The Manufacture or Production of B Naphthol a B. Disulpho Acid and B. Naphthylamine a, ẞ Disulpho Acid.
Year: 1894

page_text: Date of Application, 17th Jan., 1894
Complete Specification Left, 16th Oct., 1894-Accepted, 17th Nov., 1894 ·
PROVISIONAL SPECIFICATION.
[Communicated from abroad by THE FARBENFABRIKEN, vormals FRIEDRICH
BAYER & Co., of Elberfeld, in the Empire of Germany.]
The Manufacture or Production of B Naphthol a B. Disulpho Acid
and B. Naphthylamine a, ẞ Disulpho Acid.
I HENRY EDWARD NEWTON of The Office for Patents 6 Bream's Buildings,
Chancery Lane in the County of London, Patent Agent, do hereby declare the
nature of this invention to be as follows:-
It is known that ẞ, naphthol B. monosulpho acid, when treated with concen-
trated or fuming sulphuric acid, yields in the first place exclusively ẞ naphthol
B.B. disulpho acid (see the German Patent No. 44079, the note of Weinberg in the
Berichte der Deutschen Chemischen Gesellschaft, volume 20, page 2911, and the
paper of Armstrong & Wynne in the Proceedings of the Chemical Society of
the year 1890, page 127).
My foreign correspondents, however, have now found that the reaction proceeds
in an entirely different manner, if sulphuric acid chlorhydrine be used as sulphonating
agent, for the second sulpho group then displaces the hydrogen atom which is in
the "alpha" and "ortho" position to the hydroxylic group of the ẞ, naphthol
B. monosulpho acid, the naphthol a, ẞ disulpho acid being thus produced
with ease.
One of the methods of preparing the last named ẞ, naphthol a₁ ß disulpho acid
31
hemiaht
a1
EXAMPLE A.
PRODUCTION OF ẞ₁ NAPHTHOL a B. DISULPHO ACID.
.
1 part of the sodium salt of B, naphthol B, monosulpho acid F, is gradually intro-
duced into 3 parts of technical sulphuric acid chlorhydrine (containing 70 per cent. of
real sulphuric chlorhydrine), whilst being cooled. Hydrochloric acid in gaseous
state freely separates whilst the mass is effervescing. The liquid is then allowed
to stand at ordinary temperature (say, for about 24 hours), until a sample. taken
out, and supersaturated with a solution of sodium carbonate, cannot be coupled
with diazo benzene chloride. The sulphonated mass is then introduced into ice
water, and this liquid, when cool, is neutralised by means of lime water. After
filtering off the separated calcium sulphate (gypsum), the resulting solution of the
calcium salt of the ẞi naphthol a₁ ẞ disulpho acid is treated in the well-known
manner, in order to prepare the potassium salt of the last named acid. The
solution of this potassium salt is evaporated to dryness, and the salt thus obtained
easily dissolves in water. On adding potassium chloride to watery solutions of the
said potassium salt, the latter is precipitated in compact crystals, whilst sodium
chloride causes a precipitation in the form of needles. An addition of barium
chloride, to the above watery solutions. causes the barium salt to separate in
beautiful needles, which are fairly soluble.
-
•
I "

