Carbon Dioxide → 2-(4-(4-Chlorobutanoyl)phenyl)-2-methylpropanoic acid

HRID 1836782Notes

Reaction equation

HRID 1836782 reaction equation
[Mg].[C:2](=[O:4])=[O:3].Cl.Br[C:7]([C:10]1[CH:15]=[CH:14][C:13]([C:16](=[O:21])[CH2:17][CH2:18][CH2:19][Cl:20])=[CH:12][CH:11]=1)([CH3:9])[CH3:8].ClC(C1C=CC(C(=O)CCCCl)=CC=1)(C)C>C(#N)C.[Br-].C([N+](CC)(CC)CC)C.[Ag]>[Cl:20][CH2:19][CH2:18][CH2:17][C:16]([C:13]1[CH:12]=[CH:11][C:10]([C:7]([CH3:9])([CH3:8])[C:2]([OH:4])=[O:3])=[CH:15][CH:14]=1)=[O:21]

Participants

9

Reactant 5

HCID 280Carbon Dioxide2×HCID 313Hydrochloric AcidHCID 5462224MagnesiumHCID 100635791-Butanone, 1-[4-(1-bromo-1-methylethyl)phenyl]-4-chloro-HCID 234998621-[4-(1-Chloro-1-methyl-ethyl)-phenyl)-4-chloro-butan-1-one

Product 1

HCID 109235672-(4-(4-Chlorobutanoyl)phenyl)-2-methylpropanoic acidYield 66%

Reagents, catalysts & solvents 3

HCID 6285Tetraethylammonium BromideCatalystHCID 23954SilverCatalystHCID 6342AcetonitrileSolvent

Procedure

Fit a jacketed glass cell of about 50 mL capacity with an expanded silver mesh cathode (14 cm2 geometric area), a roughly concentric magnesium sacrificial anode, a tube to deliver carbon dioxide gas and a magnetic stir bar. Add a solution of hydrogen chloride remediated 1-[4-(1-bromo-1-methyl-ethyl)-phenyl]-4-chloro-butan-1-one and 1-[4-(1-chloro-1-methyl-ethyl)-phenyl]-4-chloro-butan-1-one (2.79 g, 89 mole %, 3:1 ratio of tertiary benzylic bromide to tertiary benzylic chloride by NMR, approximately 8.6 mmol total active tertiary benzylic halide) in acetonitrile (45 mL) and tetraethylammonium bromide (0.19 g). Close the cell and cool to −10° C. with a continuous carbon dioxide sparge for 169 minutes at an average current density of 13 mA cm−2. Warm to contents of the cell to ambient temperature, drain the contents, acidify with chilled aqueous 6M hydrochloric acid, extract and evaporate the solvent in vacuo to give the title compound (1.53 g, 66%).

Workup

  1. customClose the cell
  2. customsparge for 169 minutes at an average current density of 13 mA cm−2
  3. extractionextract
  4. customevaporate the solvent in vacuo

Sources & evidence

ORD record
ord-aed71ad8f2544e708e1839353d2d704c
Source dataset
uspto-grants-2004_08
Patent number
US06777555B2

Reaction notes

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