2,2-二苯基环丙烷-1-羧酸乙酯

反应条件: temp:18.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: The crude cyclopropane derivative, 2,2-diphenylcyclopropanyl carboxylate ethyl ester (generated through the reported one step procedure as a crude product in 107% yield) (21.3 g, 80 mmol) was dissolved in 80.0 mL AcOH at room temperature (18° C.). Into the solution was carefully added 40.0 mL concentrated H2SO4, followed by adding NaNO2 (6.1 g, 88 mmol, 1.1 eq) in several portions so that the reaction temperature did not excess 40° C. After addition, the reactants were stirred at room temperature (about 18° C.) for half an hour. And the reactants were poured into an iced water and extracted with diethyl ether (2×200 mL), the ethereal solutions were combined and washed with sat. NaHCO3 (2×100 mL), then water (100 mL) and brine (50 mL) in sequence. The washed ethereal solution was then dried over Na2SO4. After removing the desiccant, the ethereal solution was concentrated to furnish a thick oily crude product. The 1H NMR of the crude product showed that the reaction was clean and a virtual 100% yield. The thick oily crude product was stirred with 10 mL petrol to give a pale yellow solid 21.7 g, 92% yield (98% over yield in two steps based on diphenyl ketone hydrazine). did not excess 40° C After addition extracted with diethyl ether (2×200 mL) washed with sat. NaHCO3 (2×100 mL) The washed ethereal solution was then dried over Na2SO4 After removing the desiccant the ethereal solution was concentrated to furnish a thick oily crude product

反应条件: temp:18.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: The crude cyclopropane derivative, 2,2-diphenylcyclopropanyl carboxylate ethyl ester (generated through the reported one step procedure as a crude product in 107% yield) (1.14 g, 4.3 mmol) was dissolved in 4.0 mL AcOH at room temperature (18° C.). Into the solution was carefully added 2.0 mL concentrated H2SO4, followed by adding NaNO2 (0.33 g, 4.7 mmol, 1.1 eq) in several portions so that the reaction temperature did not excess 40° C. After addition, the reactants were stirred at room temperature (about 18° C.) for half an hour. And the reactants were poured into an iced water and extracted with diethyl ether (2×20 mL), the ethereal solutions were combined and washed with sat. NaHCO3 (2×20 mL), then water (20 mL) and brine (20 mL) in sequence. The washed ethereal solution was then dried over Na2SO4. After removing the desiccant, the ethereal solution was concentrated to furnish a thick oily crude product. The 1H NMR of the crude product showed that the reaction was clean and a virtual 100% yield. The thick oily crude product was stirred with 10 mL petrol to give a pale yellow solid 1.15 g, 91% yield (97% over yield in two steps based on diphenyl ketone hydrazine). did not excess 40° C After addition extracted with diethyl ether (2×20 mL) washed with sat. NaHCO3 (2×20 mL) The washed ethereal solution was then dried over Na2SO4 After removing the desiccant the ethereal solution was concentrated to furnish a thick oily crude product

反应条件: temp:18.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: The crude cyclopropane derivative, 2,2-diphenylcyclopropanyl carboxylate ethyl ester (generated through the reported one step procedure as a crude product in 107% yield) (1.14 g, 4.3 mmol) was dissolved in 4.0 mL AcOH at room temperature (18° C.). Into the solution was carefully added 2.0 mL concentrated H2SO4, followed by adding NaNO2 (0.33 g, 4.7 mmol, 1.1 eq) in several portions so that the reaction temperature did not excess 40° C. After addition, the reactants were stirred at room temperature (about 18° C.) for half an hour. And the reactants were poured into an iced water and extracted with diethyl ether (2×20 mL), the ethereal solutions were combined and washed with sat. NaHCO3 (2×20 mL), then water (20 mL) and brine (20 mL) in sequence. The washed ethereal solution was then dried over Na2SO4. After removing the desiccant, the ethereal solution was concentrated to furnish a thick oily crude product. The 1H NMR of the crude product showed that the reaction was clean and a virtual 100% yield. The thick oily crude product was stirred with 10 mL petrol to give a pale yellow solid 1.15 g, 91% yield (97% over yield in two steps based on diphenyl ketone hydrazine). did not excess 40° C After addition extracted with diethyl ether (2×20 mL) washed with sat. NaHCO3 (2×20 mL) The washed ethereal solution was then dried over Na2SO4 After removing the desiccant the ethereal solution was concentrated to furnish a thick oily crude product

