BiochemicalSystematicsand Ecology, Vol.25, No.7, pp. 677-678,1997 © 1997 ElsevierScienceLtd All rightsreserved.Printedin GreatBritain 0305-1978/97 $1700+0.00 ) Pergamon PII: S0305-1978 (97)00063-X Heartwood Constituents of Planchonella vitiensis* RICHARD C. CAMBIE,t NG ANG SER and TETSUO KOKUBUN Department of Chemistry, University of Auckland, Private Bag 92019, Auckland, New Zealand Key Word Index--Planchonella vitiensis; Sapotaceae; vanilloyl sucrose; sucrose; myo-inositol; ¢-spinasterol. Subject and Source Planchonella vidensis Gillespie (Fijian name: Sarosaro; fam. Sapotaceae) is a moderately common tree which is endemic to Fiji. Foliage of the tree was authenticated by Mr Saula Vodonaivalu, Fijian National Herbarium, University of the South Pacific (voucher No. S.V. 993). Previous Work None. Present Study Soxhlet extraction of the milled heartwood (245g) was carried out successively with light petroleum, EtOAc, and MeOH. The light petroleum extract (1.9g, 0.8%) contained hydrocarbons and aliphatic alcohols which were not examined further. Column chromatography of the EtOAc extract (1.54g, 0.6%) on silica and elution with Et20-hexane gave c¢-spinasterol (stigmasta-7,22-dien-3~-ol) (23mg), m.p. 164-165°C, [=]22 _4 ° (CHCI3) (lit. Gunasekera et aL, 1977, m.p. 162-163°C, [=]27 _2.9 o) (correct MS, IR, and 1H NMR spectra) (Gonzalez et aL, 1984; Thompson et aL, 1972), eims M ÷" 412.3710. C29H480 requires 412.3705. A portion (6.4g) of the MeOH extract (13.2g, 5.4%) was acetylated and the product fractionated repeatedly by column chromatography and PLC to give (i) myo-inositol hexaacetate (0.14g), m.p. 200-206°C (lit. Buckingham, 1994, m.p. 216-217°C) (correct IR and 13C NMR spectra) (Dorman et al., 1970); (ii) sucrose octaacetate (O.6g), m.p. and mixed m.p. 67-68°C, [CX]D+58° (CHCI3) (correct MS, 1H NMR and 13C NMR spectra) (Pare, 1987; Fukuyama et al., 1983; Kashiwada et al., 1988); and (iii) an unidentified saponin (52 mg). A further portion (2.2g) of the MeOH extract was chromatographed on silica and partially purified by PLC to give a vanilloyl sucrose (20 mg) [provisional structure (1)] as an amorphous powder, v max 3400, 1710, 1600, 1520 cm-1; eims 492. C20H28014 requires 492; 1H N M R (~H 3.90, s, O CH3; 4.06, dd, J 9.6, 4 Hz, H 2'; 4.14, dd, J 9.2, 9.2 Hz, H 4'; 4.21 br s, 2H, H 1; 4.32, dd, J 11.6, 4.5 Hz, H 6'; 4.44, dd, J 12, 4 Hz, H 6; 4.46, dd, J 11.6, 2 Hz, H 6'; 4.51, dd, J 9.2, 9.2 Hz, H 3'; 4.55, dd, J 12, 4 Hz, H 6'; 4.67, ddd, J 8, 6.4, 4 Hz, H 5; 4.75, ddd, J 9.2, 4.5, 2 Hz, H 5'; 5.27, dd, J 8, 8 Hz; 6.1 O, d, J 4 Hz, H 1'; 6.34, d, J 8 Hz, H 3; 6.90, d, 8 Hz. H 5"; 7.56, d, J 2 Hz, H 2"; 7.58, dd, 8, 2 Hz, H 6"; 8.4, br s, OH; 130 NMR 5c 57.0, OCH3; 61.2, C 6'; 63.4, C 1; 63.5, C 6; 70.2, C 4'; 72.0, C 2'; 73.1, C 5'; 73.6, C 3'; 74.8, C 4; 77.4, C 3; 82.3, C 5; 92.8, C 1'; 104.3, C 2; 114, C 2"; 116, C 5; 123, C 1"; 125, C 5"; 148, C 4"; 153, C 3"; 168.0, CO. The remaining MeOH extract and residues from the column above (5.0g) were hydrolysed with 2 M HCI under reflux for 5h. Workup and chromatography of the acid fraction on silica gave vanillic acid, m.p. and mixed m.p. 190-194°C with sublimation from 175°C (correct MS, IR and 1H NMR spectra) (Scott, 1970, 1972). Glucose and fructose were identified in the aqueous phase by TLC (EtOAc/MeOH/H20/HOAc, 13:3:3:4) (Hamburger and Hostettmann, 1985; Domon and Hostettmann, 1984). "Chemistry of Fijian Plants, Part 12. For Part 11 see Cambie, R. C., Lal, A. R., Rutledge, P. S. and Wellington, K. D. (1997) Biochem. Syst. EcoL 26, 565-566. tCorresponding author. (Received 1 May 1997; accepted 20 May 1997) 677 678 R.C. CAMBIEETAL. 6' CH2OH l HOCH2 O OH H2OH O OH I I CO 3" @OCH 3 OH 1 Chemotaxonornic Significance ¢-Spinasterol is a common constituent of Planchonella species and has been described as "the characteristic phytosterol of the Sapotaceae" (Gunasekera et aL, 1977). Vanillic acid is reported to occur widely in ferns, often as a sugar ester (Murakami and Tanaka, 1988) but hitherto has not been described as a sucrose ester from other plants. However, esters of gallic acid with sucrose (Kashiwada et aL, 1988) and of hydroxycinnamic acid and ferulic acid with sucrose have been isolated from higher plants (Hamburger and Hostettmann, 1985; Fukuyama et al., 1983; Shimomura et aL, 1986). References Buckingham, J, (Exec. ed.) (1994) Dictionary of Natural Products, Vol. 5, p. 5254. Chapman & Hall, London; Domon, B. and Hostettmann, K. (1984) Helv. Chim. Acta 67, 1310; Dorman, D. E., Angyal, J. J. and Roberts, J. D. (1970) J. Am. Chem. Soc. 92, 1351; Fukuyama, Y., Sato, T., Miura, I., Asakawa, Y. and Takemoto, T. (1983) Phytochemistry 22, 549; Gonzalez, A. G., Bermeji, J., Mediavilla, M. J. and Toledo, F. J. (1984) Rev. Latinoam. Quim. 15, 107; Gunasekera, S. P., Kumar, V., Sultanbawa, U. S. and Balasubramanian, S. (1977) Phytochemistry 16, 923; Hamburger, M. and Hostettmann, K. (1985) Phytochemistry 24, 1793; Kashiwada, Y., Nonaka, G. and Nishioka, J. (1988) Phytochemistry 27, 1469; Murakami, T. and Tanaka, T. (1988) Fortschr. Chem. Org. Naturst. 54, 1; Pare, J. R. (1987) Adv. Heretocyclic Chem. 42, 335; Scott, K. N. (1970) J. Mag. Res. 2, 361; Scott, K. N. (1972) J. Am. Chem. Soc. 92, 8564; Shimomura, H., Sashida, Y. and Mimaki, Y. (1986) Phytochemistry25, 2897; Thompson, M. J., Dutky, S. R., Patterson, G. W. and Gooden, E. L. (1972) Phytochemistry 11, 1781.