The Manufacture or Production of Colouring Matters.
Year: 1893

page_text: Date of Application, 5th Dec., 1893
Complete Specification Left, 4th Sept., 1894-Accepted, 6th Oct., 1894
[Communicated from abroad by THE FARBENFABRIKEN vormals FRIEDRICH
BAYER & Co., of Elberfeld, in the Empire of Germany.]
The Manufacture or Production of Colouring Matters.
I HENRY EDWARD NEWTON of The Office for Patents, 6 Bream's Buildings,
Chancery Lane, in the County of London, Patent Agent, do hereby declare the
nature of this invention to be as follows:-
My foreign correspondents have described in the Specification of Letters Patent
No. 19062A, dated 4th November 1891, a process for producing dye stuffs, which
consists in condensing tetra alkylated diamido benzhydrols with secondary amines
(such as monomethylaniline, monoethylauiline, monobenzlaniline, diphenylamine,
mono methyl-alpha-naphthylamine, mono ethyl-alpha-naphthylamine, inono benzyl-
alpha-naphthylamine, phenyl-alpha-naphthylamine, ortho- or para-tolyl-alpha
naphthylamine, dinaphthylamine), subsequently treating the so formed leuco
products with nitrous acid, oxidising the resulting leuco compounds containing a
nitroso amine group, and finally splitting off the nitroso group. Some of these
colouring-matters, viz. those from phenyl-alphanaphthylamine, ortho- or para-tolyl-
alphanaphthylamine, diphenylamine, or dinaphthylamine, can also be produced by
means of the process described in the Specification of Letters Patent No. 5038,
dated 18th March 1884 that is to say by allowing tetraalkyldiamidobenzophenone
chloride to act on the last named secondary amines.
Of the other dye stuffs described in the Specification of the aforesaid Letters
Patent No. 19062A", those derived from benzyl-alpha-naphthylamine can likewise
be obtained according to the process described in the Specification of the above-
mentioned Letters Patent No. 5038%, as my foreign correspondents have described
in the German Patent No. 69863, dated 17th August 1893.
My foreign correspondents have now found, that certain other of the dye stuff's
described in the Specification of Letters Patent No. 19062A", viz., those resulting
from monomethylalphanaphthylamine and monoethylalphanaphthylamine, can be
produced by means of either tetraalkyl diamidobenzophenone chloride, or tetra-
alkyldiamidobenzophenone, in the presence of phosphor haloids, or phosphor
oxy-haloids (according to the process described in the Specification of Letters
Patent No. 50384), and that analogous colouring matters result on employing
alkyloxyphenylalphanaphthylamine (such as para-methoxyphenylalphanaphthyl-
amine, para ethoxyphenylalphanaphthylamine), or analogous alkyloxy compounds,
in the process described in the Spécification of Letters Patent No. 19062Aº¹, or on
condensing these alkyloxy products with tetraalkyldiamido benzophenone chloride,
or with tetraalkyldiamidobenzophenone, in the presence of phosphor haloids,
phosphoroxy haloids, or substances acting in a similar manner.
The production of the dyestuffs from monomethylalphanaphthylamine, mono
ethyl-alpha-naphthylamine, para - alkyl- oxyphenyl-alpha-naphthylamine, or.
analogous alkyloxy compounds, and tetra alkyldiamido benzophenone, is illustrated
by the following example. The parts are by weight.

page_text: of paraethoxyphenylalphanaphthylamine. 5 parts of phosphorous oxychloride are
then gradually added with continued stirring. The reaction begins in a short time,
and after standing for some time at ordinary temperature, the mass assumes
metallic lustre and a crystalline form. After the mass has been heated for some
time at from 107 to 110 degrees centigrade, it is pulverised, and after washing with
cold water, is dissolved in diluted muriatic acid (15 per cent.), and the dyestuff is
precipitated from the muriatic solution by an addition of water.
This dyestuff easily dissolves in hot water, and produces blue shades with a
strong greenish hue on wool and on cotton which is prepared with tannic acid and
the like.
Analogous colouring matters result, if, in the above example, either tetramethyl
diamidobenzophenone is replaced by corresponding quantities of tetraethyldiamido
benzophenone, or other alkylated diamidobenzophenones, or if, in place of para-
ethoxyphenylalphanaphthylamine, equivalent quantities of paramethoxyphenyl
alpha naphthylamine, or analogous alkyloxy-products, or monomethyl alpha
naphthylamine, or mono-ethyl-alpha naphthylamine, are used.
