TY - JOUR
T1 - Phenol oxidation and biosynthesis. Part XXII. The alkaloids of erythrina lysistemon, E. abyssinica, E. poeppigiana, E. fusca, and E. lithosperma; the structure of erythratidine
AU - Barton, Derek H.R.
AU - Gunatilaka, Abeysinghe A.L.
AU - Letcher, Roy M.
AU - Lobo, Awa M.F.T.
AU - Widdowson, David A.
N1 - Funding Information:
A. Labriola, V. Deulofeu, and B. Berinzaghi, J . Org.36 I?. Koniuszy, P. F. Wiley, and K. Folkers, J . Amer. Chem.Chem., 1951, 16, 90.SOC., 1949, 71, 875880 J.C.S. Perkin IThe mass spectrum was identical with that of erythratidine(Found: M+, 331-1788. Cl,H,,N04 requires M, 331.1783).Dehydration of Erythratidine (11; R1 = R2 = Me, R3 =OMe, R4 = H, R5 = OH).-Erythratidine (103 mg) indry pyridine (2 ml) was treated with methanesulphonylchloride (0.5 ml) in dry pyridine (1 ml) at 0" during 1 h.The mixture was diluted with water (40 ml) adjusted topH 8 with sodium carbonate solution, and extracted withchloroform (5 x 10 ml). The extract was dried (Na,SO,)and evaporated and the residue was separated by p.1.c.to give (in minor amount) erysotrine, chromatographicallyidentical with authentic material, together with the 2-chloro-derivative (11; R1 = R2 = Me, R3 = OMe, R4 or R5 = C1,R6 or R4 = H) (19.6 mg 19%), m.p. 150-152" (from4.37 (lH, ni, 1-H), 5.47 (lH, m, Z-H), 6-00 (6H, s, OMe),6-53 (3H, s, OMe), and 6.00-7.93 (llH, complex, ali-phatics), m / e 349 (M+), 314, 313, 298, 293, 291, 282, 258, 257(loo%), and 256 (Found: M+, 349-1450. CI,H,,ClNO3requires M , 349-1445).3-Demetho.xyerythralidi1~one (11; R1 = R2 = Me, R3 =H, R4,R5 = O).-The crude alkaloidal fraction (135 mg)C,H,-EtOAc), T 3.28 (lH, S, 14-H), 3.45 (lH, S, 17-H),was purified by p.1.c. on alumina GI? to give 3-dei.netkoxy-erythratidinone (91 mg), m.p. 111-112° (from C,H,&htpetroleum), [a], $325" (c 0.240 in CHCl,), hmx. 231 ( E15,300) and 284 nm (35,050), vlmX 1667 cm-l, 't 3.41br(lH, s, 17-H), 3.49 (lH, s, 14-H), 3.96 (IH, m, 1-H), 6-21(3H, s, OMe), 6.32 (3H, s, OMe), and 6.48-8.15 (12H,complex, aliphatics), nz/e 299 (Aft), 272, 271 (loo%),243, 242, 222, 215, 214, 212, and 197 (Found: C, 72.1;H, 7-1; N, 4.6. C18H,1N0, requires C, 72.2; H, 7.1;N, 4.7%). The base was converted into the picrate, m.p.200-202" (from Me,CO-MeOH), (Xujol) 1680 cm-l.We thank the Gulbenkian Foundation and the BritishCouncil for financial support (to A. M. F. T. L. and A. A. L. G.respectively), Professor A. H. Jackson for ( j-)-isoboldineand (+)-glaucine, and Dr. D. S. Bhakuni for (f)-N-nororientaline. For the generous supplies of plant materialwe thank Dr. P. R. Enslin (E. Zysistemon), Dr. S. Flores(E. Peoppigiana), and Professor Ill. U. S. Sultanbawa(E. fuscn and E. Zitlzospeyma).[2/2649 Received, 221ad November, 197210 Copyright 1973 by The Chemical Societ
PY - 1973
Y1 - 1973
N2 - Erythrina lysistemon, E. abyssinica, E. poeppigiana, E. fusca, and E. lithosperma have been examined for alkaloids of biogenetic interest. In addition to the known Erythrina alkaloids, α- and β-erythroidine, eryosdine, erythraline, erythratine, and erysotrine, new alkaloids erythristemine, erythratidinone, and 3-demethoxyerythratidinone were isolated and characterised. The aporphine alkaloid isoboldine, and the benzyltetrahydroisoquinoline alkaloids (-)-orientaline and (+)-N-nororientaline were also isolated. A partial synthesis of erythratidine indicated a 2S configuration. A plausible biogenetic scheme for the new alkaloids is discussed.
AB - Erythrina lysistemon, E. abyssinica, E. poeppigiana, E. fusca, and E. lithosperma have been examined for alkaloids of biogenetic interest. In addition to the known Erythrina alkaloids, α- and β-erythroidine, eryosdine, erythraline, erythratine, and erysotrine, new alkaloids erythristemine, erythratidinone, and 3-demethoxyerythratidinone were isolated and characterised. The aporphine alkaloid isoboldine, and the benzyltetrahydroisoquinoline alkaloids (-)-orientaline and (+)-N-nororientaline were also isolated. A partial synthesis of erythratidine indicated a 2S configuration. A plausible biogenetic scheme for the new alkaloids is discussed.
UR - https://www.scopus.com/pages/publications/37049123961
UR - https://www.scopus.com/pages/publications/37049123961#tab=citedBy
U2 - 10.1039/P19730000874
DO - 10.1039/P19730000874
M3 - Article
AN - SCOPUS:37049123961
SN - 1472-7781
SP - 874
EP - 880
JO - Journal of the Chemical Society, Perkin Transactions 1
JF - Journal of the Chemical Society, Perkin Transactions 1
ER -