微波辐射无溶剂羰基化合物的硫代反应

doi:10.3724/SP.J.1095.2013.20584

摘要/Abstract

摘要： 以7个羰基化合物和五硫化二磷为原料，通过辐射下的微波、无溶剂的硫代反应，合成了7种硫羰基化合物，收率76%~93%。最佳反应条件为：羰基化合物与P2S5的摩尔比为4∶1，反应温度100 ℃，反应时间15~20 min。合成化合物的结构经1H NMR和13C NMR表征。

关键词: 微波, 无溶剂, 硫羰基化反应, 五硫化二磷

Abstract: Seven carbonyl compounds were thionated with phosphorus pentasulfide promoted by microwave irradiation under solvent-free conditions. The thiocarbonyl compounds were synthesized in 76%~93% yields. The optimized reaction conditions: the molar ratio of substrates and P2S5 is 4∶1, temperature is 100 ℃ and time is 15~20 min. The structures of products were characterized by 1H NMR and 13C NMR.

Key words: microwave-irradiation, solvent-free, thiocarbonyl reaction, phosphorus pentasulfide

中图分类号:

O622.1

杨秀琴, 付长亮. 微波辐射无溶剂羰基化合物的硫代反应[J]. 应用化学, DOI: 10.3724/SP.J.1095.2013.20584.

YANG Xiuqin*, FU Changliang. Solvent-free Thionation of Carbonyl Compounds with P2S5 under Microwave Irradiation[J]. Chinese Journal of Applied Chemistry, DOI: 10.3724/SP.J.1095.2013.20584.

参考文献

[1] MA Xiaoli,WU Minyuan,HU Yamei,et al. Relationships Between Thiopurine Methyltransferase Gene Polymorphisms and Its Enrymatic Activity[J]. Chinese J Oncol,2006,28](6):456-459(in Chinese).

马晓莉，吴敏媛，胡亚美，等. 巯嘌呤甲基转移酶基因多态性位点与酶活性的关系[J]. 中华肿瘤杂志，2006,28](6):456-459.

[2] Yuan B F,Connor T R,Wang Y S. 6-Thioguanine and S(6)-Methylthioguanine are Mutagenic in Human Cells[J]. ACS Chem Biol,2010,5](11):1021-1027.

[3] Prokopcova H,Kappe C O. Palladium(0)-Catalyzed, Copper(Ⅰ)-Mediated Coupling of Boronic Acids with Cyclic Thioamides:Selective Carbon-Carbon Bond Formation for the Functionalization of Heterocycles[J]. J Org Chem,2007,72](12):4440-4448.

[4] Schmidt R R,Heermann D. Glycosylhydrazine, 4.1H-1,2,4-Triazol-nucleoside-Synthese von Virazol[J]. Chem Ber,1981,114](8):2825-2833.

[5] Pathak A K,Pathak V L,Seitz E,et al. Antimycobacterial Agents:1.Thio Analogues of Purine[J]. J Med Chem,2004,47](1):273-276.

[6] GU Lixin,WANG Wei,JIANG Dingqiang,et al. Improved Method for the Synthesis of （3aS,6aR）-1,3-dipenzyl-hexahydro 1H-Thienoimidazole-2,4-dione[J]. Chem Res Appl,2007,19](9):1056-1058(in Chinese).

顾立新，王伟，蒋定强，等. （3aS,6aR）-1,3-二苄基-六氢-1H-噻吩并[3,4-d]咪唑-2,4-二酮制备方法的改进[J]. 化学研究与应用，2007,19](9):1056-1058.

[7] Kikugawa K,Suehiro H,Ichino M. Platelet Aggregation Inhibitors:6.2-Thioadenosine Derivatives[J]. J Med Chem,1973,16](12):1381-1388.

[8] Ikehara M. Acc. Purine 8-Cyclonucleosides[J]. Chem Res,1969,2](2):47-53.

[9] Firouzabadi H,Iranpoor N,Abbasi M. Pronounced Catalytic Effect of a Micellar Solution of Sodium Dodecyl Sulfate(SDS) on the Efficient C—S Bond Formation via an Odorless Thia-Michael Addition Reaction Through the in situ Generation of S-Alkylisothiouronium Salts[J]. Adv Synth Catal,2009,351](5):755-766.

[10] Ding Q P,Huang X G,Wu J. Diaryl Ether and Diaryl Thioether Syntheses on Solid Supports via Copper (Ⅰ)-Mediated Coupling[J]. J Comb Chem,2009,11](6):47-71.

[11] JIN Qinhan. Microwave Chemistry[M]. Beijing:Science Press，1999:215-221(in Chinese).

金钦汉. 微波化学[M]. 北京：科学出版社，1999:215-221.

[12] Klingsberg E,Papa D. Thiation with Phosphorus Pentasulfide in Pyridine Solution[J]. J Am Chem Soc,1951,73](10):4988-4989.

[13] LI Jianping， ZHANG Liping， XUE Zaikun,et al. Synthesis of Symmetrical Dithiocarbohydrazide by Microwave Irradiation under Solvent-free Condition[J]. Chinese J Synth Chem,2011,9](2):264-266(in Chinese).

李建平，张丽平，薛载坤，等. 微波促进对称二氨基硫脲衍生物的无溶剂合成[J]. 合成化学,2011,9](2):264-266.

[14] XU Jiaxi. Microwave Irradiation and Selectivities in Organic Reactions[J]. Prog Chem,2007,19](5)：700-712(in Chinese).

许家喜. 微波与有机化学反应的选择性[J]. 化学进展，2007,19](5)：700-712.

[15] Ozturk T,Ertas E,Mert O. Use of Lawesson′s Reagent in Organic Syntheses[J]. Chem Rev,2007,107](11):5210-5278.

[16] Curphey T J. Thionation with the Reagent Combination of Phosphorus Pentasulfide and Hexamethyldisiloxane[J]. J Org Chem,2002,67](18):6461-6473.

[17] TAO Zi. Thioacetamide[J]. Shanghai Chem Ind,1985,4]:57-59(in Chinese).

陶子. 硫代乙酰胺[J]. 上海化工，1985,4]:57-59.

[18] Gertrude B Elion,Elizabeth Burgi,George H. Studies on Condensed Pyrimidine Systems:IX.The Synthesis of Some 6-Substituted Purines[J]. J Am Chem Soc,1952,74](2):411-414.

[19] Kaneko K,Katayama H,Wakabayashi T,et al. Pyrimidine Derivatives:1.The Highly Regioselective 4-Thionation of Pyrimidine-2,4(1H,3H)-dione Derivatives with Lawesson Reagent[J]. Synthesis,1988,2]:152-154.

[20] Lapucha A R. A Rapid and Efficient Synthesis of Sulfur Analogues of Pyrimidine Bases[J]. Synthesis,1987,3]:256-258.