CN110396114B - 一种n-二芳基氧膦基亚砜亚胺的合成方法 - Google Patents

一种n-二芳基氧膦基亚砜亚胺的合成方法 Download PDF

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CN110396114B
CN110396114B CN201910727985.0A CN201910727985A CN110396114B CN 110396114 B CN110396114 B CN 110396114B CN 201910727985 A CN201910727985 A CN 201910727985A CN 110396114 B CN110396114 B CN 110396114B
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曾庆乐
谭明超
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Chengdu Univeristy of Technology
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Abstract

N‑二芳基氧膦基亚砜亚胺类化合物在医药、农业领域有着广泛的用途，对人类的生产生活有着深远的影响。本发明首次以亚砜亚胺一步合成N‑二芳基氧膦基亚砜亚胺类化合物的方法,即在碘单质催化苯基氧膦和芳基亚砜亚胺、杂环亚砜亚胺或者脂肪族亚砜亚胺进行N‑P键氧化偶联合成N‑二芳基氧膦基亚砜亚胺。本发明提供的方法具有反应条件绿色、简单，原料价廉易得，环境友好型等优点。

Description

一种N-二芳基氧膦基亚砜亚胺的合成方法
技术领域
该专利涉及有机合成、药物合成、有机化工的研究领域，具体的方法就是从二芳基氧膦和亚砜亚胺进行N-P键氧化偶联一步合成N-二芳基氧膦基亚砜亚胺类化合物。
背景技术
N-二芳基氧膦基亚砜亚胺广泛存在于生物医药和生物活性的化合物中(Bremner,J.；Chai,H.Biol.Fert.Soils 1989,8,227-230；Dixon,N.E.；Gazzola,C.；Watters,J.J.；Blakeley,R.L.；Zerner,B.J.Am.Chem.Soc.1975,97,4130-4131；Faraci,W.S.；Yang,B.V.；O'Rourke,D.；Spencer,R.W.Bioorgan.Med.Chem.1995,3,605-610；Oroujzadeh,N.；Delpazir,E.,Shariatinia,Z.Particul.Sci.Technol.2018,1-7)。手性N-二芳基氧膦基亚砜亚胺还可以作为手性配体和有机催化剂用于不对称催化反应(Huang,H.；Bian,G.；Zong,H.；Wang,Y.；Yang,S.；Yue,H.；Song,L.；Fan,H.Org.Lett.2016,18,2524；Ding,M.；Zhou,F.；Liu,Y.L.；Wang,C.H.；Zhao,X.L.；Zhou,J.Chem.Sci.2011,2,2035；Dong,J.；Du,D.M.Org.Biomol.Chem.2012,10,8125.)。
经典的N-二芳基氧膦基亚砜亚胺的合成方法(Harger,M.J.P.；Westlake,S.Tetrahedron 1982,38,1511-1515；Kameyama,E.；Inokuma,S.；Kuwamura,T.Bull.Chem.Soc.Japan 1976,49,1439-1440)，经典合成的主要方法：一种是通过热解和光解活性中间体亚磷酰基硝基苯胺得到N-二苯基膦基二甲基亚砜亚胺；另一种是用二苯基次膦酰氯与叠氮化合物经过一系列反应得到N-二芳基氧膦基亚砜亚胺氨化合物。该系列的方法虽得到了N-二芳基氧膦基亚砜亚胺化合物，但是合成中操作条件复杂、反应步骤较多、成本高、使用比较危险的化学试剂、并且目标产物产率低。
碘单质催化N-P氧化偶联被科研人员发现以后一直在研究，但是未见与本申请类似的文献报道。
发明内容
本发明提供一种N-二芳基氧膦基亚砜亚胺的合成方法。
本发明公开的N-二芳基氧膦基亚砜亚胺的合成方法均一步完成，即在氧化剂存在下，碘单质催化亚砜亚胺和二芳基氧膦发生N-P氧化偶联反应一步合成N-二芳基氧膦基亚砜亚胺。
结合下面的实施例更详细地阐述本发明，并认为它们是对本发明范围的限制。
具体实施方式
实施例一
往烘干带磁力搅拌子的磨口试管里加入S-甲基-S-苯基亚砜亚胺(1.5毫摩尔)、二二芳基氧膦(1.毫摩尔)、碘单质(0.1毫摩尔)、双氧水(1.0毫摩尔)、聚乙二醇400(5毫升)，最后用橡皮塞密封磨口试管。把该试管放到60℃油浴锅中加热搅拌反应24小时。然后让反应混合液冷却到室温，用硫代硫酸钠水溶液淬灭反应，用25毫升的乙酸乙酯萃取三次，合并有机相，用无水硫酸镁干燥。滤液浓缩所得的粗产物用硅胶柱层析、以石油醚：乙酸乙酯＝1:1洗脱得到白色固体N-(甲基(氧代)(苯基)-λ6-亚磺酰基)-P,P-对二苯基次膦酰胺，产率88％。
1H NMR(400MHz,CDCl3)δ8.02–7.99(m,2H),7.91–7.82(m,4H),7.64–7.59(m,1H),7.57–7.50(m,2H),7.44–7.34(m,6H),3.39(s,3H).
