The Manufacture and Production of New Disazo-dyes, and of Intermediate Products in their Preparation.
Year: 1891

page_text: Date of Application, 4th May, 1891
Complete Specification Left, 3rd Feb., 1892-Accepted, 12th Mar., 1892
PROVISIONAL SPECIFICATION.
The Manufacture and Production of New Disazo-dyes, and of
Intermediate Products in their Preparation.
1 JAMES YATE JOHNSOx of 47 Lincolns Inn Fields in the County of
Middlesex Gentleman do hereby declare the nature of this invention which has
been communicated to me from abroad by The Badische Anilin and Soda Fabrik
of Ludwigshafen on Rhine in the Empire of Germany do hereby declare the nature
of this invention to be as follows:-
The present invention is based on the discovery that the 1.1' amido naphthol-
mono-sulpho-acid described in the Specification of the application for Letters
Patent No. 9676 of 1890 has the property of combining not only with one molecular
proportion of a diazo-compound but also with two molecular proportions of certain
diazo-compounds, to yield two series of bodies viz. :-simple azo-compounds and
disazo compounds, and my foreign correspondents have discovered that certain of
these disazo-bodies are very useful dyestuffs.
Thus for instance by combination with one molecular proportion of diazo-benzene-
chloride a simple azo-compound is obtained which can be used to dye wool a red
colour but is of no considerable importance as a dye. By combination however
with two molecular proportions of the said diazo-compound a new disazodye-stuff is
obtained possessing novel and peculiar characteristics. The said dyestuff is of a
deep blue-black colour and surpasses in colouring-power those hitherto known it
further possesses very good equalising properties.
In its chemical constitution it differs from the azo-dyes of the naphthol-black
group by containing but one naphthalene nucleus.
New dyestuffs of similar nature can also be obtained by using instead of
diazo-benzene chloride other diazo-compounds such for instance as the diazo-
compound from para-toluidine and from alpha-naphthylamine and from certain
other amines and their carboxy- and sulpho-acids. The tetrazo compounds from
diamido-bases (including sulpho- and carboxy acids) can also be used. Further
although the 11 amido-naphthol-mono-sulpho-acid only has been hitherto mentioned
because on account of its peculiar chemical constitution it appears to yield the best
results, still the invention is not confined to the use of this sulpho-acid, and 1.1' amido-
naphthol itself may be used, and certain other amido-naphthols and their sulpho-acids
may also be used.
In preparing the disazo dyes from two molecular proportions of the same diazo
compound and one molecular proportion of the 1-11 amido-naphthol-mono-sulpho-
acid either the whole quantity of the diazo-compound may be caused to act on the
anido-naphthol body at once or the simple azo-compound may first be prepared
with one molecular proportion of the diazo-compound and then this intermediate
compound can be converted into the disazo dye by the action of a second molecular
proportion of the diazo compound. It is also possible to prepare mixed azo-dyestuff's
of this type by the combination of the 1'1' amido-naphthol-inono-sulpho-acid with
one molecular proportion of one diazo-compound and with one molecular proportion
of another.
The following directions for the preparation of the new disazo dyestuff from
di-azo-benzene chloride further illustrate the nature of the invention and form an
example of the application of the invention in one case. The parts are by weight.
Dissolve about two hundred parts of the 1'1' amido-naphthol-mono-sulpho-acid
obtained as described in the aforesaid Specification of the application for Letters
Patent No. 9676 of 1890 and about one thousand parts of calcined soda in about
five thousand parts of hot water. Allow the solution to cool; then add about five

page_text: thousand parts of ice stir well and run into this mixture a solution of diazo benzene
chloride which may be obtained in the well known way from about one hundred
and fifty five parts of aniline, seven hundred and seventy five parts of hydrochloric
acid (containing about thirty per cent. of real hydrochloric acid HCl) two thousand
parts of water three thousand parts of ice and one hundred and seventeen parts of
sodium nitrite.
After a short time the formation of the new dyestuff commences and a dark
precipitate with a bronze-like sheen begins to separate out. Stir well for about
twelve hours keeping the temperature between zero and plus ten degrees Centigrade,
then boil and filter hot. The new dyestuff, which is rather insoluble in water
containing salt, remains on the filter and is pressed and dried.
The new dyestuff thus obtained is a dark powder with bronze like sheen it is
readily soluble in hot water giving a blue solution and dyes wool from the acid bath
a deep blue-black colour.
