The Manufacture or Production of Alkylated Hydroxynaphthalene Sulphonic Acids and Colouring Matters therefrom.
Year: 1893

page_text: Date of Application, 16th Feb., 1893
Complete Specification Left, 16th Nov., 1893-Accepted, 23rd Dec., 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 Alkylated Hydroxynaphthalene
Sulphonic Acids and Colouring Matters therefrom.
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 found, that by heating with alkylhaloids, alkyl-
sulphates, or other alkylating agents, the basic salts of a, a-dihydroxynaphthalene-
monosulpho acids, or a, a,-dihydroxynaphthalenepolysulpho acids, having the
formulæ :
OMe
O Me
OMe
CiH,
OMe
C₁H
\SO,Me
SO,Me
\SO,Me
alkylhydroxynaphthol monosulpho acids, or alkylhydroxynaphthol poly sulpho acids,
) or salts thereof are formed one alkyl groun heing substituted for the hydrogen

page_text: The production of such alkylhydroxynaphtholsulpho acids proceeds, for example,
in a satisfactory manner, if the following a, a,-dihydroxynaphthalene sulpho acids
are employed, viz.-a, a dihydroxynaphthalene-a-monosulpho acid (obtainable
from alphanaphthol deltadisulpho S of the German Patent No. 40571, by melting
this acid, or its salts, with alkalies), a₁ a-dihydroxynaphthalenebetamonosulpho acid
(obtainable from the alpha naphtholepsilondisulpho acid of the German Patent
No. 45776, by melting this acid, or salts thereof, with alkalies), a, a-dihydroxy-
naphthalene alphadisulpho acid, (obtainable from the said alphanaphthol delta
disulpho acid S, by sulphonating, and melting the thus formed naphtholtrisulpho
acid, or salts thereof, with alkalies), a, a,-dihydroxynaphthalene beta disulpho acid
(which can be obtained by melting with alkalies the naphthosultone. disulpho acid
of the German Patent No. 56058 or salts thereof), a₁ a-dihydroxynaphthalene
sulpho acids (resulting, for example, by sulphonating a, a, dihydroxynaphthalene,
as described in the English Patent No. 14294 of 1891).
The special termination of the dihydroxynaphthalene sulpho acids, and alkyl-
hydroxynaphtholsulpho acids derived therefrom, is based on the following scheme
of naphthalene, viz. :—
PRODUCTION OF ETHOXYNAPHTHOLDISULPHO ACID FROM a₁ α-DIHYDROXY-
NAPHTHALENE B, B. DISULPHO ACID.
1 molecular proportion of the acid sodium salt of the a, a, dihydroxynaphthalene
BB, disulpho acid (so called chromotrop acid) is heated with lime, in order to
obtain the basic salt. The resulting solution, after adding one molecular proportion
of ethyl bromide, is heated for about 8 hours, at about 105 degrees centigrade, in
a salt bath. On cooling, the a₁ ethoxy a-naphthol 3, 3-disulpho acid thus
produced separates in the form of its sodium calcium salt, whilst the unaltered
chromotrop acid remains dissolved. The salt is filtered off, pressed, and dried.
A small excess of alkali is not detrimental in the production of this acid, whilst
a great excess of alkali prevents this reaction.
The other monoalkyloxynaphtholsulpho acids derived from analogous a, a dihy-
droxynaphthalene sulpho acids, are obtained in a similar manner to that described
in the above example.
In place of ethylbromide, the corresponding quantities of other ethylhaloids,
ethylsulphate, ethylsulphuric salts, or similar ethylating agents, can be used.
If the ethyl bromide employed in the above example replaced by the corre-
sponding quantities of the halogen salts of methyl, propyl, butyl, amyl, or similar alkyl
radicles of the fatty series, or by the halogen compounds of aromatic alkyls,
inclusive of the benzyl haloids, or by the corresponding alkyl sulphates, alkyl-
sulphuric salts, or, if other alkylating methods are used, the monomethoxy, mono-
propyloxy, monobutyloxy, monoamyloxy, monobenzyloxynaphtholsulpho acids,
and the like, or the salts of these acids, are obtained.
My foreign correspondents have described in the above example merely one
practical method for converting a dihydroxynaphthalene disulpho acid into the
corresponding alkylnaphtholdisulpho acid. The proportions above given can be
12

page_text: varied. In place of the acid sodium salt, the corresponding quantities of other
acid alkaline salts can be used, and the conversion of the acid salts into the basic
salts can be effected by means of other alkalies, in place of lime (calcium hydroxide).
The free dihydroxynaphthalene sulpho acids likewise can be treated, viz., in the
presence of alkalies, with the halogen alkyls, alkylsulphates, alkylsulphuric salts,
and the like. The reaction may also be effected at a somewhat higher temperature,
the formation of the alkylated acids in general being complete within a short time.
Such or similar modifications easily follow from the directions given in the
preceding example, and it is not necessary to enumerate more in detail these
variations.
My foreign correspondents have further found, that the alkyloxynaphtholsulpho
acids can be used advantageously for the production of azo dye stuffs, and they
therefore propose to employ these new acids for such purposes.
Disazo coloring matters; distinguished for the beauty and intensity of their shades,
and superior to the dye stuffs from naphthol or dihydroxynaphthalene sulpho acids
by reason of their ability to dye wool, result by combining the tetrazo derivatives
of benzidine, its analogues or homologues, with the monoalkylated dihydroxy-
naphthalene sulpho acids hereinbefore defined.
By "benzidine, the analogues and homologues thereof," my foreign correspon-
dents understand, for example, the following substances, viz.: benzidine tolidine,
diamidophenyltolyl, diamidophenolether, diamidoalkyloxy diphenyl, diamidoalkyl-
oxyphenyltolyl, diamidoazobenzene, diamidoazotoluene, diamidoazoxylene, diamido-
azoxybenzene, diamidoazoxytoluene, diamidostilbene, diamidofluorene, diamido-
naphthalene, diamido-carbazol, diamido-diphenylene oxide, diamido-ditoluylene
oxide, paraphenylene diamine, toluylene diamine, benzidine sulphone, tolidine
sulphone, diamido-phenyltolylsulphone, diamido diphenoxyacetic acid, diamido-
diphenylene ketoxime, m- p-diamidophenyl benzimidazol, amidobenzene (-toluene-
xylene), azo-alpha-naphthylamine, amidobenzene (-toluene-xylene) azo-p.-xylidine,
amidobenzene (-toluene-xylene), azo-meta amidoparacresolether, amidobenzene
(-toluene-xylene), azo-orthoamidoparacresolether, amidobenzene (toluene-xylene),
azobetaethoxyalphanaphthylamine, the sulpho or carboxylic acids thereof.
Similar diamines, and analogous sulpho or carboxylic acids thereof, which can be
converted into their tetrazo salts, either directly or by means of their mono-acetyl
products, likewise can also be employed. In place of mono acetylised diamines, the
corresponding mononitro-amines can be used, and in the latter case the first produced
nitro products must be reduced and again diazotised, whilst the mono-acetyl products
resulting from the employment of mono acetylised diamines, are treated in a suitable
manner, to split off the acetyl group, are again diazotised, and further combined
with dye stuff components.
The combination of the diazo- or tetrazo-derivatives of the above diamines, with
the alkyloxynaphtholsulpho acids herein before defined, is effected most advan-
tageously in solutions containing sodium carbonate.
The process for producing these new tetrazo dye stuffs in general, is analogous to
that which my foreign correspondents have described for the manufacture of
coloring matters from non alkylated dihydroxynaphthalene sulpho acids, for
example, in the Specifications of the following Letters Patent, viz., No. 13665,
3397, 13443%, and 5984".
In order to illustrate more in detail the production of these coloring matters, the
following example is given. The parts are by weight :-
:―
DYE STUFF OBTAINED FROM ONE MOLECULAR PROPORTION OF DIANISIDINE
AND TWO MOLECULAR PROPORTIONS OF a₁ ETHOXY-a, NAPHTHOL a MONO
SULPHO ACID.
34.2 parts of the sulphate of diamido-diphenoldimethylether, or the corresponding

