Manufacture of New Diamido-bases, Derivatives of Azimidobenzene, and of Azo Dyes from these.
Year: 1895

page_text: Date of Application, 21st Sept., 1895
Complete Specification Le't, 22nd June, 1996-Accepted, 18! Aug., 1395
PROVISIONAL SPECIFICATION.
[Communicated from abroad by THE FARBWERKE, vormals MEISTER LUCIUS
& BRUNING, of Hoechst a/Main, in the Empire of Germany, Chemical
Manufacturers.]
Manufacture of New Diamido-bases, Derivatives of Azimidobenzene,
and of Azo Dyes from these.
I, OLIVER IMRAY, of No. 28 Southampton Buildings, Chancery Lane, in the
County of London, Chartered Patent Agent, do hereby declare the nature of this
invention to be as follows:-
This invention relates to the manufacture of bases derived from the products
resulting from the action of 2.4 dinitrochlorbenzene upon aromatic amines,
namely
1) The 2.4 (a) dinitrodiphenylamine C,H,(NO₂),NH(C₂H,) which melts at
16° C., first obtained by Clemm (Ber. 111. 128) from bromodinitrobenzene, and by
Willgeroot (Ber. IX. 977) from chlorodinitrobenzene and aniline.
2) The 2.4 dinitrophenyltolylamine C,H,(NO),NH(C,H,), which melts at
123° C., first obtained by Leymann (Ber. XV., 1236) in the same way from dinitro-
chlorobenzene and orthotoluidine. Leymann attributes the melting point of
101-102°C. to his substance, but my foreign correspondents have found that dinitro-
phenyltolylamine, on repeated recrystallisation from alcohol, melts at 123° C.
The
They have discovered that in these bases the nitro radicle adjacent to the imide-
group can be reduced very smoothly by alkaline reducing agents such as ammonium-
sulphide or sodium-sulphide in alcoholic solution; by this means the corresponding
nitro-amido bases are obtained. Thus the dinitrodiphenylamine which melts at
156° C. gives a nitroamidodiphenylamine which melts at 116 to 117° C.
dinitrophenyltolylamine of melting point 123° C. gives a nitroamidophenyltolylamine
which melts at 121° C. Both substances are weak bases which form only with
strong acids salts which however are very easily dissociated by water. They are
characterized in a marked degree by their tendency to crystallise. They are
obtained from dilute alcohol in fine dark-red needles and plates, the crystals of
nitro-amido-phenyltolylamine having a splended goldengreen metallic lustre.
As derivatives of a substituted orthophenylenediamine these bases react in
exactly the same way as ortho-phenylenediamine on treating their salts with
nitrous acid, that is to say, smoothly form azimido-benzenederivatives. The
nitroamidodiphenylamine which melts at 116-117° C. produces a hitherto unknown
nitrophenylazimido-benzene C,H,(NO,)N,(C,H), which melts at 167° C.
This substance crystallises from hot glacial acetic acid, in which it is readily
soluble, in thin greenish yellow needles which are almost insoluble in alcohol and
.quite insoluble in water and quite insoluble in water. This substance is not identical
with the nitrophenylazimido-benzene which melts at 275° C. described by
Gattermann and Wichmann (Ber. XXI. 1636).
The nitroamidophenyltolylamine having a melting point 121° C. produces a new
It is
nitrotolylazimidobenzene C.H.(NO₂) N₁(C,H₁) which melts at 115° C.
easily soluble in hot alcohol and hot 50% acetic acid, and crystallises from such
solutions in fine shining yellowish brown scales.

page_text: These nitro-substitution products of azimido-benzene exhibit neither basic nor acid
properties and are very stable substances.
They dissolve unchanged in concentrated sulphuric acid and are precipitated
unchanged by treating the solution with water.
