A Process for the Production of Substituted Benzidines (Diamido- triphenyles) and Colors therefrom.
Year: 1890

page_text: Date of Application, 1st Sept., 1890
Complete Specification Left, 1st June, 1891-Accepted, 4th July, 1891
PROVISIONAL SPECIFICATION.
A Process for the Production of Substituted Benzidines (Diamido-
triphenyles) and Colors therefrom.
JOHN DAWSON of Kirkheaton Color Works near Huddersfield and ROBERT
HIRSON Ph.D. of Huddersfield do hereby declare the nature of this invention
to be as follows:-
It has often been observed that such phenoles in which the hydrogen-atom,
standing in paraposition to the hydroxyl-group, is substituted, are incapable of
combination with diazo compounds, or that such combination is only formed incom-
pletely and with difficulty. Such for instance is the behaviour of the diparadioxy-
diphenyl obtained from benzidine.
The formation of coloring matter however is remarkably easy and complete, if
one hydroxyl-group of the dioxydiphenyl is alkylated or, if a direct start is inade
with paraoxydiphenyl or its homologues or analogues. The manner in which the
coloring matters obtained from these combinations are transformed into substituted
benzidines (derivatives of the triphenyl) is shown by the following
EXAMPLE.
10 kilos. paraoxydiphenyl (which may be produced either according to Specifica-
tion 90800, or by the melting of diphenylsulpho acid with caustic soda), are dissolved
in 200 kilos. of water together with 4,5 kilos. of caustic soda and to this, when
cold, a diazobenzol solution is added, composed of 5,5 kilos. of aniline, 20 kilos. of
hydrochloric acid, 100 kilos. of water and 4,1 kilos. of nitrite of soda.
In a few minutes the azo compound has completely separated; it may be
obtained in beautiful yellow needles by crystallization with glacial acetic acid. It
is filtered off, pressed, dried and with an addition of 2 kilos. of caustic soda
dissolved in 80 kilos. of methylated spirit. Now 7,5 kilos of bromäthyl or 6,2 kilos.
of brommethyl or the corresponding quantity of chlorinethyl or -äthyl are added
and the solution heated for about 1 hour to 50 Centigrad. After cooling, the
alkylated azo compound crystallizes in red needles, sparingly soluble in hot alcohol.
It is filtered off and mixed with a solution of 20 kilos. of tin dichloride in 40 kilos.
of hydrochloric acid. When the color of the paste has turned completely white,
the mother liquor containing the tin is filtered off, the salt dissolved in as small a
quantity of hot water as possible and after filtering is precipitated by the addition
of neutral sulphate of soda.
In exactly the same way homologueous and analogueous bases will be obtained
by acting with other bases riz.:-orthotoluidine, paraxylidine, (amidoparaxyline),
a. napthylamine, orthoanisidine on paraoxydiphenyl, or by substituting for this
paraoxyphenylorthotolyl or paraoxyphenylalphanapthyl described in Specifica-
tion 90800 without substantially changing the properties of the resulting products.
Their sulphates are much more easily soluble in hot water than sulphate of benzidine,
and crystallize from it in shining needles. Their hydrochlorates are nearly insoluble
in water containing an excess of hydrochloric acid. The free bases are almost
insoluble in boiling water and could not be obtained in crystals.
A different result will be arrived at, if instead of using anilines and its homo-
logues, such of their sulpho acids are employed, in which the paraposition is not
taken up.
In this case the sulpho acids of the abovenamed benzidine derivative:
will be obtained. They possess the advantage that the coloring matters obtained by
combining them with nonsulphonated phenoles or amines are soluble in water while
such combinations in the case of benzidine are insoluble. The process by which

