Pyridine → 7-Methyl-3-nitro-5,6,7,8-tetrahydroquinolin-5-one

HRID 1276309ノート

反応式

HRID 1276309 の反応式
[N+:1](C(C=O)C=O)([O-:3])=[O:2].[Na].[N:10]1[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=1.S(Cl)(C1C=[CH:24][C:22]([CH3:23])=[CH:21][CH:20]=1)(=O)=O.CN(C)C=[O:30]>>[CH3:23][CH:22]1[CH2:24][C:15]2[N:10]=[CH:11][C:12]([N+:1]([O-:3])=[O:2])=[CH:13][C:14]=2[C:20](=[O:30])[CH2:21]1

参加物

5

反応物 4

HCID 1049PyridineHCID 6228Dimethylformamide2 回HCID 73974-Toluenesulfonyl chlorideHCID 24193465CID 24193465

生成物 1

HCID 144227827-Methyl-3-nitro-5,6,7,8-tetrahydroquinolin-5-one

反応条件

温度
-5 °C

実験手順

Sodium nitromalonaldehyde (Org. Synth. Coll., vol. 4, p. 844; 42.4 g, 0.269 mol) was dissolved in 200 ml of dimethylformamide and the resulting solution dried over 4A-type molecular sieves, recovered by filtration with 100 ml of the same solvent for wash. To the combined filtrate and wash was added pyridine (91 ml, 89 g, 1.13 mol) and the mixture cooled to -5° C. Tosyl chloride (53 g, 0.277 mol) in 200 ml of dimethylformamide was added dropwise, maintaining a temperature of -5° to -8° C., and the reaction mixture allowed to warm to room temperature. The title product of the preceding Preparation (33.6 g, 0.270 mol), dissolved by warming in 200 ml of dimethylformamide and added in a steady stream to the reaction mixture, which was then stirred for 18 hours at room temperature, then poured into 2 liters of ice and water and extracted 2×1 liter of ethyl acetate. The organic layers were combined, dried over MgSO4 and stripped to yield present title product, 33 g (61%), m.p. 64-67° C.

後処理

  1. dry with materialthe resulting solution dried over 4A-type molecular sieves
  2. filtrationrecovered by filtration with 100 ml of the same solvent
  3. washfor wash
  4. washTo the combined filtrate and wash
  5. temperaturemaintaining a temperature of -5° to -8° C.
  6. temperatureto warm to room temperature

出典と根拠

ORDレコード
ord-9768553e65e24d9d8746480550f999e4
出典データセット
uspto-grants-2000_12
特許番号
US06166031

反応ノート

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