Carbon Dioxide → (3-chlorobiphenyl-4-yl)propynoic Acid

HRID 735062Notes

Reaction equation

C([Li])CCC.[Cl:6][C:7]1[CH:8]=[C:9]([C:15]2[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=2)[CH:10]=[CH:11][C:12]=1[C:13]#[CH:14].[C:21](=[O:23])=[O:22]>C1COCC1>[Cl:6][C:7]1[CH:8]=[C:9]([C:15]2[CH:16]=[CH:17][CH:18]=[CH:19][CH:20]=2)[CH:10]=[CH:11][C:12]=1[C:13]#[C:14][C:21]([OH:23])=[O:22]

Participants

Conditions

Temperature: -60 °C

Procedure

13.8 mL (22.1 mmol) of butyllithium solution (1.6M in hexane) are added dropwise to a solution of 4.7 g (22.1 mmol) of 3-chloro-4-ethynylbiphenyl in 100 mL of absolute THF at −10° C. to −20° C. and after five minutes cooled to −60° C. At this temperature dry ice is added batchwise to the reaction mixture and it is slowly allowed to come up to ambient temperature. Then the solvent is evaporated down and the residue is extracted between ethyl acetate and 1M hydrochloric acid. The organic phase is dried, the desiccant filtered off, and the solvent concentrated by evaporation. The residue is stirred with petroleum ether, suction filtered, and dried at 80° C. in the circulating air dryer. Yield: 4.8 g (85% of theory); C15H9ClO2 (M=256.68); calc.: molecular ion peak (M+H)+: 257/259 (Cl); found: molecular ion peak (M+H)+: 257/259 (Cl); Rf value: 0.2 (silica gel, dichloromethane/methanol/glacial acetic acid (90:10:0.1)).

Workup

customto come up to ambient temperature
customThen the solvent is evaporated down
extractionthe residue is extracted between ethyl acetate and 1M hydrochloric acid
customThe organic phase is dried
filtrationthe desiccant filtered off
concentrationthe solvent concentrated by evaporation
filtrationfiltered
customdried at 80° C. in the circulating air dryer

Sources & evidence

ORD record: ord-44ccfb1e79d94df99b5ebd56eef428b5
Source dataset: uspto-grants-2009_09
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US07592373B2

Reaction notes

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