P-alkyl phenol

This type of expansion very frequently occurs among long-chain aliphatic compounds. All the fatty acids show it, and the expansion is very similar with the a-bromo-acids, the nitriles, alcohols, amides, ureas, oximes, amines, and acetamides. In all these series the expanded film is probably liquid, with a definite surface-vapour pressure, and the area is about 48 sq. A. at the lowest compression. Some other substances form similar films but of different areas the p-alkyl phenols tend to 39 sq. A. (j), and the a-monoglycerides (j) and the a-glyceryl ethers1 of long-chain alcohols,... 

One of the analogues is calix arenes which are oligomeric cyclic analogues of novolac resin derived through the condensation of p-alkyl phenols with formaldehyde. Quite re-... 

With reference to the addition reaction and the subsequent condensation reaction, phenol is trifunctional (two ortho and one para positions) and formaldehyde is bifunctional. Therefore, to obtain non-cross-linked products, the molecular weight has to be kept low, which can be achieved by using less than the theoretical amount of formaldehyde. It has been found empirically that a formaldehyde/phenol molar ratio of 0.75 1 must not be exceeded in order to avoid the formation of a cross-linked product. This molar ratio corresponds to an equivalent ratio of the functional groups of r = (2 X 0.75) (3 x 1) = 0.5. Of course, theoretically, the equivalent ratio should be 0.5 in the absence of intramolecular reactions and with quantitative reaction at all the phenol reactive sites. Yet this agreement is fortuitous, since theory cannot correspond exactly with experiment because of the occurrence of intramolecular reactions, the nonequivalence of o- and p-phenol sites in these irreversible reactions, and the formation of open-chain formal structures. Correspondingly, the so-called pseudonovolaks, the o- and p-alkyl phenols, are only bifunctional. They do not give a cross-linked product with an excess of formaldehyde and therefore cannot be cured. 

Finally, the ssmthesis of the compounds imder consideration can be effected by the condensation of two moles of a hydroxylallq lbenzyl alcohol or the corresponding benzyl halide with one mole of a p-alkyl-phenol in the presence of catalysts, as which HCl, H2SO4, ZnCl2, aromatic sulfonic acids, etc., are recommended [214] ... 

Calixarenes are the products of condensation of p-alkyl-phenols and formaldehyde, which is the main route for the synthesis of these compounds. These starting materials are those used for production of bakelite, and indeed calixarenes were first made during a study of the formation of this material [28, 29]. The product isolated was assumed to be exclusively calix[4]arene. Later, after numerous studies, it was found that a mixture of calixarenes is actually formed on reaction of the corresponding ligsons, and the precise course of the reaction depends on many factors [26, 27, 30-33]. The basic variables relevant to the one-flask process in the presence of bases are as follows ... 

Ludwig used high performance liquid chromatography to determine oligomers in p-alkyl phenol-formaldehyde resins. 

Sulfur monochloride reacts with p-alkyl phenol to produce alkyl phenol disulfide accelerator. 

Carbonless Paper. Novolaks based on p-phenylphenol and other p-alkyl phenol copolymers have proven to be valuable in the manufacture of carbonless paper. In order to keep the oxidation and yellowing of the papers low, highly hindered substituted alkyl phenolics are incorporated as antioxidants. New formulations also incorporate the phenolics as zinc and aluminum salts. 

The above is a general procedure for preparing trialkyl orthophosphates. Similar yields are obtained for trimethyl phosphate, b.p. 62°/5 mm. triethyl phosphate, b.p. 75-5°/5 mm. tri-n-propyl phosphate, b.p. 107-5°/5 mm. tri-Mo-propyl phosphate, b.p. 83-5°/5 mm. tri-wo-butyl phosphate, b.p. 117°/5-5 mm. and tri- -amyl phosphate, b.p. 167-5°/5 mm. The alkyl phosphates are excellent alkylating agents for primary aromatic amines (see Section IV,41) they can also be ua for alkylating phenols (compare Sections IV,104-105). Trimethyl phosphate also finds application as a methylating agent for aliphatie alcohols (compare Section 111,58). 

Upon formulating these relationships, phenols with branched alkyl substituents were not included in the data of a-cyclodextrin systems, though they were included in (3-cyclodextrin systems. In all the above equations, the n term was statistically significant at the 99.5 % level of confidence, indicating that the hydrophobic interaction plays a decisive role in the complexation of cyclodextrin with phenols. The Ibrnch term was statistically significant at the 99.5% level of confidence for (3-cyclo-dextrin complexes with m- and p-substituted phenols. The stability of the complexes increases with an increasing number of branches in substituents. This was ascribed to the attractive van der Waals interaction due to the close fitness of the branched substituents to the (3-cyclodextrin cavity. The steric effect of substituents was also observed for a-cyclodextrin complexes with p-substituted phenols (Eq. 22). In this case, the B parameter was used in place of Ibmch, since no phenol with a branched... 

