The Manufacture of New Colouring Matters.
Year: 1892

page_text: Date of Application, 15th Mar., 1892
Complete Specification Left, 15th Dec., 1892-Accepted, 28th Jan., 1893
PROVISIONAL SPECIFICATION.
The Manufacture of New Colouring Matters.
I, BENJAMIN WILLCOX of 47 Lincoln's Inn Fields in the County of Middlesex,
Patent Agent do hereby declare the nature of this invention (which has been
communicated to me from abroad by the Farbenfabriken vormals Friedrich Bayer
& Co. of Elberfeld in the Empire of Germany) to be as follows:-
This invention relates to the manufacture of new valuable colouring-matters
chiefly by means of the three alpha-naphthylamine-beta-mono-sulpho acids which
were first obtained by Clève either by nitrating naphthalene-beta-monosulpho acid
or by sulphonating alpha-nitro-naphthalene and subsequently reducing the mixture
of mono-nitronaphthalene-sulpho acids formed in these two processes. On separating
the isomeric acids the alpha-naphthylamine-beta-monosulpho acids y, ẞ and 8 have
been isolated which correspond with the following formula-
As my foreign correspondents have found and described the above alpha-naphthyl-
amine-beta-mono-sulpho acids are of high value especially as the tetrazo dye-stuffs
obtained in the employment of the said acids are superior to the analogous products
resulting from the employment of the other naphthylamine sulpho acids as com-
ponents. Whilst the latter colouring-matters, when fixed on cotton fibre, cannot
be directly diazotised, the new tetrazo dye-stuffs derived from the aforesaid three
acids (Clève) after having been diazotised on the fibre and the resulting diazo
derivatives combined directly with an amine, a phenol, amidophenol, sulpho or
carboxylic acid thereof, yield new and valuable dyes of very great fastness against
the action of fulling and soaping.

page_text: beta-monosulpho acids and likewise the so called mixed colouring matters con-
taining one molecular proportion of a tetrazo compound, one molecular proportion
of Clève's acids and one molecular proportion of an amine, a phenol, an amido-
phenol or a sulpho or carboxylic acid thereof can be converted not only on the
fibre but also in the usual manner into new colouring-matters by further diazotising
them and subsequently combining the resulting products with two molecular pro-
portions or one molecular proportion of an amine, a phenol or amido-phenol, or a
sulpho or carboxylic acid thereof according as the tetrazo dyes first produced
contain two free amido groups or only one such group. In coupling two com-
ponents either the same or two different components may be employed and the
salts of the following tetrazo compounds can be used for the production of these
new colouring-matters viz.: tetrazo diphenyl, tetrazo-phenyltolyl, tetrazo-ortho-
ditolyl, tetrazo-mono-methoxy diphenyl, tetrazo-mono-ethoxydiphenyl, tetrazo
mono-methoxyphenyltolyl, tetrazo-mono-ethoxyphenyltolyl, tetrazo-ortho-diphenol-
dimethyl-ether, tetrazo-ortho-diphenoldiethylether, tetrazo-diphenoxyl acetic acid,
tetrazophenylene, tetrazonaphthalene (a, as) tetrazofluorene, tetrazostilbene, tetrazo-
diphenylene oxide, tetrazoditolaylene oxide, tetrazo diphenyl sulphone tetrazo-
ditolyl sulphone and the sulpho or carboxylic acids thereof.
Instead of the three alpha-naphthylamine-beta-monosulpho acids (Clève) in a
purified or isolated state the mixture of the said acids may be employed in the
processes described in this Specification.
The number of these dye-stuffs and the variety of shades produced by them is,
of course, very great and these colouring matters are in general formed in a similar
manner to that employed in forming those which are obtained according to the
Specification of Letters Patent No. 16484 dated 13th November 1887.
In order to explain the method for the production of these new colouring matters
the following example is vivon
DYE-STUFF OBTAINED BY FURTHER DIAZOTISING THE COLOURING-MATTER
OBTAINED IN THE USUAL MANNER FROM ONE MOLECULAR PROPORTION OF 3
TETRAZODITOLYL-CHLORIDE AND TWO MOLECULAR PROPORTIONS OF
ALPHANAPHTHYLAMINE-BETA-MONOSULPHO ACID (CLEVE'S B-ACID) AND
COMBINING THE RESULTING PRODUCT
WITH TWO MOLECULAR PRO-
PORTIONS 18-DIHYDROXYNAPHTHALENE-ALPHA MONO-SULPHO ACID.
