High Reactivity of CH2 Radical in an AR–CH4 Post-Discharge

Plasma Chemistry and Plasma Processing - This work is devoted to the study of the reactivity of CH 2 radical in the post-discharge of an Ar–CH 4 microwave plasma. These radicals are...     

Reactivity of Benzamide toward Sulfonylation

Russian Journal of Organic Chemistry - The ranges of variation of the rate constant (0.031– 0.153 L·mol–1·s–1), energy of activation (21– 55 kJ/mol), and entropy...     

Reactivity of Radical Cations of Trimesitylphosphine

Anodic oxidation of trimesitylphosphine in the presence of typical nucleophilic reactants is studied by cyclic voltammetry. The results and the literature data suggest that the manifestation of radical properties is more typical for radical cations of trimesitylphosphine, because, when realizing an electrophilic path of reacting, additional energy is needed for altering the configuration of radical cations of trimesitylphosphine.     

Understanding Reactivity Patterns of Radical Cations

Over the last 15 years electron transfer activation has emerged as a valuable concept for accomplishing novel reactions and has found widespread application in the selective transformation of increasingly complex molecules. This review presents in a conceptualized manner the vast number of radical cation reactions obtained after chemical, electrochemical, and photoinduced one-electron oxidation. To familiarize the reader with the concepts of electron transfer a simple and straightforward classification of radical cation reactions has been devised to allow the presentation of a manifold of reactions in a readily understandable manner. Whenever possible, thermochemical and kinetic data are provided.     

Reactivity of trimethylcyanosilane toward the surface of silica

The reaction of the surface of silica with (CH₃)₃SiCN vapor was studied by IR spectroscopy. It was established that the chemisorption of trimethylcyanosilane belongs to the processes of electrophilic substitution of a proton in free silanol groups. The activation energy, calculated from the kinetic curves, amounts to 22±1 kJ/mole of grafted trimethylsilyl groups.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 23, No. 1, pp. 117–120, January–February, 1987.     

Reactivity of Polysaccharide Aldehydes toward N-Nucleophiles

The conversion of aldehyde groups in polysaccharide aldehydes to azomethine groups in reactions with amines and hydrazine derivatives was studied in relation to the structure of polysaccharide aldehyde and reaction conditions.     

Reactivity of Phosphaalkenes toward Carbene Complexes

Reaction of phosphaalkenes RP=C(NMe 2 ) 2 (R = t -Bu, Me 3 Si), featuring an inverse distribution of electron density about the P--C double bond, with Fischer carbene complexes [(CO) 5 M=C(OEt)Ar] (Ar=Ph, 2-MeC 6 H 4 , 2-MeOC 6 H 4 , M = Cr, W) afforded a mixture of complexes [(CO) 5 M{P(R)=C(NMe 2 ) 2 }] and [(CO) 5 M{P(R)=C(OEt)Ar}]. The treatment of phosphaalkene HP=C(NMe 2 ) 2 with compound [(CO) 5 W=C(OEt)(2-MeOC 6 H 4 )] gives rise to the formation of an ( E / Z )-mixture of [(CO) 5 W{P(CH(NMe 2 ) 2 )=C(OEt)(2-MeOC 6 H 4 )}].     

Reactivity of digallane toward nitrogen-containing compounds

The reactions of [LGa–GaL] (L = dpp-bian = 1,2-bis[(2,6-di-isopropylphenyl)imino]acenaphthene) with ammonia and pyrrolidine in toluene lead to the formation of adducts [L(NH₃)Ga–Ga(NH₃)L], [L(HNC₄H₈)Ga–GaL] and [L(HNC₄H₈)Ga–Ga(HNC₄H₈)L], respectively. In contrast, the reaction between crystalline digallane and an excess of pyrrolidine leads to the formation of compound [LGa(NC₄H₈)(HNC₄H₈)]. The complex [LGa(C₅H₅N)(μ-O)Ga(C₅H₅N)L] was obtain from reaction of digallane with N₂O in the presence of pyridine.     

Reactivity of Arylhydrazones toward Molecular Oxygen

The kinetics and mechanism of reaction of arylhydrazones with molecular oxygen were studied by gas volumetry. The reaction rate was studied in relation to the structure of arylhydrazone and kind of the solvent. The inhibiting power of the compounds toward initiated oxidation of ethylbenzene was evaluated, and the most effective compounds were found, judging from the ratio of the rate constants of the reactions with molecular oxygen and with peroxy radicals arising in the course of ethylbenzene oxidation.     

