1075-22-5Relevant academic research and scientific papers
ACYLATION AND CHLORINATION OF 3,4-DIMETHYL-cis-BICYCLONONA-3,7-DIENE
Andreev, V. A.,Anfilogova, S. N.,Pekkh, T. I.,Belikova, N. A.
, p. 119 - 123 (2007/10/02)
The acylation and chlorination of 3,4-dimethyl-cis-bicyclonona-3,7-diene takes place differently from the reaction with organic acids.During the action of acetic anhydride in the presence of stannic chloride the acetyl group adds at the C4 carbon, and the double bond of the six-membered ring is shifted to the adjacent position.In the reaction of the dichloride of iodobenzene with the diene either monochloro- or dichloro-cis-bicyclonon-7-ene is obtained, depending on the solvent.
Iodizing and chlorination of methyl-substituted cis-bicyclo[4.3.0]none-3,7-dienes
Andreyev,Bakhtin,Lukovskaya,Pekhk,Bobyleva,Anfilogova,Belikova
, p. 146 - 153 (2007/10/02)
The direction of halogenation of methyl-substituted cis-bicyclo[4.3.0]none-3,7-dienes depends considerably on the position of the methyl group. For a hydrocarbon without a substituent at C-3, the reaction proceeds with retention of the initial structure, whereas in the case of 3-methyl-substituted dienes it is accompanied by transannular cyclization with the formation of compounds of the brexane type.
Anodic Oxidation of α-Substituted p-Xylenes. Electronic and Stereoelectronic Effects of α-Substituents in the Deprotonation of Alkylaromatic Radical Cations
Baciocchi, Enrico,Mattioli, Mario,Romano, Roberta,Ruzziconi, Renzo
, p. 7154 - 7160 (2007/10/02)
The effect of α-substituents on the deprotonation rate from the benzylic position of alkylaromatic radical cations, k(CH2Z)/k(CH3), has been investigated by determining the intramolecular selectivity in the anodic oxidation in acetic acid of a α-Z-substituted p-xylenes 1 (Z = H, OMe, OH, Me, tert-butyl, OAc, COOMe, CN), 5,6-dimethylindan 4 (R = H), and 2,2,5,6-tetramethylindan 4 (R = Me).Some oxidations induced by CAN have also been carried out.It has been found that, with the exception of when Z = tert-butyl, the deprotonation rate of 1.+ is always faster from the CH2Z group than from the CH3 group, independently of the electron-donating or electron-withdrawing nature of Z.The electron-donating groups (OH, OMe, Me), however, exert a larger effect than the electron-withdrawing ones (COOMe, CN).The negligible deprotonation rate from CH2-t-Bu has been ascribed to stereoelectronic effects (the bulky tert-butyl group does not allow the C-H bonds to be collinear with the ?-system), the suggestion being nicely confirmed by the observation that the deprotonation rate from the position 1(3), relative to that from the 5(6)-methyl group, is almost identical in the radical cations of 4 (R = H and Me).The effect of the other α-substituents is mainly of electronic nature and has been rationalized on the basis of a variable transition-state structure for the deprotonation process.It is suggested that with +R groups most of the charge, in the transition state, has been transferred to the Cα-H bond where it can be stabilized by the α-substituent.With electron-withdrawing groups less charge transfer has taken place and the rate-enhancing effects of these groups is ascribed to their capability to significantly decrease the strength of the Cα-H bond.
ANOMALOUS IODINATION AND IODOCHLORINATION OF 3,4-DIMETHYL-CIS-BICYCLONONA-3,7-DIENE
Andreev, V. A.,Pekhk, T. I.,Anfilogova, S. N.,Belikova, N. A.,Bobyleva, A. A.
, p. 1269 - 1276 (2007/10/02)
The iodination and iodochlorination of 3,4-dimethyl-cis-bicyclonona-3,7-diene takes place anomalously.The addition of iodine in carbon tetrachloride leads to the tricyclic monoiodides exo-5-iodo-exo- and exo-5-iodo-endo-1,9-dimethylbrexanes.In pyridine the products from the addition of iodine and pyridine at the least substituted cyclopentene double bond 7-iodo-8-pyridinio-3,4-dimethyl-cis-bicyclonon-3-ene iodides are formed.The addition of iodine chloride in chloroform gives a mixture of the tricyclic monoiodide and the product from addition of iodine and chlorine at the cyclopentene double bond.
