Manufacture of Green and Violet Coloring Matters.
Year: 1889

page_text: Date of Application, 6th May, 1889
Complete Specification Left. 16th Jan., 1890-Accepted, 22nd Feb, 1880
PROVISIONAL SPECIFICATION.
[Communicated from abroad by THE ACTIENGESELLSCHAFT FUR ANILINFABRIKATION,
of Berlin, in the German Empire, Manufacturing Chemists]
Manufacture of Green and Violet Coloring Matters.
I, CHARLES DENTON ABEL of No. 28 Southampton Buildings, Chancery Lane in
the County of Middlesex, Consulting Engineer and Patent Agent, do hereby declare
the nature of this invention to be as follows
--
This invention relates to a manufacture of green and violet coloring matters
wherein by treating methylbenzyle-aniline and ethylbenzyle-aniline with sulphuric
acid, monochlorhydrine or fuming sulphuric acid, sulphonic acids of these bases
are obtained, which are readily condensed with aromatic aldehydes in forming leuco-
sulphonic acids by this reaction and which, by oxydation, are converted into green and
violet coloring matters
EXAMPLE I. PRODUCTION OF METHYLBENZYLE-ANILINE-SULPHONIC ACID
5 kilos of methylbenzyle amline are gradually poured into 120 kilos of fuming
sulphuric acid at from 40 to 50° Celsius, the mixture is then heated at 80° Celsius
till a portion taken out is soluble in a thin solution of caustic alkalı. 100 kilos of
water are then gradually added at 50° Celsius and the sulphonic acid is precipitated
by adding at the same temperature 100 kilos of caustic soda of 40° Be., atter which
it is filtered pressed and dried.
EXAMPLE 11. PRODUCTION OF ETHYLBENZYLE-ANILINE SULPHONIC ACID.
This sulphonic acid is obtained by sulphuration of ethylbenzyle-aniline in the same
manner as methylbenzyle-aniline-sulphonic acid is produced
The sulphonic acids of methylbenzyle aniline and ethylbenzyle aniline, as well as
then salts with alkalies are readily soluble in water; the free sulphonic acids however
may be precipitated from their solutions in water by the addition of common salt and
the free ethylbenzyle aniline-sulphonic acid can even be obtained in well formed
crystals from its concentrated solution in boiling water. The free sulphonic acids are
not soluble in alcohol, their sodium salts however are soluble in alcohol and crystallize
from concentrated solutions. The salts with potassium are soluble with difficulty even
in boiling alcohol.
80 kilos of ethylbenzy le aniline-sulphome acid, 34 kilos of benzaldehyde and
30 litres of water are heated in connection with a reflux-cooler at 110° Celsius under
continuous stirring during fiom 7 to 8 hours.
The leuco-sulphonic acid thus formed which is not soluble either in water or alcohol,
yields salts, which are readily soluble in water, but less soluble in alcohol
After the addition of 1000 litres of water it is neutralized with caustic soda and
the leuco-sulphonic acid is then precipitated at 30° Celsius by muriatic acid, filtered,
pressed and dried

page_text: b. Coloring matter from the described leuco-sulphonic acid
120 kilos of peroxyde of lead containing 34% Pb O, are carefully suspended in
1,500 litres of water and well mixed with a solution of 100 kilos of leuco-sulphonic
acid in 400 litres of water by means of 31 kilos of caustic soda of 40° Bé This
mixture is kept at a temperature of 20° Celsius Hereupon the oxydation is effected
by adding as quick as possible a solution of 45 kilos of sulphuric acid of 66° Bé.
in 300 litres of water. After stirring the mass for a while, the product of oxydation
is neutralized by a solution of 30 kilos of soda in 200 litres of water. The obtained
precipitate of lead is allowed to deposit, the solution is then filtered and the coloring
matter precipitated by common salt After it has been filtered, it is dissolved again
in 1,000 litres of cold water, the solution thus obtained is filtered and the coloring
matter is this time precipitated by a clear solution of common salt, then filtered,
pressed and dried
The obtained coloring matter is readily soluble in water but less soluble in alcohol
On the addition of weak inorganic acids the fice acid of the coloring-matter-pre-
cipitates, by adding concentrated acids, the green solution of the coloring matter
turns yellow, and the previous green color is restored again, if the solution is diluted
by water. On the addition of free alkahes the solution of the coloring-matter turns
nearly colorless
The nitro-derivates of the described acid-green are obtained in the same manner
if meta-nitrobenzaldehyde or para-nitro benzaldehyde is applied instead of benzal-
dehyde
EXAMPLE IV ACID VIOLET FROM DIMETHYL-PARA-AMIDO BENZALDEHYDE AND
ETHYLBENZYLE ANILINE-SULPHONIC ACID
If in example I the benzaldehyde is replaced by 36 kilos of dimethyl para-amido-
benzaldehyde, a leuco-sulphonic acid is obtained by condensation with ethylbenzyle-
aniline sulphonic acid, which precipitates from its solution in water by the addition of
common salt.
The leuco-sulphonic acid is converted by oxydation into a coloring matter, which
dyes on wool in acid baths deep violet shades.
If instead of dimethyl-para amido benzaldehyde, diethyl-para-amido-benzaldehyde
is applied, a coloring matter is obtained which dyes on wool bluer shades than the
corresponding methylderivative.
Dated this 6th day of May 1889
ABEL & IMRAY,
Agents for the Applicant
COMPLETE SPECIFICATION.
Manufacture of Green and Violet Coloring Matters.
I, CHARLES DENTON ABEL, of No. 28 Southampton Buildings, Chancery Lane, in
the County of London, Consulting Engineer and 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.-
This invention relates to a manufacture of green and violet coloring matters
wherein by treating methylbenzy le-aniline and ethylbenzyle-aniline with sulphuric acid
monochlorhydrine, or fuming sulphuric acid, sulphonic acids of these bases are
obtained, which are readily condensed with aromatic aldehydes forming leuco-sulphonic
acids by this reaction, which, by oxidation, are converted into green and violet
coloring matters.

