一种砜基取代的硫代磷酸酯类化合物的制备方法

1.本发明属于有机合成技术领域，具体涉及一种砜基取代的硫代磷酸酯类化合物的制备方法。


背景技术：

2.含有p-s-c键的硫代磷酸酯由于其独特的生物活性及丰富的反应活性在农药化学、医药及有机合成等领域都有很重要的应用。另一方面，基于砜基的特殊性质，含砜基的有机分子在药物化学、农业、有机合成、材料等领域有着非常广泛的应用。而含砜基的硫代磷酸酯兼具有机磷和有机砜的性质更是具有显著的生物活性，如甲拌磷砜、乙拌磷砜、卡波硫磷砜等一系列包含砜基的硫代磷酸酯类化合物在杀虫除草方面展现了巨大的潜力。然而目前该类化合物的合成方法非常有限，传统的合成方法通常需要先制备出烷基硫取代的硫代磷酸酯，再进一步氧化为含砜基的硫代磷酸酯，具有原料不易得、底物兼容性不好、反应条件苛刻、操作繁琐、不利于大规模的工业生产应用等诸多问题。


技术实现要素：

3.本发明为了克服现有技术中砜基取代的硫代磷酸酯类化合物合成条件苛刻、反应步骤长、原子经济性低、不利于大规模的工业生产等不足，而提供了一种砜基取代的硫代磷酸酯类化合物的高效制备方法，该方法利用磺酰氯为磺酰化试剂，硫代磷酸二烷基酯为硫磷酯化试剂，通过对烯烃的双官能化一步合成含砜基的硫代磷酸酯类化合物。
4.本发明为解决上述技术问题采用如下技术方案，一种砜基取代的硫代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2、硫代磷酸二烷基酯类化合物3、磺酰氯类化合物1、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，反应完全后经后处理得到目标产物砜基取代的硫代磷酸酯类化合物4，制备过程中的反应方程式为：
[0005][0006]
其中r为苯基、取代苯基、萘基、
取代苯基苯环上的取代基为c
1-6
烷基、氟、氯、溴、硝基、甲氧基、三氟甲氧基；r1为苯基、取代苯基、吡啶基，取代苯基苯环上的取代基为c
1-6
烷基、氟、氯、溴、硝基、甲氧基、三氟甲基、苯基、三氟甲氧基、r2为氢、苯基或c
1-6
烷基；r3为氢或甲基；r4为c
1-6
烷氧基或苯基；
[0007]
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])、三(2-苯基吡啶)合铱(ir(ppy)3)、三(2,2'-联吡啶)二氯化钌、2,4,5,6-四(9-咔唑基)-间苯二腈(4czipn)或曙红y(eosin y)中的一种或多种；优选地，光催化剂为三(2-苯基吡啶)合铱(ir(ppy)3)；
[0008]
所述铜催化剂为无水醋酸铜、碘化亚铜、铜粉、溴化亚铜、氯化亚铜、氯化铜、溴化铜或无水硫酸铜中的一种或多种；优选地，铜催化剂为无水醋酸铜；
[0009]
所述碱为碳酸钾、叔丁醇钠、磷酸二氢钾、三乙胺、2,6-二氧六环、碳酸氢钠或碳酸铯中的一种或多种；优选地，碱为碳酸钾；
[0010]
所述溶剂为二氯甲烷、乙醇、乙腈、甲苯、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；
[0011]
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。
[0012]
进一步限定，所述光催化剂、铜催化剂、碱、硫代磷酸二烷基酯类化合物3、磺酰氯类化合物1和烯类化合物2的投料摩尔比为0.01～0.1:0.1～1:1～3:1～3:1～3:1。
[0013]
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。
[0014]
进一步限定，反应过程的反应时间为4～24h，优选为8～12h。
[0015]
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。
[0016]
本发明与现有技术相比具有以下优点和有益效果：本发明的制备方法原料廉价易得、反应条件温和、操作方便、底物适用性好、收率较高、步骤经济性好、原子经济性好，适合于工业化生产。
具体实施方式
[0017]
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。
[0018]
实施例1
[0019][0020]
向10ml schlenk瓶中依次加三(2-苯基吡啶)合铱(4-5mg，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。称取苯乙烯1a(31.3mg，0.3mmol)、硫代磷酸二乙酯2a(102.0mg，0.6mmol)和对甲基苯磺酰氯3a(114.4mg，0.6mmol)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:123.4mg,96％；white solid；m.p.76.5
–
78.5℃；1h nmr(400mhz,cdcl3)δ7.48(d,j＝7.9hz,2h),7.18
–
7.09(m,7h),4.74
–
4.61(m,1h),4.05
–
3.91(m,4h),3.90
–
3.73(m,2h),2.32(s,3h),1.23(t,j＝7.1hz,3h),1.13(t,j＝7.1hz,3h).
13
c nmr(151mhz,cdcl3)δ144.6,138.7(d,j＝5.0hz),136.5,129.8,128.8,128.3,128.1,127.8,64.1(d,j＝6.1hz),63.9(d,j＝5.8hz),62.0(d,j＝6.0hz),44.3(d,j＝3.4hz),21.7,16.1(d,j＝7.5hz),15.9(d,j＝7.3hz).
31
p nmr(243mhz,cdcl3)δ23.15.hrms:[m na]