If the diazo-compound from aniline used in the above example be replaced by
the equivalent quantity of the corresponding compound from alpha-naphthylamine
or from para-toluidine, similar dyes are obtained giving a more greenish-blue-black
on wool.
D11
1001
J. H. JOHNSON & Co.,
47, Lincoln's Inn Fields, London, W.C., Agents.
COMPLETE SPECIFICATION.
The Manufacture and Production of New Disazo-dyes, and of
Intermediate Products in their Preparation.
I JAMES YATE JOHNSON of 47 Lincolns Inn Fields in the County of
Middlesex Gentleman do hereby declare the nature of this invention (which has
been communicated to me from abroad by The Badische Anilin 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:-
The present invention is based on the discovery that the 1'1' amido-naphthol
mono-sulpho-acid described in the Specification of Letters Patent No. 9676 of 1890
has the property of combining not only with one molecular proportion of a diazo-
compound but also with two molecular proportions of certain diazo compounds to
yield two series of bodies viz. simple azo-compounds and disazo compounds; and
my foreign correspondents have discovered that certain of these disazo bodies are
very useful dyestuffs.
Thus for instance by combination with one molecular proportion of diazo-benzene-
chloride a simple azo compound is obtained, which can be used to dye wool a red
colour but is of no considerable importance as a dye. By combination however
with two molecular proportions of the diazo-benzene-chloride a new disazo-dyestuff
is obtained, possessing novel and peculiar characteristics. The said dyestuff is of
a deep blue-black colour and surpasses in colouring-power those hitherto known
and it possesses very good equalizing properties.
New dye stuffs of similar nature can also be obtained by using instead of diazo
benzene chloride other diazo-compounds such for instance as the diazo compounds
from para-toluidine and from alpha-naphthylamine and from other amines such
as for instance ortho-toluidine, meta xylidine, para-xylidine, para-anisidine and
acetyl-para-phenylene-diamine. Further, not only the 11' amido naphthol-mono-
sulpho-acid described in the afore-mentioned Specification No. 9676 of 1890 but
also the isomeric 1'1' amido-naphthol-mono sulpho acid which can be obtained by
melting with a caustic alkali the naphthylamine disulpho acid prepared by
sulphonating the naphthylamine mono-sulpho acid S of the German Patent
No. 40571 can be employed.

page_text: In preparing the disazo-dyes from two molecular proportions of the same diazo
compound and one molecular proportion of 1.1 amido-naphthol-mono-sulpho-acid
either the whole quantity of the diazo-compound may be caused to act on the
amido-naphthol body at once (see Example I) or the simple azo-compound may
first be prepared with one molecular proportion of the diazo-compound and then
this intermediate compound can be converted into the disazo-dye by the action of a
second molecular proportion of the diazo compound (see Example II).
It is also possible to prepare mixed azo-dyestuffs of this type by the combination
of 11 amido-naphthol-mono-sulpho-acid with one molecular proportion of one
diazo-compound and with one molecular proportion of another. In this case not
only can the amines hereinbefore mentioned be used but also one molecular
proportion of the diazo compound from sulphanilic acid. Disazo-dyes obtained from
two molecular proportions of this diazo compound are of less value (see Examples III
and IV).
The following examples illustrate the nature of the invention and the manner
in which it can be carried into effect. The parts are by weight.
OF
AMIDO-
PRODUCTION OF A DISAZODYE FROM TWO MOLECULAR PROPORTIONS
1.11
ANILINE AND ONE MOLECULAR PROPORTION OF THE
NAPHTHOL MONO-SULPHO-ACID DESCRIBED IN THE SPECIFICATION OF
LETTERS PATENT No. 9676⁰⁰.
Dissolve about two hundred parts of the 1·1' amido-naphthol mono-sulpho-acid
and about one thousand parts of calcined soda in about five thousand parts of hot
water. Allow the solution to cool and then add about five thousand parts of ice,
stir well and run into this mixture a solution of diazo-benzene-chloride which may
be obtained in the well known way from about one hundred and fifty-five parts of
aniline, seven hundred and seventy five parts of hydrochloric acid (containing about
thirty per cent. of real hydrochloric acid HCl) two thousand parts of water, three
thousand parts of ice and one hundred and seventeen parts of sodium nitrite.
After a short time the formation of the new dyestuff commences and a dark
precipitate begins to separate out. Stir well for about twelve hours keeping the
temperature between zero and plus ten degrees Centigrade then boil and filter hot.
The new dyestuff (which is rather insoluble in water containing salt) remains on the
filter and is pressed and dried.
