Improvements relating to the Production of Amidophenol and Amidocresolsulpho-acids, and to the Manufacture of Colouring Matters therefrom.
Year: 1893

page_text: Date of Application. 10th July, 1893
Complete Specification Left, 27th Feb., 1894-Accepted, 12th May, 1894
PROVISIONAL DIFCIFICATION.
[Communicated from abroad by K. OEHLER, of Offenbach a/m, Grand Duchy of
Hessen, in the Empire of Germany, Manufacturer.]
Improvements relating to the Production of Amidophenol and
Amidocresolsulpho-acids, and to the Manufacture of Colouring
Matters therefrom.
I, HENRY HARRIS LAKE, of the Firm of Haseltine, Lake & Co., Patent Agents,
45 Southampton Buildings, in the County of Middlesex, do hereby declare the
nature of this invention to be as follows:-
This invention consists in the production of new amido-phenol and amidocresol-
sulpho acids and in the use thereof for the production of new dye stuffs.
The amidophenol- and amidocresol-sulpho acids are obtained by heating aniline
or toluidine, disulpho-acids with alkalies. The chemical process taking place is
represented by the following general formula:
The following are examples of my method of proceeding:
A. PRODUCTION OF THE AMIDOPHENOL- AND AMIDOCRESOL-SULPHO ACIDS.
(1.) The so called amidophenol sulpho acid III is obtained from the aniline-
ortho-di-sulpho acid (Beilstein Organ. Chemic II edit. 2 vol. page 379) by heating
up to 200° C. in an autoclave, 100 parts by weight of aniline-disulphonate of
sodium with 200 parts of caustic soda lye of 50 % The amidophenol-sulpho
acid III is precipitated from the cold melt acidulated with muriatic acid; it is
filtered off, pressed and transformed into its sodium salt, which crystallizes easily.
The pure acid reseparated from this salt is difficultly soluble in water and
crystallizes in big prismatic crystals or in long needles. It is transformed into the
isomeric amidophenol-sulpho-acid IV by heating it on the water bath with sulphuric
acid.
(2.) Production of the so-called amidophenolsulpho-acid V, from the a aniline-
metadisulpho-acid (Beilstein Organ. Chemic II edit. 2 vol. page 379) 12 parts of
acid anilinedisulphonate of potassium are heated with 36 parts of soda lye of
50% during 7 hours up to 220° C.
The melt is then dissolved in water and acidulated with muriatic acid. After
cooling it is filtered, pressed and dried the precipitated amidophenolsulpho-acid,
which is of a medium solubility in water and crystallizes in long uncoloured
needles

