CN114957323B - 一种芳基膦类化合物的合成方法 - Google Patents
一种芳基膦类化合物的合成方法 Download PDFInfo
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- -1 aryl phosphine compound Chemical class 0.000 title claims abstract description 37
- 238000001308 synthesis method Methods 0.000 title claims abstract description 14
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 title claims abstract description 8
- 229910000073 phosphorus hydride Inorganic materials 0.000 title claims abstract description 8
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000003960 organic solvent Substances 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000011737 fluorine Substances 0.000 claims abstract description 11
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 11
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 10
- 239000011593 sulfur Substances 0.000 claims abstract description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 9
- XEZNGIUYQVAUSS-UHFFFAOYSA-N 18-crown-6 Chemical compound C1COCCOCCOCCOCCOCCO1 XEZNGIUYQVAUSS-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000012074 organic phase Substances 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 7
- XBHPFCIWRHJDCP-UHFFFAOYSA-N (2-trimethylsilylphenyl) trifluoromethanesulfonate Chemical compound C[Si](C)(C)C1=CC=CC=C1OS(=O)(=O)C(F)(F)F XBHPFCIWRHJDCP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000003480 eluent Substances 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 5
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 4
- 238000001816 cooling Methods 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims abstract description 4
- 238000001914 filtration Methods 0.000 claims abstract description 4
- 239000000463 material Substances 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims abstract description 4
- 238000005406 washing Methods 0.000 claims abstract description 4
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 25
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 14
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 10
- 239000003208 petroleum Substances 0.000 claims description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- 235000003270 potassium fluoride Nutrition 0.000 claims description 5
- 239000011698 potassium fluoride Substances 0.000 claims description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 4
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical group [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 claims description 4
- FPGGTKZVZWFYPV-UHFFFAOYSA-M tetrabutylammonium fluoride Chemical compound [F-].CCCC[N+](CCCC)(CCCC)CCCC FPGGTKZVZWFYPV-UHFFFAOYSA-M 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 107
