Dimethyl iodoterephthalate → Dimethyl 2'-methyl(1,1'-biphenyl)-2.5-dicarboxylate

HRID 1068063Notes

Reaction equation

HRID 1068063 reaction equation
I[C:2]1[CH:11]=[C:10]([C:12]([O:14][CH3:15])=[O:13])[CH:9]=[CH:8][C:3]=1[C:4]([O:6][CH3:7])=[O:5].[C:16]1([CH3:25])[CH:21]=[CH:20][CH:19]=[CH:18][C:17]=1B(O)O>C1(C)C=CC=CC=1.C([O-])([O-])=O.[Na+].[Na+].C([O-])(=O)C.[Pd+2].C([O-])(=O)C.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>[CH3:25][C:16]1[CH:21]=[CH:20][CH:19]=[CH:18][C:17]=1[C:2]1[C:3]([C:4]([O:6][CH3:7])=[O:5])=[CH:8][CH:9]=[C:10]([C:12]([O:14][CH3:15])=[O:13])[CH:11]=1

Participants

7

Reactant 2

HCID 637114Dimethyl iodoterephthalateHCID 27332672-Methylphenyl boronic acid

Product 1

HCID 11277578Dimethyl 2'-methyl(1,1'-biphenyl)-2.5-dicarboxylateYield 99%

Reagents, catalysts & solvents 4

HCID 11776TriphenylphosphineCatalystHCID 167845palladium(II) acetateCatalystHCID 1140TolueneSolventHCID 10340Sodium CarbonateSolvent

Conditions

Temperature
77.5 °C

Procedure

A mixture of dimethyl iodoterephthalate (2.41 kg, 7.53 mol), ortho-tolylboronic acid (1.23 kg, 9.04 mol), palladium(II) acetate (16.9 g, 0.08 mol), and triphenylphosphine (79.0 g, 0.30 mol) in deoxygenated toluene (19 L) and 2M Na2CO3 (19 L) was vigorously mechanically stirred for 4 hours at 75-80° C. and cooled to room temperature to provide two distinct layers. The layers were separated, and the organic layer was filtered through a pad of silica gel 60 (4.79 kg of silica gel slurried with 2×10 L of MTBE) with a 40 L MTBE rinse, concentrated to 40 L, stored at 2-8° C. for 18 hours, filtered through a pad of diatomaceous earth (4.91 kg of Celite® 521 slurried in 20 L of MTBE) with a 40 L MTBE rinse to provide a solution of 2.12 kg (99%) of the desired product in MTBE.

Workup

  1. temperaturecooled to room temperature
  2. customto provide two distinct layers
  3. customThe layers were separated
  4. filtrationthe organic layer was filtered through a pad of silica gel 60 (4.79 kg of silica gel slurried with 2×10 L of MTBE) with a 40 L MTBE
  5. washrinse
  6. concentrationconcentrated to 40 L
  7. waitstored at 2-8° C. for 18 hours
  8. filtrationfiltered through a pad of diatomaceous earth (4.91 kg of Celite® 521 slurried in 20 L of MTBE) with a 40 L MTBE
  9. washrinse

Sources & evidence

ORD record
ord-8cc77ee3f67847b5895769d7d676e09d
Source dataset
uspto-grants-2001_06
Patent number
US06248919B1

Reaction notes

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