PREPARATION OF COLOURING MATTERS OBTAINED BY MEANS OF BASES DERIVED FROM THE AZOIC COMBINATIONS OF PARACRESYLOL, ETHERIFIED REDUCED CONDENSED.
Year: 1887

page_text: Date of Application, 12th Sept., 1887
Complete Left, 31st May, 1888
Complete Accepted, 6th July, 1888
[Communicated from abroad by LA SOCIÉTÉ ANONYME DES MATIÉRES COLORANTES
ET PRODUITS CHIMIQUES DE ST. DENIS, ALCIDE FRANÇOIS POIRRIER, Manu-
facturer, and DANIEL AUGUSTE ROSENSTIEHL, Chemist, all of 105, Rue Lafayette,
Paris, France.]
I, JOHN IMRAY of No. 28 Southampton Buildings Chancery Lane in the
County of Middlesex, Consulting Engineer and Patent Agent do hereby declare the
nature of this invention to be as follows:-
This invention relates to the manufacture of tetrazoic colouring matters derived
from the bases obtained by special treatment of the azoic combinations of etherified
paracresylol reduced and condensed as hereinafter described.
The process consists in subjecting these bases to the action of nitrous acid, and
combining this tetrazoic derivate with certain substances such as phenols, oxyphenols,
naphthols, oxynaphthols, primary, secondary and tertiary aromatic amines, diamines, as
well as the alkylic sulphonic and carboxylic derivates of these bodies.
PREPARATION OF COLOURING MATTERS OBTAINED BY MEANS OF
BASES
DERIVED
FROM THE AZOIC COMBINATIONS OF PARACRESYLOL, ETHERIFIED REDUCED
CONDENSED.
AND
The primary basis of the colouring matter is prepared as follows:-into an
alkaline solution of 10.8 kilos of paracresylol is poured a cooled solution of chloride
of diazobenzol obtained from 9-3 kilos of aniline. There is immediately produced a
brown precipitate which is collected on a filter, pressed and dried. 2.12 kilos of
the dried product are then dissolved in 15 litres of very strong alcohol and 0.4
kilo of caustic soda, then 2.56 kilos of iodide of ethyl are added, and the whole is
boiled for about 5 hours in a vessel with a cooling worm and return. When
etherification is completed, one third of the alcohol is distilled off and the residue is
), Ը),

page_text: poured into alkaline water and left to settle. The ether separates itself in the form
of an oily layer, which quickly solidifies, the portions that are not etherified
remaining in the liquor. The other is separated by filtration, washed in water,
filtered again and dried. 5.0 kilos of this ether are then dissolved in 15
litres of hot alcohol, and to this are added 5 litres of alcohol saturated
with ammonia gas; a current of sulphuretted hydrogen is then passed
for about half an hour through this alcoholic solution. This completes the
reduction, and there is a deposit of yellow crystals, which are scarcely soluble in
cold alcohol. These crystals are separated by decantation, dried and boiled for five
minutes in 100 litres of water with 5-0 of sulphuric acid. The solution is brown
and the sulphate of the new product converted into benzidenic derivate is separated
by cooling. Instead of using aniline as above, a corresponding quantity of
orthotoluidine may be employed, and for the paracresylol metoxylenol may be
substituted. In etherifying the azoic grouping, for iodide of ethyl may be substituted
any hydrate halogen ethers (iodide of methyl, chloride of methyl or of ethyl, bromide
of ethyl or amyl &c.).
The following is an example of the mode of preparing colouring matters obtained
by employing the product of condensation of ethylated paracresylol with orthotoluidine
combined with a-sulpho-a-naphthol.
The liquor containing 26 kilos of the new benzidenic derivate in the state of
sulphate is acidulated with hydrochloric acid and treated with 6.9 kilos of nitrite of
soda dissolved in 20 litres of water. There is thus obtained a tetrazoic derivate to
which are added 45 kilos of a-sulpho-a-naphthol in the state of soda salt and
15 kilos of carbonate of soda dissolved in 4000 litres of water. The mixture is left
at rest for several hours and a precipitate is formed by salt, giving a reddish blue
colouring matter.
By substituting for the a-sulpho-a-naphthol equivalent quantities of the following
substances, colouring matters of analogous character are produced, giving tints as
follows:
Bisulphonaphthol (salt R)
a-sulpho--naphthol
Resorcine
Metaphenelene diamine
Naphthionic acid
Sulphoconjugate ẞ-naphthylamine
a-naphthylamine
a oxynaphthoic
a dioxynaphtholine
red violet
very red violet
very red orange
brown
red
brown
brown scarcely soluble
reddish yellow
violet.
The colouring matters thus produced possess among other properties that of
dyeing cotton in an alkaline bath, wool and silk in an acid, alkaline or neutral bath,
and they take on to the various mordants or salts usually employed in dyeing.
The proportions of the reagents employed may be varied.
Dated this 12th day of September 1887.

