CN115651020A - Method for synthesizing phosphine oxide by reaction of visible light-induced electron-deficient unsaturated hydrocarbon compound and diaryl ethoxy phosphine - Google Patents
Method for synthesizing phosphine oxide by reaction of visible light-induced electron-deficient unsaturated hydrocarbon compound and diaryl ethoxy phosphine Download PDFInfo
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Abstract
The invention discloses a method for synthesizing phosphine oxide by reaction of an electron-deficient unsaturated hydrocarbon compound induced by visible light and diaryl ethoxy phosphine, belonging to the technical field of organic photocatalytic chemistry. The method comprises the following steps: dissolving the electron-deficient unsaturated hydrocarbon compound, diaryl ethoxy phosphine and photocatalyst in an organic solvent, reacting at room temperature for 12-24h under the irradiation of visible light blue light, concentrating the reaction solution by using a rotary evaporator after the reaction is finished, and separating by silica gel column chromatography to obtain the target product. The phosphine oxide synthesis method provided by the invention has the characteristics of scientificity, reasonability, simple synthesis method, good functional group compatibility, mild conditions, high chemical selectivity and the like. The reaction equation is as follows:
Description
Technical Field
The invention relates to the technical field of organic photocatalytic chemistry, in particular to a method for synthesizing phosphine oxide by the reaction of an electron-deficient unsaturated hydrocarbon compound induced by visible light and diaryl ethoxy phosphine.
Background
Phosphine oxides have unique structural features and are ideal hydrogen bond acceptors attached to a tetrahedral center with three potentially derivatized groups. Phosphine oxide structures possess sufficient chemical stability to be more polar than some classical functional groups such as amides or sulfonamides, so that the introduction of phosphine oxide structures into compounds can increase water solubility and decrease lipid solubility, and the increase in polarity of phosphine oxide analogs can increase the metabolic stability of the compounds.
To date, there are three main approaches to the construction of phosphine oxides by the formation of C-P bonds: transition metal catalyst C sp2/sp P bond coupling reaction, nucleophilic addition reaction of phosphorus-hydrogen reagent to unsaturated bond, and free radical series reaction. However, the phosphine is mainly generated by oxidation of phosphine reagent, most of which needs to be added, and the development of a novel phosphine free radical forming strategy is an important supplement to the existing method. The phosphine oxide backbone structure has obvious biological activity to provide potential for drug development. Therefore, it is very interesting to develop and research diarylphosphine oxide structural compounds innovatively.
Disclosure of Invention
The purpose of the invention is as follows: in order to overcome the defects of the prior art, the invention provides a method for synthesizing phosphine oxide by the reaction of visible light-induced electron-deficient unsaturated hydrocarbon compound and diaryl ethoxy phosphine as a supplement to the prior phosphine oxide synthesis method.
The technical scheme is as follows: in order to realize the purpose, the invention adopts the technical scheme that:
a method for synthesizing phosphine oxide by reaction of visible light-induced electron-deficient unsaturated hydrocarbon compound and diarylethoxyphosphine, wherein the phosphine oxide has a structure shown in formula I:
R 1 selected from various substituents; r 2 Selected from phenyl, p-methylphenyl, o-methylphenyl, m-methylphenyl, etc.; r 3 Selected from phenyl, p-methylphenyl, o-methylphenyl, m-methylphenyl, etc.; r is 4 Selected from methyl, ethyl, etc.; it is characterized in that the electron-deficient unsaturated hydrocarbon compound, diaryl ethoxy phosphine and photocatalyst are dissolved in an organic solvent and irradiated by visible light blue lightReacting at room temperature for 12-24h, concentrating the reaction solution by using a rotary evaporator after the reaction is finished, and separating by silica gel column chromatography to obtain the target product. The chemical process is shown in a reaction formula II:
the molar ratio of the electron-deficient unsaturated hydrocarbon compound, diaryl ethoxy phosphine and the photocatalyst is 1.0: 1.5: 0.01. The solvent is dichloromethane, the reaction temperature is room temperature, and the reaction time is 24 hours.
The beneficial effects of the invention are as follows: the synthesis method of phosphine oxide provided by the invention is scientific and reasonable, provides a new way for synthesizing phosphine oxide by reaction of visible light induced electron-deficient unsaturated hydrocarbon compound and diaryl ethoxy phosphine, and obtains phosphine oxide with various substituents by the method.
Drawings
FIG. 1 is a chemical reaction scheme for the preparation of phosphine oxides;
FIG. 2 is an NMR spectrum of Compound 3a prepared in example 1;
FIG. 3 is an NMR spectrum of Compound 3b prepared in example 2;
FIG. 4 is an NMR spectrum of compound 3c prepared in example 3;
FIG. 5 is an NMR spectrum of compound 3d prepared in example 3;
Detailed Description
The invention is described in further detail below with reference to the figures and specific examples.
The test methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.
