The Production or Manufacture of Colouring Matters, and Materials therefor. COMPOUND FROM NITROSO ETHYL-BENZYL-ANILINE SULPHO ACID AND SODIUM THIOSULPHATE
Year: 1893

page_text: Date of Application, 4th Mar., 1893
Complete Specification Left, 1st Dec., 1893-Accepted, 6th Jan., 1894
PROVISIONAL SPECIFICATION.
[Communicated from abroad by THE FARBENFABRIKEN vormals FRIEDRICH
BAYER & Co., of Elberfeld, in the Empire of Germany.]
The Production or Manufacture of Colouring Matters, and Materials
therefor.
I HENRY EDWARD NEWTON of The Office for Patents, 6 Bream's Buildings,
Chancery Lane in the County of London, Patent Agent, do hereby declare the
nature of this invention to be as follows:-
-
My foreign correspondents have found that on adding two molecular proportions
of sodium thio sulphate, dissolved in water, to a solution which is prepared by
dissolving one molecular proportion of a nitroso compound of tertiary or secondary
aromatic amines, or substituted tertiary or secondary amines, and acidulated by
means of two molecular proportions of acetic acid, and subsequently heating the
resulting liquid to the boiling point, the original yellow color of the solution soon
disappears without sulphur being separated. After a short time, the liquid shows
a color which is slightly brownish. The nitroso compound employed is thereby
converted into a new product, which my foreign correspondents believe possesses,
according to its chemical behaviour as hitherto ascertained, the following
| composition :—
THIO COMPOUND FROM NITROSO ETHYL-BENZYL-ANILINE SULPHO ACID AND
SODIUM THIOSULPHATE.
32 parts of the sodium salt of nitrosoethylbenzylaniline sulpho acid are dissolved
in 36 parts of acetic acid (containing 33 per cent. of pure acid), and the resulting
solution is added to a solution prepared by dissolving 50 parts of sodium thio
sulphate in 200 parts of water. The liquid is then heated to boiling, until the
original pure yellow color has become fawn colored. The solution thus obtained,
which contains the thio condensation product, may be employed directly for the
production of dye stuffs, or the said thio compound can be previously isolated from
the reaction mixture in any suitable manner.
If, in the foregoing example, the nitroso ethyl benzyl aniline sulpho acid is

page_text: replaced by the corresponding quantities of the nitroso compounds derived from
other tertiary amines, or from secondary amines, or by the equivalent quantities of
the nitroso derivatives of substituted tertiary or secondary amines, the reaction
proceeds in a similar manner, thio condensation products being likewise formed.
In the Specification of application for Letters Patent No. 825, dated
13th January 1893, a process for producing blue coloring matters suitable_for
dyeing by means of mordants, is described by my foreign correspondents. This
process consists in reacting with the nitroso compounds of secondary or tertiary
aromatic amines, on beta naphthoquinone sulpho acid (1:2:4), or betanaphtho-
hydroquinone sulpho acid, or the corresponding thio sulpho acids, with or without
the presence of salts of thio sulphuric acid.
My foreign correspondents have now found, that such coloring matters can be
obtained with greater ease, if the above-named condensation products from nitroso
derivatives of substituted or not substituted secondary or tertiary amines, are
allowed to act on the last named sulpho or thiosulpho acids of beta naphthoquinone
or betanaphthohydroquinone. The method of producing these coloring matters by
means of the new process, may be illustrated by the following example, the parts
being by weight.
DYE-STUFF FROM BETANAPHTHOQUINONE SULPHO ACID (1:24), AND THE
THIO COMPOUND OBTAINABLE AS DESCRIBED IN THE FOREGOING FIRST
EXAMPLE.
The solution prepared as described in the above first example, by dissolving
32 parts of the sodium salt of nitroso-ethyl-benzylaniline sulpho acid in 36 parts of
acetic acid (33 per cent.), adding 50 parts of sodium thio sulphate in a 25 per cent.
watery solution, and heating the resulting liquid until the original yellow color has
disappeared, is mixed without delay with 28 parts of the potassium salt of
betanaphthoquinone sulpho acid. The formation of the dye stuff begins immediately,
and on further heating, the coloring matter separates in crystals, shewing a
bronze-like lustre. When the formation is complete, the dye stuff is filtered off.
