Benzonitriles salts

Forms water-soluble alkali and alkaline earth metal salts. Heating with KCN gives benzonitrile and phenol is formed by fusion with NaOH or KOH. Further sulphonation at 250°C gives benzene-1,3-disulphonic acid. 

Much earlier information on the structure of diazonium ions than that derived from X-ray analyses (but still useful today) was obtained by infrared spectroscopy. The pioneers in the application of this technique to diazonium and diazo compounds were Le Fevre and his school, who provided the first IR evidence for the triple bonds by identifying the characteristic stretching vibration band at 2260 cm-1 (Aroney et al., 1955 see also Whetsel et al., 1956). Its frequency lies between the Raman frequency of dinitrogen (2330 cm-1, Schrotter, 1970) and the stretching vibration frequency of the C = N group in benzonitrile (2255 cm-1, Aroney et al., 1955). In substituted benzenediazonium salts the frequency of the NN stretching vibration follows Hammett op relationships. Electron donor substituents reduce the frequency, whereas acceptor substituents increase it. The 4-dimethylamino group, for example, shifts it by 103 cm-1 to 2177 cm-1 (Nuttall et al., 1961). This result supports the hypothesis that... 

Apparent exceptions are the constants k2 for diazonium salts with the electron-withdrawing substituents 4-C1 and 3-CN. The values of k2 for these compounds are more than a factor of 10 larger than expected on the basis of Hammett relationships. Product analyses rationalize this observation whereas in all other cases products are likely to be formed by heterolytic dediazoniation, the products from the 4-chloro-and 3-cyanobenzenediazonium ions include chlorobenzene and benzonitrile, typical compounds obtained in homolytic dediazoniations. This result corresponds to the reaction products observed by Moss et al. (1982) in micellar dediazoniation, compared with the nonmicellar reaction (see Sec. 8.3). 

The dilithium salt of a linked bis(amidinate) dianionic ligand, Li2[Me3 SiNC(Ph)N(CH2)3NC(Ph)NSiMe3] ( = U2L) was prepared in 69% yield according to Scheme 204 by reaction of dilithiated N,N -bis(trimethylsilyl)-l,3-diaminopro-pane with benzonitrile. ... 

It is noted that the reaction of aryl diazonium salts with CuCN to give benzonitrile derivatives is also called the Sandmeyer reaction. It is usually conducted in neutral solution to avoid liberation of HCN. 

Many of the early workers who studied the thermal decomposition reactions of diazocarbonyl compounds found that the addition of copper metal or copper salts allowed the reaction to be achieved at a lower temperature,<63AG(E)565, 64CB2628, 73JOU431> although no detailed study of this catalytic effect was undertaken. Alonso and Jano studied the copper-salt reaction of ethyl diazopyruvate 26 with acetonitrile and benzonitrile. The... 

The most interesting aminomethyl derivative of condensation polymers that we have prepared to date Is derived from direct reduction of poly(2-cyano-l,3-phenylene arylene ether), 20. Enchainment of benzonitrile repeat units Is accomplished by coupling 2,6-dichlorobenzonitrile with the potassium salt of bisphenol-A copolymers with lower nitrile contents can be produced by copolycondensation of bisphenol-A, 2,6-dichlorobenzonitrile and 4,4 -dichlorodiphenyl sulfone.21 The pendent nitrile function provides an active site for further elaboration. 

The data for sodium 9-anthroate in benzonitrile do not fit the pattern of the other derivatives since in this case kD + fccq > kMThis effect cannot be due to kD since this value is less than those of the other derivatives. Therefore cq must be greatly increased for the salt. This effect is thought to arise from both dynamic quenching and static quenching due to ion pairs. 

Water is involved in most of the photodecomposition reactions. Hence, nonaqueous electrolytes such as methanol, ethanol, N,N-d i methyl forma mide, acetonitrile, propylene carbonate, ethylene glycol, tetrahydrofuran, nitromethane, benzonitrile, and molten salts such as A1C13-butyl pyridium chloride are chosen. The efficiency of early cells prepared with nonaqueous solvents such as methanol and acetonitrile were low because of the high resistivity of the electrolyte, limited solubility of the redox species, and poor bulk and surface properties of the semiconductor. Recently, reasonably efficient and fairly stable cells have been prepared with nonaqueous electrolytes with a proper design of the electrolyte redox couple and by careful control of the material and surface properties [7], Results with single-crystal semiconductor electrodes can be obtained from table 2 in Ref. 15. Unfortunately, the efficiencies and stabilities achieved cannot justify the use of singlecrystal materials. Table 2 in Ref. 15 summarizes the results of liquid junction solar cells prepared with polycrystalline and thin-film semiconductors [15]. As can be seen the efficiencies are fair. Thin films provide several advantages over bulk materials. Despite these possibilities, the actual efficiencies of solid-state polycrystalline thin-film PV solar cells exceed those obtained with electrochemical PV cells [22,23]. 

