4-Chloro-6-methoxy-2-pyrimidinamine

light yellow crystalline powder

DryPowder

General procedure: Intermediates Id–f were prepared by a method similar to that for intermediates Ia–c. A solution ofNaH (5.8 mmol) in dry THF (12 mL) was cooled to 0 °C under N2, then a substituted alcohol (6.1 mmol)was added dropwise. The mixture was stirred for 15 min while maintaining the temperature at 0 °C.Next, 2-amino-4-chloro-6- substituted-pyrimidine (5.8 mmol) was added to the solution. The reactionwas continued at 62 °C for 15 h. Then the mixture was cooled to ambient temperature, and quenchedwith 1 mL of 1 M hydrochloric acid solution. The mixture was diluted with EtOAc (20 mL), washedtwice with a saturated NaHCO3 solution (20 mL) and brine (20 mL), dried with anhydrous Na2SO4and evaporated in vacuo. Finally, the residue was purified by silica gel column chromatography(EtOAc/petroleum ether) to afford compounds Id–f. 4-Chloro-6-methoxypyrimidin-2-amine (Id). White solid, mp 165–167 °C, yield = 84percent. 1H-NMR (CDCl3) δ 6.04 (s, 1H, ArH), 5.35–5.14 (m, 2H, NH2), 3.81 (s, 3H, OCH3).To a solution of 4, 6-dichloro-2-amino pyrimidine (5.0 g, 30.5 mmol) in MeOH (100 mL) was added 25percent sodium methoxide (6.59 g, 30.5 mmol). The solution was refluxed for 20 hours, at which time the methanol was removed in vacuo. The residue was dissolved in EtOAc (350 mL), washed with HIn 500mL eggplant-shaped flask, 2-Amino-4, 6-dichloropyrimidine (50.0 g, 304.9 mmol)Dissolved in tetrahydrofuran (200 mL), Sodium methoxide (32.9 g, 609.8 mmol) was added under N2 protection, Reflux 2h.The reaction was completed, cooled, the reaction liquid into the water, suction filtration, the filter cake was beaten with methanol (80mL × 1)The filtrate was filtered to obtain 2-amino-4-chloro-6-methoxypyrimidine 43.2g, the yield was 88.7percent.0262] To a solution of 4, 6-dichloro-2-amino pyrimidine (5.0 g, 30.5 mmol) in methanol (100 mL) was added 25percent sodium methoxide (6.59 g, 30.5 mmol). The solution was refluxed for 20 hours, at which time the methanol was removed in vacuo. The residue was dissolved in EtOAc (350 mL), washed with H2O (100 mL) and with NaCl(To a solution of 4, 6-dichloro-2-amino pyrimidine (5.0 g, 30.5 mmol) in MeOH (100 mL) was added 25% sodium methoxide (6.59 g, 30.5 mmol). The solution was refluxed for 20 hours, at which time the methanol was removed in vacuo. The residue was dissolved in EtOAc (350 mL), washed with H2O (100 mL) and with NaCl(sat.) (100 mL), dried over Na2SO4, filtered and concentrated yielding 4.4 g (90%) of 4-chloro- 6-methoxypyrimidine-2-ylamine.In 500mL eggplant-shaped flask, 2-Amino-4, 6-dichloropyrimidine (50.0 g, 304.9 mmol)Dissolved in tetrahydrofuran (200 mL), Sodium methoxide (32.9 g, 609.8 mmol) was added under N2 protection, Reflux 2h.The reaction was completed, cooled, the reaction liquid into the water, suction filtration, the filter cake was beaten with methanol (80mL × 1)The filtrate was filtered to obtain 2-Amino-4-anilino-6-methoxypyrimidine was synthesized using 2-amino-4, 6-dichloropyrimidine as a starting material through General procedure: Intermediates Id-f were prepared by a method similar to that for intermediates Ia-c. A solution ofNaH (5.8 mmol) in dry THF (12 mL) was cooled to 0 C under N2, then a substituted alcohol (6.1 mmol)was added dropwise. The mixture was stirred for 15 min while maintaining the temperature at 0 C.Next, 2-amino-4-chloro-6- substituted-pyrimidine (5.8 mmol) was added to the solution. The reactionwas continued at 62 C for 15 h. Then the mixture was cooled to ambient temperature, and quenchedwith 1 mL of 1 M hydrochloric acid solution. The mixture was diluted with EtOAc (20 mL), washedtwice with a saturated NaHCO3 solution (20 mL) and brine (20 mL), dried with anhydrous Na2SO4and evaporated in vacuo. Finally, the residue was purified by silica gel column chromatography(EtOAc/petroleum ether) to afford compounds Id-f. 4-Chloro-6-methoxypyrimidin-2-amine (Id). White solid, mp 165-167 C, yield = 84%. 1H-NMR (CDCl3) delta 6.04 (s, 1H, ArH), 5.35-5.14 (m, 2H, NH2), 3.81 (s, 3H, OCH3).2-Amino-4-chloro-6-methoxypyrimidine 16.4 g 2-amino-4, 6-dichloropyrimidine (purchased from Aldrich Chemical Co., Milwaukee, WI 53201) was added to 200 ml of CH3 OH. The mixture was cooled to 10 with an ice bath and 5.4 g of NaOCH3 was added in portions while maintaining the temperature. The reaction mixture was allowed to warm to ambient temperature and then heated to reflux for two hours. The reaction mixture was then allowed to cool to ambient temperature and it was stirred overnight. A yellow solid was filtered and recrystallized from butyl chloride. The resulting solid was chromatographed on a dry column of silica, and eluted with 40% EtOAc-hexane. The resulting yellow solid was further purified by recrystallization from butyl chloride. 9.4 g of product with m.p. 163-166 was obtained.2-Amino-4-chloro-6-methoxypyrimidine 16.4 g 2-amino-4, 6-dichloropyrimidine (purchased from Aldrich Chemical Co., Milwaukee, WI 53201) was added to 200 ml of CH3 OH. The mixture was cooled to 10 with an ice bath and 5.4 g of NaOCH3 was added in portions while maintaining the temperature. The reaction mixture was allowed to warm to ambient temperature and then heated to reflux for two hours. The reaction mixture was then allowed to cool to ambient temperature and it was stirred overnight. A yellow solid was filtered and recrystallized from butyl chloride. The resulting solid was chromatographed on a dry column of silica, and eluted with 40% EtOAchexane. The resulting yellow solid was further purified by recrystallization from butyl chloride. 9.4 g of product with m.p. 163-166 was obtained.0262] To a solution of 4, 6-dichloro-2-amino pyrimidine (5.0 g, 30.5 mmol) in methanol (100 mL) was added 25% sodium methoxide (6.59 g, 30.5 mmol). The solution was refluxed for 20 hours, at which time the methanol was removed in vacuo. The residue was dissolved in EtOAc (350 mL), washed with H2O (100 mL) and with NaCl(Sat.) (100 mL), dried over Na2SO4, filtered and concentrated yielding 4.4 g (90%) of 4-chloro- 6-methoxypyrimidine-2-ylamine.

Organic intermediates and pesticide intermediates can be used for the synthesis of chlorsulfuron.

Intermediates

Molecular Weight:159.57
XLogP3:1.1
Hydrogen Bond Donor Count:1
Hydrogen Bond Acceptor Count:4
Rotatable Bond Count:1
Exact Mass:159.0199395
Monoisotopic Mass:159.0199395
Topological Polar Surface Area:61
Heavy Atom Count:10
Complexity:113
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes