Hydrochloric Acid → Methyl 6-amino-3-methoxy-2-pyrazinecarboxylate

HRID 392303ノート

反応式

HRID 392303 の反応式
Br[C:2]1[N:7]=[C:6]([C:8]([O:10][CH3:11])=[O:9])[C:5]([O:12][CH3:13])=[N:4][CH:3]=1.C(=[NH:27])(C1C=CC=CC=1)C1C=CC=CC=1.CC(C)([O-])C.[Na+].Cl.[OH-].[Na+]>C1(C)C=CC=CC=1.O1CCCC1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd].C1C=CC(P(C2C=CC3C(=CC=CC=3)C=2C2C3C(=CC=CC=3)C=CC=2P(C2C=CC=CC=2)C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.O.C(Cl)(Cl)Cl>[NH2:27][C:2]1[N:7]=[C:6]([C:8]([O:10][CH3:11])=[O:9])[C:5]([O:12][CH3:13])=[N:4][CH:3]=1

参加物

12

反応物 5

HCID 313Hydrochloric AcidHCID 14798Sodium HydroxideHCID 136809Benzophenone imineHCID 22248028Methyl 6-bromo-3-methoxypyrazine-2-carboxylateHCID 23676156Sodium t-butoxide

生成物 1

HCID 22662843Methyl 6-amino-3-methoxy-2-pyrazinecarboxylate収率 43.1%

試薬・触媒・溶媒 6

HCID 634876Binap, (A+-)-触媒HCID 9811564Bis(dibenzylideneacetone)palladium触媒HCID 962Water溶媒HCID 1140Toluene溶媒HCID 6212Chloroform溶媒HCID 8028Tetrahydrofuran溶媒

反応条件

温度
80 °C

実験手順

In an atmosphere of nitrogen gas, 11.4 g of methyl 6-bromo-3-methoxy-2-pyrazinecarboxylate was dissolved in 227 mL of toluene, and 10.3 g of benzophenoneimine, 0.42 g of tris(dibenzylideneacetone)dipalladium, 0.86 g of (s)-(−)-2,2′-bis(diphenylphosphino)-1,1′-binaphthyl and 6.20 g of sodium tert-butoxide were successively added. The mixture thus obtained was stirred at 80° C. for one hour. After cooling the reaction mixture, it was filtered. The filtrate was purified by column chromatography [eluent: toluene:ethyl acetate=20:1]. The oily product thus obtained was dissolved in 140 mL of tetrahydrofuran, 7 mL of 2 mol/L hydrochloric acid was added, and the mixture thus obtained was stirred at room temperature for 15 minutes. A mixture of 200 mL of chloroform and 50 mL of water was added to the reaction mixture and then 1 mol/L sodium hydroxide was added to alkalinize the mixture, and the organic layer was separated. The organic layer thus obtained was washed with a saturated aqueous solution of sodium chloride and dried on anhydrous magnesium sulfate, and the solvent was removed under reduced pressure. The residue was purified by column chromatography [eluent: toluene:ethyl acetate=1:1] to obtain 3.64 g of methyl 6-amino-3-methoxy-2-pyrazinecarboxylate as a yellow-colored oily product.

後処理

  1. customThe mixture thus obtained
  2. temperatureAfter cooling the reaction mixture, it
  3. filtrationwas filtered
  4. customThe filtrate was purified by column chromatography [eluent: toluene:ethyl acetate=20:1]
  5. customThe oily product thus obtained
  6. customthe mixture thus obtained
  7. stirringwas stirred at room temperature for 15 minutes
  8. additionwas added to the reaction mixture
  9. customthe organic layer was separated
  10. customThe organic layer thus obtained
  11. washwas washed with a saturated aqueous solution of sodium chloride
  12. dry with materialdried on anhydrous magnesium sulfate
  13. customthe solvent was removed under reduced pressure
  14. customThe residue was purified by column chromatography [eluent: toluene:ethyl acetate=1:1]

出典と根拠

ORDレコード
ord-7e7108b74e394c45b2c42c878649cca9
出典データセット
uspto-grants-2004_10
特許番号
US06800629B2

反応ノート

読み込み中…