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Патент USA US3061647

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United States Patent O??ce
Patented Oct. 30, 1962
C1—C30 alkyl or arylalkyl amine may be used. Aromatic
amines, such as aniline, do not react with carbon dioxide
or carbon disul?de to form the N-substituted carbamate
salts. _ Amines which may be used in the preparation of
Thomas W. Martinek, Crystal Lake, 111., assignor to The
theysubstituted ammonium substituted carbamate salts in
Pure Oil Company, €hicago, 111., a corporation of
ciude methyl amine, dimethyl amine, ethyl amine, diethyl
amine, methylethyl amine, methylpropyl amine, butyl
amine, dibutyl amine, hexyl amine, dihex-yl amine, octyl
amine, dioctyl amine, dodecyl amine, stearyl amine, tri~
cosyl amine, benzyl amine, phenylethyl amine,
No Drawing. Filed Dec. 8, 1958, Ser. No. 778,582
10 Claims. (Cl. 26tl—500)
This invention is directed toa .new and improved
method for the preparation of alkali metal N-substituted
carbamates and thiocarbamates by reaction of an alkali
metal with an ammonium or substituted ammonium N
naphthylmethyl amine (CmHqCI-I2NH2), vetc.
substituted carbamate or thiocarbamate in an inert or
amines react with carbon dioxide or carbon disul?de to
form substituted ammonium substituted carbamate or
ganic liquid.
In my copending application Serial No. 762,281, ?led
September 22, 1958, now Patent No. 2,957,826, I have
described the preparation of greases which consist of
These .
thiocarbamate salts of the formula R'4NCX2NR2, where
R’ is hydrogen or C1-—C30 alkyl or aralkyl, at least one
R’ being hydrogen, X is oxygen or sulfur, and R is hydro,
gen or Q-Cgo alkyl or aralkyl, not more than one R
mineral oil or other lubricating oil thickened with metal
N-substituted carbamates, and process of preparing such 20 being hydrogen.
The metal N~substituted thiocarbamates are
well-known corrosion inhibitors.
The metal N-substi
The following non-limiting examples are illustrative of
the scope of this invention:
tuted carbamates, however, are not-reported in the litera- ~
ture and apparently have never been prepared in pure
g. of sodium and 15.6 g. of 200
vis. neutral oil was prepared by heating a mixture of
It is therefore one object of this invention to provide
sodium and neutral oil in an atmosphere of nitrogen until
an improved process for the preparation of alkali metal
the sodium had melted, ‘followed by stirring at high speed
N-substituted carbamate and thiocarbamate salts.
until a fine dispersion was e?ected. The ‘dispersion was
A feature of this invention is the provision of a proc
then cooled below the melting point of sodiumwithout
ess wherein an ammonium or substituted ammonium N
stirring. To this dispersion of sodium in neutral oil there
substituted carbamate or thiocarbamate salt is reacted
were added 20 g. of dimethylammonium dimethylcarbam
with a dispersion of an alkali metal in an inert organic
ate, H2(CH3)2NCO2N(CH3)»2, and agitation of the mix
liquid to produce the alkali metal N-su‘ostituted carbamate
ture ‘continued. A mildy exothermic reaction takes place
or thiocarbamate in very high yield and high purity.
which maintains the reaction mixture at a temperature
Other objects and features of this invention will be
of about 75 ° C. Hydrogen is evolved for a period of
come apparent from time to time throughout the speci
about 20 minutes at which time reaction is complete.
?cation and claims as hereinafter related.
The dispersion sets up into a grease-like gel (which may
This invention is based upon my discovery that am
be used as a lubricating grease) containing approximately
monium or substituted ammonium carbamates or thio
40 25 g. of sodium dimethylcarbamate, NaN(CH3)2CO2.
