分子内1,3-偶极环加成反应的研究IV某些硝酮偶极体系的热及光化学反应及区域选择性.pdfVIP

有机化学 YOUJI HUAXUE , 1989, 9, 156~162 研究论立 分子内1 ， 3一偶极环加成反应的研究 N. 某些硝恫偶极体系的热及光化学反应及区域选碎性 F东庆华*、 f轩孟吱川、贾西贝***、王学良 (北京师范大学化学系、北京) Studies on Intramolecular 1,3-Dipolar Cycloaddition Reactions IV. The Thermochemical and Photochemical Reactions of Some 1 ,3- Dipolar Nitrone Systems and Related Regioselectivities CHEN Qing• Hua* , X1E Meng-Xia*飞 JIA Xi-B甜**， W ANG Xue-Liang (Department of Chemistry, Beijing Normal University, Beijtng) Abstract: 1n this paper the thermochemical and photochemical reactions of some 1,3-dipolar nitrone systems and related regioselectivities are futher studied. The substituent effects on the reactivities of cyclization and the regioselectivities of reaction have been investigatect quantitatively by chromatographic metbods. On irridition by Hg-lamp UV of Ä注302 nm nitrones 1 form oxaziridine compounds 4 , and the latter arrange futher into amide type compounds under the Ä:::;; 270 nm , while on heating 4 reverse to cyc1oaddition products 2 and 3 through inîramolecular cycloaddition reaction. The experimental results a180 indicate that the relationship between melting points and configurations of cinnaldoximes puhlished in the 1iterature i8 not correct. The BB type (syn form) should have a lower me 1ting poin t, while the m. p. of the EZ type (anti form) should be higher. Descriptúr: J ,::;-dipolar nitrone. intramolecular cycloaddition , thermochemical and photo- chemical reaction , regioselectivity jf[ 几年来，人们:叶子 1 ， :3一偶极环加成反 结果与讨论 问的理论研究及其在什成 J~ 的应用已约予广泛 的3乓趣;有lïf: 1:lI1，[l! 0 我们曾详细地研究了 4一取 1, 3一偶极苯乙烯硝嗣体系(1 的是-个介 有 C=C 双键的共辄体系， 其结构与 1 a~l d 民末基(N-4一戊烯基)硝隅的热化学反应性能 和;民区域选择性[20] 以及映Príi 伺极体系的热和 体系有所区别。实验表明， i e 的热反应仍按 光化学反应[2b) 。本文进-步探讨了取代基效 4n+2