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

HRID 865639Notes

Reaction equation

HRID 865639 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 6E (20 g, 0.04 mol) was dissolved in absolute ethanol (200 mL). To this clear solution, 10% palladium on carbon (4 g) was added and the dark black suspension was heated to reflux under an argon atmosphere. Hydrazine hydrate (20 mL) in EtOH (20 mL) was added dropwise over 10 min to avoid bumping. The resulting brown suspension was heated at reflux for 1.5 h at which time the reaction mixture was colorless and TLC analysis (95/5; CH2Cl2 /MeOH) displayed a low RfUV active spot corresponding to the diamine. Therefore, the mixture was hot filtered through Celite and the pad rinsed with absolute ethanol (50 mL). The solvent was removed under reduced pressure and the resulting light brown oil was 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 6F. For 6F : FAB MS, M+ : m/e 432; HRMS, M+ : 432.2471 (calcd. for C20H36N2O8, 432.2482). This material was 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 was heated
  5. temperatureto reflux under an argon atmosphere
  6. temperatureThe resulting brown suspension was heated
  7. temperatureat reflux for 1.5 h at which time the reaction mixture
  8. filtrationTherefore, the mixture was hot filtered through Celite
  9. washthe pad rinsed with absolute ethanol (50 mL)
  10. customThe solvent was removed under reduced pressure
  11. customthe resulting light brown oil was dried in vacuo (in the dark) for 24 h

Sources & evidence

ORD record
ord-8469c3a7419942fea5a6b3fa0d06485d
Source dataset
uspto-grants-1996_10
Patent number
US05567687

Reaction notes

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