The Manufacture or Production of New Colouring Matters.
Year: 1892

page_text: Date of Application, 18th Aug., 1892
Complete Specification Left, 18th May, 1893-Accepted, 1st July, 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 Colouring 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:-
My foreign correspondents have described in the Specification of the English
Letters Patent granted to Benjamin Willcox, No. 8299, dated May 18th 1889, a
series of monoazo coloring matters which are obtained by combining diazotised
aromatic amido carbonic acids with certain dihydroxynaphthalenes, napththol-
carbonic acids, or hydroxycarbonic acids of the benzene series. These products can
advantageously be employed for dyeing and printing purposes.
Analogous dye stuffs have been produced by my foreign correspondents by the
combination of diazotised amidocarbonic acids with certain dihydroxynaphthalene
sulpho acids, or amido naphtholsulpho acids, as described in the Specifications of the
English Patents likewise granted to the said B. Willcox No. 18517, dated
November 19th 1889, and No. 5984, dated April 7th 1891.
In addition, my foreign correspondents have now found that such azo dye stuffs
as contain carboxylic groups, or carboxylic and hydroxyl groups (the latter two
groups either in the same nucleus or not), are in general of high technical value, as
they are capable of forming so-called lakes with the aid of mordants, and can be
advantageously employed for dyeing and printing purposes, and it is noticeable that
even those products can be used which contain sulpho groups, and therefore are
readily soluble, but less suited for dyeing unmordanted wool.
In order to produce these valuable coloring matters for dyeing and printing, the
diazoderivatives of the following amido carbonic acids can especially be used :—
ortho-, meta-, and para amido benzoic acid; ortho amido salicylic acid; para
amido salicylic acid; amidoparahydroxybenzoic acid; amidoorthocresolcarbonic
acid; amidometacresolcarbonic acid; amidoparacresolcarbonic acid; amidophthalic
acid; amidosulphobenzoic acid; amidosulphosalicylic acid; amidosulphopara-
hydroxybenzoic acid; amidosulphocresolcarbonic acid.
Analogous or homologous amidocarbonic acids, and substitution products of all
these and the above named amido carbonic acids, can however also be used with the
same or a similar result.
As second components, either such products as contain hydroxyl groups or
carboxylic groups, or certain amido compounds containing no hydroxyl or carboxylic
groups, can be employed, and my foreign correspondents have found that the
following substances are especially of high value for such purposes, viz.: phenol,
resorcinol, salicylic acid, parahydroxybenzoic acid, ortho-, meta-, and para-
cresolcarbonic acid, alpha and beta naphthol, alphanaphthol alpha monosulpho
acid (14, 15, 1-8), alphanaphtholdisulpho acid S, alphanaphthol epsilon disulpho
acid, alphanaphtholdisulpho acid (OH: SO,H: SO,H = 1: 3: 6), betanaphthol-
beta monosulpho acid 2-6, betanaphtholdeltamonosulpho acid 2-7, betanaphthol-
alphamonsulpho acid 2-8, betanaphtholdisulpho acid R and G and F, beta-
naphtholcarbonic acid, betanaphtholsulphocarbonic acid, dihydroxynaphthalene
(1-2, 15, 18, 26, 27, 2.8), dihydroxynaphthalenemonosulpho acid R and G,
dihydroxynaphthalenemonosulpho acid obtained from alphanaphtholepsilon disulpho
acid, 18 dihydroxynaphthalenealphamonsulpho acid, 18 dihydroxynaphthalene-

