Studies On The Active Constituents From The Roots And Leaves Of Craibiodendon Henryi And Synthesis Of Phloroglucinol Derivatives With Vasodilator Activities

Craibiodendron henryi W. W. Smith is a toxic species of the genus Craibiodendron of the Ericaceae family. The genus plants have been used as Chinese folk medicine for relieving pain of arthritis, stomachalgia, and paralysis. Up to the present, chemical and biological work on this plant has been limited to a report of two grayanane diterpenoids, rhodojaponin II and III. The chemical constituents from the roots and leaves of Craibiodendron henryi have been described in details and the chemical studies on the progress in naturally grayanane diterpenoids have been reviewed in this thesis.From the roots of Craibiodendron henryi, 44 compounds were isolated, 7 of which were new. On the basis of chemical and spectral analyses, these compounds were elucidated as: seven iridoid glycosides, 10-O-trans-p-coumaroyldesacetyl aspe-rulosidic acid (1), 10-O-cis-p-coumaroyldesacetyl asperulosidic acid (2), 10-O-cis-p-coumaroylscandoside (3), 10-O-trans-p-coumaroylscandoside (4), vaccinoside (5), andromedaside (6) and splendorside (7), four flavonoids, quercetin, (8), 5, 7, 3', 4'-tetrahydroxy-flavonol-3-O-rhamnicoside (9), 5, 7, 3', 4'-tetrahydroxyl-flavonol-3-O-glycoside, (10) and 5, 7, 3', 4'-tetrahydroxy-flavonol-3-O-arabinoruranoside, (11), six grayanane diterpenoids,14β-O-(2S, 3R-nilyl)-2α, 3β, 5β, 6β, 16α-pentahyd-roxygrayan-10(20)-ene (12), 14β-O-(2S, 3R-nilyl)-2α, 3β, 5β, 6β, 16α-pentahydroxy grayanane (13), rhodomollein I (14), rhodojaponin VI (15), craiobiotoxin III (16) and rhodojaponin III (17), thirteen triterpenoids, 11α-O-trans-p-coumaroyltaraxerol (18), taraxerone (19), taraxerol (20), 2α, 3β, 23, 24-tetrahydroxyolean-12-en-28-oic acid (21), oleanolic acid (22), β-amyrin (23), 23-hydroxylursan-12-en-28-oic acid (24), 2α, 3β-dihydroxyursan-12-en-28-oic acid (25), 2α, 3β, 23-trihydroxyursan-12-en-28-oic acid (26), 2α, 3β, 24-trihydroxyursan-12-en-28-oic acid (27), ursolic acid (28), 3-O-acetylursolic acid (29) and 3-O-acetyloleanolic acid (30), four tannins, proanthocyanidin A-2 (31), epicatechin-(2β→O → 7, 4β→ 8)-ent-epicatechin (32), (-)-epicatechin (33), ent-catechin-(4p → 8)-ent-epicatechin (34) and epicatechin-(4β...