The Manufacture and Production of New Acid Colouring-matters.
Year: 1893

page_text: Date of Application, 16th Feb:; 1893
Complete Specification Left, 16th Nov., 1893-Accepted, 16th Dec., 1893
PROVISIONAL SPECIFICATION.
The Manufacture and Production of New Acid Colouring-matters.
I, JAMES YATE JOHNSON of 47 Lincoln's Inn Fields in the County of Middlesex
Gentleman do hereby declare the nature of this invention (which has been communi-
cated to me from abroad by The Badische Anilin and Soda Fabrik of Ludwigs-
hafen on Rhine in the Empire of Germany) to be as follows:
This invention relates to the manufacture of new sulphonated dyes of the oxazine
class which yieid greenish-blue and blue, to violet shades on-animal-fibre. Some of
these dyes possess a most valuable degree of fastness against the action of light,
soap and alkalies, and also most readily give very even shades, a property of great
importance to the dyer.
↓
In the Specification of Letters Patent No. 4476 of 1888 granted to me, on a
communication from my foreign correspondents, there is described the manufacture
of the mono-nitroso-compounds of dimethyl-meta-amido-phenol and diethyl-meta
amido-phenol and the manufacture of basic blue dyes by condensing the said
nitroso compounds with alpha-naphthylamine and alkyl derivatives thereof. One
of these basic blue dyes is well known in the dyeing trade, under the name of
"Nile blue."
In the Specification of Letters Patent No. 10619 of 1891 granted to me, on a
communication from my foreign correspondents, the production of more greenish
blue basic dyes is described, by the use of benzyl-alpha-naphthylamine in the
condensation with the herein before mentioned nitroso-compounds.
The present invention relates to the production of acid dyes of the same class.
All attempts to produce such dyes by direct sulphonation of the basic dyes have
hitherto failed and no useful result has been attained in this way. But if in the
production of the said basic dyes, as described in the above mentioned Letters
Patent, instead of alpha-naphthylamine or its alkyl-or-benzyl derivatives, sulpho
acids thereof be used then the new valuable acid dyes are obtained.
To further illustrate the nature of the invention I give the following example in
which the preparation of one of the new dyes from alpha-naphthylamine-mono-
sulpho acid (13) and nitroso-di-ethyl-meta amido phenol is described. This is
however but a single case of the application of the invention and not only can it be
applied to the said other materials, but the details of the method of carrying it
into effect can in every case be considerably varied without departing from the
invention. The parts are by weight.
Mix together thoroughly about seventy parts of the hydrochlorate of nitroso
diethyl-meta-amido-phenol, about fifty parts of 1.31 naphthylamine-mono-sulpho-
acid and about thirty two parts crystallized sodium acetate. To this mixture add
about one hundred and fifty parts of acetic acid (containing about sixty per cent. real
acid C,H,O,). Heat on the water-bath for about twelve hours, or until the melt
has assumed a pure blue colour and no further formation of colouring matter is
observed. Dilute the entire product with about three thousand parts of water, and
add, if necessary, just enough soda solution to completely dissolve the colouring
matter, filter and salt out the dye from the solution. Collect on the filter, wash,
press and dry.
The dye so obtained is readily soluble in water giving a pure blue solution,
the colour of which is hardly changed by the addition of alkali. It dyes wool
giving a brilliant pure blue colour fast against the action of alkalis and of light.
In a manner similar to that described in the above example a number of
analogous dyes can be obtained. Thus instead of nitroso-diethyl-meta-amido-
phenol the nitroso-compounds of other di-alkyl-meta-amido phenols, and in

page_text: particular of the di-methyl compound, can be used. Similarly the nitroso com-
pounds of the alkyl derivatives of meta-amido-cresol can be employed. On the
other hand instead of the 1.31 mono sulpho acid of alpha-naphthylamine other
sulpho acids thereof can be used, as can also sulpho acids of alkylated and
benzylated alpha-naphthylamine and the like.
In the following table I give a few instances of the dyes obtained in this way by
the use of analogous materials and in each case I mention the shade obtained on
animal fibre by the use of the dye.
