Aminomethanobenzazocine intermediates

Abstract

N-Alkylated-8-aminated-2,6-methano-3-benzazocines, useful as strong analgesics, are prepared by one route comprising reduction of 8-nitro intermediates or by another route comprising Birch type reduction of 8-methoxy intermediates followed by dehydration-rearrangement of the oximes of the resulting 8-oxo intermediates.

We claim: . .1. 1,2,3,4,5,6-Hexahydro-3-Q'-8RR"N-5-X-6-Y-11-Z-11-Z'-2,6-methano-3-benzazocine having the formula ##STR11## wherein: Q' is hydrogen, benzyl, propyl, isobutyl, neopentyl, allyl, 2-methyl-2-propenyl, 2-chloro-2-propenyl, cis-3-chloro-2-propenyl, cis-3-chloro-2-butenyl, trans-3-chloro-2-butenyl, propargyl, cyclopropylmethyl or (2,2-dichlorocyclopropyl)methyl; 
     
        . .    A compound according to claim 1 wherein X is hydrogen and Z is hydrogen or an acid addition salt thereof.!.  . .3. A compound according to claim 2 wherein Y is methyl and Z' is methyl or an acid addition salt 
     
     
        thereof..!. . .4.  A compound according to claim 3 wherein R is hydrogen or an acid addition salt thereof..!. . .5. A compound according to claim 4 wherein Q' is cyclopropylmethyl or an acid addition salt thereof..!. . .6. A compound according to claim 5 wherein R" is formyl or an acid addition salt thereof..!. . .7. A compound according to claim 5 wherein R" is acetyl or an acid addition salt thereof..!. . .8. A compound according to claim 5 wherein R" is propionyl or an acid addition salt thereof..!. . .9. A compound according to claim 5 wherein R" is butyryl or an acid addition 
     
     
        salt thereof..!. 10. 1,2,3,4,5,6-Hexahydro-3-Q"-8RR"N-5X-6-Y-11-Z-11Z'-2,6-methano-3-benzazocine having the formula ##STR12## wherein: Q" is formyl, acetyl or Q* wherein Q* is propionyl, isobutyryl, pivaloyl, acryloyl, 2-methylacryloyl, 2-chloroacryloyl, cis-3-chloroacryloyl, cis-3-chlorocrotonoyl, trans-3-chlorocrotonoyl, propiolyl, cyclopropanecarbonyl or 2,2-dichlorocyclopropanecarbonyl; R is hydrogen or methyl;   R" is formyl, acetyl, propionyl, butyryl, isobutyryl, benzoyl or cyclopropanecarbonyl;   X is hydrogen, methyl or ethyl;   Y is hydrogen, methyl, ethyl, propyl, allyl or phenyl;   Z is hydrogen, methyl, . .ethyl or hydroxy.!..Iadd.or ethyl; .Iaddend.and   
     
     
       Z' is hydrogen, methyl or ethyl. 11. A compound according to claim 10 
     
     
        wherein X is hydrogen and Z is hydrogen. 12. A compound according to claim 
     
     
        11 wherein Y is methyl and Z' is methyl. 13. A compound according to claim 
     
     
        12 wherein R is hydrogen. 14. A compound according to claim 13 wherein Q" 
     
     
        is cyclopropanecarbonyl. 15. A compound according to claim 14 wherein R" 
     
     
        is cyclopropanecarbonyl. 16. A compound according to claim 13 wherein Q" 
     
     
        is acetyl. 17. A compound according to claim 16 wherein R" is acetyl. 
     
     
        18. A compound according to claim 13 wherein Q" is isobutyryl. 19. A 
     
     
        compound according to claim 18 wherein R" is isobutyryl. 20. A compound 
     
     
        according to claim 13 wherein Q" is propionyl. 21. A compound according to claim 20 wherein R" is propionyl.