CN105837625B - 一种β‑酮基取代的磷酸酯类化合物的制备方法 - Google Patents
一种β‑酮基取代的磷酸酯类化合物的制备方法 Download PDFInfo
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- 229940071125 manganese acetate Drugs 0.000 claims abstract description 7
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims abstract description 7
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- -1 2- oxo octyl Chemical group 0.000 claims description 5
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- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- CZHYKKAKFWLGJO-UHFFFAOYSA-N dimethyl phosphite Chemical compound COP([O-])OC CZHYKKAKFWLGJO-UHFFFAOYSA-N 0.000 claims description 4
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- RQKYHDHLEMEVDR-UHFFFAOYSA-N oxo-bis(phenylmethoxy)phosphanium Chemical compound C=1C=CC=CC=1CO[P+](=O)OCC1=CC=CC=C1 RQKYHDHLEMEVDR-UHFFFAOYSA-N 0.000 claims description 4
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims 1
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- NFORZJQPTUSMRL-UHFFFAOYSA-N dipropan-2-yl hydrogen phosphite Chemical compound CC(C)OP(O)OC(C)C NFORZJQPTUSMRL-UHFFFAOYSA-N 0.000 description 3
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- 125000004800 4-bromophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Br 0.000 description 2
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- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
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- 229910019142 PO4 Inorganic materials 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910001914 chlorine tetroxide Inorganic materials 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 229940095102 methyl benzoate Drugs 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
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- 239000012074 organic phase Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
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- 239000000758 substrate Substances 0.000 description 1
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- 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
