Manufacture of Condensation Products from Methylene Compounds and Aromatic Nitroso-compounds.
Year: 1899

page_text: Manufacture of Condensation Products from Methylene Compounds
and Aromatic Nitroso-compounds.
I, OLIVER IMRAY, of Birkbeck Bank Chambers, Southampton Buildings, in the
County of London, Chartered Patent Agent, do hereby declare the nature of this
invention (as communicated to me from abroad by Dr. Franz Sachs, of No. 74,
Lutzowstrasse, Berlin, in the German Empire) to be as follows:-
My foreign correspondent has found that by condensing aromatic nitroso-compounds
with methylene compounds according to the formula:
>CH₁ + NO (aromat. radical)=
>C-N-(aromat. radical)+H₂O
substances may be obtained, which have to be considered as substituted azomethine
compounds, where azomethine is represented by the group >C-N-, its chromphore
character having already been referred to in Ber. d. Deutsch. Chem. Ges. 27.3317.
· As methylene compounds are understood all those in which the proximity of a
negative group of atoms, as CO, CN, NO2, -C-C., or aromatic radicals, gives the
methylene group an acid character, besides phenols, which may be considered reacting
as methylene compounds after transformation.
As nitroso-compounds are understood the nitroso derivatives of aromatic secondary
and tertiary amines, such as nitrosodimethylaniline, as well as nitrosophenols.
The condensation of the said compounds takes place more or less easily, in some
cases on their being heated alone or in an alcoholic solution, in other cases in the
presence of alkalies or on addition of zinc chloride.
EXAMPLE I.
17.8 parts by weight of nitrosodiethylaniline and 11.7 parts by weight of
benzylcyanide are dissolved in hot alcohol while some caustic potash is added; the
solution which was green before being heated turns dark red, becoming heated by
itself, sometimes to ebullition of the alcohol, while a crystallisation begins at the
same time. On cooling, 90 per cent. of the condensation product is crystallised as
beautiful, scarlet-red, goldglittering needles having the melting point 111° C. The
compound crystallises from ethyl acetate in large, garnet-like, green-gold needles of
brilliant lustre.
brilliant lustre. ·
Analyses U18 119 Ng
C calculat 77.89 per cent.
found 77.71 per cent.
H calculat 6.92 per cent.
found 7.18 per cent.
The same coumpound is also obtained, if the given quantities of both components
are heated on the oil-bath without any addition until the evolution of water ceases.
The corresponding dimethyl compound is orange-brown; melting point 90° C.
D
037

page_text: EXAMPLE II.
3 parts by weight of nitrosodimethyaniline and 2.6 parts by weight of ethyl acetate
are heated with the same volume of alcohol. The inixture is then taken off the fire
and some concentrated caustic potash is added. The solution becomes brown and
begins again to boil until the reaction is complete. After 24 hours, brown crystals
reflecting blue separate, having the melting point of about 60° C.
Manufacture of Condensation Products from Methylene Compounds
and Aromatic Nitroso-compounds.
I, OLIVER IMRAY, of Birkbeck Bank Chambers, Southampton Buildings, in the
County of London, Chartered Patent Agent, do hereby declare the nature of this
invention (as communicated to me from abroad by Dr. Franz Sachs, of No. 74,
Lutzowstrasse, Berlin, in the German Empire) to be as follows:-
My foreign correspondent has found that by condensing aromatic nitroso-com-
pounds with methylene compounds according to the formula:

page_text: EXAMPLE II.
3 parts by weight of nitrosodimethyaniline and 26 parts by weight of ethyl acetate
are heated with the same volume of alcohol. The mixture is then taken off the fire
and some concentrated caustic potash is added. The solution becomes brown and
begins again to boil until the reaction is complete. After 24 hours, brown crystals
reflecting blue separate, having the melting point of about 50° C.
5
EXAMPLE III.
3 parts by weight of nitrosodimethylaniline and 2-3 parts by weight of diamidodi-
phenylmethanesulphone are dissolved by heating in 200 parts by weight of alcohol
and the solution is further heated for some time with a few c.c of caustic soda and
then precipitated with water.
The precipitate is dissolved in acetone and filtered; after evaporation of the
O solvent there remains a brown mase having the melting paint Da10 ri
EXAMPLE IV.
15 parts by weight of nitrosodimethylaniline and 11 parts by weight of resorcinol
are condensed in the above manner in an alcoholic solution, the product of reaction
being precipitated with water. It is a dark violet grey powder, soluble in very
5 dilute acetic acid with a green colour; it melts and decomposes at 123° C.
The solution in dilute sulphuric acid is yellow brown.

page_text: dissolved in 100 parts by weight of boiling alcohol, to which are slowly added soda-
lye of 35 per cent. strength. The whole is poured into water and the mixture is
extracted with ether to remove the unchanged benzyl cyanide, after which dilute
sulphuric acid is added.
A product separates which soon solidifies and is washed with water. Crystallised
from alcohol it forms brown needles melting at 155° C., it is insoluble in water, easily
soluble in alcohol, ether &c. On boiling with dilute sulphuric acid it is split into
benzoyl cyanide and amidophenol.
Having now particularly described and ascertained the nature of my said inven-
tion and in what manner the same is to be performed, I declare that what I
claim is
1. The herein described manufacture of condensation products from methylene
compounds and aromatic nitroso-compounds by heating in solution a mixture of a
nitroso-compound of an aromatic amine, or a nitroso-compound of a phenol, and a
methylene compound of acid character, or a phenol, with or without addition of an
alkali.
0 The products manufactured as above set forth.