Potassium Phosphate, Tribasic → 1,1-dimethylethyl 7-{4-[(methyloxy)carbonyl]phenyl}-2,3-dihydro-1,4-benzoxazepine-4(5H)-carboxylate

HRID 241184ノート

反応式

HRID 241184 の反応式
[CH3:1][O:2][C:3]([C:5]1[CH:10]=[CH:9][C:8](B(O)O)=[CH:7][CH:6]=1)=[O:4].Br[C:15]1[CH:16]=[CH:17][C:18]2[O:24][CH2:23][CH2:22][N:21]([C:25]([O:27][C:28]([CH3:31])([CH3:30])[CH3:29])=[O:26])[CH2:20][C:19]=2[CH:32]=1.P([O-])([O-])([O-])=O.[K+].[K+].[K+]>O1CCOCC1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2]>[CH3:1][O:2][C:3]([C:5]1[CH:10]=[CH:9][C:8]([C:15]2[CH:16]=[CH:17][C:18]3[O:24][CH2:23][CH2:22][N:21]([C:25]([O:27][C:28]([CH3:30])([CH3:29])[CH3:31])=[O:26])[CH2:20][C:19]=3[CH:32]=2)=[CH:7][CH:6]=1)=[O:4]

参加物

6

反応物 3

HCID 62657Potassium Phosphate, TribasicHCID 27343694-Methoxycarbonylphenylboronic acidHCID 25220760tert-Butyl 7-bromo-2,3-dihydro-1,4-benzoxazepine-4(5H)-carboxylate

生成物 1

HCID 668201301,1-dimethylethyl 7-{4-[(methyloxy)carbonyl]phenyl}-2,3-dihydro-1,4-benzoxazepine-4(5H)-carboxylate収率 61.3%

試薬・触媒・溶媒 2

HCID 44119782Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)触媒HCID 312751,4-Dioxane溶媒

実験手順

A suspension of {4-[(methyloxy)carbonyl]phenyl}boronic acid (0.36 g, 2.0 mmol), 1,1-dimethylethyl 7-bromo-2,3-dihydro-1,4-benzoxazepine-4(5H)-carboxylate (0.66 g, 2.0 mmol), [1,1′-bis(diphenylphosphino)ferrocene]dichloropalladium(II) (70.0 mg, 0.10 mmol), and tripotassium phosphate (1.30 g, 12.0 mmol) in dioxane (20 mL) was refluxed for 3 h, and then cooled to room temperature. The reaction mixture was partitioned between ethyl acetate (50 mL) and water (80 mL), the organic layer was washed with brine (40 mL), dried over sodium sulfate then filtered and concentrated. Column chromatography on silica (ethyl acetate:hexanes 1:4) gave 1,1-dimethylethyl 7-{4-[(methyloxy)carbonyl]phenyl}-2,3-dihydro-1,4-benzoxazepine-4(5H)-carboxylate (0.47 g, 60% yield). 1H NMR (400 MHZ, DMSO-D6): 8.11 (m, 2H), 7.63-7.52 (m, 2H), 7.43 (m, 2H), 7.10 (t, 1H), 4.57-4.43 (br, 2H), 4.08 (m, 2H), 3.82 (m, 2H), 1.40 (s, 9H); MS (EI) for C22H25NO5: 469 (MH+).

後処理

  1. temperaturewas refluxed for 3 h
  2. customThe reaction mixture was partitioned between ethyl acetate (50 mL) and water (80 mL)
  3. washthe organic layer was washed with brine (40 mL)
  4. dry with materialdried over sodium sulfate
  5. filtrationthen filtered
  6. concentrationconcentrated

出典と根拠

ORDレコード
ord-3aba9a92bd40493d87be03f88d361484
出典データセット
uspto-grants-2014_02
特許番号
US08648066B2

反応ノート

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