- C07F9/30—Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
- C07F9/32—Esters thereof
- C07F9/3205—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
- C07F9/3241—Esters of arylalkanephosphinic acids
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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
- C07F9/4056—Esters of arylalkanephosphonic acids
- C07F9/4059—Compounds containing the structure (RY)2P(=X)-(CH2)n-C(=O)-(CH2)m-Ar, (X, Y = O, S, Se; n>=1, m>=0)
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Abstract
本发明提供一种β‑酮基取代的磷酸酯类化合物的制备方法,以烯烃叠氮、亚磷酸酯为起始原料,在有机溶剂中,以醋酸锰为氧化剂,反应生成β‑酮基取代的磷酸酯类化合物。本发明提供的制备方法设计合理、原料易得,反应条件温和、不需高温回流、安全方便,产率高、大部分产物的产率在70%以上。是一种操作简单、快速、温和、多元化的构建β‑酮基取代的磷酸酯类化合物的方法,其中两个起始原料都可以通过一步法得到,反应原料便宜易得。本发明的所述的β‑酮基取代的磷酸酯类化合物的通式I如下:
Description
技术领域
本发明属化合物合成领域,主要涉及一种β-酮基取代的磷酸酯类化合物的制备方法。
背景技术
有机磷酸酯是一类重要的化学中间体,广泛应用于有机合成、材料化学、药物化学和配体化学等领域。其中有β-酮基取代的磷酸酯在化学合成中主要应用于C-C键的构建得到相应的烯烃、环丙烷或者是直链的酮等,目前文献中报道的用于合成β-酮基取代的磷酸酯主要包括强碱条件下甲基磷酸酯与乙酸乙酯的取代反应、α-氯代酮与亚磷酸三乙酯的取代反应等。但是目前报道的方法中,或是反应条件恶劣、亦或是底物取代基范围受限,这些因素促使开发一类新的构建β-酮基取代的磷酸酯类化合物的方法。
发明内容
本发明的目的是提供一种β-酮基取代的磷酸酯类化合物的制备方法,即将烯基叠氮类衍生物和亚磷酸酯,在醋酸锰的氧化下,在室温条件下进行反应,就可以得到目标化合物β-酮基取代的磷酸酯类化合物,结构通式如下:
本发明提供的一种β-酮基取代的磷酸酯类化合物的制备方法,具体通过以下步骤实现:
以烯烃叠氮、亚磷酸酯为起始原料,在有机溶剂中,以醋酸锰为氧化剂,反应生成的β-酮基取代的磷酸酯类化合物;烯烃叠氮、亚磷酸酯、醋酸锰的摩尔比为1:1:2,反应温度为室温,反应时间为6个小时,所得目标产物I通过硅胶色谱柱层析的方法纯化,反应式为:
其中:
R1为单取代或多取代的芳环、C1-C3链烷烃、其中单取代的芳环的取代基选用卤素、硝基、烷氧基、烷基、酯基;
R2和R3为C2-C4链烷氧基、苄氧基、芳环。
所用的溶剂选用DMF。
目标产物I通过硅胶色谱柱层析的方法纯化的洗脱剂选用石油醚:乙酸乙酯=4:1
本发明式I所示的β-酮基取代的磷酸酯类化合物为如下任一化合物:
(2-氧代-2-苯乙基)亚磷酸二乙酯(实施例1)
(2-(4-甲基苯基)-2-氧代乙基)亚磷酸二乙酯(实施例2)
(2-(3-溴-4-乙氧基苯基)2-氧代乙基)亚磷酸二乙酯(实施例3)
(2-(4-溴苯基)-2-氧代乙基)亚磷酸二乙酯(实施例4)
(2-(4-氯苯基)-2-氧代乙基)亚磷酸二乙酯(实施例5)
(2-(3-溴苯基)-2-氧代乙基)亚磷酸二乙酯(实施例6)
(2-氧代-2-(对甲苯基)乙基)亚磷酸二乙酯(实施例7)
(2-(3-硝基苯基)-2-氧代乙基)亚磷酸二乙酯(实施例8)
(2-(4-甲氧基苯基)-2-氧代乙基)亚磷酸二乙酯(实施例9)
(2-氧代辛基)亚磷酸二乙酯(实施例10)
(2-氧代-2-苯乙基)亚磷酸二甲酯(实施例11)
(2-氧代-2-苯乙基)亚磷酸二异丙酯(实施例12)
(2-氧代-2-苯乙基)亚磷酸二苄酯(实施例13)
(2-氧代-2-苯乙基)亚磷酸二苯酯(实施例14)
(2-氧代-2-苯乙基)(苯基)亚磷酸苄酯(实施例15)
(2-(3-硝基苯基)-2-氧代乙基)(苯基)亚磷酸苄酯(实施例16)。
