Hydrochloric Acid → 4-[4-[(E)-C-methyl-N-phenylmethoxycarbonimidoyl]phenyl]-1,2,4-triazolidine-3,5-dione

HRID 1746262Notes

Reaction equation

HRID 1746262 reaction equation
[C:1]([C:4]1[CH:9]=[CH:8][C:7]([N:10]2[C:14](=[O:15])[NH:13][NH:12][C:11]2=[O:16])=[CH:6][CH:5]=1)(=O)[CH3:2].Cl.[CH2:18]([O:25][NH2:26])[C:19]1[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1.Cl.O1CCOCC1>C(O)C>[CH2:18]([O:25]/[N:26]=[C:1](/[C:4]1[CH:9]=[CH:8][C:7]([N:10]2[C:14](=[O:15])[NH:13][NH:12][C:11]2=[O:16])=[CH:6][CH:5]=1)\[CH3:2])[C:19]1[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1

Participants

6

Reactant 4

HCID 313Hydrochloric AcidHCID 312751,4-DioxaneHCID 102312Benzyloxyamine hydrochlorideHCID 533076914-(4-Acetylphenyl)-1,2,4-triazolidine-3,5-dione

Product 1

HCID 893923334-[4-[(E)-C-methyl-N-phenylmethoxycarbonimidoyl]phenyl]-1,2,4-triazolidine-3,5-dioneYield 23%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Conditions

Temperature
65 °C

Procedure

To 4-(4-acetylphenyl)-1,2,4-triazolidine-3,5-dione (500 mg, 2.281 mmol) in ethanol (6.91 mL) was added O-benzylhydroxylamine hydrochloride (728 mg, 4.56 mmol) and HCl 4N in dioxane (0.277 mL, 9.12 mmol). The mixture was stirred at 65° C. for 1 hour, filtered, and then concentrated in vacuo. Saturated sodium bicarbonate added to the residue, extracted with ethyl acetate twice, dried over MgSO4, filtered, and concentrated in vacuo. Methanol/CH2Cl2 (50/50) was added, then the precipitate was filtered and dried, giving (E)-4-(4-(1-(benzyloxyimino)ethyl)-phenyl)-1,2,4-triazolidine-3,5-dione (I-5a: 167 mg, 23%) as a white solid. LC-MS (M+1) 325.1, t=1.77 minutes. 1 H NMR (400 MHz, DMSO-d6) δ ppm 2.60 (s, 3 H) 7.68 (d, J=8.84 Hz, 2 H) 8.05 (d, J=8.59 Hz, 2 H) 10.65 (s, 2 H). 1H NMR (400 MHz, CD3CN) δ ppm 2.29 (s, 3 H) 5.26 (s, 2 H) 7.37 (d, J=7.07 Hz, 1 H) 7.42 (t, J=7.33 Hz, 2 H) 7.45-7.50 (m, 2 H) 7.53 (d, J=8.59 Hz, 2 H) 7.75-7.93 (m, 4 H).

Workup

  1. filtrationfiltered
  2. concentrationconcentrated in vacuo
  3. additionSaturated sodium bicarbonate added to the residue
  4. extractionextracted with ethyl acetate twice
  5. dry with materialdried over MgSO4
  6. filtrationfiltered
  7. concentrationconcentrated in vacuo
  8. additionMethanol/CH2Cl2 (50/50) was added
  9. filtrationthe precipitate was filtered
  10. customdried

Sources & evidence

ORD record
ord-3b96ed0760b74782b5ec5886fb198e6e
Source dataset
uspto-grants-2015_10
Patent number
US09149541B2

Reaction notes

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