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Патент USA US3078306

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United btates Patent Gil-ice
3,078,296
Patented Feb. 19, 1953
2
1
with the water of reaction. The admixture is then heated
under re?ux for several hours to complete the reaction,
and the water-hydrocarbon solvent azeotrope is removed
by distillation. Any excess solvent present is then re
moved from the remaining reaction mass by distillation
and the desired nitroalkyl glycol monob-orate ester is
3,878,296
Irving
NTTROALKYL
S. liengelsdorf,
GLYCGL
CostaMQNQBQRATE
Mesa, ‘Cellini, assignor to
United §tates Borax 8: Qhernical Corporation, Los An
geles, Calif, a corporation of Nevada
No Drawing. Filed Jan. 12, 1962, Ser. No. 165,955
10 (Jlaims. (Cl. Zed-A62)
recovered as the residue.
The nitroalcohols applicable to the present invention
are Z-nitro-n-butanol and Z-nitro - 2 - methyl-n-propanol,
The present invention relates as indicated to nitroalkyl
glycol monoborate esters and has further reference to 10 both of which are commercially available compounds.
The glycol monoborates applicable to the present in
vention have the formula
means for preparing the same.
It is, therefore, the principal object of this invention
to provide as new compositions of matter nitroalkyl
glycol monoborate esters.
It is a further object of the present invention to pro
OH
vide ef?cient and economically desirable means for
preparing the nitroalkyl glycol monoborate esters.
where R is an alkylene radical of from 2 to 4 carbon
atoms in length and containing a total of from 2 to 20
Other objects of the present invention will appear as
the description proceeds.
carbon atoms. The following list is illustrative of these
To the accomplishment of the foregoing ‘and related
ends, said invention then comprises the features herein
after fully described and particularly pointed out in the
claims, the following description setting forth in detail
certain illustrative embodiments of the invention, these
being indicative, however, of but a few of the various 25
compounds:
ways in which the principle of the invention may be
employed.
Broadly stated, the present invention comprises the
nitroalkyl glycol monoborate esters having the formula
30
1,2-butanediol monoborate
Z-methyl-Z-propyl-1,3-propanediol monoborate
1,3-butanediol monoborate
1,3-propanediol monoborate
1,4-butanediol monoborate
2-methyl-2,4-pentanediol monoborate
1,2-ethanediol monoborate
2,2-dirnethyl-1,3-butanediol monoborate
2-ethyl-l,3-hexanediol monoborate
2-methyl-2-ethyl-1,3-propanediol monoborate
It is to be clearly understood that the foregoing list
is only a partial enumeration of the glycol monoborates
where R is an alkylene radical of from 2 to 4 carbon 35 applicable to the present invention and is in no way in
tended to limit the invention.
atoms in length and containing a total of from 2 to 20
So that the present invention can be more clearly un
carbon atoms, and R’ is a radical selected from the group
consisting of Z-nitro-n-butyl and 2 - nitro - 2 - methyl-n
derstood, the following examples are given for illustra
propyl.
tive purposes:
The nitroalkyl glycol monoborate esters of the present 40
invention have numerous industrial applications. These
I
A mixture of 94.2 grams (0.792 mole) of 2-nitro-n
compounds are excellent bacteriostatic agents which act
butanol, 114 grams (0.792 mole) of 2-methyl-2,4-pen
to inhibit the bacterial degradation of petroleum and
tanediol monoborate and 200 ml. of toluene was placed
petroleum fractions while they are held in storage. They
in a 500 ml. round-bottomed ?ask. The ?ask was
are also useful in antigumming agents for lubricating oils, 45 equipped with a re?ux condenser, a Dean-Stark trap and
as fuel additives which increase the e?iciency of internal
a magnetic stirrer. The reaction mixture was heated
combustion engines, and as corrosion inhibitors in hydrau
for about 5 to 6 hours under reflux at which time the
lic and cooling systems.
theoretical amount of water, 14.3 ml., had been removed.
There are several methods available for preparing the
The excess toluene was then removed by distillation and
present nitroalkyl glycol monoborate esters. They can
be prepared by treating an appropriate glycol with an
applicable nitroalcohol and boric acid or boron trioxide.
