4-Toluenesulfonyl chloride → [2-(2-{2-[2-(2-{4-[2-(2-{2-[2-(2-Azido-ethoxy)-ethoxy]-ethoxy}-ethoxy)-ethoxy]-phenoxy}-ethoxy)-ethoxy]-ethoxy}-ethoxy)-ethoxy]acetic acid tert-butyl ester

HRID 2075637ノート

反応式

HRID 2075637 の反応式
[C:1]([O:5][C:6](=[O:46])[CH2:7][O:8][CH2:9][CH2:10][O:11][CH2:12][CH2:13][O:14][CH2:15][CH2:16][O:17][CH2:18][CH2:19][O:20][CH2:21][CH2:22][O:23][C:24]1[CH:29]=[CH:28][C:27]([O:30][CH2:31][CH2:32][O:33][CH2:34][CH2:35][O:36][CH2:37][CH2:38][O:39][CH2:40][CH2:41][O:42][CH2:43][CH2:44]O)=[CH:26][CH:25]=1)([CH3:4])([CH3:3])[CH3:2].C1(C)C=CC(S(Cl)(=O)=O)=CC=1.[N-:58]=[N+:59]=[N-:60].[Na+].C(=O)([O-])O.[Na+]>N1C=CC=CC=1.CN(C)C1C=CN=CC=1.CN(C=O)C.C(OCC)(=O)C.O>[C:1]([O:5][C:6](=[O:46])[CH2:7][O:8][CH2:9][CH2:10][O:11][CH2:12][CH2:13][O:14][CH2:15][CH2:16][O:17][CH2:18][CH2:19][O:20][CH2:21][CH2:22][O:23][C:24]1[CH:29]=[CH:28][C:27]([O:30][CH2:31][CH2:32][O:33][CH2:34][CH2:35][O:36][CH2:37][CH2:38][O:39][CH2:40][CH2:41][O:42][CH2:43][CH2:44][N:58]=[N+:59]=[N-:60])=[CH:26][CH:25]=1)([CH3:4])([CH3:3])[CH3:2]

参加物

10

反応物 4

HCID 73974-Toluenesulfonyl chlorideHCID 33557Sodium AzideHCID 516892Sodium BicarbonateHCID 67089258[2-(2-{2-[2-(2-{4-[2-(2-{2-[2-(2-Hydroxy-ethoxy)-ethoxy]-ethoxy}-ethoxy)-ethoxy]-phenoxy}-ethoxy)-ethoxy]-ethoxy}-ethoxy)-ethoxy]acetic acid tert-butyl ester

生成物 1

HCID 86607044[2-(2-{2-[2-(2-{4-[2-(2-{2-[2-(2-Azido-ethoxy)-ethoxy]-ethoxy}-ethoxy)-ethoxy]-phenoxy}-ethoxy)-ethoxy]-ethoxy}-ethoxy)-ethoxy]acetic acid tert-butyl ester収率 73%

試薬・触媒・溶媒 5

HCID 142844-(Dimethylamino)pyridine触媒HCID 962Water溶媒HCID 1049Pyridine溶媒HCID 6228Dimethylformamide溶媒HCID 8857Ethyl Acetate溶媒2 回

反応条件

温度
60 °C

実験手順

To a solution of Compound 26 (254 mg, 0.451 mmol) in pyridine (1.5 ml), 4-dimethylaminopyridine (11 mg, 0.09 mmol) was added; after cooling with ice, p-toluenesulfonyl chloride (130 mg, 0.677 mmol) was added, and this was followed by stirring for 2 hours while heating to 30° C.-40° C. Ice was added thereto to stop the reaction, after which ethyl acetate and water were added. Extraction from ethyl acetate was conducted, and the combined organic phases were washed with a saturated aqueous solution of potassium hydrogen sulfate, a saturated aqueous solution of sodium hydrogen carbonate and saturated brine, and dried with sodium sulfate. Filtration and concentration under reduced pressure were conducted to yield a crude product. The crude product obtained was dissolved in DMF (1 ml), and sodium azide (264 mg, 4.1 mmol) was added thereto. The solution was heated to about 60° C., and this was followed by stirring for 90 minutes. The solution was allowed to cool to room temperature, after which it was diluted with ethyl acetate. After a saturated aqueous solution of sodium hydrogen carbonate was further added, extraction from ethyl acetate was conducted. The combined organic phases were washed with saturated brine, thereafter dried with sodium sulfate. Filtration and concentration under reduced pressure were conducted, after which the concentrate was purified by silica gel column chromatography (Yamazen YFLC Gel, eluent; ethyl acetate solution containing 10% methanol) to yield Compound 27 (colorless oil 196 mg, 73%, 2 steps).

後処理

  1. additionwas added
  2. temperaturewhile heating to 30° C.-40° C
  3. additionIce was added
  4. customthe reaction
  5. extractionExtraction from ethyl acetate
  6. washthe combined organic phases were washed with a saturated aqueous solution of potassium hydrogen sulfate
  7. dry with materiala saturated aqueous solution of sodium hydrogen carbonate and saturated brine, and dried with sodium sulfate
  8. filtrationFiltration and concentration under reduced pressure
  9. customto yield a crude product
  10. customThe crude product obtained
  11. stirringby stirring for 90 minutes
  12. temperatureto cool to room temperature
  13. extractionextraction from ethyl acetate
  14. washThe combined organic phases were washed with saturated brine
  15. dry with materialdried with sodium sulfate
  16. filtrationFiltration and concentration under reduced pressure
  17. customafter which the concentrate was purified by silica gel column chromatography (Yamazen YFLC Gel, eluent; ethyl acetate solution containing 10% methanol)

出典と根拠

ORDレコード
ord-93aa22708fc244f5866ed2b92cf95690
出典データセット
uspto-grants-2011_04
特許番号
US07919653B2

反応ノート

読み込み中…