The Manufacture and Production of New Basic Colouring Matters.
Year: 1892

page_text: Date of Application, 25th June, 1892
Complete Specification Left, 22nd Mar., 1893-Accepted, 6th May. 1393
PROVISIONAL SPECIFICATION.
The Manufacture and Production of New Basic Colouring Matters.
1 BENJAMIN WILLCOX of 47 Lincolns Inn Fields in the County of Middlesex
Patent Agent do hereby declare the nature of this invention (which has been
communicated to me by the Farbenfabriken vormals Friedrich Bayer & Co. of
Elberfeld in the Empire of Germany) to be as follows:-
This invention relates to the production of new colouring matters which are
analogous to the azo-triphenyl-methane dyes as they contain two different so called
chromopharic groups..
My foreign correspondents have succeeded in obtaining such products by starting
from amido-benzhydrols they having found that the said amido-benzhydrols react
with greater, or less, readiness on the different dyestuff's products being formed
which unite the properties of colouring matters materially modified in dyeing owing
to the hydroxylic group with those of leuco compounds and therefore can further
be oxidised into dye-stuffs which possess dyeing properties differing more or less
from those of the original products.
My foreign correspondents have obtained the best results by employing
colouring matters of the oxazine series and analogous products; for example the
so called "new-blue R" which results from the reaction of nitroso-dimethyl-
aniline or nitroso-diethyl-aniline chlorhydrate on beta-naphthol.
The products formed by the action of the amido benzhydrols with the said dye-
stuffs, and likewise the bodies derived therefrom by oxidation, are of basic nature
and produce blue colours, on cotton, mordanted with tannic acid, or the like, which
colours are fast against the action of light and alkalies. The reaction is most
practically effected in alcoholic solution at ordinary temperatures and is facilitated
by heating. The condensation can also be effected by employing glacial acetic
acid, or diluted acetic acid containing 50 per cent. of pure acetic acid and, the
hydrols may be employed either as free bases, or as hydrochlorates, or other salts.
In the employment of the salts of hydrols products are obtained which readily
dissolve in water, whilst by employing the free hydrols products result that are
insoluble in water, as they contain only one molecule of hydrochloric acid, but are
readily made soluble by the addition of hydrochloric acid. The products which
are obtained in the latter case; viz. :-in starting from the free hydrols, are
identical with those resulting when the salts of the hydrols are employed.
In order to illustrate the production of these new dye-stuffs the following
example is given.
FIRST EXAMPLE.
COLOURING MATTER OBTAINED BY CONDENSATION OF NEW-BLUE K WITH
TETRA-METHYL-DIAMIDO-BENZHYDROL.
31 kilos. of new-blue R are dissolved by means of 250 kilos. of alcohol in a
vessel provided with means for stirring, and 27 kilos. of tetra-methyl-diamido-
benzhydrol finely pulverised are introduced into the aforesaid solution whilst kept
stirred or agitated. After adding the whole quantity of the hydrol stirring is still
continued for some time and then the whole mass is heated at a temperature from
about 20 to 30 degrees centigrade till the new-blue R is no more distinguishable..
After cooling the contents of the vessel are introduced into icy cold water. The
CARaton
is filtered off dissolved in a large
COLOURING MATTER OBTAINED BY CONDENSATION OF NEW-BLUE K WITH
TETRA-METHYL-DIAMIDO-BENZHYDROL.
31 kilos. of new-blue R are dissolved by means of 250 kilos. of alcohol in a
vessel provided with means for stirring, and 27 kilos. of tetra-methyl-diamido-
benzhydrol finely pulverised are introduced into the aforesaid solution whilst kept
stirred or agitated. After adding the whole quantity of the hydrol stirring is still
continued for some time and then the whole mass is heated at a temperature from
about 20 to 30 degrees centigrade till the new-blue R is no more distinguishable.
