CN109438510B - P-炔基磷酸酯类化合物的合成方法 - Google Patents
P-炔基磷酸酯类化合物的合成方法 Download PDFInfo
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- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/40—Esters thereof
- C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
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- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/655—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms
- C07F9/65515—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms the oxygen atom being part of a five-membered ring
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- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
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- C07F9/65517—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms the oxygen atom being part of a five-membered ring condensed with carbocyclic rings or carbocyclic ring systems
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- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having sulfur atoms, with or without selenium or tellurium atoms, as the only ring hetero atoms
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Abstract
Description
技术领域
本发明涉及化学合成技术领域,特别是涉及一种P-炔基磷酸酯类化合物的合成方法。
背景技术
炔基磷酸酯是一种可以转化为其他杂环化合物的关键中间体,在有机合成及药物合成中具有重要意义,且其本身具有多种生物活性和光电导性。因而,炔基磷酸酯的制备引起了人们广泛的研究兴趣。典型的合成方法为:将六甲基二硅基氨基锂(LiHMDS)、氯磷酸二乙酯[ClP(O)(OEt)2]和LiHMDS依次加入到P-酰乙基磷酸酯的无水溶液中反应;在加入LiHMDS反应时的温度控制在-10~-78℃;加入ClP(O)(OEt)2后,体系升温至10~30℃下反应,通过反应获得各种不同取代的炔基磷酸酯类化合物。然而,在金属催化剂存在下,该反应成本高、反应条件苛刻、产率低。因此,人们一直致力于寻求在不存在任何过渡金属催化剂的情况下高产率制备炔基磷酸酯的方法。
发明内容
基于此,本发明提供了一种新的P-炔基磷酸酯类化合物的合成方法,该方法不需要用到金属催化剂,反应条件温和,并且反应的产率高。
具体技术方案如下:
一种P-炔基磷酸酯类化合物的合成方法,包括如下步骤:
在保护气体的氛围下,P-酰乙基磷酸酯类化合物、吡啶盐和有机碱在有机溶剂中进行反应,
所述P-炔基磷酸酯类化合物具有通式1所示结构,所述P-酰乙基磷酸酯类化合物具有通式2所示结构,
其中,R1和R2分别独立地选自:烷基、取代的烷基、芳基、取代的芳基、杂芳基、取代的杂芳基;
所述有机碱为分子中不含金属的胺类化合物。
在其中一些实施例中,R1和R2分别独立地选自:C1-10烷基、取代的C1-10烷基、C6-10芳基、取代的C6-10芳基、C1-9杂芳基、取代的C1-9杂芳基。
在其中一些实施例中,R1选自:C6-10芳基、R4取代的C6-10芳基、C1-9杂芳基、R4取代的C1-9杂芳基;R2选自:C1-10烷基、R4取代的C1-10烷基;R4选自:卤素、C1-4烷基、C1-4烷氧基、苯基。
在其中一些实施例中,R1选自:苯基、卤素取代的苯基、甲基取代的苯基、甲氧基取代的苯基、3、4-二亚甲氧基苯基、联苯基、萘基、甲氧基取代的萘基、呋喃基、噻吩基;R2选自:C1-4烷基。
在其中一些实施例中,所述吡啶盐选自2-氯-1-甲基碘化吡啶、1,2-二甲基碘化吡啶中的至少一种。
在其中一些实施例中,所述有机碱为三乙胺。
在其中一些实施例中,所述有机溶剂选自二氯甲烷、二氯乙烷中的至少一种。
在其中一些实施例中,所述P-酰乙基磷酸酯类化合物、所述吡啶盐和所述有机碱的摩尔比为:1:0.8-1.2:0.8-1.2。
