Chloral in acting upon aniline
Year: 1899

page_text: I, THOMAS RICHARD SHILLITO, of 15, Tooks Court, Loudon, E.C., Engineer and
Patent Agent, do hereby declare the nature of this invention a communication to
me from abroad by Messrs. John Rudolph Geigy & Co., of Basle, Switzerland, Colour
Manufacturers--to be as follows:-
Chloral in acting upon aniline, forms according to Wallach (Berl. Ber. V 251)
trichloraethylidenediphenamine C C13-CH (NHC6 H5)2. The saine compound is
obtained in substituting chloralhydrate for chloral.
My correspondents have discovered that this reaction takes another course by the
presence of chlorhydrate of hydroxylamine. As the chloral hydrate furnishes with
the latter trichloraldoxime, the aldehyde group is preserved against the action of the
aniline. On the other hand the capability of reaction of the trichloric methyl group
is thus so increased that all the chlorine enters into reaction with the aniline. There
results a compound of the formula
which can be named isonitrosoaethenyldiphenylamidine. This compound freshly
prepared, a yellow clammy oil, which dissolves in acids and alkalies, and gradually
dries up into a glassy brittle mass, shews the characteristic properties of dissolving in
cold concentrated sulphuric acid with a reddish yellow colour. By heating up to
50° 60° Centigrade this shade turns to a dark brown violet, and at 90°-100°
Centigrade it changes into an intensive yellowish red. On cooling and diluting with
ice water there results a clear yellowish red solution (by strong concentration red crystals
of a sulphate appear at first). Neutralised with sodium carbonate a new basic body is
precipitated in small yellowish brown crystals. Filtered off and recrystallised from a
mixture of benzene and petroleum ether it forms bright dark brown violet nearly
black needles which are easily soluble in alcohol, ether, and benzene. While the
alcoholic solution shews a yellowish brown colour, that in benzene is strawberry red.
By adding some caustic soda lye, the yellowish brown alcoholic solution turns to a
brilliant blue which fades after some time. These crystals melting at 126° Centi-
grade are also easily soluble as well in mineral as in organic acids. Special examina-
tion of this body has shewn that by the action of the sulphuric acid on the
isonitrosoaethenyldiphenylamidine an interior condensation had taken place by

page_text: forming a closed chain and splitting off ammonia, because the described new product.
proved to be an isatine anilide of the formula:-
that is to say, if the solution of this isatine anilide in diluted mineral acids is boiled
up it divides completely into isatine and aniline. With phenylhydrazine the anilide
gives a cinnabar red hydrazone, by which the a position of the anilide group is proved.
I. EXAMPLE OF PRODUCING α-ISATINE ANILIDE.
In a vessel fitted with a stirrer and reflux cooler a mixture of 14 parts by weight of
hydroxylamine chlorhydrate, 60 parts of water, and 90 parts of aniline is heated up
to 90° -100° Centigrade after which 33 parts of chloralbydrate are carefully added
in small portions in such a manner as to allow the violent reaction to pass over after
each addition before adding more. The mixture consisting in the beginning of two
different fluids, has become homogeneous and taken a deep yellow colour when the
reaction is finished. After allowing to cool completely, 500 parts of ice water and
120 parts of caustic soda lye of 40° Bé. are added and the whole well mixed so that
the formed isonitrosoaethenyldiphenylamidine goes in solution. The surplus of
aniline as well as the bye products insoluble in alkali are then removed by repeated
extraction with ether. Next, the solution is acidulated with acetic acid and the
nitroso compound which separates in oily drops is likewise extracted with ether. The
former remains as a thick oil after the ether has been evaporated.
One part by weight of the isonitrosonethenyldiphenylamidine is dissolved in four
parts by weight of concentrated sulphuric acid at a temperature of from 40° to 50°
Centigrade. When all is dissolved, the temperature is gradually raised to 1000-105°
Centigrade. After the colour has completely changed to a yellowish red, the acid
solution is, when cold, poured upon ice, then filtered off some resinous flakes and
neutralised with sodium carbonate. The a isatine anilide precipitated in brown
crystalline masses is then filtered off and dried at a low temperature.
II. EXAMPLE OF PRODUCING ISATINE.
One part by weight of a isatine anilide is added to a mixture of one part of
sulphuric acid and three parts of water and then gradually brought to boil. The red
paste of the sulphate of isatine anilide which has formed at first, soon dissolves in
heating up, whereupon commences the separation of isatine in brown crystals. The
lecomposition finished and the solution cooled down, the separated satine is filtered
off and recrystallised from hot water,
Dated this 27th day of July 1899.

