cyclopropylmethyl methanesulfonate

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:40.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 1,2,4-Triazole-3-thiol (20.2 g; 0.20 mol) and sodium methoxide (11.8 g; 0.22 mol) were dissolved in methanol (250 ml) and cyclopropylmethyl methanesulfonate (32.3 g; 0.215 mol) added. The mixture was refluxed for 25 min under dry nitrogen, allowed to cool to 40° C. and filtered. The solid was washed with ethyl acetate and the organic solutions combined and evaporated. The residue was dissolved in water (250 ml) and the solution extracted with ethyl acetate (2×250 ml). The extracts were combined, washed with saturated brine (200 ml), dried (Na2SO4), filtered and evaporated, giving cyclopropylmethyl 1,2,4-triazol-3-yl sulfide (19.7 g; 64%) as a pale yellow pasty solid. NMR - d(CDCl3 +CD3SOCD3 ; 90 MHz) 0.1-0.7 (4H, m), 0.9-1.4 (1H, m), 3.1 (2H, d, J=7 Hz), 8.1 (1H, s). The mixture was refluxed for 25 min under dry nitrogen filtered The solid was washed with ethyl acetate evaporated The residue was dissolved in water (250 ml) the solution extracted with ethyl acetate (2×250 ml) washed with saturated brine (200 ml) dried (Na2SO4) filtered evaporated

反応条件: temp:40.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 1,2,4-Triazole-3-thiol (20.2 g; 0.20 mol) and sodium methoxide (11.8 g; 0.22 mol) were dissolved in methanol (250 ml) and cyclopropylmethyl methanesulfonate (32.3 g; 0.215 mol) added. The mixture was refluxed for 25 min under dry nitrogen, allowed to cool to 40° C. and filtered. The solid was washed with ethyl acetate and the organic solutions combined and evaporated. The residue was dissolved in water (250 ml) and the solution extracted with ethyl acetate (2×250 ml). The extracts were combined, washed with saturated brine (200 ml), dried (Na2SO4), filtered and evaporated, giving cyclopropylmethyl 1,2,4-triazol-3-yl sulfide (19.7 g; 64%) as a pale yellow pasty solid. NMR - d(CDCl3 +CD3SOCD3 ; 90 MHz) 0.1-0.7 (4H, m), 0.9-1.4 (1H, m), 3.1 (2H, d, J=7 Hz), 8.1 (1H, s). The mixture was refluxed for 25 min under dry nitrogen filtered The solid was washed with ethyl acetate evaporated The residue was dissolved in water (250 ml) the solution extracted with ethyl acetate (2×250 ml) washed with saturated brine (200 ml) dried (Na2SO4) filtered evaporated

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Cyclopropylcarbinol (27.4 g; 0.373 mol) and methanesulfonyl chloride (47.56 g; 0.407 mol) in dry ether (250 ml) was cooled to -20° C. under dry nitrogen. Triethylamine (59 ml; 0.42 mol) is added dropwise over 45 min with external cooling so that the reaction temperature remained below -15° C. The reaction mixture was allowed to warm to room temperature over 2 h and then filtered. The solid material is washed with ether. The solutions were combined and evaporated, to afford crude cyclopropylmethyl methanesulfonate (58.36 g) as a pale yellow liquid, which was used without further purification. NMR - d(CDCl3 ; 60 MHz) 0.3-1.5 (5H, m), 3.0 (3H, s) and 4.0 (2H, d, J=7 Hz). with external cooling so that the reaction temperature remained below -15° C filtered The solid material is washed with ether evaporated

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A mixture comprising 3.8 g of ethyl 3-methyl-1H-pyrazole-5-carboxylate, 3.8 g of cyclopropylmethyl methanesulfonate and 4.6 g of tri-n-butylamine was allowed to react at 110 ° C. for three hours without using any solvent. Then the reaction mixture was allowed to cool and diethyl ether was added thereto. The obtained mixture was successively washed with 1 N hydrochloric acid, an aqueous solution of sodium hydrogencarbonate and a saturated aqueous solution of common salt and then dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure and the obtained residue was purified by column chromatography (eluent: hexane:ethyl acetate=14 : 1). Thus 0.62 g of the aimed ethyl 1-cyclobutyl-3-methyl-1H-pyrazole-5-carboxylate (compound No. 1001) (yield: 12.1 %) and 2.45 g of ethyl 1-cyclopropylmethyl-3-methyl-1H-pyrazole-5-carboxylate (yield: 54.3 %) were obtained. to react at 110 ° C. for three hours to cool The obtained mixture was successively washed with 1 N hydrochloric acid an aqueous solution of sodium hydrogencarbonate and a saturated aqueous solution of common salt and then dried over anhydrous sodium sulfate The solvent was distilled off under reduced pressure the obtained residue was purified by column chromatography (eluent: hexane:ethyl acetate=14 : 1)

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Prepared in analogy to example 3a) starting with 3-amino-1,2,4-triazole and methanesulfonic acid cyclopropylmethyl ester (Journal of the American Chemical Society 128, 3118 (2006)). The title compound was obtained as a brownish solid (Yield=25%). MS ISP (m/e): 138.1 (100) [M+]. Prepared in analogy to example 3a)

反応条件: temp:40.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 1,2,4-Triazole-3-thiol (20.2 g; 0.20 mol) and sodium methoxide (11.8 g; 0.22 mol) were dissolved in methanol (250 ml) and cyclopropylmethyl methanesulfonate (32.3 g; 0.215 mol) added. The mixture was refluxed for 25 min under dry nitrogen, allowed to cool to 40° C. and filtered. The solid was washed with ethyl acetate and the organic solutions combined and evaporated. The residue was dissolved in water (250 ml) and the solution extracted with ethyl acetate (2×250 ml). The extracts were combined, washed with saturated brine (200 ml), dried (Na2SO4), filtered and evaporated, giving cyclopropylmethyl 1,2,4-triazol-3-yl sulfide (19.7 g; 64%) as a pale yellow pasty solid. NMR - d(CDCl3 +CD3SOCD3 ; 90 MHz) 0.1-0.7 (4H, m), 0.9-1.4 (1H, m), 3.1 (2H, d, J=7 Hz), 8.1 (1H, s). The mixture was refluxed for 25 min under dry nitrogen filtered The solid was washed with ethyl acetate evaporated The residue was dissolved in water (250 ml) the solution extracted with ethyl acetate (2×250 ml) washed with saturated brine (200 ml) dried (Na2SO4) filtered evaporated