Difluoromethylthiolation reagent, preparation method and application thereof
A technology of difluoromethylthio group and reagent, applied in organic chemistry, silver-organic compounds and other directions, can solve the problems of limited applicable substrates, complicated preparation steps, low conversion rate, etc.
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Embodiment 1
[0071] Embodiment 1: the synthesis of difluoromethylthio silver complex
[0072]
[0073] where SIPrAgCF 2 The synthesis of H can refer to (Yang Gu, Xuebing Leng, QilongShen.Nat.Commun.2014,5,5405, doi:10.1038 / ncomms6405).
[0074] In the glove box, the difluoromethylation reagent SIPrAgCF 2 H (2.8g) was dissolved in 100mL THF, adding S 8 (960 mg), stirred at room temperature (10°C to 35°C) for 50 minutes. After the reaction, diatomaceous earth was filtered, half of the THF was pumped out with an oil pump, and n-pentane was added to precipitate a white solid difluoromethylthiolation reagent 1 (2.38 g, yield 82%).
[0075] Difluoromethylthio silver complex SIPrAgSCF 2 H: 1 H NMR (400MHz, d 8 -THF)δ7.56(dd, J=8.3,7.1Hz,2H),7.50–7.42(m,4H),6.74(t,J=65.2Hz,1H),4.31(s,4H),3.36(hept ,J=6.9Hz,4H),1.52(t,J=6.6Hz,24H). 19 F NMR (376MHz, d 8 -THF)δ-59.40(d, J=65.2Hz, 2F). 13 C NMR (101MHz, CDCl 3 )δ210.49-207.67 (m), 146.65, 134.47, 129.92, 124.60, 124.20 (t, J = 269.4Hz),...
Embodiment 2
[0076] Embodiment 2 Preparation of compound a1 containing difluoromethylthio
[0077]
[0078] In the glove box, tetraacetonitrile copper hexafluorophosphate (Cu(MeCN) 4 PF 6 ) (185mg, 0.5mmol, 1.0equiv) and bipyridine (bpy) (78mg, 0.5mmol, 1.0equiv) were added to the sealed tube, followed by the addition of SIPrAgSCF 2 H (290 mg, 0.5 mmol, 1.0 equiv) and (4-nitro)-phenyldiazonium salt (142 mg, 0.6 mmol, 1.2 equiv), 2 mL of MeCN. Stir at 50°C for 24h. After the reaction was completed, the reaction was rotary evaporated under reduced pressure, and the residue was subjected to flash silica gel column chromatography to obtain 95 mg of light yellow liquid with a yield of 93%. The purity is greater than 95% identified by hydrogen spectrum.
[0079] 4-Difluoromethylthio-nitrobenzene ((difluoromethyl)(4-nitrophenyl)sulfane): 1 H NMR (400MHz, CDCl 3 )δ8.23(d, J=8.6Hz, 2H), 7.72(d, J=8.7Hz, 2H), 6.94(t, J=55.8Hz, 1H). 19 F NMR (376MHz, CDCl 3 )δ-91.28(d, J=55.8Hz, 2F). 13 C...
Embodiment 3
[0080] Embodiment 3 Preparation of compound a2 containing difluoromethylthio
[0081]
[0082] In the glove box, the Cu(MeCN) 4 PF 6 (185mg, 0.5mmol, 1.0equiv) and bpy (78mg, 0.5mmol, 1.0equiv) were added to the sealed tube, followed by the addition of SIPrAgSCF 2 H (290 mg, 0.5 mmol, 1.0 equiv) and (2-cyano)-phenyldiazonium salt (130 mg, 0.6 mmol, 1.2 equiv), 2 mL of MeCN. Stir at 50°C for 24h. After the reaction was completed, the reaction was rotary evaporated under reduced pressure, and the residue was subjected to flash silica gel column chromatography to obtain 76 mg of light yellow liquid with a yield of 82%. The purity is greater than 95% identified by hydrogen spectrum.
[0083] 2-(Difluoromethylthio)benzonitrile 2-((difluoromethyl)thio)benzonitrile: 1 H NMR (400MHz, CDCl 3 )δ7.82-7.75 (m, 2H), 7.64 (td, J = 7.7, 1.5Hz, 1H), 7.56 (td, J = 7.6, 1.1Hz, 1H), 6.93 (t, J = 56.1Hz, 1H ). 19 F NMR (376MHz, CDCl 3 )δ-91.39 (d, J=56.1Hz, 2F). 13 C NMR (101MHz, CDC...
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