An ab initio and DFT study of some halogen atom transfer reactions from alkyl groups to acyl radical

Ab initio calculations using the 6-311G**, cc-pVDZ, and (valence) double-zeta pseudopotential (DZP) basis sets, with (MP2, QCISD, CCSD(T)) and without (HF) the inclusion of electron correlation, and density functional (BHandHLYP, B3LYP) calculations predict that the transition states for the reaction of acetyl radical with several alkyl halides adopt an almost collinear arrangement of attacking and leaving radicals at the halogen atom. Energy barriers (DeltaE(double dagger)) for these halogen transfer reactions of between 89.2 (chlorine transfer from methyl group) and 25.3 kJ mol(-1) (iodine transfer from tert-butyl group) are calculated at the BHandHLYP/DZP level of theory. While the difference in forward and reverse energy barriers for iodine transfer to acetyl radical is predicted to be 15.1 kJ mol(-1) for primary alkyl iodide, these values are calculated to be 6.7 and -4.2 kJ mol(-1) for secondary and tertiary alkyl iodide respectively. These data are in good agreement with available experimental data in that atom transfer radical carbonylation reactions are sluggish with primary alkyl iodides, but proceed smoothly with secondary and tertiary alkyl iodides. These calculations also predict that bromine transfer reactions involving acyl radical are also feasible at moderately high temperature.     

SN2 reactions in the gas phase. Alkyl group structural effects

The gas phase heats and entropies of S_N2-like association of bromide ions with a series of alkyl bromides are reported. Comparison of this data with published data for the same reactions in solution suggests that the alkyl group structural effects on S_N2 reactivity in solution are controlled entirely by the solvent.     

有机磷化合物的研究 X:五价膦(磷)酸酯与卤代烷在卤化钠存在下的酯烷基交换反应

A detailed study on the ester alkyl exchange reaction of various types of quinique-valent phosphorus esters with alkyl halide in the presence of sodium bromides was reported. This ester alkyl exchange reaction was evidently influenced by the structure of phosphorus esters and alkyl halides as well as by the nature of the halides of metal ions. In contrast with the reaction without sodium hadlide, the alkyl phosphinmate is more reactive than phosphonate and phosphate by treatment with alkyl halide in the presence of sodium halide. This is consistent with the high nucleophilicity of >P(CO)O- as leaving group. The reactivity of butyl halides was decreased in the following order: n-BuBr>i-BuBr=s-BuBr>t-BuBr. Alkyl iodide was proved to be more reactive than the corresponding bromide and chloride. However, the use of iodioe is limited by the formation of alkene resulted from the elimination of HI. These structural effects show the general characteristics of a nucleophilic substitution reaction. A reaction mechanism involving the formation of sodium salt intermecutiate was proposed based on the concept of HSAB principle. This reaction may, however, be used as a convenient method for the preparation of mixed esters of quinque-valent phosphorus acids.     

Wurtz-Fittig syntheses of mixed trideuteromethyl and methyl derivatives of benzene

In the Wurtz-Fittig reaction of an aryl bromide with methyl iodide no rearrangement products are produced. All reaction mechanisms involving radical intermediates are contrary to experimental results and should be rejected. Selective or even specific adsorption dominates the sequence of the Wurtz-Fittig reactions:

Aryl tribromide aryl dibromide aryl monobromide alkyl iodide, although chemical reactivity with sodium is in the reverse order, the higher ranking molecule reacting much slower. This effect may be important in other surface-localized reactions also.

By the method described, it is possible to introduce any number of trideuteromethyl groups at predetermined locations in the phenyl nucleus. Thus fifteen trideuteromethyl derivatives and mixed trideuteromethyl and methyl derivatives of benzene have been prepared (see Tables).     

有机质谱学法研究气相S_N2离子－分子反应进展

总结了近年来应用质谱方法研究气相SN2离子－分子反应的进展，主要包括气 相SN2离子－分子反应的机理，动力学和热力学的各种因素。与凝固相中反应对比 ，阐明了影响反应机理、方向与程度的决定性因素，及溶剂化效应对凝聚相中反应 的影响方式。还介绍了一些气相中特有的SN2离子－分子反应和研究气相反应特殊 的质谱学研究方法与技术。     

Reliable predictions of the thermochemistry of boron-nitrogen hydrogen storage compounds: BxNxHy, x = 2, 3

