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Патент USA US2408233

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Patented Sept. 24, 1946
UNITED STATES PATENT OFFICE
2,408,232
CHEMICAL CODIPOUNDS AND. PROCESSES
Herschel G. Smith, Wallingford, and Troy L. Can
trell, Lansdowne, Pa., assignors to Gulf Oil Cor
poration, Pittsburgh, Pa.,' .a corporation of
Pennsylvania
'
No Drawing. Application January 7; 1946,
Serial N0. 639,701
5 Claims. (Cl. 260-461)
.
1
2
This invention relates to new chemical compounds and processes and more particularly to
new aromatic amine salts of 3-methyl-butyl, 2-
.
It is insoluble in water and soluble in mineral oils
to the extent of 11.70 parts in 100 parts of oil at
20° C. It has the structural formula:
ethyl-hexyl orthophosphate which are useful for
.
~ H3? 1'1 1?
fl)
H (‘3,139
various technical purposes especially in the petro-
leum
industry.
This
application
_
is a continuation-in-part
of
‘
5
:
our copending application, Serial NO- 453,458, ?led
'
HTO_(|JT$_OTI_O_(IJ_OH
Hi0 H H
H
E 02115
The following examples illustrate but do not
August 3, 1942, which application is in turn a
limitiourinvehtion
_
,
continuation-in-part of our application, Serial No. 10 .
421,842, ?led December 5, 1941. Application Serial
7
. Example I
No. 453,458 became U. S. Patent No. 2,397,377 on
> One hundred and twenty-one pounds of di
March 26,1946.
methylam'line were added to an iron vessel
This invention has as an object the production
equipped with an air lance and 281 pounds of 3
of new chemical compounds that are technically 15 methyl-butyl, 2-ethyl-hexyl orthophosphate were
useful.‘ A further object is to prepare these new
introduced over a period of one hour; the slow
compounds by novel and easily conducted procrate of addition being desirable to maintain the
esses. A still further object is to utilize these
temperature of the reaction mixture below 185° F.
new compounds for‘ various technical purposes.
At the conclusion of this reaction, the tempera
Other objects will appearhereinafter.
20 ture was 180° F., and the pH of the mixture ‘was
These objects are accomplished in accordance
2.0. A pH of 3.0 was desired; 12.0 pounds of di
with the present invention by making aromatic
aminesalts of 3-methyl-butyl, 2-ethyl-hexyl orthophosphate. Salts having the following forniula:
'
H3? ?r 1,1
‘If
'
‘
25
the following properties:
1,1 134m
Gravity: °A.P.I ______________________ __
11-c-o-o-o-r-o-C-o-H
H35 7‘if 1
h
methylaniline were added, which brought the pH
to, 3.0. The reaction product was an oily sub
stance, readily soluble in mineral oils and having
,
‘5H III (132m
R 'IlI/R
_
I
7,
'
~
‘ '
-
V1scos1ty,S.U.V.100 F_______________ __
468
Pour: °F __________ _1__________________ __
~50
30
The reactionv product described above has the
structural formula:
'
V
35
the class consisting of methyl and ethyl groups
and hydrogen, are the preferred products of the
=
I "
H
‘
H H H
a
7
'
V '
H i‘ i ‘i is
H*"_i_i“i_j_°_i*i?
i
,
wherein R represents a substituentselected
from
present invention.
7.4
Speci?c gravity, 60°/60° F _______ __' _____ __ 1.019
[/H
H
CH
a 5
ON
I
'
g \
~
0
3
CH3
In preparing these new salts, the selected aro- 40
As the dimethylaniline isoamyl octyl phosphate
matic amine is reacted ‘ with B-methyl-butyl,‘ 2is substantially insoluble in water, the pH equiva
ethyl-hexyl orthophosphate to obtain :the desired
vlent is measured by the following expedient. Nor
aromatic amine salt thereof; the pH of the reac-
‘ mal butanol (which contains a'small amount of
tion mixture being adjusted to within the range
water) is adjusted to exact neutrality, pH=7.0,.
2.0 to 5.5 in so preparing and recovering the 45 and the sample is dissolved therein. The pH?of
amine salt. For example, dimethyl-aniline is
the solution is then measured in the ordinary way
brought into reaction. with S-methyl-butyl, 2as ‘for aqueous solutions, by electrometric or
ethyl-hexyl orthophosphate, and the pH of the
colorimetricmethod-s.
The butanol appears to
reaction mixture is adjusted to within the range
serve as a blending agent, for dissolving the sam
2 to 4. With the theoretical molecular ratio of 50 ple in the water.
the two reactants, namely 1:1, the product is apt
to be slightly too acid, with a pH below 2, and this
is taken care of by using a slight excess of the
dimethylaniline so that the molecular ratio is between 1:1 and 1:1.1.
v
It will be noted that the measured pH of the
aminophosphate is ‘low despite the fact that a
slight excess of amine is present. This is because
the reaction involves neutralizing a rather strong
‘35 acid with a very Weak base;
lsoamyl octyl orthophosphate, which is also
called 3-methyl-butyl, 2-ethyl-hexyl orthophos»
'
Example H
‘
'_
phate, is a brown, oily liquid; its speci?c gravity
One hundred and forty-nine Pounds of 01161711
is 1.009 at 24°/4° C., and its viscosity is 210, 75 and
ylaniline were added to an iron vessel equipped
29 centipoises at 25,, 50 and 75° C. respectively. 60 with an air lance, and 281 pounds of 3-methyl
2,408,232
3
4
formed ‘under the conditions of vthe jpI-I determi
nation.
