Improvements relating to the Manufacture of Sulpho, Nitrosulpho, Nitrososulpho, and Amidosulpho Acids, and to their Application for the Production of New Colouring Matters.
Year: 1887

page_text: Date of Application, 22nd Apr, 1887
Complete Left, 23rd Jan., 1888
Complete Accepted, 22nd May, 1888
Improvements relating to the Manufacture of Sulpho, Nitrosulpho,
Nitrososulpho, and Amidosulpho Acids, and to their Application
for the Production of New Colouring Matters.
I, ALFRED KERN, Doctor of Philosophy, of the firm of Kern and Sandoz, at Basle,
Switzerland, do hereby declare the nature of this invention to be as follows:-
I have succeeded in producing with mixed tertiary monamines which contain at
least two radicals of aromatic hydrocarburet, such as for example methyldiphenylamine,
ethyldiphenylamine, benzyldiphenylamine, methylbenzylaniline, dibenzylaniline,
methyl-phenyl a naphthyl-amine, methyl-phenyl, ß-naphthylamine and the like, mono
and disulpho acids heretofore unknown.
I employ the salts or the solutions of these sulpho-acids for the manufacture of a
new series of derivates of these monamines, such as
a) nitrososulpho-acids.
b) nitrosulpho-acids.
c) amidosulpho acids.
With the new bodies obtained under a) and c) I produce, by a new combination
with phenols,
phenocarbonic acids,
monamines and diamines, and their derivates,
aldehydes,
phosgene, and
chloride of sulpho carbonyl (dichlorosulphuret of carbon), sulpho colouring
maters pertaining to the category of the
Gallocyanines,
Indamines,
Indophenols,
Indulines,
Meldola,
Safranines,
Methelene Blues,
Azoics, and
Diphenyl and triphenyl methane.

page_text: under 1).
3). The process of manufacturing nitrated derivates of sulpho acid mentioned
under 1).
4). The process of manufacturing amidosulpho-acids from nitrosated and nitrated
sulpho-acids as mentioned under 2) and 3).
5). The process of manufacturing sulpho colouring matters by special combinations
of the new derivates of the mixed tertiary monamines with:
phenols,
phonocarbonic acids,
monamines and diamines and their derivates,
aldehydes,
trichloride of benzyl.
phosgene, and
chloride of sulpho carbonyl (dichlorosulphuret of carbon).
Mono and disulpho-acids are obtained from the mixed tertiary monamines by their
treatment by means of concentrated sulphuric acid, monohydrated sulphuric acid,
sulphuric acid containing anhydride, or chloride of sulphhydrite.
According to the concentration of the sulphuric acil or its proportion of anhydrous
sulphuric acid, and according to the proportions between the sulphuric acid and the
amines, the temperature to be observed can vary within 200 degrees.
For disulpho-acids greater quantities of sulphuric acid or higher temperatures than
for monosulpho-acids are necessary.
When an essay sample of amine; treated as above described, dissolves limpid in
diluted ammonia or even in cold water, which is especially the case for disulpho-acids,
the liquid mass is poured into the water or it is employed directly for the manufacturo
of nitrosulpho-acids.
The liquid mass, diluted in water, can be employed directly for the manufacture of
nitroso and amidosulpho-acids.
The salts of these sulpho-acids are obtained most easily by neutralizing the liquid
mass diluted in water with a milk of lime and by filtering hot.
The filtered solution contains the salt of lime that can be removed by evaporation.
The salt of lime can be easily transformed into another salt, for example with soda
or potash into a soda or potash salt &c.
By means of very concentrated solutions are also obtained, principally with the
salts, monosulpho acids in the form of crystals.
Sulpho acids or their salts condense with aldehydes into lenkosulpho acids which by
oxidation, for instance by means of peroxide of lead, yield green colouring matters.
If trichloride of benzyl is caused to react directly, a green colouring matter is
obtained directly.
Chloride of carbonyl and phosgene react in a hot state and yield sulpho colouring
matters extending from violef to blue, and belonging to the series of triphenylmethane.
Nitrososulpho acids are obtained by the action of azotic acid or a nitrous salt
upon an acid solution of mono and disulpho acids or their salts.
The solutions are then coloured yellow brown. The latter and also the neutralized
solutions decompose by evaporation at the ordinary atmospheric pressure. They dye
wool and silk olive.
If a solution of a salt of nitrososulpho acids, with a phenol or a phenocarbonic acid
is heated, colouring matters are obtained which extend from violet to blue and belong
to the series of Meldola and Gallocyanine colours.
Nitrosulpho acids are most easily obtained by mixing the liquid mass of sulpho acid
with nitric and sulphuric acid or according to other known methods.