Thermochemical data calculated using ab initio molecular orbital theory are reported for 16 BxNxHy compounds with x = 2, 3 and y > or = 2x. Accurate gas-phase heats of formation were obtained using coupled cluster with single and double excitations and perturbative triples (CCSD(T)) valence electron calculations extrapolated to the complete basis set (CBS) limit with additional corrections including core/valence, scalar relativistic, and spin-orbit corrections to predict the atomization energies and scaled harmonic frequencies to correct for zero point and thermal energies and estimate entropies. Computationally cheaper calculations were also performed using the G3MP2 and G3B3 variants of the Gaussian 03 method, as well as density functional theory (DFT) using the B3LYP functional. The G3MP2 heats of formation are too positive by up to approximately 6 kcal/mol as compared with CCSD(T)/CBS values. The more expensive G3B3 method predicts heats of formation that are too negative as compared with the CCSD(T)/CBS values by up to 3-4 kcal/mol. DFT using the B3LYP functional and 6-311+G** basis set predict isodesmic reaction energies to within a few kcal/mol compared with the CCSD(T)/CBS method so isodesmic reactions involving BN compounds and the analogous hydrocarbons can be used to estimate heats of formation. Heats of formation of c-B3N3H12 and c-B3N3H6 are -95.5 and -115.5 kcal/mol at 298 K, respectively, using our best calculated CCSD(T)/CBS approach. The experimental value for c-B3N3H6 appears to be approximately 7 kcal/mol too negative. Enthalpies, entropies, and free energies are calculated for many dehydrocoupling and dehydrogenation reactions that convert BNH6 to alicyclic and cyclic oligomers and H2(g). Generally, the reactions are highly exothermic and exergonic as well because of the release of 1 or more equivalents of H2(g). For c-B3N3H12 and c-B3N3H6, available experimental data for sublimation and vaporization lead to estimates of their condensed phase 298 K heats of formation: DeltaHf degrees [c-B3N3H12(s)] = -124 kcal/mol and DeltaHf degrees [c-B3N3H6(l)] = -123 kcal/mol. The reaction thermochemistries for the dehydrocoupling of BNH6(s) to c-B3N3H12(s) and the dehydrogenation of c-B3N3H12(s) to c-B3N3H6(l) are much less exothermic compared with the gas-phase reactions due to intermolecular forces which decrease in the order BNH6 > cyclo-B3N3H12 > cyclo-B3N3H6. The condensed phase reaction free energies are less negative compared with the gas-phase reactions but are still too favorable for BNH6 to be regenerated from either c-B3N3H12 or c-B3N3H6 by just an overpressure of H2.     

Evidence for single electron transfer in the reaction of a lithium enolate with a primary alkyl iodide

Evidence for a radical process in the reaction of the lithium enolate of propiophenone with a primary alkyl iodide was obtained by the observation of cyclization of an appropriate radical probe, by the trapping of the radical intermediate and by the comparison of the relative rates of reactions of the probe alkyl iodide with the corresponding bromide and tosylate.     

Reactivity analysis of ammonium dinitramide binary mixtures based on ab initio calculations and thermal analysis

Ammonium dinitramide (ADN) is a promising high energy oxidizer for rocket propellants because it offers a good oxygen balance and has a significant energy content. As a result, ADN-based energetic ionic liquid propellants (EILPs) have been studied, based on ADN combined with urea and monomethyl ammonium nitrate (MMAN). The thermal decomposition of ADN in the condensed phase affects the combustion of both pure ADN and ADN-based EILPs; thus, it is important to understand the reactions of EILPs in the condensed phase. The present study assessed the reactivity of ADN mixtures in the condensed phase, focussing on hydrogen abstraction reactions with NO₂· formed from the thermal decomposition of ADN. The potential energy surfaces of these reactions were obtained using ab initio calculations. The effects of functional groups and of carbon chain length on hydrogen abstraction by NO₂· were examined. Mixtures of ADN with urea and acetamide (AA) as amide compounds, and with MMAN and monoethanol amine nitrate (MEAN) as nitrate salts, were examined. Thermal analysis was conducted to investigate the properties of these mixtures, using differential scanning calorimetry (DSC). The calculation results shows that AA and MEAN are more reactive with ADN than urea and MMAN, which is supported by the DSC data. Hydrogen abstraction by NO₂· is evidently an important condensed phase reaction in ADN mixtures, and substances having alkyl groups and longer carbon chains are more highly reactive.

