Manufacture of Amino-oxycarbanil-carbonic Acid, and Azo Dyestuffs. therefrom Fixing on Chrome Mordants.
Year: 1896

page_text: Date of Application, 4th Aug., 1896
Complete Specification Left, 22nd Apr., 1897-Accepted, 29th May, 1897
PROVISIONAL SPECIFICATION.
[Communicated from abroad by GEORG HEINRICH WEISS, Chemist, of
24 Englische Strasse, Charlottenburg, near Berlin, in the Empire of
Germany.].
Manufacture of Amino-oxycarbanil-carbonic Acid, and Azo Dyestuffs.
therefrom Fixing on Chrome Mordants.
I, OLIVER IMRAY of No. 28 Southampton Buildings, Chancery Lane, in the
County of London, Chartered Patent Agent, do hereby declare the nature of this
invention to be as follows:-
By the action of phosgene upon a solution kept alkaline of o-aminophenol,.
carbonyl-amino-phenol, or o-oxycarbanil is obtained (as shown by Chetmicki B. B..

page_text: The latter is dissolved in water under addition of 4 times the quantity of alkali
required theoretically for its solution; phosgene is then introduced into the cold
solution (care being taken that the temperature does not rise above 35° C.), until a
sample of the still alkaline 'liquid, when treated with sodium nitrate and hydrochloric
acid, no longer exhibits any colour reaction with R-salt, a proof that nitroamido-
-salicylic acid is no longer present. A part of the newly formed body separates out
in crystals during the introduction of phosgene, precipitation taking place on the
addition of hydrochloric acid, until the reaction is acid; the precipitate is filtered
and recrystallised from hot water.
The body thus purified forms dirty white to brownish needles, easily soluble in
hot water and alcohol; insoluble in benzene. Heated above 100° it loses water of
crystallisation; it melts at 263°; it differs from nitroamido-salicylic acid by its
insolubility in hydrochloric acid.
It is transformed into a base by reduction, which necessitates about 4.23 kilos. of
the nitro-body, about 8 kilos. of tin and about 16 kilos. of hydrochloric acid.
To the nitro body is first added about 16 kilos. of hot water and half the quantity
of hydrochloric acid together with some tin, when a violent reaction takes place;
the remaining tin and hydrochloric acid are then alternatelý added in small portions,
thus keeping the reaction going energetically.
The tin is finally removed by sulphuretted hydrogen or by precipitation with
soda and the amido body is separated from the filtrate with acetate of sodium or
with acetic acid (from the soda alkaline filtrate). It crystallises in white needles,
assuming a reddish tint when exposed to air; is very slightly soluble in hot
water and alcohol, loses water of crystallisation on heating above 100° C. and
melts at 252° C.
The base is easily diazotised and combines with the usual components to
azo dyestuffs having the property of producing very fast tints on chrome-mordanted
wool. Still better results, however, are obtained by subsequently treating the
colouring matter after dyeing with bichromate of potassium.
A prominent interest is possessed by those dyestuffs which are obtained by
combining the base with a-naphthylamine or its 1-6 and 17 sulphonic acid, and
further diazotising the amido-azo compound thus produced and combining with
naphthol-dioxyuaphthaline and amidonaphtholmono and disulphonic acids. They
form black chrome-mordanted wool dyestuffs exceedingly fast to light, fulling
and soap..
The following is a description of the manufacture of such a dyestuff:
2. Dyestuff from aminooxy-carbanil carbonic acid + a naphthylamine + R-salt.
19-4 parts by weight of aminooxy-carbanil carboxylic acid are washed with
500 parts by weight of water and brought into solution by addition of 12 parts by
weight of soda lye of 33% 7 parts by weight of nitrite are dissolved in this
brown coloured solution. The mixture cooled down to +5° C. is then run into a
mixture cooled with ice of 40 parts by weight of hydrochloric acid of 22° Bé. and
500 parts by weight of water. The amino-carboxylic acid first separates out,
gradually becomes dissolved and a clear solution of the diazo compound results.
The diazotising being over, a solution of 18 parts by weight of a-naphthylamine
hydrochloride in about 1000 parts by weight of water are added whilst being well
stirred; the 'amidoazo compound at once formed separates in the form of brilliant
blue-violet crystalline needles.
By
y 'the addition of acetate of soda, the reaction is completed after 6 hours of
constant stirring.
The precipitate is separated from the mother liquor by filtration and, after
pressing, is brought into a solution with the calculated quantity of soda-lye in about
1000 parts by weight of water.
The yellow solution is then mixed with 7.parts by weight of nitrite, dissolved in
'water and slowly run into 50 parts by weight of hydrochloric acid of 22° Be., cooled
with ice.
The most appropriate temperature for this second diazotising is about 15° C.

