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CN113603719A - A kind of difluoroalkyl substituted phosphorothioate compound and preparation method thereof - Google Patents

A kind of difluoroalkyl substituted phosphorothioate compound and preparation method thereof Download PDF

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CN113603719A
CN113603719A CN202110938698.1A CN202110938698A CN113603719A CN 113603719 A CN113603719 A CN 113603719A CN 202110938698 A CN202110938698 A CN 202110938698A CN 113603719 A CN113603719 A CN 113603719A
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difluoroalkyl
compound
substituted
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cdcl
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张鹏波
张丽
高霞
张丰泉
李文武
曲威龙
喻过
舒志刚
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Xinxiang Medical University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • 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
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/16—Esters of thiophosphoric acids or thiophosphorous acids
    • C07F9/165—Esters of thiophosphoric acids
    • C07F9/1653—Esters of thiophosphoric acids with arylalkanols
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • 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
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/16—Esters of thiophosphoric acids or thiophosphorous acids
    • C07F9/165—Esters of thiophosphoric acids
    • C07F9/1651—Esters of thiophosphoric acids with hydroxyalkyl compounds with further substituents on alkyl
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    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/16—Esters of thiophosphoric acids or thiophosphorous acids
    • C07F9/165—Esters of thiophosphoric acids
    • C07F9/17—Esters of thiophosphoric acids with hydroxyalkyl compounds without further substituents on alkyl
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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
    • C07F9/6527—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07F9/653—Five-membered rings
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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
    • C07F9/547—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
    • C07F9/6552—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 six-membered ring
    • C07F9/65522—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 six-membered ring condensed with carbocyclic rings or carbocyclic ring systems

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Abstract

The invention discloses a difluoroalkyl substituted phosphate ester compound and a preparation method thereof, wherein the structural formula of the difluoroalkyl substituted phosphate ester compound is shown as the following formula:

Description

Difluoroalkyl substituted sulfur phosphate compound and preparation method thereof
Technical Field
The invention belongs to the technical field of synthesis of organic sulfur phosphate compounds, and particularly relates to a difluoroalkyl substituted sulfur phosphate compound and a preparation method thereof.
Background
The phosphoric ester is a phosphorus-containing organic compound with abundant biological activity, and particularly shows great potential in the aspects of antibiosis, tumor resistance, cholinesterase inhibition, insecticide and the like. Moreover, the sulfuric phosphate can be widely used for constructing carbon-carbon bonds, carbon-sulfur bonds and carbon-fluorine bonds as a reaction intermediate. Difluoroalkyl (CF), on the other hand2R) has unique functions in the fields of medicinal chemistry, synthetic chemistry and the like due to the special physical and chemical properties of the R). The introduction of difluoroalkyl into active molecules can generally improve the biological activity of the organic sulfur phosphate by changing the characteristics of absorption, metabolism, excretion and the like in vivo, so that the introduction of difluoroalkyl into organic sulfur phosphate molecules has wide application prospects in the fields of new drugs, pesticides, organic synthesis and the like. However, the construction method of the difluoroalkyl substituted sulfur phosphate compound is extremely limited at present. The research and development of the difluoroalkyl substituted sulfur phosphate compound constructed by using cheap and easily-obtained bulk chemicals as raw materials and having high atom economy and step economy under mild conditions greatly promote the synthesis method and the related research of the biological activity of the organophosphorus sulfate compound and the organofluorine compound.
Disclosure of Invention
The invention aims to construct a difluoroalkyl substituted sulfur phosphate compound with a novel structure and a medical application prospect and provides a preparation method of the difluoroalkyl substituted sulfur phosphate compound, which is simple and convenient to operate, high in yield, low in cost, mild in reaction condition, good in atom economy, high in selectivity and suitable for industrial production.
The invention adopts the following technical scheme for solving the technical problems, and the difluoroalkyl substituted sulfur phosphate compound is characterized in that: the structural formula of the difluoroalkyl substituted phosphate ester compound is shown as the following formula (1):
Figure BDA0003214154180000011
wherein R is
Figure BDA0003214154180000012
R1Is hydrogen, phenyl, substituted phenyl or C1-6An alkyl group; r2Is phenyl, substituted phenyl, naphthyl, pyridyl,
Figure BDA0003214154180000013
Figure BDA0003214154180000021
Figure BDA0003214154180000022
The substituent on the benzene ring of the substituted phenyl is C1-6Alkyl, fluoro, chloro, bromo, nitro, methoxy, trifluoromethyl, phenyl,
Figure BDA0003214154180000023
n is an integer of 1-20, R' is C1-6Alkyl, fluoro, chloro, bromo, nitro, methoxy, trifluoromethyl or phenyl; r3Is hydrogen, methyl or
Figure BDA0003214154180000024
R4Is C1-6Alkoxy or phenyl; r5Is C1-6Alkoxy or phenyl; x is O or S.
