1,1,1-Trifluoro-2,4-pentanedione → HCID 86719326, compound

HRID 1752813Notes

Reaction equation

HRID 1752813 reaction equation
[F:1][C:2]([F:10])([F:9])[C:3](=O)[CH2:4][C:5](=O)[CH3:6].[Cl:11][C:12]1[CH:27]=[CH:26][C:15]([O:16][CH2:17][CH2:18][S:19][C:20]2[N:24]=[C:23]([NH2:25])[NH:22][N:21]=2)=[CH:14][CH:13]=1>C(O)(=O)C>[Cl:11][C:12]1[CH:13]=[CH:14][C:15]([O:16][CH2:17][CH2:18][S:19][C:20]2[N:24]=[C:23]3[N:25]=[C:5]([CH3:6])[CH:4]=[C:3]([C:2]([F:10])([F:9])[F:1])[N:22]3[N:21]=2)=[CH:26][CH:27]=1

Participants

4

Reactant 2

HCID 739431,1,1-Trifluoro-2,4-pentanedioneHCID 1648919HCID 1648919, compound2×

Product 1

HCID 86719326HCID 86719326, compoundYield 65%

Reagents, catalysts & solvents 1

HCID 176Acetic AcidSolvent

Conditions

Temperature
135 °C

Procedure

A mixture of 1,1,1-trifluoro-2,4-pentanedione (114 mg, 0.739 mmol), 3-{[2-(4-chlorophenoxy)ethyl]sulfanyl}-1H-1,2,4-triazol-5-amine (200 mg, 0.739 mmol), and glacial acetic acid (1.5 mL) was added to a 50 mL RBF with a magnetic stirring bar. The flask was fitted with a condenser and warmed in an oil bath to a gentle reflux at 135° C. The solution was heated for 15 hours. Progress of the reaction was monitored by analytical HPLC with UV detection at 215 and 254 nm. The starting material 3-{[2-(4-chlorophenoxy)ethyl]sulfanyl}-1H-1,2,4-triazol-5-amine elutes with retention time of 6.04 min, and the product elutes with retention time of 7.98 min. The solution was allowed to cool to room temperature and added into stirring ice/water (15 mL) to precipitate the product. Solids were isolated by filtration, rinsed with 20 mL of water, and then dried under reduced pressure. The solid was dissolved in 5 mL of ethanol with gentle warming and allowed to cool. The fine white needles that formed were isolated by filtration, washed with 3 mL of cold ethanol, and dried to afford the title compound as off-white crystals (186 mg, 65% yield). EM (calc.): 388.0; MS (ESI) m/e: 389.0 (M+H)+. 1H NMR (DMSO-d6, 400 MHz) δ ppm: 7.85 (s, 1H), 7.31 (d, 2H), 7.00 (d, 2H), 4.33 (t, 2H), 3.62 (t, 2H), 2.69 (s, 3H). 19F NMR (DMSO-d6, 376 MHz) δ ppm: −67.56 (s).

Workup

  1. additionwas added to a 50 mL RBF with a magnetic stirring bar
  2. customThe flask was fitted with a condenser
  3. temperaturewarmed in an oil bath to
  4. temperatureThe solution was heated for 15 hours
  5. temperatureto cool to room temperature
  6. additionadded
  7. customto precipitate the product
  8. customSolids were isolated by filtration
  9. washrinsed with 20 mL of water
  10. customdried under reduced pressure
  11. dissolutionThe solid was dissolved in 5 mL of ethanol
  12. temperaturewith gentle warming
  13. temperatureto cool
  14. customThe fine white needles that formed
  15. customwere isolated by filtration
  16. washwashed with 3 mL of cold ethanol
  17. customdried

Sources & evidence

ORD record
ord-4971a512d25e4b649297cb3a2851f9eb
Source dataset
uspto-grants-2015_10
Patent number
US09163027B2

Reaction notes

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