- CYCLIZATION OF 2-(1'-ALKYL-2'-ALKENYL)ANILINES IN POLYPHOSPHORIC ACID
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The cyclization of 2-alkenylarylamines in polyphosphoric acid (PPA) with 1,2 and 1,3 shifts of the α-alkyl substituent of the alkenyl fragment leads to the formation of indoline and indane compounds.Cis- and trans-stereoisomers of 2-methyl-4-ethyl-1-aminoindane formed without displacement of the α-substituents as well as 2-methyl-2-propylindoline are obtained from 2-(1'-methyl-2'-pentenyl)aniline.
- Mustafin, A. G.,Gataullin, R. R.,Abdrakhmanov, I. B.,Khalilov, L. M.,Tolstikov, G. A.
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- Synthesis of 2-ethyl-2-methyl-2,3-dihydro-1H-indole, a new insecticide exhibiting juvenile hormone activity
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Catalytic hydroamination of isoprene gave N-(1,2-dimethylprop-2-en-1-yl) aniline in a preparative yield. By heating at 260°C the product was converted into 2-ethyl-2-methyl-2,3-dihydro-1H-indole, a new ecologically safe insecticide exhibiting a juvenile h
- Petrushkina,Kalinin,Ivanova,Kheinman
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p. 1953 - 1957
(2008/02/08)
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- Mechanistic studies of intramolecular CH insertion reaction of arylnitrenes: Isotope effect, configurational purity and radical clock studies
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In order to reveal the mechanism of the intramolecular CH insertion of arylnitrenes, three experiments were carried out: measurement of isotope effects, determination of the extent of configurational retention and radical clock studies. Irradiation of the deuterium-substituted azide 4-d in an inert solvent exclusively afforded the indolines 5-h and 5-d, in which the kinetic isotope effect kH/kD on the intramolecular CH insertion of the nitrene was evaluated as 12.6-14.7 at room temperature. A chiral Chromatographic analysis of the indoline 11 obtained from the optically active azide (S)-6 revealed that the enantiomeric purity of the starting azide was almost completely lost during the intramolecular CH insertion of the photolytically generated nitrene (enantiomeric excess 10%). The thermolysis of the azide 7 at 180°C mainly gave a mixture of the cyclopropyl ring-opened products 20-22, together with the intramolecular CH insertion product with an intact cyclopropyl ring 19. On the basis of these observations, we concluded that the intramolecular CH insertion of the nitrene proceeds primarily by the hydrogen abstraction-recombination mechanism. We propose, however, a small contribution of the concerted mechanism to the intramolecular CH insertion, based on the solvent dependence of the isotope effect and the extent of the configurational retention. Copyright
- Murata, Shigeru,Tsubone, Yasuhiro,Kawai, Reina,Eguchi, Daisuke,Tomioka, Hideo
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