The Manufacture or Production of New Coloring Matters.
Year: 1893

page_text: Date of Application, 10th Jan., 1893
Complete Specification Left, 9th Oct., 1893-Accepted, 11th Nov., 1893
PROVISIONAL SPECIFICATION.
[Communicated from abroad by the FARBENFABRIKEN vormals FRIEDRICH
BAYER & Co., of Elberfeld, in the Empire of Germany.]
The Manufacture or Production of New Coloring Matters.
I HENRY EDWARD NEWTON, of The Office for Patents, 6 Bream's Buildings,
Chancery Lane in the County of London, Patent Agent, do hereby declare the
nature of this invention to be as follows:-
In the Specification of the German Letters Patent No. 22714, dated
8th November 1882, a process is described for producing brown dye-stuffs, which
consists in the action of diazo compounds on the products termed "chrysoidines,"
and obtainable by acting with one molecular proportion of a diazo compound upon
one molecular proportion of an aromatic meta diamine.
According to the process described in the above Specification, on the one hand
products which are soluble in alcohol, and become soluble in water only by a
subsequent treatment with sulphonating agents, result by combining diazotised
aniline, toluidine, xylidine, cuinidine, amidoazobenzene, amidophenolmethylether,
or amidophenolethylether, with "chrysoidines," on the other hand products soluble
in water are directly obtained, if either the above named diazo derivatives are
allowed to act ou chrysoidine sulpho acids, or chrysoidine carbonic acids, or if the
diazo compounds of amines containing sulpho or carboxylic groups, are allowed to
act on chrysoidines, chrysoidine sulpho acids, or chrysoidine carbonic acids.
The coloring matters thus obtainable, it is true, are capable of dyeing wool in
acid baths, but have not attained any technical value.
My foreign correspondents have now found that products of technical value only
result if the diazo derivatives of aromatic amidohydroxy carboxy compounds are
combined with meta phenylene diamine, meta toluylene diamine, naphthylene
diamines, or substitution products thereof (employing equal molecular proportions
of these components), and if one molecular proportion of the so-formed chrysoidine-
like products is allowed to act on one molecular proportion of a diazo compound
resulting from amines, substituted amines, amido azo derivatives, and the like, or
upon ball a molecular proportion of a tetrazo compound, or upon one molecular
proportion of the intermediate products obtainable from equal molecular proportions
of tetrazo salts and amines, phenols, or derivatives thereof. By "substitution
products" of the diamines above referred to, my foreign correspondents understand,
for example, the sulpho acids derived from the said diamines, the alkylated
derivatives thereof, such as mono- di-, tri,- or tetra methyl diamine, inono-, di-, tri-,
or tetra ethyl diamine, or the corresponding phenyl-, tolyl-, benzyl-, or naphthyl
derivatives. Of course, other substituted diamines can likewise be employed.
The technical effect produced by the above coloring matters seems to be caused
especially by the simultaneous presence of hydroxyl and carboxylic groups in the
components employed (viz., amidohydroxy carboxylic products). Amongst the
latter, the following can be used, for example, viz. :-orthoamido salicylic acid
(COOH: OH: NH,=1:2:6), para amido salicylic acid (COOH: OH: NH, 1:2:4),
amido para hydroxy benzoic acid (obtainable from para bydroxybenzoic acid by
nitrating and reducing), amido ortho cresolcarbonic acid (amido ortho hydroxy
metatoluylic acid), amidometa cresol carbonic acid (amido orthohydroxy para
toluylic acid), amido paracresol carbonic acid (amido metahydroxy orthotoluylic
acid), or the sulpho derivatives of these acids.

