Roy Archibald Swaringen

Nuclear magnetic resonance and X-ray stereochemical studies on 1-benzyltetrahydroisoquinolinium salts

The relative stereochemistry at positions 1 and 2 of N,N-dialkyl-1-benzyl-1,2,3,4-tetrahydroisoquinolinium salts has been assigned via a combination of 1H and 13C n.m.r. studies and confirmed by single-crystal X-ray analysis of trans-N-3-hydroxypropyl-5′-methoxylaudanosinium perchlorate [trans-2j)] and cis-N-3-hydroxypropyl-5′-methoxylaudanosinium iodide [cis-(2h)] monohydrate. Quaternization of either laudanosine or 5′-methoxylaudanosine with an alkyl iodide leads to major isomers which possess a trans-relationship between the entering N-alkyl group and the 1-benzyl substituent; these isomers characteristically have the less shielded 1-H and N-methyl protons in deuteriochloroform. Crystals of trans-(2j) and cis-(2h) monohydrate both belong to the monoclinic system, Space group P21/c, with a= 8.123(4), b= 20.380(8), c= 16.710(6)A, β= 102.14(5)°, Z= 4 for the former, and a= 11.475(5), b= 17.749(6), c= 14.278(5)A, β= 113.51(5)°, Z= 4, for the latter compounds. Full-matrix least-squares refinement of atomic positional and thermal parameters converged at R= 0.082 [2 215 reflections] for (trans-(2j) and 0.077 [2 987 reflections] for (cis-(2h) monohydrate. The stereochemistry of the protonation products arising from these tetrahydroisoquinoline bases is also discussed.