The new dyestuff' thus obtained is a dark powder with a bronze like sheen; it is
readily soluble in hot alkaline water, giving a blue solution, and dyes wool, from the
acid bath, a deep blue-black colour.
In the above example two molecular proportions of the diazo-compound from
aniline are combined with one molecular proportion of the 1'1' amido-naphthol-
mono-sulpho-acid, and the combination is effected in a solution which is alkaline
throughout; the same dyestuff is obtained, if one molecular proportion of the
diazo-compound is first caused to react on the amido-naphthol derivative in weakly
acid solution, whereby an ordinary azo compound is obtained and then the com-
bination with the second molecular proportion to form the disazo-dye is effected in
alkaline solution. This method of procedure is in general to be recommended and
is illustrated in the next example.
PARA-XYLIDINE
1.1 AMIDO-
PRODUCTION OF A DIS-AZO-DYE FROM TWO MOLECULAR PROPORTIONS OF
AND ONE MOLECULAR PROPORTION OF
NAPHTHOL-MONO-SULPHO ACID, DESCRIBED IN THE SPECIFICATION OF
LETTERS PATENT No. 9676º0.
Dissolve about 20 parts (one molecular proportion) of the 11' amido-naphthol-

page_text: mono-sulpho-acid in about six hundred parts of boiling water adding about twenty-
two and a half parts of crystallised sodium acetate, cool the solution, stirring
thoroughly all the time, so that the crystalline precipitate which forms shall be as
fine as possible add about six hundred parts of ice and run a solution of one
molecular proportion of di-azo-para-xylene-chloride into the mixture. Continue
stirring for about ten hours, keeping the mixture cool.
The solution of this diazo compound is thus obtained ;--dissolve about ten
parts of para-xylidine in a mixture of about three hundred parts of water and
twenty five parts of hydrochloric acid (containing about thirty per cent. real
acid HCI) add about three hundred parts of ice and diazotise with five and two
fifths parts of sodium nitrite.
The next step towards the production of the desired dis-azo-dye is the combination
of the brown mono-azo-compound with a further molecular proportion of the di-azo-
para-xylene-chloride in alkaline solution. For this purpose, add about fifty parts
of calcined soda to the thin brown paste of the mono-azo-compound already
obtained, this then dissolves giving a blue red solution, add to this solution a further
quantity of the diazo-para-xylene-chloride similarly obtained from about ten parts
of para-xylidine continue stirring for a further period of ten hours, then boil and
filter off the dye (which is but slightly soluble in the salt-containing mother-liquor)
press and dry.
THE PRODUCTION OF A MIXED DIS-AZO-DYE FROM ONE MOLECULAR
PROPORTION OF SULPHANILIC ACID ONE MOLECULAR PROPORTION OF
ACETYL-PARA-PHENYLENE-DIAMINE AND ONE MOLECULAR PROPORTION
OF 111 AMIDO NAPHTHOL-MONO-SULPHO-ACID. DESCRIBED IN THE
SPECIFICATION OF LETTERS PATENT No. 9676.
Dissolve about twenty parts of the 1·1' amido-naphthol-mono-sulpho-acid in about
six hundred parts of boiling water adding in this case about nineteen parts of
sodium acetate crystals, proceeding in general as described in Example II. Cool
and add about six hundred parts of ice and then run in a solution of one molecular
proportion of diazo-benzene-sulpho-acid obtained in the well known way from
about seventeen and two fifths parts of the sodium salt of sulphanilic acid
(CH, NH, SO,Na + H₂O) thirty five parts of hydrochloric acid (containing about
thirty per cent. real acid HCl) five and seven tenths parts of sodium nitrite and the
requisite quantities of water and ice. Stir the mixture for about twelve hours,
then add to the blue-red solution obtained about seventy-five parts of calcined soda
and a solution of one molecular proportion of para-diazo-acetanilide-chloride
obtained from about thirteen parts of acetyl-para-phenylene-diamine, about twenty
five parts of hydrochloric acid (containing about thirty per cent. real acid HCl)
about two hundred parts of water, two hundred parts of ice, and about five and
seventh tenths parts of sodium nitrite.
A violet-black gelatinous liquid is formed which stir for twelve hours, then boil,
precipitate the dis-azo-dye completely with common salt, filter from the red-
coloured mother-liquor at a temperature of about eighty degrees press and dry..
