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

HRID 473920ノート

反応式

HRID 473920 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].C(=O)(O)[O-].[K+].Br[C:20]1[CH:21]=[CH:22][C:23]2[O:29][CH2:28][CH2:27][N:26]([C:30]([O:32][C:33]([CH3:36])([CH3:35])[CH3:34])=[O:31])[CH2:25][C:24]=2[CH:37]=1.CCN(C(C)C)C(C)C>O1CCOCC1.O>[CH3:1][O:2][C:3]([C:5]1[CH:10]=[CH:9][C:8]([C:20]2[CH:21]=[CH:22][C:23]3[O:29][CH2:28][CH2:27][N:26]([C:30]([O:32][C:33]([CH3:35])([CH3:34])[CH3:36])=[O:31])[CH2:25][C:24]=3[CH:37]=2)=[CH:7][CH:6]=1)=[O:4]

参加物

7

反応物 4

HCID 81531DiisopropylethylamineHCID 516893Potassium BicarbonateHCID 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 64%

試薬・触媒・溶媒 2

HCID 962Water溶媒HCID 312751,4-Dioxane溶媒

反応条件

温度
90 °C

実験手順

To a solution of 4-(methoxycarbonyl)phenylboronic acid (6.0 g, 33 mmol), potassium bicarbonate (9.1 g, 92 mmol), 1,1-dimethylethyl 7-bromo-2,3-dihydro-1,4-benzoxazepine-4(5H)-carboxylate (10 g, 31 mmol) and DIPEA (16 mL, 92 mmol) in dioxane (27 mL) and water (3 mL) was added dichloro[1,1-bis(diphenylphosphino]ferrocenepalladium (II) dichloromethane adduct (1.3 g, 1.8 mmol). The biphasic mixture was then heated at 90° C. for 2 h then partitioned with ethyl acetate and 1M hydrochloric acid. The organic layer was washed with 1M sodium hydroxide solution then dried over anhydrous magnesium sulfate, filtered and concentrated. The residue was purified by silica gel column chromatography (25% ethyl acetate in hexanes) to provide 1,1-dimethylethyl 7-{4-[(methyloxy)carbonyl]phenyl}-2,3-dihydro-1,4-benzoxazepine-4(5H)-carboxylate (7.5 g, 64% yield) as a pale yellow solid. MS (EI) for C26H23FN6O3: 384 (MH+).

後処理

  1. customthen partitioned with ethyl acetate and 1M hydrochloric acid
  2. washThe organic layer was washed with 1M sodium hydroxide solution
  3. dry with materialthen dried over anhydrous magnesium sulfate
  4. filtrationfiltered
  5. concentrationconcentrated
  6. customThe residue was purified by silica gel column chromatography (25% ethyl acetate in hexanes)

出典と根拠

ORDレコード
ord-57a353550395456ba2e99b24ddb594ab
出典データセット
uspto-grants-2014_01
特許番号
US08637499B2

反応ノート

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