Improvements in the Manufacture of Colouring Matters from Amido- naphthol-sulphonic Acids.
Year: 1891

page_text: Date of Application, 16th Sept., 1891
Complete Specification Left, 15th June, 1892-Accepted, 16th July, 1892.
PROVISIONAL SPECIFICATION.
Improvements in the Manufacture of Colouring Matters from Amido-
naphthol-sulphonic Acids.
1, SYDNEY PITT, of Sutton, in the County of Surrey, Gentleman, (a commu-
nication to me from abroad by Leopold Cassella & Co., of Frankfort-on-Main,
in the Empire of Germany, Manufacturing Chemists,) do hereby declare the
nature of this invention to be as follows:-
I.
In pursuance of researches in connection with a process described in the
Provisional Specification No. 6972" a great number of new combinations have
been met with. The above mentioned process consists of the successive action
of two equivalents of diazoic bodies (identical or different) upon amidonaphthol-
disulphonic acid H. For the first combination the above named Specification
proposes to employ the nitranilines and amidoazobenzol and for the second one a
great number of different bodies.
a) In the first place similar results are obtained if aniline, amidobenzol-sulphonic
acid, naphtylamine, 3 naphtylamine ẞ sulphonic acid or the nitro toluidines are
used.
Example: 9.3 kilos aniline are diazotised and after the free muriatic acid has
been neutralised with sodium acetate, a neutral solution of 32 kilos amido-
naphtholdisulphonic acid H is slowly added. After the lapse of a few hours the
primary colouring matter is formed. Sodium carbonate is now added to the brown
solution until its colour changes to a blueish red, which shows the alkaline reaction
to have taken place, and then that quantity of diazobenzol which is obtained
from 9.3 kilos aniline, is allowed to run into the solution. The latter, which must
be kept alkaline, now changes to a deep blue colour and the colouring matter is
now precipitated with common salt. The colouring matter thus obtained dyes wool
a blueish black.
b) In the second place besides the amines already mentioned, the following
bodies may be used the diazoazoic bodies described in the Patent No. 9214
(deriving from the products of the reaction of a naphtylamine and diazosulphonic
acids) and amidocarboxylic bodies, such as amidobenzoic acid and amidosalicylic acid.
II.
Results of equal value are obtained by the above process if tetrazoic bodies are
used instead of diazoic bodies as second reagents.
The reaction of one equivalent of colouring matters, produced from amido-
naphtholdisulphonic acid H and diazoic bodies in acid solution, upon one
equivalent of a tetrazoic body, produces intermediate products of the following
constitution—
OH
NH, } CH.
(SO.H).
(N = N
NN
R¹
R - N = N→

page_text: is then added. The intermediate product separates in the shape of a black
precipitate. A solution of 15 kilos sodium salicylate is now added. After the
lapse of a few hours the reaction will be terminated and the coloring matter is then
precipitated with common salt. It dyes wool a dark green from an acid bath and
unmordanted cotton from a neutral or an alkaline bath.
If phenol or resorcine are substituted for the salicylic acid, green colouring
matters are obtained. The combinations with meta-phenylenediamine, meta-
toluylenediamine, meta-oxydiphenylamine and ẞ naphtylaminesulphonic acids
produce grey shades; whilst those with naphthols, naphtylamines, naphthol-
sulphonic acids and amidonaphtholsulphonic acids, (such as y or H acid) produce
blueish black to black shades."
Other paradiamines may take the place of benzidine, for instance: tolidine,
methylbenzidine, diamidoethoxydiphenyl or diamidodiphenol-ether.
III.
Mixed colouring matters are formed by combining the intermediate products
obtained from tetrazoic bodies and amidonaphtholdisulphonic acid H with:
resorcine, meta-toluylene-diamine, chrysoidines, Bismarck browns or meta-
oxydiphenylamine.
Example: The tetrazoic product of 18.2 kilos benzidine is added to the solution
of 36 kilos amidonaphtholdisulphonate H and 30 kilos sodium acetate in 400 litres
water. After the intermediate body has been formed, a solution of 30 kilos
Bismarck brown (Vesuvine) in 500 litres water is added. After a lapse of 12 hours
the colouring matter will have separated in the form of a brown precipitate. It
dyes unmordanted cotton a brown shade.
Combinations with the other bodies enumerated above produce violet black
shades.
Doted this 16th day of Santember 1801
"
COMPLETE SPECIFICATION.
Improvements in the Manufacture of Colouring Matters from Amido-
naphthol-sulphonic Acids.
I, SYDNEY PITT, of Sutton, in the County of Surrey, Gentleman, (a commu-
nication to me from abroad by Leopold Cassella & Co., of Frankfort on
Main, in the Empire of Germany, Manufacturing Chemists,) 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 :-
I.
In pursuance of researches in connection with a process described in Patent
No. 6972 a great number of new combinations have been met with. The above
mentioned process consists of the successive action of two equivalents of diazoic
bodies (identical or different) upon amidonaphtholdisulphonic acid H. For the
first combination the above named Specification proposes to employ nitraniline and
amidoazobenzol and for the second one a great number of different bodies.
a.) Similar and superior results are obtained if the acid H is first combined with
one equivalent of the diazo-derivatives of aniline, amidobenzolsulphonic acid,
ẞ naphtylamine, ẞ naphtylamine mono or disulphonic acid or the nitro
toluidines.
Example: 9.3 kilos aniline are diazotised and after the free muriatic acid has
been neutralised with sodium acetate, a neutral solution of 32 kilos amidonaphthol-
disulphonic acid H is slowly added. After the lapse of a few hours the primary
colouring matter is formed. Sodium carbonate is now added to the brown solution

