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CN113603719A - 一种二氟烷基取代硫磷酸酯类化合物及其制备方法 - Google Patents

一种二氟烷基取代硫磷酸酯类化合物及其制备方法 Download PDF

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CN113603719A
CN113603719A CN202110938698.1A CN202110938698A CN113603719A CN 113603719 A CN113603719 A CN 113603719A CN 202110938698 A CN202110938698 A CN 202110938698A CN 113603719 A CN113603719 A CN 113603719A
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张鹏波
张丽
高霞
张丰泉
李文武
曲威龙
喻过
舒志刚
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Xinxiang Medical University
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Abstract

本发明公开了一种二氟烷基取代硫磷酸酯类化合物及其制备方法，其中二氟烷基取代硫磷酸酯类化合物的结构式如下式所示：

Description

一种二氟烷基取代硫磷酸酯类化合物及其制备方法
技术领域
本发明属于有机硫磷酸酯类化合物的合成技术领域，具体涉及一种二氟烷基取代硫磷酸酯类化合物及其制备方法。
背景技术
硫磷酸酯是作为一种具有丰富生物活性的含磷有机化合物，尤其在抗菌、抗肿瘤、抑制胆碱酯酶、杀虫等方面展现了巨大的潜力。不仅如此，硫磷酸酯也可作为反应中间体广泛用于构建碳碳键、碳硫键、碳氟键。另一方面，二氟烷基(CF2R)由于其特殊的物理和化学性质，在药物化学、合成化学等领域有着独特作用。在活性分子中引入二氟烷基通常可通过改变其在体内吸收、代谢和排泄等特性从而改善其生物活性，因此向有机硫磷酸酯分子中引入二氟烷基在新药、农药、有机合成等领域具有广阔的应用前景。然而目前二氟烷基取代硫磷酸酯类化合物的构建方法及其有限。研究并开发以廉价易得的大宗化学品为原料，温和条件下高原子经济性及步骤经济性地构建二氟烷基取代硫磷酸酯类化合物，将极大地推动有机磷硫酸酯化合物及有机氟化合物的合成方法及其生物活性的相关研究。
发明内容
本发明解决的技术问题是构建了一类结构新颖且具有医药应用前景的二氟烷基取代硫磷酸酯类化合物，并提供了一种操作简便、产率较高、成本较低、反应条件温和、原子经济性好、选择性高且适用于工业化生产的二氟烷基取代硫磷酸酯类化合物的制备方法。
本发明为解决上述技术问题采用如下技术方案，一种二氟烷基取代硫磷酸酯类化合物，其特征在于：该二氟烷基取代硫磷酸酯类化合物的结构式如下式(1)所示：
Figure BDA0003214154180000011
其中R为
Figure BDA0003214154180000012
R1为氢、苯基、取代苯基或C1-6烷基；R2为苯基、取代苯基、萘基、吡啶基、
Figure BDA0003214154180000013
Figure BDA0003214154180000021
Figure BDA0003214154180000022
取代苯基苯环上的取代基为C1-6烷基、氟、氯、溴、硝基、甲氧基、三氟甲基、苯基、
Figure BDA0003214154180000023
n为1～20之间的整数，R”为C1-6烷基、氟、氯、溴、硝基、甲氧基、三氟甲基或苯基；R3为氢、甲基或
Figure BDA0003214154180000024
R4为C1-6烷氧基或苯基；R5为C1-6烷氧基或苯基；X为O或S。
本发明所述的二氟烷基取代硫磷酸酯类化合物的制备方法，其特征在于具体步骤为：将烯类化合物1、硫代磷酸二乙酯类化合物2和二氟烷基卤化物3、光催化剂、铜催化剂和碱加入到溶剂中，在惰性气体氛围下于0～40℃在可见光照射下搅拌反应完全后经后处理得到目标产物二氟烷基取代硫磷酸酯类化合物4，制备过程中的反应方程式为：
Figure BDA0003214154180000025
所述光催化剂为(4,4′-二叔丁基-2,2′-联吡啶)双[(2-吡啶基)苯基]铱(III)六氟磷酸盐([Ir(dtbbpy)(ppy)2][PF6])或三(2-苯基吡啶)合铱(Ir(ppy)3)；优选地，光催化剂为(4,4′-二叔丁基-2,2′-联吡啶)双[(2-吡啶基)苯基]铱(III)六氟磷酸盐；
所述铜催化剂为醋酸铜、碘化亚铜、铜粉、溴化亚铜、氯化亚铜、氯化铜、溴化铜、醋酸亚铜或三氟甲磺酸铜；优选地，铜催化剂为醋酸铜或三氟甲磺酸铜；
所述碱为碳酸钾、叔丁醇钠、磷酸钾、叔丁醇钾、三乙胺、二异丙基乙基胺、碳酸钠或碳酸铯；优选地，碱为碳酸钾或叔丁醇钠；
所述溶剂为二氯甲烷、乙醇、乙腈、甲苯、N,N-二甲基甲酰胺、1,4-二氧六环或四氢呋喃中的一种或多种；优选的，溶剂为二氯甲烷或乙醇；
所述可见光为蓝光，采用蓝光LED灯提供可见光，蓝光LED灯的功率为6～40W。
进一步限定，所述光催化剂、铜催化剂、碱、硫代磷酸二乙酯类化合物、二氟烷基卤化物和烯类化合物的投料摩尔比为0.01～0.1:0.1～1:1.5～3:1.5～3:1.5～3:1。
进一步限定，反应过程在惰性气体保护下进行，所述惰性气体为氮气、氩气或氦气。
