The Manufacture or Production of Derivatives of Cinnamic Acid.
Year: 1899

page_text: Date of Application, 15th June, 1899
Complete Specification Left, 7th Mar., 1900-Accepted, 7th Apr., 1900
[Communicated from abroad by the Farbenfabriken vormals Friedrich Bayer & Co., of
Elberfeld, Germany.]
The Manufacture or Production of Derivatives of Cinnamic Acid.
I, HENRY EDWARD NEWTON, of the Office for Patents, 6 Bream's Buildings,
Chancery Lane, in the County of London, Patent Agent, do hereby declare the
nature of this invention to be as follows:-
My foreign correspondents have found that those derivatives of cinnamic acid
which are substituted in the ortho position to the lateral chains of the cinnamic acid,
can be easily produced by heating orthonitrosonaphthols, or preferably their salts, at
elevated temperatures. Thus, for instance, by heating the sodium salt of nitroso-
betanaphthols, orthocyanocinnamic acid is obtained, according to the following
equation:
one of the nuclei of the naphthalene molecule being split up during the reaction.
In carrying out the new process, the nitroso compounds are preferably mixed with
an indifferent body, such as sand, kieselguhr, or the like, in order to smoothen the
reaction, and to prevent the decomposition of the reaction products.
In order to illustrate the new process, the following example is given, the parts
being by weight.
EXAMPLE A.
A mixture of 20 parts of the sodium salt of nitrosobetanaphthol with about 200
parts of sand, is quickly heated to about 250 degrees Centigrade, and kept at this
temperature, with continuous stirring, until the green color of the mixture has
changed into gray. Subsequently, the mixture is extracted by means of water.
Thus, a slight brownish-colored solution is obtained, which contains the sodium salt
of the orthocyanocinnamic acid. The free acid is separated from this solution by the
addition of acids. The resulting yellowish colored precipitate is recrystallized from
nitrobenzene. Thus the pure acid is obtained in the shape of colorless needles,
melting at from 252 to 253 degrees Centigrade. It is identical with the cyano-
cinnamic acid obtained by Drory from the nitrite of dichlororthotuluic acid, acetic
anhydride, and sodium acetate (see "Berichte der Deutschen Chemischen Gesellschaft,"
Vol. 24, p. 2574).
The process proceeds in an analogous manner, if, instead of the salts of nitroso-
betanaphthol, the salts of other orthonitrosonaphthols, or of substitution products of
these bodies, are emploved.

page_text: My foreign correspondents have further found that, by treating ortho-cyano com-
pounds obtainable according to the above example, with alkaline hypochlorites, or
analogous agents, the corresponding ortho-amido compounds are obtained. On sub-
jecting, for instance, the ortho-cyano-cinnamic acid to this operation, ortho-amido-
cinnamic acid is produced. In order to illustrate this method of proceeding, the
following Example B is given, the parts being likewise by weight.
EXAMPLE B.
A solution prepared from 1 part of ortho-cyano-cinnamic acid, 12 parts of water,
and 1 part of sodium hydroxide, is mixed with a watery solution containing 0.42 parts
of sodium hypochloride. The resulting mixture is heated on a water bath for several
hours. From the solution thus obtained, the known ortho-amido-cinnamic acid is
separated in a free state in the known manner.
My foreign correspondents wish it to be understood that they do not intend to
confine themselves to the particulars given in the above examples, as these are merely
typical, and can be varied within wide limits, without altering thereby the nature of
the present invention.
Dated thin 15th day of Tuno 1900
The Manufacture or Production of Derivatives of Cinnamic Acid.
I, HENRY EDWARD NEWTON, of the Office for Patents, 6, Bream's Buildings,
Chancery Lane, in the County of London, Patent Agent, 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 :-
My foreign correspondants have found that ortho-cyano derivatives of cinnamic
acid can be easily produced by heating ortho-nitroso-beta-naphthol, or derivatives
thereof (preferably their salts), at elevated temperatures. Thus, for instance, by
heating the sodium salt of nitroso-beta-naphthol, ortho-cyano-cinnamic acid is
obtained according to the following equation:-
one of the nuclei of the naphthalene molecule being split up during the reaction.
In carrying out the new process, the nitroso compounds are preferably mixed with
an indifferent body, such as sand, kieselguhr, or the like, in order to diminish the
violence of the reaction, and to prevent the decomposition of the reaction products.
In order to illustrate the new process, the following example is given, the parts
being by weight :-

page_text: NEWTON & SON,
Agents for the Applicants.