HCID 21320559, compound → HCID 21320556, compound

HRID 918130Notes

Reaction equation

HRID 918130 reaction equation
N([O-])=[O:2].[Na+].[C:5]([C:8]1[CH:13]=[CH:12][C:11]([C:14]2[CH:19]=[CH:18][C:17]([F:20])=[CH:16][CH:15]=2)=[C:10](N)[CH:9]=1)(=[O:7])[CH3:6]>O.S(=O)(=O)(O)O>[C:5]([C:8]1[CH:13]=[CH:12][C:11]([C:14]2[CH:19]=[CH:18][C:17]([F:20])=[CH:16][CH:15]=2)=[C:10]([OH:2])[CH:9]=1)(=[O:7])[CH3:6]

Participants

5

Reactant 2

HCID 21320559HCID 21320559, compoundHCID 23668193Sodium Nitrite

Product 1

HCID 21320556HCID 21320556, compound

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 1118Sulfuric AcidSolvent2×

Procedure

A solution of sodium nitrite (12.0 g.) in water (40 ml.) was added to a stirred solution of 4-acetyl-2-amino-4'-fluorobiphenyl (36.6 g.) in 5N sulphuric acid (480 ml.), whilst maintaining the temperature of the reaction mixture at 0° - 5°C. The reaction mixture was stirred at 0° - 5°C. for a further 1 hour. The resulting cold solution of diazonium salt was poured slowly into stirred refluxing 5N sulphuric acid (400 ml.). When the addition was complete, refluxing was continued for 0.5 hour. The resulting solution was poured into ice/water, causing the precipitation of a solid which was collected, dried and dissolved in ether. The ethereal solution was extracted with dilute aqueous sodium hydroxide and the extract was acidified to precipitate a product which was extracted into ether. The ethereal extract was washed with water, dried over anhydrous sodium sulphate, and evaporated to give a product which was recrystallized from light petroleum (b.p. 80° - 100°C.) to give the novel intermediate 4-acetyl-4'-fluoro-2-hydroxybiphenyl, m.p. 152° - 154°C. A mixture of this compound (36.5 g.), dimethyl sulphate (25.2 g.) and potassium carbonate (25 g.) in anhydrous acetone (200 ml.) was refluxed with stirring overnight. Acetone was removed by evaporation, the residue poured into water, and the resulting mixture extracted with ether. The ether extract was washed with dilute sodium hydroxide solution, then with water and dried over anhydrous sodium sulphate. Ether was removed by evaporation and the residue was distilled in vacuo to give a product, b.p. 142° - 144°C./0.2 mm. which solidified on cooling. This solid was recrystallized from light petroleum (b.p. 62° - 68°C.) to give the novel intermediate 4-acetyl-4'-fluoro-2-methoxybiphenyl, m.p. 75° - 77°C.

Workup

  1. temperaturewhilst maintaining the temperature of the reaction mixture at 0° - 5°C
  2. stirringinto stirred
  3. additionWhen the addition
  4. temperaturerefluxing
  5. waitwas continued for 0.5 hour
  6. customthe precipitation of a solid which
  7. customwas collected
  8. customdried
  9. dissolutiondissolved in ether
  10. extractionThe ethereal solution was extracted with dilute aqueous sodium hydroxide
  11. customto precipitate a product which
  12. extractionwas extracted into ether
  13. extractionThe ethereal extract
  14. washwas washed with water
  15. dry with materialdried over anhydrous sodium sulphate
  16. customevaporated
  17. customto give a product which
  18. customwas recrystallized from light petroleum (b.p. 80° - 100°C.)

Sources & evidence

ORD record
ord-6e13fdc32eb2441493c51c42b886d2a3
Source dataset
uspto-grants-1976_07
Patent number
US03969402

Reaction notes

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