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Патент USA US2118495

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Patented May 24, 1938
2,118,495
UNITED STATES PATENT OFFICE
2,118,495
ALKYLANILINEMONOSULPHONIO ACIDS
AND THEIR MANUFACTURE
Samuel Coffey and Norman Hulton Haddock,
Blackley, Manchester, England, assignors to
Imperial Chemical Industries, Limited, a cor
poration of Great Britain
No Drawing. Application January 14, 1937, Se
rial No. 120,632.‘
In Great Britain January 17,
1936
10 Claims.
This invention relates to new alkylaniline
monosulphonic acids and their manufacture.
In these new alkylanilinemonosulphonic acids,
the alkyl group has 6-18 carbon atoms, and is
5 directly attached to the benzene nucleus, and
there may be other substituents directly attached
to the benzene nucleus, e. g. bromo, chloro,
methyl and hydroxy substituents.
These new alkylanilinemonosulphonic acids are
valuable dyestuff intermediates.
According to the process of the invention we
make the new alkylanilinemonosulphonic acids
by treating alkylanilines, in which the alkyl
group has 6-18 carbon atoms, and is directly at
tached to the benzene nucleus and in which there
may be other substituents directly attached to
the benzene nucleus, e. g. bromo, chloro, methyl
and hydroxy substituents, with a sulphonating
acid. Two suitable sulphonating acids are fum
ing sulphuric acid and chlorosulphonic acid.
The alkylanilines which are used as starting
materials in the process of our invention may
be made from the corresponding anilines or
N-alkylanilines by heating them, in the presence
10 Q1 of a halide of zinc or cobalt, with saturated pri
mary aliphatic alcohols having 6-18 carbon
atoms. In this process the anilines may be wholly
or partly replaced by their hydrochlorides or
hydrobromides, and the N-alkylanilines may be
30 wholly or partly replaced by their hydrochlorides
or hydrobromides, or partly replaced by the hy
drochlorides or hydrobromides of the parent
anilines. Examples of the alcohols used in mak
ing these alkylanilines are hexyl, octyl, decyl,
35 otherwise known as decanol, dodecyl, tetradecyl,
hexadecyl, and octadecyl alcohol. Hexadecyl al
cohol is the main or sole component of the al
cohols obtained by the saponi?cation of sperm
aceti: if this is obtained by the saponi?cation
40 of spermaceti its purity may depend upon the
purity of the spermaceti. Dodecyl and tetra
decyl, otherwise known as myristyl alcohol, are
obtained by the reduction of the mixed fatty
acids obtained from coconut oil and palm oil.
45 Other alcohols are likewise obtainable by reduc
tion of the fatty acids of natural fats and oils.
(See, for instance, Bouveault and Blane, Bull.
Soc. Chem. Series 3, vol. 3, pages 6'74 et seq. and
1210 et seq.) The alcohols include mixed alco
50 hols, for instance technical “lorol” which con
sists of the mixed alcohols from coconut oil fatty
acids. The alkylanilines include those speci?
cally described in the above-mentioned speci?ca~
tion, although these may not always be pure
55 compounds or single chemical compounds.
(Cl. 260-429)
One object of our invention is the provision
of new alkylanilinemonosulphonic acids, the alkyl
group of which has 6-18 carbon atoms, and is
directly attached to the benzene nucleus, and
in which there may be other substituents directly I
attached to the benzene nucleus, e. g. bromo,
chloro, methyl and hydroxy substituents.
Another object of our invention is the provi
sion of valuable dyestuif intermediates.
A still further object of our invention is the 10
provision of a process for the manufacture of
the said new alkylanilinemonosulphonic acids,
which comprises treating alkylanilines in which
the alkyl group has 6-18 carbon atoms and is
directly attached to the benzene nucleus and in 15
which there may be other substituents directly
attached to the benzene nucleus, e. g. bromo,
chloro, methyl and hydroxy substituents, with
a sulphonating acid. Further objects of our in
vention will appear hereinafter.
20
The following examples, in which parts are by
weight illustrate but do not limit the invention.
Example 1.--20 parts of p-dodecylaniline are
dissolved in 150 parts of 100% sulphuric acid
at 10-15° C. 70 parts of fuming sulphuric acid
(20%free S03) are gradually added, and the
mixture is stirred for half an hour at 10-15° 0.,
when it is poured into a mixture of ice and water.
The precipitate is ?ltered, washed with water
and dried.
'
30
The sulphonic acid is a white powder, slightly
soluble in water, but readily soluble in water con
taining a little sodium hydroxide, sodium car
bonate or ammonia. Its dilute solutions froth
on shaking, and its concentrated solutions form '
gels on standing.
.
On treating with bromine (see Abderhalden,
Handbuch der Biologischen Arbeitsmethoden,
1933, vol. 2, 2517) the acid forms a dibromo
sulphonic acid, showing that the sulphonic acid 40
group has entered in the meta position to the
amino group, i. e. that the acid is 4-dodecyl
aniline-3-sulphonic acid.
p-Dodecyl-o-toluidine is sulphonated similarly,
the resulting sulphonic acid resembling the 45
‘l-dodecylaniline-B-sulphonic acid described
above.
