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

HRID 979399
Notes
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Reaction equation

HRID 979399 reaction equation
[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]
ParticipantsConditionsProcedureWorkupSources & evidenceReaction notes

Participants

5

Reactant 3

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

Product 1

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

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent

Conditions

Temperature
-60 °C

Procedure

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-methlpyrazole-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.

Workup

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

Sources & evidence

ORD record
ord-b809f5f8d24a45e497ee6f6127592a6d
Source dataset
uspto-grants-1987_05
DOI
10.6084/m9.figshare.5104873.v1
Patent number
US04668277

Reaction notes

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On this pageParticipantsConditionsProcedureWorkupSources & evidenceReaction notes