Bifunctional compounds

From Hydrazines and P-Bifunctional Compounds. One of the oldest examples in this class is the reaction of a p-diketone with a substituted hydrazine to give a pyrazole (eq. 1). 

A variety of bifunctional compounds react with the bismaleimides to form polymers by rearrangement reactions. These include amines, sulphides and aldoximes (Figure 18.41). 

As a result of the interaction with bifunctional compounds, e.g., with hexameth-ylenediamine, disubstituted amino groups are formed providing chemical bonds... 

These results made it possible to arrive at a sufficiently well-grounded conclusion that the effect of raised heat resistance caused by the formation of intermolecular chemical bonds is not very significant, and that the usually observed considerable increase of heat resistance of PAN fibres as a result of a crosslinkage with bifunctional compounds, is caused not by the formation of intermolecular chemical bonds, as it has usually been thought45, 46, but by cyclization reactions of the nitrile groups with the formation of naphthyridine cycles47. ... 

The chemical and physical properties of the polymers obtained by these alternate methods are identical, except insofar as they are affected by differences in molecular weight. In order to avoid the confusion which would result if classification of the products were to be based on the method of synthesis actually employed in each case, it has been proposed that the substance be referred to as a condensation polymer in such instances, irrespective of whether a condensation or an addition polymerization process was used in its preparation. The cyclic compound is after all a condensation product of one or more bifunctional compounds, and in this sense the linear polymer obtained from the cyclic intermediate can be regarded as the polymeric derivative of the bifunctional monomer(s). Furthermore, each of the polymers listed in Table III may be degraded to bifunctional monomers differing in composition from the structural unit, although such degradation of polyethylene oxide and the polythioether may be difficult. Apart from the demands of any particular definition, it is clearly desirable to include all of these substances among the condensation... 

The kinetics of reactions of bifunctional compounds are especially significant in relation to polymer reactions. The esterification rate constants shown in the third column (B) of Table V for the homologous series of dibasic acids do not differ greatly from those for the monobasic acids. These differences vanish as the length of chain separating the carboxyl groups increases. 

The cyclization constant (7, which may be evaluated from the observed ratio of the two products at a given concentration c, affords a measure of the tendency for a given bifunctional compound to cyclize. A plot of log C vs. the ring size n for the lactonization of w-hydroxy acids... 

Reactions of this type are called electrochemical hydrodimerization. They are of great value for the synthesis of various bifunctional compounds. A reaction that has found wide commercial nse is the hydrodimerization of acrylonitrile to adiponitrile (the dinitrile of adipic acid) ... 

Bronlc acids containing electron-capturing subsitituents were developed by Poole and co-workers. Table 8.19 (451,535,536). In terms of volatility, stability of derivatives, and response to the electron-capture detector the 3,5-bis(trifluoromethyl)benzeneboronic acid, 2,4-dichlorobenzeneboronic acid, and 4-bromo-benzeneboronic acid were recommended for general applications. In particular, the 3,5-bis(trifluoromethyl)benzeneboronate derivatives are remarkably volatile, more so than the benzeneboronates, and are suitable for the analysis of bifunctional compounds of low volatility. All the benzeneboronate derivatives are susceptible to solvolysis which is the primary limitation to their general use for trace analysis. 

Moreover, Kim and coworkers have shown that a-amino-butyrolactones can be synthesized by a related process employing the amino acid homoserine with an unprotected hydroxy functionality [31]. In a more recent publication by the same research group, morpholin-2-one derivatives of type 9-37 have been prepared (Scheme 9.6) [32]. Herein, glycolaldehyde dimer 9-32 acts as a bifunctional compound, which first reacts with the a-amino acids 9-33 to give the iminium ions 9-34,... 

Reaction of 518 with various bifunctional compounds such as a-halogeno acids or esters results in the isolation of fused heterocyclic systems such as 520 [87IJC(B)110]. The factors affecting cyclization are dependent on the cyclizing agent as well as the nature of the side chain present in the parent compound. 

