New P–S–N containing ring systems. Reaction of 2,4-(naphthalene-1,8-diyl)-1,3,2,4-dithiadiphosphetane 2,4-disulfide and its 4-methoxynaphthalene derivative with hexamethyldisilazane
作者:Petr Kilián、Jaromír Marek、Radek Marek、Jiøí Tou·ín、Otakar Humpa、Josef Novosad、J. Derek Woollins
DOI:10.1039/a708348c
日期:——
Reaction of 2,4-(naphthalene-1,8-diyl)-1,3,2,4-dithiadiphosphetane 2,4-disulfide 1 with hexamethyldisilazane (hmds) in acetonitrile gave the N,Nâ²-bis(trimethylsilyl)acetamidinium salt of the [(C10H6)P(S)(NHSiMe3)SP(S)2]â anion 2, a product of P2S2 ring cleavage, together with the new thiazaphosphetidine (C10H6)P(S)SN(SiMe3)P(S) 3. Analogous (methoxy derived) products to 2 (2a, 2b) and 3 (3a) were obtained when 2,4-(4-methoxynaphthalene-1,8-diyl)-1,3,2,4-dithiadiphosphetane 2,4-disulfide 1a was used instead of 1. When the reaction of 1 with hmds was performed in dichloromethane a mixture of the products was obtained, from which the hexamethyldisilazan-2-ium salt of the anion of identical structure to that in 2 has been isolated. No reaction occurred when a solventless system was used. The new compounds were studied spectroscopically (one- and two-dimensional NMR, IR spectroscopy) and by X-ray crystallography (3, 3a and 4).
将 2,4-(萘-1,8-二基)-1,3,2,4-二硫二磷杂环丁烷 2,4-二硫化物 1 与六甲基二硅氮烷(hmds)在乙腈中反应,可得到 N、(C10H6)P(S)(NHSiMe3)SP(S)2]â阴离子 2 的 Nâ²-双(三甲基硅基)乙酰胺盐(P2S2 环裂解的产物),以及新的噻唑磷定 (C10H6)P(S)SN(SiMe3)P(S) 3。当用 2,4-(4-甲氧基萘-1,8-二基)-1,3,2,4-二硫二磷杂环丁烷 2,4-二硫化物 1a 代替 1 时,得到了与 2(2a、2b)和 3(3a)相似的(甲氧基衍生)产物。在使用无溶剂体系时,没有发生反应。对这些新化合物进行了光谱研究(一维和二维核磁共振、红外光谱)和 X 射线晶体学研究(3、3a 和 4)。