Benzoyl chloride → p-Methylphenyl 3,4,6-Tri-O-benzoyl-1-thio-beta-D-galactopyranoside

HRID 1745921ノート

反応式

HRID 1745921 の反応式
[S:1]([C:13]1[CH:18]=[CH:17][C:16]([CH3:19])=[CH:15][CH:14]=1)[C@@H:2]1[O:10][C@H:9]([CH2:11][OH:12])[C@H:7]([OH:8])[C@H:5]([OH:6])[C@H:3]1[OH:4].[C:20](Cl)(=[O:27])[C:21]1[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=1>C1(C)C=CC=CC=1.C1C=CC=CC=1.CCOC(C)=O>[C:20]([O:6][C@H:5]1[C@@H:7]([O:8][C:20](=[O:27])[C:21]2[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=2)[C@@H:9]([CH2:11][O:12][C:20](=[O:27])[C:21]2[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=2)[O:10][C@@H:2]([S:1][C:13]2[CH:18]=[CH:17][C:16]([CH3:19])=[CH:15][CH:14]=2)[C@@H:3]1[OH:4])(=[O:27])[C:21]1[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=1

参加物

5

反応物 2

HCID 7412Benzoyl chlorideHCID 7315241(2R,3R,4S,5R,6S)-2-(Hydroxymethyl)-6-(p-tolylthio)tetrahydro-2H-pyran-3,4,5-triol

生成物 1

HCID 69964972p-Methylphenyl 3,4,6-Tri-O-benzoyl-1-thio-beta-D-galactopyranoside収率 91.7%

試薬・触媒・溶媒 2

HCID 8857Ethyl Acetate溶媒HCID 160055Benzene, mixed with toluene, dealkylation product溶媒

実験手順

A suspended mixture of p-Methylphenyl 1-thio-β-D-galactopyranoside (Vargas-Berenguel, A. et al. J. Chem. Soc. Perkin Trans 1 1994, 3287) (100 mg, 0.350 mmol) and Bu2SnO (266 mg, 1.04 mmol) in toluene-benzene (1:1, 10 mL) was refluxed for 10 min. The mixture was concentrated to a volume of 2 mL by distillation under Ar, then the hot solution (about 100° C.) was treated with benzoyl chloride (130 μL, 1.12 mmol). After being stirred for 1 h at this temperature, the reaction mixture was diluted with EtOAc (20 mL), cooled to room temperature, filtered through Celite and concentrated. Chromatography of the residue (hexane/EtOAc, 4:1 to 2:1 to 1:1) furnished 15 (192 mg, 91.7%) as white white solid: [α]D22 +15° (c, 0.5, CHCl3); 1H-NMR (250 MHz, CDCl3), δ 5.91 (d, 1H, J=3.1 Hz, H-4), 5.43 (dd, 1H, J=3.3, 9.7 Hz, H-3), 4.720 (d, 1H, J=9.6 Hz, H-1), 4.29 (bt, 1H, J=6.5 Hz, H-5), 4.62 (dd, 1H, J=6.6 Hz, H-6) 4.37 (dd, 1H each, J=11.5 Hz, H-6′), 4.03 (t, 1H, J=9.6 Hz, H-2), 2.38 (s, 3H, Me); 13C-NMR (270 MHz, CDCl3) δ 165.98, 165.90, 165.29, 88.26, 74.97, 74.47, 68.59, 67.34, 62.45, 21.28; HRMS for C40H44O8SiCs (M+Cs) calcd 845.1581. found 845.1609.

後処理

  1. concentrationThe mixture was concentrated to a volume of 2 mL by distillation under Ar
  2. filtrationfiltered through Celite
  3. concentrationconcentrated

出典と根拠

ORDレコード
ord-70db8a6b523742de9974c2f6a50cfc4f
出典データセット
uspto-grants-2006_03
特許番号
US07019131B2

反応ノート

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