page_text: The hydrochloride of the amido-azo compound first separates in the characteristic
blue-violet needles, but soon changes into the brown coloured diazo-compound.
After 4 hours stirring at the temperature stated, the diazotising is complete.
The diazo-compound is then run into a solution, kept alkaline with soda, of
35 parts by weight of ẞ-naphtholdisulphonate of sodium R. The colouring matter
is formed at once. After several hours stirring the dyestuff is obtained as usual by
salting out and pressing. It dyes chrome-mordanted wool a deep and fast blue-
black. If in the above example the B-naphtholdisulphonic acid R be replaced by
the equivalent quantity of ẞ naphtholsulphonic acid Nev. & Winth., dyestuffs of a
similar character are obtained. Deep dark-blue dyestuffs may be obtained by
using dioxynaphthaline nono sulphonic acid G or amidonaphtholmonosulphonic
acid G.
Dated this 4th dar of August 1896
ABEL & IMRAY,
Agents for the Applicant.
Manufacture of Amino-oxycarbanil-carbonic Acid, and Azo Dyestuffs
therefrom Fixing on Chrome Mordants.
I, OLIVER IMRAY, of No. 28 Southampton Buildings, Chancery Lane, in the
County of London, Chartered Patent Agent, 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 :-
By the action of phosgene upon a solution kept alkaline of o-aminophenol,
carbonylamino-phenol, or o-oxycarbauil is obtained (as shewn by Chetnicki B. B.
XX 177) of the constitution. of

page_text: group CO, the azo dyestuffs produced with this base shew quite a remarkable
affinity for metallic mordants, with which they form excellent fast lakes. They
surpass in many respects the azo-dyestuffs dyeing on mordants known up to the
present time.
To produce the new base, my correspondent proceeds in the following manner:
1.) Dinitrosalicylic acid, obtained by nitration of salicylic acid with concentrated
nitric acid, (see Beilstein III Edit. II p. 1510) is transformed by partial reduction
with ammonium sulphide into the beautifully crystallising nitroamido-salicylic acid.
The latter is dissolved in water under addition of 4 times the quantity of alkali
required theoretically for its solution; phosgene is then introduced into the cold
solution (care being taken that the temperature does not rise above 35° C.), until
a sample of the still alkaline liquid, when treated with sodium nitrite and hydro-
chloric acid, no longer exhibits any colour reaction with R salt, a proof that.
nitroamidosalicylic acid is no longer present. A part of the newly formed body
separates out in crystals during the introduction of phosgene, precipitation taking
place on the addition of hydrochloric acid, until the reaction is acid; the precipitate
is filtered and recrystallised from hot water.
The body thus purified forms dirty white to brownish needles, easily soluble in
hot water and alcohol, insoluble in benzene. Heated above 100° it loses water of
crystallisation; it melts at 263°; it differs from nitroamido-salicylic acid by its
insolubility in hydrochloric acid.
It is transformed into a base by reduction, which necessitates about 4.23 kilos.
of the nitro-body, about 8 kilos. of tin and about 16 kilos. of hydrochloric acid.
To the nitro body is first added about 16 kilos. of hot water and half the quantity
of hydrochloric acid together with some tin, when a violent reaction takes place;
the remaining tin and hydrochloric acid are then alternately added in small portions,
thus keeping the reaction going energetically.
The tin is finally removed by sulphuretted hydrogen or by precipitation with
soda and the amido body is separated from the filtrate with acetate of sodium or
with acetic acid (from the soda alkaline filtrate). It crystallises in white needles,
assuming a reddish tint when exposed to air; it is very slightly soluble in hot
water and alcohol, loses water of crystallisation on heating above 100° C. and melts
at 252° C.
The base is easily diazotised and combines with the usual components to azodye-
stuffs having the property of producing very fast tints on chrome-mordanted wool.
Still better results, however, are obtained by subsequently treating the colouring
matter after dyeing with bichromate of potassium.
A prominent interest is possessed by those dyestuffs which are obtained by
combining the base with a-naphthylamine or its 1-6 and 1-7 sulphonic acid, and
further diazotising the amido-azo compound thus produced and combining with
naphthol-dioxynaphthaline and amidonaphtholmono and disulphonic acids. They
form black chrome-mordanted wool dyestuffs exceedingly fast to light, fulling and
soap.
The following is a description of the manufacture of such a dyestuff:
2.) Dyestuff from aminooxy-carbanil carbonic acid + a naphthylamine + R-salt.
19-4 parts by weight of aminooxy-carbanil carboxylic acid are mixed
with 500 parts by weight of water and brought into solution by addition of 12 parts
by weight of soda lye of 33%. 7 parts by weight of nitrite are dissolved in this
brown coloured solution. The mixture cooled down to +5° C. is then run into a
mixture, cooled with ice, of 40 parts by weight of hydrochloric acid of 22° Be.
and 500 parts by weight of water. The amino-carboxylic acid first separates
out, gradually becomes dissolved and a clear solution of the diazo compound
results.
The diazotising being over, a solution of 18 parts by weight of a-naphthylamine
hydrochloride in about 1,000 parts by weight of water are added whilst being well
stirred; the amidoazo compound at once formed separates in the form of brilliant
blue-violet crystalline needles.

