Water → tert-Butyl 8-isopropoxy-2,3-dihydropyrido[3,2-f][1,4]oxazepine-4(5H)-carboxylate

HRID 2191253ノート

反応式

HRID 2191253 の反応式
[CH:1]([OH:4])([CH3:3])[CH3:2].[H-].[Na+].Cl[C:8]1[CH:9]=[CH:10][C:11]2[CH2:12][N:13]([C:19]([O:21][C:22]([CH3:25])([CH3:24])[CH3:23])=[O:20])[CH2:14][CH2:15][O:16][C:17]=2[N:18]=1.O>C1(C)C=CC=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.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd].CC1C=CC(P(C2C=CC3C(=CC=CC=3)C=2C2C3C(=CC=CC=3)C=CC=2P(C2C=CC(C)=CC=2)C2C=CC(C)=CC=2)C2C=CC(C)=CC=2)=CC=1>[CH:1]([O:4][C:8]1[CH:9]=[CH:10][C:11]2[CH2:12][N:13]([C:19]([O:21][C:22]([CH3:25])([CH3:24])[CH3:23])=[O:20])[CH2:14][CH2:15][O:16][C:17]=2[N:18]=1)([CH3:3])[CH3:2]

参加物

8

反応物 4

HCID 962WaterHCID 3776IsopropanolHCID 24758Sodium hydrideHCID 57356939Tert-butyl 8-chloro-2,3-dihydropyrido[3,2-F][1,4]oxazepine-4(5H)-carboxylate

生成物 1

HCID 68429626tert-Butyl 8-isopropoxy-2,3-dihydropyrido[3,2-f][1,4]oxazepine-4(5H)-carboxylate収率 64%

試薬・触媒・溶媒 3

HCID 4189906(S)-(-)-2,2'-Bis(di-p-tolylphosphino)-1, 1'-binaphthyl触媒HCID 9811564Bis(dibenzylideneacetone)palladium触媒HCID 1140Toluene溶媒2 回

反応条件

温度
70 °C

実験手順

To a solution of isopropyl alcohol (0.081 mL) in toluene (2 mL) was added sodium hydride (0.084 g), and the resulting mixture was stirred at 70° C. for 15 min under a nitrogen atmosphere. A mixture of tert-butyl 8-chloro-2,3-dihydropyrido[3,2-f][1,4]oxazepine-4(5H)-carboxylate (0.30 g), (S)-tol-BINAP (0.022 g), Pd2(dba)3 (0.015 g) and toluene (2 mL) was added, and the resulting mixture was stirred at 100° C. for 16 hr under an argon atmosphere. The reaction solution was poured into water, and the resulting product was extracted with ethyl acetate. The organic layer was washed with water and saturated brine and dried, and the solvent was evaporated under reduced pressure. The residue was purified by silica gel column chromatography (solvent gradient; 0→40% ethyl acetate/hexane) to give tert-butyl 8-isopropoxy-2,3-dihydropyrido[3,2-f][1,4]oxazepine-4(5H)-carboxylate (0.21 g, 64%) as a colorless oil.

後処理

  1. additionwas added
  2. stirringthe resulting mixture was stirred at 100° C. for 16 hr under an argon atmosphere
  3. extractionthe resulting product was extracted with ethyl acetate
  4. washThe organic layer was washed with water and saturated brine
  5. customdried
  6. customthe solvent was evaporated under reduced pressure
  7. customThe residue was purified by silica gel column chromatography (solvent gradient; 0→40% ethyl acetate/hexane)

出典と根拠

ORDレコード
ord-65f03c7e3b0a4cef9c800b50dbc29045
出典データセット
uspto-grants-2012_12
特許番号
US08329687B2

反応ノート

読み込み中…