Synthesis and Reaction of Fluorescent, Photolabile (1-pyrenyl) methyl Esters of Carboxylic and phosphoric Acids

荧光、光不稳定的羧酸和磷酸（1-芘基）甲酯的合成和反应

• 批准号: 02640409
• 负责人: IWAMURA Michiko
• 金额: $ 1.34万
• 依托单位: Toho University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (C)
• 财政年份: 1990
• 资助国家: 日本
• 起止时间: 1990 至 1991
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-02640409/
• 关键词: Photolability; Protecting group; (1-Pyrenyl) methyl; Phosphate; Exciplex; Electron transfer; 1ーピレニルメチル基; 光分解性保護基; プロ-ブ; 1ー(αージアゾベンジル)ピレン; 光分解反応; カルボン酸1ーピレニルメチル; 光誘起電子移動

1.1-(alpha-Diazobenzyl) pyrene (DBP), which is stable at room temperature for several months, reacts with carboxylic acids to give fluorescent, photolable (1-pyrenyl) methyl esters in high yields. DBP was used for fluorescent, photolabile protection of carboxyl group of amino acids and peptides. However, DBP did not give good result for the protection of phosphoric acids. (1-pyrenyl) methyl bromide was found to react in the presence of silver oxide either with carboxylic acids or with phosphoric acids resultong in the formation of the corresponding esters in high yield. Esters are easily obtained by filtrating silver bromide formed. Esterification of uronic acids and c-AMP by this procedure is now under way.2. Mechanistic studies on photosolvolysis of (1-pyrenyl) methyl carboxylates and determination of quantum yields of the reaction were carried out. It was found that introduction of an electron withdrawing group on (1-pyrenyl) methyl group causes unusual ester O-CO cleavage in addition to CH-OCO cleavage.3. Intramolecular electron transfer in the excited states of omega-(l-pyrenyl) alkyl p-substituted benzoate was studied. Energy of exciplex formation and activation, rates constants were determined for 2-(l-pyrenyl) ethyl p-cyanobenzoates (P2CN). From the results of single-photon-counting measurement and ^1NMR NOE, it is concluded that the folded conformer of the p-cyanobenzoate is responsible to the exciplex formation. This is the first example of correlation of exciplex formation with ground state conformations.

1.1-（α-重氮苄基）芘（DBP）在室温下可稳定数月，与羧酸反应可高产率生成荧光、可光化的（1-芘基）甲酯。DBP用于氨基酸和肽的羧基的荧光、光不稳定保护。然而，DBP对磷酸的保护效果不佳。在银存在下，（1-芘基）甲基溴与羧酸或磷酸反应，高产率地生成相应的酯。酯很容易通过过滤形成的银得到。糖醛酸和cAMP的酯化反应正在进行中。对（1-芘基）甲基羧酸酯的光溶剂分解反应机理进行了研究，并测定了反应的量子产率。研究发现，在（1-芘基）甲基上引入吸电子基团，除了CH-OCO断裂外，还引起酯O-CO断裂.研究了ω-（1-芘基）烷基对位取代苯甲酸酯激发态的分子内电子转移。测定了对氰基苯甲酸2-（1-芘基）乙酯（P_2CN）的激基复合物形成能、活化能和速率常数。单光子计数测量和^1 NMR NOE结果表明，对氰基苯甲酸酯的折叠构象是激基复合物形成的原因。这是激基复合物形成与基态构象相关的第一个例子。

项目成果

3.Michiko Iwamura,Kiyoko Matsui,Shouhaku Huchibe.: "Photochemistry of 1-PyrenylmethylEsters: Substituent Effects on the Modes of Photolytic Cleavage of α-(1-Pyrenyl)benzyl Phenylacetates." Chemistry Letters. (1992)

3.Michiko Iwamura、Kiyoko Matsui、Shouhaku Huchibe.：“1-芘基甲基酯的光化学：取代基对 α-(1-芘基)苯乙酸苯甲酯光解裂解模式的影响”(1992)。

Michiko Iwamura, Kiyoko Matsui, Shouhaku Huchibe.: "Photochemistry of 1-PyrenylmethylEsters : Substituent Effects on the Modes of Photolytic Cleavage of alpla-(1-Pyrenyl) benzyl Phenylacetates." Chemistry Letters. (1992)

Michiko Iwamura、Kiyoko Matsui、Shouhaku Huchibe.：“1-芘基甲基酯的光化学：取代基对α-(1-芘基)苯乙酸苯甲酯光解裂解模式的影响。”

Michiko Iwamura, Jun Kawakami, Junko Nakamura.: "Correlation of Exciplex Formation with Ground State Conformations in beta-(1-Pyrenyl) ethyl Benzoates." Chemistry Letters. (1992)

Michiko Iwamura、Jun Kawakami、Junko Nakamura：“β-(1-芘基)乙基苯甲酸酯中激基复合物形成与基态构象的相关性。”

1.Michiko Iwamura,Chikako Hodota,Masami Ishibashi.: "1-(α-Diazobenzyl)pyrene: A Reagent for Photolabile and Fluorescent Protection of Carboxyl Groups of Amino Acids and Peptides." SYNLETT. 56-57 (1991)

1.Michiko Iwamura、Chikako Hodota、Masami Ishibashi.：“1-(α-重氮苯甲基)芘：氨基酸和肽羧基的光不稳定和荧光保护试剂 56-57 (1991)”

岩村 道子,松井 規容子,渕辺 松伯: "Photochemisluy of 1ーPyenyl methyl Esters:substitu ent Effects on the Mods of photo lytic Cleavage of 2ー(1ーPyreuyl)metnyl phenylacetates" Chemisty Letters. (1992)

Michiko Iwamura、Kiyoko Matsui、Matsuhaku Fuchibe：“1-芘基甲基酯的光化学：取代基对 2-(1-芘基)甲基苯乙酸酯光解裂解模式的影响”《化学快报》(1992)。