Laevulic acid
Laevulic acid
Laevulic
acid (β-acetylpropionic acid, γ-ketovaleric acid, butan-3-one-1-carboxylic
acid), m.p. 34oC, is the simplest γ-keto-acid. It may be prepared
via acetoacetic ester as follows:
It may also
be prepared by heating a hexose sugar, particularly laevulose, with concentrated hydrocloric acid:
C6H12O6 - CH3COCH2CH2CO2H +
HCO2H + H2O
In practice
it is customary to use cane-sugar as the starting material:
C12H22O11 -
2CH3COCH2CH2CO2H +
2HCO2H + H2O (21-22%)
By heating
dilute solutions of sucrose under pressure with hydrochloric acid, the yield is
increase to 50 per cent.
Leavulic
acid behaves as a ketone (forms oxime, etc) and as an acid (forms esters, etc).
On the other hand, many of the reactions of laevulic acid indicate that it
exists in the lactol form, i.e., hydroxylactone (this is an example of
ring-chain tautomerism) e.g.,
When heated
for some time, acid is converted into a-and β-angelica lactones (derived from
the lactol form):
A general
method for preparing y-keto-acids is to treat a ketone with lithium amide and
lithium bromoacetate; the ketone undergoes a-carboxymethylation (puterbaugh et
al., 1959)
y-keto-acids
may also be synthesized by other method. Keto-acid with the oxo group in the
d-or a higher position are very conveniently prepared by the action of a
dialkylcadmium on the half-ester acid chloride. On the other hand, d-keto-acids
may be prepared as follows from cyclohexame-1,3-dione, e.g., 5-oxoheptanoic
acid.
The cyclic
dione, since it contains an active methylene group, forms the potassium salt
which can be alkylated, and product readily undergoes fission, thus behaving
like the acyclic B-diketones. The keto-acids may be reduced byteh Wolff-Kishner
method to the corresponding saturated acid; in the above example, to heptanoic
acid. Alternatively, the alkylated ring may be opened and the carbonyl group
reduced in one step by refluxing with hydrazine in alkaline glycol solution.
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