Chloromethyl Methyl Ether → 4-[1-(Trifluoromethyl)-1-(methoxymethoxy)-2,2,2-trifluoroethyl]styrene

HRID 1007061Notes

Reaction equation

HRID 1007061 reaction equation
[F:1][C:2]([F:18])([F:17])[C:3]([C:9]1[CH:14]=[CH:13][C:12]([CH:15]=[CH2:16])=[CH:11][CH:10]=1)([OH:8])[C:4]([F:7])([F:6])[F:5].[H-].[Na+].[CH3:21][O:22][CH2:23]Cl>C1COCC1>[F:1][C:2]([F:17])([F:18])[C:3]([C:9]1[CH:14]=[CH:13][C:12]([CH:15]=[CH2:16])=[CH:11][CH:10]=1)([O:8][CH2:21][O:22][CH3:23])[C:4]([F:6])([F:5])[F:7]

Participants

5

Reactant 3

HCID 7864Chloromethyl Methyl EtherHCID 24758Sodium hydrideHCID 27823772-(4-Ethenylphenyl)-1,1,1,3,3,3-hexafluoropropan-2-ol

Product 1

HCID 225064894-[1-(Trifluoromethyl)-1-(methoxymethoxy)-2,2,2-trifluoroethyl]styreneYield 34%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

A solution of 1,1,1,3,3,3-hexafluoro-2-(4-vinylphenyl)-2-propanol (5.00 g, 18.51 mmol) in THF (10 mL)was slowly added to a mixture of NaH (60% dispersion, 968 mg, 24.20 mmol), washed with pentane, and THF (50 mL). The reaction mixture was allowed to stir at room temperature for 1 h, then cooled to −78° C. using a dry ice/acetone bath followed by the addition of chloromethyl methyl ether (1.50 mL, 19.75 mmol) in THF (5 mL). The reaction mixture was allowed to slowly warm to room temperature overnight, quenched with H2O, concentrated, and partitioned between ether/H2O. The combined extracts were washed with saturated NaHCO3, brine, dried (Na2SO4), and concentrated to provide a crude oil. This material was purified by Kugelrohr distillation (bp 65-9° C., 1.3 mm), followed by column chromatography on silica gel using 50:1 hexane/ethyl acetate to provide 1.96 g (34%) of a colorless oil; 1H NMR (CDCl3) δ 7.60 (d, 2ArH), 7.50 (d, 2ArH), 6.75 (dd, CH=), 5.85 (dd ═CHH), 5.40 (dd ═CHH), 4.85 (s, CH2), 3.60 (s, Me).

Workup

  1. washwashed with pentane, and THF (50 mL)
  2. temperaturecooled to −78° C.
  3. temperatureto slowly warm to room temperature overnight
  4. customquenched with H2O
  5. concentrationconcentrated
  6. custompartitioned between ether/H2O
  7. washThe combined extracts were washed with saturated NaHCO3, brine
  8. dry with materialdried (Na2SO4)
  9. concentrationconcentrated
  10. customto provide a crude oil
  11. distillationThis material was purified by Kugelrohr distillation (bp 65-9° C., 1.3 mm)

Sources & evidence

ORD record
ord-9efe96659a194abea14d9aecb105d3b4
Source dataset
uspto-grants-2004_09
Patent number
US06794109B2

Reaction notes

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