Irradiation phenol

Keywords methyl aryl ether, pyridine hydrochloride, microwave irradiation, phenol... 

As may be expected oxyanions of molecules known as antioxidants were also found to produce solvated electrons under irradiation. Phenolate anion in water leads to aqueous electron photoejection under 254 nm irradiation [62] and to benzosemiquinone through phenoxy radicals as shown by CIDNP arguments [63], In the case of / -naphtholate [64] the electron is photoejected from the unrelaxed singlet state [65, 66] with a low quantum yield (see Table 3) [67],... 

Figure 4. Binding of BHBM to polypropylene by UV irradiation. Phenolic OH measured by after (E) extraction.

Irradiation of PP in air leads to oxidative degradation, evidenced by discoloration and embrittlement. The extent of the degradation depends on crystallinity, MW, MWD, and chain mobility [Kadir et al., 1989 Kashiwabara and Seguchi, 1992 Williams, 1992]. Neat PP does not discolor on irradiation up to 100 kGy [Williams, 1992]. The antioxidants should be selected so as not to cause the discoloration. However, most commercial preparations containing phenolic antioxidants turn yellow on irradiation. Phenolic antioxidants produce stable phenoxyl radicals that convert into colored quinonoids. Other stabilizers and antioxidants are compounds that contain either phosphorous [Bentrude, 1965 de Paolo and Smith, 1968], sulfur [Jirackova and Pospisil, 1979], or hindered piperidine derivatives [Carlsson, et al., 1980 Felder et al., 1980 Allen et al., 1981]. A comprehensive list of stabilizers and their mode of action was given by Dexter [1992]. It is noteworthy that antioxidants and stabilizers are excluded from the crystalline regions [Winslow et al., 1966] thus they would provide protection only within the amorphous domains. 

Lithium tetrahydridoaluminate/ cobaltous chloride/irradiation Phenols from cyclic phenolethers Retention of carhon-carhon double bonds Selective and preferential reduction... 

Sodium nitrite/irradiation Phenols from ar. amines... 

Reaction that can be carried out by the oxidative coupling of radicals may also be initiated by irradiation with UV light. This procedure is especially useful if the educt contains oleflnic double bonds since they are vulnerable to the oxidants used in the usual phenol coupling reactions. Photochemically excited benzene derivatives may even attack ester carbon atoms which is generally not observed with phenol radicals (I. Ninoraiya, 1973 N.C. Yang, 1966). 

Thermolysis (115°C) or irradiation of the epoxide 3, generated from bicyclo[2.2.0]hexa-2,5-diene ( Dewar benzene") with 3-chloroperoxybenzoic acid, gives a mixture of the valence tautomers oxcpin and benzene oxide together with traces of phenol.111112... 

Due to the instability of the seven-membered heterocyclic ring, oxepin is prone to isomerization reactions to bicyclic heterocycles such as benzene oxide. Irradiation of oxepin with UV light of/. > 310 nm gives the isomeric 2-oxabicyclo[3.2.0]heptadiene(l) in high yield.12 207 At shorter wave lengths, phenol is formed predominantly.207... 

Oxepin has also been converted photochemically to phenol in 74% yield. This reaction occurs under irradiation conditions by which benzene oxide is excited to a triplet state, e.g. by irradiation in acetone as solvent.207 A rare example for a nucleophilic catalysis of the aromatization of an oxepin/benzene oxide to a phenol has been reported for /err-butyl oxepin-4-carboxylate which undergoes a rearrangement reaction in the presence of trimethylamine to give a mixture of /m-butyl 3-hydroxybenzoate (94%) and 4-hydroxybenzoate (6%).243... 

A solution of phenol (188 mg, 2 mmol) and benzonitrile (2.06 g, 20 mmol) in McCN (20 mL) was degassed by bubbling nitrogen through it and irradiated with a 16-W low-pressure mercury arc lamp (Applied Photophysics Ltd, APQ40) for 24h. The crude product was separated by flash chromatography (EtOAc/ petroleum ether 1 5) to give yellow crystals yield 79 mg (20%) mp 53-55 C. 

Enamels. The flexibility grades for the eight enamels (Table I) that were irradiated with 3-4 Mrad and 6-7.5 Mrad at 5, —30, and —90°C are shown in Table II. These data indicate that the epoxy-based enamels showed the best initial flexibility at — 90 °C and maintained their flexibility after irradiation. The preferred enamels were the epoxy phenolic with aluminum pigment, epoxy-wax and butadiene-styrene copolymer with aluminum pigment, and epoxy-wax with aluminum pigment. Tinplate adhesion before and after irradiation was satisfactory for the eight enamels. 

Extractives from Can Enamels. Earlier work reported by Pratt (1) showed that in a comparison between irradiation processing and thermal processing, no significant differences were found in the amount of extractives obtained from three commercial can enamels—epoxy phenolic, polybutadiene, and oleoresinous—in the presence of three aqueous... 

Following the same procedures described in the above-mentioned study, additional extractive data were obtained for the epoxy phenolic enamel that was irradiated at 4.7-7.1 Mrad at 25 and — 30 °C in the presence of distilled water, 3% acetic acid, and n-heptane. The changes in the amount of extractives resulting from the irradiation treatment are shown in Table IX. In the case of the water and acetic acid extractives, there was no change in either the chloroform-soluble fractions or the chloroform-insoluble fractions. In the case of the n-heptane extractives, the amount of extractives decreased when the irradiation temperature was reduced from +25 to — 30°C. Infrared spectra of the chloroform-soluble residues from the water and acetic acid extractives of the unirradiated and irradiated enamel were identical to the chloroform-soluble residues from the solvent blanks. In other words, the epoxy phenolic... 