72.4 parts, by weight, of the dye-stuff which is obtained in the well known 3
manner from one molecular proportion of tetrazoditolyl chloride and two molecular
proportions of Clève's B-acid and which possesses the following formula :—
are suspended in water and after adding a watery solution of 14 parts, by weight,
of sodium nitrite the resulting mixture is acidulated by adding slowly and on 10
cooling by ice such a quantity of hydrochloric acid as is necessary for producing
a moderately acid reaction. After about 12 hours the mixture formed is allowed
to flow into a cold watery solution of 53-4 parts, by weight, of the sodium salt of
the 1-8-dihydroxynaphthalene-alpha-mono-sulpho acid and of about 100 parts, by
weight of sodium acetate. After standing for some days, the mixture is slowly 45
heated to from 60 to 70 degrees centigrade and maintained for a short time at this
temperature in order to complete the reaction. After adding sodium carbonate or

page_text: allowed to flow into a cold solution of 24°5 parts, by weight, of the sodium salt of
alpha-naphthylamine-beta-mono sulpho acid (Clève's d-acid) and of about 50 parts,
by weight, of sodium acetate. When the formation of the intermediate product of
the formula:
CH-N-N-C1
C.H.-N=N
is completed the latter is diazotised again directly by adding to the resulting
mixture, when cool, a watery solution of 7 parts, by weight, of sodium nitrite and
the necessary quantity of hydrochloric acid. As soon as the diazotation is
finished the mixture is introduced into a watery solution of 52.4 parts, by weight,
of 1-8-dihydroxynaphthalene-mono-sulphonate of sodium and about 100 parts, by 1
weight, of sodium acetate. After standing for some hours the formation of the
dye-stuff is finished. The latter which possesses the following constitution :—
III.
My foreign correspondents have found that the alpha-naphthylamine-beta-
monosulpho acids (Clève) can be employed advantageously for the production of
new disazo-colouring matters suitable for dyeing wool black in an acid bath, by
combining with the known dye stuff components: amines, phenols, amidophenols or
amidophenolethers or the sulpho and carboxylic acids thereof, preferably with
naphthols, dihydroxynaphthalenes, amidonaphthols and the sulpho acids thereof,
the diazo compounds of those azo-bodies which are formed from amines, amido-
phenols, amidophenolethers substituted products of these compounds or sulpho or
carboxylic acids of all the named components, amidoazobenzene or its analogous
and substitution products thereof by diazotising them and subsequently com-
bining the resulting diazo products with Clève's alphanaphthylamine-beta-mono-
sulpho acids.
Of course, the alphanaphthylamine beta-mono-sulpho acids (Clève) may also be
employed in the first place a series of colours being so produced by diazotising Clève's

page_text: acius, combining again the diazo-derivatives thus formed with Cleve's acids, real-
azotising and coupling with a suitable dye-stuff component.
The process for the production of all these new disazo colouring matters may
be conducted in the known manner viz. by diazotising aniline, toluidine and the
like, combining the diazo-derivatives so obtained with alphanaphthylamine-beta-
mono-sulpho acid (Clève), rediazotising the amido azo compounds formed and
re-acting with the resulting diazo products on the said dyestuff components, colouring
matters being produced which are similar to those described in the Specification of
Letters Patent No. 3397 dated 4th March 1890.
My foreign correspondents have further obtained new disazo colouring matters
derived from para-phenylene-diamine by diazotising its mono-acetyl derivative
coupling the resulting diazo product with Clève's acid, splitting off the acetyl group,
rediazotising and combining the diazo compound so formed with the known dye-stuff
components.
IV.
My foreign correspondents have further found that direct dyeing colouring
matters of high technical value are obtained when those amido-azo compounds
which result by combining the diazo-derivatives either of the products formed by
treating para-toluidine, meta-xylidine or pseudo-cumidine with sulphur or of the
sulpho-acids of the thioamides so formed with the aforesaid alpha-naphthylamine-
beta-mono-sulpho acids (Clève) are further diazotised and combined with the known
dyestuff components, especially naphthols amido-naphthols, amidonaphtholethers,
dihydroxynaphthalenes and sulpho or carboxylic acids thereof.
