCt AgCN, whereupon an o i l y V y e r o f n - b u ty l iso cy an id e ap p eared .
It
(4 )
S
- 11 -
was found from e x p e rie n c e t h a t ap p ro x im a te ly one mole o f p o tassiu m cyanide
should be added to th e r e a c tio n m ixture f o r each .5 mole o f th e lso cy an ld e
ex p ected based on th e t h e o r e t i c a l y i e l d .
The c o n te n ts o f th e f l a s k were then steam d i s t i l l e d , end th e re a p p ea r­
ed two la y e r s in th e re c e iv in g f l a s k ; th e u p p e r la y e r c o n s is te d o f a - b u ty l
is o c y e n id e and th e low er one o f w a te r.
These la y e r s were s e p a ra te d by th e
use o f a s e p a ra to ry fu n n e l, and th e n -b u ty l leo cy en ld e was d r ie d over
sodium hydro x id e p e l l e t s .
The I socyanide was allow ed to rem ain in c o n ta c t w ith th e d ry in g ag en t
u n t i l s e v e ra l h o u rs b e fo re u s e .
I t was th e n d i s t i l l e d , and th a t f r a c tio n
w hich b o ile d betw een 1130-122°C was c o lle c te d and used in th e ex p erim en t.
A v a ria n c e in th e y ie ld s was caused by th e p re sen c e o f w a te r In th e
s i l v e r c y an id e .
As a g e n e ra l r u l e , th e b e s t y ie ld s were o b ta in e d from a
th o ro u g h ly anhydrous s a l t w hich had been d r ie d a t 120° C from 10 to 20 h o u rs .
The average y ie ld was about 26 g (.3 1 3 mole) o r about 58 p e rc e n t o f th e
th e o re tic a l.
Second?ry-butvlm agneslum bro m id e;
The p ro ced u re f o r th e p re p a ra tio n
o f th e O rlgnard re a g e n t i s g iv en by Oilmen, Z o e lln e r and D ickey
, and
i n th e p re s e n t case c o n s is ts o f a r e a c tio n betw een s e c o n d a ry -b u ty l bromide
and magnesium tu r n in g s In a b s o lu te e th e r .
In a th re e -n e c k e d f l a s k f i t t e d
w ith a r e f lu x c o n d en se r, mercury s e a l s t i r r e r , and a drop fu n n e l were
p la c e d 6 g (.2 5 mole) o f d ry magnesium tu r n in g s , 25 cc a b s o lu te e th e r ,
15-20 drops o f s e c o n d a ry -b u ty l brom ide, and a sm all c r y s t a l o f io d in e .
The l a t t e r te n d s to a c ti v a te the s u rfa c e o f the magnesium, th u s prom oting
a b e t t e r r e a c tio n .
- 12-
Onee th e r e a c tio n had he,^un1 @e in d ic a te d hy th e fo rm a tio n o f sm ell
h u b b ie s end e e l i c i t r e f lu x a c tio n , th e m otor d riv e n s t i r r e r wee s t a r t e d .
Ji s o lu tio n o f I h g ( .2 5 mole) o f s e c o n d a ry -b u ty l bromide end 12$ cc o f a b s o l­
u te e t h e r ^e e th e n p la c e d in th e drop fu n n e l »nd allow ed to flow in to th e
f l a s k a t the r a t e o f one drop p e r second.
The s t i r r i n g was co n tin u ed f o r
an a d d itio n a l o n e - h a lf h o u r a f t e r th e c o n te n ts o f th e drop fu n n e l had been
added to the fls .s k .
D uring th e c o u rse o f t h i s r e a c tio n th e a p p a ra tu s was k e p t fre e from
m o istu re by p ro v id in g th e drop fu n n e l and r e f l u x condenser w ith calcium
c h lo rid e d ry in g tu b e s .
The r e a c tio n m ix tu re was k ep t in sn anhydrous
c o n d itio n as m o istu re r e a d ily c au ses d eco m p o sitio n o f a l l o r g a n o a e ta lllc
compounds.
Sarnnrlrrv-B utvlcsdalum B rom ide:
The o rg a nocadmium compound was d e riv e d
d i r e c t l y from th e 0rganomsgneslum compound, acc o rd in g to th e procedure
su g g ested by C e e o n ^ ) ,
/ n a d d itio n a l 100 cc o f a b s o lu te e th e r was added to th e O rignard
re a g e n t to keep th e organocadmium compound in a more l i q u i d s t a t e a f t e r i t s
fo rm a tio n .
N ext, th e drop fu n n e l was removed from th e th r e e necked f l a s k ,
and was q u ic k ly re p la c e d by a tube which c o n ta in e d 45 .8 g ( .2 5 mole) o f an­
hydrous cadmium c h lo r id e .
The cadmium c h lo r id e was added to th e secondary-
butylm agnesinm b ro m id e -e th e r s o lu tio n d u rin g a p e rio d o f f i f t e e n m in u tes,
w h ile v ig o ro u s s t i r r i n g o f th e r e a c tio n m ix tu re was e f f e c t e d w ith th e m ercury
seal s tir r e r .
R eflu x o c c u rre d d u rin g th e a d d itio n o f th e cadmium c h lo r id e and f o r a
su b seq u en t o n e -h a lf h o u r.
- 13-
Syntheslfl u f Z methyl b u tp n a lt
Twenty end seven te n th s grams (.2 5
mole) o f n -b n ty l I socyanide was added to ap p ro x im ately .2 5 mole o f eecondary-butylcadm lum bromide p re p a re d acc o rd in g to the above p ro c e d u re .
T his
a d d itio n was c a r r ie d o u t a t room te m p e ratu re w ith c o n sta n t s t i r r i n g o f th e
r e a c tio n m ix tu re .
The m ixing o f th e se compounds p r e c i p i t a t e d a m ild r e f lu x
a c tio n w ith in th e c o n ta in in g v e s s e l.
V igorous s t i r r i n g was co n tin u ed f o r
a p e rio d o f f o u r ho u rs a f t e r th e com plete m ixing o f th e r e a c t a n t s .
The
r e a c tio n m ixture was th en allow ed to stan d f o r tw e n ty -fo u r h o u rs .
A l i g h t y ellow liq u id appeared on the s u rfa c e o f th e c o n te n ts o f th e
f l a s k , w h ile th e rem ain d er o f the s o lu tio n p o sse sse d th e c h a r a c t e r i s t i c
c o lo r o f th e organocadmlum compound.
An Ic e -w a te r m ix tu re was then p la c e d
around th e low er p o r tio n o f th e f l a s k c o n ta in in g th e r e a c t a n t s , th e s t i r r e r
was s t a r t e d , and s u f f i c i e n t tim e was allow ed f o r the c o n te n ts o f the f l a s k
to come In to e q u ilib riu m w ith th e te m p e ratu re o f the ic e - w a te r b a th .
D uring t h i s tim e, 120 ml o f a 6 H s u l f u r i c a c id s o lu tio n was p re p a re d ,
and t h i s , to o , was cooled to th e te m p e ratu re o f an Ic e -w a te r m ix tu re.
The
h y d r o ly s is o f th e r e a c tio n m ixture was th e n accom plished by adding the
c o ld d i l u t e a c id d ro p w lse.
D uring th e tim e o f h y d r o ly s is , th e re a c tio n
had to be w atched c a r e f u l l y , and a te m p e ratu re o f ap p ro x im ately O0C was
m a in ta in ed w ith in th e r e a c tio n v e s s e l .
The most c r i t i c s ! p a r t of the
h y d r o ly s is came d u rin g the a d d itio n o f the f i r s t few ce o f th e d ilu te a c id .
Vhen the h y d r o ly s is was com plete th e ic e -w a te r b a th was removed, th e
s t i r r i n g sto p p ed , and w ith in s e v e r a l m inutes th re e la y e r s form ed in the
fla s k .
The bottom la y e r was m ainly w a te r, w h ile the top la y e r was la r g e ly
e t h e r ; th e m iddle la y e r was s e p a ra te d by u se o f a s e p a ra to ry fu n n e l and
tr a n s fe r r e d to
p
200 a l round bottom flt's k
T his l i q u i d , d a rk red in c o lo r , wps th en s te r n d i s t i l l e d , end the d le t l l l e t e , c o n s is tin g o f tvo lp y e r s , wrs c o lle c te d In a 125 31I F lo ren ce f l a s k .
These la y e r s were s e p a ra te d w ith th e a id o f r s e p a ra to ry fu n n e l.
The u p p e r
l r y e r c o n ta in e d e th e r , and what l a t e r proved to be an a ld eh y d e , w hile the
b o tto n lc y e r was th e aqueous p o r ti o n .
