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

page_text: Date of Application, 16th Dec., 1892
· Complete Specification Left, 15th Sept., 1893-Accepted, 28th Oct., 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 Letters Patent
No. 8299, dated 18th May 1889, mono azo dye-stuffs which are suitable for dyeing
and printing, and result by combining the diazo derivatives of aromatic amido
carbonic acids with certain dihydroxynaphthalenes, naphthol carbonic acids, or
aromatic hydroxycarbonic acids.
Similar colouring matters are described by my foreign correspondents in the.
Specifications of Letters Patents No. 18517, dated 19th November 1889, and
No. 5984, dated 7th April 1891. These products are obtained by combining
diazotised amido carbonic acids with certain dihydroxynaphthalene or amido
naphtholsulpho acids.
My foreign correspondents have further described in the Specification of my
application for Letters Patent No. 14927, dated 18th August 1892, the production
of analogous dye stuffs, which are suitable for dyeing and printing, and result by
combining the diazo derivatives of amido carbonic acids, amido-hydroxy carbonic
acids, amido di-carbonic acids, amido sulfocarbonic acids, amido sulfohydroxy-
carbonic acids, with phenols, naphthols, dihydroxynaphthalenes, amido-naphthols,
sulpho- or carboxylic derivatives thereof, or with metaphenylene diamine or meta
toluylene diamine.
My foreign correspondents have now found that the amido-carbonic acids,
amido hydroxy carbonic acids, and the like, used in the process of the last named
application No. 14927 of 1892, can be replaced by amido phenol ether carbonic
Valuable mono
acids, analogues or homologues, or substitution products, thereof.
azo dye stuffs, capable of dyeing with the aid of mordants, are obtained in this
manner. If, for instance, naphthols or naphtholsulpho acids are employed as
components, products result which yield red chromium lakes with the aid of
chromium mordants, and thereby obviate a defect long felt in calico printing.
Of course, in place of naphthols and naphtholsulpho acids, other components, viz.,
all those products defined in the Specification of application No. 14927 of 1892,
likewise can be employed.
The following compounds have been found to be of an especially high value,
when employed as components, viz. :-phenol, resorcinol, salicylic acid, parahydroxy-
benzoic acid, ortho cresol carbonic acid, meta cresol carbonic acid, para cresol
carbonic acid, alpha naphthol, beta naphthol, alpha naphthol alpha monosulpho
acid (14, 15, or 1-8), alpha naphtholdisulpho acid S, alpha naphthol epsilon
disulpho acid, alpha naphtholdisulpho acid (OH: SO,H: SO,H=1:3:6), beta
naphthol beta-monosulpho acid (26), betanaphtholdelta-monosulpho acid (2-7),
beta-naphthol alpha monosulpho acid (28), beta naphtholdisulpho acid R, G,
and F, beta naphtholcarbonic acid, betanaphtholsulpho carbonic acid, dihydroxy-
naphthalene (12, 15, 18, 26, 2-7 or 2-8), dihydroxy-naphthalene monosulpho
acid R or G, dihydroxynaphthalene monosulpho acid (obtained from alpha
naphtholepsilon-disulpho acid), 1.8 dihydroxynaphthalene alpha mono sulpho
acid S, 18 dihydroxynaphthalene alpha-disulpho acid, 1.8 dihydroxy-naphthalene
beta disulpho acid, amido naphtholmonosulpho acid G and R, 1.8 amidonaphthol

