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Патент USA US2113813

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Patented Apr. 12, 1938 -4
2,113,813 1
' ' UNITED STATES PATENT OFFICE
2,113,818
. METHOD OF PRODUCING CARBOXYLIO
ACIDS FROM
NITRO’HYDROCARBONS
Samuel 13. Lippincott, Terre Bautc, lnd., mlgllm'
to Commercial Solvents Corporation, Terrc
Hante, Indl, a corporation of Maryland
No Drawing.‘ Application June 14, 1937,
Serial No. 148.108.
-
v
'2 Claims. (01. zen-1121'
My invention relates. to the production of car
boxylict acids. More ‘specifically; my, invention
relates to the production of. carboxylic acids from
primary nitrohydrocarbons.‘
5
‘
_'
-
The primary nitrohydrocarbons may be ob:
tained according to a. number' of diil'erent re
actions, but are most economically produced by
vapor phase nitration of saturated hydrocarbons
in accordance with the process of U. S. Patent
10 1,967,667 by H.- B. Hass, E. B. Hodge and-‘B. M.
Vanderbilt. The nitropara?lns produced by this
process from petroleum hydrocarbons constitute
an advantageously cheap source of aliphatic com
pounds for the production of organic chemicals.
15 I have now found that carboxylic acids may be
any particular nitrohydrocarbons‘of this series,
but is‘generally applicable to all nitrohydrocar
bons containing the group --CH2.NO2'.
,
'I'he'aeids which may be used to effect the con
version of the nitrohydrocarbons in my process
may be any sulfonic acids having dissociation
constants in excess of 10-’. Among such acids
may be mentioned ethyl sulfonic acid, benzene
sulfonic acid, m-nitro-benzene sulfonic acid,
m-sulfo-benzoic acid, p-toluene sulfonic acid, beta 10
naphthalene sulfonic acid, 1,5-nitro-naphthalene
sulfonic acid, and m-benzene disulfonic acid. It
will be evident, of course, that although any sul
fonic acid having a dissociation constant in ex- 7
cess of the speci?ed value will serve to eiiect the 15
conversion of the nitrohydrocarbon into the
sistently satisfactory yields and conversions,‘ by ' corresponding carboxylic acid, some of these
produced from these nitrohydrocarbons with con
reacting the nitrohydrocarbons 'with 'sulfonic , acids will be less advantageous than others.
acidsunder'the controlled conditions described ' Thus, I- have found that some of these acids are
less active than others and must be employed in
20 below. ,'
.
'
y
;
greater
amounts, relative tothe nitrohydrocarbon, ‘
The process of my present invention may be
brie?y described as comprising ‘ subjecting the to secure the desired degree of conversion. From
primary nitrohydrocarbon, preferably at‘a tem- _ the standpoint vof activity, . and also from the
perature ‘of 100° C. to 160° C. to the‘ action of at standpoint of raw material cost,v I prefer to utilize
benzene sulfonic acid, and I have found that the 25
25 least one mol. of a sulfonic acid, having a ‘dis "commercial ‘grades of this acid,‘ such as “65%”
sociation constant in excess of 10-’,per mol. of
nitrohydrocarbon, the initial, concentration of
said acid preferably being at least 80% by weight,‘
.and ‘providing either initially or at' a later stage
'30
sulfonic acidywhich contain some sulfuric acid
are very satisfactory in _my process, It should
be distinctly understood, however, that my in
vention is not to be limited to the use of this or .
of thev reaction at least. 1 mol. of water per mol.'of any
of the other acids mentioned above. Any
nitrohydrocar'bon to complete the conversion to
the carboxylic acid stage. According to this re . sulfonic acid having a dissociation constant in
action one mol. of hydroxylamine is formed for . excess of 10-2 vmay be used, and onelskilled in
each mol. of carboxylic acid produced, but under the art can readily choose a suitable acid‘ for
v:55
certain reaction conditions there, is- a tendency for _
thehydroxylamine to be destroyed,- and these two
the particular reaction conditions to be employed. 35
I have found that the‘ reaction of > the present
products are therefore not always recovered in invention proceeds most rapidly with very con
acid solutions, but that the reaction
equimolecular amounts. The hydroxylamine is, ' '_ .centrated
will not proceed to completion unless 1 mol. of
of course, produced in the form of a sulionic acid water
per mol. of nitrohydrocarbon is provided 40
40 salt, which maybe separated from carboxylic'acid in the reaction mixture. Thus, when employing >
and unreacted' materials in any suitable manner.
