Water → 1,4-Bis(2,2-dimethyl-3-aminopropyl)benzene

HRID 66175Notes

Reaction equation

HRID 66175 reaction equation
[CH3:1][C:2]([C:17]#[N:18])([CH3:16])[CH2:3][C:4]1[CH:9]=[CH:8][C:7]([CH2:10][C:11]([C:14]#[N:15])([CH3:13])[CH3:12])=[CH:6][CH:5]=1.[H-].C([Al+]CC(C)C)C(C)C.O>C1(C)C=CC=CC=1.CO>[CH3:12][C:11]([CH3:13])([CH2:14][NH2:15])[CH2:10][C:7]1[CH:8]=[CH:9][C:4]([CH2:3][C:2]([CH3:1])([CH3:16])[CH2:17][NH2:18])=[CH:5][CH:6]=1

Participants

6

Reactant 3

HCID 962Water2×HCID 104443251,4-Bis(2-methyl-2-cyanopropyl)benzeneHCID 21225700Diisobutylaluminumhydride

Product 1

HCID 135875561,4-Bis(2,2-dimethyl-3-aminopropyl)benzeneYield 68.1%

Reagents, catalysts & solvents 2

HCID 887MethanolSolvent2×HCID 1140TolueneSolvent2×

Procedure

In a 2-liter flask, equipped with a magnetic stirrer, a reflux condenser capped with a nigrogen bubbler, and an additional funnel, was placed 7.50 g (0.0312 M) of 1,4-bis(2-methyl-2-cyanopropyl)benzene and 300 ml of reagent grade toluene which had been passed through acid alumina under nitrogen directly into the reaction vessel. With stirring at room temperature, 107 ml of a 24.1% solution (0.150 M) of diisobutylaluminum hydride in toluene was added from the addition funnel in 28 min. The mixture was then refluxed for 16 hrs. After the mixture had been cooled in an ice-water bath, a solution of 6 ml of water in 30 ml of methanol was added dropwise with stirring. This was followed by the dropwise addition of a solution of 30 ml of water in 60 ml of methanol. The mixture was stirred vigorously for 1 hr while being cooled in the ice-water bath, and then for an additional hour at room temperature. The mixture was filtered under nitrogen, the solid was washed thoroughly on the filter with toluene, and the combined filtrate and rinsings were distilled on the water pump. The resulting residue crystallized on cooling to room temperature. Further drying on the oil pump gave 5.28 g (68%) of crude 1,4-bis(2,2-dimethyl-3-aminopropyl)benzene melting at 53°-56° to a cloudy melt. Distillation of this material through a small Vigreux still gave the product as a colorless liquid boiling at 131°-132°/0.60 mm. The solidified material melted to a clear melt at 53.5-54.75°.

Workup

  1. customIn a 2-liter flask, equipped with a magnetic stirrer, a reflux condenser
  2. customcapped with a nigrogen bubbler, and an additional funnel
  3. temperatureThe mixture was then refluxed for 16 hrs
  4. temperatureAfter the mixture had been cooled in an ice-water bath
  5. stirringwith stirring
  6. stirringThe mixture was stirred vigorously for 1 hr
  7. waitfor an additional hour at room temperature
  8. filtrationThe mixture was filtered under nitrogen
  9. washthe solid was washed thoroughly on the
  10. filtrationfilter with toluene
  11. distillationthe combined filtrate and rinsings were distilled on the water pump
  12. customThe resulting residue crystallized
  13. temperatureon cooling to room temperature
  14. customFurther drying on the oil pump

Sources & evidence

ORD record
ord-5daf64d16db045db97eb076660f9c16d
Source dataset
uspto-grants-1978_12
Patent number
US04130579

Reaction notes

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