Acetamide → HCID 69946643, 화합물

HRID 1281671노트

반응식

HRID 1281671 반응식
[Cl:1][C:2]1[C:10]([CH3:11])=[CH:9][C:5]2[N:6]=[CH:7][NH:8][C:4]=2[CH:3]=1.C(N)(=O)C.O([Si](C)(C)C)S(C(F)(F)F)(=O)=O.C(O[C@@H:32]1[O:49][CH2:48][C@@H:43]([O:44][C:45](=[O:47])[CH3:46])[C@@H:38]([O:39][C:40](=[O:42])[CH3:41])[C@H:33]1[O:34][C:35](=[O:37])[CH3:36])(=O)C.C(=O)(O)[O-].[Na+]>ClCCCl>[Cl:1][C:2]1[C:10]([CH3:11])=[CH:9][C:5]2[N:6]([C@@H:48]3[O:49][CH2:32][C@@H:33]([O:34][C:35](=[O:37])[CH3:36])[C@@H:38]([O:39][C:40](=[O:42])[CH3:41])[C@H:43]3[O:44][C:45](=[O:47])[CH3:46])[CH:7]=[N:8][C:4]=2[CH:3]=1

참가 물질

7

반응물 5

HCID 178AcetamideHCID 65367Trimethylsilyl triflateHCID 97336beta-D-Ribopyranose, 1,2,3,4-tetraacetateHCID 516892Sodium BicarbonateHCID 178422326HCID 178422326, 화합물

생성물 1

HCID 69946643HCID 69946643, 화합물

시약·촉매·용매 1

HCID 111,2-Dichloroethane용매

실험 절차

As described in General Procedure III, 5-chloro-6methylbenzimidazole (1.0 g, 6 mmol), N,O-bis(trimethylsiyl) acetamide (Aldrich, 1.3 ml, 5.2 mmol), and 1,2-dichloroethane (Aldrich Sure Seal, 300 mL) were combined and refluxed under nitrogen for 0.5 h. The solution was cooled to room temperature and trimethylsilyl triflate (Aldrich, 1.3 ml, 6.7 mmol) was added. Immediately, 2.0 g (6.3 mmol) solid 1,2,3,4-tetra-O-acetyl-b-D-ribopyranose (beta-D-ribopyranose 1,2,3,4-tetraacetate, Aldrich, Milwaukee) was added. The solution was stirred under nitrogen at reflux overnight, then poured into 7% aqueous sodium bicarbonate and extracted with chloroform. The organic layer was dried with magnesium sulfate (anhyd), filtered, and evaporated. The crude residue was purified on a silica gel column (5×20 cm, 230-400 mesh) eluting with a step gradient of 0.25 to 2.5% methanol in chloroform to give 0.07 g (0.16 mmol) 5-Chloro-6-methyl-(2,3,4-tri-O-acetyl-beta-D-ribopyranosyl)-1H-benzimidazole; MS (AP+): m/z (rel. intensity) 447 (1.0, M+23 (Na)) 1H NMR (DMSO-d6) δ8.36 (s,1H), 7.90 (s, 1H), 7.68 (s, 1H), 5.97-5.95 (d, 1H, J=9.1 Hz), 5.72-5.69 (m, 2H), 5.41-5.40 (m, 1H), 4.02-3.92 (m, 2H), 2.42 (s, 3H), 2.20 (s, 3H), 1.98 (s, 3H), 1.69 (s, 3H) and 0.090 g (0.21 mmol) 6-Chloro-5-methyl-(2,3,4-tri-O-acetyl-beta-D-ribopyranosyl)-1H-benzimidazole 1H NMR (DMSO-d6) δ8.36 (s,1H), 8.06 (s, 1H), 7.60 (s, 1H), 5.99-5.96 (d, 1H, J=9.6 Hz), 5.73-5.66 (m, 2H), 5.45-5.40 (m, 1H), 4.02-3.92 (m, 2H), 2.37 (s, 3H), 2.20 (s, 3H), 1.98 (s, 3H), 1.69 (s, 3H) and 0.13 g (0.31 mmol) of a mixture of the two regioisomers (11% total yield).

후처리

  1. temperaturerefluxed under nitrogen for 0.5 h
  2. temperatureat reflux overnight
  3. extractionextracted with chloroform
  4. dry with materialThe organic layer was dried with magnesium sulfate (anhyd)
  5. filtrationfiltered
  6. customevaporated
  7. customThe crude residue was purified on a silica gel column (5×20 cm, 230-400 mesh)
  8. washeluting with a step gradient of 0.25 to 2.5% methanol in chloroform

출처 및 근거

ORD 기록
ord-d5114685ac89480fa3413e8f0b8fd8a3
출처 데이터셋
uspto-grants-2002_09
특허 번호
US06455507B1

반응 노트

불러오는 중…