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Acetic Anhydride → allyl 2-acetamido-3,4-di-O-acetyl-2-deoxy-6-O-tolylsulfonyl-alpha-D-mannopyranoside

HRID 962425
ノート
印刷プレビュー

反応式

HRID 962425 の反応式
[C:1]([NH:4][C@H:5]1[C@@H:14]([O:15][C:16](=[O:18])[CH3:17])[C@H:13]([O:19][C:20](=[O:22])[CH3:21])[C@@H:12]([CH2:23][O:24]C(=O)C)[O:11][C@@H:6]1[O:7][CH2:8][CH:9]=[CH2:10])(=[O:3])[CH3:2].C[O-].[Na+].[C:31]1([CH3:41])[CH:36]=[CH:35][CH:34]=[CH:33][C:32]=1[S:37](Cl)(=[O:39])=[O:38].C(OC(=O)C)(=O)C>CO.N1C=CC=CC=1.C(Cl)Cl>[C:1]([NH:4][C@H:5]1[C@@H:14]([O:15][C:16](=[O:18])[CH3:17])[C@H:13]([O:19][C:20](=[O:22])[CH3:21])[C@@H:12]([CH2:23][O:24][S:37]([C:32]2[CH:33]=[CH:34][CH:35]=[CH:36][C:31]=2[CH3:41])(=[O:39])=[O:38])[O:11][C@@H:6]1[O:7][CH2:8][CH:9]=[CH2:10])(=[O:3])[CH3:2]
参加物実験手順後処理出典と根拠反応ノート

参加物

8

反応物 4

HCID 7918Acetic AnhydrideHCID 8623o-Toluenesulfonyl chlorideHCID 10942334Sodium MethoxideHCID 13968146allyl 2-acetamido-3,4,6-tri-O-acetyl-2-deoxy-alpha-D-mannopyranoside

生成物 1

HCID 86749068allyl 2-acetamido-3,4-di-O-acetyl-2-deoxy-6-O-tolylsulfonyl-alpha-D-mannopyranoside収率 44%

試薬・触媒・溶媒 3

HCID 887Methanol溶媒
HCID 1049Pyridine溶媒2 回
HCID 6344Dichloromethane溶媒2 回

実験手順

A solution of allyl 2-acetamido-3,4,6-tri-O-acetyl-2-deoxy-α-D-mannopyranoside, prepared as described above, (6.46 g, 16.7 mmol) and methanolic NaOMe (2 mL; 1M solution) in MeOH (100 mL) was stirred for two hours at room temperature, and neutralized by addition of Dowex 50W-X8 [H+]. After the resin was filtered off, the filtrate was concentrated followed by coevaporation with pyridine. A solution of tolylsulfonyl chloride (3.50 g, 18.3 mmol) in pyridine (20 mL) and CH2Cl2 (30 mL) was added dropwise to a cooled solution of the residue in pyridine (30 mL) and CH2Cl2 (50 mL) at 0°-5° C. over 30 minutes, and the mixture was stirred for 10 hours at room temperature then cooled. Acetic anhydride (30 mL) was added to the mixture, and the mixture was stirred for five hours at room temperature. The mixture was concentrated, and the residue was chromatographed on silica gel, with toluene-EtOAc (1:2), to give allyl 2-acetamido-3,4-di-O-acetyl-2-deoxy-6O-tolylsulfonyl-α-D-mannopyranoside (3.68 g, 44%);

後処理

  1. additionneutralized by addition of Dowex 50W-X8 [H+]
  2. filtrationAfter the resin was filtered off
  3. concentrationthe filtrate was concentrated
  4. temperaturethen cooled
  5. stirringthe mixture was stirred for five hours at room temperature
  6. concentrationThe mixture was concentrated
  7. customthe residue was chromatographed on silica gel, with toluene-EtOAc (1:2)

出典と根拠

ORDレコード
ord-66e8742b4a6f4f76915dacf36e6eef53
出典データセット
uspto-grants-1998_06
DOI
10.6084/m9.figshare.5104873.v1
特許番号
US05759823

反応ノート

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