在其中一些实施例中,所述反应的温度为10-40℃。
在其中一些实施例中,所述反应的时间为2-4小时。
在其中一些实施例中,所述保护气体为氮气。
本发明的新的P-炔基磷酸酯类化合物的合成方法与过去已经报道的方法相比,具有以下优点和有益效果:
(1)实用性好,反应条件温和,为室温反应,易于实现含有各种不同取代基组合的P-炔基磷酸酯衍生物的制备;(2)反应收率高(利用本发明的方法以不小于90%的收率制备得到了一系列P-炔基磷酸酯类化合物),并且反应操作简便,为一锅法反应,不需要对中间体进行分离,且目标化合物易分离和提纯;(3)原料廉价易得,不需要使用各种昂贵的芳炔试剂和金属催化剂。
附图说明
图1为化合物2a的1HNMR图谱;
图2为化合物2b的1HNMR图谱;
图3为化合物2c的1HNMR图谱;
图4为化合物2d的1HNMR图谱;
图5为化合物2e的1HNMR图谱;
图6为化合物2f的1HNMR图谱;
图7为化合物2g的1HNMR图谱;
图8为化合物2h的1HNMR图谱;
图9为化合物2i的1HNMR图谱;
图10为化合物2j的1HNMR图谱;
图11为化合物2k的1HNMR图谱;
图12为化合物2l的1HNMR图谱;
图13为化合物2m的1HNMR图谱;
图14为化合物2n的1HNMR图谱;
图15为化合物2o的1HNMR图谱;
图16为化合物2p的1HNMR图谱;
图17为化合物2q的1HNMR图谱;
图18为化合物2r的1HNMR图谱;
图19为化合物2s的1HNMR图谱。
具体实施方式
以下结合具体的实施例对本发明做进一步详细的说明。
以下实施例的制备方法如下:
1)在氮气保护下,将P-酰乙基磷酸酯类化合物(化合物1,1.0mmol),Mukaiyama试剂(1,2-二甲基碘化吡啶(DMPI))(1.0mmol)、三乙胺(1.0mmol)加入5.0mL二氯甲烷中,搅拌反应3小时。
2)用饱和氯化铵溶液猝灭反应,将混合液注入水中,用乙酸乙酯萃取,有机相用饱和食盐水洗涤,无水硫酸钠干燥,过滤后减压蒸除溶剂;残余物通过硅胶柱层析分离,淋洗液为[石油醚:乙酸乙酯=5:1],得P-炔基磷酸酯类化合物(化合物2)。
实施例1
对苯基乙炔基-P,P-二乙基膦酸酯
P-(2-Phenylethynyl)-diethyl phosphonate(2a)
1H NMR(400MHz,CDCl3)δ=7.55(d,J=7.1Hz,2H),7.45(t,J=7.5Hz,1H),7.36(t,J=7.4Hz,2H),4.26–4.18(m,4H),1.40(t,J=7.0Hz,6H)ppm.
13C NMR(100MHz,CDCl3)δ=132.8,132.7,130.8,128.7,119.7,119.6,99.4,98.9,80.0,77.0,63.4,63.3,16.3,16.2ppm.
31PNMR(160MHz,CDCl3)δ=-5.92ppm.
MS(EI):m/z=89.1(12),102.1(100),165.0(27),182.0(11),195.0(18),210.0(24),238.1(M+,16).
IR(KBr):ν=3058,2986,2934,2908,2187,1489,1444,1390,1265,1163,1024,974,857,760,690,650cm-1.
HRMS(EI):calcd.for[C12H15O3P]+:238.0759,found 238.0753.
实施例2
P-(4-甲基苯基乙炔基)-P,P-二乙基膦酸酯
P-(2-(4-Methylphenyl)ethynyl)-diethyl phosphonate(2b)
1H NMR(400MHz,CDCl3)δ=7.44(d,J=8.1Hz,2H),7.16(d,J=8.0Hz,2H),4.25–4.16(m,4H),2.37(s,3H),1.39(t,J=7.1Hz,6H)ppm.
13C NMR(100MHz,CDCl3)δ=141.5,132.7,132.7,129.4,116.5,116.5,100.1,99.5,79.3,76.3,63.3,63.3,21.8,16.3,16.2ppm.
31PNMR(160MHz,CDCl3)δ=-4.59ppm.
MS(EI):m/z=103.1(5),116.1(100),179.1(31),196.1(11),209.1(48),224.1(38),237.1(8),252.1(M+,46).
IR(KBr):ν=2985,2934,2905,2184,1508,1266,1158,1023,973,863,815,788,739,608cm-1.
HRMS(EI):calcd.for[C13H17O3P]+:252.0915,found 252.0910.
实施例3
P-(2-甲基苯基乙炔基)-P,P-二乙基膦酸酯
P-(2-(2-Methylphenyl)ethynyl)-diethyl phosphonate(2c)
1H NMR(400MHz,CDCl3)δ=7.50(d,J=7.6Hz,1H),7.32(t,J=7.5Hz,1H),7.22(d,J=7.6Hz,1H),7.17(t,J=7.6Hz,1H),4.26–4.17(m,4H),2.46(s,3H),1.39(t,J=7.1Hz,6H)ppm.