The preparation method of the difluoroalkyl substituted sulfur phosphate compound is characterized by comprising the following specific steps: adding an alkene compound 1, a diethyl thiophosphate compound 2, a difluoroalkyl halide 3, a photocatalyst, a copper catalyst and alkali into a solvent, stirring and reacting completely at 0-40 ℃ in an inert gas atmosphere under visible light irradiation, and performing post-treatment to obtain a target product difluoroalkyl substituted phosphorothioate compound 4, wherein the reaction equation in the preparation process is as follows:
Figure BDA0003214154180000025
the photocatalyst is (4,4 '-di-tert-butyl-2, 2' -bipyridine) bis [ (2-pyridyl) phenyl group]Iridium (III) hexafluorophosphate ([ Ir (dtbbpy) ((ppy)2][PF6]) Or tris (2-phenylpyridine) iridium (Ir (ppy)3) (ii) a Preferably, the photocatalyst is (4,4 '-di-tert-butyl-2, 2' -bipyridine) bis [ (2-pyridyl) phenyl group]Iridium (III) hexafluorophosphate;
the copper catalyst is copper acetate, cuprous iodide, copper powder, cuprous bromide, cuprous chloride, cupric bromide, cuprous acetate or copper trifluoromethanesulfonate; preferably, the copper catalyst is copper acetate or copper triflate;
the alkali is potassium carbonate, sodium tert-butoxide, potassium phosphate, potassium tert-butoxide, triethylamine, diisopropylethylamine, sodium carbonate or cesium carbonate; preferably, the base is potassium carbonate or sodium tert-butoxide;
the solvent is one or more of dichloromethane, ethanol, acetonitrile, toluene, N-dimethylformamide, 1, 4-dioxane or tetrahydrofuran; preferably, the solvent is dichloromethane or ethanol;
the visible light is blue light, the blue light LED lamp is adopted to provide the visible light, and the power of the blue light LED lamp is 6-40W.
The feeding molar ratio of the photocatalyst, the copper catalyst, the alkali, the thiophosphoric acid diethyl ester compound, the difluoroalkyl halide and the alkene compound is further limited to be 0.01-0.1: 0.1-1: 1.5-3: 1.
Further, the reaction process is carried out under the protection of inert gas, and the inert gas is nitrogen, argon or helium.
Further limiting, the reaction time in the reaction process is 4-24 h, preferably 8-12 h.
Further limiting, the post-reaction treatment process is as follows: and extracting the reaction liquid after the reaction is finished with ethyl acetate, drying an organic phase with anhydrous sodium sulfate, performing column chromatography separation after spin-drying, wherein a column chromatography solvent is a mixed solvent of petroleum ether and ethyl acetate in a volume ratio of 3:1.
The invention has the following advantages and beneficial effects: the invention provides a method for synthesizing a target product difluoroalkyl substituted phosphorodithioate compound at room temperature efficiently and high selectively by using an alkene compound, a thiophosphoric diethyl ester compound and a difluoroalkyl halide as raw materials under the co-catalysis of visible light/copper, wherein the preparation method has the advantages of mild conditions, cheap and easily-obtained raw materials, simplicity and easiness in operation, wide substrate applicability and higher yield, and is suitable for industrial production; the target product difluoroalkyl substituted phosphate ester compound prepared by the invention has stronger innovation in structure, and the difluoroalkyl is introduced into the active molecule organic sulfur phosphate ester molecule, so that the biological activity of the compound can be improved by changing the characteristics of absorption, metabolism, excretion and the like of the compound in vivo, and the introduction of the difluoroalkyl into the organic sulfur phosphate ester molecule has wide application prospect in the fields of new medicines, pesticides, organic synthesis and the like.
Detailed Description
The present invention is described in further detail below with reference to examples, but it should not be construed that the scope of the above subject matter of the present invention is limited to the following examples, and that all the technologies realized based on the above subject matter of the present invention belong to the scope of the present invention.
Example 1
Figure BDA0003214154180000031
To a 10mL Schlenk flask was added (4,4 '-di-tert-butyl-2, 2' -bipyridine) bis [ (2-pyridyl) phenyl group in that order]Iridium (III) hexafluorophosphate (2.8mg, 0.003mmol), anhydrous copper acetate (5.5mg, 0.03mmol) and potassium carbonate (82.8mg, 0.6mmol), stoppered and argon purgedQi is thrice. Weighing 4-methylstyrene 1a (31.2mg, 0.3mmol), diethyl thiophosphate 2a (76.5mg, 0.45mmol) and ethyl difluorobromoacetate 3a (90.9mg, 0.45mmol) to dissolve in dichloromethane solvent (2.5mL), adding them into a Schlenk bottle filled with argon by a syringe, reacting for 12h under 12W blue light irradiation at room temperature, extracting with 2x8 mL ethyl acetate after the reaction is finished, combining the organic phases, drying with anhydrous sodium sulfate, filtering, spin-drying, passing through a column with a mixed solvent of petroleum ether and ethyl acetate in a volume ratio of 3:1 to obtain the target compound 4 a. Yield 86.1mg, 70%; colourless liquid;1H NMR(400MHz,CDCl3)δ7.22-7.18(m,2H),7.12-7.08(m,2H),4.49-4.42(m，1H),4.07-3.93(m，5H),3.83-3.73(m，1H),2.96-2.81(m,2H),2.30(s,3H)，1.27-1.23(t，J＝7.2Hz，3H),1.21(t,J＝7.2Hz,3H),1.17(t,J＝7.1Hz,3H).13C NMR(151MHz，CDCl3)δ163.4(t,J＝32.3Hz),138.2，137.4(d,J＝4.3Hz),129.4，127.7，114.4(t,J＝252.6Hz),63.9(d,J＝5.9Hz),63.8(d，J＝5.6Hz)，63.1，43.89-43.8(m),42.5(td，J＝23.7，7.5Hz)，21.22,16.0(d，J＝7.6Hz)，15.9(d，J＝7.6Hz)，13.83.31P NMR(202MHz，CDCl3)δ24.22.19F NMR(471MHz，CDCl3)δ-102.53(d,J＝265.3Hz),-105.33(d,J＝265.3Hz).HRMS:[M+Na]+m/z calcd for C17H25F2NaO5PS+:433.1021，found:433.1028。
example 2
The same procedure as in example 1 was repeated except for using copper trifluoromethanesulfonate (10.8mg, 0.03mmol) in place of anhydrous copper acetate to obtain the desired product 4a in a yield of 68%.
Example 3
The same procedures used in example 1 were repeated except for using sodium tert-butoxide (57.6mg, 0.6mmol) in place of potassium carbonate to give the desired product 4a in a yield of 65%.