While aniline 3-methyl-butyl, Z-ethyl-hexyl
butyl, Z-ethyl-hexyl orthophosphate were intro
duced over a ‘period of one hour; the slow rate
of addition being desirable to maintain the tem
perature of the reaction mixture below 185° F.
At the conclusion of this reaction, the tempera
phosphate is an effective foam suppressor for use
in lubricating oils, it is more advantageous to
employ the foam suppressors prepared from 3
ture was 180° F. and the pH of the mixture was
2.0. A pH of 3.5 was desired; a further 15 pounds
methyl—butyl, Z-ethyl-hexyl phosphate and di
methyl or diethyl aniline. This advantageous
of diethylaniline were added, which brought the
class of foam suppressors may be represented by
pH to 3.5. The reaction product was an oily liq
10 the following formula:
uid which was readily soluble in mineral oils.
The reaction product of diethylaniline with 3
methyl-butyl, Z-ethyl-hexyl orthophosphate has
the following structural formula:
15
20
wherein R’ represents a methyl or ethyl group.
While the preparation of the aniline, .dimethyl
aniline, and diethylaniline salts of S-methyl
As the diethylaniline isoamyl voctyl phosphate
is substantially insoluble in water, the pH equiv
alent is measured by the expedient described
above in Example I.
butyl, Z-ethyl-hexyl orthophosphate has been
25
so limited but pertains broadly to the prepara
tion of any aromatic amine salt of S-methyl
Here again, the measured
pH of the amino-phosphate is low despite the
fact that a slight excess of amine is present.
speci?cally described above, this invention is not
butyl, 2-ethyl-hexyl orthophosphate.
Among
the aromatic amines which may be used to pre
30 pare such salts there may be mentioned aniline,
ortho-toluidine, meta-toluidine, para-toluidine,
Example III
the various isomeric xylidines, the anisidines, the
phenetidines, the nitroanilines, the chloroani
lines, the aminophenols, the aminocresols, the
phenylene diamines, the aminobiphenyls, alpha
Ninety-three pounds of aniline were added to
an iron vessel equipped with an air lance and
281 pounds of 3-methyl-butyl, Z-ethyl-hexyl 0r
naphthylamine,v beta-naphthylamine, ‘N-methyl
thophosphate were introduced over a period of
one hour; the slow rate of addition being desir
able to maintain the temperature of the reaction
mixture below 212° F. At the conclusion of this
reaction, the temperature was 180° F. and the
pH of the mixture was 2.0. A pH of 3.5 was de
sired; a further 9 pounds of aniline were added,
aniline, N-ethyl aniline, N-methyl beta-naph
thylamine, diphenylamine, phenyl beta-naph
thylamine, N-dimethyl aniline, N-diethyl aniline,
N-dibutyl aniline, N-diamyl aniline, N-methyl di
phenylamine, N-methyl phenyl beta-naphthyl
amine, N-dimethyl alpha-naphthylamine, etc.
While our invention has been described above
which brought the pH to 3.5. The reaction prod
with reference to various speci?c examples and
embodiments, it will be understood that the in
vention is not limited to such illustrative examples
and embodiments, but may be variously practiced
within the scope of the claims herein made.
uct was an oily liquid which was readily soluble
in mineral oils.
The reaction product of aniline with 3-methyl
butyl, Z-ethyl-hexyl orthophosphate has the fol
lowing structural formula:
What we claim is:
50
1. An aromatic amine salt of 3-rnethyl-butyl,
Z-ethyl-hexyl orthophosphate.
2. An aromatic amine salt of 3-methy1-buty1,
2-ethyl-hexyl orthophosphate having the for
mula:
As the aniline isoamyl octyl phosphate is sub
stantially insoluble in water, the pH equivalent 60
is measured by the following expedient. Normal
Harrow-Ores‘
Hi?
i r i’O H H.H CgH5
E30 H H
l/
R—1TI—R
butanol (which contains .a small amount of
water) is adjusted to exact neutrality, pI-I='7.0,
and the sample is dissolved therein. The pH_
of the solution is then measured in the ordi
nary way as for aqueous solutions, by electro
metric or colorimetric methods. The butanol
appears to serve ‘as a blending agent for dissolv
ing the sample in water.
It will be noted that the measured pH of this
aminophosphate is low despite the fact that a
slight excess of amine is present. This is be
cause the reaction involves neutralizing a rather
strong acid with a very weak base. Moreover,
traces of mono-, di- and tribasic acids may be 75
wherein R represents a substituent selected from
the class consisting of methyl and ethyl groups
and hydrogen.
3. The aniline salt of B-methyl-butyl, 2-ethy'l
hexyl orthophosphate.
4. The dimethylaniline salt of '3-methyl-ibutyl,
Z-ethyl-hexyl orthophosphate.
5. The diethylaniline salt of B-methyl-butyl, 2
ethyl-hexyl ortho-phosphate.
HERSCHEL G. SMITH.
TROY L. CANTRELL.
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