In a similar manner to that described in the above second example, the analogous
coloring matters can be obtained, if the product resulting from nitroso ethyl-
benzylaniline sulpho acid and sodium thio sulphate, is replaced by other thio
products derived from the nitroso derivatives of other tertiary amines, or of secondary
amines, or substitution products of tertiary and secondary amines, with salts of thio
sulphuric acid, and if these thio condensation products are allowed to act on beta
napthoquinone sulpho acid (1:2:4).
Similar dye stuffs result if, in place of the latter acid, the following products,
viz., beta naphthohydroquinone sulpho acid, betanaphthoquinone thio sulpho acid,
betanaphthohydroquinone thio sulpho acid are employed, and allowed to act on
the thio condensation products from nitroso derivatives of substituted or not
substituted tertiary or secondary amines, and salts of thio sulphuric acid.
My foreign correspondents have also found, that in place of the last named acids
(betanaphthoquinone sulpho acid, beta naphthohydroquinone sulpho acid, beta-
naphthoquinone thio sulpho acid, betanaphthohydroquinone thio sulpho acid),
analogous sulpho acids, or thio sulpho acids, derived from substituted or not
substituted naphthoquinone, or naphthohydroquinone, can likewise be used,―dye
stuffs being produced which also possess technical value.
My foreign correspondents have described, in the above first example, one
practical method for producing the condensation product from nitroso ethyl
benzylaniline sulpho acid and sodium thio sulphate. In the production of this
substance and analogous compounds, of course, they do not limit themselves to the
directions given in the said example, for the latter can be varied. Variations or
modifications can also be made in the production of dye stuffs from the said thio

page_text: condensation products, the method described in the foregoing second example being
likewise capable of variation or modification.
Dated this 4th day of March 1802
NEWTON & SON,
Agents for the Applicant.
COMPLETE SPECIFICATION.
The Production or Manufacture of Colouring Matters, and Materials
therefor.
I, HENRY EDWARD NEWTON of The Office for Patents, 6 Bream's Buildings,
Chancery Lane in the County of London, 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:-
My foreign correspondents have found that, on adding two molecular proportions
of sodium thio-sulphate, dissolved in water, to a solution prepared by dissolving
one molecular proportion of a nitroso-compound of a tertiary or secondary aromatic
amine, or substituted tertiary or secondary amine, acidulated with two molecular
proportions of acetic acid, and subsequently heating the resulting mixture to the
boiling point, the original yellow colour of the solution soon disappears, without
sulphur being separated. After a short time, the liquid is of a slightly brownish
colour. The nitroso compounds used are converted into alkylated paraphenylene-
diamine thio sulphonic acids, or substitution derivatives thereof, but probably
intermediate products are formed during this process, to which my foreign corre-
spondents ascribe the following formula :-
THIOSULPHONIC
ETHYL-BENZYL-ANILINE
ACID OBTAINED FROM NITROSO
SULPHONIC ACID AND SODIUM THIOSULPHATE.
34-2 parts of the sodium salt of nitroso ethyl benzyl aniline sulphonic acid
(1 molecular proportion) are dissolved in 200 parts of water, together with 36 parts
of acetic acid (containing 33 per cent. of pure acid, and corresponding to 2 molecular
proportions), and the resulting solution is added to a solution prepared by dissolving
50 parts of sodium thiosulphate (2 molecular proportions) in 200 parts of water.
The liquid is then heated to boiling, until the original pure yellow colour becomes

page_text: a fawn colour. The solution thus obtained, containing the thio sulphonic derivative
of paramidoethylbenzylaniline sulphonic acid, may be directly used for the
production of dye stuffs.
A solution of the analogous thiosulphonic derivative of paramidomethylbenzyl-
aniline sulphonic acid is formed, if, instead of sodium nitrosoethylbenzylaniline
sulphonate, the corresponding quantity of the sodium salt of nitrosomethylbenzyl-
anilinesulphonic acid be used.
