Реакция #50734

Уравнение реакции

HBr

HBr AcOH

3,6,9-tris(p-tolylsulfonyl)-3,6,9,15-tetraazabicyclo[9.3.1]pentadeca-1(15),11,13-triene

→

HBr

title product

Выход 71.0%

3,6,9,15-tetraazabicyclo[9.3.1]pentadeca-1(15),11,13-triene

Выход 71.0%

Растворители

AcOH

AcOH

Условия реакции

Обработка

1. 1
   Другоеprepared by the procedure of Example B) and the reaction mixture
2. 2
   Температураwas heated
3. 3
   Температураat mild reflux
4. 4
   Концентрированиеconcentrated to approximately 1/10 of the original volume
5. 5
   workup.STIRRINGThe remaining solution was stirred vigorously
6. 6
   workup.ADDITION15-20 mL of diethyl ether was added
7. 7
   ДругоеAn off-white solid formed which
8. 8
   Фильтрацияwas filtered
9. 9
   Промывкаwashed with diethyl ether
10. 10
    Другоеdried in vacuo
11. 11
    workup.DISSOLUTIONThe dry tetrahydrobromide salt was then dissolved in 10 mL of water
12. 12
    Экстракцияcontinuously extracted with chloroform for 4 hrs
13. 13
    СушкаAfter drying over anhydrous sodium sulfate
14. 14
    Другоеthe chloroform was evaporated
15. 15
    Другоеto give a light-tan oil which
16. 16
    Другоеgradually crystallized
17. 17
    Другоеupon standing at room temperature

Методика

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(p-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. An 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:

Источник