page_text: LOORING-MATTER FROM DIAZOTISED AMIDO ANISIC ACID AND ALPHA
NAPHTHOLALPHA MONOSULPHO ACID (1.4).
1.67 parts of amido anisic acid are converted into the diazo derivative by means of
7, parts of sodium nitrite and the so formed diazo product is introduced into an
alkaline solution of 25 parts of alpha naphtholalpha monosulphonate of sodium,
obtained from alpha naphtholalpha monosulpho acid (1.4). The formation of the
dye stuff immediately takes place, and, after acidulating by means of acetic acid,
the colouring matter is salted out. It is easily soluble, especially in hot water, and
vields, when printed on cotton together with chromium salts, bright red shades,
which are similar to those produced in printing alizarine together with alumina
salts.
In an analogous manner, other dye stuffs result, if the alpha naphthol alpha
mono sulpho acid (1.4) employed in the above example, is replaced by isomeric
naphtholmonosulpho acids, or by equivalent quantities of naphtholdisulpho-acids,
or other naphtholpolysulpho acids, or alpha naphthol beta naphthol, or, in general,
by the corresponding quantities of the components above defined, or if, in place of
amido anisic acid, analogous amido-phenolether carbonic acids, the analogues or
homologues or substitution products (for instance, sulpho derivatives) of these acids,
are used.
The method of producing these dye-stuffs, of course, is not restricted to the
proportions given in the above example, for these can be varied, and all methods
in use for the production of analogous dye stuffs from the components above
referred to, can likewise be employed..
The so-formed colouring-matters possess an especially high value for printing
purposes, as they yield beautiful fast shades when printed together with chromium
salts on cotton. The products obtained by means of naphthols and naphthol-sulpho
acids, are of the greatest value, as they are capable of forming, with chromium
salts, from scarlet-red to " ponceau red "lakes, which to some extent possess the
same shades as result when printing with alizarine red.
Of course, my foreign correspondents do not claim those products which are
described by Griess in the Berichte der Deutschen Chemischen Gesellschaft,
Volume XIV., page 2039, and result by combining the diazo compound of amido
anisic acid, with beta naphthol, betanaphthol monosulpho acid (2.6), or betanaph-
thol disulpho acid R. The above named author only mentions the property of
those products to dye the animal fibre, whilst according to the researches of my
foreign correspondents, these dye-stuffs, when printed with chromium salts, yield
orange-red chromium lakes.
Dated this 16th day of December 1892.
NEWTON & SON,
Agents for the Applicant

page_text: 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 Letters Patent
No. 8299 dated 18th May 1889 monoazo dye-stuffs which are suitable for dyeing
and printing, formed by combining the diazo derivatives of aromatic amido-
carboxylic acids with certain dihydroxynaphthalenes, naphtholcarboxylic acids or
aromatic hydroxycarboxylic acids.
Similar colouring-matters are described by my foreign correspondents in the
Specification of Letters Patent No. 18517 dated 19th November 1889 and
No. 5984 dated 7th April 1891. These products are obtained by combining
diazotised amidocarboxylic acids with certain dihydroxynaphthalene sulpho acids
or amidonaphthol sulpho acids.
My foreign correspondents have further described in the Specification of Letters
Patent No. 14927 granted to me and dated 18th August 1892 the production of
analogous dye-stuffs, which are suitable for dyeing and printing, produced by
combining the diazoderivatives of amidocarboxylic acids, amidohydroxycarboxylic
acids, amidodicarboxylic acids, amidosulphocarboxylic acids, amidosulphohydroxy-
carboxylic acids with phenols, naphthols, lihydroxynaphthalenes, or sulpho or
carboxylic acids thereof, or with amidonaphtholsulpho acids, or with meta-
phenylene diamine or metatoluylene diamine.
My foreign correspondents have now found that the amidocarboxylic acids,
amidohydroxycarboxylic acids and the like used in the process of the last named
Letters Patent No. 14,927 of 1892 can be replaced by amidophenolethercarboxylic
acids, homologues or substitution products thereof. Valuable monoazo dye-stuffs
capable of dyeing with the aid of mordants are obtained in this manner.
If, for instance, naphthols or naphtholsulpho acids are employed as components,
products are obtained which yield red chromium lakes with the aid of chromium
mordants, thereby obviating a defect long felt in calico printing. As a matter of
course, in place of naphthols and naphtholsulpho acids, other components viz.-all
those products defined in the Specification of Letters Patent No. 14,927 of 1892
can be employed in like manner.
The following compounds can be employed for the aforesaid purposes and can be
combined with the diazo derivatives of amido phenolethercarboxylic acids,
homologues or substitution products thereof viz.-phenol, resorcinol, salicylic acid,
orthocresolcarboxylic acid, inetacresolcarboxylic acid, alphanaphthol, betanaphthol,
alphanaphtholmonosulpho acid (1:3, 1:4, 1:5 or 1:8), alphanaphtholdisulpho
acid S, alpha-naphthol-epsilon disulpho acid, alphanaphtholdisulpho acid
(OH: SO,H: SO,H=1:3:6), beta-naphthol-beta-monosulpho acid (2:6), beta-
naphthol-delta-monosulpho acid (2 : 7), beta-naphthol-alpha-monosulpholacid (2:8),
beta-naphthol-disulpho acid R, G and F, beta naphthol carboxylic acid, beta-
naphthol sulpho carboxylic acid, dihydroxynaphthalene (1:2, 1:5, 1:8, 2:6,
2:7 or 2:8), dihydroxynaphthalene-monosulpho acid R or G, dihydroxynaph-
thalene monosulpho acid (obtained from alpha naphthol epsilon disulpho acid),
1: 8-dihydroxynaphthalene-alpha-monosulpho acid S, 1:8-dihydroxynaphtha-
lene disulpho acid (OH: OH: SO,H: SO,H =1:8:2:4), 1-8-dihydroxynaph-
thalene beta disulpho acid, amidonaphthol monosulpho acid G and Ŕ, 1·8-amido-
naphthol-beta-disulpho acid, dihydroxybenzoic acid (1:3:5).
The production of such dye-stuffs, however, is not restricted to the employment
of the last named products as second components, but other substituted or

