Reaktion #51916

Reaktionsgleichung

p-chlorobenzylamine

butyllithium

ethyl 3-(bromomethyl)-4-methyl-7-oxo-4,7-dihydrothieno[3,2-b]pyridine-6-carboxylate

allyl alcohol

→

title compound

3-[(Allyloxy)methyl]-N-(4-chlorobenzyl)-4-methyl-7-oxo-4,7-dihydrothieno[3,2-b]pyridine-6-carboxamide

Lösungsmittel

ether

—

hexanes

DMF

THF

Reaktionsbedingungen

Aufarbeitung

1. 1
   workup.ADDITIONadded via cannula to a cold (0° C.)
2. 2
   workup.STIRRINGstirred
3. 3
   workup.STIRRINGThe resulting solution is stirred at 0° C. for 20 min
4. 4
   Sonstigequenched with dil. HCl
5. 5
   Sonstigeaffords
6. 6
   Temperaturcooled
7. 7
   FiltrationThe resulting solid is filtered
8. 8
   Waschenwashed well with ether
9. 9
   Sonstigedried in vacuo

Vorschrift

To a cold (0° C.), stirred solution of 0.82 mL of allyl alcohol in 12 mL of dry THF, under argon, is added 2.1 mL of a 2.5 M solution of butyllithium in hexanes. The solution is stirred for 5 min, then added via cannula to a cold (0° C.), stirred mixture of 1.25 g of ethyl 3-(bromomethyl)-4-methyl-7-oxo-4,7-dihydrothieno[3,2-b]pyridine-6-carboxylate (Preparation 19) in 8 mL of dry DMF. The resulting solution is stirred at 0° C. for 20 min, then quenched with dil. HCl. Aqueous workup (EtOAc/dil HCl) followed by flash chromatography on silica using 3% MeOH in CH2Cl2 affords a mixture of ethyl and allyl esters (873 mg). A mixture of 165 mg of the mixed esters and 580 mg of p-chlorobenzylamine is heated at 120° C. for 18 h, then cooled and diluted with ether. The resulting solid is filtered, washed well with ether, and dried in vacuo. Flash chromatography of the solid on silica using 2% MeOH in CH2Cl2 provides 922 mg of the title compound as a pale yellow solid. Recrystallization from EtOAc affords glistening yellow prisms.

Quelle