page_text: (3.) Production of the so-called amidocresol-sulpho acid III from paratoluidine-
disulpho-acid.
100 parts of paratoluidinesulphonate of sodium (prepared by sulphurizing
paratoluidine) are heated during 5 hours up to 210-230° with 200 parts of soda
Iye of 50% After cooling the melt is dissolved in water and over-saturated with
muriatic acid. The amidocresol-sulpho acid precipitates and is purified by
re-dissolving it. The acid crystallizes in water in uncoloured needles or big
prismatic crystals.
(4.) Production of amidocresolsulpho acid from ortho- and paranitrotoluol.
Those toluidinedisulpho acids which are obtained from ortho and paranitrotoluol
by subsequent sulphurizing reduction and again sulphurizing, yield also amido-
cresolsulpho acids in the alkaline melt, by operating in the same manner as in the
foregoing example No. 3.
The amidocresolsulpho acid IV from ortho nitrotoluol crystallizes in uncoloured
leaves or needles. It is difficultly soluble in water, yields when heated with acids
an amidocresol having a melting point of 157° C.
The amidocresolsulpho-acid from para nitro-toluol is identical with the acid
obtained from disulphurized paratoluidine according to example No. 3.
(B.) DYE STUFFS FROM AMIDOPHENOL- AND AMIDOCRESOL-SULPHO ACIDS.
For the production of so called dis- or -tetrazo dye stuffs I heat either an aromatic
diazo compound with an alkaline or acid solution of amidophenol or amidocresol
sulpho acids or I diazotate these acids and treat the obtained diazo combinations in
the well known manner with amines, diamines, phenols, amidophenols, dioxy
benzols, dioxynaphthaline or their sulpho- or carbon acids.
(1.) Production of the combination: Aniline-azo-amidophenolsulpho acid III.
I prepare of 13 parts of chlorhydrate of aniline, in the usual way, an aqueous
solution of chloride of diazobenzole and pour it slowly into a diluted solution at 0°
of 22 parts of amidophenolsulphonate of sodium and 6 parts of calcined soda in
120 parts of water. After allowing it to stand for several hours I heat the mass
and precipitate the dye stuff with common salt, filter, press and dry it. The
combination of the chloride of diazobenzole with the amidophenolsulpho acid can
also be effected in solutions containing caustic soda, acetic acid or hydrochloric
acid.
The colouring matter dyes wool a grey uniform yellow; its lac-dye of alumine is
yellow and that of chromoxyde is olive yellow.
(2.) Production of the combination: Amidoazotoluol (from orthotoluidine) -azo-
amidosulpho acid III.
I prepare of 26-2 parts of hydrochlorate of amidoazotoluol an aqueous solution
of the chloride of diazo-azo-toluol and pour it slowly into a solution at 0° of
23 parts of amidophenolsulphonate of sodium and 8 parts of caustic soda in 30 times
this quantity of water. The dye stuff is formed at once in the shape of a brown
red precipitate; it is separated as described in example 1.
This dye stuff dyes wool a yellow red and distinguishes itself by a remarkable
resistance to light.
(3.) Production of the combination Amidophenolsulpho-acid-azo-salicylic acid.
To an aqueous solution of 21-1 parts of amidophenolsulphonate of sodium, I
add 20 parts of muriatic acid of 221 B. and diazotate it by pouring in at 0° C. a
concentrated solution of 6-9 parts of nitrate of soda. The diazo compound
obtained consists of a yellow white powder difficultly soluble, which is slowly
added to an alkaline solution of 15 parts of salicylic acid. The dye stuff formed
is separated as described in the first example; it dyes wool reddish yellow; its
chrome-lac is olive yellow and stands milling.
The following dye stuffs are obtained in the same manner as described in the
3 examples given above.

page_text: Tolidine-
2
"
وو
"
"
9.2 parts of benzidine are transformed in the usual manner into the chloride of
tetrazo-diphenyl and poured into an aqueous solution of 0° of 23 parts of amido-
phenolsulphonate of sodium and 8 parts of caustic soda. After some hours the
mass is heated and the dye stuff precipitated with salt. It dyes wool and cotton a
brown red.
Mixed tetrazo-dyestuffs are obtained by the combination of a tetrazo body as
for instance the chloride of tetrazodiphenyl, with one molecule of one of the new
amidophenol or amidocresolsulpho-acids to form an intermediate compound which
is then combined with one molecule of an amine, diamine, phenol, amidophenol,
dioxybenzol, dioxynaphthaline or of their sulpho or carbon acids.
So called hexazo dye stuffs are obtained by combining the dye stuffs of the
type:
✓ amidophenolsulpho acids (or amidocresol sulpho acids)