进一步限定，反应过程的反应时间为4～24h，优选为8～12h。
进一步限定，反应后处理过程为：将反应完成后的反应液用乙酸乙酯萃取，有机相用无水硫酸钠干燥，旋干后过柱分离，其中过柱溶剂为体积比3:1的石油醚与乙酸乙酯的混合溶剂。
本发明具有以下优点和有益效果：本发明提供了一种可见光/铜共催化，以烯类化合物、硫代磷酸二乙酯类化合物和二氟烷基卤化物为原料，室温下高效且高选择性地合成目标产物二氟烷基取代硫磷酸酯类化合物的方法，该制备方法条件温和，原料廉价易得、简单容易操作，底物适用性广且收率较高，适合于工业化生产；本发明制得的目标产物二氟烷基取代硫磷酸酯类化合物在结构上具有较强的创新性，通过在活性分子有机硫磷酸酯分子中引入二氟烷基可通过改变其在体内吸收、代谢和排泄等特性从而改善其生物活性，因此向有机硫磷酸酯分子中引入二氟烷基在新药、农药、有机合成等领域具有广阔的应用前景。
具体实施方式
以下通过实施例对本发明的上述内容做进一步详细说明，但不应该将此理解为本发明上述主题的范围仅限于以下的实施例，凡基于本发明上述内容实现的技术均属于本发明的范围。
实施例1
Figure BDA0003214154180000031
向10mL Schlenk瓶中依次加入(4,4′-二叔丁基-2,2′-联吡啶)双[(2-吡啶基)苯基]铱(III)六氟磷酸盐(2.8mg，0.003mmol)，无水醋酸铜(5.5mg，0.03mmol)和碳酸钾(82.8mg，0.6mmol)，塞上塞子抽换氩气三次。称取4-甲基苯乙烯1a(31.2mg，0.3mmol)、硫代磷酸二乙酯2a(76.5mg，0.45mmol)和二氟溴乙酸乙酯3a(90.9mg，0.45mmol)溶于二氯甲烷溶剂(2.5mL)，随后用注射器将其加入充满氩气的Schlenk瓶中，室温下在12W蓝光照射下反应12h，反应结束后用2x8 mL乙酸乙酯萃取，合并有机相，无水硫酸钠干燥，过滤后旋干，用体积比3:1的石油醚与乙酸乙酯的混合溶剂过柱，得到目标化合物4a。Yield:86.1mg,70％；Colourless liquid；1H NMR(400MHz,CDCl3)δ7.22-7.18(m,2H),7.12-7.08(m,2H),4.49-4.42(m，1H),4.07-3.93(m，5H),3.83-3.73(m，1H),2.96-2.81(m,2H),2.30(s,3H)，1.27-1.23(t，J＝7.2Hz，3H),1.21(t,J＝7.2Hz,3H),1.17(t,J＝7.1Hz,3H).13C NMR(151MHz，CDCl3)δ163.4(t,J＝32.3Hz),138.2，137.4(d,J＝4.3Hz),129.4，127.7，114.4(t,J＝252.6Hz),63.9(d,J＝5.9Hz),63.8(d，J＝5.6Hz)，63.1，43.89-43.8(m),42.5(td，J＝23.7，7.5Hz)，21.22,16.0(d，J＝7.6Hz)，15.9(d，J＝7.6Hz)，13.83.31P NMR(202MHz，CDCl3)δ24.22.19F NMR(471MHz，CDCl3)δ-102.53(d,J＝265.3Hz),-105.33(d,J＝265.3Hz).HRMS:[M+Na]+m/z calcd for C17H25F2NaO5PS+:433.1021，found:433.1028。
实施例2
用三氟甲磺酸铜(10.8mg，0.03mmol)代替无水醋酸铜，其余条件同实施例1，得到目标产物4a的收率为68％。
实施例3
用叔丁醇钠(57.6mg，0.6mmol)代替碳酸钾，其余条件同实施例1，得到目标产物4a的收率为65％。
实施例4
用乙醇代替二氯甲烷，其余条件同实施例1，得到目标产物4a的收率为50％。
实施例5
Figure BDA0003214154180000041
用4-甲氧基苯乙烯1b(40.2mg，0.3mmol)代替4-甲基苯乙烯1a为原料，其余条件同实施例1，得到目标化合物4b。Yield:113.7mg，89％；Colourless liquid；1H NMR(400MHz，CDCl3)δ7.29-7.25(m，2H),6.87-6.83(m，2H),4.53-4.46(m,1H),4.13-3.95(m,5H),3.89-3.80(m,1H),3.79(s,3H)，2.96-2.85(m，2H),1.27(t，J＝7.1Hz,3H),1.24(t，J＝7.1Hz,3H),1.22(t，J＝7.1Hz,3H).13C NMR(151MHz,CDCl3)δ163.4(t，J＝32.3Hz),159.5,132.3(d，J＝4.3Hz),129.1，114.5(t，J＝252.6Hz),114.04，63.8(d，J＝5.9Hz),63.7(d,J＝5.7Hz),63.11,55.4,43.7-43.6(m),42.6(td,J＝23.7,7.6Hz),16.0(d,J＝7.9Hz),15.9(d,J＝7.8Hz),13.8.31P NMR(202MHz,CDCl3)δ24.18.19F NMR(471MHz,CDCl3)δ-102.38(d,J＝265.2Hz),-105.53(d,J＝265.3Hz).HRMS:[M+H]+m/z calcd for C17H26F2O6PS+:427.1150,found:427.1145。
实施例6
Figure BDA0003214154180000051
