Year: 1898

page_text: BLO
We, VIDAL FIXED ANILINE DYES LIMITED and LOUIS HAAS, both of Rue Michel
Carré à Argenteuil (Seine et Oise) in the Republic of France, do hereby declare the
nature of this invention to be as follows:-
This invention relates to an improved process for producing new colouring matters
from the triphenylmethane, obtained by sulphuric condensation of the
tetramethylated and tetraethylated diamido-benzhydrol or its derivatives with the
aromatic hydrazines and without subsequent oxydation.
The aromatic amines of benzine or of naphtaline combine, as is known, with benzenic
hydrols in forming leuco-bases derived from triphenylmethane which can be
transformed by oxidizers (bioxide of lead, chloranil, etc. etc.) into dyes of the group of
rosanilines.
We have found that certain aromatic hydrazines could combine with tetramethylated
and tetraethylated diamido-benzhydrol or its derivatives in presence of concentrated
sulphuric acid by forming leuco bases capable of becoming transformed in the
sulphuric medium itself, without the aid of any oxidizer, into colouring stuffs for use
as dyes.
The condensation takes place at 60° to 70° at the second phase the leuco-base is
transformed, through the action of the sulphuric acid at 80° to 90° into colouring
dyes by loosing one molecule of ammoniac.

page_text: yellow colour, has after the lapse of one hour changed into a brown colour and the
colouring matter thus has been formed by the loss of one molecule of ammoniae,
which is recovered from the mother-lye after the separation of the dye.
This latter is isolated by neutralizing the solution, and is then washed and dried.
The product is a green-reddish-brown, insoluble in alkalies, slightly soluble in water,
soluble in acids and alcohol, and dyes animal fibre, in an acidulated bath, into a violet
tint.
VII.
We also obtain yellow colouring matters, insoluble in water and alkalies, soluble
in dilute alcohol and acids by condensing parachlorphenylhydrazine or para-
bromphenylhydrazine with tetramethyldiamidobenzhydrol in molecular quantities.

page_text: Ovouring matters.
We, VIDAL FIXED ANILINE DYES LIMITED and LOUIS HAAS, both of Rue Michel
Carré à Argenteuil (Seine et Oise), in the Republic of France, 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 :—
This invention relates to an improved process for producing new colouring matters
from the triphenylmethane, obtained by sulphuric condensation of the tetramethy-
lated and tetraethylated diamido-benzhydrol or its derivatives with the aromatic
hydrazines and without subsequent oxydation.
The aromatic amines of benzine or of naphthaline combine, as is known, with
benzinic hydrols in forming leuco-bases derived from triphenylmethane which can be
transformed by oxidizers (bioxide of lead, chloranile, etc. etc.,) into dyes of the group
of rosanilines.
We have found that certain aromatic hydrazines could combine with tetramethy-
lated and tetraethylated diamido-benzhydrol or its derivatives in presence of
concentrated sulphuric acid by forming leuco bases capable of becoming transformed
in the sulphuric medium itself, without the aid of any oxidizer into colouring stuffs
for use as dyes.
The condensation takes place at 60° to 70° at the second phase the leuco-base is
transformed, through the action of the sulphuric acid at 80° to 90° into colourin
dyes by loosing one molecule of ammoniac.

