The Structure of Sandaracopimaric Acid

Abstract

Sandaracopi~naric acid has been shown to be 7-epipimara-8(14),18-dienoic acid (II), and Ukita's acid to be T-epi-13p-pin1ara-9(14),18-dienoic acid (VI). A hydroxyl-containing acid from Sandarac resin is described.Sandaracopimaric acid was isolated by Henry (1) and by Tschirch and Wolff (2) from the resin of the N. African sandarac tree (Callitris qz~adrivalvis). Recently an improved isolation procedure was described by Petru and Galilc ( 3 ) , who also demonstrated that the acid belonged to the pi~naric group. They claimed (4) that both pimaric acid and sandaracopilnaric acid gave the sanle partial dehydrogenatio~l product I and hence had the sanle configuration at C-7. Even if this conclusion had been correct their xvorlc left the location of the double bond and the stereoche~nistry a t the other a s y~n~n e t r i c centers unlcnown. I n continuance of our interest in the stereochemistry of the pi~naric acids3 we have examined sandaracopirnaric acid, and proved it to be the C-7 epi~ner (11) of pimaric acid (7-epipimara-8(14) ,18-dienoic acid) .4Using the ~nethocl of Petru and Galilc (3) we obtained an ether-soluble anlrnoniu~n salt fro111 the resin. This was co~lverted into the sodium salt, which was then precipitated from its aqueous solution by addition of concentrated sodium hydroxide solution. The precipitate did not crystallize readily, so the acids liberated from it were chromatographed on silica gel. In this way a 2.2% yield of sandaracopimaric acid and a 1.3% yield of a higher ~nelting acid were obtained. The latter had m.p. 270" and [a],, -11" in ethanol.\

Isolation of Apoptosis- and Differentiation-Inducing Substances toward Human Promyelocytic Leukemia HL-60 Cells from Leaves ofJuniperus taxifolia

“…1, the CHCl 3 extract was further subjected to ether extraction, SiO 2 column chromatography, and reversed phase HPLC, or a combination of silica gel column chromatography and reversed phase HPLC, resulting in the isolation of the most active compound (4) and other five compounds (1-3, 5, 6). Their structures were elucidated as communic acid (1), 17) sandaracopimaric acid (2), 18,19) (13S)-15-hydroxylabd-8(17)-en-19-oic acid (3), 20) deoxypodophyllotoxin (4), 21) 14-hydroxyisopimaric acid (=calliphyllin) (5), 22) and 7-hydroxysandaracopimaric acid (6) 23) on the basis of spectral analyses (½ D , EI-MS, 1 H-and 13 C-NMR, together with 2D NMR (COSY, NOESY, HMQC, and HMBC experiments)). Their structures were confirmed by comparison with reported spectroscopic data, their chemical structures being shown in Fig.…”

Mutagenicity of resin acids identified in pulp and paper mill effluents using the salmonella/mammalian‐microsome assay

“…Five histidine-dependent strains of Salmonella typhimurium, TA1535, TA100, Primaric acid (85%) was obtained from Chemical Procurement Laboratories (College Point, NY),and abietic acid was puchased from Sigma Chemical Co. Eight resin acids, synthesized according to methods outlined in the literature, and their purity are neoabietic acid, 95% [ 181 ; levopimaric acid, 98% [19] ; dehydroabietic acid, 95% [20] ; 7-oxodehydroabietic acid, 95% [21] ; monochlorodehydroabietic acid, 95% [22] ; dichlorodehydroabietic acid, 95% [23] ; sandaracopimaric acid, 90% [24] ; and isopimaric acid, 98% [25] . Chemical structures are given in Figure 1.…”

Sesquiterpenoids and Diterpenoids from the Wood of Cunninghamia konishii and Their Inhibitory Activities against NO Production

“…The combined EtOAc soluble fraction was purified by repeated silica gel column chromatography and normal phase semipreparative high-performance liquid chromatography (HPLC) to obtain three new sesquiterpenoids, 2α-hydroxy-3,3,6α,9β-tetramethyltricyclo[4,3,2 1,4 ]undecane (1), 11-acetoxyeudesman-4β-ol (4), and 2α,3β-dihydroxy-4β-methyl-6,8,10-cadinatriene (6), four known sesquiterpenoids, 3,7,7,9-tetramethyloctahydro-3a,6-ethanoinden-9-ol (2) [17], cedrol (3) [18], 11-acetoxyeudesman-4α-ol (5) [19], and 4β,5β-epoxy-14-hydroxy-9-epi-β-caryophyllene (7) [20], in addition to three known compounds, sandaracopimaric acid (8) [21], elliotinol (9) [22], and 8α-hydroxy-15,16-bisnorlabda-11-en-13-one (10) [23] (Figure 1). The identification of the known compounds was established through direct comparison with the published physical and spectral data (IR (infrared), UV (ultraviolet), MS (mass spectrum), and NMR (nuclear magnetic resonance)).…”

“…Therefore, compound 1 was determined as 2α-hydroxy-3,3,6α,9β-tetramethyltricyclo[4,3,2 1,4 ]undecane with a new sesquiterpene skeleton. fraction was purified by repeated silica gel column chromatography and normal phase semipreparative high-performance liquid chromatography (HPLC) to obtain three new sesquiterpenoids, 2α-hydroxy-3,3,6α,9β-tetramethyltricyclo[4,3,2 1,4 ]undecane (1), 11-acetoxyeudesman-4β-ol (4), and 2α,3β-dihydroxy-4β-methyl-6,8,10-cadinatriene (6), four known sesquiterpenoids, 3,7,7,9-tetramethyloctahydro-3a,6-ethanoinden-9-ol (2) [17], cedrol (3) [18], 11-acetoxyeudesman-4α-ol (5) [19], and 4β,5β-epoxy-14-hydroxy-9-epi-β-caryophyllene (7) [20], in addition to three known compounds, sandaracopimaric acid (8) [21], elliotinol (9) [22], and 8α-hydroxy-15,16-bisnorlabda-11-en-13-one (10) (Table 1) and were assigned by the distortionless enhancement by polarization transfer (DEPT) experiments as four aliphatic methyl, five aliphatic methylene, two aliphatic methine, three aliphatic quaternary, and one oxygenated methine carbons. Its 1 H-NMR spectrum ( Table 1) revealed signals of the presence of one oxygenated methine (δH 3.04 (s)), three singlet methyls (δH 0.98 (s), 0.99 (s), and 1.12 (s)), and one characteristic Me-15 doublet methyl of cedrane sesquiterpenoid (δH 0.85 (d, 7.2)) [24].…”