Manufacture of Acid Colouring Matters, being the Sulphonic Acids of Alkyl Derivatives of the Diamido-diphenyl-meta-tolyl- carbinol.
Year: 1893

page_text: Date of Application, 16th Mar., 1893
Complete Specification Left, 16th Dec., 1893-Accepted, 27th Jan.,
1894
PROVISIONAL SPECIFICATION.
[Communicated from abroad by THE FARBWERKE vormals MEISTER LUCIUS AND
BRUNING, of Hoechst a/Main, in the Empire of Germany, Manufacturers.]
Manufacture of Acid Colouring Matters, being the Sulphonic Acids
of Alkyl Derivatives of the Diamido-diphenyl-meta-tolyl-
carbinol.
I, OLIVER IMRAY, of No. 28 Southampton Buildings, Chancery Lane, in the
County of London, Chartered Patent Agent, do hereby declare the nature of this
invention to be as follows:-
discovered that the alkyl-derivatives of the
PROVISIONAL SPEITIATION.
[Communicated from abroad by THE FARBWERKE vormals MEISTER LUCIUS AND
BRUNING, of Hoechst a/Main, in the Empire of Germany, Manufacturers.]
Manufacture of Acid Colouring Matters, being the Sulphonic Acids
of Alkyl Derivatives of the Diamido-diphenyl-meta-tolyl-
carbinol.
I, OLIVER IMRAY, of No. 28 Southampton Buildings, Chancery Lane, in the
County of London, Chartered Patent Agent, do hereby declare the nature of this
invention to be as follows:-
My foreign correspondents have discovered that the alkyl-derivatives of the
diamido-diphenyl-meta-tolyl-carbinol
COH
CH, Nx.
✓✓ C.H. Nx,
✓CH.
CH. CH, (meta)
belong also to the class of blue and blue green acid colouring matters that are
obtained by sulphonising diamido-triphenyl carbinols substituted in the meta position.
The leuco bases of these colouring matters are obtained by condensing meta-
tolyl-aldehyde (boiling point at from 199° to 200° C.) with secondary or tertiary
aromatic bases. These leuco bases are sulphonised and the leuco sulphonic acids
thus obtained oxydised. The same products are obtained by first oxidising the
leuco base and then sulphonising the carbinol thus obtained.
The manner of proceeding is more fully set forth in the following example:
hlaniline
are heated in a lead lined vessel furnished with an agitator to 100° C. for 3 days.
The reaction mass is rendered alkaline, and in order to separate it from volatile
constituents, it is treated with water vapour. The leuco base remaining is separated
from the alkaline liquid, boiled with water until neutral reaction ensues and
afterwards dried on the water bath.
It is in the form of a viscous mass crystallising with difficulty.
This leuco base is dissolved in the quintuple quantity of monohydrate and the
solution thus obtained is heated for some time to from 80° to 90° C. until a sample
gives a clear solution with ammonia. The liquid of the sulphonisation is poured
into water and is converted into the calcium salt in well known manner.
The leuco calcium salt is dissolved in the 50 fold quantity of water and to the
solution is added the suitable quantity (3 equivalents) of sulphuric acid, and it is
then oxidised with the necessary quantity of peroxide of lead. The blue solution
of the colouring matter is filtered off from the sulphate of lead and evaporated to
dryness.
Instead of sulphonising the leuco base and afterwards oxidising the leuco
sulphonic acid, the leuco base may be oxidised and the carbinol-a green colouring
matter sulnhonised.

page_text: EXAMPLE.
10 parts by weight of the leuco base that is to say tetra-ethyl-diamido-diphenyl-
meta-tolyl-methan are dissolved in 9-3 parts by weight of hydrochloric acid of
31 per cent. HCI, and 500 parts by weight of water; the solution is mixed with a
paste of peroxide of lead, corresponding to 5.975 parts by weight of PbO2; for
separating the lead completely, 4 parts by weight of sulphate are added and from
the green solution of the colouring matter, after having separated it from the
sulphate of lead, the base of the colouring matter is precipitated by means of
alkali. The colouring matter base is boiled with water and dried on the water bath.
For converting the base into the sulphonic acid it is treated with the quintuple
quantity of fuming sulphuric acid of 10 per cent. SO, and the solution is slightly
heated until the sulphonisation is completed. The conversion of the reaction mass
into the calcium salt is carried out in the well known manner.
It
The colouring matter is in form of a copper-red powder with metallic lustre.
dissolves in water with blue colour and dyes wool and silk in acid bath very uniform
and fast blue-green shades.
For the diethylaniline employed in the above example may be substituted any
other secondary or tertiary aromatic bases, as for example:
monomethylaniline,
monoethylaniline,
monomethyl-o-toluidine,
monoethyl-o-toluidine,
dimethylaniline,
dimethyl-o-toluidine,
diethyl-o-toluidine,
methyl-benzylaniline,
ethyl-benzylaniline.
It is only necessary to substitute for the diethylaniline of the example the
equivalent quantity of one or the other of these bases; in other respects no
alterations in the conditions of the operation have to be made than those required
as a matter of course by the chemical and physical qualities of these bodies.
Dated this 16th day of March 1893.
ABEL & IMRAY,
Agents for the Applicant.
Manufacture of Acid Colouring Matters, being the Sulphonic Acids
of Alkyl Derivatives of
carbinol.
the Diamido-diphenyl-meta-tolyl-
I, OLIVER IMRAY, of No. 28 Southampton Buildings, Chancery Lane, in the
County of London, Chartered 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 discovered that the alkyl derivatives of the
diamido-diphenyl-meta-tolyl-carbinol,

