Control of the photoreactions of carboxylic acid derivatives by use of intermolecular hydrogen bonds

利用分子间氢键控制羧酸衍生物的光反应

• 批准号: 13640535
• 负责人: KUBO Yasuo
• 金额: $ 1.54万
• 依托单位: Shimane University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2001
• 资助国家: 日本
• 起止时间: 2001 至 2002
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-13640535/
• 关键词: Photochemical Reactions; Hydrogen Bons; Carboxylid acid derivatives; Alkenes; Cycloadditions; Reaction Control; Stereo-Selectivity; Control of Orientation

The purpose of this investigation is to clarify the applicability of the control of the photoreactions of carboxylic acid derivatives by use of intermolecular hydrogen bonds.The results obtained are as follows:1. Intermolecular hydrogen bonds were found to be able to control the stereoselectivity of the photocycloadditions of aromatic carboxylic acid derivatives, such as esters and imides, with alkenes. Thus, in the [3+2]-photocycloaddition of dimenthyl 1,4-naphthalenedicarboxylate with methallyl alcohol in benzene at 0 ℃, the ratio of the of the stereoisomers of the [3+2]-adducts was 2.3 : 1, although in the [3+2]-photocycloaddition with the corresponding methyl ether the ratio of the stereoisomers was 1 : 1.3. On the other hand, in the [2+2]-photocycloaddition of N-methyl-1,8-naphthalimide with methallyl alcohol in benzene at 0 ℃, the ratio of the stereoisomers of the [2+2]-adducts was 9.0 : 1, although in the [2+2]-photocycloaddition with the corresponding methyl ether the ratio of the stereoisomers was 2.5 : 1. Furthermore, the intermolecular hydrogen bonds were found to control reactivity of the photocycloadditions as well as the stereoselectivity.2. Thus we examined the effect of the addition of alcohols and carboxylic acids on the photoproperties, especially emission properties, of the aromatic imide compounds to elucidate the possibility of the control of the reactivity of the excited aromatic imide compounds. As the results, the fluorescence intensity of N-methyl-1,8-naphthalimide was found to be remarkably increased by the addition of alcohols, such as 2-methyl-1-propanol, and carboxylic acids, such as acetic acid and 2,2,2-trifluoroacetic acid, while no such effect was observed by use of other aromatic imide compounds, such as N-methyl-1, 2-and -2,3-naphthalimide. The difference of the behavior may be attributed to the energy differences between S_1 (n,π^*) and S_2 (π,π^*) of the aromatic imide compounds.

本研究的目的是阐明利用分子间氢键控制羧酸衍生物光反应的适用性。分子间氢键被发现能够控制芳香族羧酸衍生物，如酯和酰亚胺，与烯烃的光环加成的立体选择性。因此，1，4-萘二甲酸二甲酯与甲基烯丙醇在苯中于0 ℃进行[3+2]-光环加成反应时，[3+2]-加合物的立体异构体之比为2.3：1，而与相应的甲基醚进行[3+2]-光环加成反应时，立体异构体之比为1：1.3。N-甲基-1，8-萘酰亚胺与甲基烯丙醇在苯中0 ℃ [2+2]-光环加成反应中，[2 +2]-加合物的立体异构体之比为9.0：1，而与相应的甲基醚的[2+2]-光环加成反应中，立体异构体之比为2.5：1。此外，发现分子间氢键控制了光环加成反应的反应活性和立体选择性.因此，我们研究了添加醇和羧酸对芳香酰亚胺化合物的光性能，特别是发光性能的影响，以阐明控制受激芳香酰亚胺化合物的反应性的可能性。结果发现，通过添加醇如2-甲基-1-丙醇和羧酸如乙酸和2，2，2-三氟乙酸，N-甲基-1，8-萘二甲酰亚胺的荧光强度显著增加，而使用其它芳族酰亚胺化合物如N-甲基-1，2-和-2，3-萘二甲酰亚胺没有观察到这种效果。这种行为的差异可能归因于芳香酰亚胺化合物的S_1（n，π^*）和S_2（π，π^*）之间的能量差异。