Methanol → 4-(3-Ethynylphenoxy)naphthalic anhydride

HRID 26974Notes

Reaction equation

HRID 26974 reaction equation
[CH3:1][OH:2].C(C1C=[C:7]([C:11]2[CH:16]=[C:15](S([O-])(=O)=O)[CH:14]=[CH:13][C:12]=2C)[CH:8]=CC=1)#C.[OH-:22].[K+].Br[C:25]1[C:34]2[C:29](=[CH:30][CH:31]=[CH:32][CH:33]=2)[C:28]([C:35]([O:37][C:38]([C:40]2[C:49]3[C:44](=[CH:45][CH:46]=[CH:47][CH:48]=3)[C:43](Br)=[CH:42][CH:41]=2)=[O:39])=[O:36])=[CH:27][CH:26]=1>CS(C)=O.C(Cl)Cl.C(OCC)C>[C:7]([C:11]1[CH:16]=[C:1]([CH:14]=[CH:13][CH:12]=1)[O:2][C:25]1[C:34]2[C:29](=[CH:30][CH:31]=[CH:32][CH:33]=2)[C:28]([C:35]([O:37][C:38]([C:40]2[C:49]3[C:44](=[CH:45][CH:46]=[CH:47][CH:48]=3)[C:43]([O:22][C:15]3[CH:14]=[CH:13][CH:12]=[C:11]([C:7]#[CH:8])[CH:16]=3)=[CH:42][CH:41]=2)=[O:39])=[O:36])=[CH:27][CH:26]=1)#[CH:8]

Participants

8

Reactant 4

HCID 887MethanolHCID 14797Potassium HydroxideHCID 227546443-Ethynylphenyl(p-toluenesulfonate)HCID 57234554HCID 57234554, compound

Product 1

HCID 867356404-(3-Ethynylphenoxy)naphthalic anhydrideYield 50%

Reagents, catalysts & solvents 3

HCID 679Dimethyl SulfoxideSolvent2×HCID 3283Diethyl EtherSolventHCID 6344DichloromethaneSolvent

Conditions

Temperature
100 °C

Procedure

To 100 ml of anhydrous methanol was added 20 g (0.073 mole) of 3-ethynylphenyl(p-toluenesulfonate) and 8.19 g (0.146 mole) of potassium hydroxide. The mixture was heated to reflux, under a nitrogen atmosphere and maintained at reflux for four hours. The methanol solvent was removed in vacuo at 40° C. by means of a rotary evaporator, leaving a dry, white powder. The white powder was dissolved in 100 ml of dimethylsulfoxide (DMSO) and added dropwise to a DMSO solution containing 13.8 g (0.05 mole) of 4-bromonaphthalic anhydride at 90° C. The mixture was heated at 100° C., under a nitrogen atmosphere, for 12 hours. The reaction mixture was allowed to cool to room temperature and poured into diethylether to precipitate the inorganic salts which were removed by filtration. The diethylether/DMSO solvent was removed in vacuo at 90° C., by means of a rotary evaporator leaving a residual oil. The oil was dissolved in methylene chloride and filtered through a 2""×6" dry column of silica gel while eluting the column with methylene chloride. The eluate was evaporated to dryness, yielding 7.8 g (50%) of 4-(3-ethynylphenoxy)naphthalic anhydride.

Workup

  1. temperatureThe mixture was heated
  2. temperatureto reflux, under a nitrogen atmosphere
  3. temperaturemaintained
  4. temperatureat reflux for four hours
  5. customThe methanol solvent was removed in vacuo at 40° C. by means of a rotary evaporator
  6. customleaving a dry, white powder
  7. temperatureto cool to room temperature
  8. customto precipitate the inorganic salts which
  9. customwere removed by filtration
  10. customThe diethylether/DMSO solvent was removed in vacuo at 90° C., by means of a rotary evaporator
  11. customleaving a residual oil
  12. filtrationfiltered through a 2""×6"
  13. customdry column of silica gel
  14. washwhile eluting the column with methylene chloride
  15. customThe eluate was evaporated to dryness

Sources & evidence

ORD record
ord-f7ec05d051794e1cafe523dacd44acd6
Source dataset
uspto-grants-1979_04
Patent number
US04151358

Reaction notes

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