Hydrochloric Acid → (3aS,4S,6R,6aR)-6-[6-[(2,2-Diphenylethyl)amino]-2-(ethoxycarbonyl)-9H-purin-9-yl]-2,2-dimethyltetrahydrofuro[3,4-d][1,3]dioxole-4-carboxylic acid

HRID 10469

반응식

HRID 10469 반응식
[OH:1][CH2:2][C@@H:3]1[C@H:7]2[O:8][C:9]([CH3:12])([CH3:11])[O:10][C@H:6]2[C@H:5]([N:13]2[CH:21]=[N:20][C:19]3[C:14]2=[N:15][C:16]([C:37]([O:39][CH2:40][CH3:41])=[O:38])=[N:17][C:18]=3[NH:22][CH2:23][CH:24]([C:31]2[CH:36]=[CH:35][CH:34]=[CH:33][CH:32]=2)[C:25]2[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=2)[O:4]1.P([O-])(O)(O)=[O:43].[Na+].Cl([O-])=O.[Na+].S([O-])([O-])=O.[Na+].[Na+].Cl>C(#N)C.O.Cl[O-].[Na+]>[C:31]1([CH:24]([C:25]2[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=2)[CH2:23][NH:22][C:18]2[N:17]=[C:16]([C:37]([O:39][CH2:40][CH3:41])=[O:38])[N:15]=[C:14]3[C:19]=2[N:20]=[CH:21][N:13]3[C@H:5]2[C@@H:6]3[O:10][C:9]([CH3:11])([CH3:12])[O:8][C@@H:7]3[C@@H:3]([C:2]([OH:43])=[O:1])[O:4]2)[CH:36]=[CH:35][CH:34]=[CH:33][CH:32]=1

참가 물질

9

반응물 5

HCID 313Hydrochloric AcidHCID 24437Sodium SulfiteHCID 10166440ethyl 9-[(3aR,4R,6R,6aR)-6-(hydroxymethyl)-2,2-dimethyltetrahydrofuro[3,4-d][1,3]dioxol-4-yl]-6-[(2,2-diphenylethyl)amino]-9H-purine-2-carboxylateHCID 23668197Sodium ChloriteHCID 23672064Monosodium phosphate

생성물 1

HCID 10120772(3aS,4S,6R,6aR)-6-[6-[(2,2-Diphenylethyl)amino]-2-(ethoxycarbonyl)-9H-purin-9-yl]-2,2-dimethyltetrahydrofuro[3,4-d][1,3]dioxole-4-carboxylic acid

시약·촉매·용매 3

HCID 23665760Sodium Hypochlorite촉매HCID 962Water용매3회HCID 6342Acetonitrile용매

실험 절차

To a solution of ethyl 9-[(3aR,4R,6R,6aR)-6-(hydroxymethyl)-2,2-dimethyltetrahydrofuro[3,4-d][1,3]dioxol-4-yl]-6-[(2,2-diphenylethyl)amino]-9H-purine-2-carboxylate (Preparation 66) (15.4 g, 0.0276 moles) in acetonitrile under an atmosphere of nitrogen was added 2,2,6,6-tetramethylpiperidinyl-1-oxy, free radical (0.30 g, 0.0019 moles) and aqueous sodium dihydrogen phosphate (120 ml of a 0.67M solution). The resultant mixture was heated to 45° C. with stirring. A solution of sodium chlorite (6.5 g, 0.072 moles) in water (75 ml) and a solution of sodium hypochlorite (0.32 ml of commercial solution with 12% w/v available chlorine, 0.000551 moles) in water (38 ml) were added separately and simultaneously to the stirred mixture over a period of 1 hour. The resultant mixture was then stirred at 45–50° C. for 10 hours, and for 18 hours at ambient temperature. The reaction mixture was then added to a solution of sodium sulphite (18 g, 0.143 moles) in water (300 ml) with stirring. After stirring for 5 minutes, the pH was adjusted to 3.7 by the addition of 2M aqueous hydrochloric acid and the mixture was extracted with ethyl acetate (200 ml then 100 ml). The organic phases were combined, dried over anhydrous magnesium sulphate and were then concentrated in vacuo to give the title compound (15.1 g) as a colourless foam that was used as such for the next step. If necessary, this crude product can be purified by standard means, for example by flash chromatography on silica gel.

후처리

  1. stirringwith stirring
  2. stirringAfter stirring for 5 minutes
  3. extractionthe mixture was extracted with ethyl acetate (200 ml
  4. dry with materialdried over anhydrous magnesium sulphate
  5. concentrationwere then concentrated in vacuo

출처 및 근거

ORD 기록
ord-c861fea8709446249bd3147edec32b75
출처 데이터셋
uspto-grants-2006_08
특허 번호
US07094769B2

연결된 노트

불러오는 중…