Ethanol → Ethyl 2,4,5-trifluoro-3-methylbenzoate

HRID 729365Notes

Reaction equation

HRID 729365 reaction equation
[CH3:1][C:2]1[C:3]([F:13])=[C:4]([CH:8]=[C:9]([F:12])[C:10]=1[F:11])[C:5]([OH:7])=[O:6].[C:14](Cl)(=O)[C:15](Cl)=O.C(O)C.C([O-])(O)=O.[Na+]>ClCCl.CN(C)C=O>[CH2:14]([O:6][C:5](=[O:7])[C:4]1[CH:8]=[C:9]([F:12])[C:10]([F:11])=[C:2]([CH3:1])[C:3]=1[F:13])[CH3:15]

Participants

7

Reactant 4

HCID 702EthanolHCID 65578Oxalyl chlorideHCID 516892Sodium BicarbonateHCID 118055142,4,5-Trifluoro-3-methylbenzoic acid

Product 1

HCID 21220461Ethyl 2,4,5-trifluoro-3-methylbenzoateYield 77.1%

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideCatalystHCID 6344DichloromethaneSolvent

Procedure

A solution of 3-methyl-2,4,5-trifluorobenzoic acid (Shimizu T., Asai T., Kumai S., Jpn. Kokai Tokkyo Koho (1997) Japanese Appl. JP 95-219069, 4.3 g, 22.6 mmol) in dichloromethane (100 mL) at 0° C. is treated with oxalyl chloride (4.2 g, 33 mmol) followed by N,N-dimethylformamide (2 drops). The mixture is stirred at room temperature for 3 hours, concentrated and dried in vacuo. The acid chloride is diluted with dichloromethane, cooled to 0° C., and treated with absolute ethanol (10 mL, 170 mmol). The resulting solution is stirred at room temperature for 20 hours, poured into saturated NaHCO3 solution and extracted with dichloromethane. The organic extracts are washed with brine, dried over Na2SO4, filtered, and concentrated under vacuum to afford the title compound (3.8 g). 1H NMR (200 MHz, CDCl3): δ 7.67-7.26 (m, 1H), 4.44 (q, 2H), 2.27 (dd, 3H), 1.42 (t, 3H).

Workup

  1. concentrationconcentrated
  2. customdried in vacuo
  3. additionThe acid chloride is diluted with dichloromethane
  4. temperaturecooled to 0° C.
  5. stirringThe resulting solution is stirred at room temperature for 20 hours
  6. extractionextracted with dichloromethane
  7. washThe organic extracts are washed with brine
  8. dry with materialdried over Na2SO4
  9. filtrationfiltered
  10. concentrationconcentrated under vacuum

Sources & evidence

ORD record
ord-7ab4028772ad4a0c9556c22f3dd8e534
Source dataset
uspto-grants-2009_09
Patent number
US07582627B2

Reaction notes

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