Group 2 105 series

We would be very grateful to readers who would let us know about mistakes or omissions in this volume or in other volumes in the Functional Groups series. 

In recent years The Chemistry of Functional Groups series has included three volumes on composite functional groups in which a C=C double bond was attached to another group. The chemistry of enones (edited by S. Patai and Z. Rappoport) appeared in 1989 The chemistry of enols (edited by Z. Rappoport) appeared in 1990 and The chemistry of enamines (edited by Z. Rappoport) appeared in 1994. We believe that the time has arrived for a book dealing with the combination of C=C double bonds, namely dienes and polyenes. The two double bonds can be conjugated, and conjugated dienes have a chemistry of their own, but even non-conjugated dienes show certain reactions that involve both double bonds. Allenes and cumulenes, which represent a different combination of the double bonds were treated in The chemistry ofketenes, allenes and related compounds, edited by S. Patai in 1980. 

FIGURE 1. The relationships between the methyl deviation, 5(CH3— Z), and Pauling electronegativity of the bonded Z atom in various homologous functional group series, CH3—(CH2)m—Z. See References 17b and 18... 

Elsewhere in The Chemistry of Functional Groups series appears a brief discussion on the stages in the lifetime of chemicals2. Organotin compounds are usually very toxic and they constitute a potential source of harmful pollution with both acute and longterm effects. Increasing concern with environmental and occupational issues has also contributed to the development of analytical methods. Table 1 lists organotin compounds that have found industrial application with references to occupational protection protocols where analytical methods for the particular compound can be found. 

The slopes, ag, for various n-alkyl substituted homologous series are commonly compared to the universal slope (methylene increment) of —20.6 kJmol-1 calculated for the n-alkanes9. An unanswered question is whether for Targe enough nc the methylene increment should be identical for all functionalized alkanes. In previous studies it is shown that the slopes vary, although not too widely (ca 2 kJ mol-1), and there is no discernible relationship between the functional group and a. With three exceptions, the slopes reported in Table 1 are in line with those calculated for other functional group series. 

As mentioned in the introductory section of this chapter, dediazoniation was reviewed in a volume of The Chemistry of Functional Groups series relatively recently (1983)2 and again in more detail in a monograph in 19947f. Therefore, we will concentrate here on a selection of major results published since the early 1980s on mechanisms of dediazoniations and on applications of dediazoniations in organic synthesis. 

This topic has been reviewed in The Chemistry of the Functional Groups series published in 19821. It is not the purpose of this chapter to provide a complete literature review. Rather, this chapter will discuss some of the new methods of measuring and interpreting kinetic isotope effects that have been used to determine the mechanisms of the reactions of amines and amine derivatives. 

The material reviewed in the present volume Supplement F2 The chemistry of amino, nitroso, nitro and related groups has been previously covered in the following books in the Chemistry of the Functional Groups series ... 

Sadly, Saul Patai who founded The Chemistry of Functional Groups series died in 1998, just after we started to work on the 100th volume of the series. As a long-term collaborator and co-editor of many volumes of the series, I undertook the editorship and this is the second volume to be edited since Saul Patai passed away. I plan to continue editing the series along the same lines that served for the first hundred volumes and I hope that the continuing series will be a living memorial to its founder. 

Weisman, W. (Ed.). 1998. Analysis of Petroleum Hydrocarbons, Environmental Media Total Petroleum Hydrocarbon Criteria Working Group Series. Amherst Scientific Publishers, Amherst, MA. 

Weisman, W. 1998. Analysis of Petroleum Hydrocarbons in Environmental Media. Total Petroleum Hydrocarbons Criteria Working Group Series, Vol. 1. Amherst Scientific Publishers, Amherst, MA.(See also Vol. 2, Composition of Petroleum Mixtures, 1998 Vol. 3, Selection of Representation Total Petroleum Hydrocarbons Fractions Based on Fate and Transport Considerations, 1997 Vol. 4, Development of Fraction-Specific Reference Doses and Reference Concentrations for Total Petroleum Hydrocarbons, 1997 and Vol. 5, Human Health Risk-Based Evaluation of Petroleum Contaminated Sites, Implementation of the Working Group Approach, 1999.)... 

Zdrazil and Kraus (727) studied the related hydrogenolysis of 24 esters R COOR, where R and R were alkyl groups (series 100). The catalyst was rhodium, and the temperature was 300°C. The relative reactivities of the esters could be correlated by a modified Taft equation... 

The nitro group, whether attached to aromatic or aliphatic carbon, is probably the most widely studied of the functional groups and this is in part attributed to its use as an explosophore in many energetic materials. The chemistry of the nitro group has been extensively reviewed in several excellent works including in a functional group series. " ... 

H. Eeuer in The Chemistry of Amino, Nitroso and Nitro Compounds and Their Derivatives, Ed. S. Patai. Chemistry of Eunctional Groups Series, Supplement E, Chapter 19, John Wiley Sons, Ltd, Chichester (1982). 

Alkyl azides are conveniently prepared from the reaction of alkali metal azides with an alkyl halide, tosylate, mesylate, nitrate ester or any other alkyl derivative containing a good leaving group. Reactions usually work well for primary and secondary alkyl substrates and are best conducted in polar aprotic solvents like DMF and DMSO. The synthesis and chemistry of azido compounds is the subject of a functional group series. ... 

This is another volume in The Chemistry of Functional Groups series which deals with organometallic derivatives. We have assembled the remarkable recent achievements in the synthesis, strucmre, synthetic uses and spectroscopy of organic lithium derivatives which are in daily use in the organic chemist s laboratory. 

The present book, The Chemistry of Hydroxylamines, Oximes and Hydroxamic Acids, deals with the chemistry of three related functional groups that were not hitherto treated in The Chemistry of Functional Groups series. Professor Artem Melman, then at the Hebrew University, who felt that such a book would be valuable, suggested the title and we followed his advice he also contributed a chapter. We will be grateful to other readers who suggest other topics which, in their opinion, deserve to be included in new volumes in the series. 

Guide for Authors in Preparation of Manuscripts for The Chemistry of Functional Groups series edited by Saul Patai, Wiley, Chichester, p. 3. 

I will be grateful to readers who will call my attention to mistakes or omissions in the present volume, as well as in other volumes of the Functional Groups Series. 

Cdn(Por) and HgII(Por), obtained by metallation of porphyrins with metal acetate in pyridine,17" resemble the Zn analogues in coordination behaviour. They are easily dissociated from the macro-cyclic ligand, and form five-coordinate complexes with N-donor ligands.18 In this group, the metal—ligand bonds, both cis and axial, become weaker as the metal becomes heavier (Zn > Cd > Hg) in contrast to other transition metal series but similar to other main group series (equation 23). 

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