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tert-Butyl methyl ether → 2,3,4, 6Tetra-O-benzyl-1-O-carboxymethyl-galactopyranose

HRID 1265304
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HRID 1265304 반응식
[CH2:1]([O:8][C@H:9]1[C@@H:15]([O:16][CH2:17][C:18]2[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=2)[C@H:14]([O:24][CH2:25][C:26]2[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=2)[C@@H:13]([CH2:32][O:33][CH2:34][C:35]2[CH:40]=[CH:39][CH:38]=[CH:37][CH:36]=2)[O:12][CH:10]1[OH:11])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.C([O:45][C:46](=[O:49])[CH2:47]Cl)(C)(C)C.COC(C)(C)C>[Cl-].C([N+](CCCC)(CCCC)CCCC)CCC.C1(C)C=CC=CC=1.[OH-].[K+]>[CH2:1]([O:8][C@@H:9]1[C@@H:15]([O:16][CH2:17][C:18]2[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=2)[C@@H:14]([O:24][CH2:25][C:26]2[CH:27]=[CH:28][CH:29]=[CH:30][CH:31]=2)[C@@H:13]([CH2:32][O:33][CH2:34][C:35]2[CH:36]=[CH:37][CH:38]=[CH:39][CH:40]=2)[O:12][CH:10]1[O:11][CH2:47][C:46]([OH:49])=[O:45])[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1
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참가 물질

7

반응물 3

HCID 15413tert-Butyl methyl etherHCID 66052tert-Butyl chloroacetateHCID 110169932,3,4,6-Tetra-O-benzyl-D-mannopyranose

생성물 1

HCID 102107692,3,4, 6Tetra-O-benzyl-1-O-carboxymethyl-galactopyranose

시약·촉매·용매 3

HCID 70681Tetrabutylammonium Chloride촉매
HCID 1140
Toluene
용매
HCID 14797Potassium Hydroxide용매

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온도
0 °C

실험 절차

A mixture that consists of 54.1 g (100 mmol) of 2,3,4,6-tetra-O-benzyl-mannopyranose, 1.39 g (5 mmol) of tetrabutylammonium chloride in 350 ml of toluene and 150 ml of 50% aqueous potassium hydroxide solution is cooled to 0° C. At 0° C., 30.12 g (200 mmol) of chloroacetic acid-tert-butyl ester is added in drops over 20 minutes while being stirred vigorously. It is stirred for one hour at 10° C. 250 ml of methyl-tert-butyl ether is added, the organic phase is separated, and the aqueous phase is extracted twice with 250 ml of water. The solvent of the combined organic phases is distilled off in a vacuum, and the residue is taken up in 500 ml of ethanol. 40 ml of 50% aqueous sodium hydroxide solution is added, and it is refluxed for 0.5 hour. It is cooled to 0° C., set at pH 8 with 10% aqueous hydrochloric acid, and then the solvent is distilled off (vacuum). The residue is shaken up in 300 ml of water and 500 ml of ethyl acetate, and the pH of the aqueous phase is set at 2 while being stirred (10% aqueous hydrochloric acid). The organic phase is separated, and the aqueous phase is extracted once more with 200 ml of ethyl acetate. The combined organic phases are dried on magnesium sulfate, the solvent is distilled off in a vacuum, and the residue is chromatographed on silica gel (mobile solvent: dichloromethane/n=hexane/ethanol/acetic acid=20:5:3:0.5). The product-containing fractions are concentrated by evaporation, dissolved in 400 ml of ethyl acetate and shaken out three times with 200 ml of water. Then, the organic phase is separated and evaporated to the dry state in a vacuum.

후처리

  1. stirringIt is stirred for one hour at 10° C
  2. customthe organic phase is separated
  3. extractionthe aqueous phase is extracted twice with 250 ml of water
  4. distillationThe solvent of the combined organic phases is distilled off in a vacuum
  5. addition40 ml of 50% aqueous sodium hydroxide solution is added
  6. temperatureit is refluxed for 0.5 hour
  7. temperatureIt is cooled to 0° C.
  8. distillationthe solvent is distilled off (vacuum)
  9. stirringThe residue is shaken up in 300 ml of water
  10. stirringwhile being stirred (10% aqueous hydrochloric acid)
  11. customThe organic phase is separated
  12. extractionthe aqueous phase is extracted once more with 200 ml of ethyl acetate
  13. customThe combined organic phases are dried on magnesium sulfate
  14. distillationthe solvent is distilled off in a vacuum
  15. customthe residue is chromatographed on silica gel (mobile solvent: dichloromethane/n=hexane/ethanol/acetic acid=20:5:3:0.5)
  16. concentrationThe product-containing fractions are concentrated by evaporation
  17. dissolutiondissolved in 400 ml of ethyl acetate
  18. stirringshaken out three times with 200 ml of water
  19. customThen, the organic phase is separated
  20. customevaporated to the dry state in a vacuum

출처 및 근거

ORD 기록
ord-91043719a1bf44f2b95dd2489b481501
출처 데이터셋
uspto-grants-2003_04
DOI
10.6084/m9.figshare.5104873.v1
특허 번호
US06545135B2

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