Functional groups polyfunctional

If the target molecule is polyfunctional the synthons must contain more than one functional group. 

The common method of naming aldehydes corresponds very closely to that of the related acids (see Carboxylic acids), in that the term aldehyde is added to the base name of the acid. For example, formaldehyde (qv) comes from formic acid, acetaldehyde (qv) from acetic acid, and butyraldehyde (qv) from butyric acid. If the compound contains more than two aldehyde groups, or is cycHc, the name is formed using carbaldehyde to indicate the functionaUty. The lUPAC system of aldehyde nomenclature drops the final e from the name of the parent acycHc hydrocarbon and adds al If two aldehyde functional groups are present, the suffix -dialis used. The prefix formjlis used with polyfunctional compounds. Examples of nomenclature types are shown in Table 1. 

The reactions of olefins with peracids to form epoxides allows for the selective oxidation of carbon-carbon double bonds in the presence of other functional groups which may be subject to oxidation (for example, hydroxyl groups). The epoxides that result are easily cleaved by strong acids to diols or half-esters of diols and are therefore useful intermediates in the synthesis of polyfunctional compounds. 

The physico-mechanical, thermal, and adhesion properties of the synthesized polyfunctional PSs are dependent on the nature of functional groups in the aromatic ring. In this case, the following are properties of the chlorohydrin and epoxy groups highest elasticity, resistance to strike, and adhesion properties with carboxyl and olefinics. Furthermore, the—CO—CH=CH-—COOH group was provided new properties such as the photosensitive capability. Functionalized PSs obtained are characterized by their high thermostability, adhesion, and photosensitivity. 

Although a polyfunctional organic molecule might contain several different functional groups, we must choose just one suffix for nomenclature purposes. It s not correct to use two suffixes. Thus, keto ester 1 must be named either as a ketone with an -one suffix or as an ester with an -oate suffix but can t be named as an -onoate. Similarly, amino alcohol 2 must be named either as an alcohol (-0/) or as an amine (-amine) but can t be named as an -olamine or -anritiol. 

Examples of polyfunctional carboxylic acids esterified by this method are shown in Table I. Yields are uniformly high, with the exception of those cases (maleic and fumaric acids) where some of the product appears to be lost during work-up as a result of water solubility. Even with carboxylic acids containing a second functional group (e.g., amide, nitrile) which can readily react with the oxonium salt, the more nucleophilic carboxylate anion is preferentially alkylated. The examples described in detail above illustrate the esterification of an acid containing a labile acetoxy group, which would not survive other procedures such as the traditional Fischer esterification. 

In considering step polymerisation with polyfunctional molecules a number of assumptions are made. They are (i) that all functional groups are equally reactive, (ii) that reactivity is independent of molar mass or solution viscosity, and (iii) that all reactions occur between functional groups on different molecules, i.e. there are no intramolecular reactions. It is found experimentally that these assumptions are not completely valid and tend to lead to an underestimate of the extent of reaction required to bring about gelation. 

Monomers that participate in step growth polymerization may contain more or fewer than two functional groups. Difunctional monomers create linear polymers. Trifiinctional or polyfunctional monomers introduce branches which may lead to crosslinking when they are present in sufficiently high concentrations. Monofunctional monomers terminate polymerization by capping off the reactive end of the chain. Figure 2.12 illustrates the effect of functionality on molecular structure. 

Traditionally, we create thermoset polymers during step growth polymerization by adding sufficient levels of a polyfunctional monomer to the reaction mixture so that an interconnected network can form. An example of a network formed from trifimctional monomers is shown in Fig. 2.12b). Each of the functional groups can react with compatible functional groups on monomers, dimers, trimers, oligomers, and polymers to create a three-dimensional network of polymer chains. 

Chemical Crosslinking. Only linear polymers are produced from bifunctional monomers. The reaction system must include a polyfunctional monomer, i.e., a monomer containing 3 or more functional groups per molecule, in order to produce a crosslinked polymer. However, the polyfunctional reactant and/or reaction conditions must be chosen such that crosslinking does not occur during polymerization but is delayed until the fabrication step. This objective is met differently depending on whether the synthesis involves a chain or step polymerization. In the typical... 

In some instances, treatment of polyfunctional benzylic alcohols with acid in the presence of organosilicon hydrides causes multiple functional group transformations to occur simultaneously. This phenomenon is illustrated by the reduction of the secondary benzylic alcohol function and concomitant loss of the methoxymethyl protecting group of 2-(l-hydroxydecyl)-5-methoxy-l-(methoxy-methyleneoxy)naphthalene upon treatment with Et3SiH/TFA in dichloromethane (Eq. 26).167... 

These reaction conditions also permit the chemoselective quantitative reduction of benzaldehyde to benzyl alcohol without any concomitant reduction of either acetophenone or 3,3-dimethylbutan-2-one present in the same reaction mixture.83 Additionally, this useful method permits the reduction of aldehyde functions in polyfunctional compounds without affecting amide, anhydride, eth-ylenic, bromo, chloro, or nitro groups.79,80,319... 

The correct analysis of the homologous ion series has certain limitations. Low abundances of peaks in some series require the attention and experience of a researcher. Usually alkane series are dominated in the mass spectra of the most various compounds. Fragmentation initiated by one functional group may completely suppress or notably camouflage other reactions of polyfunctional substances. In the latter case it is useful to consider IR-spectroscopy data in mass spectral interpretation. 

The synthesis of a polyfunctional molecule can always be reduced to the problem of constructing differently paired functional group relationships, which (keeping in mind generalisation 1) usually requires the creation of a carbon chain with a number of carbon atoms equal to or smaller than 6 (n < 6). 

In principle, the synthesis of a consonant molecule or a bifunctional relationship within a more complex polyfunctional molecule, does not offer too many difficulties. In fact, all the classical synthetic methods of carbon-carbon bond formation that utilise reactions which are essentially reversible, lead to consonant relationships. For instance, the book by H.O. House "Modem Synthetic Reactions" [22], after dealing, for almost 500 pages, with functional group manipulations, devotes the last 350 pages to carbon-carbon bond formation, all of which lead to consonant relationships. These methods can, actually, be reduced to the following four classical condensations (and their variants) Claisen condensation, aldol condensation, Mannich condensation and Michael addition (Table 2.5). 

There are instances where some or all parts of the concept of equal reactivity of functional groups are invalid [Kronstadt et al., 1978 Lovering and Laidler, 1962], The assumption of equal reactivities of all functional groups in a polyfunctional monomer may often be incorrect. The same is true for the assumption that the reactivity of a functional group is... 

One can easily show by substitution of different values of r, p, fA, f, and fc into Eqs. 2-139 through 2-143 that crosslinking is accelerated (i.e., pc decreases) for systems that contain closer to stoichiometric amounts of A and B functional groups (r closer to 1), systems with larger amounts of polyfunctional reactants (p closer to 1) and systems containing reactants of higher functionality (higher values of fA,fs, and fc)-... 

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