Improvements in the Manufacture of Colouring Matters.
Year: 1899

page_text: [Communicated from abroad by CHEMICAL WORKS, formerly SANDOZ, of Basle
in the Republic of Switzerland].
Improvements in the Manufacture of Colouring Matters.
I, HENRY HARRIS LAKE, of the Firm of Haseltine, Lake & Co., Patent Agents.
45, Southampton Buildings, in the County of Middlesex, do hereby declare the
nature of this invention to be as follows:-
The present invention relates to the manufacture of new azodyestuffs, dyeing
wool and silk in an acid bath bright shades varying from bluish red to violet.
These new colouring matters are produced by combining diazobodies of suitable
aromatic amidocompounds with 18 alphysulfamidonaphtoldisulphonicacids.
These latter new azocomponents are formed by condensation of alphylsulpho-
chlorides, as benzenesulphochloride ortho- and paratoluenesulphochloride,
xylenesulphochlorides with 18 amidonaphtoldisulphonicacids.
In order to obtain a quantitative sulphonation of the amidogroup in these
amidonaphtolsulphonicacids it is preferable at first to sulphonate also the
hydroxyncgroup and then to split off by suitable means hereinafter specified the
alphylsulphon radical combined with the hydroxylicgroup. The disulphonated
products neither combine with diazocompounds nor can they be diazotized by
treating them with nitrous acid. If their solution be boiled with alkali carbonates
or caustic alkalies the alphylsulphonradical combined with the hydrocylicgroup
is removed whereas the aiphylsuiphonated radical substituted in the amidogroup
remains unchanged and thus the disulphonated acids can be quantitatively
transformed into monoalphylsulphamidonaphtoldisulphonicacids.
The new most valuable azocomponents thus formed have all the characteristics
of naphtolsulphonicacids, the amidogroup being completely neutralized by the
acid alphylsulphon-radical substituted in it for instance, whereas the amidogroup
in the starting material is changed into the diazogroup by the action of nitrous
acid the alphylsulphonated amidogroup in the new products remains quite
unaffected if treated with this reagent, but, the new substances have retained the
valuable property of the initial material to react very easily with suitable diazo-
bodies producing thus very bright azocolours fast to acids alkalies and light.
The tints produced by the corresponding azocombinations derived from the
unchanged 18 amidonaphtoldisulphonicacids are much duller and do not possess
the same evenness of tint.
Besides the difference in the behaviour in the presence of nitrous acid the 1'8
alphylsulphamidonaphtoldisulphonicacid are also much more soluble than the
corresponding amidonaphtolsulphonicacids from which they are produced; they
can only be precipitated from highly concentrated solutions of their salts by
addition of an excess of strong mineral acids.
Most of the usual diazobodies combine only in alkaline solution with the new
alphylsulfamidoacids, as exceptions, may be mentioned nitrodiazobenzenes and
dichlordiazobenzenes which also react in mineral acid solution.

page_text: But with these diazobodies also the same colouring matters are always obtained
no matter if the combination be carried out in acid or in alkaline solution. The
diazoradical being therefore always and alone directed by the hydroxylicgroup
of the new alphylsulphamidonaphtoldisulphonicacids.
For the production of the new 18 alphylsulphamidonaphtoldisulphonicacids I
may proceed by way of example, as follows:
60 kilos. of 18 amidonaphtol 36 disulphonicacid (100%, acid sodium salt) are
dissolved at about 70° C. in 600 litres of water by addition of 60 kilos. of finely
powdered chalk. To this mixture 88 kilos. of paratoluenesulphochloride are now
slowly introduced during two hours, care being taken to maintain the temperature
between 700 and 80°. C. and to stir well during the-whole process of condensation.