The production test showed that the epoxy phenolic enamel was the preferred enamel for coating tinplate containers used in packaging irradiation-sterilized ham and beef. The preferred end-sealing compound for the same application was the blend of cured and uncured isobutylene-isoprene copolymer. 

The evaluation of the components of the tinplate container showed that the preferred enamel for irradiation processing was the epoxy phenolic the preferred end-sealing compound was the blend of cured and uncured isobutylene—isoprene copolymer. Component testing of tinplate and solder for possible changes in mechanical properties, microstructure, and corrosion resistance indicated that the radiation caused... 

Shelegova irradiated nitrobenzene vapor with various light sources. In the 2160—2900A region the products were phenol and N02 in the 1850—2160A region, phenol and polynitro-benzenes (Ref 3) ... 

As discussed in Section 8.10, dediazoniation in methanol or ethanol yields mixtures of the corresponding aryl ethers and arenes, except with alcohols of very low nucleo-philicity such as trifluoroethanol, in which the aryl ether is the main product. Therefore aryl ethers are, in general, synthesized by alkylation of the respective phenol. Olah and Wu (1991) demonstrated, however, that phenylalkyl and aryl ethers can be obtained in 46-88% yield from benzenediazonium tetrafluoroborate using alkoxy- and phenoxytrimethylsilanes in solution in Freon 113 (l,l,2-trichloro-l,2,2-tri-fluoroethane) at 55-60 °C with ultrasonic irradiation. As seen from the stoichiometric... 

As in the case of benzimidazole, a parallel synthesis of benzoxazoles was described. The authors report that mixing directly differently substituted o-amino phenols 193 with acylating agents 194 and heating at 200 °C for 10-15 min under microwave irradiation, a collection of benzoxazoles 195 was obtained (Scheme 70). With this reaction, a 48-member library of benzoxazoles with different substituents on the aromatic rings was obtained [125]. 

For the synthesis of coumarins, the Pechmann reaction [145] is one of the most popular synthetic routes. As the reaction is conventionally carried out at high temperature, two microwave-assisted versions have been recently described. Besson and co-workers described the cyclocondensation of different m-amino phenols 226 with /1-ketoesters 227 on graphite/montmorillonite KIO support (Scheme 83). The use of graphite was crucial in the development of the reaction conditions. In fact, microwave irradiation of the reagents using different conditions gave poor results in terms of yields and purity. The optimized conditions, using a monomode microwave system, employed... 

A solvent-free synthesis of flavones was recently reported by microwave-assisted reaction of phloroglucinol 231 and differently substituted /1-ketoesters 232 [148]. The reaction was simply carried out by mixing the phenol and the ester in an open test tube followed by irradiation for 2-3 min. The internal temperature reached 240 °C and yields were in the range from 68 to 96%. Scheme 85 describes the application of this procedure to the synthesis of the natural product chrysin 233. 

Many reactions have been shown to benefit from irradiation with ultrasound (ref. 19). We therefore decided to investigate the effect of ultrasound, different catalysts and the presence of solids on Ullmann diaryl ether synthesis. Indeed, sonication of mixtures of a phenol and a bromoaromatic compound, in the absence of solvent and presence of copper (I) iodide as catalyst and potassium carbonate as base, produces good yields of diaryl ethers at relatively low temperatures (Fig. 10) (ref 20). 

Among other compounds used to cleave carboxylic esters have been Dowex-50, Me3SiI, and KOSiMe3. Phenolic esters can be similarly cleaved in fact the reaction is usually faster for these compounds.Phenolic esters have been selectively hydrolyzed in the presence of alkyl esters on alumina, using irradiation... 

Chlorinated dibenzo ip-dioxins are contaminants of phenol-based pesticides and may enter the environment where they are subject to the action of sunlight. Rate measurements showed that 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) is more rapidly photolyzed in methanol than octachlorodi-benzo-p-dioxin. Initially TCDD yields 2,3,7-trichlorodiben-zo-p-dioxin, and subsequent reductive dechlorination is accompanied by ring fission. Pure dibenzo-p-dioxin gave polymeric material and some 2,2 -dihydroxybiphenyl on irradiation. Riboflavin-sensitized photolysis of the potential precursors of dioxins, 2,4-dichlorophenol and 2,4,5-trichloro-phenol, in water gave no detectable dioxins. The products identified were chlorinated phenoxyphenols and dihydroxy-biphenyls. In contrast, aqueous alkaline solutions of purified pentachlorophenol gave traces of octachlorodibenzo-p-dioxin on irradiation. 

H NMR data has been reported for the ethylzinc complex, Zn(TPP—NMe)Et, formed from the reaction of free-base N-methyl porphyrin H(TPP—NMe) with ZnEti. The ethyl proton chemical shifts are observed upheld, evidence that the ethyl group is coordinated to zinc near the center of the porphyrin. The complex is stable under N2 in the dark, but decomposed by a radical mechanism in visible light.The complex reacted with hindered phenols (HOAr) when irradiated with visible light to give ethane and the aryloxo complexes Zn(TPP—NMe)OAr. The reaction of Zn(TPP—NMe)Et, a secondary amine (HNEt2) and CO2 gave zinc carbamate complexes, for example Zn(TPP—NMclOiCNEti."" ... 

The Popik group has recently begun to explore the potential of phenols to photorelease ethers and alcohols attached to an ortho-hem,y c group. For example, they have shown that esters and ethers of (3-hydroxymethyl)naphthalene-2-ol (i.e., 70) efficiently release the corresponding alcohols and acids upon exposure to UV irradiation ( 0.3),50 with formation of naphthoquinone methide 71 occurring in the process (Eq. 1.17). 

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