     

SYNTHESIS OF ALKYL N-CYANO-N-SUBSTITUTED CARBAMATES AND N,N-DISUBSTITUTED CYANAMIDES1

Abstract

The reactions of S,S' methyl cyanodithioimidocarbonate with potassium hydroxide in alkyl or benzyl alcohol furnished the O-alkyl and benzyl O-potassium cyanoimidocarbonates (1–5). The reaction of the potassium salts (1,3, or 4) with a 10% excess of alkyl, allyl or benzyl halides afforded the unknown titled carbamates (6–17). The reaction of 2 with 10% excess benzyl bromide or 5 with 10% excess methyl iodide gave the same product, N-benzyl-N-methyl cyanamide (18). The reactions of 2 with 10% and 55% excess allyl bromide afforded N-allyl-N-methyl cyanamide (19) and N,N-diallyl cyanamide (20), respectively. The reaction of 3 with 28% excess of allyl iodide furnished N-allyl-N-propyl cyanamide (21).

Possible mechanisms and supporting NMR, IR and mass spectra data are discussed.     

Deuterium kinetic isotope effects in microsolvated gas-phase E2 reactions: Methanol and ethanol as solvents

The gas-phase reactions of F(-)(CH(3)OH) and F(-)(C(2)H(5)OH) with t-butyl bromide have been investigated to explore the effect of the solvent on the E2 transition state. Kinetic isotope effects (KIEs) were measured using a flowing afterglow-selected ion flow tube (FA-SIFT) mass spectrometer upon deuteration of both the alkyl halide and the alcohol. Kinetic isotope effects are significantly more pronounced than those previously observed for similar reactions of F(-)(H(2)O) with t-butyl halides. KIEs for the reaction of F(-)(CH(3)OH) with t-butyl bromide are 2.10 upon deuteration of the neutral reagent and 0.74 upon deuteration of the solvent. KIEs for the reaction of F(-)(C(2)H(5)OH) with t-butyl bromide are 3.84 upon deuteration of the neutral reagent and 0.66 upon deuteration of the solvent. The magnitude of these effects is discussed in terms of transition-state looseness. Additionally, deuteration of the neutral regent and deuteration of the solvent do not produce completely separable isotope effects, which is likely due to a crowded transition state. These results are compared to our previous work on S(N)2 and E2 solvated systems.     

Polarity of the transition state controls the reactivity of related charged phenyl radicals toward atom and group donors

Polar effects are demonstrated to be a key factor in controlling the reactivities of related charged phenyl radicals in different exothermic atom and group abstraction reactions in the gas phase. The effects of various meta substituents on the phenyl radicals' reactivity were probed via the measurement of bimolecular reaction rate constants by using Fourier transform ion cyclotron resonance mass spectrometry. This approach requires an additional, charged substituent to be present in the phenyl radical to allow mass spectrometric manipulation. The m-pyridinium group was chosen for this purpose. The substrates studied were allyl iodide, dimethyl disulfide, and tert-butyl isocyanide. Two of the reactions of interest, *I and *SCH(3) transfer, are thought to occur by concerted bimolecular homolytic substitution (S(H)2), and the third one, *CN transfer, by an addition/elimination mechanism. For all three substrates, the reaction rate was found to increase in the following order for the differently substituted phenyl radicals: CH(3) approximately H < Br approximately Cl approximately COOH < NO(2) approximately CN. This trend does not arise from differences in reaction exothermicities or bond dissociation energies but via lowering the reaction barrier by electronic effects. The stabilization of the transition state is attributed to its increased polar character. A semiquantitative measure of the barrier lowering effect for each substituent is obtained from its influence on the electron affinity of the charged radical, as the calculated (B3LYP/6-31+G(d)) adiabatic electron affinities of the radical model systems (ammonium instead of pyridinium charge site) follow the same trend as the reactivities.     

Evidence of a borderline region between E1cb and E2 elimination reaction mechanisms: a combined experimental and theoretical study of systems activated by the pyridine ring

We report a combined experimental and theoretical study to characterize the mechanism of base-induced beta-elimination reactions in systems activated by the pyridyl ring, with halogen leaving groups. The systems investigated represent borderline cases, where it is uncertain whether the reaction proceeds via a carbanion intermediate (E1cb, A(xh)D(H) + D(N)) or via the concerted loss of a proton and the halide (E2, A(N)D(E)D(N)) upon base attack. Experimentally, the Taft correlation for H/D exchange, in OD(-)/D(2)O with noneliminating substrates (1-methyl-2-(2-Xethyl)pyridinium iodide), is used to predict the expected values of the rate constants for the elimination reactions with N-methylated substrates and F, Cl, Br as the leaving group. The comparison indicates an E1cb irreversible mechanism with F, but the deviation observed with Cl and Br does not allow a conclusive assignment. The theoretical calculations show that for the N-methylated substrate with a fluoride leaving group the elimination proceeds via formation of a moderately stable carbanion. No stable anionic intermediate is instead found when the leaving group is Cl or Br, as well as for any of the nonmethylated species, indicating a concerted elimination. The methylated substrate with Cl shows however only a moderate increase in reactivity compared to the fluorinated substrate, despite the change in mechanism. Very interestingly, our analysis of the computed two-dimensional potential energy surface for the reaction with a F leaving group indeed evidences the lack of a net distinction between the E1cb and E2 reaction paths, which appear to merge smoothly into each other in these borderline cases.     