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- NMLVHEZHLMNDOW-UHFFFAOYSA-N C1=CC=C(C=C1)P(=O)(C2=CC=CC=C2)C3=CC=CC=C3SC4=CC=CC=C4 Chemical compound C1=CC=C(C=C1)P(=O)(C2=CC=CC=C2)C3=CC=CC=C3SC4=CC=CC=C4 NMLVHEZHLMNDOW-UHFFFAOYSA-N 0.000 description 2
- YFPJFKYCVYXDJK-UHFFFAOYSA-N Diphenylphosphine oxide Chemical compound C=1C=CC=CC=1[P+](=O)C1=CC=CC=C1 YFPJFKYCVYXDJK-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 125000002524 organometallic group Chemical group 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 101150041968 CDC13 gene Proteins 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000006138 lithiation reaction Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000001741 organic sulfur group Chemical group 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
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Abstract
本发明公开了一种芳基膦类化合物的合成方法,包括如下步骤:(1)将硫单质、氟源、18‑冠醚‑6、2‑(三甲基硅)苯基三氟甲烷磺酸酯、芳基膦氧化物或芳基膦酸酯化合物和有机溶剂混合后,在氮气气氛下于50‑100℃下搅拌反应10‑15h;(2)将步骤(1)所得的物料冷却至室温后,加入乙酸乙酯充分混合,再依次经过滤和乙酸乙酯洗涤,获得有机相;(3)旋干步骤(2)所得的有机相中的有机溶剂,然后进行纯化和洗脱剂淋洗,即得所述芳基膦化合物化合物。本发明可以在温和的条件下,以芳基膦氧化物或芳基膦酸酯化合物为原料高效的实现芳基膦类化合物的合成,不需要使用氯化磷,具有环境友好型的特征,符合绿色化学的理念。
Description
技术领域
本发明属于有机合成技术领域,具体涉及一种芳基膦类化合物的合成方法。
背景技术
邻硫取代的芳基膦以及邻硫取代的芳基膦氧化物和芳基膦酸酯在催化反应和有机金属化学领域中作为配体具有重要意义。通过改变硫的化合价,P/S配体在有机合成中表现出独特的反应性。尽管邻硫取代的芳基磷有广泛的应用,但获得这些分子的合成方法尚不发达。经典方法依赖于有机硫的锂化,然后与氯化磷反应。另一种方法是从有机硫化物开始LDA促进的硫代膦酸盐的Fries型重排。以往的合成方法存在官能团耐受性差、操作繁琐、多样化难等问题。
鉴于邻硫取代的芳基膦在化学合成、催化和有机金属化学中的重要性,开发有效和实用的合成方法,特别是在不添加氯化磷的情况下,是磷化学中一个有吸引力但具有挑战性的目标。
发明内容
本发明的目的在于克服现有技术缺陷,提供一种芳基膦类化合物的合成方法。
本发明的技术方案如下:
一种芳基膦类化合物的合成方法,包括如下步骤:
(1)将硫单质、氟源、18-冠醚-6、2-(三甲基硅)苯基三氟甲烷磺酸酯、芳基膦氧化物或芳基膦酸酯化合物和有机溶剂混合后,在氮气气氛下于50-100℃下搅拌反应10-15h;上述芳基膦氧化物或芳基膦酸酯化合物的结构式为以下之一:
(2)将步骤(1)所得的物料冷却至室温后,加入乙酸乙酯充分混合,再依次经过滤和乙酸乙酯洗涤,获得有机相;
(3)旋干步骤(2)所得的有机相中的有机溶剂,然后进行纯化和洗脱剂淋洗,即得所述芳基膦化合物化合物。
在本发明的一个优选实施方案中,所述氟源为氟化铯、四丁基氟化铵或氟化钾。
进一步优选的,所述氟源为氟化钾。
在本发明的一个优选实施方案中,所述有机溶剂为甲苯、1,4-二氧六环、二氯甲烷、N,N-二甲基甲酰胺、二甲基亚砜或四氢呋喃。
进一步优选的,所述有机溶剂为四氢呋喃。
在本发明的一个优选实施方案中,所述洗脱剂由石油醚和二氯甲烷组成。
进一步优选的,所述石油醚和二氯甲烷的体积比为1-5∶1。
更进一步优选的,所述石油醚和二氯甲烷的体积比为2∶1
在本发明的一个优选实施方案中,所述硫单质、氟源、18-冠醚-6、2-(三甲基硅)苯基三氟甲烷磺酸酯、芳基膦氧化物或芳基膦酸酯化合物和有机溶剂的比例为0.1-0.3mmol∶0.5-1mmol∶0.5-1mmol∶0.5-1mmol∶0.1-0.5mmol∶1-5mL。
进一步优选的,所述硫单质、氟源、18-冠醚-6、2-(三甲基硅)苯基三氟甲烷磺酸酯、芳基膦氧化物或芳基膦酸酯化合物和有机溶剂的比例为0.2mmol∶0.6mmol∶0.6mmol∶0.5mmol∶0.24mmol∶2mL。
本发明的有益效果是:
1、本发明可以在温和的条件下,以芳基膦氧化物或芳基膦酸酯化合物为原料高效的实现芳基膦类化合物的合成。
2、本发明不需要使用氯化磷,具有环境友好型的特征,符合绿色化学的理念。
3、本发明操作简单,利用分子类反应一步就可以得到芳基膦类化合物,且其原料合成简单。
具体实施方式
以下通过具体实施方式对本发明的技术方案进行进一步的说明和描述。
实施例1
本实施例的反应式如下:
(1)将0.2mmol硫单质、0.6mmol氟化钾、0.6mmol 18-冠醚-6、0.5mmol 2-(三甲基硅)苯基三氟甲烷磺酸酯和0.24mmol二苯基氧化膦加入到耐压密封反应管中,抽除空气,充入氮气后,将2mL四氢呋喃注射到耐压密封反应管中,于60℃下搅拌反应12h,反应过程中用TLC和GC进行跟踪以决定具体的反应时间;
(2)将步骤(1)所得的物料从上述耐压密封反应管取出,冷却至室温后,加入乙酸乙酯充分混合,再依次经过滤和乙酸乙酯洗涤,合并获得有机相;
(3)旋干步骤(2)所得的有机相中的四氢呋喃,经硅胶柱纯化和洗脱剂(石油醚∶二氯甲烷=2∶1)淋洗,即得二苯基(2-(苯硫基)苯基)氧化膦(4a),产率为83%。
核磁数据如下:
1H NMR(500MHz,CDCl3)δ7.74(m,4H),7.51(m,2H),7.44(m,4H),7.41-7.30(m,2H),7.18(m,5H),7.11(m,2H).
