Manufacture of Green and Blue Green Colouring Matters derived from Triphenylmethane.
Year: 1897

page_text: Date of Application, 14th Dec., 1897
PROVISIONAL SPECIFICATION.
Manufacture of Green and Blue Green Colouring Matters derived
from Triphenylmethane.
I, JOHN IMRAY, of Birkbeck Bank Chambers, Southampton Buildings, in the
County of London, Consulting Engineer and Chartered Patent Agent, do hereby
declare the nature of this invention (as communicated to me from abroad by
Société Anonyme des Matieres Colorantes et Produits Chimiques de St. Denis, of
105, Rue Lafayette, Paris, France,) to be as follows:-
In a prior application for Patent No. 18,002 of 1897, I have described as com-.
municated by my foreign correspondents the manufacture of a new substance
ortho-sulphonated metamidobenzaldehyde and of colouring matters derived from
it; the present invention, also communicated by them, relates to improvements
in the manufacture of this substance, to new transformations to which it can be
subjected, and to colouring matters derived from it.
As previously described, the meta-amidobenzaldehyde is not isolated, but the
liquor containing it is directly condensed with secondary and tertiary amines to
form leuco-bases and finally colouring matters. It has been found that the
products of condensation are considerably increased if after the reaction of the
sodium sulphite on nitrobenzaldehyde, the excess of the sulphite is removed by
ordinary means, the simplest being based on the low degree of solubility of
calcium sulphite, calcium chloride being employed as precipitating agent. It
has also been ascertained that the reaction which was described as taking place
at the boiling temperature of the mixture can also be obtained at much lower
temperatures between 52° and 102° C., and that at the highest of these tempera-
tures there is disengagement of ammonia which certainly indicates the accom-
panving formation of an orthosulphonated metahydroxyle derivative.
The orthosulphonated metamidobenzaldehyde having a free N H₂ capable of
being diazotised, my correspondents have applied to this aldehyde the general
reactions suited to diazo bodies, and thus they have obtained corresponding
chlorinated, hydroxylated and sulphonated derivatives.
EXAMPLE I.
Preparation of ortho-sulphonated metaoxybenzaldehyde.
To an aqueous solution obtained as previously described and containing 20.1
kilos. of ortho-sulphonated m-amido-benzaldehyde, after eliminating the excess
of sodium sulphite by calcium chloride, there are added 50 kilos. of sulphuric
acid at 660 B. The mixture is concentrated to a volume of 500 litres, and after
cooling, it is diazotised by adding 6.9 kilos. of sodium nitrite. After remaining
about an hour at low temperature the mixture is heated on the water bath until
the diazo-body disappears. The solution thus obtained contains the o-sulpho-
m-oxybenzaldehyde, which need not be isolated for practical use, it can be
directly used in condensation with aromatic amines,

page_text: EXAMPLE 11.
To the aqueous solution containing 20.1 kilos. of o-sulpho-m-amidobenzaldehyde,
after elimination of the sodium sulphite, and concentration to about 500 litres
there are added 100 to 150 litres of H Cl, at 21° Be., then after cooling to -5° C.,
6.9 kilos. of sodium nitrite. After an hour 15 kilos. of copper powder are added
in small doses with agitation. Nitrogen is evolved and the diazo-derivative
becomes transformed into the chloro-derivative which remains in solution, and
can be directly employed for condensation with aromatic amines.
XXX
.
EXAMPLE III.
The diazotisation of the o-sulpho-m-amidobenzaldehyde being effected as in
Example I in presence of sulphuric acid without previous elimination of the
excess of sodium sulphite, sulphurous acid is bubbled through it till saturation.
There are then added in small doses 15 kilos. of copper powder, with agitation
until the evolution of nitrogen quite ceases.
The bisulpho-derivative of the benzaldehyde remains in solution and need.not
be isolated for practical use!
1
R
In this way it is possible also to obtain very various derivatives, as described
above of the form N-N-R in which R indicates a phenol or amine residue
substituted or not.
All the various aldehydes, o-sulphonated, m-chlorinated, m-sulphonated,
m-hydroxylated are capable, like the m-amidobenzaldehyde of the former applica-
tion, of being condensed with secondary or tertiary amines, sulphonated or not,
of producing leuco-bases and finally colouring matters by oxidation.
The reactions above described for transforming o-sulpho-m-amido-aldehyde with
azo and diazo derivatives, then into chloro-, sulpho-, and hydroxyl derivatives
can also be applied to the leuco-bases and colouring matters derived from them.
Dated this 14th day of December 1897.
ABEL & LAIKAY,
Agents for the Applicant.
Manufacture of Green and Blue Green Colouring Matters derived
from Triphenylmethane.
30
I, JOHN IMRAY, of Birkbeck Bank Chambers; Southampton Buildings, in the
County of London; Consulting Engineer and Chartered Patent Agent, do hereby
declare the nature of this invention (as communicated to me from abroad by
Societé Anonyme des Matieres Colorantes et Produits Chimiques de St. Denis, of
105, Rue Lafayette, Paris, France) and in what manner the same is to be performed
to be particularly described and ascertained in and by the following statement:-
In a prior application for Patent No. 18,002 of 1897, I. have described as com-
municated by my foreign correspondents the manufacture of a new substance
ortho-sulphonated metamidobenzaldehyde and of colouring matters derived from
it; the present invention, also communicated by them, relates to improvements
in the manufacture of this substance, to new transformations to which it can be
subjected, and to colouring matters derived from it.
1
も.
As previously described, the metamidobenzaldehyde is not isolated, but the
liquor containing it is directly condensed with secondary and tertiary amines to
form leuco-bases and finally colouring matters. It has been found that the
products of condensation are considerably increased if after the reaction of the

