62782-27-8Relevant academic research and scientific papers
Substituent effects on the dehydration of arene hydrates in aqueous solution
O'Mahony, Michelle J.,More O'Ferrall, Rory A.,Boyd, Derek R.,Lam, Casey M.,O'Donoghue, Annmarie C.
supporting information, p. 989 - 996 (2014/01/06)
Rate constants have been determined by UV spectrophotometry at 25 °C for the acid-catalyzed dehydration of different types of monocyclic arene hydrates including those substituted at the 1-, 2- or 3-positions. General acid catalysis was not observed, and linear plots of pseudo-first-order rate constants for dehydration against hydronium concentration were obtained. A Hammett plot of the second-order rate constants for acid-catalyzed dehydration, kH (M-1s-1), of unsubstituted- (8a), 3-substituted (8b, 8c, 8d, 8e) and 1-substituted-benzene hydrates (14f and 14h) shows an excellent correlation with σ+ values and yields a large negative ρ-value of -6.5. The results are consistent with rate-determining formation of a benzenium ion in which direct mesomeric interaction with the substituent occurs, presumably permitted by the coplanar arrangement of the diene and carbocation centre in the intermediate. Data points for 2-substituted arene hydrates (13f, 13g, 13h, 13i) deviate negatively from the Hammett plot as direct mesomeric interaction with the substituent is not possible in the corresponding benzenium intermediates. Copyright 2013 John Wiley & Sons, Ltd. A large negative ρ-value of -6.5 is obtained in a correlation of rate constants for the acid-catalyzed dehydration of arene hydrates with σ+ values. Copyright
Composition of Mixtures of Hydrocarbons after BIRCH-Reduction of Substituted Benzenes and Acid Catalyzed Addition of Alcohols to Alkylsubstituted Cyclohexenes and Carbohexa-1,4-dienes
Beger, J.,Thomas, B.,Vogel, T.,Kirmse, K.,Lang, R.
, p. 481 - 488 (2007/10/02)
10 different benzene hydrocarbons 1, indane, tetraline, anisol and phenol are reduced by sodium in liquid ammonia in the presence of methanol to the BIRCH products 2.The product mixture compositions are determined through capillary GLC.On storage at +6 deg C some rearomatization of the 1,4-cyclohexadienes 2 occurs.Data of the 1H- and 13C-.n.m.r. spectra and also mass spectra of the BIRCH 1,4-dienes 2 are given.For comparison 4-alkoxycyclohexenes 4 and 1-alkoxy-1-methylcyclohexanes 8 are prepared and spectroscopically characterized.Acid-catalyzed addition of alcohols to the 1,4-cyclohexadienes systems is a slow process and gives the 4-alkoxy-4-alkylcyclohex-1-enes (4) only in moderate yields up to 30percent.Most of the products are dimers 5 and also oligomers 6 of the parent hydrocarbons 2.
Molecules with Twist Bent Bonds. The Synthesis, Properties, and Reactions of trans-Bicyclohept-3-ene and Certain Methylated Derivatives
Gassman, Paul G.,Bonser, Steven M.,Mlinaric-Majerski, Kata
, p. 2652 - 2662 (2007/10/02)
trans-Bicyclohept-3-ene, 7-methyl-trans-bicyclohept-3-ene, and 7,7-dimethyl-trans-bicyclohept-3-ene have been synthesized.Comparison of their ease of oxidation with the ease of oxidation of the analogous cis-bicyclohept-3-enes has been made.Both the thermal and transition-metal complex promoted rearrangements of the trans-bicyclohept-3-enes have been studied.These systems thermally convert to the cis-bicyclohept-3-enes above 100 deg C and are catalytically rearranged at ambient temperature.Trans to cis isomerization alsooccurs at ambient temperature under photoinduced single electron transfer conditions.
Molecules with Twist Bent Bonds. A Comparison of the Thermal and Transition-Metal-Complex Promoted Rearrangements of Derivatives of trans-Bicyclohept-3-ene
Gassman, Paul G.,Mlinaric-Majerski, Kata
, p. 4803 - 4806 (2007/10/02)
7-Methyl-trans-bicyclohept-3-ene has been synthesized and the thermal and transition-metal-complex promoted rearrangements of trans-bicyclohept-3-ene, 7-methyl-trans-bicyclohept-3-ene, and 7,7-dimethyl-trans-bicyclohept-3-ene have been compared.