page_text: alphadisulpho acid, 1.8 dihydroxynaphthalenebetadisulpho acid, amidonaphthol-
monsulpho acid G and R, 18 amidonaphthol beta disulpho acid, dihydroxybenzoic
acid (1. 3. 5), metaphenylene diamine and metatoluylene diamine.
This invention however is not restricted to the employment of the last named
products as second components, but other substituted or not substituted phenols and
amines of the benzene or naphthalene series also can be used.
In order to illustrate the nature of this invention and the method of producing
the new dyestuffs, the following examples are given.
DYE STUFF RESULTING BY COUPLING DIAZOTISED AMIDOPHTHALIC ACID
WITH 1.8 DIHYDROXYNAPHTHALENE.
Sixteen parts by weight of 1.8 dihydroxynapthalene are dissolved in about 50
parts of water with the addition of 4 parts by weight of sodium hydroxide. After
further adding 5 parts by weight of sodium acetate, and part by weight of acetic
acid (30 per cent.), the resulting liquid is mixed with a solution containing 23 parts
by weight of the chloride of diazophthalic acid. Muriatic acid is added
after 12 hours, and the dye stuff is filtered off and washed out by means of a
solution, in water, of common salt.
It dyes wool mordanted with chromium salts a violet black, and produces, when
printed together with chromium salts on wool, a dark red.
Of course the method of producing these coloring matters is not restricted to the
proportions of the foregoing examples, as these can be varied, and the production of
these dye stuffs and the analogues thereof obtained by the employment of the
aforesaid components, can likewise be effected by means of all those processes in
use for the manufacture of analogous azo dyes.
The shades produced by these coloring matters, when dyed on wool, mordanted
with chromium or other salts, in general, are from red, yellow, brown, blue, to

page_text: violet, and partly differ from those resulting when they are printed together with
chromium or similar salts on wool.
NEWTON & SON,
Agents for the Applicant.
COMPLETE SPECIFICATION.
The Manufacture or Production of New Colouring 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:—
. My foreign correspondents have described in the Specification of the English
Letters Patent granted to Benjamin Willcox, No. 8299, dated May 18th 1889, a
series of mono-azo colouring matters which are obtained by combining diazotised
aromatic amido carboxylic acids with certain dihydroxynaphthalenes, naphthol-
carboxylic acids, or hydroxycarboxylic acids of the benzene series. These products
can be advantageously employed for dyeing and printing purposes.
Analogous dye-stuffs have been produced by my foreign correspondents by the
combination of diazotised amidocarboxylic acids with certain dihydroxynaphthalene
sulpho acids, or amidonaphtholsulpho acids, as described in the Specifications of the
English Letters Patent likewise granted to the said Benjamin Willcox, No. 18,517,
dated November 19th 1889, and No. 5984, dated April 7th 1891.
In addition thereto, my foreign correspondents have now found, that not only the
dye stuffs described in the last named Patents, but generally those coloring matters
which contain carboxylic groups or carboxylic and hydroxyl groups (the latter two
groups either in the same nucleus or not) are, for the most part, of high technical
value, as they are capable of forming so-called lakes with mordants, and can be
advantageously employed for dyeing and printing purposes, and it is noticeable that
even those products can be used which contain sulpho groups, and therefore are
readily soluble, but less suited for dyeing unmordanted wool.
In order to produce these valuable coloring matters for dyeing and printing, the
diazo derivatives of the following amidocarboxylic acids especially can be used :-
ortho- meta-and paraamido benzoic acid, orthoamidosalicylic acid, paraamidosalicylic
acid, amidoparahydroxybenzoic acid, amidophthalic acid, amidosulphobenzoic acid,
amidosulphosalicylic acid, amidosulphoparahydroxybenzoic acid, amidosulpho cresol
carboxylic acid.
As second components, either products containing hydroxylic groups or car-
boxylic groups, or certain amido compounds not containing hydroxylic or carboxylic
groups (such as meta phenylene diamine, metatoluylene diamine) can be employed,
and my foreign correspondents have found, that the following substances especially
are of high value for such purposes, riz., phenol, resorcinol, salicylic acid, para-
hydroxybenzoic acid, ortho-, meta-, and paracresolcarboxylic acid, alpha and beta
naphthol, alphanaphthol alphamonosulpho acid (1:4, 1:5, 1:8), alphanaphthol-
disulpho acid S., alphanaphtholepsilondisulpho acid, alpha naphtholdisulpho acid
(OH: SO,H:SO,H=1:3:6), betanaphtholbetamonosulpho acid (2:6), beta-
naphtholdeltamonosulpho acid (2:7), betanaphtholalpha monosulpho acid (2:8),
betanaphtholdisulpho acid R and G and F, betanaphtholcarboxylic acid, beta-
naphthol sulphocarboxylic acid, dihydroxynaphthalene (1:5, 1:8, 2:6, 2:7, 2:8),
dihydroxynaphthalenemonosulpho acid R and G, dihydroxynaphthalenemonosulpho
acid obtained from alpha naphthol-epsilon disulpho acid, 1:8-dihydroxynaphthalene
alphamonosulpho acid, 1:8 dihydroxynaphthalenealphadisulpho acid (OH:OH:
SO,H: SO,H= 1:8:2:4), amidonaphtholinonosulpho acid G and R, 1:8-amido
naphtholbetadisulpho acid, dihydroxybenzoic acid (1:3:5), metaphenylene diamine.
and metatoluylene diamine.

