Hydrogen Substitution at

In MeOD solutions, in the presence of catalytic amounts of sodium methanolate, pentacarbonyl[methoxy(methyl)carbene]chromium(0) exchanges all hydrogen atoms of the methyl group for deuterium. Analogous molybdenum and tungsten complexes react in the same manner. 

Hydrogen atoms may also be replaced by other groups, for example, methyl groups may be introduced to the following carbene complex. 

Because of proton abstraction, anionic carbene ligands are formed as intermediates (Z denotes a base)  

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Substituent effects in the allyl ester rearrangements are very similar to those observed in the ester reverse ene-type eliminations. This is apparent from the relative rate comparisons of Table 8. At the a- and y-carbons, reaction rates are observed to increase in the order CF3 < H < CH3. The rate accelerations by methyl substitution for hydrogen at the a-carbons are factors of 40 and 23, and at the y-carbon are factors of 55 and 23. These effects should be compared with the rate accelerations by methyl for hydrogen substitution at the a-carbon in the ester ene reactions, i.e., from Table 2, i-PrOAc/EtOAc = 18.7 and t-BuOAc/i-PrOAc = 53. One may conclude that the positive formal charge densities at the a- and... 

The hydrogenation rate of olefins on Pt falls as the extent of the hydrogen substitution at the double bond by alkyl groups increases [Lebedev s rule (418)-, as the number of phenyl radicals substituting the alkyl radicals at the double bond in olefins increases the rate of hydrogenation on Pt decreases 419)]. 

The hydrogen connectivity information from DEPT NMR data are actually produced using several spectra of the same sample (Fig. 9.30 ), with the net spectrum result providing the information about the hydrogen substitution at each carbon (Fig. 9.30 ). In this text we show the peaks labeled according to the information gained from the DEPT spectra for the compound under consideration, rather than reproducing the entire family of spectra that lead to the final result. 

Alkenes in (alkene)dicarbonyl(T -cyclopentadienyl)iron(l+) cations react with carbon nucleophiles to form new C —C bonds (M. Rosenblum, 1974 A.J. Pearson, 1987). Tricarbon-yi(ri -cycIohexadienyI)iron(l-h) cations, prepared from the T] -l,3-cyclohexadiene complexes by hydride abstraction with tritylium cations, react similarly to give 5-substituted 1,3-cyclo-hexadienes, and neutral tricarbonyl(n -l,3-cyciohexadiene)iron complexes can be coupled with olefins by hydrogen transfer at > 140°C. These reactions proceed regio- and stereospecifically in the successive cyanide addition and spirocyclization at an optically pure N-allyl-N-phenyl-1,3-cyclohexadiene-l-carboxamide iron complex (A.J. Pearson, 1989). 

Although some authors propose that an enolizable /3-dicarbonyl system is essential for inflammatory activity, two analogues in which this hydrogen atom at carbon 4 has been substituted, suxibuzone (717) and pipebuzone (718), are used as antiinflammatory agents, and the latter also possesses antipyretic and analgesic properties. However, these compounds are probably not active per se and their activity is due to metabolism to phenylbutazone. 

The relative stability of the intermediates determines the position of substitution under kinetically controlled conditions. For naphthalene, the preferred site for electrophilic attack is the 1-position. Two factors can result in substitution at the 2-position. If the electrophile is very bulky, the hydrogen on the adjacent ring may cause a steric preference for attack at C-2. Under conditions of reversible substitution, where relative thermodynamic stability is the controlling factor, 2-substitution is frequently preferred. An example of this behavior is in sulfonation, where low-temperature reaction gives the 1-isomer but at elevated temperatures the 2-isomer is formed. ... 

The general mechanism for electrophilic substitution suggests that groups other than hydrogen could be displaced, provided the electrophile attacked at the substituted carbon. Substitution at a site already having a substituent is called ipso substitution and has been observed in a number of circumstances. The ease of removal of a substituent depends on its ability to accommodate a positive charge. This fector determines whether the newly attached electrophile or the substituent is eliminated from the [Pg.588]

In many applications tantalum can be substituted for platinum and gold, and there are some environments in which tantalum is more corrosion resistant than platinum. Table 3.37 lists the main chemicals for which tantalum is not a suitable substitute for platinum and, conversely, those for wliich tantalum is better than platinum. Tantalum is rapidly embrittled by nascent hydrogen even at room temperature. Therefore, it is very important to avoid the formation of galvanic couples between tantalum and other metals. 

In a first reaction step the formaldehyde 2 is protonated, which increases its reactivity for the subsequent electrophilic aromatic substitution at the benzene ring. The cationic species 4 thus formed loses a proton to give the aromatic hydroxymethyl derivative 5, which further reacts with hydrogen chloride to yield the chloromethylated product 3 ... 

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