反应详情

3.73 g (10 mmol) of 7-chloro-4,5-dihydro-3-iodo-5-methyl-6H-imidazo[1,5-a][1,4]benzodiazepin-6-one was heated to 100° in a pressure tube for 20 hours with 0.87 g of 3-methyl-1-butyne, 70 mg of bis-(triphenylphosphine)-palladium(II) dichloride and 19 mg of copper(I) iodide in 20 ml of diethylamine and 10 ml of ethylene chloride. By evaporation of the reaction mixture and chromatography of the residue on silica gel while eluting with ethyl acetate there was obtained a mixture of product and starting material of about 2:1. In order to remove the starting material, the mixture was heated under reflux the reaction mixture and chromatography of the residue on silica gel while eluting with ethyl acetate there was obtained a mixture of product and starting material of about 2:1. In order to remove the starting material, the mixture was heated under reflux for 5 hours with 0.8 ml of 2-methyl-3-butyn-2-ol, 70 mg of bis-(triphenylphosphine)-palladium(II) dichloride and 15 mg of copper(I) iodide in 15 ml of diethylamine. By evaporation of the reaction mixture and chromatography of the residue on silica gel while eluting with ethyl acetate the byproduct can be separated from the desired product. After recrystallization from ether there was obtained 7-chloro-4,5-dihydro-5-methyl-3-(3-methyl-1-butynyl)-6H-imidazo[1,5-a][1,4]benzodiazepin-6-one of melting point 128°-130°.

1. customBy evaporation of the reaction mixture and chromatography of the residue on silica gel
2. washwhile eluting with ethyl acetate
3. customthere was obtained
4. additiona mixture of product
5. customIn order to remove the starting material
6. temperaturethe mixture was heated
7. temperatureunder reflux the reaction mixture and chromatography of the residue on silica gel
8. washwhile eluting with ethyl acetate
9. customthere was obtained
10. additiona mixture of product
11. customIn order to remove the starting material
12. temperaturethe mixture was heated
13. temperatureunder reflux for 5 hours with 0.8 ml of 2-methyl-3-butyn-2-ol, 70 mg of bis-(triphenylphosphine)-palladium(II) dichloride and 15 mg of copper(I) iodide in 15 ml of diethylamine
14. customBy evaporation of the reaction mixture and chromatography of the residue on silica gel
15. washwhile eluting with ethyl acetate the byproduct
16. customcan be separated from the desired product
17. customAfter recrystallization from ether