Potassium Carbonate → 6-Methyl-3'-nitrobiphenyl-3-carboxylic acid

HRID 77718

Reaction equation

HRID 77718 reaction equation
CC1(C)C(C)(C)OB([C:9]2[CH:14]=[CH:13][CH:12]=[C:11]([N+:15]([O-:17])=[O:16])[CH:10]=2)O1.I[C:20]1[CH:21]=[C:22]([CH:26]=[CH:27][C:28]=1[CH3:29])[C:23]([OH:25])=[O:24].C(=O)([O-])[O-].[K+].[K+].C([O-])(O)=O.[Na+]>C1(C)C=CC=CC=1.C(O)CCC.O.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[CH3:29][C:28]1[C:27]([C:9]2[CH:14]=[CH:13][CH:12]=[C:11]([N+:15]([O-:17])=[O:16])[CH:10]=2)=[CH:26][C:22]([C:23]([OH:25])=[O:24])=[CH:21][CH:20]=1

Participants

9

Reactant 4

HCID 11430Potassium CarbonateHCID 516892Sodium BicarbonateHCID 6216403-Iodo-4-methylbenzoic acidHCID 112651643-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)nitrobenzene

Product 1

HCID 690465616-Methyl-3'-nitrobiphenyl-3-carboxylic acidYield 88.9%

Reagents, catalysts & solvents 4

HCID 178418397HCID 178418397, compoundCatalystHCID 2631-ButanolSolventHCID 962WaterSolventHCID 1140TolueneSolvent

Conditions

Temperature
20 °C

Procedure

4,4,5,5-Tetramethyl-2-(3-nitrophenyl)-1,3,2-dioxaborolane (5.16 g, 0.0207 mol) was mixed with 3-iodo-4-methylbenzoic acid (4.94 g, 0.0188 mol), and potassium carbonate (10.4 g, 0.0753 mol) in toluene (100 mL), 1-butanol (20 mL) and water (15 mL) and the resulting mixture was degassed by sparging nitrogen through it. To the reaction was added tetrakis(triphenylphosphine)palladium(0) (1.0 g, 0.00091 mol). The mixture was stirred rapidly and was heated to reflux for 1.5 hour. LCMS analysis showed the reaction to be complete, M+H 258. The mixture was then cooled to 20° C. The aqueous layer was discarded. To the organic layer was added saturated NaHCO3. The toluene layer was extracted with aqueous sodium bicarbonate, then discarded. The aqueous sodium bicarbonate and alcohol layers were combined, then acidified to pH 2.5 with HCl. A white solid precipitated and was separated by filtration, rinsed with water, and air dried to give 4.3 g of the product. The filtrate contained only a trace of product.

Workup

  1. customthe resulting mixture was degassed
  2. customby sparging nitrogen through it
  3. temperaturewas heated
  4. temperatureto reflux for 1.5 hour
  5. customthe reaction
  6. extractionThe toluene layer was extracted with aqueous sodium bicarbonate
  7. customA white solid precipitated
  8. customwas separated by filtration
  9. washrinsed with water, and air
  10. customdried

Sources & evidence

ORD record
ord-05d338e82e9d4232a50ed122483f3200
Source dataset
uspto-grants-2014_09
Patent number
US08841318B2

Linked notes

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