用4-三氟甲基苯乙烯1c(51.6mg，0.3mmol)代替4-甲基苯乙烯1a为原料，其余条件同实施例1，得到目标化合物4c。Yield:108.6mg,78％；Colourless liquid；1H NMR(400MHz,CDCl3)δ7.59-7.55(m,2H),7.50-7.45(m,2H),4.60-4.53(m,1H),4.09-4.01(m，3H),4.00-3.90(m,2H),3.87-3.76(m,1H),2.95-2.81(m,2H),1.23(t,J＝7.1Hz,3H),1.20(t,J＝7.1Hz,3H),1.16(t,J＝7.1Hz,3H).13C NMR(151MHz,CDCl3)δ163.3(t,J＝32.1Hz),144.9,130.5(q,J＝32.6Hz),128.4,125.7(q,J＝3.6Hz),124.0(q,J＝272.1Hz),114.3(t,J＝252.8Hz),64.1(d,J＝4.9Hz),64.06(d,J＝5.6Hz),63.3,43.43-43.27(m),42.0(td,J＝23.7,8.5Hz),15.9(d,J＝6.4Hz),15.8(d,J＝7.0Hz).13.8.31P NMR(202MHz,CDCl3)δ23.23.19F NMR(471MHz,CDCl3)δ-62.82(s),-103.34(d,J＝266.4Hz),-104.67(d,J＝266.4Hz).HRMS:[M+H]+m/z calcd for C17H23F5O5PS+:465.0918,found:465.0914。
实施例7
Figure BDA0003214154180000052
用3-溴苯乙烯1d(54.6mg，0.3mmol)代替4-甲基苯乙烯1a为原料，其余条件同实施例1，得到目标化合物4d。Yield:108.1mg,76％；Colourless liquid；1H NMR(400MHz,CDCl3)δ7.53-7.51(m,1H),7.44-7.40(m,1H),7.32-7.28(m,1H),7.21(t,J＝7.8Hz,1H),4.51-4.45(m,1H),4.14-3.94(m,5H),3.90-3.79(m,1H),2.99-2.77(m,2H),1.31-1.25(m，6H),1.21(t，J＝7.1Hz，3H).13C NMR(151MHz,CDCl3)δ163.2(t，J＝32.1Hz),142.9(d，J＝3.4Hz),131.4，130.8，130.4，126.7，122.6，114.3(t,J＝252.5Hz),64.2(d，J＝6.1Hz),64.1(d，J＝5.8Hz)，63.4，43.3(dd，J＝8.5，4.0Hz),16.0(d，J＝7.5Hz),15.9(d,J＝7.3Hz)，13.9.31P NMR(202MHz,CDCl3)δ24.80.19F NMR(471MHz,CDCl3)δ-103.26(d,J＝264.3Hz),-104.90(d,J＝264.3Hz).HRMS:[M+H]+m/z calcd for C16H23BrF2O5PS+:475.0150,found:475.0157。
实施例8
Figure BDA0003214154180000053
用2-乙烯基吡啶1e(31.5mg，0.3mmol)代替4-甲基苯乙烯1a为原料，其余条件同实施例1，得到目标化合物4e。Yield:65.5mg,55％；Colourless liquid；1H NMR(400MHz,CDCl3)δ8.56(d,J＝4.5Hz,1H),7.66-7.59(m,1H),7.31(d,J＝7.8Hz，1H),7.18(dd，J＝7.5,4.9Hz,1H),4.68-4.59(m，1H)，4.16-4.04(m,3H),4.03-3.86(m，3H)，3.28-3.14(m,1H),2.95-2.82(m,1H)，1.27-1.20(m，9H).13C NMR(151MHz，CDCl3)δ163.5(t，J＝32.3Hz)，159.1(d,J＝4.1Hz),150.0,137.0，123.2,123.1，114.7(t,J＝252.0Hz),64.0(d，J＝6.0Hz),63.2，44.7(dd，J＝7.4，3.9Hz)，40.8(td，J＝23.3，6.9Hz),16.1(d，J＝3.7Hz)，16.0(d，J＝3.9Hz)，14.0.31P NMR(202MHz,CDCl3)δ24.37.19F NMR(471MHz，CDCl3)δ-103.95(d,J＝263.1Hz),-104.84(d，J＝263.1Hz).HRMS:[M+H]+m/z calcd for C15H23F2NO5PS+:398.0997,found:398.0996。
实施例9
Figure BDA0003214154180000061
用α-甲基苯乙烯1f(35.4mg，0.3mmol)代替4-甲基苯乙烯1a为原料，其余条件同实施例1，得到目标化合物4f。Yield:97.2mg,79％；Colourless liquid；1H NMR(400MHz,CDCl3)δ7.57-7.53(m,2H),7.38-7.32(m，2H),7.29-7.25(m,1H),4.14-3.75(m，6H),3.36-3.28(m,2H),2.22(s,3H),1.27(t,J＝7.1Hz,3H),1.24(t,J＝7.1Hz,3H),1.19(t,J＝7.1Hz,3H).13C NMR(151MHz,CDCl3)δ163.6(t,J＝32.2Hz),142.0(d,J＝7.8Hz),128.3,128.0,127.1,114.8(dd,J＝255.0,251.1Hz),63.9(d,J＝6.3Hz),62.95,53.9-53.8(m),46.7(td,J＝24.0,5.2Hz),26.7,16.1(d,J＝6.1Hz),16.0(d,J＝7.1Hz),13.7.31P NMR(202MHz,CDCl3)δ21.81.19F NMR(471MHz,CDCl3)δ-96.46(d,J＝262.3Hz),-102.29(d,J＝262.3Hz).HRMS:[M+H]+m/z calcd for C17H26F2O5PS+:411.1201,found:411.1209。
