Manufacture of Blue Acid Colouring Matters of the Triphenyl- methan Series.
Year: 1893

page_text: Date of Application, 27th Nov., 1893
Complete Specification, Left, 18th Aug., 1894-Accepted, 22nd Sept., 1894
PROVISIONAL SPECIFICATION.
[Communicated from abroad by THE SOCIETY OF CHEMICAL INDUSTRY IN
BASLE, of Basle, Switzerland, Chemical Manufacturers.]
Manufacture of Blue Acid Colouring Matters of the Triphenyl-
methan Series.
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:-
By heating mixtures of equal molecular proportions of dimethyl- or diethyl-
aniline, mono-methyl or mono-ethyl-o-toluidine and m-oxybenzal-dehyde in presence
of condensing agents, a series of new unsymmetric trialkyl derivatives of diamido-
phenyl-tolyl-m-oxyphenyl-methan is obtained which, after sulphonation and oxida-
tion, give very useful blue acid colouring matters.
The dye stuffs produced according to the present invention are distinguished
from the analogous products derived from tetra-alkyl-diamido-m-oxytriphenyl-
methan by their bright blue tint on wool and silk and by the fact, of great
practical interest, that their tint does not change into green in artificial light.
The manner in which this invention is carried out may be understood from the
following examples:
a.
CONDENSATION.
12.2 kilos. of m-oxybenzaldehyde
12.0
"
"
12.0
"
"
50.0
16.0
"
95
"
כן
dimethylaniline
mono-methyl-o-toluidine
muriatic acid
sulphuric acid of 66°
are heated in an enamelled vessel on the water bath during 24 hours. The
condensation product thus formed is neutralized very carefully by an alkali, and
the oils which are not affected are expelled by steam.
The leuco base remaining in the vessel is washed two or three times with warm
water, then it is dried at 100° C. When cold, it solidifies forming a grey to pale
green mass, easily soluble in acids as well as in caustic alkalies.
For dimethyl-aniline the equivalent quantity of diethyl-aniline and for mono-
methyl-o-toluidine, the corresponding quantity of mono-ethyl-o-toluidine may be
substituted in the above example; and instead of m-oxybenzaldehyde the alkyl
ethers of m-oxybenzaldehyde may be employed.
b. SULPHONATION.
10 kilos. of the leuco base obtained as above are dissolved at 60° C. in 40 kilos.
of sulphuric acid at 66°.

