Process for the enantiospecific synthesis of intermediates...

C - Chemistry – Metallurgy – 07 – C

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260/468, 260/595

C07C 209/28 (2006.01) C07C 209/70 (2006.01) C07C 211/42 (2006.01) C07C 213/08 (2006.01) C07C 217/74 (2006.01) C07D 223/14 (2006.01)

Patent

CA 1325226

ABSTRACT Biologically active, enantiomerically substantially pure intermediates of trans-hexahydro-benzo[?]naphtho[2,1-b] azepines are prepared. The present invention involves a process for preparing compounds of the general formula 3: Image wherein: R?is Image ; Each R1 is independently H or alkyl; Q is methylene, -O- or-S-; m and n are independently variable and may each have a value of 0, 1 or 2, with the provisos that the sum of m and n is not greater than 3, that m may not equal zero when Q is -O- or -S-, and that when Q is -CH2-, m and n cannot both be zero; X is hydrogen, halo, alkyl, alkylthio, alkylsulfinyl, alkylsufonyl, hydroxy, alkoxy or trifluoromethyl; Y is hydrogen, hydroxy, alkoxy, -OC(O)NR2R3, -OC(O)-R9, - N(R1)2,-NHC(O)R1 or-OP(O)(OH)OR1, R2 and R3 are the same or different and each is hydrogen (provided that both are not hydrogen), alkyl, aralkyl, cycloalkyl, aryl, hydroxyalkyl, or alkoxyalkyl; in addition, when one of R2 and R3 is as defined above, the other may be -R4NR5R6 {wherein R4 is alkanedlyl, R5 is hydrogen or alkyl and R6 is alkyl, or R5 and R6 together with the nitrogen atom form a 1-azetidinyl, 1- pyrrolidinyl, 1-piperidinyl, 1-(4-alkylpiperazinyl), 4-morphollnyl or 1- (hexahydroazepinyl) group}; in further addition, R2 and R3 together with the nitrogen atom may form a 1-azetidinyl, 1-pyrrolidinyl, 1-piperidinyl, 4-morpholinyl, 1-(4- alkylpiperazinyl), 1-(4-alkoxyalkylpiperazinyl), 1-(4-hydroxyalkylpiperazinyl),1- (3-hydroxyazetidinyl), 1-(3-alkoxyazetidinyl), 1-(-hydroxypyrrolidinyl), 1-(3- alkoxypyrrolidinyl), 1-(3- or 4-hydroxypiperidinyl), 1-(3- or 4-alkoxypiperidinyl), 1-(4-oxopiperidinyl) or 1-(3-oxopyrrolidinyl) ring; in still further addition, when R2 is hydrogen, R3 may be - CHR7CO2R8, wherein R7 and R8 are the same or different and each is hydrogen, alkyl or aralkyl; R9 is alkyl, aralkyl, aryl, alkoxyalkyl, aryloxyalkyl, aralkoxyalkyl, cycloalkylalkyl, alkoxycarbonylalkyl, cycloalkyl, 1-adamantyl, cycloalkoxyalkyl,alkoxy, aralkyloxy, cycloalkoxy, aryloxy or -CHR7NHR8; and Z is X as defined above, amino, alkylamino or -NHC(O)R10 {wherein R10 is hydrogen, alkyl or aryl). R11 is H or alkyl; R12 is alkyl with the proviso that R11 and R12 are different, and K is hydrogen, alkoxy, hydroxyl, aryloxy or alkyl.

606860

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