1-Bromo-2,4-dinitrobenzene → 2'-Ethoxy-2,4-dinitro-biphenyl

HRID 423861

Reaction equation

HRID 423861 reaction equation
[CH2:1]([O:3][C:4]1[CH:9]=[CH:8][CH:7]=[CH:6][C:5]=1B(O)O)[CH3:2].[F-].[K+].[N+:15]([C:18]1[CH:23]=[C:22]([N+:24]([O-:26])=[O:25])[CH:21]=[CH:20][C:19]=1Br)([O-:17])=[O:16].C(P(C(C)(C)C)C(C)(C)C)(C)(C)C>C1COCC1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd]>[CH2:1]([O:3][C:4]1[CH:9]=[CH:8][CH:7]=[CH:6][C:5]=1[C:19]1[CH:20]=[CH:21][C:22]([N+:24]([O-:26])=[O:25])=[CH:23][C:18]=1[N+:15]([O-:17])=[O:16])[CH3:2]

Participants

7

Reactant 4

HCID 114411-Bromo-2,4-dinitrobenzeneHCID 83681Tris(1,1-dimethylethyl)phosphineHCID 522689Potassium FluorideHCID 2734902(2-Ethoxyphenyl)boronic acid

Product 1

HCID 574826992'-Ethoxy-2,4-dinitro-biphenylYield 82.4%

Reagents, catalysts & solvents 2

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
80 °C

Procedure

A pressure flask was charged with 2-ethoxyphenylboronic acid (0.66 g, 4.0 mmol), KF (0.77 g, 13 mmol), Pd2(dba)3 (16 mg, 0.02 mmol), and 2,4-dinitro-bromobenzene (0.99 g, 4.0 mmol) in THF (5 mL). The vessel was purged with argon for 1 min followed by the addition of tri-tert-butylphosphine (0.15 ml, 0.48 mmol, 10% solution in hexanes). The reaction vessel was purged with argon for additional 1 min., sealed and heated at 80° C. overnight. After cooling to room temperature, the solution was filtered through a plug of Celite. The filter cake was rinsed with CH2Cl2 (10 mL), and the combined organic extracts were concentrated under reduced pressure to provide the crude product 2′-ethoxy-2,4-dinitro-biphenyl (0.95 g, 82%). No further purification was performed. 1H NMR (300 MHz, CDCl3) δ 8.75 (s, 1H), 8.43 (d,J=8.7 Hz, 1H), 7.60 (d,J=8.4 Hz, 1H), 7.40 (t,J=7.8 Hz, 1H), 7.31 (d,J=7.5 Hz, 1H), 7.08 (t,J=7.5 Hz, 1H), 6.88 (d, J=8.4 Hz, 1H), 3.44 (q,J=6.6 Hz, 2H), 1.24 (t,J=6.6 Hz, 3H); HPLC ret. time 3.14 min, 10-100% CH3CN, 5 min gradient.

Workup

  1. customThe vessel was purged with argon for 1 min
  2. customThe reaction vessel was purged with argon for additional 1 min.
  3. customsealed
  4. temperatureAfter cooling to room temperature
  5. filtrationthe solution was filtered through a plug of Celite
  6. washThe filter cake was rinsed with CH2Cl2 (10 mL)
  7. concentrationthe combined organic extracts were concentrated under reduced pressure

Sources & evidence

ORD record
ord-89e7d8f89f364c2980ab997e0ba2ddf0
Source dataset
uspto-grants-2012_01
Patent number
US08101767B2

Linked notes

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