IMPROVEMENTS IN THE PRODUCTION OF BENZALDIACETATE AND CERTAIN SUBSTITUTION PRODUCTS THEREOF, AND IN THE TRANSFORMATION OF THESE BODIES RESPECTIVELY INTO CINNAMIC ACID AND THE CORRESPONDING SUBSTITUTION PRODUCTS THEREOF."
Year: 1881

page_text: LETTERS PATENT to Joseph Anthony Dixon, of 175, West George Street,
Glasgow, in the County of Lanark, North Britain, Solicitor, for an Invention
of "IMPROVEMENTS IN THE PRODUCTION OF BENZALDIACETATE AND CERTAIN
SUBSTITUTION PRODUCTS THEREOF, AND IN THE TRANSFORMATION OF THESE
BODIES RESPECTIVELY INTO CINNAMIC ACID AND THE CORRESPONDING
SUBSTITUTION PRODUCTS THEREOF." A communication from abroad by
Doctor Karl Koenig, of Hochst-am-Main, in the Empire of Germany,
a Director of the Farbwerke vorm: Meister, Lucius, and Brüning, a
Company carrying on business there as Chemical Manufacturers.
PROVISIONAL SPECIFICATION left by the said Joseph Anthony Dixon at
the Office of the Commissioners of Patents on the 22nd January 1881.
JOSEPH ANTHONY DIXON, of 175, West George Street, Glasgow, in the County
of Lanark, North Britain, Solicitor. "IMPROVEMENTS IN THE PRODUCTION OF
BENZALDIACETATE AND CERTAIN SUBSTITUTION PRODUCTS THEREOF, AND IN THE
TRANSFORMATION OF THESE BODIES RESPECTIVELY INTO CINNAMIC ACID, AND
THE CORRESPONDING SUBSTITUTION PRODUCTS THEREOF." [A communication from
abroad by Doctor Karl Koenig, of Hochst-am-Main, in the Empire of Germany,
a Director of the Farbwerke vorm: Meister, Lucius, and Brüning, a Company
carrying on business there as Chemical Manufacturers.]
6
This Invention has for its nature and objects the production of cinnamic acid
and its chlor-, brom-, and nitro-substitution derivatives by heating benzaldiacetate
C, H, CH
O CH, CO
and its chlor-, brom-, and nitro-substitution
CH, CO
derivatives respectively with anhydrous acetate of sodium, and also the production
of the said benzaldiacetate and its said substitution products in an improved way
by heating benzal chloride and its corresponding substitution products respectively
with anhydrous acetate of lead.
Benzaldiacetate, as is well known, has hitherto been obtained only by trans-
forming benzalchloride with acetate of silver (Wicke, Annalen der Chemie und
Prins &

page_text: Pharmacie, vol. 102, page 366), or by addition of acetanhydride and benzaldehyde
(Perkins, Journal of the Chemical Society, new series, v. 586, and Annalen der
Chemie und Pharmacie, vol. 146, page 373). I produce it after a new method by
the prolonged heating at a temperature of 248° to 288° F. (120-140° C.) of benzal-
chloride with anhydrous acetate of lead.
The formation of the benzaldiacetate takes place according to the formula,-
Pb =
CH, CH-
O C₂ H₂ O
0 C, H,
C, H, CH Cl, +C, H₂OO
C₂ H₂ 0 0
+ Pb Cl₂.
In an analogous manner I obtain the chlor-, brom-, and nitro-substitution
products of the benzaldiacetate from the corresponding chlor-, brom-, and nitro-
substitution products of the benzalchloride.
The preparation of cinnamic acid and of the above mentioned derivatives of this
acid respectively from benzaldiacetate and its corresponding derivatives is effected
according to this Invention by heating the benzaldiacetate, or one or other of its
said derivatives, as the case may be, with anhydrous acetate of sodium.
The following is an explicit description of my method and process :-
I heat for about 6 hours at a temperature of 248° to 288° F. (120-140° C.) 30 parts
by weight of benzalchloride with 90 parts of anhydrous acetate of lead in a suitable
vessel, in this way forming, according to the equation herein before set forth, chloride
of lead and benzaldiacetate; I then add to the mixture about 30 parts of anhydrous
acetate of sodium. Afterwards I heat for about 18-20 hours at a temperature of
356° to 428° F. (180 to 220° C.). The thus obtained smelt is first boiled in water,
and after it has been allowed to cool down I extract the cinnamic acid from the
residue by 30 parts of soda and 300 parts of water. By evaporating and
crystallising the extract I obtain the cinnamic acid in the form of the cinnamate
of sodium.
I may however also separate the benzaldiacetate from the chloride of lead by
suitable dissolving agents, such as ether, benzole, and the like solvents, or draw it
off by suitable distillation, and then heat it with acetate of sodium without any
essential difference in the final result.
If in the process above described I substitute for the benzaldiacetate its chlor-,
brom-, or nitro-substitution products, I then obtain the corresponding chlor-, brom-,
or nitro-cinnamic acids.
The described proportions and also the degrees of temperature may be varied
within certain limits.

