HASE, Tsunao

IWAGAWA, Tetsuo

岩川, 哲夫

長谷, 綱男

English

Kagoshima University Repository

Rep. Fac. Sci., Kagoshima Univ. (北ath., Phys., Chem.),No. 10, p. 37-41, 1977.●On the Constituents of the Unripe Fruitsof Osmanthus fragrans L. IByTetsuo Iwagawa and Tsunao Hase*(Received Sep. 30, 1977)From the unripe fruits of Osmanthus fragrans L. 2-(4-hy中oxyphenyl)ethanol,succinic acid, 1-0-β･D･glucosyl-(4-hydroxyphenyl)ethanol, and a caffeic ester wereisolated.Introduction and ResultsSeveral investigations have been reported ~about the constituents of the leavesland且owers2 0f Osmanthus fragrans L. var aurantiacus M. However, there has beenno reprot about the same genus, Osmanthus fragrans L. (Japanese name : Usugimokusei).And the bitter taste of the unripe fruits of this plant stimulated us to study the●chemical constituents of them. This paper describes the isolation and identification ofnon-bitter constituents from the unripe fruits of the plant. The Fig. 1 showed theproce血re of isolation.A was crystallized as colorless needles, mp 93.5-94:0, from chloroform. The mole-cular formula, C8HIOO笥was assigned on the basis of the elementary analysis and the●                                                                                                                     ●mass spectrum. The IR spectrum of A showed absorption bands at 3400cm⊥1 due toan alcoholic hydroxyl group, 3140 cm-1 due to a phenolic hydroxyl group, and 1600,1518, and 820 cm-1 due to a p-substituted phenyl group. The NMR spectrum (CD3COCD3) included the signals for an alcoholic hydroxyl group at 8 3.13 (1H, br s), aphenolic hydroxyl group at 8 8.23 (1H, br s), and a -C旦sCH2- group at 8 2.73 (2H, t,J-l Hz) and 3.73 (2H, t, J-7 Hz). Furthermore, an K W2 system at 3 6.77-7.27suggested the presence of a p-substituted phenyl group. The above data indicated thatA was 2-(4-hydroxyphenyl)ethanol.2b.B was crystallized as colorless prisms, mp 168-169-C, from ethyl acetate. The IRspectrum showed a band at 1700cm-1 ascribed to a carboxyl group. B was identifiedas succmic acid by comparing its IE spectrum with that of an authentic sample.●C, colorless prisms, mp 162-163-, has molecular formula, C14Ha007, established by●mass spectrum (high resolution). It gave green color with alcoholic ferric chloride. The* Department of (〕hemistry, Faculty of Science, Kagoshima University, Kagoshima.38 T. Iwagawa and T. HaseIR spectrum of G showed bands attributable to a hydroxyl group at 3200 cm.-1 and ap-substituted phenyl group at 1620, 1600, 1518 and 820cm-1. The NMR spectrum(C5D5N) showed the presence of a phenolic hydroxyl group at s 9.20 (1H, s), a -C旦21CH2- group at 8 3.08 (2H, t, J-7 Hz)? and four aromatic protons at s 7.48-7.55.Hydrolysis of G with 4N-hydrochloric acid yielded a crystalline compound, C8H1002,●mp 93 , and D-glucose which was confirmed by paper chromatography. The IR spec-tram of the former compound was identical with that of A, 2-(4-hydroxyphenyl)ethanol. These data suggested that G was 1-0-d-glucosyl-2-(4-hydroxyphenyl) ethanol.In addition, the coupling constant (J-7 Hz) of a doublet at 8 5.08 due to the anomericporoton in the NMR spectrum of G revealed that d瑠Iucose was linked β-onentation3.From these data G could be assigned as 1-0-β-D瑠Iucosyl-2-(4-hydroxyphenyl)ethanol.4D was isolated as an amorphous compound. It exhibited a broad hydroxyl bandat 3400 cm.-1, phenyl bands at 1600 and 1520 cm.