New iminophosphorane-mediated synthesis of thieno[3′,2′:4,5]thieno-[3,2-d]pyrimidin-4(3H)-ones and 5H-2,3-dithia-5,7-diaza-cyclopenta[c,d]indenes
New iminophosphorane-mediated synthesis of thieno[3′,2′:4,5]thieno-[3,2-d]pyrimidin-4(3H)-ones and 5H-2,3-dithia-5,7-diaza-cyclopenta[c,d]indenes
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DOI：
10.1016/j.tet.2008.07.036
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发表时间：
2008-09-15
期刊：
影响因子：
2.1
通讯作者：
Ding, Ming-Wu
中科院分区：
文献类型：
--
作者：
Liu, Ming-Guo;Hu, Yang-Gen;Ding, Ming-Wu
以3,4-二氨基噻吩[2,3-b]与过量的三苯基膦、C(2)Cl(6)和Et(3)N为原料，通过分子内双氢键的形成，选择性地制备了单亚氨基磷烷4。单亚磷烷4与芳香异氰酸酯反应生成稳定的碳二亚胺8，再用脂肪族仲胺或伯胺处理得到2-氨基取代的噻吩[3′，2′：4,5]噻吩[3,2-d]嘧啶-4(3H)- 1 10或12，催化量为EtO(-)Na（+）存在。然而，在催化量的碳酸钾存在下，碳二亚胺8通过直接环化转化为先前未报道的5h -2,3-二硫-5,7-二氮-环五[c，d]化合物13，收率高。碳二亚胺8与苯酚在催化量碳酸钾的存在下反应得到2-芳基取代噻吩[3′，2′：4,5]噻吩[3,2-d]嘧啶-4(3H)- 14和13的混合物。10m的x射线结构分析支持了结构和所提出的氨基反应性。(C) 2008 Elsevier Ltd版权所有。
Mono(iminophosphorane) 4 was selectively prepared from the reaction of 3,4-diaminothieno[2,3-b]thiophene 3 with excess triphenylphosphine, C(2)Cl(6), and Et(3)N due to intramolecular double hydrogen bond formation. Mono(iminophosphorane) 4 reacted with aromatic isocyanates to give stable carbodiimides 8, which were further treated with aliphatic secondary or primary amines to give 2-amino substituted thieno[3',2':4,5]thieno[3,2-d]pyrimidin-4(3H)-ones 10 or 12 in the presence of a catalytic amounts of EtO(-)Na(+). However, in the presence of a catalytic amounts of potassium carbonate, the carbodiimides 8 were transformed into previously unreported 5H-2,3-dithia-5,7-diaza-cyclopenta[c,d]indenes 13 via direct cyclization in high yields. The reaction of carbodiimides 8 with phenols in the presence of a catalytic amounts of potassium carbonate gave a mixture of 2-aryloxy substituted thieno[3',2':4,5]thieno[3,2-d]pyrimidin-4(3H)-ones 14 and 13. X-ray structure analysis of 10m supported the structure and the proposed reactivity of amino group. (C) 2008 Elsevier Ltd. All rights reserved.