These thiosulphonic acids, derived from paramido alkylbenzylaniline sulphonic
acids, are very soluble in water, and therefore cannot be easily isolated in a pure state.
Similar products are obtained from nitrosoalkyldiphenylamine sulphonic acid or
the like.
If the corresponding quantity of nitrosodimethylaniline hydrochloride be sub-
stituted for the sodium salt of nitrosoethylbenzylaniline sulphonic acid used in the
above first example, paramidodimethylaniline thiosulphonic acid (dimethyl-para-
phenylenediamine thio sulphonic acid) is obtained.
sulphonic acid.
Nitrosodiethylanilinehydrochloride yields diethylpara phenylenediamine-thio
Nitrosomonomethyl-orthotoluidine is converted by this process into amido-methyl-
ortho-toluidine thio sulphonic acid, which forms granular crystals, and has properties
which are in general similar to those possessed by the said thio sulphonic acids of
amido-dimethylaniline and amido-diethylaniline.
In the Specification of application for Letters Patent No. 825, dated
13th January 1893, a process for producing blue coloring matters, suitable for
dyeing by means of mordants, is described by my foreign correspondents. This
process consists in causing the nitroso compounds of secondary or tertiary aromatic
amines, or substituted secondary or tertiary amines, and alpha, beta, naphtho-
quinone alpha, monosulphonic acid, or alpha, beta, naphthohydroquinone alpha,
monosulphonic acid, to interact in the presence of salts of thio sulphuric acid.
My foreign correspondents have now found, that these colouring matters can be
obtained with greater case, if the above described alkylated paraphenylenediamine
thio sulphonic acids, or substituted alkylated paraphenylenediamine thio sulphonic
acids, are allowed to act on the said sulphonic acid of alpha, beta, naphthoquinone.
The method of producing these colouring matters by means of the new
process, may be illustrated by the following example, the parts being by weight.
DYESTUFF FROM ALPHA, BETA, NAPHTHOQUINONE-ALPHA, SULPHONIC ACID,
AND THE THIOSULPHONIC ACID OBTAINABLE AS DESCRIBED IN THE
FOREGOING FIRST EXAMPLE.
The
The solution prepared as described in the above first example, by dissolving
34.2 parts of the sodium salt of nitroso ethyl benzyl-aniline sulphonic acid in
200 parts of water and 36 parts of acetic acid (33 per cent.), adding 50 parts of sodium
thio sulphate in 200 parts of water, and heating the resulting liquid, until the original
yellow colour has disappeared, is mixed without delay with 28 parts of the
potassium salt of alpha beta₁ naphthoquinone alpha, sulphonic acid.
formation of the dyestuff immediately begins, and, on heating the liquid during
several hours, at from 80 to 100 degrees centigrade, the colouring matter separates
in crystals shewing a bronzelike lustre. When the formation of the dyestuff is
complete, it is filtered off. The product is identical with the dyestuff obtainable from
alpha, beta, naphthoquinone alpha, sulphonic acid, or alpha, beta naphthohydro-
quinone-alpha-sulphonic acid, and nitrosoethylbenzylaniline sulphonic acid, in the
presence of thiosulphates, by means of the process described in the Specification of
application for Letters Patent No. 825, dated 13th January 1893.
The analogous colouring matters can be obtained in a manner similar to that
described in the above second example, if, in place of thio sulphonic acid formed

page_text: from nitroso-ethyl-benzyl-aniline sulphonic acid and sodium thio sulphate, other
thiosulphonic acids, such as are obtainable from nitroso derivatives of tertiary or
secondary amines, or substituted tertiary and secondary amines, and salts of thio-
sulphonic acid, are used, and these thiosulphonic acids are allowed to act on alpha,
beta, naphthoquinone-alpha, sulphonic acid.
My foreign correspondents have also found, that in place of the last named acid
(alpha beta-naphthoquinone-alpha, sulphonic acid), other sulphonic acids derived
from alpha, beta, naphthoquinone can be used, dye-stuffs being produced which are
also of technical value.
