Реакция #4509

Уравнение реакции

ethyl (E)-6-(1,3-dihydro-4-hydroxy-6-methoxy-7-methyl-3-oxo-5-isobenzofuranyl)-4-methyl-4-thiohexenoate

pyridine

phosgene

→

ethyl (E)-6-(1,3-dihydro-4-carbamoyl oxy-6-methoxy-7-methyl-3-oxo-5-iso benzofuranyl)-4-methyl-4-thiohexenoate

Растворители

benzene

benzene

Условия реакции

Обработка

1. 1
   Фильтрацияthe precipitate filtered off
2. 2
   Другоеsolvent removed from the filtrate under reduced pressure
3. 3
   workup.DISSOLUTIONThe residue was dissolved in 5 ml of tetrahydrofuran and to this solution
4. 4
   workup.ADDITIONwas added dropwise a solution of ammonia in tetrahydrofuran until the reaction
5. 5
   workup.ADDITIONThe mixture was poured into water
6. 6
   Экстракцияextracted with ethyl acetate
7. 7
   СушкаThe organic solution was dried over magnesium sulfate
8. 8
   Другоеevaporated to an oil which
9. 9
   Другоеwas chromatographed on silica gel
10. 10
    Промывкаeluting with a 1:1 mixture of ethyl acetate and hexane
11. 11
    workup.STIRRINGThe purified product was stirred with a mixture of ether and hexane
12. 12
    Фильтрацияfiltered

Методика

To a solution of 500 mgs of ethyl (E)-6-(1,3-dihydro-4-hydroxy-6-methoxy-7-methyl-3-oxo-5-isobenzofuranyl)-4-methyl-4-thiohexenoate in 10 ml of benzene cooled in an ice bath was added 0.1 ml of pyridine and 6 ml of a 12.5% solution of phosgene in benzene. The solution was stirred at 25° C. overnight, the precipitate filtered off and solvent removed from the filtrate under reduced pressure. The residue was dissolved in 5 ml of tetrahydrofuran and to this solution was added dropwise a solution of ammonia in tetrahydrofuran until the reaction was complete. The mixture was poured into water and extracted with ethyl acetate. The organic solution was dried over magnesium sulfate and evaporated to an oil which was chromatographed on silica gel, eluting with a 1:1 mixture of ethyl acetate and hexane. The purified product was stirred with a mixture of ether and hexane and filtered giving ethyl (E)-6-(1,3-dihydro-4-carbamoyl oxy-6-methoxy-7-methyl-3-oxo-5-iso benzofuranyl)-4-methyl-4-thiohexenoate, mp 145°-147° C.

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