Improvements in the Manufacture of Blue-green Dyestuffs of the Triphenylmethane Series.
Year: 1899

page_text: Date of Application, 27th Nov., 1899-Accepted, 2nd June, 1900
Improvements in the Manufacture of Blue-green Dyestuffs of the
Triphenylmethane Series.
I, RIDLEY JAMES URQUHART, of 57, Barton Arcade, Manchester, in the County
of Lancaster, Consulting Engineer and Patent Agent, hereby declare the
nature of this invention which has been communicated to me by the Chemische
Fabriken vormals Weiler-ter-Meer, of Uerdingen on the Rhine, Prussia, and
in what manner the same is to be performed, to be particularly described and
ascertained in and by the following statement:
This invention consists in improvements the manufacture of dyestuffs of the
triphenylmethane series, whereby novel valuable blue-green dyestuffs of this
series containing a chlorine group in ortho position to the methane carbon,
fast to alkalies, are obtained. The improvements consist in manufacturing said
dyestuff's by condensing ortho-chlorbenzaldehyde, or ortho-chlor-benzal chloride
or their substitution products, with secondary or tertiary amines drying and
sulphonating the leuco-compounds obtained, dissolving the leuco-sulphonic acids
produced in diluted soda solution and oxidising them; or by condensing ortho-
chlorbenzaldehyde or ortho-chlorbenzal chloride or their substitution products
with sulphonic acids or sulphonic acid salts of secondary or tertiary amines;
dissolving the leuco-compounds produced, precipitating, pressing and drying
them, then redissolving in diluted soda solution and oxidising them.
In order that this invention and the manner of carrying it into effect may.
be readily understood, the following examples of the process of manufacturing
such blue green dyestuffs are described :-
-
EXAMPLE A.
The following mixture is heated under a reflux condenser for 12 hours;
58 kilogrammes of ethylbenzylaniline sulphonic acid
ortho-chlorbenzaldehyde,
14
45
"
"
"
water.
"
The leuco-sulphonic acid thus produced is dissolved in dilute_soda solution,
precipitated with hydrochloric acid, filter-pressed and dried. For conversion
into the colouring matter 25 kilogrammes of this leuco-sulphonic acid are dis-
solved in 120 litres of water and 3.8 kilogrammes of soda, and oxidised with a
paste of 8.3 kilogrammes of peroxide of lead (100%) and 7 kilogrammes of
sulphuric acid.
After oxidation is complete the excess of acid is neutralised with soda, the
lead sulphate is filtered off and the dyestuff subsequently salted out. In the
dry state this is a blue-green powder easily soluble in water and dyeing wool
and silk clear blue-green shades, whose brightness is intensified in artificia!
light. It satisfactorily resists the action of light and washing and is fast to
soap and alkalies, and gives results of great evenness.

page_text: A similar dyestuff is obtained by condensing ortho-chlorbenzaldehyde with
methylbenzylaniline sulphonic acid, then proceeding as above described.
EXAMPLE C.
A similar dyestuff of blue shade is obtained by condensing o-chlorbenzalde
hyde with the calcium salt of methylbenzylaniline sulphonic acid in a solution
of sulphuric acid and then proceeding as above described.
The same dyestuffs are obtained by condensing the free amines instead of
the sulphonic acids as is above described, with o-chlorbenzaldehyde, then sul-
phonating the leuco-bases and oxidising the leuco-sulphonic acids thus produced.
The following examples describe this proceeding,
105 kilogrammes of ethylbenzylaniline
38
24
"
"
"
و.
ortho-chlorbenzaldehyde
sulphuric acid 60° Bé
"
water
"
are heated during ten hours at 110° C. The sulphuric acid is then neutralised
with 45 kilogrammes of caustic soda (33%), that portion of the aldehyde, which
has not taken part in the reaction is distilled off by means of steam, and the
leuco-bases, thus produced, are dried. For the conversion into the sulphonic
acid, 50 kilogrammes of leuco-base are dissolved in 200 kilogrammes of con-
centrated sulphuric acid and heated at 160° C., with stirring, till a sample dis-
solves clearly in sodium carbonate. After sulphonation the mixture is poured
into ice cold water, where the leuco-sulphonic acid, thus produced, is separated.
After washing and drying, the leuco-sulphonic acid is oxidised as described
in Example A. The dyestuff thus produced, forms a blue green powder, which
is identical with the dyestuff of Example A.
EXAMPLE B¹.
If the ethylbenzylaniline in Example A¹ is replaced by the corresponding
methylcompound and the order of steps for the production of the dyestuff is
the same as above described, a dyestuff results, which is identical with the dye-
stuff of Example B.
EXAMPLE D.
For the ortho-chlorbenzaldehyde of Example A is substituted 18.5 kilo-
grammes of ortho-chlor-meta-nitrobenzaldehyde (2.5) the process being exactly
as before. On oxidation of the leuco-sulphonic acid, a valuable dyestuff is
obtained, which forms a blue-green powder, soluble in water and dyeing wool
and silk bluish-green shades fast to soap and alkalies.
EXAMPLE E.
If instead of ethylbenzylaniline sulphonic acid, the calcium salt of the corré-
sponding methylcompound is condensed with 2.5 chlornitrobenzaldehyde in the
presence of sulphuric acid, a leuco-base is produced, which gives on oxidation
a dyestuff of the same qualities but of a bluer shade.
The same dyestuffs are obtained by combining, instead of the sulphonic acids,
the free amines with 2.5 chlornitrobenzaldehyde, sulphonating the leuco-bases
thus produced, and oxidising the leuco-sulphonic acids.

