Manufacture of Mixed Anhydrides of Formic and Organic Acids, and the Preparation from these of Formylic Derivatives of Alcohols or Ammonia or of Substitution Products of Ammonia.
Year: 1899

page_text: Date of Application, 10th June, 1899
Complete Specification Left, 3rd Mar., 1900-Accepted, 14th Apr., 1900
PROVISIONAL SPECIFICATION.
Manufacture of Mixed Anhydrides of Formic and Organic Acids, and
the Preparation from these of Formylic Derivatives of Alcohols
or Ammonia or of Substitution Products of Ammonia.
I, AUGUSTE BEHAL, of 53, Rue Claude Bernard, Paris, France, Chemist, do
hereby declare the nature of this invention to be as follows:-
:―
Hitherto no mixed anhydride of formic with other organic acids has been
produced. I have found that formic acid can be readily obtained by causing
formic acid free from water to react on anhydrides of organic acids, at
moderate temperatures.
The reaction is rapid and the mixed anhydrides thus obtained may be
characterised by the fact that they are decomposed in the cold by tertiary bases
(quinoline, pyridine, dimethyl aniline) disengaging plentifully carbon
monoxide.
These mixed anhydrides act upon acyclic or cyclic alcohols to produce corre-
sponding formic ethers. They also react on polyalcoholic bodies, and on
ammonia and substitution products of ammonia.
The action of these mixed anhydrides is the following:
One of the components, the formyl group, combines with the alcohol or
the base whilst the other component produces the corresponding acid.
I shall explain by way of example the preparation of one of these mixed
anhydrides and of some of the bodies obtainable from these new mixed
anhydrides.
MIXED FORMIC ACETIC ANHYDRIDE.
The formic acetic anhydride is prepared by mixing equal molecules of formic
acid free from water, and acetic anhydride, care being taken that the tem-
perature does not exceed 50° C. The mixed anhydride at once results. It is scarcely
soluble in petroleum ether; by, agitating the product of the reaction with
petroleum ether, a considerable portion of the acetic acid is removed.
The portion not dissolved in the petroleum ether constitutes the raw mixed
formic-acetic anhydride, which is purified by fractional and repeated distilla-
tion in vacuo. It is a body freely emitting vapour with a strong pungent
odour. It is soluble in benzine, liquid at ordinary temperatures, and distils.
under atmospheric pressure at 105° to 118° C., with partial decomposition and
evolution of carbon monoxide. It distils at about 29° C. under 18 m/m pressure.
It is decomposed in the cold by tertiary bases and anhydrous sodium acetate
with abundant evolution of carbon monoxide.
FORMIATE OF CAPRYL.
To a molecule of caprylic alcohol is added while cooling somewhat more than
a molecule of mixed anhydride such as formic acetic, the reaction is very rapid.
It is found unnecessary to isolate the mixed anhydrides in a pure state, as the
1

page_text: On distilling, the first portions are acetic acid, the more highly rectified
portions are formiate of capryl. It is a liquid having aromatic odour, boiling
at 185° to 186° C, under ordinary pressure without sensible alteration. Its
density at 0° C. is 0.884.
The formiates of methyl, ethyl, propyl, iso-propyl, butyi, iso-butyl &c., can
also be produced; formiate of capryl has been chosen as an example because
it is a new body.
The formiate of heptyl obtained by the sanie process boils at 177° to 180° C
and at 0° C. has a density of 0.893.
FORMIATE OF BENZYL.
This formiate of aromatic alcohol is obtained as described for formiates of
fatty alcohols. It is a liquid of pleasant odour boiling at 200° to 203° C. under
ordinary pressure; at 0° C. its density is 1.102.
FORMIATE OF ALLYL; FORMIATE OF CINNAMYL.
It is a
The formiate of allyl, whose properties are known, is easily obtained by this
process. By causing mixed formic-acetic anhydride to react in the cold upon
cinnamic alcohol, the formiate of cinnamyl is very easily obtained.
body having aromatic odour, boiling under atmospheric pressure without de-
composition at 250° to 254° C... crystallising in a refrigerating mixture to melt
at about 0° C., at which temperature its density is 1.086.
DIFORMIATE OF GLYCOL.
This body is also prepared by the process described for formiates of mono-
valent alcohols, but it must be rectified in vacuo.
The same is done with phenyl-glycol; according to the proportions in the
mixed anhydride the mono formiate or the deformiate of phenyl glycol is
obtained.
FORMIATES OF TERPENIC ALCOHOLS.
These bodies are readily prepared by this process, I have thus obtained the
formiates of bornéol, menthol, géraniol, linalool, citronnellol terpineol, &c.,
which have known characteristics.
With anhydrous terpine is obtained diformyl-terpine. The reaction also takes
place with sesquiterpenic alcohols. With carryophyllenic alcohol is obtained
the foromiate of carryophyllenyl, and with santalol the formiate of santalyl.
FORMIAMIDE.
Ammonia gas is introduced into a solution of mixed anhydride in absolute
ether of which a considerable quantity has to be taken because formiamide is
only slightly soluble in ether.
On cooling when the solution smells strongly of ammonia gas, the ether is
separated by decanting from the crystals that are formed; the ether distilled
leaves the formiamide.
Contrary to received data, the formiamide is very slightly soluble in ether,
it crystallises very easily at zero in long characteristic needles fusible at about
4° C. It boils without decomposition at 122° C. under a pressure of 32 m.m.
FORMANILIDE.
To a molecule of mixed anhydride while cooling is added by degrees about
the corresponding quantity of aniline. The reaction product is washed with
water acidulated with hydrochloric acid; the oily residue is exhausted by means
of benzine which distilled leaves the formanilide.
So also on starting with methyl-aniline there is obtained methyl-formanilide
which melts at 8° C., is very slightly soluble in water is very soluble in alcohol,
and has at 0° C. density 1, 107.
On starting with p-ethoxyl-aniline, there is obtained formyl-p-ethoxyl-aniline,

