Molecular steric hindrance

The disadvantages associated with the Clemmensen reduction of carbonyl compounds (see 3 above), viz., (a) the production of small amounts of carbinols and unsaturated compounds as by-products, (h) the poor results obtained with many compounds of high molecular weight, (c) the non-appUcability to furan and pyrrole compounds (owing to their sensitivity to acids), and (d) the sensitivity to steric hindrance, are absent in the modified Wolff-Kishner reduction. 

The simplest and most quickly computed models are those based solely on steric hindrance. Unfortunately, these are often too inaccurate to be trusted. Molecular mechanics methods are often the method of choice due to the large amount of computation time necessary. Semiempirical methods are sometimes used when molecular mechanics does not properly represent the molecule. Ah initio methods are only viable for the very smallest molecules. These are discussed in more detail in the applicable chapters and the sources mentioned in the bibliography. 

For a carbon-carbon bond located along a polymer backbone, the preceding molecular representation must be modified to Fig. 1.8c. The chain segments on either side of the bond of interest are substituents for which the amount of steric hindrance follows a slightly different pattern than for the unsubstituted ethane. Using the same convention for [Pg.58]

Traditional adsorbents such as sihca [7631 -86-9] Si02 activated alumina [1318-23-6] AI2O2 and activated carbon [7440-44-0], C, exhibit large surface areas and micropore volumes. The surface chemical properties of these adsorbents make them potentially useful for separations by molecular class. However, the micropore size distribution is fairly broad for these materials (45). This characteristic makes them unsuitable for use in separations in which steric hindrance can potentially be exploited (see Aluminum compounds, aluminum oxide (ALUMINA) Silicon compounds, synthetic inorganic silicates). 

The isocyanates used with rigid foam systems are either polymeric MDI or specialty types of TDI. Both contain various levels of polymerized isocyanate groups which contribute to molecular weight per cross-link and also may affect reactivity due to steric hindrance of some isocyanate positions. 

Absorption, metaboHsm, and biological activities of organic compounds are influenced by molecular interactions with asymmetric biomolecules. These interactions, which involve hydrophobic, electrostatic, inductive, dipole—dipole, hydrogen bonding, van der Waals forces, steric hindrance, and inclusion complex formation give rise to enantioselective differentiation (1,2). Within a series of similar stmctures, substantial differences in biological effects, molecular mechanism of action, distribution, or metaboHc events may be observed. Eor example, (R)-carvone [6485-40-1] (1) has the odor of spearrnint whereas (5)-carvone [2244-16-8] (2) has the odor of caraway (3,4). 

Polyfumarates. Because of steric hindrance, fumarates are difficult to polymerize into high molecular-weight polymers. However, it was demonstrated during the early 1980s that bulky fumarates, such as di-/-butyl fumarate, 0 2 200 [7633-38-7] (3), can be polymerized thermally into high... 

Studies on covalent hydration of N-heterocycles (67AG(E)919,76AHC(20)117) have revealed the diagnostic value of alkyl substituents in structural assignments due to their steric hindrance effects in addition reactions. C-Methyl substituents are therefore also considered as molecular probes to solve fine-structural problems in the pteridine field. The derivatives... 

The three water ligands located at meridional positions of the J ,J -DBFOX/Ph aqua complexes may be replaced by another molecule of DBFOX/Ph ligand if steric hindrance is negligible. Based on molecular model inspection, the hetero-chiral enantiomer S,S-DBFOX/Ph looks like a candidate to replace the water ligands to form the heterochiral meso-2 l complex J ,J -DBFOX/Ph-S,S-DBFOX/... 

The stereochemical course of the reaction may be rationalized by assuming a six-mem-bered chelate which presumably exists in a chair-like conformation. Molecular models support the assumption that the nucleophile preferentially attacks from the bottom face of the complex due to the steric hindrance of the axial A-methyl group. 

For densities g < 0.92 g/cm3 plastic deformation will probably be dominated by preferential compression of disordered molecular regions. Resistance to deformation occurs largely due to bond rotation. In this case work has to be done against the steric hindrance to rotation. 

A porphinatoaluminum alkoxide is reported to be a superior initiator of c-caprolactone polymerization (44,45). A living polymer with a narrow molecular weight distribution (M /Mjj = 1.08) is ob-tmned under conditions of high conversion, in part because steric hindrance at the catalyst site reduces intra- and intermolecular transesterification. Treatment with alcohols does not quench the catalytic activity although methanol serves as a coinitiator in the presence of the aluminum species. The immortal nature of the system has been demonstrated by preparation of an AB block copolymer with ethylene oxide. The order of reactivity is e-lactone > p-lactone. 

For apple maceration, the main activity is the endopectinlyase (PL) which decreases the viscosity due to the colloidal pectin by decreasing tlie molecular weight of this substrate methylated at about 90%. In association to this PL, exo B and endoarabanase (ARAs), pectinacetylesterase (PAE), rhamnogalacturonase (RG) and other hemicellulases allow to hydrolyse side chains of the pectin, decrease the steric hindrance and make the access of pectinases to the rhamnogalacturonic backbone more easy. 

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