If all the sulphochloride be added stirring is continued for about a further two
hours at 80° C. until an acidulated- sample -taken. from the solution shows no
further formation of a diazocompound on the addition of sodium nitrite. The
solution is then heated to boiling point, and to transform the ditolylsulphamido-
amidonaphtoldisulphonicacid, that is to say, to split off the alphylsulphamido-
naphtoldisulphonicacid formed in the first reaction into the monoparatolylsulph-
radical combined with the hydroxylic group, a solution of 14-15 kilos. of caustic
soda is added and the boiling continued for an hour. Care must be taken that
the mass is still slightly alkaline at the end of the reaction. This small excess
of the caustic alkali is then neutralized preferably by muriatic acid and after
precipitation of the chalk by addition of 35 kilos. of solvay soda the solution is
filtered and can now be directly used without any further purification for the
production of colouring matters.
In the foregoing example the paratoluenesulphochloride can be substituted by
corresponding quantities of other alphyl (aromatic) sulphochlorides as benzene,
orthotoluene, xylenesulphochlorides and on the other hand instead of 1.8.3.6.
amidonaphtoldisulphonicacid the isomeric 1.8.2.4 or 1.8.4.6 amidonaphtoldi-
sulphonicacids may be used.
In the manufacture of azodyes derived from the new 1.8 alphylsulphamido-
naphtoldisulphonicacids I may proceed as follows:
The solution of the 1.8 paratolylsulphamidonaphtol 3.6 disulphonicacid described
in the foregoing example, is diluted with a solution of 10 kilos. of solvay soda
to about 1200 litres. After cooling with ice preferably to about 5° C. it is com-
bined whilst stirring with the diazobenzene solution corresponding to 14 kilos.
of aniline. The colouring matter thus formed separates almost entirely in the
form of a red crystalline precipitate, which after standing some hours may be
filtered pressed and dried.
The new colouring matter forms in a dry state a red powder soluble in alcohol,
very easily soluble in water with a bluish red colour which is only slightly
altered by the addition of alkalies or acids. Strong sulphuric acid dissolves the
dyestuff with a bluish red colour. On diluting this solution with water no altera-
tion takes place.
The colouring matter dyes wool and silk from a slightly acidulated bath, in
very clear and brilliant bluish red shades of excellent uniformity and. very good
fastness to acids, alkalies and light.
Similar dyestuffs are obtained when in the foregoing examples the 1.8.3.6
alphylsulphamidonaphtoldisulphonicacid is substituted by the isomeric 1.8.2.4
or 1.8.4.6 alphyisulphamidonaphtoldisulphonicacids and if in place of diazo-
benzene the equivalent weights of the diazocompounds of other amines their carbonic
or sulphonicacids be used; as for example ortho- and paratoluidine, meta- and
paraxylidine, mono- and dichloranilines and their homologues, paraamidoacet-
anilide meta- and paranitraniline and their homologues orthoanisidine para-
phenetidine, metamidoparakresolether, anilinesulphonicacids and their homo-
logues, amidobenzoicacids, amidoazobenzene amidoazotoluene and their
sulphonicacids, a and naphtylamine and their mono- and disulphonicacids.

page_text: The azocolours derived from sulphoconjugated amidocompounds are generally
of a greater solubility and must be precipitated from their solutions by the
addition of common salt or chloride of potash. The different dyestuffs thus
obtained dye shades varying from blue-red to blueish violet. The most blue shades
are obtained by the combinations derived from paraphenylenediamine and its
homologues. Those colouring matters can be produced either by combining
diazotized paraamidoacetanilide or its homologues with the new alphylsulph-
amidonaphtolsulphonicacids and then saponifying in the usual manner the
thus produced acetylamidoazocolouring matters, or by coupling diazoparanitrani-
line or its homologues with the new alphylsulphamidonaphtolsulphonicacids and
then reducing the nitrogroup in the thus obtained nitroazodyestuffs for instance,
by means of alkalisulphides.
The whole series of dyestuffs derived from the different 1.8 alphylsulphamido-
naphtoldisulphonicacids show the same characteristic, that is to say they are
completely destroyed by boiling them with zinc dust forming thereby a slightly
greenish yellow solution, which after acidulation on addition of an oxydizing
agent as ferichloride or bichromate of potash turns into an intense yellow.
Dated this 16th day of November 1899.
HASELTINE, LAKE & Co.,
45, Southampton Buildings, London, W.C.,
Agents for the Applicants.
improvements in the Manufacture of Colouring Matters.
