Sodium Carbonate → 3-Nitro-2'-trifluoromethyl-biphenyl-4-ylamine

HRID 1512165Notes

Reaction equation

HRID 1512165 reaction equation
Br[C:2]1[CH:7]=[CH:6][C:5]([NH2:8])=[C:4]([N+:9]([O-:11])=[O:10])[CH:3]=1.[F:12][C:13]([F:24])([F:23])[C:14]1[CH:19]=[CH:18][CH:17]=[CH:16][C:15]=1B(O)O.[Li+].[Cl-].C([O-])([O-])=O.[Na+].[Na+]>COCCOC.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>[N+:9]([C:4]1[CH:3]=[C:2]([C:15]2[CH:16]=[CH:17][CH:18]=[CH:19][C:14]=2[C:13]([F:24])([F:23])[F:12])[CH:7]=[CH:6][C:5]=1[NH2:8])([O-:11])=[O:10]

Participants

8

Reactant 4

HCID 10340Sodium CarbonateHCID 701324-Bromo-2-nitroanilineHCID 433294Lithium ChlorideHCID 27343872-(Trifluoromethyl)benzeneboronic acid

Product 1

HCID 509940363-Nitro-2'-trifluoromethyl-biphenyl-4-ylamine

Reagents, catalysts & solvents 3

HCID 178418397HCID 178418397, compoundCatalystHCID 962WaterSolventHCID 80711,2-DimethoxyethaneSolvent

Conditions

Temperature
80 °C

Procedure

A solution of 4-bromo-2-nitro-phenylamine (5.00 g, 0.0230 mol) in DME (100 mL) was treated with (2-trifluoromethylphenyl) boronic acid (5.25 g, 0.0277 mol), LiCl (0.976 g, 0.0230 mol), and 2M aqueous Na2CO3 (92.1 mL, 0.184 mol). The resulting mixture was heated to 80° C. under a stream of Argon, treated with Pd(PPh3)4 (2.66 g, 0.00230 mol) and heated to 80° C. overnight. The cooled mixture was diluted with water and extracted thrice with EtOAc. The combined organic layers were dried over MgSO4 and concentrated in vacuo. The residue was purified on a 200-g Sepra Si 50 SPE column (Isco system: flow rate=40 mL/min; eluting with EtOAc/hexanes, 5:95 v/v, over 10 min, 5:95 to 20:80, v/v over 25 min, and 20:80 to 40:60 v/v over 35 min) to yield 3-nitro-2′-trifluoromethyl-biphenyl-4-ylamine as an orange solid

Workup

  1. temperatureheated to 80° C. overnight
  2. extractionextracted thrice with EtOAc
  3. dry with materialThe combined organic layers were dried over MgSO4
  4. concentrationconcentrated in vacuo
  5. customThe residue was purified on a 200-g Sepra Si 50 SPE column (Isco system
  6. washeluting with EtOAc/hexanes, 5:95 v/v, over 10 min

Sources & evidence

ORD record
ord-89a026fabc8240acaba0c56eb5577fb1
Source dataset
uspto-grants-2012_07
Patent number
US08217060B2

Reaction notes

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