Manufacture and Production of Intermediate Products, and of Colouring Matters therefrom.
Year: 1898

page_text: Date of Application, 17th Feb., 1898
Complete Specification Left, 15th Nov., 1898-Accepted, 7th Jan.,
1899
*NOLIVOLION IN JIVNOICI LOVI
PROVISIONAL DIECIFICATION.
Manufacture and Production of Intermediate Products, and of
Colouring Matters therefrom.
We, ARTHUR GEORGE GREEN, F.I.C., F.C.S., of 13, King's Drive, Heaton Moor,
near Stockport, RENÉ LEVY, of 124, Church Street, Bradford, Manchester, both
Chemists, and THE CLAYTON ANILINE COMPANY LIMITED, Chemical Manufacturers,
of Clayton, Manchester, in the County of Lancaster, do hereby declare the nature of
this invention to be as follows:-
The invention relates to the production of para-substituted derivatives of
benzaldehyde-ortho sulphonic acid and to the preparation therefrom of colouring
matters of the triphenylmethane series which owing to the ortho position of the
sulphonic acid group to the central carbon atom, are fast against the action of
alkalies.
We have found that such parasubstituted derivatives of benzaldehyde or thosulphonic
acid are readily obtained by oxidation of the corresponding derivatives of stilbene-
ort hodisulphonic acid with permanganates in cold aqueous solution according to the
general equation.
Paradichlorostilbeneorthodisulphonic acid
CH,CI(SO₂H).CH : CH.C¸H₂C)(SO,H)
Paradibromostilbeneorthodisulphonic acid
CH,Br(SO,H).CH: CH.CH.Br(SO,B)
Paradicyanostilbeneorthodisulphonic acid
CH(CN) (SOH).CH: CH.CH (CN) (SO,H)
Paradiethoxystilbeneorthodisulphonic acid
CH(OCH.) (SO,H).CH: CH.CH(OCH) (SOH)
Paradimethoxystilbeneorthodisulphonic acid
CH¸(ОCÍ¸) (SOH).CH : CH.C¸H¸(ОCH)SOH
Stilbene paradisulphinicorthodisulphonic acid
CH(SO,H) (SO,H).CH : CH.CH,(SOH) (SOH)
Stilbeneparadicarboxyorthodisulphonic acid
C,H,(CO,H) (SỐ,H).CH:CH.CH,(CO_H) (SO,H)

page_text: These new stilbene derivatives are all obtained from diamidostilbenedisulphonic
acid by substitution of hydrogen in the amido groups, or by replacement of the amido
groups by other atoms, or radicals.
The substituted benzaldehyde sulphonic acids are converted into colouring-matters
in the usual way by condensation in acid aqueous solution with secondary, or
tertiary, aromatic amines, or their sulphonic acids, and subsequent oxidation of the
leuco compounds obtained.
The following examples illustrate the conversion of diamidostilbenedisulphonic
acid into new stilbene derivatives suitable for conversion into aldehydes.
EXAMPLE 1.
DICHLOROSTILBENEDISULPHONIC ACID,
25 lbs. of diamidostilbenedisulphonic acid are dissolved in 15 gallons of water:
containing 8 lbs. of sodium carbonate. 15 gallons of hydrochloric acid (30% HCI)
are then added and the mixture (cooled to 0° Centigrade with ice) is diazotised by
addition of 10 lbs. of sodium nitrite. When the diazotisation is complete copper
powder (about 8 lbs.) is slowly added until the evolution of nitrogen has ceased and
the tetrazo compound has gone into solution. The solution of the dichlorostilbene-
disulphonic acid thus obtained is freed from copper by the addition of sodium
sulphide, and can be employed directly for the preparation of the aldehyde. The
free acid can be isolated by evaporating the aqueous solution to dryness and
extracting with alcohol, in which it dissolves, and is obtained, on evaporation, as
a crystalline solid very soluble in water.
EXAMPLE 2.
DIETHOXYSTILBENEDISULPHONIC ACID.
The
18 lbs. of diamidostilbenedisulphonic acid are diazotised in the usual manner,
insoluble tetrazo compound is filtered off and suspended in 10 gallons of alcohol.
The mixture is warmed and copper powder is added until the evolution of nitrogen
has ceased and the precipitate has entirely dissolved. The alcohol is then distilled
off, the residue is dissolved in water and freed from copper by a stream of hydric
sulphide. On evaporation the product is obtained as a hygroscopic mass.
EXAMPLE 3.
STILBENEDISULPHINICDISULPHONIC ACID.
37 lbs. of diamidostilbenedisulphonic acid are dissolved in 15 gallons of water con-
taining 11 lbs. of sodium carbonate. The solution is acidified with 300 lbs. of 20 per
cent. sulphuric acid, cooled with ice and diazotised by addition of 14 lbs. of sodium
nitrite. The mixture is then saturated with sulphurous acid gas, and copper powder
is slowly added until the evolution of nitrogen ceases and the tetrazo compound has
gone into solution. The product is then filtered, freed from excess of sulphurous
acid by passing a stream of air through the solution and from copper salts by the
addition of sodium sulphide. After filtering from copper sulphide, the solution can
be employed directly for the preparation of the benzaldehydedisulphonic acid.

