Manufacture of New Disazo, Trisazo, and Polyazo Colouring Matters.
Year: 1896

page_text: Date of Application, 22nd June, 1896-Accepted, 25th July. 1896
COMPLETE SPECIFICATION.
[Communicated from abroad by THE SOCIETY OF CHEMICAL INDUSTRY IN
BASLE, Basle, Switzerland, Chemical Manufacturers.]
Manufacture of New Disazo, Trisazo, and Polyazo Colouring
Matters.
I, OLIVER IMRAY, of 28 Southampton Buildings, 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 :-
1. This invention is based on the observation made by my correspondents that
diazo bodies of the general formula:-
CINN-CH-C-X
(in which I may designate hydrogen, a hydronyl, onvalkyl, amide, alley!
alphylamido group), which may be obtained by diazotation of the ortho, meta and
para-amido benzylaldehydes, the ortho, meta, and para-amido benzoic acids,
the ethers of the ortho, meta, and para-amido benzoic acids, and the amides of the
ortho, meta and para amido benzoic acids, give, by their combination with the
amidonaphthol disulphonic acids 1.8, 3.6, 1.8.4.6, and 1.5.3.7, in acid solution, mono-
azo colouring matters which, although having no technical value in themselves,
can be transformed into disazo, trisazo, and polyazo colouring matters of great
value.
2. For this purpose, there are combined one molecule of monoazo colouring
matters of the general formula :-
alphylamido group), which may be obtained by diazotation of the ortho, meta and
para-amido benzylaldehydes, the ortho, meta, and para-amido benzoic acids,
the ethers of the ortho, meta, and para-amido benzoic acids, and the amides of the
ortho, meta and para amido benzoic acids, give, by their combination with the
amidonaphthol disulphonic acids 1.8, 3.6, 1.8.4.6, and 1.5.3.7, in acid solution, mono-
azo colouring matters which, although having no technical value in themselves,
can be transformed into disazo, trisazo, and polyazo colouring matters of great
value.
2. For this purpose, there are combined one molecule of monoazo colouring
matters of the general formula :-
(SO,Na).
VOH
C10H
NH,
\N = N – CH
-
C
X
(in which X has the above stated signification) either with one molecule of the
tetrazo derivatives of benzidine, tolidine, methylbenzidine, ethoxybenzidine, nitro-
benzidine, nitrotolidine, diamidodiphenylamine, diamidodiphenol ethers, diamido-
stilbene, disulphonic acid of, diamido stilbene, diamiduazo benzol, diamidoazotoluol,
diamido-benzol-azo-naphthalene, diamido benzol-azo-para-cresol ether, or with one
molecule of the bodies resulting from the diazotation of the intermediate products
obtained by the combination of one molecule of the tetrazo derivative of benzidine,
of methyl-benzidine, of tolidine, of mononitrobenzidine, of mononitrotolidine, of
diamido diphenylamine, of ethoxy benzidine, of diamido diphenol-ethers, or of
paraamido acetanilide, with one molecule of para cresidine, of a-naphthylamine in
Price 1

page_text: such, for example, as those resulting from the combination of the amidonaphthol
disulphonic acids 1.8.4.6, 1.8.3.6 and 1.5.3.7, with ortho-, meta, or para-diazo-
benzaldehyde, ortho meta or para diazo benzoic acid, an ether of the ortho, meta
or para diazo-benzoic acid, or the amide of the ortho, meta or para diazo benzoic
acid; or again, with one molecule of the monoazo colouring matters resulting from
the combination of amido naphtholdisulphonic acids 1.8.3.6, 1.8.4.6 and 1.5.3.7,
with diazo bodies such as the diazo derivatives of aniline, of ortho and para
toluidine, of xylidine, of the amido naphthol ethers, of a and ẞ naphthylamine, of
the sulpho, carboxyl, sulpho carboxyl, chlorined and nitrated derivatives of these
aromatic mono amido-compounds, as also of dehydro-thio para toluidine, of
primuline, and of the sulpho derivatives of these two last bodies, in acid
solution.
