Ion addition

A probable mechanism for this rearrangement postulates the intermediate formation of a hydroxide-ion addition complex, followed by the migration of a phenyl group as an anion ... 

Heavily fluonnated aminobenzenes, pyridines, and pyrimidines are diazotized in strong-acid media Solid sodium nitrite added directly to the fluonnated amine dissolved in 80% hydrofluonc acid, anhydrous hydrogen fluoride, or (1 1 wt/wt) 98% sulfuric acid in (86 14 wt/wt) acetic and propionic acids affords the electrophilic fluoroarenediazonium ion Addition of an electron rich aromatic to the resultant diazonium solution gives the fluoroareneazo compound [10 II] (equa tions 9 and 10)... 

The regiochemistry is determined by the regiochemistry of the fluoride ion addition reaction, that is, via the most stable perfluorocarbanion intermediate Von Werner used a similar reaction to prepare silver compounds from perfluoro-2-methyl-2-butene and perfluoro 2 methyl-2-pentene [271] Silver(I) fluoride adds to bis(ttitluoromethyl)ketene in DMF without fluoride ion catalysis [270] The analogous trifluorovinylsulfurpentafluoride reacts similarly to give the isolable pentafluorosulfur derivative [272] (equation 187)... 

NOj ions/ Addition of water to nitric acid at first diminishes its electrical conductivity by repressing the autoprotolysis reactions mentioned above. For example, at -10° the conductivity decrea.ses from 3.67 x 10 ohm cm to a minimum of 1.08 x 10" ohm" cm at 1.75 molal H2O (82.8% NjOs) before rising again due to the increasing formation of the hydroxonium ion according to the acid-base equilibrium... 

The addition of water across carbon-carbon double bonds, a reaction thoroughly investigated by Lucas and Taft, requires strong activation and is catalyzed by hydrogen ions and hydroxyl ions. Addition of water across the 0= =0 bond of aldehydes has also been studied kinetically. Whereas chloral and formaldehyde are largely hydrated (at equilibrium in dilute aqueous solution), acetaldehyde and other... 

Entry MgX,- counter-ion Additive T rq endo/exo r/o) ee endo (%) Absoiute induction Refi. 

Lster hydrolysis occurs through a typical nucleophilic acyl substitution pathway in which hydroxide ion is the nucleophile that adds to the ester carbonyl group to give a tetrahedral intermediate. Loss of alkoxide ion then gives a carboxylic acid, which is deprotonated to give the carboxylate ion. Addition of aqueous HC1 in a separate step after the saponification is complete then pro-tonates the carboxylate ion and gives the carboxylic acid (Figure 21.17). 

Ion Addition. Thus far, formation of most of the ions in Table II has been accounted for. Occurrence of the larger ions is not difficult to explain—e.g., addition of H20 to ions of masses 19, 29, 31, and 43 will give ions of masses 37, 47, 49, and 61, respectively. Other larger ions can be expected because they are usually formed in exothermic reactions of smaller ions once a hydrocarbon ion is produced, larger ions are readily formed by ... 

A number of studies have been reported concerning azide-isocyanide condensations to give tetrazoles. Early work by Beck and co-workers 18, 19) describes the addition of various isocyanides to metal azido species [Au(N3)4]", [Au(N3)2]", Au(PPh3)N3, and M(PPh3)2(N3)2, M = Pd, Pt, Hg. The products are carbon-bonded tetrazolato-metal complexes. It is not known whether metal isocyanide complexes are intermediates in these reactions. More recently inverse reactions with azide ion addition to metal isocyanide complexes were carried out, with similar results. From... 

Problem Cyanide ion addition to (36) gives a 2 1 mixture of (37) and (38), Explain. (The reagent and dipolar aprotic solvent simply ensure no confusing hydrogen-bonding. 

Both sulphate and chloride ions were found to accelerate the reaction under constant ionic strength conditions and, although medium effects may operate, pathways involving chloride and sulphate ions are possible. For the sulphate ion addition Newton and Baker conclude that the step... 

Fto. 58. Metal ion modulation of DNA-nanoparticle constructs based upon supercoil-ing. Adapted from Ref (186). Structures labelled (a) and (b) are before and after metal ion addition, respectively. 

Full details on the phosphorylation of water and alcohols by 4-nitrophenyl dihydrogen phosphate and the NfC H ) - and N(CH3) -salts of its mono- and dianion have been published 146>. Phosphoryl group transfer from the monoanion and dianion is thought to proceed via the monomeric POf ion. Addition of the sterically unhindered amine quinuclidine to an acetonitrile solution containing the phosphate monoanion and tert-butanol produces t-butyl phosphate at a faster rate than does the addition of the more hindered diisopropylethylamine. This nucleophilic catalysis of the phosphorylation reaction is also explained by the intermediacy of the POf ion. 

There are other N atoms that were not reduced, but still are present in the nitrate ions. Additional HNO, is needed to provide for these. 

The stereoselective addition of the titanium enolate of A-acetyl-4-phenyl-l,3-thiazolidine-2-thione 153 to the cyclic A-acyl iminium ion 154 is utilized in the synthesis of (-)-stemoamide, a tricyclic alkaloid <06JOC3287>. The iminium ion addition product 155 undergoes magnesium bromide-catalyzed awtz-aldol reaction with cinnamaldehyde 156 to give adduct 157, which possesses the required stereochemistry of all chiral centers for the synthesis of (-)-stemoamide. 

The electrons lost by the zinc atoms are the same electrons as those gained by the copper (II) ions. Addition of the two ionic half-equations gives the overall redox reaction ... 

The catalyst is reported to be a true solid acid without halogen ion addition. In the patent describing the process (239), a Pt/USY zeolite with an alumina binder is employed. It was claimed that the catalyst is rather insensitive to feed impurities and feedstock composition, so that feed pretreatment can be less stringent than in conventional liquid acid-catalyzed processes. The process is operated at temperatures of 323-363 K, so that the cooling requirements are less than those of lower temperature processes. The molar isobutane/alkene feed ratio is kept between 8 and 10. Alkene space velocities are not reported. Akzo claims that the alkylate quality is identical to or higher than that attained with the liquid acid-catalyzed processes. 

The Mo+ ion was generally less reactive to alkenes than the other ions. Additions of the alkene to the Mo+ and [MoO]+ with loss of H2 or 2H2 were the major reaction products similar to the alkanes. The reactions of [Mo02]+ with alkenes gave a variety of products, the major reactions being reduction by loss of an oxygen atom. 

Electronic spectroscopy has been employed to study substitution reactions of sulfoxide complexes. An interesting example (104) is the reaction of [Fe(0-Me2S0) P+ with chloride ion. Addition of one equivalent of chloride ion to a Me2SO solution of [Fe(0-Me2S0)6P+ causes a change in spectrum, but further additions have no effect. Comparisons with known compounds indicate that [Fe(0-Me2S0)5Cip+ is the major species in solution. 

Conventionally, methods such as purging, barium ion addition and freezing have been applied to control sulphate ion content in the brine feed, and as new technologies in controlling this ion, NDS and ion chromatography have been introduced [5, 6]. 

TABLE 5. Comparison of substituent effects on the relative rates of carbenium ion addition to carbon-carbon double bonds... 

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