Chloroform → 1-Ethoxycarbonyl-1,1-difluoro-2-butyl methacrylate

HRID 1182643Notes

Reaction equation

HRID 1182643 reaction equation
[CH2:1]([O:3][C:4](=[O:12])[C:5]([F:11])([F:10])[CH:6]([OH:9])[CH2:7][CH3:8])[CH3:2].C(Cl)(Cl)Cl.[C:17](Cl)(=[O:21])[C:18]([CH3:20])=[CH2:19].C(N(CC)CC)C>O>[CH2:1]([O:3][C:4]([C:5]([F:11])([F:10])[CH:6]([O:9][C:17](=[O:21])[C:18]([CH3:20])=[CH2:19])[CH2:7][CH3:8])=[O:12])[CH3:2]

Participants

6

Reactant 4

HCID 6212ChloroformHCID 8471TriethylamineHCID 13528Methacryloyl chlorideHCID 59863825Ethyl 2,2-difluoro-3-hydroxypentanoate

Product 1

HCID 598638611-Ethoxycarbonyl-1,1-difluoro-2-butyl methacrylateYield 66%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Conditions

Temperature
55 °C

Procedure

A 300 mL reactor was charged with 18.0 g (98.4 mmol) of 2,2-difluoro-3-hydroxypentanoic acid ethyl ester, 78 g of chloroform, 120 mg of an antioxidant NONFLEX MBP (a product of Seiko Chemical Co., Ltd.), 12.4 g (118.8 mmol/1.2 equivalents) of methacrylic acid chloride, and 15.0 g (148.8 mmol/1.5 equivalents) of triethylamine, followed by stirring at 55° C. for 4 hours. Then, 120 g of water was added, followed by extraction with chloroform one time. The obtained organic layer was washed with diluted hydrochloric acid and water, followed by removing water with magnesium sulfate, conducting a filtration, and distilling chloroform out, thereby obtaining 24.7 g of the target methacrylic acid 1-ethoxycarbonyl-1,1-difluoro-2-butyl ester. Upon this, purity was 66%, and yield was 66%.

Workup

  1. extractionfollowed by extraction with chloroform one time
  2. washThe obtained organic layer was washed with diluted hydrochloric acid and water
  3. customby removing water with magnesium sulfate
  4. filtrationa filtration
  5. distillationdistilling chloroform out

Sources & evidence

ORD record
ord-02c45156ab084297b6e0ef17e1bf81ff
Source dataset
uspto-grants-2014_03
Patent number
US08663903B2

Reaction notes

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