Manufacture of Azo Colouring Matters Dyeing Unmordanted Cotton in Acid, Neutral, or Alkaline Bath.
Year: 1895

page_text: Date of Application, 9th Apr., 1895
Complete Specification Left, 19th Lec., 1895-Accepted, 8th Feb., 1896
PROVISIONAL SPECIFICATION.
[Communicated from abroad by LA SOCIÉTÉ ANONYME DES MATIERES
COLORANTES ET PRODUITS CHIMIQUES DE ST. DENIS and DANIEL
AUGUSTE ROSENSTIEHL, Chemist, all of 105, Rue Lafayette, Paris,
France.]
Manufacture of Azo Colouring Matters Dyeing Unmordanted Cotton
in Acid, Neutral, or Alkaline Bath.
I, JOHN IMRAY, of No. 28 Southampton Buildings, Chancery Lane, in the
County of London, Consulting Engineer and Chartered Patent Agent, do hereby
declare the nature of this invention to be as follows:-
According to the present invention azo-colouring matters dyeing unmordanted
cotton in acid, neutral or alkaline bath are produced by diazotising the azoxyamines
hereinafter named, and in coupling the azo derivatives with naphthaline derivatives,
also to be hereinafter named.
A second process giving the same final result consists in employing, in place of
the azoxyamines, the corresponding nitramines, in diazotising them and coupling
these azo derivatives with the same naphthaline derivatives.
There are thus obtained azo derivatives of naphthaline which only dye wool and
not cotton, but by treating these colouring matters in an alkaline medium by means
of reducing agents, such as glucose, arsenious acid, or sodium sulphide, they are
transformed into colouring matters that will dye cotton, and that are identical with
those prepared by means of azox yamines.
EXAMPLE I.
11·4 kilos. of para-azoxyaniline (p. f. 1870-189° C.) in 25 kilos. of hydrochloric
acid at 20° Bé. and 100 litres boiling water. This solution is diluted to a volume
of 600 litres by means of water and ice, after which 7 kilos. of nitrite of soda.
of 98 per cent. purity dissolved in three times the quantity of water; are added..
After the reaction, the solution of para-tetrazo-azoxybenzene serves for the
following preparations :
'
1. When poured into a solution of 23.9 kilos. of amidonaphthol-sulphonic acid G,
and 21 kilos. of carbonate of soda in 150 litres water, cooled by means of ice, it
produces a black, colouring matter which is separated by adding 15 kilos. of
'sea salt.
2. By replacing the amidonaphthol-sulphonic acid G by means of amidonaphthol
sulphonic acid H of French Patent 210950, or by dioxynaphthaline sulphonic
scid, S of French Patent No. 200520, there are obtained blue colouring matters.
3. With the chromotropic acid of French Patent No. 206439, there is obtained
a violet colouring matter.
In example I the para-azoxyaniline can be replaced by its superior homologue:
para-azoxy orthotoluidine; with the same naphthaline derivatives similar colouring
matters are obtained.
While the para-azoxyamines produce colouring matters dyeing violet, blue and
black, the meta-azoxyamines produce browns.
Thus with meta-azoxyorthotoluidine, diazotised and coupled with amidonaphthol
sulphonic acid G, there is obtained a brown red colour, dyeing unmordanted.cotton
in acid, neutral or alkaline bath.