反应条件: temp:18.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: The cyclopropane derivative, 2,2-diphenylcyclopropanyl carboxylate ethyl ester (1.0 g, 3.8 mmol) was dissolved in 4.0 mL AcOH at room temperature (18° C.). Into the solution was carefully added 2.0 mL concentrated H2SO4, followed by adding NaNO2 (0.29 g, 4.1 mmol, 1.1 eq) in several portions so that the reaction temperature did not excess 40° C. After addition, the reactants were stirred at room temperature (about 18° C.) for half an hour before the reactants were poured into iced water and extracted with diethyl ether (2×20 mL), the ethereal solutions were combined and washed with sat. NaHCO3 (2×20 mL), then water (20 mL) and brine (20 mL). The washed ethereal solution was then dried over Na2SO4. After removing the desiccant, the ethereal solution was concentrated to furnish a thick oily product. The 1H NMR of the crude product showed that the reaction was clean and the yield was virtually 100%. The thick oily crude product was stirred with 10 mL petrol to give a pale yellow solid 1.07 g, 97% yield. did not excess 40° C After addition extracted with diethyl ether (2×20 mL) washed with sat. NaHCO3 (2×20 mL) The washed ethereal solution was then dried over Na2SO4 After removing the desiccant the ethereal solution was concentrated to furnish a thick oily product

反应条件: temp:18.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: The cyclopropane derivative, 2,2-diphenylcyclopropanyl carboxylate ethyl ester (0.97 g, 3.7 mmol) was dissolved in 3.7 mL CF3CO2H. Into the solution was added NaNO2 (0.28 g, 4.0 mmol, 1.1 eq.) in several ports so that the reaction temperature did not excess 40° C. After addition, the reactants were stirred at room temperature (about 18° C.) for half an hour. And the reactants were poured into an iced water and extracted with diethyl ether (2×20 mL); the ethereal solutions were combined and subsequently washed with sat. NaHCO3 (2*20 mL), then water (20 mL) and brine (20 mL). The washed ethereal solution was then dried over anhydrous Na2SO4. After removing the desiccant, the ethereal solution was concentrated to obtain a light brown oil. The crude product 1H NMR of the crude product showed that the reaction was clean and a virtual 100% yield. The crude product was further purified over silica chromatography (Rf: 0.45, eluent: 20% ethyl acetate in petrol) to obtain 5,5-diphenylisoxazoline carboxylate ethyl ester 0.958 g (89% yield) as a white solid. 1H NMR (400 MHz, CDCl3): 7.41-7.26 (10H, m), 4.34 (2H, q, J=7.1 Hz), 3.86 (2H, s), 1.36 (3H, t, J=7.1 Hz). 13C NMR (400 MHz, CDCl3): 160.54, 151.09, 142.99, 128.54, 128.02, 125.95, 94.79, 62.15, 46.78, 14.12. did not excess 40° C After addition extracted with diethyl ether (2×20 mL) subsequently washed with sat. NaHCO3 (2*20 mL) The washed ethereal solution was then dried over anhydrous Na2SO4 After removing the desiccant the ethereal solution was concentrated to obtain a light brown oil The crude product was further purified over silica chromatography (Rf: 0.45, eluent: 20% ethyl acetate in petrol)

反应条件: temp:18.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: The cyclopropane derivative, 2,2-diphenylcyclopropanyl carboxylate ethyl ester (0.97 g, 3.7 mmol) was dissolved in 3.7 mL CF3CO2H. Into the solution was added NaNO2 (0.28 g, 4.0 mmol, 1.1 eq.) in several ports so that the reaction temperature did not excess 40° C. After addition, the reactants were stirred at room temperature (about 18° C.) for half an hour. And the reactants were poured into an iced water and extracted with diethyl ether (2×20 mL); the ethereal solutions were combined and subsequently washed with sat. NaHCO3 (2*20 mL), then water (20 mL) and brine (20 mL). The washed ethereal solution was then dried over anhydrous Na2SO4. After removing the desiccant, the ethereal solution was concentrated to obtain a light brown oil. The crude product 1H NMR of the crude product showed that the reaction was clean and a virtual 100% yield. The crude product was further purified over silica chromatography (Rf: 0.45, eluent: 20% ethyl acetate in petrol) to obtain 5,5-diphenylisoxazoline carboxylate ethyl ester 0.958 g (89% yield) as a white solid. 1H NMR (400 MHz, CDCl3): 7.41-7.26 (10H, m), 4.34 (2H, q, J=7.1 Hz), 3.86 (2H, s), 1.36 (3H, t, J=7.1 Hz). 13C NMR (400 MHz, CDCl3): 160.54, 151.09, 142.99, 128.54, 128.02, 125.95, 94.79, 62.15, 46.78, 14.12. did not excess 40° C After addition extracted with diethyl ether (2×20 mL) subsequently washed with sat. NaHCO3 (2*20 mL) The washed ethereal solution was then dried over anhydrous Na2SO4 After removing the desiccant the ethereal solution was concentrated to obtain a light brown oil The crude product was further purified over silica chromatography (Rf: 0.45, eluent: 20% ethyl acetate in petrol)

