Pyridine → HCID 86746003, compound

HRID 654601Notes

Reaction equation

HRID 654601 reaction equation
[C:1]([CH2:9][N:10]1[C:15]2[C:16](=[O:25])[N:17]([CH:19]3[CH2:24][CH2:23][CH2:22][CH2:21][CH2:20]3)[CH2:18][C:14]=2[C:13](=[O:26])[N:12]2[N:27]=[C:28]([C:30]3[CH:35]=[CH:34][CH:33]=[CH:32][CH:31]=3)[CH:29]=[C:11]12)(=O)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.Cl.[NH2:37][OH:38].N1C=CC=CC=1>C(O)C>[CH:19]1([N:17]2[CH2:18][C:14]3[C:13](=[O:26])[N:12]4[N:27]=[C:28]([C:30]5[CH:35]=[CH:34][CH:33]=[CH:32][CH:31]=5)[CH:29]=[C:11]4[N:10]([CH2:9][C:1](=[N:37][OH:38])[C:2]4[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=4)[C:15]=3[C:16]2=[O:25])[CH2:24][CH2:23][CH2:22][CH2:21][CH2:20]1

Participants

5

Reactant 3

HCID 1049PyridineHCID 443297Hydroxyamine hydrochlorideHCID 14867572HCID 14867572, compound

Product 1

HCID 86746003HCID 86746003, compoundYield 60%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent3×

Procedure

A mixture of 4-(benzoylmethyl)-6-cyclohexyl-6,7-dihydro-2-phenyl-4H-pyrazolo[1,5-a]pyrrolo[3,4-d]pyrimidine-5,8-dione (see Example 4), (1.00 g.; 2.15 mmoles) and hydroxylamine hydrochloride (225 mg.; 3.23 mmole), in 4.5 ml of absolute ethanol and 1.5 of pyridine was heated to reflux, becoming homogenous. The solution deposited a precipitate with time, so another 2 ml. of ethanol was added to aid stirring. After a total of eight hours at reflux, the mixture was cooled and diluted with 15 ml. of ethanol. The mixture was suction filtered through a medium glass frit and the collected solid was washed with ethanol and dried in vacuo. The crude solid was suspended in boiling 95% ethanol (400 ml.), and chloroform was added until dissolution was achieved (70 ml.). About 50 ml. of the resulting solvent mixture was then boiled off before cooling to room temperature. This procedure afforded 624 mg. (60% yield) of the titled compound, m.p. >280° C. The NMR spectral analysis of a sample of this material indicated that a 1:1 mixture of the titled oxime isomers had been obtained. 1H NMR (DMSO d6, δ) (mixture of oxime isomers) 12.14 (s, 1H, OH), 11.12 (s, 1H, OH), 8.01 [d, 2H, J=7 Hz, 2-phenyl-H (ortho)], 7.89 (d, 2H, J=7 Hz, oxime-phenyl-H (ortho)], 7.2-7.7 (m, 17H, phenyl-H and pyrazole-H of one isomer), 6.76 (s, 1H, pyrazole-H), 6.12 (bs, 2H, (C(NOH)CH2), 5.72 (bs, 2H, C(NOH)CH2), 4.41 (s, 2H, NCH2), 4.30 (s, 2H, NCH2), 4.0 (m, 2H, cyclohexyl CH of both isomers), 1.1-1.9 (m, 20H, cyclohexyl CH2 of both isomers).

Workup

  1. temperatureto reflux
  2. temperatureAfter a total of eight hours at reflux
  3. temperaturethe mixture was cooled
  4. additiondiluted with 15 ml
  5. filtrationfiltered through a medium glass frit
  6. washthe collected solid was washed with ethanol
  7. customdried in vacuo
  8. additionwas added until dissolution
  9. customThis procedure afforded 624 mg

Sources & evidence

ORD record
ord-a02442b47948423492d7e3bbcddd64a1
Source dataset
uspto-grants-1992_07
Patent number
US05132424

Reaction notes

Loading…