page_text: quantity of another salt of dianisidine, with the addition of 30 parts of muriatic acid
(at 20 degrees Baumé) are suspended in a finely divided state in 500 parts of
water, and then, on stirring well, a solution of 13-8 parts of sodium nitrite in
150 parts of water is added. The resulting solution of tetrazo diphenolether is
allowed to flow into a soda alkaline solution of 58 parts of the sodium salt of
a, ethoxy-a, naphthol a monosulpho acid. The formation of the dye stuff, which
immediately begins, is complete within a short time. The dye stuff this produced
is salted out by adding common salt, filtered off, pressed, and dried. It produces
on unmordanted cotton, blue shades, which are fast against the action of alkalies.
Its composition corresponds with the formula:
The analogous coloring matters are obtained in the same manner, or a manner
similar to that described in the preceding second example, if, on the one hand, the
diamido-diphenoldimethyl ether employed in, the said example is replaced by the
corresponding quantities of other diamidodiphenolethers (such as diamido diphenol-
ethylether, propylether, butylether, or amylether), or by the corresponding
quantities of another of the above named diamines, sulpho or carboxylic acida
thereof, or if, on the other hand, the a₁ ethoxy-a, naphthol a-monosulpho acid is
replaced by the equivalent quantity of another monoaklyated dihydroxynaphthalene
monosulpho acid, or monoalkylated dihydroxynaphthalene polysulpho acid.
Coloring matters are obtained in this manner, which yield, for the most part,
blue shades of great fastness against the action of alkalies, and amongst these dye
stuffs, those obtained by means of a₁-alkyloxy a, naphthol sulpho acids especially
are remarkable for their ability to 66 strike very easily on the fibre, and to yield,
on wool, beautiful blue shades fast against fulling.
In
According to the researches of my foreign correspondents, the tetrazo derivatives
of the diamines hereinbefore defined can be combined not only with two molecular
proportions of monoalkylated a₁ a dihydroxynaphthalene sulpho acids, but also
with one molecular proportion of these monoalkyloxynaphtholsulpho acids.
the latter case, intermediate products result, which contain one free amido group,
and therefore can further be combined with one molecular proportion of a phenol,
an amine, a diamine, an amidophenol, amidophenolether of the benzene or naphtha-
lene series, a sulpho or carboxylic acid thereof.
The production of these intermediate products and coloring matters in general, is
effected by combining one molecular proportion of a tetrazo compound with one
molecular proportion of a monoalkylated dihydroxynaphthalene sulpho acid, the
so-called intermediate products being formed, which may then be coupled with one
molecular proportion of a phenol, an amine, or the like, or, inversely, by combining
one molecular proportion of a tetrazo salt at first with one molecular proportion of
a phenol, an amine, or the like, and then with one molecular proportion of a
monoalkylated dihydroxynaphthalene sulpho acid.
The combination of the said components with the tetrazo compounds, or with
the said intermediate products, may be effected in acid solution (for example, in

page_text: the presence of acetic, muriatic acid, or the like), or in alkaline solution, but
amines are coupled most practically in acid solution, whilst phenols are combined
more advantageously in alkaline solution. The alkylated dihydroxynaphthalene
sulpho acids are coupled most practically either in a solution containing sodium
carbonate, or in solutions containing sodium acetate.
The formation of these mixed dyestuffs is illustrated by the following example,
the norte being by weight.
COLORING MATTER RESULTING FROM EQUAL MOLECULAR
DIANISIDINE, ALPHANAPHTHOL - ALPHAMONOSULPHO
a₁-ETHOXY-a-NAPHTHOL-a-MONOSULPHO ACID.
PROPORTIONS OF
ACID (14), AND
24.4 parts of dianisidine are converted, in the usual way, in hydrochloric solution,
into the tetrazo ompound. The resulting tetrazo solution is mixed with such a
quantity of water, that the volume is 700 litres (in case the parts are kilos. by
weight), and this liquid is allowed to flow into a solution prepared by dissolving
27 parts of the sodium salt of alphanaphtholalphamonosulpho acid (14) and
30 parts of sodium acetate, in 500 parts of water. The formation of the inter-
mediate product begins within a short time, and is complete after about 4 or
It separates in voluminous dark flakes. 32 parts of the neutral sodium
salt of a, monoethoxy a naphthol-a-monosulpho acid, and 12 parts of calcinated
sodium carbonate are added. The production of the coloring matter slowly
proceeds, and is practically advanced by heating. After 24 hours, the coloring
matter is filtered off and dried. It produces, on unmordanted cotton, blue shades,
and possesses the following composition :-
5 hours.
244 parts of dianisidine are converted, in the usual way, in hydrochloric solution,
into the tetrazo ompound. The resulting tetrazo solution is mixed with such a
quantity of water, that the volume is 700 litres (in case the parts are kilos. by
weight), and this liquid is allowed to flow into a solution prepared by dissolving
27 parts of the sodium salt of alphanaphtholalphamonosulpho acid (1.4) and
30 parts of sodium acetate, in 500 parts of water. The formation of the inter-
mediate product begins within a short time, and is complete after about 4 or
5 hours. It separates in voluminous dark flakes. 32 parts of the neutral sodium
salt of a, monoethoxy a naphthol-a-monosulpho acid, and 12 parts of calcinated
sodium carbonate are added. The production of the coloring matter slowly
proceeds, and is practically advanced by heating. After 24 hours, the coloring
matter is filtered off and dried. It produces, on unmordanted cotton, blue shades,
and possesses the following composition:-
OCH,
OH
CH, N = N - C₁H
SO,Na
OC,H₁
CH, N = N - C₁,H-OH
-
OCH,
SO,Na.
The analogous products result, if, in the last example, either dianisidine is
replaced by the corresponding quantities of other analogous or homologous diamines,
or if, in place of alphanaphtholalphamonosulpho acid (14), the equivalent
quantities of an amine, a diamine, an amidophenol, an amidophenol ether of the
benzene or naphthalene series, a sulpho or carboxylic derivative of these compounds
is employed, or if the ai alkyloxy-a-naphthol-a-monosulpho acid is replaced by
the corresponding quantities of other alkyloxynaphtholsulpho acids or salts thereof.
It is no matter in what order the two different components are combined.
The intermediate products resulting from one molecular proportion of a tetrazo
compound, and one molecular proportion of an alkylated dihydroxynaphthalene
sulpho acid, can likewise be combined with one molecular proportion of another
alkylated dihydroxynaphthalene sulpho acid.
My foreign correspondents have further prepared valuable tris and tetrakisazo
dye stuffs, by combining the tetrazo salts of the diamines hereinbefore defined, or:
similar diamines, at first with one or two molecular proportions of an "amine or

