G2(+) investigation on the alpha-effect in the SN2 reactions at saturated carbon

As a continuing theoretical study on the alpha-effect in the S(N)2 reactions at saturated carbon centers, 28 gas-phase reactions have been examined computationally by using the high-level G2(+) method. The reactions include: Nu(-)+CH(3)X-->CH(3)Nu+X(-) (X=F and Cl; Nu(-)=HO(-), HS(-), CH(3)O(-), Cl(-), Br(-), HOO(-), HSO(-), FO(-), ClO(-), BrO(-), NH(2)O(-), and HC(==O)OO(-)). It was found that all alpha-nucleophiles examined exhibit downward deviations from the correlation line between the overall barriers and proton affinities for normal nucleophiles, indicating the existence of the alpha-effect in the gas phase. The transition states (TS) for the alpha-nucleophiles are characterized by less advanced C--X bond cleavages than the normal nucleophiles, leading to smaller deformation energies and overall barriers. The size of the alpha-effect is related to the electron density on the alpha-atom, and increases when the position of alpha-atom is changed from left to right and from bottom to top in the periodic table. The reaction with CH(3)F exhibits a larger alpha-effect than that with CH(3)Cl, which can be explained by a later TS and a more positively charged methyl group at the TS for CH(3)F, [NuCH(3)F](- not equal). Thus, a higher electron density on the alpha-atom and a more positive methyl moiety at the TS result in a larger alpha-effect.     

The alpha-effect in gas-phase SN2 reactions: existence and the origin of the effect

The origin of enhanced reactivity of alpha-nucleophiles in SN2 reactions was examined on the basis of computational results at the high level G2(+) method for 22 gas-phase reactions: Nu- + RCl --> RNu + Cl- [R = Et and i-Pr; Nu- = HO-, CH3O-, HS-, Cl-, Br-, NH2O-, HOO-, FO-, HSO-, ClO-, and BrO-]. The results clearly indicate the existence of the alpha-effect, whose size varies depending on the R group and the identity of the alpha-atom. The alpha-effect is larger for i-PrCl than EtCl, and for an alpha-nucleophile with a harder alpha-atom. Analyses of the present results, together with previously reported ones for MeF and MeCl reactions, reveal that several rationales so far presented to explain the alpha-effect, such as thermodynamic product stability, transition state (TS) tightness, electrostatic interaction, ET rationale, and polarizability, cannot explain the observed size of the alpha-effect. The importance of deformation energy on going from the reactant to the TS is presented.     

Double Bond Migration Mechanism in Allyl Systems Involving the Hydroxide Ion. 1. Gas-Phase and Born–Onsager Models

The reaction profile of the 1,3-prototropic rearrangement of propene involving the hydroxide ion was studied by the RHF/6-31+G*, MP2/6-31+G*, and B3LYP/6-31+G* ab initio methods within the framework of the gas-phase and Born–Onsager models (the latter including solvent effects). Propene isomerization in the presence of the hydroxide ion in the gas phase may occur with participation of a base proton with the intermediate formation of a water complex of the allyl ion. The transition state energy of this transformation is lower than the total energy of the starting hydroxide ion and propene and much lower than the sum of the energies of the isolated propenide ion and water molecule. An activation barrier arises when the solvent effect is included in calculation within the framework of the Born–Onsager model; the intermediate complex is much less stable than the complex considered in the gas-phase model. As in the latter, the mechanism of multiple bond migration is energetically preferable to the mechanism involving proton transfer to the reaction medium.     

The alpha-effect in gas-phase SN2 reactions revisited

This paper re-examines gas-phase S(N)2 reactions at saturated carbon for model reactions Nu(-) + CH(3)Cl --> CH(3)Nu + Cl(-) (Nu(-) = HO(-), MeO(-), NH(2)(-), HS(-), Cl(-), Br(-), I(-), HOO(-), MeOO(-), HSS(-), and NH(2)NH(-)) using the G2(+) theory. The calculated results show that the alpha-effect does exist in the gas-phase S(N)2 reaction at the sp(3) carbon, contrary to the currently accepted notion of the absence of the alpha-effect in the gas phase.     