气相金属催化反应综述

金属催化剂在工业、环境、能源以及生物等过程具有重要的应用.设计具有特定活性、环境友好型以及室温下具有反应活性的催化剂,需要在分子水平对金属催化剂的基元步骤,活性位点的结构以及催化反应微观机理有充分的认识.然而,由于宏观催化剂表面结构异常复杂,催化反应常受到溶剂、压力、金属颗粒团聚、催化剂表面缺陷等因素的干扰,利用现有实验仪器,从微观角度探索金属催化反应机理仍具有较大挑战,因此,对金属催化剂活性位的结构以及反应微观机理的认识还不十分清楚.质谱方法结合现代量子化学理论计算,提供了在气相条件下实验探索化学反应微观机理的有力工具,团簇反应可在隔离外界条件、可控以及可重复条件下进行,可以排除一些难以控制因素的干扰,可在化学键和分子结构水平认识金属活性位的结构以及催化反应的微观机理.气相金属团簇离子可用多种实验方法制备,与反应物分子反应后可利用多种质谱仪器探测,根据实验上所得的具有反应活性的团簇,结合现代量子化学理论模拟,得到金属催化反应的基元步骤以及微观反应机理信息,所得反应机理信息为宏观催化剂的设计提供重要理论研究基础.本综述总结了团簇实验上已经探测到的金属单原子离子、金属团簇、金属氧化物团簇和金属化合物催化的气相反应.反应物分子囊括了大量的无机和有机分子,包括CO,H2,CH4,C2H2,C2H4,C6H6,CH3OH,HCOOH,CH3COOH等.本综述主要介绍了以下三类催化反应:(1)CO催化氧化;(2)CH4催化转化;(3)催化脱羧反应,并重点关注贵金属单原子掺杂团簇独特的催化反应性.单原子催化剂可最大限度地利用有限的贵金属.在化学反应方面,单原子催化剂具有特异的反应活性,选择性以及稳定性.本综述对气相团簇反应中报道的两个重要的贵金属单原子掺杂团簇的催化反应进行了详细介绍:(1)金原子掺杂的AuAl3O3-5+团簇为首次报道的可以利用分子氧催化氧化CO的团簇单原子催化剂,我们对Au原子起催化作用的本质原因进行了介绍:(2)铂原子掺杂的PtAl3O5-7-团簇能利用分子氧催化氧化CO,该研究提出了"电负性阶梯"效应来解释Pt原子催化的微观机理,且此效应有望对大部分贵金属适用.此外,本综述对CO催化氧化反应和CH4催化转化反应的研究现状以及尚未解决的问题进行了剖析.相比CO的催化氧化反应,科学家对CH4催化转化反应机理的认识还不够深入,还需要进一步实验研究,而团簇单原子催化剂有望在此领域有所突破.     

Organofluorosilicates in organic synthesis: XV. Reaction of exo- and endo-5-norbornen-2-ylsilyl derivatives with n-bromosuccinimide. Difference in reactivity between hexacoordinate and tetracoordinate silicon compounds

The reactions of potassium 5-norbornen-2-ylpentafluorosilicate (I) and 5-norbornen-2-yltrimethylsilane (II) with NBS were examined. The former reaction gave 3-nortricyclyl bromide (IV) as the only detectable product, arising from the carbon—silicon bond cleavage. The latter reaction, however, gave 3-bromo-1-nortricyclyltrimethylsilane (V) as the major product, resulting from cleavage of the carbon—hydrogen bond α to silicon, together with IV and an unidentified product. GLC-monitoring of the reactions showed the higher reactivity of the norbornenyl derivative having the leaving group in theendo position irrespective of whether the leaving group is SiF₅ or H. Since no inhibition was observed by the addition of hydroquinone in the dark, the reactions have been regarded as homoallylic electrophilic substitutions. A concerted mechanism seems to be consistent with the experimental data. Cleavage of 1-nortricyclyltrimethylsilane by iodine monochloride to give 1-iodonortricyclene has also been studied.     