13C NMR(100MHz,CDCl3)δ=141.9,141.9,133.19,133.16,130.8,129.9,125.9,119.5,119.4,104.2,98.7,98.2,83.5,80.5,63.4,63.3,20.6,16.3,16.2ppm.
31PNMR(160MHz,CDCl3)δ=-5.87ppm.
MS(EI):m/z=103.1(10),115.1(100),178.1(18),196.1(39),224.1(5),252.1(M+,45).
IR(KBr):ν=2985,2938,2911,2182,1480,1453,1388,1265,1161,1024,974,868,785,762,647cm-1.
HRMS(EI):calcd.for[C13H17O3P]+:252.0907,found 252.0910.
实施例4
P-(3,4-二甲基苯基乙炔基)-P,P-二乙基膦酸酯
P-(2-(3,4-Dimethylphenyl)ethynyl)-diethyl phosphonate(2d)
1HNMR(400MHz,CDCl3)δ=7.32(s,1H),7.29(d,J=7.8Hz,1H),7.11(d,J=7.8Hz,1H),4.24–4.16(m,4H),2.26(s,3H),2.23(s,3H),1.38(t,J=7.1Hz,6H)ppm.
13C NMR(100MHz,CDCl3)δ=140.3,137.2,133.63,133.60,130.27,130.25,129.9,116.7,116.7,100.4,99.8,78.9,75.9,63.31,63.25,20.1,19.6,16.24,16.17ppm.
31PNMR(160MHz,CDCl3)δ=-4.48ppm.
MS(EI):m/z=115.1(39),130.1(100),193.1(10),223.1(29),238.1(17),251.1(4),266.1(M+,21).
IR(KBr):ν=2985,2938,2905,2177,1450,1451,1393,1268,1164,1024,972,803,624cm-1.
HRMS(EI):calcd.for[C14H19O3P]+:266.1072,found 266.1066.
实施例5
P-(4-甲氧基苯基乙炔基)-P,P-二乙基膦酸酯
P-(2-(4-Methoxyphenyl)ethynyl)-diethyl phosphonate(2e)
1H NMR(400MHz,CDCl3)δ=7.47(d,J=8.7Hz,2H),6.85(d,J=8.9Hz,2H),4.23–4.13(m,4H),3.80(s,3H),1.37(t,J=7.1Hz,6H)ppm.
13C NMR(100MHz,CDCl3)δ=161.5,134.50,134.48,114.3,111.4,111.3,100.2,99.6,78.7,75.7,63.23,63.17,55.5,16.23,16.16ppm.
31PNMR(160MHz,CDCl3)δ=-5.43ppm.
MS(EI):m/z=107(1),119(4),132(100),195(8),225(15),240(16),268(M+,19).
IR(KBr):ν=2982,2938,2905,2182,1603,1509,1295,1257,1172,1024,973,866,837,787cm-1.
HRMS(EI):calcd.for[C13H17O4P]+:268.0864,found 268.0859.
实施例6
P-(2,5-二甲氧基苯基乙炔基)-P,P-二乙基膦酸酯
P-(2-(2,5-Dimethoxyphenyl)ethynyl)-diethyl phosphonate(2f)
1H NMR(400MHz,CDCl3)δ=7.00(d,J=3.1Hz,1H),6.95(dd,J=9.1,3.1Hz,1H),6.81(d,J=9.1Hz,1H),4.27–4.18(m,4H),3.81(s,3H),3.75(s,3H),1.39(t,J=7.1Hz,6H)ppm.
13C NMR(100MHz,CDCl3)δ=156.23,156.21,153.1,118.9,118.48,118.45,112.3,109.3,109.2,96.6,96.1,83.5,80.6,63.4,63.3,56.4,56.0,16.24,16.17ppm.
31PNMR(160MHz,CDCl3)δ=-5.78ppm.
MS(EI):m/z=147(59),161(100),224(24),242(68),270(23),283(9),298(M+,77).
IR(KBr):ν=2985,2938,2905,2837,2181,1501,1463,1267,1234,1166,1024,962,804,724,662,611cm-1.
