Hydrochloric Acid → 1H-Indene-2-carboxylic acid, 5-chloro-2,3-dihydro-1-oxo-, methyl ester

HRID 1272574Notes

Reaction equation

HRID 1272574 reaction equation
[Cl-].[Al+3].[Cl-].[Cl-].Cl[C:6]([CH:8]([CH2:13][C:14]1[CH:19]=[CH:18][CH:17]=[C:16]([Cl:20])[CH:15]=1)[C:9]([O:11][CH3:12])=[O:10])=[O:7].Cl>ClCCCl>[Cl:20][C:16]1[CH:15]=[C:14]2[C:19](=[CH:18][CH:17]=1)[C:6](=[O:7])[CH:8]([C:9]([O:11][CH3:12])=[O:10])[CH2:13]2

Participants

5

Reactant 3

HCID 313Hydrochloric AcidHCID 6451240Aluminum(III) ChlorideHCID 11694578HCID 11694578, compound

Product 1

HCID 110423911H-Indene-2-carboxylic acid, 5-chloro-2,3-dihydro-1-oxo-, methyl esterYield 75.9%

Reagents, catalysts & solvents 1

HCID 111,2-DichloroethaneSolvent2×

Conditions

Temperature
0 °C

Procedure

Under nitrogen atmosphere, 9.0 g of anhydrous aluminum chloride and 151.3 g of 1,2-dichloroethane were stirred to yield a suspension, and the suspension was cooled to 0° C. A mixture of 7.98 g of methyl 2-chloroformyl-3-(3-chlorophenyl)-propionate prepared in Referential Example 1 and 151.3 g of 1,2-dichloroethane was added dropwise to the suspension while maintaining the temperature at 5° C. or below, followed by stirring under the same condition for 2 hours. The reaction mixture was added dropwise to 53.6 g of 1.7 percent by weight hydrochloric acid cooled to 5° C. or below, followed by stirring under the same condition for 1 hour. After separating the mixture into a 1,2-dichloroethane layer and an aqueous layer, the product in the aqueous layer was extracted with 15.1 g of 1,2-dichloroethane. This procedure was repeated a total of two times. The resulting 1,2-dichloroethane layers obtained by these procedures were collected and were washed with 33.0 g of water, followed by removal of 1,2-dichloroethane under reduced pressure. The concentrated residue was purified by silica gel column chromatography [mobile phase: hexane/ethyl acetate=4/1 (by volume)] to yield 5.21 g of methyl 5-chloro-1-oxo-2,3-dihydroindene-2-carboxylate as a beige solid in a yield of 70% on the basis of 3-(3-chlorophenyl)-2-methoxycarbonylpropionic acid.

Workup

  1. customto yield a suspension
  2. additionwas added dropwise to the suspension
  3. temperaturewhile maintaining the temperature at 5° C. or below
  4. temperaturecooled to 5° C. or below
  5. stirringby stirring under the same condition for 1 hour
  6. customAfter separating the mixture into a 1,2-dichloroethane layer
  7. extractionan aqueous layer, the product in the aqueous layer was extracted with 15.1 g of 1,2-dichloroethane
  8. customThe resulting 1,2-dichloroethane layers obtained by these procedures
  9. customwere collected
  10. washwere washed with 33.0 g of water
  11. customfollowed by removal of 1,2-dichloroethane under reduced pressure
  12. customThe concentrated residue was purified by silica gel column chromatography [mobile phase: hexane/ethyl acetate=4/1 (by volume)]

Sources & evidence

ORD record
ord-53e3566690ae452587be7c4d6ddd502a
Source dataset
uspto-grants-2007_04
Patent number
US07208621B2

Reaction notes

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