Methyl chloroformate → T-1095

HRID 1003939Notes

Reaction equation

HRID 1003939 reaction equation
[O:1]1[CH:5]=[CH:4][C:3]2[CH:6]=[C:7]([CH2:10][CH2:11][C:12]([C:14]3[C:19]([OH:20])=[CH:18][C:17]([CH3:21])=[CH:16][C:15]=3[O:22][C@@H:23]3[O:31][C@H:30]([CH2:32][OH:33])[C@@H:28]([OH:29])[C@H:26]([OH:27])[C@H:24]3[OH:25])=[O:13])[CH:8]=[CH:9][C:2]1=2.Cl[C:35]([O:37][CH3:38])=[O:36]>N1C(C)=CC(C)=CC=1C>[O:1]1[CH:5]=[CH:4][C:3]2[CH:6]=[C:7]([CH2:10][CH2:11][C:12]([C:14]3[C:19]([OH:20])=[CH:18][C:17]([CH3:21])=[CH:16][C:15]=3[O:22][C@@H:23]3[O:31][C@H:30]([CH2:32][O:33][C:35]([O:37][CH3:38])=[O:36])[C@@H:28]([OH:29])[C@H:26]([OH:27])[C@H:24]3[OH:25])=[O:13])[CH:8]=[CH:9][C:2]1=2

Participants

4

Reactant 2

HCID 6586Methyl chloroformateHCID 6918439209746-56-5

Product 1

HCID 6918410T-1095Yield 81.1%

Reagents, catalysts & solvents 1

HCID 79532,4,6-TrimethylpyridineSolvent

Conditions

Temperature
0 °C

Procedure

To a solution of 3-(5-benzo[b]furanyl)-2'-(β-D-glucopyranosyloxy)-6'-hydroxy-4'-methylpropiophenone (10 g) in 2,4,6-collidine (100 ml) is added dropwise methyl chloroformate (10.31 g) at 0° C., and the mixture is stirred at 0° C. for 23 hours. The reaction mixture is poured into ice-10% hydrochloric acid (300 ml--300 ml), and the mixture is extracted with ethyl acetate (350 ml). The organic layer is washed with water, a saturated aqueous sodium hydrogen carbonate solution, and a saturated sodium chloride solution, dried, and concentrated under reduced pressure. The residue (11.96 g) is dissolved in tetrahydrofuran (200 ml), and thereto is added t-butyl amine (20 ml), and the mixture is stirred at room temperature for four hours. The reaction mixture is poured into ice-10% hydrochloric acid (150 ml--150 ml), and extracted with ethyl acetate (250 ml). The organic layer is washed with water, a saturated aqueous sodium hydrogen carbonate solution, and a saturated sodium chloride solution, dried, and concentrated under reduced pressure. The reside is recrystallized twice from water-diethyl ether-diisopropyl ether to give 3-(5-benzo[b]furanyl)-2'-(6-O-methoxycarbonyl-β-D-glucopyranosyloxy)-6'-hydroxy-4'-methylpropiophenone (9.14 g).

Workup

  1. extractionthe mixture is extracted with ethyl acetate (350 ml)
  2. washThe organic layer is washed with water
  3. dry with materiala saturated aqueous sodium hydrogen carbonate solution, and a saturated sodium chloride solution, dried
  4. concentrationconcentrated under reduced pressure
  5. dissolutionThe residue (11.96 g) is dissolved in tetrahydrofuran (200 ml)
  6. additionis added t-butyl amine (20 ml)
  7. stirringthe mixture is stirred at room temperature for four hours
  8. additionThe reaction mixture is poured into ice-10% hydrochloric acid (150 ml--150 ml)
  9. extractionextracted with ethyl acetate (250 ml)
  10. washThe organic layer is washed with water
  11. dry with materiala saturated aqueous sodium hydrogen carbonate solution, and a saturated sodium chloride solution, dried
  12. concentrationconcentrated under reduced pressure
  13. customThe reside is recrystallized twice from water-diethyl ether-diisopropyl ether

Sources & evidence

ORD record
ord-ee525965b51b482b9cfa1ed29b205997
Source dataset
uspto-grants-2000_04
Patent number
US06048842

Reaction notes

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