Methyl group abstraction

The proposed mechanism starts with a methyl group abstraction on platinum complex 416 with the borane reagent in the presence of diyne 414 (Scheme 105). The square-planar cationic diyne-platinum(n) complex 417 is converted to the octahedral platinum(rv) hydride intermediate 418 through oxidative addition of the hydrosilane. This complex decomposes rapidly with methane release to form another tetracoordinated platinum(n) species 419, followed by platinasilylation of the triple bond. The resulting vinylplatinum 420 undergoes an intramolecular carboplatination to... 

Hydrogen is evolved in the photolysis of poly-a-methylstyrene with a quantum yield of 1.7 x 10-2, together with some carbon dioxide and carbon monoxide. This indicates that there are some bonded oxygen atoms in the polymer and it has been suggested that degradation could be due to the scission of a few weak bonds situated at random in the polymer chain [10]. No mention is made of the evolution of methane as a consequence of methyl group abstraction. It has been noticed that a yellow colour is produced on long exposure and that this remains even when the polymer has been reprecipitated [10]. 

Thus the study of chemically generated silicon ions, stimulated by earlier recoil studies that raised the possibility of ionic intermediates, has provided mechanisms for their possible participation in recoil reactions. However, it is also possible that the apparent methyl group abstraction is actually the result of insertion followed by scrambling of methyl groups and hydrogens (32). 

Benzoyl peroxide has been the most common source of phenyl radicals. But in reaction with thiazoles the benzoyloxy radical abstracts a hydrogen atom from the thiazole nucleus or from a methyl group in the case of methylthiazoles, giving by-products such as dithiazolyls or 2.2 -dithiazolylethane (183). The results obtained with benzoyl peroxide are summarized in Tables III-23, III-24. and III-25. 

Substitution Reactions. Substitution reactions can occur on the methyl group by free-radical attack. The abstraction of an aHybc hydrogen is the most favored reaction, followed by addition to that position. 

Vulcanization. Generally this is carried out by the action of peroxides, which can cross-link the chains by abstracting hydrogen atoms from the methyl groups and allowing the resulting free radicals to couple into a cross-link. Some varieties of polysdoxanes contain some vinylmethyl siloxane units, which permit sulfur vulcanization at the double bonds. Some Hquid (short-chain) siHcones can form networks at room temperature by interaction between thek active end groups. 

Treatment of 2-methylthiirane with t-butyl hydroperoxide at 150 °C in a sealed vessel gave very low yields of allyl disulfide, 2-propenethiol and thioacetone. The allyl derivatives may be derived from abstraction of a hydrogen atom from the methyl group followed by ring opening to the allylthio radical. Percarbonate derivatives of 2-hydroxymethylthiirane decompose via a free radical pathway to tar. Acrylate esters of 2-hydroxymethylthiirane undergo free radical polymerization through the double bond. 

The peroxide decomposes at elevated temperatures to give free radicals, which then abstract a hydrogen atom from the methyl group. The radicals formed then combine to form a hydrocarbon linkage. Results obtained by reacting model systems with benzoyl peroxide and analysing the reaction products are consistent with this type of mechanism. ... 

If every collision of a chlorine atom with a butane molecule resulted in hydrogen abstraction, the n-butyl/5ec-butyl radical ratio and, therefore, the 1-chloro/2-chlorobutane ratio, would be given by the relative numbers of hydrogens in the two equivalent methyl groups of CH3CH2CH2CH3 (six) compared with those in the two equivalent methylene groups (four). The product distribution expected on a statistical basis would be 60% 1-chloro-butane and 40% 2-chlorobutane. The experimentally observed product distribution, however, is 28% 1-chlorobutane and 72% 2-chlorobutane. 5ec-Butyl radical is therefore formed in greater anounts, and n-butyl radical in lesser anounts, than expected statistically. 

Structural Formula The N-methyl group in vinblastine (which see) is replaced by N-CHO. Chemical Abstracts Registry No. 2068-78-2 57-22-7 (Base)... 

The methyl groups were then deuterium-substituted. Ethanolysis of (CD3)2CHBr gave a mixture of CD3CH = CD2 and (CD3)2CHOC2H5. The elimination pathway had hAd = 6.7, whereas the substitution pathway showed no measurable kie. Clearly, these observations imply nearly complete proton abstraction in the one transition state and the lack of C-H involvement in the other. 

G(CH3S02 ) is the yield of CH3S02 radicals, AOH- and AH+ are the decrease and increase of the conductivity in basic and acidic solutions respectively, l is the specific conductivity and l(Haq+) and i(OH ) are known to be 315 and 178 fl-1 cm2, respectively. For dimethyl sulfoxide G(RS02 ) was found to be 5.46 comparing this to G(OH) = 6.0 for N20 -saturated aqueous solution leads to the conclusion that 91% of the OH radicals were added to the sulfoxide bond. There is no proof for the fate of the other 9% it is probable that they abstract hydrogen atoms from the methyl groups. 

The model is consistent with experimental observations and should provide a useful guideline for future experiments. A similar model has been proposed that is based on the addition of a methyl group to one of the carbons followed by atomic hydrogen abstraction from the methyl... 

The chemical reactivity of the organoruthenium and -osmium porphyrin complexes varies considerably, with some complexes (M(Por)R2, M(Por)R and Os(OEP)(NO)R) at least moderately air stable, while most are light sensitive and Stability is improved by handling them in the dark. Chemical transformations directly involving the methyl group have been observed for Ru(TTP) NO)Me, which inserts SO2 to form Ru(TTP)(N0) 0S(0)Me and Ru(OEP)Me which undergoes H- atom abstraction reactions with the radical trap TEMPO in benzene solution to yield Ru(OEP)(CO)(TEMPO). Isotope labeling studies indicate that the carbonyl carbon atom is derived from the methyl carbon atom. "" Reaction of... 

The partial oxidation of propylene occurs via a similar mechanism, although the surface structure of the bismuth-molybdenum oxide is much more complicated than in Fig. 9.17. As Fig. 9.18 shows, crystallographically different oxygen atoms play different roles. Bridging O atoms between Bi and Mo are believed to be responsible for C-H activation and H abstraction from the methyl group, after which the propylene adsorbs in the form of an allyl group (H2C=CH-CH2). This is most likely the rate-determining step of the mechanism. Terminal O atoms bound to Mo are considered to be those that insert in the hydrocarbon. Sites located on bismuth activate and dissociate the O2 which fills the vacancies left in the coordination of molybdenum after acrolein desorption. 

---