HRMS(EI):calcd.for[C14H19O5P]+:298.0970,found 298.0965.
实施例7
P-(2-(3,4-二亚甲氧基苯基乙炔基)-P,P-二乙基膦酸酯
P-(2-(3,4-Methylenedioxyphenyl)ethynyl)-diethyl phosphonate(2g)
1H NMR(400MHz,CDCl3)δ=7.10(d,J=8.0Hz,1H),6.95(s,1H),6.77(d,J=8.1Hz,1H),5.99(s,2H),4.23–4.15(m,4H),1.37(t,J=7.1Hz,6H)ppm.
13C NMR(100MHz,CDCl3)δ=150.1,147.7,128.43,128.41,112.61,112.55,112.18,112.16,108.8,101.9,99.8,99.3,78.4,75.4,63.32,63.27,16.24,16.17ppm.
31PNMR(160MHz,CDCl3)δ=-5.70ppm.
MS(EI):m/z=133.1(4),146.1(100),209.0(9),239.0(9),254.1(15),282.1(M+,39).
IR(KBr):ν=2986,2907,2179,1604,1505,1489,1443,1339,1253,1207,1131,1101,1029,974,822,754,664,593cm-1.
HRMS(EI):calcd.for[C13H15O5P]+:282.0657,found 282.0652.
实施例8
P-(4-氟苯基乙炔基)-P,P-二乙基膦酸酯
P-(2-(4-Fluorophenyl)ethynyl)-diethyl phosphonate(2h)
1H NMR(400MHz,CDCl3)δ=7.54(dd,J=8.6,5.4Hz,2H),7.05(t,J=8.6Hz,2H),4.25–4.15(m,4H),1.38(t,J=7.1Hz,6H)ppm.
13C NMR(100MHz,CDCl3)δ=165.2,162.7,135.04,135.01,134.95,134.9,116.3,116.1,115.84,115.80,115.78,115.7,98.3,97.7,79.9,77.0,63.4,63.3,16.24,16.18ppm.
31PNMR(160MHz,CDCl3)δ=-6.18ppm.
MS(EI):m/z=107.1(15),120.1(100),183.1(20),200.1(7),213.1(16),228.1(16),256.1(M+,10).
IR(KBr):ν=2985,2935,2905,2189,1599,1508,1267,1236,1160,1024,975,867,843,800,742cm-1.
HRMS(EI):calcd.for[C12H14FO3P]+:256.0665,found 256.0659.
实施例9
P-(4-氯苯基乙炔基)-P,P-二乙基膦酸酯
P-(2-(4-Chlorophenyl)ethynyl)-diethyl phosphonate(2i)
1H NMR(400MHz,CDCl3)δ=7.47(d,J=8.3Hz,2H),7.33(d,J=8.3Hz,2H),4.25–4.15(m,4H),1.38(t,J=7.0Hz,6H)ppm.
13C NMR(100MHz,CDCl3)δ=137.2,133.92,133.89,130.90,129.10,118.10,118.00,98.00,97.4,81.0,78.0,63.44,63.38,16.24,16.17ppm.
31PNMR(160MHz,CDCl3)δ=-5.31ppm.
MS(EI):m/z=123.1(10),136.1(100),199.9(19),229.0(20),244.0(18),272.1(M+,17).
IR(KBr):ν=2986,2935,2908,2189,1587,1488,1393,1267,1092,1022,975,858,832,762,701cm-1.
HRMS(EI):calcd.for[C12H14ClO3P]+:272.0369,found 272.0364.
实施例10
P-(4-溴苯基乙炔基)-P,P-二乙基膦酸酯
P-(2-(4-Bromophenyl)ethynyl)-diethyl phosphonate(2j)
1H NMR(400MHz,CDCl3)δ=7.50(d,J=8.5Hz,2H),7.40(d,J=8.4Hz,2H),4.25–4.16(m,4H),1.39(t,J=7.1Hz,6H)ppm.
13C NMR(100MHz,CDCl3)δ=134.1,134.0,132.1,125.6,118.61,118.56,98.0,97.5,81.2,78.2,63.5,63.4,16.3,16.2ppm.
31PNMR(160MHz,CDCl3)δ=-6.39ppm.
MS(EI):m/z=101.1(29),169.0(10),180.0(100),260(9),273.0(22),290.1(17),316.1(M+,16).
