Hydrochloric Acid → (1,1'-Biphenyl)-2-carboxylic acid, 4'-methyl-, methyl ester

HRID 2304058Notes

Reaction equation

HRID 2304058 reaction equation
CS(O[C:6]1[CH:15]=[CH:14][CH:13]=[CH:12][C:7]=1[C:8]([O:10][CH3:11])=[O:9])(=O)=O.[Br-].[C:17]1([CH3:24])[CH:22]=[CH:21][C:20]([Zn+])=[CH:19][CH:18]=1.[Cl-].[Li+].Cl>O1CCCC1.[Ni](Cl)Cl.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C([Li])CCC.O>[CH3:24][C:17]1[CH:22]=[CH:21][C:20]([C:6]2[CH:15]=[CH:14][CH:13]=[CH:12][C:7]=2[C:8]([O:10][CH3:11])=[O:9])=[CH:19][CH:18]=1

Participants

10

Reactant 4

HCID 313Hydrochloric AcidHCID 433294Lithium ChlorideHCID 1729098HCID 1729098, compoundHCID 178427806HCID 178427806, compound

Product 1

HCID 1393873(1,1'-Biphenyl)-2-carboxylic acid, 4'-methyl-, methyl esterYield 82%

Reagents, catalysts & solvents 5

HCID 11776TriphenylphosphineCatalystHCID 24385Nickel DichlorideCatalystHCID 178418339ButyllithiumCatalystHCID 962WaterSolventHCID 8028TetrahydrofuranSolvent2×

Procedure

A mixture of nickel chloride (0.11 g, 0.85 mmoles), triphenylphosphine (0.44 g, 1.7 mmoles), and dry tetrahydrofuran (25 ml), at room temperature and under inert atmosphere (nitrogen), is added with 1.6 M n-butyllithium (1.1 ml; 1.7 mmoles); the mixture is kept under stirring for 15′, then added with methyl 2-(methanesulfonyloxy)benzoate (10.1 g, 44 mmoles, prepared as described in Example 3) dissolved in dry tetrahydrofuran (10 ml). After further 15′ under stirring, the resulting mixture is added to a suspension of p-tolylzinc bromide prepared as described in Example 1, previously added with lithium chloride (2.3 g, 54 mmoles). The resulting mixture is kept at room temperature for 12 hours, then poured into a solution of water (100 ml) and 37% hydrochloric acid (25 ml); the phases are separated, the organic phase is extracted with a water-dichloromethane mixture (50 ml; 50:50); the phases are separated again and the organic one is dried over sodium sulfate and evaporated under vacuum to a residue, to obtain methyl 2-(4-methylphenyl)benzoate as an oil (8.2 g, yield 82%).

Workup

  1. stirringAfter further 15′ under stirring
  2. customprepared
  3. customthe phases are separated
  4. extractionthe organic phase is extracted with a water-dichloromethane mixture (50 ml; 50:50)
  5. customthe phases are separated again
  6. dry with materialthe organic one is dried over sodium sulfate
  7. customevaporated under vacuum to a residue

Sources & evidence

ORD record
ord-18e2114c4775446e8074b450105a9c5c
Source dataset
uspto-grants-2002_08
Patent number
US06433214B1

Reaction notes

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