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LETTERS

TO THE EDITOR

RECYCLIZATION OF 6(8)-NITRO-3-TRIFLUOROACETYL-2-PHENYLINDOLIZINE WITH FORMATION OF 5(7)-NITRO-3-PHENYLINDOLE-2-CARBOXYLIC E. V. Babaev, S. I. Bobrovskii, and Yu. G. Bundel' ACID UDC 547.759f752.07

We found that by the action of aqueous-alcoholic alkali (KOH in 50% ethanol, concentration 3 M), at room temperature, indolizines la, b readily undergo recyclization, which is accompanied by a haloformic reaction with the formation of nitroindolecarboxylic acids lla, b. We should note that compound lla is a key intermediate in the synthesis of tranquilizers nitrazepam [i] and hypnone [2]. Acylindolizine Ic, which does not contain an NO= group is deacetylated* under these conditions, forming indolizine lllc (83%).
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~

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llIa-c

I-III aX=No 2, Y=H;

bX=HoY=NO2:c

X=Y=H

Compounds la-c were obtained from indolizines llla-c and trifluoroacetic anhydride. Compound la, mp 183-185~ (from a heptane-benzene mixture), yield 96%. Compound Ib, mp 162-165~ Compound Ic, mp 63-64~ (from heptane-benzene mixture), yield 100%o (from hexane), yield 34%.

Compound lla, mp 280-283~ (from alcohol), yield 85% [according to the data in [4], mp 275-2950C (dec.)]. Compound lib, mp 268~ (from benzene), yield 80%. The structure of the described compounds was confirmed by IR, UV, PMR and mass spectroscopy and elemental analysis data. LITERATURE CITED
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S. S. Eo Ro

Inaba, H. Ishizumi, K. Mori, and H~ Yamamoto, Chemo Pharm. Bull., 1__9, 722 (1971). Sakai, S. Kitagawa, and H~ Yamamoto, Arzneim., 22, 534 (1972). T. Borrows, D. O. Holland, and J. Kenyon, J. Chem~ Soco, Noo Ii, 1083 (1946). Io Fryer, J. V~ Earley, and L. H. Sternbach, Jo Org. Chem., 32, 3798 (1967).

*The deacetylation of 3-acetyl-2-phenylindolizine, proceeding by the action of EtONa under rigorous conditions, has been already described in [3]~ M. Vo Lomonosov Moscow State University, Moscow 117234~ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. ii, p. 1570, November, 1988. Original article submitted February 17, 1988.

0009-3122/88/2411-1307512.50

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1989 Plenum Publishing Corporation

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