The α-Effect and Competing Mechanisms: The Gas-Phase Reactions of Microsolvated Anions with Methyl Formate

The enhanced reactivity of α-nucleophiles, which contain an electron lone pair adjacent to the reactive site, has been demonstrated in solution and in the gas phase and, recently, for the gas-phase S_N2 reactions of the microsolvated HOO^–(H₂O) ion with methyl chloride. In the present work, we continue to explore the significance of microsolvation on the α-effect as we compare the gas-phase reactivity of the microsolvated α-nucleophile HOO^–(H₂O) with that of microsolvated normal alkoxy nucleophiles, RO^–(H₂O), in reactions with methyl formate, where three competing reactions are possible. The results reveal enhanced reactivity of HOO^–(H₂O) towards methyl formate, and clearly demonstrate the presence of an overall α-effect for the reactions of the microsolvated α-nucleophile. The association of the nucleophiles with a single water molecule significantly lowers the degree of proton abstraction and increases the S_N2 and B_AC2 reactivity compared with the unsolvated analogs. HOO^–(H₂O) reacts with methyl formate exclusively via the B_AC2 channel. While microsolvation lowers the overall reaction efficiency, it enhances the B_AC2 reaction efficiency for all anions compared with the unsolvated analogs. This may be explained by participation of the solvent water molecule in the B_AC2 reaction in a way that continuously stabilizes the negative charge throughout the reaction.

Arylsulfonate-based nucleophile assisting leaving groups

[Chemical reaction: See text] The synthesis and unique reactivity of a series of arylsulfonate-based nucleophile assisting leaving groups (NALG) containing oligomeric ether units (including crown ethers) attached to the arylsulfonyl ring in the ortho orientation are described. The reactions of a variety of these ether-containing alkyl sulfonates with metal halides proceeded at substantially greater rates than electronically similar sulfonates. These ether-containing leaving groups also displayed marked selectivity for lithium halides relative to the corresponding sodium and potassium salts in nucleophilic displacement reactions.     

反应类等键反应方法及类反应热动力学参数计算

本文提出了反应类等键反应方法,将通常用于热力学性质计算的等键反应方法推广用于类反应中反应势垒和反应焓变的计算. 对碳氢燃料低温燃烧反应机理中的一类重要反应类：?烷基自由基过氧化氢裂解生成烯烃和HO2自由基的反应势垒和反应焓变进行了计算. 通过对该类16个反应中的5个代表反应分别在不同计算水平HF、DFT、MP2、CCSD(T)的比较计算发现,采用等键反应方法可在较低从头算级别计算得到类反应较高精度的反应势垒,提高了计算的效率和精度. 本文采用反应类等键反应方法在B3LYP/6-311G(d,p)计算水平对该类16个反应进行了反应势垒和反应焓变的计算,并建立了反应势垒和反应能的线性自由能关系：delta V=71.02+0.41?delta E.     

Barbier-Type Addition of Alkyl Halides to Aldehydes Promoted by Pentacarbonyliron

The yield and structure of products of the Barbier-type addition of alkyl halides (perfluorobutyl iodide, allyl bromide, allyl iodide, and hexyl iodide) to para-substituted benzaldehydes in the presence of pentacarbonyliron are essentially determined, on the one hand, by the ability of alkyl halide to be reduced to carbanion and, on the other, by the electrophilicity of the aldehyde reaction center which in turn depends on the nature of para-substituent in the aromatic ring.     

Photochemical reactions of 7-aminocoumarins. 4. Reaction of 4-methyl-7-diethylaminocoumarin with compounds tending to photolytic dissociation

The photochemical reactions of 4-methyl-7-diethylaminocoumarin with a series of alkyl halides including isopropyl iodide, allyl iodide, bromoacetone -bromoethyl acetate, phenacyl bromide, p-bromophenacyl bromide, and chloroacetonitrile, and aryl iodides including iodobenzene, 2-nitroiodobenzene, 3,4-dimethoxyiodobenzene, and 3-iodo-4-methyl-7-diethylaminocoumarin proceed by a radical addition mechanism to give 3-substituted aminocoumarins. A series of 3-substituted 7-aminocoumarins was also obtained as a result of the photochemical reactions of 4-methyl-7-diethylaminocoumarin, with other reagents, having photolabile chemical bonds such as dioxanyl peroxide, phenyl iodosodiacetate, and nitromethane. The luminescence characteristics of the compounds synthesized were studied.For Communication 3, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 460–469, April, 1989.