page_text: If the so formed ẞ, naphthol a, ẞ, disulpho acid is boiled during a longer period
with dilute mineral acid (containing 20 per cent. of real acid), the sulpho group in
the position "alpha" and "ortho" to the hydroxylic group, is separated again,
B, naphthol B, monosulpho acid F being thus produced.
Solutions of salts of the new acid exhibit a slight blue fluorescence. The new
acid, by heating with ammonia and ammonium chloride, is converted into a new
Snaphthylamine disulpho acid, which, on displacing the amido group by hydrogen
(that is to say, by diazotising, transforming the resulting diazo compound into the
corresponding hydrazine compound, and boiling the latter with a solution of copper
sulphate), yields naphthalene a, ẞ, disulpho acid. The so-formed naphthalene
disulpho acid can be converted into a disulpho chloride, which melts at from 122 to
123 degrees centigrade, and, according to the researches of my foreign corre-
spondents, is identical with the naphthalene a ẞ, disulpho chloride melting at
122-5 degrees centigrade, and described by Armstrong & Wynne in the Proceedings
of the Chemical Society of the year 1890, page 126.
Owing to all these reactions, the new naphtholdisulpho acid obtainable as
described in the above Example A, is represented by the following formula:
The new acid and its salts show the following properties :-The sodium salt
forms little needles soluble with readiness; the potassium salt forms compact
crystals easily soluble; the sodium salt, however, possesses a higher degree of
solubility than the potassium salt. The barium salt forms bright needles grouped
in the shape of bunches, dissolves in cold water with moderate ease, and is dissolved
by hot water with greater readiness. The solutions, in water, of its salts, exhibit a
slight blue fluorescence. On boiling the new acid or its salts with diluted acids,
the sulpho group contained in the position "alpha" is separated. Coloring matters
are not formed when the new acid, or salts thereof, are allowed to act on diazo
compounds in alkaline solutions. Naphthalene aẞ, disulpho acid is obtained if the
hydroxylic group of the new acid is replaced by the amido group, and the naphthyl-
amine disulpho acid so formed is treated in a suitable manner, in order to displace
the amido group by bydrogen.
This new naphtholdisulpho acid can either directly, or when previously
sulphonated, be converted into amido naphthalene sulpho acids, which can be used
for producing dye-stuffs, as my foreign correspondents have found.
My foreign correspondents have found some time ago that certain ẞ naphthol
polysulpho acids which contain a sulpho group in loose combination, and in the
alpha" and "ortho" position to the ẞ hydroxylic group (the said sulpho group
being separated when boiling with dilute mineral acids), can, by heating with
ammonia, be converted into ẞ naphthylamine sulpho acids, provided that the
reaction be not carried out at too elevated temperatures. The ẞ naphthol poly-
sulpho acids used in the said process were prepared by energetically sulphonating
Bnaphthol B, sulpho acid with concentrated or fuming sulphuric acid.
The researches of my foreign correspondents have now shown, that the aforesaid
new B naphthol a ẞ disulpho acid, which materially differs, by its properties
above referred to, from the ẞ, naphthol B, B. disulpho acid F, obtainable by
sulphonating ẞ naphthol ẞ sulpho acid with concentrated or fuming sulphuric
acid, can also be converted into the corresponding ẞ naphthylamine disulpho acid,
by a treatment with ammonia; however, care must be taken that the reaction does
not take place at too high a temperature.

page_text: The composition of the ẞ naphthylamine disulpho acid so formed, is represented
by the following formula :—
This is evident, as above mentioned, from the fact, that this naphthylamine
disulpho acid, after displacing the amido group by hydrogen (which process is
effected by diazotising, converting the diazo product into the hydrazine compound,
for instance, by reduction with the aid of stannons chloride, and subsequently
boiling the hydrazine product with a solution of copper sulphate), is transformed
into naphthalene a, disulpho acid, which could easily be identified by its
conversion into the disulpho chloride melting at from 122 to 123 degrees centigrade
(see Armstrong & Wynne, Proceedings of the Chemical Society, 1890, page 126).
The production of naphthylamine a disulpho acid from ẞ, naphthol
aß disulpho acid, is illustrated by the following example. The parts are by
weight:-
CONVERSION OF NAPHTHOL a 5 DISULPHO ACID INTO ₁ NAPHTHYL-
AMINE a₁ ẞ DISULPHO ACID.
10 parts of the potassium salt of the above ẞ, naphthol a ẞ, disulpho acid, are
mixed with 5 parts of ammonium chloride and 25 litres (in case the parts are kilos.
by weight) of ammonia solution (containing 25 per cent. of real ammonia). The
resulting mixture is heated during 10 hours in a vessel capable of withstanding
pressure, the vessel being placed in an oil bath which is kept, during the reaction, at
from 180 to 200 degrees centigrade. The resulting mixture is then boiled with
potash lye, until the whole of the ammonia in excess is distilled off. After filtering,
the filtrate is almost neutralised, and evaporated, until the volume is from about
20 to 30 litres (in case the parts were kilos. by weight). On cooling, the neutral
potassium salt separates, and forms beautiful bright glass-like crystals as large as
walnuts. The crystals are purified by redissolving in hot water, and evaporating
these solutions.
My foreign correspondents have proved by analysis of the potassium salt dried at
from 150 to 160 degrees, that the percentage of potassium is 20-27, which is in
accordance with the theoretical amount of potassium calculated, viz., 20:58 per cent.
The new naphthylamine disulpho acid cannot be combined with diazo benzene
chloride in solutions acidulated by means of acetic acid. The solutions of the
neutral salts exhibit a violet-blue fluorescence. If the last named acid is diazotised
in a solution rendered moderately acid by means of sulphuric acid, and if the diazo
solution so formed is slowly heated with water, the ẞ, naphthol a, b, disulpho acid
is produced again. The diazo derivative of the new naphthylamine disulpho
acid, when combined with phenols or amines, yields dye stuffs. The new acid
differs from all other naphthylamine disulpho acids by its property of being
converted into naphthalene a, ẞ disulpho acid, when the amido group contained
therein is separated, viz., replaced by hydrogen.
In order to produce the above named B₁ naphthol a₁ ẞ disulpho acid and
B₁ naphthylamine a ẞ, disulpho acid, my foreign correspondents do not limit them-
selves to the directions given in the foregoing Examples A and B, for the mode of
working can be varied, and all those methods can be used which are known and in

