A kind of diaryl methyl phosphorous oxygen compound and its synthetic method
A technology of diarylmethylphosphorus and arylmethylphosphorus, which is applied in the field of diarylmethylphosphorus oxide and its synthesis, and can solve problems such as complex operation, non-environmental friendliness, and limited range of phosphorus oxide , to achieve the effects of environmental friendliness, good substrate universality, and simple reaction operation
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Embodiment 1
[0064]
[0065] The reactor was placed in air, and 0.2mmol (56.8mg) p-methylene quinone compound (1a), 0.3mmol (60.6mg) diphenylphosphine oxy compound (2a), 0.04mmol (6.1mg) DBU were added successively, 1 mL of DCM, stirred at 40°C for 4h. After the reaction was completed, the solvent was adjusted with a rotary evaporator, and the crude product was subjected to column chromatography, and the eluent was a mixed solvent of petroleum ether and ethyl acetate to obtain 49.6 mg of diarylmethylphosphoryl oxide 3aa, with an isolated yield of 51%. .
[0066] see Figure 1 ~ Figure 3 , the characterization data of compound 3aa are as follows:
[0067] 1 H NMR (400MHz, CDCl 3 )δ7.79-7.74(m,2H),7.49-7.36(m,6H),7.29-7.24(m,3H),6.93(d,J=2.0Hz,2H),6.51(t,J=2.6Hz ,1H),6.25(dd,J=3.6,2.0Hz,1H),5.11(s,1H),4.87(d,J=12.8Hz,1H),1.29(s,18H). 13 C NMR (100MHz, CDCl 3 )δ153.1(d, J=2.9Hz), 150.1(d, J=1.4Hz), 141.6(d, J=1.9Hz), 135.5(d, J=2.3Hz), 132.4(d, J=33.7 Hz), 131.7(d, J=2.7Hz), 131.6(...
Embodiment 2
[0069]
[0070] The reactor was placed in the air, and 0.2mmol (64.4mg) p-methylene quinone compound (1b), 0.3mmol (60.6mg) diphenylphosphine oxy compound (2a), 0.04mmol (6.1mg) DBU, 1 mL of DCM, stirred at 40°C for 4h. After the reaction was completed, the solvent was adjusted with a rotary evaporator, and the crude product was subjected to column chromatography, and the eluent was a mixed solvent of petroleum ether and ethyl acetate to obtain 94.4 mg of diarylmethylphosphoryl oxide 3ba, and the separation yield was 90%. .
[0071] see Figure 4 ~ Figure 6 , the characterization data of compound 3ba are as follows:
[0072] 1 H NMR (400MHz, CDCl 3 )δ7.75-7.70(m,2H),7.46-7.33(m,7H),7.27-7.23(m,3H),7.07(d,J=2.0Hz,2H),6.97(d,J=7.6Hz ,1H),5.01(s,1H),4.58(d,J=10.0Hz,1H),2.15(s,3H),2.14(s,3H),1.29(s,18H). 13 C NMR (100MHz, CDCl 3 )δ152.6(d, J=2.5Hz), 136.5, 135.3(d, J=1.6Hz), 135.0(d, J=4.1Hz), 134.9(d, J=1.3Hz), 133.5(d, J =67.2Hz), 132.6(d, J=64.4Hz), 131.6(d, J=8.4Hz)...
Embodiment 3
[0074]
[0075] The reactor was placed in air, and 0.2mmol (42.0mg) p-methylene quinone compound (1c), 0.3mmol (60.6mg) diphenylphosphine oxy compound (2a), 0.04mmol (6.1mg) DBU, 1 mL of DCM, stirred at 40°C for 4h. After the reaction was completed, the solvent was adjusted with a rotary evaporator, and the crude product was subjected to column chromatography, and the eluent was a mixed solvent of petroleum ether and ethyl acetate to obtain 76.6 mg of diarylmethylphosphoryl oxide 3ca, and the separation yield was 93%. .
[0076] see Figure 7 ~ Figure 9 , the characterization data of compound 3ca are as follows:
[0077] 1 H NMR (400MHz, CDCl 3 )δ7.63-7.55(m,4H),7.42(d,J=7.2Hz,2H),7.34(t,J=6.4Hz,2H),7.29-7.24(m,4H),7.13-7.08(m ,3H),7.04(s,2H),5.98(s,1H),4.64(d,J=9.2Hz,1H),2.09(s,6H). 13 C NMR (100MHz, CDCl 3 )δ151.8(d, J=1.8Hz), 137.6(d, J=4.2Hz), 133.1, 132.1(d, J=1.5Hz), 131.5, 131.4(d, J=2.8Hz), 131.3(d ,J=2.6Hz),131.2129.9(d,J=7.3Hz),129.8(d,J=7.2Hz),128.4,128.2...
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