m/z calcd for c
19h25
nao5ps
2
:451.0773,found:451.0764。
[0021]
实施例2
[0022]
用溴化亚铜(4.3mg，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62.8％。
[0023]
实施例3
[0024]
用碳酸铯(195.5mg，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72％。
[0025]
实施例4
[0026]
用乙腈代替二氯甲烷，其余条件同实施例1，得到目标产物4a的收率为61.6％。
[0027]
实施例5
[0028][0029]
用1-甲基苯乙烯1b(35.5mg，0.3mmol)代替苯乙烯1a为原料，其余条件同实施例1，得到目标化合物4b。yield:103.4mg,78％；white gum；1h nmr(400mhz,cdcl3)δ7.50
–
7.43(m,2h),7.13(d,j＝8.0hz,2h),7.09
–
7.02(m,3h),6.97
–
6.90(m,1h),5.05
–
4.95(m,1h),4.14
–
3.98(m,4h),3.95
–
3.79(m,2h),2.40(s,3h),2.34(s,3h),1.30(t,j＝7.1hz,3h),1.17(t,j＝7.1hz,3h).
13
c nmr(151mhz,cdcl3)δ144.5,136.4,136.3(d,j＝5.9hz),135.9,130.8,129.7,128.1,127.8,126.5,64.1(d,j＝6.3hz),64.0(d,j＝6.1hz),61.7,39.9,21.6,19.4,16.1(d,j＝7.4hz),15.9(d,j＝7.2hz).
31
p nmr(243mhz,cdcl3)δ23.57.hrms:[m na]

m/z calcd for c
20h27
nao5ps
2
:465.0930,found:465.0936。
[0030]
实施例6
[0031][0032]
用4-甲基苯乙烯1c(35.5mg，0.3mmol)代替苯乙烯1a为原料，其余条件同实施例1，得到目标化合物4c。yield:119.4mg,90％；white solid；m.p.91.2
–
94.3℃；1h nmr(400mhz,cdcl3)δ7.49(d,j＝8.3hz,2h),7.14(d,j＝8.1hz,2h),7.07
–
7.03(m,2h),6.98
–
6.94(m,2h),4.71
–
4.61(m,1h),4.07
–
3.94(m,4h),3.90
–
3.78(m,2h),2.36(s,3h),2.26(s,3h),1.26(t,j＝7.1hz,3h),1.18(t,j＝7.1hz,3h).
13
c nmr(151mhz,cdcl3)δ144.5,138.3,136.5,135.4(d,j＝5.5hz),129.7,129.4,128.1,127.6,64.0(dd,j＝6.1,24.5hz),62.1(d,j＝5.4hz),44.1(d,j＝3.4hz),21.7,21.2,16.0(dd,j＝7.3,21.9hz).
31
p nmr(243mhz,cdcl3)δ23.29.hrms:[m h]

m/z calcd for c
20h28
o5ps
2
:443.1110,found:443.1104。
[0033]
实施例7
[0034][0035]
用3-甲基苯乙烯1d(35.5mg，0.3mmol)代替苯乙烯1a为原料，其余条件同实施例1，得到目标化合物4d。yield:122mg,92％；white solid；1h nmr(400mhz,cdcl3)δ7.48
–
7.44(m,2h),7.14(d,j＝8.1hz,2h),7.00
–
6.94(m,2h),6.88
–
6.86(m,1h),4.71
–
4.61(m,1h),4.07
–
3.94(m,4h),3.90
–
3.78(m,2h),2.36(s,3h),2.26(s,3h),1.26(t,j＝7.1hz,3h),1.18(t,j＝7.1hz,3h).
13
c nmr(151mhz,cdcl3)δ144.5,138.4,138.3(d,j＝5.4hz),136.5,129.6,129.1,128.7,128.3,128.0,125.0,64.1(d,j＝6.3hz),63.9(d,j＝5.9hz),62.0(d,j＝5.6hz),44.3(d,j＝3.5hz),21.6,21.3,16.1(d,j＝7.4hz),15.9(d,j＝7.5hz).
31
p nmr(243mhz,cdcl3)δ23.29.hrms:[m na]

