Реакция #478602

ord-90327fc22da147d785d910887f5fef09

Растворители

Условия реакции

Температура
0°CELSIUS
Подробные условия
See reaction.notes.procedure_details.

Обработка

  1. 1
    ДругоеThe resulting reaction mixture
  2. 2
    workup.STIRRINGAfter stirring for 1 h at room temperature
  3. 3
    Температураthe reaction was heated
  4. 4
    Температураto reflux
  5. 5
    workup.WAITheld there for 3 h
  6. 6
    ТемператураThe reaction was cooled
  7. 7
    ДругоеIt gave an intractable suspension
  8. 8
    ФильтрацияThe reaction mixture was filtered through a sintered glass funnel
  9. 9
    ДругоеThe layers were separated
  10. 10
    ПромывкаThe organics were washed with water
  11. 11
    Сушкаbrine, dried over magnesium sulfate
  12. 12
    Концентрированиеconcentrated
  13. 13
    workup.DISTILLATIONThe crude residue was distilled (high vacuum, 75° C.)
  14. 14
    Другоеto give 3 fractions of varying levels of purity

Методика

A flask was charged with water (42 ml), cooled to 0° C., and treated with concentrated hydrochloric acid (21.7 ml) and sulfuric acid (5.66 ml). To this was added 3-amino-5-bromobenzotrifluoride (8.77 ml, 62.5 mmol). The reaction was treated with a solution of sodium nitrite (5.39 g, 78 mmol) in water (10 mL). The resulting reaction mixture was stirred for 30 min at 0° C. The reaction was transferred to a solution of acetaldoxime (5.71 ml, 94 mmol) and copper(II) sulfate (0.499 g, 3.12 mmol) in water (30 mL) at room temperature. After stirring for 1 h at room temperature, the reaction was heated to reflux and held there for 3 h. The reaction was cooled and diluted with pentane. It gave an intractable suspension. The reaction mixture was filtered through a sintered glass funnel. The layers were separated. The organics were washed with water, then brine, dried over magnesium sulfate, and concentrated. The crude residue was distilled (high vacuum, 75° C.) to give 3 fractions of varying levels of purity. Total yield was 8.5 g (51%) with purity that ranged from 10:1 to 1:1. 1H NMR (500 MHz, CDCl3) δ ppm 8.25 (s, 1H), 8.11 (s, 1H), 7.95 (s, 1H), 2.63 (s, 3H).

Источник

DOI: 10.6084/m9.figshare.5104873.v1Патент: US08383821B2uspto-grants-2013_02