Improvements in or connected with the Manufacture and Production of Colouring Matters or Dyestuffs.
Year: 1889

page_text: Date of Application, 29th Aug., 1839
Complete Specification Left, 28th June, 1890-Accepted, 2nd Aug.. 1890
PROVISIONAL SPECIFICATION.
Improvements in or connected with the Manufacture and Production
of Colouring Matters or Dyestuffs.
1, BENJAMIN WILLCOX, of 47 Lincolns Inn Fields, in the County of Middlesex,
Patent Agent, do hereby declare the nature of this Invention, (which has been com-
municated to me from abroad by the Farbenfabriken vormals Friedrich Bayer and
Company, of Elberfeld, in the Empire of Germany,) to be as follows :—
My foreign correspondents have discovered that by heating with caustic alkalies
such as potash or soda in open or closed vessels naphthol sulpho acids such as those
described in the Specifications of German Patents Nos. 40571, 44079, and 45776, and
that obtained by boiling alpha dioxynaphthaline disulpho acid III described in the
Specification of German Patent No. 41957 wlth sulphuric acid can likewise be very
readily converted into new dioxynaphthaline mono sulpho acids and trioxynaphthaline
which in turn when acted upon by diazo or tetrazo compounds lead to the production
of very valuable azo dies or colouring matters.
The process for the production of these new naphthaline derivatives consists in
operating to produce the dioxynaphthaline monosulpho acids by introducing the soda
salt of the naphthol di sulpho acid into about three parts of caustic soda and heating
it to about 250 degrees Centigrade until a sample shows the disappearance of the
fluorescence and emits a strong odour of sulphurous acid when acidulated.
The melt is then poured into water, saturated with sulphuric acid and the acid solution
is boiled until all the sulphurous acid is eliminated.
The solution of dioxynaphthaline mono sulpho acid thus obtained is then neutralised
with soda and employed immediately in the preparation of azo dies or colouring
matters.
It is nevertheless preferable to isolate the dioxynaphthaline mono sulpho acids
formed and to purify them by crystallisation which is best effected by salting out or
it may be effected by evaporating the solutions and extracting the salt residue with
alcohol.
In order to obtain the isomeric trioxynaphthalines the materials must be heated
more highly or for a longer period according to the degree of concentration
of the alkali until a sample of the melt after being acidulated and extracted
with a volatile solvent is found to contain a considerable quantity of trioxy-
naphthaline.
The four new dioxynaphthaline monosulpho acids and the four new trioxy-
naphthalines can be employed with great advantage in the production of azo dyes
or colouring matters the dioxynaphthalines and their sulpho acids yielding very
useful dyestuffs.
By combining the hereinbefore described dioxynaphthaline monosulpho acids with
tetrazo diphenyl, tetrazo ditolyl, tetrazo phenyl tolyl, tetrazo stilbene, tetrazo fluorene,
tetrazo naphthaline (a-3) or their sulpho or carbo acids or by combining the diazo
compound of the para acetanilide with the same the acetyl group splits off the liberated
amido group being further diazotised and caused to act upon amides, phenols and
dioxynaphthalines or their sulpho or carbo acids dyestuffs or colouring matters are
obtained almost all of which are suitable for dyeing unmordanted cotton in the alkaline
bath.
Colouring matter similarly available for dyeing cotton in an alkaline bath are also
obtained when, in place of the before mentioned tetrazo compounds, the diazo com-
pounds, the diazo compound of dehydrothiotoluidine and dehydrothioxylidine or their
sulpho acids are employed these bases being obtained by heating para toluidine and
mata vliding with sulphur.

page_text: Colouring matters are obtained by the action of these diazo compounds upon the
known dioxynaphthaline sulpho acids described in the patents herein before
referred to.
In addition to the azo colouring matters which are obtained by the action of
the above mentioned tetrazo compounds and which dye cotton violet to blue a very
useful blue colouring matter is also obtained by combining the tetrazo compound of
the ortho-tolidine, of the diamido diphenol ether or the etherised exdiphenyl base
described in the Specification of the German Patent No. 44209 either with the known
dioxynaphthaline sulpho acids or with the new dioxynaphthaline sulpho acids herein-
before described.
