Phenol-aldehyde condensations compounding

A. The Basic Series.—In general, aromatic aldehydes condense with aromatic amines in the presence of zinc chloride to form triphenylmethane derivatives (0. Fischer) phenols and phenyl ethers behave similarly in the presence of concentrated sulphuric acid (Baeyer). The products formed are the leuco-compounds of well-known dyes. 

Antioxidants inhibit oxidation and are usually employed in combination with UV absorbers. Most antioxidants used for urethane coatings fall into the following classes substituted phenols, aromatic amines, condensation products of aminophenols with aldehydes, thio compounds, and phosphites. Often combinations of antioxidants from the above categories exhibit a synergistic effect. More recently Mathur et al. (125) carried out an extensive study involving the use of one to six stabilizers, selected from the above antioxidants and UV stabilizers, employing several independent test methods, to study the thermooxidation of urethane and urethane-urea films. 

The phenolic-based resin compounds are among the most widely used and well-known thermosets. Phenols react with aldehydes to give condensation products if there are free positions in the benzene ring - ortho and para to the hydroxyl group. Formaldehyde is the most reactive and is used almost exclusively in commercial production. The reaction is always catalyzed, either by acids or bases. The nature of the product greatly depends on the type of catalyst and the mole ratio of the reactants. Refer to Novolac Resins. 

The highly potent anti-HIV natural product daurichromenic acid (10-100) was synthesized by Jin and coworkers [36] using a microwave-assisted reaction of the phenol derivative 10-97 and the aldehyde 10-98 (Scheme 10.25). Normal heating gave the desired benzo[b]pyran 10-99 by a domino condensation/intramolecular SN2 -type cyclization reaction only in low yield. However, when the reaction mixture was irradiated twenty times in a microwave for 1-min intervals, 10-99 was obtained in 60% yield. This compound was then transformed into 10-100 by cleavage of the ester moiety. 

Triazolopyranopyrimidines can be prepared from the phenol-substituted triazolopyrimidines. Condensation with an aldehyde with the fused dihydropyrimidine such as 181 is followed by cyclization to give benzo-fused trihetero-cyclic compounds 182 (Equation 48) <1996CHE215>. 

Figure 4.22 The Mannich reaction occurs between an active-hydrogen-containing compound (phenol) and an amine-containing molecule in the presence of an aldehyde (formaldehyde). The condensation reaction forms stable crosslinks.

The distillate is at once extracted with ether and the extract, after having been separated from the water, is heated on the water bath until most of the ether has distilled. The residue, which contains unchanged phenol as well as the salicylaldehyde, is now vigorously shaken in a small glass-stoppered bottle with two volumes of concentrated commercial sodium bisulphite solution. A thick paste of the bisulphite compound of the aldehyde is formed. After this paste has stood for from half an hour to one hour the bisulphite compound is separated by filtration at the pump, pressed well on the filter funnel, and washed several times, first with alcohol and finally with ether, until completely free from adherent phenol. The crystals (small plates, iridescent like mother-of-pearl) are then decomposed with dilute sulphuric acid in a small round-bottomed flask whi( h is fitted with an air condenser and gently warmed on the water bath. After the liquid thus produced has cooled, the aldehyde which separates is extracted with ether and the ethereal solution is dried with anhydrous sodium sulphate. The pure aldehyde which remains when the ether is evaporated distils at 196°. The yield amounts to 10-12 g. 

When heated with a strong acid, pentoses and hexoses are dehydrated to form furfural and hydroxymethylfurfural derivatives respectively (Figure 9.20), the aldehyde groups of which will then condense with a phenolic compound to form a coloured product. This reaction forms the basis of some of the oldest qualitative tests for the detection of carbohydrates, e.g. the Molisch test using concentrated sulphuric acid and a-naphthol. 

Phenolics, A class of thermoset resins made by the condensation of phenol or phenol-containing compounds with aldehydes such as acetaldehyde or formaldehyde. 

Calixarenes [77] are defined as [l.n]metacyclophanes with its basic structural unit consisting of phenolic groups linked by ortho-methylene groups. Two examples are shown in Fig. 25. Several reviews are available on this subject [77-79]. These compounds can be synthesized by the acid- or base-catalyzed condensation reaction of a substituted phenol with formaldehyde or an aldehyde (Fig. 26). Calixarenes have also been synthesized by a stepwise reaction that sequentially add phenolic groups followed by a cyclization step. More efficient convergent synthesis have also been developed [80-82], The bowl-like structural conformation generally... 

Although formaldehyde has been most common, other aldehydes have also been used successfully for the formation of iminium ion. The Mannich reaction also proceeds with the other activated hydrogen compounds such as indole, furan, pyrrole and phenols. When primary amine is used, the Mannich base formed is a secondary amine and may undergo further condensation to yield tertiary amine. The Mannich base may eliminate an amine... 

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