Tetrahydrofuran → Allyl [2-{2-chloro-4-fluoro-5-[3-methyl-2,6-dioxo-4-(trifluoromethyl)-1,2,3,6-tetrahydropyrimidin-1-yl]phenoxy}phenoxy]acetate

HRID 1241275Notes

Reaction equation

HRID 1241275 reaction equation
[Cl:1][C:2]1[CH:19]=[C:18]([F:20])[C:17]([N:21]2[C:26](=[O:27])[CH:25]=[C:24]([C:28]([F:31])([F:30])[F:29])[N:23]([CH3:32])[C:22]2=[O:33])=[CH:16][C:3]=1[O:4][C:5]1[CH:15]=[CH:14][CH:13]=[CH:12][C:6]=1[O:7][CH2:8][C:9]([OH:11])=[O:10].O1C[CH2:37][CH2:36][CH2:35]1>S(Cl)(Cl)=O>[Cl:1][C:2]1[CH:19]=[C:18]([F:20])[C:17]([N:21]2[C:26](=[O:27])[CH:25]=[C:24]([C:28]([F:29])([F:30])[F:31])[N:23]([CH3:32])[C:22]2=[O:33])=[CH:16][C:3]=1[O:4][C:5]1[CH:15]=[CH:14][CH:13]=[CH:12][C:6]=1[O:7][CH2:8][C:9]([O:11][CH2:37][CH:36]=[CH2:35])=[O:10]

Participants

4

Reactant 2

HCID 8028TetrahydrofuranHCID 21933550[2-{2-Chloro-4-fluoro-5-[3-methyl-2,6-dioxo-4-(trifluoromethyl)-1,2,3,6-tetrahydropyrimidin-1-yl]phenoxy}phenoxy]acetic acid

Product 1

HCID 17812332Allyl [2-{2-chloro-4-fluoro-5-[3-methyl-2,6-dioxo-4-(trifluoromethyl)-1,2,3,6-tetrahydropyrimidin-1-yl]phenoxy}phenoxy]acetate

Reagents, catalysts & solvents 1

HCID 24386Thionyl ChlorideSolvent

Procedure

First, 1.0 g of [2-{2-chloro-4-fluoro-5-[3-methyl-2,6-dioxo-4-(trifluoromethyl)-1,2,3,6-tetrahydropyrimidin-1-yl]phenoxy}phenoxy]acetic acid (compound a-1) was dissolved in tetrahydrofuran, to which 0.7 ml of thionyl chloride was added under stirring, and the mixture was heated and stirred under reflux for 2 hours. After left for cooling and the subsequent concentration, the residue was dissolved in 3 ml of tetrahydrofuran (hereinafter referred to as solution B). Then, 0.7 ml of tetrahydrofuran was added to 0.05 g of allyl alcohol, to which a third part of solution B was added and 0.17 ml of pyridine was then added. After stirring at room temperature for 2 hours, 2% aqueous hydrochloric acid was poured into the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed with saturated aqueous sodium chloride solution, dried over magnesium sulfate, and then concentrated. The residue was subjected to silica gel column chromatography (eluent: hexane/ethyl acetate=5/1) to give 0.08 g of allyl [2-{2-chloro-4-fluoro-5-[3-methyl-2,6-dioxo-4-(trifluoromethyl)-1,2,3,6-tetrahydropyrimidin-1-yl]phenoxy}phenoxy]acetate (compound a-21).

Workup

  1. additionwas added
  2. temperaturethe mixture was heated
  3. stirringstirred
  4. temperatureunder reflux for 2 hours
  5. waitAfter left
  6. temperaturefor cooling
  7. concentrationthe subsequent concentration
  8. dissolutionthe residue was dissolved in 3 ml of tetrahydrofuran (
  9. additionThen, 0.7 ml of tetrahydrofuran was added to 0.05 g of allyl alcohol, to which a third part of solution B
  10. additionwas added
  11. addition0.17 ml of pyridine was then added
  12. stirringAfter stirring at room temperature for 2 hours
  13. addition2% aqueous hydrochloric acid was poured into the reaction mixture
  14. extractionthe mixture was extracted with ethyl acetate
  15. washThe organic layer was washed with saturated aqueous sodium chloride solution
  16. dry with materialdried over magnesium sulfate
  17. concentrationconcentrated

Sources & evidence

ORD record
ord-2f36321857a1434f968e6bebd5d7286c
Source dataset
uspto-grants-2006_10
Patent number
US07115544B2

Reaction notes

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