3-(叔丁氧基)-3-氧代丙酸钾

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

实验步骤: The 3-(3-nitro-phenyl)-3-oxo-propionic acid tert.-butyl ester was prepared from 3-nitrobenzoyl chloride (2.71 g, 14.6 mmol) and tert.-butyl malonate potassium salt (6.0 g, 30.0 mmol) with Et3N (4.5 mL, 32.2 mmol) and MgCl2 (3.48 g, 36.52 mmol) in CH3CN according to general procedure H (method a). The crude material (3.88 g) was transformed into the title compound by stirring in TFA/acetone with TFAA according to general procedure J (method b). Obtained as a yellow solid (2.76 g).

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

实验步骤: Prepared from 2-imidazol-1-yl-isonicotinoyl chloride hydrochloride [prepared by reaction of tert.-butyl 2-chloroisonicotinoate with imidazole and NaH in DMF at 80° C., treatment with formic acid at 50° C. and reaction with thionylchloride in toluene at 100° C.] and tert.-butyl malonate potassium salt with Et3N and MgCl2 in CH3CN according to general procedure H (method a). Obtained as a brown solid (10.8 g).

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

实验步骤: The 3-(3-nitro-phenyl)-3-oxo-propionic acid tert.-butyl ester was prepared from 3-nitrobenzoyl chloride (2.71 g, 14.6 mmol) and tert.-butyl malonate potassium salt (6.0 g, 30.0 mmol) with Et3N (4.5 mL, 32.2 mmol) and MgCl2 (3.48 g, 36.52 mmol) in CH3CN according to general procedure H (method a). The crude material (3.88 g) was transformed into the title compound by stirring in TFA/acetone with TFAA according to general procedure J (method b). Obtained as a yellow solid (2.76 g).

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

实验步骤: The 3-(3-nitro-phenyl)-3-oxo-propionic acid tert.-butyl ester was prepared from 3-nitrobenzoyl chloride (2.71 g, 14.6 mmol) and tert.-butyl malonate potassium salt (6.0 g, 30.0 mmol) with Et3N (4.5 mL, 32.2 mmol) and MgCl2 (3.48 g, 36.52 mmol) in CH3CN according to general procedure H (method a). The crude material (3.88 g) was transformed into the title compound by stirring in TFA/acetone with TFAA according to general procedure J (method b). Obtained as a yellow solid (2.76 g).

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

实验步骤: Prepared from 2-imidazol-1-yl-isonicotinoyl chloride hydrochloride [prepared by reaction of tert.-butyl 2-chloroisonicotinoate with imidazole and NaH in DMF at 80° C., treatment with formic acid at 50° C. and reaction with thionylchloride in toluene at 100° C.] and tert.-butyl malonate potassium salt with Et3N and MgCl2 in CH3CN according to general procedure H (method a). Obtained as a brown solid (10.8 g).

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

实验步骤: The 3-(3-nitro-phenyl)-3-oxo-propionic acid tert.-butyl ester was prepared from 3-nitrobenzoyl chloride (2.71 g, 14.6 mmol) and tert.-butyl malonate potassium salt (6.0 g, 30.0 mmol) with Et3N (4.5 mL, 32.2 mmol) and MgCl2 (3.48 g, 36.52 mmol) in CH3CN according to general procedure H (method a). The crude material (3.88 g) was transformed into the title compound by stirring in TFA/acetone with TFAA according to general procedure J (method b). Obtained as a yellow solid (2.76 g).

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

实验步骤: Prepared from 2-imidazol-1-yl-isonicotinoyl chloride hydrochloride [prepared by reaction of tert.-butyl 2-chloroisonicotinoate with imidazole and NaH in DMF at 80° C., treatment with formic acid at 50° C. and reaction with thionylchloride in toluene at 100° C.] and tert.-butyl malonate potassium salt with Et3N and MgCl2 in CH3CN according to general procedure H (method a). Obtained as a brown solid (10.8 g).