page_text: Analogous amidohydroxycarboxylic products, for instance, amido alkylhydroxy-
carbonic acids, analogues, homologues, or substitution thereof (such as amido-
phenolether carbonic acids, amidophenolether sulpho carbonic acids and the like),
likewise can be employed. "The last-named acids also yield products of some value,
though they do not contain a free hydroxylic group.
The process for producing these dye stuffs, in general, consists in allowing the
diazo derivatives of the above defined amidohydroxycarboxylic, or amido alkyl-
hydroxycarboxylic compounds, to act on diamines or substituted diamines, and in
combining the so-formed amido azo products of the general formula :
My foreign correspondents understand, in the above two formulae, by R, R', R²
and R³, any radicle or residue derived from benzene or naphthalene, the analogues,
homologues, or substitution products thereof.
In this manner, especially if diazo compounds containing hydroxylic, carboxylic,
or sulpho groups are employed as last components, dye stuffs are produced which
possess the valuable property of dyeing ordinary wool and mordanted wool,-brown
to brownish-black shades being obtained which are fast against the action of light
and fulling. The coloring matters obtainable as hereinbefore defined, differ
particularly in this respect from the products described in the Specification of the
German Patent No. 22714.
In order to illustrate the process of producing these new dye stuffs, the following
examples are given, the parts being by weight.
COLORING MATTER FROM PARA AMIDO SALICYLIC ACID, METAPHENYLENE
DIAMINE, AND ALPHANAPHTHYLAMINE ALPHA MONOSULPHO ACID (1.4).
The diazo, compound of amidosalicylic acid obtained in the usual manner by
means of 10 parts of sodium nitrite, is introduced into a watery solution of meta-
phenylene diamine, the weight of which corresponds to the 10 parts of sodium

page_text: nitrite employed. After standing for some hours, or after adding sodium acetate
and heating, the coloring matter having the formula:
/OH
COOH
NH₂
CH
NH₂
N=N-CH,
separates as a brown granulated mass. It is dissolved in water with the addition of
532 parts of sodium carbonate. The diazotised alphanaphthylamine alphamono-
sulpho acid (14), the weight of which corresponds to 10 parts of sodium nitrite, is
mixed with water, and the resulting mixture is slowly introduced into the above
alkaline solution of the intermediate product from diazotised amido salicylic acid
and meta phenylene diamine.
The formation of the dye stuff commences immediately, and is completed by
heating. The dye stuff, when salted out and dried, is a black powder, which easily
dissolves in hot water, and gives a brown color.
Its composition corresponds to the following formula:
DYE-STUFF FROM AMIDOSALICYLIC ACID, METAPHENYLENE DIAMINE, AND
AMIDO NAPHTHALENEAZOBENZENE SULPHO ACID.
24-7 parts of para sulphanilic acid are diazotised in the usual manner by means
of 10 parts of sodium nitrite, and the resulting diazo derivative is combined with
204 parts of alphanaphthylamine. The so-formed amido-azo compound is further
diazotised by means of 10 parts of sodium nitrite, and the diazo compound thus
produced is added to a solution (rendered and kept alkaline) of the dye stuff from
diazotised amido salicylic acid and meta phenylene diamine obtained as described in
the foregoing first example such a quantity of this dye stuff being employed
corresponds to 10 parts of sodium nitrite. The solution, originally yellow imme-
diately assumes a deep brownish black color. The reaction is completed by
boiling. The coloring matter, when salted out and dried, is a black powder easily
soluble in hot water. It produces on wool, in a neutral bath, brownish black shades,
which are fast against fulling.
Its composition corresponds to the formula :

page_text: COLORING MATTER FROM AMIDO SALICYLIC ACID, META PHENYLENE
DIAMINE, AND THE INTERMEDIATE PRODUCT FROM EQUAL MOLECULAR
PROPORTIONS OF TETRAZODIPHENYL SALT AND ALPHA NAPHTHYLAMINE
ALPHA MONO SULPHO ACID (1.4).
26-3 parts of benzidene are converted in hydrochloric solution by means of
10 parts of sodium nitrite into tetrazo diphenyl chloride, and the latter is combined
in acetic solution with 16 parts of alpha naphthylamine mono sulpho acid (1.4).
The intermediate product thus formed from equal molecular proportions of tetrazo-
diphenyl salt and alphanaphthylaminemonosulpho acid (1.4), is added to an alkaline
solution of the dye stuff from diazotised amido salicylic acid and meta phenylene
diamine, the production of which is described in the above first example, such a
quantity of this dye stuff being employed, as corresponds to 5 parts of sodium
nitrite. The reaction is completed by boiling. The complete coloring matter
produces on wool (and likewise on cotton) reddish-brown shades.
following composition :
It possesses the
In an analogous manner to that described in the foregoing three examples, other
coloring matters result, for instance, by employing, in place of para amido
salicylic acid, the isomeric acids, or the corresponding quantities of ortho-, meta-,
or para amido cresotinic acid, sulpho derivatives thereof, or amido alkylhydroxy
carbonic acids, or analogues, homologues, substitution products of all these
components. On the other hand, metaphenylene diamine can be replaced by
meta-toluylene diamine, naphthylene diamines, sulpho derivatives of these diamines,
or alkyl substitution products thereof (such as the above-defined mono alkyl-,
dialkyl-, trialkyl-, or tetraalkyl derivatives of these diamines).
The amido azo compound employed in the above second example, and resulting
from alphanaphthylamine and diazotised parasulphanilic acid, can be replaced by
analogous amidoazo products, such as are in general obtained by the combination of
diazotised amines, amido phenols, amidophenolethers of the benzene or naphthalene
series, sulpho, carboxylic, or sulpho carboxylic derivatives thereof, with amines or
substituted amines belonging to the benzene or naphthalene series.
In a similar manner as the intermediate product from equal molecular proportions
of tetrazo diphenyl salt and alpha naphthylamine alphamonosulpho acid (1-4) used
in the above third example, intermediate products in general can be employed which
result from equal molecular proportions of tetrazo compounds of diamines or
substituted diamines, and amines, phenols, amidophenols, amidophenolethers of the
benzene or naphthalene series, sulpho, carboxylic, or sulpho carboxylic derivatives
of these components. My foreign correspondents understand by diamines, also
phenylene diamine, naphthylene diamines and their substitution products, which
can be employed either as such, or as mono acetyl compounds. Of course, in
place of the mono acetyl derivatives, the mononitro derivatives of the corresponding
amines likewise can be used for producing the above tetrazo compounds.
The process is, in effect, the same if one molecular proportion of the above
chrysoidine-like products resulting from diazotised amido hydroxy carboxylic or

