Improvements in and relating to the Manufacture of Substantive Dyestuffs and of New Materials therefor.
Year: 1890

page_text: Date of Application, 19th June, 1890
Complete Specification Left, 11th Mar., 1891-Accepted, 18th Apr., 1891
PROVISIONAL SPECIFICATION.
Improvements in and relating to the Manufacture of Substantive
Dyestuffs and of New Materials therefor.
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 communicated to me from abroad by The Badische Anilin and Soda Fabrik,
of Ludwigshafen-on-Rhine, in the Empire of Germany,) to be as follows :—
This invention is based upon the discovery that, by suitable treatment, beta
naphthylamine-di-sulpho acid G can be made to yield a new alpha-naphthol-mono-
sulpho acid which can be used for instance in the manufacture of new substantive
dyestuff's.
As is well known, beta-naphthylamine-disulpho acid & results from the action of
ammonia on the corresponding beta-naphthol-di-sulpho acid (Berichte der deutschen
chemischen Gesellschaft 16, 1932; 21, 3487; German Patent, No. 27,378; Fried-
lander, Fortschritte der Theerfarbenfabrikation page 416). The above mentioned
treatment of beta-naphthylamine-di-sulpho acid & consists in the substitution of a
hydroxyl-group for a sulpho-group and the elimination of the amido group.
It appears to be immaterial in which order these operations are performed. The
amido-group may first be split off by the hydrazine method, whereby a 1-3 naphtha-
lene-disulpho acid is obtained and then in this disulpho acid a sulpho group may be
replaced by hydroxyl by melting it with a fixed caustic alkali. Or, the sulpho
group may first be replaced by hydroxyl by melting the naphthylamine disulpho
acid G with a caustic alkali thus obtaining the amido-naphthol sulpho acid G and
then from this the amido group can be split off by boiling the corresponding diazo-
compound with alcohol.
The course of these changes is illustrated thus :—
The discovery of the 1-3 naphthalene disulpho acid and of the amidonaphthol
0 sulpho acid G has already been published in England. The 13 naphthalene
disulpho acid can be obtained from the napthylamine disulpho acid by the
hydrazine method (see Armstrong and Wynne, Proceedings of the Chemical
Society [1890] No. 77 pages 12 and 13) and the amidonaphthol sulpho acid G can
be obtained for the purposes of this invention by melting together beta-naphthyl-

page_text: amine-disulpho acid G with caustic soda at a temperature of about two hundred to
two hundred and eighty degrees Centigrade, in accordance with the directions
contained in the Specification of Patent No. 15,176 of 1889.
The new alpha-naphthol-monosulpho acid obtained by either of the above ways
can be made to combine with diamido bases such as are in use for the production of
substantive dyes. Of these combinations that with dianisidine appears likely to be
of greatest technical importance.
To further illustrate and explain the nature of this invention the following
examples are given, the parts being by weight:
THE
REPLACING 1 SULPHO
THE PRODUCTION
OF
ACID BY HYDROXYL.
NEW ALPHA-NAPHTHOL-MONO-SULPHO
GROUP OF THE 1:3
ACID
NAPHTHALENE DISULPHO
BY
Take about ten parts of the sodium salt of 13 naphthalene disulpho acid obtained
as above mentioned or in any other way, and melt it with about ten parts of caustic
soda adding about four parts of water. Raise the temperature to from two
hundred to two hundred and twenty degrees Centigrade and maintain it within
this range for about an hour, or until samples of the melt withdrawn from time to
time, when tested with tetrazodiphenyl in the well known way shew no increase in
the quantity of the naphthol monosulpho acid. This point being reached, dissolve
the melt in about fifty parts of water and acidify with a mixture of about sixteen
parts of concentrated sulphuric acid and about thirty parts of water. Boil to drive
off the sulphurous acid formed and filter. Neutralise with soda, evaporate the
filtrate to dryness and extract the residue with alcohol which dissolves out the
sodium-alpha-naphthol mono sulphonate. Distil off the alcohol and so obtain this
salt in a sufficiently pure condition for technical application.