page_text: Nitrosulpho acids or their salts dissolve in, water, and give a yellow coulouring;
wool and silk are dyed yellow thereby.
Amidosulpho acids are obtained by reduction, according to the known methods of
nitroso and nitrosulpho acids. They yield colourless solutions or at most slightly
colouring solutions that become yellow with nitrous acid. These solutions contain
diazotized combinations which with phenols and amines or their sulpho acids yield
azoic colours.
If the solutions of tho amidosulpho acids are oxidized in presence of monanines or
phenols, Indanines and Indophenols are obtained. With these Indamines sulpho
safranines can be obtained.
If solutions of these amidosulpho acids are oxidized in presonce of sulphuretted
hydrogen, with or without a monamiue sulpho blues entoring into the series of
methylene bluo are obtained.
a) 21 kilograms of ethylbenzyl aniline are dissolved little by little, care being taken
to cool in 45 kilograms of sulphuric acid containing 20 per cent. of sulphuric
anhydride, then heated to a temperature of from 80 to 100 degrees.
When a sample previously taken from the mass entirely dissolves in dilute ammonia,
which takes place at the end of from to 2 hours, the sulphoconjugation is terminated,
and monosulpho acid has principally been formed.
6) 21 kilograms of ethylbenzyl aniline are dissolved and heated as above set forth
in 90 kilograms of sulphuric acid containing 20 per cent. of sulphuric anhydrido.
When a sample previously taken from the mass entirely dissolves in cold water which
is the case after beating for two hours, disulpho acid has principally been
obtained.
.
c) 10 kilograms of methyldiphenglamine are mixed with 20 kilograms of sulphuric
acid containing about 60 per cent. of sulphuric anhydride, and this mixture is left
for 12 hours to a temperature of 20 degrees.
d) 10 kilograms of methylphenylnaphthylamine are dissolved in 40 kilograms of
ordinary strong sulphuric acid and heated in a water bath until a sample previously
taken from the mass dissolves in alkalies &c. &c.
II. NITROSULPHO ACIDS. .
When the combination has taken place according to the examples given under
heading I the liquid mass which results therefrom is cooled (to a degree) near zero
and a mixture of one molecule of nitric acid (HA, O3) determined according to the
quantity of tertiary monamine under treatment, and of 3 parts of concentrated
sulphuric acid is slowly added, care being taken to agitato and cool proportionately.
Thus the molten mass of sulpho acid as obtained under the heading (la) is mixed
with 10 kilograms of nitric acid of 60 per cent., and 30 kilograms of English sulphuric
acid.
When the mixing is terminated the whole is allowed to stand for some hours and
then diluted with water.
A solution of a yellow colour is produced. By neutralizing with lime and subse-
quently filtering, the brown red solution of the lime salt is obtained from the mono-
nitrosulpho acid that can be removed by evaporation.
If more than one molecule of nitric acid is employed, more strongly nitrated acids
of sulpho amines are obtained.
Thus, for example, if, instead of 10 kilograms as above, 30 kilograms of nitric
acid of 60 per cent., and 90 kilograms of concentrated sulphuric acid are taken, a
dinitrosulpho acid of ethylbenzyl-aniline is obtained, which poured into about 350 litres