实施例10
Figure BDA0003214154180000062
用β-甲基苯乙烯1g(35.4mg，0.3mmol)代替4-甲基苯乙烯1a为原料，其余条件同实施例1，得到目标化合物4g(dr＝3:1)。Yield:70.1mg,57％；Colourless liquid；1H NMR(400MHz,CDCl3)δ7.42-7.39(m,2H),7.34-7.30(m,2H),7.28-7.24(m,1H),4.55(dd,J＝13.1,6.2Hz,1H),4.14-4.07(m,2H),4.04-3.85(m,3H),3.69-3.59(m,1H),2.89-2.78(m,1H),1.35-1.26(m,6H),1.21(t,J＝7.1Hz,3H),1.06(t,J＝7.1Hz,3H).13C NMR(151MHz,CDCl3)δ163.6(t,J＝32.5Hz),141.2,128.9,128.7,128.4,127.9,116.3(t,J＝253.8Hz),63.6(d,J＝5.4Hz),63.1,50.3-50.2(m),44.4(td,J＝21.6,8.9Hz),15.9(d,J＝7.7Hz),15.7(d,J＝7.8Hz),14.0,10.6-10.4(m).31P NMR(202MHz,CDCl3)δ25.08.19F NMR(471MHz,CDCl3)δ-107.38(d,J＝262.3Hz),-111.37(d,J＝262.3Hz).HRMS:[M+H]+m/z calcd forC17H26F2O5PS+:411.1201,found:411.1207。
实施例11
Figure BDA0003214154180000071
用肉桂酸乙酯1h(52.8mg，0.3mmol)代替4-甲基苯乙烯1a为原料，其余条件同实施例1，得到目标化合物4h(dr＝10:1)。Yield:40.7mg,29％；Colourless liquid；1H NMR(400MHz,CDCl3)δ7.45-7.41(m,2H),7.34-7.27(m,3H),4.76(dd,J＝12.2,11.1Hz,1H),4.36-4.25(m,2H),4.04-3.77(m,6H),3.48-3.37(m,1H),1.36(t,J＝7.1Hz,3H),1.28(td,J＝7.1，0.8Hz,3H),1.18(t,J＝7.2Hz，3H),1.00(td,J＝7.1,0.6Hz,3H).13C NMR(151MHz，CDCl3)δ166.8(dd,J＝2.7,1.4Hz),162.0(t,J＝31.3Hz),138.5,129.4,128.6,128.5,113.3(dd,J＝262.5,253.0Hz),63.8(d,J＝5.1Hz),63.5(d,J＝5.0Hz),63.4,62.4,56.2(td,J＝21.8,11.0Hz),47.3-47.1(m),16.0(d,J＝7.9Hz),15.7(d,J＝7.9Hz),14.2,13.8.31P NMR(202MHz，CDCl3)δ23.31.19F NMR(471MHz,CDCl3)δ-101.25(d,J＝273.2Hz),-111.81(d,J＝273.3Hz).HRMS:[M+H]+m/z calcd for C19H28F2O7PS2 +:469.1256,found:469.1260。
实施例12
Figure BDA0003214154180000072
用己烯1i(25.2mg，0.3mmol)代替4-甲基苯乙烯1a为原料，其余条件同实施例1，得到目标化合物4i。Yield:84.6mg,75％；Colourless liquid；1H NMR(400MHz,CDCl3)δ4.33-4.27(m,2H),4.19-4.05(m,4H),3.49-3.38(m,1H),2.70-2.53(m,1H),2.52-2.34(m,1H),1.85-1.65(m,2H),1.48-1.37(m,2H)，1.35-1.28(m,11H)，0.90-0.85(m,3H).13C NMR(151MHz,CDCl3)δ163.9(d,J＝32.4Hz),115.2(t,J＝252.0Hz),64.1(d,J＝6.4Hz),64.0(d,J＝6.4Hz),63.3,41.2(dd,J＝7.4,3.9Hz),40.8(qd,J＝22.5,4.2Hz),36.1(d,J＝5.3Hz),28.6,22.4,16.2(dd,J＝7.4,0.8Hz),14.1.31P NMR(202MHz,CDCl3)δ25.83.9F NMR(471MHz,CDCl3)δ-102.50(d,J＝262.1Hz),-105.71(d,J＝262.1Hz).HRMS:[M+H]+m/zcalcd for C14H28F2O5PS+:377.1358,found:377.1349。
实施例13
Figure BDA0003214154180000081