m/z calcd for c
20h27
nao5ps
2
:465.0930,found:465.0933。
[0036]
实施例8
[0037][0038]
用α-甲基苯乙烯1e(35.5mg，0.3mmol)代替苯乙烯1a为原料，其余条件同实施例1，得到目标化合物4e。yield:87.5mg,66％；white gum；1h nmr(400mhz,cdcl3)δ7.45
–
7.41(m,2h),7.39
–
7.35(m,2h),7.19
–
7.14(m,3h),7.13
–
7.09(m,2h),4.48(d,j＝14.7hz,1h),4.28(d,j＝14.7hz,1h),4.08
–
3.94(m,3h),3.92
–
3.82(m,1h),2.36(s,3h),2.34(s,3h),1.29
–
1.23(m,3h),1.21
–
1.16(m,3h).
13
c nmr(151mhz,cdcl3)δ144.2,140.4(d,j＝8.5hz),
138.0,129.7,128.3,128.0,127.7,126.8,66.7(d,j＝2.9hz),64.0(d,j＝7.1hz),63.9(d,j＝6.6hz),54.4(d,j＝4.0hz),26.7(d,j＝3.8hz),21.6,16.0(d,j＝8.0hz).
31
p nmr(243mhz,cdcl3)δ21.24.hrms:[m h]

m/z calcd for c
20h28
o5ps
2
:443.1110,found:443.1105。
[0039]
实施例9
[0040][0041]
用β-甲基苯乙烯1f(35.5mg，0.3mmol)代替苯乙烯1a为原料，其余条件同实施例1，得到目标化合物4f。yield:88.9mg,67％；white solid；m.p.102.4
–
104.1℃；1h nmr(400mhz,cdcl3)δ7.71(d,j＝7.9hz,2h),7.35
–
7.22(m,7h),5.07(dd,j＝4.0,13.1hz,1h),4.08
–
3.97(m,3h),3.71
–
3.61(m,1h),3.44
–
3.37(m,1h),2.42(s,3h),1.47(d,j＝7.0hz,3h),1.26(t,j＝7.0hz,3h),1.03(t,j＝7.0hz,3h).
13
c nmr(151mhz,cdcl3)δ144.9,140.8,135.2,129.9,129.0,128.7,128.3,128.0,65.5(d,j＝8.7hz),63.9(d,j＝5.4hz),63.7(d,j＝5.2hz),48.8(d,j＝3.1hz),21.8,16.0(d,j＝8.0hz),15.7(d,j＝7.8hz),10.8.
31
p nmr(243mhz,cdcl3)δ24.42.hrms:[m na]

m/z calcd forc
20h27
nao5ps
2
:465.0930,found:465.0922。
[0042]
实施例10
[0043][0044]
用4-甲氧基苯乙烯1g(40.3mg，0.3mmol)代替苯乙烯1a为原料，其余条件同实施例1，得到目标化合物4g。yield:126.4mg,92％；white solid；m.p.75.4
–
78.7℃；1h nmr(400mhz,cdcl3)δ7.47
–
7.42(m,2h),7.14
–
7.09(m,2h),7.08
–
7.02(m,2h),6.67
–
6.60(m,2h),4.70
–
4.60(m,1h),4.04
–
3.91(m,4h),3.88
–
3.78(m,2h),3.70(s,3h),2.32(s,3h),1.23(t,j＝7.1hz,3h),1.16(t,j＝7.1hz,3h).
13
c nmr(151mhz,cdcl3)δ159.6,144.5,136.6,130.4(d,j＝5.6hz),129.7,129.0,128.1,114.1,64.0(d,j＝6.1hz),63.9(d,j＝6.0hz),62.2(d,j＝5.5hz),55.4,44.0(d,j＝3.5hz),21.6,16.1(d,j＝7.3hz),16.0(d,j＝7.2hz).
31
p nmr(243mhz,cdcl3)δ23.33.hrms:[m na]

m/z calcd for c
20h27
nao6ps
2
:481.0879,found:481.0866。
[0045]
实施例11
[0046][0047]
用茚1h(36.3mg，0.3mmol)代替苯乙烯1a为原料，其余条件同实施例1，得到目标化
合物4h。yield:99mg,75％；white solid；m.p.89.3
–
92.5℃；1h nmr(400mhz,cdcl3)δ7.81
–
7.76(m,2h),7.40
–
7.36(m,1h),7.32
–
7.27(m,j＝2.5hz,2h),7.22
–
7.15(m,2h),7.13
–
7.08(m,1h),5.21(dd,j＝3.4,17.1hz,1h),4.45
–
4.38(m,1h),4.20
–
3.95(m,4h),3.54
–
3.37(m,2h),2.40(s,3h),1.33(t,j＝0.8,7.0hz,3h),1.28(t,j＝0.9,7.1hz,3h).
13
c nmr(151mhz,cdcl3)δ145.1,140.5(d,j＝5.5hz),139.8,134.6,129.9,129.1,128.9,127.7,125.3,124.6,70.4(d,j＝3.3hz),64.3(d,j＝6.5hz),64.1(d,j＝6.6hz),49.6(d,j＝3.8hz),32.7,21.7,16.2(d,j＝7.1hz),16.1(d,j＝7.1hz).
31
p nmr(243mhz,cdcl3)δ23.85.hrms:[m na]