Enzyme-like acceleration for the hydrolysis of a DNA model promoted by a dinuclear Zn(II) catalyst in dilute aqueous ethanol

The rates and products of cleavage of methyl (2-chloro-4-nitrophenyl) phosphate (2) promoted by a dinuclear Zn(II) complex (3) of 1,3-bis-N,N'(1,5,9-triazacyclododecyl)propane along with 1 equiv of ethoxide were investigated in ethanol solution containing small amounts of water (8 mM or=1.6 x 10(17) times relative to the background hydroxide reaction, suggesting that complex 3 promotes the hydrolysis at least 1000 times more effectively than ethanolysis.     

Gas chromatography of trimethylsilyl derivatives of alpha-methoxyalkyl hydroperoxides formed in alkene-O3 reactions

The synthesis of trimethylsilyl (TMS) hydroperoxide derivatives for gas chromatography (GC) was studied using N-methyl-N-(trimethylsilyl) trifluoroacetamide (MSTFA) for derivatization of cumene hydroperoxide (CMOOH) (alpha,alpha'-dimethylbenzyl hydroperoxide) and alpha-methoxyalkyl hydroperoxides formed by liquid- and gas-phase ozonolysis of a series of terminal alkenes in the presence of methanol (CH3OH). Derivatization efficiencies >90% were achieved over a wide range of solution concentrations. The major compounds identified by GC-mass spectrometry of the derivatized products of alkene-O3 reactions were alpha-methoxyalkyl hydroperoxides, methyl esters, and aldehydes. Yields of alpha-methoxyalkyl hydroperoxides and methyl esters were quantified using effective carbon numbers (ECNs) and used to determine the yields of stabilized Criegee intermediates (SCIs) from gas-phase ozonolysis reactions. Such measurements are important for understanding the atmospheric chemistry of alkene emissions. SCI yields measured for the reactions of 1-octene [CH3(CH2)5CH=CH2], 1-nonene [CH3(CH2)6CH=CH2 ], and 2-methyl-1-octene [CH3(CH2)5C(CH3)=CH2] are consistent with previous measurements or predictions based on literature data. SCI yields measured for the reactions of 1-decene [CH3(CH2)7CH=CH2], 1-dodecene [CH3 (CH2)9CH=CH2], and 1-tetradecene [CH3(CH2)11CH=CH2] are much lower than expected, apparently due to side reactions with low volatility aldehydes that form peroxyhemiacetals, which are not amenable to GC analysis. In general, the results indicate that off-line MSTFA derivatization can be an efficient means for increasing the stability of thermally labile hydroperoxides for identification and quantitation by GC, and offers a new approach for the analysis of these environmentally important compounds.     

Mechanistic Studies on the Transformation of Ethanol into Ethene over Fe‐ZSM‐5 Zeolite

Ethanol, through the utilization of bioethanol as a chemical resource, has received considerable industrial attention as it provides an alternative route to produce more valuable hydrocarbons. Using a density functional theory approach incorporating the M06‐L functional, which includes dispersion interactions, a large 34T nanocluster model of Fe‐ZSM‐5 zeolite in which T is a Si or Al atom is employed to examine both the stepwise and concerted mechanisms of the transformation of ethanol into ethene. For the stepwise mechanism, ethanol dehydration commences from the first hydrogen abstraction of the ethanol OH group to form the ethoxide‐hydroxide intermediate with a low activation energy of 17.7 kcal mol^?1. Consequently, the ethoxide‐hydroxide intermediate is decomposed into ethene through hydrogen abstraction from the ethoxide methyl carbon to either the OH group of hydroxide or the oxygen of the ethoxide group with high activation energies of 64.8 and 63.5 kcal mol^?1, respectively. For the concerted mechanism, ethanol transformation into the ethene product occurs in a single step without intermediate formation, with an activation energy of 32.9 kcal mol^?1.     