page_text: amido alkylhydroxy carboxylic compounds, and the above defined diamines (such
as phenylenediamine, napninyiene diamines), is combined with half a molecular
proportion of a tetrazo compound derived from diamines or substituted diamines.
In this manner, products are obtained which possess, in free state, the following
general composition :-
--
a molecular
as phenylene diamine, napninyiene alamines), is combined with nan
proportion of a tetrazo compound derived from diamines or substituted diamines.
In this manner, products are obtained which possess, in free state, the following
general composition
OH (or OR)
COOH
NH,
NH
R¹
-NNR2
N = N X
-
R'
N = N R
-
-N = N-X
соон
NH'
OH (or OR)
NH'
My foreign correspondents also here understand by R R¹ & R² any radicle or
residue derived from benzene or naphthalene, analogues, homologues, or sub-
stitution products thereof, whilst they understand by-X-X-, the residues
of substituted or not substituted paradiamines (such as benzidine and the like).
My foreign correspondents do not limit themselves to the methods described in
the above three examples for producing these dye stuffs. The processes may be
varied more
or less, and all those methods can be employed which are in use for
the production of analogous combinations. Such modifications as easily follow from
the above examples, do not alter the nature of this invention, as the latter in general
relates to the manufacture of new dye stuffs by combining diazotised amido hydroxy
carboxylic or amido alkyl hydroxy carboxylic products with substituted or not
substituted diamines and by subsequently allowing the so-formed amido azo
compounds to act on diazo derivatives of any origin whatever.
The coloring matters obtainable in the manner hereinbefore described, yield
on ordinary or mordanted wool, deep-brown or brownish black shades of great
purity, and capable of withstanding the action of light and fulling.
Dated this 10th day of January 1893.
NEWTON & SON,
Agents for the Applicants.
COMPLETE SPECIFICATION.
The Manufacture or Production of New Coloring Matters.
I, HENRY EDWARD NEWTON, of The Office for Patents, 6, Bream's Buildings,
Chancery Lane, in the County of London, 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:-
In the Specification of the German Letters Patent No. 22714, dated 8th
November 1882, a process is described for producing brown dye-stuffs, which
consists in the action of diazo compounds on the products termed " chrysoidines,"
and obtainable by acting with one molecular proportion of a diazo compound on
one molecular proportion of an aromatic meta diamine.
According to the process described in the above Specification, by combining
diazotised aniline, toluidine, xylidine, cumidine, amidoazobenzene, amidophenol-
methylether, or amidophenolethylether with "chrysoidines," products are obtained

