Year: 1886

page_text: Date of Application, 21st Sept., 1886.
Complete Left, 22nd Dec., 1886.
Complete Accepted, 19th Apr., 1887.
II.
The preparation of alkylized (methylated, ethylated etc.) amidoderivatives from
thiobenzophenone by the action of the alkylized (methylated, ethylated, etc.) amido-
20 derivatives of the chloride of thiobenzoic acid, or by direct action of dichlorosulphuret
of carbon upon tertiary aromatic amines.

page_text: The preparation colouring matters by the action of demorosuipuret of carbon
upon tertiary aromatic amines.
Dichlorosulphuret of carbon acts at a low temperature upon tertiary aromatic amines
which can be diluted with indifferent dissolvents, such as sulphuret of carbon, toluene,
etc, giving rise to amido alkylizated chlorides of thiobenzoic acid. Water decomposes
the said chlorides into acids, and the alkalies into corresponding salts.
This chloride acts when tepid upon a second molecule of a tertiary amine with or
without a means of condensation, as for example chloride of zinc, forming amido
alkylized (methylated, ethylated etc) thiobenzophenone.
These thiobenzophenones are obtained directly by the reaction of dichlorosulphuret
of carbon upon an excess of tertiary amine.
Of these new bodies which are derived from thiobenzophenone I have compared
those obtained with dimethylaniline and diethylaniline with the corresponding
derivatives of benzophenone and I have found that there is between them a great
analogy and that the formuloe of their constitution are exactly the following:
CS
C H₁ N (C H₁)2
CH₁ N (CH3)2
CS:
C₁ H, N (C₂ H.),
4
C H₁ N (C₂ H)2
4
These thiobenzophenones have as compared with the corresponding benzo-phenones
the remarkable advantage of lending themselves much more easily to reactions, on
account of the presence of sulphur, than the oxygen of the benzocphenones, thus for
example; Tetramethylamidobenzophenone is scarcely attacked by the hydrogen
becoming nascent in an acid aqueous solution whilst the corresponding thioketone is
transformed into a corresponding methane derivative giving up H₂S, or
An aqueous solution of tetramethyldiamidobenzophenone heated with an excess of
muriatic or sulphuric acid is not changed, whilst thioketone under the same conditions
forms H2S and is transformed into tetramethyldiamidobenzophenone.
This transformation of thiobenzophenone into corresponding benzophenone is
easily effected under pressure with an aqueous or slightly alcoholic solution of
ammonia, or
Tetramethyldiamidobenzoephenone is not attacked directly by ammonia, whilst
thiobenzophenone treated as hereinafter set forth is easily transformed into a yellow
colouring matter, or
By heating together a solution of tetramethyldiamidobenzoephenone and of aniline,
no reaction takes place at all whilst a solution of thiobenzoephenone and of aniline
gives HS, and from the reciprocal reaction is obtained orange yellow colouring
matter.
In the same manner is obtained brown colouring matter, by causing this thio-
benzoephenone to react upon diamines.
By heating this thiobenzophenone with secondary amines are obtained lencobases
which by oxidation are transformed into colouring matters, thus for example with
diphenylamine is obtained blue colouring matter.
In these reactions is employed with advantage a metallic oxide, such as lead oxide
in order to eliminate directly the H,S.