page_text: These colouring matters dye animal fibre into a yellow of a more green tint than
those of sulphuretted paratoluidines 1.4.3 and 1.4.2.
In all these examples the tetramethyldiamidobenzhydrol may be replaced by its
tetraethylated isomer without the obtained colouring matters being perceptibly
different from those which we have just described, as regards their solubility in
chemical agents as well as their tints upon animal fibre.
On the contrary the use of non-alcohylated diamido-benzhydrol permits of obtain-
ing colouring matters of very different tints.
II.
An equivalent quantity of orthotolylhydrazine produces a red colouring matter,
20 insoluble in water and alkalis, soluble into red in alcohol and acetic acid, into a dark
greenish yellow in dilute mineral acids and dyeing wool into a more yellow and
brighter red than the preceding.
III.
An equivalent quantity of a-benzylhydrazine. or of methyl or ethylphenylhydrazine
25 produces a colouring matter insoluble in alkalis, soluble with difficulty in water,
soluble in alcohol and dilute acids and dyeing the fibre into fuchsine-red.
IV.
An equivalent quantity of o-tolylaulphohydrazine 1.2.5, produces a colouring
matter, slightly soluble in water, soluble with difficulty in alkalis, soluble in acids,
O fairly soluble in alcohol and dyeing animal fibre into red-blue of greater beauty.
V.
The corresponding colouring matter, derived from o-tolylsulphohydrazine 1.2.4 is
analogous as regards solubilities, but dyes animal fibre into a less handsome and more
blue tint than the preceding.
The corresponding colouring matter, derived from o-tolylsulphobydrazine 1.2.4 is
analogous as regards solubilities, but dyes animal fibre into a less handsome and more
blue tint than the preceding.
VI.
Hydrazine derived from parasulphanilic acid produces a violaceous red colouring
matter slightly soluble in water and alkalis, soluble in acids.
Dated this 16th day of November 1898.

page_text: III.
An equivalent amount of o-tolylsulphohydrazine 1.2.4 produces a colouring
matter insoluble in water, soluble into yellow in the presence of dilute aoids, into
blue-green in the presence of alcohol and acetic acid, into blue in the presence of
5 dilute caustic alkalis and dyeing animal fibre into blue-violet.

page_text: II.
An equivalent quantity of orthotolylbydrazine produces a red colouring matter,
insoluble in water and alkalis, soluble into red in alcohol and acetic acid, into a dark
greenish yellow in dilute mineral acids and dyeing wool into a more yellow and
brighter red than the preceding.
An equivalent quantity of a-benzylhydrazine or of methyl or ethylphenylhydrazine
produces a colouring matter insoluble in alkalis, soluble with difficulty in water,
soluble, in alcohol and dilute acids and dyeing the fibre into fuchsine-red.
IV.
An equivalent quantity of o-tolylsulphohydrazine 1.2.5, produces a colouring
matter, slightly soluble in water, soluble with difficulty in alkalis, soluble in acids,
fairly soluble in alcohol and dyeing animal fibre into red-blue of greater beauty.
The corresponding colouring matter, derived from o-tolylsulphohydrazine 1.2.4 is
analogous as regards solubilities, but dyes animal fibre into a less handsome and more
blue tint than the preceding.
VI.
Hydrazine derived from parasulphanilic acid produces a violaceous red colouring
matter slightly soluble in water and alkalis, soluble in acids.
Having now particularly described and ascertained the nature of our said inven-
tion and in what manner the same is to be performed, we declare that what we
claim is :-
1. As products: the violet, violaceous blue, green, yellow and red colouring
matters above described.
2. As a new process: the application of the process described in our application
for Patent of even date herewith viz. No. 24183 A.D. 1898.
(a) to an equi-molecular mixture of tetramethyl or tetraethyldiamidobenzhydrol
and of hydrazines derived from: orthotoluidine, orthotoluidinemonosulphonic 1.2.5
and 1.2.4-paratoluidine, paratoluidinemonosulphonic 1.4.2 and 1.4.3-parachlorani-
line, parabromaniline :
(6) to an equi-molecular mixture of diamidobenzhydrol and of hydrazines derived
from: aniline, monomethyl, monoethyl and monobenzylaniline, orthotoluidine,
orthotoluidinemonosulphonic 1.2.5 and 1.2.4, parasulphanilic acid.
TAL: ALL
ו ז . -.1
1000
HASELTINE, LAKE & Co.,
45, Southampton Buildings, London, W.C., Agents for the Applicants.
on NAAS