Hydrochloric Acid → ethyl (2E)-2-[[2-ethyl-4-[(6-methylsulfonyl-3-pyridinyl)oxy]phenyl]hydrazinylidene]propanoate

HRID 1042134ノート

反応式

HRID 1042134 の反応式
[CH2:1]([C:3]1[CH:9]=[C:8]([O:10][C:11]2[CH:12]=[N:13][C:14]([S:17]([CH3:20])(=[O:19])=[O:18])=[CH:15][CH:16]=2)[CH:7]=[CH:6][C:4]=1[NH2:5])[CH3:2].Cl.[N:22]([O-])=O.[Na+].[CH3:26][CH:27](C(C)=O)[C:28]([O:30][CH2:31][CH3:32])=[O:29].[OH-].[K+]>O.C(O)C.CCCCCC.C(OCC)(=O)C>[CH2:1]([C:3]1[CH:9]=[C:8]([O:10][C:11]2[CH:12]=[N:13][C:14]([S:17]([CH3:20])(=[O:19])=[O:18])=[CH:15][CH:16]=2)[CH:7]=[CH:6][C:4]=1[NH:5]/[N:22]=[C:27](\[CH3:26])/[C:28]([O:30][CH2:31][CH3:32])=[O:29])[CH3:2]

参加物

10

反応物 5

HCID 313Hydrochloric AcidHCID 701Ethyl 2-methylacetoacetateHCID 14797Potassium HydroxideHCID 23668193Sodium NitriteHCID 667259082-Ethyl-4-{[6-(methylsulfonyl)pyridin-3-yl]oxy}aniline

生成物 1

HCID 87126290ethyl (2E)-2-[[2-ethyl-4-[(6-methylsulfonyl-3-pyridinyl)oxy]phenyl]hydrazinylidene]propanoate収率 66%

試薬・触媒・溶媒 4

HCID 702Ethanol溶媒2 回HCID 962Water溶媒3 回HCID 8058Hexane溶媒HCID 8857Ethyl Acetate溶媒

反応条件

温度
-7.5 °C

実験手順

A mixture of 2-ethyl-4-{[6-(methylsulfonyl)pyridin-3-yl]oxy}aniline (11.3 g), concentrated hydrochloric acid (6.8 mL), ethanol (150 mL), and water (15 mL) was cooled to −5 to −10° C., and aqueous solution (15 mL) of sodium nitrite (3.0 g) was added dropwise. After the completion of the dropwise addition, the mixture was stirred at the same temperature for 40 min. The reaction solution was added dropwise to a solution of ethyl 2-methylacetoacetate (6.1 mL) and potassium hydroxide (8.0 g) in water (100 mL) and ethanol (60 mL) at −5 to −10° C. After stirring at −10° C. for 30 min, water was added to the reaction solution, and the mixture was extracted with ethyl acetate. The organic layer was washed with saturated brine, dried over magnesium sulfate, filtered and concentrated under reduced pressure. The obtained crude product was subjected to silica gel column chromatography (ethyl acetate:hexane=25:75 to 40:60, volume ratio) to give the title compound (10.4 g, yield 66%) as a dark-red oil.

後処理

  1. additionAfter the completion of the dropwise addition
  2. stirringAfter stirring at −10° C. for 30 min
  3. extractionthe mixture was extracted with ethyl acetate
  4. washThe organic layer was washed with saturated brine
  5. dry with materialdried over magnesium sulfate
  6. filtrationfiltered
  7. concentrationconcentrated under reduced pressure
  8. customThe obtained crude product

出典と根拠

ORDレコード
ord-082369d5484549e7b4c877fc559467e8
出典データセット
uspto-grants-2013_10
特許番号
US08557805B2

反応ノート

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