Dimethylformamide → 3-(5-chloro-3-pyridyloxy)-N-(1-chloro-3-methylbut-1-yn-3-yl)butyramide

HRID 1374892ノート

反応式

HRID 1374892 の反応式
[Cl:1][C:2]1[CH:3]=[C:4]([O:8][CH:9]([CH2:13][CH3:14])[C:10](O)=O)[CH:5]=[N:6][CH:7]=1.CN(C)C=[O:18].C(Cl)(=O)C(Cl)=O.Cl.[Cl:27][C:28]#[C:29][C:30]([NH2:33])([CH3:32])[CH3:31]>ClCCl.CN(C)C1C=CN=CC=1.CCCCCC.C(OCC)(=O)C.C(N(CC)CC)C>[Cl:1][C:2]1[CH:3]=[C:4]([O:8][CH:9]([CH3:10])[CH2:13][C:14]([NH:33][C:30]([CH3:32])([CH3:31])[C:29]#[C:28][Cl:27])=[O:18])[CH:5]=[N:6][CH:7]=1

参加物

9

反応物 4

HCID 6228DimethylformamideHCID 65578Oxalyl chlorideHCID 210783581-Chloro-3-amino-3-methylbut-1-yne hydrochlorideHCID 210783782-(5-Chloro-3-pyridyloxy)butyric acid

生成物 1

HCID 210784103-(5-chloro-3-pyridyloxy)-N-(1-chloro-3-methylbut-1-yn-3-yl)butyramide

試薬・触媒・溶媒 4

HCID 142844-(Dimethylamino)pyridine触媒HCID 6344Dichloromethane溶媒3 回HCID 8471Triethylamine溶媒HCID 21226206Ethyl acetate hexane溶媒

実験手順

2-(5-Chloro-3-pyridyloxy)butyric acid (0.35 g; prepared as described in Stage 2 of Example 1) was stirred in dry dichloromethane (5 ml) containing N,N-dimethylformamide (0.1 ml) and treated dropwise with oxalyl chloride (0.145 ml) at ambient temperature. The solution was stirred for 0.5 hours and added in portions to a mixture of 1-chloro-3-amino-3-methylbut-1-yne hydrochloride (0.25 g; prepared as described below), dry triethylamine (0.68 ml) and 4-dimethylaminopyridine (0.01 g) in dry dichloromethane (5 ml) with stirring at ambient temperature. The mixture was stirred for 1 hour, stored for 18 hours, diluted with further dichloromethane, washed with aqueous sodium hydrogen carbonate, dried over magnesium sulphate and evaporated under reduced pressure to give an oil. The oil was fractionated by chromatography (silica:hexane/ethyl acetate 3:1 by volume) to give a solid that was recrystallised from hexane to give the required product as a colourless solid, 0.15 g, m.p. 78–82° C.

後処理

  1. stirringwith stirring at ambient temperature
  2. stirringThe mixture was stirred for 1 hour
  3. waitstored for 18 hours
  4. washwashed with aqueous sodium hydrogen carbonate
  5. dry with materialdried over magnesium sulphate
  6. customevaporated under reduced pressure
  7. customto give an oil
  8. customto give a solid
  9. customthat was recrystallised from hexane

出典と根拠

ORDレコード
ord-46b9e99c369242969a0eb112830f4f40
出典データセット
uspto-grants-2007_01
特許番号
US07166621B2

反応ノート

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