-1, and a conjugated ester band at●1700 cm-1 in the IR spectrum.Acetylation of D with acetic anhydride and pyridine gave an amorphouscompound, which, seemed to be pure on thin-layer chromatogram, although allattempts to crystallize it failed. The NMB, spectrum (CDC13) of the acetate showedsignals due to a C旦3CⅡ- group at 8 1.07 (3H, d, J-7 Hz), eight acethyl protons at 81.92, 2.00, 2.08, 2.15 (3Hx5, s) and 2.37 (3Hx3,. s), aromatic protons atァ7.35-7.67(6H), and conjugated trans ole丘nic protons at 8 6.42 (1H, d, J-18 Hz) and 8.02 (1H,d,.7-18 Hz).Methanolysis of D with methanolic hydrogen chloride a放)rded a methyl ester, mp●1620. The NMK, spectrum (CD3COCD3) of the latter compound showed a singlet at 83.73 (3H) due to carbomethoxy protons, two doblets at 8 6.33 (1H, d, J-18 Hz) and7.67 (1H, d, J-18 Hz) due to conjugated trans olefinic protons, a multiplet of threeprotons at 8 6.87-7.25 due to three protons of a 1,2,4-もrisubstituted phenyl group, and abroad singlet at s 8.43 due to two phenolic hydroxyl protons. These chemical andphysical properties of the methyl ester were in good agreement with those of methyl●caffeate.On the other hand, the alcoholic part of D was obtained as methyl ether by per-methylation followed by hydrolysis with alkali. The IB, spectrum of methyl etherindicated absorption bands of a hydroxyl group at 3400 cm4, and a phenyl groupat 1590 and 1510 cm-1, while in the NMR spectrum (CDC13) the signals of CH30H- groupat S 1.29 (3H, d, J-Q Hz), six methoxy protons at s 3.42 (3H, s), 3.48 (3H, s), 3.53(3H, s), 3.57 (3H, s), and 3.88 (6H, s), and aromatic protons at 8 6.89 (3H, s) wereobserved.These data suggest that D is caffeate of an alcohol with six hydroxyl groups and aphenyl group. Further investigation is in progress.On the Constituents of the Unripe Fruits of Osmanthus fragrans L. I　　　　　39Fruits (2.6 Kg)of 0. Fragransextd. with boiling water (31X 3)coned. (21)extd. withethylacetetesoln.evasi｡ぎd.chr｡mat｡.ethyl acetateJaqueous soln.MeOH-CHCl3　MeOH-CHClg MeOH-CHCla(3 :97)　　　(5:95　　　　　20:80)A (360mg)　B (6mg)　　G (1.6g) and D (5g)Fig. 1. Isolation of the compoundsExperimentalMelting points were determined on a Yanagimoto Micro Melting Point Apparatus,●and uncorrected. IK spectra were measured as Nuiol mull with a Schimadzu IK-27Eecording Infrared Spectrometer or as KBr with a Nippon Bunko IR-S Spectrometer.NMK spectra were recorded on a JEOL MH-60 Spectrometer. Chemical shfits aregiven in 8 values with TMS as the internal standard.●Extraction The unripe fruits of Osmanthus fragrans (2.6 Kg) were extractedwith boiling water (3?x3). The combined extracts were evaporated under reducedpressure to 21, and the resulting solution was extracted continuously with ethylacetate. The extract was dried over sodium sulfate, and the solvent was evaporated togive a brown residue (31.4 g) in vacuo.Isolation of A, B, C and Dfrom the residue. The residue was chromatographed ona column of silicic acid.Emtion with 3% methanol in chloroform and recrystallization from chloroformgave colorless needles (A, 360 mg), mp 93.5-94-, IE z>�"j芸^ cm-1: 3400, 1600, 1518, 820:NMR (CD3COCD3) S: 2.73 (2H, t, J-7 Hz), 3.73 (2H, t, J-7 Hz), 6.77-7.27 (4H,AJBi-q). Anal. Calcd. for C8Hl｡02: C, 69.54; H, 7.30. Found: C, 69.46; H, 7.26.Elution with 5% methanol in chloroform and recrystallization from ethyl acetategave colorless prisms (B, 6 mg), mp 168-169-. IE v莞慧cm-1: 1700, 1420, 920. TheIK spectrum was superimposable on that of succinic acid.Elution with 20% methanol in chloroform and recrystllization from ethanol gavecolorless prisms (C, 1.6 g), mp 162-163-, IR v霊芝cm-1: 3200, 1620, 1600, 1518, 820;NMR (C6D5N) S: 3.08 (2H, d, J-l Hz), 3.83-4.73 (13H) 5.08 (1H, d, J-l Hz), 7.48-7.55 (4H), 9.20 (1H, s). Mass Spectrum m/e M+300.1188 (Calcd. for C14Hl｡07 : 300.1207).Further elution with 20% methanol in chloroform gave an amorphous substance(D, 5 g), IR v蕊慧cm-1: 3400, 1700, 1600, 1520, 820; NMR (CD3COCD3) 8: 1.13 (3H, d,J-6 Hz), 6.52 (1H. d, J-17 Hz), 7.93 (1H, d, J-17 Hz).Hydrolysis of G G (102 mg) was dissolved in methanol (6 ml) and 4N- hydrochloric40 T. Iwagawa and T. Hasbacid (6 ml) was added. The solution was heated under reflux for　6 hr and wasextracted with ether.　