本发明提供一种β-酮基取代的磷酸酯类化合物的制备方法,以烯烃叠氮、亚磷酸酯为起始原料,在有机溶剂中,以醋酸锰为氧化剂,反应生成的β-酮基取代的磷酸酯类化合物。本发明提供的制备方法设计合理、原料易得,反应条件温和、不需高温回流、安全方便,产率高、大部分产物的产率在70%以上。是一种操作简单、快速、温和、多元化的构建β-酮基取代的磷酸酯类化合物的方法,其中两个起始原料都可以通过一步法得到,反应原料便宜易得,本发明的制备方法是未见报道的。
具体实施方式
本发明结合实施例作进一步的说明。
实施例1:(2-氧代-2-苯乙基)亚磷酸二乙酯的制备
将(1-叠氮基乙烯基)苯(1mmol,145mg),亚磷酸二乙酯(1.0mmol,138mg)加入玻璃封管中,后加入2.0mL的DMF,加料完毕后,在室温反应,TLC检测反应(乙酸乙酯:石油醚=1:5),6个小时后反应结束。反应液真空浓缩,浓缩液用乙酸乙酯萃取(20mL×3),有机相合并后用水洗2次,饱和食盐水洗1次,无水硫酸钠干燥,过滤,旋干得到残留物,进行柱层析分离(洗脱液为乙酸乙酯:石油醚=1:4),得到黄色液体,收率为92%。
其结构式为:
Yellow oil,236mg,yield 92%.1H NMR(500MHz,CDCl3)δ8.01(d,J=7.0Hz,2H),7.80-7.57(m,1H),7.48(t,J=8.0Hz,2H),4.16-4.10(m,4H),3.62(d,J=22.5Hz,2H),1.27(t,J=7.0Hz,6H).13C NMR(125MHz,CDCl3)δ192.1(d,J=6.25Hz),136.7,133.8,129.2,128.8,62.8(d,J=6.25Hz),38.6(d,J=128Hz),16.4(d,J=6.25Hz).HRMS(ESI):m/zcalcd for(C12H17O4P+H)+:257.0937;found:257.0930。
实施例2:(2-(4-甲基苯基)-2-氧代乙基)亚磷酸二乙酯的制备
合成方法同实施例1,只是将原料1-叠氮烯基苯换成1-叠氮烯基-4-甲基苯。淡黄色液体,收率88%,其结构式为:
Yellow oil,yield 88%.1H NMR(500MHz,CDCl3)δ7.91(d,J=8.0Hz,2H),7.28-7.27(m,2H),4.17-4.11(m,4H),3.61(d,J=22.5Hz,2H),2.42(s,3H),1.28(t,J=7.0Hz,6H).13C NMR(125MHz,CDCl3)δ191.6(d,J=7.5Hz),144.8,134.2,129.4,129.3,62.8(d,J=6.25Hz),38.5(d,J=130Hz),21.81,16.4(d,J=6.25Hz).HRMS(ESI):m/z calcd for(C13H19O4P+H)+:271.1094;found:271.1090。
实施例3:(2-(3-溴-4-乙氧基苯基)2-氧代乙基)亚磷酸二乙酯的制备
合成方法同实施例1,只是将原料1-叠氮烯基苯换成1-叠氮烯基-(3-溴-4-乙氧基)苯。黄色液体,收率79%,其结构式为:
Yellow oil,yield 79%.1H NMR(500MHz,CDCl3)δ8.21(d,J=2.0Hz,1H),7.96(dd,J=8.5,2.0Hz,2H),6.91(d,J=9.0Hz,2H),4.20-4.11(m,4H),3.55(d,J=22.5Hz,2H),1.50(t,J=7.0Hz,3H),1.29(t,J=7.0Hz,6H).13C NMR(125MHz,CDCl3)δ189.4(d,J=6.25Hz),159.8,134.7,130.6,130.5,112.4,112.0,65.3,62.8(d,J=6.25Hz),38.6(d,J=129Hz),16.4(d,J=6.25Hz),14.62.HRMS(ESI):m/z calcd for(C14H20BrO5P+H)+:379.0304;found:379.0306。
实施例4:(2-(4-溴苯基)-2-氧代乙基)亚磷酸二乙酯的制备
合成方法同实施例1,只是将原料1-叠氮烯基苯换成1-叠氮烯基-4-溴苯。黄色液体,收率73%,其结构式为:
Yellow oil,yield 73%.1H NMR(500MHz,CDCl3)δ7.88(d,J=9.0Hz,2H),7.62(d,J=9.0Hz,2H),4.15-4.10(m,4H),3.59(d,J=22.5Hz,2H),1.28(t,J=7.0Hz,6H).13C NMR(125MHz,CDCl3)δ191.1(d,J=6.25Hz),135.4,132.1,130.7,129.2,62.9(d,J=6.25Hz),38.8(d,J=128Hz),16.4(d,J=6.25Hz).HRMS(ESI):m/z calcd for(C12H16BrO4P+H)+:335.0042;found:335.0042。
实施例5:(2-(4-氯苯基)-2-氧代乙基)亚磷酸二乙酯的制备
