Anisole fluoro benzene

Titanous Chloride System. For the oxidation of toluene and fluoro-benzene, oxygen was bubbled (30 ml./min.) through titanous chloride (1-15 ml.) in 0.05N sulfuric acid (1 liter) containing the aromatic reactant (2 ml.). Under these conditions, the oxidation of anisole was negligible, and instead sulfuric acid was replaced by distilled water. The concentrations of titanous ion used are given in Tables I-IIL... 

Fluoroanisole Anisole, o-fluoro- (8) Benzene, 1-fluoro-2-methoxy- (9) (321-28-8) Potassium hexamethyidisilylamide Aldrich Potassium-(bis(trimethylsilyl)amide Silanamine, 1,1,1-trimethyl-N-(trimethylsilyl)-, potassium salt (9) (40949-94-8) Isobutyronitrile (8) Propanenitrile, 2-methyl- (9) (78-82-0)... 

The fluorination of other activated aromatic compounds, such as anisole and phenol, undergo monofluorination mainly in the ortho and para positions, whereas the fluorination of deactivated aromatics, such as nitrobenzene, trifluoromethylbenzene and benzoic acid, give predominantly the corresponding meta fluoro-derivatives which is consistent with a typical electrophilic substitution process. Also, fluoro-, chloro- and bromo-benzenes are deactivated with respect to benzene itself but are fluorinated preferentially in the ortho and para positions [139]. At higher temperatures, polychlorobenzenes undergo substitution and addition of fluorine to give chlorofluorocyclohexanes [136]. 

The products of the electrochemical perfluorination of aromatic and heteroaromatic compounds are the corresponding perfluorinated cyclic and heterocyclic alkanes.28 and also per-fluorinated derivatives of the heteroaromatic compounds. Perfluorocyclohexane is the principal product from the electrochemical fluorination of benzene and fluorobenzene. Chloro derivatives of perfluorocyclohexane are produced from chlorobenzenes. Anisoles give fully saturated per-fluoro ethers, together with cleavage products. Extensive cleavage is observed in the fluorination of benzenethiols. Chloropyridines, fluorocarbons and sulfur hexafluoride or nitrogen trifluoride are characteristic byproducts from the above scries of reactions. 

Substituted 1-fluoropyridinium triflates have been used for substitution of hydrogen by fluorine in aromatic compounds (Table 3).46"50 Thus benzene is transformed to fluorobenzene (56 % yield, l-fluoro-2,6-bis(methoxycarbonyl)pyridinium triflate), Af-ethoxycarbonylaniline gives Al-ethoxycarbonyl-2- and -4-fluoroaniline (60 and 27% yield, respectively, 1-fluoropyridinium triflate), and phenylurethane also gives the products of fluorination at position 2 (47%) and 4 (32%) of the aromatic ring [l-fluoro-2,6-bis(methoxycarbonyl)pyridinium triflate]. In the case of fluorination of anisole, 1-fluoropyridinium tetrafluoroborate gives 19% 2- and 17% 4-fluoroanisole.46... 

The electrochemical fluorination (Simons cell anhydrous HF electrolyte, sometimes with the addition of NaF to improve conductivity) of benzene, fluoro- and chloro-benzene, w-dichlorobenzene, anisole, o-chloroanisole, thiophenol, p-chloro-thiophenol, iw-thiocresol, 2-chloropyridine, and 3-chloropyridine has been examined in detail (see also p. 212). Benzene and fluorobenzene give mainly dodecafluoro-cyclohexane, but a low yield of chloroundecafluorocyclohexane is obtained from chlorobenzene, and the ethers give fully saturated perfluoroethers with some cleaved products cleavage of the thiophenols leads to extensive formation of SFe. Mixtures of perfluoro-alicyclic and -aliphatic tertiary amines are obtained by similar fluorination of AW-dialkylanilines [PhNEta and PhNMeR (R = Et, Pr, or Bu )] and the three A A -dimethyltoluidines. The relatively new technique (Vol. 2, p. 353) of controlled fluorination at a platinum anode in acetonitrile con-+ -... 

In graph 2.2, the relative reactivities compared to benzene of toluene, fluoro-, chlorobenzene and anisole are plotted as a function of their respective o -values. A linear plot starting from chlorobenzene through fluorobenzene and toluene down to anisole is expected in line with decreasing o -values. The slope of the plot however... 

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