An investigation of the mechanism of the reation of allyltriethylstannane with bromotrichloromethane by radiofrequency probing and chemically induced dynamic nuclear polarization (CIDNP)

The methods of radiofrequency probing (RFP) and chemically induced dynamic nuclear polarization (CIDNP) have been used to study the mechanism of the reaction of allyltriethylstannane with bromotrichloromethane. The CIDNP effects which have been detected prove the presence of radical stages in this reaction. An assumption has been made about a possible radical pathway for the β-decomposition of elementorganic compounds.     

Towards the truly nonempirical computation of hyperfine interactions: A contribution to the debate on the t-butyl radical

Carefully calibrated large-scale nonempirical CI computations have been performed for the isotropic hyperfine splittings of the t-butyl radical. The results have been used to interpret the effects of out-of-plane vibration of the radical center, with and without coupling to methyl rotations, on the observed splitting at the radical center. In particular, the value computed under rotation-inversion is 39 G, in good agreement with the ESR result of 45 G.     

Spectroscopy and reaction kinetics of HS radicals

A laser-induced fluorescence technique is used to monitor the HS radical concentration. The rate constants at room temperature have been determined for the reaction of HS radical with various added scavengers.     

Synthesis of ellipticine: a radical cascade protocol to aryl- and heteroaryl-annulated[b]carbazoles

[reaction: see text] Imidoyl selanides, synthesized from amides, have been used as radical precursors of imidoyl radicals in cascade reactions. The novel radical cascade has been developed for the simple synthesis of the medicinally important aryl-annulated[b]carbazoles. The protocol has been exemplified with the high-yielding total synthesis of the anticancer alkaloid ellipticine.     

Radical cations in irradiated solid <Emphasis Type="Italic">n</Emphasis>-alkanes and polyethylene

The method of time-resolved magnetic field effect (TR MFE) in recombination fluorescence of spin-correlated radical ion pairs has been used to detect and identify radical cations generated at early stages after the pulse irradiation of polyethylene and tricosane. From analysis of TR MFE curves, the widths of unresolved EPR spectra of radical cations have been determined, and their g factors have been evaluated. The results have demonstrated that, as distinct from n-alkanes, primary radical cations in polyethylene are localized on chemical defects of the polymer chain in a time of about 1 ns or less.     

对甲苯磺酰胺电还原过程的电化学-ESR研究

对一些含硫的镀镍光亮剂电还原反应曾提出过两种反应机理，一种是生成硫酸的机理，一种是脱磺酸（酞）基团的机理．Brook和Crossleyu］认为这类反应是按后一种机理进行的自由基反应，但未对中间产物作出检测．因此目前对反应机理尚无定论．为了阐明还原中间产物与反应本性，本文利用自旅捕集技术与UV光谱研究了对甲基磺欧胺在汞电机上的电还原过程．1实验1．1仪器HDVI－xFD｛－x－Y仅组装CV图测量系统；日本JE巳FElxG波谱仪；xJP七ZI新极谱仪阳春应化所）2751G紫外分光光度计．1．2主要试剂苯亚甲基叔丁基氮氧化物（PBN，由中科…     

Amides as precursors of imidoyl radicals in cyclisation reactions

Amides have been successfully used as precursors of imidoyl radicals for radical cyclisation. The amides have been converted to imidoyl selanides via reaction with phosgene to yield imidoyl chlorides followed by reaction with potassium phenylselanide. Imidoyl selanides were reacted with tributyltin hydride (Bu₃SnH) as the radical mediator with triethylborane or AIBN as initiators to yield imidoyl radicals for cyclisation reactions. Imidoyl radicals have been cyclised onto alkenes to yield 2,3-substituted-indoles and -quinolines and also onto pyrroles and indoles to give bi- and tricyclic heteroarenes.     

Photoinduced Electron Transfer Reactions of alpha-Cyclopropyl- and alpha-Epoxy Ketones. Tandem Fragmentation-Cyclization to Bi-, Tri-, and Spirocyclic Ketones

Reductive photoinduced electron transfer (PET) reactions have been performed with various bicyclic alpha-cyclopropyl-substituted ketones and tertiary amines. The reaction resulted in a regioselective cleavage of one cyclopropyl bond under formation of an exocyclic radical with an endocyclic enolate unit. In the case of bicyclic ketones with an unsaturated side chain, various bicyclic, spirocyclic, and tricyclic products are accessible via radical cyclization, depending on the position of the alkenyl substituent. In addition to triethylamine, N-silylated amines have also been used as electron donors, leading to a variety of compounds, among them are silylated fragmentation products, indicating that a proton is transferred from not only the amine radical cation but also the cationic silyl group. The intramolecular Paternó-Büchi reaction has also been studied for cyclopropane derivatives of the jasmone type leading to tetracyclic oxetanes. Finally, alpha-epoxy-substituted ketones have been investigated under PET conditions, yielding ring-opened products.     

