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Chloromethyl Methyl Ether → 1-(Methoxymethyl)oxycarbonyl-1,1-difluoro-2-butyl methacrylate

HRID 2047953
Notes
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Reaction equation

HRID 2047953 reaction equation
[C:1]([O:6][CH:7]([CH2:14][CH3:15])[C:8]([C:11]([OH:13])=[O:12])([F:10])[F:9])(=[O:5])[C:2]([CH3:4])=[CH2:3].C1[CH2:20][O:19][CH2:18]C1.COCCl>O>[C:1]([O:6][CH:7]([CH2:14][CH3:15])[C:8]([C:11]([O:13][CH2:18][O:19][CH3:20])=[O:12])([F:10])[F:9])(=[O:5])[C:2]([CH3:4])=[CH2:3]
ParticipantsConditionsProcedureWorkupSources & evidenceReaction notes

Participants

5

Reactant 3

HCID 7864Chloromethyl Methyl EtherHCID 8028TetrahydrofuranHCID 584134402,2-Difluoro-3-(methacryloyloxy)pentanoic acid

Product 1

HCID 598638321-(Methoxymethyl)oxycarbonyl-1,1-difluoro-2-butyl methacrylateYield 83%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Conditions

Temperature
0 °C

Procedure

Under nitrogen, a 20 mL reactor was charged with 70 mg (0.25 mmol) of 1-hydroxycarbonyl-1,1-difluoro-2-butyl methacrylate (purity: 78%) and 3 mL of THF (dehydrated one), followed by cooling to 0° C. Then, 65 μL (0.47 mmol, 1.9 eq) was added, followed by stirring at 0° C. for 10 min. Then, 30 μL (0.40 mmol, 1.6 eq) of chloromethyl methyl ether was added, followed by stirring at 0° C. for 20 min. Then, 5 mL of water was added to the reaction solution, followed by extraction with diisopropyl ether two times and removal of water with magnesium sulfate. After conducting filtration, diisopropyl ether was distilled off, thereby obtaining 58 mg of the target 1-(methoxymethyl)oxycarbonyl-1,1-difluoro-2-butyl methacrylate. Upon this, purity was 96%, and yield was 83%.

Workup

  1. additionThen, 65 μL (0.47 mmol, 1.9 eq) was added
  2. stirringby stirring at 0° C. for 20 min
  3. extractionfollowed by extraction with diisopropyl ether two times and removal of water with magnesium sulfate
  4. filtrationfiltration, diisopropyl ether
  5. distillationwas distilled off

Sources & evidence

ORD record
ord-b0b8664efa1940e492a87844a9c86306
Source dataset
uspto-grants-2013_11
DOI
10.6084/m9.figshare.5104873.v1
Patent number
US08592622B2

Reaction notes

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On this pageParticipantsConditionsProcedureWorkupSources & evidenceReaction notes