4. According to the choice made among the compounds mentioned above,
there will be obtained a trisazo, tetrazo, or pentazo colouring matter, that is to
say, containing three, four or five diazo groups dyeing unmordanted cotton directly
a violet-black, blue, grey, black, or green.
5. Analogous polyazo colouring matters are obtained if the monoazo colouring
matters mentioned in the first paragraph of this specification are combined in
alkaline solution with the well known intermediate product containing a free diazo
group, and resulting from the combination of one molecule of one of the bodies
mentioned in the third paragraph of this description preferably the sulpho and
carboxyl compounds, with the tetrazo bodies mentioned in the second paragraph.
6. But if one combines the monazo colouring matters mentioned in the first
paragraph with simple diazo bodies, such as the diazo derivatives of aniline, of
ortho and para toluidine, of hidine, of amido-phenol ethers, of amido bene
aldehydes, of a and B naphthylamine; of the sulpho, carboxyl, sulpho-carboxyl,
chlorined and nitrated derivatives of these monoamido compounds, of dehydro-
thioparatoluidine, of primuline or the sulpho derivatives of the two latter
bodies, there are obtained disazo colouring matters specially applicable to dyeing
wool and silk.
7. In all these preparations of disazo, trisazu or polyazo colouring matters for the
mouvazo colouring matters of the general forinule:-
aldehydes, of a and B naphthylamine; of the sulpho, carboxyl, sulpho-carboxyl,
chlorined and nitrated derivatives of these monoamido compounds, of dehydro-1
thioparatoluidine, of primuline or the sulpho derivatives of the two latter
bodies, there are obtained disazo colouring matters specially applicable to dyeing
wool and silk.
7. In all these preparations of disazo, trisazo or polyazo colouring matters for the
monoazo colouring matters of the general formulæ :-
(SO,Na),
//OH
C₁H
NH,
0
-
NN CH, CH,
-
which are produced by the combination of aromatic diazo aldehydes with the amido
naphthol-disulphonic acids mentioned, in acid solution, can be substituted the
products obtained by the reaction of the said monoazo colouring matters upon the
primary aromatic hydrazines, and the secondary aromatic asymmetric hydrazines,
that is to say, by the corresponding hydrazonazo colouring matters.
8. For this purpose may be used the aromatic hydiazines corresponding to
aniline, ortho and para toluidine, xylidine, amidophenol ethers, a and ẞ naphthyl-
amine, to the sulpho, carboxyl, sulpho-carboxyl, chlorined and nitrated derivatives
of these bodies, to dehydrothiopara-toluidine, as also methylphenylhydrazine,
ethylphenylhydrazine, methyltolyl-hydrazine, ethyltolyl-hydrazine, diphenyl
hydrazine and dipara tolyl hydrazine.
The hydrazonazo colouring matters thus obtained dye unmordanted cotton and
wool in dark blue, black and green tints of great strength.
For the amidonaphthol sulphonic acids mentioned in the 1st paragraph of this

page_text: COMBINATION OF ONE MOLECULE OF THE MONAZO COLOURING MATTER
DERIVED FROM AMIDO-NAPHTHOL DISULPHONIC ACID 1.8.3.6 AND OF
PARA-DIAZO BENZALDEHYDE, WITH ONE MOLECULE OF TETRAZO-
DIPHENYL, AND THE COMBINATION OF THE INTERMEDIATE PRODUCT
THUS OBTAINED WITH ONE MOLECULE OF NAPHTHIONATE.
6.1 kilos. of paramidobenzaldehyde are diazotised in the well known way, and
the product of the diazotation is added to a neutral solution of 16 kilos. of amido
naphthol disulphonic acid 1.8.3.6, cooled to a temperature of between 5° and 10° C.
The combination takes place almost instantaneously, the colouring matter thus
produced being precipitated in the form of violet-brown flakes.
