Year: 1887

page_text: Date of Application, 23rd Apr., 1887
Complete Left, 23rd Jan., 1888
Complete Accepted, 16th Mar., 1888
I, ALFRED KERN, of the firm of Kern and Sandoz, of Basle, Switzerland, do
hereby declare the nature of this invention to be as follows:-
:―
This invention relates to the preparation of the methylic ether of gallic acid, and
of colouring matters therefrom by the action of nitroso derivates of secondary and
tertiary aromatic monamines, the said colouring matters being applicable for dyeing
or printing.
The methylic ether of gallic acid, which has not as far as I am aware heretofore been
described, is prepared from gallic acid or tannin by the action of hydrochloric acid or
sulphuric acid upon a methyl alcoholic solution of the gallic acid or tannin.
This ether crystallizes from an alcoholic solution in anhydrous rhombic crystals at
the melting point 383° F. at normal atmospheric pressure. It dissolves easily in hot
water; and crystallizes therefrom on cooling as white felted needles which at from 212
to 230° F. lose water of crystallization.
The colouring matters which are obtained by the action of the hydrochloric nitroso
derivates of secondary and tertiary monamines upon this ether, are easily dissoluble in
water, are hydrochlorates, and dye or print upon cotton from violet to blue.
1. Preparation of ethylic ether of gallic acid.
20 parts of gallic acid, crystallized, are dissolved in a hot state in 50 parts of
methyl alcohol, and then dry hydrochloric-acid gas is introduced until the absorption
discontinues to be considerable. On cooling, a portion of the new ether crystallizes in
the form of beautiful crystals.
To obtain the whole quantity of ether the methyl alcohol is distilled, and the
residuum is dried upon an open basin heated by a water bath.
In order to purify the ether thus obtained, it is crystallized from water.

page_text: Or, 40 parts of crystallized gallic acid and 80 parts of inethyl alcohol are concentrated
with
4 parts of sulphuric acid, and slowly mixed. This mixture is kept rapidly boiling
for from 8 to 10 hours. It is then allowed to stand for 12 hours, and the methyl
alcohol is almost completely distilled. The residuum is mixed with 50 parts of filtered
cold water. The beautiful crystalline ether is washed out with a little cold water, and
dried at from 160 to 180 degrees Fahrenheit.
Or, 40 parts of good tannin and 80 parts of methyl alcohol are mixed with 12 parts
of concentrated sulphuric acid, the treatment being then continued as above described.
The ether from tannin has a grey appearance, but is identical with the ether from
gallic acid.
Preparation of purple colouring matter.
10 parts of methylic ether of gallic acid, (no matter whether prepared from gallic
acid or tannin) and 12 parts of hydrochloric nitroso-dimethylaniline are mixed with
80 parts of methyl alcohol, the mixture being then heated for 4 hours to ebullition, and
well agitated. The colouring matter forms gradually and separates as a hydrochlorate
in the form of-small-brown needles. It is subsequently cooled, filtered from the
alcohol, washed, and dried. For the purpose of purification, the colouring matter is
dissolved in water, filtered and precipitated from the filtrate with common salt.
The same colouring matter is obtained if, in lieu of methyl alcohol, ethyl alcohol
or only water is used.
TL : nó 1
2
HASELTINE, LAKE & Co.,
45, Southampton Buildings, London, W.C.,
Agents for the Applicant.

page_text: COMPLETE SPECIFICATION.
Improvements relating to the Preparation of the Methylic Ether of
Gallic Acid and to the Manufacture of Purple Colouring Matters
therefrom.
I, ALFRED KERN of the firm of Kern and Sandoz, of Basle, Switzerland, do
hereby declare the nature of this invention and in what manner the same is to
bo performed, to be particularly described and ascertained in and by the following
statement:-
This invention relates to the preparation of the methylic ether of gallic acid,
and of colouring matters therefrom by the action of nitroso-derivates of secondary
and tertiary aromatic monamines, the said colouring matters being applicable for
dyeing or printing.
The methylic ether of gallic acid, which has not as far as I am aware heretofore
been described, is prepared from gallic acid or tannin by the action of hydrochloric
acid or sulphuric acid upon a methyl alcoholic solution of the gallic acid or tannin.
This ether crystallizes from an alcoholic solution in anhydrous rhombic crystals at
the melting point 383 F. at normal atmospheric pressure. It dissolves easily in hot
water, and crystallizes therefrom on cooling as white felted needles which at from 212
to 230° F. lose water of crystallization.
The colouring matters which are obtained by the action of the hydrochloric nitroso-
derivates of secondary and tertiary monamines upon this ether, are easily dissoluble
in water, are hydrochlorates, and dye or print upon cotton from violet to blue.
1. Preparation of methylic ether of gallic acid.
20 parts of gallic acid, crystallized, are dissolved in a hot state in
50 parts of methyl alcohol, and then dry hydrochloric-acid gas is introduce: until
the absorption discontinues to be considerable. On cooling, a portion of the new
ether crystallizes in the form of beautiful crystals.
To obtain the whole quantity of ether the methyl alcohol is distilled and the residuum
is dried upon an open basin heated by a water bath.
In order to purify the ether thus obtained, it is crystallized from water.
Or, 10 parts of crytallized gallic acid and 80 parts of methyl alcohol are concentrated
with
4 parts of sulphuric acid, and slowly mixed. This mixture is kept rapidly boiling
for from 8 to 10 hours. It is then allowed to stand for 12 hours, and the methyl
alcohol is almost completely distilled. The residuum is mixed with 50 parts of filtered
cold water. The beautiful crystalline ether is washed out with a little cold water, and
dried at from 160 to 180 degrees Fahrenheit.
Or 10 parts of good tannin and 80 parts of methyl alcohol are mixed with
12 parts of concentrated sulphuric acid, the treatment being then continued as above
described.
The ether from tannin has a grey appearance, but is identical with the ether from
gallic acid.

page_text: Preparation of purple colouring matter.
10 parts of methylic ether of gallic acid, (no matter whether prepared from gallic
acid or tannin) and
12 parts of hydrochloric nitroso-dimethylaniline are mixed with
80 parts of methyl alcohol, the mixture being then heated for 4 hours to ebullition,
and well agitated. The colouring matter formis gradually and separates as a bydro-
chlorate in the form of small brown needles. It is subsequently cooled, filtered from
the alcohol and washed and dried. For the purpose of purification, the colouring
matter is dissolved in water, filtered and precipitated from tho filtrate with common
salt.
The same colouring matter is obtained if, in lieu of methyl alcohol, ethel alcohol or
only water is used.
Having now particularly described and ascertained the nature of my said inven-
tion and in what manner the same is to be performed I declare that what 1
claim is :-
First The production of methylic ether of gallic acid from gallic acid or tannin.
Second The production of colouring matter by the action of chlorhydric nitroso-
dimethylaniline on the methylic ether of gallic acid.
Dated this 23rd day of January 1888.
HASELTINE, LAKE & Co.,
45, Southampton Buildings, London, W.C.,
Agents for the Applicant.