13C NMR(101MHz,CDCl3)δ141.17,141.10,133.60,131.26,131.22,131.19,131.16,131.13,131.03,130.93,129.38,128.29,128.27,128.16,128.14,127.20,77.35,77.03,76.71,48.00,47.98.
Melting point:139-140℃.
实施例二
往烘干带磁力搅拌子的磨口试管里加入(S)-S-甲基-S-苯基亚砜亚胺(1.5摩尔)、二二芳基氧膦(1.毫摩尔)、碘单质(0.1毫摩尔)、双氧水(1.0毫摩尔)、聚乙二醇400(5毫升)，最后用橡皮塞密封磨口试管。把该试管放到60℃油浴锅中加热搅拌反应24小时。然后让反应混合液冷却到室温，用硫代硫酸钠水溶液淬灭反应，用25毫升的乙酸乙酯萃取三次，合并有机相，用无水硫酸镁干燥。滤液浓缩所得的粗产物用硅胶柱层析、以石油醚：乙酸乙酯＝1:1洗脱得到白色固体(S)-N-(甲基(氧代)(苯基)-λ6-亚磺酰基)-P,P-对二苯基次膦酰胺，产率88％。该(S)-N-(甲基(氧代)(苯基)-λ6-亚磺酰基)-P,P-对二苯基次膦酰胺在液相色谱仪上用手性液相色谱柱日本大赛璐公司生产的Chiralcel OJ-H高效柱(4.6毫米直径、250毫米长、5微米粒径)(流动相：正己烷/异丙醇体积比80/20)进行对映体过量分析，分析结果表明，该产物的对映体过量值为199％ee。[α]D 27＝+80.25(c＝0.01,EtOAc).ChiralHPLC analysis:100％ee(S form).Chiralpak OJ-H column；λ＝254nm；hexane/isopropanol＝80:20；flow rate＝0.5mL/min；tR(major)＝19.7min,tR(minor)＝23.6min.
Melting point:113.2-114.1℃.
实施例三
1-氟-4-(S-甲基亚砜亚胺)苯代替实施例一中的S-甲基-S-苯基亚砜亚胺，得到黄色固体(N-((4-氟苯基)(甲基)(氧代)-λ6-亚磺酰基)P,P-对二苯基次膦酰胺的产率为69％。
1H NMR(400MHz,CDCl3)δ8.06–7.99(m,2H),7.92–7.79(m,4H),7.47–7.35(m,6H),7.23–7.17(m,2H),3.39(s,3H).
13C NMR(101MHz,CDCl3)δ166.99,164.44,136.47,136.15,135.18,134.81,131.33,131.30,131.27,131.23,131.13,130.99,130.89,130.24,130.14,128.35,128.32,128.22,128.19,116.78,116.55,77.32,77.00,76.68,48.19,48.17.
Melting point:115-116℃.