In all cases in which tetrazo compounds are employed the process may be so con-
ducted that instead of one molecule of a tetrazo compound being caused to act as
herein before described upon two molecules of a dioxynaphthaline sulpho acid,
one molecule of one of the tetrazo compounds combines with one molecule of a
dioxynaphthaline sulpho acid and that the intermediate product thus formed combines
with one molecule of another dioxynaphthaline sulpho acid or dioxynaphthaline to
form dyestuffs or colouring matter or the tetrazo compounds unite with one molecule
of an amide or a phenol or the sulpho or carbo acids or sulpho carbo acids thereof to
form the known intermediate products which are then caused to act upon dioxynaphtha-
line and its sulpho acids.
Azo colouring matters dyeing cotton directly a black colour are obtained with these
dioxynaphthaline sulpho acids by combining the hereinbefore mentioned tetrazo com-
pounds or their sulpho or carbo acids in the first place with one or two molecules of
alpha naphthylamine or alpha amido naphthol ether, further diazotising the compounds
formed and coupling the tetrazo compound obtained with dioxynaphthalines and their
sulpho acids either directly or by the way of the intermediate product.
Azo colouring matters capable of dyeing wool a black colour in an acid bath can be
readily formed from the dioxynaphthalines or their sulpho acids by further diazotising
the azo compounds (obtained from aniline-, toluidine-, xylidine-, alpha or beta
naphthylamine mono- or disulpho acid by diazotising and the action upon alpha
naphthylamine or alpha amido naphthol ethers) and causing them to act upon the new
dioxynaphthaline hereinbefore described and its sulpho acids.
On the other hand azo colouring matters which are fast to fulling and which dye
wool (preferably mordanted previously) a blue black are obtained by further diazotising
the colouring matters (produced from diazo-oxy-benzoic acids diazo-cresol carbon
acids, diazo-oxy-benzoic-sulpho-acids diazo-benzoic acids or diazo-phthalic acid) with
alpha naphthylamine and causing them to act upon the known or the new hereinbefore
described dioxynaphthalines and their sulpho acids.
Azo colouring matters which are fast to fulling and which dye wool prepared with
a chromium mordant a blue black is obtained by further diazotising these azo colouring
matters obtained from diazo oxybenzoic acids, diazo-cresol carbon acids, diazo-benzoic
sulpho acids or diazo-phthalic acids with alpha-naphthylamine and causing them to
act upon the known and the new hereinbefore described dioxynaphthaline and its
sulpho acids.
The process for the production of this azo dye stuff or colouring matter is very
simple and consists in causing the diazo or tetrazo compounds to react in the dioxy-
naphthaline and its sulpho acids maintained alkaline to the last with soda or, when an
intermediate product is to be obtained in the first instance with the tetrazo compound
and this is to be further treated to obtain the colouring matter, one molecule of one
of the tetrazo compounds hereinbefore described is combined with one molecule of a
dioxynaphthaline or of its sulpho acid in an acetic acid solution and allowed to stand
until the filtrate of the deposit separating from the intermediate product ceases to show
any reaction with an alkaline solution of naphthol sulpho acid and then purifying the
product with phenols and amides or sulpho acids in the known manner.
The leading features of this invention may be recapitulated as follows:-
The production of new dioxynaphthaline mono sulpho acids consisting in melting

page_text: with alkalies with or without pressure at a temperature of not less than 200 degrees
centigrade the naphthol disulpho acids described in the aforesaid Specifications of
German Patents 40571, 41079 and 45776 or by boiling alpha diazo naphthaline
disulpho acid III of the Specification of German Patent 41957.
The production of new trioxynaphthalines consisting in further melting with alkalies
at a temperature of not less than 200 degrees centigrade in open or closed vessels the
naphthol disulpho acids directly or the dioxynaphthäline mono sulpho acids obtained
as hereinbefore described.
