Allyl Alcohol → 2-Cyclopropyl-7-(1-hydroxymethylvinyl)-5-methyl-6-phenyl-1,3-benzoxazole-4-carbonitrile

HRID 17617

Reaction equation

HRID 17617 reaction equation
FC(F)(F)S(O[C:7]1[C:15]2[O:14][C:13]([CH:16]3[CH2:18][CH2:17]3)=[N:12][C:11]=2[C:10]([C:19]#[N:20])=[C:9]([CH3:21])[C:8]=1[C:22]1[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=1)(=O)=O.C(N(CC)CC)C.[CH2:37]([OH:40])[CH:38]=[CH2:39]>CN(C)C=O.C1(P(C2C=CC=CC=2)[C-]2C=CC=C2)C=CC=CC=1.[C-]1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=C1.[Fe+2].C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[CH:16]1([C:13]2[O:14][C:15]3[C:11](=[C:10]([C:19]#[N:20])[C:9]([CH3:21])=[C:8]([C:22]4[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=4)[C:7]=3[C:38]([CH2:37][OH:40])=[CH2:39])[N:12]=2)[CH2:17][CH2:18]1

Participants

7

Reactant 3

HCID 7858Allyl AlcoholHCID 8471TriethylamineHCID 866308844-Cyano-2-cyclopropyl-5-methyl-6-phenyl-1,3-benzoxazol-7-yl trifluoromethanesulfonate

Product 1

HCID 685846992-Cyclopropyl-7-(1-hydroxymethylvinyl)-5-methyl-6-phenyl-1,3-benzoxazole-4-carbonitrileYield 32.5%

Reagents, catalysts & solvents 3

HCID 167845palladium(II) acetateCatalystHCID 635956Ferrocene-1,1'-bis-(diphenylphosphine)CatalystHCID 6228DimethylformamideSolvent

Conditions

Temperature
100 °C

Procedure

4-Cyano-2-cyclopropyl-5-methyl-6-phenyl-1,3-benzoxazol-7-yl trifluoromethanesulfonate (I-323) (760 mg, 1.80 mmol) was dissolved in dimethylformamide (10 ml), then triethylamine (276 μl, 1.98 mmol), allyl alcohol (209 mg, 3.60 mmol), 1,1′-bis(diphenylphosphino)ferrocene (79.8 mg, 0.144 mmol) and palladium(II) acetate (24.2 mg, 0.108 mmol) were added, followed by stirring in an oil bath at 100° C. under argon atmosphere for 16 hours. The reaction liquid was concentrated under reduced pressure, the residue was dissolved in ethyl acetate, washed with water and saturated brine. After drying over anhydrous sodium sulfate, the insoluble matter was separated by filtration, and the residue obtained by concentration was purified by silica gel column chromatography (eluent, n-hexane:ethyl acetate=1:1, v/v) to obtain the entitled compound (193 mg, 32%) as a colorless oily substance.

Workup

  1. customThe reaction liquid
  2. concentrationwas concentrated under reduced pressure
  3. dissolutionthe residue was dissolved in ethyl acetate
  4. washwashed with water and saturated brine
  5. dry with materialAfter drying over anhydrous sodium sulfate
  6. customthe insoluble matter was separated by filtration
  7. customthe residue obtained by concentration
  8. customwas purified by silica gel column chromatography (eluent, n-hexane

Sources & evidence

ORD record
ord-fcdca3eeee61483893e9bc63ac311015
Source dataset
uspto-grants-2010_06
Patent number
US07737166B2

Linked notes

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