page_text: EXAMPLE II.
13-8 kilos. of para-nitraniline (p. f. 147°) are diazotised by the well-known
process, and the product is coupled with 23.9 kilos. of amidonaphthol sulphonic
acid G dissolved in 150 litres of water with 21 kilos. of soda salt.
The nitrated colouring matter obtained by this means does not dye cotton, but
dyes wool brown.
For transforming it into matter that will dye cotton, there is added to the same
liquid in which it is formed, 100 litres of caustic soda lye of 40° Bé., and 13 kilos.
of glucose dissolved in 100 litres of water. The mass is heated to 40° C. for 4 hours
under agitation.
The nitrated matter is thus reduced and transformed into a derivative of
azoxyamine identical with that described in Example I.
By replacing para-nitraniline by para-nitro orthotoluidine fusible at 127° C. there
are obtained the same colouring matters as with para-azoxy-orthotoluidine.
In conclusion, each of the colouring matters described in Example I derived
from one of the four naphthaline compounds there mentioned, can be obtained by
the reduction according to Example 11 of the corresponding nitrated colouring
matter.
The glucose can be replaced by arsenious acid and sodium sulphide.
The caustic soda lye can in some cases be replaced by milk of lime.
Dated this 9th do of Anv: 1003
ABEL & IMRAY,
Agents for the Applicant.
Manufacture of Azo Colouring Matters Dyeing Unmordanted Cotton
in Acid, Neutral, or Alkaline Bath.
1, JOHN IMRAY, of No. 28 Southampton Buildings, Chancery Lane, in the
County of London, Consulting Engineer and Chartered 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 :-
According to the present invention, azo colouring matters dyeing unmordanted
cotton in acid, neutral or alkaline bath, are produced by diazotising the azoxyamines
hereinafter named, and in coupling the azo derivatives with naphthaline derivatives,
also to be hereinafter named.
A second process giving the same final result consists in employing, instead of
the azoxyamines, the corresponding nitramines, in diazotising them and coupling
these azo derivatives with the same naphthaline derivatives.
There are thus obtained azo derivatives of naphthaline which only dye wool and
not cotton, but by treating these colouring matters in an alkaline medium by means
of reducing agents, such as glucose, arsenious acid, or sodium sulphide, they are
transformed into colouring matters that will dye cotton, and that are identical with
those prepared by means of azoxyamines.

page_text: w me the para-azoxyamines produce colouring matters dyeing violet, blue and
black, the meta-azoxyamines produce browns.
Thus with meta-azox yorthotoluidine, diazotised and coupled with amidonaphthol-
sulphonic acid G, there is obtained a brown red colour, dyeing unmordanted cotton
in acid, neutral or alkaline bath.
EXAMPLE II.
13-8 kilos. of para-nitraniline (fusing at 147° C.) are diazotised by the well-
known process, and the product is coupled with 23.9 kilos. of amidonaphthol
sulphonic acid G dissolved in 150 litres of water with 21 kilos. of soda salt.
The nitrated colouring matter obtained by this means does not dye cotton, but.
dyes wool brown.
For transforming it into matter that will dye cotton, there is added to the same
liquid in which it is formed, 100 litres of caustic soda lye of 40° Bé. and 13 kilos..
of glucose dissolved in 100 litres of water. The mass is heated to 40° C. for 4 hours
under agitation.
The nitrated matter is thus reduced and transformed into a derivative of
azoxyamine identical with that described in Example I.
By substituting for para-nitraniline, para-nitro orthotoluidine fusible at 127° C.,.
there are obtained the same colouring matters as with para-azoxy-orthotoluidine.
In conclusion, each of the colouring matters described in Example I derived
from one of the four naphthaline compounds there mentioned, can be obtained by
the reduction according to Example I of the corresponding nitrated colouring
matter.
For the glucose can be substituted arsenious acid and sodium sulphide.
For the caustic soda lye can in some cases be substituted milk of line.
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 I
claim in respect of the manufacture of azo colouring matters is :-
1. The herein described process of coupling the azo derivatives of the azoxy--
amines above mentioned with the amido naphthol sulphonic acid G, or amido
naphthol sulphonic acid H, or with the dioxynaphthaline sulphonic acid S, or
with chromotropic acid.
2. The process of coupling the azo derivatives of the nitramines corresponding
to the azoxyamines, and the reduction of these nitrated azo bodies so as to.
transform them into colouring matters having dyeing properties like those of the
matters manufactured according to Claim 1.
3. The colouring matters manufactured as above set forth.
Dated thin 10th day
100%
ABEL & IMRAY,
Agents for the Applicant..