Hydrochloric Acid → Ethyl 3-(4'-chlorobiphenyl-4-yl)-3-oxopropionate

HRID 1820853Notes

Reaction equation

HRID 1820853 reaction equation
[C:1]([O:7][CH2:8][CH3:9])(=[O:6])[CH2:2][C:3]([O-:5])=O.C([Li])CCC.[Cl:15][C:16]1[CH:21]=[CH:20][C:19]([C:22]2[CH:27]=[CH:26][C:25](C(Cl)=O)=[CH:24][CH:23]=2)=[CH:18][CH:17]=1.Cl>C1COCC1>[Cl:15][C:16]1[CH:17]=[CH:18][C:19]([C:22]2[CH:27]=[CH:26][C:25]([C:3](=[O:5])[CH2:2][C:1]([O:7][CH2:8][CH3:9])=[O:6])=[CH:24][CH:23]=2)=[CH:20][CH:21]=1

Participants

6

Reactant 4

HCID 313Hydrochloric AcidHCID 3595298Propanedioic acid, monoethyl esterHCID 98348144'-Chlorobiphenyl-4-carbonyl chlorideHCID 178418339Butyllithium

Product 1

HCID 57892092Ethyl 3-(4'-chlorobiphenyl-4-yl)-3-oxopropionate

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
-65 °C

Procedure

4.29 g (32.5 mmol) of monoethyl malonate is dissolved in 100 mL of THF and 42.3 mL (67.7 mmol) of butyllithium solution (1.6N in hexane) is added dropwise at −60° C. The temperature is allowed to come up to −15° C., then the mixture is cooled again to −65° C. and 3.40 g (13.5 mmol) of 4′-chlorobiphenyl-4-carboxylic acid chloride (for preparation see Gazz. Chim. Ital. 1949, 79, 453.) in 30 mL of THF is added dropwise. The mixture is kept for 5 minutes at −65° C., then heated for 2 hours to ambient temperature. The mixture is poured onto 50 mL of 1N hydrochloric acid, extracted with 300 mL of diethyl ether, and the organic phase is washed with saturated sodium hydrogen carbonate solution and water and finally dried over sodium sulfate. The solvent is eliminated, the residue is recrystallized from petroleum ether and the product is dried in vacuo. Yield: 3.10 g (76% of theory); Rf value: 0.60 (silica gel, petroleum ether/ethyl acetate=5:2); m.p. 45° C.-50° C.; C17H15ClO3; EII mass spectrum: m/z=303/305 [M+H]+.

Workup

  1. customto come up to −15° C.
  2. temperatureheated for 2 hours to ambient temperature
  3. extractionextracted with 300 mL of diethyl ether
  4. washthe organic phase is washed with saturated sodium hydrogen carbonate solution and water
  5. dry with materialfinally dried over sodium sulfate
  6. customthe residue is recrystallized from petroleum ether
  7. customthe product is dried in vacuo

Sources & evidence

ORD record
ord-2c4460cc02c148a684aa9d853e8dc740
Source dataset
uspto-grants-2009_10
Patent number
US07605176B2

Reaction notes

Loading…