T his aqueous la y e r was e x tra c te d
w ith s e v e ra l s n a i l p o r tio n s o f a b s o lu te e t h e r , and th e e x t r a c t s were com­
b in e d w ith th e u p p er la y e r o f the steem d i s t i l l a t e .
The e t h e r p o rtio n weg
th e n d r ie d , f i r s t by anhydrous sodium s u l f a t e , and l a t e r by hD r i e r i t e n
(c a lc iu m s u l f a t e ) .
The e th e r s o lu tio n was d r ie d f o r 2k h o u rs , th e n t r a n s f e r r e d to a $0
ml round bottom f l a s k which was f i t t e d w ith a sm all f r a c t i o n a t i n g column,
and th e e th e r was removed.
There rem ained ap p ro x im ately 1 .5 ml o f a l i g h t
y ellow l i q u i d which was d i s t i l l e d w ith p sm all t e s t tube d i e t i l l i n g ap p ara­
tu s .
The b o ilin g p o in t was 86-87°C a t 6k0 mm.
c h a r a c t e r i s t i c o dor o f ald eh y d e.
The p ro d u c t had a s tro n g
Small p o r tio n s were te s t e d as in d ic a te d
below .
T e sts o f C o n firm a tio n :
The in fo rm a tio n l i s t e d below was o b ta in e d from H u n tre ss and
M u llik in ^ 1^
re g a rd in g 2 m ethyl b u ta n a l.
B. P .
92-93°C
0.80294
20
ao
2 ,k d ln itro p h e n y lh y d ra e o n e :
1.38960
M. P . 1 2 0 .5°C
- 15 -
nVo o u rH t o t l v e t o s t s were f i r s t conducted In o rd e r to d e te c t the
p re s e n c e o f on »ld eh y Ae? th e se were p c c o a u llsh e d w ith the use o f T o lle n 1s
re " -;e n t -nd I c h i f f 1r r e <-^ e n t.
The p r e p a r a tio n o f th ese c l a s s i f i c a t i o n
r e g e n t s , "uA th e p ro ced u re f o r t h e i r use i s H ven by ^ h rtn e r and Iu so n
(2 8
Three drops o f th e d i s t i l l a t e o b ta in e d as p ro d u ct f r o n th e above pro­
cedure were added to a p p ro x im ately 3 cc o f th e f r e s h ly p re p a re d T o lle n 1s
r e a g e n t.
A p o s i t i v e aldehyde t e s t b e» rn to appear w ith in 30 seconds a f t e r
m ixing the l i q u i d s , and c o n s is te d o f a c o a tin g o f f r e e s i l v e r d e p o site d on
th e w a lls o f th e c o n ta in in g v e s s e l.
The P c h if f *p t e s t was c a r r ie d o u t in a s im ila r manner by the a d d itio n
o f s e v e ra l drops o f th e unknown l i q u i d to 3 cc o f the f u c h s ia - a ldehyde
r e a g e n t.
V lth in a few seconds th e c o lo r le s s fu c h s ia H dehyde reag en t
tu rn e d p in k , which in d ic a te d the p re se n c e o f an aldehyde group in the un­
known li q u i d .
The Index o f r e f r a c t i o n o f th e p ro d u c t was found to be 1 .3 9 2 ,
The
v a lu e l i s t e d by 'I u llik in f o r an a u th e n tic sample o f 2-m eth y l b u t anal i s
n20 = 1.38960.
O
The b o ilin g p o in t as p re v io u s ly in d ic a te d Was 860-87°C a t 6h0 nun.
The
c o r r e c te d v a lu e o f 9 1 .6 ° a t ?60 am was o b ta in e d through th e use o f the
fo llo w in g e q u a tio n .
B. P . (c o r r e c te d ) = B. P. (o b se rv ed )
where f h a s the c o n s ta n t v alu e o f 850 f o r n o n -a s so c I f te d l i q u i d s .
Close, agreem ent e x is te d betw een th e c o n firm a to ry t e s t s and the d a ta
p e r ta in in g to 2 -methyI b u te n a l; th e r e f o r e , i t wee decided to confirm the
i d e n t i t y o f th e unknown liq u id by means o f d e r i v e t l t e t i o n .
— 16 —
Prmmermtion o f th e D e riv a tiv e
The p ro ced u re fo llo w ed In th e p r e p a r a tio n o f th e d e r iv a tiv e la th e t
g iv e n by / I l e n ^ .
The 2 ,b - d ln itro p h e n y Ih y d re z ln e re a g e n t was p rep ared by
d is s o lv in g 2 g o f 2 , h -d ln itro p h e n y !h y d ra z in e In I 5 co o f c o n c e n tra te d s u l­
f u r i c a c id .
T his s o lu tio n was th en added, w ith s t i r r i n g , to I 50 cc o f 95
p e rc e n t a lc o h o l.
The s o lu tio n was d ilu te d to 500 cc w ith d i s t i l l e d w a te r,
mixed th o ro u g h ly and f i l t e r e d .
To 5 cc o f th e 2 , b -d ln ltr o p h e n y !h y d ra z in e s o lu tio n c o n ta in e d in an
e ig h t inch t e s t tube were added 5 drops o f th e unknown sample and 5 cc
o f 95 p e rc e n t a lc o h o l.
T his m ixtu re was h e a te d to b o ilin g o v e r a low
fla m e , end two d ro p s o f c o n c e n tra te d h y d ro c h lo ric a c id were added.
The
h e a tin g was c o n tin u e d f o r an a d d itio n a l two m in u te s, end th e s o lu tio n wes
allow ed to c o o l.
N ext, d i s t i l l e d w a te r was added drop by drop to in­
c i p i e n t c lo u d in e s s , end upon f u r t h e r c o o lin g under a co ld w a te r ta p , th e
d e r iv a tiv e began to c r y s t a l l i z e o u t.
The p r e c i p i t a t e was c o lle c te d by
c e n tr if u g a tio n , d is s o lv e d in a lc o h o l and r e - p r e c i p i t a t e d by th e a d d itio n
o f w a te r.
The f i n a l p ro d u c t c o n s is te d o f s e v e ra l m illig ra m s o f a l i g h t yellow
c r y s t a l l i n e s o l i d , which was allow ed to a i r d ry f o r s e v e r a l d a y s.
Itie m e ltin g p o in t o f t h i s m a te r ia l was 119-120 C.
The m eltin g p o in t
o f th e 2 , b -d ln o tro p h e n y Ihydrezone d e r iv a tiv e o f 2-m eth y l b u ta n a l i s g iv en
as 120. 5°C.
Assuming com plete r e a c tio n in th e p r e p a r a tio n o f s e c o n d a ry -b u ty lraagnesturn bromide and secondary—butylcadm ium brom ide, th e t h e o r e t i c a l
y i e l d from th e r e a c tio n betw een a - b u ty l iso c y a n id e and s e c o n d a ry -b u ty l-
- 17 -
cpdmlun bromide i s 2 2 .3 S*
p e rc e n t o f th e t h e o r e t i c e l .
The p c tu e l y ie ld was found to be 1 .2 g o r 5 . U
— 18 —
V.
DISCUSSION Or EXPgEIM^NTfD RESULTS
Althou^b. p l p r g e r p e rc e n t o f th e th e or e t I cp I y ie ld Ie to be d e s ir e d ,
th e r e s u l t s ln d lc e te th p t th e p ro c e ss es o u tlin e d Is e s u c c e s s f u l method
f o r th e p r e p a r a tio n o f 2- methyI b u te n p l from n -b u ty l ls o c y a n id e end secondery-butylcpdm lum brom ide.
The mechanism o f th e r e a c tio n p re s e n te d in th e a b s t r a c t appears to be
a l o g i c a l e x p la n a tio n o f th e p ro c e s s , a lth o u g h no t e s t s were conducted to
e s t a b l i s h the e x a c t mechanism o f th e r e a c tio n .
The r e a c tio n s p re s e n te d can
acco u n t f o r th e fo rm atio n o f th e ald eh y d e, and were fo rm u la te d b e fo re any
o f the e x p e rim e n ta l work was u n d e rta k e n .
T his p ro c e s s es o u tlin e d does n o t ap p ear to be a p p lic a b le to la rg e
s c a le a p p lic a tio n e i t h e r i n d u s t r i a l l y o r in th e la b o r a to r y .
This f a c t i s
based upon th e low y i e l d o f aldehyde o b ta in e d , the n e c e s s ity o f p re p a rin g
a f r e s h organocadmlum compound b e fo re each ru n , the h ig h c o s t of p re p a ra ­
tio n o f the lso c y a n id e i f p re p a re d by the metnod in d ic a te d , and the extrem e
u n p le a s a n tn e s s o f w orking n e a r and h a n d lin g the I socyanides due to t h e i r
re p u ls iv e odor *nd t o x i c i t y .
