Manufacture of Monobasic Acids having the%, of Dibasic Acids andy.
Year: 1892

page_text: Date of Application, 12th Nov., 1892
Complete Specification Left, 5th Aug., 1893-Accepted, 23rd Sept., 1893
PROVISIONAL SPECIFICATION.
[Communicated from abroad by Messrs. HAARMANN & REIMER VANILLIN-
FABRIK, in Holzminden a/d Weser, in the German Empire.]
Manufacture of Monobasic Acids having the Composition CH140%, of
Dibasic Acids having the Composition CH₁4O4 and of Anhydrides
of the latter, having the Composition C₂H₁₂O9.
I, CHARLES DENTON ABEL, 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:-
My correspondents have discovered,
Firstly. That certain camphor species having the composition C10H1O, which
they have determined to be methyl-ketones, namely containing the ketone
group COCH give monobasic acid of the formula C,H₁O, under the reaction of
bromine and alkali.
Secondly. That these camphor-species can be oxidised to keton-acids by means
of dilute potassium permanganate solution, which ketone acids are converted into
dibasic acids of the formula CHO, under the reaction of bromine and alkali.
Thirdly. That the said dibasic acids give anhydrides of the formula C,H₁,O,
under the reaction of dehydrating agents.
Camphor species of the kind above referred to have been found by my
correspondents in the tansy-cil, absinth-oil, sage-oil, and thuja-oil.
Other camphor species, as for example the ordinary camphor, cannot be converted
into the said mono-basic acids, dibasic-acids and the anhydrides of the latter.
EXAMPLE.
a. The camphor C₁,HO, obtained from tansy oil by shaking with sodium
bisulphite, is treated in the proportion of 60 parts thereof with 2,500 parts of a
4 per cent. soda lye and about 180 parts of bromine. After shaking for about
four hours the liquid is freed from the bromo form produced, by extraction with
ether, and the simultaneously produced acid of the formula C,H₁O, is separated
from the alkaline solution by means of mineral acids.
The acid distils at a pressure of 15 mm. and at a temperature of 113.5°, and it
solidifies under refrigeration in the form of needles which do not melt again at
ordinary temperature.
b. From the camphor of the tansy-oil an acid may be obtained, which has been
determined by my correspondents to be a keton-acid, by oxidation at a low
temperature in the ordinary manner, with dilute solution of permanganate of
potash, which acid distils under 10 mm. pressure at 169° C., and crystallises in
laminæ or needles.
When 60 parts of this acid are dissolved in about 350 parts of a 4 per cent. soda
lye, and to this solution be added about 2,000 parts of a 4 per cent. soda lye to
which has been previously added about 150 parts of bromine, bromoform will be
separated in the same manner as stated under (a.), two isomeric dibasic-acids of the
formula C.HO, being formed which are separated in the usual manner from the
alkaline solution, and of which the one which is first separated crystallises in white
laminæ melting at a temperature of 141° C.
c. This dibasic acid is converted, by heating for half an hour with the three fold
quantity of acetic acid or acetylchloride, into an anhydride that boils under
16 mm. pressure at a temperature of 171° C., and that melts at 55° C.
The fractions of absinth-, sage-, and thuja oils boiling under a pressure of 14 mm.

page_text: at a temperature of from 80° to 90°, are converted under the conditions set forth
in a. b. and c. into products having the same composition, shewing some variations
in the melting points and the optical conditions.
The above described products are intended for use in perfumery and pharmacy.
Dated this 12th day of November 1892.
ABEL & IMRAY,
Agents for the Applicant.
COMPLETE SPECIFICATION.
Manufacture of Monobasic Acids having the Composition CH₁₂, of
Dibasic Acids having the Composition CHO. and of Anhydrides
of the latter, having the Composition C₂H₂Os.
1, CHARLES DENTON ABEL, 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 :-
My correspondents have discovered :-
Firstly. That a certain number of camphors of the composition C₁, H₁O, which
are defined by the following reactions as belonging all to one series and characterized
as members of this series by acting as methylketones (RCO CH,) give monobasic
acids of the formula C.HO, under the reaction of bromine and alkali.
2
Secondly. That the camphors of the above series can be oxidised to ketone-acids
by means of dilute potassium permanganate solution, which ketone acids are
converted into dibasic acids of the formula C,H₁O. under the reaction of bromine
and alkali.
12
Thirdly. That the said dibasic acids give anhydrides of the formula C,H₁,0,
under the reaction of dehydrating agents.
Camphors of the above series have been found by my correspondents in tansy-oil,
absinthe-oil, sage-oil and thuja-oil.
Camphors belonging to another series, as for example the ordinary camphor,
cannot be converted into the said monobasic acids, dibasic acids and the anhydrides
of the latter,
EXAMPLE.
a. The camphor CHO, obtained from tansy-oil by shaking with sodium
bisulphite, is treated in the proportion of 60 parts thereof with 2500 parts of
4 per cent. soda lye and about 180 parts of bromine. After shaking for about four
hours the liquid is freed from the produced broma-form by extraction with ether,
and the simultaneously produced acid of the formula C,H₁O, is separated from the
alkaline solution by means of mineral acids.
The acid, which my correspondents call tanacetogenic acid, distils under a
pressure of 15 m at a temperature of 113.5° and solidifies in the form of needles
in a freezing mixture.
b. From the above defined camphor an acid, which has been determined by my
correspondents to be a ketone-acid, may be obtained by oxidizing these camphors
at a low temperature in the ordinary manner with a dilute solution of permanganate
of potassium. The ketone acid obtained thereby distils under 10 / pressure
at 169° C. and crystallises in laminæ or needles.
The ketone acid has the formula C₁,H,O, and the rational formula
COCTY

page_text: When 80 parts of this acid are dissolved in about 350 parts of a 4 per cent.
soda lye, and to this solution is added about 2000 parts of a 4 per cent. soda lye to
which have been previously added about 150 parts of bromine, bromoform is
formed and separated in the same manner as stated under a; at the same time two
isomeric dibasic acids of the formula CHO̟ are formed, which are separated in
the usual manner from the alkaline solution, and of which the one, which is first
separated, crystallises in white laminæ, melting at a temperature of 141° C. My
correspondents call this acid tanacetogendicarbonic acid.
c. This dibasic acid is converted by heating it for half an hour with the three-
fold quantity of acetic acid or acetyl chloride, into au anhydride (C„H„O) that
boils under 171° C. and melts at 55° C.
The fractions of absinthe- sage- and thuja-oils boiling under a pressure of 14 "/m
at a temperature of from 80° to 90°, are converted under the conditions set forth
in a,
b and c into products having the same composition, but showing some
variations in the melting points and the optical conditions.
The above described products are intended for use in perfumery and pharmacy.
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 process for direct and indirect oxydation of camphors,
which act as methyl ketones (RCO CH₂) by bromine and alkaline lye to monobasic
acids of the formula C.HO, to dibasic acids of the formula CHO and
conversion of the dibasic acids resulting therefrom into anhydrides of the
formula C,H,,O, by dehydrating agents.
14
2. An acid of the composition CHO, and of the rational formula CH₁,CO,H,
prepared by the above described process from the camphors of tansy-oil, which is
termed tanacetogenic acid, a liquid which boils under a pressure of 15 / at a
temperature of 113.5° C. and solidifies at a low temperature.
3. An acid of the composition C.HO, and of the rational formula
4
ABEL & IMRAY,
Agents for the Applicant.