Sodium methanethiolate → 4-Methoxy-1-[2-(methylthio)ethyl]-2-nitrobenzene

HRID 1914699

Reaction equation

Br[CH2:2][CH2:3][C:4]1[CH:9]=[CH:8][C:7]([O:10][CH3:11])=[CH:6][C:5]=1[N+:12]([O-:14])=[O:13].[CH3:15][S-:16].[Na+]>CCO>[CH3:11][O:10][C:7]1[CH:8]=[CH:9][C:4]([CH2:3][CH2:2][S:16][CH3:15])=[C:5]([N+:12]([O-:14])=[O:13])[CH:6]=1

Participants

Conditions

Temperature: 25.5 °C

Procedure

A suspension of 1-(2-bromoethyl)-4-methoxy-2-nitrobenzene (14.7 g, 0.06 mol) in EtOH (150 mL) is stirred at 25-26° C. under a nitrogen atmosphere. Sodium thiomethoxide (7.9 g, 0.1 mol) is added in one portion at 25-26° C. and the reaction mixture is heated to reflux for 12 h. The solvent is removed under reduced pressure and the brown residue is taken up in cold water (100 mL). The crude product is extracted with EtOAc (2×200 mL). The organic layer is washed with water and brine (200 mL, each), then dried over Na2SO4 and the solvent is removed under reduced pressure to afford a brown oil. The crude product is purified by column chromatography (60-120 mesh silica gel, eluent 2% EtaAc in petrol ether) to give 8.3 g (67%) of the title compound as light brown liquid. 1H NMR (DMSO-d6, 400 MHz) δ 7.47-7.45 (m, 2H), 7.20-724(m 1H,), 3.81 (s, 3H), 3.01-2.97 (m, 2H), 2.69-2.66 (m, 2H), 2.05 (s, 3H). LC/MS: (ES+) 227.9.

Workup

temperaturethe reaction mixture is heated
temperatureto reflux for 12 h
customThe solvent is removed under reduced pressure
extractionThe crude product is extracted with EtOAc (2×200 mL)
washThe organic layer is washed with water and brine (200 mL
dry with materialeach), then dried over Na2SO4
customthe solvent is removed under reduced pressure
customto afford a brown oil
customThe crude product is purified by column chromatography (60-120 mesh silica gel, eluent 2% EtaAc in petrol ether)

Sources & evidence

ORD record: ord-0561b52d6756460d813ca35781699c94
Source dataset: uspto-grants-2013_12
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08614215B2

Linked notes

Loading…