Synthesis of New Plant Growth Regulators,Isomeric 1-(Dimethyloctyl)- and 1-Alkylpiperidinium and -morpholinium Halides by Telomerization of Isoprene with Secondary Amines

The known plant growth regulator, Al'den [1-(3,7-dimethyloctyl)-1-allylpiperidinium bromide], and also 1-(3,7-dimethyloctyl)-1-methylpiperidinium iodide were synthesized by treatment with allyl bromide and methyl iodide, respectively, of exhaustively hydrogenated 1-nerylpiperidine which was obtained by anionic telomerization of isoprene with piperidine. Various quaternary ammonium salts having a terpene sub- stituent with unnatural dimethyloctane skeleton, which effectively stimulate florification of Aster Chinensis L., were prepared by the action of alkyl halides on telomerization products derived from isoprene and piperidine or morpholine in the presence of palladium complexes.     

Synthesis of 2-butyl-4,9-decadienoic and 2-butyl-4,9-dimethyl-4,9-decadienoic acids,structural analogues of cygerol

2-Butyl-4,9-decadienoic and 2-butyl-4,9-dimethyl-4,9-decadienoic acids, structural isomers of 2-cyclohexylgeranylacetic acid, which is an active component of the wound healing ointment cygerol, have been synthesized. Hydrocarbon chains C₁₀ have been obtained by the one-pot method of formation of long-chain hydrocarbons, namely, by the telomerization reaction of 1,3-dienes with nucleophiles catalyzed by palladium complexes. A heterogeneous palladium-zeolite catalyst has been used for the first time in telomerization of isoprene with piperidine.     

Reaction of acetic anhydride with monoterpene amine oxides possessing the 2,7-dimethyloctane skeleton

Under the conditions of the Polonovsky reaction, N-(2,7-dimethyl-2,7-octadienyl)-N,N-dimethylamine oxide gives 2,7-dimethyl-2,7-octadienal and N-(2,7-dimethyl-2,7-octadienyl)-N-methylacetamide. Under the same conditions, N-(2,7-dimethyl-2,7-octadienyl)-N,N-dietnylamine oxide dihydrate does not undergo the Polonovsky reaction and gives the rearrangement product, O-(1-isopropenyl-5-methyl-5-hexenyl)-N,N-diethylhydroxylamine, and the hydration product, O-[1-(1-hydroxy-1-methyl)ethyi-5-methyl-5-hexenyl]-N,N-diethylhydroxylamine.The work was accomplished under the financial support of the Russian Fund for the Fundamental Research (93-03-4219).Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1588–1590, September, 1993.     

Synthesis of 6E-Nonen-1-OL from butadiene-phenol telomer

Conclusions 6E-Nonen-1-ol, theCeratitis capitata pheromone, was synthesized from the telomer of butadiene with phenol.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 5, pp. 1181–1182, May, 1982.     

Palladium(II)-catalyzed Amination of Isoprene with Aniline

The reaction of isoprene with aniline, catalyzed by the Pd(acac)₂-(RO)₃P-CF₃CO₂H system, 1 : 4 : 4 [R = Me, Et; acac = (CH₃CO)₂CH], in MeCN provides N-(3-methylbut-2-en-1-yl)aniline with a high selectivity (up to 84%) and a nearly quantitative yield (75%). At 1 : 4 : 20 and 1 : 4 : 40 molar component ratios in the catalytic system, up to 28–31% of N,N-(2,3-dimethylprop-2-en-1-yl)aniline is formed. Telomeric reaction products appear at 1 : 2 : 4 and 1 : 1 : 10 ratios.__________Translated from Zhurnal Obshchei Khimii, Vol. 75, No. 6, 2005, pp. 963–968.Original Russian Text Copyright © 2005 by Petrushkina, Mysova, Orlinkov.     

Allylic alkylation of benzoimidazole catalyzed by palladium complexes

Bis(dibenzylidenacetone)palladium is an efficient and highly selective catalyst for the formation ofN-(2,7-dimethylocta-2,7-dienyl)benzoimidazole in the allylation of benzoimidazole withN-(2,7-dimethylocta-2,7-dienyl)-N-methylpiperidinium iodide in the presence of NaH. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 357–360, February, 1999.     

Synthesis of N-isobutylamide of 2e,4e-decadienoic acid(pellitorine) from butadiene-acetic acid telomer

Conclusions The N-isobutylamide of 2E,4E-decadienoic acid (pellitorine) was synthesized from 2E,7-octadien-1-yl acetate, the telomer of butadiene with acetic acid.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 11, pp. 2589–2590, November, 1982.     

Stereoselective synthesis of E-5-decen-1-ol from E-1,6-undecadiene

Conclusions A stereoselective synthesis was carried out for E-5-decen-1-ol and E-5-decen-1-yl acetate, which are sex attractants of Anarsia Lineatella, from E-1,6-undecadiene.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 1, pp. 205–207, January, 1985.     

Synthesis of 6E,11Z-hexadecadien-1-yl acetate from telomers of butadiene with either malonic or acetoacetic ester

Conclusions The stereospecific synthesis of 6E,11Z-hexadecadien-1-yl acetate, theAntheraca polyphemus pheromone, was accomplished on the basis of the telomers of butadiene with either malonic or acetoacetic ester.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 8, pp. 1892–1893, August, 1981.