合成方法同实施例1,只是将原料1-叠氮烯基苯换成1-叠氮烯基-4-氯苯。黄色液体,收率77%,其结构式为:
Yellow oil,yield 77%.1H NMR(500MHz,CDCl3)δ7.96(d,J=8.5Hz,2H),7.45(d,J=8.5Hz,2H),4.15-4.10(m,4H),3.59(d,J=22.5Hz,2H),1.28(t,J=7.0Hz,6H).13C NMR(125MHz,CDCl3)δ190.9(d,J=6.25Hz),140.4,135.0,130.7,129.1,62.9(d,J=6.25Hz),38.8(d,J=129Hz),16.4(d,J=6.25Hz).HRMS(ESI):m/z calcd for(C12H16ClO4P+H)+:291.0547;found:291.0543。
实施例6:(2-(3-溴苯基)-2-氧代乙基)亚磷酸二乙酯的制备
合成方法同实施例1,只是将原料1-叠氮烯基苯换成1-叠氮烯基-3-溴苯。黄色液体,收率70%,其结构式为:
Yellow oil,yield 70%.1H NMR(500MHz,CDCl3)δ8.14(t,J=2.0Hz,1H),7.95(ddd,J=8.0,2.0,1.0Hz,1H),7.72(ddd,J=8.0,2.0,1.0Hz,1H),7.37(t,J=8.0Hz,1H),4.17-4.13(m,4H),3.60(d,J=22.5Hz,2H),1.30(t,J=7.0Hz,6H).13C NMR(125MHz,CDCl3)δ190.8(d,J=6.25Hz),138.3,136.6,132.2,130.3,127.8,123.1,63.0(d,J=6.25Hz),38.8(d,J=128Hz),16.4(d,J=6.25Hz).HRMS(ESI):m/z calcd for(C12H16BrO4P+H)+:335.0042;found:335.0045。
实施例7:(2-氧代-2-(对甲苯基)乙基)亚磷酸二乙酯的制备
合成方法同实施例1,只是将原料(1-叠氮基乙烯基)苯换成4-(1-叠氮基乙烯基)苯甲酸甲酯。黄色液体,收率67%,其结构式为:
Yellow oil,yield 67%.1H NMR(500MHz,CDCl3)δ8.14(d,J=8.5Hz,2H),8.07(d,J=8.5Hz,2H),4.18-4.11(m,4H),3.96(s,3H),3.66(d,J=22.5Hz,2H),1.28(t,J=7.0Hz,6H).13CNMR(125MHz,CDCl3)δ191.7(d,J=6.25Hz),166.3,139.8,134.5,129.9,129.1,123.1,63.0(d,J=6.25Hz),38.8(d,J=129Hz),16.4(d,J=6.25Hz).HRMS(ESI):m/zcalcd for(C14H19O6P+H)+:315.0992;found:315.0996。
实施例8:(2-(3-硝基苯基)-2-氧代乙基)亚磷酸二乙酯的制备
合成方法同实施例1,只是将(1-叠氮基乙烯基)苯换成1-(1-叠氮基乙烯基)3-硝基苯。黄色液体,收率81%,其结构式为:
Yellow oil,yield 81%.1H NMR(500MHz,CDCl3)δ8.86(t,J=2.0Hz 1H),8.45(ddd,J=8.0,2.0,1.0Hz,1H),8.38-8.36(m,1H),7.70(t,J=8.0Hz,1H),4.18-4.14(m,4H),3.68(d,J=23.0Hz,2H),1.30(t,J=7.0Hz,6H).13C NMR(125MHz,CDCl3)δ190.1(d,J=6.25Hz),148.6,137.9,134.7,130.0,127.9,124.1,63.1(d,J=6.5Hz),39.3(d,J=128Hz),38.75,16.4(d,J=6.25Hz).HRMS(ESI):m/z calcd for(C12H16NO6P+H)+:302.0788;found:302.0784。
实施例9:(2-(4-甲氧基苯基)-2-氧代乙基)亚磷酸二乙酯
合成步骤同实施例1,只是将(1-叠氮基乙烯基)苯换成1-(1-叠氮基乙烯基)4-甲氧基苯,得到黄色液体,收率为65%,其结构式为:
Yellow oil,yield 65%.1H NMR(500MHz,CDCl3)δ7.99(d,J=9.0Hz,2H),6.94(d,J=9.0Hz,2H),4.14-4.11(m,4H),3.87(s,3H),3.57(d,J=23Hz,2H),1.28(t,J=7.0Hz,6H).13C NMR(125MHz,CDCl3)δ190.4(d,J=6.5Hz),164.2,131.7,129.9,113.9,62.7(d,J=6.5Hz),55.7,38.5(d,J=129Hz),16.4(d,J=6.5Hz).HRMS(ESI):m/z calcd for(C13H19O5P+H)+:287.1043;found:287.1042。