13C NMR(125MHz,CDCl3)δ142.9,134.6,134.3,132.7,132.5,131.6,129.1,128.3,127.7,125.7.
31P NMR(202MHz,CDCl3)δ29.96.
实施例2
在与实施例1相同的反应条件下,研究本发明的底物的普适性和良好的官能团兼容性,将上述实施例中的二苯基氧化膦替换如下:
所得的相应产物如下:
以上各产物的核磁数据具体如下:
4a
1H NMR(500MHz,CDCl3)δ7.63(m,2H),7.59-7.51(m,1H),7.45(m,2H),7.30-7.24(m,1H),7.19-7.09(m,5H),7.05(m,2H),6.98(m,2H),6.87(m,2H),3.57(s,6H).
13C NMR(125MHz,CDCl3)δ161.2,141.4,135.8,135.0,134.3,133.9,133.5,133.3,132.2,131.8,131.1,128.8,127.0,125.2,120.6,120.3,119.6,111.2,70.3,55.3.
31P NMR(202MHz,CDCl3)δ28.0.
4d
1H NMR(500MHz,CDCl3)δ7.63(m,2H),7.47-7.40(m,2H),7.39-7.29(m,6H),7.18(m,5H),7.12(m,2H),2.34(s,6H).
13C NMR(125MHz,CDCl3)δ138.3,138.2,134.4,134.3,132.6,132.5,132.5,132.4,132.4,132.2,132.2,132.2,131.8,129.1,129.0,128.2,128.2,127.5,125.9,125.8,21.4.
31P NMR(202MHz,CDCl3)δ30.3.
4f
1H NMR(500MHz,CDCl3)δ7.70(m,2H),7.58(m,2H),7.47(m,2H),7.42-7.34(m,4H),7.25-7.17(m,5H),7.09(m,2H).
13C NMR(125MHz,CDCl3)δ142.3,134.9,134.5,134.2,133.6,132.9,132.1,131.8,131.4,130.7,129.9,129.1,127.7,126.3.
31P NMR(202MHz,CDCl3)δ26.3.
4h
1HNMR(500MHz,CDCl3)δ7.48(m,1H),7.40(m,2H),7.34(m,1H),7.29(m,2H),7.24(m,5H),7.21-7.13(m,6H),2.54(s,6H).
13C NMR(125MHz,CDCl3)δ143.5,134.5,134.0,133.3,133.0,132.2-131.7,131.4,130.4,129.6,129.2,127.9,125.6,125.2,22.0.
31P NMR(202MHz,CDCl3)δ35.6.
4j
1H NMR(500MHz,CDCl3)δ8.42(m,2H),7.93-7.83(m,6H),7.82-7.73(m,2H),7.57(m,2H),7.52(m,2H),7.46(m,1H),7.37(m,1H),7.25(m,1H),7.18(m,1H),7.10(s,5H).
13C NMR(125MHz,CDCl3)δ142.8,134.5,133.8,132.8,132.7,132.3,132.2,132.0,130.0,129.1,128.9,128.4,127.9,127.7,127.1,126.6,125.9,67.0,31.5,29.6,22.6,14.1.
31P NMR(202MHz,CDCl3)δ30.0.
4l
1HNMR(500MHz,CDCl3)δ8.17-8.07(m,1H),7.35-7.24(m,7H),7.19(m,1H),2.66(m,2H),1.34(dd,J=15.0,7.0Hz,6H),0.97(dd,J=16.3,7.2Hz,6H).
13C NMR(125MHz,CDCl3)δ135.4,135.4,134.7,132.3,132.2,131.7,131.7,131.1,129.5,127.6,126.8,126.7,27.8,27.3,17.2,17.1,16.4,16.4.
31P NMR(202MHz,CDCl3)δ53.24.
HRMS(ESI,m/z):[M+H]+Calcd for C18H24OPS+:319.1280;Found:319.1276.
4m
1H NMR(500MHz,CDCl3)δ7.95(m,1H),7.41-7.29(m,6H),7.27-7.18(m,10H),7.18-7.11(m,2H),3.72-3.59(m,4H).
13C NMR(125MHz,CDCl3)δ136.1,136.0,134.5,132.6,132.6,132.4,132.4,131.8,131.7,130.9,129.9,129.8,129.7,128.4,128.3,127.9,127.1,127.0,126.7,126.6,37.3,36.8.
