Preparation of a New ẞ-naphthylaminesulphonic Acid and of ẞ-naphthylamine, and the Preparation of Salts of ẞ-naphthyl- sulfamine Acid from the former.
Year: 1893

page_text: Date of Application, 12th Aug., 1893
Complete Specification Left, 12th May, 1894-Accepted, 23rd June, 1894
PROVISIONAL SPECIFICATION.
Preparation of a New ẞ-naphthylaminesulphonic Acid and of
ẞ-naphthylamine, and the Preparation of Salts of ẞ-naphthyl-
sulfamine Acid from the former.
I, Dr. GEORG TOBIAS, of 12 Waterloo Ufer, Berlin, S.W. Germany, Chemist,
do hereby declare the nature of this invention to be as follows:-
This invention has for object :-
:-
1. The preparation of a new and hitherto unknown ẞ-naphthylaminemono-
sulphonic acid by heating under pressure the B-naphtholsulphonic acid 2 : 1 hitherto
believed to be ẞ-naphthylsulphate or its salts with a solution of ammonia as well as
the partial or full conversion effected at one operation of this new ẞ-naphthyl-
aminesulphonic acid into ẞ-naphthylamine.
2. The preparation of the salts of ẞ-naphthylsulfamin acid formed as an unstable
intermediate product in the preparation of B-naphthylamine by heating the salts
of the B-naphthylaminsulphonic acid obtained as stated under 1.
This invention is chiefly based upon the knowledge that the acid obtained by
Armstrong (Report of the German Chemical Company XV 1882 page 202) and
Nietzki (page 305) during the transient action of English sulphuric acid upon
finely divided ẞ-naphthol at an ordinary temperature is not in accordance with the
hitherto unopposed views of the discoverers thereof, a B-naphthylsulphate but a
B-naphtholsulphonic acid, that is to say, the B-naphtholsulphonic acid 2: 1. This
acid can be profitably produced according to the directions of Nietzki. The soda
salt is entirely won in the ordinary way from the raw acid with the aid of calcium
salt by means of carbonate of soda, and by adding common salt to the concentrated
solution, or it may be separated by suitably diluting the crude acid with water and
treating the liquor with common salt as above. In order to better characterize the
nature of the substance produced which is yet very little known, I shall now
proceed to give a description of its properties.
The sodaic salts form in cold water and in 80% alcohol or spirit of wine, easily
soluble scales, while the potassic salts form shining scales, which are only slightly
soluble in hot water.
The sodaic as well as the potassic salt remains fully unaffected when the aqueous
solution is evaporated, and when heated in a dry state at a temperature greatly
exceeding 100°, only the calcic, as well as the barytie salts are decomposed when
evaporating a very concentrated solution of the same.
Diluted solutions of these salts and of the free acids strongly acidulated with
mineral acids can be boiled without decomposition upon an open fire, the conversion
into naphthol and sulphuric acid takes place slowly when boiling acidulated con-
centrated solutions but rapidly when an excess of concentrated mineral acid is
present. Neutral solutions of the acids produce with chloride of iron an intense
indigo blue coloration. Hot alcoholic solutions of the sodaic salts yield by the
addition of soda lyes crystalline scales of a "di-soda" salt having the formula
C₁H (ONa)SO,Na + 2 C,H,O which is easily soluble in water.
The solution of the same shows no fluorescence; chloride of barium precipitates
at once in hot water, a nearly insoluble deposit of a basic barytic salt. Diazo-
sulphonic acid eliminates, in the concentrated solution of the monosodaic salt to
which solution is added carbonate of soda, its sulphonic group while forming the
well known coloring matter which derives from ẞ-naphthol.
By heating for a long time in a boiler subjected to pressure the sodaic salt of the
B-naphtholsulphonic acid herein described with equal parts of a 20% solution of

page_text: ammonia in water in order to convert it into the corresponding ẞ-naphthylamine-
sulphonic acid as carried out in the usual manner with well known isomeres, a
reaction takes place at a temperature of from 220 to 230° C., whereby there is
formed amongst a number of colored products of decomposition, chiefly impure
B-naphthylamine and in a secondary mass, a salt of ẞ-naphthylaminesulphonic acid.
If on the contrary 4 to 5 parts of from 15 to 20% of an aqueous solution of
ammonia is used with 1 part of sodaic naphtholsulphonic acid there is formed
after heating at the same temperature for from 10 to 20 hours only a small quantity
of B-naphthylamine and as chief product in a much higher state of purity the
salt of the expected -naphthylaminesulphonic acid. By heating for a still longer
time or by preferably raising the temperature to from 240 to 250° C., there is
obtained with the same proportions of ingredients ẞ-naphthylamine alone or merely
predominating in the mass which naphthylamine is likewise much purer than that
won from the concentrated solution.