用化合物1j(72.0mg，0.3mmol)代替4-甲基苯乙烯1a为原料，其余条件同实施例1，得到目标化合物4j。Yield:114.9mg,72％；Colourless liquid；1H NMR(400MHz,CDCl3)δ7.75(d,J＝7.9Hz,2H),7.32(d,J＝8.0Hz,2H),4.40-4.24(m,4H),4.14-4.00(m,4H),2.80-.65(m,2H),2.41(s,3H),2.35-2.22(m,2H),1.56(s,3H),1.33-1.27(m,9H).13C NMR(101MHz,CDCl3)δ163.83(t,J＝32.3Hz),145.1,132.9,130.0,128.0,115.4(t,J＝253.5Hz),67.2,64.3(d,J＝1.3Hz),64.2(d,J＝1.3Hz),63.4,51.9(d,J＝4.2Hz),45.1(td,J＝21.8,3.7Hz),40.1-39.9(m),27.8(d,J＝8.2Hz),21.7,16.1(d,J＝1.0Hz),16.0(d,J＝1.3Hz),13.9.31P NMR(202MHz,CDCl3)δ22.0.19F NMR(376MHz,CDCl3)δ-101.09(d,J＝261.5Hz),-102.16(d,J＝261.5Hz)。HRMS:[M+H]+m/z calcd for C20H32F2O8PS2+:533.1239,found:533.1235。
实施例14
Figure BDA0003214154180000082
用化合物1k(52.5mg，0.3mmol)代替4-甲基苯乙烯1a为原料，其余条件同实施例1，得到目标化合物4k。Yield:84.1mg,60％；Colourless liquid；1H NMR(400MHz,CDCl3)δ7.26-7.14(m,5H),6.73(s,1H),4.38-4.30(m,2H),4.24(q,J＝7.1Hz,2H),4.05-3.91(m,4H),3.82-3.69(m,1H),2.75-2.60(m,4H),1.31-1.19(m,9H).13C NMR(151MHz,CDCl3)δ169.5,163.7(t,J＝32.3Hz),138.3,128.7,128.0,127.5,115.0(t,J＝252.1Hz),64.4(d,J＝6.7Hz),64.3(d,J＝6.7Hz),63.4,43.6,42.6,40.1(td,J＝23.0,5.4Hz),37.1-36.9(m),16.1(d,J＝7.2Hz),14.0.31P NMR(202MHz,CDCl3)δ24.84.19F NMR(471MHz,CDCl3)δ-103.26(d,J＝262.8Hz),-105.52(d,J＝262.8Hz).HRMS:[M+H]+m/z calcd for C19H29F2NO6PS+:468.1416,found:468.1422。
实施例15
Figure BDA0003214154180000083
用化合物1l(40.2mg，0.3mmol)代替4-甲基苯乙烯1a为原料，其余条件同实施例1，得到目标化合物4l。Yield:71.6mg,56％；Colourless liquid；1H NMR(400MHz,CDCl3)δ7.32-7.26(m,2H),7.00-6.95(m,1H),6.94-6.91(m,2H),4.34-4.25(m,3H),4.24-4.10(m,5H),3.88-3.77(m,1H),2.9-2.78(m,1H),2.70-2.55(m,1H),1.37-1.31(m,9H).13C NMR(151MHz,CDCl3)δ163.7(t,J＝32.4Hz),158.2,129.8,121.7,115.1(t,J＝252.0Hz),114.8,70.3(d,J＝2.7Hz),64.3(d,J＝6.4Hz),63.4,39.3(q,J＝3.6Hz),37.6(td,J＝23.6,6.8Hz),16.2(d,J＝2.8Hz),16.1(d,J＝2.7Hz),14.1.31P NMR(202MHz,CDCl3)δ23.30.19F NMR(376MHz,CDCl3)δ-102.94(d,J＝266.2Hz),-104.95(d,J＝266.2Hz).HRMS:[M+H]+m/z calcd for C17H26F2O6PS+:427.1150,found:427.1155。
实施例16
Figure BDA0003214154180000091
用化合物1m(45.0mg，0.3mmol)代替4-甲基苯乙烯1a为原料，其余条件同实施例1，得到目标化合物4m(dr＝1:1)。Yield:88.8mg,67％；Colourless liquid；1H NMR(400MHz,CDCl3)δ6.73-6.69(m,1H),4.30-4.24(m,2H),4.17-4.04(m,4H),3.09-2.93(m,1H),2.82-2.49(m,4H),2.44-2.27(m,2H),1.73(s,3H),1.69(s,3H),1.34-1.26(m,9H).13C NMR(151MHz,CDCl3)δ198.9,198.5,163.9(t,J＝32.9Hz),144.32,144.30,135.53,135.50,115.5(t,J＝252.1Hz),115.6(t,J＝252.1Hz),64.40(d,J＝7.0Hz),64.36(d,J＝2.9Hz),64.32(d,J＝3.8Hz),64.30(d,J＝3.6Hz),63.4,56.6(d,J＝4.3Hz),56.5(d,J＝4.4Hz),44.5(d,J＝5.8Hz),44.2(d,J＝7.5Hz),42.3-41.8(m),40.0,39.9,28.0,27.96,26.0-25.9(m),25.9-25.7(m),16.2(d,J＝2.0Hz),16.12(d,J＝2.1Hz),16.09(d,J＝3.0Hz),16.07(d,J＝4.2Hz),15.6,14.0.31P NMR(202MHz,CDCl3)δ22.66,22.56.19F NMR(471MHz,CDCl3)δ-100.49(d,J＝260.6Hz),-102.51(d,J＝260.9Hz),-103.22(d,J＝260.2Hz).HRMS:[M+H]+m/z calcd for C18H30F2O6PS+:443.1463,found:443.1458。
