反応 #312601

反応方程式

potassium hydroxide

5-benzylthio-1-methylpyrazole-4-carboxylic acid

thionyl chloride

hydrochloric acid

hydroxyamine hydrochloride

→

aimed product

収率 61.1%

5-benzylthio-1-methylpyrazole-4-carbohydroxamic acid

収率 61.1%

溶媒

tetrahydrofuran

water

toluene

tetrahydrofuran

water

反応条件

後処理

1. 1
   workup.ADDITIONwere added
2. 2
   温度refluxed for 4 hours
3. 3
   その他The residue obtained
4. 4
   workup.DISTILLATIONby distilling off the solvent
5. 5
   workup.STIRRINGAfter further stirring at 3° C. for 1.5 hour
6. 6
   抽出extracted with ethyl acetate
7. 7
   洗浄The resulting ethyl acetate solution was washed with water
8. 8
   乾燥dried over anhydrous sodium suite
9. 9
   workup.DISTILLATIONthe solvent was distilled off
10. 10
    その他The resulting residue was purified with silica gel column chromatography (developing solution: n-hexane/ethyl acetate=1/1)

実験手順

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).

出典