After having allowed the mass to remain at rest for about two hours, it is
rendered alkaline by addition 20 kilos. of carbonate of soda, which produces a
violet-blue solution of the monoazo colouring matter, that can be employed directly
for the purpose of combining the colouring matter with tetrazo compounds.
There is then added to it a solution of tetrazc-diphenyl derived from 9.2 kilos. of
benzidine.
The formation of the intermediate product is effected almost instantaneously, and
this intermediate product is entirely precipitated in the form of blackish blue
flakes. In order to transform or convert this intermediate product into a colouring
matter that will dye cotton without the use of a inordant, there is added to it a
solution of 12.5 kilos. of naphthionate, and the mass is allowed to remain at rest for
about 12 hours. It is then heated to about 80° C., and the colouring matter is
obtained by adding salt, filtering, &c. It consists of a powder of slight bronze
lustre, dissolving readily in water with a blackish blue colour. It dyes cotton not
mordanted, a blackish blue with a greenish tiuge.

page_text: EXAMPLE 2.
COMBINATION OF THE INTERMEDIATE PRODUCT RESULTING FROM THE
COMBINATION OF ONE MOLECULE OF TETRAZODITOLYL WITH ONE
MOLECULE OF THE MONOAZO COLOURING MATTER DERIVED FROM
AMIDONAPHTHOL-DISULPHONIC ACID 1.8.3.6 AND OF PARADIAZOBENZ-
ALDEHYDE WITH ONE MOLECULE OF METATOLUYLENE DIAMINE.
The monoazo colouring matter produced as in Example 1, by the combination
of the diazo substance derived from 61 kilos. of para amidobenzaldehyde with
16 kilos. of amidonaphtholdisulphonic acid 1.8.3.6 is combined in the form of a
solution rendered alkaline by means of carbonate of soda, with a solution of
tetrazoditoly derived from 10-6 kilos. of tolidine. The insoluble blackish blue
intermediate product becomes formed in a short time.
When the formation of the intermediate product is complete, there is added a
solution of 6.5 kilos. of metatoluylene diamine, and the whole is allowed to rest for
about 12 hours. The colouring matter is separated in the ordinary way. It dyes
non-mordanted cotton a fine black.
COMBINATION
OF ONE MOLECULE OF THE MONOAZO COLOURING MATTER
DERIVED FROM PARADIAZOBENZOIC ACID AND AMIDONAPHTHOL-
DISULPHONIC ACID 1.8.3.6, WITH ONE MOLECULE OF TETRAZODIANISOL,
AND THE FURTHER COMBINATION OF THE INTERMEDIATE PRODUCT
WITH ONE MOLECULE OF AMIDONAPHTHOL DISULPHONIC ACID 1.8.3.6.
13-7 kilos. of para amido benzoic acid are diazctised by means of 7 kilos. of
nitrite, and the diazo solution thus produced, is caused to flow gradually, while
continually stirring, into a cooled solution of 32 kilos. of amidonaphtholdisulphonic
acid 1.8.3.6. After allowing the mixture to rest for some hours, it is rendered
alkaline by adding carbonate of soda, and there is also added to it a solution of
tetrazodianisol resulting from the diazotation of 24.4 kilos. of diauisidine. The
intermediate product which is instantly formed, remains wholly in solution if the
solution employed is not too highly concentrated. The solution of the said
intermediate product presents an intense violet-black colour; and by adding to it
sea salt, the intermediate product is precipitated in the form of black flakes. This
precipitation is however useless for the subsequent process.
In order to effect the conversion into colouring matter, to the violet-black
solution of the intermediate product there are added 32 kilos. of amidonaphthol-

page_text: disulphonic acid 1.8.3.6, and the mixture is left alene for a long period. Com-
bination takes place comparatively slowly. After the lapse of 20 hours the
colouring matter can be separated in the usual manner.
