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

HRID 1032742Notes

Reaction equation

HRID 1032742 reaction equation
[OH:1][C:2]1[C:10]([CH2:11]/[CH:12]=[C:13](\[CH3:21])/[CH2:14][CH2:15][C:16]([O:18][CH2:19][CH3:20])=[S:17])=[C:9]([O:22][CH3:23])[C:8]([CH3:24])=[C:7]2[C:3]=1[C:4](=[O:25])[O:5][CH2:6]2.[N:26]1[CH:31]=CC=CC=1.C(Cl)(Cl)=[O:33]>C1C=CC=CC=1>[C:31]([O:1][C:2]1[C:10]([CH2:11]/[CH:12]=[C:13](\[CH3:21])/[CH2:14][CH2:15][C:16]([O:18][CH2:19][CH3:20])=[S:17])=[C:9]([O:22][CH3:23])[C:8]([CH3:24])=[C:7]2[C:3]=1[C:4](=[O:25])[O:5][CH2:6]2)(=[O:33])[NH2:26]

Participants

5

Reactant 3

HCID 1049PyridineHCID 6371PhosgeneHCID 86741995HCID 86741995, compound

Product 1

HCID 86741994ethyl (E)-6-(1,3-dihydro-4-carbamoyloxy-6-methoxy-7-methyl-3-oxo-5-isobenzofuranyl)-4-methyl-4-thiohexenoate

Reagents, catalysts & solvents 1

HCID 241BenzeneSolvent2×

Conditions

Temperature
25 °C

Procedure

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-carbamoyloxy-6-methoxy-7-methyl-3-oxo-5-isobenzofuranyl)-4-methyl-4-thiohexenoate, m.p. 145°-147° C.

Workup

  1. filtrationthe precipitate filtered off
  2. customsolvent removed from the filtrate under reduced pressure
  3. dissolutionThe residue was dissolved in 5 ml of tetrahydrofuran and to this solution
  4. additionwas added dropwise a solution of ammonia in tetrahydrofuran until the reaction
  5. additionThe mixture was poured into water
  6. extractionextracted with ethyl acetate
  7. dry with materialThe organic solution was dried over magnesium sulfate
  8. customevaporated to an oil which
  9. customwas chromatographed on silica gel
  10. washeluting with a 1:1 mixture of ethyl acetate and hexane
  11. stirringThe purified product was stirred with a mixture of ether and hexane
  12. filtrationfiltered

Sources & evidence

ORD record
ord-6d37ba752a164876ad8f6e91be5fa8cb
Source dataset
uspto-grants-1990_09
Patent number
US04959387

Reaction notes

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