Diethylamine → 2,2-Diethyl-4-methoxy-1a,2,7,7a-tetrahydro-1H-naphtho[2,3-b]azirene

HRID 2300961Notes

Reaction equation

[CH2:1]([C:3]1([CH2:17][CH3:18])[C:12]2[C:7](=[CH:8][CH:9]=[C:10]([O:13][CH3:14])[CH:11]=2)[CH2:6][CH2:5][C:4]1=[N:15]O)[CH3:2].C(NCC)C.[H-].[H-].[H-].[H-].[Li+].[Al+3]>C1COCC1>[CH2:1]([C:3]1([CH2:17][CH3:18])[C:12]2[C:7](=[CH:8][CH:9]=[C:10]([O:13][CH3:14])[CH:11]=2)[CH2:6][CH:5]2[NH:15][CH:4]12)[CH3:2]

Participants

Conditions

Temperature: 0 °C

Procedure

To a solution of the 1,1-diethyl-7-methoxy-3,4-dihydro-1H-naphthalen-2-one oxime (4.68 g, 18.96 mmol) in dry THF (100 mL) at 0° C. was added the diethylamine (4.9 mL, 47.4 mmol) and the LAH (95% powder) (2.16 g, 56.9 mmol). The mixture was stirred at 0° C. for 15 min then heated to reflux for 3 h. The gray solution was cooled down to 0° C., quenched with brine and diluted with AcOEt. The organic layer was decanted, washed with H2O (2×), brine, dried over MgSO4, filtered then evaporated. The residu was purified by a flash chromatography (3% MeOH/CH2Cl2) (3.889 g, 89%). 1H NMR (CDCl3): 6.99 (1H, d, J=8 Hz, H5), 6.76 (2H, m, H6 and H8), 3.13 (2H, m, CHCH), 2.40 (1H, broad, NH), 2.10-2.05 (2H, m), 1.84 (1H, m), 1.62 (4H, m, CH2), 1.02 (3H, t, J=7.5 Hz, CH3), 0.75 (3H, t, J=7.5 hz, CH3).

Workup

temperaturethen heated
temperatureto reflux for 3 h
temperatureThe gray solution was cooled down to 0° C.
customquenched with brine
additiondiluted with AcOEt
customThe organic layer was decanted
washwashed with H2O (2×), brine
dry with materialdried over MgSO4
filtrationfiltered
customthen evaporated
customThe residu was purified by a flash chromatography (3% MeOH/CH2Cl2) (3.889 g, 89%)

Sources & evidence

ORD record: ord-3a643af7c3d9472cbf80256666a64ea1
Source dataset: uspto-grants-2002_12
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US06498196B1

Reaction notes

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