반응 #61572

반응 방정식

3-phenacyl carboxy indole

hydrazine hydrate

MeOH

→

1,5-dihydro-3-phenyl-[1,2]diazepino[4,5,6-cd]-indol-6-one

용매

HCl

반응 조건

후처리

1. 1
   온도the solution was heated
2. 2
   온도at reflux for 3 h
3. 3
   기타The reaction was quenched with ice/water
4. 4
   추출extracted with CH2Cl2 (30 mL×3)
5. 5
   세척The organic solution was washed with water and brine
6. 6
   건조dried (Na2SO4)
7. 7
   여과filtered
8. 8
   농축concentrated
9. 9
   기타The crude product was crystallized (CH2Cl2/hexanes)

실험 절차

A solution of methyl indole-4-carboxylate (40 mg, 0.23 mmol) in dichloroethane (2 mL) was treated with benzoyl chloride (0.69 mmol) at room temperature. The orange solution was cooled with an ice/water bath and treated with aluminum chloride (0.69 mmol). The dark-orange solution was warmed to room temperature over 1 hour, then poured into ice-cold aqueous 2M HCl. The aqueous solution was adjusted to pH=9-10 with KOH (s), and extracted with CH2Cl2 (10 mL×3). The organic solution was washed with water and brine, dried (Na2SO4), filtered, and concentrated. The crude product was purified by radial chromatography (1 mm silica gel; 3% MeOH in CHCl3) to give methyl 3-phenacyl-indole-4-carboxylate as an oil, 63 mg (99%). A solution of the 3-phenacyl carboxy indole (60 mg, 0.25 mmol) in MeOH (5 mL) and conc. HCl (0.1 mL) was treated with hydrazine hydrate (36 mg, 0.73 mmol) and the solution was heated at reflux for 3 h. The reaction was quenched with ice/water, and the aqueous layer was adjusted to pH=10-11 with KOH (s) and extracted with CH2Cl2 (30 mL×3). The organic solution was washed with water and brine, dried (Na2SO4), filtered, and concentrated. The crude product was crystallized (CH2Cl2/hexanes) to give 1,5-dihydro-3-phenyl-[1,2]diazepino[4,5,6-cd]-indol-6-one, 33 mg (51%), as a bright-yellow solid. mp 177-179° C.; 1H NMR (300 MHz, d6-DMSO) δ 7.22 (m, 2H), 7.47 (m, 3H), 7.58 (m, 4H), 10.45 (s, 1H), 11.92 (br s, 1H); Anal. (C10H7N3O.0.75 H2O) C, H, N.

출처