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

HRID 473920Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 473920
[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]

Komponenten

7

Edukt 4

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

Produkt 1

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

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 962WaterLösungsmittelHCID 312751,4-DioxaneLösungsmittel

Reaktionsbedingungen

Temperatur
90 °C

Versuchsvorschrift

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+).

Aufarbeitung

  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)

Quellen und Nachweise

ORD-Eintrag
ord-57a353550395456ba2e99b24ddb594ab
Quelldatensatz
uspto-grants-2014_01
Patentnummer
US08637499B2

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