page_text: THIRD EXAMPLE.
DYE STUFF OBTAINED BY COUPLING DIAZOTISED AMIDOPHTHALIC
WITH 1:5 DIHYDROXYNAPHTHALENE.
ACID
16 parts by weight of 1:5-dihydroxy naphthalene are dissolved in about 50 parts
of water, together with 4 parts by weight of sodium hydroxide; 5 parts by weight
of sodium acetate, and part by weight of acetic acid (30 per cent.), having been
added, the resulting liquid is mixed with a solution containing 23 parts by weight
of the chloride of diazophthalic acid. At the end of about 12 hours, the mixture is
acidulated with muriatic acid, and the dye stuff is then filtered off and washed with
a solution of common salt. It dyes wool mordanted with chromium salts a violet,
and produces a yellowish-red when printed together with chromium salts.
Of course, the method of producing these coloring matters is not restricted to
the proportions of the foregoing examples, as these can be varied, and the
production of these dye stuffs, and the aualogues thereof obtained by the employ-
ment of the aforesaid components, can likewise be effected by means of the
processes in use for the manufacture of analogous azo dyes.
The shades produced by these coloring matters on wool mordanted with
chromium or other salts in general, vary from red, yellow, brown, blue, to violet,
and partly differ from those obtained by printing them together with chromium or
similar salts on wool.
My foreign correspondents have found that some of the products resulting from
the combinations herein before mentioned are of minor value. They do not claim
these products, and also those dye-stuffs are excluded which are previously
described.

page_text: My foreign correspondents find that, for dyeing and printing purposes, the
combinations of special value are those which are enumerated in the first columns
of the following tables, in the second columns of which the shades are indicated
which are produced by the respective coloring matters, when these are printed with
the aid, for instance, of printing pastes containing 62 parts by weight of acetic
starch tragacanth thickening, 30 parts by weight of the dye stuff in the form of
10 per cent. paste, and 8 parts, by weight, of chromium acetate of 20 degrees
Baumé.

page_text: III.
OLORING MATTER OBTAINABLE BY THE ACTION OF DIAZOTISED PARAAM
BENZOIC ACID
ON
-
alphanaphtholalphamonosulpho acid (1:5) -
alphanaphtholalphamonosulpho acid (1:8)
alphanaphtholdisulpho acid S
alphanaphtholepsilondisulpho acid
-
red
brown
-
-
red
alphanaphtholdisulpho acid (OH: SO₂H : SO₂H—
-
-
-
-
-
-
red
red
yellowish-red
yellowish-red
red
yellowish-brown
-
red
-
-
-
-
-
brownish-yellow
brownish-red
yellowish-brown
bluish-red
brownish-red
violet-black
1:3:6)
betanaphtholalphamonosulpho
betanaphtholdeltamonosulpho
acid (2:8)
acid (2:7)
betanaphtholdisulpho acid R
betanaphtholdisulpho acid G
betanaphtholdisulpho acid F
dihydroxynaphthalene (1:5)
dihydroxynaphthalene (2:6)
dihydroxynaphthalene (2:7)
dihydroxynaphthalene (2:8)
dihydroxynaphthalenemonosulpho acid G
dihydroxynaphthalenemonosulpho acid
acid)
(obtainable from alpha naphthol epsilon disulpho
amidonaphtholmonosulnho acid G
-
-
brown
alphanaphthol
betanaphthol
alphanaphtholalphamonosulpho acid (14)
alphanaphtholalphamonosulpho acid (1:5)
alphanaphtholalphamonosulpho acid (1:8)
alphanaphtholdisulpho acid S
alphanaphtholepsilondisulpho
acid
alphanaphtholdisulpho ac.d (OH: SO,H: S
1.2.81

