p-Toluidine → 4-(4-Methylphenyl)but-3-enenitrile

HRID 48127

反応式

HRID 48127 の反応式
F[B-](F)(F)F.[CH3:6][C:7]1[CH:12]=[CH:11][C:10]([N+]#N)=[CH:9][CH:8]=1.NC1C=CC(C)=CC=1.N([O-])=O.[Na+].[CH2:27]([C:30]#[N:31])[CH:28]=[CH2:29]>[H+].[B-](F)(F)(F)F.C(O)C.C([O-])(=O)C.[Pd+2].C([O-])(=O)C.O>[C:7]1([CH3:6])[CH:12]=[CH:11][C:10]([CH:29]=[CH:28][CH2:27][C:30]#[N:31])=[CH:9][CH:8]=1

参加物

9

反応物 4

HCID 7813p-ToluidineHCID 80093-ButenenitrileHCID 68019Benzenediazonium, 4-methyl-, tetrafluoroborate(1-) (1:1)HCID 23668193Sodium Nitrite

生成物 1

HCID 571191444-(4-Methylphenyl)but-3-enenitrile収率 53%

試薬・触媒・溶媒 4

HCID 167845palladium(II) acetate触媒HCID 702Ethanol溶媒HCID 962Water溶媒HCID 28118Tetrafluoroboric acid溶媒

反応条件

温度
46 °C

実験手順

6.17 g (0.03 mol) of 4-methyl-benzenediazonium tetrafluoroborate (mp 105-110° C.; prepared by nitrosation of p-toluidine with sodium nitrite in aqueous fluoboric acid according to A. Roe, Org. Reactions vol V, 1949,193) are suspended in 60 ml of ethanol. Allyl cyanide (4.0 g; 0.06 mol) and palladium acetate (67 mg; 0.3 mmol) are added, and the light orange suspension is heated gently to 46° C., at which temperature a gentle evolution of nitrogen is visible. The mixture is stirred at the same temperature until the nitrogen evolution ceases (ca 3 h), resulting in a dark brown clear solution. The reaction mixture is poured into 300 ml of cold water and extracted with 2×100 ml of hexane:ethyl acetate 85:15 (v:v). The organic phases are washed with saturated aqueous sodium bicarbonate, water, brine, and dried over magnesium sulfate. The light green solution is concentrated to ca 20 ml by rotary evaporation, and allowed to crystallize in the refrigerator. Filtration yields 2.5 g (53%) of 4-p-tolyl-but-3-enenitrile as very thin, colorless leaflets, mp 60-61° C., consisting of the pure (E) isomer, as determined by 1H-NMR.

後処理

  1. customresulting in a dark brown clear solution
  2. extractionextracted with 2×100 ml of hexane:ethyl acetate 85:15 (v:v)
  3. washThe organic phases are washed with saturated aqueous sodium bicarbonate, water, brine
  4. dry with materialdried over magnesium sulfate
  5. concentrationThe light green solution is concentrated to ca 20 ml by rotary evaporation
  6. customto crystallize in the refrigerator
  7. filtrationFiltration

出典と根拠

ORDレコード
ord-8588811842434d3d81c830db05944e94
出典データセット
uspto-grants-2004_03
特許番号
US06703182B1

関連ノート

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