Improvements in the Production of Dyes.
Year: 1896

page_text: PROVISIONAL SPECIFICATION.
Improvements in the Production of Dyes.
We LEON PAUL MARCHLEWSKI, of 25 Wellington Street, Higher Broughton,
Manchester, in the County of Lancaster, Chemist, and EDGAR SIDDONS WILSON,
of Arthog, Goddington Road, Strood in the County of Kent, Chemist, and
EBENEZER STEWART of 94 Queen Victoria Street in the City of London,
Merchant, do hereby declare the nature of this invention to be as follows :-
When crude cotton seed oil is refined by means of weak alkaline solutions, the
said solutions after separation from the oil contain amongst other matter a yellow
crystalline substance easily soluble in alcohol, ether and acetic acid not soluble in
water and easily soluble in alkalies. The said substance may be isolated from
other matters contained in the aforesaid solutions by treatment in the manner
provisionally specified by Edgar Siddons Wilson and Ebenezer Stewart, under the
serial number 24418 of the year 1895. The said treatment consists essentially in
submitting the solutions to fractional precipitation with earthy salts of metallic
bases which convert the fatty acids contained in the said solutions into insoluble or
not easily soluble soaps. The residual liquor is then treated with an acid such as
hydrochloric acid which will decompose alkaline carbonates or soluble sulphite as
well as the alkaline compound of the colouring matter. To the flocculent
precipitate thereby produced, we have given the name of gossypol and will
hereinafter refer to it by that name.
The said gossypol when treated as hereinafter set forth is converted into
substances which may be used to dye cotton and wool according to the treatment,
from yellow and light yellowish brown to reddish brown and dark brown or almost
black.
First. The gossypol is molecularly condensed or combined with nitroso compounds
of di-methyl-aniline and di-ethyl-aniline or their salts by heating together the said
substances in alcohol, acetic acid, or other suitable solvent; about three parts by
weight of the gossypol are mixed with two parts by weight of the nitroso compounds,
(these proportions vary according to the purity of gossypol) and the solution thereof
is boiled for several hours, after which it is poured into water, and the colouring
matter or dye is salted out or precipitated by means of common salt or equivalent
substance. The dye so produced is not soluble in water, but may be dissolved in
acetic acid or alcohol, and is used for dyeing cotton or wool by adding the solution
to the dye-vat in the usual way. With iron chrome or tin mordants a deep brown
to yellow brown shade is obtained.
The dye obtained as above set forth may be made soluble in water by converting
it into a sulphonic compound. This is effected by subjecting the said dye to the
action of fuming sulphuric acid heated to a temperature of about 125° Centigrade.
The sulphonic compound is then separated from the acid by mixing with water,
after which the said dye is precipitated or salted out by means of common salt or
like re-agent, the precipitate is then heated in an alkaline carbonate solution until
it combines with the sodium or potassium therein contained. The said compound
is soluble in water and may be used with the usual mordants for dyeing wool only,
to which it imparts a bright yellowish to dark brown colour.
Second. The gossypol is molecularly condensed or combined with a solution of

