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The Fujisawa/Deguchi Performic Acid Oxidation

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Utilization of safrole as medical raw material. VI.
New syntheses of 3,4-methylenedioxybenzyl methyl ketone.

Fujisawa, Toshiro; Deguchi, Yoshio.
J. Pharm. Soc. Japan (Yakugaku Zasshi) 74, 975-7 (1954)
Chem. Abs. Vol 49, 10958i (1955), [CAN 49:56727]


cf. C.A. 47, 3300a (1953). A soln. of 34 g. 30% H2O2 and 150 g. 80% HCO2H was treated dropwise with 32.4 g. isosafrole in 120 ml. Me2CO below 40C, the mixt. stirred 2 hrs. and let stand overnight, and the HCO2H and Me2CO removed in vacuo to give 61 g. residue (I).

I (30 g.) in 30 ml. MeOH and 180 g. 15% H2SO4 were heated 3 hrs., the mixt. cooled and extd. with Et2O, the ext. washed with water and 5% NaOH and distd. to give 10.3 g. (58%) 3,4-CH2O2C6H3CH2COMe (II), bp2 108-112C; oxime, mp. 85-8C; semicarbazone, mp. 162-3C.

[Synthesis of 3,4-methylenedioxyphenylisopropylamine from Isosafrole]
Fujisawa, Toshiro; Okada, Mitsuzo; Deguchi, Yoshio.
Jap. Pat. 8573 (1956); Chem. Abs. 52, 11965b (1958) [CAN 52:66321]


To a cooled mixt. of 34 g. 30% H2O2 and 150 g. HCO2H is dropped a mixt. of 32.4 g. isosafrole and 120 mL acetone below 40C, kept overnight, evapd. in vacuo, 60 mL MeOH and 360 g. 15% H2SO4 added, heated on H2O bath 3 hrs., cooled, extd. with ether or C6H6, and distd. in vacuo to afford 20.6 g. 3,4-methylenedioxybenzyl methyl ketone (I), bp2 108-20C.

I (23 g.) and 65 g. HCONH2 is heated at 190C 5 hrs., cooled, 100 mL H2O2 added, extd. with C6H6, the ext. evapd., 8 mL MeOH and 75 mL 15% HCl added, heated on a H2O bath 2 hrs., alkalified with caustic alkali, the oil extd. with C6H6, and the ext. distd. in vacuo to afford 11.7 g. 3,4-methylenedioxyphenylisopropylamine (II), b5 122-7.