page_text: substituted amine," further diazotising the so-formed intermediate products, and
coupling the tetrazo compounds either with two molecular proportions of the same
alkyloxynaphthol sulpho acid, or with one molecular proportion of the one alkyl-
oxynaphtholsulpho acid, and a second molecular proportion of another alkyloxy-
naphtholsulpho acid, or with one molecular proportion of an alkylated dihydroxy-
naphthalene sulpho acid, and one molecular proportion of another dye-stuff
component. My foreign correspondents understand by "amines or substituted
amines" which are employed as middle components in this Specification, all such
amido compounds, as can further be diazotised after having been combined with
diazo or tetrazo salts, such as aniline, toluidine, xylidines, cresidines, and analogues
thereof, or substitution products thereof, alphanaphthylamine amidonaphthols,
amidonaphtholethers, alphanaphthylamine betamonosulpho. acids (Cléve's ẞ or
acid), amidonaphtholsulpho acids, amidonaphtholether sulpho acids, amidonaphth-
oxyacetic acid, amidonaphthoxyacetic sulpho acid.
If the tetrazo salts are combined with one molecular proportion of an "amine or
substituted amine," intermediate products result, which still contain one free amido
group, and after diazotising again, can be coupled either with two molecular
proportions of the same alkyloxynaphtholsulpho acid, or with one molecular
proportion of the one alkyloxynaphtholsulpho acid, and one molecular proportion
of another alkyloxynaphtholsulpho acid, or at first with one molecular proportion of
an alkyloxynaphtholsulpho acid, and then with one molecular proportion of an
amine, a phenol, an amidophenol, amidophenolether of the benzene or naphthalene
series, a sulpho or carboxylic acid of these components, or, inversely, at first with
one molecular proportion of an amine, a phenol, and the like, and then with one
molecular proportion of an alkyloxynaphtholsulpho acid. In this manner, trisakis
azo dye stuffs result, which contain three proportions of the azo group
(N = N―).
The process for producing these trisakis azo dye stuffs is illustrated by the
COLORING
MATTER FROM ONE MOLECULAR PROPORTION OF TETRAZO-
DIPHENYLCHLORIDE, ONE MOLECULAR PROPORTION OF ALPHANAPHTHYL-
AMINE BETAMONOSULPHO ACID (CLÉVE'S -ACID), AND TWO MOLECULAR
PROPORTIONS OF ETHOXYNAPHTHOLDISULPHO ACID.
The solution of tetrazodiphenylchloride obtained in the usual manner from
18.4 parts (the parts are by weight) of benzidine, or the corresponding quantity of
a salt of benzidine, is allowed to flow slowly into a cold solution of 24.5 parts of
the sodium salt of Cléve's alphanaphthylamine-betamonosulpho acid 8, and 50 parts
of sodium acetate. When the formation of the intermediate product having the
formula:-
is complete, this intermediate product is further diazotised by adding a concentrated
solution, in water, of 7 parts of sodium nitrite, and subsequently adding muriatic
acid, until the liquid shews a moderately lasting acid reaction. The diazotation being
finished, the resulting mixture is introduced into a watery solution containing 4
25 parts of sodium acetate and 78-4 parts of a, ethoxy-a-naphthol B, B,-disulphonate
of sodium. The formation of the dye stuff is complete within a few hours. It is

page_text: isolated in the usual manner by salting out, filtering off, pressing, and drying. Its
composition corresponds to the following formula:
OCH
It produces bluish black shades on unmordanted cotton in an alkaline soap bath.
The analogous trisakis azo coloring matters result, if, in the preceding example,
the a ethoxy-a-naphthol-33, disulpho acid is replaced by the corresponding
quantities of other alkyloxynaphthol sulpho acids, or if, on the other hand, the
alphanaphthylaminebeta mono sulpho acid (Cléve's 8 acid) is replaced by the
isomeric acid, or by the corresponding quantities of alphanaphylamine, amido
naphthols, amidonaphtholethers, amido, naphtholsulpho acids, amidonaphtholether
sulpho acids, amidonaphthoxyacetic acid, amidonaphthoxy acetic sulpho acid,
aniline, toluidine, xylidine, cresidine, or, in general, by such amido compounds as
can be further diazotised after the combination with diazo compounds, and have
hereinbefore been briefly termed "amines or substituted amines."
Of course, the above intermediate products from equal molecular proportions of
diamines and "amines or substituted amines," after diazotation, can be coupled in
any order with one molecular proportion of an alkyloxynaphtholsulpho acid, and
one molecular proportion of another alkyloxynaphthol sulpho acid, or with one
molecular proportion of an alkyloxynaphthol sulpho acid, and one molecular
proportion of another dye stuff component. The process also is effected in the
same manner as described in the last example, if benzidine is replaced by other
diamines.
The dye stuffs thus obtained in general produce from bluish black to
shades on unmordanted cotton.
pure black
Analogous products (so called trisakisazo dye stuffs) result, if one molecular
proportion of a tetrazo salt is combined, at first, with one molecular proportion of .
a phenol, naphthol, sulpho, or carboxylic acid thereof, and if the so-formed inter-
mmediate products are coupled with one molecular proportion of an
"amine or
substituted amine," and, after diazotising again, is combined with one molecular
proportion of an alkyloxynaphtholsulpho acid. Of course, the tetrazo salts of
diamines, inversely, can be combined, at first, with one molecular proportion of an
alkyloxynaphtholsulpho acid, then with one molecular proportion of an "amine or
substituted amine," and the resulting tetrazo dye stuffs, after diazotising again,
can be combined with one molecular proportion of one of the usual dye stuff
components.
The process for producing these last-named coloring matters (trisakisazo dye
stuffs) is analogous to that illustrated by the foregoing last example.
The alkyloxynaphtholsulpho acids herein before defined, can further be employed
for the production of new valuable azo dye stuffs (tetrakisazo coloring matters).
The latter result by employing intermediate products from one molecular proportion
of a tetrazo salt, either with two molecular proportions of an "amine or substituted
amine,” or with one molecular proportion of another “amiue or substituted amine,"

