Substitution, electrophilic deuterium exchange

Electrophilic Attack. A variety of boranes, heteroboranes, and metaHaboranes undergo electrophilic substitution. SusceptibiUty of boranes to electrophilic attack is often detected by deuteron—proton exchange experiments. Eor example, electrophilic hydrogen—deuterium exchange of occurs at the l-,2-,3-, and 4-positions when exposed to DCl in the presence of AlCl (81). The trend to increasing positive sites in is... 

Azaindolizine, 5-chloro-nucleophilic substitution, 4, 458 8-Azaindolizine, 7-chloro-nucleophilic substitution, 4, 458 Azaindolizines basicity, 4, 454 electronic spectra, 4, 445 electrophilic substitution, 4, 453 halogenation, 4, 457 hydrogen/deuterium exchange, 4, 458 NMR, 4, 447, 449 nucleophilic attack, 4, 458 protonation, 4, 453 reaction with isothiocyanates, 4, 513 reactions, 5, 267 reviews, 4, 444 UV spectra, 4, 446, 449 Azaindolizines, amino-tautomerism, 4, 452... 

Beyer synthesis, 2, 474 electrolytic oxidation, 2, 325 7r-electron density calculations, 2, 316 1-electron reduction, 2, 282, 283 electrophilic halogenation, 2, 49 electrophilic substitution, 2, 49 Emmert reaction, 2, 276 food preservative, 1,411 free radical acylation, 2, 298 free radical alkylation, 2, 45, 295 free radical amidation, 2, 299 free radical arylation, 2, 295 Friedel-Crafts reactions, 2, 208 Friedlander synthesis, 2, 70, 443 fluorination, 2, 199 halogenation, 2, 40 hydrogenation, 2, 45, 284-285, 327 hydrogen-deuterium exchange, 2, 196, 286 hydroxylation, 2, 325 iodination, 2, 202, 320 ionization constants, 2, 172 IR spectra, 2, 18 lithiation, 2, 267... 

The intermediate tricyclic ketones 495 and 496 have been transformed to the methoxy-substituted derivative 97284,285) latter ketone is subject to hydrogen-deuterium exchange only under basic conditions and appears to exist entirely in the keto form despite the ready formation of its anion and successful methylation on oxygen . In agreement with the aromatic nature of 490, the hydrocarbon undergoes electrophilic substitution reactions... 

Electrophilic substitution, aromatic, 31, 130-167, 381 1,2-ti. 1,4-addition, 195 as addition/elimination, 133 complexing with substituent, 160 deuterium exchange, 131,158 electronic effects in, 148, 158, 159 energetics of, 132, 136 field effect in, 152 hyperconjugation in, 153 inductive effect in, 22,152,153,156, 160... 

The relative reactivity of different positions toward electrophilic substitution is conveniently studied by acid-catalyzed deuterium exchange reaction rates can be followed by NMR and introduction of deuterium hardly affects the reactivity of the remaining positions. In D2S04 both quinoline and quinoline 1-oxide react as the conjugate acid at positions 8 > 5, 6 > 7 > 3. 

The above considerations do not necessarily apply to reactions of electrophilic reagents with pyrazole and imidazole anions (134, 135). The imidazole anion is sometimes (diazo coupling, halogenation, deuterium exchange) substituted in the 2-position (139) and the indazole anion in the 3-position (cf. Section 3.4.1.4.5). 

The very high reactivity of pyrrole compared with furan in electrophilic substitutions is also confirmed by rate measurements of hydrogen-deuterium exchange in methanol-water-sulfuric acid mixtures53 (Table VI). The rate of exchange of pyrrole-2-d in 0.5%... 

The fluorination of quinoline was performed in a microstructured reactor operated in the annular-flow regime, which contained one microchannel with two consecutive feeds for gas and liquid [311,312]. The role of the solvent was large. The reaction was totally unselective in acetonitrile and gave only tarlike products. With formic acid, a mixture of mono- and polyfluorinated products besides tar was formed. No tar formation was observed with concentrated sulfuric acid as solvent at 0-5 °C. In this way, a high selectivity of about 91% at medium conversion was achieved. Substitution was effective only in the electron-rich benzenoid core and not in the electron-poor pyridine-type core. The reactivity at the various positions in the quinoline molecule is 5 > 8 > 6 and thus driven by the vicinity to the heteroatom nitrogen that corresponds to the electrophilic reactivity known from proton/deuterium exchange studies in strong acid media. 

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