Potassium Fluoride → 2′-Ethoxy-2-nitro[1,1′-biphenyl]-4-carbonitrile

HRID 74066

Reaction equation

HRID 74066 reaction equation
Br[C:2]1[CH:9]=[CH:8][C:5]([C:6]#[N:7])=[CH:4][C:3]=1[N+:10]([O-:12])=[O:11].[CH2:13]([O:15][C:16]1[CH:21]=[CH:20][CH:19]=[CH:18][C:17]=1B(O)O)[CH3:14].[F-].[K+]>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]>[CH2:13]([O:15][C:16]1[CH:21]=[CH:20][CH:19]=[CH:18][C:17]=1[C:2]1[CH:9]=[CH:8][C:5]([C:6]#[N:7])=[CH:4][C:3]=1[N+:10]([O-:12])=[O:11])[CH3:14]

Participants

5

Reactant 3

HCID 522689Potassium FluorideHCID 2734902(2-Ethoxyphenyl)boronic acidHCID 39268614-Bromo-3-nitrobenzonitrile

Product 1

HCID 574827042′-Ethoxy-2-nitro[1,1′-biphenyl]-4-carbonitrile

Reagents, catalysts & solvents 1

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalyst

Procedure

A 50 mL round-bottom flask was charged with 4-bromo-3-nitrobenzonitrile (1.0 g 4.4 mmol), 2-ethoxyphenylboronic acid (731 mg, 4.4 mmol), Pd2(dba)3 (18 mg, 0.022 mmol) and potassium fluoride (786 mg, 13.5 mmol). The reaction vessel was evacuated and filled with argon. Dry THF (300 mL) was added followed by the addition of P(t-Bu)3 (0.11 mL, 10% wt. in hexane). The reaction mixture was stirred at room temperature for 30 min., and then heated at 80° C. for 16 h. After cooling to room temperature, the resulting mixture was filtered through a Celite pad and concentrated. 2′-Ethoxy-2-nitrobiphenyl-4-carbonitrile was isolated as a yellow solid (1.12 g, 95%). 1H NMR (300 MHz, DMSO-d6) δ 8.51 (s, 1H), 8.20 (d, J=8.1 Hz, 1H), 7.68 (d, J=8.4 Hz, 1H), 7.41 (t, J=8.4 Hz, 1H), 7.37 (d, J=7.5 Hz, 1H), 7.08 (t, J=7.5 Hz, 1H), 7.03 (d, J=8.1 Hz, 1H), 3.91 (q, J=7.2 Hz, 2H), 1.12 (t, J=7.2 Hz, 3H); 13C NMR (75 MHz, DMSO-d6) δ 154.9, 149.7, 137.3, 137.2, 134.4, 131.5, 130.4, 128.4, 125.4, 121.8, 117.6, 112.3, 111.9, 64.1, 14.7; HPLC ret. time 2.43 min, 10-100% CH3CN, 5 min gradient; ESI-MS 269.3 m/z (MH+).

Workup

  1. customThe reaction vessel was evacuated
  2. additionfilled with argon
  3. additionDry THF (300 mL) was added
  4. additionfollowed by the addition of P(t-Bu)3 (0.11 mL, 10% wt. in hexane)
  5. temperatureheated at 80° C. for 16 h
  6. temperatureAfter cooling to room temperature
  7. filtrationthe resulting mixture was filtered through a Celite pad
  8. concentrationconcentrated

Sources & evidence

ORD record
ord-740ee38d627d41c58bf0f6f57c090550
Source dataset
uspto-grants-2014_09
Patent number
US08829204B2

Linked notes

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