Methacryloyl chloride → 1,1,1-Trifluoro-2-trifluoromethyl-2-hydroxy-5-pentyl methacrylate

HRID 393128

Reaction equation

HRID 393128 reaction equation
C([Li])CCC.[F:6][C:7]([F:19])([F:18])[C:8]([C:14]([F:17])([F:16])[F:15])([OH:13])[CH2:9][CH2:10][CH2:11][OH:12].[C:20](Cl)(=[O:24])[C:21]([CH3:23])=[CH2:22]>C1COCC1.C(OCC)C>[C:20]([O:12][CH2:11][CH2:10][CH2:9][C:8]([C:14]([F:15])([F:16])[F:17])([OH:13])[C:7]([F:18])([F:19])[F:6])(=[O:24])[C:21]([CH3:23])=[CH2:22]

Participants

6

Reactant 3

HCID 13528Methacryloyl chlorideHCID 218953625,5,5-Trifluoro-4-(trifluoromethyl)pentane-1,4-diolHCID 178418339Butyllithium

Product 1

HCID 235303631,1,1-Trifluoro-2-trifluoromethyl-2-hydroxy-5-pentyl methacrylateYield 79%

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolvent2×

Procedure

To a 3-necked, 2-L round-bottomed flask equipped with an overhead stirrer, digital thermometer and a 1-L constant-pressure addition funnel with a nitrogen inlet was added 590 mL (0.944 mol) of n-butyllithium (1.6M in hexane). The addition funnel was charged with a solution of 107 g (0.47 mol) of 1,1,1-trifluoro-2-trifluoromethyl-2,5-pentanediol in 300 mL of anhydrous THF. The flask was cooled and the diol was added dropwise with stirring while maintaining a temperature below 15° C. The resulting yellow-orange solution was stirred for an additional 2 hours at which time a solution of 54.5 g (0.52 mol) of methacryloyl chloride in 200 mL of anhydrous THF was added dropwise over 1 h at 10° C. The reaction mixture was allowed to reach room temperature overnight after which it was diluted with 500 mL of diethylether and washed with 2×500 mL of saturated ammonium chloride and brine, dried over MgSO4, evaporated and distilled at 74° C. at 1.0 mm Hg (0.5 g of phenothiazine was added to the pot prior to distillation) to yield 109 g (79%) of the title compound.

Workup

  1. temperatureThe flask was cooled
  2. temperaturewhile maintaining a temperature below 15° C
  3. additionwas added dropwise over 1 h at 10° C
  4. washwashed with 2×500 mL of saturated ammonium chloride and brine
  5. dry with materialdried over MgSO4
  6. customevaporated
  7. distillationdistilled at 74° C. at 1.0 mm Hg (0.5 g of phenothiazine
  8. additionwas added to the pot prior
  9. distillationto distillation)

Sources & evidence

ORD record
ord-becb737b2b8b43fc982319ca00036bab
Source dataset
uspto-grants-2004_10
Patent number
US06806026B2

Linked notes

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