تفاعل #11110

معادلة التفاعل

Diphenylphosphoryl azide

9-methoxy-1,3-dioxo-1,2,3,6-tetrahydropyrrolo[3,4-c]carbazole-4-carboxylic acid

Et3N

→

4-amino-9-methoxypyrrolo[3,4-c]carbazole-1,3(2H,6H)-dione

المردود 93.4%

4-Amino-9-methoxypyrrolo[3,4-c]carbazole-1,3(2H,6H)-dione

المردود 93.4%

المذيبات

t-butanol

CH2Cl2 trifluoroacetic acid

ظروف التفاعل

المعالجة

1. 1
   درجة الحرارةthe mixture was refluxed under an atmosphere of nitrogen for 16 h
2. 2
   تركيزThe solution was concentrated in vacuo
3. 3
   أخرىthe residue partitioned between EtOAc and saturated aqueous NaHCO3
4. 4
   أخرىInsoluble material was removed by filtration of the two layers through Celite
5. 5
   غسيلwashing through with more EtOAc
6. 6
   أخرىThe organic phase was dried
7. 7
   أخرىthe drying agent was removed
8. 8
   تركيزthe solution was concentrated to dryness
9. 9
   أخرىgave a yellow solid
10. 10
    تركيزAfter concentration in vacuo the residue
11. 11
    أخرىwas partitioned between EtOAc and saturated aqueous NaHCO3 solution
12. 12
    تجفيفThe EtOAc solution was dried
13. 13
    أخرىthe drying agent was removed
14. 14
    تركيزthe solution was concentrated to dryness
15. 15
    أخرىto give an orange solid which
16. 16
    أخرىchromatographed
17. 17
    غسيلElution with ethyl acetate/petroleum ether (1:1)

الإجراء التجريبي

Diphenylphosphoryl azide (1.81 mL, 8.38 mmol) was added to a mixture of the 9-methoxy-1,3-dioxo-1,2,3,6-tetrahydropyrrolo[3,4-c]carbazole-4-carboxylic acid (2.55 g, 8.22 mmol), prepared as in example 4, and Et3N (1.17 mL, 8.38 mmol) in anhydrous t-butanol (300 mL) and the mixture was refluxed under an atmosphere of nitrogen for 16 h. The solution was concentrated in vacuo and the residue partitioned between EtOAc and saturated aqueous NaHCO3. Insoluble material was removed by filtration of the two layers through Celite, washing through with more EtOAc. The organic phase was dried, the drying agent was removed and the solution was concentrated to dryness and gave a yellow solid. This material was dissolved in CH2Cl2/trifluoroacetic acid (1:1) (200 mL) and the solution was held at room temperature for 1 h. After concentration in vacuo the residue was partitioned between EtOAc and saturated aqueous NaHCO3 solution. The EtOAc solution was dried, the drying agent was removed and the solution was concentrated to dryness to give an orange solid which was adsorbed onto silica and chromatographed. Elution with ethyl acetate/petroleum ether (1:1) followed by ethyl acetate and then methanol/ethyl acetate (1:9) gave 4-amino-9-methoxypyrrolo[3,4-c]carbazole-1,3(2H,6H)-dione (6) as an orange powder (2.16 g, 93%), mp 342–345° C. 1H NMR δ [(CD3)2SO] 11.18 (s, 1H), 10.78 (br s, 1H), 8.18 (d, J=2.5 Hz, 1H), 7.29 (d, J=8.7 Hz, 1H), 7.01 (dd, J=8.7, 2.5 Hz, 1H), 6.83 (s, 1H), 6.28 (br s, 2H), 3.82 (s, 3H). Found: C, 63.05; H, 3.99; N, 14.05. C15H11N3O3, 1/2H2O requires C, 63.04; H, 4.06; N, 14.7.

المصدر