31P NMR(202MHz,CDCl3)δ35.42.
4n
1HNMR(500MHz,CDCl3)δ8.13(m,1H),7.38(m,2H),7.31(m,2H),7.28-7.22(m,4H),2.41(m,2H),2.09(m,2H),1.81(m,2H),1.68-1.58(m,6H),1.36(m,4H),1.26-1.15(m,4H),1.09-1.00(m,2H).
13C NMR(125MHz,CDCl3)δ135.8,135.8,135.3,133.6,133.5,131.6,130.2,129.5,129.5,127.3,127.3,127.3,38.0,37.5,26.5,26.4,26.4,26.3,26.3,25.7.
31P NMR(202MHz,CDCl3)δ48.82.
4o
1H NMR(500MHz,CDC13)δ7.97-7.89(m,1H),7.43-7.39(m,2H),7.35-7.28(m,4H),7.22(m,1H),7.09(m,1H),3.80(m,6H).
13C NMR(125MHz,CDCl3)δ142.0,141.9,134.9,134.9,133.9,133.1,132.8,132.8,131.0,130.8,129.4,128.1,125.7,125.6,52.8,52.8.
31P NMR(202MHz,CDCl3)δ19.66.
4q
1H NMR(500MHz,CDCl3)δ8.00(m,1H),7.47-7.40(m,2H),7.37-7.27(m,4H),7.21(m,1H),7.06(m,1H),4.88-4.72(m,2H),1.40(d,J=6.2Hz,6H),1.29(d,J=6.2Hz,6H).
13C NMR(125MHz,CDCl3)δ134.8,134.7,134.6,133.3,132.4,132.3,130.7,130.6,129.4,128.0,125.4,125.3,71.3,71.3,24.2,24.1,23.9,23.8.
31P NMR(202MHz,CDCl3)δ14.24.
4r
1HNMR(500MHz,CDCl3)δ7.98(m,1H),7.38(m,6H),7.31(m,10H),7.22(m,1H),7.12(m,1H),5.26-5.10(m,4H).
13C NMR(125MHz,CDCl3)δ136.2,136.1,134.6,134.5,134.3,132.9,132.7,132.7,131.3,131.2,129.3,128.4,128.2,128.0,127.9,125.7,125.6,67.9,67.8.
31P NMR(202MHz,CDCl3)δ17.46.
4s
1HNMR(500MHz,CDCl3)δ8.03(m,1H),7.48-7.42(m,2H),7.38-7.26(m,4H),7.21(m,1H),7.10-7.01(m,1H),4.55(m,2H),2.07-1.99(m,2H),1.89-1.83(m,2H),1.80-1.64(m,6H),1.52(m,4H),1.37-1.25(m,6H).
13C NMR(125MHz,CDCl3)δ134.7,134.6,133.3,132.2,130.5,130.4,129.4,128.0,125.3,125.2,76.0,76.0,33.8,33.7,33.5,33.5,25.3,23.6,23.6.
31P NMR(202MHz,CDCl3)δ14.34.
4u
1HNMR(500MHz,CDCl3)δ7.93(m,1H),7.81-7.72(m,2H),7.42-7.32(m,3H),7.25-7.16(m,5H),7.15-7.07(m,2H),7.05(m,1H),1.41(d,J=14.8 Hz,9H).
13C NMR(125MHz,CDCl3)δ144.3,134.9,132.9,132.9,132.7,132.1,132.1,132.0,131.9,131.5,131.5,131.0,130.9,129.0,128.9,128.4,127.8,127.7,127.7,127.5,127.2,124.6,124.5,34.9,34.3,26.2,25.9.
31P NMR(202MHz,CDCl3)δ42.81.
4v
1H NMR(500MHz,CDCl3)δ8.14(m,1H),7.81(m,2H),7.41(m,1H),7.37-7.26(m,4H),7.16(d,J=6.9Hz,3H),7.11-6.99(m,3H),4.56-4.28(m,1H),2.24-2.00(m,2H),1.64(m,2H),1.50(m,1H),1.43-1.34(m,1H),1.29-1.21(m,1H),0.99(m,1H),0.89-0.79(m,7H),0.62(d,J=6.9Hz,2H),0.54(d,J=6.9Hz,1H).