In this process the following thio compounds or sulpho-acids thereof may be
employed dehydro-thio-para-toluidine melting at 191 degrees centigrade which is
obtained by heating para-toluidine with sulphur, dehydro-thio-meta-xylidine and
dehydro-thio pseudo cumidine produced in an analogous manner from meta-xylidine
and pseudo-cumidine, the so called primuline base which is formed together with
dehydro-thio-para-toluidine on heating para-toluidine with sulphur and may
be employed either as a raw product or in a purified state and the sulpho acids of
the aforesaid four thio compounds excluding however the so called primuline.
The new colouring matters are obtained by combining the diazo derivatives of
the above mentioned thio-compounds with alphanaphthylamine-beta-mono-sulpho-
acid (Clève) diazotising the amido-azo products so formed and coupling with the
known dye stuff components: amines, phenols or amido-phenols or sulpho or
carboxylic acids thereof especially with 18-dihydroxynaphthalene sulpho acids.
In the employment of one of the three alpha-naphthylamine monosulpho acids
(Clève) as second components and for example the said dihydroxynaphthalene
sulpho acids green or greenish black shades, of high fastness are obtained.
The variety of shades is of course greater, when instead of the said dihydroxy-
naphthalene sulpho acids other dyestuff components are employed.
The following example is given in order to explain the production of these new
colouring matters.
15 COLOURING MATTER PRODUCED BY COUPLING DIAZOTISED DEHYDRO-THIO-
PARA-TOLUIDINE SULPHO ACID WITH CLEVE'S ALPHA-NAPHTHYLAMINE
MONO-SULPHO ACID, ẞ, REDIAZOTISING THE RESULTING AMIDO AZO-
COMPOUND AND COMBINING THE DIAZO PRODUCT WITH 1.8 DIHYDROXY-
NAPHTHALENE-ALPHA-MONO-SULPHO-ACID S.
50 342 parts by weight of the dehydro-thio-para toluidine mono-sulphonate of
sodium (CH.NS.NH,SO,Na) are diazotised in the usual manner by means of
7 parts by weight of sodium nitrite and the resulting diazo compound (which is
soluble with difficulty) after having been filtered off is introduced into a watery solution

page_text: of 24.3 parts by weight of the sodium salt of Clève's ẞ acid and 48 parts by weight
of sodium acetate. After about 24 hours standing the formation of the intermediate
amido-azo product of the formula :
is completed. After neutralising by means of soda lye and adding a solution of 5
7 parts by weight of sodium nitrite hydrochloric acid is allowed to flow slowly into
the mixture until the latter exhibits a moderately acid re-action. The whole mass
is then introduced into a solution in water of 26-2 parts by weight, of the 1.8 dihy-
droxynaphthalene alpha monosulphonate of sodium and 50 parts by weight of
sodium acetate. In order to complete the reaction the mixture is heated after
some time to about 60 to 70 degrees centigrade and after rendering alkaline the
dyestuff which possesses the following composition:
My foreign correspondents have further found that the alpha-naphthylamine-
beta-mono-sulpho acids (Clève) may also be employed for the production of simple
azo dye stuffs. These colouring matters are obtained in the usual manner viz.: by
combining the diazo derivatives of amines, amido-phenols amido phenolethers or
substituted products of them especially sulpho or carboxylic acids of all these
compounds with one of the alpha-naphthylamine beta-mono-sulpho acids (Clève).
Simple azo dyestuffs derived from para-phenylene-diamine have been prepared
by my foreign correspondents by diazotising mono-acetyl-para-phenylene diamine,
coupling the diazo product obtained with one of Clève's acids and subsequently
splitting off the acetyl group.
Of the great number of these dyes those which result by combining diazotised
amido carboxylic acids amido hydroxy carboxylic acid amido alkyloxy carboxylic
acids or sulpho derivatives thereof with the said acids of Clève are of especially
high value. The dyes thus formed produce on unmordanted wool from yellow to
reddish yellow colours and on wool mordanted with chromium salts from reddish
yellow to brown shades.
The manufacture of these colouring matters is to be effected in the well known
manner namely by allowing the diazo derivatives of the amines or substituted amines
employed to react on Clève's acids in moderately acid (preferably acetic acid)
solution.
The dyestuffs obtained in the employment of diazotised amido-carboxylic acids are
of high value for dyeing and printing purposes as they, after having been fixed on
the fibre by means of metallic salts, may be directly diazotised and combined with

page_text: the known dyestuff components colouring matters being produced in this manner
which produce from reddish yellow to brown shades distinguishable for their
intensity and fastness.
J. H. JOHNSON & Co.,
Agents.
COMPLETE SPECIFICATION.
The Manufacture of New Colouring Matters.