Comparative study of niobium-containing hexagonal mesoporous silicas prepared using different niobium sources

Two groups of niobium-containing hexagonal mesoporous silica (Nb-HMS) samples were prepared hydrothermally using niobium oxalate and niobium ethoxide as Nb source, respectively. The samples were characterized by XRD, N₂-adsorption, ICP-AES, UV-Vis, respectively. They were also evaluated by the epoxidation of cyclohexene with cumene hydroperoxide (CHP) as oxidant. It is revealed that the samples possess typical hexagonal mesoporous structure in which most of Nb species exist in the form of framework pentahedral coordinated state. Meanwhile, the Nb-HMS samples from niobium ethoxide give more excellent catalytic performance than those from niobium oxalate. It is likely because that the former samples have a higher total amount of Nb species and a higher proportion of isolated framework Nb species. Accordingly, niobium ethoxide is a better niobium source than niobium oxalate.     

A theoretical analysis of the free-energy profile of the different pathways in the alkaline hydrolysis of methyl formate in aqueous solution

The free-energy profile for the different reaction pathways available to the hydroxide ion and methyl formate in aqueous solution is reported for the first time. The theoretical analysis was carried out by using the cluster-continuum method recently proposed by us for calculating the free energy of solvation of ions. Unlike the gas-phase reaction, our results are consistent with the fact that the reaction occurs mainly by nucleophilic attack of the hydroxide on the carbonyl carbon to yield a tetrahedral intermediate (B(AC)2 mechanism). However, an additional pathway, in which the hydroxide ion acts as a general base and a water molecule coordinated to this ion acts as the nucleophile, is also predicted to be important. The relative importance of these pathways is calculated to be 87 % and 13 %, respectively. The tetrahedral intermediate of the hydrolysis reaction has an estimated lifetime of 10 nanoseconds, and its conjugate acid has a pK(a) of 8.8. This tetrahedral intermediate is predicted to proceed to products by two pathways: elimination of methoxide ion (84 %) and by water catalyzed elimination of methanol (16 %). The less common reaction pathway, which involves attack of the hydroxide ion on the formyl hydrogen (decarbonylation mechanism) and leads to water, carbon monoxide, and methanol, is calculated to be only 3 kcal mol(-1) less favorable than the B(AC)2 mechanism. By comparison, direct attack of the hydroxide ion on the methyl group (B(AL)2 or S(N)2 mechanism) leading to an acyl-oxygen bond cleavage has a very high free energy of activation and is not expected to be important. The theoretically observed activation free energy at 298.15 K is calculated to be 15.5 kcal mol(-1), in excellent agreement with the experimentally measured value of 15.3 kcal mol(-1). This present model allows for a clear distinction between contributions due to solvation and those due to intrinsic (gas-phase) effects and proves to yield results in very good agreement with available experimental data.     

Investigation of ethylene dimerization over faujasite zeolite by the ONIOM method.

Ethylene dimerization was investigated by using an 84T cluster of faujasite zeolite modeled by the ONIOM3(MP2/6-311++G(d,p):HF/6-31G(d):UFF) method. Concerted and stepwise mechanisms were evaluated. In the stepwise mechanism, the reaction proceeds by protonation of ethylene to form the surface ethoxide and then C--C bond formation between the ethoxide and the second ethylene molecule to give the butoxide product. The first step is rate-determining and has an activation barrier of 30.06 kcal mol(-1). The ethoxide intermediate is rather reactive and readily reacts with another ethylene molecule with a smaller activation energy of 28.87 kcal mol(-1). In the concerted mechanism, the reaction occurs in one step of simultaneous protonation and C--C bond formation. The activation barrier is calculated to be 38.08 kcal mol(-1). Therefore, the stepwise mechanism should dominate in ethylene dimerization.     