page_text: by diazotising these intermediate products, and combining with two molecular
proportions of alkyloxynaphtholsulpho acids (employing the same or two different
ones), or with one molecular proportion of an alkyloxynaphtholsulpho acid, and
one molecular proportion of another dye stuff component, or, inversely at first with
an amine, a phenol, or the like dye stuff' components, and then with an alkyloxy-
naphthol sulpho acid (likewise employing equal molecular proportions thereof).
The production of these dye stuffs, which contain four proportions of the azo
group (N=N-), and therefore are termed tetrakisazo dye stuffs, is illustrated
by the following example. The parts are by weight.
DYE STUFF FROM ONE MOLECULAR PROPORTION OF TETRAZODIPHENYL-
CHLORIDE, TWO
PROPORTIONS. OF ALPHA AMIDO BETA-
NAPHTHOLETHERBETA MONO SULPHO ACID, AND TWO MOLECULAR PRO-
MOLECULAR
PORTIONS OF a₁-ETHOXY-a-NAPHTHOL ẞ, ß-DISULPHO ACID.
184 parts of benzidene are converted, in muriatic solution, into the tetrazo
chloride by means of 14 parts of sodium nitrite, and the resulting solution. of
tetrazodiphenyl chloride is allowed to flow into a weak acetic acid solution, or
alkaline solution, of 53-4 parts of alphaamidobetanaphtholether betamonosulpho
acid. The mixture is heated for several days at 50 degrees, and finally, for a short
time, at 90 degrees centigrade. After rendering alkaline (that is to say, in case
the combination be effected in acid solution), the intermediate product is isolated
by salting out, filtering off, and pressing. This intermediate product is stirred with
a concentrated watery solution of 14 parts of sodium nitrite, and converted into its
tetrazo compound, by slowly acidulating with muriatic acid. The tetrazo chloride
is filtered off after 24 hours, and then introduced into a watery solution of 25 parts
of sodium carbonate and 78.4 parts of a₁-ethoxy-a-naphthol-ß, B-disulpho acid.
In order to complete the reaction, the mixture is heated for a short time at
90 degrees centigrade, and the dye stuff is isolated by salting out, filtering off,
pressing, and drying.
Its composition corresponds to the following formula :-
The dye stuff produces bluish black shades on unmordanted cotton.
The other tetrakisazo dye-stuffs are obtained in manner analogous to that
described in the last named example, if, on the one hand, the two molecular proportions
employed of a-ethoxy-a-naphthol-B, B-disulpho acid, are replaced by two molecular 35
proportions of other alkyloxynaplitholsulpho acids, or by one molecular proportion
of the one, and one molecular proportion of another, alkyloxynaphtholsulpho acid,

page_text: or by one molecular proportion of an alkyloxynaphtholsulpho acid, and one
molecular proportion of another dye stuff component, or, inversely, by employing,
at first, one molecular proportion of a dye stuff component, and then one molecular
proportion of an alkyloxynaphtholsulpho acid, or if, on the other hand, in place of the
two molecular proportions of amidonaphtholethersulpho acids employed as middle
components, two molecular proportions of other amidonaphtholethersulpho acids,
or, in general, two molecular proportions of "amines or substituted amines
used (employing the same "amine or substituted amine" or two different ones), or
if, finally, the benzidene above employed is replaced by the corresponding quantities
of other diamines or substitution products thereof.
"
are
The coloring matters thus obtained in general yield from bluish black, greenish
black, to pure black shades.
Valuable direct dyeing coloring matters further result, if the alkyloxynaphthol-
sulpho acids hereinbefore defined are combined with the diazo derivatives of such
amido-azo products as are obtained by diazotising the so-called thio condensation
products from paratoluidene, metaxylidine, pseudo cumidine, or analogous thio
amides, or sulpho derivatives thereof, & combining the resulting diazo compounds
with "amines or substituted amines." Amongst the so-called thio condensation
products, the following can be employed, viz. dehydro thio paratoluidine, melting
at 191 degrees centigrade, and obtainable by heating paratoluidine with sulphur;
dehydrothiometaxylidine and dehydrothio pseudocumidine, which can be obtained in
an analogous manner by heating, with sulphur, metaxyliḍine or pseudocumidine;
the so-called primuline base which is formed, for instance, together with dehydro-
thioparatoluidine by heating with sulphur, paratoluidine, and which can be used
either as raw product or in an isolated state.
However, other thio amides (such as the products known in commerce as
chromine, polychromine, thiochromogene, and the like), and the sulpho derivatives
of all these thio amides, can likewise be employed.
These coloring matters are obtained by combining the diazo derivatives of the
thio amides bereinbefore defined, or sulpho acids thereof, with "amines or
substituted amines," further diazotising the resulting amido azo products, and
coupling the so-formed diazo compounds with alkyloxynaphtholsulpho acids.
The process for producing these coloring matters is analogous to that which my
foreign correspondents have described for the production of analogous dye stuff's
derived from thio bases in the Specification of application for Letters Patent
No. 11,533.
My foreign correspondents have further employed the alkyloxynaphtholsulpho
acids herein before defined for the production of diazo coloring matters suitable for
dyeing black shades on wool in acid baths. These diazo dye stuffs result from
coupling the alkyloxynaphtholsulpho acids with the diazo derivatives of those
amido azo products which can be obtained by the combination of diazotised amines,
amido phenols, amido phenolethers of the benzene or naphthalene series, or the
diazo compounds of the substitution products thereof (especially sulpho- or
carboxylic acids thereof) with "amines or substituted amines."
The process for producing these disazo dye stuffs is effected in the usual manner,
viz., by diazotising aniline, toluidine, or the like, coupling the resulting diazo
products with an "amine or substituted amine," diazotising again the so-formed
amido azo compounds, and combining the thus obtained diazo azo products with
alkyloxynaphtholsulpho acids.
Of course, in the latter process, amido mono-alkylaniline, amido dialkylaniline,
analogous diamines alkylated in the one amido group, sulpho derivatives of such or
The monoacetyl
similar alkylated diamines, can be used as first components.
derivatives of para phenylene diamine, naphthylene diamines, analogous diamines or
substituted diamines, or sulpho acids of such or similar diamines, can likewise be
employed in the first place. If mono acetylised diamines are used, acetylised disazo
colouring matters result which can be treated in a suitable manner, in order to split
off the acetyl group. On employing mono nitro amines as first components (such as
B

page_text: nitro aniline, nitro naphthylamine, sulpho acids of nitro amines), nitro disazo dye
stuffs are obtained which can further be changed into the corresponding amido dye
stuffs by a subsequent reduction.
The alkyloxynaphtholsulpho acids also yield valuable dye-stuffs by combining
with diazo compounds. Such simple azo colouring matters, capable of dyeing wool
in acid baths, are produced by the combination of alkyloxynaphtholsulpho acids
with diazotised amines, amidophenols, amido phenol ethers of the benzene or
naphthalene series, or with the diazo derivatives of sulpho or carboxylic acids of
amines, amidophenols, amidophenolethers of the benzene or naphthalene series. In
order to produce these mono azo dye stuffs, amido monoalkylanilines, amido dialkyl-
anilines, analogous diamines alkylated in the one amido group, substitution products
of such or similar alkylated diamines can likewise be used. The mono-acetylised
diamines (such as mono-acetylphenylene diamine, mono-acetyl naphthylene diamine),
and substitution products of monoacetyldiamines can also be used; in this case,
acetylised monoazo dye stuffs result which can be changed into the corresponding
amido dye stuffs by a subsequent treatment, in order to separate the acetyl group.
If the diazo compounds of mono-nitro amines, or substituted mono-nitro amines, are
coupled with alkyloxynaphtholsulpho acids, nitro mono azo dye stuffs result, which
yield amido dye stuffs on the further reduction.
The production of the said monoazo dye stuffs, capable of dyeing wool, is
effected in the usual manner, and the shades obtained by means of these colouring
matters are different according to the amines employed.
Very valuable mono azo dye stuffs, suitable for dyeing unmordanted cotton, have
been prepared by my foreign correspondents, by combining with the alkyloxy-
naphtholsulpho acids, the diazo derivatives of the thioamides hereinbefore defined
(such as dehydrothioparatoluidine and the like), and sulpho acids thereof. The
azo colouring matters thus obtained, which produce from blue to bluish red shades
on unmordanted cotton, easily "strike on the unmordanted cotton fibre, and yield
shades excellent for their beauty and fastness against the action of acids and
alkalies.
"
The combination of the diazotised thio bases, or sulpho acids thereof, with the
mono alkyloxynaphthol sulpho acids herein before specified, is effected most
practically in soda-alkaline solution.
In order to illustrate the production of these latter dye stuffs, the following
example is given, the parts being by weight :-
DYE-STUFF FROM
:-
SIXTH EXAMPLE.
DEHYDROTHIOPARATOLUIDINE AND
DISULPHO ACID.
ETHOXYNAPHTHOL-
24 parts of dehydro thio paratoluidine (melting at 191 degrees centigrade) are,
as sulphate, diazotised by means of 7 parts of sodium nitrite at from 30 to 40 degrees
centigrade, and the resulting diazo compound is introduced into a solution prepared
by dissolving sodium carbonate and 39 parts of the sodium salt of ethoxynaphthol-
disulpho acid (obtainable by treating, with ethylhaloids, the a, a, dihydroxy-
naphthalene BB, disulpho acid or its salts) in a sufficient quantity of water. The
formation of the dye-stuff begins immediately and is complete after a short time.