page_text: By the addition of acetate of soda, the reaction is completed after 6 hours of
constant stirring. The precipitate is separated from the mother liquor by filtration.
and, after pressing, is brought into a solution with the calculated quantity of sola-
lye in about 1,000 parts by weight of water.
The yellow solution is then mixed with 7 parts by weight of nitrite, dissolved
in water and slowly run into 50 parts by weight of hydrochloric acid of 22° Bé.,.
cooled with ice.
The most appropriate temperature for this second diazotising is about 15° C.
The hydrochloride of the amido-azo compound first separates in the characteristic
blue-violet needles, but soon changes into the brown coloured diazo-compound..
After 4 hours' stirring at the temperature stated, the diazotising is complete. The
diazo compound is then run into a solution, kept alkaline with soda, of 35 parts by
weight of B-naphtholdisulphonate of sodium R. The colouring matter is formed.
at once. After several hours stirring the dyestuff is obtained as usual by salting.
out and pressing. It dyes chrome-mordanted wool a deep and fast blue-black.
If, in the above example, the B-naphtholdisulphonic acid R be replaced by the
equivalent quantity of 3 naphtholsulphonic acid (Nev. g Winth) dyestuffs of a
similar character are obtained. Deep dark-blue dyestuffs may be obtained by-
using dioxynaphthaline mono-sulphonic acid G or amidonaphtholmonosulphonic
acid G.
Having now particularly described and ascertained the nature of this inven-.
tion and in what manner the same is to be performed, I declare that what I
claim is
1. The herein described manufacture of amino-oxycarbanil carbonic acid having
the melting point 252° C. by the action of phosgene upon a solution kept alkaline
of nitroamidosalicylic acid having the melting point 220° C., and the reduction of
the nitrobody thus obtained.
2. The herein described manufacture of disazodyestuffs fixing on mordants, by the
action of the diazocompound of amino-oxycarbanil carbonic acid upon a-naphthyl-
amine or a-naphthylamine 1.6 sulphonic acid or a-naphthylamine 1.7 sulphonic acid,
and further diazotising the amidoazocompound thus produced and combining with
naphtholmono- or disulphonic acids, dioxynaphthaline mono- or- disulphonic acids,.
amidonaphthol-mono- or disulphonic acids.
3. The aminooxycarbanil carbonic acid manufactured as set forth in Claim 1.
4. The colouring matters manufactured as set forth in Claim 2.
13007
ABEL & IMRAY,
Agents for the Applicant..