Formic Acid → 5,7-di-tert-butyl-3-(4-trifluoromethyl-phenyl)-3H-benzofuran-2-one

HRID 393968ノート

反応式

HRID 393968 の反応式
[C:1]([C:5]1[CH:10]=[C:9]([C:11]([CH3:14])([CH3:13])[CH3:12])[CH:8]=[C:7]([CH:15](N2CCCCC2)[C:16]2[CH:21]=[CH:20][C:19]([C:22]([F:25])([F:24])[F:23])=[CH:18][CH:17]=2)[C:6]=1[OH:32])([CH3:4])([CH3:3])[CH3:2].[CH:33](O)=[O:34]>C1(C)C=CC=CC=1.C1C=CC(P(C2C=CC=CC=2)CCCP(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.Cl[Pd]Cl>[C:11]([C:9]1[CH:10]=[C:5]([C:1]([CH3:4])([CH3:3])[CH3:2])[C:6]2[O:32][C:33](=[O:34])[CH:15]([C:16]3[CH:21]=[CH:20][C:19]([C:22]([F:25])([F:23])[F:24])=[CH:18][CH:17]=3)[C:7]=2[CH:8]=1)([CH3:13])([CH3:12])[CH3:14]

参加物

5

反応物 2

HCID 284Formic AcidHCID 226483422,4-Di-tert-butyl-6-[piperidin-1-yl-(4-trifluoromethyl-phenyl)-methyl]-phenol

生成物 1

HCID 121621595,7-di-tert-butyl-3-(4-trifluoromethyl-phenyl)-3H-benzofuran-2-one収率 87%

試薬・触媒・溶媒 2

HCID 11017392(1,3-Bis(diphenylphosphino)propane)palladium(II) chloride触媒HCID 1140Toluene溶媒

反応条件

温度
140 °C

実験手順

A solution of 12.53 g (28.0 mmol) of compound (201), prepared according to Example 1a, in 150 ml of dry toluene is degassed using argon and then 33.6 mg (0.057 mmol) of dichloro-[1,3bis(diphenylphosphino)propane]palladium(II) and 4.22 ml (112 mmol) of formic acid are added. The autoclave is flushed with carbon monoxide and sealed, and a carbon monoxide pressure of 6 bar is then applied. The reaction mixture is maintained at 140° C. for 14 hours. After cooling to room temperature, the reaction mixture is poured into water and extracted three times using ethyl acetate. The organic phases are combined, dried over sodium sulfate and concentrated using a vacuum rotary evaporator. Filtration of the residue on silica gel using ethyl acetate and crystallisation of the pure fractions from methanol yields 9.46 g (87%) of compound (101) (Table 1), m.p. 127-128° C. Molecular weight C23H25F3O2 (390.45). Analysis, calculated: C 70.75; H 6.45%. Analysis, found: C 70.96; H 6.53%. 1HNMR (300 MHz, CDCl3, ppm): 1.23 (s, 9H); 1.37 (s, 9H); 4.83 (s, 1H); 6.97 (m, 1H); 7.31 (m, 3H); 7.57 (d, 2H).

後処理

  1. customis degassed
  2. customThe autoclave is flushed with carbon monoxide
  3. customsealed
  4. temperatureAfter cooling to room temperature
  5. additionthe reaction mixture is poured into water
  6. extractionextracted three times
  7. dry with materialdried over sodium sulfate
  8. concentrationconcentrated
  9. customa vacuum rotary evaporator
  10. filtrationFiltration of the residue on silica gel
  11. customethyl acetate and crystallisation of the pure fractions from methanol

出典と根拠

ORDレコード
ord-a93c9efc4412488c8732b30470807388
出典データセット
uspto-grants-2004_10
特許番号
US06809208B2

反応ノート

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