著者

畑中 顯和

出版者

Japan Oil Chemists' Society

雑誌

油化学 (ISSN:18842003)

巻号頁・発行日

vol.33, no.10, pp.703-714, 1984-10-20 (Released:2009-11-13)

参考文献数

112

著者

畑中 顯和

出版者

The Society of Synthetic Organic Chemistry, Japan

雑誌

有機合成化学協会誌 (ISSN:00379980)

巻号頁・発行日

vol.39, no.2, pp.142-153, 1981-02-01 (Released:2009-11-13)

参考文献数

39

被引用文献数

5 4

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The characteristic flavours in plant-, leaf alcohol, cis-3-hexenol, and leaf aldehyde, trans- 2- hexenal, are widely distributed in fresh leaves, vegetables and fruits and are responsible for the odor characteristic of the leaf. Also, both are found in some insect excretions as functioning attractants and repellents.The investigation of leaf alcohol has been carried out by Takei and Ohno et al. since 1938; from 1957, we have been studying leaf alcohol and leaf aldehyde from a number of angles : synthetic chemistry, natural products chemistry, and plant biochemistry.Recently, we focused our attention on the biosynthesis of leaf alcohol and leaf aldehyde and have demonstrated the biosynthetic pathway using Thea sinensis leaves. We know now that leaf alcohol and aldehyde are produced from cis-3-hexenal. This C6-compound, cis-3-hexenal and the C12-compound, 11-formyl-cis-9-undecenoic acid, are biosynthesized from linolenic acid by enzymatic oxygenative splitting through the addition of oxygen to the double bond between C-12 and C-13. This C12-fragment isomerizes to give 11-formyl-trans-10-undecenoic acid, traumatic half aldehyde, which is known as the “Wound Hormone”.

著者

畑中 顯和 梶原 忠彦 関谷 次郎

出版者

天然有機化合物討論会実行委員会

雑誌

天然有機化合物討論会講演要旨集 22 (ISSN:24331856)

巻号頁・発行日

pp.657-664, 1979-09-20 (Released:2017-08-18)

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Endogenous linolenic acid in Thea chloroplasts is cleaved into cis-3-hexenal and 11-formyl-cis-9-undecenoic acid via a very labile intermediate by E_2 of an enzyme system E_2 (E_2 and E'_2+E"_2) bound to the lamellae membranes of chloroplasts under aerobic condition. On the other hand, in external addition of a large amount of linoleic acid to chloroplasts, E'_2 and E"_2 activities newly are induced in addition to E_2 activity, and E'_2 catalyzes the formation of 13-Hydroperoxide and then it was cleaved to n-hexanal by E"_2. The substrate specificity of the enzyme system E_2 in Thea chloroplasts was clarified with an entire series of synthesized positional isomers, in which the position of cis-1,cis-4-pentadiene system varies from C-3 to C-13 in C_<18> fatty acid and geometrical isomers of linoleic acid. The structural requirement for the substrate of E_2 is the presence of cis-1,cis-4-pentadiene system between ω-6 and ω-10. The enantiomeric composition of the 13-Hydroperoxide produced by E'_2 was determined by GLC and NMR analysis: After a large amount of linoleic acid was incubated with tea chloroplasts, a mixture of hydroperoxides (13-hydroperoxy-cis-9,trans-11-/9-hydroperoxy-trans-10,cis-12-octadecadienoic acid=84/16: crude-I) was isolated. The major hydroperoxide of the crude-I was identified as 13-L-hydroperoxy-cis-9,trans-11-octadecadienoic acid (80) containing a small amount of its enantiomer(13-D=20). So, it was demonstrated that E'_2in Tea chloroplasts catalyzes the stereospecific oxygenation of linoleic acid to the 13-L-hydroperoxide.

著者

畑中 顯和

出版者

公益社団法人 日本農芸化学会

雑誌

化学と生物 (ISSN:0453073X)

巻号頁・発行日

vol.14, no.12, pp.788-793, 1976-12-25 (Released:2009-05-25)

参考文献数

27