I, HENRY HARRIS LAKE, of the Firm of Haseltine, Lake & Co., Patent Agents,
45, Southampton Buildings, in the County of Middlesex, 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:-
The present invention relates to the manufacture of new azodyestuffs, dyeing
wool and silk in an acid bath bright shades varying from bluish red to violet.
These new colouring matters are produced by combining diazobodies of suitable
aromatic amidocompounds with 1.8 alphylsulfamidonaphtoldisulphonicacids.
These latter new azocomponents are formed by condensation of alphylsulpho-
chlorides, as benzenesulphochloride ortho- and paratoluenesulphochloride,
xylenesulphochlorides with 18 amidonaphtoldisulphonicacids.
In order to obtain a quantitative sulphonation of the amidogroup in these
amidonaphtolsulphonicacids it is preferable at first to sulphonate also the
hydroxylicgroup and then to split off by suitable means hereinafter specified the
alphylsulphon radical combined with the hydroxylicgroup. The disulphonated
products neither combine with diazocompounds nor can they be diazotized by
treating them with nitrous acid. If their solution be boiled with alkali carbonates
or caustic alkalies the alphylsulphonradical combined with the hydroxylicgroup
is removed whereas the alphylsulphonated radical substituted in the amidogroup
remains unchanged and thus the disulphonated acids can be quantitatively
transformed into monoalphylsulphamidonaphtoldisulphonicacids.
The new most valuable azocomponents thus formed have all the characteristics
of naphtolsulphonicacids, the amidogroup being completely neutralized by the
acid alphylsulphon-radical substituted in it for instance, whereas the amidogroup
in the starting material is changed into the diazogroup by the action of nitrous
acid the alphylsulphonated amidogroups in the new products remains quite
unaffected if treated with this reagent, but the new substances have retained the

page_text: valuable property of the initial material to react very easily with suitable diazo-
bodies producing thus very bright azocolours fast to acids alkalies and light.
The tints produced by the corresponding azocombinations derived from the
unchanged 18 amidonaphtoldisulphonicacids are much duller and do not possess
the same evenness of tint.
Besides the difference in the behaviour in the presence of nitrous acid the 18
alphylsulphamidonaphtoldisulphonicacid are also much more soluble than the
corresponding amidonaphtolsulphonicacids from which they are produced; they
can only be precipitated from highly concentrated solutions of their salts by
addition of an excess of strong mineral acids.
Most of the usual diazobodies combine only in alkaline solution with the new
alphylsulfamidoacids, as exceptions, may be mentioned nitrodiazobenzenes and
dichlordiazobenzenes which also react in mineral acid solution.
But with these diazobodies also the same colouring matters are always obtained
no matter if the combination be carried out in acid or in alkaline solution. The
diazoradical being therefore always and alone directed by the hydroxylicgroup
of the new alphylsulphamidonaphtoldisulphonicacids.
For the production of the new 18 alphylsulphamidonaphtoldisulphonicacids I
may proceed by way of example, as follows:
The
60 kilos. of 18 amidonaphtol 36 disulphonicacid (100% acid sodium salt) are
dissolved at about 70° C. in 600 litres of water by addition of 60 kilos. of finely
powdered chalk. To this mixture 88 kilos. of paratoluenesulphochloride are now
slowly introduced during two hours, care being taken to maintain the temperature
between 700 and 80° C. and to stir well during the whole process of condensation.
If all the sulphochloride be added stirring is continued for about a further two
hours at 80° C. until an acidulated sample taken from the solution shows no
further formation of a diazocompound on the addition of sodium nitrite.
solution is then heated to boiling point, and to transform the ditolylsulphamido-
naphtoldisulphonicacid formed in the first reaction into the monoparatolylsulph-
amidonaphtoldisulphonicacid, that is to say, to split off the alphylsulphoradical
combined with the hydroxylic group, a solution of 14-15 kilos. of caustic soda
is added and the boiling continued for an hour. Care must be taken that the
mass is still slightly alkaline at the end of the reaction. This small excess of
the caustic alkali is then neutralized preferably by muriatic acid and after
precipitation of the chalk by addition of 35 kilos. of solvay soda the solution is
filtered and can now be directly used without any further purification for the
production of colouring matters.
