Manufacture of New Colouring Matters Dyeing from Blue-green to Blue, and of New Chloro-derivatives and Sulphonic Derivatives: of Benzoic Aldehyde therefor.
Year: 1896

page_text: This Print is in accordance with the Original Specification as it stands after
Amendment (under Section 11 of the Patents, &c., Act, 1883), as required by
the decision of the Chief Examiner of the 7th day of May 1897.
Date of Application, 9th Nov., 1896-Accepted, 24th Dec., 1896
COMPLETE SPECIFICATION (AMENDED).
[Communicated from abroad by THE SOCIETY OF CHEMICAL INDUSTRY IN
BASLE, of Basle, Switzerland, Chemical Manufacturers.]
Manufacture of New Colouring Matters Dyeing from Blue-green to
Blue, and of New Chloro-derivatives and Sulphonic Derivatives:
of Benzoic Aldehyde therefor.
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 formerly described a process of preparing blue-
green colouring matters which dye in acid bath and are derived from the products
of condensation of monobenzylorthotoluidine and monobenzylorthotoluidine sul-
phonic acid with benzaldehyde or benzoic aldehyde. They have since found that.
a whole series of chloro and sulpho derivatives of benzoic aldehyde can be
condensed with monobenzylorthotoluidine and monobenzylorthotoluidine sulphonic
acid, furnishing derivatives of triphenylmethane which can be transformed by the
action of oxidising agents into valuable colouring matters dyeing, in acid bath
blue-green to blue.
Among those derivatives of benzaldehyde or benzoic aldehyde those which
are especially suitable for the preparation of these colouring matters are the
following:-
(1) Dichlorobenzaldehyde (CHO: CI: Cl=1; 2:5) or the commercial product
which contains this body and which is obtained by chlorination of benzoic
aldehyde-
(2) The dichlorobenzaldehyde (CHO: C1: Cl=1:2:4) or the commercial'
product which contains this body, and which is prepared by means of dichloro-
toluenes :-
(3) Orthochlorobenzaldehyde :-
The metanite orthochlorobenzaldehyde which appears in the form of

page_text: (b) The products of the reaction of sodium sulphite on the bisulphite combina-
tions of the bodies mentioned from (1) to (5) at high temperature and under
pressure, that is to say :-
(a) Orthosulphobenzaldehyde :
(b) Chlorobenzaldehyde sulphonic acid (CHO: SO,H: Cl = 1:2: 5) derived
from dichlorobenzaldehyde mentioned in (1).
(e) Benzaldehydedisulphonic acid (CHO: SO,H: SO,H = 1:2:4) derived
from dichlorobenzaldehyde mentioned in (2):-
(d) Benzaldehydedisulphonic acid (CHO: SO,H: SO,H = 1:2:5) derived
from the orthochlorobenzaldehyde sulphonic acid mentioned in (5) :-
(e) The metamidobenzaldehyde orthosulphonic acid (CHO: SO,H: NH, =
1:25) derived from the metanitro-orthochlorobenzaldehyde mentioned
in (4).
The preparation of the orthochlorobenzaldehye-metasulphonic acid mentioned
in (5) and of the benzaldehyde-disulphonic acids indicated in (6 c) and (6 d) is
hereafter described in detail.
The condensation of a molecule of the bodies mentioned in (1) to (5) with two
molecules of benzylorthotoluidine or its monosulphonic derivative takes place in
the manner well known for condensing benzoic aldehyde with benzylorthotoluidine
or its mono sulphonic acid. In this condensation, as has been ascertained, for one
of the two molecules of benzylorthotoluidine or its sulpho derivative may be
substituted a molecule of the other secondary or tertiary aromatic amines and their
sulphonic derivatives, such, for example, as monomethylorthotoluidine, mono-
ethylorthotoluidine, dimethylaniline, diethylaniline, methylbenzylaniline and its
sulphoderivative, ethylbenzylaniline and its sulphoderivative, nitrobenzylmethyl-
aniline, nitrobenzylethylaniline, dibenzylaniline and its mono- and di-sulpho
derivatives, monomethylaniline, monoethylaniline, monobenzylaniline and its mono-
sulphoconjugate acid.
Also, a molecule of the new orthochlobenzaldehydemetasulphonic acid mentioned
in (5), or of the new derivatives of benzoic aldehyde mentioned in (6 c) to (6 e)
can be condensed with two molecules the same or different of the secondary or
tertiary aromatic amines which have just been mentioned.