Example 2.—52 parts of p-dodecylaniline are
dissolved in 105 parts of tetrachloroethane and
a solution of 23.3 parts of chlorosulphonic acid
in 25-30 parts of tetrachloroethane added in 20
minutes. The temperature rises during the ad
dition, and at about 80° C., hydrochloric acid
is evolved. When all the chlorosulphonic acid
is in, the temperature is raised to 120° C., in one 55
2
2,118,495
hour, during which time hydrochloric acid is
rapidly evolved, and then to 140° C. in 10 min
utes, after which, evolution of hydrochloric acid
ceases. The mixture is cooled, poured into
500-600 parts of water, neutralized with am
monia, the tetrachloroethane separated, and the
clear alkaline aqueous solution is acidi?ed with
hydrochloric acid. The precipitate is ?ltered,
washed with water, and dried.
The product is a colourless microcrystalline
10
powder, almost insoluble in water, and only spar
ingly soluble as its sodium salt.
When treated with excess of bromine, the sul
phonic acid forms a dibromo derivative, while the
sulphonic acid group is split off as sulphuric acid,
showing that it occupied an ortho position to
the amino group, i. e. that the sulphonic acid is
4-dodecylaniline-2-sulphonic acid.
p-Dodecyl-o-toluidine is sulphonated similarly
We claim:
1. Alkylaniline-sulphonic acid in which the
alkyl group is a saturated aliphatic radical having
6 to 18 carbon atoms and is directly attached to
the benzene ring, in which the benzene ring is
substituted by sulphonic acid in one of the posi
tions meta and ortho to the amino group, and a
free position of the benzene ring is substituted
by one of the group consisting of hydrogen,
methyl, chloro, bromo and hydroxy.
10
2. Dodecylaniline—sulphonic acid in which the
benzene ring is substituted by sulphonic acid in
one of the positions meta and ortho to the amino
group, and a free position of the benzene ring
is substituted by one of the group consisting of
hydrogen, methyl, chloro, bromo and hydroxy.
3. 4-dodecylaniline~3-sulphonic acid.
4. 4-dodecylaniline-2-su1phonic acid.
5. The mono-sulphonic acid of p-dodecyl-o
toluidine in which the benzene ring is substituted ‘
and the resulting sulphonic acid has similar
properties to the 4-dodecylaniline-2-sulphonic
acid just described.
Example 3.—5 parts of p-decylaniline are dis
by the sulphonic acid group in one of the posi
tions ortho and meta to the amino group.
6. The process which comprises interacting an
solved in 30 parts of tetrachloroethane and treat
ed with 2.5 parts of chlorosulphonic acid as de
scribed in Example 2. After heating to 140° C.,
is a saturated aliphatic radical having 6 to 18 ‘a
the mixture is cooled, poured into 100 parts of
water and the solution boiled.
The solution is
neutralized with ammonia, evaporated to dryness,
and the ammonium-4-decylaniline-2-sulphonate
extracted with alcohol. The ammonium salt
crystallizes in shining lea?ets. Both the ammo
nium and sodium salts are fairly readily soluble
in water.
Example 4.—p-Tetradecylaniline is treated with
chlorosulphonic acid as described in Example 2,
55 parts of p-tetradecylaniline being used instead
of 52 parts of p-dodecylaniline.
4-tetradecylaniline-2-sulphonic acid is obtained
40 as a colourless solid, sparingly soluble in water,
$1
and its ammonium and sodium salts are moder
ately and sparingly soluble respectively.
Example 5 .-22 parts of p-hexadecylaniline are
dissolved in 150 parts of 100% sulphuric acid at
15° C. 70 parts of fuming sulphuric acid (20%
free S03) are gradually added, and the mixture
stirred for an hour at 15° 0., when it is poured
into a mixture of ice and water. The 4-hexa
decylaniline-3-sulphonic acid is ?ltered, washed
50 with water and dried.
It is sparingly soluble in
water.
E a: a m p l e
6.-p-Aminohexadecylbenzene
is
treated with chlorosulphonic acid in tetrachloro
ethane as described for p-dodecylaniline in Ex
ample 2.
4-hexadecylaniline-2-sulphonic acid is ob
tained.
As many apparently widely different embodi
ments of this invention may be made without
departing from the spirit and scope thereof, it is
to be understood that we do not limit ourselves
to the speci?c embodiments thereof except as
de?ned in the appended claims.
alkylaniline compound in which the alkyl group
carbon atoms directly attached to the benzene
nucleus, in a non~aqueous reaction medium with
a sulphonating acid until an alkylaniline-mono
sulphonic acid is formed.
7. The process which comprises dissolving an 30
alkylaniline compound in which the alkyl group
is a saturated aliphatic radical having 6 to 18
carbon atoms directly attached to the benzene
nucleus in 100% sulphonic acid, adding fuming
sulphuric acid and interacting therewith at about
10° to about 15° C. until an alkylaniline-mono
sulphonic acid is formed.
8. The process which comprises dissolving an
alkylaniline compound in which the alkyl group
is a saturated aliphatic radical having 6 to 18 40
carbon atoms directly attached to the benzene
nucleus in tetrachlorethane, adding chlorosul
phonic acid and interacting therewith at about
80° to about 140° C. until an alkylaniline-mono
sulphonic acid is formed.
9. The process which comprises adding about
70 parts of fuming sulphuric acid to a sulphuric
acid solution containing about 20 parts of do
decylaniline, and interacting at temperatures of
about 10° to about 15° C. until dodccylaniline~ 50
mono-sulphonic acid is formed.
10. The process which comprises adding about
2 parts of dodecylaniline dissolved in tetrachlor
ethane to a tetrachlorethane solution containing
about 1 part of chlorosulphonic acid, raising the
temperature of the mixture to about 140" C. and
heating at said temperature until a dodecylani
line-mono-sulphonic acid is formed.
SAMUEL COFFEY.
NORMAN HULTON HADDOCK.
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