In the foregoing example the paratoluenesulphochloride can be substituted by
corresponding quantities of other alphyl (aromatic) sulphochlorides as benzene,
orthotoluene, xylenesulphochlorides and on the other hand instead of 1.8.3.6.
amidonaphtoldisulphonicacid the isomeric 1.8.2.4 or 1.8.4.6 amidonaphtoldi-
sulphonicacids may be used.
In the manufacture of azodyes derived from the new 1.8 alphylsulphamido-
naphtoldisulphonicacids I may proceed as follows:
The solution of the 1.8 paratolylsulphamidonaphtol 3.6 disulphonicacid described
in the foregoing example, is diluted with a solution of 10 kilos. of solvay soda
to about 1200 litres. After cooling with ice preferably to about 5° C. it is com-
bined whilst stirring with the diazobenzene solution corresponding to 14 kilos.
of aniline. The colouring matter thus formed separates almost entirely in the
form of a red crystalline precipitate, which after standing some hours may be
filtered pressed and dried.
The new colouring matter forms in a dry state a red powder soluble in alcohol,
very easily soluble in water with a bluish red colour which is only slightly
altered by the addition of alkalies or acids. Strong sulphuric acid dissolves the
dyestuff with a bluish red colour. On diluting this solution with water no altera-
tion takes place.
The colouring matter dyes wool and silk from a slightly acidulated bath in

page_text: very clear and brilliant bluish red shades of excellent uniformity and very good
fastness to acids, alkalies and light.
Similar dyestuffs are obtained when in the foregoing example the 1.8.3.6
alphylsulphamidonaphtoldisulphonicacid is substituted by the isomeric 1.8.2.4
or 1.8.4.6 alphylsulphamidonaphtoldisulphonicacids and if in place of diazo-
benzene the equivalent weights of the diazocompounds of other amines their carbonic
or sulphonicacids be used; as for example ortho- and paratoluidine, meta- and
paraxylidine, mono- and dichloranilines and their homologues, paraamidoacet-
anilide meta- and paranitraniline and their homologues orthoanisidine para-
phenetidine, metamidoparacresolether, anilinesulphonicacids and their homo-
logues, amidobenzoicacids, amidoazobenzene amidoazotoluene and their
sulphonicacids, a and B naphtylamine and their mono- and disulphonicacids.
The azocolours derived from sulphoconjugated amidocompounds are generally
of a greater solubility and must be precipitated from their solutions by the
addition of common salt or chloride of potash. The different dyestuffs thus
obtained from red to dark powders, easily soluble in water, dissolving in alcohol
and strong sulphuric acid with a blue red to violet colour they dye wool and silk
from an acid bath in brilliant shades varying from blue red to bluish violet.
The most blue shades are obtained by the combinations derived from parapheny-
lenediamine and its homologues. Those colouring matters can be produced either
by combining diazotized paraamidoacetanilide or its homologues with the new
alphylsulphamidonaphtolsulphonicacids and then saponifying in the usual man-
ner the thus produced acetylamidoazocolouring matters, or by coupling diazo-
paranitraniline or its homologues with the new alphylsulphamidonaphtol-
sulphonicacids and then reducing the nitrogroup in the thus obtained nitroazo-
dyestuffs for instance, by 'means of alkalisulphides.
Having now particularly described and ascertained the nature of the said
invention and in what manner the same is to be performed, as communicated to
me by my foreign correspondents, I declare that what I claim is :-
The new azodyes deriving from one molecule of a diazotized aromatic amido-
compound and one molecule of an 1.8 alphylsulphamidonaphtoldisulphonicacid
as herein before described, forming red to dark powders easily soluble in water
dissolving in alcohol and strong sulphuric acid with blue-red to violet colour the
said dyestuffs being destroyed by reduction with zinc dust forming hereby a
slightly greenish yellow solution, which when acidulated on addition of an
oxydizing agent turns into intense yellow.
Dated this 5th day of July 1900
HASELTINE, LAKE & Co.,
45, Southampton Buildings, London, W.C..
Agents for the Applicant.