After cooling the contents of the vessel are introduced into icy cold water.
basie condensation product which separates is filtered off dissolved in a large
quantity of cold water, adding a small portion of hydrochloric acid, and the
The

page_text: solution thus obtained, is filtered. The dye-stuff is precipitated from the filtrate
by the addition of zinc chloride, or common salt.
My foreign correspondents have found that it is not necessary to employ the
new-blue R in a pure state but the mixture obtained from nitroso-dimethyl-aniline-
chlorhydrate and beta-naphthol, and likewise the mixture of the analogous
components, can be directly condensed with the hydrols.
By replacing the tetra-methyl-diamido-benzhydrol of the foregoing example by
tetra-ethyl-diamido-benzhydrol, dimethyl-diethyl-diamido-benzhydrol or analogous
tetra-alkyl-diamido-benzhydrols, or by employing, instead of new-blue R, the
analogous product derived from nitroso-diethyl-aniline or similar dye-stuffs
belonging to the series of azines and oxazines, the analogous dye-stuffs are obtained
which are likewise capable of dyeing blue shades on cotton mordanted with tannic
acid, or the like.
In the same manner as the aforesaid tetra-alkyl-diamido-benzhydrols, diamido-
benzhydrol, dialkyl-mono-amido-benzhydrols, meta- or para-nitro-mono-alkyl-amido-
benzhydrols, meta- or para-nitro-dialkyl-amido-benzhydrols or the amido products
derived from the four last named nitro compounds, and analogous substances can
likewise be employed:
The following is given as an example for the further oxidation of the dye-stuffs'
obtained by condensing hydrols with colouring matters of the azine and oxazine
sories
DYE-STUFF RESULTING BY THE FURTHER OXIDATION OF THE PRODUCT
OBTAINED BY CONDENSING TETRA-METHYL-DIAMIDO-BENZHYDROL WITH
NEW-BLUE R.'
64 kilos. of the colouring matter, obtained as described in the foregoing example,
are dissolved with the application of heat in 25 kilos. of acetic acid (containing
50 per cent. of pure acid) and 3-4 kilos. of muriatic acid (containing 33 per cent. of
pure hydrochloric acid): After cooling 7.9 kilos. of a lead dioxide paste (with
3 per cent. of PbO₁) mixed with 15 litres of water are added and after some time
the lead is precipitated by means of 1.1 kilos. of sulphuric acid at 66 degrees Baumé.
The mass is then mixed with double the quantity of water and after 24 hours the
lead sulphate is filtered off, and the dye-stuff is precipitated by means of a solution
in water of common salt and zinc chloride.
The colouring matter thus obtained, as muriatic salt in combination with zinc
chloride, is similar to the condensation product of the foregoing first example and it
dyes blue shades on cotton mordanted with tannic acid, or the like, which shades
are however more intense than are those produced by the said condensation
product.
In an analogous manner the oxidation of the other dye-stuffs, obtained by con-
densing the above named amido-benzhydrols with new-blue R is effected.
By employing instead of new-blue R the analogous products belonging to the
azine or oxazine, series, viz. :-by combining them with the above named hydrols at
first condensation, products are obtained in the same manner as, that described in the
foregoing first example. The latter are basic dye-stuffs and produce blue shades on
cotton mordanted with tannic acid, or the like, and yield, by further oxidation
according to the foregoing second example, new colouring matters which differ
materially from the condensation products in the greater intensity of the shades
produced by them on cotton mordanted with tannic acid, or the like..
My foreign correspondents have further found that it is not necessary to employ
for printing purposes the complete dye-stuffs obtained by condensing hydrols with
colouring matters of the azine, or oxazine, series but that it is sufficient to use a
mixture of such two components with the addition of a solvent (for example acetic
acid) as the condensation of the two compounds..takes place at the subsequent

page_text: steaming, and the same effect results as in printing with the corresponding complete
dye-stuff's.
Dated this 25th day of June 1892.
