Hydrochloric Acid → HCID 53699063, compound

HRID 1973311Notes

Reaction equation

HRID 1973311 reaction equation
ClC1C=CC(C2[O:9]C(C#N)=C3C=2C=CC=C3)=CC=1.Cl.[N+]([O-])([O-])=O.[NH4+].[Ce+4].[N+]([O-])([O-])=O.[N+]([O-])([O-])=O.[N+]([O-])([O-])=O.[N+]([O-])([O-])=O.[CH2:42]([O:44][C:45]([C:47]1[O:48][C:49]([C:56]2[CH:61]=[CH:60][C:59]([Cl:62])=[CH:58][CH:57]=2)=[C:50]2[C:55]=1[CH:54]=[CH:53][CH:52]=[CH:51]2)=[O:46])[CH3:43]>C(O)C.C(O)(=O)C.O.CCOCC>[CH2:42]([O:44][C:45](=[O:46])[C:47]([C:55]1[CH:54]=[CH:53][CH:52]=[CH:51][C:50]=1[C:49](=[O:48])[C:56]1[CH:61]=[CH:60][C:59]([Cl:62])=[CH:58][CH:57]=1)=[O:9])[CH3:43]

Participants

9

Reactant 4

HCID 313Hydrochloric AcidHCID 9869224Ammonium cerium (IV) nitrateHCID 203517863-(4-Chlorophenyl)-2-benzofuran-1-carbonitrileHCID 53839738Ethyl 3-(4-chlorophenyl)-2-benzofuran-1-carboxylate

Product 1

HCID 53699063HCID 53699063, compound

Reagents, catalysts & solvents 4

HCID 176Acetic AcidSolventHCID 702EthanolSolventHCID 962WaterSolventHCID 3283Diethyl EtherSolvent

Procedure

A suspension of 5 g. of 3-(p-chlorophenyl)-1-cyano-isobenzofuran in 135 ml. of ether is treated with 50 ml. of a 20% solution of hydrochloric acid in ethanol and stirred at room temperature for 48 hours. The crystallized orange iminoether hydrochloride is removed by filtration under suction, washed with ether and hydrolyzed by boiling for 90 minutes with 300 ml. of water. After cooling, the separated oil is extracted with methylene chloride, the extract washed with a sodium bicarbonate solution and dried over sodium sulfate. By concentration in vacuo, there is obtained a yellow oil which is chromatographed on 150 g. of silica gel with methylene chloride as the eluant. The homogeneous fractions are combined, concentrated, and the solid residue is recrystallized from ether/hexane, 3-(p-chlorophenyl)-isobenzofuran-1-carboxylic acid ethyl ester being obtained in the form of fibrous crystals having a melting point of 99°-101° C. 11.5 G. of cerium (IV) ammonium nitrate are dissolved in 20 ml. of water and 20 ml. of glacial acetic acid. Thereafter, there are added 3.0 g. of 3-(p-chlorophenyl)-isobenzofuran-1-carboxylic acid ethyl ester and the mixture is boiled for 2-3 minutes until the color of the solution obtained changes from orange to light-yellow. After cooling, there are added 150 ml. of ice-water and the mixture is stirred for 1 hour in an ice-bath. The product which first separates as an oil solidifies. The solid is separated by decantation of the aqueous solution and is dissolved in ether. The ethereal solution is washed with 2-N sodium carbonate and water, dried over sodium sulfate and evaporated. After crystallization of the residue from ethanol, there is obtained [o-(p-chlorobenzoyl)phenyl]glyoxylic acid ethyl ester in the form of colorless crystals having a melting point of 79°-81° C.

Workup

  1. additionA suspension of 5 g
  2. customThe crystallized orange iminoether hydrochloride is removed by filtration under suction
  3. washwashed with ether
  4. temperatureAfter cooling
  5. extractionthe separated oil is extracted with methylene chloride
  6. washthe extract washed with a sodium bicarbonate solution
  7. dry with materialdried over sodium sulfate
  8. concentrationBy concentration in vacuo
  9. customthere is obtained a yellow oil which
  10. customis chromatographed on 150 g
  11. concentrationconcentrated
  12. customthe solid residue is recrystallized from ether/hexane, 3-(p-chlorophenyl)-isobenzofuran-1-carboxylic acid ethyl ester being
  13. customobtained in the form of fibrous crystals
  14. additionThereafter, there are added 3.0 g
  15. customobtained changes from orange to light-yellow
  16. temperatureAfter cooling
  17. additionthere are added 150 ml
  18. customThe solid is separated by decantation of the aqueous solution
  19. dissolutionis dissolved in ether
  20. washThe ethereal solution is washed with 2-N sodium carbonate and water
  21. dry with materialdried over sodium sulfate
  22. customevaporated
  23. customAfter crystallization of the residue from ethanol

Sources & evidence

ORD record
ord-911ac6697e1748f7ac8c0cb1e6bdb33c
Source dataset
uspto-grants-1976_12
Patent number
US03996374

Reaction notes

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