反应详情

To 40 ml of absolute ethanol was added 5.0 g (0.0194 mole) of 2-(2-chloroethyl-2,3-dihydro-4-methylpyrido[3,2-f]-1,4-oxazepine-5(4H)-thione, 3.53 g (0.021 mole) of 4-methoxy-N-methylbenzenemethanamine and 2.75 g (0.021 mole) of diisopropylethylamine and the reaction solution heated to reflux for 18 hr. Another 1.0 g (0.006 mole) of 4-methoxy-N-methylbenzenemethanamine was added and heating continued for 4 hr. An additional 1.0 g (0.006 mole) of 4-methoxy-N-methylbenzenemethanamine was added and heating continued overnight. Still an additional 0.6 g (0.0036 mole) of 4-methoxy-N-methylbenzenemethanamine was added and heating continued for 24 hr. The ethanol was removed by rotary evaporation. The residue was taken up in 100 ml of methylene chloride and treated with ~8 ml of acetic anhydride overnight. The methylene chloride was extracted with 3×100 ml of 1N hydrochloric acid. The combined aqueous extracts were washed with 2×100 ml of chloroform, cooled, basified with concentrated sodium hydroxide, and extracted into 3×100 ml of chloroform. The combined organic extracts were dried over sodium sulfate, filtered, concentrated by rotary evaporation, and triturated with isopropyl ether. Because the crystals were still impure, they were dissolved in 100 ml of methylene chloride, washed with 2×50 ml of 4N sodium hydroxide, dried over sodium sulfate, filtered, and concentrated by rotary evaporation. The residue was crystallized from isopropyl alcohol to give 4 g (56%) of yellow analytically pure crystals, m.p. 128°-30° C.

1. temperaturethe reaction solution heated
2. temperatureto reflux for 18 hr
3. temperatureheating
4. temperatureheating continued overnight
5. temperatureheating
6. waitcontinued for 24 hr
7. customThe ethanol was removed by rotary evaporation
8. additiontreated with ~8 ml of acetic anhydride overnight
9. extractionThe methylene chloride was extracted with 3×100 ml of 1N hydrochloric acid
10. washThe combined aqueous extracts were washed with 2×100 ml of chloroform
11. temperaturecooled
12. extractionextracted into 3×100 ml of chloroform
13. dry with materialThe combined organic extracts were dried over sodium sulfate
14. filtrationfiltered
15. concentrationconcentrated by rotary evaporation
16. customtriturated with isopropyl ether
17. dissolutionthey were dissolved in 100 ml of methylene chloride
18. washwashed with 2×50 ml of 4N sodium hydroxide
19. dry with materialdried over sodium sulfate
20. filtrationfiltered
21. concentrationconcentrated by rotary evaporation
22. customThe residue was crystallized from isopropyl alcohol
23. customto give 4 g (56%) of yellow analytically pure crystals, m.p. 128°-30° C.