page_text: SPECIFICATION in pursuance of the conditions of the Letters Patent filed
by the said Joseph Anthony Dixon in the Great Seal Patent Office on the
13th July 1881.
JOSEPH ANTHONY DIXON, of 175, West George Street, Glasgow, in the County
of Lanark, North Britain, Solicitor. "IMPROVEMENTS IN THE PRODUCTION OF
BENZALDIACETATE AND CERTAIN SUBSTITUTION PRODUCTS THEREOF, AND IN THE
TRANSFORMATION OF THESE BODIES RESPECTIVELY INTO CINNAMIC ACID, AND
THE CORRESPONDING SUBSTITUTION PRODUCTS THEREOF." A communication from
abroad by Doctor Karl Koenig, of Hochst-am-Main, in the Empire of Germany,
a Director of the Farbwerke vorm: Meister, Lucius, and Brüning, a Company
carrying on business there as Chemical Manufacturers.
This Invention has for its nature and objects the production of cinnamic acid
and its chlor-, brom-, and nitro-substitution derivatives, by heating benzaldiacetate
C, H, CH
OCH, CO) or C, H, CH
OCH
O C₂
OC, H₂O}) and its chlor-
brom, and nitro substitution derivatives respectively, with anhydrous acetate of
sodium, and also the production of the said benzaldiacetate, and its said substitution
products in an improved way by heating benzal-chloride, and its corresponding
substitution products respectively, with anhydrous acetate of lead.
Benzaldiacetate, as is well known, has hitherto been obtained only by
transforming benzal-chloride with acetate of silver (Wicke, Annalen der Chemie
und Pharmacie, vol. 102, page 366), or by addition of acetanhydride and
benzaldehyde (Perkins, Journal of the Chemical Society, new series, v. 586, and
Annalen der Chemie und Pharmacie, vol. 146, page 373). produce it after a new
method, by the prolonged heating, at a temperature of 248° to 288° F. (120°–140° C.)
of benzal chloride with anhydrous acetate of lead.
The formation of the benzaldiacetate takes place according to the formula,—
C₂ H, 00
CH, CH Cl₂ + C, H, OO} Pb-C, H, CH
O C₂ H, O
OC, H₂O}
+ Pb Cl₂.
In an analogous manner I obtain the chlor-, brom-, and nitro substitution products
of the benzaldiacetate from the corresponding chlor-, brom-, and nitro- substitution
products of the benzal-chloride by treating the latter substitution products with
anhydrous acetate of lead, in the same way in which I treat the benzal = chloride,
as hereinbefore described.
The preparation of cinnamic acid, and of the above mentioned derivatives of this
acid respectively, from benzaldiacetate and its corresponding derivatives, is effected,
according to this Invention, by heating the benzaldiacetate, or one or other of its
said derivatives, as the case may be, with anhydrous acetate of sodium.
The following is an explicit description of my method and process, or alternative
processes, for obtaining cinnamic acid from benzal-chloride.
I heat for about 6 hours at a temperature of 248° to 288° F. (120° to 140° C.)
30 parts by weight of benzal-chloride with 90 parts of anhydrous acetate of lead
in a suitable vessel, in this way forming, according to the equation herein before
set forth, chloride of lead and benzaldiacetate; I then add to the mixture about
30 parts of anhydrous acetate of sodium; afterwards I heat for about 18-20 hours,
at a temperature of 356° to 428° F. (180° to 220° C.).
The thus obtained smelt is first boiled in water, and after it has been allowed to
cool down I extract the cinnamic acid from the residue by 30 parts of soda, and
300 parts of water. By evaporating and crystallizing the extract I obtain the
cinnamic acid in the form of the cinnamate of sodium.
I may however first separate the benzaldiacetate from the chloride of lead by

page_text: suitable dissolving agents, such as ether, benzole, and the like solvents, or draw it
off by suitable distillation, and then heat it with acetate of sodium, without any
essential difference in the final result.
If in the process or alternative processes for obtaining cinnamic acid from benzal
chloride or benzaldiacetate above described I substitute for the benzal=chloride, or
for the benzaldiacetate, the chlor, brom, or nitro substitution products thereof
respectively, I then obtain the corresponding chlor, brom, or nitro-cinnamic acids,
in the form of their sodium salts.
The described proportions, and also the degrees of temperature, may be varied
within certain limits.
Having now described and particularly ascertained the nature of my said
Invention, and the system, mode, or manner in or under which the same is or
may be used or practically carried into effect, I would observe in conclusion that
what I consider to be novel and original, and therefore claim as the Invention
secured to me by the hereinbefore in part recited Letters is,―
First. The production of benzal-diacetate by heating benzal-chloride with
anhydrous acetate of lead, in manner herein before described.
Second. The production of the chlor-, brom-, and nitro-substitution compounds of
benzal-diacetate by the treatment of the respective chlor-, brom-, and nitro-substitution
derivatives of benzal-chloride with anhydrous acetate of lead, in manner hereinbefore
described.
Third. The production of cinnamic acid by heating the benzal-diacetate with
anhydrous acetate of sodium, and extracting the cinnamic acid from the smelt
so obtained in the form of cinnamate of sodium, all in manner herein before
described.
Fourth. The production of chlor-, brom-, and nitro cinnamic acids respectively, by
heating the chlor-, brom-, and nitro-substitution derivatives of benzal-diacetate with
anhydrous acetate of sodium, and extracting the said acids in the form of their
respective sodium salts, all in manner herein before described.
Fifth. The entire processes herein before described, together with the variations
thereof herein before described, for producing cinnamic acid from benzal-chloride or
benzal-diacetate, and for producing the chlor-, brom-, or nitro-substitution compounds
respectively, of cinnamic acid from the chlor-, brom-, or nitro-substitution com-
pounds respectively of benzal-chloride or of benzal-diacetate, and extracting the
said acids in the form of their sodium salts, all in manner hereinbefore described.
In witness whereof, I, the said Joseph Anthony Dixon, have hereunto set my
hand and seal, this Second day of July, in the year of our Lord One
thousand eight hundred and eighty one.
JOSEPH ANTHONY DIXON. (L.S.)