Patent DE-19838666-A1 (DE)
Title: Production of enamines or imines comprises reacting an alkyne with ammonia or a primary or secondary amine in the presence of a heterogeneous catalyst
Inventor: MUELLER THOMAS
IPC: C07C249/02
Filed: 1998-08-26
Abstract: Production of enamines (I) or imines (II) comprises reacting an alkyne (III) with ammonia or a primary or secondary amine in the presence of a heterogeneous catalyst and optionally isomerizing the resulting enamine to the corresponding imine.  Production of enamines of formula (I) or imines of formula (II) comprises reacting an alkyne of formula (III) with an amine of formula R<3>-NH-R<4> (IV) in the presence of a heterogeneous catalyst and, when R<3> is H, alkylsilyl, arylsilyl or alkyl aryl silyl, isomerizing the resulting enamine in situ to the corresponding imine: R<1>, R<2>  = (i) H, 1-20C alkyl, 2-20C alkenyl, 2-20C alkynyl, 3-20C cycloalkyl, 4-20C alkylcycloalkyl, 4-20C cycloalkylalkyl, aryl, 7-20C alkylaryl, 7-20C aralkyl, heterocyclyl, heterocyclylalkyl, 5-20C aryloxy, 3-20C silyloxy, 2-20C alkoxyalkyl, 6-20C aryloxyalkyl, 6-20C alkoxyaryl, 3-20C alkoxyvinyl, 3-20C aryloxyvinyl, 7-20C alkoxyaralkyl, halogen, 1-20C perfluoroalkyl, CN, 2-20C cyanoalkyl, 6-20C cyanoaryl, 1-20C alkylthio, 5-20C arylthio, 1-20C alkylsulfonyl, 5-20C arylsulfonyl, 2-20C alkylphosphinoyl, 5-20C arylphosphinoyl, 3-20C alkylsilyl, 9-20C arylsilyl or 7-20C alkyl aryl silyl, or (ii) one of R<1> and R<2> can be 21-200C alkyl or 21-200C alkenyl, or (iii) R<1> and R<2> can be linked to form 6-12C alkylene;  R<3>, R<4>  = (i) H, 1-20C alkyl, 2-20C alkenyl, 2-20C alkynyl, 3-20C cycloalkyl, 4-20C alkylcycloalkyl, 4-20C cycloalkylalkyl, aryl, substituted phenyl, 7-20C alkylaryl, 7-20C aralkyl, heterocyclyl, heterocyclylalkyl, 2-20C alkoxyalkyl, 6-20C aryloxyalkyl, 6-20C alkoxyaryl, 3-20C alkoxyvinyl, 3-20C aryloxyvinyl, 7-20C alkoxyaralkyl, 2-20C cyanoalkyl, 6-20C cyanoaryl, 3-20C alkylsilyl, 9-20C arylsilyl or 7-20C alkyl aryl silyl, or (ii) R<3> and R<4> can be linked to form (un)saturated 3-9C alkylene or alkyleneoxy. Independent claims are also included for the following:  (1) production of enamines of formula (V) and (VI) or imines of formula (VIII) and (IX) by reaction of amino alkynes of formula (VII) with a heterogeneous catalyst and, when R<3> is H, alkylsilyl, arylsilyl or alkyl aryl silyl, isomerizing the resulting enamine in situ to the corresponding imine: R<1>  = as above but excluding options (ii) and (iii);  R<3>  = as above but excluding option (ii);   R<5>+R<6> = optionally unsaturated 3-9C alkylene or alkyleneoxy; (2) production of indoles of formula (X) by intramolecular reaction of alkynes of formula (XI) in the presence of a heterogeneous catalyst:  R<3>  = as above but excluding option (ii);  R<7>-R<11>  = H, 1-20C alkyl, 2-20C alkenyl, 2-20C alkynyl, 3-20C cycloalkyl, 4-20C alkylcycloalkyl, 4-20C cycloalkylalkyl, aryl, 7-20C alkylaryl, 7-20C aralkyl, heterocyclyl, heterocyclylalkyl, 5-20C aryloxy, 3-20C silyloxy, 2-20C alkoxyalkyl, 6-20C aryloxyalkyl, 6-20C alkoxyaryl, 3-20C alkoxyvinyl, 3-20C aryloxyvinyl, 7-20C alkoxyaralkyl, halogen, 1-20C perfluoroalkyl, CN, 2-20C cyanoalkyl, 6-20C cyanoaryl, 1-20C alkylthio, 5-20C arylthio, 1-20C alkylsulfonyl, 5-20C arylsulfonyl, 2-20C alkylphosphinoyl, 5-20C arylphosphinoyl, 3-20C alkylsilyl, 9-20C arylsilyl or 7-20C alkyl aryl silyl, or   R<8>+R<9>, R<9>+R<10> or R<10>+R<11> = a fused aromatic or heterocyclic ring or an optionally unsaturated 2-9C alkylene, 7-20C aralkylene or 3-9C alkyleneoxy group; (3) production of diamines of formula (XII) and (XIII) by twofold reaction of (IV) with (III) in the presence of a heterogeneous catalyst:  (4) production of amines by catalytic hydrogenation of (I), (II), (V), (VI), (VIII), (IX) or (X). R<3>-NR<4>-CHR<1>-CHR<2>-NR<3>-R<4> (XII); R<1>-CH2-C(NR<3>R<4>)2-R<2>  (XIII).