In order to illustrate the process of producing colouring matters from the last
named sulphonic acids and the above described thiosulphonic acids, the following
example is given, the parts being by weight.
DYE-STUFF FROM DIMETHYL-PARA-PHENYLENE DIAMINE THIOSULPHONIC
ACID AND ALPHA BETA, NAPHTHOQUINONE BETA, SULPHONIC ACID.
25 parts of dimethyl-para-phenylene diamine thiosulphonic acid are dissolved in
about 750 parts of hot water, to which 25 parts of crystallised sodium acetate are
added. 28 parts of the potassium salt of alpha, beta, naphthoquinone beta,
sulphonic acid, dissolved in about 200 parts of water, are then added, and the liquid
is heated during several hours, at from 70 to 100 degrees centigrade, until the
condensation is finished. The colouring matter separates in crystals possessing
metallic lustre. It probably possesses the following formula :-
--
This colouring matter is very similar to the dyestuff obtainable by sulphonation
of the product from nitrosodimethylaniline sodium thiosulphate, and a Bi-naphtho-
quinone-a, sulphonic acid. Both produce pure blue shades on wool mordanted with
chromium salts. The analogous colouring matter obtained from diethyl-p-phenylene
diamine thiosulphonic acid, and ai 31 naphthoquinone-6-sulphonic acid, yields blue
shades having a somewhat more greenish hue on wool mordanted with chromium
salts.
If the sulpho-benzylmethyl-p-phenylene diamine thiosulphonic acid is condensed
with a B-naphthoquinone--sulphonate of potassium, a colouring matter is formed
which yields pure blue shades on wool mordanted with chromium fluoride.
The analogous dyestuff from sulpho-benzylethyl-para-phenylene diamine-thio-
sulphonic acid (the thiosulphonic acid of paramidoethyl benzylaniline sulphonic
acid) produces somewhat greener shades.
-
On condensing paramidomethyl-orthotoluidine thiosulphonic acid with the
potassium salt of alpha, beta, naphthoquinone-beta,-sulphonic acid, a dye-stuff is
obtained which dyes wool mordanted with chromium fluoride, blue shades somewhat
redder than those produced by the analogous colouring-matter from dimethyl-para-
phenylene diamine thiosulphonic acid.
The dye stuffs resulting from alpha, beta, naphthoquinone beta-monosulphonic
acid (obtainable from the corresponding alpha,-amido-beta, naphthol beta, sulphonic

page_text: acid, by means of the process described in the Berichte der Deutschen Chemischen
Gesellschaft, volume 24, page 3157), differ in being somewhat more soluble from the
colouring matters derived from alpha, beta-naphthoquinone-beta, sulphonic acid,
whilst the colouring-matters formed from alpha, beta, naphthoquinone alpha,
sulphonic acid generally yield redder shades, and are more difficultly soluble. The
said alpha, betai naphthoquinone alpha, monosulphonic acid can be prepared by
oxidising one molecular proportion of alpha, amido-beta-naphthol-alpha, sulphonic
acid, with one molecular proportion of bromine, in the presence of a suitable solvent
or diluent. The potassium salt of the said alpha beta,-naphthoquinone alpha-
monosulphonic acid, is precipitated in the form of orange-yellow crystals, on adding
potassium chloride to the liquid, after the oxidation has been effected.
When condensed with dimethyl para-phenylenediamine thiosulphonic acid, the
alpha, beta, naphthoquinone beta, alpha, disulphonate of potassium yields a
colouring matter which produces pure blue shades on wool mordanted with
chromium fluoride. The potassium salt in question can easily be obtained by
oxidising one molecular proportion of alpha, amido beta, naphthol beta, alpha
disulphonic acid with one molecular proportion of bromine, in the pressure of a
suitable solvent or diluent, and subsequently adding potassium chloride to the
liquid thus obtained. This potassium salt forms orange-coloured, readily soluble
crystals.