By nitrating these azimidobenzenes in sulphuric acid, new dinitro derivatives of
this class of bodies are obtained. Nitrophenylazimidobenzene having a melting
point 167° C. forms in this way a dinitrophenylazimidobenzene C₁₂H,N,(NO2),
which melts at 190° C. It is almost insoluble in boiling alcohol, and soluble with
great difficulty in boiling glacial acetic acid from which it crystallises in indistinct
yellowish crystalline plates.
Under the same conditions nitrotolylazimidobenzene having a melting point
115° C. produces a new dinitrotolylazimidobenzene C₁,H,N,(NO), which melts
at 201° C. Its solubility is very similar to that of the phenylderivate, but the
substance recrystallized from glacial acetic acid is pure white. The relative position
of the second nitroradicle in both substances is as yet uncertain. It may only be
presumed that the second nitroradicle introduced into both substances enters into
the benzene-ring which is not yet substituted.
Both nitro-radicles of these dinitroazinidobenzene derivatives can be readily and
smoothly reduced thus forming the bases which are the subject of this invention.
The usual agents such as tin and hydrochloric acid or iron and sulphuric acid are
suitable for this purpose. In the one case the bases are finally obtained as hydro-
chlorides, in the other the isolation of the free base from the product of the
reduction, after neutralising it with milk of lime, by extraction with boiling
water, is preferable. Dinitrophenylazimidobenzene having a melting point 190° C.
produces on reduction a diamidophenylazimidobenzene the hydrochlorate of which
has the formula C₁,N,H,(NH,), 2 HCl and forms white shining needles which
are very easily soluble in water. The free base is soluble without much difficulty
in hot water and crystallises out on cooling in thin greyish white felted needles
which contain water of crystallization. After drying at 100° C. it melts at 153° C.
The base is extremely soluble in alcohol but soluble with great difficulty in benzene,
from which it slowly crystallises out in coarse needles with glassy lustre. Dinitro-
tolylazimidobenzene having a melting point 201° C. forms on reduction a base very
similar to the above, namely diamidotolylazimidobenzene. The bydrochlorate of
this base has the composition C₁N,H,(NH), 2 HCl and is somewhat less
soluble in water than that of the phenyl compound. It is difficult to obtain the free
base in good crystals from aqueous solution because it is precipitated on cooling in
a semi-solid sticky state and only gradually becomes solid. The dry base may
however be dissolved in boiling benzene, in which it is soluble with difficulty and
it crystallises on cooling in fine hard prisms with glassy lustre which melt at 155° C.
The two bases exhibit a very characteristic difference on precipitation from solutions
of their salts by alkalies. Diamidophenylazimidobenzene is deposited in the form
of very thin needles which make the contents of the vessel gelatinize, while the
solution of diamidotolylazimidobenzene becomes milky and slowly deposits the base
in the form of oily drops, which solidify only after standing for a long time. In
this respect diamidotolylazimidobenzene shows a remarkable similarity to its mother
substance azimidobenzene.
In illustration of the details of manufacture the preparation of diamidophenylazi-
.midobenzene may be described.
1. REDUCTION OF DINITRODIPHENYLAMINE TO NITROAMIDODIPHENYLAMINE.
130 parts by weight of finely powdered dinitrodiphenylamine are stirred up with
400 parts by weight of 95% alcohol and after warming on the waterbath are mixed
with a solution of 210 parts by weight of crystallised sodium sulphide in about the
same weight of water. The reduction' begins with strong evolation of heat and is
completed without the need of further heating in a short time, while everything
goes into solution with a dark red brown color. On cooling, the nitroamidodiphenyl-

page_text: amine crystallises out completely. It is separated from the mother-liquor by filtra-
tion and from the salts which crystallise out with it by washing with water, and is
then perfectly pure. The yield is very satisfactory.
