Iodine → 6-[3-(1,1-Dimethyldecyl)-4-methoxyphenyl]-2-naphthoic acid

HRID 256785Notes

Reaction equation

HRID 256785 reaction equation
[CH3:1][C:2]([C:13]1[CH:18]=[C:17](Br)[CH:16]=[CH:15][C:14]=1[O:20][CH3:21])([CH3:12])[CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][CH2:9][CH2:10][CH3:11].[Mg].II.Br[C:26]1[CH:27]=[C:28]2[C:33](=[CH:34][CH:35]=1)[CH:32]=[C:31]([C:36]([O:38]C)=[O:37])[CH:30]=[CH:29]2>C1COCC1.[Cl-].[Zn+2].[Cl-].O>[CH3:1][C:2]([C:13]1[CH:18]=[C:17]([C:26]2[CH:27]=[C:28]3[C:33](=[CH:34][CH:35]=2)[CH:32]=[C:31]([C:36]([OH:38])=[O:37])[CH:30]=[CH:29]3)[CH:16]=[CH:15][C:14]=1[O:20][CH3:21])([CH3:12])[CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][CH2:9][CH2:10][CH3:11]

Participants

8

Reactant 4

HCID 807IodineHCID 8541342-Bromo-6-methoxycarbonylnaphthaleneHCID 5462224MagnesiumHCID 136335572-(1,1-Dimethyldecyl)-4-bromo anisole

Product 1

HCID 189527686-[3-(1,1-Dimethyldecyl)-4-methoxyphenyl]-2-naphthoic acid

Reagents, catalysts & solvents 3

HCID 3007855ZincchlorideCatalystHCID 962WaterSolventHCID 8028TetrahydrofuranSolvent3×

Conditions

Temperature
50 °C

Procedure

A solution of 16 g (45 mmol) of 2- (1,1-dimethyldecyl)-4-bromo anisole in 60 ml of THF is slowly added to 1.3 g (54 mmol) of magnesium and a crystal of iodine. The mixture is slightly heated at the beginning of the addition until the reaction of formation of the Grignard is initiated. Then the remainder of the solution containing the brominated derivative is added in a manner to maintain a regular reflux. Once the addition is complete, the mixture is stirred for 30 minutes at 50° C. and then cooled to ambient temperature. 7.4 g (54 mmol) of zinc chloride in solution in 50 ml of THF are added. The mixture is stirred for 30 minutes at ambient temperature, 6.6 g (25 mmol) of methyl 6-bromo-2-naphthoate are added and then 175 mg of NiCl2 /DPPE complex. The mixture is stirred for 3 hours at ambient temperature at which point 250 ml of water are added. The THF is eva-porated under reduced pressure and the residue is extracted with dichloromethane, dried and the solvent evaporated. The residue is purified by passage through a silica column (eluant: mixture of 60% dichlorlmethane and 40% hexane). On evaporation, a solid is obtained which is recrystallized twice in hexane to give the methyl ester of 6-[3-(1,1-dimethyldecyl)-4-methoxyphenyl]-2-naphthoic acid: 705 g (61%). Melting point: 92° C.

Workup

  1. temperatureThe mixture is slightly heated at the beginning of the addition until the reaction of formation of the Grignard
  2. additionThen the remainder of the solution containing the brominated derivative
  3. additionis added in a manner
  4. temperatureto maintain a regular reflux
  5. additionOnce the addition
  6. temperaturecooled to ambient temperature
  7. stirringThe mixture is stirred for 30 minutes at ambient temperature
  8. stirringThe mixture is stirred for 3 hours at ambient temperature at which
  9. additionare added
  10. extractionthe residue is extracted with dichloromethane
  11. customdried
  12. customthe solvent evaporated
  13. customThe residue is purified by passage through a silica column (eluant: mixture of 60% dichlorlmethane and 40% hexane)
  14. customOn evaporation
  15. customa solid is obtained which
  16. customis recrystallized twice in hexane

Sources & evidence

ORD record
ord-388f2480f0874c2fb8fa26864be531c7
Source dataset
uspto-grants-1993_11
Patent number
USRE034440

Reaction notes

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