page_text: same is to be performed a communication to
me
from abroad by Me
John Rudolph Geigy & Co, of Basle, Switzerland, Colour Manufacturers-to be
particularly described and ascertained in and by the following statement :-
Chloral in acting upon aniline forms according to Wallach (Berl. Ber. V 251).
trichloraethylidenediphenamine C C13-CH (NHC6 H5)2. The same compound is
obtained in substituting chloral hydrate for chloral.
My correspondents have discovered that this reaction takes another course by the
presence of chlorhydrate of hydroxylamine. As the chloral hydrate furnishes with
the latter trichloraldoxime, the aldehyde group is preserved against the action of the
aniline. On the other hand the capability of reaction of the trichloric methyl group
is thus so increased that all the chlorine enters into reaction with the aniline.
results a compound of the formula
There
John Rudolph Geigy & Co, of Basle, Switzerland, Colour Manufacturers-to be
particularly described and ascertained in and by the following statement :-
Chloral in acting upon aniline forms according to Wallach (Berl. Ber. V 251).
trichloraethylidenediphenamine C C13-CH (NHC6 H5)2. The same compound is
obtained in substituting chloral hydrate for chloral.
My correspondents have discovered that this reaction takes another course by the
presence of chlorhydrate of hydroxylamine. As the chloral hydrate furnishes with
the latter trichloraldoxime, the aldehyde group is preserved against the action of the
aniline. On the other hand the capability of reaction of the trichloric methyl group
is thus so increased that all the chlorine enters into reaction with the aniline.
results a compound of the formula
There
C6H5N
H
C6H5NH
NOH
which can be named isonitrosoaethenyldiphenylamidine. This compound freshly
prepared, a yellow thick oil, which gradually changes into a crystalline mass, shews
the characteristic properties to dissolve in concentrated sulphuric acid with a reddish
yellow colour. By heating up to 50° 60° Centigrade this shade turns to a dark
brown violet and at 90°-100° Centigrade it changes into an intensive yellowish red.
On cooling and diluting with ice water there results a clear yellowish red solution (by
strong concentration red crystals of a sulphate appear at first). Neutralised with
sodium carbonate a new basic body is precipitated in small yellowish brown crystals.
Filtered off and recrystallised from benzene it forms bright dark brown violet nearly
black needles which are easily soluble in warm alcohol, ether and benzene, less when
cold. While the alcoholic solution shews a yellowish brown colour, that in benzene
is strawberry red. By adding some caustic soda lye the yellowish brown alcoholic
solution turns to a brilliant blue which fades after some time. These crystals
melting at 126° Centigrade are also easily soluble as well in mineral as in organic
acids. Special examination of this body has shewn that by the action of the sulphuric
acid on the isonitrosoaethenyldiphenylamidine an interior condensation had taken
place by forming a closed chain and splitting off ammonia, because the described
new product proved to be an isatine anilide of the formula
IDALINE ANILIDE.
In a vessel fitted with a stirrer and reflux cooler a mixture of 14 parts by weight
of hydroxylamine chlorhydrate, 60 parts of water and 90 parts of aniline is heated up
to 90°-100° Centigrade after which 33 parts of chloralhydrate are carefully added
in sinal portions in such a manner as to allow the violent reaction to pass over after
each addition before adding more. The mixture, consisting in the beginning of two
different fluids, has become homogeneous and taken a deep yellow colour when the

page_text: reaction is finished. After allowing to cool completely, 500 parts of ice water and
120 parts of caustic soda lye of 40° Bé. are added and the whole well mixed so that
the formed isonitrosonethenyldiphenylamidine goes in solution. The surplus of
aniline as well as the bye products insoluble in alkali are then removed by repeated
extraction with ether. Next, the solution is acidulated with acetic acid and the
isonitroso compound which separates in oily drops is likewise extracted with ether.
The latter being evaporated the isonitrosonethenyldiphenylamidine remains as a thick
oil which crystallises after some time. Without any further purification it can be
used directly for the manufacture of a-isatine anilide. In order to prepare a perfectly
pure isonitroso compound the raw product thus obtained is dissolved in acetic acid
of 40 per cent., then diluted with water and filtered off the separated impurities.
By adding sodium carbonate to the filtered solution the pure isonitroso compound
is precipitated in yellowish flakes which are filtered off, washed and dried.
Isonitrosoaethenyldiphenylamidine forms a slight yellowish crystalline powder
melting at 131° to 132° Centigrade and dissolves easily in alcohol, ether, and
benzene, as well as in diluted acids and caustic alkalies.
One part by weight of the isonitrosoaethenyldiphenylamidine is dissolved in four
parts by weight of concentrated sulphuric acid at a temperature of from 40° to 50°
Centigrade. When all is dissolved the temperature is gradually raised to 100°-105°
Centigrade. After the colour has completely changed to a yellowish red, the acid
solution is, when cold, poured into a surplus solution of sodium carbonate to which
has been added sufficient ice. The a-isatine anilide precipitated in brown crystalline
masses is then filtered off and dried at a low temperature.
II. EXAMPLE OF PRODUCING ISATINE.
One part by weight of a-isatine anilide is added to a mixture of one part of
sulphuric acid and three parts of water and then gradually brought to boil. The
red paste of the sulphate of isatine anilide which has formed at first, soon dissolves
in heating up, whereupon commences the separation of isatine in brown crystals.
The decomposition finished and the solution cooled down, the separated isatine is
filtered off and recrystallised from hot water.
Having now particularly described and ascertained the nature of said invention
and in what manner the same is to be performed, as communicated to me by
my foreign correspondents, I declare that what I claim is :-
1. The process for the production of isonitrosoaethenyldiphenylamidine of the
formula
C6H5NH-C = NC6H5
H-C NOH
=
THOMAS R. SHILLITO,
15, Tooks Court, London, E.C.