Reduction der Ester von Thiosulfonsäuren mit einwerthigen und zweiwerthigen Alkylen durch Schwefelwasserstoff

Abstract

Reduotion der Ester von Thioealfoneiiuren mit einwerthigen und sweiwerthigen Alkylen duroh Sohwefelwaseerstoff.(Aue dem chemischen Laboratorium der technischen Hochschule zu Braunschweig.)[Eingegangen am 30. Juni.]

Indolizidines, .alpha.-arylthiohemiaminals, and .alpha.-arylsulfonylhemiaminals from a quinolizidine enamine and an arenesulfonyl chloride

“…The A series chromatography yielded, in fractions A23-A26, a 102-mg mixture of 7a-(p-toluenesulfonyl)-7-epideoxynupharidin-6-ol ( 7) and 1ß-(toluenesulfonyl)deoxynupharidin-6-ol (6), 45 mg of which was chromatographed on 15 g of Si02 (activity 2) with 100 ml of CaHa, 330 ml of 10:1 C6H6-Et20,270 ml of 8:1 C8Ha-Et20,140 ml of 6:1 C6H6-Et20, 200 ml of 3:2 C8H8-Et20, 100 ml of 1:1 C8Ha-Et20, and 50 ml of EtOH in the order given in 39 35-ml fractions (C1-C39). Combined fractions C1-C6 contained 9 mg of 6 (0.0223 mmol, 0.48%), an oil: TLC (3:2 C6H6-Et20) Rf 0.30; mp 114-118 °C; NMR 0.97 (m, 3 H, C-l CH3), 1.19 (s, 3 H, C-7 CH3), 2.45 (s, 3 H, Ar CH3), 3.67 (m, C-4 H), 3.80 (br s, OH), 4.26 (br s, 1 H, C-6 H), 6.31 (m, 1 H, 3-furyl ß H), 7.09-7.46 (ArH and 3-furyl H), 7.54 (ArH), 7.68 (ArH); ir (KBr) 2.88 (m), 6.24 (m), 6.69 (m), 6.89 (m), 6.97 (m), 7.16 (w), 7.30 (w), 7.86 (s), 8.76 (s), 11.44 (m), 12.27 (m), 12.56 (m), 12.92 µ (m); MS m/e (rel intensity) 403 (6) (M+), 385 (2), 374 (1), 248 (6), 229 (100), 228 (24), 214 (46), 200 (16), 107 (19), 96 (20), 94 (30), 91 (46), 81 (14); CD (c 0.58 mg/ml, neutral 95% EtOH, l = 0.1 dm…”

“…Fractions D16-D27 (13 mg) were combined with fractions C26-C36 (14 mg) and chromatographed on 10 g of Si02 (activity 2) with 455 ml of CH2C12 in 13 35-ml fractions and then with 10% MeOH in CH2C12 in a single fraction which yielded 15 mg of material which was applied to a 20 X 20 cm plate coated with 0.25 mm of Si02. This was developed twice with 3:2 CaHa-Et20 and the Rf 0.44 band was removed to obtain 12 mg of 7 (0.0298 mmol, 0.64%), an oil: NMR 0.88 (m, 6 H with 0.90 s, C-l CH3), 0.90 (s superposed on 0.88 m, 6 H with 0.88 m, C-7 CH3), 2.45 (s, 3 H, Ar CH3), 3.53-3.95 (m, 2 , 1 H on addition of D20, C-4 H and C-6 OH), 5.03 (br s becoming narrow on addition of D20,1 H, C-6 H), 6.74 (m, 1H, 3-furyl ß H), 7.2-7.8 (m, 6 H, 3 furyl a H and Ar H); ir (CCI4) 2.85 (w), 5.79 (w), 6.00 (w), 6.24 (m), 6.68 (m), 6.87 (s), 6.27 (m), 7.64 (s), 7.71 (s), 8.66 (s), 8.77 (s), 8.93 (s), 11.48 µ (s); MS (130 °C) m/e (rel intensity) 403 (4), 385 (12), 374 (0.4), 370 (0.6), 357 (5), 321 (6), 248 (6), 229 (100), 228 (41), 214 (40), 200 (21), 107 (36.3), 94 (53), 91 (34), 81 (25); CD (c 0.46 mg/ml, neutral 95% EtOH, l = 0.1 dm -14 600°; CD (c 0.13 mg/ml, 95% EtOH, HCIO4 added, l = 0.1 dm) [0]238 -6 1 300°; high-resolution mass spectrum (70 eV, 110 °C) obsd/calcd mass (formula) 385.1709/ 385.1712 and 385.1740/385.1712 (C22H27N03, [M -H20]+).…”