The production of all these colouring matters can also be effected by acting with
a phosphor haloid, or phosphoroxy haloid, or reagents producing the same result
on the alkylated diamidobenzophenones, and subsequently condensing the so formed
alkylated diamido benzophenone chloride with the aforesaid secondary amines.
As above mentioned, the colouring matters from alkyloxy phenylalphanaphthyl-
amine (for instance, paramethoxyphenylalphanaphthylamine, paraethoxyphenyl-
alphanaphthylamine), or analogous alkyloxy products, can also be obtained by
condensing these alkyloxy compounds with alkylated diamidobenzhydrols, converting
the so formed leuco products by treatment with nitrous acid into nitroso amine
lenco products, oxidising the latter in a suitable manner, and subsequently displacing
the nitroso group contained in the resulting oxidation products. This process is
effected by following the directions given for analogous processes in the Specifica-
tion of the above Patent No. 19062A1, that is to say, by employing the last named
secondary amines in place of those which are mentioned in that Specification.
Dated this 5th day of December 1893.
NEWTON & SON,
Agents for the Applicant.
COME MID DICITIATION.
The Manufacture or Production of Colouring Matters.
I HENRY EDWARD NEWTON of The Office for Patents, 6 Bream's Buildings,
Chancery Lane in the County of London, 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:
para-
My foreign correspondents have described in the Specification of Letters Patent
No. 19062A, dated 4th November 1891, a process for producing dye-stuffs, which
process consists in condensing tetraalkylated diamidobenzhydrols with secondary
amines (such as, for example, monomethylauiline, monethylaniline, mnonobenzylaniline,
diphenylamine, monomethylalphanaphthylamine, monethylalphanaphthylamine,
monobenzylalphanaphthylamine, phenylalphanaphthylamine, ortho- or
tolylalphanaphthylamine, dinaphthylamine), subsequently treating the so-formed
leuco products with nitrous acid, oxidising the resulting lenco compounds cou-
taining a nitrosamine group, and finally splitting off the nitroso group. Some of
these coloring matters, viz., those from phenylalphanaphthylamine, ortho or para-
tolylalphanaphthylamine, diphenylamine, or dinaphthylamine, can also be produced
by means of the process described in the Specification of Letters Patent No. 5038,
dated 18th March 1884, that is to say, by allowing tetraalkyldiamidobenzophenone

page_text: to act, in the presence of phosphorus oxyhaloid, or the like, on the last-named
secondary amines.
Of the other dye-stuff's described in the Specification of the aforesaid Letters
Patent No. 19062A", those derived from benzyl alphanaphthylamine can also be
obtained according to the process described in the Specification of the above
mentioned Letters Patent No. 5038 of 1884, as my foreign correspondents have
described in the German Patent No. 69863, dated 17th August 1892.
My foreign correspondents have now found, that certain other of the dye-stuffs
described in the Specification of the said Letters Patent No. 19062A", z., those
from monomethyl-alpha-naphthylamine, and monethyl-alpha-naphthylamine, can bo
produced by means of tetraalkyldiamidobenzophenone, in the presence of
phosphorus haloids or phosphorus oxyhaloids (according to the process described
in the Specification of Letters Patent No. 50388), and that analogous colouring-
matters are formed on using para-alkyloxyphenyl-alpha-naphthylamine (such as
para-methoxy-phenyl-alpha-naphthylamine," para-ethoxyphenyl-alpha-naphthyl-
amine), or analogous alkyloxy compounds, in the process described in the
Specification of Letters Patent No. 19062A", or on condensing these alkyloxy
products with tetraalkyldiamidobenzophenone in the presence of phosphorus
haloids, phosphorus oxyhaloids, or substances acting in a similar manner.
The said para-alkyloxyphenyl-alpha-naphthylamines have been prepared by iny
foreign correspondents by heating alpha naphthylamine with para amido alkyl-
oxybenzene hydrochloride. Thus, for instance, para methoxyphenylalpha-naphthyl-
amine is produced from alpha-naphthylamine and the hydrochloride of para-
anisidine, and para-ethoxy-alpha-naphthylamine can be produced by heating alpha-
naphthylamine with para phenetidine hydrochloride.
