Hydrochloric Acid → 2,2,2-Trifluoroethyl-2,2-difluoro-3-(methacryloyloxy)pentanoate

HRID 1776001Notes

Reaction equation

HRID 1776001 reaction equation
[F:1][C:2]([F:15])([CH:6]([O:9][C:10](=[O:14])[C:11]([CH3:13])=[CH2:12])[CH2:7][CH3:8])[C:3]([OH:5])=[O:4].C1CCC(N=C=NC2CCCCC2)CC1.[F:31][C:32]([F:36])([F:35])[CH2:33]O.Cl>ClCCl.CN(C1C=CN=CC=1)C>[F:31][C:32]([F:36])([F:35])[CH2:33][O:4][C:3](=[O:5])[C:2]([F:15])([F:1])[CH:6]([O:9][C:10](=[O:14])[C:11]([CH3:13])=[CH2:12])[CH2:7][CH3:8]

Participants

7

Reactant 4

HCID 313Hydrochloric AcidHCID 64092,2,2-TrifluoroethanolHCID 10868DicyclohexylcarbodiimideHCID 584134402,2-Difluoro-3-(methacryloyloxy)pentanoic acid

Product 1

HCID 594826902,2,2-Trifluoroethyl-2,2-difluoro-3-(methacryloyloxy)pentanoateYield 71%

Reagents, catalysts & solvents 2

HCID 142844-(Dimethylamino)pyridineCatalystHCID 6344DichloromethaneSolvent2×

Procedure

After a reaction vessel which had been sufficiently dried inside by vacuum heating was replaced with dry nitrogen, 100 mL of a solution of 22.22 g (0.1 mol) of 2,2-difluoro-3-(methacryloyloxy)pentanoic acid in dichloromethane was added into the reaction vessel, and the mixture was cooled to an ice temperature. Thereto was added 100 mL of a solution of 22.70 g (0.11 mol) of DCC in dichloromethane over 10 min, and 0.61 g (5 mmol) of DMAP and 10.40 g (0.105 mol) of 2,2,2-trifluoroethanol were further added. Thereafter, the temperature of the reaction vessel was elevated to the room temperature, followed by stirring the mixture for 2 hrs, and 300 g of 1 N aqueous hydrochloric acid was added while intimately stirring. Subsequently, dichloromethane was separated by a separatory funnel, and the aqueous layer was extracted again with dichloromethane to obtain an extraction liquid. After the extraction liquid was combined with the dichloromethane layer and washed with 1 N aqueous hydrochloric acid, the solvent of the dichloromethane layer was distilled off with an evaporator, followed by purification by column chromatography to give 21.60 g of 2,2,2-trifluoroethyl-2,2-difluoro-3-(methacryloyloxy)pentanoate (M-5) (yield: 71%).

Workup

  1. customAfter a reaction vessel which had been sufficiently dried inside by vacuum
  2. temperatureheating
  3. additionwas added into the reaction vessel
  4. customwas elevated to the room temperature
  5. stirringwhile intimately stirring
  6. customSubsequently, dichloromethane was separated by a separatory funnel
  7. extractionthe aqueous layer was extracted again with dichloromethane
  8. customto obtain
  9. extractionan extraction liquid
  10. extractionAfter the extraction liquid
  11. washwashed with 1 N aqueous hydrochloric acid
  12. distillationthe solvent of the dichloromethane layer was distilled off with an evaporator
  13. customfollowed by purification by column chromatography

Sources & evidence

ORD record
ord-e195577f1e124236b8c7ea3029eb1677
Source dataset
uspto-grants-2016_02
Patent number
US09261780B2

Reaction notes

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