J. H. JOHNSON & Co.,
47, Lincoln's Inn Fields, London, W.C., Agents.
COMPLETE SPECIFICATION.
The Manufacture and Production of New Basic Colouring Matters.
I, BENJAMIN WILLCOX of 47 Lincolns Inn Fields in the County of Middlesex,
Patent Agent do hereby declare the nature of this invention (which has been
communicated to me from abroad by Farbenfabriken vorin. Friedrich Bayer & Co.
of Elberfeld in the Empire of Germany) 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 production of new colouring matters analogous to
the azo-triphenyl-methane dyes as they contain two different so called chromophoric
groups.
My foreign correspondents have succeeded in obtaining such products by starting
from alkylated diamidobenzhydrols, they having found that alkylated diamido-
benzhydrols act with greater or less readiness on the different dye-stuffs, products
being formed in which are united the properties of colouring-matters, materially
modified in their dyeing qualities owing to the presence of the hydroxylic group,
and those of leuco compounds, and which therefore can be oxidised and thus
converted into other dye-stuffs possessing dyeing properties differing more or less
from those of the original products.
My foreign correspondents have obtained the best results by employing colouring-
matters of the oxazine series and analogous products; for example, the so called
new blue R." which results from the interaction of nitrosodimethyl-aniline- or
nitroso-diethyl-aniline hydrochloride and beta-naphthol.
The products formed by the action of the alkylated diamido-benzhydrols and the
said dye-stuff's, and likewise the bodies derived therefrom by oxidation, are of basic
nature and produce blue colours on cotton mordanted with tannic acid or the like,
which colours withstand the action of light and alkalies. The interaction is most
practically effected in alcoholic solution at about from 70 to 80 degrees centigrade.
The condensation can also be effected by employing glacial acetic acid or diluted
acetic acid (containing for instance 50 per cent. of pure acetic acid) and the
alkylated diamidobenzhydrols may be employed either in the form of a base, or of
hydro-chloride or other salt. When salts of alkylated diamidobenzhydrols are
used products are obtained which readily dissolve in water, whilst in employing
the free alkylated diamido-benzhydrols products are obtained that are insoluble in
water, as they contain only one molecule of hydrogen chloride, but they are readily
made soluble by the addition of hydrochloric acid. The products which are
obtained in the latter case, viz. by using the free alkylated diamidobenzhydrols,
are identical with those formed when the salts of the alkylated diamidobenzhydrols
are employed.
In order to illustrate the mode of producing these new dye-stuffs the following
examples are given :-

page_text: of alcohol in a vessel provided with a stirrer, and 27 kilos. of finely pulverised
tetra-methyl-diamido-benzhydrol are introduced into the aforesaid solution stirring
or agitating the while. After adding the whole quantity of the tetra-methyl-
diamido-benzhydrol stirring is continued for some time, and then the whole mass is
heated and maintained preferably at about 60 to 70 degrees centigrade till the
"new-blue R" is no longer distinguishable.
After cooling, the contents of the vessel are introduced into ice cold water.
The basic condensation product which separates is filtered off, dissolved in a large
quantity of cold water to which is added a small quantity of hydrochloric acid,
and the solution thus obtained is filtered. The dye-stuff is precipitated from the
filtrate by the addition of zinc chloride and common salt.
My foreign correspondents have found, that it is not necessary to employ the
"new-blue R" in a pure state, but that the product of the action of nitroso-
dimethyl-aniline-hydrochloride on beta-naphthol, and the products of interaction of
analogous compounds, can be directly condensed with the alkylated diamidobenz-
hydrols.
By using instead of tetra-methyl-diamido-benzhydrol corresponding quantities
of other alkylated diamidobenzhydrols or by employing, instead of new-blue R,
the analogous product derived from nitroso-diethylaniline or similar dye-stuff's
belonging to the series of oxazines, analogous dye-stuffs are obtained which also
are capable of dyeing blue shades on cotton mordanted with tannic acid, or
the like.