COMPLETE SPECIFICATION.
The Manufacture and Production of New Acid Colouring-matters.
1 JAMES YATE JOHNSON of 47 Lincoln's Inn Fields in the County of Middlesex
Gentleman do hereby declare the nature of this invention which has been com-
municated to me from abroad by The Badische Anilia and Soda Fabrik of
Ludwigshafen-on-Rhine in the Empire of Germany and in what manner the same
is to be performed to be particularly described and ascertained in and by the
following statement :-
This invention relates to the manufacture of new sulphonated dyes which yield
greenish-blue and blue to violet shades on animal fibre. Some of these dyes
possess a most valuable degree of fastness against the action of light, soap and
alkalies, and also most readily give very even shades a property of great importance
to the dyer.
In the Specification of Letters Patent No. 4476 of 1888 granted to me on a
communication from my foreign correspondents there is described the manufacture
of the mono-nitroso-compounds of dimethyl-meta-amido phenol and diethyl-meta-
amido-phenol, and the manufacture of basic blue dyes by condensing the said
nitroso-compounds with alpha-naphthylamine and alkyl derivatives thereof. One
of these basic blue dyes is well known in the dyeing trade under the name of
"Nile blue."
In the Specification of Letters Patent No. 10619 of 1891 granted to me on a
communication from my foreign correspondents, the production of more greenish-
blue basic dyes is described by the use of benzyl alpha-naphthylamine in the
condensation with the herein before mentioned nitroso compounds.
The present invention relates to the production of acid dyes by a similar process.
All attempts to produce such dyes by direct sulphonation of the basic dyes bave
hitherto failed and no useful result has been attained in this way. But my foreign
correspondents have now found that if in the production of the said basic dyes, as

page_text: described in the above mentioned Specifications of Letters Patent instead of alpha-
naphthylamine or its alkyl- or benzyl-derivatives, sulpho acids thereof be used
then the new valuable acid dyes are obtained. As suitable sulpho acids for use
according to this invention I mention as instances the mono-sulpho acids of alpha-
naphthylamine and the 14-21, 1-4.3', and 12'4' naphthylamine disulpho acids.
To further illustrate the nature of this invention and the manner in which it can
be carried into practical effect, I give the following examples. These are typical
cases of the application of this invention and not only can they be applied to the
other sulpho acids hereinbefore mentioned but the details of the method of carrying
it into effect can in every case be considerably varied without departing from the
nature of this invention particularly in the manner hereinafter explained. The
parts are by weight.
EXAMPLE 1. PREPARATION OF A NEW ACID DYE FROM 1.31 NAPHTHYL-
AMINE MONOSULPHO ACID.
Thoroughly mix together about seventy parts of the hydrochlorate of nitroso-
diethyl-meta amido phenol, about fifty parts of 1-3 naphthylamine mono-sulpho-
acid and about thirty two parts of crystallized sodium acetate. To this mixture
add about one hundred and fifty parts of acetic acid (containing about sixty per cent.
real acid C,H,O,). Heat on the water-bath for about twelve hours, or until the
melt has assumed a pure blue colour and no further formation of colouring-matter
is observed. Dilute the entire product with about three thousand parts of water
and add if necessary, just enough soda solution to dissolve the colouring matter
filter and salt out the dye from the solution. Collect on the filter, wash, -press,
and dry.
The dye so obtained is readily soluble in water giving a pure blue solution, the
colour of which is hardly changed by the addition of alkali. It dyes wool
giving a brilliant pure blue colour fast against the action of alkalis and of light.
If in the above example the conditions be varied the nature of the product and
its shade may be somewhat changed; thus if the quantity of acetate of soda used
be considerably less, or if it be entirely omitted, then the product obtained is as
free acid, wholly, or in part, difficultly soluble in water and readily changed in
colour by caustic alkalies. The formation of this last named type of dye (which I
will term type A) takes place more exclusively if glacial acetic acid be used (in
the absence of acetate of soda) as solvent in the melt instead of the more dilute
acid above described.