Does α‐effect exist in E2 reactions? A G2(+) investigation

The gas-phase base-induced bimolecular elimination (E2) reactions at saturated carbon with 13 bases, B(-) + CH3CH2Cl --> BH + CH2=CH2 + Cl(-) (B = HO, CH3O, CH3CH2O, FCH2CH2O, ClCH2CH2O, Cl, Br, FO, ClO, BrO, HOO, HSO, and H2NO), were investigated with the high-level G2(+) theory. It was found that all alpha-bases with adjacent lone pair electrons examined exhibited downward deviations from the correlation line between the overall barriers and proton affinities for the normal bases without adjacent lone pair electrons, indicating the existence of the alpha-effect in the gas phase E2 reactions. The sizes of the alpha-effect for the E2 reaction, DeltaH(alpha)(E2), span a smaller range if the alpha-atoms are on the same column in the periodic table, in contrast to the corresponding S(N)2 reactions, where the DeltaH(alpha)(S(N)2) values significantly decrease from an upper to a lower column. The origin of the alpha-effects in E2 reactions can be interpreted by the favorable orbital interaction between the lone-pair electrons and positively charged anti-bonding orbital. It is worth noticing that the neighboring electron-rich pi lobe instead of lone pair electrons could also cause the alpha-effect in E2 reaction.     

Multiplicity control in the polygeminal diazeniumdiolation of active hydrogen bearing carbons: chemistry of a new type of trianionic molecular propeller.

Over a century ago, Traube reported the reaction of four nitric oxides with acetone and sodium ethoxide to yield sodium methanebis(diazene-N-oxide-N'-hydroxylate) and sodium acetate. However, when this reaction is carried out in the presence of nitric oxide at slightly elevated pressures (35-40 psi), a product corresponding to the addition of six nitric oxides, sodium methanetris(diazene-N-oxide-N'-hydroxylate), forms as the main product in addition to a trace of the previously observed sodium methanebis(diazene-N-oxide-N'-hydroxylate) and sodium acetate. The corresponding potassium salts form when potassium hydroxide is employed as the base, while lithium hydroxide results in the formation of lithium methanebis(diazene-N-oxide-N'-hydroxylate) exclusively. Nitric oxide reacts with 3,3-dimethylbutan-2-one in the presence of sodium and potassium hydroxide in methanol to yield sodium and potassium 3,3-dimethylbutan-2-one-1,1,1-tris(diazene-N-oxide-N'-hydroxylate), respectively. In contrast, the reaction in the presence of lithium hydroxide forms lithium methanebis(diazene-N-oxide-N'-hydroxylate) and lithium pivalate. The differential reactivity of nitric oxide with acetone and 3,3-dimethylbutan-2-one in the presence of the three bases is attributed to competing hydrolytic reactions of the acetyl and trimethylacetyl group-containing intermediates. A mechanism is proposed for the nitric oxide addition to active methyl groups in these reactions, where the product distribution between the di- and trisubstituted methanes is under kinetic control of the competing reactions. The products are characterized by NMR and IR spectroscopy, differential scanning calorimetry, and elemental analysis. Two differentially hydrated forms of potassium methanetris(diazene-N-oxide-N'-hydroxylate) are characterized by single-crystal X-ray diffraction. From the metathesis reaction of the silver salt of methanetris(diazene-N-oxide-N'-hydroxylate) with ammonium iodide, the corresponding ammonium salt is isolated in 59% yield, but only trace amounts of methylated products form in the reaction of the silver salt with methyl iodide. Density functional calculations (B3LYP/6-311++G) are used to evaluate the bonding, ground-state structures, and energy landscape for the different conformers of methanetris(diazene-N-oxide-N'-hydroxylate)(3-) trianion, a new type of a molecular propeller, and its corresponding triprotonated acid.     

Secondary organic aerosol formation from low-NO(x) photooxidation of dodecane: evolution of multigeneration gas-phase chemistry and aerosol composition