Example 4
The procedure of example 1 was repeated except that ethanol was used instead of dichloromethane, whereby the desired product 4a was obtained in a yield of 50%.
Example 5
Figure BDA0003214154180000041
The same procedures used in example 1 were repeated except for using 4-methoxystyrene 1b (40.2mg, 0.3mmol) in place of 4-methylstyrene 1a as the starting material to obtain the objective compound 4 b. 113.7mg, 89%; colourless liquid;1H NMR(400MHz，CDCl3)δ7.29-7.25(m，2H),6.87-6.83(m，2H),4.53-4.46(m,1H),4.13-3.95(m,5H),3.89-3.80(m,1H),3.79(s,3H)，2.96-2.85(m，2H),1.27(t，J＝7.1Hz,3H),1.24(t，J＝7.1Hz,3H),1.22(t，J＝7.1Hz,3H).13C NMR(151MHz,CDCl3)δ163.4(t，J＝32.3Hz),159.5,132.3(d，J＝4.3Hz),129.1，114.5(t，J＝252.6Hz),114.04，63.8(d，J＝5.9Hz),63.7(d,J＝5.7Hz),63.11,55.4,43.7-43.6(m),42.6(td,J＝23.7,7.6Hz),16.0(d,J＝7.9Hz),15.9(d,J＝7.8Hz),13.8.31P NMR(202MHz,CDCl3)δ24.18.19F NMR(471MHz,CDCl3)δ-102.38(d,J＝265.2Hz),-105.53(d,J＝265.3Hz).HRMS:[M+H]+m/z calcd for C17H26F2O6PS+:427.1150,found:427.1145。
example 6
Figure BDA0003214154180000051
The same procedures used in example 1 were repeated except for using 4-trifluoromethylstyrene 1c (51.6mg, 0.3mmol) in place of 4-methylstyrene 1a as the starting material to give the objective compound 4 c. 108.6mg, 78%; colourless liquid;1H NMR(400MHz,CDCl3)δ7.59-7.55(m,2H),7.50-7.45(m,2H),4.60-4.53(m,1H),4.09-4.01(m，3H),4.00-3.90(m,2H),3.87-3.76(m,1H),2.95-2.81(m,2H),1.23(t,J＝7.1Hz,3H),1.20(t,J＝7.1Hz,3H),1.16(t,J＝7.1Hz,3H).13C NMR(151MHz,CDCl3)δ163.3(t,J＝32.1Hz),144.9,130.5(q,J＝32.6Hz),128.4,125.7(q,J＝3.6Hz),124.0(q,J＝272.1Hz),114.3(t,J＝252.8Hz),64.1(d,J＝4.9Hz),64.06(d,J＝5.6Hz),63.3,43.43-43.27(m),42.0(td,J＝23.7,8.5Hz),15.9(d,J＝6.4Hz),15.8(d,J＝7.0Hz).13.8.31P NMR(202MHz,CDCl3)δ23.23.19F NMR(471MHz,CDCl3)δ-62.82(s),-103.34(d,J＝266.4Hz),-104.67(d,J＝266.4Hz).HRMS:[M+H]+m/z calcd for C17H23F5O5PS+:465.0918,found:465.0914。
example 7
Figure BDA0003214154180000052
The procedure of example 1 was repeated except for using 3-bromostyrene 1d (54.6mg, 0.3mmol) in place of 4-methylstyrene 1a as a starting material to obtain the objective compound 4 d. 108.1mg of Yield, 76 percent; colourless liquid;1H NMR(400MHz,CDCl3)δ7.53-7.51(m,1H),7.44-7.40(m,1H),7.32-7.28(m,1H),7.21(t,J＝7.8Hz,1H),4.51-4.45(m,1H),4.14-3.94(m,5H),3.90-3.79(m,1H),2.99-2.77(m,2H),1.31-1.25(m，6H),1.21(t，J＝7.1Hz，3H).13C NMR(151MHz,CDCl3)δ163.2(t，J＝32.1Hz),142.9(d，J＝3.4Hz),131.4，130.8，130.4，126.7，122.6，114.3(t,J＝252.5Hz),64.2(d，J＝6.1Hz),64.1(d，J＝5.8Hz)，63.4，43.3(dd，J＝8.5，4.0Hz),16.0(d，J＝7.5Hz),15.9(d,J＝7.3Hz)，13.9.31P NMR(202MHz,CDCl3)δ24.80.19F NMR(471MHz,CDCl3)δ-103.26(d,J＝264.3Hz),-104.90(d,J＝264.3Hz).HRMS:[M+H]+m/z calcd for C16H23BrF2O5PS+:475.0150,found:475.0157。
example 8
Figure BDA0003214154180000053
