Hydrazine hydrate (1:1) → N~2~,N~2~,N~7~,N~7~-Tetraethyl-9-hydrazinylidene-9H-fluorene-2,7-diamine

HRID 1241224Notes

Reaction equation

HRID 1241224 reaction equation
[CH2:1]([N:3]([CH2:23][CH3:24])[C:4]1[CH:16]=[CH:15][C:14]2[C:13]3[C:8](=[CH:9][C:10]([N:17]([CH2:20][CH3:21])[CH2:18][CH3:19])=[CH:11][CH:12]=3)[C:7](=O)[C:6]=2[CH:5]=1)[CH3:2].O.[NH2:26][NH2:27]>Cl.CC(O)C>[CH2:1]([N:3]([CH2:23][CH3:24])[C:4]1[CH:16]=[CH:15][C:14]2[C:13]3[C:8](=[CH:9][C:10]([N:17]([CH2:20][CH3:21])[CH2:18][CH3:19])=[CH:11][CH:12]=3)[C:7](=[N:26][NH2:27])[C:6]=2[CH:5]=1)[CH3:2]

Participants

5

Reactant 2

HCID 24654Hydrazine hydrate (1:1)HCID 21932775HCID 21932775, compound2×

Product 1

HCID 71420888N~2~,N~2~,N~7~,N~7~-Tetraethyl-9-hydrazinylidene-9H-fluorene-2,7-diamineYield 79.2%

Reagents, catalysts & solvents 2

HCID 313Hydrochloric AcidCatalystHCID 3776IsopropanolSolvent

Procedure

2,7-Bis(diethylamino)-9-fluorenone (11.5 g, 35.66 mmol), 50 ml of 2-propanol, 98% hydrazine monohydrate (5.2 ml, 0.11 mol, from Aldrich), and 8 drops of concentrated hydrochloric acid (obtained from Aldrich) were added to a 100 ml 3-neck round bottom flask equipped with a reflux condenser and a mechanical stirrer. The mixture was refluxed with an intensive stirring until 2,7-bis(diethylamino)-9-fluorenone disappeared (1.5 hours). The reaction mixture was cooled to room temperature to form crystals. The crystals were filtered off, washed first with water, and then with a mixture of 2-propanol and n-hexane to yield 9.5 g (79%) of the hydrazone. The melting point was found to be 150–151° C. (recrystallized from 2-propanol). The 1H NMR spectrum (100 MHz) of the product in CDCl3 was characterized by the following chemical shifts (δ, ppm): 7.50–7.20 (m, 4H, Ar); 6.82–6.50 (m, 2H, Ar); 7.10 (s, br, 2H, NH2); 7.00 (q, 8H, N(CH2CH3)2); and 3.75 (t, J=7.1 Hz, 12H, N(CH2CH3)2). An elemental analysis yielded the following results in weight percent: C, 74.69; H, 8.28; N, 16.52, which compared with the following calculated values for C21H28N4 in weight percent: C, 74.96; H, 8.39; N, 16.65.

Workup

  1. customequipped with a reflux condenser and a mechanical stirrer
  2. temperatureThe mixture was refluxed with
  3. custom(1.5 hours)
  4. customto form crystals
  5. filtrationThe crystals were filtered off
  6. washwashed first with water
  7. additionwith a mixture of 2-propanol and n-hexane

Sources & evidence

ORD record
ord-776f5dfd30674bd1b04f6cbfa9ab0746
Source dataset
uspto-grants-2006_10
Patent number
US07115347B2

Reaction notes

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