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

HRID 473920노트

반응식

HRID 473920 반응식
[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]

참가 물질

7

반응물 4

HCID 81531DiisopropylethylamineHCID 516893Potassium BicarbonateHCID 27343694-Methoxycarbonylphenylboronic acidHCID 25220760tert-Butyl 7-bromo-2,3-dihydro-1,4-benzoxazepine-4(5H)-carboxylate

생성물 1

HCID 668201301,1-dimethylethyl 7-{4-[(methyloxy)carbonyl]phenyl}-2,3-dihydro-1,4-benzoxazepine-4(5H)-carboxylate수율 64%

시약·촉매·용매 2

HCID 962Water용매HCID 312751,4-Dioxane용매

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온도
90 °C

실험 절차

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+).

후처리

  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)

출처 및 근거

ORD 기록
ord-57a353550395456ba2e99b24ddb594ab
출처 데이터셋
uspto-grants-2014_01
특허 번호
US08637499B2

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