Chemical reactivity differences

Chemical reactivity differences may be calculated if for the transition state of a rate-determining step of a reaction a structural model can be given which is describable by a force field with known constants. We give only two examples. Schleyer and coworkers were able to interpret quantitatively a multitude of carbonium-ion reactivities (63, 111) in this way. Adams and Kovacic studied the pyrolysis of 3-homoadamantylacetate (I) at 550 °C and considered as transition state models the two bridgehead olefins II and III (112). From kinetic data they estimated II to be about 2 kcal mole-1 more favourable than III. 

Chemical entities discussed in this chapter as glycosyl donors share the principal structural feature C(anomeric)—sulfur atom bond with thioglycosides, discussed earlier. However, the electron density on the sulfur atom is diminished, and consequently its chemical reactivity differs considerably, because of substitution with electron-withdrawing groups such as carboxylic or phosphoric acid residues. This... 

These units can be distinguished by chemical reactivity differences (branch points are rapidly hydrolyzed) and by 31P nmr spectra. Combinations of these units can give rise to four main types of polyphosphates ... 

Although pyridazine is related to pyrimidine, its chemical reactivity differs in many respects as a result of the very polar nature of the molecule. Chemically, pyridazine is expected to undergo nucleophilic substitution as a consequence of the positive nature of the ring carbons, and to resist electrophilic attack. This has been confirmed in studies of many substituted pyridazines. Pyridazine forms salts... 

The number of primary, secondary, and tertiary alcohols on AGs ranges from a single secondary alcohol in the pseudo-disaccharide AG sporaricin A (18, Figure 6.1) to 10 alcohols in the pseudo-pentasaccharide AG lividomycin A (1). Steric hindrance and chemical reactivity differences between AG alcohols were exploited to allow selective alcohol-protecting groups manipulations. Treatment of the tetra-azido neamine derivative 45 with the benzoylation reagent 1-N-benzoyloxybenzotriazole (BzOBT) afforded the tri-O-benzoyl derivative 46 as a major product in 55% yield (Scheme 6.6a). Under these conditions, the C-5... 

Because of the differences existing between the quality of different distillation cuts and those resulting from their downstream processing, it is useful to group them according to a major characteristic. That is, they are grouped into the three principal chemical families which constitute them paraffins, naphthenes and aromatics. From a molecular point of view, their chemical reactivities follow this order ... 

Wliile the earliest TR-CIDNP work focused on radical pairs, biradicals soon became a focus of study. Biradicals are of interest because the exchange interaction between the unpaired electrons is present tliroiighoiit the biradical lifetime and, consequently, the spin physics and chemical reactivity of biradicals are markedly different from radical pairs. Work by Morozova et al [28] on polymethylene biradicals is a fiirther example of how this method can be used to separate net and multiplet effects based on time scale [28]. Figure Bl.16.11 shows how the cyclic precursor, 2,12-dihydroxy-2,12-dimethylcyclododecanone, cleaves upon 308 mn irradiation to fonn an acyl-ketyl biradical, which will be referred to as the primary biradical since it is fonned directly from the cyclic precursor. The acyl-ketyl primary biradical decarbonylates rapidly k Q > 5 x... 

Figure Cl. 1.3 shows a plot of tire chemical reactivity of small Fe, Co and Ni clusters witli FI2 as a function of size (full curves) [53]. The reactivity changes by several orders of magnitudes simply by changing tire cluster size by one atom. Botli geometrical and electronic arguments have been put fortli to explain such reactivity changes. It is found tliat tire reactivity correlates witli tire difference between tire ionization potential (IP) and tire electron affinity...

Xue Q and Yeung E S 1995 Differences in the chemical reactivity of individual molecules of an enzyme Nature 373 681-3... 

The reduction of the carboxylic group is easier in the 2-position than in the 4- or 5-positions. These differences in reductibility run parallel to chemical reactivity (58). 

Chemical reactivity and functional group transformations involving the preparation of alkyl halides from alcohols and from alkanes are the mam themes of this chapter Although the conversions of an alcohol or an alkane to an alkyl halide are both classi tied as substitutions they proceed by very different mechanisms... 

