Di-tert-butyl azodicarboxylate → Di-tert-butyl 1-(2,4-dimethoxypyrimidin-5-yl)hydrazine-1,2-dicarboxylate

HRID 873885

反応式

HRID 873885 の反応式
Br[C:2]1[C:3]([O:10][CH3:11])=[N:4][C:5]([O:8][CH3:9])=[N:6][CH:7]=1.[N:12]([C:21]([O:23][C:24]([CH3:27])([CH3:26])[CH3:25])=[O:22])=[N:13][C:14]([O:16][C:17]([CH3:20])([CH3:19])[CH3:18])=[O:15]>C1COCC1>[CH3:9][O:8][C:5]1[N:4]=[C:3]([O:10][CH3:11])[C:2]([N:12]([C:21]([O:23][C:24]([CH3:27])([CH3:26])[CH3:25])=[O:22])[NH:13][C:14]([O:16][C:17]([CH3:18])([CH3:19])[CH3:20])=[O:15])=[CH:7][N:6]=1

参加物

4

反応物 2

HCID 97268Di-tert-butyl azodicarboxylateHCID 2557195-Bromo-2,4-dimethoxypyrimidine

生成物 1

HCID 90303215Di-tert-butyl 1-(2,4-dimethoxypyrimidin-5-yl)hydrazine-1,2-dicarboxylate収率 75%

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒2 回

反応条件

温度
0 °C

実験手順

To a stirred solution of 5-bromo-2,4-dimethoxypyrimidine (400 g, 1.826 mol) in anhydrous THF (3 L) under argon and cooled down to 0° C. was added dropwise TurboGrignard (1.821 L, 2.367 mol). The resulting mixture was stirred at 0° C. until exothermic ceased then, allowed to warm up and stir at RT for 30 min. A solution of di-tert-butyl azodicarboxylate in anhydrous THF (1 L) was added dropwise to the mixture and the reaction was stirred at RT for 1 hr. The reaction was slowly quenched with a saturated aq. NH4Cl solution (2 L), diluted with EtOAc (2 L) and water (2 L) and both phases separated. The aq. phase was extracted with EtOAc (3 L), combined organic layers were washed with brine (3 L), dried over Na2SO4, filtered and concentrated under reduced pressure. The resulting yellow oil was dissolved in Hexane (3 L) and the suspension was stirred at 0° C. for 3 hr, filtrated off and dried to afford a first batch of white crystals. The mother liquor was concentrated under reduced pressure and purified to afford a second batch of white crystals. The two batches were combined to afford the title product (507 g, 1.369 mol, 75% yield) as white crystals. tR: 1.03 min (LC-MS 1); ESI-MS: 371 [M+H]+, ESI-MS: 369 [M−H]− (LC-MS 1).

後処理

  1. additionwas added dropwise TurboGrignard (1.821 L, 2.367 mol)
  2. temperatureto warm up
  3. stirringstir at RT for 30 min
  4. stirringthe reaction was stirred at RT for 1 hr
  5. customThe reaction was slowly quenched with a saturated aq. NH4Cl solution (2 L)
  6. additiondiluted with EtOAc (2 L) and water (2 L)
  7. customboth phases separated
  8. extractionThe aq. phase was extracted with EtOAc (3 L)
  9. washwere washed with brine (3 L)
  10. dry with materialdried over Na2SO4
  11. filtrationfiltered
  12. concentrationconcentrated under reduced pressure
  13. dissolutionThe resulting yellow oil was dissolved in Hexane (3 L)
  14. stirringthe suspension was stirred at 0° C. for 3 hr
  15. filtrationfiltrated off
  16. customdried
  17. customto afford a first batch of white crystals
  18. concentrationThe mother liquor was concentrated under reduced pressure
  19. custompurified
  20. customto afford a second batch of white crystals

出典と根拠

ORDレコード
ord-a2c28715dbb34837ad3e6fdbdd90346f
出典データセット
uspto-grants-2015_03
特許番号
US08975417B2

関連ノート

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