This colouring matter in the dry state is a powder having a coppery lustre, the
aqueous solution of which is of a blueish green colour. It dyes non-mordanted
cotton a greenish blue.
COMBINATION
OF THE MONOAZO
AMIDONAPHTHOLDISULPHONIC
COLOURING MATTER DERIVED FROM
ACID 1.8.3.6 AND METADIAZOBENZOIC
ACID, WITH ONE MOLECULE OF TETRAZODITOLYL, AND THE FURTHER
COMBINATION OF THE INTERMEDIATE PRODUCT WITH ONE MOLECULE
OF PHENOL.
The diazo derivative obtained by means of 6.9 kilos. of metaamidobenzoic acid,
is combined in the usual manner with 16 kilos. of amidonaphtholdisulphonic
acid 1.8.3.6. The monoazo colouring matter thus formed is first brought into the
state of solution rendered alkaline by means of carbonate of soda, and to it there
is then added a solution of tetrazoditolyl derived from 10-6 kilos. of tolidine; and
after combination of the tetrazoditolyl with the monoazo colouring matter, there is
mixed with the violet-black solution of the intermediate product a solution of
4.8 kilos. of phenol rendered alkaline by addition of carbonate of soda. After the
mixture is leit for a long period to itself, it is heated, and the colouring matter is
precipitated therefrom by addition of sea salt. The colouring matter thus obtained
dyes non-mordanted cotton fine shades of green.
COMBINATION OF ONE MOLECULE OF THE MONOAZO COLOURING MATTER
DERIVED FROM AMIDONAPHTHOLDISULPHONIC ACID 1.5.3.7 AND META-
DIAZOBENZOIC ACID, WITH ONE MOLECULE OF TETRAZODIPHENYL, AND
THE FURTHER COMBINATION OF THE INTERMEDIATE PRODUCT THUS
PRODUCED, WITH ONE MOLECULE OF METATOLUYLENEDIAMINE.
The diazo derivative obtained by means of 6.9 kilos. of metaamidobenzoic
acid, is combined in acid solution with 16 kilos. of amidonaphthol disulphonic
acid 1.5.3.7. The monoazo colouring matter brought into the state of solution
rendered alkaline by addition of carbonate of soda, has added to it a solution
of tetrazodiphenyl obtained by means of 9.2 kilos. of benzidine. After the
formation of the intermediate product, there is added to it an aqueous solution of
6.5 kilos. of metatoluylene diamine. The mixture is left alone for some hours. It
is then heated to about 80° C., and the colouring matter is separated in the usual
manner. It dyes non-mordanted cotton a blackish violet.
XA
COMBINATION OF ONE MOLECULE OF THE MONOAZO COLOURING MATTER
RESULTING FROM AMIDONAPHTHOLDISULPHONIC ACID 1.8.3.6 AND THE
DIAZO DERIVATIVE OF ANTHRANILIC ACID, WITH A MOLECULE OF
TETRAZODIPHENYL AND UNION OF THE INTERMEDIATE PRODUCT THUS
OBTAINED WITH A MOLECULE OF AMIDONAPHTHOLMONOSULPHONIC
ACID 2.8.6.
The monoazo colouring matter prepared. by meaus of the diazo derivative
of 6-9 kilos. of anthranilic acid and 16 kilos. of amidonaphtholdisulphonic
acid 1.8.3.6, is combined in solution in a liquor rendered alkaline by addition
of carbonate of soda, with the tetrazodiphenyl derivative of 9.2 kilos. of benzidine.
The black violet solution of the intermediate product thus obtained is mixed with
a solution of 12.5 kilos. of amidonaphthol monosulphonic acid 2.8.6 in water with

page_text: addition of carbonate of soda. After 10 hours the mass is heated and the
colouring matter is precipitated by addition of sea salt. It forms a black powder
which dissolves in water with blue black colour; it dyes non-mordanted cotton.
blue black shades.
