Year: 1887

page_text: Date of Application, 18th Aug., 1887
Complete Specification Left, 16th May, 1888-Accepted, 17th Aug., 1888
[Communicated from abroad by Messrs. WIRTH & Co., of Frankfort-on-the-Main
Acting as Agents of A. Leonhardt & Co., of Müklheim-on-the-Main, both in the
Empire of Germany.]
I, HENRY HARRIS LAKE, of the firm of Haseltine, Lake, & Co. Patent Agents
Southampton Buildings, in the County of Middlesex, do hereby declare the nature of
this invention to be as follows:-
This invention relates to the manufacture of alpha-naphthol-disulpho-acid and to
the production of colouring matters therefrom.
Disulpho-acids of alpha-naphthol have not heretofore been prepared in a pure state.
Such acids have only been obtained mixed with varying quantities of the lower and
higher products of sulphuration of alpha-naphthol in the several modes of treating
alpha-naphthol with sulphuric acid.
The preparation of a uniform disulpho-acid of alpha-naphthol has heretofore not
been carried into practice. It is effected, according to the first part of this invention,
by observing certain conditions of sulphuration in which mono- and trisulpho-acids of
alpha-naphthol are not obtained.
The conditions which enable this now result to be achieved are as follows:
Ordinary hydrous sulphuric acid of commerce of 65 to 66 degrees Baumé is used.
At most three parts of sulphuric acid are employed for one part of alpha-
naphthol.
•
The temperature is increased to 130 to 140 degrees, and the molten mass is
maintained at this temperature for a comparatively long time.
The disulpho-acid of alpha-naphthol thus produced has the following characteristic
properties :
It is readily soluble in concentrated sulphuric acid, and remains unchanged during
the boiling with dilute sulphuric acid (1 part of acid, 2 parts of water). Its salts are

page_text: very readily soluble, and not crystallizable. With diazo-compounds it yields azo
colouring matters, and with nitrous acid, nitroso-compounds. With dilute nitric acid
and at an increased temperature it produces, under violent development of red
vapours and changing colour into an intense red, dirty yellow colouring matters besides
a little binitronaphtholsulpho-acid.
The second part of the invention consists in the preparation of colouring matters
from the alpha-naphthol-disulpho-acid.
Into an aqueous solution, to be kept slightly acid, of alpha-naphthol-disulpho acid,
or of the calcium, barium, sodium, or potassium salt thereof, is introduced sodium
nitrite or potassium nitrite in a solid state or in aqueous solution as long as nitrous
acid is absorbed. The product thus nitrosated is nitrated by the addition of nitric
acid of commerce or of soda or potassium saltpetre and sulphuric acid at the ordinary
temperature, or by carefully raising the same to about 50 degrees Centigrade. The
yellow colouring matter which precipitates especially when carbonate of potassium is
added, is filtered, pressed and dried.
Combined with diazo-bodies the said alpha-naphthol disulpho-acid yields azo colors,
of which as examples are mentioned the following.
Orange colouring matters: diazobenzol diazoxylol.
Red colouring matters, diazonaphthionic acid, diazoazobenzol, diazoazotoluol.
Violet colouring matters, tetrazodiphenyl, tetrazostilbene, tetrazostilbene-disulpho-
acid.
ת
HASELTINE, LAKE & Co.,
45, Southampton Buildings, London,
Agents for the Applicant.