The production of a new diazo colouring matter from the dioxynaphthaline mono
sulpho acids hereinbefore referred to by the action of one molecule of the tetrazo com-
pounds of benzidine, tolidine, diamido phenyl tolyl, diamido stilbene, diamido fluorene,
diamido naphthaline (a₁ a₂) or their sulpho or carbo acids upon two molecules of the
same or by the action of the intermediate product formed from one molecule of one of
tho tetrazo compounds hereinbefore described and one molecule of a phenol, amide,
dioxynaphthaline or the sulpho or carbo acids thereof.
The production of intermediate products by the action of one molecule of the tetrazo
compounds herein before described upon one molecule of "he dioxynaphthaline monc
sulpho acids also hereinbefore described.
The production of blue direct dyeing azo colouring matter by the action of para-diazo
acetanilide or alpha diazo naphthaline azo acetanilide upon dioxynaphthaline sulpho
acids splitting off the acetyl group, further diazotising and acting upon one molecule
of naphthol or dioxynapthaline- sulpho acid.
The production of azo colouring matter dyeing cotton a blue colour by the action
of one inolecule of the tetrazo compound of ortho toli line, diamido diphenol ether or
of the etherised oxydiphenyl bases described in the Specification of German Patent
No. 44209 and the additions thereto upon one molecule of any dioxynaphthaline sulpho
acids and in particular upon the dioxynaphthaline mono sulpho acids obtained as
herein before described so as to obtain intermediate products which contain a free
diazo-group and the combination thereof with alpha- or beta- naphthol or the sulpho-
acids thereof or dioxynaphthaline sulpho acids or by the action upon dioxynaphthaline
sulpho acids of the intermediate product formed from one molecule of such tetrazo
compound with alpha or beta naphthol or their sulpho acids.
The production of azo colouring matters dyeing cotton direct a blue-black by the
combination of the tetrazo compounds of the azo bodies (obtained from the tetrazo
compound herein before referred to and one or two molecules of alpha naphthylamine
or alpha amido naphthol ethers) with dioxynaphthalines and sulpho acids.
The production of azo colouring matters (capable of dyeing cotton in an alkaline
bath) by the combination of the diazo compounds of dehydro thio toluidine or of
dehydro thio xylidine (obtained by heating para toluidine or xylidine with sulphur)
or their sulpho acid upon or with any dioxynaphthaline sulpho acid and in particular
on that obtained as hereinbefore described.
The production of azo colouring matters capable of dyeing wool black in an acid
bath by the combination of the diazo compound of the azo compound formed from
aniline-toluidine-xylidine-alpha- or beta-naphthylamine mono- or di- sulpho acids and
alpha naphthylamine or alpha amido naphthol ether upon or with any dioxynaphthaline
mono-sulpho acid and in particular upon that obtained as hereinbefore described.
The production of azo colouring matter dyeing wool black in a neutral bath or
preferably wool prepared with chromium the black die being fixed with salts of chromium
by uniting the diazo compound of the azo body (formed from diazo salicylic acids,
diazo oxy-para-oxy-benzoic acids, diazo cresol carbo acids or their sulpho acids, diazo-
benzoic acids or diazophthalic acids with alpha naphthylamine) with any dioxynaphtha-
line sulpho acid and in particular with that herein before described.
Dated this 20th day of August 1889

page_text: COMPLETE SPECIFICATION.
Improvements in or connected with the Manufacture and Production
of Colouring Matters or Dyestuffs.
I, BENJAMIN WILLCOX of 47 Lincolns Inn Fields in the County of Middlesex,
Patent Agent, do hereby declare the nature of this Invention (which has been com-
municated to me from abroad by the Farbenfabriken vorm Friedrich Bayer and
Company of Elberfeld 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:
My foreign correspondents have discovered that the two naphthol di-sulpho acids
described in the Specifications of German Patents No. 40571 and 44079 when heated
with caustic alkalies such as potash or soda in open or closed vessels, are very readily
converted into new dihydroxynaphthalene-mono-sulpho acids and trihydroxynaphtha-
lenes, which when acted upon by diazo or tetrazo compounds lead to the production
of very valuable azo dyes or colouring matters.
