联苯环辛烯木脂素衍生物的化学研究
摘要
以联苯环辛烯类木脂素五味子酯平、醇甲、醇乙和南五味子乙素为原料，合成了二十余个衍生物。
同时，研究了Claisen重排反应和Ritter反应用于这类木脂素衍生物合成中的情况，其中Ritter反应条件下生成的四环体系衍生物，是首次发现联苯环辛烯木脂素具有分子内环合的性质。对五味子酯甲在SOCl_2／Py条件下的内环合反应也作了摸索，并取得成功。
鉴定了醇乙分子内环合产物在空气中自动氧化分解的产物，并对氧化机制作了初步探讨。
合成的大部分衍生物已进行对微管蛋白聚合解聚影响的药理实验，其中化合物A7，A9，B15，C1和C5显示出了一定活性，不可忽视。
More than twenty dibenzocyclooctadlene lignan derivertives have been prepared from natural compounds schisantherin A,schisandrol A,B and kadsuranin B. Most of them were tested for the inhibition of microtubule assembly in vitro.
Among them,the four-ring compounds B6,B15,derived from schisandrol A under Ritter condition and schisantherin A with SOCl_2/Py condition, were reported at the first time and fully identified. The structure of decomposed compounds B19,B22 from the oxidation of B11 and B15 (i.e. the oxidation of α, β—, α', β'— unsaturated cyclohex ketone with β-OH) were deduced initially .
Also, the Claisen rearrangement used in the preparation of the derivertives was discussed.
同时，研究了Claisen重排反应和Ritter反应用于这类木脂素衍生物合成中的情况，其中Ritter反应条件下生成的四环体系衍生物，是首次发现联苯环辛烯木脂素具有分子内环合的性质。对五味子酯甲在SOCl_2／Py条件下的内环合反应也作了摸索，并取得成功。
鉴定了醇乙分子内环合产物在空气中自动氧化分解的产物，并对氧化机制作了初步探讨。
合成的大部分衍生物已进行对微管蛋白聚合解聚影响的药理实验，其中化合物A7，A9，B15，C1和C5显示出了一定活性，不可忽视。
More than twenty dibenzocyclooctadlene lignan derivertives have been prepared from natural compounds schisantherin A,schisandrol A,B and kadsuranin B. Most of them were tested for the inhibition of microtubule assembly in vitro.
Among them,the four-ring compounds B6,B15,derived from schisandrol A under Ritter condition and schisantherin A with SOCl_2/Py condition, were reported at the first time and fully identified. The structure of decomposed compounds B19,B22 from the oxidation of B11 and B15 (i.e. the oxidation of α, β—, α', β'— unsaturated cyclohex ketone with β-OH) were deduced initially .
Also, the Claisen rearrangement used in the preparation of the derivertives was discussed.
引文
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(19) William S. Allen et. al. J. A. C. S., 77, 1028, (1955)
(20) V. J. Traynelis et. al. J. O. C., 27, 2377, (1962)
(21) Ehud Keinan et. al. J. O. C., 43, 1020, (1978)
(22) J. H. Russel et. al, Helv. Chim. Acta., 43, 167, (1960)
(23) John J. Ritter et. al. J. A. C. S., 4048, (1948)
(24) Climans, Bull. Soc. Chin. Prance, 1383, (1966)
(25) Haaf et. al. Chem. Ber., 96, 3359, (1963)
(26) L. I. Krimen et. al. Org. Rex. 17, 213, (1969)
(27) Siden Top et. al. J. O. C., 46, 78, (1981)
(28) Cyula Schneider et. al. Tetra., 41, 3377, (1985)
(29) W. Haaf, Org, Syn. Coll. 5, p739
(30) Tan Rui et. al. Planta Medica, 50, 414, (1984)
(31) H. Koch et. al. Org. Syn. 5, p20
(32) Robet Filler et. al. Chem. Revs., 63, 21, (1963)
(33) J. A. Pegolotti et. al. J. A. C. S., 83, 325, (1961)
(2) Chem Yuh-Pan et. al. Bull. Chem. Soc. Japan 50(3) 1824 (1977)
(3) Y. Ikeya, et. al. Chem. Pharm. Jull. 30, 132 (1981)
(4) Li Lian-Niang et. al. Ilanta Medica, 297, (1984)
(5) 包天桐等 药学学报 14(11)，1(1979)
(6) 钮心懿等 中华医学杂志 55(6)，348(1978)
(7) 谢晶曦等 药学学报 16(4)，306(1981)
(8) Hiroshi Hikino et. al. Planta Medica, 213, (1984)
(9) S. M. Kupchan et. al. J. A. C. S., 95, 1335, (1973)
(10) Mohammed Taafrout et. al. Tetra. Lett., 197, (1983)
(11) L. R. Hughes et. al. Tetra. Lett., 1543, (1976)
(12) Flora Zavala et. al. J. ed. Chem., 546, (1980)
(13) Rickey P. Hicks et. al. J. Mat. Prod. 48, 357, (1985)
(14) L. Claisen et. al. Chem. (?)er., 45, 3157, (1912)
(15) (a) S. Felix et. al. Helv. Chim. Acta., 52, 1030, (1969) (b) R. Farket. et. al. Helv. Chim. Acta., 50, 1158, 2095, (1967)(16) Robet E. Ireland et. al. J. A. C. S., 102, 1155, (1980)
(17) VEB Filmfabrik Agfa Wolfen, et. al. Org. Functional Group Preparation, Vol2, p48
(18) R. O. C. Norman et. al. J. C. S. (c), 1115, (1967)
(19) William S. Allen et. al. J. A. C. S., 77, 1028, (1955)
(20) V. J. Traynelis et. al. J. O. C., 27, 2377, (1962)
(21) Ehud Keinan et. al. J. O. C., 43, 1020, (1978)
(22) J. H. Russel et. al, Helv. Chim. Acta., 43, 167, (1960)
(23) John J. Ritter et. al. J. A. C. S., 4048, (1948)
(24) Climans, Bull. Soc. Chin. Prance, 1383, (1966)
(25) Haaf et. al. Chem. Ber., 96, 3359, (1963)
(26) L. I. Krimen et. al. Org. Rex. 17, 213, (1969)
(27) Siden Top et. al. J. O. C., 46, 78, (1981)
(28) Cyula Schneider et. al. Tetra., 41, 3377, (1985)
(29) W. Haaf, Org, Syn. Coll. 5, p739
(30) Tan Rui et. al. Planta Medica, 50, 414, (1984)
(31) H. Koch et. al. Org. Syn. 5, p20
(32) Robet Filler et. al. Chem. Revs., 63, 21, (1963)
(33) J. A. Pegolotti et. al. J. A. C. S., 83, 325, (1961)