page_text: which are soluble in alcohol, and become soluble in water only on subsequent
treatment with sulphonating agents, whereas products which are soluble in water
are at once obtained, if either the above named diazo-derivatives are allowed to
act on chrysoidine sulpho acids, or chrysoidine carboxylic acids, or if the diazo
compounds of amines containing sulpho or carboxylic groups, are allowed to act
on chrysoidines, chrysoidine sulpho acids, or chrysoidine carboxylic acids.
Although the colouring-matters thus obtainable are capable of dyeing wool in
acid baths, they have not hitherto been found to be of technical value.
My foreign correspondents have discovered that products of technical value
result only if the diazo derivatives of aromatic amidohydroxycarboxylic compounds
are combined with meta phenylene diamine, meta toluylene diamine, naphthylene
diamines, or substitution products thereof (employing equal molecular proportions
of these components), and if one molecular proportion of the resulting chrysoidine-
like product is allowed to act on one molecular proportion of a diazo compound
prepared from an amine, a substituted amine, an amidoazo derivative, or the like, or
half a molecular proportion of a tetrazo compound, or on one molecular proportion of
one of the intermediate products obtainable from equal molecular proportions of a
tetrazo salt, and an amine, phenol, or derivative thereof. By "substitution products
of the diamines above referred to, my foreign correspondents understand, for
example, the sulpho acids derived from the said diamines, the alkylated derivatives
thereof (such as mono-, di-, tri-, or tetramethyldiamine; mono-, di-, tri-, or tetra-
ethyldiamine, or the corresponding phenyl-, tolyl-, benzyl-, or naphthylderivatives).
As a matter of course, other substituted diamines can also be employed.
-
-
"
The technical effect produced by such colouring-matters, seems to be especially
due to the simultaneous presence of hydroxylic and carboxylic groups in the
components employed (riz., amidohydroxycarboxylic products). Of these latter,
the following can be used, for example, viz.-ortho amidosalicylic acid (COOH:
OH NH,
:
1:26), para amidosalicylic acid (COOH OH: NH₁ = 1:2:4)
amido para hydroxybenzoic acid (obtainable from para hydroxybenzoic acid by
nitrating and reducing), amido ortho cresolcarboxylic acid (amido ortho hydroxy
meta toluylic acid), amido meta cresolcarboxylic acid (amido ortho hydroxy para
toluylic acid), amido para cresolcarboxylic acid (amido meta hydroxy ortho
toluylic acid), or the sulpho derivatives of these acids.
Analogous amidohydroxycarboxylic products, for instance, amidoalkylhydroxy-
carboxylic acids, analogues, homologues, or substitution products thereof (such as
amidophenolether carboxylic acids, amidophenolethersulpho carboxylic acids, and
the like), can also be employed. The last named acids also yield products of some
value, though they do not contain a free hydroxylic group.
The process for producing these dye-stuffs, in general, consists in allowing the
diazo derivatives of the above defined amidohydroxycarboxylic, or amidoalkyl-
hydroxycarboxylic compounds, to act on on diamines, or substituted diamines, and
in combining the resulting amidoazo products, which in the free state are of. the
general formula

page_text: phenol, or substitution derivative thereof. If, for example, simple diazo compounds
are used as last components, colouring-matters result, which, in free state, possess
the general formula:
In the above two formulæ, my foreign correspondents represent by R, R¹, R³,
and R³, any radicle or residue derived from benzene or naphthalene, the analogues,
homologues, or, substitution products thereof.
In this manner, especially if diazo compounds containing hydroxylic, carboxylic,
or sulpho groups are employed as last components, dye-stuffs are produced which
possess the valuable property of dyeing ordinary wool, and mordanted wool,
brown to brownish black shades which withstand the action of light and fulling.
The colouring-matters obtainable as hereinbefore defined, differ particularly in
this respect from the products described in the Specification of the above German
Patent No. 22714.
In order to illustrate the process of producing these new dye-stuffs, the following
examples are given, the parts being by weight.
COLOURING-MATTER FROM EQUAL MOLECULAR PROPORTIONS OF PARA AMIDO
SALICYLIC ACID, META PHENYLENE DIAMINE, AND ALPHA NAPHTHYL-
AMINE ALPHA MONOSULPHO ACID (1: 4).
After
The diazo compound of para amidosalicylic acid prepared in the usual manner by
means of 10 parts of sodium nitrite, is introduced into a solution of an amount of
meta phenylene diamine, corresponding to 10 parts of sodium nitrite.
several hours, or after adding sodium acetate, and heating, the intermediate product
having the formula (when in the free state)
separates as a brown granulated mass. It is dissolved in a solution of 32 parts of
sodium carbonate, and to this solution an amount of the diazo compound of alpha
naphthylamine alpha monosulpho acid (1: 4), corresponding to 10 parts of sodium
nitrite, mixed with a small quantity of water, is slowly added.
The formation of the dye-stuff immediately commences, and is completed by
heating. When salted out and dried, the dye-stuff is a black powder which easily
dissolves in hot water, forming a brown-coloured liquid. It is represented by the
following formula:.

