Methyl iodide → 5-Methyl-2,3-dihydrobenzo[B][1,4]dioxine-6-carbaldehyde

HRID 639032Notes

Reaction equation

[CH3:1]N(C)CCNC.[Li]CCCC.[O:13]1[C:18]2[CH:19]=[CH:20][C:21]([CH:23]=[O:24])=[CH:22][C:17]=2[O:16][CH2:15][CH2:14]1.CI>C1COCC1.Cl>[CH3:1][C:22]1[C:17]2[O:16][CH2:15][CH2:14][O:13][C:18]=2[CH:19]=[CH:20][C:21]=1[CH:23]=[O:24]

Participants

Conditions

Temperature: -15 °C

Procedure

To a solution of N,N,N′-trimethylethylenediamine (3.3 g, 32.3 mmol) in THF (100 mL) at −15° C. was dropwise added n-BuLi (19.2 mL, 30.5 mmol, 1.6 M in THF). After stirring at −15° C. for 15 minutes, a solution of solution of 1,4-benzodioxane-6-aldehyde (5.0 g, 30.5 mmol) in THF (10 mL). After 20 minutes, another batch of n-BuLi (5 mL, 3.1 mmol, 1.6 M in THF) was added and stirred for 3 h. The resulting solution was cooled down to −72° C. and the mixture was treated with MeI (25.9 g, 182.5 mmol) slowly. After stirring at −72° C. for 3 h, the mixture was diluted with HCl solution (1M in water). The aqueous layer was extracted several times with diethyl ether. The organic fractions were combined, concentrated and purified with column chromatography (silica, 5-40% ethyl acetate in hexane) to provide the title compound as an off-white compound (1.0 g, 18%): %): MS (ES) m/z 179 (M+H)+.

Workup

customat −15° C.
waitAfter 20 minutes
stirringstirred for 3 h
temperatureThe resulting solution was cooled down to −72° C.
stirringAfter stirring at −72° C. for 3 h
extractionThe aqueous layer was extracted several times with diethyl ether
concentrationconcentrated
custompurified with column chromatography (silica, 5-40% ethyl acetate in hexane)

Sources & evidence

ORD record: ord-85b69fa64c8744358f10db513be707d2
Source dataset: uspto-grants-2010_04
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US07691850B2

Reaction notes

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