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SYNTHESIS OF PIPERONYL MALEAMIDE FROM SAFROLE

Healthy Kainama
Departement of Chemistry –FKIP,Pattimura University Ambon

ABSTRACT

It has been done the synthesis of piperonyl maleamide as amide derivatives of


C-9154 antibiotic from safrole. Safrole was isolated from cullilawan oil. The synthesis
was started by isomerisation of safrole with KOH in ethanol at reflux for 8 hours,
then oxidation of isosafrole with KMnO4 using polysorbate 80 as a catalyst in acid at
40oC for 15 minutes to give piperonal. The further experimental stages were reduction
of piperonal followed by condensation of piperonyl alcohol with maleic anhydride
and chlorination - ammonolysis of the resulted piperonyl maleic acid.
The reduction of piperonal with NaBH4 afforded piperonyl alcohol in 90.7 %
yield. Condensation of piperonyl alcohol with maleic anhidryde performed in benzena
at 60oC for 6 hours gave 40.8 % piperonyl maleic acid. The amide derivative was
synthesized through chlorination of piperonyl maleic acid with SOCl2, followed by
ammonolysis to yield 48.2 % piperonyl maleamide. The purity of the products was
determined using GC, whereas their structures were elucidated using FTIR, 1HNMR
and MS
It has been done the synthesis of some esters and amide derivatives of C-9154
antibiotic from safrole. Safrole was isolated from cullilawan oil. The synthesis was
started by isomerisation of safrole with KOH in ethanol at reflux for 8 hours, then
oxidation of isosafrole with KMnO4 using polysorbate 80 as a catalyst in acid at 40oC
for 15 minutes to give piperonal. The further experimental stages were reduction of
piperonal followed by condensation of piperonyl alcohol with maleic anhydride and
chlorination - ammonolysis of the resulted piperonyl maleic acid.
The reduction of piperonal with NaBH4 afforded piperonyl alcohol in 90.7 %
yield. Condensation of piperonyl alcohol with maleic anhidryde performed in toluene
at 60oC for 6 hours gave 9.6 % piperonyl maleic acid. This reaction gave 40.8 %
piperonyl maleic acid when this was carried out in benzene under the similar
condition. Esterification of piperonyl maleic acid with ethanol in the presence of
H2SO4 afforded ethyl piperonyl maleate in 48,3 %. When p- toluene sulfonic acid was
used as the catalyst, ethyl piperonyl maleate was obtained in 77.3 % yield. The amide
derivative was synthesized through chlorination of piperonyl maleic acid with SOCl2,
followed by ammonolysis to yield 48.2 % piperonyl maleamide.
Oxymercuration-demercuration was used for the conversion of safrol to safryl
alcohol. Condensation of safryl alcohol with maleic anhydride in benzene gave 26.31
% safryl maleic acid. Esterification of safryl maleic acid with ethanol using p- toluene
sulfonic acid as the catalyst yielded 40.84 % ethyl safryl maleate. Chlorination of
safryl maleic acid using SOCl2, followed by ammonolysis failed to give safryl
maleamide probably due to the existence of relatively great steric barrier in the
structure of safryl maleic acid. The purity of the products was determined using GC,
whereas their structures were elucidated using FTIR, 1HNMR and MS