And nitration of aromatic

WOLFFENSTEIN-BOTERS REACTION. Simultaneous oxidation and nitration of aromatic compounds to nitrophcnols with nitric acid or the higher oxides of nitrogen in the presence of a mercury salt as catalyst. Hydroxynitration of benzene yields picric acid. 

There are some known unsuccessful attempts to carry out alkylation (Mel, Me2S04), halogenation (tert-butyl hypochloride) and nitration of aromatic dihydrobenzodiazepines [7, 105]. Such attempts only resulted in the destruction of the seven-membered heterocycle. As a rule, these destructive processes are typical of dihydrodiazepine systems and often manifest themselves during the synthesis and study of these compounds. Therefore, the results of the destruction of a seven-membered heterocycle are most widespread and include its decomposition into ortho-diamine and carbonyl compounds (Scheme 4.43, reactions A and B) [105, 106] and benzimidazole rearrangement accompanied by splitting out of a methyl aryl ketone molecule (Scheme 4.43, reaction C) [117]. 

Hydrolysis and saponification of esters and fats (Jeffreys et al., 1961 Donders et al., 1968 Sharma and Nanda, 1968), sulfonation and nitration of aromatic compounds (Albright and Hanson, 1969, 1975 Hanson and Ismail, 1976 Barona and Prengle, 1973), alkylation of isobutane, toluene, and phenols with... 

Bronislaw Znatowicz (1851-1917), chemist, professor at Warsaw University, co-founder and first editor-in-chief of the journal Chemik Polski, author and translator of chemical textbooks and monographs. He investigated the reduction and nitration of aromatic compounds and the production of dyes from tar, and studied the phenomenon of phosphorescence and electrolysis of organic compounds. 

Sc(OTf)3 was widely used as a Lewis acid catalyst in Friedel-Crafts acylation [38-40], amination [41], chloromethylation [42], and nitration of aromatic compounds [43]. It also exhibited a superior catalytic activity for one-pot three-component phenol-imine Friedel-Crafts reactions to give the corresponding amino acid derivatives. Among various Lewis acids including La(OTf)3, Yb(OTf)3, YbCl3, InCl3, SnCU, and TiCU, Sc(OTf)3gave the best results (Scheme 12.21) [44]. 

During my Cleveland years, I also continued and extended my studies in nitration, which I started in the early 1950s in Hungary. Conventional nitration of aromatic compounds uses mixed acid (mixture of nitric acid and sulfuric acid). The water formed in the reaetion dilutes the acid, and spent aeid disposal is beeoming a serious environ-... 

A simple kinetic order for the nitration of aromatic compounds was first established by Martinsen for nitration in sulphuric acid (Martin-sen also first observed the occurrence of a maximum in the rate of nitration, occurrii for nitration in sulphuric acid of 89-90 % concentration). The rate of nitration of nitrobenzene was found to obey a second-order rate law, first order in the concentration of the aromatic and of nitric acid. The same law certainly holds (and in many cases was explicitly demonstrated) for the compounds listed in table 2.3. 

TABLE 4.2 Nitration of aromatic compounds isomer proportions and partial rate factors ... 

The authors of this work were concerned chiefly with additions to alkenes, and evidence about the mechanism of aromatic nitration arises by analogy. Certain aspects of their work have been repeated to investigate whether the nitration of aromatic compounds shows the same phenomena ( 5-3-6). It was shown that solutions of acetyl nitrate in acetic anhydride were more powerful nitrating media for anisole and biphenyl than the corresponding solutions of nitric acid in which acetyl nitrate had not been formed furthermore, it appeared that the formation of acetyl nitrate was faster when 95-98% nitric acid was used than when 70 % nitric acid was used. 

Nitration of aromatic rings is possible by use of Pd(N03)2[356], Pd(OAc)2-NaN02[357], Pd(0Ac)2-N02[358], and Pd(0)-NO2[359], The nitration can be carried out fully catalytically by Pd(0Ac)2-N02 and oxygen. This reaction offers a promising new method of nitration without using mixed acids of HNO3 and H2SO4. 