The same procedures used in example 1 were repeated except for using 2-vinylpyridine 1e (31.5mg, 0.3mmol) in place of 4-methylstyrene 1a as the starting material to give the objective compound 4 e. Yield 65.5mg, 55%; colourless liquid;1H NMR(400MHz,CDCl3)δ8.56(d,J＝4.5Hz,1H),7.66-7.59(m,1H),7.31(d,J＝7.8Hz，1H),7.18(dd，J＝7.5,4.9Hz,1H),4.68-4.59(m，1H)，4.16-4.04(m,3H),4.03-3.86(m，3H)，3.28-3.14(m,1H),2.95-2.82(m,1H)，1.27-1.20(m，9H).13C NMR(151MHz，CDCl3)δ163.5(t，J＝32.3Hz)，159.1(d,J＝4.1Hz),150.0,137.0，123.2,123.1，114.7(t,J＝252.0Hz),64.0(d，J＝6.0Hz),63.2，44.7(dd，J＝7.4，3.9Hz)，40.8(td，J＝23.3，6.9Hz),16.1(d，J＝3.7Hz)，16.0(d，J＝3.9Hz)，14.0.31P NMR(202MHz,CDCl3)δ24.37.19F NMR(471MHz，CDCl3)δ-103.95(d,J＝263.1Hz),-104.84(d，J＝263.1Hz).HRMS:[M+H]+m/z calcd for C15H23F2NO5PS+:398.0997,found:398.0996。
example 9
Figure BDA0003214154180000061
The same procedures used in example 1 were repeated except for using α -methylstyrene 1f (35.4mg, 0.3mmol) in place of 4-methylstyrene 1a as the starting material to obtain the objective compound 4 f. 97.2mg of Yield, 79 percent; colourless liquid;1H NMR(400MHz,CDCl3)δ7.57-7.53(m,2H),7.38-7.32(m，2H),7.29-7.25(m,1H),4.14-3.75(m，6H),3.36-3.28(m,2H),2.22(s,3H),1.27(t,J＝7.1Hz,3H),1.24(t,J＝7.1Hz,3H),1.19(t,J＝7.1Hz,3H).13C NMR(151MHz,CDCl3)δ163.6(t,J＝32.2Hz),142.0(d,J＝7.8Hz),128.3,128.0,127.1,114.8(dd,J＝255.0,251.1Hz),63.9(d,J＝6.3Hz),62.95,53.9-53.8(m),46.7(td,J＝24.0,5.2Hz),26.7,16.1(d,J＝6.1Hz),16.0(d,J＝7.1Hz),13.7.31P NMR(202MHz,CDCl3)δ21.81.19F NMR(471MHz,CDCl3)δ-96.46(d,J＝262.3Hz),-102.29(d,J＝262.3Hz).HRMS:[M+H]+m/z calcd for C17H26F2O5PS+:411.1201,found:411.1209。
example 10
Figure BDA0003214154180000062
The same procedures used in example 1 were repeated except for using 1g (35.4mg, 0.3mmol) of β -methylstyrene instead of 4-methylstyrene 1a as the starting material to obtain 4g of the objective compound (dr ═ 3: 1). Yield 70.1mg, 57%; colourless liquid;1H NMR(400MHz,CDCl3)δ7.42-7.39(m,2H),7.34-7.30(m,2H),7.28-7.24(m,1H),4.55(dd,J＝13.1,6.2Hz,1H),4.14-4.07(m,2H),4.04-3.85(m,3H),3.69-3.59(m,1H),2.89-2.78(m,1H),1.35-1.26(m,6H),1.21(t,J＝7.1Hz,3H),1.06(t,J＝7.1Hz,3H).13C NMR(151MHz,CDCl3)δ163.6(t,J＝32.5Hz),141.2,128.9,128.7,128.4,127.9,116.3(t,J＝253.8Hz),63.6(d,J＝5.4Hz),63.1,50.3-50.2(m),44.4(td,J＝21.6,8.9Hz),15.9(d,J＝7.7Hz),15.7(d,J＝7.8Hz),14.0,10.6-10.4(m).31P NMR(202MHz,CDCl3)δ25.08.19F NMR(471MHz,CDCl3)δ-107.38(d,J＝262.3Hz),-111.37(d,J＝262.3Hz).HRMS:[M+H]+m/z calcd for C17H26F2O5PS+:411.1201,found:411.1207。
example 11
Figure BDA0003214154180000071
The same procedures used in example 1 were repeated except for using ethyl cinnamate 1h (52.8mg, 0.3mmol) instead of 4-methylstyrene 1a as a starting material to give the objective compound 4h (dr ═ 10: 1). Yield 40.7mg, 29%; colourless liquid;1H NMR(400MHz,CDCl3)δ7.45-7.41(m,2H),7.34-7.27(m,3H),4.76(dd,J＝12.2,11.1Hz,1H),4.36-4.25(m,2H),4.04-3.77(m,6H),3.48-3.37(m,1H),1.36(t,J＝7.1Hz,3H),1.28(td,J＝7.1，0.8Hz,3H),1.18(t,J＝7.2Hz，3H),1.00(td,J＝7.1,0.6Hz,3H).13C NMR(151MHz，CDCl3)δ166.8(dd,J＝2.7,1.4Hz),162.0(t,J＝31.3Hz),138.5,129.4,128.6,128.5,113.3(dd,J＝262.5,253.0Hz),63.8(d,J＝5.1Hz),63.5(d,J＝5.0Hz),63.4,62.4,56.2(td,J＝21.8,11.0Hz),47.3-47.1(m),16.0(d,J＝7.9Hz),15.7(d,J＝7.9Hz),14.2,13.8.31P NMR(202MHz，CDCl3)δ23.31.19F NMR(471MHz,CDCl3)δ-101.25(d,J＝273.2Hz),-111.81(d,J＝273.3Hz).HRMS:[M+H]+m/z calcd for C19H28F2O7PS2 +:469.1256,found:469.1260。
example 12
Figure BDA0003214154180000072