page_text: The analogous dye stuffs result if, in the foregoing sixth example, on the one
hand, the diazo compound of dehydrothioparatoluidine is replaced by the
corresponding quantities of the diazo derivatives of the other thioamides, or sulpho
acids thereof, or if, on the other hand, the a, ethoxy a naphthol ẞ, ẞ, disulpho
acid is replaced by equivalent quantities of other alkyloxynaphtholsulpo acids
hereinbefore defined.
My foreign correspondents have described in the foregoing examples (two, three,
four, five, and six) distinct methods, by means of which the new dye stuffs can be
prepared. Of course, they do not limit themselves to the proportions given in the
said examples. The methods described can also be varied, and all those methods
in use for the production of analogous dye stuffs can also be employed.
Deted this 16th day of February 1802
NEWTON & SON,
Agents for the Applicant.
COMPLETE SPECIFICATION.
The Manufacture or Production of Alkylated Hydroxynaphthalene
Sulphonic Acids and Colouring Matters therefrom.
I HENRY EDWARD NEWTON of The Office for Patents, 6 Breams 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 found that, by the action of alkylhaloids, or
salts of alkylsulphuric acids, or other alkylating agents, on the basic salts
of as a dihydroxynaphthalenemonosulphonic acids,, or a, a, dihydroxynaphthalene-
....1.

page_text: My foreign correspondents have also prepared the monoalkylhydroxynaphthol
sulphonic acids by treating the free dihydroxynaphthalenesulphonic acids with
alkylating agents in the presence of alkalies.
My foreign correspondents understand by "M" in the formnlæ. above given, an
alkali metal, alkali earth metal, or the like.
The production of such alkylhydroxynaphtholsulphonic acids proceeds; for
example, in a satisfactory manner, if the following a, a, dihydroxynaphthalene-
sulphonic acids are used, riz., alpha, alpha, dihydroxynaphthalene alphamono-
sulphonic acid (obtainable from alphanaphthol deltadisulphonic S. of the German
Patent No. 40571, by fusing this acid or its salts with alkalies), alpha alpha
dihydroxynaphthalenebet adisulphonic acid (which can be obtained by fusing with
alkalies the naphtho sultone disulphonic acid of the German Patent No. 56058, or
salts thereof).
The nomenclature of the dihydroxynaphthalenesulphonic acids, and alkylhydroxy-
naphtholsulphonic acids derived therefrom, referred to in this Specification, is based
on the following scheme, viz. :—
PRODUCTION OF ETHOXYNAPHTHOLDISULPHONIC ACID FROM ALPHA ALPHA
DIHYDROXYNAPHTHALENE BETA, BETA, DISULPHONIC ACID.
1 molecular proportion of the acid sodium salt of alpha, alpha, dihydroxy-
naphthalene beta, beta, disulphonic acid (so-called chromotrop acid) is heated with
lime, in order to convert it into the basic acid. The resulting solution is heated,
together with one molecular proportion of ethyl bromide, during about 8 hours, at
about 105 degrees centigrade in a salt bath. The resulting alpha, ethoxy alpha
naphthol beta, beta, disulphonic acid thus produced, separates from the liquid, as
it cools, in the form of sodium calcium salt, the unaltered chromotrop acid remaining
dissolved. The salt is filtered off, pressed, and dried. It is derived from the acid of
the formula-
the interaction.
The other monoalkyloxynaphthol sulphonic acids derived from alpha, alpha
dibydroxynaphthalene beta, beta, disulphonic acid, are obtained in a manner
analogous or similar to that described in the above first example,

page_text: In place of ethyl bromide, the corresponding quantities of other ethyl haloids, or
an ethyl sulphate, or similar ethylating agent, can be used.
If, instead of the ethyl bromide used in the above example, the corresponding
quantity of the bromide of methyl, propyl, butyl, amyl, or similar alkyl radicles of
the fatty series, or another haloid compound of such alkyls (inclusive of the benzyl
haloids), or by the corresponding quantity of alkylsulphuric salt, or if other
alkylating methods are used, the monomethoxy-, monopropoxy-, monobutoxy-,
monomyloxy-, monobenzyloxynaphtholsulphonic acids, or the salts of these acids,
are obtained.
CONVERSION OF ALPHA₁ ALPHA DIHYDROXYNAPHTHALENE ALPHA MONO-
SULPHONIC ACID INTO ETHOXY NAPHTHOL ALPHA MONOSULPHONIC
ACID.
Two molecular proportions of the acid sodium salt of alpha, alpha, dihydroxy-
naphthalene alphamonosulphonic acid, together with one molecular proportion of
dry potassium carbonate, are dissolved in water. Two molecular proportions of
ethylbromide are then added to the solution, and the mixture is heated, during
about 8 hours, at about 105 degrees centigrade. The alkaline salt of the ethoxy-
naphthol alpha monosulphonic acid (so-called acid I) separates from the liquid, as
it cools, in the form of colorless needles, which are filtered off. On adding common
salt to the filtrate, the alkaline salt of an isomeric ethoxynaphthol alphamono-
sulphonic acid (so-called acid II) is precipitated. This salt forms colorless scales,
which are readily soluble in water.
If common salt be directly added to the crude product, a mixture of the alkaline
salts of the two acids I and II is obtained.
Each of these two acids is represented by one or other of the following
formule
It is noteworthy that on alkylating the alpha, alpha, dihydroxynaphthalene
alphamonosulphonic acid, or salts thereof, two isomeric alkyloxynaphtholalphamono
sulphonic acids, or salts thereof, are obtained, whilst the alpha, alpha, dihydroxy-
naphthalene beta, beta, disulphonic acid (alpha, alpha, dihydroxynaphthalene-
betadisulphonic acid), or the salts thereof, yield but a single alkyloxynaphtholbeta-
disulphonic acid.
In order to produce dye-stuffs, the salts of the two isomeric alkyloxynaphthol-
monosulphonic acids derived from alpha, alpha, dihydroxynaphthalene alphamono
sulphonic acid, can be used, either separate or in admixture. My foreign
correspondents simply employ the mixture thereof.
My foreign correspondents have also found that, on benzlating the above alpha,
alpha, dihydroxynaphthalene sulphonic acids, or salts thereof, benzyloxynaphthol-
sulphonic acids, and dihydroxynaphthalene sulphonic benzylether, are formed
simultaneously, and that sometimes the said dihydroxynaphthalene sulphonic benzyl-
ether by far exceeds in amount the alkyloxynaphtholsulphonic acid.
The treatment of alpha, alpha, dihydroxy naphthalene beta, beta, disulphonic