II. PREPARATION OF NITROPHENYLAZIMIDOBENZENE.
115 parts by weight of nitroamidodiphenylamine are ground with 500 parts by
weight of water to a fine paste and mixed with a solution of 35 parts by weight of
sodium nitrite dissolved in 200 parts by weight of water. This mixture is then
allowed to run into 250 parts by weight of sulphuric acid of 66° Bé. well cooled with
ice, the whole being thoroughly stirred. The formation of the azimidobenzene begins
at once and is finished in a short time. It is filtered, washed until neutral, pressed
and dried. The yield is the theoretical one.
III. NITRATION OF NITROPHENYLAZIMIDOBENZENE.
120 parts by weight of dry sifted nitrophenylazimidobenzene are dissolved at a
temperature of 15-20° C. in 1000 parts by weight of sulphuric acid of 66° Bé. and,
after cooling down to 6° C. are slowly mixed while stirring with 120 parts by weight
of nitration acid containing 26 % HNO3. The temperature may finally reach 10° C.
After the nitration is finished, the whole is poured on to pounded ice and the dinitro
product thus obtained is washed out until it contains from 1 to 2% of acid. The
yield in this case is also very good.
IV. REDUCTION OF DINITROPHENYLAZIMIDOBENZENE.
The dinitrophenylazimidobenzene which still contains acid, as described in III,
is employed directly that is to say without drying, for reduction. This is carried
out, in an apparatus having an arrangement for stirring, with 280 parts by weight
of iron turnings and the same weight of water at 100° C. and the reduction is finished
in about 6 hours. It is then neutralised with milk of lime and the product of the
reaction is separated from the iron and gypsum residue by extraction with boiling
water. On cooling, the diamidophenylazimnidobenzene crystallises out in a state of
purity. The mother liquor contains very little of the base in solution.
In this case
also no loss takes place.
The preparation of diamidotolylazimidobenzene is effected just as smoothly.
It is found that the diamidobases obtained as above described are suitable for
the preparation of very valuable azo-dye-stuffs which not only dye unmordanted
cotton directly but also dye mixed goods such as half-wool and half-silk very
evenly.
The dyestuffs obtained from these bases are easily soluble and show great fastness
against light and soap. The method of preparing azo dyestuffs from these diamido-
bases is the one generally known.
The bases can be diazotised in mineral acid solution giving easily soluble brown
tetrazo compounds which react very readily with the usual azo components. The
tetrazo compounds may be combined with two like molecules or with two different
molecules of the usual components, such as amines, phenols and their sulphonic or
carboxylic acids, or amidophenols and their sulphonic acids, and thus a great
variety of tints can be produced. The resulting simple and mixed azo dyestuffs
have mostly yellow red or violet tints.
If however the tetrazo compounds are first combined with a-naphthylamine,
its 1.6 and 1.7 sulphonic acids or amido-naphtholethers, amidoazo bodies are
obtained which easily allow of further diazotising and, when coupled with the
usual components, give dyes varying in tint from blue and violet to black. Those
dyes also which are obtained from the tetrazo compounds of the diamido bases
above described and the amidonaphthol mono- and disulphonic acids, by coupling

page_text: in alkaline solution, may be further diazotised and combined with amines
phenols etc.
This second diazotising can be performed, after dyeing, in the fibre and the
colour can be developed with the substances usually employed for this purpose, for
example m-phenylenediamine, resorcinol, B-naphthol.
Deep blue green and black dyestuffs may also be obtained from the diamido
bases herein described by further treatment of the dyestuffs produced from their
tetrazo compounds and dioxynaphthaline mono- or disulphonic acid or amido-
naphthol mono- and disulphonic acid with one or two molecules of the diazo
compounds of an amine or of the sulphonic acid of an amine. The reaction of the
tetrazo-compounds upon the various components often gives a different result
according as it is carried out in a solution acidified with acetic acid or in a solution
made alkaline with soda.
For example: the product of the action of tetrazophenylazimidobenzene and
amidonaphtholsulphonic acid G in alkaline solution is totally different from that
obtained in acid solution. When producing mixed azodyestuffs it is better to
combine the first component in a solution acidified with acetic acid and the second
component, on the contrary, in a solution made alkaline with soda.
