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

HRID 401398ノート

反応式

HRID 401398 の反応式
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]

参加物

5

反応物 3

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

生成物 1

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

試薬・触媒・溶媒 1

HCID 9811564Bis(dibenzylideneacetone)palladium触媒

実験手順

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+).

後処理

  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

出典と根拠

ORDレコード
ord-6e95a957ea334cdaa27e2a0c6c9ad85a
出典データセット
uspto-grants-2014_06
特許番号
US08741925B2

反応ノート

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