반응 #9379

반응 방정식

AlCl3

Thionyl chloride

2,3-dichloro-benzoic acid

benzene

→

6,7-dichloro-1-indanone

수율 80.0%

용매

dichloroethane

반응 조건

후처리

1. 1
   온도to reflux until no more gas evolution
2. 2
   농축was concentrated
3. 3
   workup.ADDITIONThe concentrate was diluted with dichloroethane
4. 4
   기타Ethylene was bubbled through the mixture for 4 h
5. 5
   기타quenched with 4 N HCl
6. 6
   기타The resulting layers were separated
7. 7
   추출the aqueous layer was extracted with Et2O (3×250 mL)
8. 8
   세척The combined organic extracts were washed with H2O (3×150 mL), saturated NaHCO3 (3×150 mL), brine (1×150 mL)
9. 9
   건조dried over MgSO4
10. 10
    농축concentrated
11. 11
    workup.ADDITIONThe concentrate was added to a slurry of AlCl3 (9.0 g) and NaCl (2.4 g) at 130° C
12. 12
    workup.STIRRINGThe resulting mixture was stirred at 180° C. for 2 hours after which it
13. 13
    온도was cooled to room temperature
14. 14
    기타quenched with ice
15. 15
    추출The mixture was extracted with CH2Cl2 (3×500 mL)
16. 16
    농축the combined organic extracts were concentrated
17. 17
    기타purified by column chromatography

실험 절차

Thionyl chloride (5.73 mL, ˜79 mmol) and 2,3-dichloro-benzoic acid (commercially available from Aldrich) (10.0 g, 52.4 mmol) in benzene was heated to reflux until no more gas evolution was observed. After cooling to rt the mixture was concentrated. The concentrate was diluted with dichloroethane and added to AlCl3 (7.0 g, ˜53 mmol) in dichloroethane at 10–20° C. Ethylene was bubbled through the mixture for 4 h. The mixture was stirred overnight and quenched with 4 N HCl. The resulting layers were separated and the aqueous layer was extracted with Et2O (3×250 mL). The combined organic extracts were washed with H2O (3×150 mL), saturated NaHCO3 (3×150 mL), brine (1×150 mL), dried over MgSO4 and concentrated. The concentrate was added to a slurry of AlCl3 (9.0 g) and NaCl (2.4 g) at 130° C. The resulting mixture was stirred at 180° C. for 2 hours after which it was cooled to room temperature and quenched with ice followed by concentrated HCl. The mixture was extracted with CH2Cl2 (3×500 mL) and the combined organic extracts were concentrated and purified by column chromatography using 20% EtOAc:hexane eluant to give 6.8 g (80%) of 6,7-dichloro-1-indanone. Use of 6,7-dichloro-indan-1-one in Method NINETEEN produced 4-(4,5-dichloro-indan-2-yl)-1,3-dihydro-imidazole-2-thione (Compound 153).

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