Anisole diphenyl ether

Ethers. Di-re-butyl ether Anisole Diphenyl ether. 

Chlorination.1 In combination with A1C13, this reagent chlorinates alkenes to provide vinyl chlorides and chlorinates arenes, but not benzene, to provide aryl chlorides. Anisole, diphenyl ether, and N,N-dimethylaniline are chlorinated exclusively in the para-position. Bromination can be effected by the combination of 1 with aluminum bromide. 

UV solvent effect and spectral shifts, anisole, diphenyl ether, acetanilide, dimethylanilinc, iodobenzene. 

Vinyl methyl ether Vinyl isopropyl ether Vinyl butyl ether 9.4 Aromatic Ethers Methyl phenyl ether (anisole) Diphenyl ether... 

Setting Up Have at your disposal 0.5 M stock solutions of anisole, diphenyl ether, and acetanilide in 15 M(90%) aqueous acetic acid and a 0.02 Msolution of bromine in 15 M acetic acid. Calibrate the spectrophotometer to zero absorbance at 400 nm using a solution of the arene substrate in acetic acid. Prepare this solution by using a 2-mL pipet to combine 2 mL of 15 M acetic acid and 2 mL of the stock solution of the substrate arene in a clean and dry cuvette. Stir the solution to ensure homogeneity and place the cuvette in the spectrophotometer. Adjust the absorbance reading of the spectrometer to zero. Record the laboratory temperature. 

ATRP can be performed in bulk, in solution, or in a heterogeneous system (e g., emulsion, suspension). Various solvents have been used for ATRP in solution for various monomers. These include benzene, toluene, acetone, ethyl acetate, anisole, diphenyl ether, dimethyl formamide, ethylene carbonate, alcohol, water, carbon dioxide, and many others (Matyjaszewski and Xia, 2001). The use of a solvent may become necessary when the polymer formed is insoluble in its monomer. The choice of a solvent is in uenced by several factors, such as chain transfer to solvent, interactions between solvent and the catalyst, catalyst poisoning by solvent (e.g., carboxylic acids and phos-... 

SuIfona.tlon, Sulfonation is a common reaction with dialkyl sulfates, either by slow decomposition on heating with the release of SO or by attack at the sulfur end of the O—S bond (63). Reaction products are usually the dimethyl ether, methanol, sulfonic acid, and methyl sulfonates, corresponding to both routes. Reactive aromatics are commonly those with higher reactivity to electrophilic substitution at temperatures > 100° C. Tn phenylamine, diphenylmethylamine, anisole, and diphenyl ether exhibit ring sulfonation at 150—160°C, 140°C, 155—160°C, and 180—190°C, respectively, but diphenyl ketone and benzyl methyl ether do not react up to 190°C. Diphenyl amine methylates and then sulfonates. Catalysis of sulfonation of anthraquinone by dimethyl sulfate occurs with thaHium(III) oxide or mercury(II) oxide at 170°C. Alkyl interchange also gives sulfation. 

ArH = dimethoxybenzenes, anisol, xylenes, fluorene, diphenyl ether, etc R = alkyl, aryl... 

ATRP is usually performed in solution. Many solvents can be used with the proviso that they do not interact adversely with the catalyst. Common solvents include ketones (butanonc, acetone) and alcohols (2-propanol). Solvents such as anisole and diphenyl ether are frequently used for polymerizations of S and other less polar monomers to provide greater catalyst solubility. 

Smith et al. (1998) have reported selective para acetylation of anisole, phenetole, and diphenyl ether with carboxylic anhydrides at 100 °C, in the presence of catalytic quantities of zeolites H-beta. The zeolite can be recovered and recycled to give essentially the same yield as that given by fresh zeolite. 

Ethers are unaffected by sodium and by acetyl (or benzoyl) chloride. Both the purely aliphatic ethers e.g., di-n-butyl ether (C4H, )30 and the mixed aliphatic - aromatic ethers (e.g., anisole C3HSOCH3) are encountered in Solubility Group V the purely aromatic ethers e.g., diphenyl ether (C,Hj)20 are generally insoluble in concentrated sulphuric acid and are found in Solubility Group VI. The purely aliphatic ethers are very inert and their final identification may, of necessity, depend upon their physical properties (b.p., density and/or refractive index). Ethers do, however, suffer fission when heated with excess of 67 per cent, hydriodic acid, but the reaction is generally only of value for the characterisation of symmetrical ethers (R = R ) ... 

Commercial PCP preparations often contain variable amounts of chlorophenols, hexachloroben-zene, phenoxyphenols, dioxins, dibenzofurans, chlorinated diphenyl ethers, dihydroxybiphenyls, anisoles, catechols, and other chlorinated dibenzodioxin and dibenzofuran isomers. These contaminants contribute to the toxicity of PCP — sometimes significantly — although the full extent of their interactions with PCP and with each other in PCP formulations are unknown. Unless these contaminants are removed or sharply reduced in existing technical- and commercial-grade PCP formulations, efforts to establish sound PCP criteria for protection of natural resources may be hindered. 

Commercial PCB mixtures frequently contain impurities that may contribute to the 2,3,7,8-TCDD toxic equivalency factor. These impurities may include other PCBs, dioxins, dibenzofurans, naphthalenes, diphenyl ethers and toluenes, phenoxy and biphenyl anisoles, xanthenes, xanthones, anthracenes, and fluorenes (Jones etal. 1993). PCB concentrations in avian tissues sometimes correlate positively with DDE concentrations (Mora et al. 1993). Eggs of peregrine falcons (Falco peregrinus) from California, for example, contained measurable quantities of various organochlorine compounds, including dioxins, dibenzofurans, mirex, hexachlorobenzene, and / ,//-DDE at 7.1 to 26.0 mg/kg FW PCB 126 accounted for 83% of the 2,3,7,8-TCDD equivalents, but its interaction with other detectable organochlorine compounds is largely unknown (Jarman et al. 1993). 