Main-Group Metal Complexes in Selective Bond Formations Through Radical Pathways

Recent years have witnessed remarkable advances in radical reactions involving main-group metal complexes. This includes the isolation and detailed characterization of main-group metal radical compounds, but also the generation of highly reactive persistent or transient radical species. A rich arsenal of methods has been established that allows control over and exploitation of their unusual reactivity patterns. Thus, main-group metal compounds have entered the field of selective bond formations in controlled radical reactions. Transformations that used to be the domain of late transition-metal compounds have been realized, and unusual selectivities, high activities, as well as remarkable functional-group tolerances have been reported. Recent findings demonstrate the potential of main-group metal compounds to become standard tools of synthetic chemistry, catalysis, and materials science, when operating through radical pathways.     

Toward an improved understanding of the glutamate mutase system

High-level quantum chemistry calculations have been used to examine the catalytic reactions of adenosylcobalamin-dependent glutamate mutase (GM) with the natural substrate (S)-glutamic acid. We have also examined the rearrangement of (S)-2-hydroxyglutaric acid, (S)-2-thiolglutaric acid, and 2-ketoglutaric acid, all of which have previously been shown to react as substrates or inhibitors of the enzyme. Our calculations support the notion that the 100-fold difference in kcat between glutamate and 2-hydroxyglutarate is associated with the relatively high energy of the glycolyl radical intermediate compared with the glycyl radical. More generally, calculations of radical stabilization energies for a variety of substituted glycyl radical analogues indicate that modifications at the radical center can profoundly affect the relative stability of the resulting radical, leading to important mechanistic consequences. We find that the formation of a thioglycolyl radical, derived from (S)-2-thiolglutaric acid, is highly dependent on the protonation state of sulfur. The neutral radical is found to be of stability similar to that of the glycolyl radical, whereas the S- form of the thioglycolyl radical is much more stable, thus providing a rationalization for the inhibition of the enzyme by the substrate analogue 2-thiolglutarate. Two possible rearrangement pathways have been examined for the reaction of GM with 2-ketoglutaric acid, for which previous experiments had suggested no rearrangement took place. The fragmentation-recombination pathway is associated with a fragmentation step that is very endothermic (by 102.2 kJ mol-1). In contrast, the addition-elimination pathway has significantly lower energy requirements. An alternative possibility, namely, that 2-ketoglutaric acid is bound in its hydrated form, 2,2-dihydroxyglutaric acid, also leads to a pathway with relatively low energy requirements, suggesting that some rearrangement might be expected under such circumstances.     

Laser flash photolysis and pulse radiolysis study on chemical activity of VP-16 and podophyllotoxin

Time-resolved laser flash photolysis and pulse radiolysis have been used to study the chemical activity of podophyllotoxin(PPT) and etoposide(VP-16). The mechanism of photoioniza-tion of etoposide and podophyllotoxin has been confirmed and illustrated. It is demonstrated that VP-16 and PPT in aqueous solution can be photoionized at 248 nm to give hydrated electron and neutral radical resulting from rapid deprotonation of radical cation of VP-16 and PPT. The quantum yield for the photoionization of VP-16 and PPT with single-photo is 0.21 and 0.61, respectively. In addition, they can react with hydrated electron, hydrogen radical and hydroxyl radical. This will give chemists some advice on synthesizing new derivatives of podophyllotoxin in cancer treatment.     

EPR study of the relationship between ultra high molecular weight polyethylene structure and radicals formed during irradiation with high energy sources

Three different samples of ultra high molecular weight polyethylene have been irradiated with a high energy source (electron beam), and radicals have been generated. Different radical species have been assigned on the basis of their electron paramagnetic resonance spectra. Electron paramagnetic resonance data have been used also to evaluate the amount of each kind of radical that has been generated on different starting materials. The structure of the polymer (number of double bonds or crystallinity) is strictly connected to the response of the sample itself to the irradiation. A rationalization between these different parameters has been performed in order to evaluate the stability of polymer samples toward high energy irradiation processes. Copyright © 2014 John Wiley & Sons, Ltd.     

Azo compounds for free radical crosslinking of polysiloxane stationary phases

There has been much effort spent in recent years developing the technology for free radical crosslinking of polysiloxane polymers to prepare capillary columns coated with thermally stable and nonextractable stationary phases. Organic peroxides have been used extensively as the free radical initiators for the in situ polymerization of the stationary phases. However, these peroxides adversely affect the phase polarity and column activity. Seven azo compounds were studied for crosslinking efficiency. Azo compounds can be used as free radical initiators to prepare nonextractable stationary phases without the adverse effects caused by peroxides.     

Structure and reactivity of addition fragmentation agents in photochemically and thermally induced cationic polymerization

Specially designed allylic onium salts with different hetero‐atoms and various substituent patterns at the allylic double bond have been shown to be very efficient initiators for cationic polymerization. They can be used alone or in conjunction with radical initiators. The mechanism of initiation involves radical formation, radical addition and fragmentation. In some cases, oxidation reactions were found to contribute to the formation of initiating species. In this work, the role of structural parameters onto reactivity is discussed.     

