二硫杂环丁烯

二硫杂环丁烯
IUPAC名
1,2-Dithiete
系统名
1,2-Dithiacyclobut-3-ene
别名 二噻环丁烯
1,2-二噻[4]轮烯
识别
CAS号 7092-01-5
PubChem 138918
ChemSpider 122516
SMILES
 
  • c1css1
性质
化学式 C2H2S2
摩尔质量 90.17 g·mol−1
相关物质
相关化合物 硫杂环丁烯
相关化学品
若非注明，所有数据均出自标准状态（25 ℃，100 kPa）下。

二硫杂环丁烯（英语：Dithiete）是一种不饱和杂环化合物，含有两个相邻的硫原子和两个sp2杂化碳中心。衍生物统称为二硫杂环丁烯化合物或1,2-二硫杂环丁烯化合物。具有6个π电子的1,2-二硫醚是芳香族有机硫化合物的例子。一些1,2-二硫杂环丁烯化合物已被分离出来。[1][2]3,4-双(三氟甲基)-1,2-二硫杂环丁烯是一个特别稳定的例子。

未取代的1,2-二硫杂环丁烯在热解反应中生成，并在低温基质中通过微波光谱、紫外光电子能谱和红外光谱进行了表征。开环异构体二硫乙二醛的稳定性低于1,2-二硫杂环丁烯。[3]

二硫酮可以通过1,3-二硫醇-2-酮的低温光解来制备（作为反式二硫乙二醛）。[4]仅当使用具有极化函数的大基组时，量子化学计算才能重现所观察到的 1,2-二硫醚的更高稳定性。[5]

二硫杂环丁烯S2C2(CO2Me)2的结构。选定的距离和角度：rC=C = 1.362、rC-S = 1.738、rS-S = 2.072 Å、<S-S-C = 78.3°、<S-C-S = 102°.[6]

参见

延伸阅读

  • Diehl, F.; Meyer, H.; Schweig, A.; Hess, B. A.; Fabian, J. 1,2-Dithiete is more stable than 1,2-dithioglyoxal as evidenced by a combined experimental and theoretical IR spectroscopic approach. J. Am. Chem. Soc. September 1989, 111 (19): 7651–7653. doi:10.1021/ja00201a076. 
  • Vijay, D; Priyakumar, UD; Sastry, GN. Basis set and method dependence of the relative energies of C2S2H2 isomers. Chemical Physics Letters. 2004, 383 (1–2): 192–197. Bibcode:2004CPL...383..192V. doi:10.1016/j.cplett.2003.11.021. 
  • Jonas, V; Frenking, G. On the crucial importance of polarization functions for the calculation of molecules with third-row elements: the conformations of chlorocarbonyl isocyanate ClC(O)NCO and the equilibrium of 1,2-dithioglyoxal with its cyclic isomer 1,2-dithiete. Chemical Physics Letters. 1991, 177 (2): 175–183. Bibcode:1991CPL...177..175J. doi:10.1016/0009-2614(91)90064-G. 
  • Gonzalez, L; Mo, O; Yanez, M. High-level ab initio calculations on the 1,2-dithioglyoxal/1,2-dithiete isomerism. Chemical Physics Letters. 13 December 1996, 263 (3): 407–413(7). Bibcode:1996CPL...263..407G. doi:10.1016/S0009-2614(96)01240-7. 

参考资料

  1. ^ Drabowicz, J; Lewkowski, J; Kudelska, W; Zając, A. Four-membered Rings with Two Sulfur Atoms. Comprehensive Heterocyclic Chemistry III 2. 2008: 811–852. ISBN 978-0-08-044992-0. doi:10.1016/B978-008044992-0.00218-2. 
  2. ^ Zoller, U. Four-membered Rings with Two Sulfur Atoms. Comprehensive Heterocyclic Chemistry II 1B. 1996: 1113–1138. ISBN 978-0-08-096518-5. doi:10.1016/B978-008096518-5.00035-6. 
  3. ^ Reinhard Schulz; Armin Schweig; Klaus Hartke; Joachim Koester. Theory and application of photoelectron spectroscopy. 100. Variable-temperature photoelectron spectral study of 1,3-dithiol-2-one and 4,5-disubstituted 1,3-dithiol-2-ones. Thermal generation of 1,2-dithiete, 3,4-disubstituted 1,2-dithietes, and dialkyl tetrathiooxalates. Journal of the American Chemical Society. 1983, 105 (14): 4519–4528. doi:10.1021/ja00352a004. 
  4. ^ Mucha, M; Pagacza, M; Mielke, Z. Infrared detection of dithioglyoxal from photolysis of 1,3-dithiol-2-one in solid argon and nitrogen. Chemical Physics Letters. 6 June 2008, 458 (1–3): 39–43. Bibcode:2008CPL...458...39M. doi:10.1016/j.cplett.2008.04.088. 
  5. ^ Frolov, YV; Vashchenko, AV; Mal'kina, AG; Trofimov, BA. Ab initio quantum-chemical calculations of the energies and structures of 1,2-acetylenedithiol isomers. Journal of Structural Chemistry. 2009, 50 (2): 195–200. S2CID 93780466. doi:10.1007/s10947-009-0029-8. 
  6. ^ T. Shimizu; H. Murakami; Y. Kobayashi; K. Iwata; N. Kamigata. Synthesis, Structure, and Ring Conversion of 1,2-Dithiete and Related Compounds. J. Org. Chem. 1998, 63 (23): 8192–8199. doi:10.1021/jo9806714.