It appears that one molecular proportion of the alkylated diamidobenzhydrol
combines with one molecular proportion of the oxazine dye-stuff employed.
The following is given as an example of the mode of oxidising of the dye-stuffs
obtained by condensing alkylated diamido-benzhydrols with colouring-matters of
the oxazine series.
DYE-STUFF RESULTING ON FURTHER OXIDISING THE PRODUCT OBTAINED
BY CONDENSING TETRA-METHYL-DIAMIDOBENZ HYDROL WITH NEW-BLUE R
(MELDOLA-BLUE).
6.4 kilos. of the colouring-matter, obtained as described in the foregoing example,
are dissolved with the application of heat in 25 kilos. of acetic acid (containing
50 per cent. of pure acetic acid) and 3-4 kilos. of muriatic acid (containing 33 per cent.
of hydrogen chloride). After cooling 7.9 kilos. of a lead-dioxide paste (con-
taining 30 per cent. of PbO2) mixed with 15 litres of water are added and after
some time the lead is precipitated by means of 11 kilos. of sulphuric acid
(66 degrees Baumé). The mass is then mixed with double the quantity of water
and after 24 hours the lead sulphate is filtered off and the dye-stuff is precipitated
by means of a solution in water of common salt and zinc chloride. The colouring-
matter thus obtained, as chloride in combination with zinc-chloride, is similar to
the condensation product of the foregoing first example and it dyes blue shades on
cotton mordanted with tannic acid, or the like, which shades are however, more
intense than are those produced by the said condensation product.
The oxidation of the other dye-stuffs, obtained by condensing alkylated diamido-
benzhydrols with "new-blue R," is effected in an analogous manner.
By employing instead of "new-blue R" the analogous products belonging to the
oxazine series viz. :-by combining them with alkylated diamidobenzhydrols con-
densation products are obtained corresponding to that described in the foregoing
first example. They are valuable basic dye-stuffs and produce blue shades on
cotton mordanted with tannic acid, or the like, and on further oxidation according
to the foregoing second example, field new colouring-matters which differ materially
from the original condensation products affording shades of greater intensity when
used to dye cotton mordanted with tannic acid or the like.

page_text: $6
By analogues of new-blue R" my foreign correspondents understand :-
a. The products obtainable from beta-naphthol and the nitrosoderivatives of
dialkyl-aniline, mono-alkyl-aniline, mono-alkyl-ortho-toluidine.
b. The products resulting from the condensation of hydroxy-beta-naphthols:
(such as 2 6-dihydroxy-naphthalene, 2: 7 dihydroxy-naphthalene) with the.
nitroso compounds of dialkyl-aniline, mono-alkyl-aniline or mono-alkyl-ortho-
toluidine.
Of these oxazine dye-stuffs for instance the product from nitrosodimethylaniline
and 2: 7-dihydroxynaphthalene is that technically known and used as "Muscarine,"
whilst some of these oxazines have not hitherto been prepared, but can easily be:
prepared by acting with the nitroso derivatives of secondary or tertiary amines on
beta-naphthol or hydroxy-beta-naphthols in the presence of a suitable solvent or
diluent and subsequently isolating the resulting dye-stuffs for instance in the form:
of the zinc chloride double salts.
If, for example, the said "Muscarine" be condensed with tetra-methyl-diamido-
benzhydrol (which condensation can be effected in accordance with the process.
illustrated by the foregoing first example) and the product thus formed be isolated.
by means of common salt and zinc chloride, a dye-stuff is obtained which produces
blue shades on cotton prepared with tannic acid or the like and which may be
transformed by a subsequent oxidation (which oxidation can be effected in
accordance with the method described in the foregoing second example) into a new
dye-stuff which yields greener shades of great. purity and intensity.