197.6 grams (101% yield) of Z-(?-nitro-n-butoxy)-4,4,6
trimethyl-1,3,2-dioxaborinane, a colorless liquid, was re
covered. Chemical analysis of the product yielded the
In the preferred embodiment of the invention, however,
following data:
I prepare these compounds by the esteri?cation of a gly
col monobcrate with an applicable nitroalcohol. This 55 Calculated for CIOHZOBNO5:
B=4.42%
N=5.72%
method can best be illustrated by the following equation:
1C=48.93%
Mol. Wt.=245
H:8.l8%
R
B-OH + I-IO-R’ -—> R
Found in product:
o
o
B=4.43%
N=5.85%
where R and R’ are as de?ned in the foregoing broadly
C=48.8l%
M01. Wt.=25~(l
stated paragraph. This reaction will proceed when there
H=8.37%
is (an excess of either reactant. Such excess, however,
II
complicates the separation of the desired product from
A
mixture
of
119.1
grams
(1.0 mole) of 2~nitr0-n
the reaction mass, and for the sake of economy and ease 65
butanol, 116 grams (1.0 mole) of 1.3-hutanediol mono
of separation, in the preferred embodiment of the in
vention, 1 use stoichiometric amounts of the reactants.
borate and 3100 ml. of benzene was placed in a 1 liter
presence of a hydrocarbon solvent, such as benzene, tolu
ene, xylene, n-heptane, etc., which will form an azeotrope
re?ux at \which time the theoretical amount of water, 18
ml., had been removed. The excess benzene was then
round-bottomed flask. The ?ask was equipped with a
The preferred method for performing the above reac
reflux condenser, a Dean-Stark trap and a magnetic stirrer.
tion is a direct single-step process which involves admix
ing a glycol rnonoborate and a nitroalcohol in the 70 The reaction mixture was heated for about 4 hours under
3,078,298
A.
3
removed by distillation and 213.4 grams (98.3% yield) of
carbon atoms, and R’ is a radical selected from the
Z-(B-nitro-n-butoxy) - 4 - methyl - 1,3,2 - dioxaborinane, a
group consisting of Z-nitro-n-butyl and 2-nitro-2-methyl
colorless liquid, was recovered. Chemical analysis of the
n-propyl.
product yielded the following data:
Calculated for C8H16BNO5:
B=4.99%
N==6.46%
formula
C=44.27%
H=7.43%
Found in product:
B=4.92%
C=44.41%
H=7.56%
2. Nitroalkyl glycol monoborate esters having the
Mol. Wt.=217
10 where R is an alkylene radical of from 2 to 4 carbon
1N=6.57%
Mol. Wt.=225
atoms in length and containing a total of from 2 to 20
carbon atoms.
III
A mixture of 119.1 grams (1.0 mole) of 2-nitro-2
15
3. Nitroallzyl glycol monoborate esters having the
formula
methyl-n-propanol, 144 grams (1.0 mole) of Z-methyl
2,4-pentanediol monoborate and 300 ml., of xylene was
placed in a 1 liter round-bottomed ?ask. The ?ask was
equipped with a re?ux condenser, a Dean-Stark trap, and
a magnetic stirrer. The reaction mixture was heated for
about 5.5 hours under re?ux at which time the theoretical
amount, 18 ml., of water had been removed. The excess
xylene was then removed by distillation and 240 grams
where R is an alltylene radical of from 2 to 4 carbon
atoms in length and containing a total of from 2 to 20
carbon atoms.
4. 2(5 - nitro - n - butoxy) - 4,4,6 - trimethyl - 1,3,2
dioxaborinane.
(97.9% yield) of 2-(?-nitro-[i-methyl-n-propoxy)4,4,6
5. 2(/8 - nitro - l8 - methyl - n - propoxy) - 4,4,6 - tri
trirnethyl-1,3,2-dioxaborinane, a colorless liquid was re
methyl-1,3,2-dioxaborinane.
covered. Chemical analysis of the product yielded the
following data:
Calculated for C10H20BNO5:
borinane.