page_text: dichlorosulphuret of carbon into violet colouring matters capable of extending to blue,
and in presence of bases of quinolein into green colouring matters.
It may here be pointed out that these colours of quinolein are transformed by
reduction into violet intermediate colouring matter.
If thiobenzoephenone is dissolved in phenols, and chloride of zinc or concentrated
sulphuric acid is by degrees added hot in small quantities, the formation of colouring
matters also takes place.
The reaction of CS Cl, upon tertiary aromatic amines indicates already at the time
of the formation of thiobenzophenone the appearance of violet and blue colouring
matters. This secondary reaction may become a principal reaction, if to the tertiary
amines are previously added means of condensation, such as chloride of zinc, chlorate
of alumina or the like, and if for the reaction of dichlorosulphuret of carbon is
employed a higher temperature than for the formation of thiobenzoephenone.
The chlorides of benzoic acid can likewise be transformed in presence of tertiary
amines, products of condensation and dichlorosulphuret of carbon directly into
colouring matters.
Preparation of amido-alkylized chlorides of thiobenzoic acid and of the acid itself.
In an enamelled pot, the cover of which allows the passage of a stirrer, are cooled
by iced water to a temperature of about 0° Celsius 24- 200 kilograms of dimethylaniline
diluted with 120 kilograms of sulphuret of carbon.
To this is added by degrees while continually stirring
11.500 kilograms of dichlorosulphuret of carbon diluted with 23 kilograms of
sulphuret of carbon. The temperature during the operation must remain as indicated
above and the stirring is continued for six hours to the end of the reaction.
When the reaction is terminated, which it is easy to ascertain by the absence of the
odour characteristic of dichlorosulphuret of carbon, the sulphuret of carbon is distilled
first, and after alkylization the dimethylaniline by means of a current of steam.
In the liquid remaining in the retort is the salt of dimethylamidothiobenzoic acid.
The soda salt of this acid is very soluble in water and crystallizes only in a very
concentrated solution. The diluted acetic acid sets free the dimethylamidothiobenzoic
acid its formula is
Preparation of amidoalkylized thiobenzophenones.
Into 50 kilograms of dimethylaniline cooled to a temperature of 0° Celsius are
introduced while stirring continually.
10 kilograms of dichlorosulphuret of carbon diluted with 30 kilograms of sulphuret
of carbon.
The mass becomes viscous by degrees. To finish the reaction the temperature is
raised to 35° Celsius. To extract the ketone formed there are two manners of
proceeding.
1. Highly diluted hydrochloric acid is added to neutralize the dimethylaniline and
the sulphuret of carbon is carried away by a current of steam.
After cooling, the ketone presents itself in a crystalline form in the liquid, and it is
only necessary to filter, wash and dry.
2. The whole is rendered alkaline, which enables the sulphuret of carbon and
dimethylaniline to be got rid of at the same time by means of a current of steam
from water.
of carbon.
The mass becomes viscous by degrees. To finish the reaction the temperature is
raised to 35° Celsius. To extract the ketone formed there are two manners of
proceeding.
1. Highly diluted hydrochloric acid is added to neutralize the dimethylaniline and
the sulphuret of carbon is carried away by a current of steam.
After cooling, the ketone presents itself in a crystalline form in the liquid, and it is
only necessary to filter, wash and dry.
2. The whole is rendered alkaline, which enables the sulphuret of carbon and
dimethylaniline to be got rid of at the same time by means of a current of steam
from water.

page_text: 15
The fusion is afterwards heated as indicated, in the above example.

page_text: Improvements relating to Substances Chiefly Designed for Use in
the Preparation of Colouring Matters and to the Manufacture
of Colouring Matters therefrom.
I, Dr. ALFRED KERN, of Basle, Switzerland, 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 :-
This invention relates to the manufacture of alkylized (methylated, ethylated etc)
amidoderivates and of various colouring matters as hereinafter set forth.
I have succeeded in producing by the action of dichlorosulphuret of carbon CSCI,
upon tertiary aromatic amines a new series of organic bodies derived from thiobenzoic
acid and thiobenzophenone, which serve for obtaining yellow, orange, brown, violet,
blue and green colouring matters.
Moreover, I prepare directly by the action of dichlorosulphuret of carbon upon
tertiary aromatic amines violet and blue colouring matters.
For convenience of description I classify my said invention generally under the
four following heads, viz ;—
11.
The preparation of alkylized (methylated, ethylated etc) amido-derivatives of
thiobenzophenone by the action of the alkylized (methylated, ethylated etc.) amido-
derivatives of the chloride of thiobenzoic acid, or by direct action of dichlorosulphuret
of carbon upon tertiary aromatic amines.

