1-Chloro-2-nitrobenzene → 3′,4′,5′-Trifluoro-2-nitro-1,1′-biphenyl

HRID 1257489Notes

Reaction equation

HRID 1257489 reaction equation
[F:1][C:2]1[CH:3]=[C:4](B(O)O)[CH:5]=[C:6]([F:9])[C:7]=1[F:8].[OH-].[Na+].[N+:15]([C:18]1[CH:23]=[CH:22][CH:21]=[CH:20][C:19]=1Cl)([O-:17])=[O:16]>O1CCCC1.COC(C)(C)C.[Pd](Cl)Cl>[F:1][C:2]1[CH:3]=[C:4]([C:19]2[CH:20]=[CH:21][CH:22]=[CH:23][C:18]=2[N+:15]([O-:17])=[O:16])[CH:5]=[C:6]([F:9])[C:7]=1[F:8]

Participants

7

Reactant 3

HCID 69451-Chloro-2-nitrobenzeneHCID 14798Sodium HydroxideHCID 2734671(3,4,5-Trifluorophenyl)boronic Acid (contains varying amounts of Anhydride)

Product 1

HCID 509926663′,4′,5′-Trifluoro-2-nitro-1,1′-biphenyl

Reagents, catalysts & solvents 3

HCID 24290Palladium ChlorideCatalystHCID 8028TetrahydrofuranSolventHCID 15413tert-Butyl methyl etherSolvent

Conditions

Temperature
105 °C

Procedure

A well-inertized pressure vessel was initially charged with a mixture of 49.6 g (0.113 mol) of a 40% solution of 3,4,5-trifluorophenylboronic acid in tetrahydrofuran from preliminary stage a) with 121.6 g (0.304 mol) of a 10% sodium hydroxide solution and 19.7 g (0.124 mol) of 2-nitrochlorobenzene. The particular ligand was then added at room temperature, the mixture was stirred and the palladium(II) chloride was finally added. Subsequently, the reaction mixture was heated to 105° C. This established a pressure of approx. 3-4 bar. After about 12 hours of reaction time, the pressure vessel was decompressed to standard pressure and cooled to 30° C., and the reaction mixture was discharged. For workup, the reaction mixture was taken up in tert-butyl methyl ether, the phases were separated and the aqueous phase re-extracted twice with tert-butyl methyl ether. The solvents were distilled off completely under reduced pressure, the final weight was determined and the content of the crude 3,4,5-trifluoro-2′-nitrobiphenyl was analyzed by means of quantitative HPLC. If desired, the crude 3,4,5-trifluoro-2′-nitrobiphenyl can be purified further, for example by crystallization from isobutanol.

Workup

  1. additionThe particular ligand was then added at room temperature
  2. customAfter about 12 hours of reaction time
  3. temperaturecooled to 30° C.
  4. customthe phases were separated
  5. extractionthe aqueous phase re-extracted twice with tert-butyl methyl ether
  6. distillationThe solvents were distilled off completely under reduced pressure

Sources & evidence

ORD record
ord-a9c53de16d964318a7ee146146a9170c
Source dataset
uspto-grants-2013_06
Patent number
US08461390B2

Reaction notes

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