page_text: until its colour changes to a blueish red, which shows the alkaline reaction to have
taken place, and then that quantity of diazobenzol, which is obtained from 9.3 kilos
aniline is allowed to run into the solution. The latter, which must be kept alkaline
now changes to a deep blue colour and the colouring matter is now precipitated
with common salt. The colouring matter thus obtained dyes wool a blueish
black.
b.) For the second combination with the acid H the following diazocompounds
may be used: the diazoazoic bodies described in Patent No. 9214% (deriving from
the products of the reaction of a naphtylamine and diazosulphonic acids) and
amidocarboxylic bodies, such as amidobenzoic acid and amidosalicylic acid.
Crest pro
phenols or amines.
CONIUNTU
group by may
Example: 13.8 kilos of paranitraniline are diazotised and added to an acid or
neutral solution of 32 kilos amidonaphtholdisulphonic acid H. When the reaction
is terminated the solution is made alkaline by addition of sodium carbonate and
that quantity of tetrazo-diphenyl, which is obtained from 18.4 kilos benzidine, is
then added. The intermediate product separates in the shape of a black
precipitate. A solution of 15 kilos sodium salicylate is now added. After the
lapse of a few hours the reaction will be terminated and the colouring matter is
then precipitated with common salt. It dyes wool a dark green from an acid bath
and unmordanted cotton from a neutral or an alkaline bath.
If phenol, cresol or resorcine are substituted for the salicylic acid, green colouring
matters are obtained. The combinations with metaphenylene-diamine, meta-
toluylenediamine, meta-amidophenol, meta-oxydiphenylamine and 3 naphtylamine-
sulphonic acids produce grey shades; whilst those with naphthols, dioxynaphtalenes,
aphtylamines, naphtholsulphonic acids, dioxynaphtalene-sulphoacids and amido-
naphtholsulphonic acids, (such as y or H acids) produce blueish black to black
Shades.
Other paradiamines may take the place of benzidine, for instance: tolidine,
methylbenzidine, diamidoethoxydiphenyl, diamidodiphenolether or p. phenylene-
Mixed colouring matters are formed by combining the intermediate products
obtained from tetrazoic bodies and amidonaphtholdisulphonic acid H with:
resorcine, meta-toluylenediamine, chrysoidines, Bismarck browns or meta-
oxydiphenyl-amine.
Example: The tetrazoic product of 18.2 kilos benzidine is added to the solution
of 36 kilos amidonaphtholdisulphonate H and 30 kilos sodium acetate in 400 litres
water. After the intermediate hody has been formed, a solution of 30 kilos
Bismarck brown (Vesuvine) in 500 litres water is added. After a lapse of 12 hours
the colouring matter will have separated in the form of a brown precipitate. It
dyes unmordanted cotton a brown shade.
Combinations with the other bodies enumerated above produce violet black
shades.

page_text: 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 process of producing new dis-azo-dyes by reacting with one molecule of
the diazoderivatives of aniline, amidoazobenzolmono- or disulpho acid, ẞ naphtyl-
amine naphtylaminemono- or disulpho acid. nitrotoluidines, upon one molecule of
amido-naphtholdisulpho acid H in an acid solution and combining the thus obtained
product in alkaline solution with a second molecule of a diazocompound substantially
as described.
2. The process of producing new dis-azo-dyes by using in the process of Patent
No. 6972 (Claim 7) or in the process of this present Specification (Claim 1) the
following diazo bodies for the second combination: a.) the diaz-azoic bodies
deriving from the products of the reaction of a naphtylamine and diazosulpho or
dinzocarboxylic acids. b.) the diazo derivatives of amidocarboxylic acids sub-
- stantially as described.
17.
3. The process of producing azo-dyes by combining one molecule of a dyestuff
produced from amidonaphtholdisulpho acid H and a diazo body in acid solution
with one molecule of a tetrazo derivative of a paradiamine in alkaline solution
and combining the thus obtained intermediate product with phenols or amines or
amido-phenolic bodies substantially as described.
4. The process of producing mixed azo-dyes by combining paratetrazo-bodies
with one equivalent of amidonaphtholdisulpho acid H in an alkaline solution and
one equivalent of resorcine, metatoluylenediamine, chrysoidine, or Bismarck
brown, substantially as described.
5. As new articles of manufacture the new colouring matters hereinbefore
-described.
Dated this 7th day of June 1892
CARPMAEL & Co.,
Agents for the Applicant.