The same procedures used in example 1 were repeated except for using hexene 1i (25.2mg, 0.3mmol) in place of 4-methylstyrene 1a as the starting material to obtain the objective compound 4 i. Yield 84.6mg, 75%; colourless liquid;1H NMR(400MHz,CDCl3)δ4.33-4.27(m,2H),4.19-4.05(m,4H),3.49-3.38(m,1H),2.70-2.53(m,1H),2.52-2.34(m,1H),1.85-1.65(m,2H),1.48-1.37(m,2H)，1.35-1.28(m,11H)，0.90-0.85(m,3H).13C NMR(151MHz,CDCl3)δ163.9(d,J＝32.4Hz),115.2(t,J＝252.0Hz),64.1(d,J＝6.4Hz),64.0(d,J＝6.4Hz),63.3,41.2(dd,J＝7.4,3.9Hz),40.8(qd,J＝22.5,4.2Hz),36.1(d,J＝5.3Hz),28.6,22.4,16.2(dd,J＝7.4,0.8Hz),14.1.31P NMR(202MHz,CDCl3)δ25.83.9F NMR(471MHz,CDCl3)δ-102.50(d,J＝262.1Hz),-105.71(d,J＝262.1Hz).HRMS:[M+H]+m/z calcd for C14H28F2O5PS+:377.1358,found:377.1349。
example 13
Figure BDA0003214154180000081
The same procedures used in example 1 were repeated except for using the compound 1j (72.0mg, 0.3mmol) in place of the 4-methylstyrene 1a as the starting material to obtain the objective compound 4 j. Yield 114.9mg, 72%; colourless liquid;1H NMR(400MHz,CDCl3)δ7.75(d,J＝7.9Hz,2H),7.32(d,J＝8.0Hz,2H),4.40-4.24(m,4H),4.14-4.00(m,4H),2.80-.65(m,2H),2.41(s,3H),2.35-2.22(m,2H),1.56(s,3H),1.33-1.27(m,9H).13C NMR(101MHz,CDCl3)δ163.83(t,J＝32.3Hz),145.1,132.9,130.0,128.0,115.4(t,J＝253.5Hz),67.2,64.3(d,J＝1.3Hz),64.2(d,J＝1.3Hz),63.4,51.9(d,J＝4.2Hz),45.1(td,J＝21.8,3.7Hz),40.1-39.9(m),27.8(d,J＝8.2Hz),21.7,16.1(d,J＝1.0Hz),16.0(d,J＝1.3Hz),13.9.31P NMR(202MHz,CDCl3)δ22.0.19F NMR(376MHz,CDCl3)δ-101.09(d,J＝261.5Hz),-102.16(d,J＝261.5Hz)。HRMS:[M+H]+m/z calcd for C20H32F2O8PS2+:533.1239,found:533.1235。
example 14
Figure BDA0003214154180000082
The same procedures used in example 1 were repeated except for using compound 1k (52.5mg, 0.3mmol) in place of 4-methylstyrene 1a as the starting material to give the objective compound 4 k. Yield 84.1mg, 60%; colourless liquid;1H NMR(400MHz,CDCl3)δ7.26-7.14(m,5H),6.73(s,1H),4.38-4.30(m,2H),4.24(q,J＝7.1Hz,2H),4.05-3.91(m,4H),3.82-3.69(m,1H),2.75-2.60(m,4H),1.31-1.19(m,9H).13C NMR(151MHz,CDCl3)δ169.5,163.7(t,J＝32.3Hz),138.3,128.7,128.0,127.5,115.0(t,J＝252.1Hz),64.4(d,J＝6.7Hz),64.3(d,J＝6.7Hz),63.4,43.6,42.6,40.1(td,J＝23.0,5.4Hz),37.1-36.9(m),16.1(d,J＝7.2Hz),14.0.31P NMR(202MHz,CDCl3)δ24.84.19F NMR(471MHz,CDCl3)δ-103.26(d,J＝262.8Hz),-105.52(d,J＝262.8Hz).HRMS:[M+H]+m/z calcd for C19H29F2NO6PS+:468.1416,found:468.1422。
example 15
Figure BDA0003214154180000083
Using 1l (40.2mg, 0.3mmol) of the compound instead of 4-methylstyrene 1a as a starting material, 4l of the objective compound was obtained in the same manner as in example 1. Yield 71.6mg, 56%; colourless liquid; 1H NMR (400MHz, CDCl3) δ 7.32-7.26(m,2H),7.00-6.95(m,1H),6.94-6.91(m,2H),4.34-4.25(m,3H),4.24-4.10(m,5H),3.88-3.77(m,1H),2.9-2.78(m,1H),2.70-2.55(m,1H),1.37-1.31(m,9H), 13C NMR (151MHz, CDCl3) δ 163.7(t, J-32.4 Hz),158.2,129.8,121.7,115.1(t, J-252.0 Hz),114.8,70.3(d, J-2.7 Hz),64.3(d, J-6.4 Hz),63.4,39.3(q, 6.37, 6.23H), 3619H, 19H, 3J-3H, 19H, 3J-6.7 Hz, 3J-19H, 3J-3H, 19H, 3J-3H, 19H, 3H, 19H, 3 g, 3H, 3H, 19H, 3H, 19H, 3H, 19H, 3H, 19H, 3H, 19H, 3, 19H, 3H, etc., P, 19H, P, 19H, 18H, P, 19H, P, 19H, P, j266.2 Hz. [ M + H ] + M/z calcd for C17H26F2O6PS +:427.1150, found: 427.1155.
