Izawa Takuya, Nakayama Koji, Uchida Noritaka, Nojima Kazuhiro
Faculty of Pharmaceutical Sciences, Josai University.
Wavefunction, Inc.-Japan Branch Office.
Chem Pharm Bull (Tokyo). 2018 May 1;66(5):581-584. doi: 10.1248/cpb.c17-00938. Epub 2018 Feb 22.
Dehydroacetic acid (1) was found to induce photoisomerization, converting aldrin (3) and dieldrin (4) into photoaldrin (5) and photodieldrin (6), respectively, not only when irradiated with artificial light at wavelengths longer than 290 nm in air but also when exposed to sunlight in air. By contrast, sodium dehydroacetate (2) induced both photoisomerization, primarily converting 3 to 5 and photoepoxidation, partially forming 6. Thus, because 2 is usually used as a water-soluble antiseptic, photo-erethism might occur due to the isomerization and epoxidation properties of this compound. The difference between the photoreactivity of 1 and that of 2 might be attributed to the spin density of the odd electron on the carbon atom in the respective radicals that were formed after photo-excited 1 and 2 caused H-abstraction.
发现脱氢乙酸（1）能诱导光异构化，不仅在空气中用波长大于290 nm的人造光照射时，而且在空气中暴露于阳光时，能分别将艾氏剂（3）和狄氏剂（4）转化为光艾氏剂（5）和光狄氏剂（6）。相比之下，脱氢乙酸钠（2）既诱导光异构化，主要将3转化为5，又诱导光环氧化，部分形成6。因此，由于2通常用作水溶性防腐剂，该化合物的异构化和环氧化特性可能会导致光过敏反应。1和2的光反应性差异可能归因于光激发的1和2引起氢原子提取后形成的相应自由基中碳原子上奇电子的自旋密度。
