Ethyl 2-methylacetoacetate → HCID 178422301, compound

HRID 1361457Notes

Reaction equation

HRID 1361457 reaction equation
FC(F)(F)OC1C=CC(OC2C=CC(N)=CC=2C)=CC=1.CC(C(C)=O)C(OCC)=O.C1(C)C=CC(S(O)(=O)=O)=CC=1.[F:42][C:43]([F:67])([F:66])[O:44][C:45]1[CH:65]=[CH:64][C:48]([O:49][C:50]2[C:51]([CH3:63])=[C:52]3[C:57](=[CH:58][CH:59]=2)[N:56]=[C:55]([CH3:60])[C:54]([CH3:61])=[C:53]3[OH:62])=[CH:47][CH:46]=1>C1(C)C(C)=CC=CC=1>[F:66][C:43]([F:42])([F:67])[O:44][C:45]1[CH:65]=[CH:64][C:48]([O:49][C:50]2[CH:59]=[C:58]3[C:57](=[CH:52][C:51]=2[CH3:63])[N:56]=[C:55]([CH3:60])[C:54]([CH3:61])=[C:53]3[OH:62])=[CH:47][CH:46]=1

Participants

6

Reactant 4

HCID 701Ethyl 2-methylacetoacetateHCID 6101p-Toluenesulfonic acidHCID 66921898HCID 66921898, compoundHCID 178432213HCID 178432213, compound

Product 1

HCID 178422301HCID 178422301, compoundYield 100%

Reagents, catalysts & solvents 1

HCID 7237O-XyleneSolvent

Procedure

A solution of 2.2 g of 4-(4-trifluoromethoxyphenoxy)-3-methyl-aniline, 2.6 g of ethyl 2-methylacetoacetate, and 1.52 g of p-toluenesulfonic acid dissolved in 81 mL of xylene was heated under reflux for 12 hr. This reaction solution was cooled, and the precipitated crystals were then collected by filtration and were washed with distilled water and n-hexane to give 3.88 g of a mixture of 6-(4-trifluoromethoxyphenoxy)-4-hydroxy-2,3,5-trimethyl-quinoline with 6-(4-trifluoromethoxyphenoxy)-4-hydroxy-2,3,7-trimethyl-quinoline (yield 100%). The crystals of the mixture (2.9 g) thus obtained were stirred in 30 mL of acetic anhydride with heating at 120 to 125° C. for 2 hr. The reaction solution was concentrated, ethyl acetate was then added to the concentrate, and the mixture was washed with saturated brine. The solvent was then removed under the reduced pressure, and the crude product was purified by column chromatography on silica gel (BW300, manufactured by Fuji Sylysia Chemical Ltd., solvent: n-hexane/ethyl acetate) to give 0.4 g of 4-acetoxy-6-(4-trifluoromethoxyphenoxy)-2,3,5-trimethyl-quinoline (yield 12.4%) and 0.19 g of 4-acetoxy-6-(4-trifluoromethoxyphenoxy)-2,3,7-trimethyl-quinoline (yield 6%).

Workup

  1. temperaturewas heated
  2. temperatureunder reflux for 12 hr
  3. temperatureThis reaction solution was cooled
  4. filtrationthe precipitated crystals were then collected by filtration
  5. washwere washed with distilled water and n-hexane

Sources & evidence

ORD record
ord-17a9e24ddc854140a7eba705667421e0
Source dataset
uspto-grants-2011_02
Patent number
US07880006B2

Reaction notes

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