The scdaic salt of the B-naphthylaminesulphonic acid thus obtained is readily
soluble in water, and when allowed to cool, fully precipitated in the form of
crystalline scales from its hot and not too highly diluted solution by the addition
of common salt. The potassic and ammoniacal salts act in the same manner.
The diluted solution of this salt shows a feeble violet fluorescence. The diazo-
sulphonic acid extracted therefrom has the form of a clean yellow crystalline
powder which is not readily soluble. By boiling with diluted sulphuric acid
the same yields naphtholsulphonic acid, which has assisted in its formation, and
is further converted by known methods into dichlornaphthaline 1:2 melting at
a temperature of 34° C. The B-naphthylaminesulphonic acid herein described
remains unchanged when heated to a temperature of 250° C.; but if its dried
salt, the sodaic or ammoniacal salt for instance is heated for a long time in a
thoroughly dry atmosphere at a temperature of about 230° C., the same is
converted into salts of the isomeric B-naphthylsulfamin acid according to the
cavation
The new salts thus obtained are soluble in water and are precipitated from their
solution by common salt in the form of flakes or scales; their neutral and alkaline
solutions can be boiled without being decomposed. They are decomposed by the
mineral acids and with the aid of heat into B-naphthylamine and bisulphate.
If hydrochloric acid and nitrite of soda is introduced into their cold solution, a
clear yellow liquor is obtained which acts in the same manner as the solution of a
B-diazonaphthaline salt, and can be similarly used in the preparation of insoluble
dyeing material for fibres for instance.
The salts of the B-naphthylsulfamin acid can, in consequence of the easy
separability of their sulphonic group, he used as well as the above new ẞ-naphthyl-
aminsulphonic acid as a substitute for B-naphthylamine in the preparation of the
already known B-naphthylaminesulphonic acids by means of sulphuric acid.
The B-naphthylamine obtained from the B-naphtholsulphonic acid 2:1 by
heating with several times its weight of aqueous ammonia is as compared with
that obtained directly from naphthol free from dinaphthylamine and naphthol, this
results from the fact, that the B-naphthylamin is here formed by hydrolysis of the
B-naphthylsulfamin acid. The mode of operation is as follows
1. B-naphthylaminesulphonic acid 2: 1.
10 kg, of the sodaic salt of naphtholsulphonic acid 2:1 are heated in a boiler
subjected to pressure for from 10 to 20 hours at from 220-230° C. with 50 kg.
of a 15 to 20% aqueous solution of, ammonia. After the ammonia has been
driven off and cooling has twice taken place, the ẞ-naphthylamine is removed
by filtering from the products of the reaction while the B-naphthylaminesulphonic
acid is separated by means of hydrochloric acid, or as a sodaic salt by common salt
when treating a solution which is first concentrated by evaporation.

page_text: The salt of the naphtholaulphonic acid which may still remain is previously won
back as a basic barium salt which is nearly insoluble.
2. To prepare B-naphthylamine, the foregoing mixture is heated to a temperature
higher by 20° C. than the former, and the ẞ-naphthylamine which is obtained
after cooling partly in the form of crystalline scales and partly in the shape of a
fused crystalline cake is utilized directly after having been dried and ground, or
after a previous distillation. The filtrate may be still further treated with a view
to recovering any B-naphthylaminesulphonic acid which may still be present.
3. To obtain a sodaic salt of 3-naphthylsulfamin acid, a previously well dried
sodaic salt of the B-naphthylaminesulphonic acid obtained in the manner described
in § 1 is treated in a boiler furnished with stirring means, and placed in an air or
oil bath, and heated at a temperature of about 230° C. until the cold diluted
solution when tested allows the separation of neither B-naphthylaminesulphonic
acid after the addition of hydrochloric acid nor diazosulphonic acid after the
addition of nitrite of soda.
1 1
7
L 1000
H. GARDNER,
Patent Agent, 166, Fleet Street, London,
Agent for the said Dr. Georg Tobias.
COMPLETE SPECIFICATION.
Preparation of a New 3-naphthylaminesulphonic Acid and ẞ-naph-
thylamine, and the Preparation of Salts of ẞ-naphthylsulfamine
Acid from the former.