‘The carboxylic acid may be recovered from the _
reaction mixture according to known methods
such as distillation or extraction.
.
anhydrous acids, a ?nal conversion of nitrohy
drocarb'onv to carboxylic acid of the order of 50%
is obtained‘; but optimum conversion may then
The nitrohydrocarbons which are suitablegfor be secured by introducing 1 mol. of water per
my process constitute the primary nitrohydro - mol. of .nitrohydrocarbon, and continuing the
carbons, as, for example, the primary. nitro-' reaction until the intermediate products are com
para?ins, and the arylor cycloalkyl substituted
primary nitropara?ins such as phenyl-nitro
methane or 1-nitro-2~cyclohexylethane.‘ _‘I'h,e
pletely transformed to the carboxylic acid stage. ‘ '
By this method it is possible to accelerate the ?rst
stage of the reaction with resulting decrease in
primary nitroparailins containing two or more ‘ I the overall reaction time. The reaction is strong
carbon atoms are particularly S111t€(1/'-1-Ol‘ use in ly exothermic, however, and the high reaction
my process. Among the nitropa'ra?lns; nitro ' velocity secured by the use of very concentrated
acids may cause di?iculty unless adequate cool
ethane, l-nitropropane, l-nitr'obutane,‘ and 1
nitro-2-methyl propane are particularly advan
ing means are provided. For this reason-it is
tageous in ._that their boiling points constitute
suitable reaction temperatures, and the reaction
desirable to utilize an acid solution containing a
mixture may thus be simply re?uxed to effect the
60
conversion. It should, be distinctly understood,
however, that my invention is not to be limited to
certain'amount of water, preferably approxl- ,'
mately- 1 mol. of water per mol. of nitrohydro- _' _ '
_ carbon. However, in the case of the lower mo
lecular weight sulfonic acids the presence of 1
2
mol. of water per mol. of acid may lower the con
C. At "the end of this period 9 parts'of water
centration below the optimum for conversion.
was introduced, and‘the mixture was further re-'
?uxed for. 10 minutes.
most satisfactory reaction mixture constitutes 1 were secured:
Thus, in the case of benzene sulfonic acid, the
_mol. of nitrohydrocarbon, and 1 mol. of benzene ‘
sulfonic acid in the form of 95% acid (constitut—
ing 1 mol. of acid and 1/2 mol. of water) ._ With
this mixture the acid concentration is sufficiently
high to give rise to a rapid reaction rate without '
10 undue dimculty from the standpoint ofrheat evo
lution, and one-half of the required amount of
water for the reaction is present in the initial
mixture. In this case the remaining one-half of
the required water may be added at the con
15 clusion- of the initial reaction, and the mixture
The _ following
results. -
Yield‘besed on
Conversion beeed
Product
nitropropene
reacted
on nitm pane
intr need
Proplonicaeid .............. _-
91%
91% '
_
'
Example III
A reaction mixture comprising 89 parts by
weight of l-nitropropane and 190 parts of p
toluene s'ulfonic acid (consisting of 172 parts 15
then further re?uxed for 5-15 minutes; or the
acid and 18 parts water of crystallization) was
additional water may be provided in the proce
dure utilized‘ for recovering the products, as, for
example, in a steam distillation. In general, it
may be said that the preferred acid concentra
re?uxed with stirring for 6'hours. During this
period the reaction temperature ranged from 125 -
to 131°C. The following results were secured:
tion is that which will give rise to a. rapid con
version rate without unduly rapid evolution of
heat, which will be sui?ciently miscible with the
nitrohydrocarbon to insure ease of reaction, and
25 which will give rise to a ?nal solution in which
the resulting hydroxylamine salt is insoluble. I
An acid of 80% to 100% concentration will us
ually be found _to be-satisfactory, and prelim
inary experiments will readily determine the op
30 timum\ concentration for any particular 'acid
- l0
Yield based on
nitropropane
Product
reacted
Propionic acid_r ____________ .-
Conversion based
on nitro mpene
‘
90%
in
need
74%
l
I
.
.
