Malononitrile → HCID 15398672, compound

HRID 431436Notes

Reaction equation

HRID 431436 reaction equation
[C:1]([C:4]1[CH:5]=[C:6]2[C:11](=[CH:12][CH:13]=1)[CH:10]=[C:9]([N:14]1[CH2:19][CH2:18][N:17]([C:20]([O:22][C:23]([CH3:26])([CH3:25])[CH3:24])=[O:21])[CH2:16][CH2:15]1)[CH:8]=[CH:7]2)(=O)[CH3:2].[C:27](#[N:31])[CH2:28][C:29]#[N:30]>N1C=CC=CC=1>[C:23]([O:22][C:20]([N:17]1[CH2:16][CH2:15][N:14]([C:9]2[CH:8]=[CH:7][C:6]3[C:11](=[CH:12][CH:13]=[C:4]([C:1]([CH3:2])=[C:28]([C:27]#[N:31])[C:29]#[N:30])[CH:5]=3)[CH:10]=2)[CH2:19][CH2:18]1)=[O:21])([CH3:24])([CH3:25])[CH3:26]

Participants

4

Reactant 2

HCID 8010Malononitrile2×HCID 9928533HCID 9928533, compound

Product 1

HCID 15398672HCID 15398672, compoundYield 77%

Reagents, catalysts & solvents 1

HCID 1049PyridineSolvent

Procedure

tert-Butyl 4-(6-acetyl-2-naphthyl)-1-piperazinecarboxylate (177 mg, 0.5 mmol), prepared as described in Example 1(d), was heated with 40 mg (0.6 mmol) of malononitrile in 4 mL pyridine at 105-110° C. After 5.5 hours, an additional 24 mg of malononitrile was added, and heating was continued for a total of 12 hours and 40 minutes. The mixture was cooled and evaporated in vacuo. Polar components of the mixture were removed by column chromatography (70-230 mesh silica, φ20×120 mm, chloroform), and the product, tert-butyl-4-[6-(2,2-dicyano-1-methylvinyl)-2-naphthy]-1-piperazinecarboxylate, was finally purified by radial chromatography (silica, 2 mm, chloroform). 155 mg (77%) of tert-butyl-4-[6-(2,2-dicyano-1-methylvinyl)-2-naphthyl]-1-piperazinecarboxylate were obtained, which, after recrystallization from dichloromethane-petroleum ether mixture, melted at 169-171° C. Anal. Calculated for C24H26N4O2: C, 71.62; H, 6.51; N, 13.92. Found: C, 71.62; H, 6.66; N, 13.87. 1H NMR: δ1.50 (s, 9H, —C(CH3)3), 2.72 (s, 3H, CH3), 3.34 and 3.64 (t, J=5.1 Hz, 8H, piperazine), 7.09 (d, 1H, 5-H), 7.33 (dd, 1H 7-H), 7.58 (dd, 1H, 3-H), 7.74(d, 1H, 4-H), 7.81 (d, 1H, 8-H), 8.02 (d, 1H, 1-H); J5,7=2 Hz, J7,8=9.1 Hz, J1,3=2 Hz, J3,4=9.1 Hz.

Workup

  1. temperatureheating
  2. customwas continued for a total of 12 hours and 40 minutes
  3. temperatureThe mixture was cooled
  4. customevaporated in vacuo
  5. customPolar components of the mixture were removed by column chromatography (70-230 mesh silica
  6. customφ20×120 mm, chloroform), and the product, tert-butyl-4-[6-(2,2-dicyano-1-methylvinyl)-2-naphthy]-1-piperazinecarboxylate, was finally purified by radial chromatography (silica, 2 mm, chloroform)

Sources & evidence

ORD record
ord-72cc755c92b546aea3e87378ba006a07
Source dataset
uspto-grants-2003_12
Patent number
US06660530B2

Reaction notes

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