Hydrochloric Acid → 2,2,5,7-Tetramethyl-6-(nitromethylthio)chroman

HRID 2081807Notes

Reaction equation

[CH3:1][C:2]1([CH3:15])[CH2:11][CH2:10][C:9]2[C:4](=[CH:5][C:6]([CH3:14])=[C:7]([SH:13])[C:8]=2[CH3:12])[O:3]1.[OH-].[Na+].[N+:18]([CH3:21])([O-:20])=[O:19].Cl>O.[Fe-3](C#N)(C#N)(C#N)(C#N)(C#N)C#N.[K+].[K+].[K+].CCOCC>[CH3:1][C:2]1([CH3:15])[CH2:11][CH2:10][C:9]2[C:4](=[CH:5][C:6]([CH3:14])=[C:7]([S:13][CH2:21][N+:18]([O-:20])=[O:19])[C:8]=2[CH3:12])[O:3]1

Participants

Conditions

Temperature: 15 °C

Procedure

The thiol (B) was added to a solution of sodium hydroxide (2.8 g, 70 mM) in water (30 ml) and stirred vigorously for 30 minutes. Nitromethane (2.3 ml, 42.5 mM) was added, followed immediately by ether (75 ml). The reaction mixture was cooled to 15° C. in a cold water bath, then a solution of potassium ferricyanide (17.2 g, 52.3 mM) in water (43 ml) was added in a steady stream and the reaction mixture was stirred at ambient temperature overnight. The mixture was acidified with 2M hydrochloric acid and extracted with ethyl acetate. The extracts were washed with water, brine, then dried (Na2SO4) and evaporated. The residual oil was purified by flash chromatography, eluting with hexane/toluene (4:1 v/v, increasing in polarity to 2:1 v/v), to give 2,2,5,7-tetramethyl-6-(nitromethylthio)chroman (3.1 g, 32% yield) as a gum; NMR: 1.3(6H,s), 1.82(2H,t), 2.4(6H, 2d), 2.61(2H,t), 5.18(2H,s), 6.6(1H,s).

Workup

stirringthe reaction mixture was stirred at ambient temperature overnight
extractionextracted with ethyl acetate
washThe extracts were washed with water, brine
dry with materialdried (Na2SO4)
customevaporated
customThe residual oil was purified by flash chromatography
washeluting with hexane/toluene (4:1 v/v, increasing in polarity to 2:1 v/v)

Sources & evidence

ORD record: ord-4d2b45baa8024de28c2b55d98f55883b
Source dataset: uspto-grants-1993_02
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US05185452

Reaction notes

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