page_text: use for similar purposes; however, care must be taken that the conversion of
Binaphthol a B disulpho acid into ẞ₁ naphthylamine a₁ ẞ disulpho acid be
effected at not too high temperatures.
Dated this 17th do- of Ta 1901
NEWTON & SON,
Agents for the Applicant.
COMPLETE SPECIFICATION.
The Manufacture or Production of Beta, Naphthol Alpha, Beta.
Disulpho Aoid and Beta, Naphthylamine Alpha, Beta, Disulpho
Acid.
I, HENRY EDWARD NEWTON, of The Office for Patents, 6 Bream's Buildings,
Chancery Lane, in the County of London, Patent Agent, 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 :-
It is known that when beta, naphthol-beta-monosulphonic acid is sulphonated
with concentrated or fuming sulphuric acid, it yields, in the first place, exclusively
beta, naphthol-beta, beta-disulphonic acid (see the German Patent No. 44079,
the note of Weinberg in the Berichte der Deutschen Chemischen Gesellschaft,
volume 20, page 2911, and the paper of Armstrong & Wynne in the Proceedings
of the Chemical Society of the year 1890, page 127).
My foreign correspondents, however, have now found that the action proceeds in
an entirely different manner, if sulphuric chlorhydrin be used as sulphonating
agent, the second sulphonic group displacing the hydrogen atom which is in the
“alpha ortho” position relatively to the hydroxyl group of the beta, naphthol beta
monosulphonic acid,-beta, naphthol alpha, beta, disulphonic acid being thus
produced with ease.
One of the methods of preparing the said beta, naphthol-alpha, beta.
disulphonic acid, is illustrated by the following example, the parts being by
weight.
FIRST EXAMPLE.
PRODUCTION OF BETA₁ NAPHTHOL ALPHA BETA. DISULPHONIC ACID.
1 part of the sodium salt of beta, naphthol beta, monosulphonic acid F, is gradually
introduced into 3 parts of cooled technical sulphuric chlorhydrin (containing 70 per
cent. of real sulphuric chlorhydrin). Hydrogen chloride is freely evolved, the mass
effervescing. The liquid mixture is allowed to stand at the ordinary temperature,
say during about 24 hours, until it is found that a sample supersaturated with a
solution of sodium carbonate cannot be coupled with diazobenzene chloride. The
sulphonated mass is then introduced into ice water, the cool liquid is neutralised
with milk of lime, and the calcium salt is then converted into the potassium salt.
The solution of the potassium salt is evaporated to dryness. The potassium salt
thus obtained easily dissolves in water, but on adding potassium chloride to the
solution, the salt is precipitated in compact crystals, whilst sodium chloride causes
a precipitation in the form of needles. On adding barium chloride, the barium
salt separates in beautiful needles, which are moderately soluble.
•
If the beta-naphthol-alpha, beta-disulphonic acid thus produced be boiled
during a prolonged period with dilute mineral acids (continuing 20 per cent. of real
acid), the sulphonic group in the "alpha ortho" position relatively to the hydroxyl
is again separated, beta-naphthol beta, monosulphonic acid F being formed.
Solutions of salts of the new acid exhibit a slight blue fluorescence. By heating
the new acid with ammonia and ammonium chloride, it is converted into a new
beta-naphthylamine disulphonic acid, from which, by displacing the amido group

page_text: by hydrogen (that is to say, by diazotising, and transforming the diazo compound
into the corresponding hydrazine compound, and boiling the latter with a solution
of copper sulphate), naphthalene-alpha, beta,-disulphonic acid may be obtained.
The said naphthalenedisulphonic acid affords a disulphonic chloride melting at from
122 to 123 degrees centigrade, identical with the naphthalene alpha, beta, disulphonic
chloride melting at 122-125 degrees centigrade described by Armstrong & Wynne
in the Proceedings of the Chemical Society of the year 1890, page 126.
Hence it follows, that the new beta-naphtholdisulphonic acid obtainable as
described in the above first example, is represented by the following formula :—
The new acid and its salts have the following properties. The sodium salt forms
readily soluble small needles, the potassium salt easily soluble compact crystals,
the sodium salt being, however, more soluble than the potassium salt. The barium
salt forms brilliant needles grouped in bunches, dissolving in cold water with
moderate ease, and, more readily in hot water. Aqueous solutions of the salts
exhibit a slight blue fluorescence. On boiling the new acid or its salts with
diluted acids, the sulphonic group in the "alpha" position is separated. Colouring
matters are not formed, when the new acid, or salts thereof, are allowed to act on
diazo compounds in alkaline solutions.
This new naphtholdisulphonic acid can be converted either directly, or after
sulphonation, into amido naphthalenesulphonic acids, which can be used for
producing dye-stuffs.
56
My foreign correspondents some time ago ascertained that certain beta-naphthol
polysulphonic acids containing a sulphonic group in loose combination in the
alpha ortho" position relatively to the beta hydroxyl group (the which sulphonic
group is separated by boiling with dilute mineral acids), can be converted by
heating with ammonia into beta-naphthylamine sulphonic acids, provided that the
action be not carried out at too elevated a temperature. The beta-naphthol
polysulphonic acids referred to were prepared by energetically sulphonating beta,
naphthol-beta, sulphonic acid with concentrated or fuming sulphuric acid.
The researches of my foreign correspondents have now shewn, that the new beta
naphthol alpha, beta-disulphonic acid which has properties above referred to,
materially different from those of beta, naphthol beta, beta, disulphonic acid F
obtainable by sulphonating beta, naphthol-beta-sulphonic acid with concentrated
or fuming sulphuric acid, can be converted into the corresponding beta-naphthyl-
aminedisulphonic acid by treatment with ammonia, but care must be taken that the
action does not take place at too high a temperature.
The composition of the beta naphthylaminedisulphonic acid so formed is
represented by the following formula :—

