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

HRID 504978

反応式

HRID 504978 の反応式
[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]

参加物

4

反応物 2

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

生成物 1

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

試薬・触媒・溶媒 1

HCID 6344Dichloromethane溶媒

実験手順

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).

後処理

  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)

出典と根拠

ORDレコード
ord-b53c55cc724240548946abbe5b82f917
出典データセット
uspto-grants-2010_08
特許番号
US07781157B2

関連ノート

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