page_text: the aforenamed new bases or their sulpho neids may be converted into coloring
matters, capable of dying unmordanted cotton in a soap bath, follows in its broad
lines the methods given in numerous previous Specifications of which latent, 4415,
1884, may be considered as the prototype.
Generally speaking the colors obtained with napihylaminsulpho acids are
yellower, those obtained from naptholsulplio acids are redder than the corresponding
combinations of benziline.
Useful results have been obtained with metaanilinesulpho acid, napthionic acid,
betamapthylaminbetamonosulpho acid, betanaphylamideltamonosulpho acid, di-
methylanilinesulpho neid and methylnapthylaminesulpho acid, with salycilic acid,
resorcine, a napthol and a. sulpho acid, napthol and ẞ3. sulpho neid: with
chrysoidine and Bismark brown.
Likewise coloring matters may be formed by acting with one molecule of the
diazo-combination of one of the new bases on one molecule of one of the afore-
named chemicals and after combination has taken place, combining the intermediate
product thus formed with one molecule of another of the aforemained chemicals, a
method likewise described in numerous Patents, Patent 15290° 1885 being the
first in which the manufacture of such non-ymetrical coloring matters is
described.
Date this Uìth day of August 1800
JOHN DAWSON,
ROBERT HIRSCH, Ph.D.
COMPLETE SPECIFICATION.
A Process for the Production of Substituted Benzidines (Diamido-
triphenyles) and Colors therefrom.
We, Jons Dawsox of Kirkheaton Color Works near Huddersfield and
ROBERT Hinsen Ph.D. of Huldersfield 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 :-
It has often been observed that such phenoles in which the hydrogen-atom,
standing in paraposition to the hydroxyl group is substituted, are incapable of
combination with diazo compounds, or that such combination is only formed
incompletely and with difficulty. Such for instance is the behaviour of the
diparadioxydiphenyl obtained from benzidine.
The formation of coloring matter however is remarkably easy & complete, if
one hydroxyl-group of the dioxydiphenyl is alkylated or, if a direct start is made
with paraoxydiphenyl or its homologues or analogues. The manner in which the
coloring matters obtained from these combinations are transformed into substituted
benzidines (derivatives of the triphenyl) is shown by the following

page_text: hot alcohol. It is filtered off and mixed with a solution of 20 kilos. of tin dichloride
in 40 kilos of hydrochloric acid. When the color of the paste has turned com-
pletely white, the mother liquor containing the tin is filtered off, the salt dissolved
in as small a quantity of hot water as possible and after filtering is precipitated by
the addition of neutral sulphate of soda.
In exactly the same way homologneous and analogueous bases will be obtained
by acting with other bases, riz.:-orthotoluidine, paraxylidine, (amidoparaxylidine)
a napthylamine, ortho-anisidine, on paraoxydiphenyl, or by substituting for this
parnoxyphenylorthotolyl or paraoxyphenylalphanapthyl described in Specifica-
tion 9080 without substantially changing the properties of the resulting products.
Their sulphates are much more easily soluble in hot water, than sulphate of
benzidine, and crystallize from it in shining needles. Their hydrochlorates are
nearly insoluble in water containing an excess of hydrochloric acid. The free
bases are almost insoluble in boiling water an could not be obtained in crystals.
A different result will be arrived at if, instead of using aniline and its homo-
logues such of their sulpho-acids are employed, in which the paraposition is
not taken up.
In this case the sulpho-acids of the above named benzidine
derivatives will be obtained. They possess the advantage that the coloring matters
obtained by combining them with nonsulphonated phenoles or amines are soluble
in water while such combinations in the case of benzidine are insoluble. The
process by which the afore-named new bases or their sulpho-acids may be converted
into coloring matters capable of dyeing unmordanted cotton in a soap bath, follows
in its broad lines the methods given in numerous previous Specifications of which
Patent 4415 1884, may be considered as the prototype.
Generally speaking the colors obtained with napthylaminesulpho acids are
yellower, those obtained from naptholsulpho acids are redder, than the corre-
sponding combinations of benzidine.
Useful results have been obtained with meta-aniline-sulpho acid, napthionic acid,
betanapthylamidobetamonosulpho acid, betanapthylamindeltamonosulpho acid, di-
methylanilinesulpho acid and methylnapthylaminesulpho acid with salycilic acid,
resorcine, a napthol and a sulpho acid, ẞ napthol, and ẞ sulpho acid with
chrysöidine and Bismarck brown.
Likewise coloring matters may be formed by acting with one molecule of the
diazo-combination of one of the new bases on one molecule of one of the afore-
named chemicals, and after combination has taken place, combining the inter-
mediate product thus formed with one molecule of another of the afore-named
chemicals, a method likewise described in numerous Patents, Patent 15296* 1885
being the first Patent in which the manufacture of such nonsymetrical coloring
matters is described.
Having now particularly described and ascertained the nature of my said
invention and in what manner the same is to be performed, I declare, that what I
claim, is
(1) The production of substituted benzidines (diamidotriphenyles) from para-
oxydiphenyl substantially as hereinbefore described.
(2) The production of azo coloring matters from the said substituted benzidines
(diamidotriphenyles) as here substantially as herein before mentioned.
1001
JOHN DAWSON.
ROBERT HIRSCH.