In real systems (hydrocarbon-02-catalyst), various oxidation products, such as alcohols, aldehydes, ketones, bifunctional compounds, are formed in the course of oxidation. Many of them readily react with ion-oxidants in oxidative reactions. Therefore, radicals are generated via several routes in the developed oxidative process, and the ratio of rates of these processes changes with the development of the process [5], The products of hydrocarbon oxidation interact with the catalyst and change the ligand sphere around the transition metal ion. This phenomenon was studied for the decomposition of sec-decyl hydroperoxide to free radicals catalyzed by cupric stearate in the presence of alcohol, ketone, and carbon acid [70-74], The addition of all these compounds was found to lower the effective rate constant of catalytic hydroperoxide decomposition. The experimental data are in agreement with the following scheme of the parallel equilibrium reactions with the formation of Cu-hydroperoxide complexes with a lower activity. 

Metal-deactivating antioxidants. Transition metal compounds decompose hydroperoxides with the formation of free radicals, thereby increasing the rate of oxidation. Such an enhanced oxidation can be slowed down by the addition of a compound that interacts with metal ions to form complexes that are inactive with respect to hydroperoxides. Diamines, hydroxy acids, and other bifunctional compounds exemplify this type of antioxidants. 

Figure 7.8 Modeled 1,4 interstrand and 1,5 intrastrand cross-links formed by platinum bifunctional compound BBR3464.

Bis-pyrimidine derivatives were prepared by the reaction of the hydroxyethyl derivatives of pyrimidine with various bifunctional compounds such as dichloro-siloxane derivatives (Figure 3) (20). 

The coupling reaction of acetylenic carbinols was also extended to the thiophene series (80). The diacetylenic glycols were of particular interest, since they provide convenient synthetic routes to bifunctional compounds difficult to prepare by other means. The coupling reaction, which took place, could be represented as follows ... 

The electrooxidation of thiophenol [19], 2-mercaptobenzothiazole [22], 6- and 2-thiopurine [23], 2-thiopyridine [24] results in their disulfide derivatives in good yields. Bifunctional compound, 2,6-purinedi-thiol [23] can form first a 6,6 -disulflde (4), and then, by subsequent oxidation of the latter, give a cyclic product with two S - S bridges (Scheme 5). 

Mangelings, D., Hardies, N., Maftouh, M., Suteu, C., Massart, D.L., Vander Heyden, Y. Enantioseparations of basic and bifunctional compounds by capillary electrochromatography using polysaccharide stationary phases. Electrophoresis 2003, 24, 2567-2576. 

Amino acids are bifunctional compounds and the basic structural units/building blocks of proteins. In chemistry, an ct-amino acid consists of an amino group, a carboxyl group, an R-group, and a hydrogen atom which is bonded to the a-carbon. The R-group represents a side chain specific to each amino acid and... 

Epoxides are extremely useful intermediates in organic synthesis since they react with a variety of nucleophiles suffering opening of the epoxide ring with retention or inversion of configuration at the carbon undergoing attack. Thus, the development of highly stereoselective methods for the synthesis of certain chiral epoxides, such as the methods under discussion, has enabled the asymmetric synthesis of a wide variety of 1,2-bifunctional compounds. 

The dimerization of functional alkenes such as acrylates and acrylonitrile represents an attractive route to obtain bifunctional compounds such as dicarboxylates and diamine, respectively. The head-to-tail dimerizahon of acrylates and vinyl ketones was catalyzed by an iridium hydride complex generated in situ from [IrCl(cod)]2 and alcohols in the presence of P(OMe)3 and Na2C03 [26]. The reaction of butyl acrylate 51 in the presence of [IrCl(cod)]2 in 1-butanol led to a head-to-tail dimer, 2-methyl-2-pentenedioic acid dibutyl ester (53%), along with butyl propionate (35%) which is formed by hydrogen transfer from 1-butanol. In order to avoid... 

Condensation polymerizations (polycondensations) are stepwise reactions between bifunctional or polyfunctional components, with elimination of small molecules such as water, alcohol, or hydrogen and the formation of macromo-lecular substances. For the preparation of linear condensation polymers from bifunctional compounds (the same considerations apply to polyfunctional compounds which then lead to branched, hyperbranched, or crosslinked condensation polymers) there are basically two possibilities. One either starts from a monomer which has two unlike groups suitable for polycondensation (AB type), or one starts from two different monomers, each possessing a pair of identical reactive groups that can react with each other (AABB type). An example of the AB type is the polycondensation of hydroxycarboxylic acids ... 

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