page_text: a crystallised body melting at 68.5° C., soluble in hot water, and very soluble in
alcohol.
On starting with ortho-amido-phenol there is obtained formyl-o-amido phenol
which melts at 129° C., is very slightly soluble in benzine even when boiling,
but is soluble in alcohol and in alkalies.
On starting with urea, formyl-urea is obtained, and from phenyl-hydrazine is
obtained formyl-phenyl-hydrazine.
These known bodies are very easily obtained.
Manufacture of Mixed Anhydrides of Formic and Organic Acids, and
the Preparation from these of Formylic Derivatives of Alcohols
or Ammonia or of Substitution Products of Ammonia.
I, AUGUSTE BEHAL, of 53, Rue Claude Bernard, Paris, France, Chemist, 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 follow-
ing statement:-
Hitherto no mixed anhydride of formic with other organic acids has been
produced. I have found that such mixed anhydrides can be readily obtained
by causing formic acid free from water to react with anhydrides of organic
acids, at moderate temperatures.
The reaction is rapid and the mixed anhydrides thus obtained may be
characterised by the fact that they are decomposed in the cold by tertiary bases
(quinoline, pyridine, dimethyl aniline) disengaging plentifully carbon
monoxide.
These mixed anhydrides act upon acyclic or cyclic alcohols to produce corre-
sponding formic ethers. They also react on polyalcoholic bodies, and on
ammonia and substitution products of ammonia (N H, R and NH R¹ R²).
The action of these mixed anhydrides is the following:.
One of the components, the formyl group, combines with the alcohol or
the base whilst the other component produces the corresponding acid.
The following examples illustrate the preparation of these mixed anhydrides
and of the bodies obtainable by means of them.
MIXED FORMIC ACETIC ANITYDRIDE.
The formic acetic anhydride is prepared by mixing equal molecules of formic
acid free from water, and acetic anhydride, care being taken that the tem-
perature does not exceed 50° C. The mixed anhydride is at once produced.
It is scarcely soluble in petroleum ether; by agitating the product of the re-
action with petroleum ether, a considerable portion of the acetic acid is removed.
The portion not dissolved in the petroleum ether constitutes the crude mixed
formic-acetic anhydride, which is purified by repeated fractional, distilla-
tion in acuo. It is a body freely emitting vapour with a strong pungent
odour. It is soluble in benzine, liquid at ordinary temperatures, and distils
under atmospheric pressure at 105° to 118° C., with partial decomposition and
evolution of carbon monoxide.
It distils at about 29° C. under 18 mm pressure,

