Enantiomerically enriched 1-phenylethylamines

摘要

Production of enantiomerically enriched 1-(mono-, di- or trinitro-phenyl)-ethylamine derivatives (I) comprises reacting a nitro-acetophenone derivative (III) with a hydroxylamine compound (IV), reducing the obtained oxime compound (V) using a complex borohydride and an acid in organic solvent to give (I) in racemic form and enantiomerically enriching using an enantiomerically enriched acid. Production of enantiomerically enriched 1-(mono-, di- or trinitro-phenyl)-ethylamine derivatives of formula (I) comprises: (1) reacting an acetophenone derivative of formula (III) with a hydroxylamine compound of formula R5>ONH2.aHX (IV) to give an oxime of formula (V); (2) reducing (V) using a complex borohydride and an acid in organic solvent to give (I) in racemic form, and (3) enantiomerically enriching the product using an enantiomerically enriched acid. [Image] n : 1-3; m : 0 to (5-n); R1>1-12C alkyl, 1-12C alkoxy, 1-12C alkylthio, 5-14C aryl, 5-14C aryloxy, 6-15C aralkyl, 6-15C aralkoxy, F, Cl, CN, optionally protected CHO, optionally protected OH, optionally protected SH, 1-12C haloalkyl, 1-12C haloalkoxy, 1-12C haloalkylthio, A-B'-C(O)-E or A-E; A : a direct bond, 1-8C alkylene, 1-8C alkenylene or 1-8C haloalkylene; B' : a direct bond, O, S or NR2>; R2>H, 1-8C alkyl, 6-15C aralkyl or 5-14C aryl; E : OR3> or N(R4>)2; R3>1-8C alkyl, 6-15C aralkyl or 5-14C aryl; R4>H, 1-8C alkyl, 6-15C aralkyl or 5-14C aryl, or N(R4>)24-12C cyclic amino; a : 0 or 1; R5>H or 1-12C alkyl, and X : anion. Independent claims are included for new diastereomerically enriched salts of (I) having formula (I).HRx> (I') and new enantiomerically enriched salts of (I) having formula (I).HX' (I''). Rx>anion of an enantiomerically enriched organic acid, and X' : halide.