Hydrogen Bromide → 4-bromophthalonitrile

HRID 1890406ノート

反応式

HRID 1890406 の反応式
N[C:2]1[CH:3]=[C:4]([C:10]#[N:11])[C:5](=[CH:8][CH:9]=1)[C:6]#[N:7].O.N([O-])=O.[Na+].C(Cl)Cl.[BrH:20]>>[Br:20][C:2]1[CH:3]=[C:4]([C:10]#[N:11])[C:5](=[CH:8][CH:9]=1)[C:6]#[N:7]

参加物

6

反応物 5

HCID 260Hydrogen Bromide2 回HCID 962WaterHCID 6344DichloromethaneHCID 925291,2-Benzenedicarbonitrile, 4-amino-2 回HCID 23668193Sodium Nitrite

生成物 1

HCID 113562234-bromophthalonitrile

反応条件

温度
-10 °C

実験手順

Compound 4 (24 g, 0.17 mol) was suspended in a stirring solution of 100 ml HBr (48%) and 100 ml of H2O cooled to −10° C. Sodium nitrite (14 g, 0.20 mol) was dissolved in ice water and added dropwise to the solution of 4-aminophthalonitrile. The exothermic reaction was carefully monitored and kept under 0° C. After 2 hours of stirring, the solution was added dropwise to a solution of Cu(I)Br (27 g, 0.18 mol) in 100 ml of HBr (48%) at −3° C. and stirred at 0° C. for 2 hours. To minimize foaming as well as increase the yield, methylene chloride was added to the solution and the reaction was allowed to proceed overnight for at least 24 hours. The organic layer was removed, and the aqueous layer was also extracted with toluene. The combined organic layers were washed with water, Na2S2O3 (saturated aqueous solution), water, brine, water, dried over MgSO4 and evaporated under reduced pressure. 25 g of an orange product were collected (73%). 1H NMR (CDCl3) δ: 7.99 (d, 1H), 7.94-7.91 (dd, 1H), 7.72-7.70 (d, 1H).6 13C{1H}NMR (CDCl3) 136.68, 136.42, 134.44, 128.19, 117.39, 114.76, 114.65, 114.04 ppm.

後処理

  1. customThe exothermic reaction
  2. customkept under 0° C
  3. stirringstirred at 0° C. for 2 hours
  4. additionwas added to the solution
  5. waitto proceed overnight for at least 24 hours
  6. customThe organic layer was removed
  7. extractionthe aqueous layer was also extracted with toluene
  8. washThe combined organic layers were washed with water, Na2S2O3 (saturated aqueous solution), water, brine, water
  9. dry with materialdried over MgSO4
  10. customevaporated under reduced pressure
  11. custom25 g of an orange product were collected (73%)

出典と根拠

ORDレコード
ord-de316d9a8391495ba7894a58ffbf7874
出典データセット
uspto-grants-2013_08
特許番号
US08507153B2

反応ノート

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