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(+/-)-trans-3-(tert-butyl-dimethylsilanyloxy)-cyclopentylamine[ No CAS ]
C17H29N3O3SSi[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
With triethylamine; In 1,4-dioxane; for 1h;Heating / reflux;
A solution of <strong>[74840-34-9]4-chloro-2-methylthio-5-pyrimidinecarboxylate</strong> (900 mg, 3.87 mmol) (Aldrich) and triethylamine (1.1 ML, 870 mg, 7.74 mmol) (Aldrich) in dioxane (50 ML) was treated with (+-)-trans-3-(tert-butyl-dimethyl-silanyloxy)-cyclopentylamine (840 mg, 3.87 mmol) (from Example 9c supra).The mixture was stirred at reflux for 1 hour, then cooled and partitioned between brine and ethyl acetate.The organic layer was collected, dried over sodium sulfate, filtered and concentrated to a residue that was purified by silica gel column chromatography using a 0-20percent ethyl acetate in hexanes gradient.The product isolated from this purification was then dissolved in anhydrous tetrahydrofuran (80 ML) and the resulting solution was cooled to 0° C. Followed addition in-portions of lithium aluminum hydride (440 mg, 11.61 mmol) (Aldrich) and the resulting mixture was allowed to warm to room temperature.After overnight stirring the reaction mixture was poured slowly into a vigorously stirred mixture of ethyl acetate and saturated aqueous potassium sodium tartrate solution.The organic layer was collected, dried over sodium sulfate, filtered and concentrated to an off white solid.This intermediate was then dissolved in dichloromethane (80 ML) and the resulting solution was treated with manganese dioxide (3.36 g, 38.70 mmol) (Aldrich).After overnight stirring the solids were filtered off, washed with tetrahydrofuran (approximately 30 ML) and the combined organic layer was concentrated to a residue that upon a silica gel column purification with 0-50percent diethyl ether in hexanes gradient gave (+-)-4-[trans-3-(tert-butyl-dimethyl-silanyloxy)-cyclopentylamino]-2-methylsulfanyl-pyrimidine-5-carbaldehyde as a viscous colorless oil. (Yield 888 mg, 62percent). HRMS m/z calcd for C17H29N3O2SSi [M+H]+: 368.1823. Found:368.1826.
A. 4-methoxy-2-methylsulfanyl-pyrimidine-5-carbonyl chloride A suspension of ethyl 4-chloro-2-methylthio-5-pyrimidinecarboxylate (3 g, 12.9 mmol) in 40 mL methanol and 20 mL 1N NaOH solution was heated at 50° C. for 12 hrs. The reaction mixture was poured onto ice water and acidified with conc. HCl. The white creamy mixture was extracted with EtOAc. The organic fractions were dried (Na2SO4) filtered and the filtrate was concentrated to give a white solid (2 g). The solid was dissolved in 50 mL of CH2Cl2, and cooled under N2 in an ice-water bath. To the reaction was slowly added oxalyl chloride (2 mL, 19 mmol) and a drop of DMF. The reaction mixture was stirred at rt for 5 h. The reaction mixture was concentrated to give the title compound as a brown solid. This material was used in the next step without further purification.
With oxalyl dichloride;N,N-dimethyl-formamide; In dichloromethane; at 20℃; for 5h;
A suspension of ethyl <strong>[74840-34-9]4-chloro-2-methylthio-5-pyrimidinecarboxylate</strong> (3 g, 12.9 mmol) in 40 mL methanol and 20 mL 1N NaOH solution was heated at 50° C. for 12 hrs. The reaction mixture was poured onto ice water and acidified with conc. HCl. The white creamy mixture was extracted with EtOAc. The organic fractions were dried (Na2SO4) filtered and the filtrate was concentrated to give a white solid (2 g). The solid was dissolved in 50 mL of CH2Cl2, and cooled under N2 in an ice-water bath. To the reaction was slowly added oxalyl chloride (2 mL, 19 mmol) and a drop of DMF. The reaction mixture was stirred at rt for 5 h. The reaction mixture was concentrated to give the title compound as a brown solid. This material was used in the next step without further purification.
4-ethoxy-2-(methylthio)pyrimidine-5-carboxylic acid[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
91.8%
With sodium hydroxide; In water; for 1h;Reflux;
2 g (6.6 mmol) of the starting material 1 'was dissolved in 10 ml of absolute ethanol,0.68 g of NaOH solid, 10 ml of water,Raise the temperature to reflux.After 1 h, TLC showed complete reaction.Rotate the ethanol, adjust the pH to 3 with 6NHCl,There is a lot of solid precipitation.Extraction can be obtained in white crystals 1.69g, the yield of 91.8percent.
4-chloro-2-(methylsulfanyl)pyrimidine-5-carboxamide[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
98.94%
Preparation of Compound II:4-chloro2-methylthiopyrimidine-5-formic acidI (25.60g, 0.12mol)Suspended in 100 mL of tetrahydrofuran,Add oxalyl chloride (16.67 g, 0.13 mol),Add 2 drops of DMF,Stir at 35 degrees for 1 hour,Add to the reaction solution23mL 22percent ammonia solution,Stir for 15 hours under 15 degrees.An off-white solid precipitates, suction filtration,The filter cake was washed twice with 10 mL of water.After the filter cake is dried by phosphorus pentoxide,Obtained 25.21 g of a white solid compound II,The yield was 98.94percent.
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