Triphenylphosphine → 2-oxo-2H-1-benzopyran-7-yl 4-methoxycarbonyloxybenzoate

HRID 2120514Notes

Reaction equation

HRID 2120514 reaction equation
C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[OH:20][C:21]1[CH:30]=[C:29]2[C:24]([CH:25]=[CH:26][C:27](=[O:31])[O:28]2)=[CH:23][CH:22]=1.[CH3:32][O:33][C:34]([O:36][C:37]1[CH:45]=[CH:44][C:40]([C:41](O)=[O:42])=[CH:39][CH:38]=1)=[O:35].N(C(OCC)=O)=NC(OCC)=O>O1CCCC1>[CH3:32][O:33][C:34]([O:36][C:37]1[CH:45]=[CH:44][C:40]([C:41]([O:20][C:21]2[CH:22]=[CH:23][C:24]3[CH:25]=[CH:26][C:27](=[O:31])[O:28][C:29]=3[CH:30]=2)=[O:42])=[CH:39][CH:38]=1)=[O:35]

Participants

6

Reactant 4

HCID 11776TriphenylphosphineHCID 220568ethyl N-ethoxycarbonyliminocarbamateHCID 5281426UmbelliferoneHCID 222422684-[(Methoxycarbonyl)oxy]benzoic acid

Product 1

HCID 234351152-oxo-2H-1-benzopyran-7-yl 4-methoxycarbonyloxybenzoateYield 70.3%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

13.4 g triphenylphosphine is added to a solution of 8.3 g 7-hydroxycoumarin, 10.0 g 4-methoxycarbonyloxybenzoic acid, 8.9 g diethyl azodicarboxylate and 50 ml tetrahydrofuran at 0° C. The reaction mixture was stirred overnight at room temperature, filtered to remove inorganic material and the filtrate evaporated down, taken up in warm hexane, filtered to remove inorganic material and evaporated down again. The residue is purified by column chromatography on silica gel using hexane/ethyl acetate (1/1 v/v) as eluent and recrystallisation from acetonitrile to yield 12.2 g of 2-oxo-2H-1-benzopyran-7-yl 4-methoxycarbonyloxybenzoate.

Workup

  1. filtrationfiltered
  2. customto remove inorganic material
  3. customthe filtrate evaporated down
  4. filtrationfiltered
  5. customto remove inorganic material
  6. customevaporated down again
  7. customThe residue is purified by column chromatography on silica gel
  8. customrecrystallisation from acetonitrile

Sources & evidence

ORD record
ord-12c2b528fafa40829cf1317985f30be4
Source dataset
uspto-grants-2004_02
Patent number
US06692797B1

Reaction notes

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