Sodium Hydroxide → 1-(2,3,4,6-Tetra-O-acetyl-beta-D-glucopyranosyloxy)-pyridin-2(1H)-one

HRID 336096ノート

反応式

HRID 336096 の反応式
[OH:1][N:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]1=[O:8].[C:9]([OH:12])(=[O:11])[CH3:10].[C:13]([OH:16])(=[O:15])[CH3:14].[C:17]([OH:20])(=[O:19])[CH3:18].[C:21]([OH:24])(=[O:23])[CH3:22].Br[C@@:26]1([O:35][C@H:34]([CH2:36]O)[C@@H:32](O)[C@H:30](O)[C@H:28]1O)O.[OH-].[Na+]>ClCCl.[Br-].C([N+](CCCC)(CCCC)CCCC)CCC.C(OCC)(=O)C>[C:9]([O:12][C@@H:28]1[C@@H:30]([O:15][C:13](=[O:16])[CH3:14])[C@H:32]([O:19][C:17](=[O:20])[CH3:18])[C@@H:34]([CH2:36][O:23][C:21](=[O:24])[CH3:22])[O:35][C@H:26]1[O:1][N:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]1=[O:8])(=[O:11])[CH3:10]

参加物

7

反応物 3

HCID 14798Sodium HydroxideHCID 69975HydroxypyridinoneHCID 866603511-Bromo alpha-D glucose tetraacetate

生成物 1

HCID 679959261-(2,3,4,6-Tetra-O-acetyl-beta-D-glucopyranosyloxy)-pyridin-2(1H)-one収率 29%

試薬・触媒・溶媒 3

HCID 74236Tetrabutylammonium Bromide触媒HCID 6344Dichloromethane溶媒HCID 8857Ethyl Acetate溶媒

反応条件

温度
35 °C

実験手順

1-Hydroxypyridine-2(1H)-one (1, 0.50 g, 4.5 mmol) was dissolved in 10 mL of dichloromethane. To this was added 1-bromo-α-D-glucose tetraacetate (0.74 g, 1.8 mmol) and tetrabutylammonium bromide (0.58 g, 1.8 mmol). After heating to 35° C., 10 mL of 1.0 M NaOH was added. The heterogeneous reaction mixture was vigorously stirred for 3 h. After cooling to room temperature, the reaction was diluted with 20 mL of ethyl acetate then washed 2× with 1.0 M NaOH (20 mL) followed by water and brine. The organic layer was dried over MgSO4, filtered, and concentrated for silica gel column purification in 2% MeOH in CH2Cl2 yielding an off-white solid in 29% yield (0.23 g). 1H NMR (500 MHz, CDCl3) δ=7.51 (dd, J1=6.9 Hz, J2=1.8 Hz, 1H), 7.28 (dt, J1=8.6 Hz, J2=2.9 Hz, 1H), 6.60 (dd, J1=9.8 Hz, J2=1.8 Hz, 1H), 6.04 (dt, J1=6.9 Hz, J2=1.7 Hz, 1H), 5.29 (t, J=9.2 Hz, 1H), 5.21 (d, J=8.6 Hz, 1H), 5.16 (t, J=9.8 Hz, 1H), 5.09 (t, J=9.8 Hz, 1H), 4.26 (dd, J1=12.6 Hz, J2=5.2 Hz, 1H, CHCHaHbOAc), 4.09 (dd, J1=12.1H, J2=2.3 Hz, 1H, CHCHaHbOAc), 3.68 (dq, J1=10.3 Hz, J2=2.3 Hz, 1H, CHCHaHbOAc), 2.16 (s, 3H), 2.02 (s, 3H), 2.00 (s, 6H). 13C NMR (125 MHz, CDCl3) δ=170.5, 170.1, 169.9, 169.5, 157.9, 139.3, 137.8, 122.8, 104.3, 103.5, 77.5, 72.3, 69.3, 68.0, 61.4, 20.7. ESI-MS(+): m/z 441.77[M+H]+, 464.06[M+Na]+.

後処理

  1. temperatureAfter cooling to room temperature
  2. washthen washed 2× with 1.0 M NaOH (20 mL)
  3. dry with materialThe organic layer was dried over MgSO4
  4. filtrationfiltered
  5. concentrationconcentrated for silica gel column purification in 2% MeOH in CH2Cl2 yielding an off-white solid in 29% yield (0.23 g)

出典と根拠

ORDレコード
ord-2433a6192d5f4389acaf70a7ce2545f5
出典データセット
uspto-grants-2014_11
特許番号
US08889638B2

反応ノート

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