Improvements in the Manufacture of Colouring Matters of the Rosaniline Series
Year: 1898

page_text: Date of Application, 28th Dec, 1898
Complete Specification Left, 10th Jan, 1899-Accepted, 22nd Apr., 1899
PROVISIONAL SPECIFICATION,
Improvements in the Manufacture of Colouring Matters of the
Rosaniline Series.
I, THOMAS RICHARD SHILLITO, of 15, Tooks Court, London, E.C, Patent Agent,
do hereby declare the nature of this invention, a communication to me from abroad
by Messieurs John Rudolph Geigy & Co., of Basle, Switzerland, Colour Manu-
facturers, to be as follows
Since my correspondents came to know the important influence of those groups
which enter in ortho position to the methane carbon in the colouring matters of the
malachite green series, as regards the shade as well as the fastness to the action of
alkalies, the number of these colouring matters as well as of the processes for
manufacturing the same has quite considerably increased
It is therefore very
surprising that only a small number of colouring matters of the rosamline series
being substituted in ortho position to the methane carbon are known of For instance
my correspondents know of only two basic colouring matters of this kind, the
monochloro and the trichloro crystallised violet (German Patent Specification
No 90771) The reason of this peculiar fact 19 seen partly in the expensive. paitly
in the impossible production of the necessary aromatic amidoaldehydes Helped
out of this diffienlty by the process of our Provisional Specification No 17135 ot
1898 communicated to me by my said foreign correspondents, these have obtained a
whole series of colouring matters belonging to the 10saniline series and being once.
twice, and thrice substituted in ortho position, and have found that with each
substitutive group in ortho position the shade of the original colouring matter turns
gradually from violet to blue and green, thus for instance, a violet colouring
matter passes over in blueish violet by angle, in a blue by double, and in a blueish
green by tuple substitution
My correspondents have obtained a further variation in the shade by starting
from monoalkylated amidoaldehydes besides the dialkylated Farther they have
ascertained that in the case of double substitution the effect of the ortho
substituting groups is nearly the same if they are in the same benzene ring or if
they are distributed about two phenyl groups, or if the substitution is accomplished
by chlorine or by methyl groups.
EXAMPLES.
I. 164 kilos of dimethyl-p-amido-o-tolayl-aldehyde, 30 kilos. of dimethylaniline,
and 30 kilos of concentrated muriatic acid are boiled together, in a kettle lined
with lead and provided with a reflux cooler, from 10 to 15 hours. As soon as no
more aldehyde can be traced by the reaction with paraphenylenediamine, a solution
of carbonate of soda is added and the excess of amine is duiven off by steam. The
leuko base, remaining as a grey granulous substance, 18 filtered, washed, and dried.
In order to oxidise the same, 88 7 kilos of said leuko base are dissolved in 43.5 kilos.
of muriatic acid of 28.6 per cent) free from sulphuric acid and 4000 liters (of water
11
11