I BENJAMIN WILLCOX of 47 Lincoln's Inn Fields in the County of Middlesex
Patent Agent do hereby declare the nature of this invention (which has been
communicated to me from abroad by Farbenfabriken vorm. Friedr. Bayer & Co.
of Elberfeld in the Empire of Germany) and in what manner the same is to be
performed to be particularly described and ascertained in and by the following
statement:
This invention relates to the manufacture of new valuable colouring matters by
means of alphanaphthylamine-beta-monosulpho acids which were first obtained by
Clève either by nitrating naphthalene-beta-mono-sulpho acid or by sulphonating
alpha-nitronaphthalene and subsequently reducing the mixture of mono-nitro-
naphthalenesulpho acids formed in these two processes. On separating the isomeric
acids the alphanaphthylamine-beta-monosulpho acids gamma, beta and delta have
been isolated which correspond with the following formulæ :--
As my foreign correspondents have found and described in the Specification of
Letters Patent No. 22641A dated 28th December 1891 the above alphanaphthyl-
aminemonosulpho acids beta and delta are of high value, especially as the tetrazo
dye-stuffs obtained by the employment of these two acids are superior to the
analogous products resulting from the employment of other naphthylamine sulpho
acids as components. Whilst the latter colouring-matters, when fixed on cotton
fibre, cannot be directly diazotised, the tetrazo dye-stuffs derived from Clève's
alpha naphthylaminemonosulpho acids beta and delta can be diazotised on the fibre
and by combining the resulting diazo derivatives directly with an amine, a phenol,
an amidophenol or a sulpho or carboxylic acid thereof new and valuable dyes
producing other shades are obtained.
My foreign correspondents have further stated in the Specification of Letters
Patent No. 22641 dated 28th December 1891, that the so called symmetrical dye

page_text: stuffs obtained in the usual manner by combining one molecular proportion of a
tetrazo compound and two molecular proportions of Clève's alphanaphthylamine-
monosulpho acids (beta or delta) and likewise the so called mixed colouring
matters containing one molecular proportion of a tetrazo compound, one molecular
proportion of Clève's acid beta or delta and one molecular proportion of an amine,
a phenol, an amidophenol or a sulpho or carboxylic acid thereof can be converted,
not only on the fibre, but also in the usual manner into new colouring-matters by
further diazotising them and subsequently combining the resulting products with
two molecular proportions or one molecular proportion of an amine, a phenol or
amidophenol or a sulpho or carboxylic acid thereof, according as the tetrazo dyes
first produced contain two free amido groups or only one such group. In coupling
two components either the same or two different components may be employed.
According to the process described in the last named Specification my foreign
correspondents have prepared analogous dye-stuffs derived from paraphenylene
diamine. In order to produce these dye-stuffs from paraphenylenc diamine, the
monoacetyl derivative of the latter is first diazotised and then the resulting diazo
compound is allowed to act on Clève's alphanaphthylaminemonosulpho acid (beta
or delta). After splitting off the acetyl group, the resulting diamido product is
again diazotised and combined either with Cleve's acids (beta or delta) or with
other dye-stuff components; products resulting which contain two free amido
groups or only one such group."
The following examples are given, in order to illustrate the production of these
dye-stuffs derived from paraphenylene diamine. The parts are by weight.
COLOURING-MATTER OBTAINED FROM MONOACETYLPARAPHENYLENE DIAMINE
BY COUPLING ITS DIAZO-DERIVATIVE WITH ONE MOLECULAR PROPOR-
TION OF CLEVE'S BETA ACID, SPLITTING OFF THE ACETYL GROUP,
REDIAZOTISING THE RESULTING DIAMIDO PRODUCT AND COUPLING THE
TETRAZO DERIVATIVE THEREOF WITH TWO MOLECULAR PROPORTIONS
OF CLEVE'S DELTA ACID.
1.5 parts of monoacetyl paraphenylenediamine are mixed with 5 parts of water
and 2.5 parts of hydrochloric acid (containing 30 per cent. of pure acid). After
cooling by ice & concentrated solution in water of 0.7 parts of sodium nitrite is
added, in order to produce the diazo derivative of acetylparaphenylenediamine.