13C NMR(125MHz,CDCl3)δ135.4,134.6,134.5,133.9,133.8,132.2,131.8,131.7,131.2,131.1,130.7,129.2,128.2,128.1,127.3,127.2,127.2,36.2,35.6,26.5,26.4,26.4,26.3,25.8,25.8,25.6,25.6,25.3,25.3.
31P NMR(202MHz,CDCl3)δ35.75.
4w
1H NMR(500MHz,CDCl3)δ8.00(m,1H),7.70-7.64(m,2H),7.45-7.41(m,1H),7.38-7.33(m,3H),7.31-7.27(m,1H),7.25-7.12(m,9H),7.11-7.05(m,2H),4.20(m,1H),3.98(t,J=15.0Hz,1H).
13C NMR(125MHz,CDCl3)δ134.7,134.7,134.6,132.9,132.8,132.4,132.4,131.5,131.5,131.4,131.3,131.1,131.1,130.2,130.1,129.2,128.3,128.3,128.3,128.2,127.6,126.7,126.6,126.6,36.4,35.8.
31P NMR(202MHz,CDCl3)δ29.77(d,J=4.8Hz).
4y
1H NMR(500MHz,CDCl3)δ8.01(m,1H),7.70-7.65(m,2H),7.62(m,1H),7.46(d,J=7.9Hz,1H),7.43-7.38(m,2H),7.36-7.30(m,3H),7.24-7.16(m,5H),7.09-7.01(m,3H),4.36-4.20(m,2H).
13C NMR(125MHz,CDCl3)δ134.9,134.2,134.1,133.2,133.1,132.8,132.7,132.6,132.5,132.1,132.1,131.6,131.6,131.4,131.2,131.2,129.2,128.4,128.3,128.3,128.2,127.5,127.3,126.7,126.6,35.9,35.4.
31P NMR(202MHz,CDCl3)δ29.69.
4aa
1H NMR(500MHz,CDCl3)δ8.07(m,1H),7.85(m,2H),7.50-7.41(m,1H),7.37(m,2H),7.34-7.27(m,2H),7.20(m,3H),7.09(m,3H),4.84(m,1H),2.36-2.19(m,4H),1.80-1.67(m,1H),1.54-1.40(m,1H).
13C NMR(125MHz,CDCl3)δ134.8,134.2,134.1,132.5,132.5,132.1,132.0,131.9,131.8,131.7,129.1,128.1,128.0,127.7,126.0,125.7,77.2,69.3,69.3,32.3,32.3,32.2,32.1,13.0.
31P NMR(202MHz,CDCl3)δ28.12.
4ab
1H NMR(500MHz,CDCl3)δ8.08(m,1H),7.85(m,2H),7.48-7.41(m,1H),7.37(m,2H),7.34-7.26(m,2H),7.19(m,3H),7.08(m,3H),5.52-5.45(m,1H),5.39-5.32(m,1H),4.11-4.01(m,2H),2.55-2.46(m,2H),2.02(m,2H),0.92(t,J=7.5Hz,3H).
13C NMR(125MHz,CDCl3)δ134.6,134.2,134.1,132.6,132.6,132.4,132.0,132.0,131.9,131.9,131.8,131.8,129.1,128.1,128.0,127.6,126.0,125.9,123.4,64.3,64.3,28.6,28.6,20.6,14.1.
31P NMR(202MHz,CDCl3)δ29.89.
4ac
1H NMR(500MHz,CDCl3)δ8.09(m,1H),7.90-7.84(m,2H),7.48-7.43(m,1H),7.38(m,2H),7.34-7.27(m,2H),7.22-7.17(m,3H),7.12-7.06(m,3H),4.14(m,2H),2.61(m,2H),2.12(m,2H),1.08(t,J=7.5Hz,3H).
13C NMR(125MHz,CDCl3)δ134.6,134.2,134.1,132.7,132.6,132.5,132.1,132.1,132.0,132.0,131.9,131.9,129.1,128.1,128.0,127.7,126.0,125.9,83.7,74.6,63.2,63.2,21.2,21.1,14.0,12.3.
31P NMR(202MHz,CDCl3)δ30.26.
4ad
1H NMR(500MHz,CDCl3)δ8.04(m,1H),7.91-7.80(m,2H),7.44(m,1H),7.37(m,2H),7.32-7.25(m,3H),7.21-7.15(m,3H),7.09-7.02(m,3H),4.71(m,1H),3.76-3.63(m,2H),3.28(m,2H),1.93-1.72(m,4H),1.43(s,9H).