实施例17
Figure BDA0003214154180000092
用化合物1n(118.2mg，0.3mmol)代替4-甲基苯乙烯1a为原料，其余条件同实施例1，得到目标化合物4n。Yield:135.8mg,66％；Colourless liquid；1H NMR(400MHz,CDCl3)δ9.19(s,1H),7.61-7.59(m,2H),7.55-7.46(m,4H),7.38-7.25(m,6H),7.21(d,J＝7.8Hz,2H),4.55-4.40(m,1H),4.08-3.93(m,4H),3.86-3.76(m,1H),3.23(t,J＝6.73Hz,2H),2.97-2.76(m,4H),1.23-1.12(m,9H).13C NMR(151MHz,CDCl3)δ170.1,163.3(t,J＝32.4Hz),162.6,145.7,138.5,135.6(d,J＝3.3Hz),134.9,132.3,128.8(2C,overlap),128.7(2C,overlap),128.4,128.3,128.0,126.5,119.8,114.4(t,J＝252.1Hz),64.0(d,J＝6.1Hz),63.9(d,J＝5.8Hz),63.2,43.7,42.4(td,J＝23.6,7.4Hz),33.9,24.0,15.9(d,J＝5.4Hz),15.9(d,J＝5.1Hz),13.8.31P NMR(202MHz,CDCl3)δ23.87.19F NMR(471MHz,CDCl3)δ-102.71(d,J＝265.3Hz),-105.17(d,J＝265.3Hz).HRMS:[M+Na]+m/z calcd forC34H37F2N2NaO7PS+:709.1919,found:709.1924。
实施例18
Figure BDA0003214154180000101
用化合物1o(118.2mg，0.3mmol)代替4-甲基苯乙烯1a为原料，其余条件同实施例1，得到目标化合物4o(dr＝1:1)。Yield:86.4mg,42％；Colourless liquid；1H NMR(600MHz,CDCl3)δ7.79(dd,J＝8.6,3.0Hz,1H),6.70(d,J＝3.1Hz,1H),6.47-6.39(m,2H),5.29-5.16(m,1H),4.93-4.91(m,1H),4.60–4.56(m,1H),4.32-4.25(m,2H),4.19-4.06(m,5H),3.81(d,J＝3.9Hz,1H),3.76(s,3H),3.71(s,3H),3.33-3.21(m,2H),3.10-2.82(m,2H),1.34-1.28(m,9H).13C NMR(151MHz,CDCl3)δ189.07,189.06,166.8,166.7,163.89(t,J＝32.2Hz),163.86(t,J＝32.2Hz),157.84,157.82,149.6,147.5,143.9,130.1,115.6(t,J＝252.1Hz),115.5(t,J＝252.1Hz),113.7,112.79,112.76,110.45,110.42,104.9,104.77,104.73,104.71,101.0,89.3(d,J＝5.5Hz),89.1(d,J＝4.5Hz),72.37,72.35,66.3,64.5(d,J＝7.1Hz),64.4(d,J＝7.5Hz),64.37(d,J＝4.8Hz),64.32(d,J＝4.5Hz),63.4,63.3,56.4,55.9,44.6,41.5(t,J＝22.1Hz),40.8(t,J＝24.2Hz),29.0,28.4,23.3,21.0,16.2(d,J＝2.6Hz),16.1(d,J＝2.6Hz),16.06(d,J＝2.2Hz),16.02(d,J＝2.3Hz),14.0(d,J＝1.6Hz).31P NMR(202MHz,CDCl3)δ22.48,22.01.19F NMR(471MHz,CDCl3)δ-100.04(d,J＝263.6Hz),-100.05(d,J＝263.6Hz),-101.00(d,J＝263.6Hz),-101.46(d,J＝262.9Hz).HRMS:[M+H]+m/z calcd for C31H38F2O11PS+:687.1835,found:687.1844。
实施例19
Figure BDA0003214154180000102