The extended photooxidation of and secondary organic aerosol (SOA) formation from dodecane (C(12)H(26)) under low-NO(x) conditions, such that RO(2) + HO(2) chemistry dominates the fate of the peroxy radicals, is studied in the Caltech Environmental Chamber based on simultaneous gas and particle-phase measurements. A mechanism simulation indicates that greater than 67% of the initial carbon ends up as fourth and higher generation products after 10 h of reaction, and simulated trends for seven species are supported by gas-phase measurements. A characteristic set of hydroperoxide gas-phase products are formed under these low-NO(x) conditions. Production of semivolatile hydroperoxide species within three generations of chemistry is consistent with observed initial aerosol growth. Continued gas-phase oxidation of these semivolatile species produces multifunctional low volatility compounds. This study elucidates the complex evolution of the gas-phase photooxidation chemistry and subsequent SOA formation through a novel approach comparing molecular level information from a chemical ionization mass spectrometer (CIMS) and high m/z ion fragments from an Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS). Combination of these techniques reveals that particle-phase chemistry leading to peroxyhemiacetal formation is the likely mechanism by which these species are incorporated in the particle phase. The current findings are relevant toward understanding atmospheric SOA formation and aging from the "unresolved complex mixture," comprising, in part, long-chain alkanes.     

Reactivity of alkyl versus silyl peroxides. The consequences of 1, 2-silicon bridging on the epoxidation of alkenes with silyl hydroperoxides and bis(trialkylsilyl)peroxides

The bond dissociation energies for a series of silyl peroxides have been calculated at the G2 and CBS-Q levels of theory. A comparison is made with the O-O BDE of the corresponding dialkyl peroxides, and the effect of the O-O bond strength on the activation barrier for oxygen atom transfer is discussed. The O-O bond dissociation enthalpies (DeltaH(298)) for bis (trimethylsilyl) peroxide (1) and trimethylsilyl hydroperoxide (2) are 54.8 and 53.1 kcal/mol, respectively at the G2 (MP2) and CBS-Q levels of theory. The O-O bond dissociation energies computed at G2 and G2(MP2) levels for bis(tert-butyl) peroxide and tert-butyl hydroperoxide are 45.2 and 48.3 kcal/mol, respectively. The barrier height for 1,2-methyl migration from silicon to oxygen in trimethylsilyl hydroperoxide is 47.9 kcal/mol (MP4//MP2/6-31G). The activation energy for the oxidation of trimethylamine to its N-oxide by bis(trimethylsilyl) peroxide is 28.2 kcal/mol (B3LYP/6-311+G(3df,2p)// B3LYP/6-31G(d)). 1,2-Silicon bridging in the transition state for oxygen atom transfer to a nucleophilic amine results in a significant reduction in the barrier height. The barrier for the epoxidation of E-2-butene with bis(dimethyl(trifluoromethyl))silyl peroxide is 25.8 kcal/mol; a reduction of 7.5 kcal/mol relative to epoxidation with 1. The activation energy calculated for the epoxidation of E-2-butene with F(3)SiOOSiF(3) is reduced to only 2.2 kcal/mol reflecting the inductive effect of the electronegative fluorine atoms.     

BECKMANN-Umlagerung und Fragmentierung; V. Teil Mechanismus der 7-Zentren-Fragmentierung von 1-Oxo-5-oximino-9-methyl-trans-decalin. Fragmentierungsreaktionen, 22. Mitteilung

The reaction rates of heterolytic fragmentation of 5-(p, -toluenesulfonyloxyimino)-1-oxo-9-methyl-trans-decalin ( 1 ), induced by sodium hydroxide in 80% ethanol and by sodium ethoxide in 100% ethanol, has been determined. The reaction of the oxime tosylate 1 with sodium ethoxide is first order with respect to both reactants. A similar base-dependence is observed in the reaction of the oxime tosylate 1 with sodium hydroxide. These results are explained in terms of an addition-fragmentation mechanism. This involves reversible addition of NaOH or NaOC₂H₅ to the carbonyl group of the oxime tosylate 1 and concerted fragmentation of the addition compounds 5a and 5b , yielding 9-cyano-6-methyl-trans-non-5-enoic acid ( 4a ) and the corresponding ethyl ester 4b , respectively. These reaction appear to be the first cases of concerted and stereospecific 7-centre fragmentation.     