Example 1
5-bromo-2-vinylpyridine 1a (0.1mmol, 1.0equiv, 18.4 mg), diphenylethoxyphosphine 2a (0.15mmol, 1.5equiv, 34.5 mg), ir [ dF (CF) 3 )ppy] 2 (dtbbpy)]PF 6 (1 mol%,0.001mmol, 1.1mg) and DCM (3 mL, 0.03M) were added sequentially to a 4mL clear glass vial equipped with magnetons. After bubbling with nitrogen for 5 minutes to remove oxygen, the vial was sealed and placed under blue light for irradiation. The reaction mixture was monitored by TLC until the starting 5-bromo-2-vinylpyridine 1a was consumed. After the reaction is finished, concentrating the reaction solution by using a rotary evaporator, and then carrying out silica gel column chromatography separation to obtain the target product 3a.
Spectrogram analysis data 3a
1 H NMR(400MHz，CDCl 3 )δ8.51(s，1H)，7.75(dd，J＝11.5，7.6Hz，4H)，7.62(dd，J＝8.3，2.2Hz，1H)，7.54-7.41(m，6H)，7.02(d，J＝8.3Hz，1H)，3.08(q，J＝9.1Hz，2H)，2.76(td，J＝10.3，6.0Hz，2H). 13 C NMR(101MHz，CDCl 3 )δ158.7(d，J＝14.0Hz)，150.3，138.9，132.7(d，J＝98.0Hz)，131.8(d，J＝3.0Hz)，130.8(d，J＝9.0Hz)，128.7(d，J＝12.0Hz)，124.5，118.4，29.2(d，J＝3.0Hz)，29.0(d，J＝71.0Hz). 31 P NMR(162MHz，CDCl 3 )δ31.8.HRMS(ESI，m/z)calcd for C 19 H 18 BrNOP[M+H] + ：386.0304，found：386.0299.
Example 2
The experimental results are shown in Table 1, except that 1b is used instead of 1a in example 1 and the conditions are the same as in example 1.
2-isopropenylbenzothiazole 1b (0.1mmol, 1.0equiv, 17.5 mg), diphenylethoxyphosphine 2a (0.15mmol, 1.5equiv, 34.5 mg), ir [ dF (CF) 3 )ppy] 2 (dtbbpy)]PF 6 (1 mol%,0.001mmol, 1.1mg) and DCM (3 mL, 0.03M) were added sequentially to a 4mL clear glass vial equipped with magnetons. After bubbling with nitrogen for 5 minutes to remove oxygen, the vial was sealed and placed under blue light for irradiation. The reaction mixture was monitored by TLC until the starting material 2-isopropenylbenzothiazole 1b was consumed. After the reaction is finished, concentrating the reaction solution by using a rotary evaporator, and passing through a silica gel column layerSeparating and separating to obtain the target product 3b.
Spectrogram analysis data 3b
1 H NMR(600MHz，CDCl 3 )δ7.90(dt，J＝8.2，0.8Hz，1H)，7.82-7.71(m，5H)，7.52-7.49(m，1H)，7.48-7.43(m，2H)，7.43-7.41(m，1H)，7.36-7.29(m，4H)，3.89-3.79(m，1H)，3.24(ddd，J＝15.2，8.7，5.3Hz，1H)，2.72(ddd，J＝15.2，12.6，8.1Hz，1H)，1.60(d，J＝7.0Hz，3H). 13 C NMR(151MHz，CDCl 3 )δ175.9(d，J＝11.5Hz)，152.7，134.7，133.8(d，J＝99.2Hz)，132.0(d，J＝98.9Hz)，131.8(d，J＝2.8Hz)，131.5(d，J＝2.8Hz)，130.9(d，J＝9.4Hz)，130.5(d，J＝9.3Hz)，128.7(d，J＝11.7Hz)，128.4(d，J＝11.9Hz)，125.9，124.9，122.6，121.5，36.3(d，J＝70.3Hz)，33.6(d，J＝2.5Hz)，22.8(d，J＝5.5Hz). 31 P NMR(243MHz，CDCl 3 )δ29.6.HRMS(ESI，m/z)calcd for C 22 H 21 NOPS[M+H] + ：378.1076，found：378.1072.
Example 3
The experimental results are shown in Table 1, except that 1c is used instead of 1a in example 1, 2b is used instead of 2a in example 1, and the other conditions are the same as in example 1.
2-vinylpyridine 1c (0.1mmol, 1.0equiv, 10.5 mg), di-p-methylphenylethoxyphosphine 2b (0.15mmol, 1.5equiv, 38.7 mg), ir [ dF (CF) 3 )ppy] 2 (dtbbpy)]PF 6 (1 mol%,0.001mmol, 1.1mg) and DCM (3 mL, 0.03M) were added sequentially to a 4mL clear glass vial equipped with magnetons. After bubbling with nitrogen for 5 minutes to remove oxygen, the vial was sealed and placed under blue light for irradiation. The reaction mixture was monitored by TLC until the starting material 2-vinylpyridine 1c was consumed. After the reaction is finished, concentrating the reaction solution by using a rotary evaporator, and performing chromatographic separation by using a silica gel column to obtain a target product 3c.