m/z calcd for c
20h25
nao5ps
2
:463.0773,found:463.0776。
[0048]
实施例12
[0049][0050]
用4-溴苯乙烯1i(54.9mg，0.3mmol)代替苯乙烯1a为原料，其余条件同实施例1，得到目标化合物4i。yield:106.5mg,70％；white gum；1h nmr(400mhz,cdcl3)δ7.52
–
7.44(m,2h),7.31
–
7.28(m,1h),7.22
–
7.14(m,4h),7.08(t,j＝7.8hz,1h),4.72
–
4.62(m,1h),4.13
–
3.99(m,3h),3.99
–
3.93(m,1h),3.91
–
3.82(m,2h),2.39(s,3h),1.29(t,j＝7.1hz,3h),1.21(t,j＝7.0hz,3h).
13
c nmr(151mhz,cdcl3)δ144.9,137.4(d,j＝5.0hz),136.1,131.7,129.7,129.5,127.9,122.3,64.2(d,j＝6.2hz),64.1(d,j＝6.2hz),61.7(d,j＝6.1hz),43.6(d,j＝3.4hz),21.7,16.1(d,j＝7.3hz),15.9(d,j＝7.4hz).
31
p nmr(243mhz,cdcl3)δ22.60.hrms:[m na]

m/z calcd for c
19h24
brnao5ps
2
:528.9878,found:528.9881。
[0051]
实施例13
[0052][0053]
用3-溴苯乙烯1j(54.9mg，0.3mmol)代替苯乙烯1a为原料，其余条件同实施例1，得到目标化合物4j。yield:97.4mg,64％；white gum；1h nmr(400mhz,cdcl3)δ7.50
–
7.46(m,2h),7.31
–
7.27(m,1h),7.21
–
7.14(m,4h),7.08(t,j＝7.8hz,1h),4.72
–
4.62(m,1h),4.11
–
3.93(m,4h),3.93
–
3.82(m,2h),2.38(s,3h),1.29(t,j＝7.1hz,3h),1.21(t,j＝7.1hz,3h).
13
c nmr(151mhz,cdcl3)δ144.9,140.8(d,j＝4.9hz),136.1,131.3,130.7,130.3,129.8,127.9,126.8,122.6,64.2(d,j＝6.3hz),64.1(d,j＝5.9hz),61.7(d,j＝6.3hz),43.7(d,j＝3.4hz),21.7,16.0(d,j＝7.2hz),15.9(d,j＝7.3hz).
31
p nmr(243mhz,cdcl3)δ22.57.hrms:[m h]

m/z calcd for c
19h25
bro5ps
2
:507.0059,found:507.0052。
[0054]
实施例14
[0055][0056]
用4-氯苯乙烯1k(41.6mg，0.3mmol)代替苯乙烯1a为原料，其余条件同实施例1，得到目标化合物4k。yield:115.1mg,83％；white solid；m.p.75.4
–
78.9℃；1h nmr(400mhz,cdcl3)δ7.45(d,j＝7.9hz,2h),7.14(d,j＝7.9hz,2h),7.09(s,4h),4.71
–
4.61(m,1h),4.05
–
3.91(m,4h),3.89
–
3.80(m,2h),2.35(s,3h),1.23(t,j＝7.1hz,3h),1.17(t,j＝7.1hz,3h).
13
c nmr(151mhz,cdcl3)δ144.9,137.1(d,j＝5.1hz),136.3,134.3,129.8,129.3,128.9,128.0,64.2(d,j＝6.2hz),64.1(d,j＝6.0hz),61.9(d,j＝6.0hz),43.7(d,j＝3.6hz),21.7,16.1(d,j＝7.2hz),16.0(d,j＝7.2hz).
31
p nmr(243mhz,cdcl3)δ22.68.hrms:[m na]

m/z calcd for c
19h24
clnao5ps
2
:485.0384,found:485.0387。
[0057]
实施例15
[0058][0059]
用3-氯苯乙烯1l(41.6mg，0.3mmol)代替苯乙烯1a为原料，其余条件同实施例1，得到目标化合物4l。yield:123.5mg,89％；white gum；1h nmr(400mhz,cdcl3)δ7.46(d,j＝7.9hz,2h),7.12(d,j＝16.3hz,5h),7.03(s,1h),4.70
–
4.59(m,1h),4.07
–
3.90(m,4h),3.89
–
3.79(m,2h),2.34(s,3h),1.24(t,j＝7.1hz,3h),1.17(t,j＝7.1hz,3h).
13
c nmr(151mhz,cdcl3)δ144.9,140.6(d,j＝4.9hz),136.1,134.5,130.1,129.8,128.4,128.0,127.9,126.3,64.2(d,j＝6.3hz),64.1(d,j＝6.0hz),61.7(d,j＝6.1hz),43.7(d,j＝3.4hz),16.0(d,j＝7.3hz),15.9(d,j＝7.4hz).
31
p nmr(243mhz,cdcl3)δ22.66.hrms:[m na]

