Phenols aldehydes from

Table 6.2.7. Yields of phenolic aldehydes from several plant species and their lignin preparations on nitrobenzene oxidation (yield in mol % 1C, unit)1... 

About 175 cc. of hydrochloric acid is required to neutralize the excess sodium hydroxide and to liberate the phenolic aldehyde from its sodium salt. 

The formation of phenolic aldehydes from phenols, chloroform and alkali is known as the Reimer-Tiemann Reaction, as shown under ... 

Fomecin A and B, Phenolic Aldehydes from the Basidiomycete Pomes juniperi-... 

Formation of phenolic aldehydes from phenols, chloroform and alkali ... 

The Gattermann-Koch formylatioii was found unsuited to the preparation of aldehydes from phenols and phenol ethers such aldehydes may be obtained by Gatteimann s aldehyde reaction. 

Phenol - aldehyde polymers. L. Baekland (1909) first demonstrated the possibilities of the reaction between phenol and formaldehyde from the commercial view point. Condensation in the presence of either... 

Reasonable procedures for manufacturing resoles and novolacs are presented in subsequent sections. These procedures utilize the a concept known in the industry as programmed formaldehyde addition to avoid the problems mentioned above as well as aiding in control of the exothermic reactions resulting from the manufacture of the desired phenol-aldehyde products. These reactions are also extremely exothermic. 

Phenolics or phenol-aldehydes include the important commercial phenolic resin bakelite based on phenol and formaldehyde. A one-step process produces resol resin from more than one molecule of formaldehyde per phenol molecule. A two-step process uses an excess of phenol to produce novolacs - resins that have no reactive methylol groups and must be mixed with an aldehyde o undergo further reaction. 

The synthesis of a large number of y-pyrones and y-pyranols from enamines has been brought about through the use of a wide variety of bifunctional molecules. These molecules include phenolic aldehydes (126,127), phenolic Mannich bases (128), ketal esters (129), and diketene (120-132). All of these molecules have an electrophilic carbonyl group and a nucleophilic oxygen center in relative 1,4 positions. This is illustrated by the reaction between salicylaldehyde (101) and the morpholine enamine of cyclohexanone to give pyranol 102 in a quantitative yield (127). 

Related Methods Section 48 (Aldehydes from Alcohols and Phenols). 

In Table 15 are recorded the dissociation constants of certain phenolic compounds. From these data it becomes obvious that the introduction of aldehyde groups, or other substituents, changes the dissociation constant of phenolic hydroxyls by over one-hundred fold. Moreover, oxidation studies carried out in this laboratory have shown that the native lignins from bagasse, white Scots pine and birch contain... 

We have found several examples in which adjacent cationic charge centers are shown to activate carboxonium electrophiles. A convenient method for studying this activation is through the use of the hydroxyalkylation reaction, a commercially important, acid-catalyzed condensation of aldehydes and ketones with arenes.10 It is used for example in the synthesis of bis-phenol A from acetone and phenol (eq 6). While protonated acetone is able to react with activated arenes like phenol, it is not capable of reacting with less nucleophilic... 

Other 4-nitrophenyl esters have also been reported to be substrates of various hydrolases. For example, 4-nitrophenyl hexanoate (7.19) was hydrolyzed by bovine serum albumin [39], The affinity of the substrate for the macromolecule was found to be high (Km/n = 0.040 mM, where n is the number of sites), but the reaction itself was slow ( = 5 10-3 s-1, where k2 is the first-order rate constant of the formation of the phenol product from the enzyme-substrate complex). Another ester, 4-nitrophenyl pivalate (7.20), was hydrolyzed by cytoplasmic aldehyde dehydrogenase at a maximum velocity ca. 1/3 and an affinity ca. 1/20 those of the acetate [40], However, the rate-limiting steps were different for the two substrates, namely acylation of the enzyme for the pivalate, and acyl-enzyme hydrolysis for the acetate (see Chapt. 3). 

Table I. Amounts of Phenolic Acids and Phenolic Aldehydes Released from Graminaceous Cell Walls by Treatment with Sodium Hydroxide...

There is also evidence that at least some of the phenolic aldehydes and dehydrodiferulic acid (Figure 1) are linked covalently to cell wall polysaccharides. When ryegrass cell walls were treated with cellulase, the aldehydes and the acid were released as water-soluble carbohydrate-aromatic compounds from which the aromatics were released by cold sodium hydroxide treatment (6,7). This suggests that these compounds are either ether-linked or, in the case of the acid, ester-linked to the polysaccharides. 

Oglialoro modification of, 708 Perkin triangle, 108, 218f Kon modification of, 109 Peroxides, detection of, in ether, 163 removal from diethyl ether, 163 removal from isopropyl alcohol, 886 Petroleum ether, purification of, 174 Phenacetin, 996, 997 1 10-Phenanthroline, 991, 992 p-Phenetidine, 997, 998 Phenetole, 665,670 Phenobarbitone, 1003,1004,1005 Phenol, 595, 613 Phenol aldehyde polymers, 1016 formation of, 1022 Phenolphthalein, 984, 985 action as indicator, 984 ... 

Since the Friedel-Crafts reaction when applied to the phenol ethers yields the corresponding ketones far more easily than the same reaction applied to hydrocarbons (see Reaction XX. (6) (iv.)), it is noteworthy that the above reaction does not apply to the phenol ethers. To obtain aldehydes from them or from phenols, a modified method must be used (see pp. 104, 106). 

Aliphatic aldehydes and ketones and also aliphatic-aromatic ketones can be converted into the corresponding hydrocarbons alkyl-phenols can be obtained from phenolic-aldehydes and -ketones p-hydroxy-benzophenone yields p-benzylphenol benzoin and benzil yield dibenzyl anthraquinone yields anthracene dihydride. 

The Gatterman-Koch formylation is unsuitable for the preparation of aldehydes from phenols and phenolic ethers owing to the formation of complexes with the Lewis acid. 

Phenols are smoothly converted into phenolic aldehydes by reaction with chloroform in the presence of base (the Reimer-Tiemann reaction). This overall formylation reaction is of interest in that it involves the generation from chloroform and alkali of the reactive intermediate, dichlorocarbene (2). This effects electrophilic substitution in the reactive phenolate ions giving the benzylidene dichloride (3) which is hydrolysed by the alkaline medium to the corresponding hydroxyaldehyde. The phenolic aldehyde is isolated from the reaction medium after acidification. 

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