page_text: sodium sulphite on nitrobenzaldehyde, the excess of the sulphite is removed by
ordinary means, the simplest being based on the low degree of solubility of
calcium sulphite, calcium chloride being employed as precipitating agent.. It
has also been ascertained that the reaction which was described as taking place
at the boiling temperature of the mixture can also be obtained at much lower
temperatures between 52° and 102° C., and that at the highest of these tempera-
tures there is disengagement of ammonia which certainly indicates the accom-
panying formation of an orthosulphonated metahydroxyle derivative.
The orthosulphonated metamidobenzaldehyde having a free N H, capable of
being diazotised my correspondents have applied to this aldehyde the general
reactions suited to diazo bodies, and thus they have obtained corresponding
chlorinated hydroxylated and sulphonated derivatives.
EXAMPLE I.
Preparation of orthosulphonated metaoxybenzaldehyde.
To an aqueous solution obtained as previously described in the Specification
No. 18.002 of 1897, and containing 20.1 kilos. of ortho-sulphonated m-amido-
benzaldehyde, after eliminating the excess of sodium sulphite by calcium chloride,
there are added 50 kilos. of sulphuric acid at 66° B. The mixture is concen-
trated to a volume of 500 litres, and after cooling, it is diazotised by adding
6.9 kilos. of sodium nitrite. After remaining about an hour at low temperature
the mixture is heated on the water bath until the diazo-body disappears.
The solution thus obtained contains the o-sulpho-m-oxybenzaldehyde, which
need not be isolated for practical use, it can be directly used in condensation with
aromatic amines.
EXAMPLE III.
To the aqueous solution containing 20.1 kilos. of o-sulpho-m-amidobenzaldehyde,
after elimination of the sodium sulphite and concentration to about 500 litres
there are added 100 to 150 litres of H Cl at 21° Bé., then after cooling to -5° C.,
6.9 kilos. of sodium nitrite. After an hour 15 kilos. of copper powder are added
in small doses with agitation. Nitrogen is evolved and the diazo derivative
becomes transformed into the chloro-derivative which remains in solution, and
can be directly employed for condensation with aromatic amines.
EXAMPLE III.
The diazotisation of the o-sulpho-m-amidobenzaldehyde being effected as in
Example I in presence of sulphuric acid without previous elimination of the
excess of sodium sulphite, sulphurous acid is bubbled through it till saturation.
There are then added in small doses 15 kilos. of copper powder, with agitation
until the evolution of nitrogen quite ceases.
The bisulpho-derivative of the benzaldehyde remains in solution and need not
be isolated for practical use.
It is possible also to obtain very various derivatives, of the form B-N=N-R
in which B indicates the benzaldehyde group and R indicates a phenol or amine
residue substituted or not.
All the various aldehydes, o-sulphonated, m-chlorinated, m-sulphonated.
m-hydroxylated are capable, like the m-amidobenzaldehyde of the former Specifica-
tion No. 18002 of 1897, of being condensed with secondary or tertiary amines,
sulphonated or not, for producing leuco-bases and finally colouring matters by
oxidation
The reactions above described for transforming o-sulpho-m-amido-benzaldehyde
into azo- and diazo derivatives, and the latter into chloro-, sulpho- and hydroxyl-
compounds, can also be applied to the leuco-bases and colouring matters derived
from these leuco-bases.

page_text: Having now particularly described and ascertained the nature of this invention
and in what manner the same is to be performed, I declare that what I claim
is:-
1. The herein described manufacture of orthosulphonated metamidobenzaldehyde.
2. The transformation as herein described of the orthosulphonated metamido-
benzaldehyde into azo- or diazo-derivatives and of the latter into chlorinated,
sulphonated or hydroxylated compounds.
3. The transformation as herein described of the leuco-bases and colouring
matters manufactured according to the Specification No. 18002 of 1897, into
azo- or diazo derivatives and of the latter into chlorinated, sulphonated or hydro-
xylated compounds of the kind referred to in the preceding claim.
4. The substances manufactured as set forth in the preceding claims.
D
VALLY
ABEL & IMRAY,
Agents for the Applicant.
ABEL & IMRAY,
Agents for the Applicant.