New diterpenoid components of the oleoresin ofPinus pumila

Pumilol, a Diterpenoid with a Rare Strobane Skeleton from Pinus pumila (Pinaceae)

“…The crude extract was separated using column chromatography over silica gel to yield a diterpenoid, pumilol (1), possessing the rare strobane diterpenoid skeleton ( Figure 1). In addition to pumilol, 17 known compounds including four labdanes: agatholic acid (2), [3] [4] 18-O-succinylagatholic acid (3), [3] labda-8 (17),13-dien-15-oic acid (4) [4][5][6] and agathic acid (5) [3] [4] ; four abietanes: dehydroabietic acid (6), [4 -6] 15-hydroxydehydroabietic acid (7), [4 -6] 15-hydroxy-7oxodehydroabietic acid (8) [6] and 7a,15-dihydroxydehydroabietic acid (9) [7] ; one abietane: isopimaric acid (10) [4] [5] ; three serratane triterpenoids: 3b-methoxyserrat-14-en-21-one (11), [8] 21b-hydroxy-3b-methoxyserrat-14-ene (12), [8] 21b-acetoxy-3b-methoxyserrat-14-ene (13) [8] ; four borneol ester derivatives: bornyl (E)-4hydroxycinnamate (14), [3] bornyl (E)-ferulate (15), [3] bornyl (Z)-4-hydroxycinnamate (16), [3] bornyl (Z)-ferulate (17) [3] [9] and catechin (18) [10] were also isolated (Figure 1).…”

“…Fractions 62 – 64 eluted using hexane/methylene chloride 2:3 gave compounds 11 (53 mg, 3 β ‐methoxyserrat‐14‐en‐21‐one) and 13 (5 mg, 21 β ‐acetoxy‐3 β ‐methoxyserrat‐14‐ene) on further purification using hexane/methylene chloride 1:1 on 1 cm diameter SiO 2 column chromatography, fractions 68 – 69 eluted using hexane/methylene chloride 1:4 gave compounds 12 (5 mg, 21 β ‐hydroxy‐3 β ‐methoxyserrat‐14‐ene), 15 (4 mg, bornyl ( E )‐ferulate) and 17 (133 mg, bornyl ( Z )‐ferulate) [ ][ ] on further purification using 100% methylene chloride on 1 cm diameter SiO 2 column chromatography. Fractions 90 – 110 eluted using 100% methylene chloride gave compounds 14 (bornyl ( E )‐4‐hydroxycinnamate) and 16 (20 mg, bornyl ( Z )‐4‐hydroxycinnamate) and fractions 115 – 120 eluted using 1% methanol in methylene chloride gave compound 6 (30 mg, dehydroabietic acid) and 8 (13 mg, 15‐hydroxy‐7‐oxodehydroabietic acid) . Fractions 129 – 139 eluted using 5% methanol in methylene chloride gave compounds 4 (15 mg, labda‐8(17),13‐dien‐15‐oic acid), [ ][ ] 6 (dehydroabietic acid), 7 (10 mg, 15‐hydroxydehydroabietic acid) [ ][ ] and 10 (13 mg, isopimaric acid).…”

“…Fractions 90 – 110 eluted using 100% methylene chloride gave compounds 14 (bornyl ( E )‐4‐hydroxycinnamate) and 16 (20 mg, bornyl ( Z )‐4‐hydroxycinnamate) and fractions 115 – 120 eluted using 1% methanol in methylene chloride gave compound 6 (30 mg, dehydroabietic acid) and 8 (13 mg, 15‐hydroxy‐7‐oxodehydroabietic acid) . Fractions 129 – 139 eluted using 5% methanol in methylene chloride gave compounds 4 (15 mg, labda‐8(17),13‐dien‐15‐oic acid), [ ][ ] 6 (dehydroabietic acid), 7 (10 mg, 15‐hydroxydehydroabietic acid) [ ][ ] and 10 (13 mg, isopimaric acid). [ ][ ] Fractions 139 – 140 eluted using 10% methanol in methylene chloride gave compound 2 (21 mg, agatholic acid) [ ][ ] whereas fractions 150 – 157 gave compounds 3 (40 mg, 18‐ O ‐succinylagatholic acid) and 5 (18 mg, agathic acid) [ ][ ] on further purification using 5% methanol in methylene chloride on 1 cm diameter SiO 2 column chromatography.…”

“…Fractions 129 – 139 eluted using 5% methanol in methylene chloride gave compounds 4 (15 mg, labda‐8(17),13‐dien‐15‐oic acid), [ ][ ] 6 (dehydroabietic acid), 7 (10 mg, 15‐hydroxydehydroabietic acid) [ ][ ] and 10 (13 mg, isopimaric acid). [ ][ ] Fractions 139 – 140 eluted using 10% methanol in methylene chloride gave compound 2 (21 mg, agatholic acid) [ ][ ] whereas fractions 150 – 157 gave compounds 3 (40 mg, 18‐ O ‐succinylagatholic acid) and 5 (18 mg, agathic acid) [ ][ ] on further purification using 5% methanol in methylene chloride on 1 cm diameter SiO 2 column chromatography. Fraction 150 – 158 eluted using 10% methanol in methylene chloride gave compounds 9 (8 mg, 7 α ,15‐dihydroxydehydroabietic acid) and 18 (13 mg, catechin) on further purification using 5% methanol in methylene chloride on 1 cm diameter SiO 2 column chromatography.…”

“…[ ][ ] Previously, the oleoresins of P . pumila , collected on the eastern shore of Lake Baikal and the Poronai region of Sakhalin oblast, were investigated and a range of monoterpenoids were detected using GLC methods, and labdane, abietane, cembrane and isopimarane diterpenoid acids were isolated from complex mixtures, usually after methylation . Material collected in Khabarovsk, Russia was investigated in this study.…”