The process for the production of the aforesaid new dihydroxynaphthalene-mono-
sulpho acids consists in melting the naphthol disulpho acids with alkalies with or
without pressure and at a temperature of not less than about 200 degrees centigrade.
For example about one part by weight of the sodium salt of the naphthol-disulpho
acid is heated with about three parts of caustic soda in a closed vessel to about
250 degrees centigrade until a sample shows the disappearance of fluorescence and
emits a strong odour of sulphurous acid, when acidulated. The melt is then poured
into water saturated with sulphuric acid and the acid solution boiled until all the
sulphurous acid is eliminated. The solution of the dihydroxynaphthalene-mono-sulpho
acid thus obtained is then neutralised with carbonate of soda and employed immediately
in the preparation of azo dyes or colouring matters.
It is nevertheless preferable to isolate the dihydroxynaphthalene-mono-sulpho acids
thus formed and to purify them by crystallization, which is best effected by salting
out or if this is impossible by evaporating the solutions and extracting the salt residue
with alcohol.
The trihydroxynaphthalenes are produced in like manner either directly from the
naphthol-disulpho-acids by continuing the melting process at a temperature of not
less than 200 degrees centigrade or by subjecting the dihydroxynaphthalene-mono-
sulpho acids obtained as hereinbefore described, to a further melting process.
In manufacturing these trihydroxynaphthalenes the materials must be heated more
highly or for a longer period according to the degree of concentration of the alkali
until a sample of the melt after being acidulated and extracted with a volatile solvent
is found to contain a considerable quantity of trihydroxynaphthalene.
The two new dihydroxynaphthalene-mono-sulpho acids and the two new trihydroxy
naphthalenes can be employed with great advantage in the production of azo dyes or
colouring matters, the dihydroxynaphthalene-sulpho-acids in particular yielding very
useful dyestuffs.
The dihydroxynaphthalene-mono-sulpho acid can be employed for obtaining new
disazo colouring matters for example by allowing two molecular proportions of the
acid to be acted on by one molecular proportion of a tetrazo compound of benzidine,
ortho-tolidine, diamido-phenyl-tolyl, diamido-stilbene, diamido-fluorene, a¹ a² diamido-
naphthalene or their sulpho or carboxy acids or by allowing one molecular proportion
of the acid to be acted on by an intermediate product formed from one molecular
proportion of one of the aforesaid tetrazo compounds and one molecular proportion of
a phenol, an amide, a dihydroxynaphthalene or their sulpho or carboxy acids.
By combining the herein before described dihydroxynaphthalene-mono-sulpho acids
with tetrazo-diphenyl, ortho-tetrazo-ditolyl, tetrazo-phenyl-tolyl, tetrazo-stilbene,
tetrazo-fluorene (a' a²) tetrazo-naphthalene or their sulpho or carboxy acids, or by
combining the diazo compound of para-acetanilide with the same, splitting off the
acetyl group, diazotising the liberated amido group and causing the diazo compound

page_text: to act upon amides, phenols and dihydroxynaphthalenes or their sulpho or carboxy
acids dyestuffs or colouring matters are obtained, almost all of which are suitable for
dyeing unmordanted cotton in an alkaline bath. Colouring matters which are similarly
available for dyeing cotton in an alkaline bath are also obtained when, in place of the
before mentioned tetrazo-compounds, the diazo-compound of this toluidine and thioxy-
lidline or their sulpho acids are employed, these bases being obtained by heating para-
toluidine and meta-xylidine with sulphur.
Valuable colouring matters are furthermore obtained by the action of these dinzo or
tetrazo compounds upon the known dihydroxynaphthalene-sulpho acids described in
the French Patent No. 172392.
Blue direct dyeing azo colouring matters are obtained by the action of para-diazo-
acetanilide or alpha-diazo-naphthalene-azo-acetanilide upon the dihydroxynaphthalene-
sulpho acids, splitting off the acetyl group and causing the diazo-compound to act
upon one molecular proportion of a naphthol or hydroxynaphthalene-sulpho acid.
