N,N-Diethylaniline → Methyl 2-Chloro-5-iodonicotinate

HRID 1199806ノート

反応式

HRID 1199806 の反応式
[I:1][C:2]1[CH:3]=[C:4]([C:8]([O:10][CH3:11])=[O:9])[CH2:5][NH:6][CH:7]=1.CCN(C1C=CC=CC=1)CC.P(Cl)(Cl)([Cl:25])=O>[Cl-].C([N+](CC)(CC)CC)C1C=CC=CC=1.C(#N)C.O>[Cl:25][C:5]1[C:4]([C:8]([O:10][CH3:11])=[O:9])=[CH:3][C:2]([I:1])=[CH:7][N:6]=1

参加物

7

反応物 3

HCID 7061N,N-DiethylanilineHCID 24813Phosphorus oxychlorideHCID 20073492Methyl 5-iodo-1,2-dihydro-3-pyridinecarboxylate

生成物 1

HCID 2764559Methyl 2-Chloro-5-iodonicotinate収率 52%

試薬・触媒・溶媒 3

HCID 962Water触媒HCID 66133Benzyl triethylammonium chloride触媒HCID 6342Acetonitrile溶媒

実験手順

To a mixture containing 2.0 g of methyl 5-iodo-1,2-dihydro-3-pyridinecarboxylate, 1.6 g of diethylaniline, 1.64 g of benzyltriethylammonium chloride and 3.6 ml of distilled phosphorus oxychloride in 100 ml of dry acetonitrile are added 15 drops of water. The mixture is heated under reflux for 18 hours. After cooling the reaction mixture to room temperature, the solvent is removed under reduced pressure and the residue taken up in methylene chloride and extracted with water. The organic solution is dried over anhydrous sodium sulfate and concentrated under reduced pressure. The residue is chromatographed on a column of flash silica gel using methylene chloride as the eluent. Evaporation of the eluent yields a pale yellowish solid which is recrystallized from aqueous ethanol to give 1.1 g (52%) of methyl 2-chloro-5-iodo-3-pyridinecarboxylate as a white solid: m.p. 73°-73.5° C.; NMR (80 MHz, CDCl3) delta 3.96 (s, 3H), 8.43 (d, 1H, J= 2.3 Hz), 8.71 (d, 1H, J=2.3 Hz).

後処理

  1. temperatureThe mixture is heated
  2. temperatureunder reflux for 18 hours
  3. customthe solvent is removed under reduced pressure
  4. extractionextracted with water
  5. dry with materialThe organic solution is dried over anhydrous sodium sulfate
  6. concentrationconcentrated under reduced pressure
  7. customThe residue is chromatographed on a column of flash silica gel
  8. customEvaporation of the eluent
  9. customyields a pale yellowish solid which
  10. customis recrystallized from aqueous ethanol

出典と根拠

ORDレコード
ord-4dd813f9e0e64cc49d5963822b11a32e
出典データセット
uspto-grants-1990_02
特許番号
US04902796

反応ノート

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