The Manufacture or Production of Azo Colouring Matters.
Year: 1893

page_text: Date of Application, 27th Jan., 1893
Complete Specification Left, 23rd Oct., 1893-Accepted, 25th 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 Azo 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:-
It is known that coloring matters capable of producing dark, or chiefly black
shades, on unmordanted wool, have been prepared hitherto almost exclusively from
amido azo compounds (such as sulpho acids of amido azo benzene, benzene azo
naphthylamine, amnido-azo-naphthalene or the like), which in general result from
the action of diazotised amido sulpho acids on primary amines, and this process of
production is effected by diazotising the said amido nzo derivatives, and combining
the resulting diazo compounds with naphthols, dihydroxynaphthalenes, or sulpho
acids thereof, with metaphenylene diamine, its alkyl or phenyl derivatives, with
alpha or beta-naphthylamine, or with alkyl derivatives of alpha and beta-
naphthylamine.
Analogons coloring matters which contain naphthylamine sulpho acids as last com-
ponents, have not been put on the market up to the present time. Obviously the
latter fact is caused by the valueless properties of the coloring matters obtained
by acting with diazotised amidoazo compounds on the most employed unphthyl-
amine sulpho acids, as the dye stuffs thus produced only yield from brown to
reddish-brown shades of no value.
My foreign correspondents have now found, that amongst the naphthylamine
sulpho acids (when employed as last components), one shows a noticeable difference
of behaviour, viz., the 1-8 naphthylaminemonosupho acid, or alphanaphthylamine-
monosulpho acid S. (NH, SO,H=1:8), as this latter acid, when coupled with
diazo derivatives of amido azo compounds, yields technically valuable dye stuffa,
from violet black, bluish black, to pure black, which my foreign correspondents
have first ascertained by experiments. The coloring matters thus produced aro
remarkable for the intensity of their shades, and moreover possess the high
advantage of striking on unmordanted wool in neutral baths, and if amido azo
mono sulpho acids be used, of yielding shades which are absolutely fast against the
action of fulling.
One method of producing these new azo coloring matters, is illustrated in detail
in the following oxample, the parts being by weight.
|COLORING MATTER FROM BETANAPHTHYLAMIÑĖBETAMONOSULPHO ACID (2º6),
ALPHANAPHTHYLAMINE, AND 18 NAPHTHYLAMINEMONOSULPHO AOID.
22-3 parts of beta naphthylaminebetamonosulpho acid (2-6) are diazotised in the
usual manner in muriatic solution by means of 7 parts of sodium nitrite. The
resulting diazo compound is introduced into a solution prepared by dissolving
18 parts of alpbanaphthylamine hydrochlorate in about 500 parts of water.
After standing for some time, or (to quicken the process) by adding sodium acetate,
COLORING MATTER FROM BETANAPHTHYLAMIÑÉBETAMONOSULPHO acid (2'6),
ALPHANAPHTHYLAMINE, AND 18 NAPHTHYLAMINEMONOSULPHO AOID.
22-3 parts of beta naphthylaminebetamonosulpho acid (2-6) are diazotised in the
usual manner in muriatic solution by means of 7 parts of sodium nitrite. The
resulting diazo compound is introduced into a solution prepared by dissolving
18 parts of alpbanaphthylamine hydrochlorate in about 500 parts of water.
After standing for some time, or (to quicken the process) by adding sodium acetate,
and heating gently, the production of the amido azo product is complete. The
latter is filtered off and redissolved in about 500 parts of water, with the addition
of 4 parts of sodium hydroxide (NaOH). After adding a concentrated watory
solution of 7 parts of sodium nitrite, the resulting liquid is acidulated by means
of about 30 parts of hydrochloric acid at 21 degrees Baumé. In this manner, the

page_text: first precipitated dark brown dye stuff acid, is transformed into the light brown
diazo-azo-compound, which is filtered off, and then is allowed to flow, on stirring,
into a solution of 25 parts of the sodium salt of 1-8 naphthylaminemonosulpho
acid. After standing for several hours, the coloring matter is salted out, and when
filtered off and dried, it appears as a brownish black powder which dissolves in
water with dark violet color. It produces on uumordauted wool, in a neutral or
weak acetic acid bath, deep bluish black shades, which are fast against the action
of light, acids, and fulling.