13C NMR(125MHz,CDCl3)δ154.6,141.4,134.4,134.0,133.9,132.6,132.6,132.4,131.9,131.8,131.7,129.1,128.1,128.0,127.7,125.9,125.8,79.5,77.3,77.2,77.0,76.8,71.9,71.8,28.3.
31P NMR(202MHz,CDCl3)δ29.35.
4ae
1H NMR(500MHz,CDCl3)δ8.16(m,1H),7.93-7.83(m,2H),7.45-7.39(m,1H),7.34(m,2H),7.30-7.25(m,2H),7.21-7.12(m,3H),7.04(m,3H),4.69(m,1H),2.31(m,2H),2.17(d,J=4.0Hz,1H),2.05(d,J=3.9Hz,1H),1.87(m,1H),1.82-1.74(m,3H),1.72-1.63(m,4H),1.60-1.54(m,2H).
13C NMR(125MHz,CDCl3)δ134.7,134.0,133.9,132.5,132.3,131.9,131.8,131.8,131.8,131.5,129.0,127.9,127.8,127.6,125.8,125.7,79.6,79.6,37.3,36.2,36.2,33.7,33.6,31.5,31.4,27.2,26.7.
31P NMR(202MHz,CDCl3)δ27.98.
4af
1H NMR(500MHz,CDCl3)δ8.42(m,1H),8.09-8.00(m,2H),7.68-7.55(m,2H),7.50-7.40(m,2H),7.38(m,2H),7.30-7.25(m,1H),7.23-7.12(m,5H),7.01-6.93(m.2H).
13C NMR(125MHz,CDCl3)δ141.9,135.7,135.7,134.5,133.7,133.6,133.0,132.9,132.7,132.7,131.9,130.4,130.3,130.3,129.1,128.0,127.9,127.6,126.4,126.3,125.4,124.8,124.4,124.3,123.3,123.2,121.5,120.6,120.6.
31P NMR(202MHz,CDCl3)δ20.94.
4ag
1H NMR(500MHz,CDCl3)δ8.07(m,1H),7.89-7.82(m,2H),7.38(m,2H),7.34-7.26(m,2H),7.20(m,3H),7.13-7.04(m,3H),4.20-4.11(m,2H),1.39(t,J=7.0Hz,3H).
13C NMR(125MHz,CDCl3)δ134.6,134.3,134.2,132.6,132.6,132.5,132.0,131.9,131.9,131.8,131.8,129.1,128.1,128.0,127.7,126.0,125.9,61.2,61.1,16.4,16.4.
31P NMR(202MHz,CDCl3)δ29.9.
4ai
1H NMR(500MHz,CDCl3)δ8.08(m,1H),7.88-7.81(m,2H),7.42-7.37(m,1H),7.33(m,2H),7.25(m,2H),7.18-7.12(m,3H),7.04(m,3H),4.70(m,1H),2.00-1.84(m,4H),1.72-1.64(m,2H),1.52(m,4H),1.37(m,2H).
13C NMR(125MHz,CDCl3)δ134.7,134.0,133.9,132.4,132.8,132.3,131.9,131.8,131.8,131.7,131.5,131.4,129.0,127.9,127.8,127.5,125.7,125.6,77.6,77.6,35.8,35.8,35.8,35.7,28.0,22.1,22.1.
31P NMR(202MHz,CDCl3)δ27.94.
4ak
1H NMR(500MHz,CDCl3)δ8.09(m,1H),7.94-7.83(m,2H),7.46(m,1H),7.39(m,2H),7.36-7.29(m,2H),7.21(m,3H),7.10(m,3H),5.56(m,1H),4.62(m,1H),4.33(m,2H),4.26-4.12(m,2H),1.51(d,J=3.0Hz,3H),1.41(d,J=12.4Hz,3H),1.34-1.30(m,6H).
13C NMR(125MHz,CDCl3)δ134.5,134.3,134.2,134.2,132.6,132.6,132.6,132.3,132.2,132.2,132.1,132.1,132.0,131.9,131.9,131.9,131.8,131.8,131.6,131.7,129.1,129.0,128.1,128.0,127.7,127.5,126.0,125.9,125.8,109.4,109.4,108.7,96.2,96.2,67.6,67.5,67.3,67.2,63.6,63.5,63.4,26.0,25.9,25.8,24.9,24.4,24.3.
