Synthesis of 4-spiro[cyclopropanecholestan-3.beta.-ol]

Stereochemistry of the N-methyl group in salts of tropane alkaloids

“…Trace B: 2.57-2.73 ppm axial,equatorial N-CH3 region (0.25X reduced intensity). Trace C: 5.12-5.18 ppm region showing H (3) overlapped with ( ), (0.25X reduced intensity). Trace D: N-H. scopolamine diastereomers.…”

“…A leaf puncture bioassay test similar to that previously reported for corn and sorghum was conducted on rice cultivara S-201, Samnam, Nakdong, Aichi-asahi, ES-18, and IR-8. 4 6-Epiophiobolin I (1): colorless oil (0.5 mg/8 L); R¡ 0.50 (A) and 0.21 (B); [a]D -4°( c 0.4, CHC13); EILRMS, m/z (relative intensity) 384 (21), 366 (85), 266 (35), 257 (31), 199 (27), 165 (90), 109 (100); EIHRMS, C^KaA (M+; obsd m/z 384.2665, caled m/z 384.2666) and C25H3402 (M+ -H20; obsd m/z 366.2559, caled m/z 366.2560); NMR (250 MHz) 6.04 (1 H, d, J = 8.1 Hz, H8), 5.99 (1 H, s, H4), 5.09 (1 H, d, d, J = 1.2, 9.9 Hz, H18), 4.40 (1 H, d, d, d, J = 5.5, 8.8, 8.8 Hz, H17), 3.87 (2 H, s, H21), 3.55 (1 H, d, J = 6.5 Hz, H6), 3.17 (1 H, m, H2), 2.05 (3 H, s, H20), 1.70 (3 H, s, H24), 1.67 (3 H, s, H25), 1.04 (3 H, d, J = 7.1Hz, H23), 0.79 (3 H, s, H22).…”

“…Bis(p-bromobenzoate) of 3: Rf 0.75 (CHCl3/MeOH, 50:1); NMR (250 MHz) 7.91 (1 H, d, J = 8.3 Hz, Ar ), 7.80 (1 H,d,=/ = 8.3 Hz, Ar H), 7.56 (1 H, d, J = 8.3 Hz, Ar ), 7.51 (1 H, J = 8.3 Hz, Ar ), 6.00 (1 H, s, H4), 5.95 (1 H, d, J = 5.8 Hz, H8), 5.73 (1 H, d, J = 13.4 Hz, H21), 5.65 (1 H, d, J = 13.4 Hz, H21), 5.04 (1 H, d, J = 8.5 Hz, H18), 4.51 (1 H, d,d,</ = 7.2,15.0 Hz, H17), 3.74 (1 H, d, J = 10.9 Hz, H2), 2.02 (3 H, s, H20), 1.57 (3 H, s, H24), 1.53 (3 H, s, H25), 1.19 (3 H, s, H22), 1.02 (3 H, d, J = 6.8 Hz, H23).…”