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: Diphenylketone hydrazone (8.9 g, 45.4 mmol) in DCM (19 mL) was mixed with KI (0.45 g) in water (0.6 mL) and benzyldimethyloctylammonium chloride (10 mg). To the mixture was added the aqueous solution composing of 25% NaOH (27 mL), water (18 mL), and sodium chlorite (12-14%, 28 mL) at 5° C. with vigorous stirring. Twenty minutes later after addition, the stirring was turned off to let the reaction mixture separate. The red DCM solution was separated and dried over anhydrous Na2SO4. After removing the desiccant, the solvent was removed under reduced pressure; the residue was re-dissolved in hexane, and the unreacted hydrazone and side product was insoluble in hexane and removed by filtration. The red hexane diphenyl diazomethane solution was added to ethyl acrylate (13.6 g, 136 mmol) at 50° C. within 30 mints. When the red colour fade off the solvent and excess of ethyl acrylate was removed under reduced pressure to give crude product with 94% purity in 56-94% yield. Twenty minutes later after addition separate The red DCM solution was separated dried over anhydrous Na2SO4 After removing the desiccant the solvent was removed under reduced pressure the residue was re-dissolved in hexane removed by filtration When the red colour fade off the solvent and excess of ethyl acrylate was removed under reduced pressure to give crude product with 94% purity in 56-94% yield

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: Diphenylketone hydrazone (3.92 g, 20 mmol) was mixed with yellow mercury oxide (4.33 g, 20 mmol) in 40 mL petroleum. The mixture was stirred at the temperature less than 20° C. for 16 hours. The deep red solution of diphenyl diazomethane in petroleum was added into ethyl acrylate (6.0 g, 60 mmol) at 50° C. in ten minutes. When the red colour fade off the solvent and excess of ethyl acrylate were removed under reduced pressure and the crude product obtained was further purified over silica chromatography to furnish 2,2-diphenylcyclopropanyl carboxylate ethyl ester 5.11 g (96% yield) as a pale yellow oil. 1H NMR (400 MHz, CDCl3): 7.36-7.17 (10H, m), 4.00-3.83 (2H, m), 2.54 (1H, dd, J=8.3, 6.0 Hz), 2.17 (1H, dd, J=1H, dd, 6.0, 4.8 Hz), 1.59 (1H, dd, J=8.3, 4.8 Hz), 1.01 (3H, t, J=7.1 Hz). When the red colour fade off the solvent and excess of ethyl acrylate were removed under reduced pressure the crude product obtained was further purified over silica chromatography

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: Diphenylketone hydrazone (3.92 g, 20 mmol) was mixed with yellow mercury oxide (4.33 g, 20 mmol) in 40 mL petroleum. The mixture was stirred at the temperature less than 20° C. for 16 hours. The deep red solution of diphenyl diazomethane in petroleum was added into ethyl acrylate (6.0 g, 60 mmol) at 50° C. in ten minutes. When the red colour fade off the solvent and excess of ethyl acrylate were removed under reduced pressure and the crude product obtained was further purified over silica chromatography to furnish 2,2-diphenylcyclopropanyl carboxylate ethyl ester 5.11 g (96% yield) as a pale yellow oil. 1H NMR (400 MHz, CDCl3): 7.36-7.17 (10H, m), 4.00-3.83 (2H, m), 2.54 (1H, dd, J=8.3, 6.0 Hz), 2.17 (1H, dd, J=1H, dd, 6.0, 4.8 Hz), 1.59 (1H, dd, J=8.3, 4.8 Hz), 1.01 (3H, t, J=7.1 Hz). When the red colour fade off the solvent and excess of ethyl acrylate were removed under reduced pressure the crude product obtained was further purified over silica chromatography