In all cases are obtained derivatives of triphenylmethane which can be trans-
formed under the influence of oxidising agents, such as potassium bichromate,
lead peroxide, manganese binoxide &c., into colouring matters varying from green
blue to blue, and distinguished partly by their great dyeing power, as well as by the
purity and uniformity of the shades which they furnish.
These colouring matters contain from one to four sulpho groups according as the
condensation products employed for their production comes from a molecule of a
chloro-monosulpho or disulpho derivative of benzoic aldehyde, and from two
molecules of aromatic amines not sulphonated or sulphobenzylated, or from a
molecule of an aromatic amine not sulphonated and of an aromatic amine
sulphobenzylated.
The products resulting from the condensation of a molecule of the bodies
mentioned in (1) to (6) with two molecules of benzylortho-toluidine sulphonic acid
or with a molecule of benzylorthotoluidine sulphonic acid, and a molecule of the
other secondary and tertiary aromatic amines or of the sulpho derivatives of these
amines, which have been mentioned above, can naturally also be prepared by
sulphonating at once by means of monohydrated sulphuric acid or fuming-sulphuric
acid the derivatives of triphenylmethane obtained by substituting benzylortho-
toluidine for benzylorthotoludine sulphonic acid. In the same manner, the con-
densation products obtained by aid of methylbenzylaniline, ethylbenzylaniline,
monobenzylaniline and dibenzylaniline, can be transformed by sulphonation into
sulpho derivatives furnishing by oxidation, colouring matters having properties
analogous to those resulting from the derivatives of triphenylmethane which are
obtained by direct use of methylbenzylaniline sulphonic acid, ethylbenzylaniline

page_text: I. PREPARATION OF THE NEW CHLORO DERIVATIVES AND. SULPHONIC
DERIVATIVES OF BENZOIC ALDEHYDE ;
(a) PREPARATION OF ORTHO-CHLORO-BENZ ALDEHYDE METASULPHONIC ACID.
1 part of orthochlorobenzaldehyde is introduced into 5 parts of fuming sulphuric
acid of 30 per cent., while constantly agitating and taking care by cooling to prevent
the temperature of the mixture from rising above 10° C. After agitating for about
two hours it is slowly heated up to 80° to 85° C., and it is kept at this temperature
until a sample diluted with water has not the odour of chlorobenzaldehyde when it
is heated.
The product of the reaction is then poured into ice water and neutralised in the
usual way by lime.
When the calcium sulphate thus formed is separated from the solution, the latter
is evaporated till formation of a metallic pellicle; by cooling the calcium salt of
ortho-chlorobenzaldehyde metasulphonic acid then separates in form of yellow scales,
which are separated by filtration, pressed and dried.
(b)
TRANSFORMATION OF ORTHO-CHLOROBENZALDEHYDE METASULPHONIC
ACID INTO BENZALDEHYDE ORTHO-META DISULPHONIC ACID.
200 litres of a 10 per cent. solution of sodium bisulphite are neutralised by
soda lye, and then heated with 20 kilos. of the calcium salt of ortho-chloro-
benzaldehyde meta sulphonic acid (obtained as set forth in (a)) in a closed vessel
for 8 to 10 hours to about 180° to 200° C.
After cooling the vessel is opened, and to the solution are added 15 kilos.
of concentrated sulphuric acid, and the excess of sulphurous acid is then driven off
by boiling.
After separation of the calcium sulphate, the solution which contains benzalde-
hydedisulphonic acid is ready to be employed for producing colouring matters.
(c)
TRANSFORMATION OF
THE
DERIVED FROM BICHLORO TOLUENE INTO BENZALDEHYDE DISULPHONIC
ORTHOPARADICHLOROBENZALDEHYDE
ACID (CHO:SOH:SO,H=1:2:4).
100 parts of dichlorobenzaldehyde (CHO: C1: Cl=1:2:4) are mixed with
600 parts of a 10 per cent. solution of sodium bisulphite and have added to them
100 parts of 30 per cent. soda lye, and 240 parts of water.
The whole is heated in a closed vessel for 6 to 8 hours under a pressure
of 8 to 9 atmospheres. After cooling the contents of the vessel, they are acidulated
by 140 parts of concentrated sulphuric acid.
In order to eliminate excess of sulphurous acid as well as the traces of bichloro-
benzaldehyde not attacked, the product is heated for some time.
