Реакция #216615

Уравнение реакции

4-methoxy-5-methylthiochroman-6-carboxylic acid-1,1-dioxide

potassium carbonate

1-ethyl-5-hydroxypyrazole

triethylamine

thionyl chloride

→

Compound 34

4-methoxy-5-methyl-6-(1-ethyl-5-hydroxypyrazol-4-yl)carbonylthiochroman-1,1-dioxide

Растворители

chloroform

water

1,4-dioxane

Условия реакции

Обработка

1. 1
   Другоеto react at 60° C. for 30 minutes
2. 2
   workup.DISTILLATIONan excess of thionyl chloride was distilled off under reduced pressure
3. 3
   workup.DISSOLUTIONThe remaining oil was dissolved in 5,0 ml of chloroform
4. 4
   Другоеto react
5. 5
   Другоеto react at room temperature for 2 hours
6. 6
   Промывкаthe reaction mixture was washed with 5% hydrochloric acid
7. 7
   Сушкаdried over anhydrous sodium sulfate
8. 8
   workup.DISTILLATIONthe chloroform was distilled off under reduced pressure
9. 9
   workup.ADDITIONAdded to the remaining oil
10. 10
    Другоеto react at 130° C. for 2 hours
11. 11
    Температураto cool
12. 12
    workup.DISSOLUTIONthe reaction mixture was dissolved
13. 13
    Промывкаwashed with ether
14. 14
    ДругоеThe aqueous layer was separated
15. 15
    workup.ADDITION5% hydrochloric acid was added
16. 16
    ЭкстракцияThe precipitated oil was extracted with ethyl acetate
17. 17
    Сушкаthe extract was dried over anhydrous sodium sulfate
18. 18
    workup.DISTILLATIONThen, the ethyl acetate was distilled off under reduced pressure

Методика

A 100-ml flask was charged with 1.0 g (0.0037 mol) of 4-methoxy-5-methylthiochroman-6-carboxylic acid-1,1-dioxide shown in Table 5, left column, and 5.0 ml of thionyl chloride, and the mixture was allowed to react at 60° C. for 30 minutes. After the reaction was completed, an excess of thionyl chloride was distilled off under reduced pressure. The remaining oil was dissolved in 5,0 ml of chloroform, and was added to a mixture of 0.41 g (0.0037 mol) of 1-ethyl-5-hydroxypyrazole, 0.37 g (0.0037 mol) of triethylamine and 20 ml of chloroform in another 200-ml flask, and the resultant mixture was allowed to react. After the mixture was allowed to react at room temperature for 2 hours, the reaction mixture was washed with 5% hydrochloric acid and dried over anhydrous sodium sulfate, and the chloroform was distilled off under reduced pressure. Added to the remaining oil were 0.77 g (0.0056 mol) of anhydrous potassium carbonate and 1.0 ml of 1,4-dioxane, and the mixture was allowed to react at 130° C. for 2 hours. After allowed to cool, the reaction mixture was dissolved by adding 20 ml of water, and washed with ether. The aqueous layer was separated, and 5% hydrochloric acid was added to adjust the pH to 1. The precipitated oil was extracted with ethyl acetate, and the extract was dried over anhydrous sodium sulfate. Then, the ethyl acetate was distilled off under reduced pressure to give 4-methoxy-5-methyl-6-(1-ethyl-5-hydroxypyrazol-4-yl)carbonylthiochroman-1,1-dioxide (Compound 34) shown in Table 5, right column.

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