Spectrogram analysis data 3c
1 H NMR(400MHz，CDCl 3 )δ8.50(d，J＝5.0Hz，1H)，7.67(dd，J＝11.4，7.7Hz，4H)，7.58(t，J＝7.7Hz，1H)，7.27(dd，J＝8.5，2.7Hz，4H)，7.18(d，J＝7.8Hz，1H)，7.16-7.10(m，1H)，3.13(q，J＝8.5Hz，2H)，2.77(td，J＝11.3，10.9，6.7Hz，2H)，2.38(s，6H). 13 C NMR(101MHz，CDCl 3 )δ160.2(d，J＝15.0Hz)，148.7，142.1(d，J＝2.7Hz)，137.0，130.8(d，J＝9.7Hz)，129.7(d，J＝100.6Hz)，129.4(d，J＝12.0Hz)，123.4，121.6，29.6(d，J＝2.8Hz)，29.4(d，J＝71.1Hz)，21.5. 31 P NMR(162MHz，CDCl 3 )δ32.6.HRMS(ESI，m/z)calcd for C 21 H 23 NOP[M+H] + ：336.1512，found：336.1510.
Example 4
The same conditions as in example 1 were used except that 1d was used instead of 1a in example 1, and the results of the experiment are shown in Table 1.
Isobornyl methacrylate 1d (0.1mmol, 1.0equiv.,22.2 mg), diphenylethoxyphosphine 2a (0.15mmol, 1.5equiv.,34.5 mg), ir [ dF (CF) dF 3 )ppy] 2 (dtbbpy)]PF 6 (1 mol%,0.001mmol, 1.1mg) and DCM (3 mL, 0.03M) were added sequentially to a 4mL clear glass vial equipped with magnetons. After bubbling with nitrogen for 5 minutes to remove oxygen, the vial was sealed and placed under blue light for irradiation. The reaction mixture was monitored by TLC until the starting isobornyl methacrylate 1d was consumed. After the reaction is finished, concentrating the reaction solution by using a rotary evaporator, and separating by silica gel column chromatography to obtain a target product 3d.
Spectrogram analysis data 3d
1 H NMR(400MHz，CDCl 3 )δ7.77(dd，J＝11.4，7.7Hz，4H)，7.50(dt，J＝15.7，7.5Hz，6H)，4.52(ddd，J＝17.5，9.3，5.4Hz，1H)，2.93(tq，J＝12.6，7.0Hz，2H)，2.31(ddd，J＝18.6，9.5，5.1Hz，1H)，1.73-1.65(m，3H)，1.64-1.50(m，2H)，1.32-1.26(m，4H)，1.10(d，J＝13.6Hz，1H)，0.93(d，J＝4.8Hz，3H)，0.84-0.76(m，6H). 13 C NMR(101MHz，CDCl 3 )δ177.4-171.7(m，1C)，133.9(d，J＝3.0Hz)，132.9(d，J＝3.3Hz)，132.6(d，J＝6.2Hz)，131.9(t，J＝2.9Hz)，131.6(d，J＝6.6Hz)，131.0(d，J＝3.7Hz)，130.9(d，J＝3.6Hz)，130.6(d，J＝9.2Hz)，128.8(d，J＝2.8Hz)，128.6(d，J＝2.8Hz)，81.6(d，J＝19.8Hz)，48.7，48.6，46.9，44.9，38.8，38.6，34.1(d，J＝2.5Hz)，34.0(d，J＝2.5Hz)，33.7(d，J＝4.4Hz)，33.0(d，J＝6.4Hz)，32.3(d，J＝6.6Hz)，27.0(d，J＝1.9Hz)，20.0(d，J＝13.4Hz)，19.2(d，J＝5.7Hz)，18.9(d，J＝5.3Hz)，11.4(d，J＝3.0Hz). 31 P NMR(162MHz，CDCl 3 )δ31.1.HRMS(ESI，m/z)calcd for C 26 H 34 O 3 P[M+H] + ：425.2240，found：425.2235.
TABLE 1
Claims (3)
1. A method for synthesizing phosphine oxide by reaction of visible light-induced electron-deficient unsaturated hydrocarbon compound and diarylethoxyphosphine, wherein the phosphine oxide has a structure shown in formula I:
R 1 selected from various substituents; r 2 Selected from phenyl, p-methylphenyl, o-methylphenyl, m-methylphenyl, etc.; r 3 Selected from phenyl, p-methylphenyl, o-methylphenyl, m-methylphenyl, etc.; r 4 Selected from methyl, ethyl, etc.; characterized in that the electron-deficient unsaturated hydrocarbon compound is a diarylethoxy groupDissolving phosphine and a photocatalyst in an organic solvent, reacting for 12-24h at room temperature under the irradiation of visible light blue light, concentrating the reaction solution by using a rotary evaporator after the reaction is finished, and separating by silica gel column chromatography to obtain a target product. The chemical process is shown in a reaction formula II:
2. the method according to claim 1, wherein the molar ratio of the electron-deficient unsaturated hydrocarbon compound, the diarylethoxyphosphine, and the photocatalyst is 1.0: 1.5: 0.01.
3. The method of claim 1, wherein: the solvent is dichloromethane, the reaction temperature is room temperature, the visible light is blue light, and the reaction time is 24 hours.
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