Methyl iodide → 2,3,4,5-tetramethoxytoluene

HRID 353030

Reaction equation

[CH3:1][O:2][C:3]1[CH:8]=[CH:7][C:6]([O:9][CH3:10])=[C:5]([O:11][CH3:12])[C:4]=1[O:13][CH3:14].[CH3:15]N(CCN(C)C)C.[Li]CCCC.CCCCCC.CI>C1COCC1>[CH3:1][O:2][C:3]1[C:4]([O:13][CH3:14])=[C:5]([O:11][CH3:12])[C:6]([O:9][CH3:10])=[CH:7][C:8]=1[CH3:15]

Participants

Conditions

Temperature: 0 °C

Procedure

Syper, L. et al., Tetrahedron 36:123 (1980). To a solution of 1,2,3,4-tetramethoxybenzene 12 (4.0 g, 20.2 mmol) and TMEDA (6 mL, 38.0 mmol) in hexanes (44 mL) and THF (80 mL) at 0° C. under Ar, n-BuLi in hexane (1.6 M, 25.6 mmol) was added dropwise over a 10 min period and the reaction stirred for 30 min at 0° C. under Ar. Subsequent to dropwise addition of CH3I (20 mL, 160 mmol) over an 8 min period, the reaction was stirred for 3 h at 0° C. under Ar and then quenched by addition of aqueous NH4Cl and ether (20 mL). The organic layer was sequentially washed with concentrated NH4OH, water, and brine. Drying and concentration of the organic layer was followed by purification of the residue by flash chromatography (hexanes, hexanes/EtOAc, 19:1, v/v) to afford 13 as a clear oil (3.6 g, 83%). 1H NMR (CDCl3): δ6.45 (s, 1 H), 3.93 (s, 3 H), 3.87 (s, 3 H), 3.82 (s, 3 H), 3.79 (s, 3 H), 2.23 (s, 3 H). 13C NMR (CDCl3): δ149.0, 146.9, 145.3, 140.7, 125.7, 108.2, 61.0, 60.9, 60.5, 55.9, 15.7.

Workup

stirringthe reaction was stirred for 3 h at 0° C. under Ar
customquenched by addition of aqueous NH4Cl and ether (20 mL)
washThe organic layer was sequentially washed with concentrated NH4OH, water, and brine
customDrying
customconcentration of the organic layer was followed by purification of the residue by flash chromatography (hexanes, hexanes/EtOAc, 19:1

Sources & evidence

ORD record: ord-3f2644736c3c4aa6917f6ae72bb49d96
Source dataset: uspto-grants-2004_06
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US06750049B1

Linked notes

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