carbamates of the formula R'4NCX2NR2, where R is of
alkyl and aralkyl radicals, at least one R’ being hydrogen,
This grease-like gel is dispersed in hexane to precipitate
the sodium dimethyl carbamate. The slurry which is
formed is ?ltered and the sodium dimethylcarbamate is
rewashed with hexane and ?nally stripped with nitrogen
will react with alkali metals, such as sodium, potassium,
lithium, cesium, rubidium, or francium, or mixtures there
to yield 24.5 g. of sodium dimethylcarbamate, a White
crystalline salt, of about 95% purity,
of, in dispersion in an inert organic liquid to produce
the alkali metal carbamate or thiocarbamate b-y displace
A dispersion of 5.75 g. of sodium in 15.6 g. of 200
vis. neutral oil is prepared ‘by heating a mixture of so
dium and neutral oil in an atmosphere of nitrogen until
the group consisting of hydrogen and CFC“, alkyl and
aralkyl radicals, not more than one R being hydrogen,
and R’ is of the group consisting of hydrogen and C1-C30
ment of hydrogen and an amine (or ammonia) from
the ammonium or substituted ammonium N-substituted
carbamate or thiocarbamate salt.
the sodium has melted, followed by stirring at high speed
In carrying out this invention, the ammonium or sub
until a ?ne dispersion is elfected. The dispersion is then
stituted ammonium N-substituted carbamate or thiocar
cooled below the melting point of sodium Without stirring.
bamate salts may be prepared by any conventional 55 To this dispersion of sodium in neutral oil, there is added
process. For example, ammonia will react with carbon
41.5 g. of dimethylammonium dimethyldithiocarbamate,
dioxide or carbon disul?de to produce ammonium car
bamate or ammonium thiocarbamate. The ammonium
H2 ( CH3 ) ZNCSZN ( CH3 ) -2
carbamate or thiocarbamate may be reacted with an ole
and 60 g. of 200 vis. neutral oil. A mildy exothermic
?n to produce an ammonium or substituted ammonium 60 reaction takes place which maintains the temperature of
N-substituted carbamate or thiocarbamate wherein the
the reaction mixture at about 75° C. During the period
ole?n is added to the hydrogen atoms of the salt. Simi~
of reaction, hydrogen is evolved continuously from the
larly, primary and secondary amines react with carbon
mixture. At the end about 20 minutes, hydrogen evolu
dioxide or“ carbon disul?de to form substituted ammo
tion ceases, and the mixture has formed a semi-?uid
nium'N-substituted carbamates or thiocarbamates which 65 gelatinous product. This product is then diluted with
may be used in this reaction. The ammonium or sub
benzene to precipitate sodium dimethyldithiocarbamate
stituted ammonium N-substituted carbamate or thiocar
and ?ltered to recover the product. The product is re
bamate salts may also be prepared by reaction of
washed with benzene, re?ltered, and ?nally stripped with
N-substituted carbamic acids or N-substituted thiocar
nitrogen to yield 35 g. of sodium dimethyldithiocar
bamic acids with ammonia or primary, secondary, or 70 barn-ate. The yield of sodium dimethyldithiocarbamate
tertiary amines. In the reaction of amines with carbon
is about 95 % of the pure salt, of about 98% purity.
dioxide or carbon disul?de any primary or secondary
In a series of additional runs, other substituted am
monium N-substituted carbamates and thiocarbamates
are reacted with dispersions of sodium, potassium, and
lithium in various inert organic liquids as reaction media
to produce the desired sodium, potassium, or lithium
N-substituted carbamate or thiocarbama-te salts. The
wish it to be understood that within the scope of the ap
pended claims this invention may be practiced otherwise
reaction medium, and the product salt are all set forth
than as speci?cally described herein.
What is claimed is:
l. A method of preparing substituted carbamate salts
of the formula R2NCX2M, where M is an alkali metal.
X is a member of the group consisting ofoxygen and sul
fur, and R is a member of the group consisting of hy—
in Table l, as follows:
drogen and C1—C30 alkyl and aralkyl- radicals, not more
carbamates and metals which are used as reactants in
these experiments, the temperature each experiment, the
Table I
M Tact-(1311).,
Reaction Medium
200 vis. Neutral Oil
75 _.-_._d0_
60 __.._d0_
N( CH3)2C OzN'3._
Hexane _ .
