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Construction of Chiral Photochromic System Controlled by Steric Factors

位阻因素控制的手性光致变色体系的构建

基本信息

批准号：
10640530
负责人：
YOKOYAMA Yayoi
金额：
$ 2.3万
依托单位：
Tokyo Kasei Gakuin University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
1998
资助国家：
日本
起止时间：
1998 至 1999
项目状态：
已结题

项目摘要

A sterically demanding and thermally irreversible bisthienylfulgides, 3,4-bis[1-(2,5-dimenthyl-3-thienyl) ethylidene]-3,4-dihydro-2,5-furandione, was synthesized by Pd-catalyzed carbonylation of the corresponding 2-butyne-1,4-diol derivatives and their photochromic bihaviers were studied.Treatment of trichloroethene with butyllithium followed by reaction of 3-acyl-2,5-dimenthylthiophene gave the acetylenediol in 45% yield. Reaction of acetylenediol with carbon monoxide in the presence of Pd(Oac)ィイD22ィエD2 afforded bisthienylfulgides as a mixture geometric isomers. These isomers were separated by silica gel column chromatography to obtain EE, EZ, and ZZ in 4, 3, and 1% yields, respectivity. The identification f geometric isomers was done by ィイD11ィエD1H NMR and their photochromic behaviors were studied. 366-nm light irradiation to the toluene solution of ZZ afforded EZ, EE, and two colored closed forms(CィイD2EEィエD2, CィイD2EZィエD2). Two colored closed forms changed EE and EZ upon 554-nm light irradiation. Two colored forms(CィイD2EEィエD2, CィイD2EZィエD2)obtained from EE and EZ were diastereomeic with each other. At photostationary state o 366-nm light irradiation, the ratio of concentration of the isomers, EE/EZ/ZZ/CィイD2EEィエD2/ CィイD2EZィエD2, was 17/14/8/58/3. The most notable feature is the highly diastereoselective formation of CィイD2EEィエD2 (90% de).

以2-丁炔-1，4-二醇及其光致变色双色剂为原料，在钯的催化作用下，合成了空间要求高、热不可逆的二硫代黄酮类化合物3，4-双[1-(2，5-二乙基-3-亚硫基)乙叉]-3，4-二氢-2，5-呋喃二酮。三氯乙烯与丁基锂反应，3-酰基-2，5-二乙基噻吩制得乙酰二醇产率为45%。在Pd(OAc)ィイD22ィエD2存在下，乙炔二醇与一氧化碳反应生成混合几何异构体。用硅胶柱层析分离得到EE、EZ和ZZ，产率分别为4%、3%和1%。用ィイD11ィエD1H核磁共振对几何异构体进行了鉴定，并研究了它们的光致变色行为。366 nm的光照射ZZ的甲苯溶液，得到EZ、EE和两种有色闭合形式(CィイD2EEィエD2，CィイD2EZィエD2)。在554 nm光照射下，两种有色闭合形式改变了Ee和EZ。从EE和EZ获得的两种有色形式(CィイD2EEィエD2，CィイD2EZィエD2)彼此非对映。在366 nm光照射下，Ee/EZ/ZZ/CィイD2EEィエD2/CィイD2EZィエD2的浓度比为17/14/8/58/3。最显著的特征是CィイD2EEィエD2的高度非对映选择性形成(90%De)。