Acetic Acid → 3-Chloro-[1,1'-biphenyl]-2-carboxaldehyde

HRID 1065567Notes

Reaction equation

HRID 1065567 reaction equation
Br[CH2:2][C:3]1[C:8]([Cl:9])=[CH:7][CH:6]=[CH:5][C:4]=1[C:10]1[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=1.C1N2CN3CN(C2)CN1C3.C(O)(=[O:28])C.[Cl-].[Na+]>C(Cl)(Cl)Cl.O>[Cl:9][C:8]1[CH:7]=[CH:6][CH:5]=[C:4]([C:10]2[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=2)[C:3]=1[CH:2]=[O:28]

Participants

7

Reactant 4

HCID 176Acetic AcidHCID 4101HexamethylenetetramineHCID 5234Sodium ChlorideHCID 133207002-(Bromomethyl)-3-chloro-1,1'-biphenyl

Product 1

HCID 132166793-Chloro-[1,1'-biphenyl]-2-carboxaldehyde

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6212ChloroformSolvent

Procedure

A stirred solution of 2-bromomethyl-3-chloro-[1,1'-biphenyl] (18.7 g, 0.067 mole) and hexamethylenetetraamine (9.3 g, 0.067 mole) in 200 ml of chloroform was heated at reflux for 221/2 hours. The reaction mixture was cooled and the solvent evaporated under reduced pressure to give a residue. To the residue was added 250 ml of a 1:1 solution of concentrated acetic acid:water. The mixture was heated at reflux for approximately 22 hours, then cooled. The mixture was saturated with sodium chloride and extracted with four 200 ml portions of methylene chloride. The extracts were combined, washed with saturated aqueous sodium chloride solution, followed by saturated aqueous sodium bicarbonate solution, and dried over anhydrous potassium carbonate. The mixture was filtered and the filtrate evaporated under reduced pressure to give a residue. The residue was subjected to column chromatography on silica gel, elution first with toluene:n-heptane (9:1), followed by toluene:methylene chloride (1:1), and finally methylene chloride to give 3-chloro-[1,1'-biphenyl]-2-carboxaldehyde (3.4 g) as an oil.

Workup

  1. temperatureat reflux for 221/2 hours
  2. temperatureThe reaction mixture was cooled
  3. customthe solvent evaporated under reduced pressure
  4. customto give a residue
  5. temperatureThe mixture was heated
  6. temperatureat reflux for approximately 22 hours
  7. temperaturecooled
  8. extractionextracted with four 200 ml portions of methylene chloride
  9. washwashed with saturated aqueous sodium chloride solution
  10. dry with materialdried over anhydrous potassium carbonate
  11. filtrationThe mixture was filtered
  12. customthe filtrate evaporated under reduced pressure
  13. customto give a residue
  14. washThe residue was subjected to column chromatography on silica gel, elution first with toluene:n-heptane (9:1)

Sources & evidence

ORD record
ord-3425b05ff4bd4fc6afeb18266b0a7d67
Source dataset
uspto-grants-1982_05
Patent number
US04329518

Reaction notes

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