In the last preceding example the diazo-benzene sulpho acid can be combined
with the 11 amido naphthol mono-sulpho-acid in the presence of hydrochloric acid
instead of acetic-acid. For this purpose dissolve the amido-naphthol derivative in
the boiling water adding sufficient soda cool the solution add hydrochloric acid in
sufficient quantity to just acidify and then run in the diazo-benzene-sulpho acid
stir for twenty-four hours, then dissolve the brown mono-azo-compound formed by
adding seventy five parts of calcined soda and proceed with the treatment as above
described.
If in this Example III the order of combination with the diazo-compounds be
changed so that the amido-naphthol sulpho-acid be first treated with the diazo-
acetanilic-chloride in acid solution and subsequently with the sulphanilic acid in

page_text: alkaline solution then an isomeric dye is produced which is characterised by a
degree of solubility in water containing salt in solution higher than that of the
product obtained as described in Example III. Further the product obtained by
proceeding as described in Example III can be completely precipitated from its
aqueous solution as a green precipitate by hydrochloric acid but the isomeric dye
gives a blue-violet precipitate and cannot readily be so completely precipitated.
EXAMPLE IV.
PREPARATION OF DISAZO-DYE ISOMERIC WITH THAT PRODUCED A$
DESCRIBED IN EXAMPLE III.
Dissolve about twenty parts 1·11 amido-naphthol-mono sulpho-acid in about six
hundred parts of boiling water adding about twenty one and a half parts of
crystallized sodium acetate, allow to cool, add ice and stir as hereinbefore described
then run in a solution of the diazo-compound obtained as described in Example III
from about thirteen parts of acetyl-para-phenylene-diamine. Stir for twelve hours
and then add about sixty five parts of calcined soda in the form of a twenty five
per cent. solution when the brown mono-azo-compound partially dissolves with a
red-violet colour. Next run in the solution of diazo-benzene-sulpho-acid obtained
as mentioned in Example III from seventeen and two fifths parts of sodium
sulphanilate. Continue stirring for twelve hours more; boil, salt out, filter off the
red mother liquor, press and dry.
Instead of using the 11' amido-naphthol-mono-sulpho-acid described in the
Specification No. 9676 of 1890, as described in the above examples, the same
quantity of the hereinbefore mentioned isomeric acid can be substituted, when
isomeric dyes result.
From the explanation and examples hereinbefore given the combination of the
diazo compounds from the other amido-compounds hereinbefore mentioned with 1.11
amido-naphthol-mono-sulpho-acids to produce new disazo dyes according to this
invention can without further description be readily accomplished by any one skilled
in the art of manufacturing azo-dyes.
Having now particularly described and ascertained the nature of the said inven-
tion and in what manner the same is to be performed 1 declare that what I
claim is.
1. The manufacture of disazodyes by the combination of two molecular proportions
of a diazo compound from one of the bases hereinbefore mentioned with one molecular
proportion of one of the 1·11 amido-naphthol-mono-sulpho-acids hereinbefore
mentioned substantially as hereinbefore described.
2. The manufacture of disazodyes by first combining one molecular proportion of
one of the 11 amido-naphthol-mono-sulpho-acids hereinbefore mentioned with one
molecular proportion of a diazo compound from one of the bases herein before
mentioned and so producing a mono-azo-compound then converting this into a disazo
dye by treatment with a further molecular proportion of either the same or a
different diazo compound derived from a base hereinbefore mentioned, or from
sulphanilic acid, all substantially as herein before described.
3. The manufacture of disazo-dyes, first by combining one molecular proportion
of one of the 11' amido-naphthol-mono-sulpho-acids hereinbefore mentioned, with
one molecular proportion of the diazo-compound from sulphanilic-acid and so
producing a mono-azo-compound; then converting this into a disazo dye, by
treatment with a further molecular proportion of a diazo-compound derived
from one of the bases hereinbefore mentioned all substantially as hereinbefore
described.
4. In the manufacture of dis-azo-dyes from the 11' amido-naphthol-mono-
sulpho-acids the production of mono-azo-compounds substantially as hereinbefore
described.

page_text: 5. The conversion of the mono-azo-compounds of the 1'1' amido-naphthol-mono-
sulplio-acids hereinbefore mentioned into disazo-dyes, substantially as hereinbefore
described.
6. As new articles of manufacture the new disazo dyes, such as are obtained by
the processes herein described; and the new mono-azo-compounds obtainable as
intermediate products in their manufacture as hereinbefore described.
Dated this 3rd day of January 1892.
J. H. JOHNSON & Co.,
Agents.