COMBINATION OF A MOLECULE OF THE MONOAZO COLOURING MATTER
DERIVED FROM AMIDONAPHTHOLDISULPHONIC ACID 1.8.3.6 AND THE
METHYLIC ETHER OF METADIAZO BENZOIC ACID, WITH A MOLECULE OF
TETRAZODIPHENYL, AND THE FURTHER UNION OF THE INTERMEDIATE
PRODUCT OBTAINED WITH A MOLECULE OF
ACID 1.4.
NAPHTHOLSULPHONIC
7.6 kilos. of the methylic ether of metaamidobenzoic acid are transformed:
into a diazo derivative which is combined with 16 kilos. of amidonaphthol-
disulphonic acid 1.8.3.6. To the solution of this monoazo colouring matter,
obtained by addition of carbonate of soda, is added the quantity of tetrazodiphenyl
obtained by diazotation of 9-2 kilos. of benzidine. The intermediate product >
immediately precipitates as black flakes. When the whole of the tetrazɔdiphenyl
is combined with the monoazo colouring matter, an aqueous solution is added of:
13 kilos. of naphtholsulphonic acid 1.4, the mass is left to itself for some time,.
then heated, and the colouring matter is separated by sea salt. It dyes non-
mordanted cotton deep blue.
COMBINATION OF THE MONOAZO COLOURING MATTER DERIVED FROM AMIDO-
NAPHTHOL DISULPHONIC ACID 1.8.3.6 AND METADIAZO BENZAMIDE WITH A
MOLECULE OF TETRAZODITOLYL AND FURTHER COMBINATION OF THE
OBTAINED INTERMEDIATE PRODUCT WITH A MOLECULE OF PHENOL.
NH,
6-8 kilos. of metamidobenzamide (C.H.
(CH, PH
CONH,
are diazotised, and the
resulting diazo derivative is combined with 16 kilos. of amidonaphtholdisulphonic
acid 1.8.3.6 in neutral or slightly acid solution.
The monoazo colouring matter being formed, the mass is rendered alkaline by
addition of 20 kilos. of carbonate of soda and has added to it the quantity of
tetrazoditolyl obtained by diazotation of 10-6 kilos. of tolidine. The intermediate
product formed precipitates in blue black flakes. Finally there is added a solution
of 4-7 kilos. of phenol including carbonate of soda and the whole is left to itself
for about 20 hours. The colouring matter formed is recovered in the usual way.
It is a powder of coppery lustre, dissolves readily in water with blue green colour
and directly dyes non-mordanted cotton intense green.
If, in the preceding examples, 1 to 9 inclusive for the monoazo colouring matter
mentioned be substituted the other monoazo colouring matters mentioned in the
first paragraph of this description, the formation of immediate and final colouring
matters takes place in a similar manner.
It is also evident that the simple or compound tetrazo bodies mentioned in the
second paragraph of this description may be employed instead of the tetrazo bodies
mentioned in the 9 examples, for the preparation of the intermediate products
without any substantial alteration of the processes.
It is the same in respect of substitution for the bodies mentioned in the
9 examples to be finally combined with the intermediate products, as for these may
be substituted the bodies mentioned in the third paragraph of this description.

page_text: Combination of a molecule of a monoazo colouring matter of the general
formula :-
with a molecule of an intermediate product resulting from the union of a molecule
of the tetrazo derivative of the paradiamines mentioned in the second paragraph
of this description or of the bodies resulting from the diazotation of the inter-
mediate products mentioned in the same paragraph, and of a molecule of one of
the bodies mentioned in the third paragraph.
COMBINATION OF THE MONOAZO COLOURING MATTER DERIVED FROM AMIDO-
NAPHTHOLDISULPHONIC ACID 1.8.3.6 AND PARADIAZOBENZALDEHYDE
WITH A MOLECULE OF THE INTERMEDIATE PRODUCT RESULTING FROM
THE UNION OF A MOLECULE OF TETRAZODIPHENYL WITH A MOLECULE
OF NAPHTHIONATE.