Example 16
Figure BDA0003214154180000091
The same procedures used in example 1 were repeated except for using compound 1m (45.0mg, 0.3mmol) instead of 4-methylstyrene 1a as the starting material to give the objective compound 4m (dr ═ 1: 1). 88.8mg of Yield, 67%; colourless liquid;1H NMR(400MHz,CDCl3)δ6.73-6.69(m,1H),4.30-4.24(m,2H),4.17-4.04(m,4H),3.09-2.93(m,1H),2.82-2.49(m,4H),2.44-2.27(m,2H),1.73(s,3H),1.69(s,3H),1.34-1.26(m,9H).13C NMR(151MHz,CDCl3)δ198.9,198.5,163.9(t,J＝32.9Hz),144.32,144.30,135.53,135.50,115.5(t,J＝252.1Hz),115.6(t,J＝252.1Hz),64.40(d,J＝7.0Hz),64.36(d,J＝2.9Hz),64.32(d,J＝3.8Hz),64.30(d,J＝3.6Hz),63.4,56.6(d,J＝4.3Hz),56.5(d,J＝4.4Hz),44.5(d,J＝5.8Hz),44.2(d,J＝7.5Hz),42.3-41.8(m),40.0,39.9,28.0,27.96,26.0-25.9(m),25.9-25.7(m),16.2(d,J＝2.0Hz),16.12(d,J＝2.1Hz),16.09(d,J＝3.0Hz),16.07(d,J＝4.2Hz),15.6,14.0.31P NMR(202MHz,CDCl3)δ22.66,22.56.19F NMR(471MHz,CDCl3)δ-100.49(d,J＝260.6Hz),-102.51(d,J＝260.9Hz),-103.22(d,J＝260.2Hz).HRMS:[M+H]+m/z calcd for C18H30F2O6PS+:443.1463,found:443.1458。
example 17
Figure BDA0003214154180000092
The same procedures used in example 1 were repeated except for using the compound 1n (118.2mg, 0.3mmol) in place of 4-methylstyrene 1a as a starting material to obtain the objective compound 4 n. Yield 135.8mg, 66%; colourless liquid;1H NMR(400MHz,CDCl3)δ9.19(s,1H),7.61-7.59(m,2H),7.55-7.46(m,4H),7.38-7.25(m,6H),7.21(d,J＝7.8Hz,2H),4.55-4.40(m,1H),4.08-3.93(m,4H),3.86-3.76(m,1H),3.23(t,J＝6.73Hz,2H),2.97-2.76(m,4H),1.23-1.12(m,9H).13C NMR(151MHz,CDCl3)δ170.1,163.3(t,J＝32.4Hz),162.6,145.7,138.5,135.6(d,J＝3.3Hz),134.9,132.3,128.8(2C,overlap),128.7(2C,overlap),128.4,128.3,128.0,126.5,119.8,114.4(t,J＝252.1Hz),64.0(d,J＝6.1Hz),63.9(d,J＝5.8Hz),63.2,43.7,42.4(td,J＝23.6,7.4Hz),33.9,24.0,15.9(d,J＝5.4Hz),15.9(d,J＝5.1Hz),13.8.31P NMR(202MHz,CDCl3)δ23.87.19F NMR(471MHz,CDCl3)δ-102.71(d,J＝265.3Hz),-105.17(d,J＝265.3Hz).HRMS:[M+Na]+m/z calcd for C34H37F2N2NaO7PS+:709.1919,found:709.1924。
example 18
Figure BDA0003214154180000101
The same procedures used in example 1 were repeated except for using compound 1o (118.2mg, 0.3mmol) instead of 4-methylstyrene 1a as the starting material to give the objective compound 4o (dr ═ 1: 1). Yield 86.4mg, 42%; colourless liquid;1H NMR(600MHz,CDCl3)δ7.79(dd,J＝8.6,3.0Hz,1H),6.70(d,J＝3.1Hz,1H),6.47-6.39(m,2H),5.29-5.16(m,1H),4.93-4.91(m,1H),4.60–4.56(m,1H),4.32-4.25(m,2H),4.19-4.06(m,5H),3.81(d,J＝3.9Hz,1H),3.76(s,3H),3.71(s,3H),3.33-3.21(m,2H),3.10-2.82(m,2H),1.34-1.28(m,9H).13C NMR(151MHz,CDCl3)δ189.07,189.06,166.8,166.7,163.89(t,J＝32.2Hz),163.86(t,J＝32.2Hz),157.84,157.82,149.6,147.5,143.9,130.1,115.6(t,J＝252.1Hz),115.5(t,J＝252.1Hz),113.7,112.79,112.76,110.45,110.42,104.9,104.77,104.73,104.71,101.0,89.3(d,J＝5.5Hz),89.1(d,J＝4.5Hz),72.37,72.35,66.3,64.5(d,J＝7.1Hz),64.4(d,J＝7.5Hz),64.37(d,J＝4.8Hz),64.32(d,J＝4.5Hz),63.4,63.3,56.4,55.9,44.6,41.5(t,J＝22.1Hz),40.8(t,J＝24.2Hz),29.0,28.4,23.3,21.0,16.2(d,J＝2.6Hz),16.1(d,J＝2.6Hz),16.06(d,J＝2.2Hz),16.02(d,J＝2.3Hz),14.0(d,J＝1.6Hz).31P NMR(202MHz,CDCl3)δ22.48,22.01.19F NMR(471MHz,CDCl3)δ-100.04(d,J＝263.6Hz),-100.05(d,J＝263.6Hz),-101.00(d,J＝263.6Hz),-101.46(d,J＝262.9Hz).HRMS:[M+H]+m/z calcd for C31H38F2O11PS+:687.1835,found:687.1844。
example 19
Figure BDA0003214154180000102
The same procedures used in example 1 were repeated except for using compound 1p (74.1mg, 0.3mmol) instead of 4-methylstyrene 1a as the starting material to give the objective compound 3n (dr ═ 1: 1). Yield 77.6mg, 48%; colourless liquid;1H NMR(400MHz,CDCl3)δ7.31-7.21(m,3H),7.16-7.11(m,2H),6.48(s,1H),4.86(dd,J＝13.2,6.5Hz,1H),4.33(q,J＝7.1Hz,2H),4.22-4.08(m,4H),3.84-3.74(m,1H),3.71(s,3H),3.19-3.03(m,2H),2.87-2.63(m,4H),1.38-1.32(m,9H).13C NMR(151MHz,CDCl3)δ171.9,169.1(d,J＝10.6Hz),163.6(t,J＝32.3Hz),136.0(d,J＝3.0Hz),129.3(d,J＝2.3Hz),128.7,127.2,115.0(t,J＝252.0Hz),64.3(d,J＝6.7Hz),64.24(d,J＝6.0Hz),64.20(d,J＝6.2Hz),63.3,53.4,52.4,42.5-42.3(m),39.8(tt,J＝22.8,4.7Hz),38.0(d,J＝6.0Hz),36.6-36.5(m),16.1(d,J＝7.3Hz),14.0.31P NMR(202MHz,CDCl3)δ24.88.19F NMR(471MHz,CDCl3)δ-102.73(d,J＝100.1Hz),-103.29(d,J＝100.0Hz),-105.34(d,J＝71.3Hz),-105.90(d,J＝71.3Hz).HRMS:[M+H]+m/z calcd for C22H33F2NO8PS+:540.1627,found:540.1634。
