反应详情

8 g of 10-hydroxy-10,11-dihydro-5,10-imino-[5H]-dibenzo (a,d) cycloheptene-11-one dl were added at 10° C to 400 ml of dioxane containing 16 g of lithium aluminum hydride and the mixture was refluxed for 3 days. 8 g of lithium aluminum hydride were added thereto and the mixture was refluxed for another 48 hours and after cooling, 700 ml of tetrahydrofuran, 150 ml of isopropanol, 50 ml of water and then 250 ml of concentrated hydrochloric acid were added thereto. The tetrahydrofuran and the dioxane were distilled off and 1000 ml of methylene chloride containing 20% methanol were added thereto. The mixture was made alkaline with sodium hydroxide addition and was extracted with methylene chloride containing 20% methanol. The extracts were washed with water, dried over magnesium sulfate and concentrated to dryness. The oil residue was dissolved in methylene chloride and the solution was washed with 2N hydrochloric acid. The combined acid wash waters were made alkaline with sodium hydroxide and extracted twice with ether. The ether solution was washed with water, dried over magnesium sulfate and concentrated to dryness under reduced pressure. The residue was chromatographed over silica gel and was eluted with a 92.5-7.5 chloroform-methanol mixture. Crystallization from methylene chloride gave 11-hydroxy-10,11-dihydro-5,10-imino-[5H]-dibenzo (a,d) cycloheptene dl cis melting at 200° and then 210° C.

1. temperaturethe mixture was refluxed for 3 days
2. temperaturethe mixture was refluxed for another 48 hours
3. temperatureafter cooling
4. distillationThe tetrahydrofuran and the dioxane were distilled off
5. addition1000 ml of methylene chloride containing 20% methanol were added
6. additionwith sodium hydroxide addition
7. extractionwas extracted with methylene chloride containing 20% methanol
8. washThe extracts were washed with water
9. dry with materialdried over magnesium sulfate
10. concentrationconcentrated to dryness
11. dissolutionThe oil residue was dissolved in methylene chloride
12. washthe solution was washed with 2N hydrochloric acid
13. washThe combined acid wash waters
14. extractionextracted twice with ether
15. washThe ether solution was washed with water
16. dry with materialdried over magnesium sulfate
17. concentrationconcentrated to dryness under reduced pressure
18. customThe residue was chromatographed over silica gel
19. washwas eluted with a 92.5-7.5 chloroform-methanol mixture
20. customCrystallization from methylene chloride