R e s u lts o f a more s i g n i f i c a n t n a tu re may be r e a liz e d by employing
d i f f e r e n t co m binations o f r e a c t a n t s .
M ethyl lso cy a n id e would perhaps be
a more s u ita b le c erb y lem in e, as I t ap p ears to be more r e a c tiv e then th e
o th e r members o f I t s homologous s e r i e s .
F u r th e r , th e wide v a r ie ty o f
o rg a n o m e ta lllc compounds makes a v a ila b le an alm ost l i m i t l e s s number o f
s t a r t i n g m a te r ia ls .
The p a r t i c i p a t i o n o f n - b u ty l lso cy a n id e in t h i s ty p e o f re a c tio n may
be assumed to be c o n tra ry to th e fin d in g s o f Gilman, who, how ever, b ased
- 19
h i* r e p o r t on th e r e a c tio n s betw een cerb y lem in es end orgpnomp^ne s I u b com­
pounds.
**
20
II. SUMMARY
1»
A re p o tio n h^e been shown to o c c u r betw een secondF ry-butylcsdalum
brom ide end n - b u ty l le o c y e n ld e .
2.
The h y d ro ly s is o f th te r e e c tlo n m ix tu re y ie ld e d 2 -m eth y l b u trn e l in
th e amount o f
p e rc e n t o f th e t h e o r e t i c a l .
P ro d u c tio n o f an a ld e ­
hyde through th e u se o f n - b u ty l le o c y a n ld e ap p ears to be c o n tra ry to
th e r e s u l t s o b ta in e d by p re v io u s I n v e s tig a t o r s .
3.
The n a tu re o f th e aldehyde o b ta in e d a s p ro d u c t I s d eterm in ed by th e
a lk y l h a lid e employed In the orgenocedmlum compound p r e p a r a tio n , and
Ie n o t dependent upon th e lao cy a n ld e u se d .
h.
A lo g i c a l mechanism Is su g g este d which o u tlin e s the c o u rse o f the
r e a c tio n .
5.
I t i s su g g ested th a t su bsequen t I n v e s tig a tio n u sin g d i f f e r e n t o rg sn o m e ta llic compounds end o th e r lso c y a n Id e e , co u ld prove s i g n i f i c a n t from
th e s ta n d p o in t o f a s c e r ta in in g which r e a c ta n ts produce th e g r e a te s t
y i e l d o f a ld eh y d e .
- 21-
Zaiii II.
X.
ABSTRACT
A r e a c tio n m ix tu re c o n s is tin g o f th e sodium s a l t o f n itr o e th a n e end
n ic k e l carb o n y l in a s o lv e n t o f cy clo h ex an e, mps s u b je c te d to h ig h p re s ­
s u re s o f carbon monoxide.
T his r e a c tio n m ix tu re y ie ld e d , upon h y d r o ly s is ,
F su b sta n c e p o s s e s s in g a s o l u b i l i t y which co u ld n o t r e a d i l y be accounted
fo r.
T his s u b sta n c e i s n o t o b ta in e d in th e absence o f n ic k e l c arb o n y l,
o r when cyclohexane i t s e l f i s s u b je c te d to carbon monoxide u n d er p re s s u re
in th e p re se n c e o f n ic k e l c a rb o n y l.
The u n id e n tif ie d su b sta n c e is de­
composed by steam d i s t i l l a t i o n , sim ple d i s t i l l a t i o n , and vacuum d i s t i l ­
l a t i o n , and c an n o t be c r y s t a l l i s e d s a t i s f a c t o r i l y even a t low tempera­
tu re s .
P o s itiv e S c h l f f 1e and T o lle n 1s t e s t s were o b ta in e d by use o f th e
a p p ro p ria te re a g e n t and th e unknown su b sta n c e .
I e r i v a t i z a t i o n o f the un­
i d e n t i f i e d m a te r ia l h a s n o t been p o s s ib le .
A d d itio n a l in v e s t ig a ti o n o f th e u n id e n tif ie d su b sta n c e i s bein g con­
d u c ted
- 22 -
U.
INTRODUCTION
The use o f cerbon monoxide a s e so u rce o f th e c arb o n y l group in ad d i­
tio n r e a c tio n s i s o f * re a t Im portance, and co n se q u e n tly , h a s found many
a p p lic a tio n s o f com m ercial and te c h n ic a l v a lu e .
A ccording to Suthke
( 12 )
,
th e s y n th e s is o f benzaldehyde may be accom plished a c c o rd in g to th e fo llo w ­
in g re a c tio n s
®6h 6 + CO
anhydrous AlCl^ Ti
p re s s u re
c h lo rid e
C6H5CHO
The s y n th e s is o f ald eh y d es by r e a c tio n s between o l e f i n s , carbon mon­
oxide and hydrogen In the p re se n c e o f c o b a lt carb o n y l u n d e r c o n d itio n s
( 2 5 ) ( 32)
o f h ig h p re s s u re h a s a ls o been d e m o n strated
. T h is s y n th e s is Is
known as th e "oxo" p ro c e s s .
F u rth erm o re, c o n sid e ra b le i n v e s t ig a ti o n has
been conducted re g a rd in g th e r e a c tio n s betw een carbon monoxide a t h ig h
(mm)
p r e s s u r e s and e s t e r s , e th e r s , end a lc o h o ls
. The p ro d u c tio n of a c e t i c
(29)
a c id in good y i e l d h as been re p o rte d by Singh and Krase
acco rd in g to
th e fo llo w in g e q u a tio n :
CH OH + CO
3
A ctiv e C
H3POzt
P, B, I
,
CE1COOH
J
The a d a p t a b i l i t y to In d u s try o f h ig h p re s s u re methods o f s y n th e s is
h as g r e a t l y I n t e n s i f i e d th e amount o f I n v e s tig a tio n In t h i s f i e l d w ith in
re c e n t y e ars.
The numerous l i t e r a t u r e r e fe re n c e s p e r ta in in g to high
p re s s u re r e a c tio n s was one f a c t o r which prom pted th e in v e s tig a tio n con­
s id e r e d in t h i s p a p e r.
The o r i g i n a l aim was th e s y n th e s is o f 2 - n lt r o -
p ro p a n a l by » r e a c tio n betw een th e sodium s a l t o f n ltr o e th a n e and carbon
monoxide un d er c o n d itio n s o f h ig h p r e s s u r e .
«* 23 **■
III.
THE0HS7IC/L DISCUSSIOH
Up to th e p r e s e n t tim e no work h^e been re p o rte d w hich d e a ls w ith a
r e a c tio n in v o lv in g carbon monoxide and th e s a l t s o f n i t r o p a r a f f i n s ; in
f a c t , i t ap p ears t h a t v e ry l i t t l e
i n v e s t ig a ti o n h a s been conducted u s in g
carbon monoxide and o rg a n ic s a l t s o f any ty p e .
S c h e lb le r and F r i k e l l ^ ^
r e p o r t th e fo rm a tio n o f a b i-v p .le n t carbon
atom r e s u l t i n g from th e h ig h p re s s u re r e a c tio n betw een carb o n monoxide
and sodium e t h y l a t e ,
x / O-CH2CHCH-CH-ONa 4- CO ------------ > .C x
3 2
x ONa
The fin d in g s o f th e se w o rk e rs, how ever, have n ev er been s u b s ta n tia te d ,
and a c c o rd in g to S t a h l e r ^ 0 z , th e above r e a c tio n i s I n c o r r e c t and S ta b le r
s u g g e s ts , in s te a d , an a d d itio n p ro d u c t o f th e type
CE3CH2ONa + CO ----------- > CE3CH2-O-C
O0
-N a
The e x is te n c e o f an a d d itio n p ro d u c t betw een th e s a l t and carbon mon­
o x id e does seem to h=>ve been s u b s ta n tia te d even though c o n c lu s iv e p ro o f as
to th e c o r r e c t mechanism ap p ears to be la c k in g .
The c o n c lu s io n s drawn from th e work o f Hsmmich, e t e l
b*sed upon
r e s u l t s ob ta in ed from p a ra c h o r and d ip o le moment m easurem ents, e s ta b lis h e s
th e s tr u c tu r e o f carbon monoxide a s being*
—
,__
JC ^
+
Os
The work o f P a u lin g and Sherman^22'*, how ever, in d ic a te s t h a t reso n an ce
e x i s t s betw een s e v e r a l s t r u c t u r e s .
T h e ir c o n c lu sio n s were b a se d upon
ev id en ce g a th e re d from resonance energy d a te and e l e c t r i c d ip o le moment
- 24
m easurem ent*.