When the diazotisation is finished, the liquid is added to a solution in water of
2.45 parts of the sodium salt of Clève's alphanaphthylaminemonosulpho acid (beta)
and 5 parts of sodium acetate. After standing for several hours the combination
is complete. The resulting liquid is neutralised by means of sodium carbonate and
is introduced into a boiling solution obtained by dissolving 0-5 parts of sodium
hydroxide (soda) in 5 parts of water. The acetyl group is separated by heating
for some time and by salting out, filtering off, and pressing; a product is obtained
having the following formula :-
In order to diazotise this, it is mixed with water and after adding a concentrated
solution in water of 14 parts of sodium nitrite hydrochloric acid in small excess 45
is run in. If the formation of the tetrazo salt be complete, the mixture is
added to a solution in water of 4-9 parts of the sodium salt of Cleve's, alphanaph-
thylamine monosulpho acid (delta) and about 10 parts of sodium acetate. In

page_text: order to promote the action, the mixture is heated for some time at about
60 degrees centigrade. After cooling the resulting mixture is neutralised by
means of sodium carbonate, and the dye-stuff represented by the formula :-
'
18 Isolated by salting out, nitering on, pressing
drying
unmordanted cotton bluish-black shades and yields similar shades when dyed on
wool.
SECOND EXAMPLE.
DYE-STUFF RESULTING FROM THE COMBINATION OF DIAZOTISED MONO-
ACETYLPHENYLENE DIAMINE WITH ONE MOLECULAR PROPORTION OF
CLÈVE'S BETA ACID, BY SPLITTING OFF THE ACETYL GROUP, REDIAZO-
TISING AND COMBINING THE RESULTING TETRAZO COMPOUND WITH ONE
AND
MOLECULAR PROPORTION OF CLEVE'S DELTA ACID
ONE MOLE-
CULAR PROPORTION OF 1.8-DIHYDROXYNAPHTHALENE ALPHA MONO-
SULPHO ACID.
The diamido azo compound obtained as described in the foregoing example
from 1-5 parts of monoacetylparaphenylene diamine and having the formula :-
is converted by means of 14 parts of sodium nitrite and the necessary quantity of
hydrochloric acid into its tetrazo chloride. The resulting mixture is added to a
solution in water of 2.45 parts of the sodium salt of Clève's alphanaphthylamine
When the
monosulpho acid (delta) and about 5 parts of sodium acetate.
combination is completed, a solution prepared by dissolving 2-62 parts of the
sodium salt of 1-8 dihydroxynaphthalene alphamonosulpho acid and 5 parts of
sodium acetate in water is added. After several hours the mixture is heated for
some time at 60 degrees centigrade, in order to complete the action. The
mixture is then rendered alkaline by adding sodium carbonate or soda-lye, and the
dye-stuff is isolated by salting out, filtering (off, pressing and drying. Judging
from the manner in which it is formed it possesses the following composition:
:-

page_text: SO,Na
The other dye-stuffs derived from paraphenylene diamine are obtained in a
manner analogous to that described in the foregoing two examples viz.: by
coupling diazotised monoacetyl paraphenylene diamine first with one molecular
proportion of Clève's delta-acid (in place of the beta-acid employed in the above
example), splitting off the acetyl group, rediazotising and combining the resulting
tetrazo derivative with two molecular proportions of Clève's beta- or gamma-acid
or with two molecular proportions of a mixture of Clève's beta- and delta-acids
or with one molecular proportion of either of these two acids (in place of two
molecular proportions of the delta-acid as indicated in the above first example) or
by coupling the said tetrazo derivative with one molecular proportion of Clève's
beta-acid (instead of delta-acid as indicated in the above second example) or by
replacing the dihydroxynaphthalenemonosulpho acid employed in the foregoing
second example by other dye-stuff components or by combining the said tetrazo
compound first with one molecular proportion of a dye-stuff component and then
with one molecular proportion of Clève's alphanaphthylaminemonosulpho acid
(beta, gamma or delta). Of course the said tetrazo compounds can be combined
with two molecular proportious of all known dye-stuff components (employing
either the same or two different components).
The shades produced by these colouring-matters on unmordanted cotton are in
general from bluish black, or greenish-black to pure black. Similar shades result,
when these products are employed for dyeing wool in suitable baths.
My foreign correspondents do not limit themselves to the proportions given in
the above two examples which describe merely two methods for producing two
dye-stuffs derived from paraphenylene diamine. Of course the manufacture of
these products and of the analogues thereof can be varied and can be effected
by means of all the processes in use for analogous operations.
