Hydrogen Sulfide → Methyl 3-methoxy-2-[2-(2-isopropoxy-6-trifluoromethylpyrimidin-4-yloxymethyl) phenyl]acrylate

HRID 991172Notes

Reaction equation

HRID 991172 reaction equation
[CH:1]([O:4][C:5]1[N:10]=[C:9]([OH:11])[CH:8]=[C:7]([C:12]([F:15])([F:14])[F:13])[N:6]=1)([CH3:3])[CH3:2].P(OCC)(OCC)OCC.[CH3:26][O:27][CH:28]=[C:29]([C:34]1[CH:39]=[CH:38][CH:37]=[CH:36][C:35]=1[CH2:40]Br)[C:30]([O:32][CH3:33])=[O:31].S>CCCCCCCC.O.[Cu].[Cu].O>[CH3:26][O:27][CH:28]=[C:29]([C:34]1[CH:39]=[CH:38][CH:37]=[CH:36][C:35]=1[CH2:40][O:11][C:9]1[CH:8]=[C:7]([C:12]([F:14])([F:15])[F:13])[N:6]=[C:5]([O:4][CH:1]([CH3:3])[CH3:2])[N:10]=1)[C:30]([O:32][CH3:33])=[O:31]

Participants

8

Reactant 4

HCID 402Hydrogen SulfideHCID 31215Triethyl phosphiteHCID 53395349Methyl 2-[2-(bromomethyl)phenyl]-3-methoxyprop-2-enoateHCID 178458952HCID 178458952, compound

Product 1

HCID 53395020Methyl 3-methoxy-2-[2-(2-isopropoxy-6-trifluoromethylpyrimidin-4-yloxymethyl) phenyl]acrylateYield 67%

Reagents, catalysts & solvents 3

HCID 14830Dicopper oxideCatalystHCID 356OctaneSolvent2×HCID 962WaterSolvent3×

Conditions

Temperature
100 °C

Procedure

2.22 g of 2-isopropoxy-6-trifluoromethyl-4-hydroxypyrimidine and 0.86 g of copper suboxide were suspended in 30 ml of octane. The suspension was refluxed until no water was recognized to form, while formed water was being taken into a quantitative water receiver. 1.86 g of triethyl phosphite was added, and, 30 minutes later, 3.65 g of methyl 3-methoxy-2-(2-bromomethylphenyl)acrylate was added at an instance. The reaction was carried out for 5 hours at reflux of octane. The solution was cooled down to 100° C. Hydrogen sulfide gas was blown into the solution at a rate of 15-30 ml/min for an hour. The resultant was stirred for 30 minutes. The formed precipitate was filtrated and washed with 9 ml of octane. The mixed solution of the obtained filtrate and washing was analyzed with high-performance liquid chromatography. The reaction yield was 72%. Octane was concentrated under reduced pressure. To the residue were added 10.3 ml of ethanol and 3.9 ml of water, and heated to 64° C. to dissolve. The resulting solution was left to cool over night. 2.8 ml of a mixed solution of ethanol/water (7/1) was added to it and cooled down to 5° C. to deposit crystals fully. The crystals were filtrated, washed with 1.4 ml of a mixed solution of ethanol/water (7/1) twice to give 2.46 g (yield 67%) of the target compound with melting point of 109˜110° C.

Workup

  1. customto form
  2. filtrationThe formed precipitate was filtrated
  3. washwashed with 9 ml of octane
  4. washThe mixed solution of the obtained filtrate and washing
  5. customThe reaction yield was 72%
  6. concentrationOctane was concentrated under reduced pressure
  7. additionTo the residue were added 10.3 ml of ethanol and 3.9 ml of water
  8. temperatureheated to 64° C.
  9. dissolutionto dissolve
  10. waitThe resulting solution was left
  11. temperatureto cool over night
  12. addition2.8 ml of a mixed solution of ethanol/water (7/1) was added to it
  13. temperaturecooled down to 5° C.
  14. filtrationThe crystals were filtrated
  15. washwashed with 1.4 ml of a mixed solution of ethanol/water (7/1) twice

Sources & evidence

ORD record
ord-4be0045e794243ffbc11c11d331d3a0d
Source dataset
uspto-grants-2002_10
Patent number
US06462195B1

Reaction notes

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