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

实验步骤: 14.8 g (0.1 mol) of phthalic anhydride and 9.9 g (0.05 mol) of potassium tert-butyl malonate are added to 200 ml of toluene, and the reaction mixture is heated under reflux for 6 hours. After terminating the reaction, 100 ml of water is added, and an organic layer is separated out. The organic layer is washed with 100 ml of 5%-aqueous ammonium bicarbonate solution, and toluene is distilled off under a reduced pressure. The residue thus obtained is purified by column chromatography, to give 6.4 g (0.026 mol) of tert-butyl (Z)-3-phthalidylideneacetate. The yield is 52.0%. the reaction mixture is heated under reflux for 6 hours After terminating the reaction, 100 ml of water is added an organic layer is separated out The organic layer is washed with 100 ml of 5%-aqueous ammonium bicarbonate solution, and toluene is distilled off under a reduced pressure The residue thus obtained is purified by column chromatography

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

实验步骤: The 3-(3-nitro-phenyl)-3-oxo-propionic acid tert.-butyl ester was prepared from 3-nitrobenzoyl chloride (2.71 g, 14.6 mmol) and tert.-butyl malonate potassium salt (6.0 g, 30.0 mmol) with Et3N (4.5 mL, 32.2 mmol) and MgCl2 (3.48 g, 36.52 mmol) in CH3CN according to general procedure H (method a). The crude material (3.88 g) was transformed into the title compound by stirring in TFA/acetone with TFAA according to general procedure J (method b). Obtained as a yellow solid (2.76 g).

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

实验步骤: Prepared from 2-imidazol-1-yl-isonicotinoyl chloride hydrochloride [prepared by reaction of tert.-butyl 2-chloroisonicotinoate with imidazole and NaH in DMF at 80° C., treatment with formic acid at 50° C. and reaction with thionylchloride in toluene at 100° C.] and tert.-butyl malonate potassium salt with Et3N and MgCl2 in CH3CN according to general procedure H (method a). Obtained as a brown solid (10.8 g).

反应条件: temp:10.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: Into a one-liter four-necked flask were poured 43.9 g (0.125 mole) of (3R)-5-benzyloxycarbonylamino-3-(2-tetrahydropyranyloxy)pentanoic acid (2-c) obtained in the above process B and 290 ml of acetonitrile. Furthermore, 19.6 g (0.121 mole) of N,N'-carbonyldiimidazole was added to the contents over a period of 15 minutes in a nitrogen stream with stirring. Gas evolution was observed. Approximately 30 minutes later the gas evolution was nearly complete. Then, the contents were cooled to approximately 10° C., and 35.2 g (0.178 mole) of potassium malonate tert-butyl ester and next 11.4 g (0.119 mole) of magnesium chloride were separately added thereto. After stirring for 1 hour at the same temperature, the contents were heated to 50° C. and allowed to react for 2 hours. After removing acetonitrile by distillation, 150 ml of ethyl acetate and 200 ml of a 5 wt % aqueous hydrochloric acid solution were added to thereby adjust the pH to 4.5. After separating the aqueous layer, the organic layer was neutralized by adding 25 ml of a 5 wt % aqueous sodium bicarbonate solution. The organic layer was washed with saturated sodium chloride solution and then dried with magnesium sulfate. The solvent was then removed by distillation, to thereby obtain 72.3 g of a crude oily product. The crude product was purified with a silica gel column using hexane/ethyl acetate=1/1 as an eluent to obtain the intended oily product (1). The yield was 57.8 g (79%). Approximately 30 minutes After stirring for 1 hour at the same temperature the contents were heated to 50° C. to react for 2 hours After removing acetonitrile by distillation, 150 ml of ethyl acetate and 200 ml of a 5 wt % aqueous hydrochloric acid solution were added After separating the aqueous layer by adding 25 ml of a 5 wt % aqueous sodium bicarbonate solution The organic layer was washed with saturated sodium chloride solution dried with magnesium sulfate The solvent was then removed by distillation to thereby obtain 72.3 g of a crude oily product The crude product was purified with a silica gel column

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

实验步骤: The title compound was prepared from 3-[1,2,3]triazol-1-yl-benzoic acid [prepared by refluxing of methyl 3-azidobenzoate [CAS-No. 93066-93-4] in trimethylsilylacetylene, followed by saponification with aqueous NaOH in refluxing EtOH] (10.0 g, 52.86 mmol) by activation with ethyl chloroformate/Et3N and reaction with mono tert.-butyl malonate potassium salt with Et3N and MgCl2 in CH3CN according to general procedure K (method a). Obtained as an orange oil (11.55 g).