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The Nitroparaffins

The Nitroparaffins

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THE
KITROPARAFFINS
H.
B.
HASS
AND
ELIZABETH
F.
RILEY
Department
of
Chemistry, Purdue University, and Purdue Research Foundation, Lafayette,IndianaReceived May
6,
1941
CONTENTS
I.
Introduction..
........................................
....................
373
11.
The Victor Meyer reaction..
.................................................
374
111.
Miscellaneous methods
of
introducing the nitro group into aliphatic compounds..
374
IV. Liquid-phase nitration
of
saturated hydrocarbons.
............................
376
VI.
Synthesis
of
aliphatic polynitro compounds
....................
383
V. Vapor-phase nitration..
......................................
1.
Reduction to
2.
Reduction to
.................................
3903.
Reduction to
................
392
1.
Action
of
mineral acids to yield hydroxamic acids and carboxylic acids.
3953.
The red-white-and-blue reaction.
..................................
399
2.
Bction
of
mineral acids upon salts
of
aci-nitroparaffins..
...........
398
C.
Action
of
bases upon nitroparaffins.
....................
1.
Halogenation in the presence
of
bases..
...........
2.
Halogenation in the absence
of
bases
........................
405
E.
Condensation with aldehydes to yield nit
01s.
....................
406
1.
Derivatives
of
nitroalcohols..
...................
.......
408
F.
Condensation with aldehydes to yield nitroolefins
.......................
409
1.
Other syntheses
of
nitroolefins.
....................................
411
2.
Reduction
of
nitroolefins to amines..
...........
..
4123.
Reduction
of
nitroolefins to aldoximes, ketoxim
.
.
412
4.
hddition
of
nitroolefins to cyclopentadiene
.........................
413
5.
Addition
of
nitroolefins to compounds containing active hydrogen.,
.
414
G.
Reaction
of
aryldiazonium salts with salts
of
aci-nitroparaffins
,
.
.
,
.
.
,
. .
415416
I.
Analytical reactions
of
nitroparaffins..
.
....................
416
D.
Halogenation..
.......................................
H. Addition
of
nitroparaffins to activated double bonds..
...
I. INTRODUCTION
In May,
1940,
the first productionofnitroparaffins on an industrial scaleoccurred at the plant
of
the Commercial Solvents Corporation, Peoria, Illinois.The process involved the newly invented vapor-phase nitration technic, which
was
first
employed by
Hass,
Hodge, and Vanderbilt
(132, 133, 134)
at PurdueUniversity, and which has been in active development since the autumn
of
1930.
By
nitrating
t'he
propane
of
natural gas andofpetroleum,
which
is available in
373
 