My foreign correspondents have described, in the preceding example, ono method
of producing a dye stuff of the series hereinbefore defined, but they do not limit
themselves to the proportions above given, as the latter can be varied, and the
production of the said dye stuffs can be effected by means of those methods which
are in use for the manufacture of analogous coloring matters.
"
Dresstulls analogous to that which is obtained according to the above example
result, if, in the said example, on the one hand, betanaphthylaminebotamonosulpho
acid (26) is replaced by the isomeric alpha or betanaphthylaminemonosulpho
acids, or by the corresponding quantities of alpha or betanaphthylamine polysulpho
acids, amidobenzene sulpho acids (such as sulphanilic acids, toluidone sulpho acids,
xylidine sulpho acids, analogues or homologues thereof), or, speaking broadly, if
"amines or substituted amines are employed as first components, or if, on the
other hand, in place of alphanaphthylamine as second component, "substitution
derivatives of alphanaphthylamine," aniline, toluidine, xylidine, amido cresol-
ether, the analogues or homologues of all these compounds are used, and if,
subsequently, the resulting sulpho acids of amido azo-naphthalene, benzeneazo-
naphthylamine, amidoazobenzene, and the like, are diazotised and combined with
alphanaphthylamine alphamonosulpho acid (1.8).
The resulting dye stuffs produce on ordinary wool, in a neutral or weak acetic
acid bath, from violet black bluish black, to pure black shades, possessing a high
intensity and great fastness.
My foreign correspondents understand by the above said "amines or substituted
amines," the following products, viz., amines, amidphenols, amidophenolethers of
the benzene or naphthalene series, the derivatives of all these compounds, chiefly
the sulpho, carbonic, and sulpho carbonic acids thereof, and they understand by the
above substitution derivatives of alphanaphthylamine" which are employed as
second components in the same manner as alphanaphthylamine, auiline, toluidene,
and the like, the following products, wis., naphthylaminesulpho acids, amido
naphthols, amidonaphtholethers, amidonaphtholsulpho acids, amidonaphtholether-
sulpho acids, amidonaphthoxyacetic acids, amidonaphthoxyacetic sulpho acids, or
the like.
Of course, in place of the amines employed as first components, amido
Azo benzene, amidoazotoluene, amido azo xylene, the analogues and homo-
logues thereof, the substitution products thereof (such as sulpho acids), diamines,
the one amido group of which can be diazotised (on starting, for example,
from the corresponding mono-acetyl derivatives), such as phenylene diamine,
toluylene diamine, naphthylene diamine, and the derivatives thereof, mononitro-
amines and their derivatives can be used. If mono acetylised diamines are
employed as first components, the resulting acetylised dye stuffs must be treated
in a suitable manner, in order to split off the acetyl group, whilst in the employ-
ment of nitro amido compounde as first components, the finally obtained uitro
coloring matters must be reduced. All such or similar combinations are included
in the present invention, as the lattor, in general, relates to the production of
azo dye stuffs by combining alphanaphthylamine alphamonosulpho acid S
(NH, SO,H=1:8) with the diazo derivatives of amido azo products.
Dated this 27th day of January 1893.

page_text: COMPLETE SPECIFICATION.
The Manufacture or Production of Azo 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 bo performed, to be
particularly described and ascertained in and by the following statement :—
It is known that coloring matters capable of producing dark, or chiefly_blaok
shades, on uumordanted wool, have hitherto been almost exclusively prepared from
amido azo compounds (sulpho acids of amido azobenzene, benzeneazonaphthylamine,
amidoazonaphthylene, or the like), such as are obtained by the action of diazotised
amidosulpho acids on primary amines, and that they are produced by diazotising
the said amidoazo derivatives, and combining the resulting diazo compounds with
naphthols, dihydroxynaphthalenes, or sulpho acids thereof, with metaphenylene-
diamine, its alkyl or phenyl derivatives, with alpha or batanaphthylamine, or with
alkyl derivatives of alpha and betanaphthylamine.
