Improvements in the Manufacture and Production of Azo Dyestuffs or Colouring Matters suitable for Dyeing Cotton.
Year: 1897

page_text: Date of Application, 30th Mar., 1897
Complete Specification Left, 30th Dec., 1897-Accepted, 26th Feb., 1898
Improvements in the Manufacture and Production of Azo Dyestuffs
or Colouring Matters suitable for Dyeing Cotton.
I, GEORGE WILLIAM JOHNSON, of 47, Lincoln's Inn Fields, in the County of London,
Patent Agent, do hereby declare the nature of this invention (which has been
communicated to me froin abroad by Kalle & Co., of Biobrich-on-Rhine, in the Empire
of Germany) to be as follows:-
This invention relates to the manufacture of new polyazo-colouring matters or
colouring matters suitable for use in dyeing unmordanted cotton and containing at least
one molecular proportion of a naphthalene derivative (amido-naphthol sulpho acid,
dioxynaphthalenesulpho acid, or metanaphthylenediamine sulpho acid), combined
with two molecular proportions of a dinzo compound. The shades produced on cotton
by means of these dyestuffs or colouring matters vary from blue to green and from
brown to black.
The constitution of the said new dyestuffs or colouring matters can be expressed
by the following general formulae :

page_text: such for instance as benzidine, tolidine, dianisidine, diamnidodiphenylamine, para-
phenylenediamine, and X represents the 1.8. amido naphthol-4.6. disulpho acid (K)
or the 1.8. dioxynaphthalene-4.6 disulpho acid (K).
D represents 1.3. naphthylene diamine 6. sulpho acid; R represents the diazo
derivatives of the mono amines usually employed (such for instance as diazobenzol,
nitrodiazobenzol, diazonapht balene diazobenzylsulpho acid, para diazodehydrothio-
toluol); C and C₁ represent any amine, phenol amidophenol, or any sulpho or carbo
derivative of the same or any azo colour, which can be combined with a diazo body.
In order to illustrate the manner in which this invention may be carried out I
give the following examples but the invention is not limited thereto.
14.6 kilos. of alpha-naphthylamine are dissolved in water, by means of 30 kilos. of
hydrochloric acid of 20° Bé. and diazotised by the addition of 6.9 kilos. of sodium
nitrite. The diazo compound formed is combined with 34.1 kilos. of the acid sodium
Balt of 1.8 amidonaphthol 4.6 disulpho acid (K) dissolved in 1000 litres of water.
After stirring for several hours sodium acetate is added to the mixture and then the
diazo solution obtained in the usual manner from 18-4 kilos. of benzidine is run into
the mixture whilst well agitated. After about au hour the formation of the inter-
mediate product is finished. It is then added to a solution of 1.3 naphthylenediamine
6 sulpho acid rendered alkaline by an excess of soda. After stirring for say 12 hours
the dyestuff is precipitated by means of common salt and is pressed and dried. It
dyes unmordanted cotton black.
By replacing the alpha naphthylamine if the example by dehydrotbio para toluidine
sulpho acid or para nitraniline, or amidobenzylsulpho acid, or amidosalicylic acid, or
other amine or a sulpho or carbo acid thereof, various other shades of black are
obtained. By employing other diamines instead of that of benzidine the shade of
the dyestuff or colouring matter is not greatly altered. If, instead of the 1.8
amidonaphthol 4.6 disulpho acid (K) the corresponding dioxynaphthalene disulpho
acid (K) be used, black dyestuffs are obtained having rather less affinity for
cotton
18.4 kilos. of benzidine are diazotized and added to an alkaline solution of
24-5 kilos. of 1.7 naphthylamine sulpho acid. After several hours the liquid is cooled
down to 0° Centigrade mixed with a solution of 6-9 kilos. of sodium nitrite and
acidulated by means of hydrochloric acid. The tetrazo compound formed is run into
a solution of the azo colour, obtained by combining para nitrodiazobenzol with 1.8
ainidonaphthol 4.6 disulpho acid in the presence of free mineral acid. On the
addition of an excess of sodium acetate an intermediate product is formed, which
separates from the liquid. As soon as this reaction is finished a solution of 25 kilos.
of 1.3 naphthylenediamine 6 sulpho acid and of an excess of soda is added. After
about 12 hours stirring the liquor is heated up and the dyestuff or colouring matter
is precipitated from the said liquor by adding common salt. It dyes cotton black.
