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Abstraction, of atoms

Arynes are intermediates in certain reactions of aromatic compounds, especially in some nucleophilic substitution reactions. They are generated by abstraction of atoms or atomic groups from adjacent positions in the nucleus and react as strong electrophiles and as dienophiles in fast addition reactions. An example of a reaction occurring via an aryne is the amination of o-chlorotoluene (1) with potassium amide in liquid ammonia. According to the mechanism given, the intermediate 3-methylbenzyne (2) is first formed and subsequent addition of ammonia to the triple bond yields o-amino-toluene (3) and m-aminotoluene (4). It was found that partial rearrangement of the ortho to the meta isomer actually occurs. [Pg.121]

The reaction of 01D above can be shown to be important as the ultraviolet photolysis of N02, which gives rise to 01D,62 results in the production of IO in the presence of CF3I.26 The abstraction of atomic oxygen from N02 by I(52Ph) would be an endothermic process. Thus although reaction (99) appears to be established, its contribution following the photolysis of CF3/03 mixtures may not be quantitatively assessed. The importance of reaction (98) therefore remains in doubt. [Pg.67]

Exercise 10-28 Bromotrichloromethane, BrCC 3, adds to 1-octene by a radical-chain mechanism on heating in the presence of a peroxide catalyst. Use the bond-energy tables to devise a feasible mechanism for this reaction and work out the most likely structure for the product. Show your reasoning. Show the most likely product of addition of BrCCI3 to 1-octyne. [Note Radical-chain reactions involve abstraction of atoms, not abstraction of groups.]... [Pg.390]

Abstraction of atoms or free radicals from stable molecules... [Pg.234]

The modern view of matter developed from John Dalton s theory which, for the first time, combined the abstractions of atom and element into a single practically useful concept, albeit at the cost of unwanted diversity. Resolution of the dilemma, by postulating hydrogen as the common building block of more complex atoms, was resisted so fiercely that the alleged author, William Prout, had to publish his proposal anonymously. The importance of number was at the heart of his hypothesis. Despite experimental evidence which contradicted the notion, Prout s hypothesis was not without support and remained alive until its final vindication in the discovery of isotopes and atomic number, which ironically also signalled the demise of atomic particle theory. [Pg.163]

Atom abstraction occurs when a dissociation reaction occurs on a surface in which one of the dissociation products sticks to the surface, while another is emitted. If the chemisorption reaction is particularly exothennic, the excess energy generated by chemical bond fomiation can be chaimelled into the kinetic energy of the desorbed dissociation fragment. An example of atom abstraction involves the reaction of molecular halogens with Si surfaces [27, 28]. In this case, one halogen atom chemisorbs while the other atom is ejected from the surface. [Pg.295]

Finally, it should also be clear that ER reactions do not necessarily yield a gas-phase product. The new molecule may be trapped on the surface. There is evidence for an ER mechanism in the addition of incident Ft atoms to ethylene and benzene on Cii(l 11) [91], and in the abstraction of Ft atoms from cyclohexane by incident D atoms [92], and the direct addition of Ft atoms to CO on Rii(OOl) [93]. [Pg.914]

Abstract. Molecular dynamics (MD) simulations of proteins provide descriptions of atomic motions, which allow to relate observable properties of proteins to microscopic processes. Unfortunately, such MD simulations require an enormous amount of computer time and, therefore, are limited to time scales of nanoseconds. We describe first a fast multiple time step structure adapted multipole method (FA-MUSAMM) to speed up the evaluation of the computationally most demanding Coulomb interactions in solvated protein models, secondly an application of this method aiming at a microscopic understanding of single molecule atomic force microscopy experiments, and, thirdly, a new method to predict slow conformational motions at microsecond time scales. [Pg.78]

Step 4 Abstraction of a hydrogen atom from hydrogen bromide by the free radical formed m step 3... [Pg.244]

An additional effect of the use of an organic medium in the catalyst preparation is creation of mote defects in the crystalline lattice when compared to a catalyst made by the aqueous route (123). These defects persist in the active phase and are thought to result in creation of strong Lewis acid sites on the surface of the catalysts (123,127). These sites ate viewed as being responsible for the activation of butane on the catalyst surface by means of abstraction of a hydrogen atom. [Pg.454]

Vulcanization. Generally this is carried out by the action of peroxides, which can cross-link the chains by abstracting hydrogen atoms from the methyl groups and allowing the resulting free radicals to couple into a cross-link. Some varieties of polysdoxanes contain some vinylmethyl siloxane units, which permit sulfur vulcanization at the double bonds. Some Hquid (short-chain) siHcones can form networks at room temperature by interaction between thek active end groups. [Pg.470]

Descriptions of Physical Objects, Processes, or Abstract Concepts. Eor example, pumps can be described as devices that move fluids. They have input and output ports, need a source of energy, and may have mechanical components such as impellers or pistons. Similarly, the process of flow can be described as a coherent movement of a Hquid, gas, or coUections of soHd particles. Flow is characterized by direction and rate of movement (flow rate). An example of an abstract concept is chemical reaction, which can be described in terms of reactants and conditions. Descriptions such as these can be viewed as stmctured coUections of atomic facts about some common entity. In cases where the descriptions are known to be partial or incomplete, the representation scheme has to be able to express the associated uncertainty. [Pg.531]