实施例四
1-氟-2-(S-甲基亚砜亚胺)苯代替实施例一中的S-甲基-S-苯基亚砜亚胺，得到白色固体(N-((2-氟苯基)(甲基)(氧代)-λ6-亚磺酰基)P,P-对二苯基次膦酰胺的产率为61％。
1H NMR(400MHz,CDCl3)δ7.92(td,J＝7.8,1.7Hz,1H),7.75(dddd,J＝8.5,6.9,5.8,1.5Hz,4H),7.57–7.50(m,1H),7.38–7.27(m,6H),7.24–7.19(m,1H),7.15–7.09(m,1H),3.49(s,3H).
13C NMR(101MHz,CDCl3)δ160.30,157.75,136.33,136.08,135.99,134.84,131.20,131.17,131.14,131.08,131.06,130.98,129.72,128.22,128.20,128.09,128.07,124.78,124.74,117.36,117.15,77.34,77.02,76.70,47.11.
Melting point:123.9-126.4℃.
实施例五
1-氯-3-(S-甲基亚砜亚胺)苯代替实施例一中的S-甲基-S-苯基亚砜亚胺，得到白色固体(N-((3-氯苯基)(甲基)(氧代)-λ6-亚磺酰基)P,P-对二苯基次膦酰胺的产率为75％。
1H NMR(400MHz,CDCl3)δ7.97(t,J＝1.8Hz,1H),7.94–7.81(m,5H),7.60(ddd,J＝8.0,2.0,1.1Hz,1H),7.49(dd,J＝10.6,5.1Hz,1H),7.47–7.36(m,6H),3.42(s,3H).
13C NMR(101MHz,CDCl3)δ142.85,142.79,136.39,136.04,135.57,135.10,134.69,133.76,131.36,131.33,131.31,131.28,131.22,131.12,131.00,130.90,130.71,128.35,128.33,128.22,128.20,127.34,125.41,77.33,77.01,76.69,47.90,47.88.
Melting point:119-120℃.
实施例六
1-氯-2-(S-甲基亚砜亚胺)苯代替实施例一中的S-甲基-S-苯基亚砜亚胺，得到白色固体(N-((2-氯苯基)(甲基)(氧代)-λ6-亚磺酰基)P,P-对二苯基次膦酰胺的产率为58％。
1H NMR(400MHz,CDCl3)δ8.21–8.17(m,1H),7.87–7.78(m,4H),7.55–7.47(m,2H),7.43–7.31(m,7H),3.62(s,3H).
13C NMR(101MHz,CDCl3)δ138.13,138.06,136.43,136.14,135.14,134.80,134.61,132.27,132.17,131.20,131.17,131.14,131.12,131.09,131.03,130.68,128.18,128.05,127.50,77.36,77.04,76.72,45.84,45.81.
Melting point:124-127℃.
实施例七
1-溴-3-(S-甲基亚砜亚胺)苯代替实施例一中的S-甲基-S-苯基亚砜亚胺，得到白色固体(N-((3-溴苯基)(甲基)(氧代)-λ6-亚磺酰基)P,P-对二苯基次膦酰胺的产率为71％。
1H NMR(400MHz,CDCl3)δ8.09(t,J＝1.8Hz,1H),7.94(ddd,J＝7.9,1.6,0.9Hz,1H),7.89–7.80(m,4H),7.73(ddd,J＝8.0,1.8,0.8Hz,1H),7.44–7.34(m,7H),3.39(s,3H).
13C NMR(101MHz,CDCl3)δ142.94,142.88,136.68,131.37,131.34,131.33,131.30,131.22,131.11,131.00,130.92,130.90,130.13,129.92,128.35,128.34,128.22,128.21,127.76,125.86,123.27,77.35,77.03,76.71,47.92,47.90.
Melting point:118-120℃.
实施例八
1-溴-4-(S-甲基亚砜亚胺)苯代替实施例一中的S-甲基-S-苯基亚砜亚胺，得到黄色固体(N-((4-溴苯基)(甲基)(氧代)-λ6-亚磺酰基)P,P-对二苯基次膦酰胺的产率为59％。
1H NMR(400MHz,CDCl3)δ7.91–7.79(m,6H),7.67(d,J＝8.7Hz,2H),7.45–7.35(m,6H),3.38(s,3H).