page_text: THIRD EXAMPLE.
PRODUCTION OF ALPHA BENZYLOXY ALPHA, NAPHTHOL BETA, BETA,
DISULPHONIC ACID.
20 parts of the acid sodium salt of alpha, alpha, dihydroxynaphthalene beta,
beta, disulphonic acid, together with 4 parts of potassium carbonate, are dissolved
in water, and after adding 7 parts of benzylchloride, the mixture is heated at from
80 to 100 degrees centigrade, being kept constantly stirred until the benzylchloride
is no longer distinguishable. The alpha, benzyloxy alpha, naphthol beta, beta,
disulphonate of sodium separates when the resulting solution is saturated with
common salt, the sodium salt of the alpha, alpha, dihydroxynaphthalene beta,
sulphonic monobenzylether beta, sulphonic acid formed during the operation
remaining dissolved. The latter acid can be precipitated in the form of barium
salt, by adding barium chloride to the filtrate (obtained after filtering off the
precipitated sodium salt of benzyloxynaphtholdisulphonic acid), and by subsequently
boiling the resulting solution.
In the above examples, my foreign correspondents have described merely several
distinct practical methods of converting alpha, alpha, dihydroxynaphthalene-
sulphonic acids into the corresponding alkyloxynaphthol sulphonic acids. The
proportions above given can be varied. In place of the acid sodium salt, the
corresponding quantities of other acid alkaline salts can be used, and the conversion
of the acid salts into the basic salts can be effected by means of alkalies other than lime
(calciumhydroxide), or potassium carbonate. The dihydroxynaphthalene sulphonic
acids can also be directly subjected to the action of the alkyl haloids, alkyl sulphuric
salts, or other alkylating agents, in the presence of alkalies. The action may also
be effected at a somewhat higher temperature, and the formation of the alkylated
acids is generally completed within a shorter time under such conditions. Such or
similar modifications easily follow from the directions given in the preceding
examples, and it is not necessary to refer to these variations more in detail.
The researches of my foreign correspondents have shown that the alkyloxy-
naphtholsulphonic acids can be used advantageously for the production of azo dye
stuffs, and they therefore propose to employ these new acids for such purposes.
Disazo coloring matters distinguished on account of the beauty and intensity of
their shades, and superior, to the dye-stuffs from naphthol or dihydroxynaphthalene-
sulphonic acids, as they are capable of dyeing both cotton and wool, are obtained
by combining the tetrazo derivatives of "benzidine, the analogues and homologues
thereof," with the monoalkyloxynaphtholsulphonic acids.
By "benzidine, the analogues and homologues thereof," my foreign correspondents
understand, for example, the following substances, viz.:-benzidine, tolidine,
diamidophenyltolyl, diamidodiphenolether, diamidoalkyloxydiphenyl, diamidoalkyl-
oxyphenyltolyl, diamidoazobenzene, diamidoazotoluene, diamidoazoxylene, diainido-
azoxybenzene, diamidoazoxytoluene, diamidostilbene, diamidofluorene, diamido-
naphthalene, diamidocarbazol, diamidodiphenylene oxide, diamidotoluylene oxide,
paraphenylene diamine, toluylene, diamine, benzidene sulphone, tolidine sulphone,
diamidophenyltolyl sulphone, diamidodiphenoxyacetic acid, diamidodiphenylene
ketoxine, diamido phenylbenzimidazol, amido benzene, (-toluene, -xylene) azo-
alpha-naphthylamine, amido benzene (-toluene, -xylene) azoparaxylidine, amido
benzene (-toluene, -xylene) azometaamidoparacresolether, amido benzene (-toluene,
-xylene), azorthamidoparacresol ether, amido benzene (-toluene, -xylene) azobeta-
ethoxyalphanaphthylamine, the sulphonic or carboxylic acids thereof.
Similar diamines, or diamine sulphonic acids of the benzene or naphthalene series,
however, which can be converted into their tetrazo salts, either directly, or by
means of their monacetyl derivatives, can also be used. The corresponding mono->
nitramines can be used in place of monacetylated diamines, in which case the

page_text: nitroazo products which are first formed must be reduced, and the resulting amido-
azo compounds again diazotised, while the monacetyl amidoazo compounds which
result on using monacetylated diamines, are treated in a suitable manner, in order
to split off the acetyl group, and the amido azo compounds so produced are again
diazotised, and further combined with dye-stuff components.
The combination of the diazo or tetrazo derivatives of the above diamines, with
the alkyloxynaphtholsulphonic acids hereinbefore defined, is most advantageously
effected in solutions containing sodium carbonate.
The process of producing these new tetrazo dye-stuffs is in general analogous to
that which my foreign correspondents have described for the manufacture of
coloring matters from unalkylated dihydroxynaphthalene sulphonic acids, for
example, in the Specifications of the following Letters Patent, viz., No. 136658,
3397, 134430, and 5984".
In order to illustrate the mode of producing these coloring matters more in
detail, the following example is given. The parts are by weight.
DYE STUFF OBTAINED FROM ONE MOLECULAR PROPORTION OF DIANISIDINE
AND TWO MOLECULAR PROPORTIONS OF ALPHAL ETHOXY ALPHA NAPHTHOL
ALPHA MONOSULPHONIC ACID.
34-2 parts of the sulphate of diamido. diphenol dimethylether, or the corre-
sponding quantity of another salt of dianisidine, together with 30 parts of
muriatic acid (20 degrees Beaumé), are suspended in a finely divided state in
500 parts of water, and a solution of 13-8 parts of sodium nitrite in 150 parts of
water is then stirred in. The resulting solution of tetrazodiphenolether is allowed
to flow into a solution (rendered alkaline with sodium carbonate) of 58 parts of the
sodium salt of alpha, ethoxy alpha naphthol alpha monosulphonic acid (using the
mixture of the salts of the two alpha, ethoxy alpha, naphtholalphamonosulphonic
acids obtainable as described in the above second example). The formation of the
dye stuff begins at once, and is complete within a short time. The dye stuff thus
produced is then salted out by adding common salt, filtered off, pressed, and dried.
On unmordanted cotton it produces blue shades which withstand the action of
alkalies. Its composition is represented by the following formula :-
OCH
SO,Na.
The analogous "symmetrical" coloring matters are obtained in the same manner,
or in a manner similar to that described in the preceding fourth example, if, on
the one hand, instead of the diamido diphenol dimethylether used in the said
example, the corresponding quantities of other diamidodiphenolethers, or another of
the above named diamines, sulphonic or carboxylic acids thereof, be used; or if, on
the other hand, instead of the alpha, ethoxy alpha, naphthol alpha mono sulphonic
acid, the equivalent quantity of another mono-alkylated dihydroxy naphthalene
sulphonic acid be used.
Symmetrical coloring matters are obtained in this manner, which chiefly yield

