Реакция #1264699

Уравнение реакции

((1S,4R)-7,7-dimethyl-2-oxobicyclo[2.2.1]heptan-1-yl)methanesulfonic acid

3-amino-6-(1-phenylcyclopropyl)pyridine-2(1H)-thione

methyl 4-(chlorocarbonyl)-3-nitrobenzoate

water

→

methyl 3-nitro-4-(5-(1-phenylcyclopropyl)thiazolo[5,4-b]pyridine-2-yl)benzoate

Растворители

toluene

EtOAc

toluene

Условия реакции

Обработка

1. 1
   Температураcooled
2. 2
   Температураreflux condenser
3. 3
   ДругоеAfter bubbling
4. 4
   Температураheating
5. 5
   Температураheating
6. 6
   workup.WAITcontinued overnight
7. 7
   Другоеto give a dark brown solution
8. 8
   ТемператураThe reaction mixture was cooled to ambient temperature
9. 9
   Промывкаwashed with water
10. 10
    СушкаThe organic layer was dried over sodium sulfate
11. 11
    Фильтрацияfiltered
12. 12
    Концентрированиеconcentrated in vacuo
13. 13
    Другоеto give a brown oil
14. 14
    ДругоеPurification by silica gel chromatography, 40 g, 0-30% EA/hexanes

Методика

A slurry of 3-amino-6-(1-phenylcyclopropyl)pyridine-2(1H)-thione (1.00 g, 4.13 mmol) and methyl 4-(chlorocarbonyl)-3-nitrobenzoate (1.11 g, 4.54 mmol) in 10 mL toluene was heated under nitrogen with a water cooled reflux condenser was heated in a 120° C. oil bath. After bubbling had subsided, ((1S,4R)-7,7-dimethyl-2-oxobicyclo[2.2.1]heptan-1-yl)methanesulfonic acid (0.479 g, 2.06 mmol) was added through the condenser and heating continued for 30 min. The slurry was treated with 5 mL toluene to and heating continued overnight to give a dark brown solution. The reaction mixture was cooled to ambient temperature, then diluted with EtOAc, washed with water, sat'd aq. Bicarbonate, and brine. The organic layer was dried over sodium sulfate, filtered, and concentrated in vacuo to give a brown oil. Purification by silica gel chromatography, 40 g, 0-30% EA/hexanes gave methyl 3-nitro-4-(5-(1-phenylcyclopropyl)thiazolo[5,4-b]pyridine-2-yl)benzoate as a light brown solid. MS (ESI) m/z: Calculated: 431.1; Observed: 432.0 (M++1).

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