Allyl chloroformate → 1-(2,2,2-Trifluoroethyl)-3-(3,5-dichlorophenyl)-4-allyloxycarbonyl-4,5-dihydro-1,2,4-triazin-6-one

HRID 1726925Notes

Reaction equation

HRID 1726925 reaction equation
[F:1][C:2]([F:20])([F:19])[CH2:3][N:4]1[C:9](=[O:10])[CH2:8][NH:7][C:6]([C:11]2[CH:16]=[C:15]([Cl:17])[CH:14]=[C:13]([Cl:18])[CH:12]=2)=[N:5]1.[H-].[Na+].Cl[C:24]([O:26][CH2:27][CH:28]=[CH2:29])=[O:25]>O1CCCC1>[F:20][C:2]([F:1])([F:19])[CH2:3][N:4]1[C:9](=[O:10])[CH2:8][N:7]([C:24]([O:26][CH2:27][CH:28]=[CH2:29])=[O:25])[C:6]([C:11]2[CH:12]=[C:13]([Cl:18])[CH:14]=[C:15]([Cl:17])[CH:16]=2)=[N:5]1

Participants

5

Reactant 3

HCID 18052Allyl chloroformateHCID 24758Sodium hydrideHCID 1785167591-(2,2,2-Trifluoroethyl)-3-(3,5-dichlorophenyl)-4,5-dihydro-1,2,4-triazin-6-one

Product 1

HCID 689583941-(2,2,2-Trifluoroethyl)-3-(3,5-dichlorophenyl)-4-allyloxycarbonyl-4,5-dihydro-1,2,4-triazin-6-oneYield 93.2%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

To a solution of 1-(2,2,2-trifluoroethyl)-3-(3,5-dichlorophenyl)-4,5-dihydro-1,2,4-triazin-6-one (110 mg, 0.34 mmol) in 5 mL tetrahydrofuran at was added sodium hydride (30 mg, 0.67 mmol). After the reaction stirred 5 min, the allyl chloroformate (0.07 mL, 0.67 mmol) was added dropwise. After the reaction was heated at reflux for 6 h, it was quenched with water and diluted with ethyl acetate. The two layers were separated and the aqueous phase was extracted with ethyl acetate (3×5 mL). The combined organic extracts were dried over MgSO4, filtered, and concentrated in vacuo. Flash column chromatography (100% hexanes-10% ethyl acetate/hexanes) afforded the acylated product 1-(2,2,2-trifluoroethyl)-3-(3,5-dichlorophenyl)-4-allyloxycarbonyl-4,5-dihydro-1,2,4-triazin-6-one (130 mg, 93%) as a yellow oil in 100% purity by gas chromatography (GC).

Workup

  1. temperatureAfter the reaction was heated
  2. temperatureat reflux for 6 h
  3. customit was quenched with water
  4. additiondiluted with ethyl acetate
  5. customThe two layers were separated
  6. extractionthe aqueous phase was extracted with ethyl acetate (3×5 mL)
  7. dry with materialThe combined organic extracts were dried over MgSO4
  8. filtrationfiltered
  9. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-5149ef1e60874350bad214f4c2148c0c
Source dataset
uspto-grants-2009_02
Patent number
US07494996B2

Reaction notes

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