实施例10:(2-氧代辛基)亚磷酸二乙酯
合成步骤同实施例1,只是将(1-叠氮基乙烯基)苯换成1-叠氮基辛烯基,得到黄色液体,收率为90%,其结构式为:
Yellow oil,yield 90%.1H NMR(500MHz,CDCl3)δ4.16-4.09(m,4H),3.05(d,J=23.0Hz,2H),2.59(t,J=7.5Hz,2H),1.57-1.53(m,2H),1.32(t,J=7.0Hz,6H),1.28-1.26(m,6H),0.85(t,J=7.0Hz,3H).13C NMR(125MHz,CDCl3)δ202.2(d,J=6.25Hz),62.6(d,J=6.25Hz),44.2,42.5(d,J=128Hz),31.7,28.7,23.5,22.6,16.4(d,J=6.25Hz),14.1.HRMS(ESI):m/z calcd for(C12H25O4P+H)+:265.1563;found:265.1559。
实施例11:(2-氧代-2-苯乙基)亚磷酸二甲酯
合成步骤同实施例1,只是将亚磷酸二乙酯换成亚磷酸二甲酯得到黄色液体,收率为88%,其结构式为:
Yellow oil,yield 88%.1H NMR(500MHz,CDCl3)δ8.00(dd,J=8.0,1.5Hz,2H),7.60(t,J=7.5Hz,1H),7.49(t,J=7.5Hz,2H),3.79(s,3H),3.77(s,3H),3.64(d,J=22.5Hz,2H).13CNMR(125MHz,CDCl3)δ191.9(d,J=6.25Hz),136.6,134.0,129.1,128.9,53.3(d,J=6.25Hz),38.1,37.1.HRMS(ESI):m/z calcd for(C10H13O4P+H)+:229.0624;found:229.0626。
实施例12:(2-氧代-2-苯乙基)亚磷酸二异丙酯
合成步骤同实施例1,只是将亚磷酸二乙酯换成亚磷酸二异丙酯,得到黄色液体,收率为84%,其结构式为:
Yellow oil,yield 84%.1H NMR(500MHz,CDCl3)δ8.01(dd,J=8.5,1.5Hz,2H),7.60-7.54(m,1H),7.47(t,J=7.5Hz,2H),4.74-4.70(m,2H),3.59(d,J=23.0Hz,2H),1.27(dd,J=6.0,4.0Hz,12H).13C NMR(125MHz,CDCl3)δ192.3(d,J=6.25Hz),136.9,133.6,129.3,128.6,71.6(d,J=6.25Hz),39.9(d,J=129Hz),24.1(d,J=3.75Hz),23.9(d,J=5.0Hz).HRMS(ESI):m/zcalcd for(C14H21O4P+H)+:285.1250;found:285.1251。
实施例13:(2-氧代-2-苯乙基)亚磷酸二苄酯
合成步骤同实施例1,只是将亚磷酸二乙酯换成亚磷酸二苄酯,得到黄色液体,收率为77%,其结构式为:
Yellow oil,yield 77%.1H NMR(500MHz,CDCl3)δ7.95(dd,J=8.5,1.5Hz,2H),7.59-7.54(m,1H),7.45-7.41(m,2H),7.34-7.27(m,10H)5.09-4.99(m,4H),3.65(d,J=23.0Hz,2H).13CNMR(125MHz,CDCl3)δ191.7(d,J=7.5Hz),136.5(d,J=2.5Hz),135.9(d,J=6.25Hz),133.7,129.0,128.7,128.6,128.5,128.1,68.1(d,J=6.25Hz),38.7(d,J=131Hz).HRMS(ESI):m/zcalcd for(C22H21O4P+H)+:381.1250;found:381.1252。
实施例14:(2-氧代-2-苯乙基)亚磷酸二苯酯
合成步骤同实施例1,只是将亚磷酸二乙酯换成亚磷酸二苯酯,得到白色固体,收率为69%,其结构式为:
White solid,yield 69%.1H NMR(500MHz,CDCl3)δ7.99(d,J=8.0Hz,2H),7.80(dd,J=12.0,7.5Hz,4H),7.55-7.51(m,3H),7.48-7.38(m,6H),4.14(d,J=15.0Hz,2H).13CNMR(125MHz,CDCl3)δ193.0(d,J=6.25Hz),137.1,133.7,132.5,132.3(d,J=3.75Hz),131.8,131.6,131.3,131.2,129.4,128.8,128.7,128.6,43.5(d,J=57.5Hz).HRMS(ESI):m/z calcd for(C20H18O2P+H)+:321.1044;found:321.1044。