IVa tetrachlorides with diphenyl ether and anisole. J. Amer. chem. Soc. 69, 1515 (1947)-... 

The influence of diphenyl ether and anisole on the association of the polystyryllithium and 1,1-di-phenylmethyllithium active centers has been measured. Severe disaggregation of the polystyryllithium dimers, present in pure benzene, was found to occur at levels of ether addition at which several reliable kinetic studies reported in the literature unequivocally demonstrate a 1/2 order dependence upon polystyryllithium. These results indicate that a necessary connection between the degree of aggregation of organo1ithium polymers and the observed kinetic order of the propagation reaction need not exist. 

Several studies have appeared (12,13,14) in which the propagation reactions involving styryllithium were examined in mixed solvent systems comprising benzene or toluene and ethers. The kinetics were examined under conditions where the ether concentration was held constant and the active center concentration varied. In most cases, the kinetic orders of the reactions were identical to those observed in the absence of the ether. Thus, in part, the conclusion was reached (13,14) that the ethers did not alter the dimeric association state of polystyryllithium. The ethers used were tetrahydrofuran, diphenyl ether, anisole, and the ortho and para isomers of ethylanisole. 

We have examined the influence of diphenyl ether and anisole on the association of the polystyryllithium and the 1,1-diphenyl-methyllithium active centers in benzene solution. The analytical tool used was the vacuum viscometry method (1 .2. 2. ) which utilizes concentrated solutions of polystyryllithium and the terminated polymer in the entanglement regime. Our results show that the presence of these ethers can alter the association states of the foregoing active centers. These findings parallel previous work (2) involving tetrahydrofuran. 

Figure 1 contains chromatograms of polystyrenes prepared anionically in the presence of anisole and diphenyl ether. The narrow molecular weight distributions of these samples demonstrate that no detectable termination took place during the polymerizations. This lack of a termination step, regarding anisole, is in agreement with the polymerization results (34,35,36,37) where this ether was used as a co-solvent. 

The above comments should not be taken as claims that anisole and diphenyl ether cannot be metallated by organolithium species. For example, alkyllithiums are known (38,39,40) to react with anisole, usually in the ortho position. However, these reactions are generally slow, particularly at ambient temperature and when the ether is diluted with a hydrocarbon solvent. Our results merely indicate that active center deactivation via metallation of these aromatic ethers is not a serious problem during the time span of our measurements with species that are, at least, partially delocalized (33J ... 

Table I contains the association values, Nw, for the poly-styryllithium and 1,1-diphenylmethyllithium active centers in the presence of diphenyl ether or anisole. The influence on polysty-ryllithium association by the aromatic ethers is, as expected, less dramatic than observed (2) for tetrahydrofuran (THF) where the value for the equilibrium constant , of the following, was evaluated to be about 2xl02 ...

The data of Table I shows that anisole has proportionally a greater effect on the association of the 1,1-diphenylmethyllithium active center than does diphenyl ether. This difference may, in part, be due to steric effects involving the latter ether and the... 

The Influence of Diphenyl Ether and Anisole on the Association of the Poly(styryl) - and... 

Methyl benzoate, anisole, and diphenyl ether each give sandwich compounds with chromium vapor, although in rather low yield (32, 55, 110). Chromium appears to attack alkyl ethers and this deoxygenation probably competes with complexation with the aromatic oxygen compounds. No simple product has been isolated from chromium atoms and aniline, but bis(7V,7V-dimethylaniline)chromium has been prepared (32). The behavior of molybdenum and tungsten vapors closely resembles that of chromium in reactions with oxygen- and nitrogen-substituted arenes (113). 

The validity of the viscosity measurements regarding the reported52) influence of anisole and diphenyl ether on the association of the poly(styryl)lithium dimers has, though, been questioned 78-160>161>. Suffice it to note that the fallacies in the data provided 160,161) have been commented upon elsewhere 162). Even though it is well-known that ethereal solvents can interact with organolithium compounds, no explanation was given 78,160,161 as to why aromatic ethers should be completely exempt from this general behavior. 

Table 5—Summary of Electrophilic Substitution Reactions of Phenol, Diphenyl Ether, and Anisole... 

The available rate data for the substitution reactions of phenol, diphenyl ether, and anisole are summarized in Table 5. The elucidation of the reactivity of phenol is hindered by its partial conversion in basic media into the more reactive phenoxide anion. Because of the high reaction velocity of phenol and the even greater reactivity of phenoxide ion the relative rates are difficult to evaluate. Study of the bromination of substituted phenols (Bell and Spencer, 1959 Bell and Rawlinson, 1961) by electrochemical techniques suitable for fast reactions indicates the significance of both reaction paths even under acidic conditions. 

Rafikov et al. [35] describe a correlation between the electron-donating capacity of substituted benzenes and the efficiency of adduct formation with maleic anhydride. This is only valid if similar compounds are compared. The ionization potentials of benzene and toluene are 9.246 and 8.820 eV, respectively the yields of adduct formation are 70% and 30%, respectively. In the series of halogenobenzenes, the ionization potentials are as follows fluorobenzene, 9.195 eV chlorobenzene, 9.080 eV bromobenzene, 9.030 eV the yields of adducts are 7%, 2%, and <1%, respectively. Anisole and diphenyl ether, with ionization potentials of 8.220 and 8.090 eV, respectively, do not give adducts with maleic anhydride. It thus seems that an increase in the electron-donating capacity of the benzene derivative leads to a decrease in the yield of photoadducts. 

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