9.2 kilos. of benzidine are diazotised and the tetrazo derivative obtained is
combined with 12-3 kilos. of naphthionate dissolved in water having carbonate of
soda added to it. After formation of the intermediate product, there is added to
it a solution of the monoazo colouring matter obtained by the combination of the
diazo derivative of 61 kilos. of paraamidobenzaldehyde with 16 kilos. of amido-
naphtholdisulphonic acid 1.8.3.6 in acid liquor, the said solution having in the first
place been rendered alkaline by addition of carbonate of soda. The mass is left
to itself for about 12 hours, then heated, and the colouring matter is collected by
adding salt, filtering &c. It dyes non-mordanted cotton blue black.
COMBINATION OF A MOLECULE OF THE MONOAZO COLOURING MATTER 2
DERIVED FROM AMIDONAPHTHOLDISULPHONIC ACID 1.8.3.6 AND META-:
DIAZOBENZOIC ACID WITH A MOLECULE OF THE INTERMEDIATE
PRODUCT RESULTING FROM THE UNION OF A MOLECULE OF TETRAZO-
DIPHENYL AND OF A MOLECULE OF CRESOTINIC ACID (ORTHO
OXYUTOLIC ACID).
The monoazo colouring matter resulting from the combination of 16 kilos. of
amidonaphtholdisulphonic acid 1.8.3.6 with the diazo derivative of 6.9 kilos. of
metaamidobenzoic acid, is united in form of a solution in liquor containing carbonate
of soda with the intermediate product
3
COOH
resulting from the coupling of the tetrazo diphenyl derived from 9.2 kilos. of
benzidine with 76 kilos. of cresotinic acid (ortho oxytoluic acid) in the usual
manner, in water with addition of carbonate of soda, in which the said intermediate
product is suspended.

page_text: The mixture is left for some time to itself, as the combination gces on slowly.
The product is then carefully heated, and the colouring matter is precipitated by
addition of salt. It dyes non-mordanted cotton russet green.
The combination takes place in a manner quite similar when other intermediate
products are employed containing a free diazo group, such as can be obtained by
coupling a molecule of the simple or compound tetrazo bodies mentioned in the
second paragraph of this description, with a molecule of the bodies mentioned in
the third paragraph.
The process is not substantially altered if with the said intermediate products be
combined the other monoazo colouring matters mentioned in the first paragraph of
this specification.
Combination of mone
colouring matters having the general formula
COMBINATION OF A MOLECULE OF THE MONOAZO COLOURING MATTER
DERIVED FROM AMIDONAPHTHOL DISULPHONIC ACID 1.8.3.6 AND META-
DIAZOBENZALDEHYDE WITH A MOLECULE OF DIAZOBENZOL.
The red colouring matter prepared by the combination of the diazo derivative
from 12 kilos. of metaamidobenzaldehyde with 32 kilos. of amidonaphthol-
disulphonic acid 1.8.3.6 in acid solution is added a solution containing carbonate of
soda to the solution of diazobenzol obtained by diazotising 9-3 kilos. of aniline. The
mixture becomes rapidly coloured blue black, with partial precipitation of the diazo
colouring matter formed. After leaving the mass to itself for about 12 hours, it is
heated and the colouring matter is separated by adding salt, filtering &c. It forms
a powder of bronze lustre, and dissolves in water with blue colour. It dyes wool
in acid bath blue black shades.
COMBINATION OF A MOLECULE OF THE MONOAZO COLOURING MATTER
DERIVED FROM AMIDONAPHTHOLDISULPHONIC ACID 1.8.3.6 AND PARA-
DIAZOBENZOIC ACID, WITH A. MOLECULE OF DIAZOBENZOL.
13-7 kilos. of paraamidobenzoic acid are diazotised and the solution of the
diazo derivative obtained is mixed with a neutral solution of 32 kilos. of amido-
naphtholdisulphonic acid 1.8.3.6. After leaving the mixture to itself several
hours, the solution is alkalised by addition of 30 kilos. of carbonate of soda and
there is added to it the diazobenzol obtained by diazotising 9.3 kilos. of aniline.
