Discussion section

Aromatic pyrazoles and indazoles, in the broad sense defined in Sections 4.04.1.1.1 and 4.04.1.1.2, will be discussed here. Tautomerism has already been discussed (Section 4.04.1.5) and acid-base equilibria will be considered in Section 4.04.2.1.3. These two topics are closely related (Scheme 10) as a common anion (156a) or a common cation (156b) is generally involved in the mechanism of proton transfer (e.g. 78T2259). For aromatic pyrazoles with exocyclic conjugation there is also a common anion (157) for the three tautomeric forms... 

The general discussion (Section 4.02.1.4.1) on reactivity and orientation in azoles should be consulted as some of the conclusions reported therein are germane to this discussion. Pyrazole is less reactive towards electrophiles than pyrrole. As a neutral molecule it reacts as readily as benzene and, as an anion, as readily as phenol (diazo coupling, nitrosation, etc.). Pyrazole cations, formed in strong acidic media, show a pronounced deactivation (nitration, sulfonation, Friedel-Crafts reactions, etc.). For the same reasons quaternary pyrazolium salts normally do not react with electrophiles. 

The stereochemistry of pyrazolines and pyrazolidines has already been discussed (Section 4.04.1.4.3). Optically active A - and A -pyrazolines have seldom been described (77JA2740, 79CJC360), but cis-trans isomeric pairs are common. The C-4 acid-catalyzed epimerization involves the mechanism shown in Scheme 38 (70TL3099), but in spite of some inconclusive arguments the C-5 epimerization has never been established with certainty. 

The fact that an OH or OR group in position 3 or 5 enhances the reactivity of the pyrazolic 4-position towards electrophiles has already been discussed (Section 4.04.2.1.3). Likewise, the non-aromatic reactivity of 2-pyrazolin-5-ones has been examined in Section 4.04.2.2.1(ii). 

Another example of the analogy between pyrazole and chlorine is provided by the alkaline cleavage of l-(2,4-dinitrophenyl)pyrazoles. As occurs with l-chloro-2,4-dinitrobenzene, the phenyl substituent bond is broken with concomitant formation of 2,4-dinitrophenol and chlorine or pyrazole anions, respectively (66AHC(6)347). Heterocyclization of iV-arylpyrazoles involving a nitrene has already been discussed (Section 4.04.2.1.8(i)). Another example, related to the Pschorr reaction, is the photochemical cyclization of (515) to (516) (80CJC1880). An unusual transfer of chlorine to the side-chain of a pyrazole derivative was observed when the amine (517 X = H, Y = NH2) was diazotized in hydrochloric acid and subsequently treated with copper powder (72TL3637). The product (517 X = Cl, Y = H) was isolated. 

The gedanken" experiment in Section 3 4.4.2 results in equation 3.4.4-2 suggesting the operations of summation and multiplication in the algebraic sense - not as probabilities. Since this is a simulation why are not the results correct until given the probability interpretation Hint refer to the Venn Diagram discussion (Section 2.2)... 

Figure 6-18. T(, single irystalpolan/ed fluorescence spectra al 4.2 K. The main vibronic bands built On the origin and on the A, B, and C false origins arc indicated. See text for discussion (Section 6.6.1).

Another standard procedure, involving reaction of imincs with acyl halides, has already been discussed (Section 1.4.5.2.1.1.). 

The cycloaddition reactions of thiophene oxides and dioxides (290 and 291280,281) have already been discussed (Section V.A). 

As already discussed (Section 2.2.1.3), interchange reactions are also implicated in the formation of random copolyesters exhibiting the most probable molar mass distribution when polyester blends are melt mixed. They are also involved in the randomization of block copolyesters taking place in the melt upon heating.2,m 211... 

Equations 10.142 and 10.143 give the point value of NA at time t. The average values Na can then be obtained by applying the age distribution functions obtained by Higbie and by Danckwerts, respectively, as discussed Section 10.5.2. 

This chapter has the following structure in Sect. 3.2 the common characteristics of experiments are discussed. Conditions that are needed for proper comparison of experimental and theoretical results are formulated in Sect. 3.3. In Sect. 3.4 the data of flow of incompressible fluids in smooth and rough micro-channels are discussed. Section 3.5 deals with gas flows. The data on transition from laminar to turbulent flow are presented in Sect. 3.6. Effect of measurement accuracy is estimated in Sect. 3.7. A discussion on the flow in capillary tubes is given in Sect. 3.8. 

