Piperidine → HCID 178426287, compound

HRID 1752777Notes

Reaction equation

HRID 1752777 reaction equation
[CH3:1][C:2](=O)[CH2:3][C:4](=O)[CH3:5].[NH2:8][C:9]1[N:13]=[C:12]([SH:14])[NH:11][N:10]=1.N1CCCCC1>C(O)(=O)C>[CH3:1][C:2]1[CH:3]=[C:4]([CH3:5])[N:10]2[N:11]=[C:12]([SH:14])[N:13]=[C:9]2[N:8]=1

Participants

5

Reactant 3

HCID 8082PiperidineHCID 31261AcetylacetoneHCID 1785092965-amino-1H-1,2,4-triazole-3-thiol2×

Product 1

HCID 178426287HCID 178426287, compoundYield 82%

Reagents, catalysts & solvents 1

HCID 176Acetic AcidSolvent

Conditions

Temperature
125 °C

Procedure

A mixture of 2,4-pentanedione (6.46 g, 64.6 mmol), 3-amino-5-mercapto-1,2,4-triazole (7.5 g, 64.6 mmol), glacial acetic acid (230 mL), and piperidine (0.58 mL, 5.9 mmol) was added to a 500 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 125° C. The mixture was heated for 45 hours, and solids remained visible in the flask throughout the heating period. Progress of the reaction was monitored by analytical HPLC with UV detection at 215 and 254 nm. The starting material 3-amino-5-mercapto-1,2,4-triazole elutes rapidly with retention time of 1.05 min, and the product elutes with retention time of 1.87 min. The mixture was cooled to room temperature. Solids were isolated by filtration, rinsed with 75 mL of acetic acid, and then dried under reduced pressure to afford the title compound as a pale yellow powder (9.5 g, 82% yield). A sample of 120 mg was recrystallized in warm acetic acid to afford 60 mg (50% recovery) of fine off-white needles, while the crude powder was used in the next step. 1H NMR (DMSO-d6+CDCl3, 400 MHz) δ ppm: 14.05 (br s, 1H), 7.25 (s, 1H), 2.67 (s, 3H), 2.56 (s, 3H). (NMR from crystalline material.)

Workup

  1. additionwas added to a 500 mL RBF with a magnetic stirring bar
  2. customThe flask was fitted with a condenser
  3. temperaturewarmed in an oil bath to
  4. temperatureThe mixture was heated for 45 hours
  5. temperatureThe mixture was cooled to room temperature
  6. customSolids were isolated by filtration
  7. washrinsed with 75 mL of acetic acid
  8. customdried under reduced pressure

Sources & evidence

ORD record
ord-7bbe990f2d27475795225df6856c1adf
Source dataset
uspto-grants-2015_10
Patent number
US09163027B2

Reaction notes

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