Manufacture of Azo Coloring Matters derived from Azoxyamines.
Year: 1890

page_text: Date of Application, 23rd July, 1890
Complete Specification Left 10th Ant 1801-Accented 16th May 1891
PROVISIONAL SPECIFICATION.
[Communicated from abroad by LA SOCIÉTÉ ANONYME DES MATIÈRES
COLORANTES ET PRODUITS CHIMIQUES DE ST. DENIS, of 105, Rue
Lafayette, Paris, France.]
Manufacture of Azo Coloring Matters derived from Azoxyamines.
I, JOHN IMRAY, 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 to be as follows :-
In the Specification to my application for Letters Patent dated 15th April 1890
No. 5736 was described a manufacture of azo-coloring matters derived from
azoxyamines, which consisted in principle in reducing in an alkaline medium the
nitrated azo coloring.matters obtained in coupling by known processes nitramines
with phenols and amines or their sulphonated, carboxylized, and hydroxylized
derivatives.
The examples of this process given in the said Specification related to cases
where the new coloring matter is distinguished by the property of dyeing vegetable.
fibres without mordant.
According to the present invention coloring matters are obtained which have the
property of dyeing mordanted wool various shades of yellow that withstand exposure
to light, air and fulling, by coupling the diazo derivative of the various nitramines
with salicylic acid and the homologous creosotic acids.
Example I. Preparation of oxyazoic yellow coloring matter by aid of
metanitraniline.
13.8 kilo of metanitraniline, 35.5 k. of commercial hydrochloric acid are dissolved
in 1500 litres of water; the solution cooled is diazotised with 22.5 kilo of nitrite of
soda containing 33 % of pure nitrite.
This solution containing the diazo derivate is poured into 1,000 litres of an
aqueous solution containing 13-8 k. of salicylic acid in the state of a soda salt. The
mixture is left at rest for several hours,, after which there are introduced 284 litres
of soda lye at 40° Bé. and 16 kilo of glucose at 80 % and the temperature of the
mixture is raised to 40° or 60° C. for 6 or 8 hours. The conclusion of the reaction
can be ascertained when a dyeing trial shews that the coloring matter has lost the
property of dyeing wool not mordanted, in an acid bath. When this point is
attained, the liquor is acidified by sulphuric acid or hydrochloric acid, and the
precipitate obtained is collected on a filter, washed, dried and dissolved in 28 litres
of caustic soda solution at 40° B. There is thus formed a soda salt soluble in
water which is the new colouring matter, which is advantageously dealt with in the
form of paste. This colouring matter dyes wool, mordanted with oxide of
chromium, a greenish yellow of great fastness.
Example II. If in the preceding example paranitraniline or a mixture of meta
and paranitraniline be employed, colouring matters are produced of a more orange
tint which will withstand fulling.
Example III. The nitramines derived from the homologues of aniline may be
used instead of the nitrated anilines. The operation is carried out as in Example I,
substituting for the nitraniline equivalent quantities of other nitramines which may
be used either pure or mixed. The temperature and the proportions of the other
reagents are the same as in Example I. The time of the reaction is longer and it
s ascertained to be complete by making trial dyes, referred to a pattern.
The colour obtained on wool mordanted with chromium oxide is always more
greenish than that of the nitrated derivate which serves as raw material.

page_text: Example IV. The salicylic acid in Example I, II & III may have substituted
for it, its homologues, the various isomeric cresotic acids. In all these cases yellow
colouring matters of various shades are obtained and are of the same order, in
respect of fastness, as indigo blue or alizarine red.
Dated this 22nd dor of Iul 1900
ABEL & IMRAY,
Agents for the Applicant.
COMPLETE SPECIFICATION.
Manufacture of Azo Coloring Matters derived from Azoxyamines.
I, JOHN IMRAY, 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 :-
In the Specification to my application for Letters Patent dated 15th April 1890
No. 5736 was described a manufacture of azo coloring matters derived from
azoxyamines, which consisted, in principle, in reducing in an alkaline medium the
nitrated azo coloring matters obtained in coupling by known processes nitramines
with phenols and amines or their sulphonated, carboxylized and hydroxylized
derivatives.
The examples of this process given in the said Specification related to cases
where the new coloring matter is distinguished by the property of dyeing vegetable
fibres without mordant.
According to the present invention, coloring matters are obtained which have
the property of dyeing mordanted wool various shades of yellow, that withstand
exposure to light, air and fulling, by coupling the diazo derivatives of the various
nitramines with salicylic acid or the homologous creosotic acids.
Example I. Preparation of oxyazoic yellow coloring matter by aid of
metanitraniline.
13.8 kilo of metanitraniline & 35.5 kilo of commercial hydrochloric acid are
dissolved in 1500 litres of water; the solution cooled is diazotised with 22.5 kilo of
nitrite of soda containing 33% of pure
nitrite.
This solution containing the diazo derivate is poured into 1000 litres of an
aqueous solution containing 13.8 kilo of salicylic acid in the state of a soda salt.
The mixture is left at rest for several hours, after which there are introduced
284 litres of soda lye at 40° Bé. and 16 kilo of glucose at 80% and the temperature
of the mixture is raised to 40° or 60° C. for 6 or 8 hours. The conclusion of the
reaction can be ascertained when a dyeing trial shews that the coloring matter has
lost the property of dyeing wool not mordanted, in an acid bath.
When this point is attained, the liquor is acidified by sulphuric acid or hydro-
chloric acid, and the precipitate obtained is collected on a filter, washed, dried and
dissolved in 28 litres of caustic soda solution at 40° B. There is thus formed a
soda salt soluble in water which is the new coloring matter, which is advantageously
dealt with in the form of paste. This colouring matter dyes wool mordanted with
oxide of chromium, a greenish yellow of great fastness.
Example II. If in the preceding example paranitraniline or a mixture of meta
and paranitraniline be employed, coloring matters are produced of a more orange
tint which will withstand fulling.
Example III. The nitramines derived from the homologues of aniline may be
used instead of the nitrated anilines. The operation is carried out as in Example I,
substituting for the nitraniline equivalent quantities of other nitramines which may
be used either pure or mixed. The temperature and the proportions of the other
reagents are the same as in Example I.
The time of the reaction is longer and it is ascertained to be complete by making
trial dyes; referred to a pattern.

page_text: The colour obtained on wool mordanted with chromium oxide is always more
greenish than that of the nitrated derivate which serves as raw material.
Example IV. The salicylic acid in Examples I, II, and III may have substituted
for it, its homologues, the various isomeric cresotic acids. In all these cases yellow
coloring matters of various shades are obtained and are of the same order, in respect
of fastness, as indigo blue or alizarine red.
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 is :-
The manufacture of azo coloring matters by coupling diazo derivatives of
nitramines with salicylic acid or its homologues the various isomeric cresotic acids,
substantially as described.
ABEL & IMRAY,
Agents for the Applicant.