Propiolic Acid → 2-chloro-5-[3,6-dihydro-2,6-dioxo-3-methyl-4-trifluoromethyl-1(2H)-pyrimidinyl]-4-fluorophenyl propiolate

HRID 1722966Notes

Reaction equation

HRID 1722966 reaction equation
[C:1]([OH:5])(=[O:4])[C:2]#[CH:3].C1(N=C=NC2CCCCC2)CCCCC1.[Cl:21][C:22]1[C:27](O)=[CH:26][C:25]([N:29]2[C:34](=[O:35])[CH:33]=[C:32]([C:36]([F:39])([F:38])[F:37])[N:31]([CH3:40])[C:30]2=[O:41])=[C:24]([F:42])[CH:23]=1>C(Cl)Cl>[C:1]([O:5][C:27]1[CH:26]=[C:25]([N:29]2[C:34](=[O:35])[CH:33]=[C:32]([C:36]([F:38])([F:39])[F:37])[N:31]([CH3:40])[C:30]2=[O:41])[C:24]([F:42])=[CH:23][C:22]=1[Cl:21])(=[O:4])[C:2]#[CH:3]

Participants

5

Reactant 3

HCID 10110Propiolic AcidHCID 10868DicyclohexylcarbodiimideHCID 112677571-methyl-6-trifluoromethyl-3-(4-chloro-2-fluoro-5-hydroxyphenyl)-2,4(1H,3H)-pyrimidinedione

Product 1

HCID 200261282-chloro-5-[3,6-dihydro-2,6-dioxo-3-methyl-4-trifluoromethyl-1(2H)-pyrimidinyl]-4-fluorophenyl propiolate

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent3×

Conditions

Temperature
0 °C

Procedure

A solution of 0.68 g of propiolic acid in 5 ml of methylene chloride is added dropwise at 0° C. while stirring during 5 minutes to a solution of 2.18 g of N,N'-dicyclohexylcarbodiimide in 10 ml of methylene chloride and the mixture is stirred at 0° C. for 15 minutes. solution of 1.5 g of 3-(4-chloro-2-fluoro-5-hydroxyphenyl)-1-methyl-6 -trifluoromethyl-2,4(1H,3H)-pyrimidinedione in 10 ml of methylene chloride is added dropwise while stirring during 20 minutes and the mixture is stirred at 0° C. for 2 hours. Insoluble constituents are filtered off under suction and the filtrate is evaporated to dryness under reduced pressure. The residue is purified by chromatography on a silica gel column using ethyl acetate/n-hexane (1:7) as the eluent. There is obtained 2-chloro-5-[3,6-dihydro-2,6-dioxo-3-methyl -4-trifluoromethyl-1(2H)-pyrimidinyl]-4-fluorophenyl propiolate. 1H-NMR (CDCl3. 400 MHz: 7.40 ppm (d,1H), 7.21 ppm 1(d,1H), 6.36 ppm (s,1H), 3.56 ppm (d,3H). 3.15 ppm (s,1H),

Workup

  1. stirringwhile stirring during 20 minutes
  2. stirringthe mixture is stirred at 0° C. for 2 hours
  3. filtrationInsoluble constituents are filtered off under suction
  4. customthe filtrate is evaporated to dryness under reduced pressure
  5. customThe residue is purified by chromatography on a silica gel column

Sources & evidence

ORD record
ord-9ef441dfe87b4a6c8687f2ef6578e345
Source dataset
uspto-grants-1989_08
Patent number
US04859229

Reaction notes

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