Year: 1898

page_text: Date of Application, 10th Jan., 1898
Complete Specification Left, 19th Sept., 1898-Accepted, 12th Nov.,
1898
Halfacture
I, CHARLES DENTON ABEL, of Birkbeck Bank Chambers, Southampton Buildings,
Chancery Lane, in the County of London, Consulting Engineer and Chartered Patent
Agent, do hereby declare the nature of this invention (as communicated to me from
abroad by The Actien Gesellschaft für Anilin Fabrikation, of Berlin, in the Empire of
Germany, Chemical Manufacturers) to be as follows:-
My foreign correspondents have discovered that yellow, orange-red to yellowish-
brown colouring matters are produced by the action of 8-oxy-a-naphthoquinone
derivatives upon hydrazines or their sulphonic or carboxylic substitution products.
These colouring matters are very valuable in consequence of their extraordinary
A condensation
intensity, their great equalizing power, and their brilliant tints.
product of B-oxy-u-naphthoquinone with phenylhydrazine has been already described
by Zincke and Thelen (Ber. d.d. chem. Ges. Vol. 17 P. 1809), but this product
cannot be used as a dyestuff, because it is not soluble, except with great difficulty.
Condensation products, however, of hydrazines with substituted 8-oxy-a-naphtho-
quinone, as for instance oxynaphthoquinone sulphonic acid, nitrooxynaphthoquinone
&c., have not been described hitherto.
Moreover, from B-oxy-a-naphthoquinone itself less strong and brilliant dyes are
obtained with insufficient yield, while strong and brilliant dyes are produced by
means of substituted B-oxy-a-naphthoquinones without difficulty and with good
yield.
The difference is probably caused by the fact that the position 3 of the quinone
nucleus is free in one case, while it is substituted in the other.
For effecting the condensation, my foreign correspondents have found that a suit-
able method is to heat a mixture of B-oxynaphthoquinone derivatives and of hydrazine
derivatives in aqueous solution at a temperature of from 40° to 80° C., sodium acetate
being preferably added.
The product thus obtained, for instance, from B-oxynaphthoquinonesulphonic acid
and phenylhydrazine sulphonic acid dyes wool 'n an acidified bath a strong and
brilliant orange yellow.
Similar dyestuffs are obtained by substituting phenylhydrazine or hydrazine
derived from meta amidobenzoic acid for phenylhydrazine sulphonic acid, while by
means of hydrazine derived from amidonaphtholdisulphonic acid H a yellowish-red
dyestuff is obtained.
Analogous products are obtained by the action of nitro-oxy-a-naphthoquinone upon
the above named hydrazine derivatives. For instance phenylhydrazine sulphonic
acid produces a pure greenish-yellow dyestuff, while hydrazine derived from meta-
amidobenzoic acid yields a yellow one and hydrazine derived from amidonaphthol-
disulphonic acid H a yellowish-brown one.
Dated this 10th day of January 1898.

