Ethanol → HCID 54298288, compound

HRID 1377938Notes

Reaction equation

HRID 1377938 reaction equation
[CH3:1][C@H:2]1[CH2:7][C:6]2[CH:8]=[C:9]3[O:14][CH2:13][O:12][C:10]3=[CH:11][C:5]=2[C:4]([C:16]2[CH:21]=[CH:20][C:19]([N+:22]([O-:24])=[O:23])=[CH:18][CH:17]=2)(O)[O:3]1.C[NH:26][NH:27][C:28]([NH2:30])=[O:29].[CH2:31](O)C>Cl>[OH:3][C@@H:2]([CH3:1])[CH2:7][C:6]1[C:5]([C:4]([C:16]2[CH:21]=[CH:20][C:19]([N+:22]([O-:24])=[O:23])=[CH:18][CH:17]=2)=[N:26][NH:27][C:28]([NH:30][CH3:31])=[O:29])=[CH:11][C:10]2[O:12][CH2:13][O:14][C:9]=2[CH:8]=1

Participants

5

Reactant 3

HCID 702EthanolHCID 3330102Hydrazinecarboxamide, 2-methyl-HCID 9883927HCID 9883927, compound

Product 1

HCID 54298288HCID 54298288, compoundYield 81.2%

Reagents, catalysts & solvents 1

HCID 313Hydrochloric AcidCatalyst

Procedure

In a nitrogen blanketed flask was dissolved 5.17 g (15.70 mmol) of the intermediate of Example 5 in 30 mL of ethanol. To this stirring solution was added 1.75 g (19.7 mmol) of methyl semicarbazide. The mixture was heated to reflux to dissolve the solids and then 5 drops of conc. HCl was added. Over 1 h at reflux, yellow solids precipitated out of solution. After 1 h, HPLC analysis indicated complete reaction, 38.2% and 55.4% of 2 product isomers and no remaining starting material. The yellow slurry was slowly cooled to ambient temperature to stir for 1 h and then stirred for 30 min. in an ice water bath. The mixture was filtered through coarse glass. The solids were washed with ethanol and dried under vacuum at 50° C. to afford 5.08 g (81.2%) of the title compound as a yellow solid, mp=238° C. HPLC assay indicated two isomers, 46.2%+53.1%. MS (FD+)=400. IR: 1692, 1345 cm-1. 1H NMR (DMSO): δ0.90 (t, 3, J=6); 2.22 (m, 2); 2.72 (d, 3, J=5); 3.63 (m, 1); 4.42 (d, 1/2, J=6); 4.58 (d, 1/2, J=6); 6.10 (s,2); 6.69 (d, 1, J=8); 7.05 (d, 1, J=10); 7.32 (br. t, 1, J=4); 7.85 (d, 2, J=9); 8.18 (d, 2, J=9); 8.62 (d, 1, J=8). 13C NMR (DMSO): δ24.27, 24.51, 27.18, 43.30, 43.73, 67.09, 67.47, 102.45, 108.95, 109.19, 111.50, 111.54, 112.41, 112.45, 124.40, 124.48, 124.69, 128.35, 133.47, 133.69, 144.55, 144.61, 144.68, 144.79, 147.71, 147.76, 148.06, 149.39, 149.54, 156.11, 156.23. Anal. Calcd for: C19H20N4O6 : C, 57.00; H, 5.03; N, 13.99; Found: C, 57.72; H, 5.01; N, 13.99.

Workup

  1. temperatureThe mixture was heated
  2. temperatureto reflux
  3. dissolutionto dissolve the solids
  4. temperatureOver 1 h at reflux
  5. customyellow solids precipitated out of solution
  6. customreaction, 38.2% and 55.4% of 2 product isomers
  7. stirringstirred for 30 min. in an ice water bath
  8. filtrationThe mixture was filtered through coarse glass
  9. washThe solids were washed with ethanol
  10. customdried under vacuum at 50° C.

Sources & evidence

ORD record
ord-ebca2a8280414ad2a53998f1057d0805
Source dataset
uspto-grants-1997_09
Patent number
US05665878

Reaction notes

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