acture of 1 and Meta-nitroanisidine and of Colouring Matters therefrom.
Year: 1897

page_text: Date of Application, 5th Nov., 1897
Complete Specification Left, 27th July, 1898-Accepted, 1st Oct., 1898
acture of
1
and Meta-nitroanisidine and of Colouring
Matters therefrom.
I, OLIVER IMRAY, of Birkbeck Bank Chambers, Southampton Buildings, Chancery
Lane, in the County of London, Chartered Patent Agent, do hereby declare the
nature of this invention (as communicated to me from abroad by the Fabriques
de Produits Chimiques de Thann et Mulhouse, à Thann, Alsace) to be as
follows:-
Liebig's Annalen 207 page 242 describes the preparation of mononitroacetanisi-
dine.
By the reaction of concentrated nitric acid on orthoacetanisidine a mixture of
para- and metanitroacetanisidine, in various proportions, is always obtained, depending
on the manner in which the operation is carried out. By saponification of these
aceto derivatives, a mixture of nitroanisidine is obtained, which is separated by dilute
sulphuric acid.
The reaction can be done in such a way that only the meta-derivative is formed,
but it has not yet been possible to obtain the para-derivative alone.
A few examples may serve to explain the manner in which this process is
carried on.
1). 20 kilos. of orthoacetanisidine are introduced whilst cooling into a mixture of
120 kilos. of nitric acid of 38° Bé. and 100 kilos. of glacial acetic acid.
After a few
minutes the nitration is complete. By pouring the mixture into water the nitroaceto-
derivatives are precipitated. They consist of about 66 per cent. of para- and 34 per
cent. of meta-derivative.
2). 12 kilos. of acetanisidine are introduced slowly into 200 kilos. of nitric acid of
41° Bé. the temperature being maintained between 25° and 40° C. and the nitro
derivatives are separated by pouring into water. The product contains about 75 per
cent. of para- and 25 per cent. of meta-derivative.
3). 10 kilos. of acetanisidine are dissolved in a mixture of 40 kilos. of sulphuric
acid of 66° Bé. and 20 kilos. glacial acetic acid. To this mixture cooled to 0° C. are
added 8.4 kilos. of nitric acid of 40° Bé. diluted with 16.8 kilos. of sulphuric acid
of 66° Bé. By pouring in to water metanitroacetanisidine is separated in a state of
purity.
4). To 12.3 kilos. of orthoanisidine dissolved in 123 kilos. of sulphuric acid of
66° Bé. and cooled to 0° C. are added slowly a mixture of 9.35 kilos. of nitric acid of
42° Bé., and 40 kilos. of sulphuric acid of 66° Bé. The liquid is poured into water
and the metanitroanisidine is precipitated by means of caustic soda.
The nitroacetanisidines obtained according to processes 1, 2 and 3 are saponified
in the usual manner, either with alkali or with acid.
In order to separate the para- from the meta-derivative, one part of the mixture is
dissolved in eight parts of sulphuric acid of 25 per cent. whilst heating. Afterwards
ten parts of cold water are added and the whole is allowed to stand for a short
time

page_text: The para-derivative which has weak basic properties separates, whilst the meta-
derivative remains in the mother liquor and may be precipitated by an
alkali.
Both present themselves in the shape of yellow needles, insoluble in water, soluble
in alcohol, ether and other organic solvents; the para-derivative has a fusing point of
139° 140° C. the meta derivative of 117°-118° C.
Both may be diazotised. The diazo derivatives combine with amines, phenols,
amidophenols and the carboxylic and sulpho derivates of the same, yielding azo-
colouring matters.
Especially by combination of the diazo with ẞ-naphthol on cloth goods reds and
pinks are obtained.
Dated this 5th day of November 1897
Manufacture of Para- and Meta-nitroanisidine and of Colouring
Matters therefrom.
I, OLIVER IMRAY, of Birkbeck Bank Chambers, Southampton Buildings, Chancery
Lane, in the County of London, Chartered Patent Agent, do hereby declare the
nature of this invention (as communicated to me from abroad by the Fabriques
de Produits Chimiques de Thann et Mulhouse, à Thann, Alsace) and in what manner
the same is to be performed to be particularly described and ascertained in and by
the following statement:-
Liebig's Annalen 207 page 242 describes the preparation of mononitro-
acetanisidine.
By the reaction of concentrated nitric acid on orthoacetanisidine a mixture of
para- and metanitroacetanisidine, in various proportions is always obtained depending
on the manner in which the operation is carried out. By saponification of these
aceto-derivatives, a mixture of nitroanisidine is obtained, which is separated by dilute
sulphuric acid.
The reaction can be done in such a way that only the meta-derivative is formed,
but it has not yet been possible to obtain the para-derivative alone.
A few examples may serve to explain the manner in which this process is
carried on.
(1.) 20 kilos. of orthoacetanisidine are introduced whilst cooling into a mixture of
120 kilos. of nitric acid of 38° Bé. and 100 kilos. of glacial acetic acid. After a few
minutes the nitration is complete. By pouring the mixture into water the nitroaceto-
derivatives are precipitated. They consist of about 66 per cent. of para- and 34 per
cent. of meta-derivative.
(2) 12 kilos. of acetanisidine are introduced slowly into 200 kilos. of nitric acid of
41° Bé. the temperature being maintained between 25° and 40° C. and the nitro-
derivatives are separated by pouring into water. The product contains about
75 per cent. of para- and 25 per cent. of meta-derivative.
(3). 10 kilos. of acetanisidine are dissolved in a mixture of 40 kilos. of sulphuric
acid of 66° Bé. and 20 kilos. glacial acetic acid. To this mixture cooled to 0° C. are
added 8.4 kilos. of nitric acid of 40° Bé. diluted with 16-8 kilos. of sulphuric acid of
66° Bé. By pouring in to water metanitroacetanisidine is separated in a state of
purity.
(4). To 12.3 kilos. of orthoanisidine dissolved in 123 kilos. of sulphuric acid of
66° Bé. and cooled to 0° C. are added slowly a mixture of 9.35 kilos. of nitric

page_text: acid of 42° Bé., and 40 kilos. of sulphuric acid of 66° Bé. The liquid is poured into
water and the metanitroanisidine is precipitated by means of caustic soda.
The nitro-acetanisidines obtained according to processes 1, 2 and 3 are saponified
in the usual manner either with alkali or with acid.
In order to separate the para- from the meta-derivative, one part of the mixture is
dissolved in eight parts of sulphuric acid of 25 per cent. whilst heating. Afterwards
ten parts of cold water are added and the whole is allowed to stand for a short
time.
The para-derivative which has weak basic properties separates, whilst the meta-
derivative remains in the mother liquor and may be precipitated by an alkali.
Both present themselves in the shape of yellow needles, insoluble in water, soluble
in alcohol, ether and other organic solvents; the para-derivative has a fusing point
of 139°-140° C. the meta-derivative 117°-118° C. Both may be diazotised. The
diazo-derivatives combine with amines, phenols, amidophenols and the carboxylic and
sulpho-derivatives of the same, yielding azo-colouring matters.
Especially by combination of the diazo-derivative with ẞ-naphthol on cloth goods
reds and pinks are obtained.
the
Having now particularly described and ascertained
nature of this
invention and in what manner the same is to be performed, I declare that what
I claim is :-
1. The manufacture of para- and meta-nitroanisidine substantially as described.
2. The manufacture of azo-colouring matters by diazotising para- and meta-
nitroanisidine and combining them with amines, phenols, amido-phenols and the
carboxylic and sulphonic derivatives of the same.
ABEL & IMRAY,
Agents for the Applicant.