page_text: C. UXIDATION.
The oxidation of the sulphonated liquid may be easily effected with the
theoretical quantity of a peroxide, such as peroxide of lead or manganese, or
with chromic acid.
The solution obtained according to Example 6 is diluted with 6 kilos. of sulphuric
acid and oxidized by addition of 2.8 kilos. of sodium bichromate.
The chrome oxide is precipitated with ammonia, filtered, and the solution of the
colouring matter is evaporated, producing a dye stuff in the form of a powder
having a metallic lustre, easily soluble in water with a blue colour.
and silk blue in an acidulated bath.
It dyes wool
Analogous dye stuffs are produced by oxidizing first the tri alkyl-diamido-
phenyl-tolyl-m-oxyphenyl-methan (Example a) in the usual way known for the
production of dye stuffs of the malachite green series, and by sulphonating the
basic colouring matters thus obtained with 4 to 8 kilos. of fuming sulphuric acid at
a temperature under 30° C.
Dated this 27th day of November 1893.
ABEL & IMRAY,
Agents for the Applicant.
COMPLETE SPECIFICATION
Manufacture of Blue Acid Colouring Matters of the Triphenyl-
methan Series.
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 :-
By heating mixtures of equal molecular proportions of dimethyl or diethyl-
aniline, mono-methyl or mono-ethyl-o-toluidine and m-oxybenzal-dehyde in presence
of condensing agents, a series of new unsymmetric trialkyl derivatives of diamido-
phenyl-tolyl-m-oxyphenyl-methan is obtained which, after sulphonation and oxida-
tion, give very useful blue acid colouring matters.
The dye stuffs produced according to the present invention are distinguished
from the analogous products derived from tetra-alkyl-diamido-m-oxytriphenyl-
methan by their bright blue tint on wool and ɛilk, and by the fact, of great
practical interest, that their tint does not change into green in artificial light.
The manner in which this invention is carried out may be understood from the
following examples :
Manufacture of Blue Acid Colouring Matters of the Triphenyl-
methan Series.
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 :-
By heating mixtures of equal molecular proportions of dimethyl or diethyl-
aniline, mono-methyl or mono-ethyl-o-toluidine and m-oxybenzal-dehyde in presence
of condensing agents, a series of new unsymmetric trialkyl derivatives of diamido-
phenyl-tolyl-m-oxyphenyl-methan is obtained which, after sulphonation and oxida-
tion, give very useful blue acid colouring matters.
The dye stuffs produced according to the present invention are distinguished
from the analogous products derived from tetra-alkyl-diamido-m-oxytriphenyl-
methan by their bright blue tint on wool and silk, and by the fact, of great
practical interest, that their tint does not change into green in artificial light.
The manner in which this invention is carried out may be understood from the
following examples:
a. CONDENSATION.
12.2 kilos. of m-oxybenzaldehyde
وو
12.0
"
"
12.0
"
50.0
16.0
39
"
"
وو
dimethylaniline
mono-methyl-o-toluidine
muriatic acid
sulphuric acid of 66° Beaumé
are heated in an enamelled vessel on the water bath during 24 hours. The
condensation product thus formed is neutralized very carefully by an alkali, and
the oils which are not affected are expelled by steam.
The leuco base remaining in the vessel is washed two or three times with warm
water, then it is dried at 100° C. When cold, it solidifies forming a grey to pale
green mass, easily soluble in acids as well as in caustic alkalies.

page_text: For dimethyl-aniline the equivalent quantity of diethyl-aniline and for mono-
methyl-o-toluidine, the corresponding quantity of mono-ethyl-o-toluidine may be
substituted in the above example; and instead of m-oxybenzaldehyde the alkyl
ethers of m-oxybenzaldehyde may be employed.
The oxidation of the sulphonated liquid may be easily effected with the
theoretical quantity of a peroxide, such as peroxide of lead or manganese, or with
chromic acid.
The solution obtained according to Example is diluted with six kilos. of
sulphuric acid and oxidized by addition of 2.8 kilos. of sodium bichromate.
The chrome oxide is precipitated with ammonia, filtered, and the solution of the
colouring matter is evaporated, producing a dye stuff in the form of a powder
having a metallic lustre, easily soluble in water with a blue colour. It dyes wool
or silk blue in an acidulated bath.
Analogous dye stuffs are produced by oxidizing first the tri alkyl-diamido-
phenyl-tolyl-m-oxyphenyl-methan (Example a) in the usual way known for the
production of dye stuffs of the malachite green series, and by sulphonating the
basic colouring matters thus obtained with 4 to 8 kilos. of fuming sulphuric acid at
a temperature under 30° C.
Having now particularly described and ascertained the nature of this inveu-
tion and in what manner the same is to be performed, I declare that what I
claim is :-
1. The production of the sulphonic acids of unsymmetrical trialkyl derivatives
of diamido-phenyl-tolyl-meta-oxyphenyl methan by heating mixtures of equal
inolecular proportions of dimethyl- or diethyl aniline, mono-methyl or mono-ethyl-
ortho-toluidine and meta-oxybenzaldehyde in presence of condensing agents and
subsequent sulphonating of the resulting leuco-compounds, substantially as
described.
2. The manufacture of blue acid colouring matters of the triphenyl methan
series by oxidising the sulphonic acids referred to in the preceding claim with a
peroxide such as peroxide of lead or manganese or with chromic acid, substantially
as described.
3. As new products the leuco bases produced as set forth in the first claim.
4. As new products the blue acid dye stuffs manufactured as set forth in the
second claim.
Thated this 10th dew of Ano 1801
ABEL & IMRAY,
Agents for the Applicant.