ACID BY
THE PRODUCTION OF THE NEW ALPHA-NAPHTHOL MONO SULPHO
ELIMINATING THE AMIDO GROUP FROM AMIDO-NAPHTHOL-SULPHO-ACID G.
Dissolve about six parts of amido-naphthol-mono-sulpho acid G (or an alkaline
salt thereof) [obtained by melting the corresponding beta naphthylamine disulpho
acid with a caustic alkali as above mentioned or in any other way] in about one
hundred parts of water and one part of sodiumhydrate, and add to this solution
about seven and a half parts of a solution of sodium nitrite (containing about twenty
five per cent. of NaNO2) and about sixty parts of ice, then stir well and add all at
once, about nine parts of hydrochloric acid (containing about 34 per cent. of HCI).
Stir for say about twelve hours and then filter off the diazocompound formed and
mix it with about one hundred and twenty five parts of alcohol; boil in a vessel
connected with a reflux or inverted condenser until the diazo compound is completely
decomposed which can be ascertained by adding a little sodium carbonate solution
to a test portion. The production of a violet colour proves the presence of
undecomposed diazo-compound; when all is decomposed no violet colour is formed.
This point being reached, the alcohol is distilled off, the residue is neutralised with
sodium carbonate solution and evaporated to dryness, and then the product consists
mainly of the desired alpha-naphthol mono sulpho acid in the form of its sodium
salt.
The new alpha-naphthol-mono-sulphoacid is (both as free acid and in the form of
its sodium salt) readily soluble in alcohol and water and it yields on treatment with
nitrous acid an intensely yellow solution which after reduction with zinc dust and
ammonia becomes only pale yellow again on exposure to the air. It has the
substituting groups in the meta- or 13 position to one another, as they are herein-
before represented.

page_text: PRODUCTION OF A PURE BLUE SUBSTANTIVE DYESTUFF FROM ТПЕ NEW
ALPHA NAPHTHOL-MONO-SULPHO ACID AND DIANISIDINE.
Take about thirty one and seven tenths parts of ortho-dianisidine-dichlorhydrate,
dissolve in about six hundred parts of water and add about forty parts of hydro-
chloric acid (containing about 25 per cent. HCI) cool down to below five degrees
Centigrade and then run in about fourteen parts of sodium nitrite dissolved in about
sixty parts of water. Allow the mixture to stand for about twelve hours.
Make a solution of the sodium salt of the new naphthol sulphoacid obtained as
above described in Examples 1 and 2 and take so much of the sodium salt, that the
solution shall contain about forty five parts of pure alpha-naphthol-monosulpho acid
and dissolve also in this, about thirty parts of calcined soda and then run in the
solution of the tetrazo compound, stir for about twelve hours, then filter, press, wash
with alcohol to remove a reddish blue impurity from the dyestuff formed, and dry.
The dyestuff is thus obtained as a brownish-black amorphous powder.
The new dyestuff dyes cotton from the boiling alkaline bath a pure blue colour.
It differs from the dyestuff known as Benzazurine as it yields a purer blue which
can readily be seen by comparing patterns dyed in similar strengths. The
superiority of the new dyestuff is more noticeable by gas or lamp light when the
colour still looks pure blue, whereas by such light material dyed with Benzazurine
assumes a more reddish and duller shade.
Dated this 19th day of June 1890.
J. H. JOHNSON & Co.
COMPLETE SPECIFICATION.
Improvements in and relating to the Manufacture of Substantive
Dyestuffs and of New Materials therefor.
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 communicated to me from abroad by 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 :-
This invention is based upon the discovery that by suitable treatment beta-
naphthylamine-di-sulpho-acid G can be made to yield a new alpha-naphthol-mono-
sulpho-acid which can be used for instance in the manufacture of new substantive
dyestuff's.
