反应详情

温度

200 °C

To a solution of 4.36 g of 2-methylthio-3-cyano-5-ethoxycarbonylthiophene, obtained according to Example IV (a), in 40 ml of dioxane, is added while stirring 40 ml of 2N NaOH. After stirring for two hours the reaction mixture is acidified with 45 ml 2N Hcl. The precipitated 5-carboxythiophene compound is sucked off, washed with water and recrystallized from acetonitrile; yield 3.01 g; melting point 230°-234° C. This 5-carboxythiophene compound in an amount of 1.99 g together with 4 ml of quinoline and 0.4 g of Cu-powder is heated on 200° C. during approx. 15 minutes. After cooling down, diethylether, water and 20 ml 2N Hcl are added. The ether phase is separated off, washed with water, dried, decolorized with charcoal, filtered and evaporated. 2-Methylthio-3-cyanothiophene is obtained in a yield of 0.92 g as an oil; Rf (CH2Cl2)=0.45. The reaction is repeated with larger quantities. The last product in an amount of 6.98 g is added dropwise to a mixture of 7.1 ml of ClSO3H and 8.9 g of Pcl5 under stirring and cooling to below 20° C. After stirring for half an hour at room temperature, the mixture is poured on ice. The formed precipitate is sucked off, washed with water and dissolved in methylene chloride. After drying, decolorizing with charcoal, filtration, adding diisopropylether and evaporating methylene chloride, the desired 2-methylthio-3-cyano-5-chlorosulphonylthiophene precipitates in an amount of 7.60 g; melting point 112°-115° C. The above chlorosulphonyl compound is converted to the corresponding methylsulphonyl compound via the corresponding sodium sulphinate by adding 7.50 g to 7.6 g of Na2SO3 and 10.1 g of NaHCO3 in 60 ml of water. While stirring the reaction mixture is warmed slowly up to 70° C. and stirred at 70° C. for half an hour. To the solution obtained 3.75 ml of methyl iodide is added; reflux for 5 hours. After evaporating the volatile components in vacuo, the formed precipitate is sucked off, washed with water and recrystallized from methanol. 2-Methylthio-3-cyano-5-methylsulphonylthiophene is obtained in a yield of 2.88 g; melting point 126°-128° C.

1. additionis added
2. washwashed with water
3. customrecrystallized from acetonitrile
4. temperatureAfter cooling down
5. additiondiethylether, water and 20 ml 2N Hcl are added
6. customThe ether phase is separated off
7. washwashed with water
8. customdried
9. filtrationfiltered
10. customevaporated