The mixture beconies quickly coloured blue. After leaving it alone several hours,
the colouring matter is precipitated from it by adding salt and filtering. In a dry
state this colouring matter is a powder of bronze lustre; it dissolves in water with
blue colour. It dyes wool with acid bath blue black.
P

page_text: COMBINATION OF A MOLECULE OF THE MONOAZO COLOURING MATTER
DERIVED FROM AMIDONAPHTHOLDISULPHONIC ACID 1.8.3.6 AND META-
DIAZOBENZOIC ACID WITH A MOLECULE OF a-DIAZONAPHTHALENE.
To the red colouring matter obtained by combining the diazo derivative of
13.7 kilos. of metaamidobenzoic acid with 32 kilos. of amidonaphtholdisulphonic
acid 1.8.3.6, is added the solution of diazonaphthalene derived from 14.3 kilos. of
a-naphthylamine, the said red colouring matter being in the form of a solution
containing carbonate of soda. The red colour of the mixture gradually changes
to blue. In 10 hours the combination is complete, and the colouring matter is
separated in the usual way. It dyes wool intense blue black.
The preparation of other diazo colouring matters is conducted in a similar
manner if, for the monoazo colouring matters used in Examples 12, 13 and 14, be
substituted the other monoazo colouring matters mentioned in the first paragraph
of this specification. Likewise for the simple diazo bodies (diazo benzol, a diazo-
naphthalene) indicated in Examples 12, 13 and 14'as being combined with mono-
azo colouring matters, may be substituted the diazo derivatives of the other.
monoamido compounds mentioned in the sixth paragraph of this specification.
Combination of a hydrazonazo colouring matter having the general formula :-
COMBINATION OF A MOLECULE OF THE MONOAZO COLOURING MATTER
DERIVED FROM AMIDONAPHTHOLDISULPHONIC ACID 1.8.3.6 AND META-
DIAZOBENZOIC ACID WITH A MOLECULE OF a-DIAZONAPHTHALENE.
To the red colouring matter obtained by combining the diazo derivative of
13-7 kilos. of metaamidobenzoic acid with 32 kilos. of amidonaphtholdisulphonic
acid 1.8.3.6, is added the solution of diazonaphthalene derived from 14.3 kilos, of
a-naphthylamine, the said red colouring matter being in the form of a solution
containing carbonate of soda. The red colour of the mixture gradually changes
to blue. In 10 hours the combination is complete, and the colouring matter is
separated in the usual way. It dyes wool intense blue black.
The preparation of other diazo colouring matters is conducted in a similar
manner if, for the monoazo colouring matters used in Examples 12, 13 and 14, be
substituted the other monoazo colouring matters mentioned in the first paragraph
of this specification. Likewise for the simple diazo bodies (diazo benzol, a diazo-
naphthalene) indicated in Examples 12, 13 and 14'as being combined with mono-
azo colouring matters, may be substituted the diazo derivatives of the other.
monoamido compounds mentioned in the sixth paragraph of this specification.
Combination of a hydrazonazo colouring matter having the general formula :-
(SO,Na),
OH
.
Cio H
NH,
NNCH
CHENN
X
Y
(in which X indicates an aromatic radical for the hydrogen of which may be
partially substituted sulpho, carboxyl, hydroxyl, or nitro groups or chlorine,
while indicates hydrogen or än alkyl radical, phenyl or tolyl) with a' molecule
of one of the tetrazo, bodies mentioned in 'the second paragraph of this specification,
and union of the intermediate product obtained with a molecule of "one of the
bodies mentioned in the third paragraph.
derived from amidonaphthöldisulphonic acid 1.8.3.6 pparadiazobenzaldehyde
and phenylhydrazine, with a molecule of tetrazodiphenyl, and coupling of the
resulting intermediate product with a molecule of amidonaphthol disulphonic
acid 1.8.3.6.

