1,3,5‐Triazapenta‐1,3‐dienes: Useful Building Blocks for the Synthesis of1,2‐Dihydro‐1,3,5‐triazines and Oligonitriles
1,3,5‐Triazapenta‐1,3‐dienes: Useful Building Blocks for the Synthesis of1,2‐Dihydro‐1,3,5‐triazines and Oligonitriles
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1,3,5-三氮杂五环-1,3-二烯：用于合成 1,2-二氢-1,3,5-三嗪和低聚腈的有用结构单元
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发表时间：
2006
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通讯作者：
E. Würthwein
中科院分区：
文献类型：
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作者：
Nadine Heße;R. Fröhlich;B. Wibbeling;E. Würthwein
由脒和亚胺酰氯2制备的1，3，5-三氮杂五二烯1已被用作与各种亲电试剂反应的亲核结构单元。与醛4得到1，2-二氢三嗪3，而酮5得到3或1，3，5-三氮杂六-1，3，5-三烯6，这取决于1的取代模式。酰氯7与1反应，得到1-氧杂-3，5，7-三氮杂庚-1，3，5-三烯8;以类似的方式，亚氨酰氯2生成新的1，3，5，7-四氮杂庚-1，3，5-三烯9。用1处理N-苯甲酰基苯亚氨酰氯10，得到1-氧杂-3，5，7，9-四氮杂壬-1，3，5，7-四烯11，或根据取代方式，得到它们的具有1，2-二氢三嗪结构的环互变异构化合物1,2。3，5，7，9-五烯（14），具有推拉取代模式的长寡腈。所有的新化合物进行了全面的表征，包括X-射线衍射的每一种类型，而扭曲的三维结构的开链化合物。采用密度泛函理论（DFT）[B3 LYP/6-31+G（d，p）水平]研究了1，3，5-三氮杂环戊二烯异构体的相对能量，以及所选实例的环-链互变异构现象.（© Wiley-VCH Verlag GmbH & Co. KGaA，69451魏因海姆，德国，2006）
1,3,5-Triazapentadienes 1, prepared from amidines and imidoyl chlorides 2, have been used as nucleophilic building blocks for the reactions with various electrophilic reagents. With aldehydes 4 1,2-dihydrotriazines 3 were obtained, whereas ketones 5 gave 3 or 1,3,5-triazahexa-1,3,5-trienes 6, depending on the substitution pattern of 1. Acyl chlorides 7 reacted with 1 to give 1-oxa-3,5,7-triazahepta-1,3,5-trienes 8; in a similar manner imidoyl chlorides 2 gave rise to the formation of the new 1,3,5,7-tetraazahepta-1,3,5-trienes 9. Treatment of N-benzoylbenzimidoyl chloride 10 with 1 afforded the 1-oxa-3,5,7,9-tetraazanona-1,3,5,7-tetraenes 11, or, depending on the substitution pattern, their ring-tautomeric compounds 12 with 1,2-dihydrotriazine structures.1-Oxa-3,5-diazinium salt 13 as cyclic electrophile produced, when treated with 1g, 1-oxa-3,5,7,9,11-pentaazaundeca-1,3,5,7,9-pentaene (14), a long oligonitrile with push-pull substitution pattern. All new compounds were completely characterized including X-ray diffraction for each type, indicating rather twisted three-dimensional structures for the open-chain compounds. The relative energies of 1,3,5-triazapentadiene isomers were studied by DFT calculations [level: B3LYP/6-31+G(d,p)], as well as the ring-chain tautomerism of selected examples. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)