I, Dr. GEORG TOBIAS, of 12 Waterlooufer, Berlin, S.W. Germany, Chemist,
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 has for object :-
1. The preparation of a new and hitherto unknown ẞ-naphthylaminemonosulphonic
acid by heating under pressure the B-naphtholsulphonic acid 2: 1 hitherto believed
to be B-naphthylsulphate or its salts with a solution of ammonia as well as the
partial or full conversion effected at one operation of this new ẞ-naphthylamine-
sulphonic acid into ẞ-naphthylamine.
2. The preparation of the salts of ẞ-naphthylsulfamine acid formed as an unstable
intermediate product in the preparation of B-napthylamine by heating the salts of
the B-napthylaminesulphonic acid obtained as stated under 1.
This invention is chiefly based upon the knowledge that the acid obtained by
Armstrong (Report of the German Chemical Society XV 1882, page 202) and
Nietzki (page 305) during the transient action of English sulphuric acid upon finely
divided -naphthol at an ordinary temperature is not in accordance with the
hitherto unopposed views of the discoverers thereof, a B-naphthylsulphate but a
B-naphtholsulphonic acid, that is to say, the B-naphtholsulphonic acid 2: 1.
This acid can be profitably produced according to the directions of Nietzki.
The soda salt is entirely won in the ordinary way from the raw acid with the aid
of calcium salt by means of carbonate of soda, and by adding common salt to the
concentrated solution, or it may be separated by suitably diluting the crude acid
with water and treating the liquor with common salt as above. In order to better
characterize the nature of the substance produced which is yet very little known, I
shall now proceed to give a description of its properties.
The sodaic salts form in cold water and in 80% alcohol or spirit of wine,
easily soluble scales, while the potassic salts form shining scales, which are only
slightly soluble in hot water.
The sodaic as well as the potassic salt remains fully unaffected when the aqueous
solution is evaporated, and when heated in a dry state at a temperature greatly

page_text: exceeding 100°, only the calcic, as well as the barytic salts are decomposed when
evaporating a very concentrated solution of the same.
Diluted solutions of these salts and of the free acids strongly acidulated with
mineral acids can be boiled without decomposition upon an open fire, the conversion
into naphthol and sulphuric acid takes place slowly when boiling acidulated
concentrated solutions but rapidly when an excess of concentrated mineral acid is
present. Neutral solutions of the acids produce with chloride of irou an intense
indigo blue coloration. Hot alcoholic solutions of the sodaic salts yield by the
addition of soda lyes crystalline scales of a "di-soda" salt having the formula
CH (ONa)SO,Na + 2 C,H.O which is easily soluble in water.
The solution of the same shows no fluorescence; chloride of barium precipitates
at once in hot water, a nearly insoluble deposit of a basic barytic salt.
In the concentrated solution of the nonosodaic salt to which solution is added
carbonate of soda diazosulphonic acid eliminates the sulphonic group of this mono-
sodaic salt while forming the well known coloring matter which derives from
B-naphthol.
By heating for a long time in a boiler subjected to pressure the sodaic salt of the
B-naphtholsulphonic acid herein described with equal parts of a 20% solution of
ammonia in water in order to convert it into the corresponding B-naphthylamine-
sulphonic acid as carried out in the usual manner with well known isomeres, a
reaction takes place at a temperature of from 220 to 230° C., whereby there
is formed amongst a number of colored products of decomposition, chiefly
impure ẞ-naphthylamine and in a secondary mass, a salt of B-naphthylaminesulphonic
acid.
If on the contrary 4 to 5 parts of from 15 to 20 % of an aqueous solution of
ammonia is used with 1 part of sodaic naphtholsulphonic acid there is formed after
heating at the same temperature for from 10 to 20 hours only a small quantity of
B-naphthylamine and as chief product in a much higher state of purity the salt of
the expected B-naphthylaminesulphonic acid.
By heating for a still longer time, or by preferably raising the temperature to
from 240 to 250° C., there is obtained with the same proportions of ingredients
-naphthylamine alone or merely predominating in the mass which naphthylamine
is likewise much purer than that won from the concentrated solution.
The sodaic salt of the naphthylaminesulphonic acid thus obtained is readily
soluble in water, and when allowed to cool, is fully precipitated in the form of
crystalline scales from its hot and not too highly diluted solution by the addition of
common salt. The potassic and ammoniacal salts act in the same manner.
diluted solution of the pure salt shows no fluorescence. The ẞ-naphthylamine-
sulphonic acid crystallizes in scales or needles.
