Year: 1899

page_text: ''
Date of Application, 15th Nov., 1899
Complete Specification Left, 9th Aug., 1900-Accepted, 15th Sept., 1900
By Derivatives.
1, 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:-
.
-
My foreign correspondents have found a valuable new process by means of which it
is possible to transform betanaphthylamine and its derivatives into beta
dinaphthylamine, or the corresponding dinaphthylamine derivatives. This
process consists in heating beta-naphthylamine, or its derivatives, with sulphurous
acid, or with salts of this acid. The new reaction proceeds as follows:-
A condensation of two molecules of the beta-naphthylamine derivative takes
place under evolution of one molecule of ammonia, a beta-dinaphthylamine derivative
being thus obtained. In case, for instance, beta-naphthylamine is used, the reaction
takes place according to the following equation, beta-dinaphthylamine and ammonia
being formed:
16 On using beta-naphthylamine sulphonic acids, the symmetrical beta-dinaphthy-
lamine sulphonic acids are produced, whilst from beta-amidonaphthol sulphonic acids,
the symmetrical dioxydinaphthylamine sulphonic acids are obtained.
In order to illustrate the new process more fully, the following examples are given,
1
LAMINE BETA-SULPHONIC ACID.
In a vessel lined with lead, and provided with a stirrer and a reflux condenser, a
misture prepared from 400 parts of the sodium salt of beta,-naphthylamine-beta-
monosulphonic acid, 1000 parts of water, and 1000 parts of a sodiumbisulphite
25 solution, of 40 degrees Baumé, is heated at from 90 to 100 degrees Centigrade.

page_text: After a short time, a clear solution results. On further heating, a precipitate con-
sisting of small white crystals is separated, which increases during the reaction. After
having heated for about 24 hours, the process will be finished. The separated crystals
are filtered off without previously cooling. The body thus obtained is the sodium salt
of an acid having the formula:
It is purified by dissolving it in hot water, and precipitating it by the addition of
common salt. This sodium salt is soluble with greater difficulty in water than the
sodium salt of beta,-naphthylamine-beta-sulphonic acid. The watery solution of this
new salt exhibits a green fluorescence. When treated with nitrous acid in an acid
solution, the new acid yields a nitrosamine compound which is nearly colorless.
PRODUCTION OF DIOXY-BETA-DINAPHTHYLAMINE DISULPHONIC ACID FROM BETA₁-AMIDO-
ALPHA-NAPHTHOL-BETA-MONOSULPHONIC ACID.
A mixture prepared from 200 parts of heta-amido-alpha-naphthol-beta-mono-
sulphonic acid and 200 parts of hot water, is dissolved in caustic soda-lye. In a vessel
lined with lead, and provided with a stirrer and a reflux condenser, the solution thus
obtained is mixed with 700 parts of a sodium bisulphite solution, of 33 degrees
Baumé, and then heated, at from 80 to 100 degrees Centigrade, until a diluted test-
portion, when mixed with an excess of hydrochloric acid, is (even when allowed to
stand for a while) found to yield no longer a precipitate of beta-amido-alpha¸-
naphthol-beta-sulphonic acid.
Subsequently, the reaction mixture is strongly acidulated by means of hydrochloric
acid. On cooling, a large quantity of a crystalline, nearly white, mass separates. It
is filtered off, dissolved in a small quantity of water, and again precipitated by. the
addition of an excess of hydrochloric acid. The dioxydinaphthylamine disulphonic-
acid thus produced, forms white needles. It has the following formula:
The free acid, as well as the alkaline salts thereof, are very readily soluble in water.
The solution of the sodium salt shows a weak blueish fluorescence.
The process proceeds in an analogous manner if, instead of the compounds
mentioned in the above examples, other beta-naphthylamine derivatives, or other salts
of sulphurous acid are employed. If beta-naphthylamine itself, which is soluble with
difficulty, is used, it is profitable to perform the reaction in an alcoholic solution:
My foreign correspondents wish to point out that they do not intend to confine g
themselves to the particulars given in the above Specification, as the examples con-
tained therein are merely typical, and can be varied within wide limits. Thus, for