Nitrations can be performed in homogeneous media, using tetramethylene sulfone or nitromethane (nitroethane) as solvent. A large variety of aromatic compounds have been nitrated with nitronium salts in excellent yields in nonaqueous media. Sensitive compounds, otherwise easily hydroly2ed or oxidized by nitric acid, can be nitrated without secondary effects. Nitration of aromatic compounds is considered an irreversible reaction. However, the reversibihty of the reaction has been demonstrated in some cases, eg, 9-nitroanthracene, as well as pentamethylnitrobenzene transnitrate benzene, toluene, and mesitylene in the presence of superacids (158) (see Nitration). 

Zeohtes have recendy been employed as soHd catalysts for the vapor-phase nitration of aromatics with nitric acid. Additional research is required to improve yields and to niinimi2e loss of catalytic activity as the nitration progresses (see Molecularsieves). 

Nitration. Direct nitration of aromatic amines with nitric acid is not a satisfactory method, because the amino group is susceptible to oxidation. The amino group can be protected by acetylation, and the acetylamino derivative is then used in the nitration step. Nitration of acetanilide in sulfuric acid yields the 4-nitro compound that is hydroly2ed to -rutroaruline [100-01-6]. 

Liquid/hquid reactions of industrial importance are fairly numerous. A hst of 26 classes of reactions with 61 references has been compiled by Doraiswamy and Sharma Heterogeneou.s Reactions, Wiley, 1984). They also indicate the kind of reactor normally used in each case. The reactions range from such prosaic examples as making soap with alkali, nitration of aromatics to make explosives, and alkylation of C4S with sulfuric acid to make improved gasoline, to some much less familiar operations. 

Particular reactions can occur in either or both phases or near the interface. Nitration of aromatics with HNO3-H2SO4 occurs in the aqueous phase (Albright and Hanson, eds.. Industrial and Laboratoiy Nitration.s, ACS Symposium Series 22 [1975]). An industrial example of reaction in both phases is the oximation of cyclohexanone, a step in the manufacture of caprolactam for nylon (Rod, Proc. 4th Interna-tional/6th European Symposium on Chemical Reactions, Heidelberg, Pergamon, 1976, p. 275). The reaction between butene and isobutane... 

Impurities can sometimes be removed by conversion to derivatives under conditions where the major component does not react or reacts much more slowly. For example, normal (straight-chain) paraffins can be freed from unsaturated and branched-chain components by taking advantage of the greater reactivity of the latter with chlorosulfonic acid or bromine. Similarly, the preferential nitration of aromatic hydrocarbons can be used to remove e.g. benzene or toluene from cyclohexane by shaking for several hours with a mixture of concentrated nitric acid (25%), sulfuric acid (58%), and water (17%). 

Because of Us high polarity and low nucleophilicity, a trifluoroacetic acid medium is usually used for the investigation of such carbocationic processes as solvolysis, protonation of alkenes, skeletal rearrangements, and hydride shifts [22-24] It also has been used for several synthetically useful reachons, such as electrophilic aromatic substitution [25], reductions [26, 27], and oxidations [28] Trifluoroacetic acid is a good medium for the nitration of aromatic compounds Nitration of benzene or toluene with sodium nitrate in trifluoroacetic acid is almost quantitative after 4 h at room temperature [25] Under these conditions, toluene gives the usual mixture of mononitrotoluenes in an o m p ratio of 61 6 2 6 35 8 A trifluoroacetic acid medium can be used for the reduction of acids, ketones, and alcohols with sodium borohydnde [26] or triethylsilane [27] Diary Iketones are smoothly reduced by sodium borohydnde in trifluoroacetic acid to diarylmethanes (equation 13)... 

Tnflic acid is an excellent catalyst for the nitration of aromatic compounds [.S7]. In a mixture with nitnc acid, it forms the highly electrophilic nitronium inflate, which can be isolated as a white crystalline solid Nitronium inflate is a powerful nitrating reagent in inert organie solvents and in tnflic acid or sulfuric acid. It nitrates benzene, toluene, chlorobenzene, nitrobenzene, m-xylene, and benzotn-fluoride quantitatively in the temperature range of-110 to 30 °C with exeeptionally high positional selectivity [87],... 

