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The -Hydrogen Abstraction

The stability of the metal—alkyl bond toward )S-hydrogen abstraction depends on the metal, its valency state and, very importantly, on the ligand environment. Conditions have been found which provide the transition metals of the left-hand end of the transition-metal series with a relatively high stability Ti,V, Cr, Mo can build good polymerization catalysts, and these have found industrial application for the production of polyethylene and copolymers. [Pg.4]

A different pattern is found with the right-hand end of the transition-metal series. These metals are much more prone to -hydrogen abstraction from an attached alkyl group. This is why complexes based on these metals — e.g. Ni (16) or Rh (17) — are particularly well suited [Pg.4]

Of these two routes only the first has been successful so far. Active oligomerization catalysts have been reported to produce linear olefins in the range of interest th consist of Ti(IV) or Zr(IV) compounds in combination with aluminum alkyls (see Section 3). [Pg.5]

The lability of many transition metal—alkyl compounds toward reduction is a further feature in this type of catalysis. Formally, the reaction may be written  [Pg.5]

This mechanism has been corroborated by the isolation of a binuclear zirconium (IV) complex [Pg.6]


NBS can also be used to brominate alkanes. For example, cyclopropane, cyclopentane, and cyclohexane give the corresponding bromides when irradiated in a solution of NBS in dichloromethane. Under these conditions, the succinimidyl radical appears to be involved as the hydrogen-abstracting intermediate ... [Pg.706]

Another reagent which effects chlorination by a radical mechanism is f-butyl hypochlorite. The hydrogen-abstracting species in the chain mechanism is the f-butoxy radical. [Pg.706]

The addition of S—H compounds to alkenes by a radical-chain mechanism is a quite general and efficient reaction. The mechanism is analogous to that for hydrogen bromide addition. The energetics of both the hydrogen abstraction and addition steps are favorable. Entries 16 and 17 in Scheme 12.5 are examples. [Pg.714]

Substitution, addition, and group transfer reactions can occur intramolecularly. Intramolecular substitution reactions that involve hydrogen abstraction have some important synthetic applications, since they permit functionalization of carbon atoms relatively remote from the initial reaction site. ° The preference for a six-membered cyclic transition state in the hydrogen abstraction step imparts position selectivity to the process ... [Pg.718]

For a given hydrogen donor S—H, replacement by S—D leads to a decreased rate of reduction, relative to nonproductive decay to the ground state." This decreased rate is consistent with a primary isotope effect in the hydrogen abstraction step,... [Pg.754]

Instead of using thermal energy to trigger the hydrogen abstraction mechanism, photo-induced reactions can be also be used to successfully crosslink acrylic PSAs [74-76], In this case, photoactive compounds, such as for example those containing benzophenone, anthraquinone or triazine nuclei are compounded with the polymer or copolymerized as one of the monomers. After drying, the adhesive... [Pg.495]

In most cases the carbon radical formed in the hydrogen abstraction step 2 will react with the radical R formed in the homolysis of the X—R bond. However, a cage reaction does not seem to be involved in this step. This has been established in the nitrite photolysis and probably applies to hypohalites as well. In the lead tetraacetate reaction, the steps following the oxyradical formation leading to tetrahydrofuran derivatives are less clear. [Pg.240]

The hydrogen abstraction from —SH groups is faster than from —OH groups. Hebeish et al. [9] and Misra et al. [10,11] reported the chain-transfer method of initiation of graft copolymerization onto cellulosic substrates with azobisisobutyronitrile (AIBN) and benzoyl peroxide (BPO) as initiators. [Pg.503]

The hydrogen abstraction addition ratio is generally greater in reactions of heteroatom-centered radicals than it is with carbon-centered radicals. One factor is the relative strengths of the bonds being formed and broken in the two reactions (Table 1.6). The difference in exothermicity (A) between abstraction and addition reactions is much greater for heteroatom-centered radicals than it is for carbon-centered radicals. For example, for an alkoxy as opposed to an alkyl radical, abstraction is favored over addition by ca 30 kJ mol"1. The extent to which this is reflected in the rates of addition and abstraction will, however, depend on the particular substrate and the other influences discussed above. [Pg.35]

For allyl acetate a significant deuterium isotope effect supports the hydrogen abstraction mechanism (Scheme 6,31).183 Allyl compounds with weaker CTT-X bonds (113 X=SR, S02R, Bi etc.) may also give chain transfer by an addition-fragmentation mechanism (Section 6.2.3). [Pg.319]

