Chloroform methanol → HCID 54174272, compound

HRID 1587474Notes

Reaction equation

HRID 1587474 reaction equation
[C@H:1]1([O:12][CH2:13][C:14]2[O:18][C:17]([C:19]([OH:21])=[O:20])=[CH:16][CH:15]=2)[O:9][C@H:8]([CH2:10][OH:11])[C@@H:6]([OH:7])[C@H:4]([OH:5])[C@H:2]1[OH:3].[CH:22](Cl)(Cl)Cl.CO>CO.O>[CH3:22][O:20][C:19]([C:17]1[O:18][C:14]([CH2:13][O:12][C@H:1]2[O:9][C@H:8]([CH2:10][OH:11])[C@@H:6]([OH:7])[C@H:4]([OH:5])[C@H:2]2[OH:3])=[CH:15][CH:16]=1)=[O:21]

Participants

5

Reactant 2

HCID 21584188Chloroform methanolHCID 54561663HCID 54561663, compound3×

Product 1

HCID 54174272HCID 54174272, compoundYield 84%

Reagents, catalysts & solvents 2

HCID 887MethanolSolventHCID 962WaterSolvent

Procedure

To produce diazomethane, 1.0 g (10 mmol) N-methyl-N-nitrosourea was added portionwise with cooling to 20 ml diethyl ether to which 7 ml of 40% KOH had been added to form a lower layer, in such a way that the reaction temperature did not exceed +5° C. 30 min after the last addition the yellow organic phase was separated off and allowed to stand for 3 h over a little solid KOH. Enough of the ethereal solution of diazomethane thus obtained was added at room temperature with stirring during a period of 15 min to a solution of 500 mg (1.6 mmol) GMF carboxylic acid (formula 4, product of Example 4) in 18 ml methanol and 2 ml water for the yellow colour just to remain and no further evolution of gas to be observed. After a further 15 min stirring the reaction was complete (TLC monitoring with mobile solvent chloroform/methanol (2:1), Rf (educt)=0, Rf (product)= 0.41), whereupon the solvent was removed under vacuum and the crude product was purified by elution from a silica gel column (3×20 cm) with chloroform/methanol (2:1). Concentration of the fractions containing the product gave 440 mg (84%) of colourless syrup with [α]D20 =+113° (c=0.8, methanol), which gradually crystallised on scratching; m.p. 72° C.

Workup

  1. additionwas added at room temperature
  2. customwhereupon the solvent was removed under vacuum
  3. customthe crude product was purified by elution from a silica gel column (3×20 cm) with chloroform/methanol (2:1)
  4. additionConcentration of the fractions containing the product

Sources & evidence

ORD record
ord-118fb59a1508491fbe8e1a74ead79441
Source dataset
uspto-grants-1993_06
Patent number
US05218098

Reaction notes

Loading…