Methanol → Methyl 5-cyano-2-methylbenzoate

HRID 1348908

反応式

HRID 1348908 の反応式
Cl[C:2]1[CH:3]=[C:4]([CH:7]=[CH:8][C:9]=1[CH3:10])[C:5]#[N:6].[C:11](=[O:14])([O-])[O-:12].[Li+].[Li+].[CH3:17]O>Cl[Pd]Cl.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.[Fe+2]>[C:5]([C:4]1[CH:7]=[CH:8][C:9]([CH3:10])=[C:2]([CH:3]=1)[C:11]([O:12][CH3:17])=[O:14])#[N:6]

参加物

6

反応物 3

HCID 887MethanolHCID 11125Lithium CarbonateHCID 888943-Chloro-p-toluonitrile

生成物 1

HCID 9989736Methyl 5-cyano-2-methylbenzoate収率 50%

試薬・触媒・溶媒 2

HCID 24290Palladium Chloride触媒HCID 635956Ferrocene-1,1'-bis-(diphenylphosphine)触媒

反応条件

温度
140 °C

実験手順

A solution of 3-chloro-4-methylbenzonitrile (25.0 g, 0.165 mol) in methanol (250 mL) in a steel reaction vessel was treated with lithium carbonate (13.4 g, 0.182 mol) and PdCl2.dppf (6.75 g). The vessel was purged with nitrogen, sealed, and heated to 140° C. at 400 psi for 17 hours, filtered and concentrated. The concentrate was treated with ethyl acetate, washed with saturated NaHCO3, dried (MgSO4), filtered, and concentrated. The concentrate was purified by flash chromatography on silica gel with 95:5 to 85:15 hexanes/ethyl acetate to provide 14.4 g (50%) of the desired product. MS (DCI/NH3) m/z 193.0 (M+NH4)+; 1H NMR (CDCl3) δ 8.22 (d, 1H), 7.67 (dd, 1H), 7.37 (d, 1H), 3.93 (s, 3H), 2.68 (s, 3H).

後処理

  1. customThe vessel was purged with nitrogen
  2. customsealed
  3. filtrationfiltered
  4. concentrationconcentrated
  5. additionThe concentrate was treated with ethyl acetate
  6. washwashed with saturated NaHCO3
  7. dry with materialdried (MgSO4)
  8. filtrationfiltered
  9. concentrationconcentrated
  10. customThe concentrate was purified by flash chromatography on silica gel with 95:5 to 85:15 hexanes/ethyl acetate

出典と根拠

ORDレコード
ord-6cd35102c56348cbbb0f024b5472186a
出典データセット
uspto-grants-2007_05
特許番号
US07211595B2

関連ノート

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