Reaction #56630

Reaction equation

2,5,6-Trichloro-3-formyl-1-(β-D-ribofuranosyl)indole

methyl hydrazinocarboxylate

water

→

4.31

Yield 85.0%

2,5,6-Trichloro-3-[N-(methoxycarbonylamino)iminomethylidene]-1-(β-D-ribofuranosyl)indole

Yield 85.0%

Solvents

MeOH

Conditions

Workup

1. 1
   TemperatureThe resulting solution was heated on a 60 C oil bath for 16 h
2. 2
   Otherthe solvent evaporated to approx 50 mL
3. 3
   TemperatureThe resulting suspension was cooled to 4C
4. 4
   Filtrationfiltered
5. 5
   Washthe solids rinsed with cold water (25 mL)
6. 6
   OtherThe solids were recrystallized

Procedure

2,5,6-Trichloro-3-formyl-1-(β-D-ribofuranosyl)indole (4.3, 122 mg, 0.32 mmol) was dissolved in MeOH (10 mL) to which was added methyl hydrazinocarboxylate (115 mg, 1.3 mmol). The resulting solution was heated on a 60 C oil bath for 16 h, then cooled to room temperature and poured into 100 mL of water, and the solvent evaporated to approx 50 mL. The resulting suspension was cooled to 4C, then filtered and the solids rinsed with cold water (25 mL). The solids were recrystallized from boiling EtOAc/hexane to yield 123 mg (85%) of 4.31 as a pale pink crystalline solid: mp 217-219 C; Rf 0.2 (10% MeOH/CHCl3); 1H-NMR (500 MHz, DMSO-d6): δ 11.17 (b, 1H, D2O exch.), 8.54 (s, 1H), 8.42 (s, 1H), 8.22 (b, 1H), 5.92 (d, 1H), 5.42-5.37 (m, 2H, D2O exch.), 5.25 (d, 1H, D2O exch.), 4.43 (q, 1H), 4.15 (d, 1H), 3.98 (d, 1H), 3.72 (b, 5H). 13C-NMR (125 MHz, DMSO-d6): δ 153.88, 133.17, 129.33, 126.08, 124.96, 124.06, 122.17, 115.34, 108.59, 88.76, 86.03, 71.30, 69.73, 69.62, 61.07, 52.04. HRMS (ES) m/z calcd. for C16H16Cl3N3O6·Na 474.0002, found 473.9999. Anal calcd for C16H16Cl3N3O6·¼H2O: C, 42.03; H, 3.64; N, 9.19. Found: C, 42.11; H, 3.92; N, 9.18.

Source