page_text: are heated during ten hours at 110° C. in a vessel with a reflux condenser.
After Condensation the sulphuric acid is neutralised with 45 kilogrammes of
caustic soda (33%), the leuco-base filterpressed and dried. For the conversion
into the sulphonic acid 50 kilogrammes of leuco-base are heated with 200 kilo-
grammes of concentrated sulphuric acid at 160° C., with stirring, till a sample
dissolves clearly in sodium carbonate. After sulphonation the mixture is poured
into ice cold water and the separated leuco-base washed, filter-pressed and dried.
For conversion into the dyestuff the process is the same as is described in
Example A. The dyestuff thus produced is identical with the dyestuff, described
in Example D.
are heated during ten hours at 110° C. in a vessel with a reflux condenser.
After condensation the sulphuric acid is neutralised with 45 kilogrammes of
caustic soda (33%), the leuco-base filterpressed and dried. For the conversion
into the sulphonic acid 50 kilogrammes of leuco-base are heated with 200 kilo-
grammes of concentrated sulphuric acid at 160° C., with stirring, till a sample
dissolves clearly in sodium carbonate. After sulphonation the mixture is poured
into ice cold water and the separated leuco-base washed, filter-pressed and dried.
For conversion into the dyestuff the process is the same as is described in
Example A. The dyestuff thus produced is identical with the dyestuff, described
in Example D.
EXAMPLE E¹.
If in Example D₁ the ethylbenzylaniline is replaced by the corresponding
methylcompound and the process is carried out as above described, a dyestuff
results which is identical with the dyestuff described in Example E.
Having now particularly described and ascertained the nature of my said
invention and in what manner the same is to be performed, I declare that what
I claim is:-
1. The process of manufacturing triphenylmethane dyestuff's containing a
chlorine group in ortho position to the methane carbon, which process consists
in heating in a reflux condenser ortho-chlorbenzaldehyde or ortho-chlorbenzal
chloride or their substitution products, with secondary or tertiary amines, dry-
ing and sulphonating the leuco-compounds produced, dissolving the leuco-
sulphonic acids thus obtained in diluted soda solution and oxidising them, sub-
stantially as described.
2. The process of manufacturing triphenylmethane dye-stuffs containing a
chlorine group in ortho-position to the methane carbon, which process consists
in heating in a reflux condenser ortho-chlorbenzaldehyde or ortho-chlorbenzal
chloride or their substitution products with sulphonic acids of secondary or
tertiary amines or with salts of said acids, dissolving the leuco-compounds pro-
duced, precipitating, filter-pressing and drying, then re-dissolving in diluted
soda solution and oxidising them, substantially as described.
3. The process of manufacturing triphenylmethane dye-stuffs which process
consists in heating in a reflux condenser ortho-chlorbenzaldehyde or ortho-
chlorbenzal chloride or their substitution products with ethylbenzylaniline, or
methylbenzylaniline, sulphonating the leuco-compounds produced, dissolving
the products in diluted soda solution and oxidising them, substantially as
described.
4. The process of manufacturing triphenylmethane dye-stuffs which process
consists in heating in a reflux condenser ortho-chlorbenzaldehyde or ortho-
chlorbenzal chloride or ortho-chlor-meta-nitrobenzaldehyde with ethylbenzyl-
aniline sulphonic acid or with methylbenzylaniline sulphonic acid, dissolving
the leuco-sulphonic acid produced in dilute soda solution, precipitating, filter-
pressing and drying the same, re-dissolving the product in dilute soda solution
and oxidising it, substantially as described.
5. The processes or methods of producing blue-green dye-stuffs substantially
as herein before described with reference to Examples A B, C, D, E, A¹, B¹, D¹
and E¹.
G. The manufacture and use of blue-green dyestuffs produced substantially
as hereinbefore described and claimed in the preceding claims.
Dated this 22nd day of November 1899.
R. J. URQUHART, C.E.,
Chartered Patent Agent, Manchester & Liverpool.