Isopentenyl pyrophosphate and dimethylallyl pyrophosphate are structurally sim liar—both contain a double bond and a pyrophosphate ester unit—but the chemical reactivity expressed by each is different The principal site of reaction m dimethylallyl pyrophosphate is the carbon that bears the pyrophosphate group Pyrophosphate is a reasonably good leaving group m nucleophilic substitution reactions especially when as in dimethylallyl pyrophosphate it is located at an allylic carbon Isopentenyl pyrophosphate on the other hand does not have its leaving group attached to an allylic carbon and is far less reactive than dimethylallyl pyrophosphate toward nucleophilic reagents The principal site of reaction m isopentenyl pyrophosphate is the carbon-carbon double bond which like the double bonds of simple alkenes is reactive toward electrophiles... 

One of the most sensitive tests of the dependence of chemical reactivity on the size of the reacting molecules is the comparison of the rates of reaction for compounds which are members of a homologous series with different chain lengths. Studies by Flory and others on the rates of esterification and saponification of esters were the first investigations conducted to clarify the dependence of reactivity on molecular size. The rate constants for these reactions are observed to converge quite rapidly to a constant value which is independent of molecular size, after an initial dependence on molecular size for small molecules. The effect is reminiscent of the discussion on the uniqueness of end groups in connection with Example 1.1. In the esterification of carboxylic acids, for example, the rate constants are different for acetic, propionic, and butyric acids, but constant for carboxyUc acids with 4-18 carbon atoms. This observation on nonpolymeric compounds has been generalized to apply to polymerization reactions as well. The latter are subject to several complications which are not involved in the study of simple model compounds, but when these complications are properly considered, the independence of reactivity on molecular size has been repeatedly verified. 

In this chapter we deal exclusively with homopolymers. The important case of copolymers formed by the chain mechanism is taken up in the next chapter. The case of copolymerization offers an excellent framework for the comparison of chemical reactivities between different monomer molecules. Accordingly, we defer this topic until Chap. 7, although it is also pertinent to the differences in the homopolymerization reactions of different monomers. 

The known binary compounds of sulfur and fluorine range in character from ephemeral to rock-like and provide excellent examples of the influence of electronic and stmctural factors on chemical reactivity. These marked differences are also reflected in the diversified technological utiUty. 

Checklists. A checklist is simply a detailed Hst of safety considerations. The purpose of this Hst is to provide a reminder to safety issues such as chemical reactivity, fire and explosion hazards, toxicity, and so forth. This type of checklist is used to determine hazards, and differs from a procedure checklist which is used to ensure that the correct procedure is followed. 

Many of these features are interrelated. Finely divided soHds such as talc [14807-96-6] are excellent barriers to mechanical interlocking and interdiffusion. They also reduce the area of contact over which short-range intermolecular forces can interact. Because compatibiUty of different polymers is the exception rather than the rule, preformed sheets of a different polymer usually prevent interdiffusion and are an effective way of controlling adhesion, provided no new strong interfacial interactions are thereby introduced. Surface tension and thermodynamic work of adhesion are interrelated, as shown in equations 1, 2, and 3, and are a direct consequence of the intermolecular forces that also control adsorption and chemical reactivity. 

Results obtained at high temperatures indicate that the solubihties of the crystalline modifications of sihca are in the order tridymite > cristobahte > quartz, an order that parallels to some extent the chemical reactivity of these forms. Lower values for solubihty of crystalline as compared to amorphous sihca are consistent with the free-energy differences between them. 

Sihcate solutions of equivalent composition may exhibit different physical properties and chemical reactivities because of differences in the distributions of polymer sihcate species. This effect is keenly observed in commercial alkah sihcate solutions with compositions that he in the metastable region near the solubihty limit of amorphous sihca. Experimental studies have shown that the precipitation boundaries of sodium sihcate solutions expand as a function of time, depending on the concentration of metal salts (29,58). Apparently, the high viscosity of concentrated alkah sihcate solutions contributes to the slow approach to equihbrium. 

Ratios of U and U to Th and Ra daughters, combined with differences in chemical reactivity have been used to investigate the formation and weathering of limestone in karst soils of the Jura Mountains, and of the mountains in the central part of Switzerland. Uranium contained within calcite is released during weathering, and migrates as stable uranyl(VI) carbonato complexes through the soil. In contrast, the uranium decay products, Th and Ra,... 

All the N-unsubstituted pyrazoles (129) in solution (and probably in the gas phase) are mixtures of annular tautomers in different proportions, depending on the nature of the substituents R and R. In the majority of cases the difference of free energy between both tautomers is low enough for the chemical reactivity to be unrelated to the equilibrium constant. 

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