‘
Example IV
A reaction mixture comprising 89' parts by
weight of l-nitropropane and 226 parts of beta
naphthalene sulfonic acid (208 parts acid and 18 30
parts water of crystallization) was re?uxed with
under the reaction conditions tpbe employed.
stirring for 3% hours. During this period the
The reaction temperature "is preferably main
reaction temperature'ranged from 120 to 125° C.
tained between 100° C. and 160° C. At tempera
tures lower than 100° C. the reaction velocity ‘The following results were secured:
35 tends to become irnsatisi’actorily low, and at tem
peratures above 160° C. there is an increased ten
dency for decomposition reactions to take place.
It will be evident, however, that higher tempera
’tures may be-suitably employed if the time of
40 reaction is reduced su?lciently' to avoid undue
'
I
Product
.
‘
' - Conversion
Yield based on
nitropropure _
_
Propionic acid“; ___________ __
'
based on
nitro
propane intro
WM
duoed
85%
78%
decomposition of the products. ' In a continuous
process, for example, higher temperatures may be)
used in certain cases by increasing the space ve
locity in the reaction zone to a point at which
45 the decomposition reactions proceed only to a
, very slight extent.
-
My invention may beillustrated by the follow
ing speci?c examples in which various nitrohy
drocarbons are converted to the corresponding
carboxylic acids by the use of a number of di?’er
ent types of acids as converting agents.
Example V
'
_ -
A reactionv mixture comprising 89 parts by
weight of l-nitropropane and 158 parts .of "65%"
‘commercial benrene sulfonic acid was re?uxed
for‘ 3 hours. The reaction temperature ranged
from 130 to 146° C. At the end of this period,
,18 parts of water was introduced, and the mix
ture was‘ further re?uxed for 10 minutes. The
following results were secured:
Example I
.
A reaction ' mixturefcomprising' 75 parts by
65 weight of nitroethan‘e,’ ‘ 158 parts, of commercial
“65%” benzene sulfonic acid was re?uxed with
stirring for approximately 4 'hours. The reaction
temperature during this period ranged from 118
to 142° C. At the end of this period'18 parts of
Yieldbesedon
»
Product
nitropropene
Pmpionicacid _____ -‘. ____
"
01%
Example VI '
p
Conversion
besedon nitro~
0695'
'
water were introduced, and the mixture was fur
ther re?uxed for 10 minutes.
suits were secured:
" Product
65
.
A-reacuonmrxture comprising 103 parts by
following »re-_ weight
or l-nitrobutane, 158 parts or commercial '
V “65%" benzene sulfonic acid was re?uxed with
Yield based on_
Conyerxionbased ,
nitroethene
‘
reacted
Acetic acid ......... ,_s._._._____,
91%
>on nitroethane
_
introduced -
‘ v90%
’
stirring for 3 hours. During this-period there
‘action temperature ranged from 145 to 158' C.
-At'the end of this period, 18 parts of water was
introduced, and the mixture was further re?uxed
for 10 minutes. The following results were se
cured:
"
lmmlell-
'
'
»
*
‘A reaction'mixture comprising 89‘ parts by‘
‘weight of l-nitropropane, 158
.
,propeneintro
of benzene
.sulfonic acid and '9 parts of water was ‘re?uxed.
with stirring for 8 hours. The reaction“ temper
75 ature during this period ranged from 120 to 135°
Product
'Yieldbesedon Conversionbued
'
nitrobutenere-
on nitmbntene
acted
introduced
90%-
sag,
_
pummeled. ............... ..x -
-
3
"2. process for'the production of fatty acids
Example v11
_
from primary nitroparamns, which comprises
A reaction-mixture comprising 103 parts by ‘subjecting the nitropara?ln at a temperature
- weight of 1-ni'tro-2-methy1 propane, 158 parts of in excess of 100° C. ‘to the action of atleast an
commercial “65%" benzene sulfonic acid was re ‘ equimolecular amount of a sulfonic acid having a
. ?uxed with stirring for 3 hours. The reaction dissociation constant in excess of 10-2, the initial
temperature ranged from 140to 148° C. At the
10
end oi.’ this period, 18 parts of water was intro
duced, and the mixture was further re?uxed for
10 minutes’. The following results were secured:
concentration of said acid being at least 80% by
weight, and providing at least 1 mol. of - water per‘
mol. of ‘nitropara?in to complete the conversion
to ‘the carboxylic acid stage.
