Nitrogen → HCID 131724267, compound

HRID 1295786Notes

Reaction equation

HRID 1295786 reaction equation
[CH2:1]([CH:9]([CH2:56][CH2:57][CH2:58][CH2:59][CH2:60][CH2:61][CH2:62][CH2:63][CH2:64][CH3:65])[CH2:10][C:11]1[C:12]([CH2:36][CH:37]([CH2:48][CH2:49][CH2:50][CH2:51][CH2:52][CH2:53][CH2:54][CH3:55])[CH2:38][CH2:39][CH2:40][CH2:41][CH2:42][CH2:43][CH2:44][CH2:45][CH2:46][CH3:47])=[C:13]([CH2:16][CH:17]([CH2:28][CH2:29][CH2:30][CH2:31][CH2:32][CH2:33][CH2:34][CH3:35])[CH2:18][CH2:19][CH2:20][CH2:21][CH2:22][CH2:23][CH2:24][CH2:25][CH2:26][CH3:27])[CH2:14][CH:15]=1)[CH2:2][CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH3:8].[N:66]#N.[CH2:68]1[CH2:72]OC[CH2:69]1.C([Li])CCC>C(=O)=O.CC(C)=O.CCCCCC>[CH2:1]([CH:9]([CH2:56][CH2:57][CH2:58][CH2:59][CH2:60][CH2:61][CH2:62][CH2:63][CH2:64][CH3:65])[CH2:10][C:11]1[CH:15]=[CH:14][C:13]([CH2:16][CH:17]([CH2:28][CH2:29][CH2:30][CH2:31][CH2:32][CH2:33][CH2:34][CH3:35])[CH2:18][CH2:19][CH2:20][CH2:21][CH2:22][CH2:23][CH2:24][CH2:25][CH2:26][CH3:27])([CH2:69][CH2:68][C:72]#[N:66])[C:12]=1[CH2:36][CH:37]([CH2:48][CH2:49][CH2:50][CH2:51][CH2:52][CH2:53][CH2:54][CH3:55])[CH2:38][CH2:39][CH2:40][CH2:41][CH2:42][CH2:43][CH2:44][CH2:45][CH2:46][CH3:47])[CH2:2][CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH3:8]

Participants

7

Reactant 4

HCID 947NitrogenHCID 8028TetrahydrofuranHCID 14094256HCID 14094256, compoundHCID 178418339Butyllithium

Product 1

HCID 131724267HCID 131724267, compound

Reagents, catalysts & solvents 2

HCID 8058HexaneSolventHCID 18522661Acetone cardiceSolvent

Procedure

Tris(2-octyldodecyl)cyclopentadiene (18.12 grams, 20 m mol) was placed in a 3-necked round bottom flask equipped with an additional funnel, a gas inlet adapter, and a septum. After flashing with dried N2 for 2 minutes, 50 ml of dried THF (distilled over K) was added. The solution was cooled in dry ice/acetone bath, followed injected 8.4 M n-butyl lithium in hexane solution (2.40 ml; 20 m mol). The dry ice/acetone bath was removed, and the resulting dark red solution was stirred at room temperature for 1 hour, followed by cooling in dry ice/acetone bath. 3-Bromopropionitrile (2.70 grams, 20 m mol) in 10 ml dried THF solution was then dropwise added from the additional funnel. After the addition, the reaction solution was stirred at room temperature for another 3 hours. The reaction was slowly quenched with 10 ml water. The organic layer was separated, and the aqueous layer was extracted with 50 ml hexane. The organic layers were combined, dried over MgSO4, filtered, and rota-vaporized to give 19.6 grams of yellow liquid. The crude reaction product was purified by column chromatography on SiO2 eluting with 5% ethyl acetate/hexane. The unreacted tri(2-octyldodecyl)cyclopentadiene (3.66 grams) was recovered and the title compound (12.83 grams) was isolated. FTIR: 2248 cm−1 (C≡N); 13C NMR (4 isomers): 152.5–129.1 ppm (C═C), 120.8–119.6 ppm (4 peaks; C≡N), 59.5 ppm, 56.9 ppm, 51.3 ppm, 41.1 ppm, 39.5–26.4 ppm, 22.7 ppm, 14.1 ppm

Workup

  1. customequipped with an additional funnel, a gas inlet adapter
  2. customThe dry ice/acetone bath was removed
  3. temperatureby cooling in dry ice/acetone bath
  4. addition3-Bromopropionitrile (2.70 grams, 20 m mol) in 10 ml dried THF solution was then dropwise added from the additional funnel
  5. additionAfter the addition
  6. stirringthe reaction solution was stirred at room temperature for another 3 hours
  7. customThe reaction was slowly quenched with 10 ml water
  8. customThe organic layer was separated
  9. extractionthe aqueous layer was extracted with 50 ml hexane
  10. dry with materialdried over MgSO4
  11. filtrationfiltered

Sources & evidence

ORD record
ord-2b15782348ed4922b89042b8371249f5
Source dataset
uspto-grants-2007_07
Patent number
US07244522B2

Reaction notes

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