Ammonium Chloride → 7-(1-Allylbut-3-enyl)-2-cyclopropyl-5-methyl-6-phenyl-1,3-benzoxazole-4-carbonitrile

HRID 17588

Reaction equation

HRID 17588 reaction equation
[CH:1]([Mg]Br)=[CH2:2].[CH:5]1([C:8]2[O:9][C:10]3[C:11](=[C:13]([C:30]#[N:31])[C:14]([CH3:29])=[C:15]([C:23]4[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=4)[C:16]=3[CH:17]([CH2:21]I)[CH2:18][CH:19]=[CH2:20])[N:12]=2)[CH2:7][CH2:6]1.[Cl-].[NH4+]>O1CCCC1.[Cu]I>[CH2:18]([CH:17]([C:16]1[C:15]([C:23]2[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=2)=[C:14]([CH3:29])[C:13]([C:30]#[N:31])=[C:11]2[C:10]=1[O:9][C:8]([CH:5]1[CH2:7][CH2:6]1)=[N:12]2)[CH2:21][CH:1]=[CH2:2])[CH:19]=[CH2:20]

Participants

6

Reactant 3

HCID 25517Ammonium ChlorideHCID 685847562-Cyclopropyl-7-(l iodomethylbut-3-enyl)-5-methyl-6-phenyl-1,3-benzoxazole-4-carbonitrileHCID 178418507HCID 178418507, compound

Product 1

HCID 685853567-(1-Allylbut-3-enyl)-2-cyclopropyl-5-methyl-6-phenyl-1,3-benzoxazole-4-carbonitrileYield 73%

Reagents, catalysts & solvents 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
0 °C

Procedure

Copper (I) iodide (52 mg, 0.27 mmol) was suspended in tetrahydrofuran (3 ml), and under nitrogen atmosphere at −30° C., vinylmagnesium bromide (1 M tetrahydrofuran solution) (2.72 ml, 2.72 mmol) was dropwise added. The solution was stirred at the same temperature for 30 minutes, then a solution of 2-cyclopropyl-7-(l iodomethylbut-3-enyl)-5-methyl-6-phenyl-1,3-benzoxazole-4-carbonitrile (I-298)(425 mg, 0.91 mmol) dissolved in tetrahydrofuran (6 ml) was gradually added. After stirring at the same temperature for 1 hour and 20 minutes and heating up to 0° C., aqueous saturated ammonium chloride solution was added, followed by further stirring for 30 minutes. This was extracted three times with ethyl acetate. The organic layers were combined, washed with saturated brine, and dried over anhydrous sodium sulfate. The insoluble matter was separated by filtration, the solvent was evaporated away, and the resulting residue was purified by middle-pressure liquid chromatography (eluent, n-hexane:ethyl acetate=9:1, v/v) to obtain the entitled compound (243 mg, 73%) as a colorless gel.

Workup

  1. additionwas gradually added
  2. stirringAfter stirring at the same temperature for 1 hour and 20 minutes
  3. stirringby further stirring for 30 minutes
  4. extractionThis was extracted three times with ethyl acetate
  5. washwashed with saturated brine
  6. dry with materialdried over anhydrous sodium sulfate
  7. customThe insoluble matter was separated by filtration
  8. customthe solvent was evaporated away
  9. customthe resulting residue was purified by middle-pressure liquid chromatography (eluent, n-hexane

Sources & evidence

ORD record
ord-6738f05c3bc14712871758cf0d8cb6fa
Source dataset
uspto-grants-2010_06
Patent number
US07737166B2

Linked notes

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