1-Butanol → Methacrylic acid 1-(n-butoxycarbonyl)-1,1-difluoro-2-butyl ester

HRID 2360534Notes

Reaction equation

HRID 2360534 reaction equation
[CH2:1]([OH:5])[CH2:2][CH2:3][CH3:4].C(OC(C)C)(C)C.C(N(CC)CC)C.Cl[C:21]([C:23]([F:34])([F:33])[CH:24]([O:27][C:28](=[O:32])[C:29]([CH3:31])=[CH2:30])[CH2:25][CH3:26])=[O:22]>>[CH2:1]([O:5][C:21]([C:23]([F:33])([F:34])[CH:24]([O:27][C:28](=[O:32])[C:29]([CH3:31])=[CH2:30])[CH2:25][CH3:26])=[O:22])[CH2:2][CH2:3][CH3:4]

Participants

5

Reactant 4

HCID 2631-ButanolHCID 7914Diisopropyl EtherHCID 8471TriethylamineHCID 58352381Methacrylic acid 1-chlorocarbonyl-1,1-difluoro-2-butyl ester

Product 1

HCID 86663489Methacrylic acid 1-(n-butoxycarbonyl)-1,1-difluoro-2-butyl esterYield 91.1%

Conditions

Temperature
0 °C

Procedure

Into a 1 L glass flask with a dropping funnel, 62.8 g (0.847 mol, 1.2 eq) of n-butanol, 510 g of diisopropyl ether, 100 g (0.988 mol, 1.4 eq) of triethylamine and 1 g of antioxidant “Nonflex MBP” (manufactured by Seiko Chemical Co., Ltd.) were added. The resulting solution was cooled to 0° C. and stirred, followed by dropping thereto 170 g (purity: 99%, 0.706 mol) of methacrylic acid 1-chlorocarbonyl-1,1-difluoro-2-butyl ester. The thus-obtained reaction solution was stirred for 1 hour at room temperature. The completion of the reaction was confirmed by 19F NMR. The reaction-completed solution was separated into an organic layer and an aqueous layer by the addition of 500 mL of water. The organic layer was dehydrated with magnesium sulfate, filtrated, and then, concentrated under a reduced pressure. The concentration residue was subjected to distillation under a reduced pressure. With this, 179 g of methacrylic acid 1-(n-butoxycarbonyl)-1,1-difluoro-2-butyl ester was obtained as a colorless transparent liquid (yield: 91%, purity: 99%).

Workup

  1. addition” (manufactured by Seiko Chemical Co., Ltd.) were added
  2. customThe thus-obtained reaction solution
  3. stirringwas stirred for 1 hour at room temperature
  4. customThe reaction-completed solution was separated into an organic layer
  5. additionan aqueous layer by the addition of 500 mL of water
  6. filtrationfiltrated
  7. concentrationconcentrated under a reduced pressure
  8. distillationThe concentration residue was subjected to distillation under a reduced pressure

Sources & evidence

ORD record
ord-61770f73d3f64fcdbd3f75849c83f717
Source dataset
uspto-grants-2014_04
Patent number
US08686098B2

Reaction notes

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