用化合物1p(74.1mg，0.3mmol)代替4-甲基苯乙烯1a为原料，，其余条件同实施例1，得到目标化合物3n(dr＝1:1)。Yield:77.6mg,48％；Colourless liquid；1H NMR(400MHz,CDCl3)δ7.31-7.21(m,3H),7.16-7.11(m,2H),6.48(s,1H),4.86(dd,J＝13.2,6.5Hz,1H),4.33(q,J＝7.1Hz,2H),4.22-4.08(m,4H),3.84-3.74(m,1H),3.71(s,3H),3.19-3.03(m,2H),2.87-2.63(m,4H),1.38-1.32(m,9H).13C NMR(151MHz,CDCl3)δ171.9,169.1(d,J＝10.6Hz),163.6(t,J＝32.3Hz),136.0(d,J＝3.0Hz),129.3(d,J＝2.3Hz),128.7,127.2,115.0(t,J＝252.0Hz),64.3(d,J＝6.7Hz),64.24(d,J＝6.0Hz),64.20(d,J＝6.2Hz),63.3,53.4,52.4,42.5-42.3(m),39.8(tt,J＝22.8,4.7Hz),38.0(d,J＝6.0Hz),36.6-36.5(m),16.1(d,J＝7.3Hz),14.0.31P NMR(202MHz,CDCl3)δ24.88.19F NMR(471MHz,CDCl3)δ-102.73(d,J＝100.1Hz),-103.29(d,J＝100.0Hz),-105.34(d,J＝71.3Hz),-105.90(d,J＝71.3Hz).HRMS:[M+H]+m/z calcd for C22H33F2NO8PS+:540.1627,found:540.1634。
实施例20
Figure BDA0003214154180000111
用硫代磷酸二异丙酯2b(89.1mg，0.45mmol)代替硫代磷酸二乙酯2a为原料，其余条件同实施例1，得到目标化合物4q。Yield:114.5mg,90％；Colourless liquid；1H NMR(400MHz,CDCl3)δ7.36-7.29(m,4H),7.28-7.24(m,1H),4.71-4.63(m,1H),4.60-4.48(m,2H),4.00-3.92(m,2H),1.32(d,J＝6.2Hz,3H),1.25-1.19(m,12H).13C NMR(151MHz,CDCl3)δ163.4(t,J＝32.3Hz),140.3(d,J＝5.1Hz),128.8,128.3,128.0,114.5(dd,J＝253.3,250.8Hz),73.24(d,J＝6.4Hz),73.18(d,J＝6.8Hz),63.0,44.2-44.1(m),42.5(td,J＝23.6,6.7Hz),23.9(d,J＝3.9Hz),23.8(d,J＝4.1Hz),23.6(d,J＝5.7Hz),23.5(d,J＝5.7Hz),13.8.31P NMR(202MHz,CDCl3)δ21.61.19F NMR(471MHz,CDCl3)δ-101.82(d,J＝265.0Hz),-105.74(d,J＝265.0Hz).HRMS:[M+Na]+m/z calcd for C18H27F2NaO5PS2 +:447.1177,found:447.1173。
实施例21
Figure BDA0003214154180000112
用硫代磷酸二丁酯2c(101.7mg，0.45mmol)代替硫代磷酸二乙酯2a为原料，其余条件同实施例1，得到目标化合物4r。Yield:120.7mg,89％；Colourless liquid；1H NMR(400MHz,CDCl3)δ7.37-7.24(m,5H),4.57-4.47(m,1H),4.04-3.83(m,5H),3.78-3.70(m,1H),2.99-2.82(m,2H),1.61-1.46(m,4H),1.38-1.28(m,4H),1.27-1.19(m,3H),0.92-0.85(m,6H).13C NMR(151MHz,CDCl3)δ163.3(t,J＝32.2Hz),140.5(d,J＝3.8Hz),114.4(t,J＝253.8Hz),128.7,128.2,127.9,67.44(d,J＝6.2Hz),67.40(d,J＝5.1Hz),44.0-43.9(m),42.4(td,J＝23.8,7.8Hz),32.0(t,J＝7.5Hz),18.7(d,J＝1.5Hz),13.8,13.6.31P NMR(202MHz,CDCl3)δ24.07.19F NMR(471MHz,CDCl3)δ-102.34(d,J＝265.6Hz),-105.38(d,J＝265.6Hz).HRMS:[M+H]+m/z calcd for C20H32F2O5PS+:453.1671,found:453.1681。
实施例22
Figure BDA0003214154180000121
用二硫代磷酸二乙酯2d(83.3mg，0.45mmol)代替硫代磷酸二乙酯2a为原料，其余条件同实施例1，得到目标化合物4s。Yield:100.4mg,81％；Colourless liquid；1H NMR(400MHz,CDCl3)δ7.35-7.24(m,5H),4.57-4.47(m,1H),4.15-3.94(m,5H),3.78-3.68(m,1H),2.93-2.83(m,2H),1.28(t,J＝7.1Hz,3H),1.24(t,J＝7.2Hz,3H),1.16(t,J＝7.1Hz,3H).13C NMR(151MHz,CDCl3)δ163.4(t,J＝32.2Hz),140.4(d,J＝4.0Hz),128.8,128.3,128.0,114.5(t,J＝252.0Hz),64.3(d,J＝5.9Hz),64.1(d,J＝5.5Hz),63.2,46.5-46.3(m),42.4(td,J＝23.6,6.8Hz),15.8(d,J＝8.7Hz),15.7(d,J＝8.8Hz),13.9.31P NMR(202MHz,CDCl3)δ89.62.19F NMR(471MHz,CDCl3)δ-102.34(d,J＝264.9Hz),-105.13(d,J＝264.9Hz).HRMS:[M+Na]+m/z calcd for C16H23F2NaO4PS2 +:435.0636,found:435.0640。