page_text: EXAMPLE I. PRODUCTION OF METHYLBENZYLE-ANILINE SULPHONIC ACID.
50 kilos of methylbenzyle aniline are gradually poured into 120 kilos of fuming
sulphuric acid at from 40° to 50° Celsius, the mixture is then heated at 80° Celsius
till a portion taken out is soluble in a thin solution of caustic alkalı
100 kilos of
water are then gradually added at 50° Celsius and the sulphonic acid is precipitated
by adding at the same temperature 100 kilos of caustic soda of 40° Be after which
it is filtered, pressed, and dried
EXAMPLE II PRODUCTION OF ETHYLBENZYLE-ANILINE SULPHONIC ACID.
This sulphonic acid is obtained by sulphuration of ethylbenzyle anthine in the same
manner as methylbenzyle amiline sulphonic acid is produced
The sulphonic acids of methylbenzy le-aniline and ethylbenzyle-amline, as well as
their salts with alkalies, are readily soluble in water, the free sulphonic acids however
may be precipitated from their solutions in water by the addition of common salt and
the free ethylbenzyle-aniline sulphonic acid can even be obtained in well formed
crystals from its concentrated solution in boiling water. The free sulphonic acids are
not soluble in alcohol, then sodium salts however are soluble in alcohol and crystallize
fiom concentrated solutions The salts with potassium are soluble with difficulty even
in boiling alcohol.
80 kilos of ethylbenzyle-amline sulphonic acid, 34 kilos of benzaldehyde and
30 litres of water are heated in connection with a reflux cooler at 110° Celsius under
continuous sting during 78 hours
The leuco sulphonic acid thus formed, which is not soluble either in water or
alcohol, yields salts, which are readily soluble in water but less soluble in alcohol
After the addition of 1000 litres of water it is neutralized with caustic soda and
the leuco-sulphonic acid is then precipitated at 30° Celsius by muuatic acid, filtered,
pressed, and dried
b Coloring matter from the described leucosulphonic acid
120 kilos of peroxide of lead containing 34% Pb O, are carefully suspended in
1500 litres of water and well mixed with a solution of 100 kilos of leuco sulphonic
Thuis
acid in 400 litres of water by means of 31 kilos of caustic soda of 40° Bé
mixture is kept at a temperature of 20° Celsius Hereupon the oxidation 13
effected by adding as quick as possible a solution of 45 kilos of sulphuric acid of
66° Be in 300 litres of water.
After stirring the mass for a while the product of oxidation 15 neutralized by a
solution of 30 kilos of soda in 200 litres of water The obtained precipitate of
lead is allowed to deposit, the solution 13 then filtered and the coloring matter
precipitated by common salt After it has been filtered, it is dissolved again in
1000 litres of cold water, the solution thus obtained is filtered and the coloring
matter is this time precipitated by a clear solution of common salt, then filtered,
pressed and dried.
The obtained coloring matter is readily soluble in water but less soluble in alcohol.
On the addition of weak inorganic acids the free acid of the coloring matter precipi-
tites, by adding concentrated acids the green solution of the colouring matter tuins
yellow and the previous green colour is restored again, it the solution is diluted by
water On the addition of free alkalies the solution of the coloring mitter turns nearly
colourless

page_text: The nitro-derivatives of the described acid green are obtained in the same manner
if meta-nitrobenzaldehyde or para-nitro-benzaldehyde is applied instead of benzal-
dehyde.
EXAMPLE IV. ACID VIOLET FROM DIMETHYL-PARA-AMIDO BENZALDEHYDE AND
ETHYLBENZYLE-ANILINE SULPHONIC ACID.
If in Example I the benzaldehyde is replaced by 36 kilos of dimethyl-para-amido
benzaldehyde a leuco-sulphonic acid is obtained by condensation with ethylbenzyle
aniline sulphonic acid, which precipitates from its solution in water by the addition of
common salt. The leuco-sulphonic acid is converted by oxidation into a coloring
matter which dyes on wool in acid baths deep violet shades If instead of dimethyl-
para-amido-benzaldehyde, diethyl-para-amido-benzaldehyde is applied, a colouring
matter is obtained which dyes on wool bluer shades than the corresponding methyl
denvative.
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 18:
1 The production of methylbenzyle-aniline-sulphonic acid and ethylbenzyle aniline-
sulphonic acid by sulphuration of methylbenzyle aniline and ethylbenzy le-amline with
fuming sulphuric acid or sulphuric acid-monochlorhydrine
2 The production of leuco sulphonic acids by condensation of the sulphonic acids of
methyl and ethyl benzyle aniline with aromatic aldehydes.
3 The conversion of the leuco-sulphonic acids, referred to in claim 2, by oxidation
into green or violet coloring matters
Dated this 16th day of January 1890
ABEL & IMRAY,
Agents for the Applicant