8 二、三のトリテルペンケトンの光反応
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概要
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Photochemical reaction of friedelin (1), shionone (2), norfriedelin (3), lupan-3-one (4), and 1,5,5,9-tetramethyl-2-trans-decalone (36) was investigated. The products formed from friedelin (1) in various solvents are summarized in Table 1. Since 1 bears no hydrogen atom on the δ-carbon atom, an acylalkyl biradical produced from 1 can not give a δ,ε-unsaturated aldehyde via a 6-membered transition state, but give the ketene (16) by hydrogen transfer from C-2 to the alkyl radical. In protic solvents, 16 gave addition products such as the seco-acid (12) and the seco-ester (10). In aprotic solvents, 16 survived and suffered autoxidation in the subsequent separation procedures to give the seconor-aldehyde (7) and the seconor-acid (13). The acylalkyl biradical also gave 1 and 4-epifriedelin (9) by recyclization, norfriedelane (5)(along with its 4-epimer) and the unsaturated nor-hydrocarbon (6) by decarbonylation, and an ε,ζ-unsaturated aldehyde (8)via an 8-membered transition state. 4-Epishionone (23) was obtained on irradiation of 2. Photochemical interconversion between norfriedelin (3) and the unsaturated aldehyde (24) was observed. Irradiation of the decalone (36), a bicyclic model compound related to 1, and the subsequent separation work-up gave the secoaldehyde (37), the seconor-acid (38), and the seco-acid (39). Photoreaction of lupan-3-one (4) in n-hexane gave three seco derivatives (27, 29, and 30), besides the seconor-acid (28) formed during the subsequent work-up. A lactone (31) was also obtained. Putranjivic acid (17) was synthesized in one step from 1.
- 天然有機化合物討論会の論文
- 1974-10-01
著者
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廣田 洋
東大理
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露木 孝彦
東大理
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高橋 武美
東大理
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山田 修三
電通大
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露木 孝彦
Department of Chemistry, Faculty of Science, The University of Tokyo
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高橋 武美
日大・農獣医・応用生物
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露木 孝彦
Department Of Chemistry Faculty Of Science The University Of Tokyo
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白崎 英一
東大理
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青柳 玲子
東大理
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舘江 栃郎
東大理
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山田 修三
東大理
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Stevenson R.
ブランダイス大
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