Methyl Acrylate → E-methyl 6,6,6-trifluoro-5-hydroxy-5-(trifluoromethyl)hex-2-enoate

HRID 504978

반응식

HRID 504978 반응식
[C:1]([O:5][CH3:6])(=[O:4])[CH:2]=[CH2:3].[F:7][C:8]([F:19])([F:18])[C:9]([C:14]([F:17])([F:16])[F:15])([OH:13])[CH2:10]C=C>ClCCl>[F:7][C:8]([F:18])([F:19])[C:9]([OH:13])([C:14]([F:16])([F:15])[F:17])[CH2:10]/[CH:3]=[CH:2]/[C:1]([O:5][CH3:6])=[O:4]

참가 물질

4

반응물 2

HCID 7294Methyl AcrylateHCID 3288704-Penten-2-ol, 1,1,1-trifluoro-2-(trifluoromethyl)-

생성물 1

HCID 59429090E-methyl 6,6,6-trifluoro-5-hydroxy-5-(trifluoromethyl)hex-2-enoate수율 65.3%

시약·촉매·용매 1

HCID 6344Dichloromethane용매

실험 절차

To a 250 mL 3 neck roundbottom flask with reflux condenser and Teflon-coated magnetic stir bar was added methyl acrylate (9.10 g, 105.7 mmol, 1.1 eq.), 1,1,1-trifluoro-2-trifluoromethyl-pent-4-ene-2-ol (20 g, 96.1 mmol, 1 eq.) and 100 mL of anhydrous dichloromethane. The solution was heated to reflux under nitrogen and 300 mg of the Hoveyda-Grubbs 2nd generation ruthenium metathesis catalyst (0.048 mmol, 0.005 eq.) was added in 4 portions over 4 hours. The reaction was heated an additional 12 hours after which the product was purified by vacuum distillation (65° C., 6 Torr) and column chromatography (silica gel, 80:20 hexane:ethyl acetate eluent) to afford 16.7 g of methyl 6,6,6-trifluoro-5-hydroxy-5-(trifluoromethyl)hex-2-enoate (I) as colorless liquid (E/Z=2.15:1) contaminated with a small amount (0.15 eq.) of 1,1,1,8,8,8-hexafluoro-2,7-di(trifluoromethyl)-oct-4-ene-2,7-diol (E/Z=6.7:1).

후처리

  1. temperatureThe solution was heated
  2. temperatureto reflux under nitrogen
  3. temperatureThe reaction was heated an additional 12 hours after which the product
  4. distillationwas purified by vacuum distillation (65° C., 6 Torr) and column chromatography (silica gel, 80:20 hexane:ethyl acetate eluent)

출처 및 근거

ORD 기록
ord-b53c55cc724240548946abbe5b82f917
출처 데이터셋
uspto-grants-2010_08
특허 번호
US07781157B2

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