I t now ap p ears lo g i c a l to pssume th a t th e cerbon monoxide
m olecule re p o n e te s about e q u a lly among th e th r e e s tr u c tu r e s
"+
—
4-
—
iO * 0 :
iC : t Os
:C : : : 0 :
I
II
III
>, s im ila r s i t u a t i o n was found to e x i s t re g a rd in g th e s tr u c tu r e o f the
sodium s a l t s o f n l t r o p e r e f f In s .
Some o r i g i n a l work p e r t i n e n t to the s a l t
fo rm a tio n o f n l t r o p a r a f f i n s was done by Kuhn and A lb re c h t
(17)
and th e se
/0
N
xO-
B i
Na +
:o :
I
R1
B - C s
W
H
I
tu r e s
____ I
w orkers concluded t h a t th e s a l t s a re c o r r e c t l y re p re s e n te d by th e s tru c ­
C : N.
+ ' 0'
M
—
IV
V
Upon f u r t h e r I n v e s tig a tio n K o rn b lu m ^ ^ end h is a s s o c ia te s determ ined
e x p e rim e n ta lly t h a t resonance a c tu a lly e x i s t s w ith in th e s a l t s o f n l t r o
p a r a f f i n s , and t h a t a s l i g h t m o d ific a tio n o f the above s t r u c t u r e was nec­
e ssa ry .
Bie reso n an ce s tr u c tu r e p re s e n te d Is
Tl
/U
E - C - N z
<- + xO"
VI
Whitmore^
B-C
N
VII
s u g g e sts th a t e th y le n e , end o le f in s in g e n e r a l, may be
c o n v e rte d In to " a c tiv a te d su b sta n c e s" u n d e r s u ita b le c o n d itio n s .
The p ro ­
posed e le c tr o n i c c o n f ig u r a tio n f o r e th y le n e In th e "norm al" and " a c tiv a te d "
form s a re ;
- 25 -
H S
H l -C i i b j H
<------------- *■
H
H
H s C t C i H
T ill
IX
Form X III , th e normpl form . I s seen to c o n te in e double "bond, w hereas
In form IX, th e p c tlv s te d m o lecu le, th e d ouble bond i s opened end e p e i r o f
e le c tr o n s h a s become a s s o c ia te d w ith th e Carbon atom on th e l e f t .
The v a l i d i t y o f form IX h as been re a so n a b ly w e ll s u b s ta n tia te d by th e
work o f B a r t l e t t and T a r b e l l ^ \
and, T e rry and K ie h e lb e r g e r ^ " ^ .
B a rtle tt
and T e rb e ll have shown th a t th e f i r s t s te p in the a d d itio n o f halogens to
e th y le n e lin k a g e s le a d s to th e fo rm a tio n o f an ion o f th e type
,
K1
R2 - C
:
X
P
„
C-R4
The s i m i l a r i t y e x is t in g betw een th e a c ti v a te d form o f e th y le n e end
th a t o f form TI o f th e sodium s a l t o f a n l t r o p a r a f f i n is a t once e.p p eren t.
The mechanism pro p o sed f o r the a d d itio n o f carbon monoxide to form TI o f
th e sodium s a l t o f a n l t r o p a r a f f i n i s
B1
R - C - N
-
*0
4 xQ -
He* 4
i C I O : —----- >
4—
R1
Z/0
R - C - N
•c
O
,‘0 ;
>n e q u iv a le n t a d d itio n p ro d u c t i s a ls o assumed to r e s u l t from a
r e a c tio n betw een form T H o f the n l t r o p a r a f f i n s a l t and cprbon monoxide.
In th e in v e s t ig a ti o n u n d er c o n s id e ra tio n n ic k e l c arb o n y l was employed
re a c a t a l y s t , th u s draw ing a c lo s e r analogy betw een the carb o n monoxiden i t r o p a r a f f i n s a l t r e a c tio n , end t h a t o f th e "oxo" p ro c e ss f o r the n r e p e r e tio n o f ald eh y d es from a r e a c tio n in v o lv in g o l e f i n s , carbon monoxide,
»nd hydrogen in the p re se n c e o f c o b a lt c a rb o n y l.
F u rth erm o re, th e use o f
- 26 -
n ic k e l ce s c c t c l y e t h=s been re p o rte d by S c h s lc h ^ ^ ) in r p ro c e s s inv o lv ­
in g e r e a c tio n betw een o l e f i n s end Cerbon monoxide f o r th e p re p a ra tio n o f
oxygen c o n ta in in g d e r i v a t i v e s .
A lthough th e mOxo1* p ro c e ss employs hydrogen
as e n e c e s sa ry component o f th e r e a c tio n m ix tu re , i t Wes ses'omed th s t hydro­
l y s i s o f th e sodium s a l t o f n i t r o e thpne~c$rbon monoxide r e a c tio n m ixture
would r e s u l t in aldehyde fo rm atio n a cc o rd in g to the fo llo w in g mechanIemi
R
H
C
I
R -C
H--C
. 0:
Na+ ------ >
Na +
HOH
F
R - C H--Q
•6-
/"
X0
Na +
R — C — NOn
X
XI
■§
Ih e hydrogen ion m ig ra tio n shown in X is a lo g ic a l s te p in the forma­
tio n o f a more s ta b le m o lecu le, and would v e ry l i k e l y o c c u r.
Ih e p ro d u c t r e s u l t i n g from th e above r e a c tio n i s 2- n l t r o p r o p a n a l.
T h e o r e tic a lly , a compound o f t h i s ty re should e n te r in to a g r e a t many
r e a c tio n s , making p o s s ib le th e s y n th e s is o f a wide v a r i e t y o f new m a te r ia ls .
By em ploying th e r i g h t c o n d itio n s , re d u c tio n o f 2 - n itro p ro p a n e l should
y i e l d a m ix tu re o f 2- n itr o p r o p a n o l, 2-m m inopropenal, and 2-a m ln o p ro p an o l.
The o x id a tio n o f 2 -n itro p ro p a n a l should y i e l d e lp h a - n itr o - p r o p io n ic a c id .
A c e ta l fo rm atio n should be p o s s ib le from e r e a c tio n betw een 2 -n itro p ro p a n a l
and an a lc o h o l.
Thus i t is a p p a re n t th a t 2 -n itro p ro p a n a l c o u ld form th e
s t a r t i n g m a te r ia l from which a la rg e number o f compounds co u ld be p re­
p a re d .
- 27 -
IT .
EXPERIMENT'!
The F t r r t t n ^ m p te r ir lr were th e sodium s r l t o f n ttr o e th e n e , cy clo h ex en e,
e srb o n monoxide snd n ic k e l c s rh o n y l.
The l e t t e r th re e compounds were p u r­
chased from *n i n d u s t r i a l source end employed w ith o u t f u r t h e r p u r i f i c a t i o n .
J-Q rgr^tus:
> com plete d e s c r ip ti o n o f th e American In stru m en t Compeny1e high p re s ­
su re r e a c tio n e p p e r^ tu s is n o t p re s e n te d h e re f o r th e equipm ent i s o f e
S tm d e rd ty p e .
E s s e n t l e l l y , the a p p a ra tu s c o n s is ts o f p. heavy a llo y s t e e l
bomb h av in g e c a p e c ity o f 125 cc which h o ld s th e re a c tin g m a te r ia ls , and
w hich i s f i t t e d w ith a p re s s u re gege which I n d ic a te s th e i n t e r n a l p re s s u re
o f th e bomb in pounds p e r square in c h .
!Rie bom b-pressure gage u n i t i s
mounted in a h e e tin g ja c k e t, and th e e n t i r e assem bly is e g g ite te d by means
o f m o to r-ro ck er e rm system .
The h e a tin g o f the bomb i s a u to m a tic a lly e f f e c ­
te d by means o f an e l e c t r i c py ro m eter u sed in c o n ju n c tio n w ith a thermo­
couple which i s in s e r te d th ro u g h th e end of th e h e a tin g j a c k e t in to the
r e a r p o r tio n o f th e bomb.
The compressed g a s , as o b ta in e d from the m etal
c y lin d e r s , is s u b je c te d to f u r t h e r com pression by the use o f a m anually
o p e ra te d o i l b o o s te r pump; th e charge o f com pressed gas i s th en d e liv e re d
from the b o o s te r pump in to th e bomb through a s e r ie s o f f o u r c o n n e c tio n s.
P r e s s u r e s o f a p p ro x im a te ly 8000 pounds p e r square inch (53^ atm ospheres)
can s a f e ly be m a in ta in e d w ith in th e bomb.
p .
g .