page_text: reddish violet, violet, and, for the most part blue shades of great fastness, in presence
of alkalies. Amongst these dye stuffs, those obtained by means of alpha, alkyloxy
alpha, naphtholsulphonic acids are especially remarkable on account of the
readiness with which they dye the fibre, producing beautiful shades both on ordinary
and chromated wool, which withstand fulling.
The production of "symmetrical" disazo dye stuffs from monaceto diamines is
illustrated by the following example. The parts are by weight.
COLORING MATTER FROM ACETPARAPHENYLENE DIAMINE AND ALPHA1
ETHOXY ALPHA NAPHTHOL BETA, BETA, DISULPHONIC ACID.
15 parts of acetparaphenylene diamine are dissolved in 200 parts of water,
together with 45 parts of muriatic acid (21 degrees Baumé). The resulting
solution is cooled by ice, and slowly mixed with a solution, in water, of 7 parts of
sodium nitrite. The formation of the diazo compound is completed after about an
hour. The diazo compound is then added to a well cooled solution containing
39 parts of the disodium salt of alpha, ethoxy alpha, naphthol beta, beta, disul-
phonic acid rendered alkaline by means of sodium carbonate. When the formation
of the intermediate product is complete, the latter is filtered off. It has the
composition represented by the formula :-
SO,Na
This intermediate product is mixed with about 300 parts of. water and 60 parts
of soda lye (35 degrees Baumé), and the mixture is heated to boiling, and kept at
this temperature until the acetyl group is split off. The liquid having cooled, a
slight excess of muriatic acid is added, and the amido benzene azo product is then
diazotised in the usual manner by means of 7 parts of sodium nitrite. The finished
diazo product is introduced into a solution prepared by dissolving 39 parts of alpha1
ethoxy alpha, naphthol beta, beta, disulphonate of sodium in water, and which has
been rendered alkaline by means of sodium carbonate. The formation of the
dye-stuff is complete at the end of several hours. The dye stuff is then salted out,
filtered off, pressed, and dried. It produces on unmordanted cotton, greyish blue
shades, which withstand the action of alkalies, and is represented by the following

page_text: The foregoing fifth example is typical of the method of producing "symmetrical'
tetrazo dye stuffs from alkyloxynaphtholsulphonic acids by means of monaceto
diamines. My foreign correspondents, however, do not limit themselves to the
directions given, as these can be varied, for instance, the separation of the acetyl
group can also be effected by heating the acetylamido azo product with acids.
My foreign correspondents have ascertained that the coloring matter obtainable
as described in the above fifth example, can also be produced by diazotising one
molecular proportion of paranitraniline, coupling the resulting diazoderivative with
one molecular proportion of alpha-ethoxy-alpha, naphthol-beta, beta, disulphonic
acid, or a salt thereof, reducing the nitro-azo product thus formed, diazotising the
resulting amidoazo product, and subsequently coupling the diazo azo compound with
one molecular proportion of alpha, ethoxy-alpha, naphthol beta, beta, disulphonic
acid, or a salt thereof.
The production of "symmetrical" disazo dyestuffs derived from other aceto-
diamines, or mononitramido coinpounds of the benzene or naphthalene series, or from
sulphonic acids thereof, is effected in an analogous manner.
According to the researches of 'my foreign correspondents, the tetrazoderivatives
of the diamines herein before defined; can be combined not only with two molecular
proportions of monoalkylated alpha, alpha, dihydroxynaphthalene sulphonic acids,
but also with one molecular proportion of these monoalkyloxynaphtholsulphonic
acids. In the latter case, intermediate products are formed containing one free
amido group, and which therefore can be further combined with one molecular
proportion of a phenol, an amine, a diamine, an amidophenol, an amidophenolether
of the benzene or naphthalene series, a sulphonic or carboxylic acid thereof.
The production of these intermediate products, and of "mixed" colouring matters
in general, is effected by combining one molecular proportion of a tetrazo compound
with one molecular proportion of a monoalkylated dihydroxynaphthalene sulphonic
acid, the so called intermediate products being formed, which may then be coupled
with one molecular proportion of a phenol, an amine, a diamine, or another dye-
stuff component, or, inversely, by combining one molecular proportion of a tetrazo
salt, at first with one molecular proportion of a phenol, an amine, or the like, and
then with one molecular proportion of a monoalkylated dihydroxynaphthalene
sulphonic acid.
The combination of the said components, with the tetrazo compounds, or with
the said intermediate products, may be effected in acid solution (for example, in
the presence of acetic or muriatic acid or the like), or in alkaline solution, but
amines are best coupled in acid solutions, whilst phenols are more advantageously
combined in alkaline solution. The alkylated dihydroxynaphthalene sulphonic-
acids are best coupled either in a solution containing sodium carbonate, or in
solutions containing sodium acetate.
The formation of these "mixed"
example, the parts being by weight:
dye-stuffs is illustrated by the following
COLOURING MATTER RESULTING FROM EQUAL MOLECULAR PROPORTIONS or
DIANISIDINE, ALPHA NAPHTHOL ALPHA MONO-SULPHONIC ACID (1:4),
AND ALPHA ETHOXY-ALPHA, NAPHTHOL ALPHA MONOSULPHONIC ACID.
244 parts of dianisidine are converted, in the usual way, into the tetrazo com-
pound; the resulting solution of the tetrazo salt is mixed with such a quantity of
water, that the volume is 700 litres (in case the parts are kilos. by. weight), and the
mixture is allowed to flow into a solution prepared by dissolving 24.6 parts of the
sodium salt of alphanaphthol alpha-mono sulphonic acid (1:4), and 30 parts of
sodium acetate, in 500 parts of water.
The formation of the intermediate product begins within a short time, and is
complete at the end of about 4 or 5 hours. It separates in voluminous dark flakes.
с

page_text: 32 parts of the neutral sodium salts of alpha, ethoxy-alpha-naphthol alpha mono-
sulphonic acid and 12 parts of ignited sodium carbonate are added. The production
of the colouring matter slowly proceeds, and may, with advantage, be advanced by
heating. After 24 hours, the colouring matter is filtered off and dried. It
produces blue shades on unmordanted cotton, and is represented by the following
formula :-
The analogous "mixed products are formed, if, in the last example, the corre-
sponding quantities of other analogous or homologous diamines be used in place of
dianisidine, or if, in place of alpha-naphtholalphamono sulphonic acid (14), the
equivalent quantities of an amine, a diamine, an amidophenol, an amidophenolether
of the benzene or naphthalené series, a sulphonic or carboxylic derivative of these
components, be used, or if, instead of the alpha, alkyloxy alpha, naphthol alpha
monosulphonic acid, the corresponding quantities of other alkyloxynaphtholsulphonic
acids, or salts thereof, be taken. It does not matter, in what order the two
different components are combined.
The intermediate products formed from one molecular proportion of a tetrazo
compound, and one molecular proportion of an alkylated dihydroxy-naphthalene
sulphonic acid, can likewise be combined with one molecular proportion of another
alkylated dihydroxynaphthalene sulphonic acid.
Mixed disazo dye-stuffs derived from alkyloxynaphtholsulphonic acids can also
be obtained from monacetodiamines, mononitramines of the benzene or naphthalene
series, or sulphonic acids thereof.
The production of these dyestuffs is analogous to the herein before defined
production of the symmetrical disazo dye-stuffs obtainable from monaceto diamines,
mono-nitramines of the benzene or naphthalene series, or sulphonic acids thereof.
The following table is given in order to illustrate the variety of colouring
matters obtainable by means of the process herein before defined, and the shades
produced by these dyestuffs.
In the first column of this table, the different components of some "symmetrical "
and "mixed" colouring matters of this new series are indicated, the shades