Free Radical Reactivity of a Phosphaalkene Explored Through Studies of Radical Isotopologues

Muonium (Mu), an H atom analogue, is employed to probe the addition of free radicals to the P=C bond of a phosphaalkene. Specifically, two unprecedented muoniated free radicals, MesP^.?CMu(Me)₂ ( 1 a , minor product) and MesPMu?C^.Me₂ ( 1 b , major product), were detected by muon spin spectroscopy (μSR) when a solution of MesP=CMe₂ ( 1 : Mes=2,4,6‐trimethylphenyl) was exposed to a beam of positive muons (μ⁺). The μ⁺ serves as a source of Mu (that is, Mu=μ⁺+e^?). To confirm the identity of the major product 1 b , its spectral features were compared to its isotopologue, MesPH‐C^.(Me)CH₂Mu ( 2 a ). Conveniently, 2 a is the sole product of the reaction of MesPH(CMe=CH₂) ( 2 ) with Mu. For all observed radicals, muon, proton, and phosphorus hyperfine coupling constants were determined by μSR and compared to DFT‐calculated values.     

Umpolung Reactivity of Aldehydes toward Carbon Dioxide

Carbon dioxide is an intrinsically stable molecule. Therefore, its activation requires extra energy input in the form of reactive reagents and/or activated catalysts and, often, harsh reaction conditions. Reported here is a direct carboxylation reaction of aromatic aldehydes with carbon dioxide to afford α‐keto acids as added‐value products. In situ generation of a reactive cyanohydrin was the key to the successful carboxylation reaction under operationally mild reaction conditions (25–40 °C, 1 atm CO₂). The resulting α‐keto acids served as a platform for α‐amino acid synthesis by reductive amination reactions, illustrating the chemical synthesis of essential bioactive molecules from carbon dioxide.     

Reactivity of ketene dithiolates toward alkyl bromides

The reactivity of barbituric/thiobarbituric ketene dithiolates with bromoacetic ester and phenacyl bromide is studied. J. Heterocyclic Chem., (2011).     

Reactivity of aromatic compounds toward diphenylcarbonyl oxide

The reactivity of organic compounds (PhH, PhMe, PhF, PhCl, PhOH, PhOEt, PhCHO, Ph₂CO, PhCN, Ph₂S, Ph₂SO, Ph₂SO₂, andp-Me₂C₆H₄) toward diphenylcarbonyl oxide Ph₂COO was characterized by thek ₃₃/k ₃₁ ratio, wherek ₃₃ andk ₃₁ are the rate constants for the reactions of Ph₂COO with the arene and diphenyldiazomethane Ph₂CN₂, respectively. The values ofk ₃₃/k ₃₁ vary from 2.6·10⁻³ (PhCN) to 0.65 (Ph₂S) (70°C, MeCN). The reaction is preceded by formation of a complex with charge transfer from a substrate to Ph₂COO. In the reactions with aromatic substances (except for Ph₂SO, PhCHO, and Ph₂CO), carbonyl oxide behaves as an electrophile. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2197–2201, November, 1998.     

Reactivity of diacyloxyiodobenzenes toward trivalent phosphorus nucleophiles

The reaction of diacyloxyiodobenzenes and tetravalent phosphorus nucleophiles was investigated. It was established that both H‐phosphonates and secondary phosphine oxides react with diacetoxyiodobenzene in alcohols in the presence of sodium alcoholates yielding trialkyl phosphates and alkyl phosphinates respectively. For this transformation reactive intermediate 6 is proposed. In contrast to this, the treatment of diacetoxyiodobenzene with 3 equiv of sodium diisopropyl phosphite in THF produces diisopropyl 1‐(diisopropoxyphosphinyl)ethylphosphonate with excellent yield. It was found that diacyloxyiodobenzene/PR₃ system may serve as an acylating agent; the acylation process can proceed via carboxylic acid anhydride or acylphosphonium salt 17 depending on the protocol used. New very efficient method for synthesis of 2,4,6‐trimethylbenzoic anhydride was developed. © 2003 Wiley Periodicals, Inc. Heteroatom Chem 14:352–359, 2003; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/hc.10161     

Reactivity of Mitsunobu reagent toward carbonyl compounds

[reaction: see text] The nitrogen-based nucleophile generated from azodicarboxylate and triphenylphosphine displayed an excellent reactivity toward carbonyl compounds to generate a variety of different final products depending on the substituent pattern on the carbonyl carbon. From the structures of these adducts, a straightforward mechanistic interpretation for the formation of different products is provided.     

