Ammonium Chloride → Diethyl 5-ethylpyridine-2,3-dicarboxylate

HRID 742203

反応式

HRID 742203 の反応式
C(O[CH:4]=[C:5]([C:11]([C:13]([O:15][CH2:16][CH3:17])=[O:14])=O)[C:6]([O:8][CH2:9][CH3:10])=[O:7])C.O1CC[N:21]([CH:24]=[CH:25][CH2:26][CH3:27])CC1.[NH4+].[Cl-]>CO.C(O)(=O)C>[CH2:26]([C:25]1[CH:4]=[C:5]([C:6]([O:8][CH2:9][CH3:10])=[O:7])[C:11]([C:13]([O:15][CH2:16][CH3:17])=[O:14])=[N:21][CH:24]=1)[CH3:27]

参加物

6

反応物 3

HCID 25517Ammonium ChlorideHCID 40590Diethyl 2-(ethoxymethylidene)-3-oxobutanedioateHCID 5809771-Morpholinobutene

生成物 1

HCID 10857926Diethyl 5-ethylpyridine-2,3-dicarboxylate

試薬・触媒・溶媒 2

HCID 176Acetic Acid溶媒HCID 887Methanol溶媒

実験手順

To a solution of diethyl ethoxymethyleneoxalacetate (43.2 g, 0.16 mol) dissolved in CH3OH (150 mL) at -10° under N2 is added 1-morpholinobutene (25 g, 0.16 mol). The reaction is slowly warmed to room temperature over three hours, after which the CH3OH is removed in vacuo. The residue is dissolved in acetic acid (100 mL) and this solution slowly added to NH4Cl (34.2 g, 0.64 mol) dissolved in acetic acid (200 mL) at 50°-70°. The reaction is then heated to 90°-95° for two hours and 30 minutes, concentrated in vacuo, partitioned between water and the CH2Cl2, and the organic phase chromatographed over silica gel with CH2Cl2 --CH3CN (95:5) elution to give the product as an oil. Distillation at 123°-155° at 0.15 mm gives the product (23.4 g, 83% pure, 55%).

後処理

  1. customafter which the CH3OH is removed in vacuo
  2. dissolutionThe residue is dissolved in acetic acid (100 mL)
  3. temperatureThe reaction is then heated to 90°-95° for two hours and 30 minutes
  4. concentrationconcentrated in vacuo
  5. custompartitioned between water
  6. customthe CH2Cl2, and the organic phase chromatographed over silica gel with CH2Cl2 --CH3CN (95:5) elution

出典と根拠

ORDレコード
ord-9c4e9098250441b298de33a0ad2f23cb
出典データセット
uspto-grants-1996_09
特許番号
US05554579

関連ノート

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