反应条件: temp:18.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: The crude cyclopropane derivative, 2,2-diphenylcyclopropanyl carboxylate ethyl ester (generated through the reported one step procedure as a crude product in 107% yield) (21.3 g, 80 mmol) was dissolved in 80.0 mL AcOH at room temperature (18° C.). Into the solution was carefully added 40.0 mL concentrated H2SO4, followed by adding NaNO2 (6.1 g, 88 mmol, 1.1 eq) in several portions so that the reaction temperature did not excess 40° C. After addition, the reactants were stirred at room temperature (about 18° C.) for half an hour. And the reactants were poured into an iced water and extracted with diethyl ether (2×200 mL), the ethereal solutions were combined and washed with sat. NaHCO3 (2×100 mL), then water (100 mL) and brine (50 mL) in sequence. The washed ethereal solution was then dried over Na2SO4. After removing the desiccant, the ethereal solution was concentrated to furnish a thick oily crude product. The 1H NMR of the crude product showed that the reaction was clean and a virtual 100% yield. The thick oily crude product was stirred with 10 mL petrol to give a pale yellow solid 21.7 g, 92% yield (98% over yield in two steps based on diphenyl ketone hydrazine). did not excess 40° C After addition extracted with diethyl ether (2×200 mL) washed with sat. NaHCO3 (2×100 mL) The washed ethereal solution was then dried over Na2SO4 After removing the desiccant the ethereal solution was concentrated to furnish a thick oily crude product

反应条件: temp:18.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: The crude cyclopropane derivative, 2,2-diphenylcyclopropanyl carboxylate ethyl ester (generated through the reported one step procedure as a crude product in 107% yield) (1.14 g, 4.3 mmol) was dissolved in 4.0 mL AcOH at room temperature (18° C.). Into the solution was carefully added 2.0 mL concentrated H2SO4, followed by adding NaNO2 (0.33 g, 4.7 mmol, 1.1 eq) in several portions so that the reaction temperature did not excess 40° C. After addition, the reactants were stirred at room temperature (about 18° C.) for half an hour. And the reactants were poured into an iced water and extracted with diethyl ether (2×20 mL), the ethereal solutions were combined and washed with sat. NaHCO3 (2×20 mL), then water (20 mL) and brine (20 mL) in sequence. The washed ethereal solution was then dried over Na2SO4. After removing the desiccant, the ethereal solution was concentrated to furnish a thick oily crude product. The 1H NMR of the crude product showed that the reaction was clean and a virtual 100% yield. The thick oily crude product was stirred with 10 mL petrol to give a pale yellow solid 1.15 g, 91% yield (97% over yield in two steps based on diphenyl ketone hydrazine). did not excess 40° C After addition extracted with diethyl ether (2×20 mL) washed with sat. NaHCO3 (2×20 mL) The washed ethereal solution was then dried over Na2SO4 After removing the desiccant the ethereal solution was concentrated to furnish a thick oily crude product

反应条件: temp:18.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: The cyclopropane derivative, 2,2-diphenylcyclopropanyl carboxylate ethyl ester (1.0 g, 3.8 mmol) was dissolved in 4.0 mL AcOH at room temperature (18° C.). Into the solution was carefully added 2.0 mL concentrated H2SO4, followed by adding NaNO2 (0.29 g, 4.1 mmol, 1.1 eq) in several portions so that the reaction temperature did not excess 40° C. After addition, the reactants were stirred at room temperature (about 18° C.) for half an hour before the reactants were poured into iced water and extracted with diethyl ether (2×20 mL), the ethereal solutions were combined and washed with sat. NaHCO3 (2×20 mL), then water (20 mL) and brine (20 mL). The washed ethereal solution was then dried over Na2SO4. After removing the desiccant, the ethereal solution was concentrated to furnish a thick oily product. The 1H NMR of the crude product showed that the reaction was clean and the yield was virtually 100%. The thick oily crude product was stirred with 10 mL petrol to give a pale yellow solid 1.07 g, 97% yield. did not excess 40° C After addition extracted with diethyl ether (2×20 mL) washed with sat. NaHCO3 (2×20 mL) The washed ethereal solution was then dried over Na2SO4 After removing the desiccant the ethereal solution was concentrated to furnish a thick oily product