> p re s s u re in e x ce ss o f 8000
I . causes th e ru p tu re o f th e s a f e ty d i s c , which a u to m a tic a lly re ­
le a s e s th e e n t i r e bomb c h a rg e .
w ith in th e r e a c tio n m ix tu re .
T em peratures up to ItOO0C can be o b tain ed
- 28 -
P re n p rp tlo n o f th e Sod1Ixua S a lt o f M ltroethpne
Thle subatpnee was p re p a re d In a manner s im ila r to t h a t suggested by
Kuhn and A lb re c h t
(l?)
.
Three hundred and tw enty cc (7 .9 5 a o le ) o f m ethanol
was p la c e d in a th re e neck f l a s k which was p ro v id e d w ith a m otor d riv e n
s t i r r e r , r e f lu x c o n d en se r, and a c o rk .
The f la c k was su rro u n d ed by an Ic e -
w a te r b a th , as th e m aintenance o f a low te m p e ratu re th ro u g h o u t th e r e a c tio n
was n e c e s s a ry .
Twenty th re e gram# ( l mole) o f sodium w ire was added to th e
c o ld m ethanol In ap p ro x im a te ly f iv e p o r tio n s o v er a p e rio d o f te n m in u tes.
V igorous s t i r r i n g was e f f e c te d d u rin g th e a d d itio n o f th e sodium, and com­
p l e t e d isa p p e a ra n c e o f the sodium w*s accom plished w ith in f iv e m inutes a f t e r
th e l a s t p o r tio n had been added.
The c o n te n ts o f th e f l a s k were th en t r a n s f e r r e d to a la r g e b eak er,
whereupon 75 cc ( I mole) o f n l t r o e thane was added w ith s t l r r l n ; .
Almost
im m ediately, th e In s o lu b le sodIxun s a l t o f n ltr o e th e n e p r e c i p i t a t e d o u t, end
was removed from th e excess m ethanol by s u c tio n f i l t r a t i o n .
The f i l t e r e d s a l t was washed w ith s e v e r a l p o rtio n s o f c o ld m ethanol,
p la c e d in s la r g e c r y s t a l l i s i n g d is h , and th e n allow ed to a i r d ry .
(Under
no c irc u m sta n c e s should th e s a l t be d r ie d In an oven, a s i t ap p ears to be
ex tre m ely e x p lo s iv e w h ile s t i l l m o ist w ith m ethanol.
T his In fo rm atio n was
o b ta in e d a t th e expense o f an e l e c t r i c d ry in g oven which was com pletely
dem olished as a r e s u l t o f such an e x p lo s io n .)
The sodium s a l t o f n ltr o e th e n e was o b ta in e d In y ie ld s o f approxim ate­
l y e ig h ty - f i v e p e rc e n t of th e t h e o r e t i c a l a c c o rd in g to th e procedure j u s t
d e s c rib e d
- 29 -
T yp lcp l P rocedure f o r S r r e r lm ent p I Runp
p ro ced u re o f c h arg in g th e bomh end th e subsequent h y d ro ly s is o f
th e r e a c tio n m ixture used d u rin g th e co u rse o f t h i s in v e s t ig a ti o n is o u t­
lin e d as fo llo w s :
Ten grams (.1 0 3 mole) o f th e dry sodium s a l t o f n i t r o -
e thane was mixed w ith 35 ml ( . 32k mole) cyclohexene and one h a l f ml (.0 0 3 8 5
m ole) o f n ic k e l c a rb o n y l.
The m ix tu re was p la c e d in th e bomb and i t s con­
s is te n c y wee s u f f i c i e n t l y l i q u i d to allow thorough m ixing d u rin g the tim e
th e bomb was b e in g a g i t a t e d .
Carbon monoxide was th en fo rc e d in to th e
r e a c tio n m ixture a t p re s s u re s ra n g in g from 2400 p . s . I . to 5000 p . s . i .
T em peratures o f from 23°C to I ? 5°C were m ain ta in ed d u rin g th e course o f
th e r e a c tio n .
A f te r s u f f i c i e n t time had been allow ed f o r th e r e a c tio n , u s u a lly about
30 m in u te s, th e bomb was removed from the h e a tin g j a c k e t, c o o led in a w a te r
b a th i f n e c e s s a ry , end v e n ted in r hood.
The p re s s u re gage and bomb head
were th e n removed and th e c o n te n ts o f th e bomb were t r a n s f e r r e d to a th re e
neck f l a s k .
The h y d ro ly s is which fo llo w ed wee c a r r ie d o u t in e hood a ls o ,
f o r th e p re se n c e o f n ic k e l c a rb o n y l was e v id e n t from i t s c h a r a c t e r i s t i c
o d o r.
The th re e neck f l a s k was p ro v id e d w ith a r e f lu x c o n d e n se r, motor
d riv e n s t i r r e r , end a drop fu n n e l.
In th e drop fu n n e l w ere p ie c e d a c o ld
s o lu tio n o f 15 cc d i s t i l l e d w a ter and 2 .7 5 cc (.0 5 2 5 mole) c o n c e n tra te d
s u l f u r i c a c id (e p . g r , 1 . 8351) I t h i s was allow ed to flow dropw ise in to th e
c o n te n ts o f th e f l a s k .
Very l i t t l e h e a t wa.s g e n e ra te d d u rin g the co u rse
o f th e h y d r o ly s is , end a f t e r th e c o n te n ts o f th e drop fu n n e l had been
added to the f l a s k , s t i r r i n g was c o n tin u e d f o r an a d d itio n a l f iv e m in u te s.
- ]0 -
T h is r e a c tio n m ix tu re wss th e n tr a n s f e r r e d to e s e p a ra to ry fu n n e l whereupon
th re e Im m iscible Ip y e rs-A 1 S 1 end C form ed.
Leyer A, th e to p I e y e r 1 was
found to c o n s is t l a r g e ly o f cycloh ex en e; s sm ell amount o f th e re g e n e ra te d
n ltr o e th a n e was a ls o c o n ta in e d in t h i s la y e r as in d ic a te d by th e b o ilin g
p o in ts o b ta in e d by f r a c t i o n a t i o n .
Layer B1 th e m a te ria l w ith which t h i s
work i s p r im a r ily concerned, was p r e s e n t in th e amount o f ap p ro x im ately 4
cc.
The bottom la y e r C1 proved to be th e aqueous la y e r w hich c o n tain ed
some d is s o lv e d in o rg a n ic s a l t s .
L ayer B was c u sto m a rily d r ie d w ith sodium s u l f a t e , fo llo w e d by sm all
q u a n t i t i e s o f calciu m s u l f a t e .
Layer B gave o f f a. gas s im ila r in charac­
t e r to t h a t e n su in g from a c a rb o n a te d b e v e ra g e .
Small b u b b le s o f gas
escaped from i t s s u rfa c e a t a v e ry h ig h r a t e , and a 4 cc p o r tio n would
e x h ib it t h i s phenomenon f o r a p e rio d o f s e v e r a l days w ith d e c re a sin g gas
e m is sio n .
I t was found t h a t t h i s b u b b lin g a c t i v i t y could be h a lte d by
s o l i d i f y i n g th e unknown l i q u id in a m ix tu re o f d ry ice and a c e to n e .
Bubb­
lin g would resume once th e fro z e n su b stan ce was p e rm itte d to l i q u i f y .
Layer
B was found to be In s o lu b le in cy clo h ex an e, b u t so lu b le in n ltr o e th a n e ,
e t h e r , a lc o h o l and v a rio u s o th e r o rg a n ic s o lv e n ts .
Layer B, o b ta in e d from
ru n s in which th e bomb te m p eratu re was about 150°C, ap p eared to polym erize
sp o n tan e o u sly a f t e r s ta n d in g f o r a p e rio d o f th re e o r f o u r d a y s, g iv in g a
d a rk c o lo re d , v is c o u s . In s o lu b le m a te r ia l.
V arying c o n d itio n s o f p r e s s u r e , te m p e ra tu re , c a t a l y s t and le n g th o f
tim e p e rm itte d f o r r e a c tio n were employed in an attem p t to o b ta in a d d itio n ­
a l in fo rm a tio n re g a rd in g th e fo rm a tio n o f th e th re e im m iscib le la y e r s upon
h y d r o ly s is o f th e r e a c tio n m ix tu re .
- 31 -
A»
E f f e c t o f V c r l r t lone In P roced u re on Yla id o f P roduct
I.
E fisl
I t wee found t h r t th e a p p lic a tio n o f h e a t to a ty p ic a l bomb charge,
had l i t t l e o r no e f f e c t upon the y ie ld o f la y e r B.
T em peratures o f from
150o to 185° C were m a in ta in ed f o r p e rio d s o f from one to s i x h o u rs , ac conpan led by v a rio u s p re s s u re s o f carbon monoxide.