10
'
3. A process for. the production of fatty acids
’
-
Yield based on
Product
Conversionbased
-
nitromethylpro-' gaonggfamigtgzf pane reacted
Isobutyric acid‘.-.- ___________ -L
76%
dueed
_\
.
-
from primary nitropara?ins, which ' comprises
subjecting the nitroparamn at a temperature
of 100“ C. to 160° C. to the action of at least an
equimolecular amount of a sulfonic acid having
a dissociation constant in excess of 10-2, the con
10%
centration of said'acid being [such that‘ there is
It is to be understood, of course, that the above . present in. the reaction mixture approximately
examples are illustrative only, and that my in;
vention is not to be construed as limited to the ,
particular materials or‘ procedures set iorth.
Numerous modifications of procedure will natué
rallyoccurtothoséskilledinthearhandmyim
ventlon includes any such modi?cations or the
use of any obvious equivalents. For example, as
1 moi. of water per mol. of nitro;
'
41. A process for the production of fatty acids‘ 20
from primary nitroparaiiins, which comprises
subjecting the nitroparamn at a temperature»
of 100° C. to 160° (xto-the action 'of ‘at least an
equimolecuiar amount of benzene sulfonic acid,
the ‘initial concentration of said acid being at
has previously been mentioned, the reaction may least 80%, byweight, and providing at least 1"
be carried out under super-atmospheric pressure... mol. of water per mol. 0! nitropara?i'n to com-_ '
and by increasing the pressure a higher reaction plete the conversion to the carboxylic acid-stage.‘
5. A process for the production of fatty acids
lower boiling nitrohydrocarbons, such as nitro .i'rom primary nitr, which comprises
subjectingv ‘the nitroparaiiin at a temperature
ethane, with a resulting incrmse in speed of con
version. In general, it may be said that a pres-_ of 1009 C. to 160° C. tow the action of at least an
sure should be employed which will insure liquid equimolemular amount of _p.toluene sulfonic
phase conditions at the reaction temperature acid, the initial concentration 0! said acid being"
at least 80% by weight, and providing at least 1 _'
utilized. Likewise,.it will be evident that my in
vention can be carried out in a continuous main; moi. oi‘ water per mol._oi niito com
1 ner by employing a reaction tube or vessel main- r plete the conversion- to the carboxylic acid stage.
6. A process for the production of. fatty acids
tained at the desired reaction-temperature, and
temperature may be secured in the case of the
,
passing the reaction mixtures through the treated
40 aone'at' a space velocity suihcient to eiiect the
desired reaction ‘and minimize decomposition re
from primary ni
~Y~-:
-. r- -:
which comprises
subjecting the nltroparaiiin at. a temperature‘
of 100° 0. to 160° C. to the action of at‘least an
equimolecular amount of betarnaphthalene sul
actions. It will also be apparent that my process
‘is applicable to the treatment of mixtures of ni
trohydrocarbons as well as single compounds. and
Ionic acid, the initial concentration ‘of said'acid
totheuseoimixedacidsastheconvertingagents
least 1 moL'of water per mol. of nitroparai'?n to
complete the conversion to the vcarboxylic acid
as well as the single acids employed in vtime above
examples. _Aii such modi?cations which are not
excludedrby the scope of the appended claims are 7
to be considered as included in my invention. _
'My invention now having been described, what
being ‘at least 80% by weight,_and providing at~
' - stage.
a
-'l. A process for the production-o1 fatty acids
from primary ni
which comprises
reacting the hi
at 'a temperature
‘ of 100' C. to 160° C. with at least an equimolec
1. A process for the "production 61mm‘ ' ular amount of benzene suitonic acid of approxi
acids. from primary nitrohydrocarbons, which mately 95%‘concentration, and subsequently in- "
I claim is:
_
-
i
‘
-
troducing additional water to‘provide a total of
at least 1 mol. of ‘water-per moi. of nitroparai?n
' sultvonic acid'having a dissociation constant in ' to complete the conversion to the carboniic acid
comprises subjecting the hydrocarbon to the
-55 action of at least an equimoiecul'ar amount or a
8168*‘ of 10"- and, providing at ‘least 1 mol. at m.
"at" Per-mm- “! 11in to
the conversionto
:
I
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