It is thus anticipated that compressive stress inhibits while tensile stress promotes chemical processes which necessitate a rehybridization of the carbon atom from the sp3 to the sp2 state, regardless of the reaction mechanism. This tendency has been verified for model ring-compounds during the hydrogen abstraction reactions by ozone and methyl radicals the abstraction rate increases from cyclopropane (c3) to cyclononane (c9), then decreases afterwards in the order anticipated from Es [79]. The following relationship was derived for this type of reactions ... [Pg.105]

The hydrogen abstraction from the Si-H moiety of silanes is fundamentally important for these reactions. Kinetic studies have been performed with many types of silicon hydrides and with a large variety of radicals and been reviewed periodically. The data can be interpreted in terms of the electronic properties of the silanes imparted by substituents for each attacking radical. In brevity, we compared in Figure 1 the rate constants of hydrogen abstraction from a variety of reducing systems by primary alkyl radicals at ca. 80°C. ... [Pg.124]

The acyl selenide 19 affords the decarbonylated )S-lactam in good yield. A N-hydroxypyridine-2-thione ester 20 is used in the key step to construct the chiral cis-cyclopropane structure in compounds designed as antidopaminergic agents. The observed high cis selectivity is due to the hydrogen abstraction from the sterically demanding (TMSlsSiH, which occurs from the less-hindered side of the intermediate cyclopropyl radical. [Pg.129]

Scheme 20 HOMO-LUMO interaction in the perepoxide quasi-intermediate for the cis-effect and the regioselectivity (percent) of the hydrogen abstractions... Scheme 20 HOMO-LUMO interaction in the perepoxide quasi-intermediate for the cis-effect and the regioselectivity (percent) of the hydrogen abstractions...
Scheme 3.1 Possible reaction steps in the hydrogen abstraction reaction of fluoranil with 2-propanol. Note FA= fluoranil, (CH3)2CHOH = 2-propanaol, FAH = fluoranil ketyl radical, FA = fluoranil radical anion. Scheme 3.1 Possible reaction steps in the hydrogen abstraction reaction of fluoranil with 2-propanol. Note FA= fluoranil, (CH3)2CHOH = 2-propanaol, FAH = fluoranil ketyl radical, FA = fluoranil radical anion.
The reaction with active methylene compounds results in the hydrogen abstraction to give the alcohol and the organogold derivatives.178... [Pg.1005]

Figure 2. Concentration of components in the hydrogen abstraction series of reactions in the presence of an acceptor (9) (---), model predicted curve (9), octa-... Figure 2. Concentration of components in the hydrogen abstraction series of reactions in the presence of an acceptor (9) (---), model predicted curve (9), octa-...
The reactions of fluorine atoms with hydrocarbons are similar to those of active nitrogen in that they provide an essentially universal response. Fluorine atoms abstract H atoms from hydrocarbons at near-collisional reaction rates. Reactions with fluorine are highly exothermic, forming strong H—F (=570 kJ mol-1) and C—F (=485 kJ mol-1) bonds while breaking much weaker C—H (=414 kJ mor1) and C—C (=368 kJ mol-1) bonds. The hydrogen abstraction reaction... [Pg.366]

Alternatively, if some of the reaction occurs by the hydrogen abstraction-recombination route proceeding through free radicals, then some mono-deuteriated (crossed) products will be formed (14). The former result is taken to be characteristic of the reaction of a singlet carbene, the latter that of a triplet. [Pg.329]


See other pages where The -Hydrogen Abstraction is mentioned: [Pg.391]    [Pg.712]    [Pg.758]    [Pg.495]    [Pg.150]    [Pg.547]    [Pg.338]    [Pg.915]    [Pg.137]    [Pg.160]    [Pg.1463]    [Pg.42]    [Pg.892]    [Pg.33]    [Pg.34]    [Pg.915]    [Pg.78]    [Pg.438]    [Pg.435]    [Pg.983]    [Pg.1121]    [Pg.272]    [Pg.353]    [Pg.130]    [Pg.21]    [Pg.199]    [Pg.253]    [Pg.806]    [Pg.142]    [Pg.725]    [Pg.177]    [Pg.200]   


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Hydrogen Abstraction by Groups Other Than the Carbonyl

Hydrogen abstraction

Hydrogen abstraction, in the solid state

Intramolecular Hydrogen Abstraction by the C—O Double Bond

The Abstraction of Hydrogen and Halogen Atoms

The Abstracts

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