Manufacture of Compounds of P-Amido-phenol Ethers and Aromatic Oxyaldehydes.
Year: 1893

page_text: Date of Application, 25th Feb., 1893
Complete Specification Left, 25th Nov., 1893-Accepted, 30th Dec., 1893
PROVISIONAL SPECIFICATION.
[Communicated from abroad by THE SOCIETY OF CHEMICAL INDUSTRY IN
BASLE, of Basle, Switzerland, Chemical Manufacturers.]
Manufacture of Compounds of P-Amido-phenol Ethers and Aromatic
Oxyaldehydes.
I, OLIVER IMRAY, of No. 28, Southampton Buildings, Chancery Lane, in the
County of London, Chartered Patent Agent, do hereby declare the nature of this
invention to be as follows:-
In mixing equivalent quantities of para amido phenol ethers and of aromatic
oxyaldehydes with or without subsequent addition of diluting agents such as alcohol,
ether etc. new condensation products are formed, with spontaneous heating and
separation of water.
Amongst these products there are especially those obtained from the action of
salicylaldehyde upon p-phenetidine or p-anisidine, which distinguish themselves by
their valuable therapeutic properties.
The reaction which takes place for instance with p-phenetidine and salicylaldehydo
may be expressed by the following equation:
EXAMPLE I.
The solutions of 23 parts of salicylaldehyde in 100 parts of alcohol and of
26 parts of p-phenetidine in 100 parts of alcohol, are mixed together at ordinary
temperature.
After a short time and with spontaneous heating there separates out from this
mixture a magma of yellowish coloured flat needles. It is left to stand for 1 to
2 hours and then the crystals are pressed and dried, or crystallised again from their
solution in warm alcohol.
The substance thus obtained consists of pale-yellowish glittering needles which
melt at 90° to 91° C. They are insoluble in water, and sparingly soluble in dilute
hot caustic soda-lye. The substance, however, dissolves easily in ether, benzene
and warm alcohol with a pale-yellow coloration; when treated with dilute acids, it
is decomposed into phenetidine and salicylaldehyde.
When, instead of p-phenetidine, the equivalent quantity of p-anisidine is used, as
in the preceding example, a similar medical compound, which crystallises in pale
yellow leaves of the melting point 80°-82° C. is obtained.

page_text: Berichte der Deutschen Chemischen Gesellschaft XXV (92) p. 2754) is alkylised
with molecular proportions of caustic alkalies and alkylizing agents.
In order to prepare the ethyl ether of o-oxybenzylidene-p-amido phenol, for
instance: 17 parts of o-oxybenzylidene p-amido phenol are dissolved in 50 parts of
alcohol and 4.5 parts of hydrate of caustic alkali and heated in the refrigerating
apparatus with 9 parts of bromethyl until the bromethyl has disappeared. On
cooling, the new product separates in the form of yellowish leaves.
By recrystallisation, it is obtained pure in the form of small pale-yellow needles
having a fusion point of 90°-91°-5 C., which correspond to the above described
substance obtained by the condensation of p-phenetidine with salicylaldehyde.
By the like process the methyl ether of o-oxybenzylidene-p-amidophenol is
obtained.
The products above described may be advantageously employed medically as
antipyretics and anti neuralgics.
Dated this 25th day of February 1893.
ABEL & IMRAY,
Agents for the Applicant.
COMPLETE SPECIFICATION.
Manufacture of Compounds of P-Amido-phenol Ethers and Aromatic
Oxyaldehydes.
1, OLIVER IMRAY, of No. 28 Southampton Buildings, Chancery Lane, in the
County of London, Chartered 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 :-
In mixing equivalent quantities of para-amido-phenol ethers and of aromatic
oxyaldehydes with or without subsequent addition of diluting agents such as
alcohol, ether etc. new condensation products are formed, with spontaneous heating
and separation of water.
Amongst these products there are especially those obtained from the action of
salicylaldehyde upon p-phenetidine or p-anisidine, which distinguish themselves by
their valuable therapeutic properties.
The reaction which takes place for instance with p-phenetidine and salicyl-
aldehyde may be expressed by the following equation :
EXAMPLE I.
The solutions of 23 parts of salicylaldehyde in 100 parts of alcohol and of
26 parts of p-phentidine in 100 parts of alcohol are mixed together at ordinary
temperature.
After a short time and with spontaneous heating there separates out from this
mixture a magma of yellowish coloured flat needles. It is left to stand for 1 to
2 hours and then the crystals are pressed and dried, or crystallised again from their
solution in warm alcohol.

page_text: The substance thus obtained consists of pale yellowish glittering needles which
melt at 90° to 91° C. They are insoluble in water, and sparingly soluble in dilute
hot caustic soda lye.
The substance, however, dissolves easily in ether, benzene, and warm alcohol
with a pale yellow coloration; when treated with dilute acids, it is decomposed
into phenetidine and salicylaldehyde.
When, instead of p-phenetidine, the equivalent quantity of p-anisidine is used, as
in the preceding example, a similar medical compound which crystallises in pale
yellow leaves of the melting point 80°-82° C. is obtained.
EXAMPLE II.
Condensation products, similar to those described in Example I, are obtained,
when o-oxybenzylidene-p-amido-phenol having the fusion point 135° C. (vide
Berichte der Deutschen Chemischen Gesellschaft XXV (92) p. 2754) is alkylised
with molecular proportions of caustic alkalies and alkylizing agents.
In order to prepare the ethyl ether of o-oxybenzylidene-p-amido phenol, for
instance: 17 parts of o-oxybenzylidene p-amido phenol are dissolved in 50 parts of
alcohol and 45 parts of hydrate of caustic alkali and heated with 9 parts of
bromethyl until the bromethyl has disappeared.
On cooling, the new product separates in the form of yellowish leaves.
By recrystallisation, it is obtained pure in the form of small pale yellow needles
having a fusion point of 90°-91°.5 C., which correspond to the above described
substance obtained by the condensation of p-phenetidine with salicylaldehyde.
By the like process the methyl ether of o-oxybenzylidene-p-amidophenol is
obtained.
The products above described may be advantageously employed medically as
as antipyretics and anti neuralgics.
Having now particularly described and ascertained the nature of this inven
tion and in what manner the same is to be performed, I declare that what I
claim is :-
1. The manufacture of compounds of p-amido-phenol ethers and aromatic oxy
aldehydes by condensation of molecular proportions of salicylaldehyde and of
p-phenctidine or p-anisidine, substantially as herein before described as Example I.
2. The manufacture of compounds of p-amido phenol ethers and aromatic
oxy aldehydes by alkylizing o-oxybenzylidene-p-amido-phenol in treating with
alkylizing agents, substantially as hereinbefore described as Example II.
3. As new articles of manufacture the compounds of p-amido-phenol ethers and
aromatic aldehydes manufactured in the manner referred to in Claims 1 and 2.
Dated this 25th day of November 1893.
ABEL & IMRAY,
Agents for the Applicant.