Methyl iodide → 2,2-Bis(4-chlorophenyl)propanoic acid

HRID 2078122Notes

Reaction equation

HRID 2078122 reaction equation
[H-].[Na+].[Cl:3][C:4]1[CH:9]=[CH:8][C:7]([CH:10]([C:16]2[CH:21]=[CH:20][C:19]([Cl:22])=[CH:18][CH:17]=2)[C:11]([O:13]CC)=[O:12])=[CH:6][CH:5]=1.[CH3:23]I>CN(C=O)C.CCOC(C)=O>[Cl:22][C:19]1[CH:18]=[CH:17][C:16]([C:10]([C:7]2[CH:8]=[CH:9][C:4]([Cl:3])=[CH:5][CH:6]=2)([CH3:23])[C:11]([OH:13])=[O:12])=[CH:21][CH:20]=1

Participants

6

Reactant 3

HCID 6328Methyl iodideHCID 24758Sodium hydrideHCID 101291Benzeneacetic acid, 4-chloro-alpha-(4-chlorophenyl)-, ethyl ester

Product 1

HCID 135116882,2-Bis(4-chlorophenyl)propanoic acidYield 57.4%

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideSolvent2×HCID 8857Ethyl AcetateSolvent

Conditions

Temperature
0 °C

Procedure

A solution of NaH (60% dispersion in mineral oil) (2.1 g, 53 mmol) in DMF (100 mL) in a 500 mL round bottom flask was cooled 0° C. A solution of ethyl 2,2-bis(4-chlorophenyl)acetate (5.47 g, 18 mmol) and MeI (3.3 mL, 53 mmol) in DMF (50 mL) was added dropwise over 15 minutes. The mixture was stirred at 0° C. for 15 minutes and then allowed to warm to room temperature and stirred for 20 hours. A mixture of products was observed by LC/MS. The solution was diluted with EtOAc (200 mL), and then washed with 10% HCl(aq) (200 mL), with deionized water (200 mL), and then with brine (100 mL). The organic layer was dried over MgSO4, concentrated, and dried in vacuo to give 10.11 g crude product which was purified by flash column chromatography (silica, 0-100%, hexane/EtOAc) to give 2,2-bis(4-chlorophenyl)propanoic acid (3.05 g).

Workup

  1. temperatureto warm to room temperature
  2. stirringstirred for 20 hours
  3. additionA mixture of products
  4. washwashed with 10% HCl(aq) (200 mL), with deionized water (200 mL)
  5. dry with materialThe organic layer was dried over MgSO4
  6. concentrationconcentrated
  7. customdried in vacuo
  8. customto give 10.11 g crude product which
  9. customwas purified by flash column chromatography (silica, 0-100%, hexane/EtOAc)

Sources & evidence

ORD record
ord-e074ad44141243b4b7d62b7b70f6bbbc
Source dataset
uspto-grants-2011_04
Patent number
US07928139B2

Reaction notes

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