page_text: 19 per cent. of peroxide of lead. In order to precipitate the lead there are added
after 2 hours still 25 kilos of Glauber's salt, then heated up to 80° C, and filtered
from the sulphate of lead. The colouring matter may be precipitated by common
salt, when dry it forms green lamina of a metallic lustre, very soluble in water
with a blue violet shade. Its solution mixed with ammonia is only discoloured after
Bome time, the carbinol base being precipitated Mineral acids as with all rosanı-
line colours alter the shade to green and yellow, getting blue violet again when
dilated with water
II 149 kilos. of monoethyl-p-amidobenzaldehyde, 30 kilos of m-chlorodimethyl-
aniline and 30 kilos of concentrated muriatic acid are heated in a kettle with
reflux cooler during 15 hours. 456 kilos of the leuko base remaining after the
removal of the sui plus of amine by steam, are dissolved in 55 kilos. of pure
muriatic acid (286 per cent) and 5000 liters of water and oxidised by addition of
119 5 kilos. of a paste containing 19 per cent of peroxide of lead After the lead
has been precipitated by means of Glauber's salt, the solution 18 filtered and
precipitated with common salt The colouring matter is obtained in bronze
looking lamina, very soluble in water with reddish violet shade Mixed with
ammonia the solution is at once discoloured and the carbinol base precipitated in
greenish flocks.
III By condensation of diethyl-p-amidobenzaldehyde with m-chlorodiethyl-
aniline my correspondents obtain a leuko base which may be oxidised to a colouring
matter of a reddish metallic Instre, very soluble in water with a blue shade, similar
to that of the colouring matter known in the market under the name of Victoria
Blue B Mixed with ammonia the solution is only discoloured after some time.
Silk, wool, and tannin mordanted cotton are dyed in a remarkably brilhant and
pnre shade
IV. Orthochlorodiethyl-p-amidobenzaldehyde condensed with metachlordiethyl-
aniline as above described, and oxidised, furnishes a colouring matter of a copper
like metallic lustre which 18 very soluble in water with a beautiful greenish .blue
colour and dyes silk, wool, and mordanted cotton in an extremely pure greenish
blue shade.
Dated this 28th day of December 1898
THOMAS R SHILLITO,
15, Tooks Court, London, E C
Improvements in the Manufacture of Colouring Matters of the
Rosaniline Series.
I, THOMAS RICHARD SHILLITO, of 15, Tooks Court, London, EC, Patent Agent,
do hereby declare the nature of this invention and in what manner the same is to be
performed, a communication to me from abroad by Messienrs John Rudolph Geigy
& Co, of Basle, Switzerland, Colour Manufacturers, to be particularly described and
ascertained in and by the following statement
Since
my correspondents came to know the important influence of those groups
which enter in ortho position to the methane carbon in the colouring matters of the
malachite green series, as regards the shade as well as the fastness to the action of
alkalies, the number of these colouring matters as well as of the processes for
manufacturing the same has quite considerably increased It is therefore very
surprising that only a small number of colouring matters of the rosaniline series
being substituted in ortho position are known of For instance my correspondents
know of only two basic colouring matters of this kind, the monochloro and the

page_text: trichloro crystallised violet (German Patent Specification No. 90771) The reason
of this peculiar fact is seen partly in the expensive, partly in the impossible
production of the necessary aromatic amidoaldehydes Helped out of this difficulty
by the process of my Patent Specification No 17135 of 1898 cominumicated to ine
by my said foreign correspondents, these have obtained a whole series of colouring
matters belonging to the rosautline series and being once, twice, and thrice
substituted in ortho position, and have found that with each substitutive group in
ortho position the shade of the original colouring matter turns gradually from violet
to blue and green; thus for instance, a violet colouring matter passes over in blueish
violet by single, in a blue by double, and in a blueish green by triple substitution.
My correspondents have obtamed a further variation in the shade by starting
from monoalkylated amido-aldehydes besides the dialkylated. Further they have
ascertained that in the case of double substatutson the effect of the ortho substituting
groups 19 nearly the same if they are in the same benzene ing or if they are
distributed about two phenyl groups, or if the substitution is accomplished by
chlorine or by methyl groups
EXAMPLES:
I. 164 kilos. of dimethyl-p-amido-o-toluylaldehyde, 80 kilos of dimethylaniline
and 30 kilos of concentrated muriatic acid are boiled together, in a kettle lined with
lead and provided with a reflux cooler, from 10 to 15 hous As soon as no more
aldehyde can be traced by the reaction with paraphenylenediamine, a solution of
carbonate of soda is added and the excess of amine is driven off by steam. The
lenko base, remaining as a grey grannlous substance, is filtered, washed, and dried.
In order to oxidise the same, 38-7 kilos of said lenko base are dissolved in 43 5 kilos
of muriatic acid (of 286 per cent) free from sulphuric acid and 4000 liters of water
and then whilst stirring, rapidly mixed with 1195 kilos. of a pasto containing
19 per cent of peroxide of lead. In order to precipitate the lead, there me added
after 2 hours still, 25 kilos. of Glauber's salt, then heated up to 80° C. and
filtered from the sulphate of lead The colouring matter may be precipitated by
common salt, when diy it forms green lamma of & metallic lustre, very
Boluble in water with a blue violet shade. Its solution mixed with ammonia is only
discoloured after some time, the carbinol base being precipitated. Mineral acids, as
with all rosaniline colours, alter the shade to green and yellow, getting blue violet
agam when diluted with water.
II. 149 kilos. of monoethyl-p-amidobenzaldehyde, 30 kilos. of m-chlorodimethyl-
aniline and 30 kilos of concentrated muriatic acid are heated in a kettle with reflex
cooler daring 15 hours 456 kilos. of the leuko base romaining after the removal of
the surplus of amine by steam, are dissolved in 55 kilos. of pure muriatic acid
(28 6 per cent.) and 5000 liters of water and oxidised by addition of 119.5 kilos of
a paste containing 19 per cent. of peroxide of lead After the lead has been pre-
cipitated by means of Glauber's salt, the solution is filtered and precipitated with
common salt The colouring matter is obtained in bronze looking lamina, very
soluble in water with reddish violet shade Mixed with ammonia the solution 18 at
once discoloured and the carbinol base precipitated in greenish flocks.
III. By coudensation of diethyl-p-amidobenzaldehyde with m-chlorodiethylanı-
line my correspondents obtain a leuko base which may be oxidised to a colouring
matter of a reddish metallic lustre, very soluble in water with a blue shade similar
to that of the colouring matter known in the market under the name of Victoria
Blue B. Mixed with ammonia the solution is only discoloured after some time.
Silk, wool, and tannin mordanted cotton are dyed in a remarkably brilliant and pure
shade
IV. Orthochlorodiethyl-p-amidobenzaldehyde condensed with metachlordiethyl-
aniline as above described, and oxidised, furnishes a colouring matter of a copper
like metallic lustre which is very soluble in water with a beautiful greenish blue colour
and dyes silk, wool, and mordanted cotton in an extretnely pure greenish blue
shade.