The remaining solution contains benzaldehyde disulphonic acid (CHO.: SO,H:
SO,H 1:2:4) seeing that by boiling it with sulphite solutions, the orthopara-
dichlorobenzaldehyde exchanges not only its atom of chlorine which is in the
ortho" position, but also that in the "para" position for a sulpho group.
The solution thus obtained may be used directly for condensation of amines.

page_text: EXAMPLE I. COLOURING MATTER DERIVED FROM A MOLECULE OF
DICHLOROBENZALDEHYDE (CHO: Cl: Cl = 1: 2: 5) AND TWO MOLECULES
OF BENZYLORTHOTOLUIDINE SULPHONIC ACID.
13.5 parts of bichloro benzaldehyde (CHO: Cl: Cl = 1:2:5) and 15 parts of
benzylorthotoluidine sulphonic acid are heated with 25 parts of sulphuric acid
of 40 per cent., for about 8 hours to 110° C.
The reaction product is then dissolved in an aqueous solution of sodium carbonate,
from which the disulpho leuco compound is precipitated by adding sulphuric
acid.
The precipitate thus obtained is separated from the mother liquor and is digested
with chalk in order to transform it into a calcium salt of the disulpho leuco
compound mentioned; the solution of this salt is then evaporated to dryness.
To transform the product into colouring matter, 7.5 parts of the calcium salt of
the disulpho leuco compound dry, are dissolved in 200 parts of water, and the
necessary quantity of sulphuric acid is added, after which there is added to
the mass 6 parts of a 40 per cent. peroxide of lead paste at ordinary temperature,
with careful agitation.
The lead sulphate is separated by filtration from the intense blue liquor from
which the colouring matter is separated by addition of sea salt, filtration
pressing &c.
It is a powder with bronze lustre easily soluble in water with blue colour.
EXAMPLE 3. COLOURING MATTER DERIVED FROM A MOLECULE OF ORTHO-
CHLOROBENZALDEHYDEMETASULPHONIC ACID AND TWO MOLECULES OF
METHYL BENZYL ANILINE SULPHONIC ACID.
24 parts of orthochlorobenzaldehyde metasulphonate of calcium are heated to
boiling with 600 parts of a 10 per cent. solution of methyl-benzyl aniline sulphonate
of calcium and 10 parts of concentrated sulphuric acid for about 8 hours.
After cooling a second addition of 10 parts of sulphuric acid is made and the
trisulphonic leuco-compound is transformed into colouring matter by adding to it
60 parts of 40 per cent. paste of lead peroxide. When the oxidation is completed
the product is neutralised by lime and the solution after being cleared by filtration
from calcium sulphate and lead sulphate is evaporated to dryness.

page_text: product is boiled with dilute hydrochloric acid in order to separate the small
quantities of methylbenzylaniline not attacked, and is then dried."
10 parts of the disulphonic leuco compound thus obtained are dissolved in
1000 parts of water care being taken to add the desired quantity of sodium
carbonate; the solution obtained is acidulated with sulphuric acid and oxidised by
the desired quantity of lead peroxide.
When the oxidation is completed, the product is neutralised with chalk, and the
solution of the colouring matter cleared from lead and calcium sulphates is
evaporated to dryness. It is a powder with coppery lustre, readily soluble in
water in acid bath it dyes wool intense blue.
When in this example benzylorthotoluidine or ethylbenzylaniline is substituted
for the methylbenzylaniline, colouring matters are obtained of more bluish shades.
The condensation takes place in a similar manner if dimethylaniline or diethyl-
aniline be employed. The products derived from the benzylated bases can be
transformed by sulphonation into trisulphonic and tetrasulphonic acids, furnishing
by ulterior oxidation colouring matters which are very readily soluble, and can
also be prepared directly by condensing a molecule of benzylaldehydedisulphonic
acid with two molecules the same or different of methylbenzylaniline sulphonic
acid, ethylbenzylaniline sulphonic acid or benzylorthotoluidine sulphonic acid.
EXAMPLE 7.
COLOURING MATTER DERIVED FROM ONE MOLECULE OF
. BENZALDEHYDE-DISULPHONIC ACID (CHO: SO,H: SO,H=1:2:4) AND
TWO MOLECULES OF ETHYLBENZYLANILINE.