The h y d r o ly s is p ro d u ct o f
a h e a te d r e a c tio n m ixture appeared to be i d e n t i c a l to t h a t o f an unheated
m ix tu re , e x ce p t t h a t i t s c o lo r was somewhat d a rk e r.
%.
Omission o f N ic k el Cf rb on v l
S e v e ra l a tte m p ts were made to d eterm in e th e source o f la y e r B; th e
p ro c e d u re employed i s e s s e n t i a l l y th e one d e sc rib e d below .
Ten greme o f
th e d ry sodium s a l t o f n i t r o e thane in e s o lv e n t o f 35 cc o f cyclohexane was
s u b je c te d to a p r e s s u r e o f 3115 P« a* i . o f carbon monoxide f o r a p e rio d o f
30 m in u te s.
No h e a t was a p p lie d to th e r e a c tio n m ix tu re .
Upon the subse­
q u en t h y d ro ly s is o f th e bomb charge only two la y e r s a p p ea re d , th e u s u a l
m id d le, re d -b la c k la y e r , b e in g c o m p letely a b s e n t.
2«
Om ission o f S a lt
Uhen the bomb charge c o n s is te d o f one h a l f cc o f n ic k e l carb o n y l end
35 cc o f cyclohexane under a p re s s u re o f 3115 P* a. I . o f carb o n monoxide,
th e h y d ro ly s is p ro d u c t c o n s is te d o f o n ly two la y e r s , la y e r B a g ain b e in g
a b s e n t.
I t was th e n concluded t h a t b o th n ic k e l carb o n y l and th e sodium
s a l t o f n ltr o e th e n e were n e c e s sa ry bomb charge components f o r th e fo rm a tio n
o f th e th re e la y e r s upon h y d r o ly s is .
Use o f g a i t C on tain in g M ethyl >lc o h o l
— 32 —
S ev erp l ru n s were rasde u e ln » th e s tsn d p rd b o a t c h a rg e ; however, in
th e s e in s ta n c e s th e sodium s a l t o f n itr o e th e n e wee n o t c o m p le te ly fre e
from m ethanol.
On one o c c a sio n th e i n i t i a l p re s s u re o f 2500 p . e. i , o f
cprbon monoxide a t 25°C in c re a s e d to e v a lu e o f about 3600 p . s . I . e t s
te m p e ratu re o f 150°C.
S h o rtly a f t e r t h i s p r e s s u r e had been a tta in e d , th e
s a f e ty d is c was ru p tu re d , in d ic a tin g th a t a tremendous p r e s s u r e had sudden­
ly been developed w ith in th e bomb.
There rem ained o n ly a sm all ch ar r e s i ­
due o f the r e a c ta n ts w ith in the bomb.
In th e case o f th e o th e r runs u n d er
c o n s id e r a tio n , th o se em ploying a s a l t m o ist w ith m ethanol, e i t h e r no m iddle
l a y e r o r a m iddle la y e r w ith a g r e a t l y reduced p e rc e n t o f y i e l d r e s u lte d
from th e h y d r o ly s is o f th e bomb c h a rg e .
Ji.
I a P resen ce o f Hydrogen
On one o c c a sio n a ty p ic a l bomb charge u n d e r a p re s s u re o f 2000 p . s . i .
o f carbon monoxide was s u b je c te d to an a d d itio n a l 1600 p . s . I . o f hydro­
gen, and a te m p e ratu re o f I 50°C w^s employed.
An ex trem ely h ig h p re s s u re
o f 7600 p . s . I . was developed w ith in th e bomb d u rin g the c o u rse o f th e
h e a tin g ; how ever, th e f i n a l h y d ro ly s is p ro d u c t c o n tain ed th e custom ary
th re e im m iscible li q u i d s w hich appeared to be I d e n tic a l w ith th o se o b ta in ­
ed when th e hydrogen had been o m itte d .
£.
K y d ro lv sis o f Rim P re v io u s to P r e s s u r in g w ith Carbon Monoxide
A ty p ic a l bomb charge was h y d ro ly sed w ith o u t f i r s t b e in g s u b je c t to
carbon monoxide u n d e r h ig h p r e s s u r e .
o f o n ly la y e r s A end C.
The h y d ro ly s is caused th e fo rm atio n
Layer B was n o n - e x is te n t.
The h e a v ie r la y e r con­
s i s t e d o f w a te r which c o n ta in e d some s o lu b le in o rg a n ic m a te r ia l, p ro b ab ly
- 33 -
sodium su lfF te.
The top leyer war, frrctioneted end wre found to consist of
two fractions; these were id en tified by meens of their b o ilin g points, end
proved to be nltroethene end cyclohexane.
Z-
Variations in Pressure
It wee observed that a pressure drop of approximately I?5 p. s. I.
resulted when the reactants in the borib were nickel carbonyl, cyclohexane,
and carbon monoxide, the sa lt being omitted.
A series
increasing the carbon monoxide pressure from 2^00 p.
at intervals of about 500 p. e. I.
e.
of runs was made by
I. to hb80 p. s. I.
In every case the to ta l pressure drop
over a period of 30 minutes was found to be approximately constant at about
175 P» s • I.
In the eases of greater in it ia l pressure, i t was noticed that
the pressure drop of 175 ?• e» I. was obtained within fiv e to ten minutes,
there being no noticeable pressure change after that time.
The same to ta l
ureasure drop was found to resu lt when a standard bomb charge was employed.
The theoretical pressure drop resulting from the addition of one mole of
carbon monoxide to one mole of the sodium s a lt of nltroethane at a pres­
sure of 3000 p. s. I. ^nd a temperature of 25°C is 5700 p. s . I.
In the
ease o f a typical bomb charge the th eoretical pressure drop is 570 p. s. i .
A to ta l pressure drop of 175 P- «• I- indicated a pressure drop of
approximately 31 percent of the th eoretical.
Attempts a t p u r i f i c a t i o n jlf. Layer g,
JL-
D is tilla tio n at Ornlruary Pressure
The f i r s t attempt made to iso la te and purify layer 3 was by the method
o f ordinary d is t illa t io n .
A small d is t illin g flask-water cooled condenser
— 34 —
o u t f i t was employed.
Normsl d i s t i l l a t i o n to o k p la c e d u rin g th e I n i t i a l
s ta g e s o f b e s tin g , end e b o ilin g p o in t o f 75°""85 C was re c o rd e d .
Suddenly,
w ith th e d i s t i l l a t i o n about o n e -q u a rte r co m p lete, the te m p e ra tu re w ith in
th e d i s t i l l i n g f l a s k ro se to 135°C, and th e re rem ained o n ly a ch arred
re s id u e o f la y e r B.
2.,
Vpcuum D i s t i l l a t i o n
Vacuum d i s t i l l a t i o n was employed n ex t in an a tte m p t to o b ta in la y e r B
In s p u re s t a t e .
In th e f i r s t In s ta n c e , a vacuum o f 40 mm was m a in tain ed ,
and an o i l b a th h e ld c o n s ta n t a t a te m p e ratu re o f 4$ C was u sed to remove
any low b o ilin g m a te r ia l t h a t m ight have been p re s e n t as Im p u r itie s w ith in
la y e r B.
A few cc o f d i s t i l l a t e was o b ta in e d a t t h i s te m p e ra tu re , b u t as
th e te m p e ra tu re o f th e o i l b a th was r a is e d , deco m p o sitio n o f th e m a te ria l
w ith in th e f l a s k took p la c e .
On s e v e ra l o c c a sio n s th e deco m p o sitio n was
so v i o l e n t t h a t some damage was caused to th e vacuum d i s t i l l a t i o n appara­
tu s .
Vacuum d i s t i l l a t i o n un d er p r e s s u r e s a s low as 10 mm was t r i e d , b u t
in ev ery case com plete c h a rrin g o f la y e r B r e s u lte d .
N ltro e th a n e can be
d i s t i l l e d In a norm al manner w ith o u t dan g er o f spontaneous d eco m p o sitio n .
3..
Steam D i s t i l l a t i o n
The d i s t i l l a t e r e s u l t i n g from th e steam d i s t i l l a t i o n o f la y e r B c o n s is ­
te d o f two im m iscib le l i q u i d s .
These li q u i d s were i d e n t i f i e d by means o f
t h e i r b o ilin g p o in ts and were found to be w a te r and n i t r o e th a n e .
A lthough
la y e r B was in s o lu b le in cyclohexane b e fo re b e in g s u b je c te d to steam d is ­
t i l l a t i o n , th e n itr o e th a n e p o r tio n o f th e d i s t i l l a t e was r e a d i l y s o lu b le
in cy clo h ex an e.
