Aminosulfenates in the electrophilic addition reactions

The reactions of methyl and ethyl diethylaminosulfenates and ethyl piperidinylsulfenate with cyclohexene and norbornene in the presence of chloro- or bromotrimethysilanes were studied.     

Phosphinates as new electrophilic partners for cross-coupling reactions

The use of enol phosphinates as electrophiles for cross-coupling reactions has been explored. Both boronic acids (Suzuki-Miyaura reaction) and stannanes (Stille reaction) couple efficiently with lactam derived phosphinates.     

A theoretical study of electrophilic reactions

The electronic structures of protonated formyl and acetylium cations and their deprotonation paths leading to HCO⁺, COH⁺ and CH₃CO⁺have been studied by means of ab initio calculations. The results support Olah's theory that dipositive species can be the de facto reagents in electrophilic reactions.     

Investigation of the electrophilic reactions of 5-hydroxypyrimidine

The possibility of the electrophilic substitution of various positions of the 5-hydroxypyrimidine ring in a weakly basic medium is demonstrated in the case of aminomethylation and diazo coupling. It was found that the ortho positions of 5-hydroxypyrimidine are more reactive than the para position with respect to the hydroxy group.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 393–396, March, 1982.     

Phase-transfer catalysis in reactions of electrophilic aromatic substitution

Electrophilic substitution in aromatic compounds under conditions of phase-transfer catalysis is considered. Catalysts of phase transfer of electrophilic reagents are used; their efficiency and the mechanism of their action in organic solvent-water systems are discussed.This review is based on materials of the report delivered at the Conference Phase-Transfer Catalysis. New Ideas and Methods (March 1994).Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1895–1900, October, 1995.     

A new method for the activation of ethyl benzenesulfenate in electrophilic addition reactions

Reactions of unsaturated compounds with the PhSOEt-SOHal₂ and PhSOEt-Me₃SiHal systems (Hal = Cl or Br) were proposed as a new route to haloalkyl phenyl sulfides. With acyclic and mono- and bicyclic alkenes and dienes as examples, the regio- and stereoselectivity of the reactions were studied.     

New electrophilic reactions of 2,2′-bisindolyls with acid chlorides and carbodienophiles

Some new acylation and cyclization reactions of 2,2′-bisindolyls 1, 2 are described. The product patterns constitute acyl derivatives 3, 4, 5 and an aldehyde 7 , indolo[2,3-a]carbazoles 6, 14, 17, 19, 20 and cyclopentadiindoles 22 and 24 . In the reaction with aryne or diazotated anthranilic acid, a 3-benzoylindole derivative 9 and phenylindolyl azo dye 10 are formed. N-methylmaleimide reacts with 2,2′-bisindolyl 2 via Michael type addition, dehydrogenation and cyclization to several functionalized or anellated indole derivatives 11, 12, 13 and 14 , respectively.     

Spontaneous copolymerizations in the reactions of electronrich dienes with electrophilic olefins

The spontaneous thermal reactions of electron-rich dienes with electrophilic olefins lead to both [4+2] cycloadducts and copolymers. The mechanism proposed for the initiation of the copolymerization involves the formation of a 2-hexene-1, 6-diradical. Structure-reactivity relationships are discussed.     

Enzymatic reactions in supercritical gases

The enzyme polyphenol oxidase has been found to be catalytically active in supercritical carbon dioxide and fluoroform: it readily oxidizesp-cresol andp-chlorophenol to their correspondingo-benzoquinones.     

Steric factor in electrophilic substitution reactions of aromatic hydrocarbons

Summary In supplementation of previous work on halomethylation reactions, the nitration, chlorination, bromination, and iodination of toluene, ethylbenzene, and eumene were investigated. By the method of oxidizing the derivatives formed, the relative amounts of o- and p-isomers were determined quantitatively, and the results reveal the steric effects of substituents in the aromatic nucleus on orientation in all of the above-mentioned electrophilic substitution reactions.     

Gas-phase electrophilic addition reactions of chlorinated alkyl ions

Chemical ionization was used to study gas-phase electrophilic addition reactions of chloromethyl ions ([CH_xCl_3-x]⁺, x = 0, 1, 2) with a number of substituted benzenes (C₆H₅Y, Y = NH₂, OH, CHO, CN, NO₂). Mass-analyzed ion kinetic energy spectrometry was used to characterize the reaction products with respect to the site of electrophilic addition (ring v. substituent). In some cases, examination of secondary reaction products (ion–molecule adduct which has undergone an elimination reaction in the ion source) aided in establishing the original site of electrophilic addition. Aniline, benzonitrile and nitrobenzene exhibited preferential substituent interaction, while phenol and benzaldehyde gave a mixture of ring and substituent reaction products. These gas-phase results differ considerably from solution-phase Friedel–Crafts alkylation; however, they are consistent with the notion of preferential σ-bond formation at polarizable centers of negative charge.     

Potential applications of passive sampling for monitoring non-polar industrial pollutants in the aqueous environment in support of REACH

Possible roles of passive sampling within the context of the European REACH legislation are discussed. Passive samplers can provide information on environmental concentrations, fate and behaviour of substances of concern. They can potentially replace biota in the assessment of bioavailability, having advantages including lower cost and variability, and greater repeatability and acceptability on ethical grounds. Where remedial actions (e.g., product withdrawal, replacement or redesign) may be required, wrong decisions are potentially very costly. Against this background it may be possible to develop strategies based on passive sampling that will protect the environment from potential damage whilst minimising operational costs.