实施例23
Figure BDA0003214154180000122
用二氟溴乙酰苯胺3b(112.1mg，0.45mmol)代替硫代磷酸二乙酯2a为原料，其余条件同实施例1，得到目标化合物4t。Yield:79.7mg,60％；Colourless liquid；1H NMR(400MHz,CDCl3)δ8.44(s,1H),7.52-7.48(m,2H),7.37-7.25(m,6H),7.22-7.12(m,2H),4.64-4.57(m,1H),4.03-3.93(m,1H),3.9-3.84(m,2H),3.82-3.71(m,1H),3.13-2.90(m,2H).1.15(t,J＝7.1Hz,3H),1.13(t,J＝7.2Hz,3H).13C NMR(151MHz,CDCl3)δ161.5(t,J＝28.1Hz),141.0(d,J＝3.6Hz),136.3,129.1,128.8,127.6,125.5,120.5,116.5(t,J＝255.8Hz),63.94(d,J＝2.5Hz),63.90(d,J＝2.0Hz),44.0(dd,J＝7.4,4.2Hz),41.6(td,J＝23.7,8.1Hz),15.9(d,J＝8.0Hz),15.8(d,J＝8.0Hz).31P NMR(202MHz,CDCl3)δ24.20.19FNMR(471MHz,CDCl3)δ-102.80(d,J＝258.1Hz),-103.82(d,J＝258.2Hz).HRMS:[M+Na]+m/zcalcd for C20H24F2NNaO4PS+:466.1024,found:466.1018。
以上实施例描述了本发明的基本原理、主要特征及优点，本行业的技术人员应该了解，本发明不受上述实施例的限制，上述实施例和说明书中描述的只是说明本发明的原理，在不脱离本发明原理的范围下，本发明还会有各种变化和改进，这些变化和改进均落入本发明保护的范围内。

Claims (6)

1.一种二氟烷基取代硫磷酸酯类化合物，其特征在于：该二氟烷基取代硫磷酸酯类化合物的结构式如下式(1)所示：
Figure FDA0003214154170000011
其中R为
Figure FDA0003214154170000012
R1为氢、苯基、取代苯基或C1-6烷基；R2为苯基、取代苯基、萘基、吡啶基、
Figure FDA0003214154170000013
Figure FDA0003214154170000014
Figure FDA0003214154170000015
取代苯基苯环上的取代基为C1-6烷基、氟、氯、溴、硝基、甲氧基、三氟甲基、苯基、
Figure FDA0003214154170000016
n为1～20之间的整数，R”为C1-6烷基、氟、氯、溴、硝基、甲氧基、三氟甲基或苯基；R3为氢、甲基或
Figure FDA0003214154170000017
R4为C1-6烷氧基或苯基；R5为C1-6烷氧基或苯基；X为O或S。
2.一种权利要求1所述的二氟烷基取代硫磷酸酯类化合物的制备方法，其特征在于具体步骤为：将烯类化合物1、硫代磷酸二乙酯类化合物2和二氟烷基卤化物3、光催化剂、铜催化剂和碱加入到溶剂中，在惰性气体氛围下于0～40℃在可见光照射下搅拌反应完全后经后处理得到目标产物二氟烷基取代硫磷酸酯类化合物4，制备过程中的反应方程式为：
Figure FDA0003214154170000021
所述光催化剂为(4,4'-二叔丁基-2,2'-联吡啶)双[(2-吡啶基)苯基]铱(III)六氟磷酸盐([Ir(dtbbpy)(ppy)2][PF6])或三(2-苯基吡啶)合铱(Ir(ppy)3)；
所述铜催化剂为醋酸铜、碘化亚铜、铜粉、溴化亚铜、氯化亚铜、氯化铜、溴化铜、醋酸亚铜或三氟甲磺酸铜；
所述碱为碳酸钾、叔丁醇钠、磷酸钾、叔丁醇钾、三乙胺、二异丙基乙基胺、碳酸钠或碳酸铯；
所述溶剂为二氯甲烷、乙醇、乙腈、甲苯、N,N-二甲基甲酰胺、1,4-二氧六环或四氢呋喃中的一种或多种；
所述可见光为蓝光，采用蓝光LED灯提供可见光，蓝光LED灯的功率为6～40W。
3.根据权利要求2所述的权利要求1所述的二氟烷基取代硫磷酸酯类化合物的制备方法，其特征在于：所述光催化剂、铜催化剂、碱、硫代磷酸二乙酯类化合物、二氟烷基卤化物和烯类化合物的投料摩尔比为0.01～0.1:0.1～1:1.5～3:1.5～3:1.5～3:1。
4.根据权利要求2所述的权利要求1所述的二氟烷基取代硫磷酸酯类化合物的制备方法，其特征在于：反应过程在惰性气体保护下进行，所述惰性气体为氮气、氩气或氦气。
5.根据权利要求2所述的权利要求1所述的二氟烷基取代硫磷酸酯类化合物的制备方法，其特征在于：反应过程的反应时间为4～24h，优选为8～12h。
6.根据权利要求2所述的权利要求1所述的二氟烷基取代硫磷酸酯类化合物的制备方法，其特征在于反应后处理过程为：将反应完成后的反应液用乙酸乙酯萃取，有机相用无水硫酸钠干燥，旋干后过柱分离，其中过柱溶剂为体积比3:1的石油醚与乙酸乙酯的混合溶剂。
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