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Sulfur Dioxide → Lithium 3-chloro-4-ethoxycarbonyl-1-methylpyrazole-5-sulfinate

HRID 1789574
ノート
印刷プレビュー

反応式

HRID 1789574 の反応式
[Cl:1][C:2]1[C:6]([C:7]([O:9][CH2:10][CH3:11])=[O:8])=[CH:5][N:4]([CH3:12])[N:3]=1.C([N-]C(C)C)(C)C.[Li+:20].[S:21](=[O:23])=[O:22]>C(OCC)C>[Cl:1][C:2]1[C:6]([C:7]([O:9][CH2:10][CH3:11])=[O:8])=[C:5]([S:21]([O-:23])=[O:22])[N:4]([CH3:12])[N:3]=1.[Li+:20]
参加物反応条件実験手順後処理出典と根拠反応ノート

参加物

5

反応物 3

HCID 1119Sulfur DioxideHCID 2724682Lithium diisopropylamideHCID 13687029Ethyl 3-chloro-1-methyl-1H-pyrazole-4-carboxylate

生成物 1

HCID 23704643Lithium 3-chloro-4-ethoxycarbonyl-1-methylpyrazole-5-sulfinate

試薬・触媒・溶媒 1

HCID 3283Diethyl Ether溶媒

反応条件

温度
-60 °C

実験手順

5.0 g of ethyl 3-chloro-1-methylpyrazole-4-carboxylate was dispersed in dry diethyl ether under cooling at -60° C. or lower. Into this solution there was added lithium diisopropylamide (1.2 molar equivalent) and after stirring for an hour sulfur dioxide gas was passed into this solution for 30 minutes. After stirring at -60° C. for 2 hours the reaction mixture was stirred at room temperature for 2 hours. Filtration and drying of the precipitate gave 6.0 g of lithium 3-chloro-4-ethoxycarbonyl-1-methylpyrazole-5-sulfinate. This product was added into a solution of 100 ml of ice-water and 100 ml of dichloromethane and 6.0 g of N-chloro succinimide was added thereinto at 0°-5° C. After stirring for 45 minutes at room temperature the dichloromethane layer was separated and water layer was extracted with 100 ml of dichloromethane. The combined dichloromethane solution of 3-chloro-4-ethoxycarbonyl-1-methylpyrazole-5-sulfonyl chloride (b.p.: 133° C./ 0.25 mmHg.) was added dropwise into 80 ml of aqueous ammonia (28%) under cooling at 10° C. After stirring for an hour, evaporation of the solvent gave 3.6 g of 3-chloro-4-ethoxycarbonyl-1-methylpyrazole-5-sulfonamide. m.p.: 121°-123° C.

後処理

  1. stirringwas stirred at room temperature for 2 hours
  2. filtrationFiltration
  3. customdrying of the precipitate

出典と根拠

ORDレコード
ord-e765de5f47654addb30791e3c03fffd2
出典データセット
uspto-grants-1987_08
DOI
10.6084/m9.figshare.5104873.v1
特許番号
US04689417

反応ノート

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