Sodium hydride → 1-(8-Chloronaphthalen-2-yl)-2-(methanesulfinyl)-2-(methylsulfanyl)ethan-1-one

HRID 1154540Notes

Reaction equation

[H-].[Na+].[Cl:3][C:4]1[CH:5]=[CH:6][CH:7]=[C:8]2[C:13]=1[CH:12]=[C:11]([C:14]([O:16]CC)=O)[CH:10]=[CH:9]2.[CH3:19][S:20][CH2:21][S:22]([CH3:24])=[O:23]>CN(C)C=O>[O:16]=[C:14]([C:11]1[CH:10]=[CH:9][C:8]2[C:13](=[C:4]([Cl:3])[CH:5]=[CH:6][CH:7]=2)[CH:12]=1)[CH:21]([S:20][CH3:19])[S:22]([CH3:24])=[O:23]

Participants

Conditions

Temperature: 25 °C

Procedure

A suspension of 9.2 g sodium hydride in 50 ml of N,N-dimethylformamide was added in one portion to a stirred solution of 5.6 g (24 mM) of ethyl 8-chloro-2-naphthylformate and 4.4 g (36 mM) of methyl methylthiomethyl sulfoxide in 10 ml of N,N-dimethylformamide. The reaction mixture was stirred for four hours at 25° C., and then concentrated to dryness. The product was dissolved in 250 ml of ethyl acetate and the solution was washed with 5% hydrochloric acid, saturated sodium bicarbonate and brine. The solution was dried and the solvent was removed by evaporation to give 4.73 g (63% yield) of 1-oxo-1-(8-chloro-2-naphthyl)-2-methylthio-2-methylsulfinylethane. A solution of 3.12 g (10 mM) of the product in 150 ml of formic acid and 12 ml of acetic anhydride was stirred at 65° C. for thirty minutes. To the reaction mixture were added 856 mg (4 mM) of sodium periodate and stirring was continued for an additional fifteen minutes. The reaction mixture was cooled and concentrated to dryness, and the product was dissolved in ethyl acetate, washed with sodium bicarbonate and brine, and the solvent was removed to give 1.2 g (46% yield) of methylthio α-oxo-α-(8-chloro-2-naphthyl)acetate.

Workup

concentrationconcentrated to dryness
dissolutionThe product was dissolved in 250 ml of ethyl acetate
washthe solution was washed with 5% hydrochloric acid, saturated sodium bicarbonate and brine
customThe solution was dried
customthe solvent was removed by evaporation

Sources & evidence

ORD record: ord-72bd5ec085124781a86e389bfc4babaf
Source dataset: uspto-grants-1984_12
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US04490370

Reaction notes

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