page_text: in a beautiful yellow.
III. NITROSULPHO ACIDS.
The sulpho liquid mass obtained as set forth under the headings I a) or I b) is poured
into 300 litres of water. It is left to cool to the ordinary temperature, and added
thereto little by little, while continually stirring, are
6.900 kilograms of nitrite of soda (plus the quantity necessary for the SO, part and
which must be determined for each operation) dissolved in 50 litres of water.
The solution is left to stand, which then gets a yellow-brown colour, for some hours
in order to have the reaction complete. It is then neutralized by means of a lime
milk, and caused to boil by steam, then passed to the filter press.
The greenish yellow solution contains soda salt of the mono or disulpho acid of
nitrosobenzylethylaniline.
The other tertiary amines which I have mentioned belave exactly alike the quantity
of nitrite of soda varies alone according to the molecule of the amine.
If the production of the lime salt or another salt has been commenced with, to the
solution of the latter is added the equivalent quantity of muriatic or sulphuric aid, and
after this the solution of nitrite of soda as above stated.
IV. AMIDOSULPHO ACIDS.
a) The molten mass of mononitrosulpho acid obtained as described under
heading II is poured into water, zinc or tin is added, and heating takes place until
the yellow colour of the nitrated derivate has disappeared.
b) The solution of nitrososulpho acid obtained as set forth under heading III is
reduced by means of zinc or tin or in general by means of hydrogen in the nascent
state, sulphurous acid, thiosulphates, hydrogen sulphuretted in a slightly acid solution
or in an ammoniacal solution, zinc powder in an ammoniacal solution, or the like.
The solution is nearly colourless and serves directly for the manufacture of the
various colouring matters above enumerated.
Dated this 2nd day of A-11007
HASELTINE, LAKE & Co.,
45, Southampton Buildings, London,
Agents for the Applicant.

page_text: phosgene, and
chloride of sulpho carbonyl (dichlorosulphuret of carbon).
Mono and disulpho acids are obtained from the mixed tertiary monamines by their
treatment by means of concentrated sulphuric acid monohydrated sulphuric acid,
sulphuric acid containing anhydride, or chloride of sulphhydride.
According to the concentration of the sulphuric acid or its proportion of anhydrous
sulphuric acid, and according to the proportions between the sulphuric acid and the
amines, the temperature to be observed can vary within 200 degrees.
For disulpho acids greater quantities of sulphuric acid or higher temperatures than
for monosulpho acids are necessary.
When an essay sample of amine, treated as above described, dissolves limpid in
diluted ammonia or even in cold water, which is especially the case for disulpho acids,
the liquid mass is poured into the water or it is employed directly for the manufacture
of nitrosulpho acids.
The liquid mass, diluted in water, can be employed directly for the manufacture of
nitroso and amidosulpho acids.
The salts of these sulpho-acids are obtained most easily by neutralizing the liquid
mass diluted in water with a milk of lime and by filtering hot.
The filtered solution contains the salt of lime that can be removed by evaporation.
The salt of lime can be easily transformed into another salt, for example with soda
or potash into a soda or potash salt.
By means of very concentrated solutions are also obtained, principally with the
salts, monosulpho acids in the form of crystals.
Sulpho acids or their salts condense with aldehydes into lenkosulpho acids which
by oxidation, for instance by means of peroxide of lead, yield green colouring
matters.
If trichloride of benzyl is caused to react directly, a green colouring matter is
obtained directly.
Chloride of carbonyl and phosgene react in a hot state and yield sulpho colouring
matters extending from violet to blue, and belonging to the series of triphenyl-
methane.
Nitrososulpho acids are obtained by the action of nitrous acid or a nitrous salt upon
an acid solution of mono and disulpho acids or their salts.
The solutions are then coloured yellow brown. The latter and also the neutralized
solutions decompose by evaporation at the ordinary atmospheric pressure. They dye
wool and silk olive.
If a solution of a salt of nitrososulpho acids witha phenol or a pheno-carbonic acid is
heated, colouring matters are obtained which extend from violet to blue and belong to
the series of Meldola and Gallocyanine colours.
Nitrosulpho acids are most easily obtained by mixing the liquid mass of sulpho acid
with nitric and sulphuric acid or according to other known methods.
Nitrosulpho acids or their salts dissolve in water, and give a yellow colour; wool 5
and silk are dyed yellow thereby.
:

page_text: Amidosulpho acids are obtained by reduction, according to the known methods, of
nitroso and nitrosulpho acids. They yield colourless solutions or at most slightly
colouring solutions that become yellow with nitrous acid. These solutions contain
diazotized combinations which with phenols and amines or their sulpho acids yield
azoic colours.
If the solutions of the amidosulpho acids are oxidized in presence of monamines
or phenols, indamines and indophenols are obtained. With these indamines sulpho
safranines can be obtained.
If solutions of these amidosulpho acids are oxidized in presence of sulphuretted
hydrogen, with or without a monamine, sulpho blues entering into the series of
methylene blue are obtained.

