Hydrazine hydrate (1:1) → HCID 18624977, compound

HRID 566835Notes

Reaction equation

HRID 566835 reaction equation
[CH3:1][O:2][CH2:3][CH2:4][O:5][CH2:6][CH2:7][O:8][CH2:9][CH2:10][O:11][C:12]1[CH:17]=[C:16]([N+]([O-])=O)[C:15]([N+:21]([O-])=O)=[CH:14][C:13]=1[O:24][CH2:25][CH2:26][O:27][CH2:28][CH2:29][O:30][CH2:31][CH2:32][O:33][CH3:34].O.[NH2:36]N.C(Cl)Cl.CO>C(O)C.[Pd]>[NH2:21][C:15]1[CH:16]=[CH:17][C:12]([O:11][CH2:10][CH2:9][O:8][CH2:7][CH2:6][O:5][CH2:4][CH2:3][O:2][CH3:1])=[C:13]([O:24][CH2:25][CH2:26][O:27][CH2:28][CH2:29][O:30][CH2:31][CH2:32][O:33][CH3:34])[C:14]=1[NH2:36]

Participants

6

Reactant 3

HCID 24654Hydrazine hydrate (1:1)HCID 154090031,2-Bis{2-[2-(2-methoxyethoxy)ethoxy]ethoxy}-4,5-dinitrobenzeneHCID 21226129Dichloromethane methanol

Product 1

HCID 18624977HCID 18624977, compoundYield 89%

Reagents, catalysts & solvents 2

HCID 23938PalladiumCatalystHCID 702EthanolSolvent2×

Procedure

In an oven dried 500 mL round bottom flask, equipped with a Claisen adapter, pressure equalizing dropping funnel, and reflux condenser, 1,2-bis[2-[2-(2-methoxyethoxy)ethoxy]ethoxy]-4,5-dinitrobenzene (Formula E) (20 g, 0.04 mol) is dissolved in absolute ethanol (200 mL). To this clear solution, 10% palladium on carbon (4 g) is added and the dark black suspension is heated to reflux under an argon atmosphere. Hydrazine hydrate (20 mL) in EtOH (20 mL) is added dropwise over 10 min to avoid bumping. The resulting brown suspension is heated at reflux for 1.5 h at which time the reaction mixture is colorless and TLC analysis (95/5; CH2Cl2/MeOH) displays a low R∫UV active spot corresponding to the diamine. Therefore, the mixture is hot filtered through Celite and the pad rinsed with absolute ethanol (50 mL). The solvent is removed under reduced pressure and the resulting light brown oil is dried in vacuo (in the dark) for 24 h to yield 15.55 g (89%) of 1,2-diamino-bis[2-[2-(2-methoxyethoxy)ethoxy]ethoxy]benzene (Formula F). For Formula F: FAB MS,M+: m/e 432; HRMS, M+: 432.2471 (calcd. for C20H36N2O8, 432.2482). This material is taken to the next step without further purification.

Workup

  1. customIn an oven dried 500 mL round bottom flask
  2. customequipped with a Claisen adapter, pressure
  3. temperaturereflux condenser
  4. temperaturethe dark black suspension is heated
  5. temperatureto reflux under an argon atmosphere
  6. temperatureThe resulting brown suspension is heated
  7. temperatureat reflux for 1.5 h at which time the reaction mixture
  8. filtrationTherefore, the mixture is hot filtered through Celite
  9. washthe pad rinsed with absolute ethanol (50 mL)
  10. customThe solvent is removed under reduced pressure
  11. customthe resulting light brown oil is dried in vacuo (in the dark) for 24 h

Sources & evidence

ORD record
ord-c814e8c172724057baa3c8c0e8133fac
Source dataset
uspto-grants-2001_01
Patent number
US06176842B1

Reaction notes

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