Diethyl Ether → 2-Ethyl-6-methylbenzoic acid

HRID 1976969Notes

Reaction equation

HRID 1976969 reaction equation
[CH2:1]([C:3]1[CH:8]=[CH:7][CH:6]=[C:5]([CH3:9])[C:4]=1I)[CH3:2].C(#N)C.C(N(CC)CC)C.[C]=[O:22].CC[O:25][CH2:26]C>[OH-].[Na+].CC([O-])=O.CC([O-])=O.[Pd+2].C1C=CC(P(C2C=CC=CC=2)CCCP(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.O>[CH2:1]([C:3]1[CH:8]=[CH:7][CH:6]=[C:5]([CH3:9])[C:4]=1[C:26]([OH:25])=[O:22])[CH3:2]

Participants

10

Reactant 5

HCID 3283Diethyl EtherHCID 6342AcetonitrileHCID 8471TriethylamineHCID 27341951-Ethyl-2-iodo-3-methylbenzeneHCID 178418416HCID 178418416, compound4×

Product 1

HCID 120442292-Ethyl-6-methylbenzoic acidYield 72.5%

Reagents, catalysts & solvents 4

HCID 812191,3-Bis(diphenylphosphino)propaneCatalystHCID 167845palladium(II) acetateCatalystHCID 962WaterSolventHCID 14798Sodium HydroxideSolvent

Procedure

A 250 mL pressure bottle was charged with 2-ethyl-6-methyliodobenzene (30.07 mmol, 7.4 g), Pd(OAc)2 (1.43 mmol, 334 mg) and dppp (1.43 mmol, 620 mg). The flask was closed with a septum and evacuated three times with argon. Then, acetonitrile (96 mL), triethylamine (189 mmol, 19.0 g, 26.25 mL) and water (19.1 mL) were added successively by the aid of syringe. Then, the rubber septum was replaced with teflon lined cap connected to a carbon monoxide source. The flask was now pressurized with carbon monoxide (40 psi) and the excess pressure was released. This process was repeated three times and finally the mixture was stirred for 5 min under 40 psi carbon monoxide pressure. The flask was then disconnected from the carbon monoxide cylinder and immersed in a preheated oil bath (83-85° C.). The reaction mixture turned black in 1 hr and was stirred for another 14 hr at this temperature. Then, the reaction mixture was cooled to room temperature and the pressure was released. The resulting mixture was diluted with ether (200 mL) and 1.0N NaOH (20 mL). The formed acid was extracted into water (2×100 mL). The combined water extracts were neutralized with 1.0N HCl and the acid was extracted into dichloromethane (3×100 mL). The combined dichloromethane extracts were washed with brine solution and dried over MgSO4. Filtration of the drying agent and removal of solvent under vacuum gave 3.58 g (72.5%) of a viscous brown oil which slowly solidfied overnight. HR MS: Obs. mass. 164.0833. Calcd. mass. 164.0837 (M+).

Workup

  1. customThe flask was closed with a septum
  2. customevacuated three times with argon
  3. customlined cap
  4. customimmersed in a preheated oil bath
  5. custom(83-85° C.)
  6. extractionThe formed acid was extracted into water (2×100 mL)
  7. extractionthe acid was extracted into dichloromethane (3×100 mL)
  8. washThe combined dichloromethane extracts were washed with brine solution
  9. dry with materialdried over MgSO4
  10. filtrationFiltration of the drying agent and removal of solvent under vacuum

Sources & evidence

ORD record
ord-6c6edc0be1374a86b57d149313870456
Source dataset
uspto-grants-2001_05
Patent number
US06229011B1

Reaction notes

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