page_text: V. MANUFACTURE OF COLOURING MATTERS.
(a) If for instance the solution of soda salt obtained of the nitrosobenzylethyl-
aniline-mono or disulpho acid as in example III, is slightly acidulated with acetic
acid or even sulphuric acid or muriatic acid (the two latter to be used with care) a
_adding 9 kilos of gallic acid and by heating the same to the boiling point the solution
will change in a few minutes and adopt a blue violet colour. By leaving in contact a
few hours the whole of the colouring matters is developed and can be separated by_
adding a solution of common salt, the colouring matters thus obtained resembles a
resinous mass which should then be washed with a weak solution of salt and dried
on the bath.
This colour is soluble in water and can be used for dyeing and printing.
(b) By adding to the salt solution of the nitroso-combination 7 kilos of a naphthol
in fine powder and by boiling, the colour of the solution turns dark blue. After
leaving the same in contact a few hours the colouring matters may be separated with
common salt.
(c) By adding to the salt solution of the nitroso combination instead of naphthol,
-for instance, 6,5 kilos aniline salt and bringing the same to the boiling point gradually
a magenta red solution is obtained. The colouring matters of this solution separate
partly through the cooling of the liquid, however the same can be separated at once
with salt.
(d) A colour similar to methelene blue that dyes silk and wool blue in an acidulated
bath is obtained if the solution of an amidosulpho-acid manufactured according to
example I II or III and IV is added to an equal quantity of a tertiary amine for
instance, dimethylaniline or one of its sulpho-acids for instance, the sulpho-acid of
ethylbenzylaniline obtained as per example I, the solution is to bo well saturated

page_text: with sulphureted hydrogen and afterwards oxidized with chromato of potash. The
solution turns blue, the colouring matters separate by mixing with sulphur, but can
be separated from the latter by dissolving and reprecipitating.
(e) By adding a solution of an amidosulpho acid obtained as per example IV to a
quantity of nitrous acid a light. yellow solution of a diazo combination is obtained;
the same can be combined to azoic colours in the usual way with phenols, for instance,
the diazo combination of amido-benzylethylaniline-sulpho acid gives with a naphthol
a brown colour and with ẞ naphthol a brown colour.
(f) By heating and constantly stirring the salts of the sulpho-acids manufactured
as per example I in water solution along with benzotrichlorid and by neutralizing
little by little tho muriatic acid which forms itself with chalk powder, intensive
coloured green solutions are obtained which can either be used direct as acid green or
out of which the colouring matters can be separated with salt.
(9) By keeping the salts of the sulpho-acids obtained as per example I after having
dried and pulverized the samo well, in suspension with toluol and introducing phosgen
or adding thiophosgen and by boiling a few hours at the outlet cooler, violet colouring
matters are formed. The toluol is drawn off and the remainder has to be dried.
Having now particularly described and ascertained the nature of my said inven-
tion and in what manner the same is to be performed I declare that what I
claim is:-.
First The new products as above specified and also the processes described for
their preparation, and particularly the manufacture of mono- and disulpho acids or
their corresponding salts from mixed tertiary monamines containing 2 or 3 radicals of
aromatic hydrocarburet.
Second The manufacture of nitrososulpho acids derived from sulpho acids or tho
salts of sulpho acids, the production of which has been claimed in the first claiming
clause.
Third The manufacture of nitro-sulpho acids derived from sulpho acids or the
salts of sulpho acid, the preparation of which has been claimed in the first claiming
clause.
Fourth The preparation of amido-sulpho acids derived from nitro or nitrososulpho
acids, the production of which has been claimed in the second and third claiming
clauses.
Fifth The manufacture of new sulpho colouring matters pertaining to the series
above specified, by the employment of new derivates of mixed tertiary monamiñes
claimed in the first, second, third, and fourth claiming clauses.
DL:
1
C
1000