Analogous coloring matters which contaiu naphthylamine sulpho acids as last
components, have not been put on the market up to the present time, owing to the
valueless character of the coloring matters obtained by acting with diazotisod
ainido azo compounds on the naphthylamine sulpho acids most usually employed,―
the dye-stuffs thus produced only yielding from brown to reddish brown shades of
no value.
My foreign correspondents have, however, found that one of the naphthylamine
sulpho acids (when employed as last component) shows a noticeable difference in
behaviour, riz., tho alpha, naphthylamine-alpha-monosulpho acid, or alphanaphthyl-
aminemonosulpho acid S (NH,: SO,H=1:8), as when coupled with diazo-
derivatives of amido compounds, this acid yields technically valuable dye-stuffs,
varying chiefly from brown, violet black, bluish-black, to pure black. The coloring
matters thus produced are remarkable on account of the intensity of the shades
which they produce, and moreover possess the great advantage of dyeing
uninordanted wool in neutral baths, yielding shades, in the case of those produced
from amido azo mono sulpho acids, which absolutely withstand fulling.
One method of producing these new azo coloring matters is illustrated in detail
in the following example, the parts being by weight
COLORING MATTER FROM BETANAPHTHYLAMINE BETAMONOSULPHO
ACID (2:6), ALPHANAPHTHYLamine and alpha, naphthYLAMINE-
ALPHA MONO SULPHO AOID.
22-3 parts of betanaphthylamine beta mono sulpho acid (2:6) are diazotised in
the usual manner, in the presence of muriatic acid, by means of 7 parts of sodium
nitrite. The resulting diazo compound is then introduced into a solution prepared
by dissolving 18 parts of alphanaphthylamine hydrochloride in about 500 parts of
water. Either the mixture is allowed to stand, or the process is quickened by
adding sodium acetate and gently henting. The resulting amidoazo compound
having been filtered off, is mixed with, or dissolved in, about 500 parts of water to
which 4 parts of sodium hydroxide (NaOH) have been added. After adding a
concentrated watery solution of 7 parts of sodium nitrite, the liquid is acidulated
with about 30 parts of muriatic acid (21 degrees Bauma). The dark brown dye-
stuff acid which is at first precipitated, becomes eventually transformed into the
light brown diazo azo compound, which is filtered off and stirred into a solution of
25 parts of the sodium salt of alpha, naphthylamine alpha, mono sulpho acid, to
which sodium acetate is added with advantage. After standing during several
hours, the coloring matter is salted out, filtered off, and dried. It is a brownish
black powder which dissolves in water, forming a dark violet colored solution. It

page_text: produces on unmordanted wool, in a neutral or weak acetio noid bath, deep violet-
black shades which withstand light, acids, and fulling.
My foreign correspondents have described in the preceding example, one method
of producing a dye-stuff of the series hereinbefore defined; but they do not limit
themselves to tho directions above given, as these can be varied, and the production
of the said dye-stuff's can be effected by means of all the methods which are in use
for the manufacture of analogous coloring matters.
Dye-stuffs analogous to that which is obtained according to the above example,
are formed, if, in the said example, on the one hand, bata naphthylamine beta
mono sulpho acid (26) is replaced by the isomeric alpha or betanaphthylamine
mono sulpho acids, or by the corresponding quantities of alpha or beta naphthyl-
amine poly sulpho acids, amido benzene sulpho acids (such as sulphanilic acids,
toluidine sulpho acids, xylidine sulpho acids, analogues or homologues thereof), or,
speaking broadly, if "amines or substituted amines of the benzene or naphthalene
sories"
are employed as first component, or if, on the other hand, in place of
alphanaphthylamine as second component, "substitution derivatives of alpha
naphthylamine," or paraxylidine, amido cresolether, the analogues or homologues of
all these compounds, are used, and if, subsequently, the resulting amido azo products
are diazotised, and combined with the said alpha, naphthylamine alpha, monosulpho
acid (NH, SO,H = 1 : 8).
:
The resulting dye-stuffs produce from dark brown to violet-black, bluish-black,
and puro black shades, on ordinary wool, in concentrated dyeing baths which aro
either neutral, or have been rendered moderately acid by means of acetic acid.