In general,
the products obtained by condensing alkylated diamido-benzhydrols with the
oxazine dye-stuffs derived from betanaphthol or hydroxybetanaphthols produce
from blue to greenish-blue shades on cotton prepared with tannic acid, whilst the
dye-stuffs resulting from further oxidation mostly yield shades possessing a greater:
intensity.
The dye-stuffs obtained from the nitroso-derivatives of benzylated-amines (such
as methyl-benzyl-aniline, ethyl-benzyl-aniline and dibenzyl-aniline) are of especial
value, as the shades produced therewith are of a beautiful greenish-blue.
My foreign correspondents have further found that it is not necessary to employ
for printing purposes the "finished " dye-stuffs obtained by condensing alkylated
diamido-benzhydrols with colouring-matters of the oxazine series, but that it is.
sufficient to use a mixture of such two components together with a suitable diluent.
or solvent (for example acetic acid, alcohol or the like), as the condensation of the
two compounds can take place during the subsequent steaming operation, and the
effect is the same as that resulting on printing with the corresponding "finished
dye-stuffs.
"
3.
My foreign correspondents have described in the above two examples a method
of producing a colouring-matter by condensation of "new-blue R with tetra-
methyl-diamidobenzhydrol, and a method of converting the dye-stuff so formed into
a new colouring-matter by oxidation, but it is to be understood that the invention.
is not limited to the directions given in the said examples, as the methods.
illustrated therein can be varied, without departing from the nature of this.
invention which in general relates :-
A. to the production of new dye-stuffs by the condensation of alkylated diamido-.
benzhydrols with oxazine colouring-matters including such oxazine dye-stuffs as
are obtainable from beta-naphthol or hydroxy-beta-naphthols or the crude mixtures.
resulting from the interaction of their components.
B to the conversion of the dye-stuffs so formed by oxidation into new colouring-
matters, and, C, to the production on the fibre of the colouring-matters defined.
under A from their components.
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 I claim is :-
1. The production of colouring-matters from alkylated diamidobenzhydrols and
oxazine dye-stuffs.

page_text: 2. The process for producing dye-stuffs by condensing in the presence of suitable
solvents or diluents alkylated diamidobenzhydrols with the oxazine dye-stuffs
obtainable by the action of nitrosoderivatives of dialkyl-aniline, mono-alkyl-aniline,
mono-alkyl-ortho-toluidine on beta-naphthol- or hydroxy-beta-naphthols.
3. The production of dye-stuffs by directly condensing (in the presence of
suitable solvents or diluents) alkylated diamído-benzhydrols with the mixtures
obtained in preparing oxazine colouring-matters by the action of nitrosoderivatives
of alkylated amines on beta-naphthol or hydroxy-beta-naphthols without previously
isolating the resulting oxazine dye-stuffs.
4. The conversion of the colouring-matters obtained by the processes claimed by
the foregoing Claims 2 or 3, or by any other process producing the like result, into
other new dye-stuffs by treatment with oxidising agents.
5. The production of dye-stuffs by condensing alkylated diamido-benzhydrols
either with the isolated oxazine colouring-matters, or directly with the mixtures
which are obtained in preparing oxazine colouring-matters from the nitroso
compounds of dialkyl-aniline, mono-alkyl-aniline or mono-alkyl-ortho-toluidine and
beta-naphthol or hydroxy-beta-naphthols and subsequently oxidising the conden-
sation products so produced.
6. In the production of colours on fibres the process which consists in printing
with printing pastes containing a mixture of alkylated diamidobenzhydrols and
oxazine dye-stuffs.
7. As new articles of manufacture the new dye-stuffs which are obtained by the
processes defined in the foregoing Claims 1, 2, 3, 4 and 5 or by any other process
producing the like result.
8. Fibres or textures printed with printing pastes containing a mixture of
alkylated diamidobenzhydrols and oxazine colouring-matters.
Dated this 19th dor of Marah 1802