The
The diazosulphonic acid obtained therefrom has the form of a clean yellow
crystalline powder which is not readily soluble. By boiling with diluted sulphuric
acid the same yields naphtholsulphonic acid, which has assisted in its formation, and
is further converted by known methods, into dichlornaphthaline 1:2 melting at a
temperature of 34° C. The B-naphthylaminesulphonic acid herein described
remains unchanged when heated to a temperature of 250° C.; but if its dried salt,
the sodaic or ammoniacal salt for instance is heated for a long time in a thoroughly
dry atmosphere at a temperature of about 230° C., the same is converted into salts
of the isomeric B-naphthylsulfamine acid according to the equation
10
(2) (1)
(2)
The new salts thus obtained are soluble in water, and are precipitated from their 5
solution by common salt in the form of flakes or scales; their neutral and alkaline
solutions can be boiled, without being decomposed. They are decomposed by the
mineral acids and with the aid of heat into ẞ-naphthylamine and bisulpbate.
If hydrochloric acid and nitrite of soda is introduced into their cold solution, a
clear yellow liquor is obtained which acts in the same manner as the solution of a 5

page_text: B-diazonaphthaline salt, and can be similarly used in the preparation of insoluble.
dyeing material for fibres for instance.
The salts of the B-naphthylsulfamine acid can, in consequence of the easy
separability of their sulphonic group, be used as well as the above new ẞ-napthyl-.
aminesulphonic acid as a substitute for B-naphthylamine in the preparation of the
already known ẞ-naphthylaminesulphonic acids by means of sulphuric acid.
The B-naphthylamine obtained from the B-naphtholsulphonic acid 2:1 by heating
with several times its weight of aqueous ammonia is as compared with that obtained
directly from naphthol free from dinaphthylamine and naphthol, this results from
the fact, that the B-naphthylamine is here formed by hydrolysis of the ẞ-naphthyl--
sulfamine acid. The mode of operation is as follows:
1. B-naphthylaminesulphonic acid 2:1.
10 kg. of the sodaic salt of naphtholsulphonic acid 2:1 are heated in a boiler
subjected to pressure for from 10 to 20 hours at from 220-230° C. with 50 kg. of
a 15 to 20% aqueous solution of ammonia. After the ammonia has been driven off
and cooling has twice taken place, the B-naphthylamine is removed by filtering-
from the products of the reaction while the B-naphthylaminesulphonic acid is.
separated by means of hydrochloric acid, or as a sodaic salt by cominon salt when
treating a solution which is first concentrated by evaporation.
The salt of the naphtholsulphonic acid which may still remain is previously won.
back as a basic barium salt which is nearly insoluble.
2. To prepare C-naphthylamine, the foregoing mixture is heated to a temperature.
higher by 20° C. than the former, and the B-naphthylamine which is obtained after
cooling partly in the form of crystalline scales, and partly in the shape of a fused
crystalline cake is utilized directly after having been dried and ground, or after a
previous distillation. The filtrate may be still further treated with a view to.
recovering any ẞ-napthylaminesulphonic acid which may still be present.
3. To obtain a sodaic salt of B-naphthylsulfamine acid, a previously well dried
sodaic salt of the B-naphthylaminesulphonic acid obtained in the manner described
in § 1 is treated in a boiler furnished with stirring means, and placed in an air or
oil bath, and heated at a temperature of about 230° C. until the cold diluted solution.
when tested allows the separation of neither B-naphthylaminesulphonic acid after
the addition of hydrochloric acid nor diazosulphonic acid after the addition of
nitrite of soda.
Having now particularly described and ascertained the nature of this inven--
tion and in what manner the same is to be performed, I declare that what I
claim is :-
1. The manufacture of new ẞ-naphthylaminemonosulfophonic acid by heating
under pressure the ẞ-naphtholsulphonic acid 2: 1 or its salts with aqueous ammonia
substantially in the manner herein before described.
2. The manufacture of B-naphthylamine by heating under pressure the 6-naphthyl-
aminemonosulphonic acid described and claimed in the first claiming clause or by
heating under pressure the B-naphtholsulphonic acid 2:1 or its salts with aqueous.
ammonia substantially in the manner herein before described.
3. The manufacture of the salts of the B-naphthylsulfamine acid by heating the
salts of the B-naphthylaminesulphonic acid, described and claimed in the first
claiming clause, substantially in the manner herein before described.
4. As article of manufacture the new ẞ-naphthylaminemonosulphonic acid_
manufactured as set forth in the first claiming clause.
STIL
ليم1
1
H. GARDNER,
Patent Agent, 166 Fleet Street, London,
Agent for the said Dr. Georg Tobias.
H. GARDNER,
Patent Agent, 166 Fleet Street, London,
Agent for the said Dr. Georg Tobias.