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

HRID 1382012노트

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HRID 1382012 반응식
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

참가 물질

5

반응물 3

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

생성물 1

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

시약·촉매·용매 1

HCID 962Water용매

실험 절차

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)δ3.40 (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 =286 H), 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, M+), 109 (100), 81 (34), 53 (36). Anal. Calcd. for C7H5F3O2 : C, 47.20; H, 2.83. Found: C, 47.42; H, 2.80.

후처리

  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)

출처 및 근거

ORD 기록
ord-4fb6fd2c71f2401d9f57947084d67c71
출처 데이터셋
uspto-grants-1989_02
특허 번호
US04804773

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