If in Example 2, the unsymmetrical tetrazo compound obtained from benzidine
and 1.7 naphthylamine sulpho acid be replaced by the compound obtained from
benzidine and alpha naphthylamine or by the compound obtained from benzidine
and 2.8 amidonaphtol 6 sulpho acid (G) similar black dyestuffs are obtained, which
differ only with regard to solubility in water and intensity of shade. By using other
diamines instead of that of benzidine the shade is scarcely altered. Dyestuffs of
somewhat redder shade and having less affinity for the fibre are obtained if the
auidonaphtholdisulpho acid be replaced by the corresponding dioxynaphthalene-
disulpho acid,

page_text: The intermediate product prepared in the usual manner from 184 kilos. of
benzidine and 13.8 kilos. of salicylic acid is combined in alkaline solution with
24-5 kilos. of sodium salt of 1.6 (or 1.7) naphthylamine sulpho acid. The formation
of the dyestuff or colouring matter being finished, 7 kilos. of sodium nitrite are
added to the mass, which is then acidulated by means of hydrochloric acid. As soon
as the whole of the nitrite is used up, the diazo compound obtained is put into
reaction in alkaline solution with the azo colour formed by combining 34-1 kilos.
of 1.8 amidonaphthol 4.6 disulpho acid (K) with a molecular proportion of alpha
dinzo naphthalene in acid solution.
The new dyestuff or colouring matter partly separates from the liquid. After some
hours the mass is heated up and the dyestuff is completely precipitated by adding
cominon salt. It dyes unmordanted cotton brown.
By replacing the salicylic acid by other oxycarbonic acids or by using cther
paradiamines instead of those of benzidine, the shade of the dyestuff is not much
altered. Much deeper shades however are obtained with the products containing
2-8 amidonaphthol 6. sulpho acid (G) instead of the 1.7. naphthylamine sulphoacid.
EXAMPLE 5.
31.3 kilos. of the mixed azo dyestuff obtained from equal molecular proportions
of tetrazodiphenyl, salicylic acid and 1.3 naphthylene diamine 6 sulpho acid are acted
upon in aqueous alkaline solution by a diazosolution prepared in the usual manner
from 4.65 kilos. of aniline. After about 12 hours the formation of the dyestuff or
colouring matter is finished. It is precipitated from the heated combination liquid
by means of common salt. It dyes unmordanted cotton reddish-brown.
The same dyestuff is produced if the intermediate product prepared from molecular
proportions of tetrazo diphenyl and salicylic acid be put into reaction with an equal
molecular proportion of the nzo colour formed by combining diazobenzol with
1.3 naphthylenediamine 6 disulpho neid.
Instead of the intermediate product prepared from tetrazodiphenyl and salicylic
acid other similar compounds can be used for instance those obtained by combining
the tetrazodiphenyl or an other suitable tetrazo compound with equal molecular

page_text: proportions of 1.4 naphtholsulpho acid, or of 1.4 naphthylamine sulpho acid, or of
2.8 amidonaphthol 6. sulpho acid G, or of a mouoazo dye or colour suitable for the
purpose.
In this manner dyestuffs are obtained ranging in shade from blueish-red to
blueish-violet and black. Instead of the aniline in Example 5 other diazotised
monoamines can be used such as naphthylamine para nitraniline sulphanilic acid or
nonhthiania auid
The diazo solution prepared from 6-9 kilos. of para nitraniline is run into au
alkaline solution of 36-3 kilos. of the dyestuff or colouring matter prepared from
tetrazodiphenyl and two molecular proportions of 1.3 naphthylenediamine 6. sulpho
acid. After agitating for about 12 hours the formation of the new dyestuff or
colouring matter is completed. The mass is then heated up and the dyestuff is
precipitated by means of common salt. It dyes unmordanted cotton blueish-red.
A red more yellow in shade is obtained by using aniline instead of para nitraniline.
EXAMPLE 7.
