Hydrochloric Acid → tert-Butyl 2-(trifluoromethyl)acrylate

HRID 1454218Notes

Reaction equation

HRID 1454218 reaction equation
C(Cl)(=O)C(Cl)=O.[F:7][C:8]([F:15])([F:14])[C:9](=[CH2:13])[C:10]([OH:12])=[O:11].[C:16](O)([CH3:19])([CH3:18])[CH3:17].N1C=CC=CC=1.Cl>C(Cl)Cl>[F:7][C:8]([F:15])([F:14])[C:9](=[CH2:13])[C:10]([O:12][C:16]([CH3:19])([CH3:18])[CH3:17])=[O:11]

Participants

7

Reactant 5

HCID 313Hydrochloric AcidHCID 1049PyridineHCID 6386tert-ButanolHCID 65578Oxalyl chlorideHCID 5876942-(Trifluoromethyl)acrylic acid

Product 1

HCID 2782282tert-Butyl 2-(trifluoromethyl)acrylateYield 70%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Procedure

Oxalyl chloride (87.3 g, 0.68 mol) was added to a solution of TFMAA (15.0 g, 0.11 mol) in methylene chloride (90 mL) in a dropwise manner at room temperature under a nitrogen atmosphere. The solution was heated to reflux for 5 hours, and the solvent and excess reagent were removed on a rotary evaporator. The resulting acid chloride was added to a stirred solution consisting of t-butanol (44 g, 0.59 mmol) and pyridine (33.6 g, 0.42 mol) in dichloromethane at 0° C. over a 10 min period. After stirring overnight at room temperature, the solution was neutralized with diluted aqueous HCl and washed with saturated aqueous sodium bicarbonate. The organic phase was removed, and the aqueous phase was extracted with pentane. The combined organic solvents were reduced to a small volume by distillation and then the residue was chromatographed on a column of silica gel. The product was re-purified by distillation to give 14.0 g of TBTFMA as a colorless liquid (70%).

Workup

  1. temperatureThe solution was heated
  2. temperatureto reflux for 5 hours
  3. customthe solvent and excess reagent were removed on a rotary evaporator
  4. additionThe resulting acid chloride was added to a stirred solution
  5. washwashed with saturated aqueous sodium bicarbonate
  6. customThe organic phase was removed
  7. extractionthe aqueous phase was extracted with pentane
  8. distillationThe combined organic solvents were reduced to a small volume by distillation
  9. customthe residue was chromatographed on a column of silica gel
  10. distillationThe product was re-purified by distillation

Sources & evidence

ORD record
ord-51e3dce5f3194861a1bd66e786c0f98d
Source dataset
uspto-grants-2009_01
Patent number
US07479364B2

Reaction notes

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