page_text: betanaphtholalphamonosulpho
betanaphtholdeltamonosulpho
acid (2:8
acid (2:7)
betanaphtholdisulpho acid G
betanaphtholdisulpho acid F
dihydroxynaphthalene (1:5)
dihydroxynaphthalene (2:6)
dihydroxynaphthalene (2:7)
dihydroxynaphthalene (2:8)
-
dihydroxynaphthalenemonosulpho acid
amidonaphtholmonosulpho acid G
amidonaphtholmonosulpho acid R
metaphenylene diamine
metatoluylene diamine
-

page_text: amidonaphtholmonosulpho acid G-
amidonaphtholmonosulpho acid R -
metaphenylene diamine
metatoluylene diamine
-
dark brown
reddish brown
light brown
brownish-black

page_text: XI.
COLORING MATTER OBTAINABLE BY THE ACTION OF
PHTHALIC ACID
ON
DI
parahydroxybenzoic acid
yello
betanaphtholsulphocarboxylic acid.
alphanaphtholalphamonosulpho acid (1:4)
alphanaphtholalphamonosulpho acid (1:5)
brow
brow
dark
alphanaphtholalphamonosulpho
acid (1:8)
yello
alphanaphtholdisulpho acid S
red
alphanaphtholepsilondisulpho
acid.
red
alphanaphtholdisulpho acid (OH: SO₂H: SO₂H=
1:3:6)
-
reddis
betanaphtholalphamonosulpho acid (2:8)
yellow
betanaphtholbetamonosulpho-acid (2:6)
yellow
betanaphtholdeltamonosulpho
acid (2:7)
betanaphtholdisulpho acid R
betanaphtholdisulpho acid G-
betanaphtholdisulpho acid F
-
red
dihydroxynaphthalene (1:5)
brown
red
yellow
yellow
dihydroxynaphthalene (2:7)
yellow
dihydroxynaphthalene (2:8)
dark
dihydroxynaphthalenemonosulpho
acid R
-
dark
-
brown
-
brown
-
yellow
dihydroxynaphthalenemonosulpho acid G
amidonaphtholmonosulpho acid G
metatoluylene diamine
Having now particularly described and ascertained the n
invention and in what manner the same is to be performed, a
me from abroad, I declare that what I claim is :—
1. The process for producing azo coloring matters suitab
printing purposes, which process consists :-
(a) In acting with diazotised orthoamidobenzoic acid on al
monosulpho acid (1:5), alphanaphtholalphamonosulpho
naphtholdisulpho acid S, alphamaphatholepsilondisulpho a
disulpho acid (OH: SO,H: SO,H=1:3:6), betanaphth
acid (2:8), betanaphtholdeltamonosulpho acid (2:7), be
acid R, betanaphtholdisulpho acid G, betanaphthol
dihydroxynaphthalene (1:5), dihydroxynaphthalene (
naphthalene (28), dihydroxynaphthalenemonosulpho a
naphthalenemonosulpho acid (obtainable from alphanapht
acid), amidonaphtholmonosulpho acid G, metapheny
metatoluylene diamine.
:
(b) In acting with diazotised meta amidobenzoic acid on pa
acid, alphanaphtholalphamonosulpho acid (1:5), alph
acid S, alphanaphtholepsilondisulpho acid, alphanaph
(OH SO,H: SO3H=1:3:6), betanaphtholalphamonos
betanaphtholdeltamonosulpho acid (2:7), betanaphthol
dihydroxynaphthalene (1:5), dihydroxynaphthalene (
naphthalene (2:7), dihydroxynaphthalene. (2:8) dihy
monosulpho acid G, dihydroxynaphthalenemonosulpho aci
alphanaphtholepsilondisulpho acid), amidonaphtholmon
metaphenylene diamine, or metatoluylene diamine.