In addition to the azo colouring matters which are obtained by the action of the
above mentioned tetrazo compounds and which dye cotton violet to blue, very useful
blue colouring matters for dyeing unmordanted cotton are also obtained by combining
the tetrazo compounds of orthotolidine, of diamido-diphenolether or the etherized
oxydiphenyl bases described in the Specification of the German Patent No. 41209
either with known dihydroxynaphthalene-sulpho acids or with the new dihydroxy-
naphthalene-sulpho acids hereinbefore described.
In all cases in which tetrazo compounds are employed the process may be so
conducted that instead of one molecular proportion of a tetrazo compound being caused
to act as herein before described upon two molecular proportions of a dihydroxy-
naphthalene-sulpho acid, one molecular proportion of one of the tetrazo compounds is
caused to combine with one molecular proportion of a dihydroxynaphthalene sulpho
acid so as to form an intermediate product containing a free diazo group which may
then be combined with one molecular proportion of another dihydroxynaphthalene-
sulpho acid or dihydroxynaphthalene to form dyestuffs or colouring matter or the
tetrazo compounds may be united with one molecular proportion of an amide or a
phenol or the sulpho or carboxy acids or sulpho carbo acids thereof to form the
known intermediate products which are then caused to act upon the dihydroxy-
naphthalenes or sulpho acids.
Azo colouring matters dyeing cotton directly a blue black colour are obtained
from dihydroxynaphthalenes and their sulpho acids by combining the hereinbefore
mentioned tetrazo compounds or their sulpho or carboxy acids in the first place with
one or two molecular proportions of alpha-naphthylamine or alpha-amido-naphthol
ether then further diazotising the compounds thus formed and coupling the tetrazo
compound so obtained with dihydroxynaphthalenes or their sulpho acids, either
directly or by the way of the intermediate product.
Azo colouring matters capable of dyeing wool a black colour in an acid bath can
be readily formed from dihydroxynaphthalenes or their sulpho acids by further
diazotising the azo compounds (obtained from the diazo compounds of aniline,
toluidine, xylidine-alpha or beta naphthalamine-mono or disulpho acids and alpha-
naphthylamine or alpha-amido-naphthol ethers) and causing them to act upon the
dihydroxynaphthalene mono sulpho acids obtained as herein before described.
On the other hand azo colouring matters which are fast to fulling and which dye
wool in a neutral bath (or preferably prepared with a chromium mordant) a blue
black, are obtained by further diazotising the colouring matters produced from diazo
salicylic acids, diazo-para hydroxybenzoic acids, diazo-cresol-carboxy acids diazo
benzoic acids or diazo-phthalic acids or their sulpho acids, with alpha-naphthylamine
or amido naphthol ether and causing the diazotised products to act upon the known
or the new dihydroxynaphthalene sulpho acids herein before describe !.
The process for the production of all these azo dyestuffs or colouring matters is very
simple and consists in causing the diazo or tetrazo compounds to act on the dihydroxy-
naphthalenes or their sulpho acids the liquid being maintained alkaline throughout

page_text: with soda, or when an intermediate product is to be formed in the first instance from
the tetrazo compound and this is to be further treated to obtain the colouring matter,
one molecular roportion of one of the tetrazo compounds herein before described is
combined with one molecular proportion of a dihydroxynaphthalene or of its sulpho
acid in an acetic acid solution and the mixture is allowed to stand until the filtrate
from the deposit of the intermediate product ceases to shew any reaction with an
alkaline solution of naphthol sulpho acid whereupon the intermediate product is
combined with phenols or amides or sulpho acids in the known manner.
Having now particularly described and ascertained the nature of the said
invention and in what manner the same is to be performed I declare that what I
I claim is
I. The production of new dihydroxynaphthalene mono sulpho acids by melting
with alkalies with or without pressure at a temperature of not less than 200 degrees
centigrade the naphthol disulpho acids described in the Specifications of the Gorman
Patents Nos. 40,571 and 44,079.
II. The production of new trihydroxynaphthalenes by melting with alkalies at a
temperature of not less than 200 degrees Centigrade in open or closed vessels the
naphthol disulpho acids or the dihydroxyraphthalene-mono sulpho acids referred to in
the preceding claiming clause.