page_text: EXAMPLE 4. DIACETAMIDOSTILBENEDISULPHONIC ACID,
The sodium salt of diamidostilbenedisulphonic acid in fine powder is boiled for
several hours with a mixture of acetic acid and acetic anhydride. The product is
filtered off and dissolved in boiling water and sodium carbonate. On cooling the
5 sparingly soluble sodium salt of diacetamidostilbenedisulphonic acid crystallises
out.
EXAMPLE 7.
PARAETHOXYBENZALDEHYDEORTHOSULPHONIC ACID.
13 lbs. of crude diethoxystilbenedisulphonic acid as obtained under the foregoing
Example 2 are dissolved in 50 gallons of water, neutralised with sodium carbonate
and cooled to 5°-10° Centigrade. Into this solution whilst rapidly agitated a cold
After
solution of 5 lbs. of potassium permanganate in 10 gallons of water is run.
filtration from oxide of manganese the solution of the aldehyde is neutralised and
concentrated by evaporation.
EXAMPLE 8.
BENZALDEHYDEORTHOPARADISULPHONIC ACID.
A solution of
By oxidation of stilbenedisulphinicdisulphonic acid with potassium permanganate
the conversion of the stilbene group into the two aldehyde groups is accompanied
by the simultaneous oxidation of the sulphinic to sulphonic groups.
32 lbs. of stilbenedisulphinic-disulphonic acid as obtained under the foregoing
Example 3 is so oxidised by the gradual addition of a cold solution of 30 lbs. of
potassium permanganate in 50 gallons of water.
After filtration from oxide of
manganese, the solution of the aldehyde is neutralised with hydrochloric acid and
concentrated.
EXAMPLE 9.
PARAACETAMIDOBENZALDEHYDEORTHOSULPHONIC ACID.
20 lbs. of the sodium salt of diacetamidostilbene disulphonic acid as obtained
under the foregoing Example 4, are oxidised by the addition of 8 lbs. of potassium
permanganate in the manner described in the preceding examples. The solution of
the aldehyde gives a bright orange precipitate with tolidine hydrochloride. By con-
densation with secondary and tertiary aromatic amines it gives rise to leuco