374
H.
B.
HASS
AND
ELIZABETH
F.
RILEY
practically unlimited quantities, the first
four
nitroparaffins are produced:nitromethane, nitroethane, l-nitropropane, and 2-nitropropane.The nitrationof any of the volatile higher or lower homologs of the paraffinic or naphthenicseries can be accomplished by the same general procedure. From our mostinexpensive organic raw materials it is thus possible to obtain nitro derivativesby the action of the acid which the researches of Haber and Ostwald have placedamong our most available and cheapest inorganic reagents.
It
is thereforean appropriate time to review’ the syntheses, properties, uses, and reactionsof the nitroparaffins and their immediate derivatives.
11.
THE
VICTOR
MEYER
REACTIONIn 1872 Meyer and Stuber (271) reported that the reaction between amyliodide and silver nitrite had yielded nitropentane and amyl nitrite. At thattime the aromatic nitro derivatives were already of substantial importance,since Mauvein had been made by Perkin sixteen years before and the anilinedye industry was in active development.
It
is not surprising, therefore, thatthis first synthesis of
a
nitroparaffin2 should have aroused general interest andresulted in the publication
of
a considerable number of papers. The VictorMeyer reaction has been reviewed and extended by Reynolds and Adkins (329),
so
that no detailed discussion need be given here.
It
should be mentioned, how-ever, that it has been found suitable for producing not only nitroparaffins butalso polynitroparaffins
(55),
nitroalcohols
(81),
nitroolefins
(56,
260),
nitroethers,nitroketones, and many other aliphatic nitro compounds.Salts of a-halocarboxylic acids react similarly even with sodium nitrite andyield salts of a-nitrocarboxylic acids which readily decompose, producing nitro-paraffins and metallic bicarbonates. Kolbe (202) reported this reaction onlyfive months after hleyer and Stiiber’s first announcement of the nitroparaffins?The reasons for the wide differences between the ratios of organic nitrite andnitro derivative obtained from various organic halides and metallic nitrites arestill obscure. Reynolds and Adkins have postulated that an addition complexis formed between the two reagents and that every constituent of the complex
is
thus in a position to influence the further course of the reaction to yield eithernitrite
or
nitro compound.
It
is probably of significance that nitrites readilyrearrange
to
nitro derivatives at elevated temperatures (287). The yield maytherefore fluctuate with the amount of local overheating.
111.
MISCELLANEOUS
ETHODS
F
INTRODUCING
HE
NITRO GROUP
INTO
ALIPHATIC
OMPOUXDS
Thusmethylamine, ethylamine, tert-butylamine, and benzylamine have been oxidized
to
the corresponding nitro compounds. Bamberger and Seligman (18) give thefollowing equations
:
94), Hass
(131),
and Gabriel
(107,
108).
the very extensive literature, the present article is by no means exhaustive.
*
Chloropicrin and bromopicrin had been made much earlier (365, 366).
3
For
a recommended laboratory procedure, see
Organic
Syntheses
(291).
(a)
A primary amine may be oxidized directly to a nitroparaffin.
1
Brief reviews of this general nature have recently appeared by Hurd
(115),
Ellis (93,Because
of
the limitations of time and space and
 
THE
NITROPARAFFINS
375
HC(OH)=KOH
7
L
CHiNHz
+
CSNHOH
+
CHz=NOH
1
I
HzO
+
HCN CHzNOzH+ C&NOzHCOOH
(b)
Halonitroparaffins may be treated with zinc alkyls to replace one, two,Bevad
(32, 33)
obtained tertiary
(c)
By using a metallic derivative
of
an aci-nitroparaffin and an alkyl halide,or three halogen atoms with alkyl groups.nitrobutane by the action of dimethylzinc upon chloropicrin.one obtains either a nitronic ester or a higher nitro derivative.
Rz
C=N02
M*
+
RX
Rz
C=N02
R
+
MX
L
RZCR’
+
MX
I
NO2
*
(M
=
K,
Ka,
r
Ag)
This reaction has recently been reviewed and extended by Brown and Shriner
(57),
Thurston and Shriner
(378),
and Weisler
(398).
The nitronic esters arefrequently instable, decomposing as follows
:
0
t
RzC=N-OCHzR’
+
RaCeNOH
+
R’CHO
As
in the Victor Meyer reaction, very different ratios of nitro derivative to by-product are observed, depending upon the particular reactants. There is someevidence
(398)
that high yields of nitro derivative correlate positively with thelability of the halogen atom. In the related synthesis of the dinitroparaffins
(cf.
section
VI)
by the reaction
X
I
R2C=N02Na
+
RzCNO2
+
RzC-CR2
+
NaX
II
NO2 NO2best yields were obtained with iodides and poorest with chlorides; these resultsare, of course, in harmony with the above generalization. -41kyl sulfates arealso suitable as alkylating reagents for nitroparaffins
(11).
(d)
An alkyl nitrite may be caused to rearrange to form
a
nitroparaffin
(111,
287).
When ethyl nitrite and hydrogen are passed over finely divided nickelor nickelized asbestos, amines are formed. This reaction is ascribed
to
pre-liminary rearrangement of the nitrite to nitroparaffin.Thereactions between olefins and the oxides
of
nitrogen are complex and quiteworthy
of
a separate review; apparently either or both of the doubly bound
(e)
Certain olefins will add nitrogen tetroxide
to
yield dinitroparafis.

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