Hydrochloric Acid → (3RS,4SR)-3-(3,4-dimethoxyphenyl)-4-nitrocyclohexanone

HRID 1050829Notes

Reaction equation

[CH3:1][O:2][C:3]1[CH:8]=[CH:7][C:6](/[CH:9]=[CH:10]/[N+:11]([O-:13])=[O:12])=[CH:5][C:4]=1[O:14][CH3:15].C[Si](C)(C)[O:18][C:19]([CH:21]=[CH2:22])=[CH2:20].C1(C)C=CC=CC=1.Cl>C(OCC)(=O)C>[CH3:15][O:14][C:4]1[CH:5]=[C:6]([CH:9]2[CH:10]([N+:11]([O-:13])=[O:12])[CH2:22][CH2:21][C:19](=[O:18])[CH2:20]2)[CH:7]=[CH:8][C:3]=1[O:2][CH3:1]

Participants

Conditions

Temperature: 140 °C

Procedure

90.0 g of 3,4-dimethoxy-ω-nitrostyrene (compound G2), 90 ml of 2-trimethylsilyloxy-1,3-butadiene and 180 ml of abs. Toluene are put in an autoclave, where the mixture is stirred at 140° C. for 2 days and then cooled. After addition of 1000 ml of ethyl acetate, 300 ml of a 2 N solution of hydrochloric acid are dropped under stirring. The phases are separated and the aqueous layer is extracted three times with dichloromethane. The combined organic extracts are washed with saturated sodium hydrogencarbonate solution, dried over magnesium sulfate and the solvents are removed under reduced pressure to give 150 g of the crude title compound. Further purification is carried out by chromatography on silica gel using petroleum ether/ethyl acetate in the ratio 1/1 as eluent to give 81.5 g (67% of theory) of the pure title compound.

Workup

temperaturecooled
additionare dropped
stirringunder stirring
customThe phases are separated
extractionthe aqueous layer is extracted three times with dichloromethane
washThe combined organic extracts are washed with saturated sodium hydrogencarbonate solution
dry with materialdried over magnesium sulfate
customthe solvents are removed under reduced pressure
customto give 150 g of the crude title compound
customFurther purification

Sources & evidence

ORD record: ord-03d0efd27c914d79986f312f796bcd0e
Source dataset: uspto-grants-2016_07
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US09387205B2

Reaction notes

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