Dated this 21st day of September 1895.
ABEL & IMRAY,
Agents for the Applicant.
Manufacture of New Diamido-bases, Derivatives of Azimidobenzene,
and of Azo Dyes from these.
I, OLIVER IMRAY, of No. 28 Southampton Buildings, Chancery Lane, in the
County of London, Chartered 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 bases derived from the products
resulting from the action of 2.4 dinitrochlorbenzene upon aromatic amines,
namely:
―
1) The 2.4 (a) dinitrodiphenylamine C,H2(NO₂),NH(CH) which melts
at 156° C., first obtained by Clemm (Ber. 111. 128) from bromodinitrobenzene,
and by Willgeroot (Ber. IX. 977) from chlordinitrobenzene and aniline.
2) The 2.4 dinitrophenyltolylamine C,H,(NO,),NH(C,H,), which melts at
123° C. first obtained by Leyman (Ber. XV. 1236), in the same way from
dinitrochlorobenzene and orthotoluidine. Leymann attributes the melting point
of 101-102° C. to his substance, but my foreign correspondents have found
that dinitrophenyltolylamine, on repeated recrystallisation from alcohol, melts
at 123° C.
They have discovered that in these hases the nitro radicle adjacent to the imide-
group can be reduced very smoothly by alkaline reducing agents such as ammonium-
sulphide or sodium-sulphide in alcoholic solution; by this means the corresponding
nitro-amido bases are obtained. Thus the dinitrodiphenylamine which melts
at 156° C. gives a nitroamidodiphenylamine which melts at 116° to 117° C. The
dinitrophenyltolylamine of melting point 123° C. gives a nitroamidophenyltolyl-
amine which melts at 121° C. Both substances are weak buses which form only
with strong acids salts, which however are very easily dissociated by water. They
are characterized in a marked degree by their tendency to crystallise. They are
obtained from dilute alcohol in fine dark red needles and plates, the crystals of
nitro amido-phenyltolylamine having a splendid goldengreen metallic lustre.
As derivatives of a substituted orthophenylenediamine, these bases react in

page_text: exactly the same way as ortho-phenylenediamine on treating their salts with
nitrous acid; that is to say, smoothly form azimido-benzene derivatives. The
nitroamidodiphenylamine which melts at 116°-117° C. produces a hitherto unknown
nitrophenylazimidobenzene C,H,(NO,)N,(CH), which melts at 167° C.
This substance crystallises from hot glacial acetic acid, in which it is readily
soluble, in thin greenish yellow needles which are almost insoluble in alcohol and
quite insoluble in water. This substance is not identical with the nitrophenyl-
azimidobenzene which melts at 275° C. described by Gattermann and Wichmann
(Ber. XXI. 1636).
The nitroamidophenyltolylamine having a melting point 121° C. produces a new
nitrotolylazimidobenzene CH, (NO2) N (C,H,) which melts at 115° C. It is
easily soluble in hot alcohol and hot 50% acetic acid, and crystallises from such
solutions in fine shining yellowish brown scales.
These nitro substitution products of azimidobenzene exhibit neither basic nor
acid properties, and are very stable substances.
They dissolve unchanged in concentrated sulphuric acid and are precipitated
unchanged by treating the solution with water.
By nitrating these azimidobenzenes in sulphuric acid new dinitro derivatives of
this class of bodies are obtained. Nitrophenylazimidobenzene having a melting
point 167° C. forms in this way a dinitrophenylazimidobenzene C₁₂H,N, (NO),
which melts at 190° C. It is almost insoluble in boiling alcohol and soluble with
great difficulty in boiling glacial acetic acid, from which it crystallises in indistinct
yellowish crystalline plates
Under the same conditions, nitrotolylazimidobenzene having a melting point
115° C. produces a new dinitrotolylazimidobenzene C₁,H,N, (NO2), which melts
at 201° C. Its solubility is very similar to that of the phenylderivative, but the
substance, recrystallized from glacial acetic acid, is pure white. The relative
position of the second nitroradicle in both substances is as yet uncertain. It may
only be presumed that the second nitro radicle introduced into both substances
enters into the benzene ring which is not yet substituted.
