Hydrochloric Acid → HCID 57752439, compound

HRID 225419Notes

Reaction equation

HRID 225419 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.O1CCCC1.O.CN(C)C=O>[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 8028TetrahydrofuranSolvent2×

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 suite, 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. stirringAfter further stirring at 3° C. for 1.5 hour
  6. extractionextracted with ethyl acetate
  7. washThe resulting ethyl acetate solution was washed with water
  8. dry with materialdried over anhydrous sodium suite
  9. distillationthe solvent was distilled off
  10. customThe resulting residue was purified with silica gel column chromatography (developing solution: n-hexane/ethyl acetate=1/1)

Sources & evidence

ORD record
ord-c92f01eee99e4b8ba6ad2315657a2574
Source dataset
uspto-grants-2009_07
Patent number
US07557067B2

Reaction notes

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