Phenyl Subject

Subject Phenyl acetones by electrolytic oxidation From "guest" ... 

Protection Against Flex Cracking. Most antioxidants including waxes provide oxidation protection under static conditions. However, most of them are not effective in mbber products subjected to dynamic flexing, eg, sidewall compounds in tires. The best dynamic protection is provided by either /V-alkyl-/V-phenyl or diaryl-/)-phenylene diamines. 

Although most nonionic organic chemicals are subject to low energy bonding mechanisms, sorption of phenyl- and other substituted-urea pesticides such as diuron to sod or sod components has been attributed to a variety of mechanisms, depending on the sorbent. The mechanisms include hydrophobic interactions, cation bridging, van der Waals forces, and charge-transfer complexes. 

Allyl groups are subject to oxidative deprotection with Chromiapillared Montmorillonite Clay, -BuOOH, CH2CI2, isooctane, 85% yield. Allylamines are cleaved in 84—90% yield, and allyl phenyl ethers are cleaved in 80% yield. 

Reaction of anthanilic acid 112 with acid anhydrides afforded the corresponding imide derivatives 113. Subjecting 113 to intramolecular Wittig cyclization has been achieved by treatment with A-phenyl(triphe-nylphosphoranylidene)etheneimine in toluene or dioxane whereby the corresponding pyrroloquinolines 116 were obtained (94TL9229). The intermediate 115 resulting from the rearrangement of 114 could be isolated when the reaction was done at room temperature (Scheme 22). 

Phenyl-ethyl alcohol can be prepared by numerous methods, several of which are the subject-matter of patents. It may be prepared, for example, by the conversion of phenyl-bromo-lactic acid into phenyl-acetaldehyde, and then reducing this body with sodium. Or it may be prepared by reducing phenyl-acetic esters with sodium and absolute alcohol in the folio-wing manner —... 

A solution containing 741 g (5.0 mols) of 1-phenyl-2-propylidenylhydrazine, 300 g (5.0 mols) of glacial acetic acid and 900 cc of absolute ethanol was subjected to hydrogenation at 1,875 psi of hydrogen in the presence of 10 gof platinum oxide catalyst and at a temperature of 30°C to 50°C (variation due to exothermic reaction). The catalyst was removed by filtration and the solvent and acetic acid were distilled. The residue was taken up In water and made strongly alkaline by the addition of solid potassium hydroxide. The alkaline mixture was extracted with ether and the ether extracts dried with potassium carbonate. The product was collected by fractional distillation, BP B5°C (0.30 mm) yield 512 g (68%). 

In the reaction of 88 with /(-phenethyl bromide, l-phenethyl-3-phenylpropyl methyl sulfoxide and bis-3-phenylpropyl sulfoxide, besides 3-phenylpropyl methyl sulfoxide are obtained118. Sulfoxides, bearing a /1-hydrogen to the sulfmyl function, give olefins upon thermolysis. Utilizing this reaction, Trost and Bridges120 alkylated benzyl phenyl sulfoxide, 3,4-methylenedioxybenzyl phenyl sulfoxide, phenylthiomethyl phenyl sulfoxide, phenylsulfinylmethyl phenyl sulfoxide and cyanomethyl phenyl sulfoxide with alkyl, allyl and benzyl halides and subjected these sulfoxides to thermolysis, obtaining olefins in one-pot processes. 

In recent years a lot of investigations have been made on this subject. E.g. Maciel and co-workers 41,42) found that several of the most prominent signals in the CP/M AS NMR spectra can be tentatively assigned for Norway spruce lignin to specific carbon atoms in the phenyl propane unit. Further also in the solid state the signals at about 105 ppm are indicative of hardwood. 

The bromination of the phenyl group in TgPhg has been reported by He et al. but few characterization data were given. The product, Tg[C6H4-Br]g, obtained in a 60% yield was subject to Pd catalyzed arylations to form the first organic-based quantum dot-like materials (Figure 19). ... 

The intermolecular C-C bond formation mediated by (TMSlsSiH has been the subject of several synthetically useful investigations. The effect of the bulky (TMSfsSiH can be appreciated in the example of jS- or -substituted a-methylenebutyrolactones with -BuI (Reaction 65). The formation of a,P- or a,y-disubstituted lactones was obtained in good yields and diastereoselectivity, when one of the substituents is a phenyl ring. 

The mechanism of the Willgerodt reaction is not completely known, but some conceivable mechanisms can be excluded. Thus, one might suppose that the alkyl group becomes completely detached from the ring and then attacks it with its other end. However, this possibility is ruled out by experiments such as the following When isobutyl phenyl ketone (42) is subjected to the Willgerodt reaction, the product is 43, not 44, which would arise if the end carbon of the ketone became bonded to the ring in the product ... 

B. Solvolysis of Phosphoric Acid Derivatives.—Interest continues in neighbouring-group participation in the solvolysis of phosphate esters. As a potential model compound for investigating the mechanism of ribo-nuclease action, the phenyl hydrogen phosphate ester of c/j-3,4-tetrahydro-furandiol (24) has been the subject of a detailed study. Above (and probably also below) pH 4 hydrolysis gives solely the cyclic phosphate (25)... 

Two types of sulfoximinocarboxylates (analogous to sulfinylcarboxylates 16), namely 5 -aryl-5 -methoxycarbonylmethyl-A(-methyl sulfoximine 36 and -methyl-5 -phenyl-A(-ethoxycarbonyl sulfoximine 37, were subjected to hydrolysis in the presence of PLE in a phosphate buffer. As a result of a kinetic resolution, both the enantiomerically enriched recovered substrates and the products of hydrolysis and subsequent decarboxylation 38 and 39, respectively, were obtained with moderate to good ees (Equations 20 and 21). Interestingly, in each case the enantiomers of the substrates, having opposite spatial arrangement of the analogous substituents, were preferentially hydrolysed. This was explained in terms of the Jones PLE active site model. ... 

To obtain a better understanding of the reaction mechanism, some compounds that are considered to he intermediates were subjected to the reaction. Various reaction courses can be considered as illustrated in Fig. 21. Path A a-Methyltropic acid is oxidized to a-phenyl-a-methylmalonic acid. Then, the malonate is converted to optically active a-phenylpropionate hy arylmalonate decarboxylase. In order to confirm this assumption, incubation of the malonic acid with Rhodococcus sp. was carried out. The result obtained was the total recovery of the substrate, indicating that no decarboxylase is present in this bacterium. Path B a-Methyltropic acid is converted to racemic a-phenylpropionic acid, which is deracemized to optically active propionic acid. To examine the possibility of this route, racemic a-phenylpropionic acid was subjected to the reaction to observe... 

Other transition metals have received much less attention. Complexes of palladium and 2-amino-phenyl-containing formazans have been reported.397 Mercury complexes of tridentate formazans have been studied.398 Silver complexes of tridentate benzothiazolyl-containing formazans have also been studied.399 Recently, alkali and alkaline earth metals have been the subject of many studies. Formazans such as 228 and 229 as well as the macrocyclic 204 have received considerable attention as metal-specific analytical reagents.400-41 1... 

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