Ethyl Acetate → HCID 57513837, compound

HRID 2368425Notes

Reaction equation

HRID 2368425 reaction equation
[F:1][C:2]([F:16])([F:15])[C:3](=O)[CH2:4][C:5]([C:7]1[CH:12]=[CH:11][C:10]([CH3:13])=[CH:9][CH:8]=1)=[O:6].BrN1C(=O)CCC1=O.[NH2:25][C:26]([NH2:28])=[S:27].CCOC(C)=O>ClCCl>[NH2:28][C:26]1[S:27][C:4]([C:5]([C:7]2[CH:12]=[CH:11][C:10]([CH3:13])=[CH:9][CH:8]=2)=[O:6])=[C:3]([C:2]([F:16])([F:15])[F:1])[N:25]=1

Participants

6

Reactant 4

HCID 8857Ethyl AcetateHCID 67184N-bromobutanimideHCID 5501934,4,4-Trifluoro-1-(4-methylphenyl)butane-1,3-dioneHCID 2723790Thiourea

Product 1

HCID 57513837HCID 57513837, compound

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Conditions

Temperature
70 °C

Procedure

4,4,4-trifluoro-1-p-tolylbutane-1,3-dione (4 g, 17.4 mmol) in 100 mL dichloromethane at 0° C. under N2 was treated in portions with 3.09 g (17.4 mmol) N-bromosuccinimide. A white precipitate gradually formed. After 4.5 h solids were filtered off, the filtrate was washed with water and brine and dried over Na2SO4, then evaporated. The residue was taken up in 100 mL EtOH, treated with 1.32 g (17.4 mmol)thiourea and 1.04 g (17.4 mmol) silica and heated at 70° C. overnight. The reaction was cooled, filtered and evaporated. The crude was taken up in EtOAc, washed with NaHCO3 and brine, dried over Na2SO4 and evaporated. Trituration with Et2O: heptane provided 1.31 g desired as a yellow solid, still containing impurities. Chromatography (SiO2, EtOAc: dichloromethane) provided the title compound. The filtrate from the trituration also contained desired material and was similarly purified to provide the title compound. LCMS (method A) 287.1 (M+H), 285.2 (M−H). 1H-NMR (400 MHz, Chloroform-d) ppm 2.45 (s, 3H), 5.68 (br s, 2H), 7.29 (d, J=7.96 Hz, 2H), 7.77 (d, J−8.21 Hz, 2H).

Workup

  1. customA white precipitate gradually formed
  2. filtrationAfter 4.5 h solids were filtered off
  3. washthe filtrate was washed with water and brine
  4. dry with materialdried over Na2SO4
  5. customevaporated
  6. temperatureThe reaction was cooled
  7. filtrationfiltered
  8. customevaporated
  9. washwashed with NaHCO3 and brine
  10. dry with materialdried over Na2SO4
  11. customevaporated
  12. customTrituration with Et2O: heptane provided 1.31 g

Sources & evidence

ORD record
ord-2496bee709334438bcd3ad5f971d40de
Source dataset
uspto-grants-2014_04
Patent number
US08703761B2

Reaction notes

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