Both nitro radicles of these dinitroazimidobenzene derivatives can be readily
and smoothly reduced, thus forming the bases which are the subject of this
invention. The usual agents such as tin and hydrochloric acid or iron and
sulphuric acid are suitable for this purpose. In the one case the bases are finally
obtained as hydrochlorides, in the other the isolation of the free base from the
product of the reduction, after neutralising it with milk of lime, by extraction
with boiling water, is preferable. Dinitrophenylazimidobenzene having a melting
point 190° C. produces on reduction a diamidophenylazimidobenzene the hydro-
chloride of which has the formula C,,N,H, (NH),. 2 HCI and forms white
shining needles which are very easily soluble in water. The free base is soluble
without much difficulty in hot water and crystallizes out on cooling in thin greyish
white felted needles which contain water of crystallization. After drying at 100° C.
it melts at 153° C. The base is extremely soluble in alcohol but soluble with
great difficulty in benzene, from which it slowly crystallises out in coarse needles
with glassy lustre. Dinitrotolylazimidobenzene, having a melting point 201° C.,
forms on reduction a base very similar to the above namely diamidotolylazimido-
benzene. The hydrochloride of this base has the composition C₁N,H, (NH₂) 2 HCI
and is sourewhat less soluble in water than that of the phenyl compound. It is
difficult to obtain the free base in good crystals from aqueous solution because it is
precipitated on cooling in a semi solid sticky state and only gradually becomes
solid. The dry base may however be dissolved in boiling benzene, in which it is
soluble with difficulty and it crystallises on cooling in fine hard prisms with glassy
lustre, which meli at 155° C. The two bases exhibit a very characteristic
difference on precipitation from solutions of their salts by alkalies.
Diamido-
phenylazimidobenzene is deposited in the form of very thin needles which make
the contents of the vessel gelatinize, while the solution of diamidotolylazimido
benzene becomes milky and slowly deposits the base in the form of oily drops,

page_text: which solidify only after standing for a long time. In this respect diamido-
tolylazimidobenzene shows a remarkable similarity to its mother substance
azimidobenzene.
In illustration of the details of manufacture, the preparation of diamidophenyl-
azimidobenzene may be described.
1. REDUCTION OF DINITRODIPHENYLAMINE TO NITROAMIDODIPHENYL-
AMINE.
up
130 parts by weight of finely powdered dinitrodiphenylamine are stirred with
400 parts by weight of 95% alcohol and after warming on the water bath are
mixed with a solution of 210 parts by weight of crystallised sodium sulphide in
about the same weight of water. The reduction begins with strong evolution of
heat and is completed without the need of further heating in a short time, while
everything goes into solution with a dark red brown color. On cooling, the
nitroamidodiphenylamine crystallises out completely. It is separated from the
mother liquor by filtration and from the salts which crystallise out with it by
washing with water and is then perfectly pure. The yield is very satisfactory.
II. PREPARATION OF NITROPHENYLAZIMIDOBENZENE.
115 parts by weight of nitroamidodiphenylamine are ground with 500 parts by
weight of water to a fine paste and mixed with a solution of 35 parts by weight of
sodium nitrite dissolved in 2:0 parts by weight of water. This mixture is then
allowed to run into 250 parts by weight of sulphuric acid of 66° Bé. well cooled
with ice, the whole being thoroughly stirred. The formation of the azimidobenzene
begins at once and is finished in a short time. It is filtered, washed until neutral,
pressed and dried. The yield is the theoretical one.