The a-oxoalkanephosphonic acids may also serve as starting materials for other interesting structures. They can be reacted with phenols catalyzed by Lewis acids adding two p-hydroxyphenyl groups [145]. This reaction may be of some interest by using long-chain alkyl phenols. 

The availability of Nafion on silica has not only lowered the cost of the resin but also has made it versatile (Sun et al., 1997 Harmer et al., 1998). A number of industrially important reactions have been attempted, with considerable success, with these catalysts. Consider the Fries rearrangement of phenyl acetate to p-acetyl phenol (/t-hydroxy acetophenone). This has been accomplished by Hoelderich and co-workers (Heidekum, 1998). In the ca.se of alkylation of benzene with benzyl alcohol, Amberlyst-15 and p-toluene sulphonic acid are ineffective and Nafion on silica works well at 80 °C. 

P. E. Chaplanov, A. D. Chemikov, O. G. Mironov, G. N. Semanov, A. G. Svinukhov, A. G. Yaremenko, F. V. Linchevskij, N. A. Melnik, 1. A. Murashev, and I. S. Akhmetzhanov. Removing oils and petroleum products from water surfaces—using mixture of oxyethylated alkyl-phenol, alkyl-phosphate and fatty acid diethanolamine. Patent SU 1325816-A, 1992. 

Experiments carried out by feeding TBPE only over H-MWW, showed that the O-alkylated product do not rearrange to C-alkylated phenol derivatives in our conditions, but it is hydrolysed to phenol. So, TBPE is not a reaction intermediate and perforce O-and C-alkylation are parallel reactions. Also o-TBP and p-TBP were fed each of them alone over our catalysts. As it could be observed in Fig. lb, o-TBP convert to p-TBP (by transalkylation) and in minor extent 2,4-DTBP (by disproportionation), while p-TBP (results not shown here) convert to 2,4-DTBP (by disproportionation). Because the transalkylation and disproportionation are bimolecular reactions and need large spaces, it is plausible to suppose that the alkylation could not take place in the pores, but on the external surface of H-MWW zeolites. 

Cresex [Cresol extraction] One of the Sorbex processes. This one extracts p- or m-cresol from mixed cresols, and ciesols as a class from higher alkyl phenols. By 1990, one plant had been licensed. 

Other ketones may be reduced by this same procedure. The submitters report that the following have been reduced with yields of 70-90 per cent 0- and p-butyryl phenols, 0- and p-valeryl phenols, 0- and />-caproyl phenols, 0- and />-heptanoyl phenols, 0- and -octanoyl phenols, o- and />-pelargonyl phenols, o- and />-undecylyl phenols. The same procedure applies to acyl resorcinols and acyl chlororesorcinols. Caproyl and octanoyl resorcinols reduce to the corresponding alkyl derivatives in yields of 70-80 per cent. Butyryl, valeryl, caproyl, heptanoyl,... 

Alkyl and aiyl arenediazoates ( diazoethers ) are generally unstable and even explosive eompoimds. They are produeed by interaetion of aleohols with (explosive) bis(arenediazo) oxides, or of p-bloeked phenols with diazonium salts. The thio analogues are similar. Individually indexed eompounds are ... 

Fraction 8 (Figure 5 5) is mostly alkylated phenols and indanols with a trace amount of smaller alkanes. The base line shift is due to the co-elution of several large phenolic species in many isomeric forms. Fraction 9 (Figure 5-6) does not contain any alkanes. The ratio of the o-cresols to m, p-cresols increases from fraction 8 to 9. Both m-cresol and p-cresol are structurally longer than o-cresol. Some long aromatic species such as biphenyls also appear in this fraction. Compared to fraction 8, the phenols in fraction 9 are of shorter size... 

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. 

Experimental procedures are given in Expt 6.107 for o- and p-hydroxy-propiophenones (R = Et). The ortho-para ratio in the product is influenced by the nature of the alkyl residue, the temperature, the solvent and the amount of aluminium chloride used generally low temperatures favour the formation of p-hydroxyketones. It is usually possible to separate the two hydroxyketones by fractional distillation under reduced pressure through an efficient fractionating column or by steam distillation the ortho isomers, being chelated, are more steam volatile. It may be mentioned that Clemmensen reduction (cf. Sections 5.1.3, p. 476 and 6.1.1, p. 826) of the hydroxyketones affords an excellent route to alkyl phenols. 

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