page_text: Example: 10-6 parts of tolidine are transformed in the usual way into the
chloride of tetrazo-ditolyl and poured into an aqueous solution at 0° of 10-6 parts
of amidophenolsulphonate of sodium and the same quantity of soda. When the
formation of the intermediate compound is terminated, 5.4 parts of metaphenylen-
diamine are added and thus an intermediate dye stuff is formed which is treated
with 117 parts of diazo naphtionic acid in an aqueous solution. After standing
24 hours I heat the mass and precipitate the dye stuff with common salt. The
dye stuff thus obtained dyes unmordanted cotton a dark claret; the other dye stuff
produced with resorcine dyes corinth.
Dated this 10th day of July 1893.
HASELTINE, LAKE & Co.,
45; Southampton Buildings, London, W.C., Agents for the Applicant.
COMPLETE SPECIFICATION.
Improvements relating to the Production of Amidophenol and
Amidocresolsulpho-acids, and to the Manufacture of Colouring
Matters therefrom.
I, HENRY HARRIS LAKE, of the Firm of Haseltine, Lake & Co., Patent
Agents 45 Southampton Buildings, in the County of Middlesex, do hereby
declare the nature of this invention and in what manner the same is to be
performed, to be particularly described and ascertained in and by the following
statement :-
This invention consists in the production of new amidophenol and amidocresol-
sulpho acids and in the use thereof for the production of new dye stuffs.
The amidophenol- and amidocresol-sulpho acids are obtained by heating aniline-
or toluidine-disulpho acids with alkalies. The chemical process taking place is
represented by the following general formula:
CnHgn – 9 NH, (SO,Na), + 2NaOH = CnHạn – 9NH,ONaSO,Na +
SO.Na + H₂O.
The following are examples of my method of proceeding:
A. PRODUCTION OF THE AMIDOPHENOL- AND AMIDOCRESOL-SULPHO ACIDS.
1. The so-called amidophenol sulpho acid III, is obtained from the aniline-ortho-
disulpho acid (Beilstein Organ. Chemic II edit. 2 vol. page 379) by heating up
to 200° C. in an autoclave, 100 parts by weight of aniline-disulphate of sodium
with 200 parts of caustic soda lye of 50%: The amidophenol-sulpho acid III is
precipitated from the cold melt acidulated with muriatic acid; it is filtered off
pressed and transformed into its sodium salt, which crystallizes easily. The pure
acid reseparated from this salt is difficultly soluble in water and crystallizes in big
prismatic crystals or in long needles. It is transformed into the isomeric
amidophenol-sulpho-acid IV by heating it on the water bath with sulphuric acid.
2. Production of the so-called amidophenolsulpho-acid V. from the a-aniline-
metadisulpho-acid (Beilstein Organ. Chemic II edit. 2 vol. page 379) 12 parts of
acid anilinedisulphate of potassium are heated with 36 parts of soda lye of 50%
during 7 hours up to 220° C. The melt is then dissolved in water and acidulated
with muriatic acid. After cooling it is filtered, pressed and dried; the precipitated
amidophenolsulpho-acid, which is of a medium solubility in water and crystallizes
in long uncoloured needles.

page_text: 3. Production of the so-called amidocresol-sulpho acid III from paratoluidine-
disulpho-acid.
100 parts of paratoluidinedisulphonate of sodium (prepared by sulphurizing
paratoluidine) are heated during 5 hours up to 210-230° with 200 parts of soda
lye of 50%. After cooling the melt is dissolved in water and over-saturated with
muriatic acid. The amidocresolsulpho acid precipitates and is purified by
redissolving it. The acid crystallizes in water in uncoloured needles or big
prismatic crystals.
4. Production of amidocresolsulpho acid from ortho- and paranitrotoluol.
Those toluidinedisulpho-acids, which are obtained from ortho- and paranitro-
toluol by subsequent sulphurizing, reduction and again sulphurizing, yield also
amidocresolsulpho-acids in the alkaline melt, by operating in the same manner as
in the foregoing example No. 3.
The amidocresolsulpho acid IV from ortho nitrotoluol crystallizes in uncoloured
leaves or needles. It is difficultly soluble in water and yields, when heated with
acids an amidocresol having a melting point of 157° C.
The amidocresolsulpho-acid from paranitrotoluol is identical with the acid
obtained from disulphurized paratoluidine according to example No. 3.
B. DYE STUFFS FROM AMIDOPHENOL- AND AMIDOCRESOL-sulpho Acids.
For the production of so-called dis- or tetrazo dye stuffs I treat either an
aromatic diazo compound with an alkaline or acid solution of amidophenol- or
amidocresolsulpho acids or I diazotate these acids and treat the obtained diazo
combinations in the well known manner with amines, diamines, phenols, amido-
phenols, dioxy-benzols, dioxynaphthaline or their sulpho- or carbon acids.
I
1. Production of the combination: Benzene-azo-amidophenolsulpho acid III.
prepare of 13 parts of chlorhydrate of aniline, in the.usual way, an aqueous
solution of chloride of diazobenzole and pour it slowly into a diluted solution
at 0° of 22 parts of amidophenolsulphonate of sodium and parts of calcined soda
in 120 parts of water. After allowing it to stand for several hours I heat the mass
and precipitate the dye stuff with common salt, filter, press and dry it. The
combination of the chloride of diazobenzole with the amido-phenolsulpho acid can
also be effected in solutions containing caustic soda, acetic acid or hydrochloric
acid.
The colouring matter dyes wool a grey uniform yellow; its lake-dye of alumine
is yellow and that of chromoxide is olive yellow.
2. Production of the combination: Amido-azotoluol (from orthotoluidine) -azo-
amidophenolsulpho acid III.
I prepare of 26-2 parts of hydrochlorate of amidoazotoluol an aqueous solution
of the chloride of diazo-azo-toluol and pour it slowly into a solution at 0° of
23 parts of amidophenolsulphonate of sodium and 8 parts of caustic soda in 30 times
this quantity of water. The dye stuff is formed at once in the shape of a brown
red precipitate; it is separated as described in example 1.
This dye stuff dyes wool a yellow red and distinguishes itself by a remarkable
resistance to light.
3. Production of the combination Amidophenolsulpho-acid-azo-salicylic acid.
To an aqueous solution of 21.1 parts of amidophenolsulphate of sodium, I add
20 parts of muriatic acid of 224° B. and diazotate it by pouring in at 0° C. a
concentrated solution of 6-9 parts of nitrite of soda. The diazo compound obtained
consists of a yellow white powder difficultly soluble, which is slowly added to an
alkaline solution of 15 parts of salicylic acid. The dye stuff formed is separated
as described in the first example; it dyes wool a reddish yellow; its chrome-lake is.
olive yellow and stands milling.
The following dye stuffs are obtained in the same manner as described in the
3 examples given above.