m/z calcd for c
19h24
clnao5ps
2
:485.0384,found:485.0377。
[0060]
实施例16
[0061][0062]
用4-叔丁基苯乙烯1m(48.1mg，0.3mmol)代替苯乙烯1a为原料，其余条件同实施例1，得到目标化合物4m。yield:124.9mg,86％；white solid；m.p.83.4
–
85.6℃；1h nmr(400mhz,cdcl3)δ7.47
–
7.40(m,2h),7.15
–
7.10(m,2h),7.09
–
7.04(m,4h),4.74
–
4.65(m,1h),4.06
–
3.88(m,5h),3.82
–
3.72(m,1h),2.32(s,3h),1.28
–
1.21(m,12h),1.13(t,j＝0.9,7.1hz,3h).
13
c nmr(151mhz,cdcl3)δ151.3,144.2,136.5(d,j＝2.4hz),135.2(d,j＝2.2,5.4hz),129.5,128.0,127.4,125.5,63.9(d,j＝6.1hz),63.7(d,j＝5.7hz),61.9(d,j＝5.7hz),44.1(d,j＝3.7hz),34.5,31.3,21.6,16.0(d,j＝7.3hz),15.8(d,j＝7.4hz).
31
p nmr(243mhz,cdcl3)δ23.20.hrms:[m na]

m/z calcd for c
23h33
nao5ps
2
:507.1399,found:
507.1408。
[0063]
实施例17
[0064][0065]
用4-硝基苯乙烯1n(44.8mg，0.3mmol)代替苯乙烯1a为原料，其余条件同实施例1，得到目标化合物4n。yield:96.5mg,68％；white solid；m.p.76.4
–
79.3℃；1h nmr(400mhz,cdcl3)δ8.06
–
8.02(m,2h),7.54
–
7.50(m,2h),7.43
–
7.39(m,2h),7.18(d,j＝8.1hz,2h),4.85
–
4.75(m,1h),4.08
–
3.94(m,4h),3.93
–
3.85(m,2h),2.36(s,3h),1.25
–
1.17(m,6h).
13
c nmr(151mhz,cdcl3)δ147.5,146.0(d,j＝4.6hz),145.3,136.1(d,j＝2.7hz),129.9,129.0,128.0,123.8,64.3(d,j＝6.4hz),64.2(d,j＝6.2hz),61.4(d,j＝6.5hz),43.3(d,j＝3.4hz),21.6,16.0(d,j＝7.0hz),15.9(d,j＝7.4hz).
31
p nmr(243mhz,cdcl3)δ21.96.hrms:[m na]

m/z calcd for c
19h24
nnao7ps
2
:496.0624,found:496.0635。
[0066]
实施例18
[0067][0068]
用4-苯基苯乙烯1o(54.1mg，0.3mmol)代替苯乙烯1a为原料，其余条件同实施例1，得到目标化合物4o。yield:128.5mg,85％；white solid；m.p.68.9
–
71.3℃；1h nmr(400mhz,cdcl3)δ7.52
–
7.46(m,4h),7.44
–
7.40(m,2h),7.39
–
7.32(m,3h),7.25
–
7.21(m,2h),7.10(d,j＝8.0hz,2h),4.84
–
4.73(m,1h),4.10
–
3.85(m,6h),2.27(s,3h),1.28(t,j＝7.1hz,3h),1.19(t,j＝7.1hz,3h).
13
c nmr(151mhz,cdcl3)δ144.6,141.3,140.3,137.4(d,j＝5.1hz),136.5,129.7,129.0,128.3,128.1,127.7,127.4,127.0,64.2(d,j＝6.2hz),64.0(d,j＝5.9hz),62.0(d,j＝6.0hz),44.1(d,j＝3.5hz),21.6,16.0(d,j＝7.5hz),15.8(d,j＝7.4hz).
31
p nmr(243mhz,cdcl3)δ23.17.hrms:[m na]

m/z calcd for c
25h29
nao5ps
2
:527.1086,found:527.1072。
[0069]
实施例19
[0070][0071]
用4-氟苯乙烯1p(36.7mg，0.3mmol)代替苯乙烯1a为原料，其余条件同实施例1，得到目标化合物4p。yield:105.7mg,79％；white solid；m.p.80.4
–
81.9℃；1h nmr(400mhz,cdcl3)δ7.51
–
7.47(m,2h),7.19
–
7.14(m,4h),6.89
–
6.82(m,2h),4.74
–
4.66(m,1h),4.08
–
3.91(m,4h),3.89
–
3.79(m,2h),2.35(s,3h),1.24(t,j＝7.1hz,3h),1.18(t,j＝7.1hz,3h).
13
c nmr(151mhz,cdcl3)δ162.5(d,j＝248.2hz),144.9,136.4,134.6(t,j＝4.3hz),
129.8,129.7(d,j＝8.3hz),128.1,115.7(d,j＝21.8hz),64.2(d,6.1hz),64.1(d,6.0hz),62.1(d,j＝6.1hz),43.6(d,j＝3.7hz),21.7,16.1(d,j＝7.2hz),16.0(d,j＝7.2hz).
31
p nmr(243mhz,cdcl3)δ22.91.
19
f nmr(471mhz,cdcl3)δ-113.13.hrms:[m na]