page_text: 10 gallons of a solution containing 11.3 lbs. of the sodium salt of parachloro-
benzaldehyde orthosulphonic acid as obtained under the foregoing Example 6 are
boiled for fifteen hours with 16 lbs. of dimethylaniline and 10 lbs. of concentrated
sulphuric acid. The solution is then made alkaline and unaltered dimethylaniline is
distilled off with steam. On cooling, and adding a little salt, the leuco compound
separates out as a resinous mass. 9 lbs. of the dry leuco compound thus obtained
are dissolved in 300 gallons of water. 10 lbs. of sulphuric acid are added, and the
mixture is oxidised by the addition of 46 lbs. of lead peroxide paste (10 per cent.
PbO2) at a temperature of 45° Centigrade. After neutralisation with ammonia the
precipitated lead sulphate is filtered off and the solution of the colouring-matter is
evaporated until the colouring-matter separates out. After drying it forms a bronzy
powder which dyes wool and silk, from an acid bath, a bright greenish-blue
unaffected by alkalies. It also dyes tannin-mordanted cotton from a neutral
bath.
EXAMPLE 12.
8 gallons of a 10 per cent. solution of the sodium salt of paraethoxybenzalde-
hydeorthosulphonic acid, prepared according to the foregoing Example 7, are boiled
for fifteen hours with 12 lbs. of dimethylaniline and 8 lbs. of sulphuric acid. After
neutralising, and distilling off the excess of dimethylaniline, the leuco compound
separates as a viscid mass, which becomes solid on cooling. The leuco compound
thus obtained is dissolved in 80 gallons of water, acidified with 10 lbs. of sulphuric
acid, and oxidised by the addition of 70 lbs. of 10 per cent, lead peroxide paste.
The solution, after neutralisation, and filtration, from lead sulphate, deposits the
8 gallons of a 10 per cent. solution of the sodium salt of paraethoxybenzalde-
hydeorthosulphonic acid, prepared according to the foregoing Example 7, are boiled
for fifteen hours with 12 lbs. of dimethylaniline and 8 lbs. of sulphuric acid. After
neutralising, and distilling off the excess of dimethylaniline, the leuco compound
separates as a viscid mass, which becomes solid on cooling. The leuco compound
thus obtained is dissolved in 80 gallons of water, acidified with 10 lbs. of sulphuric
acid, and oxidised by the addition of 70 lbs. of 10 per cent. lead peroxide paste.
The solution, after neutralisation, and filtration, from lead sulphate, deposits the

page_text: colouring-matter on concentration. It dyes wool and silk, from an acid bath, a
beautiful clear greenish-blue which is not affected by alkalies.
Dated this 17th day of February 1898.
JOHNSONS & WILLCOX,
47, Lincoln's Inn Fields, London, W.C., Agents.
Manufacture and Production of Intermediate Products, and of
Colouring Matters therefrom.
We, ARTHUR GEORGE GREEN, F.I.C., F.C.S., of 13, Kings Drive, Heaton Moor,
near Stockport, RENE LEVY, of 124, Church Street, Bradford, Manchester, both
Chemists, and THE CLAYTON ANILINE COMPANY LIMITED, Chemical Manufacturers,
of Clayton, Manchester, in the County of Lancaster, do hereby declare the nature of
this invention and in what manner the same is to be perforined, to be particularly
described and ascertained in and by the following statement:-
The invention relates to the production of certain parasubstituted derivatives of
benzaldehyde-ortho-sulphonic acid and to the preparation, therefrom, of colouring
matters of the triphenylmethane series, which, owing to the ortho position of the
sulphonic acid group to the central carbon atom, are fast against the action of
alkalies.
We have found that such parasubstituted derivatives of benzaldehydeorthosulphonic
acid are readily obtained by oxidation of the corresponding derivatives of stilbene-
ortho-disulphonic acid with permanganates in cold aqueous solution according to the
general equation:

page_text: The substituted benzaldehyde sulphonic acids are converted into colouring matters
by condensation in the usual way in acid aqueous solution with secondary, or tertiary
aromatic amines, or their sulphonic acids, and subsequent oxidation of the leuco
compounds obtained.
The following examples illustrate the conversion of diamidostilbenedisulphonic
acid into new stilbene derivatives suitable for conversion into aldehydes.
EXAMPLE 1.-DICHLOROSTILBENEDISULPHONIC ACID.
25 lbs. of diamidostilbenedisulphonic acid are dissolved in 15 gallons of water con-
taining 8 lbs. of sodium carbonate, 15 gallons of hydrochloric acid (30% HCI) are
then added and the mixture (cooled to 0° Centigrade by means of ice) is diazotised
by the addition of 10 lbs. of sodium nitrite. When the diazotisation is complete
copper powder, (about 8 lbs.), is slowly added until the evolution of nitrogen has
ceased and the tetrazo compound has gone into solution. The solution of the di-
chlorostilbenedisulphonic acid thus obtained is freed from copper by the addition of
sodium sulphide, and can be employed directly for the preparation of the aldehyde.
The free acid can be isolated by evaporating the aqueous solution to dryness and
extracting by means of alcohol, in which it dissolves, and is obtained, on evaporation,
as a crystalline solid very soluble in water.
EXAMPLE 2.-STILBENEDISULPHINICDISULPHONIC ACID.

page_text: and copper powder iss lowly added until the evolution of nitrogen ceases and the tetrazo
compound has gone into solution. The product is then filtered, free from excess of
sulphurous acid, by passing a stream of air through the solution, and from copper
salts by the addition of sodium sulphide. After filtering from copper sulphide, the
solution can be employed directly for the preparation of the benzaldehydedisulphonic
acid,
solution, whilst rapidly agitated, a cold solution of 54 lbs. of potassium permanganate
in 10 gallons of water is run. The mixture is then warmed, to coagulate the oxide
of manganese, and filtered. The filtrate, after neutralisation, and concentration to
proper strength, is employed directly for the preparation of colouring-matters.
EXAMPLE 4. BENZALDEHYDEORTHOPARADISULPHONIC ACID.
By oxidation of stilbenedisulphinicdisulphonic acid with potassium permanganate
the conversion of the stilbene group into the two aldehyde groups is accompanied by
the simultaneous oxidation of the sulphinic to sulphonic groups. A solution of
32 lbs. of stilbenedisulphinicdisulphonic acid as obtained under the foregoing
Example 2 is oxidised by the gradual addition of a cold solution of 30 lbs. of
After filtration from oxide of
potassium permanganate in 50 gallons of water.
manganese, the solution of the aldehyde is neutralised with hydrochloric acid and
concentrated.
PREPARATION OF COLOURING MATTERS.
The conversion of the hereinbefore described para substituted benzaldehyde ortho-
sulphonic acids into colouring-matters of the triphenyl-methane series is performed
by boiling in acid aqueous solution with a secondary, or tertiary, aromatic amine, or
its sulphonic acid. Amongst those amines especially suitable for this purpose may be
mentioned the following:-
Dimethylaniline, diethylaniline, benzylethylaniline, benzylmethylaniline, benzyl-
ethylaniline sulphonic acids, benzylmethylaniline sulphonic acids, dibenzylaniline-
sulphonic acids, methylorthotoluidine, ethylorthotoluidine, benzylorthotoluidine,
benzylorthotoluidine sulphonic acids, and the like. In place of employing two
molecular proportions of the same amine there may may be used a mixture of one
molecular proportion of one amine and one molecular proportion of another amine.
In cases where the condensation is performed with unsulphonated benzylated amines
it is usually advisable to further sulphonate the leuco compound before oxidation.
The oxidation of the leuco compounds into colouring-matters can be performed by
means of lead peroxide, manganese-dioxide, ferric chloride, potassium bichromate
potassium permanganate and the like.
The general method of carrying out the process is illustrated by the following
examples:

page_text: 4. The manufacture and production of blue to green colouring-matters of the
triphenylmethane series characterised by the following steps:-(a) Replacement of
the amido groups in diamidostilbenedisulphonic acid by chlorine, cyanogen, ethoxyl,
methoxyl, sulphinic groups, sulphonic groups, or carboxy groups. (b) Oxidation of
the product with potassium permanganate in cold aqueous solution. (c) Condensation
of the aldehyde obtained with a secondary or tertiary aromatic amine or sulphonic
acid thereof. (d) Oxidation of the leuco compound obtained into the colouring-
matter.
JOHNSONS & WILLCOX,
47, Lincoln's Inn Fields, London, W.C., Agents.