page_text: ortho-nitroso-naphthols (a-nitroso ẞ-naphthol, or ẞ-nitroso a-naphthol) in con-
centrated sulphuric acid at a temperature of about 70° Centigrade. The compound
produced is separated from the solution, by being poured into water and precipitated
or salted out as before set forth.
The dye obtained, dyes wool yellowish-brown and brown according to the
mordant; it dyes also unmordanted wool to some extent brownish tint.
Dated the 4th der of May 1906
Improvements in the Production of Dyes.
We, LEON PAUL MARCHLEWSKI, of 25, Wellington Street, Higher Broughton,
Manchester, in the County of Lancaster, Chemist, and EDGAR SIDDONS WILSON,
of Arthog, Goddington Road, Strood, in the County of Kent, Chemist, and
EBENEZER STEWART, of 94 Queen Victoria Street, in the City of London,
Merchant, 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:-
When crude cotton-seed oil is refined by means of weak alkaline solutions, the
solutions after separation from the oil contain amongst other matters, a substance
which after a series of crystallisations from glacial acetic acid and from alcohol can
be obtained as yellow crystals, easily soluble in alcohol, ether, and boiling acetic
acid, not soluble in water and easily soluble in alkalies. The said substance may
be isolated from other matters contained in the aforesaid solutions by treatment in
the manner specified by Edgar Siddons Wilson and Ebenezer Stewart, under the
serial number 24418 of the year 1895. The said treatment consists essentially in
submitting the solutions to fractional precipitation with earthy salts of metallic
bases, which convert the fatty acids contained in the said solutions into insoluble
or not easily soluble soaps. The residual liquor is then treated with an acid such
as hydrochloric acid, which will decompose alkaline carbonates and the like, as
well as, the alkaline compound of the colouring matter. To the flocculent
precipitate thereby produced we have given the name of gossypol, and will
hereinafter refer to it by that name.
The said gossypol, obtained either as above set forth or otherwise, when treated
as hereinafter set forth is converted into substances which may be used to dye
cotton and wool according to the treatment, from yellow and light yellowish brown
to reddish brown and dark brown to almost black."
First. The gossypol is molecularly condensed or combined with nitroso compounds
of di-methyl-aniline and di-ethyl-aniline or their salts by heating together the said
substances in alcohol, acetic acid, or other suitable solvent; about three parts by
weight of the gossypol are mixed with two parts by weight of the nitroso coinpounds
(these proportions vary according to the purity of the gossypol), and the
solution thereof is boiled for several hours, after which it is poured into water, and
the coloring matter or dye is salted out or precipitated by means of common salt
or equivalent substance. The dye so produced is not soluble in water, but may be
dissolved in acetic acid, or alcohol, and is used for dyeing cotton or wool by adding
the solution to the dye-vat in the usual way. With iron chrome or tin mordants a
deep brown to yellow brown shade is obtained.
The dye obtained as above set forth may be made soluble in water by converting
it into a sulphonic compound. This is effected by subjecting the said dye to the
action of fuming sulphuric acid heated to a temperature of about 125° Centigrade.

page_text: The sulphonic compound is then separated from the acid by mixing with water and
precipitating the color by means of common salt or like re-agent; the precipitate
is then heated in an alkaline carbonate solution until it combines with the sodium
or potassium therein contained. The said compound is soluble in water and may
be used with the usual mordants for dyeing wool, to which it imparts a bright
yellowish to dark brown color.
Second. The gossypol is molecularly condensed or combined with a solution of
ortho-nitroso-naphthol (a-nitroso-ẞ-naphthol, or ẞ-nitroso-a-naphthol) in concen-
trated sulphuric acid at a temperature of about 55° to 70° Centigrade. The
compound produced is separated from the solution by being poured into water
and precipitated or salted out as before set forth.
The dye obtained dyes wool yellowish-brown and brown according to the
mordant; it dyes also unmordanted wool to some extent a brownish tint.
Having now ascertained and particularly described the nature of the said inven-
tion and in what manner the same is to be performed, we declare that what we
claim is.
First. The process of producing dyes by combining the substance hereinbefore
called gossypol, or equivalent substance, with nitroso-di-methyl-aniline or nitroso-
di-ethyl-aniline, or their equivalents, through the medium of a solvent and heat,
substantially as set forth.
Second. The process of producing dyes by combining the substance, hereinbefore
alled gossypol, or equivalent substance, with nitroso-di-methyl-aniline or nitroso-
di-ethyl-aniline, or their equivalents, through the medium of a solvent and heat,
precipitating, and then treating the precipitate with fuming sulphuric acid, or
other sulphonating agent, substantially as set forth.
Third. The process of producing dyes by combining the substance hereinbefore
called gossypol, or equivalent substance with an ortho-nitroso-naphthol through the
medium of a solution of sulphuric acid substantially as set forth.
Fourth. Dyes produced by the processes, or their equivalents, substantially as
hereinbefore set forth.
1907
J. KING,
Agent.