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Synthesis of some derivatives of alkaloids. XIV

L. Dúbravková, I. Ježo, P. Šefčovič, and Z. Votický

Slovak Academy of Sciences, Bratislava


Abstract: cf. C.A. 52, 11870e. The synthesis of (±)-calycotomine (I), 1-hydroxymethyl-6,7-di-methoxy-1,2,3,4-tetrahydroisoquinoline, is described. To Na benzylate (from 34.5 g. Na and 700 g. PhCH2OH) was added 71.5 g. ClCH2CO2H in 200 ml. PhCH2OH, the mixt. heated on a waterbath 30 min., H2O added, the mixt. extd. with Et2O, the aq. layer acidified, extd. with Et2O, and distd. giving 90% benzyloxyacetic acid (II), b11 117°, n22D 1.5270. II (16.6 g.) in 50 ml. Decalin was added to 18.1 g. homoveratrylamine (III) in 50 ml. Decalin. After standing 30 min. the mixt. was distd. slowly until the b.p. of Decalin was reached, then in vacuo to remove the remaining Decalin, and the product recrystd. from H2O to give 91% N-homoveratrylbenzyloxyacetamide (IV), m. 68-9°. IV (32.9 g.) in 250 ml. PhMe and 50 g. POCl3 was refluxed 1-2 hrs., excess POCl3 removed in vacuo, the residue dissolved in H2O, decolorized with C, evapd. to dryness in vacuo, the product redissolved in H2O, made alk. with 40% NaOH, extd. with Et2O, dried over K2CO3, and the Et2O removed giving 35% O-benzyldehydrocalycotomine (V); HCl salt, m. 93°; picrate, m. 146°; H2PtCl6 salt, m. 174°. V H2PtCl6 salt (15.2 g.) in 300 ml. H2O and 1 ml. concd. HCl was hydrogenated over 0.1 g. Pd-C, the catalyst filtered off, the residue evapd. to dryness, dissolved in H2O, made alk. with 40% NaOH, extd. with Et2O, dried, and the Et2O removed giving 70% O-benzlcalycotomine (VI), m. 32-3°; HCl salt, m. 208-9°; H2PtCl6 salt, m. 191-2°. VI.HCl (7 g.) was boiled with 120 ml. 1:1 HCl 2 hrs., the soln. evapd. to dryness in vacuo, the residue dissolved in H2O, made alk. with 40% NaOH, the product filtered off, and recrystd. from C6H6-petr. ether to give a nearly quant. yield of I, m. 135-6° λ 240 (log ε 3.49) and 290 mμ (log ε 3.65); HCl salt, m. 192°; HClO4 salt, m. 174°; N-Me deriv. HCl salt, m. 221-3° (picrate, m. 162-3°; H2PtCl6 salt, m. 172-3°).

Full paper in Portable Document Format: 128a459.pdf (in Slovak)


Chemical Papers 12 (8) 459–463 (1958)

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