Dichloromethane → HCID 86594211、化合物

HRID 2357147ノート

反応式

HRID 2357147 の反応式
[C:1]([NH:9][C:10]1[C:11]2[N:12]=[CH:13][N:14]([C:23]=2[N:24]=[CH:25][N:26]=1)[C@@H:15]1[O:22][C@H:19]([CH2:20][OH:21])[C@@H:17]([OH:18])[CH2:16]1)(=[O:8])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[C:27]([C:35]1[CH:36]=[CH:37][C:38]([N+:48]([O-:50])=[O:49])=[C:39]([CH:41]([CH3:47])[CH2:42][O:43][C:44](Cl)=[O:45])[CH:40]=1)(=[O:34])[C:28]1[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=1.C(Cl)Cl>N1C=CC=CC=1>[C:1]([NH:9][C:10]1[C:11]2[N:12]=[CH:13][N:14]([C:23]=2[N:24]=[CH:25][N:26]=1)[C@@H:15]1[O:22][C@H:19]([CH2:20][O:21][C:44]([O:43][CH2:42][CH:41]([C:39]2[CH:40]=[C:35]([C:27](=[O:34])[C:28]3[CH:29]=[CH:30][CH:31]=[CH:32][CH:33]=3)[CH:36]=[CH:37][C:38]=2[N+:48]([O-:50])=[O:49])[CH3:47])=[O:45])[C@@H:17]([OH:18])[CH2:16]1)(=[O:8])[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

参加物

5

反応物 3

HCID 6344DichloromethaneHCID 107558N-benzoyl-2'-deoxyadenosineHCID 85991107HCID 85991107、化合物

生成物 1

HCID 86594211HCID 86594211、化合物収率 57%

試薬・触媒・溶媒 1

HCID 1049Pyridine溶媒2 回

反応条件

温度
0 °C

実験手順

N6-benzoyl-2′-deoxyadenosine (23.63 g, 67 mmol) was dried by coevaporation with abs. pyridine (3×100 mL), dissolved in pyridine (400 mL) and cooled to 0° C. A solution of 2-(5-benzoyl-2-nitrophenyl)-1-propyl oxycarbonylchloride (19f) (35 mmol, prepared from 10.00 g of alcohol 4f) in abs. CH2Cl2 (100 mL) was added drop wise over a period of 2.5 hours. After stirring over night at ambient temperature the reaction mixture was concentrated in vacuo, dissolved in CH2Cl2 and washed with water (2×200 mL). Excess N6-benzoyl-2′-deoxyadenosine precipitated as a crystalline solid from the aqueous phase and was recovered by filtration. The organic phase was diluted with toluene (100 mL), concentrated in vacuo and purified by silica column chromatography (315 g silica, column diameter 5.5 cm, gradient: CH2Cl2 to CH2Cl2/methanol 100:5) to provide 13.20 g (19.8 mmol, 57%) of the product 29 as a slightly yellow foam. 1H-NMR (250 MHz, DMSO-d6): δ 11.02 and 11.01 (2 s, 2H, NH), 8.67 (s, 1H, H—C(2)), 8.51 and 8.50 (2 s, 2H, H—C(8)), 8.00-7.48 (m, 13H, arom.), 6.46 (m, 1H, H—C(1′)), 5.47 (d, 1H, HO—C(3′)), 4.46 (m, 1H, H—C(3′)), 4.28 (m, 4H, 2×CH2), 4.03 (m, 1H, H—C(4′)), 3.50 (m, β-CH), 2.86 (m, 1H, H—C(2″)), 2.40 (m, 1H, H—C(2′)), 1.28 (d, 3H, γ-CH3).

後処理

  1. concentrationwas concentrated in vacuo
  2. dissolutiondissolved in CH2Cl2
  3. washwashed with water (2×200 mL)
  4. customExcess N6-benzoyl-2′-deoxyadenosine precipitated as a crystalline solid from the aqueous phase
  5. filtrationwas recovered by filtration
  6. additionThe organic phase was diluted with toluene (100 mL)
  7. concentrationconcentrated in vacuo
  8. custompurified by silica column chromatography (315 g silica, column diameter 5.5 cm, gradient: CH2Cl2 to CH2Cl2/methanol 100:5)

出典と根拠

ORDレコード
ord-c644f005e3e34e068de1de6e71b1cec4
出典データセット
uspto-grants-2010_07
特許番号
US07759513B2

反応ノート

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