Whenever an empirical formula does not show how the elements are combined in groups, it is followed by a linearized structural formula, which reveals the connectivity of the compound(s) underlying the empirical formula and serves to distinguish substances which are identical in composition but differ in the arrangement of elements. The nonpermuted empirical formulas are followed by keywords. They describe the context in which the compounds represented by the empirical formulas are discussed. Section numbers direct the reader to relevant positions in the book. 

A brief discussion of the systematics of solvent effects on the p/, pr, and values of Tables II and III is presented in the discussion section. However, it is worthy of note here that sets 7, 37, 38, 39, 40, and 41, which involve nonhydroxylic solvents, are fitted with comparable precision to that for reaction series in aqueous or mixed aqueous organic solvents. The present analysis does not support the previous assignment (7b) of ion-pair formation of benzoic acids... 

Most chemicals used in the procedure will appear in the index. Thus, there will generally be entries for all starting materials, reagents, intermediates, important by-products, and final products. Most products shown in the Tables in the discus.sion sections of this volume are included unless the compounds are quite similar in which case a general descriptive name was entered. Chemicals generally nut indexed included coiimion solvents, standard inorganic acids and bases, reactants shown in the Tables, and compounds cited in the discussion section in connection with other methods of preparation. 

Each student or group of students may work on a different process, or the whole class may work on the same process. The advantage of the latter method is that the whole class can meet weekly to discuss their results. This has worked very successfully at Ohio University. In the discussion sections, the various groups present their conclusions, and everyone, especially the instructor, benefits from the multitude of varied and imaginative ideas. 

As previously discussed (Section 3 in Chapter 3), the Ba-free catalyst showed no significant storage capacity of NO under lean condition and accordingly no N2 was formed upon the H2 switch over this sample. A different picture was apparent for the... 

R. E. Bastick, in discussion section of paper E. W. Taylor, The Plastic Deformation of Optical Glass, Jour. Soc. Glass Tech., 34,75 (1950). 

Such carbonyls may be further oxidized using potassium permanganate (KMnO and perchloric acid (HCIO4) to convert all of these groups into carboxylic acids. Once functionalized in this manner, the nanotubes can be fully dispersed in aqueous systems. Kordas et al. (2006) used these derivatives to print nanotube patterns on paper or polymer surfaces to create conductive patterns for potential use in electronic circuitry. The carboxylates also may be used as conjugation sites to link other ligands or proteins to the nanotube surface using a carbodiimide reaction as previously discussed (Section 1, this chapter Chapter 2, Section 1.11 Chapter 3, Section 1). 

As depicted in Scheme 1, reductive and oxidative cleavages may follow either a concerted or a stepwise mechanism. How the dynamics of concerted electron transfer/bond breaking reactions (heretofore called dissociative electron transfers) may be modeled, and particularly what the contribution is of bond breaking to the activation barrier, is the first question we will discuss (Section 2). In this area, the most numerous studies have concerned thermal heterogeneous (electrochemical) and homogeneous reactions. 

This chapter provides a basis of theory for solid state NMR and a brief review of experimental aspects. The main focus of the discussion section is on the application of solid state NMR techniques to the study of polymorphism. 

As has already been discussed (Section m.B.3) we were able to demonstrate that the three C3H2 isomers cyclopropenylidene (2), propargylene (36), and vinylidenecarbene (37), interconvert photochemically in low-temperature matrices. Unlike 36 vinylidenecarbene (37) was predicted to be a singlet.108-110 To aid the spectroscopic identification of S-37 we calculated (MP2/6-31G ) IR frequencies and intensities of this species.26 Comparison with the experimental IR spectrum (most intense band at 1952 cm-1) confirmed the allenic structure S-37. For T-37 a completely different IR spectrum was expected. An additional structural proof for S-37 was its reversible transformation into the other two C3H2 isomers S-2 and T-36. 

In a second example, we calculate how pH affects sorption onto hydrous ferric oxide, expanding on our discussion (Section 10.4) of Dzombak and Morel s (1990) surface complexation model. We start as before, setting the dataset of surface reactions, suppressing the ferric minerals hematite (Fe203) and goethite (FeOOH), and specifying the amount of ferric oxide [represented in the calculation by Fe(OH)3 precipitate] in the system... 

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