page_text: instance, instead of heating the beta-naphthylamine derivatives with the sulphurous
acid, or, its salts, in open vessels, this reaction can also be performed in autoclaves.
Dated this 15th day of Now 1000
NEWTON & SON,
Agents for the Applicant.
A New Process for the Production of Dinaphthylamine Derivatives.
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 :--
My foreign correspondents have found a valuable new process by means of which it
is possible to transform beta-naphthylamine and its derivatives into beta-dinaphthyl-
amine, or the corresponding dinaphthylamine derivatives. This process consists
in heating beta-naphthylamine, or its derivatives, with sulphurous acid, or with salts
of this acid. The new reaction proceeds as follows:-A condensation of two molecules
of the beta-naphthylamine derivative takes place under evolution of one molecule of
ammonia, a beta-dinaphthylamine derivative being thus obtained. In case, for
instance, beta-naphthylamine is used, the reaction takes place according to the
following equation, beta-dinaphthylamine and ammonia being formed :-
On using beta-naphthylamine sulphonic acids, the symmetrical beta-dinaphthyl
amine sulphonic acids are produced, whilst from beta-amido-naphthol sulphonic acids,
the symmetrical dioxydinaphthylamine sulphonic acids are obtained.
In order to illustrate the new process more fally, the following examples are given,
the parts being by weight :—
LAMINE-BETA-SULPHONIC ACID.
In a vessel lined with lead, and provided with a stirrer and a reflux condenser, a
mixture prepared from 400 parts of the sodium salt of beta-naphthylamine-beta-
mono-sulphonic acid, 1600 parts of water, and 1000 parts of a sodium bisulphite
solution, of 40 degrees Baumé, is heated at from 90 to 100 degrees Centigrade.
After a short time, a clear, solution results.
On further heating, a precipitate consisting of small white crystals is separated,
which increases during the reaction. After having heated for about 24 hours, the

page_text: process will be finished. The separated crystals are filtered off without previously
cooling. The body thus obtained is the sodium salt of an acid having the formula:
It is purified by dissolving it in hot water, and precipitating it by the addition of
common salt. This sodium salt is soluble with greater difficulty in water than the
sodium salt of beta,-naphthylamine-beta-sulphonic acid. The watery solution of the
When treated with nitrous acid in an acid
new salt exhibits a green fluorescence.
solution, the new acid yields a nitrosamine compound, which is nearly colorless.
PRODUCTION OF DIVA IDEIA-DINATHUTHANAND VIDUMA
ALPHA-NAPHTHOL-BETA-MONOSULPHONIC ACID.
A mixture prepared from 200 parts of beta-amido-alpha-naphthol-beta,-mono-
sulphonic acid, and 200 parts of hot water, is dissolved in caustic soda-lye. In a
vessel lined with lead, and provided with a stirrer and a reflux condenser, the
solution thus obtained is mixed with 700 parts of a sodium-bisulphite solution of
33 degrees Banmé, and then heated at from 80 to 100 degrees Centigrade, until.a
diluted test portion, when mixed with an excess of hydrochloric acid, is (even when
allowed to stand for a while) found to yield no longer a precipitate of beta-auniḍo-
alpha-naphthol-beta-sulphonic acid.
Subsequently the reaction mixture is strongly acidulated by means of hydrochloric
acid. On cooling, a large quantity of a crystalline, nearly white mass separates. It
is filtered off, dissolved in a small quantity of water, and again precipitated by
the addition of an excess of hydrochloric acid. The dioxydinaphthylamine
It has the following
disulphonic acid thus produced forms white needles.
formnla:
The free acid, as well as the alkaline salts thereof, are readily soluble in water.
The solution of the sodium salt shows a weak blueish fluorescence.
The process proceeds in an analogous manner if, instead of the compounds
mentioned in the above examples, other beta-naphthylamine derivatives, or other
salts of sulphurous acid, are employed. If beta-naphthylamine itself, which is
soluble with difficulty, is used, it is profitable to perform the reaction in an alcoholic
solution.
My foreign correspondents wish to point out that they do not intend to confine
themselves to the particulars given in the above specification, as the examples
contained therein are merely typical, and can be varied within wide limits. Thus,
for instance, instead of heating the beta-naphthylamine derivatives with the

page_text: sulphurous acid, or its salts, in open vessels, this reaction can also be performed in
autoclaves.
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 process for the transformation of beta-naphthylamine and its derivatives,
into beta-dinaphthylamine and its derivatives, which process consists in treating
beta-naphthylamine and its derivatives with sulphurous acid; or salts thereof,
substantially as described,
2. As new articles of manufacture, the new bodies obtainable by the process
herein before described and claimed.