13C NMR(101MHz,CDCl3)δ140.19,132.68,131.31,131.23,131.13,131.01,130.91,128.99,128.86,128.36,128.32,128.23,128.19,77.33,77.01,76.69,47.95.
Melting point:149-153℃.
实施例九
1-硝基-4-(S-甲基亚砜亚胺)苯代替实施例一中的S-甲基-S-苯基亚砜亚胺，得到黄色油状液体(N-((4-硝基苯基)(甲基)(氧代)-λ6-亚磺酰基)P,P-对二苯基次膦酰胺的产率为49％。
1H NMR(400MHz,dmso)δ8.33(d,J＝8.5Hz,2H),8.16(d,J＝8.4Hz,2H),7.62(ddd,J＝32.2,19.8,13.6Hz,4H),7.53–7.26(m,6H),3.55(s,3H).
13C NMR(101MHz,CDCl3)δ150.66,146.79,131.59,131.56,131.53,131.18,131.08,130.98,130.88,128.83,128.48,128.42,128.35,128.29,124.58,77.36,77.04,76.72,47.57.
实施例十
S-苯基-S-乙基亚砜亚胺代替实施例一中的S-甲基-S-苯基亚砜亚胺，得到黄色油状液体N-(乙基(氧代)(苯基)-λ6-亚磺酰基)-P,P-对二苯基次膦酰胺的产率为68％。
1H NMR(400MHz,CDCl3)δ7.97–7.91(m,2H),7.91–7.79(m,4H),7.64–7.58(m,1H),7.56–7.48(m,2H),7.44–7.29(m,6H),3.55(qd,J＝7.2,3.1Hz,2H),1.19(t,J＝7.3Hz,3H).
13C NMR(101MHz,CDCl3)δ138.28,138.21,136.84,136.57,135.54,135.23,133.56,131.25,131.14,131.11,131.08,131.06,131.02,130.96,129.21,128.22,128.20,128.17,128.09,128.07,77.35,77.04,76.72,54.09,54.07,8.25.
实施例十一
S-苯基-S-环丙基亚砜亚胺代替实施例一中的S-甲基-S-苯基亚砜亚胺，得到白色固体N-(环丙基(氧代)(苯基)-λ6-亚磺酰基)-P,P-对二苯基次膦酰胺的产率为51％。
1H NMR(400MHz,CDCl3)δ8.00–7.92(m,2H),7.92–7.76(m,4H),7.58(t,J＝7.4Hz,1H),7.49(t,J＝7.6Hz,2H),7.43–7.26(m,6H),2.84(ddd,J＝12.6,8.1,4.9Hz,1H),1.32–1.18(m,2H),0.93(dqd,J＝15.7,9.4,5.1Hz,2H).
13C NMR(101MHz,CDCl3)δ141.09,141.05,136.89,136.55,135.60,135.20,133.24,131.43,131.32,131.25,131.11,131.08,131.01,130.97,129.19,129.10,128.17,128.15,128.04,128.01,127.87,127.50,77.35,77.04,76.72,35.92,35.88,6.92,6.84.
Melting point:123.2-125℃.
实施例十二
S,S-二苯基亚砜亚胺代替实施例一中的S-甲基-S-苯基亚砜亚胺，得到白色固体N-(氧代二苯基-λ6-亚磺酰基)-P,P-二苯基次膦酰胺的产率为70％。
1H NMR(400MHz,CDCl3)δ7.95(dt,J＝3.5,1.9Hz,4H),7.84–7.76(m,4H),7.51–7.45(m,2H),7.45–7.38(m,4H),7.38–7.35(m,2H),7.31(dddd,J＝8.4,6.7,3.3,1.4Hz,4H).
13C NMR(101MHz,CDCl3)δ142.02,141.98,136.28,134.97,132.99,131.32,131.21,131.01,130.98,129.15,128.07,127.94,127.56,77.33,77.01,76.69.
Melting point:124-126.4℃.