page_text: unsubstituted phenols of the benzene or naphthalene series can be used in like
manner.
The production of these dye-stuffs in general is effected in the usual manner
viz. by allowing the diazo derivatives of amidophenolethercarboxylic acids,
homologues or substitution products thereof (for instance sulpho derivatives
thereof) to act in suitable alkaline or acid solutions on the components hereinbefore
defined.
In order to illustrate the method of producing these colouring-matters, the
following example is given.
FIRST EXAMPLE.
COLOURING-MATTER FROM DIAZOTISED
AMIDOANISIC ACID AND ALPHA-
NAPHTHOL-ALPHA-MONOSULPHO ACID (1:4).
167 parts of amidoanisic acid are diazotised by means of 7 parts of sodium
nitrite and the resulting diazo product is introduced into an alkaline solution of
25 parts of alpha-uaphthol-a-mono-sulphonate of sodium obtained from alpha-
naphthol-alpha-monosulpho acid (1:4).
The formation of the dye-stuff immediately takes place and, after acidulating by
means of acetic acid, the colouring-matter is salted out. It is easily soluble,
especially in hot water and when printed on cotton together with chromium salts,
yields bright red shades, which are similar to those produced on printing alizarin
together with alumina salts.
Other dye stuffs are found in an analogous manner if the alpha naphthol alpha
monosulpho acid (14) employed in the above example is replaced by isomeric
naphthol monosulpho acids or by equivalent quantities of naphtholdisulpho acids or
other naphtholpolysulpho acids or alpha-naphthol, beta-naphthol or in general by
the corresponding quantities of the components above defined, or if in place of
amidoanisic acid analogous amidophenolethercarboxylic acids (for instance amido-
ethylsalicylic acid), the homologues or substitution products (for instance sulpho
derivatives) of these acids are used.
The method of producing these dye-stuffs, as a matter of course, is not restricted
to the directions given in the above example, as these can be varied and all
methods in use for the production of analogous dye-stuffs can be employed.
The so formed colouring-matters are of especially high value for printing
purposes as they yield beautiful fast shades when printed together with chromium
Balts on cotton. The products obtained by means of alpha naphthol sulpho acids
are of the greatest value, as they are capable of forming with chromium salts,
red lakes, some of which exhibit shades like those obtained on printing with
alizarin-red..
Amongst the last named colouring-matters, for instance, those are especially
important which can be obtained by combining diazotised amidoanisic acid with
alpha-naphthol mono sulpho acid 1:3 or 1:4 or 1:5, or by coupling the diazo
derivative of amidoethylsalicylic acid with alphanaphtholmonosulpho acid 1:3 or
14 or 15. As a matter of course, my foreign correspondents do not claim
those products which are described by Griess in the Berichte der Deutschen
Chemischen Gesellschaft, Volume XIV, page 2039 formed by combining the
diazo compound of amidoanisic acid with beta naphthol, beta naphtholmono
sulpho acid (26) or with beta naphthol disulpho acid R. The above-named
author only calls attention to the property of those products of dyeing animal
fibres, whilst the researches of my foreign correspondents have shown that these
dye-stuffs yield orange-red chromium lakes when printed with chromium salts.
Having now particularly described and ascertained the nature of the said inven-
tion and in what manner the same is to be performed, as communicated to me from
abroad, I declare that what I claim is :-
1. The production of monoazo dye-stuffs which process consists in combining

page_text: the diazo derivatives of amidoanisic acid or amidoethylsalicylic acid with alpha-
naphtholmonosulpho acid 1:3 or 1:4 or 1: 5.
2. As new products of manufacture the new monoazo colouring-matters produced
by means of the process hereinbefore defined or by any other process affording
the same result.
71
1
1000
NEWTON & SON,
Agents for the Applicant.