Manufacture of New Bases and Colouring Matters therefrom.
Year: 1892

page_text: Date of Application, 15th Feb., 1892
Complete Specification Left, 10th Nov., 1892-Accepted, 10th Dec., 1892
PROVISIONAL SPECIFICATION.
[Communicated from abroad by THE ACTIEN GESELLSCHAFT FÜR ANILIN
FABRIKATION, of Berlin, in the Empire of Germany, Manufacturing
Chemists.]
Manufacture of New Bases and Colouring Matters therefrom.
1, CHARLES DENTON ABEL, 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 :—
are generally prepared in the following manner.
One molecule of a diazo body is caused to react upon one molecule of p-xylidine
in an acid solution; instead of pure xylidine the commercial mixture of xylidines
may be employed; in this case such a quantity of diazo body is used as corresponds
to the quantity of pure p-xylidine contained in the commercial product.
The diazo derivatives, which may be used in this process are those obtained from
aniline, nitraniline and their homologues, the naphthylamines or the sulpho and
carbo acids of these bases.
The products, resulting from the combination with bases, such as aniline,
nitraniline, naphthylamine etc., resemble in their general properties amidoazo benzene
or its homologues and analogues; the products which may be obtained, when the
diazo derivatives of the above mentioned sulpho or carbo acids are combined with
p-xylidine are dyestuffs, similar to the sulpho acids of amido benzene etc., and dye
wool in an acidulated bath with orange yellow to red orange shades; these colours
may partly also be fixed on wool previously mordanted with chromium salts.
II.
My foreign correspondents have further found, that the amidoazo compounds,
obtained according to the process described under head I may be rediazotised and
O combined with the sulpho acids of the naphtholes, dioxynaphthalines or amido-
naphtholes.
The colouring matters, resulting from this combination possess the general

page_text: afterwards combined in an alkaline solution with one molecule of a naphthole dioxy-
naphthaline, amidonaphthole or their sulpho acids.
The colouring matters obtained in this way dye wool in an acidulated bath, with
shades varying from yellowish red to Bordeaux and violet brown.
My foreign correspondents have discovered that the tetrazo compound, derived
from the base, described under head III may be used for the production of valuable
azo colouring matters, which possess the property of dyeing directly unmordanted
cotton.
These new dyestuffs are prepared generally in such a way that one molecule of
the tetrazo-compound is caused to react upon two molecules of a sulpho acid of the
naphtholes, dioxynaphthalenes, amidonaphtholes, naphthylamines or of the phenol-
carbo-acids; the sulpbo or carbo acids are employed according to their nature either
in alkaline solution or in presence of acetate of soda.
The sulpho acids of the naphtholes and dioxynaphthalenes yield blue to violet
colours the colouring matters obtained with naphthylamine sulpho acids are
brownish violet, those derived from the amidonaphthol sulpho acids are blue black;
by the combination with phenol-carbo acids, for instance salicylic acid, orange to
brown colouring matters are obtained.
The new diamido base may also be used for the production of mixed azo dyes, by
first combining the tetrazo-compound with one molecule of a phenol amine, amido-
phenol or their sulpho and carbo acids and reacting afterwards with the inter-
mediate product formed thereby upon one molecule of another of the aforesaid
substances.
Dated this 15th day of February 1892.
ABEL & IMRAY,
Agents for the Applicant.

page_text: COMPLETE SPECIFICATION.
Manufacture of New Bases and Colouring Matters therefrom.
I, CHARLES DENTON ABEL, 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 :-
:
:
My foreign correspondents have discovered that p-xylidine (CH, NH, CH,
=1:2:4) behaves in so far different from its isomers viz.: m-xylidine
(CH, NH, CH, = 1:4:3) and o-xylidine (CH, NH, CH,=1:4:2) that
by combination with diazo compounds it yields directly real amido azo bodies, without
forming an intermediate diazo amido compound.
The products obtained in this way which correspond to the general formula :
are generally prepared in the following manner.
One molecule of a diazo body is caused to react upon one molecule of p xylidine
in an acid solution; instead of pure xylidine the commercial mixture of xylidines
may be employed; in this case such a quantity of diazo body is used as corresponds
to the quantity of pure p-xylidine contained in the commercial product.
The diazo derivatives, which may be used in this process are those obtained from
aniline, nitraniline and their homologues the naphthylamines or the sulpho and
carbo acids of these bases.
The products, resulting from the combination with bases, such as aniline,
nitraniline, naphthylamine &c. resemble in their general properties amido azo
benzene or its homologues and analogues; the products which may be obtained,
when the diazo derivatives of the above mentioned sulpho or carbo acids are com-
bined with p-xylidine are dyestuffs, similar to the sulpho acids of amido benzene etc.
and dye wool in an acidulated bath with orange yellow to red orange shades; these
colours may partly also be fixed on wool previously mordanted with chromium
salts.
The following is given as an example for the production of the before mentioned
colouring matters.
17-3 kilos of sulphanilic acid are converted in the well known manner into p-diazo
benzenesulpho acid; the latter is then combined with 12-1 kilos of para-xylidine
which have previously been dissolved in diluted hydrochloric acid; the mixture is
well stirred for some hours and the red brown precipitate formed in this way is
dissolved by neutralizing with an alkali and heating to about 90° Cels. The
yellow solution is filtered and the colouring matter is precipitated with salt. It
dyes wool in an acidulated bath an orange yellow shade and may also be fixed on
wool by means of chromium mordants.
In an analogous manner the other colouring matters corresponding to the above
mentioned type may be prepared.