Role of the somersault rearrangement in the oxidation step for flavin monooxygenases (FMO). A comparison between FMO and conventional xenobiotic oxidation with hydroperoxides

Model quantum mechanical calculations presented for C-4a-flavin hydroperoxide (FlHOOH) at the B3LYP/6-311+G(d,p) level suggest a new mechanism for flavoprotein monooxygenase (FMO) oxidation involving a concerted homolytic O-O bond cleavage in concert with hydroxyl radical transfer from the flavin hydroperoxide rather than an S(N)2-like displacement by the substrate on the C-4a-hydroperoxide OOH group. Homolytic O-O bond cleavage in a somersault-like rearrangement of hydroperoxide C-4a-flavinhydroperoxide (1) (FLHO-OH → FLHO···HO) produces an internally hydrogen-bonded HO(?) radical intermediate with a classical activation barrier of 27.0 kcal/mol. Model hydroperoxide 1 is used to describe the transition state for the key oxidation step in the paradigm aromatic hydroxylase, p-hydroxybenzoate hydroxylase (PHBH). A comparison of the electron distribution in the transition structures for the PHBH hydroxylation of p-hydroxybenzoic acid (ΔE(?) = 23.0 kcal/mol) with that of oxidation of trimethylamine (ΔE(?) = 22.3 kcal/mol) and dimethyl sulfide (ΔE? = 14.1 kcal/mol) also suggests a mechanism involving a somersault mechanism in concert with transfer of an HO(?) radical to the nucleophilic heteroatom center with a hydrogen transfer back to the FLH-O residue after the barrier is crossed to produce the final product, FLH-OH. In each case the hydroxylation barrier was less than that of the O-O rearrangement barrier in the absence of a substrate supporting an overall concerted process. All three transition structures bear a resemblance to the TS for the comparable hydroxylation of isobutane (ΔE(?) = 29.2 kcal/mol) and for simple Fenton oxidation by aqueous iron(III) hydroperoxides. To our surprise the oxidation of N- and S-nucleophiles with conventional oxidants such as alkyl hydroperoxides and peracids also proceeds by HO(?) radical transfer in a manner quite similar to that for tricyclic hydroperoxide 1. Stabilization of the developing oxyradical produced by somersault rearrangement for concerted enzymatic oxidation with tricyclic hydroperoxide 1 results in a reduced overall activation barrier.     

Solvent effect on the alpha-effect: ground-state versus transition-state effects; a combined calorimetric and kinetic investigation

In a study of the solvent effect on the alpha-effect, second-order rate constants (kNu-) have been determined spectrophotometrically for reactions of a series of substituted phenyl acetates with butan-2,3-dione monoximate (Ox-, alpha-nucleophile) and p-chlorophenoxide (p-ClPhO-, reference nucleophile) in DMSO-H2O (DMSO = dimethyl sulfoxide) mixtures of varying compositions at 25.0 +/- 0.1 degrees C. The magnitude of the alpha-effect, kOx-/kp-ClPhO-, increases as the DMSO content in the medium increases up to 40-50 mol %, reaching 500, one of the largest alpha-effect values, and then decreases on further addition of DMSO, resulting in a bell-shaped alpha-effect profile regardless of the nature of the substrates. The magnitude of the alpha-effect is found to be significantly dependent on the substrates (or, more quantitatively, on beta(nuc)). Thus, beta(nuc) is an important predictor of the magnitude of the alpha-effect. The bell-shaped alpha-effect profile found in the present system is attributed to the differential change in the sensitivity of the medium effect on the Ox- and p-ClPhO- systems but not due to a change in the reaction mechanism or to a drastic change in the basicity of the two nucleophiles on addition of DMSO to the medium. Through application of calorimetric measurements of ground-state solvation combined with the diagnostic beta(nuc) values, it is shown that the transition-state effect is more dominant than the ground-state effect as the origin of the alpha-effect in the present system.     