OH自由基总反应性的实地测量

OH自由基作为大气氧化性的重要衡量指标,其去除途径仍无法完全准确地被量化,OH自由基总反应性作为描述OH自由基总去除能力和大气氧化性的重要参数,是OH自由基收支闭合分析的关键参数.OH自由基活性高、寿命短,其反应活性的准确测量具有挑战性.本综述总结了OH自由基总反应性的实地测量方法,并对移动注射-激光诱导荧光法、闪光光解-激光诱导荧光法、化学离子质谱法和相对反应活性法四种方法的测量原理、仪器架构等进行了系统阐述,综合分析认为闪光光解-激光诱导荧光法是目前OH自由基总反应性测量技术的发展方向.同时进一步总结了OH自由基总反应性在城市、森林和郊区等大气环境下的化学行为等,并对研究难点和可能的重点研究方向进行了探讨.     

Reactivity of the 1,2-Diphenytethyl Radical in a Solvent Cage

The 1,2-diphcnylethyl radical and derivatives were generated from photolysis of tran-f-stilbene and its derivatives 1–13 with secondary amines as quenchers. The 1,2-diphenylelhyl radicals that escaped from the solvent cage were trapped by 2-methyl-2-nitrosopropane (MNP) and were detected by the HPLCEPR method. The yield of the spin adduct is greater for tertiary amines. The smaller yields of the spin adduct formed from secondary amines are ascribed to greater reactivities of the 1,2-diphenylethyl and dialkylamino radicals within the solvent cage.     

三接触弯曲构型的蓝移氢键CH3…Y的理论研究

运用量子化学从头算方法, 在MP2/6-311＋＋G(d,p), MP2/6-311＋＋G(2df,2p), MP2/6-311＋＋G(3df,3pd)和QCISD/6-311＋＋G(d,p)水平上, 研究了CH₃F, CH₃Cl和CH₃Br作为质子给体与Cl^－, Br^－作为质子接受体形成的氢键CH₃…Y. 计算结果表明: 6种复合物中C—H键收缩, 伸缩振动频率增大, 形成蓝移氢键. 分子中原子(Atoms in Molecules, AIM)分析表明, 这些复合物的电子密度拓扑性质与普通氢键有着本质的不同, 在Y…H之间不存在键临界点, 而在Y与C之间存在键临界点, 因此这些相互作用严格地不能称为氢键. 自然键轨道(Natural bond orbital, NBO)分析表明, 在这些复合物中弯曲的CH…Y的特殊结构使得分子间超共轭n(Y)®σ*(C—H)减小到可以忽略; 质子接受体的电子密度没有转移到σ*(C—H)上, 而是转移到了σ*(C—X) (X＝F, Cl, Br)上; 存在一定程度的重杂化; 分子内超共轭相互作用减小使得σ*(C—H)的电子密度减少. 这些因素共同导致C—H伸缩振动频率的蓝移.     

Reactivity of the CHBr2+ dication toward molecular hydrogen

Structural aspects as well as the stability and reactivity of the CHBr(2+) dication are studied both experimentally and theoretically. Translational energy distributions of the CHBr(+) products from charge transfer between CHBr(2+) and Kr indicate that the dication exists in two isomeric forms, H-C-Br(2+) and C-Br-H(2+). In the reaction of CHBr(2+) with H(2), the dominant channel corresponds to proton transfer leading to CBr(+) + H(3)(+). Other reaction channels involve the formation of the intermediates CH(3)Br(2+) and CH(2)BrH(2+), respectively. Both of the latter dications can either lose a proton to form CH(2)Br(+) or undergo a spin-isomerization followed by cleavage of the C-Br bond. The proposed mechanisms are supported by DFT calculations and deuterium labeling experiments.