page_text: DYE-STUFF FROM PARA AMIDO SALICYLIC ACID, META PHENYLENE DIAMINE,
AND AMIDONAPHTHALENE-AZO-BENZENE SULPHO ACID.
24-7 parts of para sulphanilic acid are diazotised in the usual manner by means
of 10 parts of sodium nitrite, and the resulting diazo derivative is combined with
20-4 parts of alpha naphthylamine. The resulting amidoazo compound is further
diazotised by means of 10 parts of sodium nitrite, and the diazo compound thus
produced is added to a solution (rendered and kept alkaline) of the dye-stuff from
diazotised amido salicylic acid and meta phenylene diamine, obtained as described
in the foregoing first example, a quantity of this dye-stuff being employed which
corresponds to 10 parts of sodium nitrite. The originally yellow solution imme-
diately assumes a deep brownish-black colour. The reaction is completed by
boiling. The colouring-matter, when salted out and dried, is a black powder
which easily dissolves in hot water. It produces on wool, in a neutral bath,
brownish black shades, which withstand fulling. Its composition is represented by
the formula:
COLOURING-MATTER FROM AMIDOSALICYLIC ACID, METAPHENYLENE DIAMINE,
AND THE INTERMEDIATE PRODUCT FROM EQUAL MOLECULAR PROPOR-
TIONS OF TETRAZO DIPHENYL SALT AND ALPHA NAPHTHYLAMINE ALPHA
MONO SULPHO ACID (1:4).
26-3 parts of benzidine are converted in hydrochloric solution, by means of
10 parts of sodium nitrite, into tetrazodiphenyl chloride, and the latter is allowed
to act on 16 parts of alpha naphthylamine monosulpho acid (1: 4) in a solution
rendered acid by means of acetic acid. The intermediate product thus formed
from equal molecular proportions of the tetrazodiphenyl salt and alpha naphthyl-
amine mono sulpho acid (1: 4) is added to an alkaline solution of the dye-stuff
from diazotised paramido salicylic acid and meta phenylene diamine, the production
of which is described in the above first example, à quantity of this dye-stuff being
employed corresponding to 5 parts of sodium nitrite. The reaction is completed
by boiling. The finished colouring-matter produces on wool (and also on cotton)
reddish-brown shades. It is represented by the following formula :-

page_text: Other colouring-matters are formed in a manner analogous to that described in
the foregoing three examples; for instance, on employing, in place of para amido-
salicylic acid, the isomeric acids, or the corresponding quantities of ortho-, meta-,
or para amido cresolinic acid, sulpho derivatives thereof, or amido alkylhydroxy-
carboxylic acids, or analogues, homologues, or substitution products of all these
components. On the other hand, meta phenylene diamine can be replaced by meta
toluylene diamine, naphthylene diamines, sulpho derivatives of these diamines, or
alkyl substitution products thereof (such as the above defined monoalkyl-, dialkyl-,
trialkyl, or tetraalkyl derivatives of these diamines), or the sulpho derivatives
thereof. The alphanaphthylamine sulpho acid (1:4) employed in the above first
example, can be replaced by other amido compounds.
The amidoazo compound employed in the above second example, and resulting
from alpha naphthylamine and diazotised para sulphanilic acid, can be replaced by
analogous amidoazo products, such as are obtained by the combination of diazotised
amines, amidophenols, amidophenolethers of the benzene or naphthalene series,
sulpho-, carboxylic-, or sulpho-carboxylic derivatives thereof, with amines or
substituted amines belonging to the benzene or naphthalene series.
In place of the intermediate product from equal molecular proportions of a
tetrazo diphenyl salt and alpha naphthylamine alpha monosulpho acid (14) used
in the above third example, intermediate products in general can be used, such as
result from the combination of equal molecular proportions of tetrazo compounds of
diamines or substituted diamines, and amines, phenols, amidophenols, amidophenol-
ethers of the benzene or naphthalene series, sulpho-, carboxylic, or sulpho carboxylic
derivatives of these components.
My foreign correspondents also reckon phenylene diamine, naphthylene diamines,
and their substitution products, as diamines which can be employed either as such,
or as monacetyl compounds. As a matter of course, in place of the monacetyl
derivatives, the mononitro derivatives of the corresponding amines can also be used
for producing the tetrazo compounds here referred to.
The process is, in effect, the same, if one molecular proportion of the above
mentioned chrysoidine-like products, formed from diazotised amidohydroxy
carboxylic- or amidoalkylhydroxy-carboxylic compounds, and the above defined
diamines (such as phenylene diamine, naphthylene diamines), is combined with half
a molecular proportion of a tetrazo compound derived from a diamine or substituted
diamine. In this manner, products are obtained, the composition of which, in the
free state, is represented by the following general formula :-