page_text: Having described the process by means of the foregoing four typical examples it
may further be mentioned that after the same process a series of colouring matters
as given underneath may likewise be obtained
Blneish violet to blue and greenish blue colouring matters obtained by treating
the products of condensation of

page_text: Having now particularly described and ascertained the nature of s
d in what manner the same is to be performed, as communicated
reign correspondents, I declare that what I claim is
-
1. The manufacture and prodnation of alkylated leuko derivatives of
nies, once, twice and thrice substituted in ortho position to the me
the condensation of
one
molecule
nonomethyl-p-amidobenzaldehyde
monoethyl-p-amidobenzaldehyde
nonomethyl-p-ainido-m-toluyaldehyde
monoethyl-p-amido-m-toluylaldehyde
dimethyl-p-amidobenzaldehyde
ot
diethyl-p-amidobenzaldehyde
In-chloroinonomethylaniline
m-chloromonoethylamiline
d of
with
two
dimethyl-m-toluidine
diethyl-in-toluidine
molecules m-chloromonomethyl-o-tolaidine
of in-chloromonoethyl-o-toluidine
ulle
m-chlorodimethylaniline
m-chlorodiethylanilme
(o-chloromonomethyl-p-andobenzaldehyde
o-chloromonoethyl-p-amidobenzaldehyde
anolecule o-chloromonomethyl-p-amido-m-toluylaldehyde
ut
o-chloi omonoethyl-p-amdo-m-toluylaldehyde
o-chlorodiethyl-p-amidobonzaldehyde
monomethylaniline
monoethylaniline
dimethylaniline
diethylaniline
with
monomethyl-o-tolmidine
two monoethyl-o-toluidine
molecules m-chloromonomethylaniline

page_text: from blueish violet to blue and greenish blue, by treating the products of
condensation obtained as set forth in Claim 1 by- oxidising agents such as for
instance peroxides or chromic acid, substantially as described
3 As new products, the colouring matters which can be obtained by the process
set forth in Claim 2, substantially as described
Leted this 10th ow of La1900
THOMAS R SHILLITO,
15, Tooks Court, London, E C