The tetrazodiphenyl solution obtained from 184 kilos. of benzidine is put into
reaction, in the presence of an excess of soda, with the azo colour obtained by
combining 13-8 kilos. of paranitraniline and 23.8 kilos. of 1.3 naphthylenediamine
6. sulpho acid in acid solution. After the completion of the formation of the
jutermediate product so obtained an alkaline solution of 13-8 kilos. of salicylic acid
is added. The new dyestuff or colouring matter produced in this manner dyes
unmordanted cotton a maroon shade. If 2.8 amidonaphthol 6. sulphoacid (G) be
used instead of salicylic acid a violet cotton dyestuff or colouring matter is
produced.
Dated this 20th day of March 1807
JOHNSONS & WILLCOX,
47, Lincoln's Inn Fields, London, W.C., Agents.
Improvements in the Manufacture and Production of Azo Dyestuffs
or Colouring Matters suitable for Dyeing Ootton.
I, GEORGE WILLIAM JOHNSON, of 47, Lincoln's Inn Fields, in the County of London,
Chartered Patent Agent, do hereby declare the nature of this invention (which has
been communicated to me from abroad by Kalle & Co., of Biebrich-on-Rhine, 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 manufacture of new polyazo colouring matters, or
colouring matters suitable for use in dyeing unmordanted cotton, aud containing at
least one molecular proportion of a naphthalene derivative (amido-naphthol sulpho
acid, dioxynaphthalene sulpho acid, or meta-naphthylenediamine sulpho acid),
combined with two molecular proportions of a diuzo-compound. The shades produced
on cotton by means of these dyestuffs, or colouring matters, vary from blue to green
and from brown to black.

page_text: The constitution of the said new dyestuffs, or colouring matters, can be expressed-
by the following general formulae :-
In these general formulae P represents one of the diamines usually employed,
such, for instance, as benzidine, tolidine, dianisidine, diamidodiphenylamine, para-
phenylenediamine, and X represents the 1.8 amidonaphtol-4.6-disulpho acid (K) or
the 1.8-dioxynaphthalene-4.6-disulpho acid (K).
D represents 1.3-naphthylenediamine-6-sulpho acid; R represents the diazo.
derivatives of the monoamines usually employed (such for instance as diazobenzol,
nitrodiazobenzol, diazonaphthalene, diazobenzylsulpho acid, and para-diazodehydro-
thio-toluol); C represents any amine, phenol, amidophenol, or any sulpho- or carbo
derivative of the same, or any azo colour, which can be combined with a diazo
body.
In order to illustrate the manuer in which this invention may be carried ont I
give the following examples, but the invention is not limited thereto.
143 kilos. of alpha-naphthylamine are dissolved in water, by means of 30 kilos. of
hydrochloric acid of 20° Bé. and diazotised by the addition of 60 kilos. of sodium
nitrite. The diazo-compound formed is combined with 34:1 kilos. of the acid sodium
salt of 1.8 amidonaphthol-4.6-disulpho acid (K) dissolved in 1000 litres of water.
After stirring for several hours, sodium acetate is added to the mixture and then the
diazo solution, obtained in the usual manner from 184 kilos. of benzidine, is run into
the mixture whilst well agitated. After about an hour the formation of the
intermediate product is finished. It is then added to a solution of 1.3-naphthylene-.
diamine-6-sulpho acid, rendered alkaline by an excess of soda. After stirring

page_text: for say 12 hours the dyestuff is precipitated by means of cominon salt and is pressed
and dried. It dyes unmordanted cotton black.
By replacing the alpha-naphthylamine of the example, by dehydrothio-para-
toluidine sulpho acid, or para-nitraniline, or amido-benzylsulpho acid, or another
amine, or a sulpho, or carbo, acid thereof, various shades of black are obtained. By
employing other diamines instead of that of benzidine the shade of the dyestuff, or
colouring matter, is not greatly altered. If instead of the 1.8-amidonaphthol-4.6-
disulpho acid (K) the corresponding dievynaphthalene disulphe neid (!) be used,
black dyestuffs are obtained having rather less affinity for cotton.
black dyestuffs are obtained having rather less affinity for cotton.
EXAMPLE 2.