Various cation radical salts [(ppy)Au(S-S) 2 anion 11solvent (S-S = CgH4Sg or CgH4Sg02, anion = PF6, BF4 , AsFfi. TaFfi. solvent = PhCl, n = 0-0.5) were prepared by constant current electrolysis of their benzonitrile or chlorobenzene solutions containing (Bu Xanion) as electrolyte [26, 27, 35, 37]. 

Treatment of 102 with lithium or sodium borates in the presence of trimethylphosphane or benzonitrile gave the plumbylidyne complex salts 104 and 105 (Equation (37)).112,112a... 

Cycloadditions to a cyano group are comparatively rare. The high-temperature reactions of 1,3-dienes, e.g. butadiene, isoprene and 2-chloro-l,3-butadiene, with dicyanogen, propionitrile or benzonitrile result in formation of pyridines (equation 80)70. Sulfonyl cyanides 147, obtained by the action of cyanogen chloride on sodium salts of sulfinic acids, add to dienes to give dihydropyridines 148, which are transformed into pyridines 149 by oxidation (equation 81)71. 

It has been found that 3-azapyrylium salts 57 and 58 are obtained in reactions of pinacolone as well as vinyl chlorides 59 with N-acylnitrilium salt 56 (91ZOR2479 92ZOR2577). The acylation of vinyl chlorides 59 in benzonitrile also leads to salts 60 (91ZOR1986). The same salts 55 are formed as intermediates by acylation of acetylenes in the presence of nitriles (88ZOR1605). Vinyl chlorides and acetylenes are both direct derivatives of carbonyl compounds with the same oxidation level (72MI2 85KGS1443). 

The reactive cation (101) may be generated either by protonation and dehydration of the A-hydroxymethylamide (100) or by the Lewis acid-catalyzed removal of a chloride ion from an A-chloromethylamide (102). Addition of the cation (101) to benzonitrile afforded a 2,6-diphenyl-4jy-l,3,5-oxadiazinium salt (103) in 39% yield, while addition to phenylacetylene gave 2,6-diphenyl-4.ff-l,3-oxazinium hexachloro-stannate (104) in 99% yield. 

Another semiconducting fulleride salt, [Ru(bpy)3](C5o)2 with bpy = 2,2 -bipyridine, crystallizes on the Pt electrode surface out of dichloromethane solutions saturated with [Ru(bpy)3]PF5 within a few minutes [79]. The NIR spectra of benzonitrile solutions of this salt demonstrate that the only fulleride anion present is 55 . The temperature dependence of the conductivity is typical for a semiconductor, with the room temperature conductivity being 0.01 S cm and the activation energy 0.1 kj mol (0.15 eV). It was postulated that there is an electronic overlap between the two ions of this salt leading to a donation of electron density from the 55 to the ligand orbitals in the [Ru(bpy)3] " AI 0.7) [79]. 

Reaction of the 5-substituted aminothiadiazole (88 R = Bu ) with aryl nitriles produced amidines (89) in yields dependent on the reactivity of the nitriles (Scheme 14). Decreasing the electron density of the cyano group by such electron-withdrawing groups as p-nitrophenyl-, and 2- and 4-cyanopyridyl, led to higher yields as compared to unsubstituted benzonitrile. A bis thiadiazole (92 R = Bu ) was prepared by reacting the sodium salt of (88) with 2-methanesulfonyl-5-(-butyl-1,3,4-thiadiazole (91) <84JHC1377>. 

N-Alkylnitrilium salts, prepared from benzonitriles and SbQs, acylate activated aromatic compounds under mild conditions. The resulting benzophenone imines can be cyclised and hydrolysed providing a good route to substituted xanthones (Scheme 34) <99 JOC4050>. 

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