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

HRID 1789574
Notizen
Druckvorschau

Reaktionsgleichung

Reaktionsgleichung von HRID 1789574
[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]
KomponentenReaktionsbedingungenVersuchsvorschriftAufarbeitungQuellen und NachweiseNotizen zur Reaktion

Komponenten

5

Edukt 3

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

Produkt 1

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

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 3283Diethyl EtherLösungsmittel

Reaktionsbedingungen

Temperatur
-60 °C

Versuchsvorschrift

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.

Aufarbeitung

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

Quellen und Nachweise

ORD-Eintrag
ord-e765de5f47654addb30791e3c03fffd2
Quelldatensatz
uspto-grants-1987_08
DOI
10.6084/m9.figshare.5104873.v1
Patentnummer
US04689417

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