m/z calcd for c
19h24
fnao5ps
2
:469.0679,found:469.0665。
[0072]
实施例20
[0073][0074]
用4-三氟甲基苯乙烯1q(51.7mg，0.3mmol)代替苯乙烯1a为原料，其余条件同实施例1，得到目标化合物4q。yield:117.6mg,79％；white solid；m.p.94.7
–
98.5℃；1h nmr(400mhz,cdcl3)δ7.44
–
7.42(m,2h),7.39
–
7.36(m,2h),7.32
–
7.28(m,2h),7.11
–
7.09(m,2h),4.80
–
4.74(m,1h),4.07
–
3.91(m,5h),3.90
–
3.83(m,1h),2.36(s,3h),1.24(t,j＝0.9,7.1hz,3h),1.17(t,j＝0.9,7.1hz,3h).
13
c nmr(151mhz,cdcl3)δ145.0,142.6(d,j＝4.9hz),136.2(d,j＝2.1hz),130.4(q,j＝32.4hz),129.8,128.5,128.0,125.6(q,j＝3.8hz),123.9(q,j＝272.2hz),64.3(d,j＝6.4hz),64.2(d,j＝6.2hz),61.6(d,j＝6.0hz),43.8(d,j＝3.4hz),21.5,16.0(d,j＝7.2hz),15.9(d,j＝7.4hz).
31
p nmr(243mhz,cdcl3)δ22.33.
19
f nmr(471mhz,cdcl3)δ-62.75.hrms:[m h]

m/z calcd for c
20h25
f3o5ps
2
:497.0828,found:497.0835。
[0075]
实施例21
[0076][0077]
用2-乙烯基吡啶1r(32.6mg，0.3mmol)代替苯乙烯1a为原料，其余条件同实施例1，得到目标化合物4r。yield:76mg,59％；white solid；m.p.71.4
–
73.6℃；1h nmr(400mhz,cdcl3)δ8.38
–
8.32(m,1h),7.62
–
7.57(m,1h),7.54(d,j＝8.3hz,2h),7.32
–
7.29(m,1h),7.18(d,j＝8.0hz,2h),7.14
–
7.08(m,1h),4.87
–
4.78(m,1h),4.42(dd,j＝10.7,14.2hz,1h),4.17
–
3.94(m,4h),3.90(dd,j＝3.4,14.2hz,1h),2.38(s,3h),1.28(t,j＝0.9,7.0hz,6h).
13
c nmr(101mhz,cdcl3)δ156.9(d,j＝5.1hz),149.8,144.6,136.8,136.3,129.7,128.0,123.7,123.0,64.1(d,j＝5.7hz),64.1(d,j＝5.9hz),60.6(d,j＝5.5hz),44.9(d,j＝3.0hz),21.6,16.05(d,j＝7.1hz),16.04(d,j＝7.1hz).
31
p nmr(162mhz,cdcl3)δ23.59.hrms:[m h]

m/z calcd for c
18h25
no5ps
2
:430.0906,found:430.0910。
[0078]
实施例22
[0079][0080]
用化合物1s(117mg，0.3mmol)代替苯乙烯1a为原料，其余条件同实施例1，得到目标化合物4s(dr＝1:1)。yield:175.6mg,82％；white gum；1h nmr(400mhz,cdcl3)δ7.86(dd,j＝8.0,15.9hz,2h),7.57(d,j＝7.9hz,1h),7.50(d,j＝7.9hz,1h),7.31(dd,j＝8.1,12.7hz,2h),7.19(dd,j＝8.0,14.6hz,2h),5.92(d,j＝3.7hz,1h),5.46(d,j＝2.6hz,1h),4.79
–
4.68(m,1h),4.58(d,j＝3.7hz,1h),4.36
–
4.24(m,2h),4.13
–
3.94(m,6h),3.92
–
3.80(m,2h),2.36(d,j＝7.6hz,3h),1.53(s,3h),1.39(d,j＝2.5hz,3h),1.30(s,3h),1.27
–
1.22(m,6h),1.21
–
1.16(m,3h).
13
c nmr(151mhz,cdcl3)δ164.7,164.7,145.2,145.1,144.6(d,j＝5.0hz),144.3(d,j＝5.1hz),136.32,136.28,130.3,130.2,130.0,129.95,129.5,128.23,128.20,128.18,128.1,112.6,109.64,109.62,105.29,105.26,83.54,83.53,80.10,80.06,72.71,72.68,67.51,67.45,64.4(d,j＝6.5hz),64.3(d,j＝6.2hz),64.25(d,6.2hz),61.76(d,j＝6.6hz),61.71(d,j＝6.6hz),43.8(d,j＝3.3hz),43.7(d,j＝3.3hz),27.1(d,j＝6.1hz),26.9,26.4,25.4,21.79,21.76,21.69,16.1(d,j＝7.3hz),16.05(d,j＝7.2hz),16.0(d,j＝7.3hz).
31
p nmr(243mhz,cdcl3)δ22.49.hrms:[m na]