page_text: belong also to the class of blue and blue green acid colouring matters that are
obtained by sulphonising diamido-triphenyl carbinols substituted in the meta
position.
The leuco bases of these colouring matters are obtained by condensing meta-
tolyl-aldehyde (boiling point at from 1990 to 200° C.) with secondary or tertiary
aromatic bases. These leuco bases are sulphonised and the leuco sulphonic acids
thus obtained oxydised. The same products are obtained by first oxidising the
leuco base and then sulphonising the carbinol thus obtained.
The manner of proceeding is more fully set forth in the following example:
are heated in a lead lined vessel furnished with an agitator to 100° C. for 3 days.
The reaction mass is rendered alkaline, and in order to separate it from volatile
constituents, it is treated with water vapour. The leuco base remaining is separated
from the alkaline liquid, boiled with water until neutral reaction ensues and after-
wards dried on the water bath.
It is in the form of a viscous mass crystallising with difficulty.
This leuco base is dissolved in the quintuple quantity of sulphuric acid mono-
hydrate and the solution thus obtained is heated for some time to from 80° to 90° C.
until a sample gives a clear solution with aminonia. The liquid of the sulphonisa-
tion is poured into water and is converted into the calcium salt in well known
manner.
The leuco calcium salt is dissolved in the 50 fold quantity of water and to the
solution is added the suitable quantity (3 equivalents) of sulphuric acid, and it is
then oxidised with the necessary quantity of peroxide of lead. The blue solution
of the colouring matter is filtered off from the sulphate of lead and evaporated to
dryness.
Instead of sulphonising the leuco base and afterwards oxidising the leuco sulphonic
acid, the leuco base may be oxidised and the carbinol-a green colouring matter―
sulphonised.
EXAMPLE.
10 parts by weight of the leuco base that is to say tetra-ethyl-diamido-diphenyl-
meta-tolyl-methan are dissolved in 9-3 parts by weight of hydrochloric acid of
31 per cent. HCl, and 500 parts by weight of water; the solution is mixed with a paste
of peroxide of lead, corresponding to 5.975 parts by weight of PbO2; for separating
the lead completely, 4 parts by weight of sodium sulphate are added and from the
green solution of the colouring matter, after having separated it from the sulphate
of lead, the base of the colouring matter is precipitated by means of alkali.
colouring matter base is boiled with water and dried on the water bath. For
converting the base into the sulphonic acid it is treated with the quintuple quantity
of fuming sulphuric acid of 10 per cent. SO, and the solution is slightly heated until
the sulphonisation is completed. The conversion of the reaction mass into the
calcium salt is carried out in the well known manner.
The
The colouring matter is in form of a copper-red powder with metallic lustre. It
dissolves in water with blue colour and dyes wool and silk in acid bath very uniform
and fast blue-green shades.
For the diethylaniline employed in the above example may be substituted any
other secondary or tertiary aromatic bases, as for example:
monomethylaniline,
10 parts by weight of the leuco base that is to say tetra-ethyl-diamido-diphenyl-
meta-tolyl-methan are dissolved in 9-3 parts by weight of hydrochloric acid of
31 per cent. HCl, and 500 parts by weight of water; the solution is mixed with a paste
of peroxide of lead, corresponding to 5.975 parts by weight of PbO2; for separating
the lead completely, 4 parts by weight of sodium sulphate are added and from the
green solution of the colouring matter, after having separated it from the sulphate
of lead, the base of the colouring matter is precipitated by means of alkali. The
colouring matter base is boiled with water and dried on the water bath. For
converting the base into the sulphonic acid it is treated with the quintuple quantity
of fuming sulphuric acid of 10 per cent. SO, and the solution is slightly heated until
the sulphonisation is completed. The conversion of the reaction mass into the
calcium salt is carried out in the well known manner.
The colouring matter is in form of a copper-red powder with metallic lustre. It
dissolves in water with blue colour and dyes wool and silk in acid bath very uniform
and fast blue-green shades.
For the diethylaniline employed in the above example may be substituted any
other secondary or tertiary aromatic bases, as for example:
monomethylaniline,

page_text: ethyl-benzylaniline.
It is only necessary to substitute for the diethylaniline of the example the
equivalent quantity of one or the other of these bases; in other respects no alterations
in the conditions of the operation have to be made other than those required as a
matter of course by the chemical and physical qualities of these bodies.
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 manufacture of acid colouring matters by condensing metatolylaldehyde
with aromatic bases, such as hereinbefore mentioned, into alkylised diamido-diphenyl-
meta-tolyl-methans, sulphonising the leuco bases thus produced by treatment with
sulphuric acid or fuming sulphuric acid and oxidising the leuco-sulphonic acids, or by
first oxidising the leuco base and afterwards sulphonising the basic coloring matter,
thus produced, substantially as described.
2. The acid coloring matters manufactured as above set forth.
ABEL & IMRAY,
Agents for the Applicant.