Year: 1897

page_text: 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 discovered some time ago, that acid dye-stuffs of the
triphenylmethane series, capable of resisting the action of alkalies, could be obtained
by condensing alkylated diamidobenzhydrols with meta-sulphanilic acid, or analogous
acids of the benzene series containing the amido group in the meta position to the
sulphonic group, converting the leuco-compounds thus formed into so-called sulphinic
sulphonic acids (such process consisting in acting with sulphurous acid and copper
powder on the diazo derivatives of the first-named leuco compounds), and finally
oxidizing the said sulphinic sulphonic acids, disulphonic acids of malachite green dye-
stuffs being thus produced.
My foreign correspondents have now found, that the process above referred to, can
also be applied to those leuco compounds which result from the condensation of
alkylated diamidobenzhydrols with naphthylamine sulphonic acids, and that dye-
stuffs of special value are obtained from such leuco compounds as contain the amido
group of the naphthalene nucleus in the ortho position to the methane carbon. The
last-defined leuco products are produced by condensing alkylated diamido benzhydrols
with those naphthylamine sulphonic acids which, when combined with diazo com-
pounds; yield azo products containing the azo group in the ortho position to the
amido group. Such naphthylamine sulphonic acids are, for instance, alpha, alpha,
naphthionic acid, alpha,, alpha, naphthionic acid, alpha, naphthylamine alpha, beta.
disulphonic acid; but analogous sulphonic acids of the naphthalene series can also be
used..
In order to illustrate the process, my foreign correspondents give the following
example, which is merely typical. The parts are by weight.

page_text: able, and a test portion of the mixture clearly dissolves in sodium carbonate solution.
At this stage, the greenish-yellow solution produced is allowed to cool, the condensa-
tion product being thus separated in the form of slightly yellow crystals. According
to the researches of my foreign correspondents, it has the following formula, viz. :-
Such a quantity of this condensation product as corresponds with 7 parts of sodium
nitrite is dissolved in 400 parts of water and 100 parts of sulphuric acid (66 degrees
Baumé), and the icy-cold solution formed (while being strongly stirred) is diazotised
by means of a solution in water of 7 parts of sodium nitrite., The diazo solution is
then allowed to flow into a liquid obtained by dissolving 20 parts of, sulphur dioxide
in 200 parts of water, to which are added 10 parts of freshly prepared copper
powder, taking care that the temperature does not rise above zero, Centigrade, and
that the mixture is well stirred. As soon as nitrogen is no longer evolved, the
whole mass, which contains the sulphinic sulphonic acid in. the form of crystals, is
heated to about 25 degrees Centigrade, in order to redissolve the said sulphinic
sulphonic acid. After removing the copper powder by filtration, the sulphinic
sulphonic acid is precipitated from the filtrate by allowing the latter to cool, and by
adding sodium sulphate. It separates, in the form of its sulphate, as colorless
crystals, and is subsequently converted into the neutral sodium salt. 56.8 parts of
the latter sodium salt are dissolved in 400.parts of water, and a solution of 11 parts
of potassium permanganate is allowed to flow into the said solution, which is cooled
and well stirred: After the oxidation is finished, the manganese dioxide thus formed
is filtered off, and the excess of alkali contained in the filtrate is- neutralised!.. The
resulting solution of the disulphonic acid is finally oxidised in, the well-known
manner by means of lead dioxide, after adding the calculated quantity of acid. The
finished dye-stuff (after removing the lead) is isolated by salting out. It forms
brownish crystals, and produces clear greenish-blue and even shades, when dyed on
wool in acid baths. The shades thus obtained are fast against the action of
alkalies.
The process illustrated by the above example proceeds in a similar manner, if the
condensation product resulting from tetramethyldiamido benzhydrol and alpha, alpha,
naphthylamine sulphonic acid, is replaced by other analogous leuco compounds
containing the amido group in the ortho position to the methane carbon, as herein-
before described.

page_text: My foreign correspondents do not intend to limit themselves to the particulars
given in the above example, which is merely typical, as the directions contained
therein can be varied within wide limits.
DOL
T1005
NEWTON & SON,
Agents for the Applicant.
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 :-
In the Specification of Letters Patent No. 3452%, my foreign correspondents
have described a process for producing acid dyestuffs of the triphenylmethane series,
capable of resisting the action of alkalies,, which process consiste in condensing
alkylated diamidobenzhydrols with metasulphanilic acid, or analogous acids of the
benzene series, containing the amido group in the meta position to the sulphonic
group; converting the leuco compounds thus formed into so-called sulphinic sul-
phonic acids (such process consisting in acting with sulphurous acid and copper
powder on the diazo derivatives of the first named leuco compounds); and finally
oxidising the said sulphinic sulphonic acids,-sulphonic dyestuffs of the malachite
green.series being thus produced.
My foreign correspondents have now found that the process above referred to can
also be applied to those leuco compounds which result from the condensation of
alkylated diamidobenzhydrols with alphanaphthylamine sulphonic acids, and contain
the amido group of the naphthalene nucleus in the ortho position to the methane
carbon, greenish-blue to blue dyestuffs of high value being thus obtained. The
last-defined leuco products are produced by condensing alkylated diamidobenzhydrols.
with those alphanaphthylamine aulphonic acids which, when combined with diazo
compounds, yield azo products containing the azo group in the ortho position to the
amido group. Such naphthylamine sulphonic acids are, for instance, alpha, alpha,
naphthionic acid, alpha, alpha, naphthionic acid, alpha, naphthylamine alpha, beta.
disulphonic acid, alpha, naphthylamine-alpha, beta, disulphonic acid.
Of course
analogous sulphonic acids of the naphthalene series can be likewise used.
In order to illustrate the process, my foreign correspondents give the following.
example, which is merely typical! The parts are by weight.
A hot solution of 24.5 parts of the sodium salt of 15 naphthylaminsulphonic acid
in 50 parts of water is stirred into a liquid prepared by dissolving 27 parts of tetra-
methyldiamidobenzhydrol in a solution of 20 parts of sulphuric acid (66 degrees
Baumé) in 500 parts of water.
.
The mixture is heated at about 80 degrees Centigrade, until the hydrol used! is.no
longer distinguishable, and a test portion of the mixture clearly dissolves in sodium
carbonate solution. At this stage, the greenish-yellow solution is allowed to cool, and
the condensation product separates in the form of slightly coloured crystals, which
can be completely purified by a recrystallisation by means of hot dilute sulphuric