31P NMR(202MHz,CDCl3)δ31.66,30.83.
4al
1H NMR(500MHz,CDCl3)δ8.06(m,1H),7.89-7.81(m,2H),7.45-7.40(m,1H),7.36(m,2H),7.27(m,2H),7.17(m,3H),7.11-7.03(m,3H),5.33-5.21(m,1H),4.34(m,1H),2.58-2.36(m,3H),2.20-2.11(m,1H),2.08(s,3H),2.05-1.88(m,3H),1.85-1.75(m,2H),1.66-1.39(m,7H),1.27-1.06(m,3H),1.00(s,3H),0.93-0.87(m,1H),0.59(s,3H).
13C NMR(125MHz,CDCl3)δ209.3,141.4,141.3,139.6,139.5,134.8,134.1,134.0,134.0,132.4,132.0,131.9,131.8,131.7,131.6,131.60,129.0,128.0,128.0,127.8,127.9,127.6,125.9,125.8,122.4,122.3,76.2,76.2,63.5,56.7,49.7,43.8,40.4,40.4,40.3,38.6,36.9,36.3,31.6,31.6,31.6,31.4,30.1,30.1,30.0,30.0,24.3,22.7,20.9,19.2,13.1.
31P NMR(202MHz,CDCl3)δ28.38(d,J=7.0Hz).
4am
1H NMR(500MHz,CDCl3)δ8.08-8.00(m,1H),7.88-7.77(m,2H),7.42(m,1H),7.35(m,2H),7.27(m,2H),7.16(m,3H),7.08-7.02(m,3H),5.04(m,1H),4.09(m,2H),1.93(m,2H),1.78(m,1H),1.65(d,J=6.9Hz,1H),1.62(s,3H),1.54(s,3H),1.50(dd,J=10.9,4.7Hz,1H),1.31(m,1H),1.14(m,1H),0.86(dd,J=9.3,6.6Hz,3H).
13C NMR(125MHz,CDCl3)δ134.6,134.2,134.1,132.5,132.5,132.5,132.2,131.9,131.9,131.9,131.8,131.7,131.1,130.8,129.1,128.1,128.0,127.6,125.9,125.8,124.5,63.3,63.3,37.5,37.3,36.8,36.8,29.0,25.6,25.26,19.3,19.2,17.6.
31P NMR(202MHz,CDCl3)δ29.76(d,J=5.1Hz).
4an
1H NMR(500MHz,CDCl3)δ8.12-8.04(m,1H),7.89-7.82(m,2H),7.45(1H),7.38(m,2H),7.34-7.26(m,2H),7.19(m,3H),7.13-7.04(m,3H),5.15-4.99(m,1H),4.20-4.04(m,2H),1.96(m,2H),1.87-1.75(m,1H),1.71-1.67(m,1H),1.67-1.63(m,3H),1.57(s,3H),1.54(d,J=7.2Hz,1H),1.39-1.30(m,1H),1.17(m,1H),0.89(dd,J=9.3,6.6Hz,3H).
13C NMR(125MHz,CDCl3)δ134.6,134.2,134.2,134.2,134.2,132.6,132.5,132.5,132.0,131.9,131.8,131.8,131.7,131.1,130.8,129.1,128.1,128.0,127.7,126.0,125.9,124.5,63.3,63.3,37.4,37.3,36.9,36.8,29.0,25.6,25.3,19.3,19.2,17.6.
31P NMR(202MHz,CDCl3)δ29.76(d,J=5.1Hz).
4ao
1HNMR(500MHz,CDCl3)δ8.14(m,1H),7.81(m,2H),7.41(m,1H),7.37-7.26(m,4H),7.16(d,J=6.9Hz,3H),7.11-6.99(m,3H),4.56-4.28(m,1H),2.24-2.00(m,2H),1.64(m,2H),1.50(m,1H),1.43-1.34(m,1H),1.29-1.21
(m,1H),0.99(m,1H),0.89-0.79(m,7H),0.62(d,J=6.9Hz,2H),0.54(d,J=6.9Hz,1H).
