Zissimou Georgia A, Kourtellaris Andreas, Manoli Maria, Koutentis Panayiotis A
Department of Chemistry , University of Cyprus , P.O. Box 20537, 1678 Nicosia , Cyprus.
J Org Chem. 2018 Aug 17;83(16):9391-9402. doi: 10.1021/acs.joc.8b01311. Epub 2018 Jul 17.
Modifying the para-quinonimine 1,3-diphenyl-1,2,4-benzotriazin-7(1 H)-one (2a) ( E -1.20 V), by replacing the N1-phenyl by pentafluorophenyl, the C3-phenyl by trifluoromethyl, or the C7 carbonyl by ylidenemalononitrile, led to improved electron affinities as determined by cyclic voltammetry and computational studies. Combining structural changes further improved electron accepting abilities: the most electron deficient analogues ( E ∼ -0.65 V) involved combining the ylidenemalononitrile groups at C7 with the trifluoromethyl groups at C3. 1,2,5-Thiadiazolo fusion at C5-C6 did not affect the redox behavior but did enhance the UV-vis absorption profile. During the synthesis of the thiadiazolo analogues, 1,4-thiazino-fused analogues 6 were obtained in low yield, which thermally ring contract to the triazafluoranthenones 7. Compounds are fully characterized, and X-ray data are provided for selected analogues.
通过将对醌亚胺1,3-二苯基-1,2,4-苯并三嗪-7(1H)-酮(2a)(E -1.20 V)的N1-苯基用五氟苯基取代、C3-苯基用三氟甲基取代或C7羰基用亚甲基丙二腈取代，通过循环伏安法和计算研究确定，其电子亲和力得到了提高。进一步结合结构变化提高了电子接受能力：电子最缺乏的类似物(E ∼ -0.65 V)涉及在C7处结合亚甲基丙二腈基团和在C3处结合三氟甲基基团。在C5-C6处进行1,2,5-噻二唑稠合不影响氧化还原行为，但确实增强了紫外-可见吸收谱。在噻二唑类似物的合成过程中，以低产率得到了1,4-噻嗪稠合类似物6，其热环收缩为三氮杂荧蒽酮7。对化合物进行了全面表征，并提供了选定类似物的X射线数据。