III. NITRATION OF NITROPHENYLAZIMIDOBENZENE.
120 parts by weight of dry sifted nitrophenylazimidobenzene are dissolved at a
temperature of 15°-20° C. in 1000 parts by weight of sulphuric acid of 66° Bé.,
and, after cooling down to 6° C., are slowly mixed while stirring with 120 parts by
weight of nitration acid containing 26% HNO3. The temperature may finally
reach 10° C. After the nitration is finished the whole is poured on to pounded ice
and the dinitro product thus obtained is washed out until it contains from 1 to
2% of acid. The yield in this case is also very good.
IV. REDUCTION OF DINITROPHENYLAZIMIDOBENZENE.
The dinitrophenylazimidobenzene which still contains acid, as described in III,
is employed directly, that is to say, without drying, for reduction. This is carried
out, in an apparatus having an arrangement for stirring, with 280 parts by weight
of iron turnings and the same weight of water at 100° C. and the reduction is
finished in about 6 hours. It is then neutralised with milk of lime and the product
of the reaction is separated from the iron and gypsum residue by extraction with
boiling water. On cooling, the diamidophenylazimidobenzene crystallises out in
a state of purity. The mother liquor contains very little of the base in solution.
In this case also no loss takes place.
The preparation of diamidotolylazimidobenzen is effected just as smoothly.
It is found that the diamido bases obtained as above described are suitable for
the preparation of very valuable azo dye stuffs, which not only dye unmordanted
cotton directly but also dye mixed goods, such as half wool and half silk very
evenly.
The dye stuffs obtained from the bases are easily soluble, and show great fastness

page_text: against light and soap. The method of preparing azo-dyestuffs from these diamido
bases is the one generally known.
The bases can be diazotised in mineral acid solution, giving easily soluble brown
The
tetrazo compounds, which react very readily with the usual azo components.
tetrazo compound may be combined with two like molecules or with two different
molecules of the usual components, such as amines, phenols and their sulphonic or
carboxylic acids, or amidophenols and their sulphonic acids, and thus a great
variety of tints can be produced. The resulting simple and mixed azo dyestuffs
have mostly yellow red or violet tints.
If however the tetrazo compounds are first combined with a naphthylamine, its
1.6 and 1.7 sulphouic acids or amido naphtholethers, amidazo bodies are obtained
which easily allow of further diazotising and, when coupled with the usual com-
ponents, give dyes varying in tint from blue and violet to black. These dyes also
which are obtained from the tetrazo compounds of the diamido bases above described
and the amidonaphthol mono- and disulphonic acids, by coupling in alkaline solution,
may be further diazotised and combined with amines, phenols &c.
This second diazotising can be performed after dyeing, in the fibre, and the colour
can be developed with the substances usually employed for this purpose, for
example in phenylenediamine, resorcinol, ẞ naphthol.
Deep blue, green and black dyestuffs may also be obtained from the diamido
bases herein described by further treatment of the dyestuffs produced from their
tetrazo compounds and dioxynaphthalene, mono- or disulphonic acid or amido-
naphthol mono and disulphonic acid with one or two molecules of the diazo
compounds of an amine or of the sulphonic acid of an amine. The reaction of the
tetrazo compounds upon the various components often gives a different result,
according as it is carried out in a solution acidified with acetic acid, or in a solution
made alkaline with soda.
For example, the product of the action of tetrazo-phenylazimido-benzene and
amidonaphthol sulphonic acid G in alkaline solution is totally different from that
obtained in acid solution. When producing mixed azo-dye-stuffs, it is better to
combine the first component in a solution acidified with acetic acid, and the second
component on the contrary in a solution made alkaline with soda.
Having now particularly described and ascertained the nature of my said
invention and in what manner the same is to be performed 1 declare that what
I claim is :-
1. The herein described manufacture of diamido aromatic substitution derivatives
of azimidobenzene by successive partial reduction, conversion into azimido com-
pound, nitration and reduction of the diphenylamine derivatives obtained from
2.4 dinitro chlorobenzene, or 2.4 dinitrobromo-benzene and aromatic amines.
