Sulfurous Acid → HCID 19083162, compound

HRID 963669Notes

Reaction equation

HRID 963669 reaction equation
C[N:2]1C=C2C(C=CC=C2)=N1.C([Li])CCC.S(=O)(O)O.NOS(O)(=O)=O.[OH-].[Na+].[CH3:28][N:29]1[C:37]([S:38]([O-:40])=[O:39])=[C:36]2[C:31]([CH:32]=[CH:33][CH:34]=[CH:35]2)=[N:30]1.[Li+]>C(OCC)C.O.CCCCCC>[CH3:28][N:29]1[C:37]([S:38]([NH2:2])(=[O:40])=[O:39])=[C:36]2[C:31]([CH:32]=[CH:33][CH:34]=[CH:35]2)=[N:30]1

Participants

10

Reactant 6

HCID 1100Sulfurous AcidHCID 14798Sodium HydroxideHCID 76284hydroxylamine-O-sulfonic acidHCID 1383642-Methyl-2H-indazoleHCID 23675697HCID 23675697, compoundHCID 178418339Butyllithium

Product 1

HCID 19083162HCID 19083162, compoundYield 58%

Reagents, catalysts & solvents 3

HCID 962WaterSolvent2×HCID 3283Diethyl EtherSolvent2×HCID 8058HexaneSolvent

Conditions

Temperature
-30 °C

Procedure

A solution containing 9.5 g (72 mmol) of 2-methyl-2H-indazole in 200 ml of ethyl ether, was cooled to -30° C., and 61.4 g (144 mmol) of n-butyl lithium (a 15% hexane solution) was dropwise added thereto. The mixture was stirred for one hour at the same temperature, and then an excess amount of sulfurous acid gas was blown thereinto for 3 hours at a temperature of not higher than -20° C. After completion of the reaction, the mixture was returned to room temperature, stirred for 12 hours and then diluted with ethyl ether. The product was subjected to filtration. The crystals were dried to obtain crude lithium 2-methyl-2H-indazole-3-sulfinate. This product was used for the subsequent reaction without purification. 48.8 g (430 mmol) of hydroxylamine-O-sulfonic acid was gradually added to a solution containing 17.2 g (430 mmol) of sodium hydroxide in water (300 ml) under cooling with ice (not higher than 10° C.). This solution was added all at once to a solution containing the crude lithium 2-methyl-2H-indazole-3-sulfinate previously prepared in water (100 ml), and then the mixture was stirred for 12 hours at room temperature. Formed crystals were collected by filtration to obtain 8.8 g (yield: 58%) of 2-methyl-2H-indazole-3-sulfonamide (slightly yellow granular crystals). Melting point: 181°-183° C.

Workup

  1. waitfor 3 hours at a temperature of not higher than -20° C
  2. customAfter completion of the reaction
  3. customwas returned to room temperature
  4. stirringstirred for 12 hours
  5. filtrationThe product was subjected to filtration
  6. customThe crystals were dried
  7. customto obtain crude lithium 2-methyl-2H-indazole-3-sulfinate
  8. customThis product was used for the subsequent reaction without purification
  9. temperatureunder cooling with ice (not higher than 10° C.)
  10. additionThis solution was added all at once to a solution
  11. stirringthe mixture was stirred for 12 hours at room temperature
  12. customFormed crystals
  13. filtrationwere collected by filtration

Sources & evidence

ORD record
ord-0e67187764064899b4c0a27d3da88450
Source dataset
uspto-grants-1998_06
Patent number
US05763616

Reaction notes

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