Dimethylformamide → 3-(2,5-Dimethyl-5-hexene-3-oxy)phthalonitrile

HRID 264710

Reaction equation

HRID 264710 reaction equation
[H-].[Na+].CN(C)C=O.[CH3:8][CH:9]([CH:11]([OH:16])[CH2:12][C:13]([CH3:15])=[CH2:14])[CH3:10].[N+]([C:20]1[CH:27]=[CH:26][CH:25]=[C:22]([C:23]#[N:24])[C:21]=1[C:28]#[N:29])([O-])=O>C1(C)C=CC=CC=1.O>[CH3:8][CH:9]([CH:11]([O:16][C:20]1[CH:27]=[CH:26][CH:25]=[C:22]([C:23]#[N:24])[C:21]=1[C:28]#[N:29])[CH2:12][C:13]([CH3:15])=[CH2:14])[CH3:10]

Participants

7

Reactant 4

HCID 6228Dimethylformamide2×HCID 24758Sodium hydrideHCID 1442642,5-Dimethyl-5-hexen-3-olHCID 1626521,2-Benzenedicarbonitrile, 3-nitro-

Product 1

HCID 189210253-(2,5-Dimethyl-5-hexene-3-oxy)phthalonitrileYield 86%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 1140TolueneSolvent

Procedure

9.6 g (0.24 mol) of 60% sodium hydride and 150 ml of N,N-dimethylformamide were placed in a container equipped with a stirrer, a reflux condenser and a nitrogen-introducing tube, and the solution was then stirred under the feed of nitrogen. Afterward, 32 g (0.25 mol) of 2,5-dimethyl-5-hexene-3-ol was added dropwise thereto at 20°-30° C. over 1 hour, and the solution was then stirred at the same temperature for 3 hours to prepare a sodium alcoholate solution. Next, 34.6 g (0.2 mol) of 3-nitrophthalonitrile and 150 ml of N,N-dimethylformamide were placed in a container equipped with a stirrer, and the above-mentioned sodium alcoholate solution was then added dropwise at 0° C. or less over 5 hours. After completion of the addition, the temperature of the solution was raised up to a level of 20°-30° C., and the solution was then stirred for 2 hours to bring reaction to an end. The thus obtained reaction solution was poured into 3 l of water and then stirred for 30 minutes, and 500 ml of toluene were added. After stirring for 30 minutes, the solution was allowed to stand to separate a toluene layer. After toluene was distilled off under reduced pressure, recrystallization was carried out from 500 ml of n-hexane to obtain 43.7 g of 3-(2,5-dimethyl-5-hexene-3-oxy)phthalonitrile (yield=86.0%).

Workup

  1. customequipped with a stirrer, a reflux condenser
  2. additiona nitrogen-introducing tube
  3. stirringthe solution was then stirred at the same temperature for 3 hours
  4. customequipped with a stirrer
  5. additionAfter completion of the addition
  6. temperaturethe temperature of the solution was raised up to a level of 20°-30° C.
  7. stirringthe solution was then stirred for 2 hours
  8. customreaction to an end
  9. customThe thus obtained reaction solution
  10. stirringstirred for 30 minutes
  11. stirringAfter stirring for 30 minutes
  12. customto separate a toluene layer
  13. distillationAfter toluene was distilled off under reduced pressure, recrystallization

Sources & evidence

ORD record
ord-7ccf62e69dda49949bbb4cfd36fb977d
Source dataset
uspto-grants-1997_07
Patent number
US05646273

Linked notes

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