Reaktion #1264699

Reaktionsgleichung

((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

Lösungsmittel

toluene

EtOAc

toluene

Reaktionsbedingungen

Aufarbeitung

1. 1
   Temperaturcooled
2. 2
   Temperaturreflux condenser
3. 3
   SonstigeAfter bubbling
4. 4
   Temperaturheating
5. 5
   Temperaturheating
6. 6
   workup.WAITcontinued overnight
7. 7
   Sonstigeto give a dark brown solution
8. 8
   TemperaturThe reaction mixture was cooled to ambient temperature
9. 9
   Waschenwashed with water
10. 10
    TrocknenThe organic layer was dried over sodium sulfate
11. 11
    Filtrationfiltered
12. 12
    Einengenconcentrated in vacuo
13. 13
    Sonstigeto give a brown oil
14. 14
    SonstigePurification by silica gel chromatography, 40 g, 0-30% EA/hexanes

Vorschrift

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).

Quelle