page_text: Improvements in the Manufacture of Alpha-naphtholdisulpho-acid
and in the Production of Colouring Matters therefrom.
I, HENRY HARRIS LAKE, of the firm of Haseltine, Lake & Co., Patent Agents,
Southampton Buildings, in the County of Middlesex, 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 :-
This invention relates to the manufacture of alpha-naphtholdisulpho-acid and to the
production of colouring matters therefrom.
Disulpho-acids of alpha-naphthol have not heretofore been prepared in a pure state.
Such acids have only been obtained mixed with varying quantities of the lower and
higher products of sulphuration of alpha-naphthol in the several modes of treating
alpha-naphthol with sulphuric acid.
The preparation of a uniform disulpho-acid of alpha-naphthol has heretofore not
been carried into practice. It is effected, according to one part of this invention, by
observing certain conditions of sulphuration in which mono- and trisulpho-acids of
alpha-naphthol are not obtained.
The conditions which enable this new result to be achieved are as follows:-
Ordinary hydrous sulphuric acid of commerce of 65 to 66 degrees Baumé (about
93% of anhydrous acid) is used.
From two to at most three parts of sulphuric acid are employed for one part of
alpha-naphthol.
The temperature is increased to 125-130 degrees Centigrade, and the molten mass
is maintained at this temperature for about two hours.
The disulpho-acid of alpha-naphthol thus produced has the following characteristic
properties:
It is readily soluble in concentrated sulphuric acid, and remains unchanged during
the boiling with dilute sulphuric acid (1 part of acid, 3 parts of water). Its salts are
very readily soluble, and hardly crystallizable. With diazo-compounds it yields azo-
colouring matters, and with nitrous acid, nitroso-compounds. With dilute nitric acid.
and at an increased temperature it produces, with violent development of red
vapours, and changing colour into an intense red, dirty yellow colouring matters
besides a litttle binitronaphtholsulpho-acid.
The second and third part of the invention consist in the preparation of colouring
matters from this alpha-naphthol-disulpho-acid.
A quantity of 40 kilogrammes of alpha-naphthol is, for instance, transformed into.
disulpho-acid according to the conditions above specified.
Into an aqueous solution, to be kept slightly acid, of this alphanaphtholdisulpho-
acid, or of the calcium, barium, sodium, or potassium salt thereof, is introduced sodium
nitrite or potassium nitrite in a solid state or in an aqueous solution as long as nitrous
acid is absorbed. The product thus nitrosated is nitrated by the addition of 100 kilo-
grammes of nitric acid of commerce or of a corresponding quantity of soda-saltpetre
or potash-saltpetre and sulphuric acid at the ordinary temperature or while carefully
raising the same to about 50 degrees centigrade. The yellow colouring matter
which precipitates, especially when carbonate of potassium is added, is filtered, pressed
and dried.

page_text: Combined with diazo-bodies the said alpha-naphtholdisulpho-acid yields azo-colours
of which, as examples, we mention the following:
:-
Orange colouring matters: diazobenzol, diazoxylol. Red colouring matters: diazo-
naphthionic acid, diazoazobenzol, diazoazotoluol.
Violet colouring matters: tetrazodiphenyl, tetrazostilbene, tetrazostilbenedisulpho-
acid.
The production of the azo-colours is effected in a manner well known to chemists.
The following are examples.
(a) 29 kilogrammes of alpha-naphthol is transformed into disulpho-acid according to
the conditions above specified. The disulpho-acid thus obtained is converted into its
sodium salt, and to an alkaline aqueous solution of this sodium salt is added a solution
of diazoxylol, prepared in a known manner from 23 kilogrammes of xylidine. The
orange colouring matter is formed "instantly; it is precipitated by means of dilute
sulphuric acid and common salt.
(b) Tetrazostilbene prepared in a known way from 20 kilogrammes of diamido-
stilbene; the violet colouring matter is formed after allowing the same to stand for
some time; it is precipitated by means of common salt.
I am well aware that alphanaphtholdisulpho-acid has already been prepared by the
action of sulphuric acid upon naphthol, the known processes do not, however, yield a
uniform product, but only a mixture of lower and higher products of sulphuration,
and the distinguishing feature of the above described process of manufacturing a
uniform disulpho-acid consists in the difference in the proportion and strength of the
sulphuric acid used and in the temperature and time at and during which the operation
takes place as hereinbefore stated.
I am also aware that the mixtures obtained by the said known processes have already
been treated with nitrite and nitric acid and also with aromatic diazo-derivatives in
order to obtain colouring matters.
I do not claim in general the action of sulphuric acid upon naphthol, nor do I
claim in general the action of nitrite and nitric acid or of diazo-derivatives upon alpha-
naphtholdisulpho-acid.
I am aware that it has been proposed to prepare a mixture of sulpho acids for use
in the manufacture of colouring matters under the following conditions viz. :-10 parts
by weight of alpha-naphthol dissolved at a temperature of 100 degrees centigrade in
40 parts by weight of ordinary commercial rectified sulphuric acid marking about
170 degrees on Twaddell's hydrometer the temperature to be increased after the
naphthol is dissolved to about 130 degrees centigrade and kept at that temperature for
about one hour.
I therefore make no claim for this method of preparing a mixture of sulpho acids.
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 by my
foreign Correspondents I declare that what I claim is :―
First. The process of producing a uniform alphanaphthol-disulpho-acid, substantially
as set forth.
Second. Obtaining yellow colouring matter by a continuation of the said process,
consisting in treating the product of the said process with nitrite of sodium, and
nitrating the intermediate product, substantially as set forth.
Third. Obtaining orange, red or violet colouring matters by a continuation of the
process specified in the first claiming (clause, consisting in treating the product of
the said process with diazo-derivatives of aromatic amines, substantially as set
forth.

