Year: 1896

page_text: Date of Application, 11th Mar., 1896
Complete Specification Left, 7th Dec., 1896-Accepted, 9th Jan., 1897
I, OLIVER IMRAY of No. 28 Southampton Buildings in the County of London,
Chartered Patent Agent, do hereby declare the nature of this invention to be as
follows:-
By the action of iodine upon the esters of oxy-benzoic acids, their iodo-
derivatives are formed; the same products can be obtained by esterification of
the indo-acids corresponding to the iodo-esters.
If the iode-oxyacid ester is prepared by the action of iodine upon oxyacid ester,
it is necessary, in order to obtain a good yield, to combine or decompose the
hydriodic acid formed, by the addition of alkalies, carbonates, acetates, metallic
oxides or oxidising agents, such as iodic acid or chlorine.
To produce di-iodosalicylic acid esters my foreign correspondents proceed in the
following manner :-
2 molecular proportions of iodine dissolved in alcohol or other solvent, are
introduced into a solution of 1 molecule of salicylic acid-ester with alcohol or the
like, an excess of mercuric oxide HgO, zinc oxide ZnO or lead oxide Pb() or the
like is then added.
On cooling, the iodo-ester crystallises out from the filtered solution, which has
been previously freed from mercuric iodide Hgl, by means of ammonium sulphide
(H.N),S.
2 molecular proportions of iodine dissolved in iodide of potassium IK are run
into a solution of 1 molecular proportion of salicylic acid-ester in one equivalent
of dilute aqueous alkali, two further equivalents of alkali being then added.
After the reaction is completed, an acid is added, for instance, sulphuric acid
which decomposes the partly precipitated alkaline salts and thus the free di-iodo-
esters are obtained.
The same di-iodosalicylic acid-esters may be obtained by the esterification of
di-iodosalicylic acid, as described in the following examples:-
A solution of di-iodosalicylic acid in methyl alcohol is saturated with hydrochloric
acid and the ester thus formed is precipitated with water. Or the salts of di-iodo-
salicylic acid are treated with alkylhalogenide, thus for instance the methyl-ester
is obtained by heating the silver salt of di-iodosalicylic acid with methyl iodide.
The di-iodo-salicylic acid methyl-ester melts at 110° C.; it crystallises in thin
long brilliant needles, which are fairly soluble in hot alcohol (about 10 parts),
with difficulty in cold alcobol, very easily in ether.
Di-iodosalicylic acid ethyl-ester melts at 132° C., it crystallises in quadrilateral,
almost square tablets and is considerably less soluble in alcohol and ether than the
methyl-ester; both esters are with difficulty soluble in water.
The new esters are to be employed therapeutically.
ABEL & IMRAY,
Agents for the Applicant.

page_text: I, OLIVER IMRAY, of No. 28 Southampton Buildings, 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 :-
By the action of iodine upon the esters of oxy-benzoic acids, their iodo-
derivatives are formed; the same products can be obtained by esterification of the
iodo-acids corresponding to the iodo-esters.
If the iodo-oxyacid ester is prepared by the action of iodine upon oxyacid ester,
it is necessary, in order to obtain a good yield, to combine or decompose the
hydriodic acid formed by the addition of alkalies, carbonates, acetites, metallic
oxides or oxidising agents, such as iodic acid or chlorine.
To produce di-iodosalicylic acid esters my foreign correspondents proceed in the
following manner :-
2 molecular proportions of iodine dissolved in alcohol or other solvent, are
introduced into a solution of 1 molecule of salicylic acid-ester with alcohol or the
like, an excess of mercuric oxide HgO, zinc oxide Z.O or lead oxide PbO or the
like is then added.
On cooling, the iodo-ester crystallises out from the filtered solution, which has
been previously freed from mercuric iodide HgI, by means of ammonium sulphide
(H.N),S.
2 molecular proportions of iodine dissolved in iodide of potassium IK are run
into a solution of 1 molecular proportion of salicylic acid-ester in one equivalent
of dilute aqueous alkali, two further equivalents of alkali being then added.
After the reaction is completed, an acid is added, for instance, sulphuric acid
which decomposes the partly precipitated alkaline salts and thus the free di-iodo-
esters are obtained.
The same di-iodosalicylic acid-esters may be obtained by the esterification of
di-iodosalicylic acid, as described in the following examples:-
A solution of di-iodosalicylic acid in methyl alcohol is saturated with hydrochloric
acid and the ester thus formed is precipitated with water. Or the salts of
di-iodosalicylic acid are treated with alkylhalogenide, thus for instance the methyl-
ester is obtained by heating the silver salt of di-iodo-salicylic acid with methyl
iodide.
The di-iodo-salicylic acid methyl-ester melts at 110° C.; it crystallises in thin
long brilliant needles, which are fairly soluble in hot alcohol (about 10 parts), with
difficulty in cold alcohol, very easily in ether.
Di-iodosalicylic acid ethyl-ester melts at 132° C., it crystallises in quadrilateral,
almost square tablets and is considerably less soluble in alcohol and ether than the
methyl-ester; both esters are with difficulty soluble in water.
The new esters are to be employed therapeutically.
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. Manufacture of ester of iodo-oxy-benzoic acid by iodizing salicylic acid ester
or by esterification of di-iodo-salicylic acid, substantially as described.
2. As a new product the alkylester of di-iodo-oxy-benzoic acid being a white

page_text: crystalline compound, soluble with difficulty in water, but easily soluble in alcohol
and ether, and having the formula :