S. Rajagopal, Michael E. Brooks, Thach-Mien D. Nguyen
Sep 29, 2003
Citations
0
Influential Citations
11
Citations
Journal
Tetrahedron
Abstract
Abstract We report the synthesis of N-acetoxy-N-(1-methyl-5H-pyrido[4,5-b]indol-3-yl)acetamide, 7 , its N-pivaloyloxy analogue, 9 , and improved synthesis of indole-2-acetonitrile, 3 (70% in five steps from indole-2-carboxylic acid), the carcinogenic amine Trp-P-2, 4 (40% from 3 ), and the nitro compound, 5 (40% from 4 by oxidation with H2O2 using Mo(CO)6 catalyst). In aqueous solution at neutral pH, 7 primarily undergoes C–O bond cleavage to yield the hydroxamic acid, 8 , but under the same conditions the sterically hindered 9 decomposes predominately by N–O bond cleavage with a pH independent rate constant that is 7.5-fold smaller than that for 7 . In the pH range 0.5–7.0 three different processes for the decomposition of 9 were detected by kinetics. Only the process that dominates at neutral pH generates a nitrenium species that can be trapped by N3−.