page_text: Date of Application, 18th Aug., 1887
Complete Specification Left, 16th May, 1888
Complete Specification Accepted, 17th Aug., 1888
[Communicated from abroad by Messrs. WIRTH & Co., of Frankfort-on-the-Main
Acting as Agents of A. Leonhardt & Co., of Müklheim-on-the-Main, both in the
Empire of Germany.]
Improvements in the Manufacture of Alpha-naphtholdisulpho-acid
and in the Production of Colouring Matters therefrom.
I, HENRY HARRIS LAKE, of the firm of Haseltine, Lake, & Co. Patent Agents
Southampton Buildings, in the County of Middlesex, do hereby declare the nature of
this invention to be as follows:-
This invention relates to the manufacture of alpha-naphthol-disulpho-acid and to
the production of colouring matters therefrom.
Disulpho-acids of alpha-naphthol have not heretofore been prepared in a pure state.
Such acids have only been obtained mixed with varying quantities of the lower and
higher products of sulphuration of alpha-naphthol in the several modes of treating
alpha-naphthol with sulphuric acid.
The preparation of a uniform disulpho-acid of alpha-naphthol has heretofore not
been carried into practice. It is effected, according to the first part of this invention,
by observing certain conditions of sulphuration in which mono- and trisulpho-acids of
alpha-naphthol are not obtained.
The conditions which enable this new result to be achieved are as follows:
Ordinary hydrous sulphuric acid of commerce of 65 to 66 degrees Baumé is used.
At most three parts of sulphuric acid are employed for one part of alpha-
naphthol.
The temperature is increased to 130 to 140 degrees, and the molten mass is
maintained at this temperature for a comparatively long time.
The disulpho-acid of alpha-naphthol thus produced has the following characteristic
properties:
It is readily soluble in concentrated sulphuric acid, and remains unchanged during
the boiling with dilute sulphuric acid (1 part of acid, 2 parts of water). Its salts are

page_text: very readily soluble, and not crystallizable. With diazo compounds it yields azo
colouring matters, and with nitrous acid, nitroso-compounds. With dilute nitric acid
and at an increased temperature it produces, under violent developement of red
vapours and changing color into an intense red, dirty yellow colouring matters besides
a little binitronaphtholsulpho-acid.
The second part of the invention consists in the preparation of colouring matters
from the alpha-naphthol-disulpho-acid.
Into an aqueous solution, to be kept slightly acid, of alpha-naphthol-disulpho-acid,
or of the calcium, barium, sodium, or potassium salt thereof, is introduced sodium
nitrite or potassium nitrite in a solid state or in aqueous solution as long as nitrous
acid is absorbed. The product thus nitrosated is nitrated by the addition of nitric
acid of commerce or of soda or-potassium saltpetre and sulphuric acid at the ordinary
temperature, or by carefully raising the same to about 50 degrees Centigrade. Tho
yellow colouring matter which precipitates especially when carbonate of potassium is
added, is filtered, pressed and dried.
Combined with diazo-bodies the said alpha-naphthol disulpho-acid yields azo colors,
of which as examples are mentioned the following.
Orange colouring matters: diazobenzol diazoxylol.
Red colouring matters, diazonaphthionic acid, diazoazobenzol, diazoazotoluoĺ.
Violet colouring matters, tetrazodiphenyl, tetrazostilbene, tetrazostilbene-disulpho-
acid.
Do
C
1007
HASELTINE, LAKE & Co.,
45, Southampton Buildings, London,
Agents for the Applicant.