page_text: Production of New Tetrazolo Colouring matters.
I, JOHN IMRAY of No. 28 Southampton Buildings, Chancery Lane in the County
of Middlesex, 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:-
This invention relates to the manufacture of tetrazoic colouring matters derived
from the bases obtained by special treatment of the azöic combinations of etherified
paracresylol reduced and condensed as hereinafter described.
The process consists in subjecting these bases to the action of nitrous acid, and
combining this tetrazoic derivate with certain substances such as phenols, oxyphenols,
naphthols, oxynaphthols, primary, secondary and tertiary aromatic amines, diamines,
as well as the alkylic, sulphonic and carboxylic derivates of these bodies.
PREPARATION OF COLOURING MATTERS OBTAINED BY MEANS OF BASES DERIVED
FROM THE AZÖIC COMBINATIONS OF PARACRESYLOL ETHEREFIED REDUCED AND
CONDENSED.
The primary basis of the colouring matter is prepared as follows:-into an alkaline
solution of 10.8 kilos of paracresylol is poured a cooled solution of chloride of
diazobenzol obtained from 9.3 kilos of aniline. There is immediately produced a
brown precipitate which is collected on a filter, pressed and dried. 2.12 kilos of the
dried product are then dissolved in 15 litres of very strong alcohol and 0.4 kilos of
caustic soda, then 2.56 kilos of iodide of ethyl are added, and the whole is boiled for
about 5 hours in a vessel with a cooling worm and return. When etherification is
completed, one third of the alcohol is distilled off and the residue poured into
alkaline water and left to settle. The ether separates itself in the form of an oily
layer, which quickly solidifies, the portions that are not etherified remaining in the
liquor. The ether is separated by filtration, washed in water, filtered again and dried.
5.0 kilos of this ether are then dissolved in 15 litres of hot alcohol, and to this are
added 5 litres of alcohol saturated with ammonia gas; a current of sulphuretted
hydrogen is then passed for about half an hour through this alcoholic solution. This
completes the reduction, and there is a deposit of yellow crystals, which are scarcely
soluble in cold alcohol. These crystals are separated by decantation, dried and boiled
for five minutes in 100 litres of water with 50 of sulphuric acid. The solution is
brown and the sulphate of the new product converted into benzidenic derivate is
separated by cooling. Instead of using anilin as above, a corresponding quantity of
ortholuidine may be employed, and, for the paracresylol, metaxylenol may be
substituted. In etherifying the azoic grouping, for iodide of ethyl may be substituted
any hydrate halogen ethers (iodide of methyl, chloride of methyl or ethyl, bromide
of ethyl or amyl &c.).

page_text: PREPARATION OF THE COLOURING MATTERS.
The following is an example of the mode of preparing colouring matters obtained
by employing the product of condensation of ethylated paracresylol with orthotoluidine
combined with a-sulpho-a-naphthol.
The liquor containing 26 kilos of the new benzidenic derivate in the state of
sulphate is acidulated with hydrochloric acid and treated with 6.9 kilos of nitrite
of soda dissolved in 20 litres of water. There is thus obtained a tetrazoic derivate to
which are added 45 kilos of a-sulpho-a-naphthol in the state of soda salt and 15 kilos
of carbonate of soda dissolved in 4000 litres of water. The mixture is left at rest for
several hours and a precipitate is formed by salt, giving a reddish blue colouring
matter.
By substituting for the a-sulpho-a-naphthol equivalent quantities of the following
substances, colouring matters of analogous character are produced giving tints as
follows:
Bisulphonaphthol (salt R)
a-sulpho--naphthol
Resorcine
Metaphenylene diamine
Naphthionic acid
Sulphoconjugate-ẞ-naphthylamine
a-naphthylamine
a-oxynaphthoic acid
a-dioxynapthaline
red violet
very red violet
very red orange
brown
red
brown
brown scarcely soluble
reddish yellow
violet.
The colouring matters thus produced possess, among other properties, that of
dyeing cotton in an alkaline bath, wool and silk in an acid, alkaline or neutral bath,
and they take on to the various mordants or salts usually employed in dyeing.
The proportions of the reagents employed may be varied.
Having now particularly described and ascertained the nature of this invention
and in what manner the same is to be performed I declare that what 1 claim is :-
The production and use of new tetrazoic colouring matters obtained by combining,
as set forth, the azoic derivates of paracresylol or metaxylenol with phenols,
oxyphenols, naphthols, oxynaphthols, primary, secondary or tertiary amines, and
diamines as well as the alkylic, sulphonic and carboxylic derivates of any of these
bodies.
D
1