The extract was washed with water, dried and the solventwas removed to give a Orystalline material (28 mg), mp 930, m vi慧GmJ: 3400, 1600,1518, 820. Anal. Calcd. for C8Hl｡02: C, 69.54; H, 7.30. Found: C, 69.43; H, 7.28.The IK spectrum was identical with that of　2-(4-hydroxyphenyl) ethanol. Theaqueous solution was evaporated to dryness under reduced pressure and the residuewas dissolved in a small amount water. The presence of glucose in the residue wasconfirmed by paper chromatography｡Aceihylation of D D (100 mg) was acethylated with acetiO anhydride (2 ml) andpyridme (2 ml). The crude product was chromatograplied on a Ooloum of siliOic acid(15 g). Elution with 2% methanol in chloroform gave an amorphous material (42 mg)3IR pgg…1cmJ: 1760, 1640, 1500, 1200; NME (CDCU 8: 1.07 (3H, d, J-7 Hz), 1.92,2.00, 2.08, 2.15 (3Hx5, s), 2.37 (3Hx3,㌔ s), 6.42 (1H, d, J-18 Hz), 7.37-7.67 (6H),8.02 (1H, d, J-18 Hz).Methanolysis of D D (2.5 g) was dissolved in methanol (15 ml) saturated withhydrogen chloride. The solution was stirred for 18 hr at 10-, and then diluted with waterand extracted with ether. The extract was washed with water, dried and the solventwas removed to give an amorphous material. The Orude material was Ohromatographedon a column of silicic acid (75 g). Elution with 5% methanol in chloroform andrecrystallization from water gave Oolorless needles, mp 162-, IB, v禁Br cmJ: 3480, 3080,1660, 1540; NME (Cl)gCOCD,) 8: 3.73 (3H, s), 6.33 (1H, d, J-18 Hz), 6.87-7.25 (3H,m), 7.67 (1H, d, J-18 Hz), 8.43 (2H, br s). Mass Spectrum m/e M+194.0558 (CalOd.for CIOHl｡04: 194.0568).Permethylation of D followed by alkali hydrolysis Sodium hydride (500 mg) washeated with dimethyl sulfoxide (10 ml) at 700 under nitrogen. To this solution, D (300mg) in dimethyl sulfoxide (5 ml) was added and the mixture was stirred for 1 hr andadded with methyl iodide (3 ml). The reaction mixture was stirred further for 3 kr at70 , and poured into ice water, and extracted with ether. The extract was washed withwater, dried and the solvent was removed to give a crude material. The crude materialwas chromatographed on a column of silicic a¢id (10 g).瓦Iution with 2% methanol inchloroform gave an oily material (220 mg). The oily material was dissolved in methanol(5 ml) and 2虹sodium hydroxide (5 ml). The solution was refluxed for 2 kr, and wasdiluted with water and extracted with ether. The extraOもwas wasted with water, dried,and the solvent was removed to give an oily material (66 mg). The oily material waschromatographed on a column of siliciO acid (5 g). Elation with chloroform gave anoily material (38 mg), IRv莞慧0m-1: 3400, 1590, 1510; NMR (CDC13) 8: 1.29 (3H, d,J-6 Hz), 3.42, 3.48, 3.53, 3.57 (each 3H, s), 3.88 (6H, s), 6.89 (3H, s).Acknowledgements We are grateful to Dr. M. Nakatani, Kagoshima University forvaluable discussions. We are also indebted to Mr. K. Mitsunaga for help in collection of也e plant.On the Constituents of the Unripe Fruits of Osmanthus fragrans L. I　　　　　41References1 a) K. Yoshitama, M. Ozaki, M. Fuzii, and K. Hayashi, Schokubutsugaku Zasshi 85, 303(1955).b) H. Inouye, K. Inoue, T. Mshioka, and M. Kaniwa, Phytochemistry 14, 2029 (1975).2　a) T. Mizuno, T. Kimpyo, and K. Hagashi, Nippon Nogei-Kagaku Kaishi, 29, 203 (1955).b) T. Ishigro, N. Koga, K. Takemura, and T. Marujima, YakugaJcu Zasshi 75, 781 (1955).c) T. Ishigro, N. Koga, and K. Nara, Yakugaku Zasshi 77, 566 (1957).d) T. Ishigro, N. Koga, and K. Nara, YaJcgaku Zasshi 78, 287 (1958).3　L.M. Jackman, Forsehritte der Chemie Organischer Naturstoffe Vol. 23, p. 315. Springer-Verlag, Vienna (1955).4　L. Birkofer, C. Kaiser, and U. Thomas, Z. fur Naturofrsch. 23b, 1051 (1968).

ウスギモクセイの未熟果実の成分について I

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ウスギモクセイの未熟果実の成分について I

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