Acetonitrile → 2-Chloromethyl-3,5,6-trimethyl-[1,4]benzoquinone

HRID 63806

Reaction equation

[Cl:1][CH2:2][C:3]1[C:8]([CH3:9])=[C:7]([O:10]C)[C:6]([CH3:12])=[C:5]([CH3:13])[C:4]=1[O:14]C.C(#N)C.O=[N+]([O-])[O-].[O-][N+](=O)[O-].[O-][N+](=O)[O-].[O-][N+](=O)[O-].[O-][N+](=O)[O-].[O-][N+](=O)[O-].[Ce+4].[NH4+].[NH4+]>O>[Cl:1][CH2:2][C:3]1[C:4](=[O:14])[C:5]([CH3:13])=[C:6]([CH3:12])[C:7](=[O:10])[C:8]=1[CH3:9]

Participants

Conditions

Temperature: 0 °C

Procedure

A flask was charged with 1-chloromethyl-2,5-dimethoxy-3,4,6-trimethyl-benzene (Ex-1B-3) (6.37 g, 27.9 mmol) and ACN (10 mL) then cooled to 0° C. A solution of CAN (31.3 g, 57.1 mmol) in water (10 mL) was added to the flask. After 1 h the reaction mixture was extracted with MTBE (3×50 mL). The combined MTBE layers were then washed with water (50 mL), dried over MgSO4, filtered and concentrated by rotary evaporation. Trituration of the crude product with MeOH yielded 4.49 g of 2-chloromethyl-3,5,6-trimethyl-[1,4]benzoquinone (Ex-1B-4) (81%) as a bright orange-yellow solid. 1H NMR (400 MHz, CDCl3) δ (ppm): 4.77 (s, 2H), 2.17 (s, 3H), 2.07 (s, 3H), 2.06 (s, 3H).

Workup

extractionAfter 1 h the reaction mixture was extracted with MTBE (3×50 mL)
washThe combined MTBE layers were then washed with water (50 mL)
dry with materialdried over MgSO4
filtrationfiltered
concentrationconcentrated by rotary evaporation

Sources & evidence

ORD record: ord-b1bb2187f6bf4db9b69e81d6345ac86a
Source dataset: uspto-grants-2016_09
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US09447006B2

Linked notes

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