1,4-Dibromobenzene → 2,3,4,6-tetra-O-benzyl-1-C-[2-(benzyloxy)-5-[(4-bromophenyl)(hydroxy)methyl]-4-methylphenyl]-D-glucopyranose

HRID 1009863ノート

反応式

HRID 1009863 の反応式
Br[C:2]1[CH:7]=[CH:6][C:5]([Br:8])=[CH:4][CH:3]=1.C([Li])CCC.CCCCCC.[CH2:20]([O:27][C@@H:28]1[C@@H:34]([O:35][CH2:36][C:37]2[CH:42]=[CH:41][CH:40]=[CH:39][CH:38]=2)[C@H:33]([O:43][CH2:44][C:45]2[CH:50]=[CH:49][CH:48]=[CH:47][CH:46]=2)[C@@H:32]([CH2:51][O:52][CH2:53][C:54]2[CH:59]=[CH:58][CH:57]=[CH:56][CH:55]=2)[O:31][C:29]1([C:60]1[CH:65]=[C:64]([CH:66]=[O:67])[C:63]([CH3:68])=[CH:62][C:61]=1[O:69][CH2:70][C:71]1[CH:76]=[CH:75][CH:74]=[CH:73][CH:72]=1)[OH:30])[C:21]1[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=1.[Cl-].[NH4+]>O1CCCC1>[CH2:20]([O:27][C@@H:28]1[C@@H:34]([O:35][CH2:36][C:37]2[CH:38]=[CH:39][CH:40]=[CH:41][CH:42]=2)[C@H:33]([O:43][CH2:44][C:45]2[CH:50]=[CH:49][CH:48]=[CH:47][CH:46]=2)[C@@H:32]([CH2:51][O:52][CH2:53][C:54]2[CH:55]=[CH:56][CH:57]=[CH:58][CH:59]=2)[O:31][C:29]1([C:60]1[CH:65]=[C:64]([CH:66]([C:2]2[CH:7]=[CH:6][C:5]([Br:8])=[CH:4][CH:3]=2)[OH:67])[C:63]([CH3:68])=[CH:62][C:61]=1[O:69][CH2:70][C:71]1[CH:72]=[CH:73][CH:74]=[CH:75][CH:76]=1)[OH:30])[C:21]1[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=1

参加物

7

反応物 5

HCID 78041,4-DibromobenzeneHCID 8058HexaneHCID 25517Ammonium ChlorideHCID 86638438HCID 86638438、化合物HCID 178418339Butyllithium

生成物 1

HCID 866384392,3,4,6-tetra-O-benzyl-1-C-[2-(benzyloxy)-5-[(4-bromophenyl)(hydroxy)methyl]-4-methylphenyl]-D-glucopyranose収率 46%

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒2 回

実験手順

To a tetrahydrofuran solution (80 mL) of 1,4-dibromobenzene (6.20 g, 26.1 mmol) was added dropwise under nitrogen atmosphere at −78° C. a 2.67 M n-butyllithium solution in hexane (10.5 mL, 26.1 mmol), and the mixture was stirred for 15 minutes at the same temperature. Then a tetrahydrofuran solution (20 mL) of 2,3,4,6-tetra-O-benzyl-1-C-[2-(benzyloxy)-5-formyl-4-methylphenyl]-D-glucopyranose (10.0 g, 13.0 mmol) was added dropwise, and the mixture was stirred for 30 minutes at the same temperature. To the reaction solution was added a saturated aqueous solution of ammonium chloride, and the resulting mixture was extracted with ethyl acetate. The organic layer was washed with brine, and dried with anhydrous magnesium sulfate. The drying agent was filtered off, and the solvent was evaporated under reduced pressure. Thus obtained residue was purified with silica gel column chromatography (hexane:ethyl acetate=2:1). In addition, the residue was further purified with NH type silica gel column chromatography (hexane:ethyl acetate=1:1) to obtain the yellow oily title compound (5.50 g, 46%) as a diastereomeric mixture.

後処理

  1. stirringthe mixture was stirred for 30 minutes at the same temperature
  2. extractionthe resulting mixture was extracted with ethyl acetate
  3. washThe organic layer was washed with brine
  4. dry with materialdried with anhydrous magnesium sulfate
  5. filtrationThe drying agent was filtered off
  6. customthe solvent was evaporated under reduced pressure
  7. customThus obtained residue was purified with silica gel column chromatography (hexane:ethyl acetate=2:1)
  8. customIn addition, the residue was further purified with NH type silica gel column chromatography (hexane:ethyl acetate=1:1)

出典と根拠

ORDレコード
ord-218af9e8803e40fabee6485f1927bbc4
出典データセット
uspto-grants-2011_07
特許番号
US07973012B2

反応ノート

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