The Manufacture or Production of Dye Stuffs.
Year: 1893

page_text: Date of Application, 5th Aug., 1893
Complete Specification Left, 4th May, 1894-Accepted, 9th June, 1894
PROVISIONAL SPECIFICATION.
[Communicated from abroad by THE FARBENFABRIKEN vormals FRIEDRICH
BAYER & Co., of Elberfeld, in the Empire of Germany.]
The Manufacture or Production of Dye Stuffs.
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:-
1.
It is known that oxazine coloring matters producing from violet to blue shades,
are obtained by the interaction of nitroso compounds of secondary or tertiary
aromatic amines and betanaphthol, or betanaphthol derivatives (for instance, beta
dihydroxynaphthalenes), and it is also known that azine dye stuffs, yielding from
red to violet shades, result, if the above nitroso products are allowed to act on
alpha or beta naphthylamine. The coloring matters hitherto obtained from
amidonaphthols and nitroso compounds, yield from greyish to black shades, and are
of no technical value.
My foreign correspondents have now found that valuable oxazine dyestuffs result
on employing acetylated amido betanaphthols, or analognes thereof, and that the
coloring inatters so formed can be employed either directly, or after previously
separating the acetyl group or the like. The analogues of acetylated amidobeta.
naphthols which can be used in place of acetylated amidobetanaphthol, are, for
instance, the benzolated derivatives of amidobetanaphthols, or, in general, those
amido betanaphthols, or derivatives thereof, in which the hydrogen of the amido
group is replaced by acid radicles or alkyl groups, including the benzylidene
group.
The process in general consists in allowing nitroso derivatives of secondary or
tertiary aromatic amines, or azo dye stuffs capable of producing the same effect, to
act on the acetyl or benzoyl or benzylidine derivatives of amido beta naphthols (or
on analogous amido betanaphthols substituted in the amido group), in the presence
of a solvent or diluent, such as alcohol, acetic acid, or the like, whilst heat is
employed until the formation of dye ceases, which is distinguishable when the
nitroso product employed has disappeared.
The following example is given in order to illustrate the nature of this invention
and the manner in which it can be carried into practical effect. The parts are
by weight
COLORING MATTER FROM NITROSO DIMETHYL ANILINE HYDROCHLORIDE AND
ACETYLATED a₁ AMIDO ẞ, NAPHTHOL.
A solution, prepared by dissolving 20-2 parts of aceto a, amido Ba naphthol, and
28 parts of nitrosodimethylanilinehydrochloride, in 300 parts of alcohol, or glacial
acetic acid, is heated at from 40 to 80 degrees C. As soon as the nitroso compound
employed is no longer distinguishable, the mixture is poured into water, and the
dyestuff is salted out by the addition of common salt. It produces greenish-blue
shades on cotton prepared with tannic acid or the like.
If the acetyl group contained in the dye-stuff thus obtained is separated, for
instance, by heating with acids, a coloring matter results which my foreign
D

page_text: correspondents have proved to be identical with the dyestuff from nitroso meta-
hydroxydimethyl aniline and alphanaphthylamine (kuown in commerce as Nile
blue).
The other coloring matters result in a manner analogous to that described in the
above example, if either in place of the nitroso compound above used, the nitroso
derivatives of other tertiary amines, or of secondary amines, or the nitroso
compounds of substituted aromatic secondary or tertiary amines, or of other
derivatives thereof, or azo dye stuffs capable of producing the same effect, are
employed, or if the acetylated a, amido 3 naphthol is replaced by isomeric
acetylated amido beta naphthols, or sulpho or carboxylic or other derivatives of
acetylated amido beta naphthols, or by the corresponding benzoyl or benzylidene
compounds, or any of those amidobetanaphthols, amido betanaphtholsulpho acids, or
amido betanaphthol carboxylic acids, in which hydrogen atoms of the amido group
are substituted by acid radicles, alkyl groups, or in any other manner.
The coloring matters thus obtainable in general produce greenish-blue shades on
cotton prepared with tannic acid or the like. In case they are obtained from acid
derivatives or benzylidine products of amidonaphthols, or the like, they can (by
subsequently separating the groups contained in the amido group) be converted
into new dye-stuffs, the shades of which differ more or less from those obtained with
the former products.
My foreign correspondents have described in the above example, a distinct
method of preparing one of the dye-stuffs hereinbefore defined, but they do not
limit themselves to the directions above given, as the latter can be varied, and all
those methods known and in use for the production of analogous dyestuffs, can also
here be employed.
Such modifications do not alter the nature of the present invention, as the latter
in general relates to the production of dye stuffs from nitroso compounds, or azo
dye stuffs capable of producing the same effect, and amido betanaphthols,
substituted in the amido groups, or derivatives of such substituted amidobeta
naphthols.
Dated this 4th day of August 1893.
NEWTON & SON,
Agents for the Applicant.
COMPLETE SPECIFICATION.
The Manufacture or Production of Dye Stuffs.
I HENRY EDWARD NEWTON of The Office for Patents, 6 Bream's Buildings
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 :---
It is known, that oxazine colouring matters, producing from violet to blue shades,
are obtained by the interaction of nitrozo-compounds of secondary or tertiary
aromatic amines and beta naphthol or beta naphthol derivatives (for instance, beta
dihydroxynaphthalenes), and it is also known, that azine dye-stuffs, yielding from
red to violet shades, are produced if such nitroso compounds are allowed to act on
alpha or beta naphthylamine. The colouring matters hitherto obtained from
amido naphthols and nitroso compounds yield from greyish to black shades, and
are of no technical value.
My foreign correspondents have now found that valuable oxazine dye-stuffs
are formed on using acetylated or analogous substituted amido-beta-naphthols, and
that the colouring matters so formed can be used either directly, or after previously
separating the acetyl group. The process proceeds in an analogous manner,
other acid derivatives of amido-beta-naphthols are used in place of the acetylated
amido beta-naphthols. For instance, the benzoyl derivatives of amido-beta-
if

