Ethyl Acetate → Methyl 2-cyano-6-methylisonicotinate

HRID 2071151

反応式

HRID 2071151 の反応式
Cl[C:2]1[CH:3]=[C:4]([CH:9]=[C:10]([CH3:12])[N:11]=1)[C:5]([O:7][CH3:8])=O.[CH3:13]COC(C)=O.[NH4+:19].[OH-:20]>CN(C=O)C.[C-]#N.[C-]#N.[Zn+2].C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[C:13]([C:2]1[CH:3]=[C:4]([CH:9]=[C:10]([CH3:12])[N:11]=1)[C:5]([O:7][CH3:8])=[O:20])#[N:19]

参加物

7

反応物 3

HCID 8857Ethyl AcetateHCID 14923Ammonium HydroxideHCID 2759833Methyl 2-Chloro-6-methylisonicotinate

生成物 1

HCID 58802283Methyl 2-cyano-6-methylisonicotinate収率 68%

試薬・触媒・溶媒 3

HCID 11186Zinc cyanide (Zn(CN)2)触媒HCID 178418397HCID 178418397、化合物触媒HCID 6228Dimethylformamide溶媒

反応条件

温度
80 °C

実験手順

To a solution of 2.03 g (11 mmol) of methyl 2-chloro-6-methylisonicotinate (Aldrich) in 20 mL of DMF (degassed) was added 1.14 g (9.73 mmol) of Zn(CN)2 and 1.18 g (1.02 mmol) of Pd(PPh3)4. The mixture was stirred at 80° C. for 12.5 h, and EtOAc and 20 mL of 10% NH4OH aqueous solution were added. The organic layer was washed with 20 mL of 10% NH4OH and 20 mL of brine. The combined aqueous layers were reextracted with EtOAc and washed with brine. The combined extracts were dried over Na2SO4, filtered, and concentrated. Purification by flash silica gel chromatography (30% EtOAc/hexanes) provided 1.3 g of methyl 2-cyano-6-methylisonicotinate in 68% yield.

後処理

  1. washThe organic layer was washed with 20 mL of 10% NH4OH and 20 mL of brine
  2. washwashed with brine
  3. dry with materialThe combined extracts were dried over Na2SO4
  4. filtrationfiltered
  5. concentrationconcentrated
  6. customPurification by flash silica gel chromatography (30% EtOAc/hexanes)

出典と根拠

ORDレコード
ord-11532bef617c47be9faf70fd496de537
出典データセット
uspto-grants-2012_10
特許番号
US08299267B2

関連ノート

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