Triethylamine → HCID 12391804, compound

HRID 1532414Notes

Reaction equation

HRID 1532414 reaction equation
[OH:1][C:2]1[CH:11]=[C:10]2[C:5]([CH:6]=[CH:7][C:8](=[O:12])[O:9]2)=[CH:4][CH:3]=1.C(N(CC)CC)C.[C:20](Cl)(=[O:24])[C:21]([CH3:23])=[CH2:22]>O1CCCC1.CN(C)C1C=CN=CC=1>[CH3:23][C:21](=[CH2:22])[C:20]([O:1][C:2]1[CH:3]=[CH:4][C:5]2[CH:6]=[CH:7][C:8](=[O:12])[O:9][C:10]=2[CH:11]=1)=[O:24]

Participants

6

Reactant 3

HCID 8471TriethylamineHCID 13528Methacryloyl chlorideHCID 5281426Umbelliferone

Product 1

HCID 12391804HCID 12391804, compoundYield 75.4%

Reagents, catalysts & solvents 2

HCID 142844-(Dimethylamino)pyridineCatalystHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
15 °C

Procedure

40 g (247 mmol) of 7-hydroxy-coumarin (umbelliferone) were suspended in 700 ml of tetrahydrofuran and treated in succession with 38 ml (271 mmol) of triethylamine and 0.603 g (5 mmol) of 4-dimethylaminopyridine (DMAP). 28.4 g (271 mmol) of methacryloyl chloride were added dropwise to the suspension, cooled to about 15° C., in the course of 30 minutes. The reaction batch was stirred at room temperature for 4 hours and subsequently filtered over a thin silica gel layer. The silica gel layer was rinsed thoroughly with THF. After evaporation of the solvent the crude product was dissolved in about 300 ml of dichloromethane and treated with 1.5 l of ethanol. The dichloromethane was again removed on a rotary evaporator. The product crystallized from the remaining ethanolic solution overnight in a refrigerator. It was filtered off, dried and recrystallized once again from 1.1 l of ethanol according to the described procedure. Filtration and drying at 40° C. in a water-jet vacuum gave 42.9 g of 2-oxo-2H-1-benzopyran-7-yl 2-methyl-acrylate as white crystals. λmax. (in CH2Cl2)=312.6 nm (ε=9610 l/mol cm) and 282.3 nm (ε=11450 l/mol cm).

Workup

  1. filtrationsubsequently filtered over a thin silica gel layer
  2. washThe silica gel layer was rinsed thoroughly with THF
  3. customAfter evaporation of the solvent the crude product
  4. dissolutionwas dissolved in about 300 ml of dichloromethane
  5. additiontreated with 1.5 l of ethanol
  6. customThe dichloromethane was again removed on a rotary evaporator
  7. customThe product crystallized from the remaining ethanolic solution overnight in a refrigerator
  8. filtrationIt was filtered off
  9. customdried
  10. customrecrystallized once again from 1.1 l of ethanol according to the described procedure
  11. filtrationFiltration
  12. dry with materialdrying at 40° C. in a water-jet vacuum

Sources & evidence

ORD record
ord-0c74c0fa730a427e9a1b718997099a2d
Source dataset
uspto-grants-2001_03
Patent number
US06201087B1

Reaction notes

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