On allowing alpha, beta-naphthoquinone-alpha, alpha, disulphonic acid, or salts
thereof, to act on dialkylpara-phenylenediamine thiosulphonic acid, or the like, the
same dye-stuffs are formed as are obtained by means of alpha₁ beta, naphtho-
quinone alpha-sulphonic acid, as the sulphonic group in the position alpha, is split
off during the condensation. The aforesaid alpha, beta, naphthoquinone alpha,
alpha, disulphonic acid, can be produced by reducing the azo dye-stuffs derived
from alpha, naphthol-alpha, alpha-disulphonic and oxidising the amido-alpha,
naphthol alpha, alpha, disulphonic acid, with one molecular proportion of bromine.
It is preferably salted out by means of potassium chloride. The resulting
potassium salt forms beautiful orange-red crystals which dissolve with difficulty in
water in presence of potassium chloride.
In the above second and third examples, my foreign correspondents have
described distinct methods of producing colouring matters from alkylated para-
phenylene diamine thiosulphonic acids or substitution derivatives thereof.
However, they do not limit themselves to the directions above given, as these can
be varied without the nature of this invention being altered by such modifi-
cations.
Having now particularly described and ascertained the nature of the said inven-
tion and in what manner the same is to be performed (as communicated to me
from abroad), I declare that what I claim is :-
1. The production of alkylated paraphenylenediamine thiosulphonic acids, or
substitution derivatives thereof, by heating the nitroso derivatives of secondary or
tertiary aromatic amines, or substitution products thereof, with a thio-sulphuric
salt, in the presence of acetic acid, or agents acting in a similar manner.
2. The process for producing dimethyl para phenylenediamine thiosulphonic
acid, diethylpara-phenylenediamine thiosulphonic acid, paramidomono-methylortho-
toluidinethiosulphonic acid, paramidomonoethylorthotoluidine thio sulphonic acid,
sulphobenzyl methyl para-phenylenediamine thiosulphonic acid, sulphobenzylethyl
para phenylene-diaminethiosulphonic acid, sulpho para-midomethyldiphenylamine
thiosulphonic acid, or sulphoparamidoethyldiphenylamine thiosulphonic acid,
which process consists in heating one molecular proportion of the nitroso derivatives
of respectively dimethylaniline, diethylaniline, monomethyl-ortho-toluidine, mono-
ethyl-ortho-toluidine, methylbenzylaniline sulphonic acid, ethylbenzylaniline-
sulphonic acid, methyldiphenylaminesulphonic acid, or ethyldiphenylaminesulphonic
acid, with two molecular proportions of sodium thiosulphate in the presence of two
molecular proportions of acetic acid.

page_text: 3. The production of colouring matters from alkylated para phenylenediamine
thiosulphonic acids, or substitution products thereof, and certain sulphonic acids of
alpha, beta, naphthoquinone.
4. The process for producing dye-stuffs, which process consists in condensing one
molecular proportion of dimethyl-para-phenylene diamine thio sulphonic acid,
diethyl-para-phenylenediamine-thiosulphonic acid, paramidomono-methyl-ortho-
toluidine thio sulphonic acid, paramidomonoethylortho-toluidine thio sulphonic acid,
sulphobenzylmethyl para-phenylene diamine thio sulphonic acid, sulphobenzyl-
ethyl paraphenylene diamine thio sulphonic acid, sulphoparamidomethyldiphenyl-
amine thiosulphonic acid, or sulpho paramido ethyldiphenylaminethiosulphonic acid,
with one molecular proportion of an alkaline salt of alpha, beta, naphthoquinone
alpha, monosulphonic acid, alpha, beta, naphthoquinone-beta,-monosulphonic acid,
alpha, beta, naphthoquinone beta, monosulphonic acid, alpha, beta, naphthoquinone-
alpha-sulphonic acid, alpha, beta, naphthoquinone alpha, alpha, disulphonic acid,
or alpha, beta, naphthoquinone beta, alpha-disulphonic acid.
5. As new products of manufacture, the new colouring matters produced
by the processes hereinbefore defined or by any other way affording the same
result.
Dated this 20th dow of November 1802
NEWTON & SON,
Agents for the Applicant.