2-chloro-6-methylsulfanylbenzaldehyde

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

Procedure: 6-Chloro-2-(methythio)benzaldehyde (11.6 g, 75.16 mmol), and hydroxylamine hydrochloride (5.75 g, 82.86 mmol) were combined in ethanol (100 ml). Diethylamide (11.5 ml, 82.86 mmol) was slowly added to the solution and it was allowed to stir at room temperature overnight. After the completion of the reaction, the reaction mixture was concentrated under reduced pressure, diluted with ethyl acetate and then washed successively with water and saturated aqueous sodium bicarbonate solution. The organic layer was dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure to yield (E)-2-chloro-6-(methylthio)benzaldehyde oxime (12.37 g) as a white solid. (This method is general for other 2-(methythio)benzaldehydes). 1H NMR (300 MHz, DMSO-d6): 11.62 (s, 1H), 8.22 (s, 1H), 7.20-7.40 (m, 3H), 2.41 ppm (s, 3H). MW=202 confirmed by LC-MS, tr=3.58 min (Method B) MH+=203. After the completion of the reaction the reaction mixture was concentrated under reduced pressure diluted with ethyl acetate washed successively with water and saturated aqueous sodium bicarbonate solution The organic layer was dried over anhydrous sodium sulfate filtered concentrated under reduced pressure

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

Procedure: 6-Chloro-2-(methythio)benzaldehyde (11.6 g, 75.16 mmol), and hydroxylamine hydrochloride (5.75 g, 82.86 mmol) were combined in ethanol (100 ml). Diethylamide (11.5 ml, 82.86 mmol) was slowly added to the solution and it was allowed to stir at room temperature overnight. After the completion of the reaction, the reaction mixture was concentrated under reduced pressure, diluted with ethyl acetate and then washed successively with water and saturated aqueous sodium bicarbonate solution. The organic layer was dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure to yield (E)-2-chloro-6-(methylthio)benzaldehyde oxime (12.37 g) as a white solid. (This method is general for other 2-(methythio)benzaldehydes). 1H NMR (300 MHz, DMSO-d6): 11.62 (s, 1H), 8.22 (s, 1H), 7.20-7.40 (m, 3H), 2.41 ppm (s, 3H). MW=202 confirmed by LC-MS, tr=3.58 min (Method B) MH+=203. After the completion of the reaction the reaction mixture was concentrated under reduced pressure diluted with ethyl acetate washed successively with water and saturated aqueous sodium bicarbonate solution The organic layer was dried over anhydrous sodium sulfate filtered concentrated under reduced pressure

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

Procedure: To a solution of 2,6-dichlorobenzaldehyde (20 g, 114.28 mmol) in N,N-dimethylformamide (200 ml), sodium thiomethoxide (8.81 g, 125.7 mmol) was added at 0° C. The reaction mixture was allowed to warm to room temperature overnight, then poured into water. A yellow precipitate was collected by vacuum filtration and dried to afford 2-chloro-6-(methylthio)benzaldehyde (11. g), as a light yellow solid. (This method is general for other 2-haloaldehydes). 1H NMR (300 MHz, CDCl3): 10.6 (s, 1H), 7.4 (t, 1H), 7.2 (dd, 2H), 2.4 ppm (s, 3H). MW=187 confirmed by LC-MS, tr=13.18 min (Method Y) MH+=188. A yellow precipitate was collected by vacuum filtration dried

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

Procedure: To a solution of 2,6-dichlorobenzaldehyde (20 g, 114.28 mmol) in N,N-dimethylformamide (200 ml), sodium thiomethoxide (8.81 g, 125.7 mmol) was added at 0° C. The reaction mixture was allowed to warm to room temperature overnight, then poured into water. A yellow precipitate was collected by vacuum filtration and dried to afford 2-chloro-6-(methylthio)benzaldehyde (11. g), as a light yellow solid. (This method is general for other 2-haloaldehydes). 1H NMR (300 MHz, CDCl3): 10.6 (s, 1H), 7.4 (t, 1H), 7.2 (dd, 2H), 2.4 ppm (s, 3H). MW=187 confirmed by LC-MS, tr=13.18 min (Method Y) MH+=188. A yellow precipitate was collected by vacuum filtration dried

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

Procedure: 6-Chloro-2-(methythio)benzaldehyde (11.6 g, 75.16 mmol), and hydroxylamine hydrochloride (5.75 g, 82.86 mmol) were combined in ethanol (100 ml). Diethylamide (11.5 ml, 82.86 mmol) was slowly added to the solution and it was allowed to stir at room temperature overnight. After the completion of the reaction, the reaction mixture was concentrated under reduced pressure, diluted with ethyl acetate and then washed successively with water and saturated aqueous sodium bicarbonate solution. The organic layer was dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure to yield (E)-2-chloro-6-(methylthio)benzaldehyde oxime (12.37 g) as a white solid. (This method is general for other 2-(methythio)benzaldehydes). 1H NMR (300 MHz, DMSO-d6): 11.62 (s, 1H), 8.22 (s, 1H), 7.20-7.40 (m, 3H), 2.41 ppm (s, 3H). MW=202 confirmed by LC-MS, tr=3.58 min (Method B) MH+=203. After the completion of the reaction the reaction mixture was concentrated under reduced pressure diluted with ethyl acetate washed successively with water and saturated aqueous sodium bicarbonate solution The organic layer was dried over anhydrous sodium sulfate filtered concentrated under reduced pressure

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

Procedure: To a solution of 2,6-dichlorobenzaldehyde (20 g, 114.28 mmol) in N,N-dimethylformamide (200 ml), sodium thiomethoxide (8.81 g, 125.7 mmol) was added at 0° C. The reaction mixture was allowed to warm to room temperature overnight, then poured into water. A yellow precipitate was collected by vacuum filtration and dried to afford 2-chloro-6-(methylthio)benzaldehyde (11. g), as a light yellow solid. (This method is general for other 2-haloaldehydes). 1H NMR (300 MHz, CDCl3): 10.6 (s, 1H), 7.4 (t, 1H), 7.2 (dd, 2H), 2.4 ppm (s, 3H). MW=187 confirmed by LC-MS, tr=13.18 min (Method Y) MH+=188. A yellow precipitate was collected by vacuum filtration dried