page_text: I, CHARLES DENTON ABEL, of Birkbeck Bank Chambers, Southampton Buildings,
Chancery Lane, in the County of London, Consulting Engineer and Chartered
Patent Agent, do hereby declare the nature of this invention (as communicated to me
from abroad by The Actien Gesellschaft für Anilin Fabrikation, of Berlin, in the
Empire of Germany, Chemical Manufacturers,) and in what manner the same is to
be performed to be particularly described and ascertained in and by the following
statement:-
--
My foreign correspondents have discovered that yellow, orange-red to yellowish-
brown colouring matters are produced by the action of ẞ-oxy-a-naphthoquinone
derivates upon hydrazines or their sulphonic or carboxylic substitution products.
These colouring matters are very valuable in consequence of their extraordinary
intensity, their great equalizing power, and their brilliant tints. A condensation
product of ẞ-oxy-a-naphthoquinone with phenylhydrazine has been already described
by Zincke and Thelen (Ber. d.d. chem. Ges. Vol. 17, P. 1809), but this product
cannot be used as a dyestuff, because it is not soluble, except with great difficulty.
Condensation products, however, of hydrazines with substituted ẞ-oxy-a-naphtho-
quinone, as for instance oxynaphthoquinone-sulphonic acid, nitrooxynaphthoquinone
&c., have not been described hitherto.
Moreover, from ẞ-oxy-a-naphthoquinone itself less strong and brilliant dyes are
obtained with insufficient yield, while strong and brilliant dyes are produced
by means of substituted ẞ-oxy-a-naphthoquinones without difficulty and with good
yield.
The difference is probably caused by the fact that the position 3 of the quinone
nucleus is free in one case, while it is substituted in the other.
For effecting the condensation, ny foreign correspondents have found that a
suitable method is to heat a mixture of ẞ-oxynaphthoquinone derivatives and of
hydrazine derivatives in aqueous solution at a temperature of from 40° to 80° C.
sodium acetate being preferably added.
The product thus obtained, for instance, from ẞ-oxynaphthoquinonesulphonic acid
and phenylhydrazine-sulphonic acid dyes wool in an acidified bath a strong and
brilliant orange yellow.
•
Similar dyestuffs are obtained by substituting phenylhydrazine or the hydrazine
derived from meta-amidobenzoic acid for phenylhydrazine-sulphonic acid, while by
means of the hydrazine derived from amido-naphtholdisulphonic acid H a yellowish-
red dyestuff is obtained.
Analogous products are obtained by the action of nitro-oxy-a-naphthoquinone upon
the above named hydrazine derivatives. For instance phenylhydrazine-sulphonic
acid produces a pure greenish-yellow dyestuff, while the hydrazine derived from
meta-amidobenzoic acid yields a yellow one and the hydrazine derived from
amidonaphtholdisulphonic acid H a yellowish-brown-one.
The following examples may serve to illustrate this new process :--
1.) A solution of 17-8 kilos. of phenyl-hydrazinesulphonic acid and of 14 kilos. of
sodium acetate in 560 litres of water is added to 27.6 kilos. of the sodium salt of
P-oxy-a-naphthoquinonesulphonic acid, dissolved in 840 litres of water. The mixture
is heated to 45° C. during 6 hours. The temperature is then allowed to rise to 80° C.
and the dyestuff formed is precipitated by addition of common salt. The new
colouring matter thus obtained dyes wool in acid-bath orange-yellow tints of great
strength and brilliancy.
. Similar products are obtained by substituting in the above example molecular

page_text: proportions of phenylhydrazine or of the hydrazine derived from meta-amidobenzoic
acid for the phenylhydrazinesulphonic acid. The dyestuffs obtained from these pro-
ducts are less soluble than the one first described. Furthermore, a yellowish red
dyestuff is obtained in an analogous manner by using the hydrazine derived from
amidonaphtholdisulphonic acid H.
All these colouring matters dissolve in concentrated sulphuric acid with brilliant
eosine-red colour.
2.) 21.9 kilos. of nitrooxy-a-naphthoquinone and 17.8 kilos. of phenylhydrazine-
sulphonic acid are suspended in 1500 litres of water and heated to 45°C. while
being well stirred, until the hydrazinesulphonic acid has completely dissolved.
42 kilos. of sodium acetate are then added, the temperature is raised to 80° C. and
the dyestuff is precipitated by addition of common salt. It dyes wool in acid-bath
pure greenish-yellow tints.
By substituting in the above example the hydrazine derived from meta-amido-
benzoic acid for the phenylhydrazinesulphonic acid a similar yellow colouring matter
is obtained while the hydrazine prepared from amidonaphtholdisulphonic acid H
yields under analogous conditions a brownish-yellow dyestuff. The colouring
matters prepared in the manner described closely resemble those obtained as in
Example 1).
Having now particularly described and ascertained the nature of this inveu-
tion and in what manner the same is to be performed, I declare that what. I
clain is-
1. The herein described manufacture of new colouring matters by the action of
B-oxy-a-naphthoquinone derivatives such as B-oxy-a-naphthoquinonesulphonic acid
or nitro-ẞ-oxy-a-naphthoquinone on hydrazines, such as phenylhydrazine, phenyl-
hydrazinesulphonic acid, the hydrazine derived from meta-amidobenzoic acid, or the
hydrazine derived from amidonaphtholdisulphonic acid H.
2. The new colouring matters obtained as set forth in Claim 1.