page_text: Improvements in the Manufacture of Alpha-naphtholdisulpho-acid
and in the Production of Colouring Matters therefrom.
1, HENRY HARRIS LAKE, of the firm of Haseltine, Lake & Co., Patent Agents,
Southampton Buildings, in the County of Middlesex, 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 :-
This invention relates to the manufacture of alpha-naphtholdisulpho-acid and to the
production of colouring matters therefrom.
Disulpho-acids of alpha-naphthol have not heretofore been prepared in a pure state.
Such acids have only been obtained mixed with varying quantities of the lower and
higher products of sulphuration of alpha-naphthol in the several modes of treating
alpha-naphthol with sulphuric acid.
The preparation of a uniform disulpho-acid of alpha-naphthol has heretofore not
been carried into practice. It is effected, according to one part of this invention, by
observing certain conditions of sulphuration in which mono- and trisulpho-acids of
alpha-naphthol are not obtained.
The conditions which enable this new result to be achieved are as follows:-
Ordinary hydrous sulphuric acid of commerce of 65 to 66 degrees Baumé (about
93% of anhydrous acid) is used.
From two to at most three parts of sulphuric acid are employed for one part of
alpha-naphthol.
The temperature is increased to 125-130 degrees Centigrade, and the molten mass
is maintained at this temperature for about two hours.
The disulpho-acid of alpha-naphthol thus produced has the following characteristic
properties:
It is readily soluble in concentrated sulphuric acid, and remains unchanged during
the boiling with dilute sulphuric acid (1 part of acid, 3 parts of water). Its salts are
very readily soluble, and hardly crystallizable. With diazo-compounds it yields azo-
colouring matters, and with nitrous acid, nitroso-compounds. With dilute nitric acid
and at an increased temperature it produces, with violent developement of red
vapours, and changing colour into an intense red, dirty yellow colouring matters
besides a little binitronaphtholsulpho-acid.
The second and third part of the invention consist in the preparation of colouring
matters from this alpha-naphthol-disulpho-acid.
A quantity of 40 kilogrammes of alpha-naphthol is, for instance, transformed into
disulpho-acid according to the conditions above specified.
Into an aqueous solution, to be kept slightly acid, of this alphanaphtholdisulpho-
acid, or of the calcium, barium, sodium, or potassium salt thereof, is introduced sodium
nitrite or potassium nitrite in a solid state or in an aqueous solution as long as nitrous
acid is absorbed. The product thus nitrosated is nitrated by the addition of 100 kilo-
grammes of nitric acid of commerce or of a corresponding quantity of soda-saltpetre

page_text: or potash-saltpetre and sulphuric acid at the ordinary temperature or while carefully
raising the same to about 50 degrees centigrade. The yellow colouring matter
which precipitates, especially when carbonate of potassium is added, is filtered, pressed
and dried.
Combined with diazo-bodies the said alpha-naphtholdisulpho-acid yields azo-colours
of which, as examples, we mention the following
Orange colouring matters: diazobenzol, diazoxylol. Red colouring matters: diazo-
naphthionic acid, diazoazobenzol, diazoazotoluol.
Violet colouring matters: tetrazodiphenyl,. tetrazostilbene, tetrazostilbenedisulpho-
acid.
The production of the azo-colours is effected in a manner well known to chemists.
The following are examples.
(a) 29 kilogrammes of alpha-naphthol is transformed into disulpho-acid according to
the conditions above specified. The disulpho-acid thus obtained is converted into its
sodium salt, and to an alkaline aqueous solution of this sodium salt is added a solution
of diazoxylol, prepared in a known manner from 23 kilogrammes of xylidine. The
orange colouring matter is formed instantly; it is precipitated by means of dilute
sulphuric acid and common salt.
(b) Tetrazostilbene prepared in a known way from 20 kilogrammes of diamido-
stilbene; the violet colouring matter is formed after allowing the same to stand for
some time; it is precipitated by means of common salt.
I am well aware that alphanaphtholdisulpho-acid has already been prepared by the
action of sulphuric acid upon naphthol, the known processes do not, however, yield a
uniform product, but only a mixture of lower and bigher products of sulphuration,
and the distinguishing feature of the above described process of manufacturing a
uniform disulpho-acid consists in the difference in the proportion and strength of the
sulphuric acid used and in the temperature and time at and during which the operation
takes place as hereinbefore stated.
I am also aware that the mixtures obtained by the said known processes have already
been treated with nitrite and nitric acid and also with aromatic diazo-derivatives in
order to obtain colouring matters.
I do not claim in general the action of sulphuric acid upon naphthol, nor do I
claim in general the action of nitrite and nitric acid or of diazo-derivatives upon alpha-
naphtholdisulpho-acid.
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 by my
foreign Correspondents I declare that what I claim is :―
First. The process of producing a uniform alphanaphthol-disulpho-acid, substantially
as set forth.
Second. Obtaining yellow colouring matter by a continuation of the said process,
consisting in treating the product of the said process with nitrite of sodium, and
nitrating the intermediate product, substantially as set forth.
Third. Obtaining orange, red or violet colouring matters by a continuation of the
process specified in the first claiming clause, consisting in treating the product of
the said process with diazo-derivatives of aromatic amines, substantially as sets
forth.
T