2. The manufacture from the diamido-bases above referred to of simple and
mixed azo dyestuffs, directly dyeing unmordanted cotton and silk, such as,
(a) Yellow, red, violet and orange, simple dyestuffs obtained by the action of
1 molecule of tetrazo- phenyl- or tolyl-azimidobenzene upon 2 molecules of
an amine or its sulphonic acid, such as m-phenylenediamine, m-toluylene-
diaminesulphonic acid; mono- or disulphonic acids of a or B-naphtylamine,
as for instance naphthionic acid, ẞ naphtylaminesulphonic acid F,
ẞ naphthylamine sulphonic acid II, Brönner, ẞ naphthylaminesulphonic
acid R or G, 1 molecule of tetrazo compound and 2 molecules of a phenol or
its sulphonic or carboxylic acid, for example, phenol, resorcinol, salicylic
acid, o-cresotic acid, a- or ẞ naphthol mono- or disulphonic acid, for instance,
a-naphtholsulphonic acid Neville-Winther, a naphthol sulphonic acid or
Bnaphtholsulphonic acid, Schaffer dioxy naphthaline-mono sulphonic acid S,
dioxynaphthaline- ß-disulphonic acid, dioxynaphthoësulphonic acid German
Patent 67000 1 molecule, tetrazo-compound and 2 molecules amidonaphthol-
mono- or disulphonic acid, for instance, amidonaphtholmono-sulphonic

page_text: acid G, or amidonaphtholdisulphonic acid H or any known amidonaphthol-
sulphonic acid.
(6) Yellow, brown, red, or violet mixed diazo dye stuffs made from 1 molecule
of tetrazo-phenyl- or tolyl-azimido benzene and 2 different molecules of the
components of azo-dyestuffs mentioned in (a).
For example: 1 mol. tetrazo phenyl- or tolylazimidobenzene and 1 mol.
naphthionic acid, and 1 mol. resorcinol or ẞ naphthyl amine sulphonic acid,
Brönner or amidonaphtholsulphonic acid G.
(c) Red, violet or blue polyazo-dyestuffs characterised by the process that
the tetrazo-compound of diamido- phenyl- or tolylazimido-benzene is first
combined with 1 mol. or with 2 mol. of a naphthylamine or of its 1.6
and 1.7 sulphonic acids, or with amidonaphtholether to form an amido
azo-compound, that this compound is then further diazotised and combined
with 1 mol or with 2 mol, of the components mentioned in (a).
For example: The dyestuff obtained from 1 mol. of tetrazo phenyl or tolyl-
azimidobenzene and 2 molecules of a naphthylamine is again diazotised and
combined with 2 mol. of a naphthol disulphonic acid 1.4.7 in alkaline
solution. Instead of the bodies mentioned, the mono- and disulphonic acids
of amidonaphthol may be employed in case they have been combined in an
alkaline solution; for example, the dyestuff obtained from 1 mcl. of tetrazo
phenyl- or tolylazimido benzene and 2 mol. of amidonaphthol disulphonic
acid H combined in alkaline solution, then again diazotised and combined
with 2 mol. of ẞ naphtholdisulphonic acid R in a solution made alkaline
with soda.
(d) Violet and green, poly-azo-dyestuffs, characterised by the process that
1 mol. of the tetrazo-compound of diamidophenyl- or tolylazimidobenzene
is combined with 2 mol. of a 1.8 dioxynaphthaline mono- or disulphonic acid
and that the dyestuff thus formed is then treated with the diazo-compound
of an amine or of the sulphonic acid of an amine.
For example: The dyestuff obtained from 1 mol. tetrazo- phenyl- or tolyl-
azimidobenzene and 2 mol. of amidonaphtholdisulphonic acid H is then
treated with 2 mol, of diazo-p-nitrobenzene or with 2 mol. of diazonaph-
thionic acid.
The products and dyestuffs manufactured as set forth in the preceding
OS.
Dated this 16th day of June 1896.
ABEL & IMRAY,.
Agents for the Applicant.