实施例15:(2-氧代-2-苯乙基)(苯基)亚磷酸苄酯
合成步骤同实施例1,只是将亚磷酸二乙酯换成苄基苯基次膦酸,得到黄色液体,收率为80%,其结构式为:
Yellow oil,yield 80%.1H NMR(500MHz,CDCl3)δ7.95-7.94(m,2H),7.81-7.76(m,2H),7.55(t,J=7.5Hz,2H),7.47-7.40(m,4H),7.30-7.29(m,3H),7.24-7.22(m,2H),5.12(dd,J=11.5,7.0Hz,1H),4.85(dd,J=11.5,7.0Hz,1H),3.84(dq,J=19.0,9.5Hz,2H).13C NMR(125MHz,CDCl3)δ192.2(d,J=5.0Hz),136.9,136.1(d,J=6.25Hz),133.7,133.0(d,J=2.5Hz),132.1,132.0,129.2,128.9,128.7,128.7(d,J=7.5Hz),128.4,127.9,66.7(d,J=5.0Hz),43.2(d,J=85.0Hz).HRMS(ESI):m/z calcd for(C21H20O3P+H)+:351.1150;found:351.1159。
实施例16:(2-(3-硝基苯基)-2-氧代乙基)(苯基)亚磷酸苄酯
合成步骤同实施例1,只是将(1-叠氮基乙烯基)换成1-(1-叠氮基乙烯基)3-硝基苯,亚磷酸二乙酯换成苄基苯基次膦酸得到黄色液体,收率为74%,其结构式为:
Yellow oil,yield 74%.1H NMR(500MHz,CDCl3)δ8.71(t,J=2.0Hz,1H),8.38-8.37(m,1H),8.30(d,J=7.5Hz,1H),7.80-7.76(m,2H),7.63-7.56(m,2H),7.49-7.46(m,2H),7.29-7.28(m,3H),7.24-7.23(m,2H),5.11(dd,J=11.5,7.5 Hz,1H),4.83(dd,J=11.5,7.5 Hz,1H),3.86(d,J=18.0 Hz,2H).13C NMR(125 MHz,CDCl3)δ190.2(d,J=5.0Hz),148.4,138.0,135.6(d,J=6.25 Hz),134.8,133.3(d,J=2.5 Hz),132.0,131.9,129.9,129.1,129.0,128.7,128.2,127.8,124.1,67.1(d,J=6.25 Hz),43.7(d,J=83.8Hz).HRMS(ESI):m/z calcd for(C21H19NO5P+H)+:396.1001;found:396.1005。
Claims (4)
1.一种β-酮基取代的磷酸酯类化合物的制备方法,其特征在于,通过以下步骤实现:
以烯烃叠氮、亚磷酸酯为起始原料,在有机溶剂中,以醋酸锰为氧化剂,反应生成的β-酮基取代的磷酸酯类化合物,烯烃叠氮、亚磷酸酯、醋酸锰的摩尔比为1:1:2,反应温度为室温,反应时间为6个小时,所得目标产物I通过硅胶色谱柱层析的方法纯化,反应式为:
其中:
R1为单取代或多取代的芳环、C1-C3链烷烃、其中单取代的芳环的取代基选用卤素、硝基、烷氧基、烷基、酯基;
R2和R3为C2-C4链烷氧基、苄氧基、芳环。
2.根据权利要求1所述的一种β-酮基取代的磷酸酯类化合物的制备方法,其特征在于,所用的溶剂选用DMF。
3.根据权利要求1所述的一种β-酮基取代的磷酸酯类化合物的制备方法,其特征在于,目标产物I通过硅胶色谱柱层析的方法纯化的洗脱剂选用石油醚:乙酸乙酯=4:1。
4.根据权利要求1所述的一种β-酮基取代的磷酸酯类化合物的制备方法,其特征在于,目标产物I为:
(2-氧代-2-苯乙基)亚磷酸二乙酯
(2-(4-甲基苯基)-2-氧代乙基)亚磷酸二乙酯
(2-(3-溴-4-乙氧基苯基)2-氧代乙基)亚磷酸二乙酯
(2-(4-溴苯基)-2-氧代乙基)亚磷酸二乙酯
(2-(4-氯苯基)-2-氧代乙基)亚磷酸二乙酯
(2-(3-溴苯基)-2-氧代乙基)亚磷酸二乙酯
(2-氧代-2-(对甲苯基)乙基)亚磷酸二乙酯
(2-(3-硝基苯基)-2-氧代乙基)亚磷酸二乙酯
(2-(4-甲氧基苯基)-2-氧代乙基)亚磷酸二乙酯
(2-氧代辛基)亚磷酸二乙酯
(2-氧代-2-苯乙基)亚磷酸二甲酯
(2-氧代-2-苯乙基)亚磷酸二异丙酯
(2-氧代-2-苯乙基)亚磷酸二苄酯
(2-氧代-2-苯乙基)亚磷酸二苯酯
(2-氧代-2-苯乙基)(苯基)亚磷酸苄酯
(2-(3-硝基苯基)-2-氧代乙基)(苯基)亚磷酸苄酯。
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