18.4 kilos. of benzidine are diazotized and added to an alkaline, solution of 24.5 kilos.
of 1.7-naphthylamine sulpho acid. After several hours the liquid is cooled down
to 0° Centigrado mixed with a solution of 6-9 kilos. of sodium nitrite and acidulated
by means of hydrochloric acid. The tetrazo compound formed is run into a solution
of the azo colour, obtained by combining para-nit rodiazobenzol with 1.8-amido-
naplitbol-4.6-disulpho acid in the presence of free mineral acid. On the addition
of an excess of sodium acetate an intermediate product is formed, which separates
from the liquid. As soon as this reaction is finished a solution of 25 kilos. of
1.3-naphthylenediamine-6-sulpho acid and of an excess of soda is added. After
about 12 hours stirring, the liquor is heated up and the dyestuff or colouring
matter is precipitated from the said liquor by adding common salt. It dyes cotton
black.
If in the Example 2, the unsymmetrical tetrazo compound obtained from benzidine
and 1.7-naphthylamine sulpho acid be replaced by the compound obtained from
benzidine and alpha-naphthylamine or by the compound obtained from benzidine and
2.8-amidonaphthol-6-sulpho acid (G) similar black dyestuffs are obtained, which
differ only with regard to solubility in water and intensity of shade. By using
other diamines, instead of that of benzidine, the shade is scarcely altered. Dyestuffs
of somewhat redder shade and having less affinity for the fibre are obtained, if the
amido-naphtholdisulpho acid be replaced by the corresponding dioxy-naphthalene
dianlubo said
The intermediate product prepared, in the usual manner, from 18.4 kilos. of
benzidine and 13-8 kilos. of salicylic acid is combined, in alkaline solution, with
24-5 kilos. of sodium salt of 1.6 (or 1.7) naphthylamine sulpho acid. The formation
of the dyestuff, or colouring natter, being finished, 7 kilos. of sodium nitrite are
added to the mass, which is then acidulated by means of hydrochloric acid. As soon
as the whole of the nitrite is used up, the diazo compound obtained is put into
reaction, in alkaline solution, with the azo colour formed by combining 34-1 kilos. of
1.8-amidonaphthol-4.6-disulpho acid (K) with a molecular proportion of alpha-diazo-
naphthalene in acid solution.
The new dyestuff, or colouring matter, partly separates from the liquid. After
some hours the mass is heated up and the dyestuff is completely precipitated by
adding common salt. It dyes unmordanted cotton brown. By replacing the
salicylic acid by other oxycarbonic acids, or by using other para diamines instead of
those of benzidine, the shade of the dyestuff is not much altered. Much deeper
shades however are obtained with the products containing 2.8-amidonaphthol-6-
sulpho acid (G) instead of the 1.7-naphthylamine sulpho acid.

page_text: upon, in aqueous alkaline solution, by a diazo solution prepared in the usual manner
from 4-65 kilos. of aniline. After about 12 hours the formation of the dyestuff or
colouring matter is finished. It is precipitated from the heated combination liquid
by means of common salt. It dies unmordanted cotton reddish brown. The dyestuff
can also be produced, and in a purer state, if the intermediate product prepared from
molecular proportions of tetrazo diphenyl and salicylic acid be put into reaction with an
equal molecular proportion of the azo colour formed by combining diazobenzol with
1.3-naphthylenediamine-6-sulpho acid.
The diazo solution prepared from 6.9 kilos. of paranitraniline is run into an alkaline
solution of 36-3 kilos. of the dyestuff, or colouring matter, prepared from tetrazo-
diphenyl and two molecular proportions of 1.3 naphthylenediamine-6-sulpho acid,
After agitating for about 12 hours the formation of the new dyestuff, or colouring
inutter, is completed. The mass is then heated up and the dye stuff is precipitated
by means of common salt. It dyes unmordanted cotton blueish-red. A red, more
yellow in shade, is obtained by using aniline instead of para-nitraniline.
EXAMPLE 7.
The tetrazodiphenyl solution obtained from 18.4 kilos. of benzidine is put into
reaction, in the presence of an excess of soda, with the azo colour obtained by
combining 13.8 kilos. of para-nitraniline and 23-8-kilos. of 1.3-naphthylenediamine-6-
sulpho acid in acid solution. After the completion of the formation of the intermediate
product so obtained, an alkaline solution of 13.8 kilos. of salicylic acid is added. The
new dyestuff, or colouring inatter, produced in this manner, dyes unmordanted cotton
a maroon shade. If 2.8-ainidonaphthol-6-sulpho acid (G) be used instead of salicylic
acid a violet colton dyestuff, or colouring matter, is produced.