- 35 -
C r y s tg lltz p tlo n Pt Lov Tmmnmreturm
An mttempt vee mrnde to c r y s t a l l i s e la y e r B a t a Iov te m p e ra tu re , remove
th e s o lv e n t, and th u s r e t a i n a p u re p ro d u c t.
A pproxim ately one cc o f l a y e r
B V=S d is s o lv e d in th re e cc o f e th a n o l c o n ta in e d in a t e s t tubes th i s v e s­
s e l was p la c e d In an p c eto n e -d ry ic e m ix tu re which m a in ta in ed a tem p eratu re
o f about - 83°C.
e th a n o l s o lu tio n .
W ithin a p e rio d o f s e v e ra l m in u tes, c r y s t a l s formed in th e
I t is to be n o te d th a t th e m e ltin g p o in t o f pure
e th a n o l i s known to be -112°C .
A sm all H lrs c h f i l t e r f u n n e l, surrounded
by an a c e to n e -d ry ic e m ix tu re , was u sed to a id in the s e p a r a tio n o f th e
c r y s t a l s from th e s o lv e n t.
E f f e c tiv e s e p a ra tio n o f th e c r y s t a l s by t h i s
method was n o t p r a c t i c a l , a lth o u g h a few I n d iv id u a l c r y s t a l s were i s o la te d .
The i s o l a t e d s u b sta n c e was found to be la r g e ly In o rg an ic in n a tu re .
JSU A ttem pts i s . I d e n t i f y Layer
(1 )
and P rep a re L e r iv a tlv e s
S c h lf f 1S and T o lle n 1s T est
S c h i f f s and T o lle n 1s t e s t s were conducted in an a tte m p t to determ ine
th e p re se n c e o f an aldehyde lin k a g e w ith in la y e r B.
C o n clu siv e t e s t s were
n o t o b ta in e d , how ever, f o r i t was found t h a t n itr o e th s n e a ls o caused th e
appearance o f a p o s i t i v e t e s t in b o th c a s e s .
I t was o bserved t h a t when e q u al amounts o f la y e r B and n itr o e th s n e
were added to th e above-m entioned re a g e n ts c o n ta in e d in d i f f e r e n t t e s t
tu b e s , p o s itiv e t e s t s were developed much more q u ic k ly in th e case o f
la y e r B.
(2 )
2 .h -d in ltro n h e n y !h y d ra z in e and S e a ic a rb s z id e H y d ro ch lo rid e
I t was im p o ssib le to o b ta in a r e a c tio n betw een t h i s l i q u i d and 2 ,4 - d i -
- 36 -
n i t rophenyI i v u r p z iue u r s e ^ io e rb b s id e h y d ro c h lo rid e .
The method f o r th e
p r e p a r a tio n o f tn e se d e r iv e tiv e e i s t h e t d e s c rib e d by S h r in e r end Fuson
(3 )
(26)
S c h lf f 1B .Bese F o r a e tion
An a tte m p t wee made to form a S c n if f 1s b ase by i n t e r a c t i o n o f la y e r B
and p - t o I u id I n e .
(U)
There appeared to be no r e a c tio n .
A cetal For m atIon
A s ta n d a rd r e a c tio n f o r a c e ta l p r e p a r a tio n in v o lv e s i n t e r a c t i o n be­
tween an aldehyde and an a lc o h o l.
In th e p r e s e n t case la y e r B was h e a te d
w ith an e q u iv a le n t amount o f a lc o h o l in th e p re sen c e o f calciu m c h lo rin e .
The r e a c tio n m ix tu re c o n ta in e d no a c e ta l, th u s tn e i d e n t i t y o f la y e r B was
s t i l l unknown.
(5)
Oxidation
I t was o bserved th a t a one p e rc e n t s o lu tio n o f p o ta ssiu m perm anganate
was r e a d ily reduced when b ro u g h t in to c o n ta c t w ith la y e r B; i t was, th e re ­
f o r e . p o s tu la te d t h a t an o x id iz e b le group e x is te d in th e u n id e n tif ie d
s u b s ta n c e .
H itro e th a n e was found to e x h ib it t h i s p ro p e rty a ls o .
The o x id a tio n was c a r r ie d o u t u s in g a f i v e p e rc e n t p o ta ssiu m perman­
g a n ate s o lu tio n .
This was added to th e t y p i c a l bomb charge a f t e r a p re s ­
su re o f U200 p . s . i . o f carbon monoxide had been e x e rte d on i t f o r a
p e rio d o f 30 m inutes b u t b e fo re h y d ro ly s is was a tte m p te d .
The excess p o ta s ­
sium perm anganate and p r e c i p i t a t e d manganese d io x id e were s e p a ra te d from th e
aqueous s o lu tio n by c e n tr if u g a tio n .
vacuo to a volume o f about 15 c c .
The w a te r p o r tio n was d i s t i l l e d in
By th e a d d itio n o f a b s o lu te a lc o h o l to
th e aqueous la y e r and by re p e a te d vacuum d i s t i l l a t i o n s , t h i s w a ter was re ­
- 37 -
moved ee e component of th e e z e o tro p lc e lc o h o l-w e te r m ix tu re .
There r e -
rneined in th e e le o h o I s o lu tio n e g re y -w h ite s o lid which was se p a ra te d from
th e e th a n o l by f i l t r a t i o n .
The s o lid was th en a i r d r ie d .
The h y d ro ly s is o f t h i s s a l t w ith th e c a lc u la te d amount o f s u lf u r ic
a c id was c a r r ie d o u t in a sm all th re e neck f l a s k in a s o lu tio n o f a b s o lu te
e th e r,
t brown g a s , p ro b a b ly n itr o g e n d io x id e , was g iv en o f f d u rin g th e
h y d r o ly s is .
The e t h e r la y e r was d r ie d w ith p h o sp h o ric a n h y d rid e and subse­
q u e n tly vacuum d i s t i l l e d .
There rem ained in th e d i s t i l l i n g f l a s k a. y e llo w -
w h ite s o lid which was r e c r y s t a l l i z e d from carbon d i s u l f i d e .
c r y s t a l s m elted a t a te m p eratu re o f 80°C.
The pure
A n e u t r a l i z a t i o n e q u iv a le n t was
run u s in g .1235 S o f th e r e c r y s t a l l i z e d s o lid d is s o lv e d in 50 cc o f a lc o h o l;
th e s o lu tio n was t i t r a t e d w ith s ta n d a rd sodium hydroxide (.1 6 8 5 N) u sin g
p h e n o lp h th a le in a s an in d ic a to r .
Seven and e le v e n one h u n d re d th s cc o f
a l k a l i was re q u ire d f o r n e u t r a l i z a t i o n .
N. S . =
Of „.S£ffl^le,,.ji; J,QOQ_____
volume o f a l k a l i x n o rm a lity .
The m o le c u lar w eig h t i s e q u a l to th e p ro d u c t o f th e n e u t r a l i z a t i o n e q u iv a l­
e n t end th e number o f a c id ic groups in th e m o lecu le.
The m o lecu lar w eig h t
was c a lc u la te d as 103 on th e assum ption t h a t th e unknown s o l i d c o n tain ed
one carb o x y l g ro u p .
N itr o - a c e tic a c id h as a m e ltin g p o in t o f 8 4 °, and a
m o le c u la r w eight o f 105: th u s i t was concluded t h a t n i t r o - a c e t i c a c id , and
n o t a Ip h a -n itr o p r o p Io n ic a c id , was th e p ro d u c t o b ta in e d from th e o x id a tio n
o f th e bomb c h a rg e .
(6)
E e d u c tlo a
The re d u c tio n o f lp y e r B wee a ttem p ted p t hydrogen p r e s s u r e e rpn»ln»
from 50 p . s . I . to 3000 p . e. I .
Absolute ethenol wes used
ps
t solvent.
Two c p tp ly s ts were u se d , one b e in g U. 0 . P . n ic k e l c a t a l y s t , ^nd the o th e r
Adpjm1e p l o t Inum d io x id e .
In ev ery case th e re d u c tio n p ro d u c ts sm elled
s tr o n g ly o f am ine, p ro b a b ly due to the p re se n c e o f e th y lrm ln e ; fu rth e rm o re ,
th e e n t i r e reduced l l o u l d d i s t i l l e d f t s te m p e ratu re below IlO 0C.
A ll o f
th e p ro d u c ts which m ight r e s u l t from th e re d u c tio n o f 2- n ltr o p ro p a n a I,
would e i t h e r be s o lid a t room te m p e ra tu re , o r have p b o ilin g p o in t w ith in
th e range 16$0«-195°C.
