O-Xylene → 7-(phenylmethoxy)-8-(2-propenyl)-4H-1-benzopyran-4-one

HRID 2210072Notes

Reaction equation

HRID 2210072 reaction equation
[OH:1][C:2]1[C:7]([CH2:8][CH:9]=[CH2:10])=[C:6]([O:11][CH2:12][C:13]2[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=2)[CH:5]=[CH:4][C:3]=1[C:19](=[O:21])[CH3:20].[CH3:22]OC(OC)N(C)C.C1(C)C(C)=CC=CC=1.O.C1(C)C=CC(S(O)(=O)=O)=CC=1>O.CCOCC.C(O)C.CO>[C:13]1([CH2:12][O:11][C:6]2[CH:5]=[CH:4][C:3]3[C:19](=[O:21])[CH:20]=[CH:22][O:1][C:2]=3[C:7]=2[CH2:8][CH:9]=[CH2:10])[CH:14]=[CH:15][CH:16]=[CH:17][CH:18]=1

Participants

9

Reactant 4

HCID 7237O-XyleneHCID 78373Dimethylformamide dimethyl acetalHCID 521998p-Toluenesulfonic acid monohydrateHCID 150480411-[2-Hydroxy-4-(phenylmethoxy)-3-(2-propenyl)phenyl]ethanone

Product 1

HCID 193799307-(phenylmethoxy)-8-(2-propenyl)-4H-1-benzopyran-4-oneYield 67.6%

Reagents, catalysts & solvents 4

HCID 702EthanolSolventHCID 887MethanolSolventHCID 962WaterSolventHCID 3283Diethyl EtherSolvent

Procedure

A mixture of 5.0 g (17.73 mmol) of 1-[2-hydroxy-4-(phenylmethoxy)-3-(2-propenyl)phenyl]ethanone, 2.3 g (19.48 mmol) of dimethylformamide dimethyl acetal, and 5.0 mL of xylene was stirred and heated in a 120°-130° C. oil-bath as methanol was distilled out using a 3 in. Vigreux column, over a 2.5 hr period. The bath temperature was then raised to 150°-160° C. and the reaction mixture was stirred at this temperature for an additional 30 min. The mixture was cooled and concentrated at 60° C./high vacuum. To the viscous, red-brown, oily residue was added 3.7 g (19.48 mmol) of p-toluenesulfonic acid monohydrate and 50 mL of ethanol. The resulting solution was stirred and refluxed for 24 hr, then cooled and diluted with water. Work-up with ether in the usual manner gave a crude product which was recrystallized from hexane-ethyl acetate. There was obtained 3.5 g (67.6%) of 7-(phenylmethoxy)-8-(2-propenyl)-4H-1-benzopyran-4-one as a yellow solid, mp 90°-92° C.

Workup

  1. distillationwas distilled out
  2. temperatureThe bath temperature was then raised to 150°-160° C.
  3. stirringthe reaction mixture was stirred at this temperature for an additional 30 min
  4. temperatureThe mixture was cooled
  5. concentrationconcentrated at 60° C./high vacuum
  6. stirringThe resulting solution was stirred
  7. temperaturerefluxed for 24 hr
  8. temperaturecooled
  9. customgave a crude product which
  10. customwas recrystallized from hexane-ethyl acetate

Sources & evidence

ORD record
ord-9b0c91652c9e4e7784496719dd9f3b57
Source dataset
uspto-grants-1995_10
Patent number
US05457124

Reaction notes

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