An ab initio and density functional theory study of radical-clock reactions

Density functional theory (DFT) and ab initio (CBS-RAD) calculations have been used to investigate a series of "radical clock" reactions. The calculated activation energies suggest that the barriers for these radical rearrangements are determined almost exclusively by the enthalpy effect with no evidence of significant polar effects. The ring-closure reactions to cyclopentylmethyl radical derivatives and the ring opening of cyclopropylmethyl radicals give different correlations between the calculated heat of reaction and barrier, but the two types of reaction are internally consistent.     

Catalysis of Radical Reactions: A Radical Chemistry Perspective

The area of catalysis of radical reactions has recently flourished. Various reaction conditions have been discovered and explained in terms of catalytic cycles. These cycles rarely stand alone as unique paths from substrates to products. Instead, most radical reactions have innate chains which form products without any catalyst. How do we know if a species added in “catalytic amounts” is a catalyst, an initiator, or something else? Herein we critically address both catalyst‐free and catalytic radical reactions through the lens of radical chemistry. Basic principles of kinetics and thermodynamics are used to address problems of initiation, propagation, and inhibition of radical chains. The catalysis of radical reactions differs from other areas of catalysis. Whereas efficient innate chain reactions are difficult to catalyze because individual steps are fast, both inefficient chain processes and non‐chain processes afford diverse opportunities for catalysis, as illustrated with selected examples.     

Glutathione radical cation in the gas phase; generation, structure and fragmentation

Two different chemical methods have been used to form glutathione radical cations: (1) collision-induced dissociations (CIDs) of the ternary complex [Cu(II)(tpy)(M)]˙(2+) (M = GSH, tpy = 2,2':6',2'-terpyridine) and (2) homolysis of the S-NO bond in protonated S-nitrosoglutathione. The radical cations, M˙(+), were trapped and additional CIDs were performed. They gave virtually identical CID spectra, suggesting a facile interconversion between initial structures prior to fragmentation. DFT calculations at the B3LYP/6-31++G(d,p) level of theory have been used to study interconversion between different isomers of the glutathione radical cation and to examine mechanisms by which these ions fragment. The N-terminal α-carbon-centred radical cation, strongly stabilized by the captodative effect, is at the global minimum, which is 8.5 kcal mol(-1) lower in enthalpy than the lowest energy conformer of the S-centred radical cation. The barrier against interconversion is 18.1 kcal mol(-1) above the S-centred radical.     

Do hydroxyl radical-water clusters, OH(H2O)n, n = 1-5, exist in the atmosphere?

It has been speculated that the presence of OH(H2O)n clusters in the troposphere could have significant effects on the solar absorption balance and the reactivity of the hydroxyl radical. We have used the G3 and G3B3 model chemistries to model the structures and predict the frequencies of hydroxyl radical/water clusters containing one to five water molecules. The reaction between hydroxyl radical clusters and methane was examined as a function of water cluster size to gain an understanding of how cluster size affects the hydroxyl radical reactivity.     

Radical reactions involving esters of fumaric acid—I. Copolymerizations

¹⁴C-labelled samples of diethyl-, ethyl n-hexyl- and di-n-hexyl fumarates have been used in studies at 60° of their radical copolymerizations with styrene and with vinyl acetate. Changing the diluent from benzene to dimethylformamide in some of the copolymerizations had no effect on the compositions of the copolymers. Monomer reactivity ratios have been calculated for most of the systems; comparisons have been made of the reactivities of the fumarate esters towards the polyvinyl acetate radical.     

Phase Transfer Catalyzed Dehydrogenation Synthesis of Azo Ureas From Aryl Substituted Semicarbazide

Phase transfer catalyzed dehydrogenation synthesis azo Ureas Compounds have been studied. Ten of the compounds were Synthesized by the reaction of aryl Substituted Semicarbazied Compounds with phase transfer catalyst–“Galvinoxyl” radical between two phase under mild Conditions. The products are obtained in 90–99(%) yield. Their structure are identified by elemental analysis, IR, ¹HNMR, MS spectra. A possible mechanism is suggested by a “Galvinoxyl” radical act on aryl substituted semicarbazide formed azo compounds.

Synthesis of bis (Substituted phenyl) Carbodiazone Compounds (ArN = NCON = NAr') have been reported¹, As another part of our studies, 1, 4-di-Substituted azo Compounds (ArNHCON=NAr') Were Synthesized by the reaction of Substituted Semicarbazide Compounds With a phase transfer Catalyst-“Galvinoxyl” radical, which has been acted as a radical Scavenger², yet, “Galvinoxyl” radical used as phase transfer Catalyst have not been reported so far. Azo Compounds have been widely utilized as dyes and analytical reagents. They can also be used as material of non - linear optics, optic information storring material in Laser dish and dyes with oil solubility in photochromy in modern technology^3,4. Recently, many noteworthy Studies show that azobenzene derivative Possess Very good optic remembering and photoelectric properties⁵, optical Switching and Image storege by means of Azobenzene Liquid - Crystal Films⁶. The preparation of the azo compounds which have the Connection of -N = N- and hydrocarbyl group have been described in many Literatures^7,8.. In this paper, a new reaction of phase transfer Catalyzed dehydrogenation of aryl Substituted Semicarbazide