氯代烷烃、硫粉和氢亚磷酸酯一步合成S-烷基硫磷酸酯
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摘要
S-苄基硫磷酸酯和S-烷基硫磷酸酯在农药中有着重要的应用。本文发展了一种无需催化剂,仅在碱作用下,氯代烷烃、硫粉以及氢亚磷酸酯三组份一步生成S-烷基硫磷酸酯的绿色经济方法,该反应可以在一步反应中同时构建磷—硫键和碳—硫键。以苄氯及衍生物、硫粉、氢亚磷酸酯在碳酸铯的促进下,室温反应,共合成了17个S-苄基硫磷酸酯,产率为70%～99%。同时,实现了脂肪链的氯代烃、硫粉和氢亚磷酸酯的反应,在三乙胺的促进下,在空气中60℃反应,共合成了13个S-烷基硫磷酸酯,产率为45%～93%。本方法在合成上和工业上将具有较好的应用前景。
Organophosphorus compounds bearing C-S-P( O) bonds have received increasing attention due to their well-documented biological properties in the fields of pharmaceuticals and agrochemicals. We have developed a novel,simple and efficient carbon( alkyl)-sulfur-phosphorus bond-forming reaction to access S-alkyl phosphorothioates. This transformation would provide a new pathway for the formation of P—S and C—S bonds in one reaction. Altogether,seventeen S-benzyl phosphothioates were prepared in 70% ～ 99%yields by a one-pot CsCO_3-promoted coupling reaction of benzyl chloride, elemental sulfur, and H-phosphonates. Among them, thirteen pharmacologically and synthetically important S-alkyl phosphorothioates were synthesized in 45% ～ 93% yields under air in the presence of triethylamine without any transition metal catalysts. In addition,utilization of common and readily available sulfur powder(S_8) and R_2P(O)H compounds as the components should make this multicomponent reaction much more attractive both fundamentally and synthetically.
Organophosphorus compounds bearing C-S-P( O) bonds have received increasing attention due to their well-documented biological properties in the fields of pharmaceuticals and agrochemicals. We have developed a novel,simple and efficient carbon( alkyl)-sulfur-phosphorus bond-forming reaction to access S-alkyl phosphorothioates. This transformation would provide a new pathway for the formation of P—S and C—S bonds in one reaction. Altogether,seventeen S-benzyl phosphothioates were prepared in 70% ～ 99%yields by a one-pot CsCO_3-promoted coupling reaction of benzyl chloride, elemental sulfur, and H-phosphonates. Among them, thirteen pharmacologically and synthetically important S-alkyl phosphorothioates were synthesized in 45% ～ 93% yields under air in the presence of triethylamine without any transition metal catalysts. In addition,utilization of common and readily available sulfur powder(S_8) and R_2P(O)H compounds as the components should make this multicomponent reaction much more attractive both fundamentally and synthetically.
引文
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[23]Gao Y X,Tang G,Cao Y,et al. A Novel and General Method for the Formation of S-Aryl,Se-aryl,and Te-Aryl Phosphorochalcogenoates[J]. Synthesis,2009,(7):1081-1086.
[24]Zhang L,Zhang P,Li X,et al. Synthesis of S-Arylphosphorothioates by Copper-Ctalyzed Posphorothiolation of Daryliodonium and Aenediazonium Salts[J]. J Org Chem,2016,81(13):5588-5594.
[2]Kasagami T,Miyamoto T,Yamamoto I. Activated Transformations of Organophosphorus Insecticides in the Case of Non-AChE Inhibitory Oxons[J]. Pest Manage Sci,2002,58(11):1107-1117.
[3]MilliganJ F,Uhlenbeck O C. Determination of RNA-Protein Contacts Using Thiophosphate Substitutions[J]. Biochemistry,1989,28(7):2849-2855.
[4]Morrison D C. The Reaction of Sulfenyl Chlorides with Trialkyl Phosphites[J]. J Am Chem Soc,1955,77(1):181-182.
[5]Torii S,Tanaka H,Sayo N. Electrosynthesis of Heteroatom-Heteroatom Bonds. 4. Direct Cross-Coupling of Dialkyl(or Diaryl)Phosphites with Disulfides by a Sodium Bromide Promoted Electrolytic Procedure[J]. J Org Chem,1979,44(16):2938-2941.
[6]Renard P Y,Schwebel H,Vayron P,et al. Easy Access to Phosphonothioates[J]. Chem Eur J,2002,8(13):2910-2916.