page_text: This is evident, as above mentioned, from the fact that, by displacing the amido
group in this naphthylaminedisulphonic acid by hydrogen (which process is effected
by diazotising, converting the diazo compound into the hydrazine compound, for
instance, by reduction with the aid of stannous chloride, and subsequently boiling
the hydrazine with a solution of copper sulphate), it is transformed into naphthalene
alpha beta-disulphonic acid, easily identified by its conversion into the disulphonic
chloride melting at from 122 to 123 degrees centigrade (see Armstrong & Wynne,
Proceedings of the Chemical Society 1890, page 126).
The production of beta, naphthylamine alpha, beta, disulphonic acid from beta,
naphthol-alpha, beta disulphonic acid, is illustrated by the following example.
The parts are by weight.
CONVERSION OF BETA₁-NAPHTHOL-ALPHA BETA DISULPHONIC ACID INTO
BETA NAPHTHYLAMINE ALPHA, BETA-DISULPHONIC ACID.
10 parts of the potassium salt of the above beta, naphthol alpha, beta, disulphonic
acid are mixed with 5 parts of ammonium chloride and 25 litres (in case the parts are
kilos. by weight) of ammonia solution (containing 25 per cent. of real ammonia).
The mixture is heated during 10 hours in a vessel capable of withstanding pressure,
the vessel being placed in an oil bath which is kept at from 180 to 200 degrees
centigrade. Potash lye is then added, and the mixture is boiled until the whole
of the ammonia in excess is distilled off, then filtered; the filtrate having been
almost neutralised, is evaporated until its volume is from about 20 to 30 litres
(in case the parts are kilos. by weight). As the liquid cools, the neutral potassium
salt separates in beautiful bright glass-like crystals, as large as walnuts. The
crystals are purified by recrystallization.
The new beta naphthylaminedisulphonic acid cannot be combined with diazo-
benzene chloride in solutions acidulated with acetic acid. Solutions of the neutral
salts exhibit a violet-blue fluorescence. If the acid be diazotised in a solution
rendered moderately acid with sulphuric acid, and the diazo solution be then
slowly heated with water, beta-naphthol-alpha, beta-disulphonic acid is reproduced.
The diazo derivative of the new betanaphthylaminedisulphonic acid yields dye-
stuffs when combined when combined with phenols or amines. The new acid
differs from all other beta-naphthylaminedisulphonic acids by its property of being
converted into naphthalene-alpha, beta, disulphonic acid, when the amido group
contained therein is displaced by hydrogen.
In order to produce the above-named beta, naphthol-alpha, beta, disulphonic
acid and beta, naphthylamine-alpha, beta-disulphonic acid, my foreign corre-
spondents do not limit themselves to the directions given in the foregoing
Examples One and Two, as the mode of working can be varied, and all methods
can be used which are known and in use for similar purposes, but care must always
be taken that the conversion of beta, naphthol-alpha, beta-disulphonic into beta
naphthylamine-alpha, beta, disulphonic acid be effected at not too high a
temperature.
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
from abroad), I declare that what I claim is :-
1. The production of beta, naphthol-alpha, beta-disulphonic acid, by the action
on beta naphthol-beta, monosulphonic acid, or salts thereof, of sulphurio
chlorhydrin.
2. The process for producing beta-naphthylamine-alpha, beta-disulphonic acid,
which process consists in heating beta, naphthol-alpha, beta, disulphonic acid, or
salts thereof, respectively, either with ammonia alone, or together with ammonium
salts, at moderately elevated temperatures.

page_text: 3. As new products of manufacture,
a.) Beta, naphthol-alpha, beta-disulphonic acid;
b.) Beta, naphthylamine-alpha-beta disulphonic acid,
produced by the processes hereinbefore defined, or by any other means affording
the same result.
1004
NEWTON & SON,
Agents for the Applicant.