Nitration and sulfonation of aromatic compounds probably occur via the formation of the nitryl and sulfonyl cations ... 

The reaction with HNO3 is quantitative, and the presence of large concentrations of the nitronium ion, NOi ", in solutions of HNO3, MNO3 and N2O5 in H2SO4 enable a detailed interpretation to be given of the nitration of aromatic hydrocarbons by these solutions. 

One example of normal-phase liquid chromatography coupled to gas chromatography is the determination of alkylated, oxygenated and nitrated polycyclic aromatic compounds (PACs) in urban air particulate extracts (97). Since such extracts are very complex, LC-GC is the best possible separation technique. A quartz microfibre filter retains the particulate material and supercritical fluid extraction (SPE) with CO2 and a toluene modifier extracts the organic components from the dust particles. The final extract is then dissolved in -hexane and analysed by NPLC. The transfer at 100 p.1 min of different fractions to the GC system by an on-column interface enabled many PACs to be detected by an ion-trap detector. A flame ionization detector (PID) and a 350 p.1 loop interface was used to quantify the identified compounds. The experimental conditions employed are shown in Table 13.2. 

Nitromum tetrafluoroborate, from nitric acid, boron tnfluonde, and hy drogen fluoride, 47, 56 m nitration of aromatic rings, 47,... 

Notable examples of general synthetic procedures in Volume 47 include the synthesis of aromatic aldehydes (from dichloro-methyl methyl ether), aliphatic aldehydes (from alkyl halides and trimethylamine oxide and by oxidation of alcohols using dimethyl sulfoxide, dicyclohexylcarbodiimide, and pyridinum trifluoro-acetate the latter method is particularly useful since the conditions are so mild), carbethoxycycloalkanones (from sodium hydride, diethyl carbonate, and the cycloalkanone), m-dialkylbenzenes (from the />-isomer by isomerization with hydrogen fluoride and boron trifluoride), and the deamination of amines (by conversion to the nitrosoamide and thermolysis to the ester). Other general methods are represented by the synthesis of 1 J-difluoroolefins (from sodium chlorodifluoroacetate, triphenyl phosphine, and an aldehyde or ketone), the nitration of aromatic rings (with ni-tronium tetrafluoroborate), the reductive methylation of aromatic nitro compounds (with formaldehyde and hydrogen), the synthesis of dialkyl ketones (from carboxylic acids and iron powder), and the preparation of 1-substituted cyclopropanols (from the condensation of a 1,3-dichloro-2-propanol derivative and ethyl-... 

Mercuric Nitrate (Mercury Nitrate, Mercury Pemitrate). Hg(NO3)2 0, mw 342.61, OB to HgO and N2 +26.4% wh deliq powd or colorl crysts, mp 79°, bp dec, d 4.39g/cc. Sol in w and nitric acid, insol in ale. Prepd by action of hot nitric acid on ale. Highly toxic and a dangerous fire risk in contact with organic materials, It has been used for the nitration of aromatic organic compds and in the prepn of MF... 

Several lesser known nitrating agents, which have been used on a lab scale are metal nitrates in the presence of acetic acid or acetic anhydride, tetranitromethane and hexanitroethane in an alkaline medium, and nitroguanidine in soln in sulfuric acid, used for the nitration of aromatic... 

Bordwell and Garbisch71 contested this conclusion since they found that nitric acid in acetic anhydride prepared at —10 °C contained a much less effective nitrating species (the nitric acid could be recovered quantitatively) than when mixed at 25 °C and cooled to —10 °C (the nitric acid being then mostly unrecoverable). Further, these latter solutions reacted with alkenes to give predominantly cis addition products (nitro-acetates), whi h indicates association of the nitronium ion with some other species. It has been argued72 that this does not necessarily follow, since nitration of aromatics may involve a different... 

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