Flexible conformation derivatives

In general, 1,4-oxazepines and 1,4-thiazepine derivatives are stable compounds. Many of the (di)benzo derivatives are crystalline, while some of the more flexible monocyclic derivatives may be liquids. Conjugated (benzo)thiazepine derivatives can lose sulfur on heating, forming (fused) pyridines. This aspect of their reactivity is treated in Section 13.09.5. The completely or partially reduced derivatives of the title heterocycles and the benzo analogues may adapt different conformations, which has already been discussed in Section 13.09.2. The study of the tautomerism of lactams 9 has also been mentioned in Section 13.09.2. 

In lakes, the pool of dissolved organic carbon (DOC) is dominated by dissolved humic substances (up to 80% of the DOC). Lake humic substances are similar to soil humic substances in that carboxyl, hydroxyl, phenol, and probably methoxyl groups are of major significance. Fluorescence spectra of DOC may be interpreted in terms of the different geochemical origins of DOC (e.g., allochthonous versus algal derived). One or more moieties of dissolved humic substances are produced autochthonously mechanisms may include polymerization of phenols (promoted by transition metals), Maillard condensations, or oxidation via phenolase systems. Aliphatic structural units in dissolved humic substances provide a flexible conformation to the humic substance molecule. ... 

Finally, 3D pharmacophores can be used to provide a naturally partitioned space. By com bining the pharmacophore keys of a set of molecules one can determine how many of th potential 3- or 4- point pharmacophores are accessible to the set and easily identify thos which are not represented. This use of pharmacophores is the basis of a method namei Pharmacophore-Derived Queries (PDQ) [Pickett et al. 1996]. One feature of this particula method is that most molecules will occupy more than one cell (as nearly all molecules wil contain more than one 3-point pharmacophore due to the functionality present an( conformational flexibility). This contrasts with the usual situation, wherein each molecul occupies just one cell. 

For 1,3-dithiolanes the ring is flexible and only small energy differences are observed between the diastereoisomeric 2,4-dialkyl derivatives. The 1,3-oxathiolane ring is less mobile and pseudoaxial 2- or 5-alkyl groups possess conformational energy differences (cf. 113 114) see also the discussion of conformational behavior in Section 4.01.4.3. 

Dithiolane (132) derivatives also possess non-planar skeletons the most important conformation is probably of symmetry C2 (half-chair). The dithiolane ring may be quite flexible and a minimum energy. conformation is only well defined if there is a bulky substituent at the 2-position. 

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