As is well known, beta-naphthylamine-di-sulpho-acid G, results from the action
of ammonia on the corresponding beta-naphthol-di-sulpho-acid (Berichte der
deutschen chemischen Gesellschaft 16 1932; 21 3487 German Patent No. 27378;
Friedlander's Fortschritte der Theerfarbenfabrikation, page 416).
The above mentioned treatment of beta-naphthylamine-di-sulpho acid G consists
in the substitution of a hydroxyl-group for a sulpho-group and the elimination of
the amido-group.
It appears to be immaterial in which order these operations are performed. The
amido group may first be split off by the hydrazine method whereby a 1-3 naphtha-
lenc-di-sulpho-acid is obtained and then in this disulpho-acid a sulpho-group may be
replaced by hydroxyl by melting it with a fixed caustic alkali. Or the sulpho-
group may first be replaced by hydroxyl by melting the naphthylamine disulpho
acid G with a caustic alkali thus obtaining the amido-naphthol-sulpho-acid G and
then from this the amido-group can be split off by boiling the corresponding di-azo-
compound with alcohol.

page_text: sulpho-acid G
The discovery of the 13 naphthalene-disulpho-acid and of the amido naphthol
sulpho acid G has already been published in England. The 1-3 naphthalene-di-
sulpho-acid can be obtained from the naphthylamine di-sulpho acid G by the
hydrazine method (scc Armstrong and Wynne, Proceedings of the Chemical
Society [1890] No. 77, pages 12 and 13) and the amido naphthol sulpho acid G can
be obtained for the purposes of this invention by melting together beta-naphthyl-
amine-di-sulpho-acid G with caustic soda at a temperature of about two hundred to
two hundred and eighty degrees Centigrade in accordance with the directions
contained in the Specification of Letters Patent No. 15176 of 1889.
The new alpha naphthol monosulpho-acid obtained by either of the above ways
can be made to combine with diamido bases such as are in use for the production of
substantive dyes. Of these combinations that with dianisidine appears likely to be
of greatest technical importance.
The following examples illustrate the manner in which this invention can be
carried into practical effect. The parts are by weight.
THE PRODUCTION OF THE NEW ALPHA-NAPHTHOL-MONO-SULPHO-ACID
BY
REPLACING A SULPHO-GROUP OF THE 13 NAPHTHALENE DISULPHO-ACID
BY HYDROXYL.
Take about ten parts of the sodium salt of 1-3 naphthalene disulpho-acid obtained
as above mentioned or in any other way and melt it with about ten parts of caustic
soda adding about four parts of water. Raise the temperature to from two hundred
to two hundred and twenty degrees Centigrade and maintain it within this range
for about an hour, or until samples of the melt, withdrawn from time to time, when
tested with tetrazo-diphenyl in the well known way, shew no increase in the quantity
of the naphthol monosulpho-acid. This point being reached, dissolve the melt in
about fifty parts of water and acidify with a mixture of about sixteen parts of
concentrated sulphuric acid and about thirty parts of water. Boil to drive off the

page_text: sulphurous acid formed and filter; neutralize with soda; evaporate the filtrate to
dryness and extract the residue with alcohol which dissolves out the sodium-alpha-
naphthol-mono-sulphonate. Distil off the alcohol and so obtain this salt in a
sufficiently pure condition for technical application.
THE PRODUCTION OF THE NEW ALPHA-NAPHTHOL-MONO-SULPHO-ACID BY
ELIMINATING THE AMIDO GROUP FROM AMIDO-NAPHTHOL-SULPHO-ACID G.