Reactions of the hydroperoxide anion with dimethyl methylphosphonate in an ion trap mass spectrometer: evidence for a gas phase alpha-effect

The gas phase degradation reactions of the chemical warfare agent (CWA) simulant, dimethyl methylphosphonate (DMMP), with the hydroperoxide anion (HOO(-)) were investigated using a modified quadrupole ion trap mass spectrometer. The HOO(-) anion reacts readily with neutral DMMP forming two significant product ions at m/z 109 and m/z 123. The major reaction pathways correspond to (i) the nucleophilic substitution at carbon to form [CH(3)P(O)(OCH(3))O](-) (m/z 109) in a highly exothermic process and (ii) exothermic proton transfer. The branching ratios of the two reaction pathways, 89% and 11% respectively, indicate that the former reaction is significantly faster than the latter. This is in contrast to the trend for the methoxide anion with DMMP, where proton transfer dominates. The difference in the observed reactivities of the HOO(-) and CH(3)O(-) anions can be considered as evidence for an alpha-effect in the gas phase and is supported by electronic structure calculations at the B3LYP/aug-cc-pVTZ//B3LYP/6-31+G(d) level of theory that indicate the S(N)2(carbon) process has an activation energy 7.8 kJ mol(-1) lower for HOO(-) as compared to CH(3)O(-). A similar alpha-effect was calculated for nucleophilic addition-elimination at phosphorus, but this process--an important step in the perhydrolysis degradation of CWAs in solution--was not observed to occur with DMMP in the gas phase. A theoretical investigation revealed that all processes are energetically accessible with negative activation energies. However, comparison of the relative Arrhenius pre-exponential factors indicate that substitution at phosphorus is not kinetically competitive with respect to the S(N)2(carbon) and deprotonation processes.     

Catalytic action of metallic salts in autoxidation and polymerization. IV. Polymerization of methyl methacrylate by cobalt(II) or (III) acetylacetonate–tert-butyl hydroperoxide or dioxane hydroperoxide

Polymerization of methyl methacrylate was carried out by four initiating systems, namely, cobalt(II) or (III) acetylacetonate–tert-butyl hydroperoxide (t-Bu HPO) or dioxane hydroperoxide (DOX HPO). Dioxane hydroperoxide systems were much more effective for the polymerization of methyl methacrylate than tert-butyl hydroperoxide systems, and cobaltous acetylacetonate was more effective than cobaltic acetylacetonate in both hydroperoxides. The initiating activity order and activation energy for the polymerization were as follows: Co(acac)₂–DOX HPO (E_a-9.3 kcal/mole) > Co (acac)₃–DOX HPO (E_a = 12.4 kcal/mole) > Co(acac)₂–t-Bu HPO (E_a = 15.1 kcal/mole) > Co(acac)₃–t-Bu HPO (E_a-18.5 kcal/mole). The effects of conversion and hydroperoxide concentration on the degree of polymerization were also examined. The kinetic data on the decomposition of hydroperoxides catalyzed by cobalt salts gave a little information for the interpretation of polymerization process.     

Theoretical study on the mechanism of reaction between 3‐hydroxy‐3‐methyl‐2‐butanone and malononitrile catalyzed by magnesium ethoxide

The mechanism of reaction between 3‐hydroxy‐3‐methyl‐2‐butanone and malononitrile for the synthesis of 2‐dicyanomethylene‐4,5,5‐trimethyl‐2,5‐dihydrofuran‐3‐carbonitrile catalyzed by magnesium ethoxide was investigated by density functional theory (DFT). The geometries and the frequencies of reactants, intermediates, transition states, and products were calculated at the B3LYP/6–31G(d) level. The vibration analysis and the IRC analysis demonstrated the authenticity of transition states, and the reaction processes were confirmed by the changes of charge density at bond‐forming critical point. The results indicated that magnesium ethoxide is an effective catalyst in the synthesis of 2‐dicyanomethylene‐4,5,5‐trimethyl‐2,5‐dihydrofuran‐3‐carbonitrile from malononitrile and 3‐hydroxy‐3‐methyl‐2‐butanone. The activation energy of reaction with magnesium ethoxide decreased by 102.37 kJ mol^?1 compared with that of the reaction without it. The mechanism of reaction with catalyst magnesium ethoxide differs from that of reaction without it. © 2008 Wiley Periodicals, Inc. Int J Chem Kinet 41: 227–235, 2009