Arsenic Acid → alpha-Methyl-2-phenyl-6-quinolineacetic acid

HRID 1282953Notes

Reaction equation

HRID 1282953 reaction equation
C(=O)C=CC1C=CC=CC=1.NC1C=CC(CC(O)=O)=CC=1.[As](=O)(O)(O)O.P(=O)(O)(O)O.[OH-].[Na+].[C:34](=[O:37])([O-])[O-:35].[Na+].[Na+].[C:40]1([C:46]2[CH:55]=[CH:54][C:53]3[C:48](=[CH:49][CH:50]=[C:51]([CH2:56][C:57](O)=O)[CH:52]=3)[N:47]=2)[CH:45]=[CH:44][CH:43]=[CH:42][CH:41]=1>C(O)C.O.CO.CCCCC>[CH3:57][CH:56]([C:51]1[CH:52]=[C:53]2[C:48](=[CH:49][CH:50]=1)[N:47]=[C:46]([C:40]1[CH:45]=[CH:44][CH:43]=[CH:42][CH:41]=1)[CH:55]=[CH:54]2)[C:34]([OH:35])=[O:37]

Participants

10

Reactant 7

HCID 234Arsenic AcidHCID 3073-Phenylprop-2-EnalHCID 1004Phosphoric AcidHCID 10340Sodium CarbonateHCID 145334-Aminophenylacetic acidHCID 14798Sodium HydroxideHCID 215205512-Phenyl-6-quinolineacetic acid

Product 1

HCID 54348609alpha-Methyl-2-phenyl-6-quinolineacetic acid

Reagents, catalysts & solvents 2

HCID 19096565Water ethanolSolventHCID 86733799Methanol pentaneSolvent

Conditions

Temperature
120 °C

Procedure

45 ml of cinnamaldehyde are added dropwise to a mixture of 38 g of p-aminophenylacetic acid, 71 g of arsenic acid and 300 ml of phosphoric acid. The reaction mixture is stirred for 2 hours at 120°C, 50 ml of polyphosphoric acid are then added and the whole is again stirred for 16 hours at 110°-120°C. The reaction mixture is cooled to 0°C and adjusted to a pH of 5-6 first with 2 N sodium hydroxide solution and then with solid sodium carbonate. This suspension is extracted with ethyl acetate and the organic phases are then extracted 6 times with 50 ml of 1 N hydrochloric acid at a time. The hydrochloric extracts are combined and a few pinches of sodium nitrite are added. The solution is left to stand for 15 minutes at room temperature and is then adjusted to pH 5.6, using a pH-meter, by adding sodium carbonate. This solution is extracted with ethyl acetate and the organic layers are washed with water, dried over sodium sulphate and evaporated. The residue obtained is crude 2-phenyl-6-quinolineacetic acid. Melting point 176°-179°C (from methanol-pentane). α-Methyl-2-phenyl-6-quinolineacetic acid of melting point 161°-162°C (from ethanol-water) is obtained analogously.

Workup

  1. stirringthe whole is again stirred for 16 hours at 110°-120°C
  2. temperatureThe reaction mixture is cooled to 0°C
  3. extractionThis suspension is extracted with ethyl acetate
  4. extractionthe organic phases are then extracted 6 times with 50 ml of 1 N hydrochloric acid at a time
  5. additiona few pinches of sodium nitrite are added
  6. waitThe solution is left
  7. waitto stand for 15 minutes at room temperature
  8. additionby adding sodium carbonate
  9. extractionThis solution is extracted with ethyl acetate
  10. washthe organic layers are washed with water
  11. dry with materialdried over sodium sulphate
  12. customevaporated
  13. customThe residue obtained

Sources & evidence

ORD record
ord-0cb9394ba2864d2bb6ae25bcb278982a
Source dataset
uspto-grants-1976_08
Patent number
US03973022

Reaction notes

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