page_text: My foreign correspondents do not limit themselves to the methods of producing
these dye-stuffs described in the above three examples. The processes may be
varied more or less, and all these methods can be employed which are in use for the
production of analogous combinations. Modifications such as easily follow from
the directions given in the above examples, do not alter the nature of this invention,
which, in general, relates to the manufacture of new dye-stuffs by the combination
of diazotised amido hydroxycarboxylic or amidoalkylhydroxycarboxylic products,
with substituted or unsubstituted diamines, and subsequently allowing the resulting
amidoazo compounds to act on diazo derivatives of any origin whatever..
The colouring matters obtainable in the manner hereinbefore described, in general
produce on ordinary or mordanted wool, brown or brownish-black shades of great
purity, and capable of withstanding the action of light and fulling.
In order to more fully illustrate the great number of dye-stuffs which are
obtainable by means of the processes herein before defined, my foreign correspondents
enumerate in the following tables, several combinations of special value, the shades
produced thereby on ordinary wool being noted in the last column.

page_text: ONE MOLECULAR PROPORTION OF THE INTERMEDIATE
PRODUCT FROM META PHENYLENE DIAMINE AND
DIAZOTISED PARAMIDOSALICYLIC ACID, COUPLED
WITH ONE MOLECULAR PROPORTION OF THE DIAZO
DERIVATIVES OF THE FOLLOWING AMIDO AZO
COMPOUNDS -
SHADES
PRODUCED ON
UNMORDANTED
WOOL :-
Amidoazo benzene sulpho acid
reddish-brown
Alphanaphthylamine + diazotised metamidobenzene sulpho brownish-black
acid
Alphanaphthylamine + diazotised paramidobenzene sulpho brownish-black
acid
Alphanaphthylamine + diazotised alpha naphthylamine-beta- brown
monosulpho acid (1: 2)
Alphanaphthylamine + diazotised alphanaphthylamine-alpha- brown
monosulpho acid (1:4)
Alphanaphthylamine + diazotised alphanaphthylamine-beta- brownish-black
mono-sulpho acid (1:6)
Alphanaphthylamine + diazotised-beta naphthylamine-beta-
monosulpho acid (2:6)
Alphanaphthylamine + diazotised betanaphthylamine-delta
monosulpho acid (2:7)
Alphanaphthylamine + diazotised alpha
epsilon-disulpho acid
naphthylamine-
Alphanaphthylamine + diazotised beta-naphthylamine di-
sulpho acid G.
Alphanaphthylamine-beta-monosulpho acid (1:6) + diazo-
tised aniline
Alphanaphthylamine beta-monosulpho acid (16) + diazo-
tised alphanaphthylamine
Alphanaphthylamine beta mono sulpho acid (1:6) + diazo-
tised alphanaphthylamine alpho mono sulpho acid (1:4)
Alphanaphthylamine beta monosulpho acid (1:6)+ diazo-
tised alpha naphthylamine beta monosulpho acid (1 : 6)
.:
brownish-black
brown with a greyish
hue
reddish-brown with
a greyish tinge.
brownish-black
from brown to
brownish-black
from dark-brown to
brownish-black
from greyish-brown
to blackish-brown
from greyish-brown
to blackish-brown
III.
ONE MOLECULAR PROPORTION OF THE INTERMEDIATE
PRODUCT FROM META PHENYLENE DIAMINE AND
DIAZOTISED PARAMIDOSALICYLIC ACID, COUPLED
WITH ONE MOLECULAR PROPORTION OF THE INTER-
MEDIATE PRODUCT FROM EQUAL MOLECULAR PRO-
PORTIONS OF :-
SHADES
PRODUCED ON
UNMORDANTED
WOOL :-
Tetrazo diphenyl chloride + alpha naphthylamine alpha mono
sulpho acid (1:4)
45 Tetrazo diphenyl chloride + alpha naphthylamine beta mono
sulpho acid (16)
Tetrazo diphenyl chloride + alphanaphthol alpha mono-
sulpho acid (15)
reddish-brown
from greyish-violet
to brownish-black
reddish-brown