R eduction was e ls e a ttem p ted u s in g hydro io d ic a c id
end red phosphorus a c c o rd in g to th e p ro c e d u re su g g ested by Ecarrow and
( 24 )
A lle n
. The r e s u l t s were n e g a tiv e .
£•
L R eactio n In v o lv in g th e S a lt o f Z -iiltro rro u a n e
D u r in ' th e c o u rse o f t h i s work I t ap p eared th e t a s a l t o f a n ltr o
compound which c o n ta in e d no a Iphs hydrogen m ight y ie ld s f i n a l p ro d u ct o f
a more s ta b le n a t u r e .
The sodium s a l t o f 2- n ltro p ro p a n e was employed In
a tte m p t to confirm t h i s th e o ry .
On s e v e ra l o c c a s io n s th e sodium s a l t o f 2 -n itro p ro p e n e was mixed
w ith cyclohexane and n ic k e l c a rb o n y l, ^nd p la c e d under a h ig h p re s su re o f
carbon monoxide.
H y d ro ly sis caused th e fo rm a tio n o f a l i g h t green s o l i d ,
which was e a s i l y sublim ed to a. p u re w h ite s o l i d .
s u b sta n c e was found to be 760-77°C .
The m e ltin g p o in t o f t h i s
The sublim ed s o lid d is s o lv e d in c o lo r ­
l e s s o rg a n ic s o lv e n ts w ith the p ro d u c tio n o f a g re e n -b lu e c o lo re d liq u id ;
t h i s i s c h a r a c t e r i s t i c o f n ltr o s o and p e e u d o n itro so compounds.
A d d itio n a l
-39I n r e e t i ^ s t l o n I n d ic s te d t h s t th e w h ite c r y s t e l l i n e s o lid wss p ro p y l pseudon l t r o l , CH^C(NOg)NOCEj.
(27)
The m e ltin g p o in t jiv e n by S c h o llx
fo r th is
compound i s 76° .
I t was su b se q u e n tly d is c o v e re d t h s t th e a c i d i f i c a t i o n o f th e sodium
s a l t o f 2-n itro p ro p e n e r e s u lte d in th e fo rm a tio n o f p ro p y l p e e u d o n itro le ,
th u s th e carbon monoxide p la y e d no p a r t in th e r e a c tio n .
I t was f u r t h e r
found t h a t p ro p y l p e e u d o n itro le i s p re p a re d i n d u s t r i a l l y by a r e a c tio n o f
2—n itro p ro p a n e w ith c o n c e n tra te d a l k a l i
2- n itro p ro p a n e was c o n se q u e n tly h a lte d .
( 21)
.
F u r th e r I n v e s tig a tio n u s in g
-UO-
V.
DI SCUSSIOH 0£ EXPERIMENTAL RESULTS
Steam d i e t i l l a t i o n o f la y e r B y ie ld e d n itr o e th a n e a s one o f the p ro ­
d u c ts .
The f a c t t h a t n itr o e th a n e i s s o lu b le in cyclohexane w hereas la y e r
B i s n o t, a f f o r d s p ro o f th a t a su b sta n c e d i f f e r e n t from th e s t a r t i n g
m a te r ia ls r e s u lte d from a ty p i c a l ru n .
The e x p e rim e n ta l r e s u l t s In d ic a te th = t th e h y d ro ly s is p ro d u c t o f a
ty p ic a l bomb charge which had n o t been s u b je c te d to h ig h p r e s s u r e s o f
carbon monoxide c o n ta in e d no la y e r B, w h ereas, a p r e s s u r iz e d re a c tio n
m ix tu re y ie ld e d la y e r B upon h y d r o ly s is ,
fu rth e rm o re , i t was experimen­
t a l l y shown t h a t b o th n ic k e l c arb o n y l and th e sodium s a l t o f n i t r o e thane
were n e c e s s a ry r e a c ta n ts f o r th e fo rm atio n o f la y e r B.
The id en tical pressure drops resu ltin g from the carbon monoxide
pressurizing of a typical bomb charge, and a reaction mixture which con­
tained no s a lt, suggest that the pressure drop was due to the so lu b ility
of carbon monoxide in the solvent.
Rie i n s t a b i l i t y o f la y e r B, e s p e c ia ll y a t e le v a te d te m p e ra tu re s,
may be I n te r p r e te d as I n d ic a tin g th e e x ie ta n c e o f an e x tre m ely u n s ta b le
m o le c u le.
Such a m olecule c o u ld p o s s ib ly r e s u l t from a c o o rd in a tio n
p ro d u c t formed betw een carbon monoxide and n itr o e th a n e a f t e r th e h y d ro ly s is
o f a ty p ic a l bomb c h a rg e .
c o o rd in a tio n p ro d u c t.
CO[CE ( C ^ ) r NO2H j2 i s su g g ested a s a p o s s ib le
T his th e o ry can a ls o acco u n t f o r th e e f fe rv e s c e n t
a c t i v i t y o f la y e r B.
Carbon monoxide, i f r e le a s e d from la y e r B, could a c t a s a reducing
a g e n t, and th u s b rin g about a more q u ic k ly developed T o lle n 1s and S c h i f f s
— 41 —
t e s t , th a n th o se r e s u ltin '* from th e u se o f n t t r o ethane and th e re s p e c tiv e
re a g e n t.
The f a c t th a t la y e r 3 o b ta in e d from ru n s in which th e bomb was h e a te d
te n d s to p o ly m erize on s ta n d in g , su g g e sts th e p re sen c e o f an u n s a tu ra te d
g ro u p in g , such as th e c arb o n y l g ro u p .
M aldehyde group, i f p re s e n t in
la y e r B, should have e x h ib ite d th e c h a r a c t e r i s t i c p r o p e r tie s o f t h i s
g ro u p , y e t th e i n a b i l i t y o f la y e r B to e n te r In to r e a c tio n w ith 2 , 4 - d i n l t r o p h e n y lh y d ra f in e , sem icarb azid e h y d ro c h lo rid e , e th a n o l, and p - t o lu ld in e in ­
d i c a t e s th a t 2 - n itro p ro p e n a l was n o t a c o n s ti tu e n t o f la y e r B.
A d d itio n a l in v e s t ig a ti o n o f la y e r 3 may r e v e a l th e tr u e id e n t i t y o f
t h i s su b sta n c e .
Al p r e s e n t, evidence in d ic a te s t h a t carbon monoxide does
n o t r e a c t w ith th e sodium s a l t o f n ltr o e th a n e w ith the p ro d u c tio n o f a
c a rb o n y l .group c o n ta in in g compound.
— lf'2 —
V I. STZfliRT
1.
The p e ld h y d ro ly e la o f a p r e s s u r iz e d bomb chsr»e c o n s is tin g o f carbon
monoxide, n ic k e l c a rb o n y l, th e sodium s a l t o f n ltr o e th p n e In cyclo­
hexane, caused th e fo rm atio n o f th re e Im m iscible l i q u i d s .
th e top l a y e r , c o n s is te d o f cyclohexane and n ltr o e th a n e .
th e m iddle l a y e r , was th e u n id e n tif ie d m a te r ia l.
L iquid A,
Layer B,
L ayer C, the bottom
l a y e r , was composed o f w a te r and In o rg a n ic s a l t s .
2.
Layer B was o f an u n s ta b le n a tu r e , and i t s p u r i f i c a t i o n was no t pos­
s ib le ,
3.
The f a i l u r e o f la y e r B to r e a c t w ith 2 , h -d in ltro p h e n y !h y d ra z in e , setnlc a rb a z ld e h y d ro c h lo rid e , a lc o h o l and p - t o I u id In e , i n d ic a te s th a t 2- n i t r o p ro p e n s l was n o t p r e s e n t.
b.
I t i s su g g ested t h a t la y e r B c o n s is te d o f a c o o rd in a tio n compound form ed
betw een carbon monoxide and n ltr o e th a n e .
VII.
;CE30WI&D9M3NT
The p u th o r w ish es to te k e t h i s o p p o rtu n ity to e x p re ss h ie s in c e re
p p p re c ie tlo n pnd thpnks to D r. Ip u ren ce 0 . B in d e r, J r . f o r h i s p e rs o n a l
guldpnce pnd I n s p i r a t i o n d u rin g t h i s r e s e a r c h , end to th e s t a f f o f th e
C hem istry D epartm ent f o r t h e i r many h e lp f u l s u g g e s tio n s .
He e lso w ishes
to thank th e O ffic e o f Hsvp I H eseprch o f th e Departm ent o f Hpvy f o r th e
g ra n t which made t h i s in v e s t ig a ti o n p o s s ib le .
m i.
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MONTANA STATE UNIVERSITY LIBRARIES
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