The shades are of great intensity and fastness.
66
My foreign correspondents in general understand by the above said "amines
or substituted ninines," the following products, viz., amines, amido phenols,
amido-phenolethers, amidoazo products of the benzene or naphthalene series,
the derivatives of all these compounds, chiefly the sulpho, carboxylic, and
sulpho-carboxylic acids thereof, and they mean, by the above expression,
substitution derivatives of alpha naphthylamine" which are employed as second
components in the same manner as alphanaphthylamine, para xylidine, amido
cresolether, and the like, the following products, viz., alphanaphthylamine beta
sulpho acids (alpha, beta, or alpha, beta, or alpha, beta,), amidonaphthols, amido-
naphtholethers, amidonaphtholsulpho acids, amidonaphthol ether sulpho acids,
amidonaphthoxyacetic acids, amidonaphthoxyacetic sulpho acids, or the like. The
use of those amido compounds, as middle or second components, is naturally
excluded, which, when combined with dinzo derivatives, do not yield truc
dinzotisable amidoazo products.
Instead of first producing amidoqzo compounds by coupling an amido product
with a diazo derivative of an amido compound, amido azo products (such as amido
azobenzene, amido azotolueue, or sulpho acids thereof) may be directly used for the
production of coloring matters, by allowing the diazo derivatives of these amido
azo products to act on the said alpha, uaphthylamine alpha, monosulpho acid.
The researches of my foreign correspondents have also shown, that in place of
the amines employed as first components, amido azobenzene, amido azotoluene,
amido azoxylene, the analogues and homologues thereof, the substitution products
thereof (especially sulpho acids), diamines (the one amido group of which can be
diazotised by starting, for example, from the corresponding monoacetylderivatives),
such as phenylene diamine, toluylene diamine, naphthylene diamine, and the
derivatives thereof, mononitroamines and their derivatives, can be used. If mono
acetylated diamines are employed as first compound, the resulting acetylated dye-
stuffs must be treated in a suitable manner, in order to split off the acetyl group,
whilst, on using nitro amido compounds as first components, the resulting nitro
coloring matters must be reduced. Those coloring matters are of special value
which are obtained by combining the said alpha, naphthylamine alpha, monosulpho
acid with the diazo derivatives of amido benzene azosalicylic acid, amidotoluene
azu salicylic acid, amidoxylene axo salicylic acid, amidouaphthaleneazosalicylic acid,

page_text: or analogous or homologous amido azohydroxycarboxylic acids (such as are derived
from cresotinic acid, naphtholcarboxylic acid, or the like), or sulpho derivatives
thereof. These dye-stuffs can be formed by coupling the diazo derivatives of
monacetylparaphenylene diamine, monacetyltoluylene diamine, monacotylxylylene
diamine, monacetylnaphthylene diamino, or sulpho derivatives thereof, with
hydroxycarboxylic acids (such as salicylic acid, cresotiuic acid, naphthalcarboxylic
acid, or the like, or sulpho derivatives thereof), splitting off the acetyl group,
rediazotising the resulting amido nzo compounds, and subsequently combining the
diazo dorivatives with the said alpha, naphthylamine alpha, monosulpho acid. The
same coloring matters can also be prepared if, in place of the aforesaid monacetyl
diamines, the corresponding mononitroamines are employed, viz., by coupling the
diazo derivatives of paranitraniline, nitrotoluidine, nitroxylidine, nitronaphthyl-
amine, or the like, or sulpho derivatives thereof, with hydroxycarboxylic acids
(such as salicylic acid, cresotinic acid, naphtholcarboxylic acid, or the like),
reducing the resulting nitro nzo compounds, and combining the diazo compounds of
the amido azo products thus obtained with the said alpha, naphthylamine alpha,
monosulpho acid. All such or similar combinations are included in the prosent
invention, which relates generally to the production of azo dye-stuffs by combining
alpha naphthylaming alpha monosulpho acid, or alpha naphthylaminomono sulpho
acid S (NH,: 80,H=1:8), with the diazo derivatives of amido azo compounds.
