Water → 6,8-difluoro-7-hydroxy-4-methylcoumarin-3-carboxylic acid ethyl ester beta-D-glucuronic acid methyl ester triacetate

HRID 355408Notes

Reaction equation

HRID 355408 reaction equation
[OH-].[Na+].O.[F:4][C:5]1[CH:6]=[C:7]2[C:12](=[C:13]([F:16])[C:14]=1[OH:15])[O:11][C:10](=[O:17])[CH:9]=[C:8]2[CH3:18].[CH3:19][O:20][C:21](=[O:42])[C@H:22]1[O:28][C@:26](Br)([OH:27])[C@H:25]([O:30]C(=O)C)[C@@H:24]([O:34]C(=O)C)[C@@H:23]1[O:38]C(=O)C>C(Cl)Cl.[Br-].C([N+](CCCC)(CCCC)CCCC)CCC>[C:10]([OH:17])(=[O:11])[CH3:9].[C:21]([OH:42])(=[O:20])[CH3:22].[C:10]([OH:17])(=[O:11])[CH3:9].[CH3:19][O:20][C:21](=[O:42])[C@H:22]1[O:28][C@@H:26]([OH:27])[C@H:25]([OH:30])[C@@H:24]([OH:34])[C@@H:23]1[OH:38].[CH2:22]([O:28][C:26]([C:9]1[C:10](=[O:17])[O:11][C:12]2[C:7]([C:8]=1[CH3:18])=[CH:6][C:5]([F:4])=[C:14]([OH:15])[C:13]=2[F:16])=[O:27])[CH3:21]

Participants

7

Reactant 4

HCID 962Water2×HCID 14798Sodium HydroxideHCID 10176707Marina BlueHCID 54062351methyl 2,3,4-tri-O-acetyl-1-bromo-alpha-d-glucopyranuronate

Product 1

HCID 867532796,8-difluoro-7-hydroxy-4-methylcoumarin-3-carboxylic acid ethyl ester beta-D-glucuronic acid methyl ester triacetate

Reagents, catalysts & solvents 2

HCID 74236Tetrabutylammonium BromideCatalystHCID 6344DichloromethaneSolvent

Procedure

A solution of 10% NaOH in water (1.5 eq) is added to a 0.1M solution of Compound 5 (1.0 eq) in CH2Cl2, followed by the addition of 1-bromo-2,3,4-tri-O-acetyl-α-D-glucopyranuronic acid methyl ester (1.6 eq) and tetrabutylammonium bromide (1.5 eq). The reaction mixture is stirred vigorously for 16 hours, then poured into 5 volumes of water. The product is extracted with CHCl3 (2×), washed with brine, dried over anhydrous MgSO4, and concentrated in vacuo. The residue is then purified by silica gel column chromatography (eluted with CHCl3 /MeOH) to yield Compound 21.

Workup

  1. extractionThe product is extracted with CHCl3 (2×)
  2. washwashed with brine
  3. dry with materialdried over anhydrous MgSO4
  4. concentrationconcentrated in vacuo
  5. customThe residue is then purified by silica gel column chromatography (eluted with CHCl3 /MeOH)

Sources & evidence

ORD record
ord-16d4436aaa9b4171a47a52fc078a8222
Source dataset
uspto-grants-1998_11
Patent number
US05830912

Reaction notes

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