Butyl lithium-catalyzed stereoselective telomerization of 1,3-diene - a novel synthesis of N,N-dialkyl(octa-cis-2,6-dienyl)amine derivative -

✍ Scribed by Kunihiko Takabe; Takao Katagiri; Juntaro Tanaka

• Book ID: 104245302
• Publisher: Elsevier Science
• Year: 1972
• Tongue: French
• Weight: 225 KB
• Volume: 13
• Category: Article
• ISSN: 0040-4039
• DOI: 10.1016/s0040-4039(01)94221-2

✦ Synopsis

Palladium or nickel complex-catalyzed telomerizations of 1,3-dienes with active hydrogen compounds (carboxylic acids 1) , alcohols 11, 2) , active methylene compounds3), water4) and amines5)) h ave been reported to yield the corresponding octa-2,7-dienyl derivatives mainly.

We now report the n-butyl lithium-catalyzed telomerixation of 1,3-diene with set-amine6) as the novel synthetic method for N,N-dialkyl(octa-cis-2,6-dienyl)amine

For example, an ether solution(6.5 ml) of n-butyl lithium(0.01 mol) was added to oxygen free benzene(20 ml) solution of butaAl,3-diene(12 ml, 0.15 mol) and diethylamine(3.65 g, 0.05 mol) in a pressure bottle and the mixture was agitated at 50°C for 8 hours.

After the reaction, 10 ml ethanol was added to the reaction mixture.

Fractional distillation of the reaction product(5.5 g> gave N,N-diethyl-(but-2-enyl)amine(3.4 g> at bp 43-45'C/20 mmHg and N,N-diethyl(octa-cis-2,6-dienyl) amine(2.0 g) at bp 50-52'C/l.5 mmHg. Separation and identification of stereoisomers were achieved by i.r., n.m.r. and mass spectra after g.1.c. fractionation.