反应详情

A solution of HBr and AcOH was prepared by mixing 48% HBr and glacial AcOH in a 64:35 ratio. To 112 mL of the HBr/AcOH mixture was added 5.5 g (8.2 mmol) of 3,6,9-tris(ρ-tolylsulfonyl)-3,6,9,15-tetraazabicyclo[9.3.1]pentadeca-1(15),11,13-triene (prepared by the procedure of Example B) and the reaction mixture was heated at mild reflux with constant stirring for 72 hrs. The reaction mixture was then cooled to room temperature and concentrated to approximately 1/10 of the original volume. The remaining solution was stirred vigorously and 15-20 mL of diethyl ether was added. A off-white solid formed which was filtered, washed with diethyl ether, and dried in vacuo. The dry tetrahydrobromide salt was then dissolved in 10 mL of water, adjusted to pH 9.5 with NaOH (50% w/w) and continuously extracted with chloroform for 4 hrs. After drying over anhydrous sodium sulfate, the chloroform was evaporated to give a Light-tan oil which gradually crystallized upon standing at room temperature to yield 1.2 g (71%) of the title product, mp 86°-88° C. and further characterized by:

1. customprepared by the procedure of Example B) and the reaction mixture
2. temperaturewas heated
3. temperatureat mild reflux
4. concentrationconcentrated to approximately 1/10 of the original volume
5. stirringThe remaining solution was stirred vigorously
6. addition15-20 mL of diethyl ether was added
7. customA off-white solid formed which
8. filtrationwas filtered
9. washwashed with diethyl ether
10. customdried in vacuo
11. dissolutionThe dry tetrahydrobromide salt was then dissolved in 10 mL of water
12. extractioncontinuously extracted with chloroform for 4 hrs
13. dry with materialAfter drying over anhydrous sodium sulfate
14. customthe chloroform was evaporated
15. customto give a Light-tan oil which
16. customgradually crystallized
17. customupon standing at room temperature