Compounds of sulfur and selenium with nitrogen

Chapter 15 Compounds of sulfur and selenium with nitrogen 463... 

Compendium of Organic Synthetic Methods, Volume 6, presents the functional group transformations and difunctional compound preparations of 1983, 1984, 1985, and 1986. The classification schemes of the first five volumes have been followed but a new chapter has been added. Each literature citation now includes all authors and the text concludes with an Author Index. The new Chapter 15 classifies the oxides of nitrogen, sulfur, and selenium with section headings identical to Chapters 1-14. The difunctional compounds now appear in Chapter 16. The experienced user of the Compendium will require no special instructions for the use of the new oxides chapter or the complete volume. 

Tellurium Halides. Tellurium forms the dihalides TeCl and TeBi, but not Tel2. However, it forms tetrahalides with all four halogens. Tellurium decafluoride [53214-07-6] and hexafluoride can also be prepared. No monohalide, Te2X2, is believed to exist. Tellurium does not form well-defined oxyhalides as do sulfur and selenium. The tellurium halides show varying tendencies to form complexes and addition compounds with nitrogen compounds such as ammonia, pyridine, simple and substituted thioureas and anilines, and ethylenediamine, as well as sulfur trioxide and the chlorides of other elements. 

Photoelectron spectroscopy has demonstrated that there is no linear correlation between the ionization energies and p values of azoles <84JHC269>. The gas phase photoelectron spectra of a series of hydantoin derivatives (32) have been compared with those of model compounds, and with the results of HAM/3 and CNDO/S calculations. Evidence is found for significant interactions between the 7r-orbitals and the chalcogen atoms for sulfur and selenium derivatives. In contrast, n-orbitals of the nitrogen atoms are localized in the whole series of compoimds, especially in the oxy analogues and in monosubstituted derivatives <88JST(175)447>. 

The twofold extrusion of nitrogen and sulfur and selenium and sulfur from 1-thia- and l-selena-3,4-diazolines(77), readily available from the reaction of diazoalkanes with thio- and selenaketones, respectively, as well as from the reductive coupling of carbonyl compounds such as 78, is the preferred method for preparation of olefins of type I and II (98,99). Examples of the extrusion method, developed by Barton (100), and the McMurry reaction (101) are given in Scheme 1. 

Iodine forms compounds with all elements except the noble gases, sulfur, and selenium, but only reacts indirectly with carbon, nitrogen, oxygen, and some noble metals. Ferric and cupric salts, and compounds of vanadium, chromium, and manganese in their highest oxidation status are reduced in acid solution by iodide ions, with liberation of free iodine. Iodine reacts with hydrocarbons, but equilibria are often unfavorable because hydrogen iodine is liberated, which may reduce the alkyl iodide to the hydrocarbon with formation of iodine. 

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