Hydrochloric Acid → HCID 57752439, compound

HRID 2234163Notes

Reaction equation

HRID 2234163 reaction equation
[CH2:1]([S:8][C:9]1[N:13]([CH3:14])[N:12]=[CH:11][C:10]=1[C:15]([OH:17])=O)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.S(Cl)(Cl)=O.Cl.[OH:23][NH2:24].[OH-].[K+].Cl>C1(C)C=CC=CC=1.O.CN(C)C=O.O1CCCC1>[CH2:1]([S:8][C:9]1[N:13]([CH3:14])[N:12]=[CH:11][C:10]=1[C:15]([NH:24][OH:23])=[O:17])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

10

Reactant 5

HCID 313Hydrochloric AcidHCID 14797Potassium HydroxideHCID 24386Thionyl ChlorideHCID 443297Hydroxyamine hydrochlorideHCID 14049140HCID 14049140, compound

Product 1

HCID 57752439HCID 57752439, compoundYield 61.1%

Reagents, catalysts & solvents 4

HCID 6228DimethylformamideCatalystHCID 962WaterSolvent2×HCID 1140TolueneSolventHCID 8028TetrahydrofuranSolvent

Procedure

In a suspension of 5-benzylthio-1-methylpyrazole-4-carboxylic acid (15.9 g, 64.0 mmol) in toluene (100 ml), thionyl chloride (11.4 g, 95.8 mmol) and N,N-dimethylformamide (0.1 g) were added, and refluxed for 4 hours. The residue obtained by distilling off the solvent was dissolved in tetrahydrofuran (40 ml). On the other hand, in a solution of hydroxyamine hydrochloride (13.3 g, 191 mmol) in water (40 ml), a solution of 85% potassium hydroxide (12.6 g, 191 mmol) in water (40 ml) was added at 5-15° C., and stirred at room temperature for 15 minutes. Then, the above-mentioned tetrahydrofuran solution was added dropwise at 3-15° C. After further stirring at 3° C. for 1.5 hour, the mixture was adjusted to pH 3-4 by adding 35% hydrochloric acid (20 ml) and extracted with ethyl acetate. The resulting ethyl acetate solution was washed with water, dried over anhydrous sodium sulfate, and the solvent was distilled off. The resulting residue was purified with silica gel column chromatography (developing solution: n-hexane/ethyl acetate=1/1) to obtain the aimed product (10.3 g). Resinous substance. Proton nuclear magnetic resonance chemical shift values δ (ppm) (in CDCl3) 3.42 (s, 3H), 3.95 (s, 2H), 6.93-7.01 (m, 2H), 7.20-7.28 (m, 3H), 8.04 (s, 1H), 9.76 (brs, 1H).

Workup

  1. additionwere added
  2. temperaturerefluxed for 4 hours
  3. customThe residue obtained
  4. distillationby distilling off the solvent
  5. dissolutionwas dissolved in tetrahydrofuran (40 ml)
  6. stirringAfter further stirring at 3° C. for 1.5 hour
  7. extractionextracted with ethyl acetate
  8. washThe resulting ethyl acetate solution was washed with water
  9. dry with materialdried over anhydrous sodium sulfate
  10. distillationthe solvent was distilled off
  11. customThe resulting residue was purified with silica gel column chromatography (developing solution: n-hexane/ethyl acetate=1/1)

Sources & evidence

ORD record
ord-8b9e2e6b59a54e96b3c61b3cd9c10053
Source dataset
uspto-grants-2010_05
Patent number
US07709636B2

Reaction notes

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