page_text: colts
toluene, etc, giving rise to amido alkalizated chlorides of thiobenzoic acid. Water
decomposes the said chlorides into
and the alkalios into corresponding
poids,
This chloride acts when tepid upon a second molecule of a tertiary amine with or
without a means of condensation, as for example chloride of zinc, forming amido
alkylized (methylated, ethylated etc.) thiobenzophenone.
These thiobenzophenones are obtained directly by the reaction of dichlorosulphuret
of carbon upon an excess of tertiary amine.
Of these new bodies which are derived from thiobenzophenone I have compared
those obtained with dimethylamiline and diethylamiline with the corresponding
derivatives of benzophenone and I have found that there is between them a great
analogy and that the formulo of their constitution are exactly the following ;—
This chloride acts when tepid upon a second molecule of a tertiary amine with or
without a means of condensation, as for example chloride of zinc, forming amido
alkylized (methylated, ethylated etc.) thiobenzophenone.
These thiobenzophenones are obtained directly by the reaction of dichlorosulphuret
of carbon upon an excess of tertiary amine.
Of these new bodies which are derived from thiobenzophenone I have compared
those obtained with dimethylamiline and diethylamiline with the corresponding
derivatives of benzophenone and I have found that there is between them a great
analogy and that the formulo of their constitution are exactly the following ;-
CS
C₁ H₁ N (CH3)2
\C, H, N (CH3)2
US:
4
C H N (C₂ H₂),
C. HN (C₂ H),
:-
These thiobenzophenones have as compared with the corresponding benzophenones
the remarkable advantage of lending themselves much more easily to reactions, on
account of the presence of sulphur, than the oxygen of the benzophenones, thus for
example; Tetramethylamidobenzophenone is scarcely attacked by the hydrogen
becoming nascent in an acid aqueous solution, whilst the corresponding thioketone is
transformed into a corresponding methane derivative giving up H, S, or
An aqueous solution of tetramethyldiamidobenzophenone heated with an excess of
muriatic or sulphuric acid is not changed, whilst thioketone under the same conditions
forms H, S and is transformed into tetramethyldiamidobenzophenone.
This transformation of thiobenzophenone into corresponding benzophenone is easily
effected under pressure with an aqueous or slightly alcoholic solution of ammonia. Or
Tetramethyldiamidobenzophenone is not attacked directly by ammonia, whilst
thiobenzophenone treated as hereinafter set forth is easily transformed into a yellow
colouring matter. Or
By heating together a solution of tetramethyldiamidobenzophenone and of aniline,
no reaction takes place at all, whilst a solution of thiobenzophenone and of aniline
gives H, S, and from the reciprocal reaction is obtained orange yellow colouring
matter.
In the same manner is obtained brown colouring matter, by causing this thioben-
zophenone to react upon diamines.
By heating this thiobenzophenone with secondary amines are obtained lencobases
which by oxidation are transformed into colouring matters thus for example with
diphenylamine is obtained blue colouring matter.
In these reactions is employed with advantage a metallic oxide, such as lead oxide,
in order to eliminate directly the H, S.
This thiobenzophenone is transformed in presence of aromatic tertiary amines by
dichlorosulphuret of carbon into violet colouring matters capable of extending to blue,
and in presence of bases of quinolein into green colouring matters.
It may here be pointed out that these colours of quinolein are transformed by
reduction into violet intermediate colouring matter.
If thiobenzophenone is dissolved in phenols, and chloride of zinc or concentrated
sulphuric acid is by degrees added hot in small quantities, the formation of colouring
matters also takes place.
The reaction of US Cl, upon tertiary aromatic amines indicates already at the time
of the formation of thiobenzophenone the appearance of violet and blue colouring
matters. This secondary reaction may become a principal reaction if to the tertiary
amines are previously added means of condensation, such as chloride of zinc, chloride
of alumina or the like, and if for the reaction of dichlorosulphuret of carbon is
employed a higher temperature than for the formation of thiobenzophenone.
The chlorides of benzoic acid can likewise be transformed in presence of tertiary
amines, agents of condensation and dichlorosulphuret of carbon directly into colouring
matters.

