Chemical anisole

Anisole is a colourless and almost odourless liquid, having b.p. 154°, and dy 0-99. Like the aliphatic ethers, it is chemically inert, although of course the phenyl group shows the normal aromatic reactions. 

Anisole (500 g.) was purified by washing twice with 60 ml. of 2N sodium hydroxide, twice with 50 ml. of water, drying over anhydrous magnesium sulfate, and distillation, b.p. 43-46° (20 mm.). The checkers used anisole obtained from Kanto Chemical Co., Ltd., Japan. 

Anisole supplied by Eastman Organic Chemicals is satisfactory. 

Shell Chemical Company), exhibits a maximum at 300 nm, corresponding to that of the model chromophore anisole. The fluorescence intensity decreases monotonically with increasing concentration of 2,4-dihydroxybenzophenone (DHB) and, furthermore, decreases with time on continued excitation (274 nm) in the spectrophotometer. The fluorescence loss with time may be resolved into two exponential decays. Initially, a relatively rapid fluorescence loss is observed within 20 sec, followed by a slower loss. Loss constants for the initial (k ) and secondary (kj) exponential decays for 1.5 ym films (on glass slides) containing varying concentrations of DHB are provided in Table I (entries 1-3). The initial loss constants are seen to decrease more markedly with increasing DHB concentration than the secondary constants. 

Friedel-Crafts acylation is widely used for the production of aromatic ketones applied as intermediates in both fine chemicals and pharmaceutical industries. The reaction is carried out by using conventional homogenous catalysts, which represents significant technical and environmental problems. The present work reports the results obtained in the Friedel-Crafts acylation of aromatic substrates (anisole and 2-methoxynaphthalene) catalyzed by Beta zeolite obtained by crystallization of silanized seeds. This material exhibits hierarchical porosity and enhanced textural properties. For the anisole acylation, the catalytic activity over the conventional Beta zeolite is slightly higher than with the modified Beta material, probably due to the relatively small size of this substrate and the weaker acidity of the last sample. However, the opposite occurred in the acylation of a bulky substrate (2-methoxynaphthalene), with the modified Beta showing a higher conversion. This result is interpreted due to the presence of a hierarchical porosity in this material, which favors the accessibility to the active sites. 

Chain-transfer by Anisole in the Cationic Polymerisation of Isobutene, J. Penfold and P.H. Plesch, Proceedings of the Chemical Society, 1961, 311. 

Although Christ51 examined 170 shifts of some substituted nitrobenzenes 35 years ago, only at the beginning of the following decade did systematic studies of the substituent effects on 170 chemical shifts appear in the literature with the first reports52,53 of substituted anisoles, acetophenones and benzaldehides. The potential of this probe as a measure of substituent electronic effects was demonstrated. 

In the field of fine chemical synthesis there is an urgent need to substitute the cleaner technologies for the old polluting ones. It is hoped that the large economic and environmental benefits brought by the recently developed catalysis processes—acetylation of anisole and of veratrole, Beckmann rearrangement, and so forth—will initiate great strides in this field. 

Fig. 6.37. Energetics of formaldehyde loss from anisole. The inset shows the composite metastable peak due to two different amounts of kinetic energy release. Adapted from Ref. [129] with permission. American Chemical Society, 1973.

CASRN 15457-05-3 molecular formula C13H7F3N2O5 FW 328.20 Chemical/Physical. When fluorodifen as an aqueous suspension was irradiated using UV light (A, = 300 nm), 4-nitrophenol and 4-(trifluoromethyl)-2-aminophenol formed as the major products (>90% of total product formation). In addition, 4-(trifluoromethyl)-2-nitrophenol formed as a minor product (<1%) as well as 4-hydroxy-3-nitrobenzoic acid. In methanol, photolysis of fluorodifen yielded 4-nitrophenol and 2-amino-4-(trifluoromethyl)anisole. In cyclohexanone, 4-nitrophenol and 3-(trifluoromethyl)nitrobenzene were formed (Ruzo et al., 1980). 

Anisole Additives in gasoline to boost octane, used for the production of dyes, agricultural chemicals and antioxidants. 

Seddon and coworkers studied the Friedel-Crafts acylations of toluene, chlorobenzene and anisole with acetyl chloride in [emim][Al2Cl7] and obtained excellent regioselectivities to the para isomer, Scheme 9. Similarly, the fragrance chemical, traseolide, was obtained in 99% yield as a single isomer. Scheme 10. It should be noted, however, that the question of product recovery from the reaction medium still needs to be addressed in these systems. 

Equivalent protons. All hydrogens which are in identical environments have the same chemical shift and therefore absorb at the same frequency they are said to be chemically equivalent. This can arise in two ways. Firstly, the protons are equivalent if they are bonded to the same carbon atom which is also free to rotate. For example, the three protons in a methyl group are equivalent and appear as a singlet (see the spectra of toluene, anisole or acetophenone above), and the two protons of a methylene group, provided that it can rotate freely, are identical and appear as a singlet (see the spectrum of phenylacetic acid above) frequently this is not the case with methylene groups in cyclic systems where rotation is restricted. 

Organosulfur compounds are especially useful for C-fluorine bond forming reactions with (difluoroiodo)arenes. For example, dithioketal derivatives of benzophenones are readily converted to diaryldifluoromethanes with two equivalents of DFIT in dichloromethane [105]. This transformation has also been effected with electro chemically prepared p-(difluoroiodo)anisole/Et3N 3HF, and by anodic oxidations of p-iodoanisole in acetonitrile solutions containing Et3N 3HF and dithioketal substrates (Scheme 35) [96]. Under the latter conditions, p-(difluoroiodo)anisole is continuously regenerated, and the iodoarene was employed at catalytic levels for high yield conversions of the dithioketals to diaryldifluoromethanes. 

Figure 2.5 Relative occupancy (%) of the intracrystalline volume of a H-BEA zeolite during the transformation of a 2 1 molar anisole - acetic anhydride mixture in a batch reactor, assuming no adsorption of acetic acid and full occupancy of the micropores. Anisole ( ), acetic anhydride (o) and 4-methoxyacetophenone (x). Reprinted from Journal of Catalysis, Vol. 187, Derouane et al., Zeolite catalysts as solid solvents in Fine Chemicals synthesis 1. Catalyst deactivation in the Friedel-Crafts acetylation of anisole, pp. 209-218, copyright (1999), with permission from Elsevier...

Derouane, E. G., Dillon, C. J., Bethell, D., Derouane Abd-Hamid, S. B. Zeolite catalysts as solid solvents in fine chemicals synthesis-1. Catalyst deactivation in the Friedel-Crafts acetylation of anisole, J. Catal., 1999, 187, 209-218. 

The primary chemicals associated with taints are solvents or inks, aliphatic aldehydes and ketones, phenols or halogenated phenols, and anisoles (Lord, 2003). 

Several chemical oxidants produce the NIH shift in the hydroxylation of 4-anisole-2H.681 Significantly, the system consisting of f-Bu02H-Mo(CO)6 induced deuterium migration the most. This reagent is known to effect many other reactions characteristic of monooxygenases. The yields obtained in these hydroxylations were not reported. 

Anodic chlorination of toluene and anisole using graphite electrodes, chemically modified with a-cyclodextrin, results in higher para selectivity in comparison to chlorination with NaOCl in presence of a-cyclodextrin in solution384. Similar results are observed with a Pt electrode38. ... 

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