4-chloro-2-methoxybenzenecarbothioamide

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: In ethanol (50 ml), 4-chloro-2-methoxythiobenzamide (4.00 g, 20.0 mmol) prepared in the Step 7-1-2 was suspended, and ethyl 2-chloroacetoacetate (3.62 g, 22.0 mmol) was added to the suspension. The mixture was heated under reflux overnight. After the mixture was allowed to cool, the solvent was distilled off under a reduced pressure, and ethyl acetate and a saturated sodium bicarbonate solution were added to the mixture. The resulting mixture was subjected to extraction with ethyl acetate. The extract was dried over anhydrous magnesium sulfate and then concentrated. The residue was suspended in ethyl acetate-n-hexane (ethyl acetate:n-hexane=1:1) and separated by filtration. The separated product was washed with the same solvent and dried under a reduced pressure to give the title compound (4.84 g, 78%) as a light-yellow powder. The mixture was heated under reflux overnight to cool the solvent was distilled off under a reduced pressure, and ethyl acetate a saturated sodium bicarbonate solution were added to the mixture The resulting mixture was subjected to extraction with ethyl acetate The extract was dried over anhydrous magnesium sulfate concentrated separated by filtration The separated product was washed with the same solvent dried under a reduced pressure

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: In tetrahydrofuran (100 ml), 4-chloro-2-methoxybenzamide (9.40 g, 50.6 mmol) prepared in the Step 7-1-1 and Lawesson's reagent (10.2 g, 25.3 mmol) were suspended, and the suspension was heated under reflux for 2 hours. After the suspension was allowed to cool, a saturated sodium bicarbonate solution was added to the suspension to stop the reaction. Then the reaction mixture was subjected to extraction with ethyl acetate, and the extract was dried over anhydrous magnesium sulfate and then concentrated. The concentrate was purified by silica gel column chromatography (n-hexane:ethyl acetate=1:1) to give the title compound (6.63 g, 65%) as a yellow powder. the suspension was heated under reflux for 2 hours to cool the reaction Then the reaction mixture was subjected to extraction with ethyl acetate the extract was dried over anhydrous magnesium sulfate concentrated The concentrate was purified by silica gel column chromatography (n-hexane:ethyl acetate=1:1)