page_text: The diazo derivative from 6-1 kilos. of paraamidobenzaldehyde is combined with
16 kilos. of amidonaphtholdisulphonic acid in acetic solution; when the com-
bination is effected, there are added to the acetic solution 5-4 kilos. of phenyl-
bydrazine, and the mixture is heated for 2 hours to 60° or 70° C. The red colour
of the solution gradually changes to blue. The product is then alkalised by
addition of carbonate of soda, cooled by ice and has added to it a solution of
tetrazodiphenyl derived from 9-2 kilos. of benzidine. In 2 hours the formation of
the intermediate product is complete, and it precipitates as black insoluble flakes.
The product is finally mixed with a solution of 16 kilos. of amidonaphthol-.
disulphonic acid 1.8.3.6 in water having carbonate of soda added to it. The
whole is left alone for a long time. It is then heated and the colouring matter is.
separated by adding salt, filtering &c. The new hydrazenpolyazo colouring matter
dyes cotton blue.
The operation is the same substituting for the hydrazonazo colouring matter in
this example the other hydrazonmonoazo colouring matters mentioned in the
seventh and eighth paragraphs of this specification. In preparing the intermediate
products may naturally be employed all the simple or compound tetrazo bodies
mentioned in the second paragraph of this specification, and these intermediate
products may be combined with any of the bodies mentioned in the third
paragraph.
Farther, if the hydrazonmonoazo colouring matters be acted on by a simple
diazo body derived from the monoamido compounds mentioned in the sixth
paragraph of this specification, according to the methods given in Examples 12, 13.
and 14, there will be obtained hydrazondisazo colouring matters specially
applicable to the dyeing of wool and silk.
Finally it is, to be understood that these hydrazondisazo and hydrazonpolyazo.
colouring matters may be prepared by condensing the aromatic hydrazines
mentioned in the eighth paragraph of this specification, in acetic solution with the.
disazo and polyazo colouring matters obtained as in Examples 1, 2 ani 3, and 12,
13 and 14, in solution, or upon the fibre.
Having now particularly described and ascertained the nature of my said inven-
tion and in what manner the same is to be performed I declare that what I
claim is :-
1. The manufacture of new disazo, trisazo and polyazo colouring matters from.
primary mono-azo colouring matters having the general formula

page_text: By making a molecule of the said monoazo colouring matters react on a
molecule of the intermediate products containing still a free diazo group,
which are obtained by the combination of a molecule of the tetrazo
compounds mentioned in the second paragraph of this specification with a
molecule of the bodies mentioned in the third paragraph.
By making a molecule of the said monoazo colouring matters react on a
molecule of the diazo derivatives of the monoamido compounds mentioned in
the sixth paragraph of this specification.
By substituting, in the processes stated in the preceding paragraphs a) b)
and c) for the monoazo colouring matters derived from the amidonaphthol-
sulphonic acids, 1.8.3.6, 1.8.4.6, and 1.5.3.7 and the diazobenzaldehydes,
the products resulting from the condensation of the said monoazo colouring
matters with the primary aromatic hydrazines, the secondary asymmetric
aromatic hydrazines, and the sulpho, carboxyl, nitrate and chlorined
derivatives of the primary aromatic hydrazines and the secondary
asymmetric aromatic hydrazines:-
By condensing with the aromatic hydrazines mentioned in the preceding
paragraph the colouring, matters obtained by the above processes a) b), c)
and derivatives of a monoazo colouring matter obtained by the combination
of ortho, meta or paradiazobenzaldehyde with an amidonaphtholdisulphonic
acid, 1.8.3.6, 1.8.4.6 or 1.5.3.7.
The new disazo, trisazo and polyazo colouring matters manufactured as above
th.
The intermediate products prepared as set forth in Claim 1 (a).
ABEL & IMRAY,
Agents for the Applicant.