13C NMR(125MHz,CDCl3)δ135.2,134.9,134.0,133.9,133.9,133.9,132.5,132.4,132.4,132.4,132.3,132.2,132.0,131.9,131.9,131.8,131.8,131.7,131.6,131.5,129.1,129.1,128.0,128.0,128.0,127.9,127.63,127.6,126.1,125.9,125.9,125.8,48.9,48.8,48.8,48.8,43.6,43.3,34.1,31.6,31.6,25.7,25.6,22.8,22.0,22.0,21.2,21.2,15.4,15.3.
31P NMR(202MHz,CDCl3)δ27.85.
4ap
1H NMR(500MHz,CDCl3)δ8.06(m,1H),7.89-7.81(m,2H),7.45-7.40(m,1H),7.36(m,2H),7.27(m,2H),7.17m,3H),7.11-7.03(m,3H),5.33-5.21(m,1H),4.34(m,1H),2.58-2.36(m,3H),2.20-2.11(m,1H),2.08(s,3H),2.05-1.88(m,3H),1.85-1.75(m,2H),1.66-1.39(m,7H),1.27-1.06(m,3H),1.00(s,3H),0.93-0.87(m,1H),0.59(s,3H).
13C NMR(125MHz,CDCl3)δ209.3,141.4,141.3,139.6,139.5,134.8,134.1,134.0,134.0,132.4,132.0,131.91,131.8,131.7,131.6,131.60,129.0,128.0,128.0,127.8,127.9,127.6,125.9,125.8,122.4,122.3,76.2,76.2,63.5,56.7,49.7,43.8,40.4,40.4,40.3,38.6,36.9,36.3,31.6,31.6,31.6,31.4,30.1,30.1,30.0,30.0,24.3,22.7,20.9,19.2,13.1.
31P NMR(202MHz,CDCl3)δ28.38(d,J=7.0Hz).
以上所述,仅为本发明的较佳实施例而已,故不能依此限定本发明实施的范围,即依本发明专利范围及说明书内容所作的等效变化与修饰,皆应仍属本发明涵盖的范围内。
Claims (9)
1.一种芳基膦类化合物的合成方法,其特征在于:包括如下步骤:
(1)将硫单质、氟源、18-冠醚-6、2-(三甲基硅)苯基三氟甲烷磺酸酯、芳基膦氧化物或芳基膦酸酯化合物和有机溶剂混合后,在氮气气氛下于50-100℃下搅拌反应10-15h;上述氟源为氟化铯、四丁基氟化铵或氟化钾,上述芳基膦氧化物或芳基膦酸酯化合物的结构式为以下之一:
(2)将步骤(1)所得的物料冷却至室温后,加入乙酸乙酯充分混合,再依次经过滤和乙酸乙酯洗涤,获得有机相;
(3)旋干步骤(2)所得的有机相中的有机溶剂,然后进行纯化和洗脱剂淋洗,即得所述芳基膦化合物,该芳基膦化合物的结构式为如下之一:
2.如权利要求1所述的合成方法,其特征在于:所述氟源为氟化钾。
3.如权利要求1所述的合成方法,其特征在于:所述有机溶剂为甲苯、1,4-二氧六环、二氯甲烷、N,N-二甲基甲酰胺、二甲基亚砜或四氢呋喃。
4.如权利要求3所述的合成方法,其特征在于:所述有机溶剂为四氢呋喃。
5.如权利要求1所述的合成方法,其特征在于:所述洗脱剂由石油醚和二氯甲烷组成。
6.如权利要求5所述的合成方法,其特征在于:所述石油醚和二氯甲烷的体积比为1-5∶1。
7.如权利要求6所述的合成方法,其特征在于:所述石油醚和二氯甲烷的体积比为2∶1。
8.如权利要求1所述的合成方法,其特征在于:所述硫单质、氟源、18-冠醚-6、2-(三甲基硅)苯基三氟甲烷磺酸酯、芳基膦氧化物或芳基膦酸酯化合物和有机溶剂的比例为0.1-0.3mmol:0.5-1mmol:0.5-1mmol:0.5-1mmol:0.1-0.5mmol:1-5mL。
9.如权利要求8所述的合成方法,其特征在于:所述硫单质、氟源、18-冠醚-6、2-(三甲基硅)苯基三氟甲烷磺酸酯、芳基膦氧化物或芳基膦酸酯化合物和有机溶剂的比例为0.2mmol:0.6mmol:0.6mmol:0.5mmol:0.24mmol:2mL。
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