New approaches to synthesis of tris[1,2,4]triazolo[1,3,5]triazines
New approaches to synthesis of tris[1,2,4]triazolo[1,3,5]triazines
复制标题
三[1,2,4]三唑并[1,3,5]三嗪的合成新方法
DOI：
--
复制
发表时间：
2005
期刊：
影响因子：
--
通讯作者：
Y. Strelenko
中科院分区：
文献类型：
--
作者：
V. Tartakovsky;A. E. Frumkin;A. M. Churakov;Y. Strelenko
3-R-5-氯-1，2，4-三唑(R=Cl，Ph)热环化得到2，6，10-Tri-R-tris[1，2，4]triazolo[1，5-a:1′，5′c:1″，5″-e][1，3，5]triazines 5(R=Ph)和7(R=Cl)。这些化合物是这类杂环的第一个代表，其结构已明确确立。用亲核剂(H2O/NaOH，NH3)处理这些化合物，得到三个1，2，4-三氮唑环连接成链的化合物。例如，用碱处理环状化合物5可得到3-phenyl-1-3-phenyl-1-(3-phenyl-1H-1，2，4-triazol-5-yl)-1，2，4-triazol-5-yl-1H-1，2，4-triazol-5-one.用HCl/SbCl5处理3，7，11-triphenyltris[1，2，4]triazolo[4，3-a:4′，3′c:4″，3″-e][1，3，5]triazine(2)导致三嗪开环，产生5-(3-chloro-5-phenyl-1，2，4-triazol-4-yl)-3-phenyl-4-(5-phenyl-1H-1，2，4-triazol-3-yl)-1，2，4-triazole.后者的热环化反应生成3，7，10-triphenyltris[1，2，4]triazolo[1，5-a:4′，3′c:4″，3″-e][1，3，5]triazine(13)。环状化合物2和环状化合物13的热分解都伴随着二氢重排生成3，6，10-triphenyl-tris[1，2，4]triazolo[1，5-a:1′，5‘-c：4“，3”-e][1，3，5]三嗪(14)。化合物13和14是具有该骨架的环状化合物的第一个代表。~(13)C核磁共振波谱可以确定一系列三[1，2，4]三唑并[1，3，5]三嗪的异构体类型。
Thermal cyclization of 3-R-5-chloro-1,2,4-triazoles (R = Cl, Ph) afforded 2,6,10-tri-R- tris[1,2,4]triazolo[1,5-a:1′,5′c:1″,5″-e][1,3,5]triazines 5 (R = Ph) and 7 (R = Cl). These compounds are first representatives of this class of heterocycles, whose structures were unambiguously established. Treatment of these compounds with nucleophiles (H2O/NaOH, NH3) results in the triazine ring opening to give compounds consisting of three 1,2,4-triazole rings linked in a chain. For example, treatment of cyclic compound 5 with aqueous alkali affords 3-phenyl-1-3-phenyl-1-(3-phenyl-1H-1,2,4-triazol-5-yl)-1,2,4-triazol-5-yl-1H-1,2,4-triazol-5-one. Treatment of 3,7,11-triphenyltris[1,2,4]triazolo[4,3-a:4′,3′c:4″,3″-e][1,3,5]triazine (2) with HCl/SbCl5 leads to the triazine ring opening giving rise to 5-(3-chloro-5-phenyl-1,2,4-triazol-4-yl)-3-phenyl-4-(5-phenyl-1H-1,2,4-triazol-3-yl)-1,2,4-triazole. Thermal cyclization of the latter produces 3,7,10-triphenyltris[1,2,4]triazolo[1,5-a:4′,3′c:4″,3″-e][1,3,5]triazine (13). Thermolysis of both cyclic compound 2 and cyclic compound 13 is accompanied by the Dimroth rearrangement to yield 3,6,10-triphenyl-tris[1,2,4]triazolo[1,5-a:1′, 5′-c:4″,3″-e][1,3,5]triazine (14). Compounds 13 and 14 are the first representatives of cyclic compounds with this skeleton. 13C NMR spectroscopy allows the determination of the isomer type in a series of tris[1,2,4]triazolo[1,3,5]triazines.