The dyes of the first mentioned type (which I will term type B) are characterized
by the following properties. In the form of alkali salts they are readily soluble
in water and from their solutions the free acid is not, or not completely, precipitated
by the addition of acetic acid. This type of dye fixes itself on wool from the acid
bath giving even shades of blue to violet which are fast against the action of light
and resist in a very high degree the action of alkalies and washing.
On the other hand, the dyes of type A are also readily soluble in water when in
the form of alkaline salts but the solutions obtained are precipitated by addition
of acetic acid. They dye wool giving beautiful greenish-blue shades which are not
fast against alkalies but are changed thereby to red-violet or red. The dyes of
this type should therefore not be used when fastness against alkalies is required.
Some of the alpha-naphthylamine sulpho acids yield both types of dye according
to the conditions observed in the operation of melting and from these, of course,
mixed products can be obtained. Others yield only the one type under all practical
conditions of operation. Thus the 1-31 and 1.21 naphthylamine monosulpho acids
yield both types of dye, the 1.3, 1.4 and 1.4¹ acids always yield dyes of the type B
and the 12 and 1.1' acids give the dyes of the type A only.
The examples which now follow will serve to illustrate more particularly the
formation of these types of dye.

page_text: EXAMPLE 2.. PREPARATION OF A NEW ACID DYE FROM 1.2 NAPHTHYL-
AMINE-MONO SULPHOACID.
Proceed in the manner described in the foregoing example but taking about
fifty parts of 12 naphthylamine-monosulpho acid instead of the same quantity of
the 13 naphthylamine-sulpho acid. The dye when obtained as sodium salt is
readily soluble in water and yields violet-red aqueous solutions which turn bluish-
green on the addition of acetic acid the free acid separating out. In caustic
alkalies it gives red solutions. The free acid is only with difficulty soluble in
water.
EXAMPLE 3. PREPARATION OF A NEW ACID DYE FROM 14 NAPHTHYL-
AMINE SULPHO-ACID (NAPHTHIONIC ACID).
Proceed as described in the former examples taking the corresponding quantity
of naphthionic acid or preferably (as free naphthionic acid is not readily soluble in
sodium acetate) take the sodium salt thereof as the equivalent of the free acid and
sodium acetate used in the cases herein before described and work with a more
dilute melt to avoid difficulty in stirring. Thus mix about sixty five parts of
crystallized sodium naphthionate, about forty five parts of water about seventy
parts of nitroso-diethyl-meta-amido-phenol and about fifty-four parts of acetic acid
containing about thirty per cent. real acid' (C,HO2). Heat on the boiling water-
bath for about ten hours then dilute with about nine hundred parts of cold water
filter off the precipitate, wash with cold water and then dissolve in about two
thousand four hundred parts of hot water, containing about six parts of ammonia
solution (twenty per cent. NH,). When cold precipitate the dye with common salt,
press, and dry.
The dye so obtained dissolves readily in water yielding a violet-blue solution
which is only slightly changed in colour by the addition of an alkali.
In a similar manner to that described in the above examples a number of
analogous dyes can be obtained by using the other sulpho acids herein before
mentioned. Further instead of nitroso diethyl-meta-amido-phenol the nitroso com-
pounds of other di-alkyl-meta-amido-phenols, and, in particular, of the di-methyl-
compound, can be used. Similarly the nitroso-compounds of the alkyl-derivatives
of meta-amido-cresol 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 I declare that what I
claim is.
1. The manufacture of new acid colouring matters by heating together nitroso-
dialkyl meta-amido-phenol compounds with alpha-naphthylamine-sulpho acids
substantially as herein before described.
2. The manufacture of new acid colouring matters by heating together di-methyl
or di-ethyl-meta amido-phenol with the alpha-naphthylamine-sulpho acids herein-
before named in the presence or absence of sodium acetate and using glacial or
diluted acetic acid as a diluent or solvent in the melt all substantially as herein-
before set forth.
3. The manufacture of new acid colouring matters substantially in the manner
herein before described in the examples.
4. As new products the new acid colouring matters such as can be obtained
substantially as hereinbefore described.
Dated this 16th day of November 1893.
J. H. JOHNSON & Co.,
47, Lincoln's Inn Fields, Agents.