[7]Liu Y C,Lee C F. N-Chlorosuccinimide-Promoted Synthesis of Thiophosphates from Thiols and Phosphonates under Mild Conditions[J]. Green Chem,2014,16(1):357-364.
[8]Panmand D S,Tiwari A D,Panda S S,et al. New Benzotriazole-Based Reagents for the Phosphonylation of Various N-,O-,and S-Nucleophiles[J]. Tetrahedron Lett,2014,55(43):5898-5901.
[9]Philippitsch V,Hammerschmidt F. Rearrangement of Lithiated S-Alkyl O,O-Dialkyl Thiophosphates:Scope and Stereochemistry of the Thiophosphate Mercaptophosphonate Rearrangement[J]. Org Biomol Chem,2011,9:5220-5227.
[10]Wang J,Huang X,Ni Z,et al. TBPB-Promoted Metal-Free Synthesis of Thiophosphinate/Phosphonothioate by Direct P—S Bond Coupling[J]. Green Chem,2015,17(1):314-319.
[11]Watanabe Y,Inoue S,Yamamoto T,et al. Phosphorothioate Synthesis Based on the Redox Reaction of Phosphite with Tellurium(Ⅳ)Chloride[J]. Synthesis,1995,(10):1243-1244.
[12]Kaboudin B. A Simple and New Method for the Synthesis of Thiophosphates[J]. Tetrahedron Lett,2002,43(48):8713-8714.
[13]Kaboudin B,Emadi S,Norouzi H. A Convenient Method for the Synthesis of Phosphorothioates and Their Anticholinesterase Activities[J]. Phosphorus Sulfur Silicon Relat Elem,2004,179(3):585-590.
[14]Han X,Wu J. Ga(OTf)3-Catalyzed Direct Substitution of Alcohols with Sulfur Nucleophiles[J]. Org Lett,2010,12(24):5780-5782.
[15]Zhu Y,Chen T,Li S,et al. Efficient Pd-Catalyzed Dehydrogenative Coupling of P(O)H with RSH:A Precise Construction of P(O)—S Bonds[J]. J Am Chem Soc,2016,138(18):5825-5828.
[16]Wang W M,Liu L J,Yao L,et al. Stereospecific Preparations of P-Stereogenic Phosphonothioates and Phosphonoselenoates[J]. J Org Chem,2016,81(15):6843-6847.
[17]Xu J,Zhang L,Li X,et al. Phosphorothiolation of Aryl Boronic Acids Using P(O)H Compounds and Elemental Sulfur[J].Org Lett,2016,18(6):1266-1269.
[18]Zhang X,Shi Z,Shao C,et al. Three-Component Coupling Reaction in Water:A One-Pot Protocol for the Construction of P-S-C(sp3)and P-Se-C(sp3)Bonds[J]. Eur J Org Chem,2017,2017(14):1884-1888.
[19]Zhang P,Ying J,Tang G,et al. Phosphinodifluoroalkylation of Alkynes Using P(O)H Compounds and Ethyl Difluoroiodoacetate[J]. Org Chem Front,2017,4:2054-2057.
[20]Zhang P,Gao Y,Zhang L,et al. Copper-Catalyzed Cycloaddition Between Secondary Phosphine Oxides and Alkynes:Synthesis of Benzophosphole Oxides[J]. Adv Synth Catal,2016,358(1):138-142.
[21]Gao Y,Lu G,Zhang P,et al. A Cascade Phosphinoylation/Cyclization/Desulfonylation Process for the Synthesis of3-Phosphinoylindoles[J]. Org Lett,2016,18(6):1242-1245.
[22]Chen S,Zhang P,Shu W,et al. Cascade Phosphinoylation/Cyclization/Isomerization Process for the Synthesis of2-Phosphinoyl-9-Hpyrrolo[1,2-a]indoles[J]. Org Lett,2016,18(21):5712-5715.
[23]Gao Y X,Tang G,Cao Y,et al. A Novel and General Method for the Formation of S-Aryl,Se-aryl,and Te-Aryl Phosphorochalcogenoates[J]. Synthesis,2009,(7):1081-1086.
[24]Zhang L,Zhang P,Li X,et al. Synthesis of S-Arylphosphorothioates by Copper-Ctalyzed Posphorothiolation of Daryliodonium and Aenediazonium Salts[J]. J Org Chem,2016,81(13):5588-5594.