m/z calcd for c
32h43
nao
12
ps
2
:737.1826,found:737.1820。
[0081]
实施例23
[0082][0083]
用化合物1t(52.8mg，0.3mmol)代替苯乙烯1a为原料，其余条件同实施例1，得到目标化合物4t。yield:111mg,74％；white gum；1h nmr(400mhz,cdcl3)δ7.86(d,j＝8.0hz,2h),7.51(d,j＝7.9hz,2h),7.27(d,j＝8.0hz,2h),7.16(d,j＝7.9hz,2h),4.83
–
4.70(m,1h),4.37(q,j＝7.1hz,2h),4.10
–
3.95(m,4h),3.94
–
3.81(m,2h),2.37(s,3h),1.39(t,j＝7.1hz,3h),1.27(t,j＝7.1hz,3h),1.20(t,j＝7.1hz,3h).
13
c nmr(151mhz,cdcl3)δ166.0,144.9,143.5(d,j＝4.7hz),136.2,130.4,130.0,129.8,128.1,127.9,64.2(d,j＝6.4hz),64.1(d,j＝6.1hz),61.7(d,j＝6.1hz),61.2,43.8(d,j＝3.4hz),21.6,16.0(d,j＝7.2hz),15.9(d,j＝7.2hz),14.4.
31
p nmr(243mhz,cdcl3)δ22.63.hrms:[m na]

m/z calcd for c
22h29
nao7ps
2
:523.0985,found:523.0976。
[0084]
实施例24
[0085][0086]
用化合物1u(120mg，0.3mmol)代替苯乙烯1a为原料，其余条件同实施例1，得到目标化合物4u。yield:175.1mg,81％；white gum；1h nmr(400mhz,cdcl3)δ8.97
–
8.83(m,1h),7.63
–
7.59(m,2h),7.57
–
7.53(m,2h),7.50
–
7.46(m,2h),7.38
–
7.30(m,8h),7.13
–
7.09(m,2h),7.07(dt,j＝2.3,8.6hz,2h),4.71
–
4.65(m,1h),4.04
–
3.94(m,4h),3.88
–
3.82(m,2h),3.28
–
3.21(m,2h),2.95
–
2.89(m,2h),2.30
–
2.27(m,3h),1.24(dd,j＝4.5,7.4hz,3h),1.18(dd,j＝4.4,6.9hz,3h).
13
c nmr(151mhz,cdcl3)δ170.1(d,j＝5.3hz),162.6,145.8,144.9(d,j＝3.8hz),136.3(d,j＝4.3hz),134.9,132.4(d,j＝3.9hz),129.8,128.8(d,j＝7.4hz),128.4(t,j＝5.5hz),128.0(d,j＝7.5hz),126.6,64.2(dd,j＝6.3,15.1hz),62.1(d,j＝5.6hz),44.0(d,j＝3.4hz),34.0,24.0(d,j＝4.2hz),21.6,16.1(dd,j＝7.3,11.8hz).
31
p nmr(243mhz,cdcl3)δ23.22.hrms:[m h]

m/z calcd for c
37h40
n2o8ps
2
:719.2009,found:719.2016。
[0087]
实施例25
[0088][0089]
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4v。yield:131.4mg,96％；white gum；m.p.102.3
–
105.2℃；1h nmr(400mhz,cdcl3)δ7.46(d,j＝8.1hz,2h),7.15(s,5h),7.11(d,j＝8.1hz,2h),4.76
–
4.65(m,1h),4.65
–
4.47(m,2h),4.08(dd,j＝4.3,14.6hz,1h),3.89(dd,j＝10.7,14.5hz,1h),2.32(s,3h),1.29
–
1.19(m,9h),1.16(d,j＝6.2hz,3h).
13
c nmr(151mhz,cdcl3)δ144.5,138.5(d,j＝6.3hz),136.6,129.7,128.8,128.3,128.1,127.9,73.5(d,j＝6.8hz),73.4(d,j＝6.8hz),62.1(d,j＝4.7hz),44.5(d,j＝3.7hz),23.9(d,j＝4.0hz),23.8(d,j＝4.1hz),23.7(d,j＝5.6hz),23.5(d,j＝5.5hz),21.7.
31
p nmr(243mhz,cdcl3)δ20.81.hrms:[m na]

