반응 #439206

반응 방정식

2-acetoxymethoxy-1,3-diacetoxypropane

2-Nitroimidazole

1-[2-hydroxy-1-(hydroxymethyl)ethoxy]methyl-2-nitroimidazole

dibutyl tin oxide

sodium phosphate

ammonia

1-[2-hydroxy-1-(hydroxymethyl)ethoxy]methyl-2-nitroimidazole

hexamethyldisilazane

→

1-[1-acetoxymethyl-2-(hydroxy)ethoxy]methyl-2-nitroimidazole

용매

acetonitrile

toluene

반응 조건

후처리

1. 1
   기타The solvent was removed under reduced pressure, and anhydrous methylene chloride (16 mL) and anhydrous tetrahydrofuran (4 mL)
2. 2
   workup.ADDITIONwere added to the residue
3. 3
   workup.ADDITIONacetyl chloride (171 mg) was added to the mixture
4. 4
   기타To the resultant reaction mixture
5. 5
   workup.ADDITIONwas added
6. 6
   여과the resultant mixture was subjected to filtration
7. 7
   추출The resultant residue was subjected to extraction with chloroform (10 mL×3)
8. 8
   추출the thus-obtained extract
9. 9
   workup.ADDITIONwas mixed with the filtrate
10. 10
    기타the mixture was separated
11. 11
    기타obtaining an organic layer
12. 12
    건조The organic layer was dried over sodium sulfate
13. 13
    기타purified through silica gel chromatography

실험 절차

2-Nitroimidazole was subjected to trimethylsilylation by use of hexamethyldisilazane in acetonitrile, and the resultant compound and 2-acetoxymethoxy-1,3-diacetoxypropane were subjected to condensation by use of stannic chloride serving as a catalyst. The resultant product was deprotected by use of methanolic ammonia, to thereby obtain 1-[2-hydroxy-1-(hydroxymethyl)ethoxy]methyl-2-nitroimidazole. The thus-obtained 1-[2-hydroxy-1-(hydroxymethyl)ethoxy]methyl-2-nitroimidazole (0.5 g) was refluxed for two hours together with dibutyl tin oxide (0.6 g) in anhydrous toluene in the presence of molecular sieves having a pore size of 4 Å. The solvent was removed under reduced pressure, and anhydrous methylene chloride (16 mL) and anhydrous tetrahydrofuran (4 mL) were added to the residue. The resultant mixture was cooled to 0° C., and acetyl chloride (171 mg) was added to the mixture, and then the mixture was stirred for 30 minutes. To the resultant reaction mixture, a sodium phosphate buffer having a pH of 7.1 (10 mL) was added, and the resultant mixture was subjected to filtration. The resultant residue was subjected to extraction with chloroform (10 mL×3), and the thus-obtained extract was mixed with the filtrate, and the mixture was separated, thereby obtaining an organic layer. The organic layer was dried over sodium sulfate, and then fractionated and purified through silica gel chromatography, to thereby yield the title compound, 1-[1-acetoxymethyl-2-(hydroxy)ethoxy]methyl-2-nitroimidazole (265 mg).

출처