IMPROVEMENTS IN THE MANUFACTURE OF COLORING MATTERS, AND OF PRODUCTS FROM WHICH COLORING MATTERS MAY BE OBTAINED
Year: 1878

page_text: LETTERS PATENT to Jean Albert Pabst, of 41, Boulevard St. Michael, and
Adam Charles Girard, of 20, Rue des Ecoles, both in the City of Paris, in the
Republic of France, Chemists, for the Invention of "IMPROVEMENTS IN THE
MANUFACTURE OF COLORING MATTERS, AND OF PRODUCTS FROM WHICH
COLORING MATTERS MAY BE OBTAINED.”
Sealed the 10th January 1879, and dated the 13th July 1878.
PROVISIONAL SPECIFICATION left by the said Jean Albert Pabst and Adam
Charles Girard at the Office of the Commissioners of Patents on the 13th
July 1878.
JEAN ALBERT PABST, of 41, Boulevard St. Michael, and ADAM CHARLES GIRARD,
of 20, Rue des Ecoles, both in the City of Paris, in the Republic of France,
Chemists. "IMPROVEMENTS IN THE MANUFACTURE OF COLORING MATTERS, AND OF
PRODUCTS FROM WHICH COLORING MATTERS MAY BE OBTAINED."
This Invention has for its object improvements in the manufacture of coloring
matters, and of products from which coloring matters may be obtained.
We obtain the diazo, azo, and amido-azo derivatives of the aromatic series by
causing nitroso-sulphuric acid, in the form of crystals from the leaden chambers, or
generally its crystallized combinations, employed either in the solid state or dissolved
in acids, such as sulphuric, nitric, or acetic, to re-act upon solutions in water acidu-
lated with sulphuric, nitric, or acetic acid of the primary, secondary, or tertiary
aromatic amines, and generally of all the amido. derivatives of the hydrocarbons,
such as benzole, napthaline, anthracine, and their homologues, such as toluole, xylole,
and others; or upon the amido derivatives of the phenols, for example, picramic
acid or amido-phenol; or upon the amido derivatives of the sulpho-conjugated acids,
such as sulphanilic acid; or upon the amido derivatives of the quinones, such as
Price Adl

page_text: amido-anthraquinone or amido-alizarine and the analogous derivatives corresponding
to the before-mentioned hydrocarbons. For example, we obtain amido-azobenzol
by dissolving aniline in water containing 25 per cent. of glacial acetic acid or in
weak nitric acid. This solution is kept in cold water, and whilst it is constantly
agitated nitroso-sulphuric crystals are added little by little until on filtering a small
sample of the product and supersaturating with a little caustic soda oily drops of
aniline are no longer separated. It is then precipitated with water, washed, and
then made to crystallize out of hot hydrochloric acid by precipitating with common
salt, and crystals are obtained of hydrochlorate of amido-azobenzol, which may be
used in the preparation of this substance or of its salts by the ordinary means.

page_text: SPECIFICATION in pursuance of the conditions of the Letters Patent filed by.
the said Jean Albert Pabst and Adam Charles Girard in the Great Seal Patent
Office on the 13th January 1879.
JEAN ALBERT PABST, of 41, Boulevard St. Michael, and ADAM CHARLES GIRARD,
of 20, Rue des Ecoles, both in the City of Paris, in the Republic of France,
Chemists. "IMPROVEMENTS IN THE MANUFACTURE OF COLORING MATTERS, AND OF
PRODUCTS FROM WHICH COLORING MATTERS MAY BE OBTAINED."
This Invention has for its object improvements in the manufacture of coloring
matters, and of products from which coloring matters may be obtained.
In order to obtain azo, diazo; and amido-azo derivatives suitable for the production
of coloring matters we make use of the so-called "leaden chamber crystals" (sul-
phate of nitroxyl) and other nitroxyle derivatives.
The leaden chamber crystals, as the name implies, are sometimes produced in the
chambers of the sulphuric acid manufacturer; we shall, however, in the first place
state other and more convenient methods for producing this substance. We shall
then describe methods for the production of other nitroxyle derivatives, and after-
wards processes for the production, by the aid of nitroxyl derivatives, of azo, diazo,.
and amido-azo derivatives, and for the application of these latter in the manufacture
of coloring matters.

page_text: 2. Treat an aqueous solution of sulphate of naphtylamine made with 2.26 kilos.
of naphtylamine with 1 kilo. of leaden chamber crystals. The sulphate of amido-
azonaphtaline or azodi-naphtyldiamine is thus obtained, which, heated with acetate
of naphtylamine, gives Magdala red, a colouring matter.
3. The vapour of chloride of nitroxyl obtained from one kilo. of leaden chamber
crystals and 700 grammnes of chloride of sodium is passed into an aqueous paste
containing 1.300 kilo. of sulphanilic acid; a precipitate is thus obtained formed of
diazophenyl sulphurous acid, which, treated with either 1.45 kilo. anhydrous
resorcine sulphite of sodium in a slightly alkaline solution, gives an orange coloring
matter; or with 1-250 kilo. of diphenylamine it gives similarly an orange coloring
matter.
4. Take for 1' kilo. of leaden chamber crystals 1.66 kilo. of naphtylamine
sulphurous acid, the paste of diazo derivative thus obtained, washed in water and
treated with 1700 kilo. of dixylidine, gives a ponceau coloring matter; or again,
with 1.300 kilo. of diphenylamine it gives an orange coloring matter; or again,
with 1 kilo. of ẞ naphtol it gives a garnet red coloring matter.
Again, by the employment of these leaden chamber crystals or the chloride of
nitroxyl we are able to prepare the azo derivatives of amidophenol and of amidodi-
nitrophenol described by M. Griess in the year 1859. For 1 kilo. of leaden chamber
crystals 820 grammes of amidophenol or 1-250 kilo. of picramic acid dissolved in
sulphuric acid diluted with four times its volume of water are employed. For the
chloride of nitroxyl a watery paste of the same bodies is all that is necessary: The
latter diazo products can also be employed to prepare coloring matters.
Alizerine sulphite of soda in slight excess upon diazo-dinitrophenol gives a very
fast brown coloring matter. In the same way the sulpho-congugated acid of
rosaniline in slight excess and in the presence of a slightly alkaline liquid gives
with diazo-dinitrophenol a garnet-red coloring matter.
C
Again, by re-acting upon alizarine in paste with sulphuric acid for several days
with 1 k. 500 leaden chamber crystals for 1 k. alizarine on precipitating with water
in large quantity (15 times the weight of water) nitro-alizarine, a coloring matter in
very common use, is obtained.
What we claim is,―
First. The production, by means of leaden chamber crystals and derivatives, of
nitroxyl of azo, diazo, and amido-azo derivatives suitable for the preparation of
coloring matters.
Second. The use of leaden chamber crystals and derivatives of nitroxyl in the
manufacture of coloring matters, substantially as described.
In witness whereof, we, the said Jean Albert Pabst and Adam Charles Girard,
have hereunto set our hands and seals, this Seventh day of January, in the
year of our Lord One thousand eight hundred and seventy-nine.
Signed, sealed, and delivered
by the above-named Jean
Albert Pabst and Adam
Charles Girard in the pre-
sence of
HENRY WILLOUGHBY,
British Vice Consul at Paris.
J. A. IADOL.
(107.)
A. CH. GIRARD. (L.S.)