Methyl Acrylate → Methyl (2E)-3-(3-fluoro-2-((((2-methoxy-5-(trifluoromethyl)phenyl)amino)carbonyl)amino)phenyl)-2-propenoate

HRID 387193Notes

Reaction equation

HRID 387193 reaction equation
[F:1][C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1[NH:8][C:9]([NH:11][C:12]1[CH:17]=[C:16]([C:18]([F:21])([F:20])[F:19])[CH:15]=[CH:14][C:13]=1[O:22][CH3:23])=[O:10].OS(O)(=O)=O.O=S(=O)=O.[C:33]([O:37][CH3:38])(=[O:36])[CH:34]=[CH2:35]>C(O)(=O)C.C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[F:1][C:2]1[C:3]([NH:8][C:9]([NH:11][C:12]2[CH:17]=[C:16]([C:18]([F:21])([F:20])[F:19])[CH:15]=[CH:14][C:13]=2[O:22][CH3:23])=[O:10])=[C:4](/[CH:35]=[CH:34]/[C:33]([O:37][CH3:38])=[O:36])[CH:5]=[CH:6][CH:7]=1

Participants

6

Reactant 3

HCID 7294Methyl AcrylateHCID 24681Fuming sulfuric acidHCID 57857532N-(2-fluorophenyl)-N'-[2-methoxy-5-(trifluoromethyl)phenyl]urea

Product 1

HCID 57857531Methyl (2E)-3-(3-fluoro-2-((((2-methoxy-5-(trifluoromethyl)phenyl)amino)carbonyl)amino)phenyl)-2-propenoateYield 74.4%

Reagents, catalysts & solvents 2

HCID 167845palladium(II) acetateCatalystHCID 176Acetic AcidSolvent

Procedure

N-(2-Fluorophenyl)-N′-[2-methoxy-5-(trifluoromethyl)phenyl]urea (0.225 kg) is dissolved in acetic acid (6.75 l) and treated with palladium acetate (30.3 g). 65% strength oleum (247.5 g) is then metered in and methyl acrylate (90 g) is subsequently added. The solution is stirred at room temperature overnight. Subsequently, acetic acid (3740 g) is distilled off at 30° C. and ca. 30 mbar. The suspension is treated with water (2.25 l) and stirred for ca. 1 hour. The product is filtered off with suction, washed twice with water (0.5 l) and dried at 50° C. overnight in the vacuum drying oven using entraining nitrogen. A total of 210.3 g of methyl (2E)-3-{3-fluoro-2-[({[2-methoxy-5-(trifluoromethyl)phenyl]amino}carbonyl)amino]phenyl}acrylate are obtained as a solid, corresponding to 72.2% of theory.

Workup

  1. additionis subsequently added
  2. distillationSubsequently, acetic acid (3740 g) is distilled off at 30° C.
  3. additionThe suspension is treated with water (2.25 l)
  4. stirringstirred for ca. 1 hour
  5. filtrationThe product is filtered off with suction
  6. washwashed twice with water (0.5 l)
  7. customdried at 50° C. overnight in the vacuum
  8. customdrying oven

Sources & evidence

ORD record
ord-91f76e224aa14d338eb4d24bf8625b55
Source dataset
uspto-grants-2013_02
Patent number
US08372972B2

Reaction notes

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