반응 #1851974

반응 방정식

hydrogen chloride

Oxalyl chloride

3-[(4-fluorophenyl)sulfonyl]propanoic acid

AlCl3

→

6-fluoro-2,3-dihydro-4H-1-benzothiopyran-4-one

수율 93.3%

용매

water

dichloromethane

반응 조건

후처리

1. 1
   농축was concentrated under reduced pressure to a residue
2. 2
   온도cooled to 0° C. in an ice bath
3. 3
   workup.ADDITIONCS2 (1 mL) was added
4. 4
   온도to warm to room temperature
5. 5
   workup.STIRRINGstirred over night
6. 6
   workup.STIRRINGstirred
7. 7
   추출extracted with dichloromethane (3×150 mL)
8. 8
   세척washed with brine (1×100 mL) and water (1×100 mL)
9. 9
   건조dried (sodium sulfate)
10. 10
    농축concentrated to a yellow solid
11. 11
    기타The solid was purified by flash column chromatography on 100 g silica gel
12. 12
    세척eluting 10% ethyl acetate in hexanes

실험 절차

3-[(4-fluorophenyl)sulfonyl]propanoic acid (3 g, 15 mmol) was dissolved in dichloromethane (30 mL ) and cooled to 0° C. in an ice bath. Oxalyl chloride (10 mL) was added slowly, dimethyl formamide (1 drop) was added and the reaction mixture was stirred at 0° C. for 0.5 hours. At which point the reaction was concentrated under reduced pressure to a residue, then resuspended in dichloromethane and cooled to 0° C. in an ice bath, CS2 (1 mL) was added and AlCl3 (4 g, 15 mmol) was added slowly. The reaction mixture was then allowed to warm to room temperature and stirred over night. Ice chips and water (250 mL) were added and stirred. Concentrated hydrogen chloride was added until pH of 2, and extracted with dichloromethane (3×150 mL). Organics were combined, washed with brine (1×100 mL) and water (1×100 mL), dried (sodium sulfate), and concentrated to a yellow solid. The solid was purified by flash column chromatography on 100 g silica gel, eluting 10% ethyl acetate in hexanes to give 6-fluoro-2,3-dihydro-4H-1-benzothiopyran-4-one (2.55 g, 93%). 1H NMR (CDCl3, 300 MHz): δ 7.80-7.76 (m, 1H), 7.27-7.23 (m, 2H), 7.15-7.09 (m, 1H), 3.23 (t, 2H, J=6.4 Hz), 2.97 (t, 2H, J=6.4 Hz) ppm.

출처