In order to illustrate the variety of coloring matters obtainable by means of the
process herein before defined, and the slindes produced by these dye-stuffs, the
following table is given, in the first column of which the different components of
some coloring matters of this new series are indicated, the shades obtainable respec-
tively in diluted and concentrated dyeing baths, by means of the corresponding
dye-stuffs, being indicated in the second and third columos.
acid +
acid +
amidoazobenzene +
amidoazotoluene +
amidoazobenzenesulpho
amidobenzeneazosalicylic
aniline+alpha,naphthylamino-
beta monosulpho acid +
aniline+alpha naphthylamine-
beta,monosulpho acid +
aniline+alpha,naphthylamine-
beta monosulpho acid +
paramidobenzenesulpho acid +
alphanaphthylamine +
paramidosalicylio acid + alpha-
naphthylamine +
alpha,naphthylaminobeta
mono-
sulpho+alphanaphthylamine
beta naphthylamine alpha,mor
sulpho acid + alphs naphth
amine +
beta naphthylamino
beta mo
sulpho acid + alpha naphth
amine +
alpha,uaphthylamine
beta,be
disulpho acid + alpha naphth
amine +
amidoazobenzene +
amidoazotoluene +
amidoazobenzenesulpho acid +
amidobenzeneazosalicylic acid +
aniline+alpha,naphthylamino-
beta monosulpho acid +
aniline+alpha naphthylamine-
beta,monosulpho acid +
aniline+alpha, naphthylamine-
beta monosulpho acid +
paramidobenzenesulpho acid +
alphanaphthylamine +
parainidosalicylic acid + alpha-
naphthylamine +
alpha,naphthylaminobeta mono-
sulpho+alphanaphthylamine +
beta naphthylamine alpha,moro-
sulpho acid + alpha naphthyl-
amine +
beta naphthylamino beta mono-
sulpho acid + alpha naphthyl-
amine +
alpha,uaphthylamine
beta,beta
disulpho acid + alpha naphthyl-
amine +
alpha,naphthylamine alpha monosulpho acid
brownish
bluish rod
reddish vi
reddish b
greyish b
greyish bl
greyish bl
greyish vi
blackish
brownish
bluish bla
bluish ble
bluish gr

page_text: 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, 1 declare that what I claim is :-
1. The production of azo coloring matters by combining oue molecular proportion
of alpha, naphthylaminealpha, monosulpho acid (NH, SO,H=1:8) with one
molecular proportion of a diazotised amido azo compound.
2. The process for producing azo dye stuffs, which process consists in coupling
one molecular proportion of alpha, naphthylamine alpha, mono sulpho acid with
one molecular proportion of the dinzo derivatives of amido azobenzene, amido azo
toluene, anido azoxylene, or the like, or sulpho acids thereof, or amido benzene azo
salicylic acid, amido toluene azo salicylic acid, amido xylenenzosalicylic acid,
amidonaphthalene azosalicylic acid, or analogous or homologous amido azo hydroxy-
carboxylic acids (derived from cresotinic acid, naphtholcarboxylic acid, or the
like), or sulpho derivatives of such amido azo products, or with one molecular pro-
portion of the diazo derivatives of those amido azo compounds which are formed
by combining one molecular proportion of diazotised amines, amido phenols, amido
phenolethere, amido azo compounds of the benzene or naphthalene series, sulpho or
carboxylic, or sulpho carboxylic acids thereof, with one molecular proportion of
the following components: alphanaphthylamine alpha, unphthylamine-beta, mono-
sulpho acid, alpha, naphthylamine heta, monosulpho acid, alpha, naphthylamine
beta, monosulpho acid, amidonaphthol, amidonaphtholether, amido naphthol sulpho
acid, amidonaphtholether sulpho acid, amido naphthoxy acetic acid, or amido-
naphthoxy acetic sulpho acid (excluding however those of the last named com-
ponents which, when combined with diazo derivatives, do not yield true diazotisable
amidoazo compounds.
3. As new products of manufacture, the new coloring matters obtainable by
means of the processes herein before defined, or by any other process producing the
same result.
De
NEWTON & SON,
Agents for the Applicant.