page_text: c) In acting with diazotised paraamidobenzoic acid on alphanaphthol alpha-
monosulpho acid (1:5), alphanaphthol alphamonosulpho acid (1:8), alpha-
naphtholdisulpho acid S, alphanaphtholepsilondisulpho acid, alphanaphthol-
disulpho acid (OH:SO,H:SO,H = 1:3:6), betanaphtholalphamonosulpho
acid (2:8), betanaphtholdeltamonosulpho acid (2:7), betanaphtholdisulpho
acid R, betanaphtholdisulpho acid G, betanaphtholdisulpho acid F,
dihydroxynaphthalene (1:5), dihydroxynaphthalene (2:6), dihydroxy-
naphthalene (2:7), dihydroxynaphthalene (2-8), dihydroxynaphthalene-
monosulpho acid G, dihydroxynaphthalenemonosulpho acid (obtainable from
alphanaphtholepsilondisulpho acid), amidonaphtholmonosulpho acid G,
metaphenylenediamine, or meta toluylenediamine.
diamine.
d) In acting with diazotised amidosulphobenzoic acid on phenol, salicylic acid,
parahydroxybenzoic acid, orthocresolcarboxylic acid, metacresolcarboxylic
acid, paracresolcarboxylic acid, betanaphtholsulphocarboxylic acid, alpha-
naphthol, betanaphthol, alphanaphthol alphamonosulpho acid (1:4), alpha-
naphthol alphamonosulpho acid (:5), alphanaphthol alphamonosulpho
acid (8), alphanaphtholdisulpho acid S, alphanaphtholepsilondisulpho acid,
alphanaphtholdisulpho acid (OH:SO,H: SO,H = 1:3:6), betanaphthol
alphamonosulpho acid (2:8), betanaphthol detamonosulpho acid (2:7), beta-
naphtholdisulpho acid G, betanaphtholdisulpho acid F, dihydroxy-
naphthalene (1:5), dihydroxynaphthalene (2:6), dihydroxynaphthalene (2:7),
dihydroxynaphthalene (2:8), dihydroxynaphthalenemonosulpho acid G,
amidonaphtholmonosulpho acid G, amidonaphthol monosulpho acid R, meta-
phenylene diamine, or metatoluylene diamine.
e) In acting with diazotised orthoamidosalicylic acid on betanaphtholsulpho
carboxylic acid, alphanaphtholalphamono sulpho acid (1:5), alphanaphthol-
disulpho acid S, alphanaphtholepsilondisulpho acid, betanaphtholdelta-
monosulpho acid (2:7), betanaphtholdisulpho acid R, dihydroxy-
naphthalene (1:5), dihydroxynaphthalene (2:6), dihydroxynaphthalene (2:8),
dihydroxynaphthalenemonosulpho acid R, dihydroxynaphthalenemonosulpho
acid G, dihydroxynaphthalenemonosulpho acid (obtainable from alpha-
naphtholepsilondisulpho acid), amidonaphtholmonosulpho acid G, amido-
naphtholmonosulpho acid R, metaphenylene diamine, or metatoluylene
f) In acting with diazotised paraamidosalicylic acid on betanaphtholsulpho-
carboxylic acid, alphanaphthol alphamonosulpho acid (1:5), alphanaphthol
disulpho acid S, alphanaphtholepsilondisulpho acid, betanaphthol dolta-
monosulpho acid (2:7) be anaphtholdisulpho acid R, dihydroxy-
naphthalene (1:5), dihydroxynaphthalene (2:6), dihydroxynaphthalene (2:8),
dihydroxynaphthalenemonosulpho acid G, dihydroxynaphthalenemonosulpho
acid (obtainable from alphanaphtholepsilondisulpho acid), amidonaphthol-
monosulpho acid G, amidonaphtholmonosulpho acid R, metaphenylene
diamine, or metatoluylene diamine.
9) In acting with diazotised amidoparahydroxybenzoic acid on phenol,
resorcinol, salicylic acid, orthocresolcarboxylic acid, metacresolcarboxylic
acid, betanaphtholsulphocarboxylic acid, alphanaphthol, betanaphthol,
alphanaphthol alphamonosulpho acid (1:4), alphanaphthol alphamonosulpho
acid (1:5), alphanaphthol alphamonosulpho acid (1:8), alphanaphthol-
disulpho acid S, alphanaphtholepsilondisulpho acid, betanaphthol-betamono-
sulpho acid (2:6), betanaphthol deltamonosulpho acid (2:7), betanaphthol-
disulpho acid R, dihydroxynaphthalene (1:5), dihydroxynaphthalene (2:6),
dihydroxynaphthalene (2:7), dihydroxynaphthalene (2:8), dihydroxy-
naphthalenemonosulpho acid R, dihydroxynaphthalenemonosulpho acid G,
dihydroxynaphthalenemonosulpho acid (obtainable from alphanaphthol-
epsilondisulpho acid), amidonaphtholmonosulpho acid G, meta phenylene
diamine, or meta toluylene diamine.

