Various functional groups

Numerous diamines and aromatic dianhydrides have been investigated. WhoUy aromatic Pis have been stmctiirally modified by incorporating various functional groups, such as ether, carbonyl, sulfide, sulfone, methylene, isopropjlidene, perfluoroisopropyUdene, bipyridyls, sdoxane, methyl phosphine oxide, or various combinations of these, into the polymer backbone to achieve improved properties. The chemistry and apphcations of Pis have been described in several review articles (4). 

Table 6. Behavior of Various Functional Groups Toward Hydride Reagents ...

Metal Amalgams and Hydrides. Metal hydrides and amalgams are sometimes the preferred method of reducing various functional groups in the laboratory, especially when the necessary equipment for catalytic hydrogenations is unavailable. However, these reagents are usually too expensive to make their use on a large commercial scale feasible. 

AletalHydrides. Metal hydrides can sometimes be used to prepare amines by reduction of various functional groups, but they are seldom the preferred method. Most metal hydrides do not reduce nitro compounds at all (64), although aUphatic nitro compounds can be reduced to amines with lithium aluminum hydride. When aromatic amines are reduced with this reagent, a2o compounds are produced. Nitriles, on the other hand, can be reduced to amines with lithium aluminum hydride or sodium borohydride under certain conditions. Other functional groups which can be reduced to amines using metal hydrides include amides, oximes, isocyanates, isothiocyanates, and a2ides (64). 

The radical stabilization provided by various functional groups results in reduced bond dissociation energies for bonds to the stabilized radical center. Some bond dissociation energy values are given in Table 12.6. As an example of the effect of substituents on bond dissociation energies, it can be seen that the primary C—H bonds in acetonitrile (86 kcal/mol) and acetone (92kcal/mol) are significantly weaker than a primaiy C—H... 

Kim et al, observed a number of facts gleaned from C-NMR that led to an overall picture of the reactivity of various hydroxymethyl phenols (HMPs) [144, 148], Grenier-Loustalot and co-workers did a number of important experiments that expanded Kim s findings and clearly delineated the reactivity of the various functional groups position-by-position [128], The two studies show excellent agreement. The materials that follow are drawn from these two reports without further citation. As shown in Scheme 5, the condensation of 2-HMP at pH 8 and 60°C resulted in only one product. This product is the result of p-attack on the ring by the hydroxymethyl group. 

Catalytic hydrogenation has been utilized extensively in steroid research, and the method has been found to be of great value for the selective and stereospecific reduction of various functional groups. A number of empirical correlations concerning selectivity and product stereochemistry compiled for steroid hydrogenations has been listed in a previous review. ... 

Since the stereochemical course of a catalytic hydrogenation is dependent on several factors, " an understanding of the mechanism of the reaction can help in the selection of optimal reaction conditions more reliably than mere copying of a published recipe . In the first section the factors which can influence the product stereochemistry will be discussed from a mechanistic viewpoint. In subsequent sections the hydrogenation of various functional groups in the steroid ring system will be considered. In these sections both mechanistic and empirical correlations will be utilized with the primary emphasis being placed on selective and stereospecific reactions. 

In some reactions intramolecular chalcogen nitrogen interactions may lead to stereochemical control. For example, selenenyl bromides react with C=C double bonds, providing a convenient method of introducing various functional groups. The reaction proceeds readily, but affords a racemic mixture. The modified reagent 15.22 contains a chiral amine in close interaction with the selenium atom. It reacts with olefins affording up to 97% ee of isomer A (Scheme 15.2). ... 

Tlie constrLiction of carbocydic cotnpoutidi by ring-annulation procedures frequently plays a prominent role in total syntliesis. Tlie tolerance of various functional groups in tlie zinc reagents employed in copper-catalyzed asymmetric 1,4-additions fornis tlie basis for tliree novd catalytic enantioselective annulation metliods discussed bete. 

The unsaturated substituent in the carbene complex 1 often is aromatic or heteroaromatic, but can also be olefinic. The reaction conditions of the Dotz procedure are mild various functional groups are tolerated. Yields are often high. The use of chromium hexacarbonyl is disadvantageous, since this compound is considered to be carcinogenic however to date it cannot be replaced by a less toxic compound. Of particular interest is the benzo-anellation procedure for the synthesis of anthra-cyclinones, which are potentially cytostatic agents. ... 

With respect to the olefinic substrate, various functional groups are tolerated, e.g. ester, ether, carboxy or cyano groups. Primary and secondary allylic alcohols, e.g. 14, react with concomitant migration of the double bond, to give an enol derivative, which then tautomerizes to the corresponding aldehyde (e.g. 15) or ketone ... 

Additional examples of the synthetic utility of this procedure are demonstrated in Eqs 3 50-3 53 The nitro and nitroalkyl groups in the products are Further converted into various Functional groups such as carbonyl, amino, and alkyl groups This is discussed in Chapter 6... 

This relatively new class of CSPs incorporates glycopeptides attached covalently to silica gel. These CSPs can be used in the normal phase, reversed phase, and polar organic modes in LC [62]. Various functional groups on the macrocyclic antibiotic molecule provide opportunities for tt-tt complexation, hydrogen bonding, and steric interactions between the analyte and the chiral selector. Association of the analyte... 

This procedure provides a convenient method for the esterification ol a wide variety of carboxylic acids. The reaction proceeds smoothly with sterically hindered acids6 and with acids which contain various functional groups. Esters are obtained in high purity using Kugelrohr distillation as the sole purification technique. In cases where traces of dichloromethane present no problems, the crude product is usually pure enough to be used directly in subsequent reactions. Methyl and ethyl ethers of phenols may also be prepared by this procedure (see Note 8). 

Interestingly, comparison of the values of pAHB and the acidity constants pKa in a series of the same family of compounds, such as carbonyl compounds, amines, pyridines and sulphoxides, shows that a good correlation exists between p/CHB and pgiving straight lines in each series of compounds with parallel slopes. This enables one to calculate the difference of the several pKa values at the same p/CHB value, and vice versa. Thus, at p= 0, p/CHB values of various functional groups were determined and are shown in Table 13. 

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