page_text: naphthols can be used. In the latter case, dye-stuffs are first obtained containing
a benzoyl radicle, which are converted into new colouring matters on separating
the benzoyl group by a suitable treatment.
The process for producing the dye-stuffs herein before defined, in general consists
in allowing nitroso derivatives of secondary or tertiary aromatic amines to act on
the acetyl or benzoyl or similar derivatives of amido-beta-naphthols in the presence
of a solvent or diluent, such as alcohol, acetic acid, or the like, heat being
applied until the formation of dye ceases, which is indicated by the disappearance
of the nitroso compound.
A good result is obtained on using acetylated or benzoylated alpha-amido-beta,
naphthol. The said alpha, amido beta, naphthol can be obtained by fusing alpha,
naphthylamine-beta, monosulphonic acid, or alkaline salts thereof, with alkalies.
The acetyl derivative of alpha, amido-beta, naphthol. is produced, for instance,
on adding the calculated quantity of acetic anhydride to a mixture of 1 part by
weight of the said amidonaphthol, and 3 parts, by weight, of glacial acetic acid.
Heat is spontaneously evolved, the acetoamidonaphthol separating out in a
crystalline state. It is purified by washing with diluted acetic acid, and filtered off.
The researches of my foreign correspondents have also shown that the acetylated
mixture can be directly used for the production of the dye-stuffs hereinbefore
defined.
The following example is given, in order to illustrate the nature of this invention
and the manner in which it can be carried out in practice. The parts are by
COLOURING-MATTER FROM NITROSO DIMETHYL-ANILINE HYDROCHLORIDE
AND ACETYLAted alpha, AMIDO BETA, NAPHTHOL.
A solution prepared by dissolving 20°1 parts of acetalpha, amido beta, naphthol
and 37 parts of nitroso dimethylaniline hydrochloride in 300 parts of alcohol, or
glacial acetic acid, is heated at from 60 to 100 degrees centigrade. As soon as the
nitroso compound is no longer distinguishable, the mixture is poured into water,
and the dye-stuff is salted out by means of common salt. It readily dissolves in
water, affording a blue coloured solution, and produces blue shades of a slight
reddish hue on cotton prepared with tannic acid or the like.
If the acetyl group contained in the dye-stuff thus obtained is separated, for
instance, by heating with acids, a colouring matter is obtained which produces on
cotton prepared with tannic acid, or the like, greenish blue shades, and which my
foreign correspondents have proved to be different from the dye-stuff from nitroso
meta hydroxydimethylaniline and alphanaphthylamine (known in commerce as Nile
blue).
The other colouring matters are formed in a manner analogous to that described
in the foregoing example, if either in place of the nitroso compound therein speci-
fied, corresponding quantities of the nitroso derivatives of other tertiary amines or
of secondary amines, or the nitroso compounds of substituted aromatic secondary
or tertiary amines are used, or if, in place of acetylated alpha, amido-beta, naphthol,
the corresponding proportion of benzoylated alpha, amido-beta, naphthol be taken.
If benzoylated amidonaphthol he used, dye-stuffs are obtained containing a benzoyl
radicle, which are converted into other new colouring matters ou subsequently
separating the benzoyl group.
Among nitroso derivatives, those, for instance, can be used which are derived
from monomethylaniline, monethylaniline, dimethylaniline, diethylaniline, mono-
methyl-ortho-toluidine, or monethyl-ortho-toluidine.
The colouring matters herein before defined produce blue shades on cotton
prepared with tannic acid or the like. The dye-stuffs first obtained, containing an
acid radicle (such as acetyl, benzoyl, or the like), in general are more soluble, and
produce, on cotton prepared with tannic acid or the like, somewhat redder shades

page_text: than the colouring matters obtained on separating from them the acetyl, benzoyl,
or similar group.
My foreign correspondents have described in the above example a distinct method
of preparing one of the dye-stuffs hereinbefore defined, but they do not limit them-
selves to the directions above given, as the latter can be varied, and all methods
known and in use for the production of analogous dye-stuffs can also be used.
Such modifications do not alter the nature of the present invention, as the latter
in general relates to the production of dye-stuffs from nitroso compounds and
amido-beta-naphthols containing acid radicles in the amido groups.
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 oxazine colouring matters from nitroso derivatives of
secondary or tertiary aromatic amines, or substituted amines, and amido-beta
naphthols containing acid radicles in the amido groups, subsequently removing the
-acid radicles or not, as may be desirable.
2. The process for producing oxazine dye-stuffs, which process consists in
allowing nitroso derivatives of. monomethylaniline, monethylaniline, dimethylaniline,
diethylaniline, monomethyl-ortho-toluidine, or monethyl-ortho-toluidine, to act in
the presence of suitable solvents or diluents on monacetylated or monobenzoylated
alpha amido beta, naphthol.
3. The conversion of the colouring matters obtainable as described in the
foregoing second claim, into new dye-stuffs, by a subsequent treatment, in order to
remove the acetyl or benzoyl group.
4. As new products of manufacture, the new dye-stuffs produced by the process
herein before defined, or by any other means affording the same result.
Dated this 4th day of May 1894.
NEWTON & SON,
Agents for the Applicant.