page_text: =
amidobenzeneazoalpha-naphthylamine + molecular propor-
tion of alpha ethoxy alpha,-naphthol alpha-mono-
sulphonic acid + 1 molecular proportion of alpha-
naphthol alpha, mono-sulphonic acid
bluish
grey
Very valuable monazo dye-stuffs, suitable for dyeing unmordanted cotton, have
been prepared by my foreign correspondents by combining with the alkyloxy-
naphtholsulphonic acids, the diazo derivatives of the so-called thio condensation
products from para toluidine, metaxylidine, pseudocumidine, or analogous thio
amido compounds, or sulphonic derivatives thereof. The following of these
so-called thio condensation products can be thus used, viz:-dehydrothio-para-
toluidine (melting at 191 degrees centigrade, and obtainable by heating para-
toluidine with sulphur), dehydrothiometaxylidine, and dehydrothio pseudo cumidine.
(which can be obtained in an analogous manner by heating metaxylidine or pseudo
cumidine with sulphur), the so-called primuline base which is formed together with
dehydrothio-para-toluidine, by heating paratoluidine with sulphur, and which can
be used either in its crude or purified state. But other thio amido products (such
as the products known in commerce as chromine, polychromine, thiochromogene,
and the sulphonic derivatives of all these thio amido products, can also be used,
the azo colouring matters thus obtained, which produce chiefly bluish-red shades on
unmordanted cotton, and easily "strike" on unmordanted cotton fibre, yielding
shades which are excellent on account of their beauty and their fastness in presence
of acids and alkalies.
The combination of the diazotised thio bases, or sulphonic acids thereof, with the
monoalkyloxynaphthol sulphonic acids hereinbefore specified, is most practically
effected in a solution rendered alkaline with sodium carbonate.
In order to illustrate the production of these thio dye-stuffs, the following
example is given, the parts being by weight :—

page_text: primuline base +1 molecular proportion of alpha, ethoxy
alpha, naphthol beta, beta, disulphonic acid
bluish roset
dehydrothiopseudo cumidine + 1 molecular proportion of
alpha benzyloxy-alpha, naphthol beta, beta, disul-
phonic acid
dark bluish-red
In the foregoing examples (four, five six, and seven), my foreign correspondents
have described distinct methods by means of which the new dye-stuffs can be
prepared, but, they do not limit themselves to the directions given in the said
examples. The methods described can also be varied, and all the methods in use
for the production of analogous dyestuffs can be employed.
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 salts of alkyloxynaphtholsulphonic acids, by treating the
neutral or basic salts of alpha, alpha, dihydroxynaphthalenesulphonic acids with
alkylhaloids, alkylsulphuric salts, or other alkylating agents, or by treating the
free alpha, alpha, dihydroxynaphthalene sulphonic acids, in the presence of alkalies,
with alkylhaloids, alkylsulphuric salts, or other alkylating agents.
2. The process for producing salts of two isomeric alpha, methoxy alpha
naphthol alpha monosulphonic acids, by treating the neutral or basic salts of alpha,
alpha, dihydroxynaphthalene alpha monosulphonic acid with methylhaloids, or
methylsulphuric salts, or by treating the free alpha, alpha, dihydroxynaphthalene
alpha monosulphonic acid, in the presence of alkalies, with alkylhaloids or

page_text: alkylsulphuric salts, subsequently isolating the salts of the resulting two
isomeric methoxy naphthol alphamonosulpho acids, or not, as may be desirable.
3. The production of salts of two isomeric alpha, ethoxy-alpha, naphthol alpha
monosulphonic acids, by treating the neutral or basic salts of alpha, alpha,
dihydroxynaphthalene alpha mono sulphonic acid, with ethylhaloids or ethyl
sulphuric salts, or by treating the free alpha, alpha, dihydroxynaphthalene alpha
monosulphonic acid, in the presence of alkalies, with ethylhaloids or ethylsulphuric
Balts, subsequently isolating the salts of the resulting two isomeric ethoxynaphthol
alpha monosulpho acids, or not, as may be desirable.
4. The process for producing salts of alpha, methoxy alpha, naphthol, beta,
beta, disulphonic acid, or alpha, ethoxy alpha, naphthol beta, beta, disulphonic
acid, by treating the neutral or basic salts of alpha, alpha, dihydroxynaphthalene
beta, beta, disulphonic acid, or by treating the free alpha, alpha dihydroxy-
naphthalene beta, beta, disulphonic acid, in the presence of alkalies, with methyl-
haloids, or methylsulphuric salts, ethylhaloids or ethylsulphuric salts, respectively.
5. The production of salts of alpha benzyloxy alpha, naphthol beta, beta,
disulphonic acid, which process consists in subjecting the neutral or basic salts of
alpha, alpha, dihydroxynaphthalene beta, beta, disulphonic acid to the action of
benzyl haloids, or the free alpha, alpha, dihydroxynaphthalene beta, beta,
disulphonic acid to the action of benzyl haloids in the presence of alkalies, and
subsequently separating the salts of the alpha, benzyloxy alpha, naphthol beta
beta, disulphonic acid from the salts of the alpha, alpha, dihydroxynaphthalene
beta, sulphonic benzylether beta, monosulphonic acid simultaneously formed in this
process.
6. The production of dye stuffs by means of alkyloxynaphtholsulphonic acids
(such as alpha, methoxy alpha, naphthol sulphonic acids, alplia₁ ethoxy alpha
naphtholsulphonic acids, alpha, benzyloxy-alpha, naphthol sulphonic acids, or the
like) derived from alpha, alpha, dihydroxynaphthalene sulphonic acids.
7. The process for producing disazo colouring matters, the which process consists
in coupling one molecular proportion of a tetrazo salt of a paradiamine either,
with two molecular proportions of a salt of an alkyloxynaphtholsulphonic acid
derived from alpha, alpha, dihydroxynaphthalene sulphonic acid (employing either
the salt of the same alkyloxynaphtholsulphonic acid, or the salts of two different
alkyloxynaphtholsulphonic acids), or with one molecular proportion of a salt of
alkyl oxynaphtholsulphonic acid and one molecular proportion of another dye
stuff component, or, inversely, first with one molecular proportion of a dyestuff
component, and then with one molecular proportion of a salt of an alkyloxy-
naphtholsulphonic acid.
8. The process for producing azo dye stuffs by coupling one molecular
proportion of an alkyloxynaphthol sulphonic acid (derived from alpha, alpha
dibydroxynaphthalene sulphonic acids), with one molecular proportion of the diazo
derivative of debydrothio para toluidine, dehydrothio meta xylidine, dehydrothio
pseudocumidine, primulin base, or analogous thio amido products, or sulphonic
derivatives thereof.
9. As new products of manufacture:―
a.) The new alkyloxynaphthol sulphonic acids, (such as
manner hereinbe-
fore defined, or
other way
alpha, methoxy alpha, naphthol alpha sulphonic acid, Produced in the
alpha, ethoxy alpha, naphthol alpha sulphonic acid,
alpha, methoxy alpha, naphthol beta, beta, disulphonic
acid, alpha, ethoxy alpha, naphthol beta, beta,"
disulphonic acid, alpha, benzyloxy alpha-naphthol
beta, beta, disulphonic acid, or the like), derived from
alpha, alpha dihydroxynaphthalene sulphonic acids;
b.) The new colouring matters.
in
any
affording the same
result.