m/z calcd for c
21h29
nao5ps
2
:479.1086,found:479.1071。
[0090]
实施例26
[0091][0092]
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4w。yield:127.8mg,88％；white solid；m.p.52.3
–
54.5℃；1h nmr(400mhz,cdcl3)δ7.51
–
6.90(m,9h),4.76
–
4.55(m,1h),4.10
–
3.60(m,6h),2.35(s,3h),1.60
–
1.10(m,8h),0.95
–
0.65(m,6h).
13
c nmr(151mhz,cdcl3)δ144.6,138.7(d,j＝
5.1hz),136.5,129.8,128.8,128.3,128.1,127.9,67.7(d,j＝6.6hz),67.6(d,j＝6.3hz),62.1(d,j＝5.6hz),44.3(d,j＝3.4hz),32.1(d,j＝7.2hz),32.0(d,j＝7.2hz),21.7,18.7(d,j＝5.2hz),13.7(d,j＝2.6hz).
31
p nmr(243mhz,cdcl3)δ23.31.hrms:[m na]

m/z calcd for c
23h33
nao5ps
2
:507.1399,found:507.1394。
[0093]
实施例27
[0094][0095]
用苯磺酰氯3b(106mg,0.6mmol)代替对甲基苯磺酰氯3a为原料，其余条件同实施例1，得到目标化合物4x。yield:114.3mg,92％；white solid；m.p.75.3
–
77.8℃；1h nmr(400mhz,cdcl3)δ7.62
–
7.55(m,2h),7.50
–
7.44(m,1h),7.36
–
7.29(m,2h),7.18
–
7.12(m,5h),4.75
–
4.66(m,1h),4.06
–
3.94(m,4h),3.93
–
3.76(m,2h),1.24(t,j＝1.1,7.1hz,3h),1.14(t,j＝1.2,7.1hz,3h).
13
c nmr(151mhz,cdcl3)δ139.4,138.5(d,j＝5.0hz),133.6,129.1,128.8,128.5,128.0,127.8,64.1(d,j＝6.2hz),63.9(d,j＝5.8hz),62.0(d,j＝5.7hz),44.3(d,j＝3.6hz),16.1(d,j＝7.2hz),15.9(d,j＝7.3hz).
31
p nmr(243mhz,cdcl3)δ23.09.hrms:[m na]

m/z calcd for c
18h23
nao5ps
2
:437.0617,found:437.0613。
[0096]
实施例28
[0097][0098]
用4-三氟甲氧基苯磺酰氯3c(156.4mg,0.6mmol)代替对甲基苯磺酰氯3a为原料，其余条件同实施例1，得到目标化合物4y。yield:143.4mg,96％；white solid；m.p.63.4-65.6℃；1h nmr(400mhz,cdcl3)δ7.59
–
7.55(m,2h),7.14
–
7.01(m,7h),4.78
–
4.64(m,1h),4.08
–
3.79(m,6h),1.24(t,j＝1.8,7.1hz,3h),1.16(t,j＝7.1hz,3h).
13
c nmr(151mhz,cdcl3)δ152.7,138.0(d,j＝5.4hz),137.7,130.3,128.9,128.6,127.9,120.9,120.1(d,j＝259.6hz),64.2(d,j＝6.4hz),64.1(d,j＝6.1hz),62.0(d,j＝5.4hz),44.3(d,j＝3.4hz),16.1(d,j＝7.2hz),16.0(d,j＝7.2hz).
31
p nmr(243mhz,cdcl3)δ22.86.
19
f nmr(471mhz,cdcl3)δ-57.68.hrms:[m na]

m/z calcd for c
19h22
f3nao6ps
2
:521.0440,found:521.0436。
[0099]
实施例29
[0100][0101]
用丁基磺酰氯3d(94mg,0.6mmol)代替对甲基苯磺酰氯3a为原料，其余条件同实施例1，得到目标化合物4z。yield:83.9mg,71％；white solid；m.p.84.3
–
85.6℃；1h nmr(400mhz,cdcl3)δ7.49
–
7.31(m,5h),4.85
–
4.71(m,1h),4.18
–
4.01(m,3h),3.90
–
3.67(m,3h),2.56
–
2.38(m,2h),1.72
–
1.52(m,2h),1.32(t,j＝7.1hz,3h),1.26
–
1.12(m,5h),0.81(t,j＝7.4hz,3h).
13
c nmr(151mhz,cdcl3)δ139.3(d,j＝4.9hz),129.3,128.9,128.0,64.3(d,j＝6.1hz),64.1(d,j＝6.0hz),59.4(d,j＝6.3hz),54.0,44.4(d,j＝3.5hz),23.8,21.6,16.1(d,j＝7.3hz),15.9(d,j＝7.4hz),13.5.
31
p nmr(243mhz,cdcl3)δ23.01.hrms:[m h]

m/z calcd for c
16h28
o5ps
2
:395.1110,found:395.1100。
[0102]
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。