Having now particularly described and ascertained the nature of the said inven-
tion and in what mauner the same is to be performed 1 declare that what I
claim is :-
1. The process of manufacturing poly-azo-colouring matters by combining one of
the usually employed tetrazolized para-diamines with one molecular proportion of a
mono-azo-colour formed by acid combination of 1.8-amido-naphthol 4.6-disulpho
acid (K) with a suitable diazo-compound and putting the intermediate body so

page_text: obtained into reaction with an equimolecular proportion of 1.3-naphthylene-diamine
6-sulpho acid.
2. The process of manufacturing poly-azo-colouring matters by combining the
assymetrical tetrazo-compounds, obtained by re-diazotizing the intermediate products
from one molecular proportion of one of the usually employed tetrazotized
para-diamines and one molecular proportion of alpha-naphthylamine or 1.6 or 1.7
naphthylaminesulpho-acid or 2.8-amido naphthol 6 sulpho acid (G) with one
inolecular proportion of a mono-azo-colour forined by acid combination of 1.8-amido-
naphthol 4.6 disulpho-acid (K) with a suitable diazo-compound, and one molecular
proportion of 1.3 naphthylenediamine 6 sulpho acid.
3. The process of manufacturing poly-azo-colouring matters by combining one of
the usually employed tetrazotized para-diamines first with one molecular proportion of
Balioylic or cresotinic acid and thon with one molecular proportion of 1.6 or 1.7
naphthylamine sulpho-acid or 2.8 amidonaphthol 6 sulpho-acid (G) re-dinzotizing the
body so formed and combining with one molecular proportion of a mono-azo-colour
obtained by acid combination of 1.8 amidonaphthol 4.6 disulpho-acid (K) with a
suitable diazo-body.
4. The process of manufacturing poly-azo-colouring matters by using in the
processes claimed in either of the preceding claiming clauses as mono-azo-colours
derived from 1.8 amidonaphthol 4.6 disulpho-acid (K) those compounds which are
obtained by combining the said 1.8 amidonaphthol 4.6 disulpho-acid (K) in acid
solution with one molecular proportion of the diazo dorivative of aniline, or of
alpha-naphthylamine, or of para-nitraniline or of amidobenzylsulpho-acid, or of
sulphanilic acid.
5. The process of manufacturing poly-azo-colouring matters by combining the
intermediate body formed from one molecular proportion of one of the usually
employed tetrazotized para-diamines, and one molecular proportion of salicylic acid
or 1.4 naphthylamine sulpho-acid or 1.4 naphtholsulpho-acid or 2.8 amidonaphthol
6 sulpho-acid (G) with an equimolecular proportion of a mono-azo-colour formed by
combining one molecular proportion of 1.3 naphthylenediamine 6 sulpho acid with
one molecular proportion of a suitable diazo-compound.
6. The process of manufacturing poly-azo-colouring matters by combining one
molecular proportion of one of the usually employed tetrazotized para-diamines with a
mono-azo-colour, obtained from one molecular proportion of 1.3 naphthylenediamine 6
sulpho-acid and one molecular proportion of a suitable diazo-body, and putting the
intermediate product so obtained into reaction with one molecular proportion of
salicylic acid or of 1.4 naphthylamine sulpho-acid or 1.4 naphtholsulpho-aoid or
2.8 amidonaphthol 6 sulpho-acid (G).
7. The process of manufacturing poly-azo-colouring matters by using in the
processes claimed in the preceding fifth and sixth claiming clauses as mono-azo-
colours derived from 1.3 naphthylenediamine 6 sulpho-acid those compounds which
are obtained by combining the said 1.3-naphthylenediamine 6 sulpho-acid with
an equimolecular proportion of the diazo-derivative of aniline, or of alphanaphthyl-
amine, or of sulphanilic acid or of naphthionic acid or of paranitraniline.
8. The new poly-azo colouring matters substantially such as are produced by the
processes herein before described and claimed by the preceding fourth and seventh
claiming clauses.