The Dehydration of 2-Phenylcyclohexanone Cyanohydrin: 6-Phenyl-Δ¹-cyclohexenecarbonitrile and 2-Phenyl-Δ¹-cyclohexenecarbonitrile

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“…The product was purified by preparative TLC with the solvent system ethyl acetatecyclohexane (4:1) to give a colorless oil (homogeneous by TLC) (84 mg, 71%): IR (film) 1745 (CO), 1720 cm"1 (CO); NMR 5.57 (d br, I, C2oH), 5.45 (dd, 1, J = 15.5 and 6.2 Hz, C14H), 5.36 (d, 1, C9H), 5.32 (d, 1, CgH), 5.25 (d, 1, J = 9.2 Hz, C16H), 5.04 (dd, 1, J = 15.5 and 8.2 Hz, C13H), 4.95 (m, 1, C5H), 4.77 (t, 1, J = 9.5 and 9.5 Hz, C6H), 4.11 (br, C22H), 3.95 (m, 1, C3H), 3.84 (dd, 1, J = 2.2 and 10.5 HZ, Ci8H), 3.71 (dd, 1, J = 5.7 and 9.5 Hz, C7H), 3.04 (m, 1, C15H), 2.70 (dd, 1, J = 5.5 and 16.0 HZ, C2H), 2.48 (dd, 1, J = 5.5 and 16.0 Hz), 2.39 (m, 1, C4H), 2.34 (m, 1, C4H), 2.00 (s, 3, CH3CO), 1.98 (s, 3, CH3CO), 1.64 (s, 3, CH3C=), 1.57 (s, 3, CH3C=), 1.01 (m, 6, 27-CH3 and 28-CH3), 0. 87 (t, 3, 24-CH3); mass spectrum m/e (rel intensity) 558 (10), 529 (32), 463 (14), 345 (7), 245 (32), 193 (100), 165 (57), 125 (70). Found: M+ -29, 529.2939; C30H4iO8 requires 529.2801.…”

“…A few drops of methanol were added and the solvents were removed at reduced pressure to give a colorless oil. The product was purified by preparative TLC with the solvent system ethyl acetatecyclohexane (4:1) to give a colorless oil (homogeneous by TLC) (30 mg, 79%): IR (film) 1740 cm"1 (CO); NMR 5.58 (d br, 1, C20H), 5.46 (dd, 1, C14H), 5.37 (d, 1, C9H), 5.35 (d, 1, C8H), 5.25 (d, 1, Ci6H), 5.06 (dd, 1, C13H), 4.97 (m" 1, C5H), 4.77 (t, 1, C6H), 4.13 (m, 3, C22H + Ci, 2 H), 3.86 (dd, 1, C1SH), 3.68 (dd, 1, C7H), 3.62 (m, 1, C3H), 3.07 (m, 1, C15H), 2.16 (m, 1, C4H), 2.10 (m, 1, C4H), 2.04 (s, 3, CH3CO), 2.03 (s, 3, CH3CO), 1.99 (s, 3, CHsCO), 1.64 (s, 3, CH3C=), 1.59 (s, 3, CH3C=), 1.05 (m, 6, 27-CH3 and 28-CH3), 0.89 (t, 3, 24-CH3); mass spectrum rate (rel intensity) 586 (10), 557 (50), 491 (20), 431 (6), 371 (20), 193 (100).…”

“…Methyl 6-Hydroxy-5-oxopolyangioate (10). Silver carbonate on celite (2.0 g) was added to a solution of methyl 5,6-dihydroxypolyangioate (200 mg) in toluene (100 mL).…”

“…The mixture was heated at 65 °C for 20 h. After removal of solvent, chromatography of the residue on silica gel (10% MeOH/EtOAc) yielded Nmethylcelacinnine (7,13 mg): UV (MeOH) Xmax 224 (infl), 279 nm (e tion was filtered and the filtrate was concentrated to dryness. The residue was heated at 140 °C for 20 h and then separated by TLC on silica gel (10% MeOH/EtOAc) to yield the degradation product (10, 1 mg): MS m/e (rel intensity) 433 (3), 334 (27), 302 (13), 257 (33), 243 (98), 188 (85), 187 (100), 155 (10), 143 (12), 131 (100), 129 (21).…”

“…Rechromatography of the mixture on alumina (15% MeOH/CH2Cl2) yielded N,N'-dicinnamoylspermidine (11,248 mg): mp 127 °C; UV (MeOH) Xmax 223,276 nm (e 29 600,41 000); IR (KBr) 2.90, 3.03,6.06,6.22,6.45 µ ; MS m/e (rel intensity) 405 (M+, 5), 336 (7), 335 (6), 314 (5), 274 (9), 245 (13), 205 (36), 188 (30), 131 (100), 127 (29), 115 (4), 103 (98), 101 (4). Additionally, bands were obtained for maytenine (12, 2.3 g)17 and for ',.//"-dicinnamoylspermidine (13,9 mg): mp 107 °C; UV (MeOH) Xmax 223, 278 nm (e 27 300, 40 500); IR (KBr) 2.90, 3.08, 5.97,6.15,6.45; MSm/e (rel intensity) 405 (M+, 4), 387 (4), 335 (8), 300 (8), 274 (10), 257 (10), 245 (14), 231 (10), 205 (36), 188 (34), 159 (56), 153 (16), 131 (100), 127 (26), 115 (6), 103 (98), 101 (5).…”