Ethyl Acetate → HCID 14625409, compound

HRID 2107817Notes

Reaction equation

HRID 2107817 reaction equation
[N+:1]([C:4]1[CH:9]=[CH:8][CH:7]=[CH:6][C:5]=1[N:10]1[CH2:16][CH2:15][N:14]([CH2:17][C:18]2[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=2)[CH2:13][CH2:12][NH:11]1)([O-])=O.[C:24](OCC)(=[O:26])C>COCCOC.[Pd]>[C:18]1([CH2:17][N:14]2[CH2:15][CH2:16][N:10]3[C:5]4[CH:6]=[CH:7][CH:8]=[CH:9][C:4]=4[NH:1][C:24](=[O:26])[N:11]3[CH2:12][CH2:13]2)[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=1

Participants

5

Reactant 2

HCID 8857Ethyl AcetateHCID 14625404HCID 14625404, compound

Product 1

HCID 14625409HCID 14625409, compound

Reagents, catalysts & solvents 2

HCID 23938PalladiumCatalystHCID 80711,2-DimethoxyethaneSolvent

Procedure

Hexahydro-1-(2-nitrophenyl)-5-(phenylmethyl)-1H-1,2,5-triazepine (10.0 g) in 1,2-dimethoxyethane (250 ml) was hydrogenated at over 10% palladium on carbon (2.5 g) at room temperature and atmospheric pressure until theoretical uptake had been achieved. At this stage the reaction solution was colorless and t.l.c. on Alox-25 uv254 plates (Brinkmann) with ethyl acetate as developer showed a single component. The mixture was filtered through Celite and the filter pad washed with 1,2-dimethyloxyethane. The filtrate was evaporated to approximately 150 ml and 1,1-carbonyldiimidazole (20 g) was added. The solution was evaporated to dryness and the residue was dissolved in chloroform and applied to a column (75×6.4 cm) of dry column grade neutral alumina prepacked in chloroform. Elution with chloroform removed a major component from the column. Fractions were monitored by t.l.c. on Alox-25 un254 plates with ethyl acetate as developer. Appropriate fractions were evaporated and the crude titled product was crystallized from chloroform-heptane (seeding); wt. 7.56 g (77%), mp=129°-131°. Two crystallizations from the same solvent gave pure product, mp=127°-128°.

Workup

  1. filtrationThe mixture was filtered through Celite
  2. washthe filter pad washed with 1,2-dimethyloxyethane
  3. customThe filtrate was evaporated to approximately 150 ml and 1,1-carbonyldiimidazole (20 g)
  4. additionwas added
  5. customThe solution was evaporated to dryness
  6. dissolutionthe residue was dissolved in chloroform
  7. washElution with chloroform
  8. customremoved a major component from the column
  9. customAppropriate fractions were evaporated
  10. customthe crude titled product was crystallized from chloroform-heptane (seeding)
  11. customTwo crystallizations from the same solvent
  12. customgave pure product, mp=127°-128°

Sources & evidence

ORD record
ord-935b5e5142c944b0a1473e58fb4353db
Source dataset
uspto-grants-1990_06
Patent number
US04935515

Reaction notes

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