page_text: EXAMPLES OF MANUFACTURE.
I.
Preparation of amido-alkylized chlorides of thiobenzoic acid and of the acid itself.
In an enamelled pot, the cover of which allows the passage of a stirrer, are cooled
by iced water to a temperature of about 0° Celsius 24.200 Kilograms of dimethyla-
niline diluted with 120 Kilograms of sulphuret of carbon.
To this is added by degrees while continually stirring
11.500 kilograms of dichlorosulphuret of carbon diluted with 23 kilograms of
sulphuret of carbon. The temperature during the operation must remain as indicated
above and the stirring is continued for six hours to the end of the reaction.
When the reaction is terminated, which it is easy to ascertain by the absence of the
odour characteristic of dichlorosulphuret of carbon, the sulphuret of carbon is distilled
first, and, after alkalization the dimethylaniline by means of a current of steam.
In the liquid remaining in the retort is the salt of dimethylamido-thiobenzoic acid.
The soda salt of this acid is very soluble in water and crystallizes only in a very
concentrated solution. The diluted acetic acid sets free the dimethylamido-thiobenzoic
acid, its formula is

page_text: kilograms of phenyl a naphthylamine are added 15 kilograms of toluene and
4 kilograms of dichlorosulphuret of carbon. By heating the whole in a water bath at
100° Celsius blue colouring matter is obtained.
Preparation of violet colouring matter.
VI.
To a solution of 10 kilograms of tetramethylamidobenzophenone in 17 kilograms of.
dimethylaniline are added, by means of a funnel having a cock, while stirring,
5 kilograms of dichlorosulphuret of carbon.
The temperature during the operation must not increase. To terminate the reaction
the vessel is heated in a water bath so as to reach 100° Celsius in half an hour. For 1
two hours this temperature is maintained, while continuing to stir.
To extract the colouring matter the mass which has a beautiful copper colour is
dissolved in 500 litres of hot water. To this solution is added a quantity of muriatic
acid necessary for saturating the dimethylaniline. The solution is heated to a boiling
point and 100 kilograms of a solution of marine salt are added, the violet crystallizes ?
by cooling and can be purified. .
VIII.
Direct preparation of violet colouring matter.
Into an apparatus provided with a stirrer and heated in a water bath are put
50 kilogram of dimethylaniline and 5 kilograms of chloride of zinc in fine powder,
which is regulated to a temperature of from 25° to 30° Celsius.
To this are poured slowly in 3 hours 15 kilograms of dichlorosulphuret of carbon
great care being taken that the temperature of the mixture does not exceed
40° Celsius.
After this operation the stirring is still continued for two hours, and the temperature
is raised to 60° Celsius.
The fusion is afterwards heated as indicated in the above example.
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 :-
First. The preparation of alkylized, (methylated, ethylated etc.) amido-derivatives
of the chloride of thiobenzoic acid, and derivatives of the acid itself, by the action of
dichlorosulphuret of carbon upon tertiary aromatic amines.
Second. The preparation of alkylized (methylated, ethylated, etc.) amido derivatives
of thiobenzophenone by the action of alkylizated amido-derivatives of the chloride of
thiobenzoic acid, or by direct action of dichlorosulphuret of carbon upon the
tertiary aromatic amines.
Third. The preparation of colouring matter by condensation of this new series of
organic bodies nained under the above heads I and II with ammonia or with ammonia
substitution products or phenols.
Fourth. The preparation of colouring matters by the action of dichlorosulphuret of
carbon upon tertiary aromatic amines.
Deted this 92nd dox of December 1886
HASELTINE, LAKE & Co.,
45, Southampton Buildings, London, W.C.,
Agents for the Applicant.