Aniline Anisole

In addition to benzene and alkylbenzenes several other aromatics (nitrobenzene, aniline, anisole, benzoic acid, etc.) were hydrogenated, usually with much lower rates. Benzoic acid and benzoates gave the corresponding cyclohexyl derivatives, however, in case of acetophenone some deoxygenation was also observed with the Ru-3 catalyst [158]. This latter observation raises some doubts regarding the truly homogeneous nature of the reaction. 

Analytical Procedures for Explosives and for Primary Materials Used for their Manufacture are described under corresponding primary materials, such as Aniline, Anisole, Benzene, Toluene, etc... 

Quite a number of other high explosives were introduced during this period nitro derivatives of aniline, anisole, diphenylamine, cresols, xylenols, etc. Some of these were used as bursting charges and some as boosters, the outstanding representative of the booster explosives being trinitrophenylmethyinitramine (Tetryl). 

Some monosubstituted benzenes are named as substituted benzenes (for example, bromobenzene, nitrobenzene) others have names that incorporate the substituent (for example, toluene, phenol, aniline, anisole). 

Arenediazonium ions are relatively weak electrophiles, and therefore react only with electron-rich aromatic substrates like aryl amines and phenols. Aromatic compounds like anisole, mesitylene, acylated anilines or phenolic esters are ordinarily not reactive enough to be suitable substrates however they may be coupled... 

Electrostatic potential map—cont d ammonia, 145 aniline, 925 anilinium ion, 925 anisole, 111 18]annulene, 535 arene, 74 azulene, 541 benzaldehyde, 565, 704 benzene, 44, 521, 565 benzenediazonium ion, 945 benzoquinone, 631 benzyl carbocation, 377 benzyne, 576 borane, 223... 

Amyl bromide [Pentane, 1-bromo-], 82 Aniline [Benzenamine], 122 Anilines, o-alkylation of, 15 Anisole [Benzene, methoxy-], 48 Amsyl chloride [Benzene, l-(chloromethyl)-... 

Thioacetals eliminate to vinylsulfides in the presence of CuOTf (Scheme 46).192 Cu1 and Cu11 triflates are mild Lewis acids for Friedel-Crafts acylation and alkylation reactions. CuOTf effectively catalyzes the reaction of anisole with selenoesters.193,194 Copper(II) sulfate promotes epoxide ring opening reactions in the presence of pyridine,195 with retention of configuration being observed. Cu(OTf)2 is a catalyst for the ring opening of aziridine by aniline.196... 

Electron-rich aromatic compounds, such as phenol, anisole and A,./V-dimethylaniline, add to bis(2-trichloroethyl) azodicarboxylate under the influence of lithium perchlorate, boron trifluoride etherate or zinc chloride to yield para-substituted products 74, which are transformed into the anilines 75 by means of zinc and acetic acid86. Triflic acid (trifluoromethanesulphonic acid) catalyses the reactions of phenyl azide with benzene, toluene, chlorobenzene and naphthalene, to give TV-arylanilines (equation 34)87. 

Hitherto, thio ether formation has clearly been proved only in the case of the ji-donor substituted 4-nitrosophenetol and the electron-rich l-methyl-2-nitrosoimidazole. The low yields of this adduct (about 2% at 1 1- and about 10% at 1 5-stoichiometry for 4-nitrosophenetol reacting with GSH56) may be the reason for its rare discovery. However, other nitrosoarenes should yield this family, too. Semiempirical molecular orbital calculations (MNDO) indicate a similar positive charge at the exposition of the N-(methylthiol-S -yl)-aniline cation and -4-anisole cation as well (Scheme 6). Furthermore, formation of l-(glutathion-S -yl)-2-naphthylamine was reported to occur in mixtures of 2-nitrosonaphthalene and GSH12. 

The high selectivity of homolytic acylation of protonated heteroaromatic bases and the fact that under the same experimental conditions homocyclic substrates (benzene, anisole, nitrobenzene, protonated aniline, and A,A-dimethylaniline) are not attacked, indicate that polar effects play a dominant role. Only aromatic substrates with very strong electron-deficient character give rise to significant homolytic acylation. 

Analytical applications of RPC, classification 279 Angiotensin II, 290 Aniline, 265 Anisocratic elution, 92 Anisole, 182, 183 Anisopycnic slurries, 147... 

Srivastava et al. showed that the parent nitrenium ion is capable of adding to simple aromatics such as benzene, toluene and anisole (91) to give aniline derivatives (92a-c, Fig. 13.47). Unfortunately, these reactions give a distribution of regio-isomers as well as products derived from competing hydride and/or hydrogen atom transfer. 

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