page_text: It is decomposed in the cold by tertiary bases and by anhydrous sodium
acetate with abundant evolution of carbon monoxide.
MIXED FORMIC PROPIONIC ANHYDRIDE.
This is prepared by mixing equal molecular proportions of formic acid free
from water, and propionic anhydride. Heat is evolved and the mixed anhydride
is at once produced. In vacuo it distils without change, but when distilled at
the ordinary pressure it decomposes, carbon monoxide being evolved. Like
formic acetic anhydride, it decomposes in contact with quinoline, yielding carbon
monoxide. It reacts with alcohols in the cold giving formic ethers; for example
with hexylic alcohol it vields hexylformiate.
Mixed formic isobutyric anhydride and mixed formic isovaleric anhydride are
prepared in a similar manner; the evolution of heat is less marked than in pre-
ceding cases. They react with alcohols yielding formiates.
FORMIATE OF CAPRYL.
To one molecular proportion of caprylic alcohol is added while cooling some-
what more than one molecular proportion of mixed anhydride such as formic
acetic anhydride the reaction is very rapid. It is found unnecessary to isolate
the mixed anhydrides in a pure state, as the free acetic acid does not interfere
with the reaction.
On distilling, the first portions are acetic acid, the more highly rectified
portions are formiate of capryl. It is a liquid having aromatic odour. boiling
at 185° to 186° C., under ordinary pressure without sensible alteration. Its
density at 0° C. is 0.884.
The formiates of methyl, ethyl, propyl, iso-propyl, butyl, iso-butyl &c., can
also be produced; formiate of capryl has been chosen as an example because it
is a new body.
The formiate of heptyl obtained by the same process boils at 177° to 180° C
and at 0° C. has a density of 0.893.
FORMIATE OF BENZYL.
This formiate of aromatic alcohol is obtained as described for formiates of
fatty alcohols. It is a liquid of pleasant odour boiling at 200° to 203° C. under
ordinary pressure; at 0° C. its density is 1.102.
FORMIATE OF ALLYL; FORMIATE OF CINNAMYL.
The formiate of allyl, whose properties are known, is easily obtained by this
process. By causing mixed formic-acetic anhydride to react in the cold upon
cinnamic alcohol, the formiate of cinnamyl is very easily obtained. It is a
body having aromatic odour, boiling under atmospheric pressure without de-
composition at 250° to 254° C., it crystallises in a refrigerating mixture and melt
at about 0° C., at which temperature its density is 1.086.
DIFORMIATE OF GLYCOL.
This body is also prepared by the process described for formiates of mono-
valent alcohols, but it must be rectified in vacuo.
The same is done with phenylglycol; according to the proportions of the
nixed anhydride the mono formiate or the diformiate of phenylglycol is
obtained.
FORMIATES OF TERPENIC ALCOHOLS.
These bodies are readily prepared by this process, I have thus obtained the
formiates of borneol, menthol, geraniol, linolool, citronnellol, terpineol &c.,
which have known characteristics.
With anhydrous terpine is obtained diformyl-terpine. The reaction also takes
place with sesquiterpenic alcohols. With carryophyllenic alcohol is obtained
the formiate of carryophyllenyl, and with santalol the formiate of santalyl.

page_text: FORMIAMIDE.
Ammonia gas is introduced into a solution of mixed anhydride in absolute
ether of which a considerable quantity has to be taken because formiamide is
only slightly soluble in ether.
Un cooling when the solution smells strongly of ammonia gas, the ether is
separated by decanting from the crystals that are formed; the ether distilled
leaves the formiamide.
Contrary to received data, the formiamide is very slightly soluble in ether,
it crystallises very easily at zero in long characteristic needles fusible at about
4° C. It boils without decomposition at 122° C. under a pressure of 32 m.m.
FORMANILIDE.
To one molecule of mixed anhydride while cooling is added by degrees about
the corresponding quantity of aniline. The reaction product is washed with
water acidulated with hydrochloric acid; the oily residue is exhausted by means
of benzene which distilled leaves the formanilide.
So also on starting with methyl-aniline there is obtained methyl-formanilide
which melts at 8° C., is very slightly soluble in water is very soluble in alcohol,
and has at 0° C. density 1.107.
On starting with para-ethoxy-aniline there is obtained formyl-para-ethoxy-
aniline, a crystallised body melting at 68° C., soluble in hot water and very
soluble in alcohol.
On starting with ortho-amido-phenol there is obtained formyl-ortho-amido-
phenol which melts at 129° C., is very slightly soluble in benzene even when
boiling, but is soluble in alcohol and in alkalies.
On starting with urea, formyl-urea is obtained, and from phenyl-hydrazine is
obtained formyl-phenyl hydrazine.
These known bodies are very easily obtained.
Having now particularly described and ascertained the nature of my said
invention and in what manner the same is to be performed, I declare that what
I claim is :-
1. The herein described manufacture of mixed anhydride of formic acid and
organic acids by causing formic acid free from water to react with anhydride of
organic acids at moderate temperatures.
2. The mixed anhydrides manufactured as above set forth.
3. Process for the preparation of formylic derivatives of alcohols or ammonia
or substitution products of ammonia by causing the said alcohols, ammonia or
substitution products of ammonia to react with mixed anhydrides of formic
acid and organic acids, substantially as described.
4. The new products prepared as above set forth.
Dated this 3rd day of March 1900.