page_text: Two MOLECULAR PROPORTIONS OF THE INTERMEDIATE
PRODUCT FROM EQUAL MOLECULAR PROPORTIONS OF
META PHENYLENE DIAMINE AND DIAZOTISED PARA-
MIDO SALICYLIC ACID, COUPLED WITH ONE MOLE-
CULAR PROPORTION OF THE TETRAZO DERIVATIVE
OF-
SHADE
PRODUCED ON
UNMORDANTED
WOOL
Laving now particularly described and ascertained the nature of this inven-
and in what manner the same is to be performed, as. communicated to me
a abroad, I declare that what I claim is :-
The production of azo dye-stuffs, which process consists in allowing diazo or
azo compounds to act on such amidoazo compounds as result from the combi-
on of diazotised aromatic amidohydroxycarboxylic, or amido alkylhydroxy-
boxylic products, with metadiamines or substituted metadiamines.
:
The process of producing azo dye-stuffs by combining one molecular
portion of salicylic acid azo-meta phenylene diamine (obtainable from equal
ecular proportions of meta phenylene diamine and diazotised paramidosalicylic
), or analogues or homologues thereof:
a) with one molecular proportion of the diazo derivatives of aniline, toluidine,
paramido phenol, metamidobenzene sulpho acid, paramido benzene sulpho
acid, ortho toluidine sulpho acid, paramidophenol sulpho acid, orthamido-
benzoic acid, alpha naphthylamine, beta naphthylamine, alpha naphthyl-
amine beta mono sulpho acid (1:2), alpha naphthylamine alpha mono sulpho
acid (14), alpha naphthylamine alpha mono sulpho acid (1:5), alpha
naphthylamine beta monosulpho acid (16), alpha naphthylamine beta
monosulpho acid (1:7), beta naphthylamine beta monosulpho acid (2:6),
beta naphthylamine delta monosulpho acid (2:7), beta naphthylamine
disulpho acid F, amidonaphtholdisulpho acid (NH, SO₂H: "SO,H: OH
= 1:3:6:8), or primuline ;-
b) with one molecular proportion of amidoazo benzene sulpho acid, or with one
molecular proportion of the amidoazo products obtainable from alpha
naphthylamine + diazotised metamido benzene sulpho acid, alpha naphthyl-
amine + diazotised paramidobenzene sulpho acid, alpha naphthylamine
+diazotised alphanaphthylamine beta mono sulpho acid (1:2), alpha
naphthylamine + diazotised alpha naphthylamine alpho monosulpho
acid (14), alpha naphthylamine + diazotised alpha naphthylamine beta
monosulpho acid (16), alpha naphthylamine + diazotised betanaphthyl-
amine beta monosulpho acid (2:6), alphanaphthylamine + diazotised beta
naphthylamine delta monusulpho acid (2:7), alpha naphthylamine + diazo-
tised alpha naphthylamine-epsilon disulpho acid, alpha naphthylamine
+diazotised beta naphthylamine disulpho acid G., alpha naphthylamine
betamonosulpho acid (16) + diazotised aniline, alpha naphthylamine beta
mono sulpho acid (16) + diazotised alpha naphthylamine, alpha naphthyl-
amine beta mono sulpho acid (1 : 6) + diazotised alpha naphthylamine-alpha
mono sulpho acid (14), or alpha naphthylamine-beta-monosulpho acid (1:6)
+diazotised alpha naphthylamine beta mouo sulpho acid (1:6); or
c) with one molecular proportion of the intermediate products from equi-
molecular proportions of tetrazodiphenylchloride and alpha naphthylamine

page_text: alpho mono sulpho acid (1:4), alpha naphthylamine beta monosulpho.
acid (16), or alpho naphthol-alpha-monosulpho acid (1:5); or
d) with half a molecular proportion of the tetrazo derivative of benzidine
disulpho acid.
3. As new products of manufacture, the new colouring-matters obtainable by
means of the process hereinbefore described, or by any other process affording
the same result.
NEWTON & SON,
Agents for the Applicant.