Large ring heterocyclic radicals are not particularly well known as a class. Their behavior often resembles that of their alicyclic counterparts, except for transannular reactions, such as the intramolecular cyclization of 1-azacyclononan-l-yl (Scheme 1) (72CJCH67). As is the case with alicyclic ethers, oxepane in the reaction with r-butoxy radical suffers abstraction of a hydrogen atom from the 2-position in the first reaction step (Scheme 2) (76TL439). [Pg.19]

Treatment of 2-methylthiirane with t-butyl hydroperoxide at 150 °C in a sealed vessel gave very low yields of allyl disulfide, 2-propenethiol and thioacetone. The allyl derivatives may be derived from abstraction of a hydrogen atom from the methyl group followed by ring opening to the allylthio radical. Percarbonate derivatives of 2-hydroxymethylthiirane decompose via a free radical pathway to tar. Acrylate esters of 2-hydroxymethylthiirane undergo free radical polymerization through the double bond. [Pg.167]

Fig. 1. Examples of temperature dependence of the rate constant for the reactions in which the low-temperature rate-constant limit has been observed 1. hydrogen transfer in the excited singlet state of the molecule represented by (6.16) 2. molecular reorientation in methane crystal 3. internal rotation of CHj group in radical (6.25) 4. inversion of radical (6.40) 5. hydrogen transfer in halved molecule (6.16) 6. isomerization of molecule (6.17) in excited triplet state 7. tautomerization in the ground state of 7-azoindole dimer (6.1) 8. polymerization of formaldehyde in reaction (6.44) 9. limiting stage (6.45) of (a) chain hydrobromination, (b) chlorination and (c) bromination of ethylene 10. isomerization of radical (6.18) 11. abstraction of H atom by methyl radical from methanol matrix [reaction (6.19)] 12. radical pair isomerization in dimethylglyoxime crystals [Toriyama et al. 1977]. Fig. 1. Examples of temperature dependence of the rate constant for the reactions in which the low-temperature rate-constant limit has been observed 1. hydrogen transfer in the excited singlet state of the molecule represented by (6.16) 2. molecular reorientation in methane crystal 3. internal rotation of CHj group in radical (6.25) 4. inversion of radical (6.40) 5. hydrogen transfer in halved molecule (6.16) 6. isomerization of molecule (6.17) in excited triplet state 7. tautomerization in the ground state of 7-azoindole dimer (6.1) 8. polymerization of formaldehyde in reaction (6.44) 9. limiting stage (6.45) of (a) chain hydrobromination, (b) chlorination and (c) bromination of ethylene 10. isomerization of radical (6.18) 11. abstraction of H atom by methyl radical from methanol matrix [reaction (6.19)] 12. radical pair isomerization in dimethylglyoxime crystals [Toriyama et al. 1977].
We start with the reaction of abstraction of a hydrogen atom by a CH3 radical from molecules of different matrices (see, e.g., Le Roy et al. [1980], Pacey [1979]). These systems were the first to display the need to go beyond the one-dimensional consideration. The experimental data are presented in table 2 together with the barrier heights and widths calculated so as to fit the theoretical dependence (2.1) with a symmetric gaussian barrier. [Pg.94]

Abstraction of an H atom from crystalline and glass-like matrices of saturated organic compounds (RH) gives rise to formation of a matrix radical R,... [Pg.110]

Radicals also rapidly abstract hydrogen atoms from many types of solvents, and most radicals are highly reactive toward oxygen. [Pg.665]

Important differences are seen when the reactions of the other halogens are compared to bromination. In the case of chlorination, although the same chain mechanism is operative as for bromination, there is a key difference in the greatly diminished selectivity of the chlorination. For example, the pri sec selectivity in 2,3-dimethylbutane for chlorination is 1 3.6 in typical solvents. Because of the greater reactivity of the chlorine atom, abstractions of primary, secondary, and tertiary hydrogens are all exothermic. As a result of this exothermicity, the stability of the product radical has less influence on the activation energy. In terms of Hammond s postulate (Section 4.4.2), the transition state would be expected to be more reactant-like. As an example of the low selectivity, ethylbenzene is chlorinated at both the methyl and the methylene positions, despite the much greater stability of the benzyl radical ... [Pg.703]

Bromotrichloromethane can also be used effectively in the addition reaction. Because of the preferential abstraction of bromine, a trichloromethyl unit is added to the less substituted carbon atom of the alkene ... [Pg.712]


See other pages where Abstraction, of atoms is mentioned: [Pg.801]    [Pg.265]    [Pg.377]    [Pg.137]    [Pg.132]    [Pg.801]    [Pg.265]    [Pg.377]    [Pg.137]    [Pg.132]    [Pg.914]    [Pg.1597]    [Pg.365]    [Pg.8]    [Pg.443]    [Pg.431]    [Pg.47]    [Pg.415]    [Pg.437]    [Pg.348]    [Pg.459]    [Pg.455]    [Pg.22]    [Pg.144]    [Pg.27]    [Pg.47]    [Pg.692]    [Pg.697]    [Pg.703]    [Pg.712]   


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Abstraction of Atoms and Radicals

Abstraction of H atoms

Abstraction of a halogen atom

Abstraction of hydrogen atoms

Atom Abstraction and Combination of the Resulting Radical with a Second Metal

Atom abstraction-induced ring-opening polymerization of chalcogenido-bridged metallocenophanes

Atom abstractions

Hydrogen Atom Abstraction at C5 Formation of Purine 5,8-Cyclonucleosides

The Abstraction of Hydrogen and Halogen Atoms

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