It is evident that the products having the formula :-
NH,
and which can be obtained by the combination of diazotised monoacetylparaphenylene
diamine with Clève's alphanaphthylamine beta monosulpho acid (beta or delta) and
by subsequently splitting off the acetyl group can also be treated with one molecular
proportion of sodium nitrite in moderately acidulated solutions. In this manner diazo
salts result which may then be combined with one molecular proportion of a dye-
stuff component (inclusively Clève's alphanaphthylamine beta monosulpho acids beta 3
or delta). Of course the resulting products can likewise be further diazotised and
combined with suitable dye-stuff components. The production of these dye-stuffs...
in general is effected in the manner hereinbefore described.
My foreign correspondents have stated in the Specification of Letters Patent
No. 22641 dated 28th December 1891 that Clève's alphanaphthylamine beta mono-4
sulpho acids (beta and delta) can be employed advantageously for the production of

page_text: new diazo colouring matters suitable for dyeing wool black in an acid bath by
combining with the known dye-stuff components (viz. amines, phenols, amidophenols
or amidophenolethers, or the sulpho and carboxylic acids thereof, preferably with
naphthols, dihydroxynaphthalenes, amidonaphthols and the sulpho acids thereof,)
the diazo compounds of those azo bodies which are formed from amines (also
amidophenols, amidophenolethers, substituted products of these compounds or sulpho
or carboxylic acids of all the named components, including the above two alpha-
naphthylamine beta monosulpho acids of Clève) by diazotising them and subsequently
combining the resulting diazo products with Clève's alphanaphthylamine monosulpho
acids (beta or delta).
In addition thereto my foreign correspondents have now found that analogous
valuable dye-stuffs are obtained by combining the diazo derivatives of amidoazo-
benzene or analogues and substitution products thereof with Clève's alphanaphthyl-
aminemonosulpho acids (beta or delta) rediazotising the resulting amido azo
products, and coupling the diazo compounds thus formed with the known dye-stuff
components viz.: amines, phenols, amido phenols, amidophenol ethers or sulpho or
carboxylic acids thereof including the two alpha naphthylaminebetamonosulpho acids
of Clève (beta and delta).
If in place of amidoazobenzene monoacetylparaphenylene diamine is employed
and the diazo derivative of the latter is combined with Clève's beta or delta acid
and if the resulting amido azo product be rediazotised and combined with the known
dye-stuff components above enumerated analogous products result, after finally
splitting off the acetyl group.
The production of all these dye-stuffs from amidoazobenzene and analogues
thereof or paraphenylene diamine is effected in the manner described in the Speci-
fication of Letters Patent No. 22641 dated 28th December 1891.
My foreign correspondents have further found, that direct dyeing colouring-
matters of high technical value are obtained when those amido azo compounds
which result by combining the diazo derivatives either of the products formed by
treating paratoluidine, metaxylidine or pseudocumidine with sulphur, or of the
sulpho acids of the thioamides so formed with the aforesaid alphanaphthylamine beta
monosulpho acids (beta or delta) of Clève are further diazotised and then combined
with the known dye-stuff components, especially naphthols, amidonaphthols, amido-
naphtholethers, dihydroxynaphthalenes and sulpho or carboxylic acids thereof,
including Clève's alpha naphthylamine beta monosulpho acids (beta or delta).
In this process the following thio compounds or sulpho acids thereof may be
employed viz. dehydro-thio-para-toluidine melting at 191 degrees centigrade
obtainable by heating paratoluidine with sulphur, dehydro-thio-meta-xylidine and
dehydro-thio-pseudo-cumidine produced in an analogous manner from meta-xylidine
and pseudo-cumidine, the so called primuline base which is formed together with
dehydro-thio-para-toluidine on heating para-toluidine with sulphur and may be
employed either as a raw product or in a purified state and the sulpho acids of the
aforesaid four thio compounds excluding however the so called primuline.
The new colouring matters are obtained by combining the diazo derivatives of
the above mentioned thio compounds either with Clève's alpha-naphthylamine-beta-
mono-sulpho acid (beta or delta), diazotising the amido azo products so formed and
coupling with the known dye stuff components: amines, phenols or amidophenols or
sulpho or carboxylic acids thereof, especially with 1-8-dihydroxynaphthalene
sulpho acids.
In the employment of Clève's alpha-naphthylamine beta-monosulpho acids (beta
or delta) as second components and for example the said dihydroxynaphthalene
sulpho acids dyestuffs are obtained which produce green or greenish-black shades of
great fastness.
The variety of shades is, of course, greater, when instead of the said dihydroxy-
naphthalene sulpho acids other dyestuff components are employed.
The following example is given in order to explain the production of these new
colouring matters. The parts are by weight.