B=4.42%
C=48.93%
H:8.18%
Found in product:
B=4.37%
C=48.99%
H=8.l2%
N=5.72%
Mol. Wt.=245
6. 2(,8 - nitro - n - butoxy) - 4 - methyl - 1,3,2 ' dioxa
7. 2(? - nitro - p - methyl - n - propoxy) - 5 - methyl
30
S-propyl-1,3,2-dioxaborinane.
8. The method for preparing nitroalkyl glycol mono~
borate esters having the formula
0
N=5.64%
M01. Wt.=256
R/ \ 13-0-11’
35
\ /
0
where R is an alkylene radial of from 2 to 4 carbon atoms
in length and containing a total of from 2 to 20 carbon
IV
A mixture of 119.1 grams (1.0 mole) of 2-nitro-2
atoms, and R’ is a radical selected from the group con
methyl-n-propanol, 158 grams (1.0 mole) of 2-methyl-2
propyl-1,3-propanediol monoborate and 250 ml. of tolu
sisting of 2-nitro-n~buty1 and 2-nitro-2-methyl-n-propyl,
ene was placed in a 1 liter round-bottomed ?ask.
material selected from the group consisting of Z-nitro-n
which comprises admixing glycol monoborate with a
The
?ask was equipped with a re?ux condenser, a Dean-Stark
trap, and a magnetic stirrer. The reaction mixture was
heated for about 6 hours under re?ux at which time the
theoretical amount of water, 18 ml., had been removed.
The excess toluene was then removed by distillation and
butanol and Z-nitro~2-methyl-n-propanol, heating said
257.3 grams (99.3% yield) of 2(;3—nitro-?-rnethyl-n-pro
vent and recovering said nitroalkyl glycol monoborate
poxy)~5-methyl-5-propyl-1,3,2-dioxaborinane, a colorless _
ester.
admixture under re?ux in the presence of a hydrocarbon
solvent inert to the reactants, removing the water of re
action as an azeotrope with said hydrocarbon solvent by
distillation, distilling off the remaining hydrocarbon sol
9. The method for preparing nitroalkyl glycol mono
low-melting solid was recovered. Chemical analysis of
the product yielded the following data:
Calculated for C11I-I22BNO5:
B=4.18%
C=50.99%
borate esters having the formula
.
N=5.41%
M01. Wt.=259
55
H=8.56%
where R is an alkylene radical of from 2 to 4 carbon
Found in product:
atoms in length and containing a total of from 2 to 20
B=4.l6%
N=5.37%
carbon atoms, which comprises admixing a glycol mono
C=51.14%
Mol. Wt.=265
60 borate with Z-nitro-n-butanol in about a 1:1 molar ratio,
H=8.59%
heating said admixture under a re?ux in the presence of
Other modes of applying the principle of the invention
a hydrocarbon solvent inert to the reactants, removing the
may be employed, change being made as regards the de
tails described, provided the features stated in any of the
following claims or the equivalent of such be employed.
water of reaction as an azeotrope with said hydrocarbon
solvent by distillation, distilling oil the remaining hydro
carbon solvent and recovering said nitroalkyl glycol mono
1, therefore, particularly point out and distinctly claim
borate ester.
as my invention:
10. The method for preparing nitroalkyl glycol mono~
borate esters having the formula
1. Nitroalkyl glycol monoborate esters having the
the formula
70
where R is an alkylene radical of from 2 to 4 carbon
atoms in length and containing a total of from 2 to 20
where R is an alkylene radical of from 2 to 4 carbon
atoms in length and containing a total of from 2 to 20
3,078,296
5
carbon atoms, which comprises admixing a glycol monobQY?te with 2-1’!itfo-iz-methyl-n-pfopa?ol in about a 111
molar ratio, heating said admixture under ‘re?ux in the
presence ‘of a hydrocarbon solvent inert to the reactants,
removing the water of reaction as an azeotrope with said 5
6
hydrocarbon solvent by distillation, distilling off the re
maining hydrocarbon solvent and recovering said nitro
alkyl glycol monoborate ester,
No references cited.
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