_-___d0 .... __
Toluene _____________ __
* M is an alkali metal, R‘ is hydrogen or (‘Jr-Ca; alkyl or
aralkyl, not more than one Re being hydrogen, and R' is by
grogen or C1-Cao alkyl or aralkyl, at least one R’ being hy
The potassium dispersion which is used in Example 6 of
Table I is prepared by heating potassium metal in toluene
to a temperature just above the melting point of potas
sium, accompanied by vigorous agitation using a’ high
speed stirrer. The N-n-butyl ammonium N-n-butyl car?
bamate is added to the dispersion of potassium in toluene
with continued agitation. The lithium dispersions are 40
than one R being‘ hydrogen, which comprises‘ reacting a
substitutedv ammonium carbamate‘ salt of the formula
R’4NCX2NR2, Where R and X areas previously de?ned,
and R’ is a member of the group'consisting of hydrogen"
and Ci-Cau alkyl and; aralkyl‘ radicals, at least oneR'
being hydrogen, with a dispersion of an alkali metal in
pared in high-boiling liquids, such as mineral oil. The
preparation of the lithium dispersion requires that lithi-
an organic liquid which is thermally stable and inert un
der the conditions of the reaction, at a temperature of‘
about 02200“ C., which is not in excess of the decom
position’ temperature of either the‘ reactants-or the prod
um metal and the mineral oil (or other highlboiling’
ucts, and recovering the product salt.
more difficult to prepare and in all cases must be pre
liquid) be heated toga temperature above the melting
point of lithium and subjected to considerable agitation‘
with a high-speed stirrer. A lithium dispersion tends tov
settle very rapidly and so, the substituted ammonium
N-subs‘tiituted carbamates or- thioca-rbamates must be
added to the dispersion while maintaining continuous
agitation with a high-speed stirrer. In Examples 4~6, 8,
and 9 the product salt- is recovered directly by evapora-~
tion of the organic liquid. In each of the various ex
2. A method in accordance with claim- 1 in which the
organic liquid is'selected from the group‘ consisting of
mineral oil, hexane, benzene, toluene, and tetrahydro
3. A‘ method in: accordance with claim 2» in‘ which X
4. A method in‘ accordance with claim 2 in which the’
organic liquid isivolatile and- the‘ product is recovered by’
evaporation of said liquid.’
5. A'method in accordance with‘ cl‘aim‘2 in whichtthee
amples, the alkali metal displaces‘ the substituted am
organic liquid is non-volatile, and the product is remonium portion of the N-s'ubstituted carbamate salt' to
yield the alkali metal salt, evolved hydrogen, and am 55 covered by'washing with a volatile solvent‘ followed by'v
stripping the solvent from the product.
monia orv the displaced amine. In the. case of the lower
6. A method in accordance‘ with‘ claim 2 in which7 Mi
molecular-weight’ amines, separation is effected by stripe
ping or by‘distillation, while the high-boiling amines, e.g.,
stearylamine, is separated by solvent‘ extraction.
,In this process the reaction‘ may be carried out using 60
any alkali metal and any ammonium or N-substituted
is sodium.
7.- A method in accordance with claim 2 in which Mr
is ' potassium.
8; A method in accordance with claim 2 in which My
ammonium N-substituted- carbamate‘ or- thioca-rbamate as
is lithium.
above described. The reaction may be carried out in any
9. A method‘ in accordance with claim 2’ in‘ which a‘
sodium dispersion in a hydrocarbonis reactedv with di-'
inert organic liquid, i.e.,. .any'organic liquid which. is un
reactive and. thermally stable under‘ the conditions of the 65 methylammonium dimethylcarbamate and sodium di
process. The‘ pressure of‘thei process is not critical and
me'thylcarbamate is recovered ‘as the product.
is usually atmospheric, although subatmospheric and
superatmospheric pressures maybe used where appropri
10. A method in accordance with claim 2 in which
?nely divided lithium is reacted with n-hexylarn'monium
The reaction temperature is not critical and may
n-hexylcarbamate in hexane and lithium n-hexylcar
vary from 0° to 200° C. or higher provided that the de 70 bamate is recovered as the product;
composition temperature of the reactants» or products is
not exceeded.
i ‘
While I have described my invention fully and com
References Cited in the ?le of this patent
pletely, as required by thepatent statutes, with’ special
Franklin, “The Nitrogen System of’ Compounds,” page
emphasis upon several‘ preferred embodiments thereof, I 75 .27 (1947)} (Copy in Pat; Off. Sci. Lib.)
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