Dissolve about six parts of amido-naphthol-sulpho-acid G (or an alkaline salt
thereof) [obtained by melting the corresponding beta-naphthylamine disulpho-acid
with a caustic alkali as above mentioned or in any other way] in about one hundred
parts of water and one part of sodium hydrate and add to this solution about seven
and a half parts of a solution of sodium nitrite (containing about twenty five per
cent. of NaNO) and about sixty parts of ice, then stir well and add all at once about
nine parts of hydrochloric acid (containing about 34 per cent. of HCl). Stir for say
about 12 hours and then filter off the diazo-compound formed and mix it with about
one hundred and twenty five parts of alcohol; boil in a vessel connected with a
reflux or inverted condenser until the diazo-compound is completely decomposed
which can be ascertained by adding a little sodium carbonate solution to a test
portion. The production of a violet colour proves the presence of undecomposed
di-azo-compound when all is decomposed no violet colour is formed. This point
being reached the alcohol is distilled off, the residue is neutralized with sodium
carbonate solution and evaporated to dryness and then the product consists mainly
of the desired alpha-naphthol-mono-sulpho acid in the form of its sodium salt.
The new alpha-naphthol-mono-sulpho-acid is (both as free acid and in the form
of its sodium salt (readily soluble in alcohol and water and it yields on treatment
with nitrous acid an intensely yellow solution which after reduction with zinc-dust
and ammonia becomes only pale yellow again on exposure to the air. It has the
substituting groups in the meta- or 1-3 position to one another as they are herein-
before renresented
PRODUCTION OF A PURE BLUE SUBSTANTIVE DYESTUFF FROM THE NEW
ALPHA-NAPHTHIOL-MONO-SULPIO ACID AND DIANISIDINE.
Take about thirty one and seven tenths parts of ortho-dianisidine-dichlorhydrate
dissolve in about six hundred parts of water and add about forty parts of hydro-
chloric acid (containing about twenty five per cent. HCl) cool down to below five
degrees Centigrade and then run in about fourteen parts of sodium nitrite dissolved
in about sixty parts of water. Allow the mixture to stand for about twelve hours.
Make a solution of the sodium salt of the new alpha naphthol mono-sulpho-acid
obtained as above described in Examples and 2 and take so much of the
sodium salt that the solution shall contain about forty five parts of pure alpha-
naphthol-monosulpho acid; and dissolve also in this, about thirty parts of calcined
soda and then run in the solution of the tetrazo-compound, stir for about twelve
hours, then filter press wash with alcohol to remove a reddish blue impurity from
the dye-stuff formed, and dry. The dyestuff is thus obtained as a brownish black
amorphous powder.
The new dyestuff' dyes cotton from the boiling alkaline bath a pure blue colour.
It differs from the dyestuff' known as benzazurine as it yields a purer blue which can
readily be seen by comparing patterns, dyed in similar strengths of the respective
dyestuffs. The superiority of the new dyestuff is more noticeable by gas or lamp
light, when the colour still looks pure blue whereas by such light material dyed
with benzazuline assumes a more reddish and duller shade.

page_text: Having now particularly described and ascertained the nature of the said inven-
tion, and in what manner the same is to be performed, I declare that what I
claim is :-
(1) The manufacture of 13 alpha-naphthol-mono-sulpho-acid a new material
for the manufacture of dyestuffs by treating 1-3 naphthalene disulpho acid in an
alkaline melt substantially as hereinbefore described.
(2) The manufacture of 13 alpha-naphthol mono-sulpho-acid a new material for
the manufacture of dyestuff's by eliminating the amido group from amido-naphthol-
sulpho acid G substantially as hereinbefore described.
(3) The manufacture of substantive dyes by the combination of processes
consisting in preparing 1-3 alpha naphthol-mono-sulpho-acid in either of the ways
claimed in the preceding claiming clauses and combining the said sulpho-acid with
the tetrazo-compounds in use in the manufacture of substantive dyes all substantially
as hereinbefore described.
(4) As a new article of manufacture the 13 alpha naphthol mono-sulpho-acid
hereinbefore described.
(5) As a new article of manufacture the blue substantive dyestuff derived from
the tetrazo-compound of dianisidine and 1-3 alpha naphthol mono-sulpho acid
hereinbefore described.
Dated thin 114h dow of Mach 1901
J. H. JOHNSON & Co.,
Agents.