“…This mixture was rechromatographed (C' series, 10 g of A1203, activity 2) using first benzene and collecting four 20-ml fractions (C'l-C'4) and six 35-ml fractions (C'5-C'10). Fractions C'4-C'8 contained a total of 90 mg of the pure title compound, 4 (0.242 mmol, 8.2%), an oil: TLC (CaHa) Rf 0.25; NMR 0.92 (d, J = 5 Hz, 3 H, C-l CH3), 1.14 (s, C-7 CH3), 2.33 (s, 3 H, ArCH3), 3.12 (br s, 1 H, C-6 OH), 3.75 (d of d, «7 = 4 and 8 Hz, 1 H, C-4 H), 4.03 (br s, 1 H, C-6 H), 6.29 (m, 1 H, 3-furyl ß H), 6.93-7.53 (m, 6 H, 3-furyl a H and ArH); ir (liquid film) 2.86 (m), 6.23 (w), 6.72 (m), 6.94 (m), 7.20 (m), 7.34 (m), 11.48 (s), 12.34 (m), 12.72 µ (m); uv (neutral 95% EtOH) Xmax 264 nm (e 452); uv (95% EtOH, HC104 added) Xmaxi 283 nm (e 3270), Xmax2 274 nm (3350), Xmax3 242 nm (5900); CD (c 0.43 mg/ml, neutral 95% EtOH, 1 = 0. Conversion of 7d-(p-Tolylthio)deoxynupharidin-6-ol (4) to Its Immonium Perchlorate.…”

“…Thereafter the MeOH was vacuum evaporated, the residue mixed with CaHa, the solids removed by filtration, and the filtrate concentrated and added to a column of 15 g of A1203 (activity 2) which was eluted successively with 100 ml of CaHa, 50 ml of 9:1 C8H8-Et20, and 50 ml of 3:2 C8H8-Et20 in 20-ml fractions. Fraction 1 yielded 26 mg of 10: mp 88-89 °C; TLC (8:2 C8H8-Et20) Rf 0.9; NMR 0.84 (br s, 3 H, C-l CH3), 1.22 (s, 3 H, C-7 CH3), 1.77 (d, J = 11 Hz, C-6 ax H), 2.29 (s, 3 H, ArCH3), 2.75 (d, J = 11 Hz, 2 H with 2.88 d of d, C-6 eq H), 2.88 (d of d, J = 4 and 8 Hz, 2 H with 2.75, C-4 H), 6.17 (m, 1 H, 3-furyl ß H), 6.78-7.37 (m, 6 H, 3-furyl a H and ArH); ir (liquid film) 3.66 (m), 6.26 (w), 6.68 (m), 6.72 (m), 7.24 (m), 7.28 (m), 11.42 µ (s); MS m/e (rel intensity) 355 (17) (M+), 267 (12), 232 (92), 231 (43), 220 (16), 178 (20), 136 (34), 107 (23), 96 (49), 94 (100), 84 (56), 81 (22).…”

“…The reaction mixture was concentrated and chromatographed on 7 g of A1203 (activity 2) which was eluted successively with 30 ml of C8H8,100 ml of 9:1 C8H8-Et20, and 100 ml of 4:1 CaH8-Et20 in seven 30-35-ml fractions. Fraction 1 yielded 3 mg of 11: mp 170-172 °C; TLC (7:3 C8H8-Et20) Rf 0.8; NMR (100 MHz) 0.96 (d,=/ = 5 Hz, 6 H with 0.97 s, C-l CH3), 0.97 (s superposed on 0.96 d, 6 H with 0.96 d, C-7 CH3), 1.75 (d, J = 12.4 Hz, C-6 ax H), 2.35 (s, 3 H, ArCH3), 2.90 (d, J = 12.4 Hz, 2 H with 2.94, d of d, C-6 eq H), 2.94 (d of d, J = 3 and 8 Hz, C-4 H), 6.54 (m, 3-furyl ß H), 6.95-7.25 (m, 3-furyl a H and Ar H); ir (liquid film) 3.62 (w), 6.00 (w), 6.23 (w), 6.69 (m), 6.90 (m), 7.29 (m), 11.42 (s), 12.28 (s), 12.69 µ (s); MS m/e (rel intensity) 355 (6) T h i s c o n t e n t i s (M+), 233 (74), 232 (38), 231 (45), 220 (15), 178 (30), 136 (30), 107 (34), 96 (100), 94 (61), 81 (45).…”