Diethyl Ether → 7-Bromo-4-(chloromethyl)-5-methyl-2,3-dihydrobenzo[b]oxepine

HRID 1911021Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1911021
[Br:1][C:2]1[CH:15]=[CH:14][C:5]2[O:6][CH2:7][CH2:8][C:9]([CH2:12]O)=[C:10]([CH3:11])[C:4]=2[CH:3]=1.CCN(C(C)C)C(C)C.CS([Cl:29])(=O)=O.C(OCC)C>ClCCl>[Br:1][C:2]1[CH:15]=[CH:14][C:5]2[O:6][CH2:7][CH2:8][C:9]([CH2:12][Cl:29])=[C:10]([CH3:11])[C:4]=2[CH:3]=1

Komponenten

6

Edukt 4

HCID 3283Diethyl EtherHCID 31297Methanesulfonyl chlorideHCID 81531DiisopropylethylamineHCID 71060798(7-Bromo-5-methyl-2,3-dihydrobenzo[b]oxepin-4-yl)methanol

Produkt 1

HCID 866854227-Bromo-4-(chloromethyl)-5-methyl-2,3-dihydrobenzo[b]oxepineAusbeute 125 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 6344DichloromethaneLösungsmittel

Versuchsvorschrift

To a solution of (7-bromo-5-methyl-2,3-dihydrobenzo[b]oxepin-4-yl)methanol from step H6 (1.53 g, 5.68 mmol) in dichloromethane (10 mL) was added DIPEA (2.98 mL, 17.1 mmol) followed by methanesulfonyl chloride (0.886 mL, 11.4 mmol) at 0° C. The mixture was allowed to gradually warm up to rt. After 18 h at rt, diethyl ether (50 mL) was added, the mixture was washed with water, and the organic layer was separated, dried over sodium sulfate, filtered, and concentrated in vacuo to give 7-bromo-4-(chloromethyl)-5-methyl-2,3-dihydrobenzo[b]oxepine (2.05 g, 7.13 mmol, 125% yield). The crude material was used in the next step without further purification. 1H NMR (500 MHz, chloroform-d) δ 7.40 (d, J=2.4 Hz, 1H), 7.36-7.32 (m, 1H), 6.96 (s, 1H), 4.56 (t, J=6.3 Hz, 2H), 4.37 (s, 2H), 2.34 (t, J=1.0 Hz, 2H), 2.17 (s, 3H).

Aufarbeitung

  1. washthe mixture was washed with water
  2. customthe organic layer was separated
  3. dry with materialdried over sodium sulfate
  4. filtrationfiltered
  5. concentrationconcentrated in vacuo

Quellen und Nachweise

ORD-Eintrag
ord-fc37837b7c414d4796642631ffffac42
Quelldatensatz
uspto-grants-2013_12
Patentnummer
US08604024B2

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