page_text: 4) In acting with diazotised amidosulphosalicylic acid on betanaphtholsulpho-
carboxylic acid, alphanaphtholalphamonosulpho acid (1:5), alphanaphthol-
disulpho acid S, alphanaphtholepsilondisulpho acid, betanaphthol delta-
monosulpho acid (2:7), betanaphtholdisulpho acid R, betanaphtholdisulpho
acid F, dihydroxynaphthalene (1:5), dihydroxynaphthalene (2:6), di-
hydroxynaphthalene (2:8), dihydroxynaphthalenemonosulpho acid G, di-
hydroxynaphthalenemonosulpho acid (obtainable from alphanaphtholepsilon-
disulpho acid), amidonaphtholmonosulpho acid G, amidonaphtholmonosulpho
acid R, metaphenylene diamine, or metatoluylene diamine.
(i) In acting with diazotised amidosulphoparahydroxybenzoic acid on phenol,
resorcinol, betanaphtholcarboxylic acid, alphanaphthol, betanaphthol, alpha-
naphthol alphamonosulpho acid (1:4), alphanaphthol alphamonosulpho
acid (1:5), alphanaphthol alphamonosulpho acid (1:8), alphanaphthol-
disulpho acid S, alphanaphtholepsilondisulpho acid, betanaphthol deltamono-
sulpho acid (2:7), betanaphtholdisulpho acid R, betanaphtholdisulpho acid F,
dihydroxynaphthalene (1:8), dihydroxynaphthalene (2:6) dihydroxy-
naphthalene (2:7) dihydroxynaphthalenemonosulpho acid G, dihydroxy-
naphthalenemonosulpho acid (obtainable from alphanaphtholepsilondisulpho
acid), 1:8 dihydroxynaphthalene alphamonosulpho acid, 1:3:5-dihydroxy-
benzoic acid, metaphenylene diamine, or metatoluylene diamine..
k) In acting with diazotised amidosulphocresolcarboxylic acid on resorcinol,
alphanaphthol alphamonosulpho acid (1:8), alphanaphtholdisulpho acid S,
dihydroxynaphthalene (2:7), or dihydroxynaphthalenemonosulpho acid
(obtainable from alphanaphtholepsilondisulpho acid).
(4) In acting with diazotised amidophthalic acid on parahydroxybenzoic acid,
betanaphtholsulphocarboxylic acid, alphanaphthol alphamonosulpho
acid (1:4), alphanaphthol alphamonosulpho acid (1:5), alphanaphthol alpha-
monosulpho (1:8), alphanaphtholdisulpho acid S, alphanaphtholepsilon-
disulpho acid, alphanaphtholdisulpho acid (OH:SO,H: SO,H = 1:3:6),
betanaphthol alphamonosulpho acid (2:8), betanaphthol betamonosulpho
acid (2:6), betanaphthol deltamonosulpho acid (2:7), betanaphtholdisulpho
acid R, betanaphtholdisulpho acid G, betanaphtholdisulpho acid F, di-
hydroxynaphthalene (1:5), dihydroxynaphthalene (2:7). dihydroxy-
naphthalene (2:8), dihydroxynaphthalenemonosulpho acid R, dihydroxy-
naphthalenemonosulpho acid G, amidonaphtholmonosulpho acid G, or
metatoluylene diamine.
As new manufactures, the new coloring matters obtainable by means of
processes hereinbefore described, or by any other way producing the same
Dated this 18th day of May 1802
NEWTON & SON,
Agents for the Applicant.