example 20
Figure BDA0003214154180000111
Using diisopropyl thiophosphate 2b (89.1mg, 0.45mmol) instead of diethyl thiophosphate 2a as a starting material, the same procedures as in example 1 were repeated to give the objective compound 4 q. Yield 114.5mg, 90%; colourless liquid;1H NMR(400MHz,CDCl3)δ7.36-7.29(m,4H),7.28-7.24(m,1H),4.71-4.63(m,1H),4.60-4.48(m,2H),4.00-3.92(m,2H),1.32(d,J＝6.2Hz,3H),1.25-1.19(m,12H).13C NMR(151MHz,CDCl3)δ163.4(t,J＝32.3Hz),140.3(d,J＝5.1Hz),128.8,128.3,128.0,114.5(dd,J＝253.3,250.8Hz),73.24(d,J＝6.4Hz),73.18(d,J＝6.8Hz),63.0,44.2-44.1(m),42.5(td,J＝23.6,6.7Hz),23.9(d,J＝3.9Hz),23.8(d,J＝4.1Hz),23.6(d,J＝5.7Hz),23.5(d,J＝5.7Hz),13.8.31P NMR(202MHz,CDCl3)δ21.61.19F NMR(471MHz,CDCl3)δ-101.82(d,J＝265.0Hz),-105.74(d,J＝265.0Hz).HRMS:[M+Na]+m/z calcd for C18H27F2NaO5PS2 +:447.1177,found:447.1173。
example 21
Figure BDA0003214154180000112
The same procedures used in example 1 were repeated except for using dibutyl thiophosphate 2c (101.7mg, 0.45mmol) in place of diethyl thiophosphate 2a as a starting material to give the objective compound 4 r. Yield 120.7mg, 89%; colourless liquid;1H NMR(400MHz,CDCl3)δ7.37-7.24(m,5H),4.57-4.47(m,1H),4.04-3.83(m,5H),3.78-3.70(m,1H),2.99-2.82(m,2H),1.61-1.46(m,4H),1.38-1.28(m,4H),1.27-1.19(m,3H),0.92-0.85(m,6H).13C NMR(151MHz,CDCl3)δ163.3(t,J＝32.2Hz),140.5(d,J＝3.8Hz),114.4(t,J＝253.8Hz),128.7,128.2,127.9,67.44(d,J＝6.2Hz),67.40(d,J＝5.1Hz),44.0-43.9(m),42.4(td,J＝23.8,7.8Hz),32.0(t,J＝7.5Hz),18.7(d,J＝1.5Hz),13.8,13.6.31P NMR(202MHz,CDCl3)δ24.07.19F NMR(471MHz,CDCl3)δ-102.34(d,J＝265.6Hz),-105.38(d,J＝265.6Hz).HRMS:[M+H]+m/z calcd for C20H32F2O5PS+:453.1671,found:453.1681。
example 22
Figure BDA0003214154180000121
Using diethyl dithiophosphate 2d (83.3mg, 0.45mmol) instead of diethyl thiophosphate 2a as a starting material, the same procedure as in example 1 was repeated to obtain the objective compound 4 s. Yield 100.4mg, 81%; colourless liquid;1H NMR(400MHz,CDCl3)δ7.35-7.24(m,5H),4.57-4.47(m,1H),4.15-3.94(m,5H),3.78-3.68(m,1H),2.93-2.83(m,2H),1.28(t,J＝7.1Hz,3H),1.24(t,J＝7.2Hz,3H),1.16(t,J＝7.1Hz,3H).13C NMR(151MHz,CDCl3)δ163.4(t,J＝32.2Hz),140.4(d,J＝4.0Hz),128.8,128.3,128.0,114.5(t,J＝252.0Hz),64.3(d,J＝5.9Hz),64.1(d,J＝5.5Hz),63.2,46.5-46.3(m),42.4(td,J＝23.6,6.8Hz),15.8(d,J＝8.7Hz),15.7(d,J＝8.8Hz),13.9.31P NMR(202MHz,CDCl3)δ89.62.19F NMR(471MHz,CDCl3)δ-102.34(d,J＝264.9Hz),-105.13(d,J＝264.9Hz).HRMS:[M+Na]+m/z calcd for C16H23F2NaO4PS2 +:435.0636,found:435.0640。
example 23
Figure BDA0003214154180000122
The same procedures used in example 1 were repeated except for using difluorobromoacetylamide 3b (112.1mg, 0.45mmol) in place of diethyl thiophosphate 2a as the starting material to give the objective compound 4 t. Yield 79.7mg, 60%; colourless liquid;1H NMR(400MHz,CDCl3)δ8.44(s,1H),7.52-7.48(m,2H),7.37-7.25(m,6H),7.22-7.12(m,2H),4.64-4.57(m,1H),4.03-3.93(m,1H),3.9-3.84(m,2H),3.82-3.71(m,1H),3.13-2.90(m,2H).1.15(t,J＝7.1Hz,3H),1.13(t,J＝7.2Hz,3H).13C NMR(151MHz,CDCl3)δ161.5(t,J＝28.1Hz),141.0(d,J＝3.6Hz),136.3,129.1,128.8,127.6,125.5,120.5,116.5(t,J＝255.8Hz),63.94(d,J＝2.5Hz),63.90(d,J＝2.0Hz),44.0(dd,J＝7.4,4.2Hz),41.6(td,J＝23.7,8.1Hz),15.9(d,J＝8.0Hz),15.8(d,J＝8.0Hz).31P NMR(202MHz,CDCl3)δ24.20.19F NMR(471MHz,CDCl3)δ-102.80(d,J＝258.1Hz),-103.82(d,J＝258.2Hz).HRMS:[M+Na]+m/z calcd for C20H24F2NNaO4PS+:466.1024,found:466.1018。
the foregoing embodiments illustrate the principles, principal features and advantages of the invention, and it will be understood by those skilled in the art that the invention is not limited to the foregoing embodiments, which are merely illustrative of the principles of the invention, and that various changes and modifications may be made therein without departing from the scope of the principles of the invention.