实施例十三
S-甲基S-(2-甲氧基苯基)亚砜亚胺代替实施例一中的S-甲基-S-苯基亚砜亚胺，得到白色固体N-((2-甲氧基苯基)(甲基)(氧代)-λ6-亚磺酰基)-P,P-对二苯基次膦酰胺的产率为82％。
1H NMR(400MHz,CDCl3)δ7.98(dt,J＝6.7,3.4Hz,1H),7.86–7.75(m,4H),7.54(ddd,J＝8.3,7.5,1.7Hz,1H),7.43–7.29(m,6H),7.08–7.00(m,1H),6.93(d,J＝8.3Hz,1H),3.73(s,3H),3.56(s,3H).
13C NMR(101MHz,CDCl3)δ156.76,137.06,136.79,135.75,135.44,131.17,131.09,131.07,130.99,130.90,130.87,130.84,129.61,128.55,128.49,128.10,128.05,127.97,127.92,120.61,112.21,77.33,77.01,76.69,55.83,46.05,46.02.
Melting point:143-144℃.
实施例十四
S-苯基-S-(苯基甲基)亚砜亚胺代替实施例一中的S-甲基-S-苯基亚砜亚胺，得到黄色油状液体N-(苄基(氧代)(苯基)-λ6-亚磺酰基)-P,P-二苯基次膦酰胺的产率为65％。
1H NMR(400MHz,CDCl3)δ7.85(ddd,J＝19.9,12.6,7.0Hz,4H),7.63(d,J＝7.4Hz,2H),7.55(t,J＝7.5Hz,1H),7.46–7.33(m,8H),7.22(d,J＝7.5Hz,1H),7.11(t,J＝7.6Hz,2H),6.98(d,J＝7.3Hz,2H),4.77(s,2H).
13C NMR(101MHz,CDCl3)δ133.59,131.24,131.17,131.08,130.98,128.78,128.75,128.62,128.26,128.22,128.12,128.09,77.32,77.01,76.69,66.17.
实施例十五
S，S-二苄基亚砜亚胺代替实施例一中的S-甲基-S-苯基亚砜亚胺，得到白色固体N-(二苄基(氧代)(苯基)-λ6-亚磺酰基)-P,P-二苯基次膦酰胺的产率为58％。
1H NMR(400MHz,CDCl3)δ7.68–7.59(m,4H),7.41–7.35(m,8H),7.35–7.26(m,8H),4.47(q,J＝13.7Hz,4H).
13C NMR(101MHz,CDCl3)δ131.48,130.99,130.89,129.13,128.75,128.12,127.99,127.25,77.31,77.00,76.68,60.97.
Melting point:198.4-199℃
实施例十六
S，S-二丁基亚砜亚胺代替实施例一中的S-甲基-S-苯基亚砜亚胺，得到黄色油状液体N-(二丁基(氧代)(苯基)-λ6-亚磺酰基)-P,P-二苯基次膦酰胺的产率为60％。
1H NMR(400MHz,CDCl3)δ7.86–7.78(m,4H),7.44–7.33(m,6H),3.35–3.17(m,4H),1.81–1.76(m,4H),1.41(dt,J＝13.0,6.6Hz,4H),0.92–0.86(m,6H).
13C NMR(101MHz,CDCl3)δ136.96,135.64,131.05,131.03,131.00,130.95,128.20,128.07,77.32,77.01,76.69,55.06,55.03,54.36,24.29,21.72,21.54,13.61,13.54.
实施例十七
S-甲基-S-(2-吡啶基)-亚砜亚胺代替实施例一中的S-甲基-S-苯基亚砜亚胺，得到白色固体N-(甲基(氧代)(吡啶-2-基)-λ6-亚磺酰基)-P,P-对二苯基次膦酰胺的产率为73％。
1H NMR(400MHz,CDCl3)δ8.60(ddd,J＝4.7,1.7,0.9Hz,1H),8.14(dt,J＝7.9,1.0Hz,1H),7.87(td,J＝7.8,1.7Hz,1H),7.84–7.75(m,4H),7.46(ddd,J＝7.7,4.7,1.1Hz,1H),7.43–7.30(m,6H),3.52(d,J＝0.6Hz,3H).
13C NMR(101MHz,CDCl3)δ149.71,138.32,136.29,136.19,134.98,134.86,131.18,131.16,131.15,131.13,131.08,130.98,128.22,128.09,127.23,121.21,77.37,77.05,76.73,43.11,43.07.