:

page_text: THIRD EXAMPLE.
COLOURING-MATTER PRODUCED BY COUPLING DIAZOTISED DEHYDRO-THIO-
PARA-TOLUIDINE-SULPHO ACID WITH CLEVE'S ALPHA-NAPHTHYLAMINE-
MONOSULPHO ACID (BETA), REDIAZOTISING THE RESULTING AMIDOAZO
COMPOUND AND COMBINING THE DIAZO PRODUCT WITH 1.8-DIHYDROXY-
NAPHTHALENE-ALPHA-MONOSULPHO ACID S.
34.2 parts of the dehydro-thio-para-toluidine-mono-sulphonate of sodium
(CH,NS.NH,SO,Na) are diazotised in the usual manner by means of 7 parts of
sodium nitrite, and the resulting diazo compound (which is soluble with difficulty)
after having been filtered off is introduced into a solution in water of 24.5 parts of
the sodium salt of Clève's beta-acid and 48 parts of sodium acetate. After standing
about 24 hours the formation of the intermediate amido-azo-product of the
formula.
5
is completed. After neutralizing by means of soda-lye and adding a solution of 16
7 parts of sodium nitrite hydrochloric acid is allowed to flow slowly into the
mixture, until the latter exhibits a moderately acid reaction. The whole mass is
then introduced into a solution in water of 26-2 parts of the 1.8-dihydroxy-
naphthalene alpha-monosulphonate of sodium and 50 parts of sodium acetate.
order to complete the reaction, the mixture is heated after some time to about 20
from 60 to 70 degrees centigrade. It is then rendered alkaline, and the dyestuff
Dossessing the following composition:
In
is salted out, filtered off, pressed and dried.
It produces on unmordanted cotton in an alkaline soap bath a pure bluish-green
colour.
In a similar manner, the analogous dyestuffs derived from the above named thio-
compounds or sulpho acids thereof are obtained viz.: by employing in place of
dehydro-thio-para-toluidine sulpho acid the analogous sulpho acids of dehydro-
thio-meta-xylidine and dehydrothio-pseudo cumidine or the unsulphonated thio
compounds such as dehydrothio-paratoluidine, dehydrothiometaxylidine and dehy-
drothio-pseudo cumidine or mixtures of these sulpho acids or thio compounds
containing no sulpho group or by replacing Clève's alphanaphthylamine monosulpho
acid (beta) employed as middle component by the isomeric delta-acid or by a
mixture of these two acids, or finally by using in place of 1.8-dihydroxynaphthalene
alpha-monosulpho acid another dyestuff component from the series of amines,
phenols, amidophenols, amidophenolethers, sulpho or carboxylic acids thereof,
including Clève's alpha naphthylamine beta monosulpho acids (beta and delta).
The shades produced by these products on unmordanted cotton are in general
from bluish-green to greenish-black.
My foreign correspondents have further found that the alpha-naphthylamine-
beta-monosulpho acids (Clève) may also be employed for the production of simple

page_text: azo dyestuffs. These colouring matters are obtained in the usual manner viz. by
combining the diazo derivatives of amines, amidophenols, amidophenolethers or
substituted products thereof especially sulpho or carboxylic acids of all these
compounds with one of the said alpha-naphthylamine beta-monosulpho acids
(Clève).
Of the great number of these dyes those which result on combining diazotised
amido carboxylic acids, amido hydroxycarboxylic acids, amidoalkyloxycarboxylic
acids or sulpho derivatives thereof with the said acids of Clève are of especially
high value. The dyes thus formed produce on unmordanted wool from yellow to
reddish-yellow colours and on wool inordanted with chromium salts from reddish-
yellow to brown shades.
The manufacture of these colouring-matters is effected in the well known manner,
namely by allowing the diazo derivatives of the amines or substituted amines
employed to act on Clève's acids in moderately acid (preferably acetic acid)
solution.
The dyestuffs obtained by the employment of diazotised amido carboxylic acids
are of high value for dyeing and printing purposes as when fixed on the fibre by
means of metallic salts, they may be directly diazotised and combined with the
known dyestuff components, colouring-matters being produced in this manner which
give from reddish yellow to brown and black shades distinguishable for their
intensity and fastness.