IR(KBr):ν=2985,2938,2905,2187,1483,1391,1265,1164,1025,976,857,823,761,680cm-1.
HRMS(EI):calcd.for[C12H14BrO3P]+:315.9864,found 315.9858.
实施例11
P-(4-碘苯基乙炔基)-P,P-二乙基膦酸酯
P-(2-(4-Iodophenyl)ethynyl)-diethyl phosphonate(2k)
1H NMR(400MHz,CDCl3)δ=7.70(dd,J=10.1,8.4Hz,2H),7.24(dd,J=11.3,5.9Hz,2H),4.23–4.13(m,4H),1.37(m,6H)ppm.
13C NMR(100MHz,CDCl3)δ=138.1,138.0,133.92,133.90,130.8,119.1,119.0,98.2,97.7,81.4,78.4,63.5,63.4,16.3,16.2ppm.
31PNMR(160MHz,CDCl3)δ=-5.30ppm.
MS(EI):m/z=89.1(11),101.1(32),164.1(6),193.1(4),209.1(15),228.0(100),290.9(16),321.0(20),336.0(25),364.0(M+,27).
IR(KBr):ν=2984,2938,2902,2187,1479,1392,1263,1024,975,856,820,760,668cm-1.
HRMS(EI):calcd.for[C12H14IO3P]+:363.9725,found 363.9720.
实施例12
P-联苯基乙炔基-P,P-二乙基膦酸酯
P-(2-Bi phenylethynyl)-diethyl phosphonate(2l)
1H NMR(400MHz,CDCl3)δ=7.64–7.55(m,6H),7.44(t,J=7.5Hz,2H),7.37(t,J=7.3Hz,1H),4.28–4.19(m,4H),1.41(t,J=7.1Hz,6H)ppm.
13C NMR(100MHz,CDCl3)δ=143.5,139.7,133.2,133.1,129.0,128.3,127.3,127.2,118.3,118.2,99.4,99.0,80.5,77.4,63.4,63.3,16.3,16.2ppm.
31PNMR(160MHz,CDCl3)δ=-5.93ppm.
MS(EI):m/z=165.1(15),178.1(100),241.1(7),271.1(14),286.1(19),314.2(M+,38).
IR(KBr):ν=3036,2982,2938,2908,2184,1485,1265,1023,974,861,765,695,635cm-1.
HRMS(EI):calcd.for[C18H19O3P]+:314.1072,found 314.1066.
实施例13
P-(2-萘基乙炔基)-P,P-二乙基膦酸酯
P-(2-(2-Naphthalenyl)ethynyl)-diethyl phosphonate(2m)
1H NMR(400MHz,CDCl3)δ=8.10(s,1H),7.84–7.78(m,3H),7.56–7.49(m,3H),4.29–4.21(m,4H),1.41(t,J=7.1Hz,6H)ppm.
13C NMR(100MHz,CDCl3)δ=133.89,133.86,133.85,132.5,128.5,128.1,128.0,127.94,127.92,127.89,127.1,116.73,116.67,99.8,99.3,80.0,77.1,63.4,63.3,16.3,16.2ppm.
31PNMR(160MHz,CDCl3)δ=-5.94ppm.
MS(EI):m/z=139.1(14),152.1(100),215.1(7),245.1(10),260.1(16),288.1(M+,34).
IR(KBr):ν=3057,2985,2932,2908,2185,1266,1159,1024,964,905,861,792,750,632,592cm-1.
HRMS(EI):calcd.for[C16H17O3P]+:288.0915,found 288.0910.
实施例14
P-((6-甲氧基-2-萘基)乙炔基)-P,P-二乙基膦酸酯
P-(2-(6-Methoxy-2-naphthalenyl)ethynyl)-diethyl phosphonate(2n)
1H NMR(400MHz,CDCl3)δ=8.02(s,1H),7.68(dd,J=8.5,5.1Hz,2H),7.49(d,J=8.5Hz,1H),7.16(d,J=9.0Hz,1H),7.09(s,1H),4.29–4.19(m,4H),3.90(s,3H),1.41(t,J=7.0Hz,6H)ppm.
13C NMR(100MHz,CDCl3)δ=159.4,135.5,133.7,133.6,129.7,128.7,128.6,128.0,127.2,120.1,114.2,114.1,105.9,100.5,99.9,79.4,76.4,63.34,63.29,55.5,16.3,16.2ppm.