实施例十九
S，S-二乙基亚砜亚胺代替实施例一中的S-甲基-S-苯基亚砜亚胺，得到白色油状液体N-(二乙基(氧代)(苯基)-λ6-亚磺酰基)-P,P-二苯基次膦酰胺的产率为66％。
1H NMR(400MHz,CDCl3)δ7.86–7.78(m,4H),7.43–7.32(m,6H),3.36–3.23(m,4H),1.40–1.34(m,6H).
13C NMR(101MHz,CDCl3)δ136.93,135.61,131.05,131.02,130.91,128.21,128.08,77.37,77.05,76.73,49.00,48.97,7.11.
实施例二十
二(3,5-二甲基苯基)氧膦代替实施例一中的二二芳基氧膦，得到黄色固体P,P-双(3,5-二甲基苯基)-N-(甲基(氧代)(苯基)-λ6-硫杂环丁烷)次膦酰胺的产率为54％。
1H NMR(400MHz,CDCl3)δ8.03(dt,J＝3.4,2.3Hz,2H),7.66–7.60(m,1H),7.57–7.52(m,3H),7.51–7.45(m,3H),7.06(s,2H),3.38(s,3H),2.31(d,J＝4.5Hz,12H).
13C NMR(101MHz,CDCl3)δ141.41,141.35,137.85,137.81,137.71,137.67,136.52,136.19,135.25,134.85,133.44,133.01,132.98,132.87,132.84,129.28,128.84,128.73,128.61,128.51,127.25,77.32,77.00,76.69,47.77,47.75,21.30,21.29,21.28,21.28.
Melting point:158.6-161℃.
实施例二十一
二(4-甲基苯基)氧膦代替实施例一中的二二芳基氧膦，得到黄色固体N-(甲基(氧代)(苯基)-λ6-亚磺酰基)-P,P-对二对甲苯基次膦酰胺的产率为69％。
1H NMR(400MHz,CDCl3)δ8.03(ddd,J＝7.1,3.0,1.8Hz,2H),7.82–7.71(m,4H),7.66–7.60(m,1H),7.58–7.51(m,2H),7.24–7.15(m,4H),3.39(s,3H),2.34(s,6H).
13C NMR(101MHz,CDCl3)δ141.44,141.41,141.37,141.34,141.29,133.81,133.51,132.51,132.13,131.27,131.16,131.01,130.91,129.34,129.04,129.00,128.90,128.87,127.27,77.34,77.02,76.71,47.93,47.91,21.54.
Melting point:123.5-124.9℃.

Claims (1)

1.一种N-二芳基氧膦基亚砜亚胺类化合物的合成方法，其特征在于：在氧化剂双氧水存在下，聚乙二醇400作溶剂，碘单质催化二芳基氧膦和亚砜亚胺进行N-P键氧化偶联一步合成N-二芳基氧膦基亚砜亚胺类化合物；所述的亚砜亚胺选自S-甲基-S-苯基亚砜亚胺、1-氟-4-(S-甲基亚砜亚胺)苯、1-氟-2-(S-甲基亚砜亚胺)苯、1-氯-3-(S-甲基亚砜亚胺)苯、1-氯-2-(S-甲基亚砜亚胺)苯、1-溴-3-(S-甲基亚砜亚胺)苯、1-溴-4-(S-甲基亚砜亚胺)苯、1-硝基-4-(S-甲基亚砜亚胺)苯、S-苯基-S-乙基亚砜亚胺、S-苯基-S-环丙基亚砜亚胺、S,S-二苯基亚砜亚胺、S-甲基S-(2-甲氧基苯基)亚砜亚胺、S-苯基-S-(苯基甲基)亚砜亚胺、S，S-二苄基亚砜亚胺、S，S-二丁基亚砜亚胺、S，S-二乙基亚砜亚胺、S-甲基-S-(2-吡啶基)-亚砜亚胺、S构型S-甲基-S-苯基亚砜亚胺和消旋的S-甲基-S-苯基亚砜亚胺；所述的二芳基氧膦选自二苯基氧膦、二(4-甲基苯基)氧膦、二(3,5-二甲基苯基)氧膦。
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