Of course, the last defined simple azo dyestuffs resulting from the combination.
of diazotised amines, amidophenols, amidophenolethers or sulpho- or carboxylio
acids thereof, including Clève's alphanaphthylamine-beta-monosulpho acids (beta
or delta acid) with Clève's alphanaphthylaminemonosulpho acid (beta or delta)
can in general be converted into other colouring matters by subsequently diazo-
tising and coupling with the known components viz. amines, phenols, amido-
phenols, amidophenolethers or sulpho or carboxylic acids thereof including Clève's.
alphanaphthylamine monosulpho acids (beta or delta acid), so called disazo dye--
stuffs being produced which my foreign correspondents have already described
in the Specification of Letters Patent No. 22641 dated 28th December 1891.
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 production of new dyestuffs by combining one molecular proportion
of the diazo derivative of monoacetylparaphenylenediamine with one molecular
proportion of Clève's alphanaphthylamine-beta-mono-sulpho acid (beta or delta)
or a mixture of these two acids, by splitting off the acetyl group, rediazotising
the so formed diamidoazo products and coupling the so formed tetrazo salts
either with two molecular proportions of Clève's alpha-naphthylamine-beta-mono--
sulpho acids (beta or delta) or with one molecular proportion of either of these
two acids or first with one molecular proportion of Clève's alpha-naphthylamine-
beta-monosulpho acid (beta or delta) and then with one molecular proportion of
another dyestuff component from the series of amines, phenols, amidophenols,
amidophenolethers or the sulpho or carboxylic acids thereof, or inversely first
with one molecular proportion of the last named components and then with one
molecular proportion of Clève's alphanaphthylamine-beta-monosulpho acids (beta
or delta) or in general by combining the resulting tetrazo salts with two mole-
cular proportions of the known dyestuff components viz.: amines, phenols,
amidophenols, amidophenolethers, the sulpho or carboxylic derivatives thereof
(employing either the same components or two different ones).
2. The production of dyestuffs by combining one molecular proportion of the
diazo derivative of monoacetylparaphenylene diamine with one molecular pro-
portion of Clève's alphanaphthylamine beta monosulpho acid (beta or delta) or
a mixture of these two acids, by splitting off the acetyl group, converting the:
so formed diamido azo compound by means of one molecular proportion of

page_text: "
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sodium nitrite into its monodiazo compound and coupling the resulting diazo
product with one molecular proportion of the known dyestuff components (including
Clève's alpha-naphthylamine-beta-monosulpho acid beta or delta).
3. The manufacture of new dyestuffs by combining one molecular proportion
of the diazo derivatives of amidoazobenzene analogues and homologues thereof.
or the sulpho acids of these amidoazo compounds with one molecular proportion
of Clève's alpha-naphthylamine-beta-monosulpho acid (beta or delta),rediazotising
and combining the so formed diazo salts with one molecular proportion of the known
dyestuff components such as amines, phenols, amidophenols, amidophenolethers or
sulpho or carboxylic acids thereof, including Clève's alphanaphthylamine beta
monosulpho acids (beta or delta).
4. The process for producing new dyestuffs by combining one molecular proportion
of diazotised monoacetylparaphenylene diamine with one molecular proportion of
Clève's alpha-naphthylamine-beta-monosulpho acid (beta or delta), rediazotising
and combining the so formed diazo compounds with one molecular proportion of
the known dystuff components such as amines, phenols, amidophenols, amidophenol-
ethers or sulpho- or carboxylic acids thereof, including Clève's alpha-naphthyl-
amine beta-monosulpho acids (beta or delta) and splitting off the acetyl group.
5. The production of new dyestuffs by combining one molecular proportion of
diazotised dehydrothioparatoluidine, dehydrothio-meta-xylidine, dehydrothio-
pseudo-cumidine, the so called primuline base or the sulpho acids of the aforesaid
four thio compounds (excluding however the so called primuline) with one molecular
proportion of Clève's alpha-naphthylamine-beta-monosulpho acid (beta or delta),
rediazotising the so formed amido azo products and combining the resulting diazo
derivatives with the kuown dyestuff components such as amines, phenols, amido-
phenols, amidophenolethers or sulpho- or carboxylic acids thereof, including Clève's
alphanaphthylamine monosulpho acids (beta or delta).
6. The manufacture of simple azo dye-stuffs by combining one molecular
tion of diazotised amines, amidophenols, amidophenolethers or sulpho- or carboxylic
propor-
acids thereof (inclusively Clève's alpha-naphthylamine-beta-monosulpho acids (beta
or delta) with one molecular proportion of Clève's alpha naphthylamine-monosulpho
acids (beta or delta).
7. As new articles of manufacture the new dyestuffs hereinbefore defined.