Manufacture of Vanilloyl Carbonic Acid and of Vanilline by its Transformation.
Year: 1891

page_text: Date of Application, 8th Oct., 1891
Complete Specification Left, 10th June, 1882-Accepted, 20th Aug., 1892
PROVISIONAL SPECIFICATION.
[Communicated from abroad by LA SOCIÉTÉ DE LAIRE ET CIE, of 92, Rue St.
Charles, Paris, France, Chemists.]
Manufacture of Vanilloyl Carbonic Acid and of Vanilline by its
Transformation.
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:-
My foreign correspondents have found that when acetylengenol C'H' (CH' –
C'H=CH³) (OCH³) (OCO'CH') and acetylisoengenol C³H³ (CH=CH-
CH') (OCH³) (OCO'CH³) are oxidised in the processes usually adopted for
production of vanilline, there is often obtained, besides the vanilline, a substance
which has not hitherto been noticed or described. It may be termed vanilloyl-
carbonic acid, formula C'H' (COC'O³H) (OCH') (O'H). Crude vanilline often
contains a considerable proportion of this and its purification is thus rendered more
difficult. The two substances, vanilline and vanilloylcarbonic acid go together into
an aqueous solution of bisulphite of soda when their mixture is treated by this
reagent either directly or in solution in ether or other like solvent.
The vanilloylcarbonic acid can be separated from the vanilline in either of two
ways:-
1. By agitating an ether solution of the two substances with water containing in
suspension carbonate of magnesia, lime, baryta or strontin, or in solution bicar-
bonate of soda or potash, a salt of the vanilloylcarbonic acid soluble in water being
thus formed.
2. By precipitating regularly and fractionally by alcohol the aqueous not con-
centrated solution of the double compounds of vanilloylcarbonic acid and of vanilline
with bisulphite of soda; the double compound of the vanilloylcarbonic acid being
first separated.
Vanilloylcarbonic acid set free by sulphuric acid from aqueous solutions of its
salts or from its double compound with bisulphite of soda, is taken up by ether.
After evaporation of the ether, the oil which remains can be dried in vacuo
at 50° 60° C., and crystallised in benzene. When separated in this manner the
vanilloylcarbonic acid fuses at 134° C. and, when it is heated beyond this, it
separates into vanilline and carbonic acid.
Dated this 8th day of October 1891.
ABEL & IMRAY,
Agents for the Applicant.
COMPLETE SPECIFICATION.
Manufacture of Vanilloyl Carbonic Acid and of Vanilline by its
Transformation.
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 and in what manner the same is to be performed, to be particularly
described and ascertained in and by the following statement :-
-
-
My foreign correspondents have found that when acetylengenol C.H, (CH, –
C'H =
CH) OCH,) (OCO'CH,) and acetylisoengenol C.H, (CH=CH-
CH) (ОCH) (OCO'CH,) are oxidised in the processes usually adopted for

page_text: production of vanilline, there is often obtained, besides the vanilline, a substance
which has not hitherto been noticed or described.
It may be termed vanilloyl carbonic acid, formula C¸H, (COC³O,H) (OCH₂)
(OH). Crude vanilline often contains a considerable proportion of this and its
purification is thus rendered more difficult. The two substances vanilline and
vanilloylcarbonic acid go together into an aqueous solution of bisulphite of soda
when their mixture is treated by this reagent either directly or in solution in ether
or other like solvent. The vanilloylcarbonic acid can be separated from the
vanilline in either of two ways.
1. By agitating an ether solution of the two substances with water containing
in suspension carbonate of magnesia, lime, baryta, or strontia, or in solution bicar-
bonate of soda or potash, a salt of the vanilloylcarbonic acid soluble in water being
thus formed.
2. By precipitating regularly and fractionally by alcohol the aqueous not con-
centrated solution of the double compounds of vanilloylcarbonic acid and of vanilline
with bisulphite of soda, the double compound of the vanilloylcarbonic acid being
first separated.
Vanilloylcarbonic acid set free by sulphuric acid from aqueous solutions of its
salts or from its double compound with bisulphite of soda, is taken up by ether.
After evaporation of the ether, the oil which remains can be dried in vacuo
at 50°-60° C. and crystallised in benzene.
When separated in this manner the vanilloylcarbonic acid fuses at 134° C. and,
when it is heated beyond this, it separates into vanilline and carbonic acid.
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 vanilloylcarbonic acid, and the means of separating it
from vanilline, as herein described.
2. The application of vanilloylcarbonic acid in the manufacture of vanilline by
separating it into vanilline and carbonic acid, as herein described.
Dated this 10th day of June 1892.
FAST
A
ADEL & IMRAT,
Agents for the Applicant.