150 parts of a 10 per cent. solution of benzaldehyde-disulphonic acid (CHO:
SO,H: SO,H=1:2:4) are heated on the water bath with 21 parts of ethyl-
benzylaniline for about 10 hours.
After cooling, the aqueous solution is decanted from the resinous product of
condensation which is deposited at the bottom of the vessel. This condensation
product is then dissolved in a dilute solution of sodium carbonate and from the
solution thus obtained the disulphonic acid is precipitated afresh by addition of
sulphuric acid, after which it is separated by filtration and dried.
10 parts of the dry disulphonic leuco-compound are dissolved in 250 parts of
water containing the requisite quantity of sodium carbonate.
The solution is then acidulated with acetic acid, and bas introduced into it while
hot 8 parts of 40 per cent. peroxide of lead paste, care being taken to constantly
stir the mass while adding the peroxide of lead.
After completion of the oxidation, the lead is precipitated by an addition of
Glauber's salts, and the colouring matter is precipitated from the filtered liquid by
an addition of sea salt. It consists of a powder with coppery lustre, dissolving in
water with blue colour. It dyes wool in an acid bath greenish blue.
For the preparation of mixed colouring matters, there is substituted for one
molecule that is to say 10-5 parts of ethy benzylaniline, in the preceding example
an equivalent quantity of dimethylaniline (7-5 parts), of methylbenzylaniline
sulphonic acid (14 parts) &c., without substantially departing from the process.
Having now particularly described and ascertained the nature of my inven-
tion and in what mauner the same is to be performed I am aware that it has
been proposed to produce colouring matters by condensing orthosulphobenzaldehyde
with certain alkylated aromatic amines, or their sulpho acids, and oxidising the
leuko-compounds thus obtained, and I make no claim to such production, but I
declare that what I claim is :-
1. The preparation of orthochlorobenzaldehydemetasulphonic acid, of amido-
benzaldehyde mono sulphonic acid (CHO: SO,H: NH, 1:2:5), of benzaldehyde
disulphonic acid (CHO: SO,H: SO,H = 1:2:4), and of benzaldehyde disulphonic
acid (CHO SOH SO H-1.9.5
sevibed

page_text: 2. The preparation of derivatives of triphenylmethane by the condensation of a
molecule of dichlorobenzaldehyde (CHO: CI: Cl=1:2:4), of orthochlorobenz-
aldehyde, of metanitro orthochlorobenzaldehyde, of orthosulphobenzaldehyde, of
orthochlorobenzaldehyde metasulphonic acid, of metachlorobenzaldehyde ortho-
sulphonic acid, of meta amidobenzaldehyde orthosulphonic acid, or of benzaldehyde
disulphonic acid (CHO: SO,H: SO,H=1:2:4 or 1:2:5) with
(a) two molecules of benzylorthotoluidine or its sulphonic derivative, or
(b) a molecule of benzylorthotoluidine or its sulphonic derivative and a mole-.
cule of another secondary or tertiary aromatic amine or of a sulphonate
derivative of such an amine.
3. The preparation of derivatives of triphenylmethane by condensation of the
derivatives of benzoic aldehyde mentioned in Claim 1 with two molecules the same.
or different of the following secondary and tertiary aromatic amines monomethyl
orthotoluidine, monoethyl orthotoluidine, dimethylaniline, diethylaniline, methyl-
benzyl aniline, methyl benzylaniline sulphonic acid, ethylbenzylaniline, ethylbenzyl-.
aniline sulphonic acid, nitrobenzylmethylaniline, nitrobenzyl-ethylaniline, dibenzyl-
aniline, dibenzylaniline monosulphonic acid, dibenzylaniline disulphonic acid,
monomethylaniline, monoethylaniline, monobenzylaniline and monobenzylaniline
sulphonic acid.
4. The preparation of colouring matters of the tri-phenylmethane series dyeing
from green blue to blue in acid baths by treating the condensation products.
obtained as set forth in Claims 2 and 3 by oxidising agents such for instance as
peroxides or chromic acid.
5. As new products applicable to the manufacture of colouring matters, the
derivatives of benzoic aldehyde mentioned in Claim 1, as well as the derivatives
of triphenylmethane which can be obtained by the process set forth in Claims 2-
and 3.
6. As new products the colouring matters which can be obtained by the process.
set forth in Claim 4.
Dated this 9th day of November 1896
ABEL & IMRAY,
Agents for the Applicant..