Hydrochloric Acid → 4-Hydroxy-4-trifluoromethyl-2,5-cyclohexadien-1-one

HRID 1085346ノート

反応式

HRID 1085346 の反応式
C([Si](CC)(CC)[O:4][C:5]1([C:12]([F:15])([F:14])[F:13])[CH:10]=[CH:9][C:8](=[O:11])[CH:7]=[CH:6]1)C.Cl.C(O)C>O>[OH:4][C:5]1([C:12]([F:13])([F:14])[F:15])[CH:6]=[CH:7][C:8](=[O:11])[CH:9]=[CH:10]1

参加物

5

反応物 3

HCID 313Hydrochloric AcidHCID 702EthanolHCID 143434944-Triethylsiloxy-4-trifluoromethyl-2,5-cyclohexadien-1-one

生成物 1

HCID 138691094-Hydroxy-4-trifluoromethyl-2,5-cyclohexadien-1-one収率 90%

試薬・触媒・溶媒 1

HCID 962Water溶媒

実験手順

A mixture of 200 mg (0.68 mmol) of 4-triethylsiloxy-4-trifluoromethyl-2,5-cyclohexadien-1-one and 1 mL of a solution of 1 part 37% hydrochloric acid in 9 parts absolute ethanol was heated at reflux overnight and poured into 10 mL of water. The resulting aqueous mixture was extracted with three 10 mL portions of dichloromethane. Combination, drying (MgSO4), and concentration of the organic layers afforded a residue which was purified by PTLC (one 2 mm silica gel plate eluted with 1% methanol--99% dichloromethane) to give 109 mg (89% yield) of 4-hydroxy-4-trifluoromethyl-2,5-cyclohexadien-1-one. An analytical sample was obtained by crystallization from dichloromethane-hexane: mp 84-86° C.; 1H NMR (CDCl3) δ 3.40 (broad s, 1H), 6.40 (d, 2H, J=10 Hz), 6.89 (d, 2H, J=10 Hz); 13C NMR (CDCl3) 70.2 (q, JCF =30 Hz), 125. 0 (q, JCF =286H), 132.2 (d), 142. 7 (d), 184.5 (s) ppm; 19F NMR (CDCl3) relative to CFCl3) -79.6 ppm (s); IR (KBr) 3374, 3105, 3022, 2919, 1693, 1671, 1632, 1620, 1396, 1249, 1235, 1195, 1174, 1089, 1078, 1003, 988, 980, 973, 863, 698 cm-1; mass spectrum (70 eV) m/z (relative intensity) 178 (5, M30), 109 (100), 81 (34), 53 (36). Anal. Calcd. for C7H5F3O2:C, 47.20; H, 2.83. Found: C, 47.42; H, 2.80.

後処理

  1. temperaturewas heated
  2. temperatureat reflux overnight
  3. extractionThe resulting aqueous mixture was extracted with three 10 mL portions of dichloromethane
  4. dry with materialCombination, drying (MgSO4), and concentration of the organic layers
  5. customafforded a residue which
  6. customwas purified by PTLC (one 2 mm silica gel plate eluted with 1% methanol--99% dichloromethane)

出典と根拠

ORDレコード
ord-dc2db28566f7481ea42890c39b74218d
出典データセット
uspto-grants-1991_04
特許番号
US05008425

反応ノート

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