page_text: acid. According to the researches of my foreign correspondents, this condensation
product has the following formula, viz. :-
Such a quantity of this product, as corresponds with 7 parts of sodium nitrite is
dissolved in 400 parts of water and 100 parts of sulphuric acid (60 degrees Batimé),
and the icy-cold solution, while being strongly stirred, is diazotised by means of a
solution in water of 7 parts of sodium nitrite. Subsequently, 20 parts of sulphur
dioxide are introduced into the diazo solution, and then 15 parts of freshly prepared
copper powder,.in the shape of a paste, are added, taking care that the temperature
does not rise above zero Centigrade, and that the mixture is well stirred. When
nitrogen is no longer evolved, 200 parts of finely pulverized common salt are added
to the mass, which contains the sulphinic sulphonic acid in the form of crystals.
After allowing the mixture to stand for a while, the sulphinic sulphonic acid is
separated from the liquid by filtration, and is subsequently washed with a common
salt solution.
The residue remaining on the filter is treated with. a sodium carbonate solution,
and the solution thus obtained' is separated from the undissolved copper powder by
filtration.
On acidulating this solution by the addition of a mineral acid, the free sulphinic
sulphonic acid is precipitated in the shape of nearly colorless crystals.
52.4 parts of this acid are dissolved in a solution of 8 parts of sodium hydroxide
in 500 parts of water, and a sodium hypochlorite solution containing. 7-1 parts of
active chlorine is allowed to flow slowly into the said solution, which is well cooled
and stirred: Thus, the sulphinic group is transformed into the sulphonic group.
After neutralizing, the solution is mixed with 100 parts of a 50 per cent. acetio
acid, and 10 parts of sulphuric acid (66 degrees Baumé); and 160 parts of a lead
dioxide paste containing 15 per cent. of PbO, are also added, the temperature being
kept at about 30 degrees Centigrade. Finally, the mixture is filtered, in order to
remove the lead sulphate, and the finished dyestuff is precipitated from the filtrate
by means of common salt.
It forms brownish crystals, and produces clear greenish-blue and even shades when
dyed on wool in acid baths. The shades thus obtained are fast against the action of
alkalies.
'
The process illustrated by the above example proceeds in a similar manner, if the
condensation product resulting from tetramethyldianidobenzhydrol and alpha,
alpha, naphthylamine sulphonic acid; is replaced by other of the above - defined
1

page_text: leuco compounds containing the amido group'in the ortho position to the methane
carbon, as hereinbefore defined.
Naturally my foreign correspondents do not intend to limit themselves to the
particulars given in the above example, which is merely typical, as the directions
contained therein can be varied within wide limits.
. 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 process for producing new intermediate products, that is to say, leuco
sulphonic acids of the diphenylnaphthylmethane series which contain an amido
group in ortho position to the methane carbon, by condensing alkylated diamido
benzhydrols with such alpha-naphthylamine sulphonic acids which, when combined
with diazo compounds, yield azo products, containing the azo group in the ortho
position to the amido group, substantially as bereinbefore described.
2. The production of new leuco sulphinic-sulphonic acids of the diphenylnaphthyl-
methane series, by diazotising the leuco compounds referred to in the above Claim
One, and transforming the diazo group of the bodies thus obtained into the sulphinic
group, substantially as herein before described.
3. The manufacture of new acid dye-stuffs of the diphenylnaphthylmethane series,
by transforming the leuco sulphinic sulphonic acids obtainable according to the fore-
going Claim 2, into the corresponding dye-stuff sulphonic acids by means of
oxydising agents, substantially as herein before described.
4. The process for producing new acid dye-stuffs of the diphenylnaphthylmethane
series, by first condensing alkylated: diamido benzhydrols with such alphanaphthyl-
amine sulphonic acids which, when combined with diazo compounds, yield azo
products containing the azo group in the ortho-position to the amido group;
secondly, diazotising the resulting leuco compounds; thirdly, transforming the diazo
groups of the bodies thus obtained into the.sulphinic groups; and, finally, changing.
the so-produced leuco compounds into the corresponding dye stuff sulphonic acids,
by means of oxidising agents, substantially as herein before defined.
5. As new articles of manufacture, the new intermédiate products and dye-stuffs
herein before defined.