1II. The production of new disazo colouring matters from the dihydroxynapthaline-
mono sulpho acids hereinbefore referred to by the action of one molecular proportion
of the tetrazo compounds of benzidine, orthotolidine, diamido phenyl- tolyl, diamido-
stilbene, diamido fluorene, diamido-naphthalene (a' a²) or their sulpho or carboxy
acids upon two molec.lar proportions of one of the said dihydroxynaphthalene-mono-
sulpho acids or hy the action of the intermediate products formed from one molecular
proportion of one of the tetrazo compounds herein before referred to and one molecular
proportion of a phenol, amide, dihydroxynaphthalene or the sulpho or carboxy acids
thereof upon one molecular proportion of the same.
IV. The production of intermediate products by the action of one molecular
proportion of one of the tetrazo compounds herein specified in the 3rd and 6th
claiming clauses upon one molecular proportion of one of the new dihydroxy-
naphthalene mono sulpho acids.
V. The production of blue direct dyeing azo colouring matter by acting with
para-diazo-acetanilide or alpha-diazo-naphthalene-azo-acetanilide upon hydroxy-
naphthalene-sulpho acids splitting off the acetyl group, further diazotising the free
amido group and acting with the diazo compound upon one molecular proportion of
a naphthol or dihydroxynaphthalene-sulpho-acid.
VI. The production of azo colouring matters dyeing unmordanted cotton a blue
colour (a) by the action of one molecular proportion of the tetrazo compound of
orthotolidine, diamido-diphenol ether or of the etherised oxydiphenyl bases described
in the Specification of German Patent No. 44209, upon two molecular proportions of
any dihydroxynaphthalene-sulpho acids and in particular upon the new dihydroxy-
naphthalene-mono-sulpho acids hereinbefore described or upon one molecular propor-
tion thereof so as to obtain intermediate products containing a free diazo group
which are then combined with the dihydroxynaphthalene sulpho acids or (b) by the
action of the intermediate product formed from one molecular proportion of the
aforesaid tetrazo compound with alpha or Leta naphthol or their sulpho acids upon
dihydroxynaphthalene sulpho neis.
VII. The production of azo colouring matters dyeing cotton directly a blue black
by the combination of the tetrazo compounds of the azo bodies (obtained from the
tetrazo compounds herein specified in the 3rd and 6th claiming clauses and one or two
molecular proportions of alpha-naphthylamine or alpha-amido-naphthol ethers) with
dihydroxynaphthalenes or their sulpho acids substantially as hereinbefore described.
VIII. The production of azo colouring matters (capable of dyeing cotton in an
alkaline bath) by the combination of the diazo compounds of thiotoluidine or of

page_text: thioxylidine (obtained by heating para toluidine or metaxylidine with sulphur) or their
sulpho acid upon or with a dihydroxynapthalene-sulpho acid obtained as hereinbefore
described or otherwise.
IX. The production of azo colouring matters capable of dyeing wool black in an
acid bath by the combination of the diazo compounds of the azo compound formed
from aniline-toluidine-xylidine-alpha- or beta naphthylamine-mono or di-sulpho acids
and alpha naphthylamine or alpha-amido-naphthol ethers upon or with one of the
new dihydroxynaphthalene mono sulpho acids obtained as hereinbefore described or
otherwise.
X. The production of azo colouring matter dyeing wool black in a neutral bath or
preferably wool prepared with chromium salts by combining the diazo compounds of
the azo bodies (forined from diazo-salicylic acids, diazo-para-hydroxy-benzoic acids,
diazo cresol-carboxy acids or their sulpho acids, diazo-benzoic acids or diazo phthalic
acids with alpha naphthylamine (or amidonaphtholether) with any dihydroxy
naphthalene-sulpho acid and in particular with those herein before described.
XI. As new articles of manufacture the several products such as are obtained
according to the processes hereinbefore claimed under the several claiming clauses
I to X.
Dotal this 2011 JT 1000
J. H. JOHNSON & Co.,
Agents.