page_text: amidophenolsulpho acids (or amidocresol sulpho acids)

page_text: Example: 10-6 parts of tolidine are transformed in the usual way into the
chloride of tetrazo-ditolyl and poured into an aqueous solution at 0° of 10-6 parts
of amidophenol-sulphonate of sodium and the same quantity of soda. When the
formation of the intermediate compound is terminated, 5.4 parts of metaphenylen-
diamine are added and thus an intermediate dye stuff is formed which is treated
with 117 parts of diazo naphtionic acid in an aqueous solution. After standing
24 hours I beat the mass and precipitate the dye stuff with common salt.. The dye
stuff thus obtained dyes unmordanted cotton a dark claret; the other dye stuff
produced with resorcine dyes corinth.
Having now particularly described and ascertained the nature of the said.
invention, and in what manner the same is to be performed, as communicated.
to me by my foreign correspondent, I declare that what I claim is :-
1. The method of producing
a. Amidophenolsulpho acid III from aniline-orthodisulpho acid.
b.
V.
"
"
,,
a - aniline
acid.
-
meta - disulpho
c. Amidocresolsulpho
III
"
"
d.
"
IV.
"
"
disulphurated paratoluidine
or from paratoluidine-di-
sulpho-acid obtained from
paranitro-toluol.
orthotoluidine-disulpho-acid
obtained from ortho-uitro-
toluol.
By heating these di-
sulpho acids
with
alkalies to 200-230°.
2. The method of producing dis- and tetrazo dye stuffs consisting in the reaction-
of an aromatic diazo- or tetrazo compound upon au alkaline or acid solution of
one of the amidophenol- or amidocresolsulpho acids named in Claim 1, or by com--
bining in the well-known manner of Griess the diazo combination of one of these
amidophenol- or amidocresolsulpho acids with an amine, phenol, diamine, amido-
phenol, dioxybenzol, dioxynaphthaline or with a sulpho- or carbon acid of these-
bodies.
3. The method of producing mixed tetrazo-dyestuffs consisting in combining
the tetrazodiphenylchloride, tetrazoditolylchloride or the tetrazo combination of
any other paradiamine with one molecule of one of the amidophenol- or amido-
cresolsulpho-acids named in Claim 1 to form an intermediate compound and
then by combining this latter with one molecule of an amine, phenol, diamine,
amidophenol, dioxybenzol, dioxynaphthaline or a sulpho- or carbon acid of one of
these bodies.
4. The method of producing hexazo dye stuffs consisting in the combination of
one of the dye stuffs of the type
camidophenolsulpho-acid (or amidocresolsulpho-acid)
Benzidine
Benzidines
resorcine (or metaphenylinediamine)
obtained by the method of Claim 3 with a further molecule of an aromatic diazo
combination.
5. As new articles of manufacture
(a) The amidophenol- and amidocresol-sulpho acids named in the first claim..
(b) The dye stuffs produced by means of these acids and the methods of the
second, third and fourth claims.
Dated this 26th day of February, 1894.
HASELTINE, LAKE & Co.,
45, Southampton Buildings, London, W.C., Agents for the Applicant..