DFT and ab-initio study on the mechanism of the gas-phase elimination kinetics of 1-chloro-3-methylbut-2-ene and 3-chloro-3-methylbut-1-ene and their isomerization
نویسندگان
چکیده
The mechanisms of the gas-phase elimination kinetics of 1-chloro-3-methylbut-2-ene and 3-chloro-3-methylbut-1ene and their interconversion have been examined at MP2 and DFT levels of theory. These halide substrates yield isoprene and hydrogen chloride. The results MPW1PW91 calculations agree with the experimental kinetic parameters showing the elimination reaction occurs at greater rate for 1-chloro-3-methylbut-2-ene than that for the 3-chloro-3-methylbut-1-ene isomer. The mechanism for the molecular elimination of 1-chloro-3-methylbut-2-ene suggests proceeding through an uncommon sixmembered cyclic transition state for alkyl halides in the gas phase, while 3-chloro-3-methylbut-1-ene eliminates through the usual four-membered cyclic transition state. The elongation and subsequent polarization of the C-Cl bond, in the direction of C. . . Clδ−, is rate determining step of these reactions. The isomerization of 1-chloro-3-methylbut-2-ene and 3-chloro-3methylbut-1-ene was additionally studied. The 1-chloro-3-methylbut-2-ene converts to 3-chloro-3-methylbut-1-ene easier than the reverse reaction. This means that 1-chloro-3-methylbut-2-ene was found thermodynamically more stable than 3-chloro-3methylbut-1-ene.
منابع مشابه
Kinetics inversion of chloro-olefine in the solid acid system
The reaction kinetics of the isomerization 3,4-dichlorobutene-1 to 1,4-dichlorobutene-2 was investigated by using gas-liquid chromatography method in the presence of Fe2O3/MgO as solid catalyst in the temperature range 25-55°C. Fe2O3/MgO has been prepared by the support saturation method, tested in the isomerization of 3, 4-dichlorobutene-1 into 1, 4-dichlorobutene-2. This catalyst shows a high...
متن کاملKinetics inversion of chloro-olefine in the solid acid system
The reaction kinetics of the isomerization 3,4-dichlorobutene-1 to 1,4-dichlorobutene-2 was investigated by using gas-liquid chromatography method in the presence of Fe2O3/MgO as solid catalyst in the temperature range 25-55°C. Fe2O3/MgO has been prepared by the support saturation method, tested in the isomerization of 3, 4-dichlorobutene-1 into 1, 4-dichlorobutene-2. This catalyst shows a high...
متن کاملAb initio Study of Simple Mg-Ene Reactions of Propenyl Magnesium Halides and Ethylene (Type-I Intermolecular Reaction)
The insertion of an olefinic C=C bond into a metal-carbon bond is of potential interest as a preparativeroute to new products and as results of C-C coupling reactions to organic compounds. The allyl compoundsof Mg, react with an olefin by inversion of the allyl group via a six center transition state. These precyclicreactions may be one of the most important classes of organic reactions. The re...
متن کاملAb initio and DFT studies on tautomerism of 5-methyl cytosine in gaseous phase
Ab initio and DFT methods have been used to study the seven tautomeric forms of 5-methylcytosine molecule.The related tautomer in gas phase have been studied at HF/6-31G, HF/6-31G* and B3LYP/6-31G* levels oftheory. The structures,enthalpies,entropies,Gibbs free energies,relative tautomerization energies of tautomersand tautomeric equilibrium constants were compared and analyzed along with full ...
متن کاملAcylphloroglucinol Derivatives from the South African Helichrysum niveum and Their Biological Activities.
Phytochemical investigation of aerial parts of Helichrysum niveum (H. niveum) using different chromatographic methods including semi-preparative HPLC afforded three new (1-3) and six known (4-10) acylphloroglucinols alongside a known dialcohol triterpene (11). The structures of the isolated compounds were characterized accordingly as 1-benzoyl-3 (3-methylbut-2-enylacetate)-phloroglucinol (helin...
متن کاملذخیره در منابع من
با ذخیره ی این منبع در منابع من، دسترسی به آن را برای استفاده های بعدی آسان تر کنید
برای دانلود متن کامل این مقاله و بیش از 32 میلیون مقاله دیگر ابتدا ثبت نام کنید
ثبت ناماگر عضو سایت هستید لطفا وارد حساب کاربری خود شوید
ورودعنوان ژورنال:
- J. Comput. Meth. in Science and Engineering
دوره 12 شماره
صفحات -
تاریخ انتشار 2012