31PNMR(160MHz,CDCl3)δ=-5.65ppm.
MS(EI):m/z=139.1(21),182.1(100),244.1(9),275.1(7),290.1(19),318.1(M+,61).
IR(KBr):ν=2985,2935,2905,2179,1625,1480,1391,1263,1262,1162,1024,970,941,784,703,638cm-1.
HRMS calcd.for[C17H19O4P]+:318.1021,found 318.1015.
实施例15
P-(2-呋喃基乙炔基)-P,P-二乙基膦酸酯
P-(2-(2-Furanyl)ethynyl)-diethyl phosphonate(2o)
1H NMR(400MHz,CDCl3)δ=7.45(d,J=0.8Hz,1H),6.85(d,J=3.5Hz,1H),6.42(dd,J=3.4,1.7Hz,1H),4.23–4.14(m,4H),1.36(t,J=7.1Hz,6H)ppm.
13C NMR(100MHz,CDCl3)δ=145.9,134.6,134.5,120.24,120.22,111.4,88.9,88.3,85.1,82.2,63.6,63.5,16.2,16.1ppm.
31PNMR(160MHz,CDCl3)δ=-6.79ppm.
MS(EI):m/z=92.1(100),155.1(15),172.1(7),185.1(17),200.1(8),228.1(M+,19).
IR(KBr):ν=3122,2987,2938,2908,2183,1471,1391,1267,1215,1162,1024,977,944,811,757cm-1.
HRMS(EI):calcd.for[C10H13O4P]+:228.0546,found 228.0546.
实施例16
P-(2-噻吩基乙炔基)-P,P-二乙基膦酸酯
P-(2-(2-Thiophenyl)ethynyl)-diethyl phosphonate(2p)
1H NMR(400MHz,CDCl3)δ=7.42(d,J=5.2Hz,2H),7.01(t,J=4.3Hz,1H),4.19(m,4H),1.37(t,J=7.0Hz,6H)ppm.
13C NMR(100MHz,CDCl3)δ=136.1,136.0,130.7,127.5,119.33,119.27,92.8,92.3,84.0,81.0,63.44,63.38,16.23,16.16ppm.
31PNMR(160MHz,CDCl3)δ=-6.27ppm.
MS(EI):m/z=95.1(6),108.1(100),171.0(12),201.0(15),216.1(12),244.1(M+,13).
IR(KBr):ν=3077,2986,2938,2908,2174,1263,1174,1023,976,852,801,715,638cm-1.
HRMS(EI):calcd.for[C10H13O3PS]+:244.0319,found 244.0318.
实施例17
对苯基乙炔基-P,P-二甲基膦酸酯
P-(2-Phenylethynyl)-dimethyl phosphonate(2q)
1H NMR(400MHz,CDCl3)δ=7.54(d,J=7.5Hz,2H),7.44(t,J=7.4Hz,1H),7.35(t,J=7.6Hz,2H),3.83(d,J=12.3Hz,6H)ppm.
13C NMR(100MHz,CDCl3)δ=132.8,132.7,130.9,128.7,119.30,119.28,100.3,99.8,78.4,75.4,53.53,53.47ppm.
31P NMR(160MHz,CDCl3)δ=-2.77ppm.
MS(EI):m/z=89(9),102(100),115(48),179(6),195(6),210(M+,22).
IR(KBr):ν=3063,3000,2956,2852,2187,1492,1450,1271,1179,1033,861,840,765,689,647cm-1.
HRMS(EI)calcd.for[C10H11O3P]+:210.0448,found 210.0440.
实施例18
对苯基乙炔基-P,P-二异丙基膦酸酯
P-(2-Phenylethynyl)-bis(1-methylethyl)phosphonate(2r)
1H NMR(400MHz,CDCl3)δ=7.51(d,J=7.5Hz,2H),7.40(t,J=7.4Hz,1H),7.33(t,J=7.5Hz,2H),4.84–4.71(m,2H),1.37(d,J=6.1Hz,12H)ppm.
13C NMR(100MHz,CDCl3)δ=132.53,132.50,130.6,128.6,119.9,119.8,98.4,97.9,81.4,78.4,72.40,72.35,24.0,23.9,23.7,23.6ppm.
31PNMR(160MHz,CDCl3)δ=-8.60ppm.