Claims (6)

1. A difluoroalkyl substituted sulfur phosphate compound is characterized in that: the structural formula of the difluoroalkyl substituted phosphate ester compound is shown as the following formula (1):
Figure FDA0003214154170000011
wherein R is
Figure FDA0003214154170000012
R1Is hydrogen, phenyl, substituted phenyl or C1-6An alkyl group; r2Is phenyl, substituted phenyl, naphthyl, pyridyl,
Figure FDA0003214154170000013
Figure FDA0003214154170000014
Figure FDA0003214154170000015
The substituent on the benzene ring of the substituted phenyl is C1-6Alkyl, fluoro, chloro, bromo, nitro, methoxy, trifluoromethyl, phenyl,
Figure FDA0003214154170000016
n is an integer of 1-20, R' is C1-6Alkyl, fluoro, chloro, bromo, nitro, methoxy, trifluoromethyl or phenyl; r3Is hydrogen, methyl or
Figure FDA0003214154170000017
R4Is C1-6Alkoxy or phenyl; r5Is C1-6Alkoxy or phenyl; x is O or S.
2. A preparation method of the difluoroalkyl substituted sulfur phosphate compound as claimed in claim 1, which is characterized by comprising the following specific steps: adding an alkene compound 1, a diethyl thiophosphate compound 2, a difluoroalkyl halide 3, a photocatalyst, a copper catalyst and alkali into a solvent, stirring and reacting completely at 0-40 ℃ in an inert gas atmosphere under visible light irradiation, and performing post-treatment to obtain a target product difluoroalkyl substituted phosphorothioate compound 4, wherein the reaction equation in the preparation process is as follows:
Figure FDA0003214154170000021
the photocatalyst is (4,4 '-di-tert-butyl-2, 2' -bipyridine) bis [ (2-pyridyl) phenyl group]Iridium (III) hexafluorophosphate ([ Ir (dtbbpy) ((ppy)2][PF6]) Or tris (2-phenylpyridine) iridium (Ir (ppy)3)；
The copper catalyst is copper acetate, cuprous iodide, copper powder, cuprous bromide, cuprous chloride, cupric bromide, cuprous acetate or copper trifluoromethanesulfonate;
the alkali is potassium carbonate, sodium tert-butoxide, potassium phosphate, potassium tert-butoxide, triethylamine, diisopropylethylamine, sodium carbonate or cesium carbonate;
the solvent is one or more of dichloromethane, ethanol, acetonitrile, toluene, N-dimethylformamide, 1, 4-dioxane or tetrahydrofuran;
the visible light is blue light, the blue light LED lamp is adopted to provide the visible light, and the power of the blue light LED lamp is 6-40W.
3. The method for producing a difluoroalkyl-substituted thiophosphate compound as set forth in claim 1, wherein: the feeding molar ratio of the photocatalyst, the copper catalyst, the alkali, the diethyl thiophosphate compound, the difluoroalkyl halide and the alkene compound is 0.01-0.1: 0.1-1: 1.5-3: 1.
4. The method for producing a difluoroalkyl-substituted thiophosphate compound as set forth in claim 1, wherein: the reaction process is carried out under the protection of inert gas, and the inert gas is nitrogen, argon or helium.
5. The method for producing a difluoroalkyl-substituted thiophosphate compound as set forth in claim 1, wherein: the reaction time in the reaction process is 4-24 h, preferably 8-12 h.
6. The method for preparing difluoroalkyl substituted thiophosphoric acid ester compound as claimed in claim 1, which is characterized in that the post-reaction treatment process is: and extracting the reaction liquid after the reaction is finished with ethyl acetate, drying an organic phase with anhydrous sodium sulfate, performing column chromatography separation after spin-drying, wherein a column chromatography solvent is a mixed solvent of petroleum ether and ethyl acetate in a volume ratio of 3:1.
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WO1991000294A1 (en) * 1989-06-30 1991-01-10 Commonwealth Scientific And Industrial Research Organisation Monoclonal and polyclonal antibodies and test method for determination of fenitrothion and closely related organophosphates
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WO2015165295A1 (en) * 2014-04-28 2015-11-05 湖南大学 Method for preparing phosphinate/phosphite/phosphate compounds by using compounds containing p(o)-oh
CN112552342A (en) * 2020-12-07 2021-03-26 新乡医学院 Difluoroalkyl-containing tetra-substituted alkenyl phosphine oxide compound and preparation method thereof

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CN114853807A (en) * 2022-04-11 2022-08-05 中国科学院西北高原生物研究所 A kind of alkyl phosphorothioate and light-induced preparation method thereof
CN115232164A (en) * 2022-07-04 2022-10-25 新乡医学院 A kind of preparation method of phosphorothioate compound substituted by sulfone group

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