page_text: and their preparation may generally be carried out in the following way.
A diluted solution of the colouring matter which is obtained according to the
directions given under head I from 17.3 kilos of sulphanilic acid and 12.1 kilos
para-xylidine is mixed with a solution of 6-9 kilos nitrite of soda and the mixture is
slowly poured at ordinary temperature and whilst stirring energetically into an
excess of diluted hydrochloric acid. The diazo compound which separates for the
greatest part in the shape of light brown flakes is introduced into an alkaline
solution of 34.8 kilos 6 naphtholdisulphonate of sodium (R salt). After some time
the mixture is gently heated and the colouring matter is salted out. It dyes wool
in an acidulated bath a Bordeaux shade.
In an analogous manner the other colouring matters corresponding to the afore-
said general formula may be prepared; according to the components employed,
their shades vary from yellowish red to Bordeaux and violet brown.
III.
My foreign correspondents have also discovered that the nitroamidoazo compound
which results according to the process described under head II from the combina-
tion of p-nitrodiazobenzene with p-xylidine may be reduced by means of alkali-
sulphides forming in this way a new diamido base of the following constitution.
NH,CH N = NCH.NH.
The preparation of this base may be carried out as follows. 3 parts by weight of
the nitroazoamido compound are suspended in about 40 parts of alcohol, the mixture
is heated to about 70° C. and then an aqueous solution of 2 parts of crystallised
sodium sulphide is slowly added in small portions; when the addition of the sulphide
is completed the mixture is heated for a short time to boiling.
The diamido base formed enters in solution during the reaction with an orange
colour and may be obtained in the shape of brownish lustrous crystal leaves by
pouring this solution into hot water.
The new base is readily soluble in alcohol, ether or benzene; in diluted acids it
dissolves with deep orange colour and is precipitated from this solution by the
addition of alkalies in the form of yellow flakes.
By the action of two molecules of nitrous acid the base may be converted into a
IV.
My foreign correspondents have discovered that the tetrazo compound, derived
from the base, described under head III may be used for the production of
valuable azo colouring matters, which possess the property of dyeing directly
unmordanted cotton.
These new dyestuffs are prepared generally in such a way that one molecule of
the tetrazo compound is caused to react upon two molecules of a sulpho acid of the
naphtholes, dioxynaphthalenes, amidonaphtholes, naphthylamines, or of the phenol
carbo acids; the sulpho or carbo acids are employed according to their nature
either in alkaline solution or in presence of acetate of soda. For instance, 23.9 kilos
of the before described diamido base are dissolved in water and hydrochloric acid.
and diazotised by means of 14 kilos of nitrite of soda. The orange yellow solution
of the tetrazo compound formed in this way is poured into an alkaline solution
of 49.2 a naphthol a monosulphonate of soda. After some time the mixture is

page_text: gently heated and the colouring matter is salted out; it dyes unmordanted cotton a
dark blue shade.
The sulpho acids of the naphtholes and dioxynaphthalenes yield blue to violet
colours; the colouring matters obtained with naphthylamine sulpho acids are
brownish violet, those derived from the amidonaphthol sulpho acids are blue black;
by the combination with phenol carbo acids, for instance salicylic acid, orange to
brown colouring matters are obtained.
The new diamido base may also be used for the production of mixed azo dyes, by
first combining the tetrazo compound with one molecule of a phenol amine,
amidophenol or their sulpho and carbo acids and reacting afterwards with the
intermediate product formed thereby upon one molecule of another of the aforesaid
substances.
The preparation of such mixed colouring matters is carried out in a suitable
manner well known to chemists.
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 manufacture of amido azo bodies by combining para-xylidine with the
diazo derivatives of aniline, nitraniline and their homologues, of the naphthylamines
or of the sulpho and carbo acids of these bases.
2. The manufacture of colouring matters, by diazotising the amido azo bodies
obtained according to the first claim and combining the same with the sulpho acids
of the naphthols, dioxynaphthalenes and amidonaphtholes.
3. The manufacture of a new diamido base by reducing the amido azo body
resulting, according to the first claim, from the combination of para nitro-
diazobenzene and para xylidine, by means of alkali sulphides.
4. The manufacture of colouring matters, by combining one molecule of the
tetrazo compound of the diamido base obtained as set forth in the preceding claim
with two equal or different molecules of the sulpho acids of the naphtholes,
dioxynaphthalines, naphthylamines, amidonaphthols or of phenol carbo acids.
5. As new manufactures, the products resulting from the several processes set
forth in the preceding claims Nos. 1 to 4.
Dated this 10th day of November 1892.
ABEL & IMRAY,
Agents for the Applicant.