MS(EI):m/z=89(17),102(100),165(55),183(78),209(80),225(69),266(M+,3).
IR(KBr):ν=3063,3000,2956,2852,2187,1492,1450,1271,1179,1033,861,840,765,689,647cm-1.
HRMS(EI)calcd.for[C14H19O3P]+:266.1061,found 266.1066.
实施例19
对苯基乙炔基-P,P-二正丁基膦酸酯
P-(2-Phenylethynyl)-dibutyl phosphonate(2s)
1H NMR(400MHz,CDCl3)δ=7.53(d,J=7.1Hz,2H),7.42(t,J=7.5Hz,1H),7.34(t,J=7.4Hz,2H),4.13(dd,J=14.2,6.7Hz,4H),1.74–1.65(m,4H),1.48–1.38(m,4H),0.92(t,J=7.4Hz,6H)ppm.
13C NMR(100MHz,CDCl3)δ=132.7,132.6,130.7,128.6,119.7,119.6,99.4,98.8,79.9,76.9,70.0,66.9,32.3,32.2,18.8,13.6ppm.
31PNMR(160MHz,CDCl3)δ=-5.60ppm.
MS(EI):m/z=89(6),102(36),165(30),183(100),209(7),223(6),239(27),294(M+,1.5).
IR(KBr):ν=2961,2935,2869,2187,1465,1271,1066,1025,992,900,858,761,695,653cm-1.
HRMS(EI)calcd.for[C16H23O3P]+:294.1374,found 294.1379.
实施例1-实施例19的产物收率如下表所示:
以上所述实施例的各技术特征可以进行任意的组合,为使描述简洁,未对上述实施例中的各个技术特征所有可能的组合都进行描述,然而,只要这些技术特征的组合不存在矛盾,都应当认为是本说明书记载的范围。
以上所述实施例仅表达了本发明的几种实施方式,其描述较为具体和详细,但并不能因此而理解为对发明专利范围的限制。应当指出的是,对于本领域的普通技术人员来说,在不脱离本发明构思的前提下,还可以做出若干变形和改进,这些都属于本发明的保护范围。因此,本发明专利的保护范围应以所附权利要求为准。
Claims (9)
2.根据权利要求1所述的P-炔基磷酸酯类化合物的合成方法,其特征在于,R1和R2分别独立地选自:C1-10烷基、取代的C1-10烷基、C6-10芳基、取代的C6-10芳基、C1-9杂芳基、取代的C1-9杂芳基。
3.根据权利要求2所述的P-炔基磷酸酯类化合物的合成方法,其特征在于,R1选自:C6-10芳基、R4取代的C6-10芳基、C1-9杂芳基、R4取代的C1-9杂芳基;R2选自:C1-10烷基、R4取代的C1-10烷基;R4选自:卤素、C1-4烷基、C1-4烷氧基、苯基。
4.根据权利要求3所述的P-炔基磷酸酯类化合物的合成方法,其特征在于,R1选自:苯基、卤素取代的苯基、甲基取代的苯基、甲氧基取代的苯基、3、4-二亚甲氧基苯基、联苯基、萘基、甲氧基取代的萘基、呋喃基、噻吩基;R2选自:C1-4烷基。
5.根据权利要求1-4任一项所述的P-炔基磷酸酯类化合物的合成方法,其特征在于,所述有机溶剂选自二氯甲烷、二氯乙烷中的至少一种。
6.根据权利要求1-4任一项所述的P-炔基磷酸酯类化合物的合成方法,其特征在于,所述P-酰乙基磷酸酯类化合物、所述吡啶盐和所述有机碱的摩尔比为:1:0.8-1.2:0.8-1.2。
7.根据权利要求1-4任一项所述的P-炔基磷酸酯类化合物的合成方法,其特征在于,所述反应的温度为10-40℃。
8.根据权利要求1-4任一项所述的P-炔基磷酸酯类化合物的合成方法,其特征在于,所述反应的时间为2-4小时。
9.根据权利要求1-4任一项所述的P-炔基磷酸酯类化合物的合成方法,其特征在于,所述保护气体为氮气。
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"Facile Synthesis of 1-Alkynylphosphonates";Jong Eoun Hong et al.,;《SYNTHETIC COMMUNICATIONS》;20060815;第26卷(第8期);第1563-1567页 * |
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