2-Butenoic acid, 4,4,4-trifluoro-3-(methylamino)-, ethyl ester → Butafenacil

HRID 1533434Notes

Reaction equation

HRID 1533434 reaction equation
C(O[C:4](=[O:13])[CH:5]=[C:6]([NH:11][CH3:12])[C:7]([F:10])([F:9])[F:8])C.[CH2:14]([O:17][C:18]([C:20]([O:23][C:24](=[O:35])[C:25]1[CH:30]=[C:29]([N:31]=[C:32]=[O:33])[CH:28]=[CH:27][C:26]=1[Cl:34])([CH3:22])[CH3:21])=[O:19])[CH:15]=[CH2:16]>CN(C)C=O>[CH2:14]([O:17][C:18]([C:20]([O:23][C:24](=[O:35])[C:25]1[CH:30]=[C:29]([N:31]2[C:4](=[O:13])[CH:5]=[C:6]([C:7]([F:8])([F:9])[F:10])[N:11]([CH3:12])[C:32]2=[O:33])[CH:28]=[CH:27][C:26]=1[Cl:34])([CH3:22])[CH3:21])=[O:19])[CH:15]=[CH2:16]

Participants

4

Reactant 2

HCID 27588682-Butenoic acid, 4,4,4-trifluoro-3-(methylamino)-, ethyl esterHCID 109362161,1-Dimethyl-2-oxo-2-(2-propen-1-yloxy)ethyl 2-chloro-5-isocyanatobenzoate

Product 1

HCID 11826859ButafenacilYield 89%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Conditions

Temperature
40 °C

Procedure

0.347 g of potassium tert.butylate (content: 97%, 0.003 mols) are suspended in 30 g of anhydrous dimethylformamide (water content <0.01%), and heated to a temperature of 40° C. Subsequently, 1.97 g of 3-methylamino-4,4,4-trifluorobut-2-enoic acid ethyl ester (content: 99.5%, 0.01 mols) are added at a temperature of 40 to 45° C., and this temperature is maintained for a further 30 minutes, whereby a red-brown solution is produced. After cooling the reaction mixture to a temperature of 0° C., 3.51 g of 5-isocyanato-2-chloro-benzoic acid 1-allyloxycarbonyl-1-methyl-ethyl-ester (content: 97%, 0.0105 mols) are dispensed in over the course of 30 minutes, whereby the temperature is maintained at between 0 and 5° C. After removing the cooling bath, the resultant dark brown solution is stirred for a further 30 minutes, and the pH value of the now dark red solution is adjusted to pH 7 with 2.7 g of 1 M HCl [the content of 2-chloro-5-(3,6-dihydro-2,6-dioxo-3-methyl-4-trifluoromethyl-1-(2H)pyrimidinyl)-benzoic acid 1-allyloxyoarbonyl-1-methyl-ethyl-ester in this solution is 11%, which corresponds to a yield of 89%]. The solvent is subsequently distilled off in a rotary evaporator, and the residue (5.6 g) is recrystallised in 12 g of isopropyl alcohol [the inorganic salts are removed by hot filtration]. After drying in a vacuum drying chamber (60° C. for 12 hours), 4.10 g (86.3% of theory) of 2-ohloro-5-(3,6-dihydro-2,6-dioxo-3-methyl-4-trifluoromethyl-1-(2H)pyrimidinyl)-benzoic acid 1-allyloxycarbonyl-1-methyl-ethyl-ester are obtained in a content of 99%.

Workup

  1. temperaturethis temperature is maintained for a further 30 minutes
  2. customwhereby a red-brown solution is produced
  3. customare dispensed in over the course of 30 minutes, whereby
  4. temperatureis maintained at between 0 and 5° C
  5. customAfter removing the cooling bath
  6. distillationThe solvent is subsequently distilled off in a rotary evaporator
  7. customthe residue (5.6 g) is recrystallised in 12 g of isopropyl alcohol [the inorganic salts
  8. customare removed by hot filtration]
  9. customAfter drying in a vacuum
  10. dry with materialdrying chamber (60° C. for 12 hours), 4.10 g (86.3% of theory) of 2-ohloro-5-(3,6-dihydro-2,6-dioxo-3-methyl-4-trifluoromethyl-1-(2H)pyrimidinyl)-benzoic acid 1-allyloxycarbonyl-1-methyl-ethyl-ester
  11. customare obtained in a content of 99%

Sources & evidence

ORD record
ord-c91a38b0cbcb4fae8de584f7e3c84455
Source dataset
uspto-grants-2001_03
Patent number
US06207830B1

Reaction notes

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