The production of the dye-stuffs from monomethyl-alpha-naphthylamine, mon-
ethyl-alpha-naphthylamine, para-ethoxyphenyl-alpha-naphthylamine, or analogous
alkyloxy compounds, and tetraalkyldiamidobenzophenone, is illustrated by the
The nanks una his weight
COLOURING-MATTER FROM
TETRAMETHYLDIAMIDOBENZOPHENONE
PARAETHOXYPHENYL-ALPHA-NAPHTHYLAMINE.
AND
8 parts of tetramethyldiamidobenzophenone are thoroughly mixed with 8.1 parts
of para-ethoxyphenyl-alpha-naphthylamine. 5 parts of phosphorus oxychloride
are then gradually added, the mass being continually stirred. The action soon
begins, and, after standing for some time at the ordinary temperature, the mixture
assumes metallic lustre and a crystalline form. After heating the mass during
some time, at from 107 to 110 degrees centigrade, it is pulverised, then washed
with cold water, and dissolved in dilute muriatic acid (containing 15 per cent. of
pure acid); the dye-stuff is precipitated from the muriatic solution by adding
water.
This dye-stuff easily dissolves in hot water, and produces blue shades of a
strong greenish hue on wool, and also on cottou prepared with tannic acid or
the like.
Analogous colouring-matters are formed, if, in the above example, instead of
tetramethyl-diamidobenzophenone, corresponding quantities of tetraethyldiamido-
benzophenone, or other tetraalkylated diamidobenzophenones, are used, or if
equivalent quantities of para methoxy phenyl-alpha-naphthylamine, or analogous
alkyloxy products, or monomethyl-alpha-naphthylamine, or monoethyl-alpha-
naphthylamine, are used in place of para-ethoxyphenyl-alpha-naphthylamine. As
above mentioned, the colouring-matters from alkyloxyphenyl-alpha-naphthylamine
(such as, for instance, para methoxyphenyl-alpha-naphthylamine, para-ethoxy-
phenyl-alpha-naphthylamine), or analogous alkyloxy products can also be obtained
by condensing these alkyloxy compounds with tetraalkylated diamidobenzhydrols,

page_text: converting the leuco products thus formed, by means of nitrous acid, into so-called
nitrosamine leuco products, oxidising the latter in a suitable manner, and sub-
sequently displacing the nitroso group contained in the oxidation products. This
process is effected by following the directions given for analogous processes in
the Specification of the above Patent No. 19062A", that is to say, by using the
last-named secondary amines in place of those which are mentioned in that
Specification.
Having now particularly described and ascertained the nature of the said inven-
tion and in what manner the same is to be performed, as communicated to me
from abroad, I declare that what I claim is :-
1. The production of colouring-matters by condensing monomethyl-alpha-
naphthylamine, monethyl-alpha-naphthylamine, para-alkyloxyphenyl-alpha-naph-
thylamine (such as para-methoxyphenyl-alpha-naphthylamine, para-ethoxy-
phenyl-alpha-naphthylamine), with tetraalkylated diamidobenzophenones in the
presence of phosphorus haloids, phosphorusoxy haloids, or agents acting in a
similar manner.
2. The process for producing leuco compounds, which process consists in
condensing tetraalkylated diamido benzhydrols with para-alkyloxyphenyl-alpha-
naphthylamines (such as para-methoxyphenyl-alpha-naphthylamine, para-ethoxy-
alpha-naphthylamine).
3. The production of lenco compounds containing a nitrosamine group by the
action of nitrous acid on the leuco products obtained by the combination of
tetraalkylated diamidobenzhydrols with para-alkyloxyphenyl-alpha-naphthylamines
(such as paramethoxy phenyl-alpha-naphthylamine, paraethoxyphenyl-alpha-naph-
thylamine).
4. The transformation of the leuco compounds defined in the preceding third
claim into colouring-matters also containing a nitrosamine group, by oxidising the
said leuco compounds.
5. The process for producing dye-stuffs by splitting off the nitroso group from
the products defined in the foregoing fourth claim.
6. As new products of manufacture, the new leuco compounds and dye-stuffs
derived from paraalkyloxyphenyl-alpha-naphthylamines (such as paramethoxy-
phenyl-alpha-naphthylamine, para-ethoxyphenyl-alpha-naphthylamine), and pro-
duced by means of the processes hereinbefore defined, or by any other means
affording the same result.
Dated this 28th day of August 1894.
NEWTON & SON,
Agents for the Applicant.