Radical hydrogen

With 2-methyl- and 2,4-dimethylthiazole, the methyl thiirenium ion (m/e 72) is obtained, which can easily lose a hydrogen radical to give the ml ell ion (confirmed by the metastable peak). This latter can rearrange by ring expansion to give the thietenyl cation whose structure was confirmed in certain spectra by the presence of a metastable peak corresponding to the decomposition of the m/e 71 ion to give the thioformyl cation m/e 45, probably by elimination of acetylene. 

Irradiation of ethyleneimine (341,342) with light of short wavelength ia the gas phase has been carried out direcdy and with sensitization (343—349). Photolysis products found were hydrogen, nitrogen, ethylene, ammonium, saturated hydrocarbons (methane, ethane, propane, / -butane), and the dimer of the ethyleneimino radical. The nature and the amount of the reaction products is highly dependent on the conditions used. For example, the photoproducts identified ia a fast flow photoreactor iacluded hydrocyanic acid and acetonitrile (345), ia addition to those found ia a steady state system. The reaction of hydrogen radicals with ethyleneimine results ia the formation of hydrocyanic acid ia addition to methane (350). Important processes ia the photolysis of ethyleneimine are nitrene extmsion and homolysis of the N—H bond, as suggested and simulated by ab initio SCF calculations (351). The occurrence of ethyleneimine as an iatermediate ia the photolytic formation of hydrocyanic acid from acetylene and ammonia ia the atmosphere of the planet Jupiter has been postulated (352), but is disputed (353). 

In H abstraction, a hydrogen radical reacts with a molecule (primarily a paraffin) and produces a hydrogen molecule and a radical. In the same way, a methyl radical reacts to produce a radical and methane. Similar reactions with other radicals (ethyl and propyl) can also occur. In addition, some radicals like H, CH, etc, are added to olefins to form heavier radicals. 

Information regarding the position of the substituents can be obtained from the mass spectra of the enamines of cyclic ketones. For instance in the case of the morpholine enamine of 3-methylcyclohexanone, which is shown to be a 2 1 mixture of/ and isomers by NMR spectroscopy, the fragmentation of the radical ion from the /) isomer results in the loss of a methyl radical from the C-3 position. The d isomer gives a complicated spectrum due to the loss of the hydrogen radical. 

Sixteen non- to trimethyl-substituted thiazoloquinolines of these types were inveshgated under electron impact mass spectra thiazoloquinolines lose carbon monosulhde (CS) from the thiazole and HCN from both heterocyclic nuclei. When 2-methylthiazoloquinolines fragment, the hydrogen radical and a loss of a neutral... 

The very reactive phenyl radical reacts with the aromatic substrate 2, present in the reaction mixture. Subsequent loss of a hydrogen radical, which then combines with 7 to give 4, yields a biaryl coupling product e.g. the unsymmetrical biphenyl derivative 3 ... 

Similar electrodes may be used for the cathodic hydrogenation of aromatic or olefinic systems (Danger and Dandi, 1963, 1964), and again the cell may be used as a battery if the anode reaction is the ionization of hydrogen. Typical substrates are ethylene and benzene which certainly will not undergo direct reduction at the potentials observed at the working electrode (approximately 0-0 V versus N.H.E.) so that it must be presumed that at these catalytic electrodes the mechanism involves adsorbed hydrogen radicals. 

This process involves a series of reactions, including dissolution, hydrogen reactions and chlorine withdrawal [20], The second type of reactions include reduction of protons at the catalyst by electron transfer yielding hydrogen radicals that are consumed by reaction or give elemental hydrogen otherwise. 

V.N. Tsivenko, Adsorption of Nitrogen Atoms and Nitrogen-Hydrogen Radicals on Oxide Adsorbents by Electxoconductivity Technique, PhD (Chemistry) Thesis, Moscow, 1973... 

V.I. Tsivenko, Studies of Adsorption Nitrogen Atoms and Nitrogen-Hydrogen Radicals on Oxide Adsorbents by Electroconductivity Technique, PhD (Chemistry) Thesis, Moscow, 1973 B.S. Agayan, I.A. Myasnikov and V.I. Tsivenko, Zhum. Fiz. Khimii, 47 (1973) 1292 - 1296... 

If we assume that donor signals of the sensor are controlled by adsorption of antimony-hydrogen radicals the radicals of SbH3 adsorbed... 

Route A. Cleavage of the 5,6 and 1,7 bonds (or vice versa) eliminates an ethylene unit. This elimination is generally followed by the loss of a hydrogen radical and the ester function, leading to the relatively stable N-methylpyri-dinium cation (m/z 94). 

Routes C, D, and E. In these routes the C-3 ester function is cleaved under forms of RCOO% RCO-, and RCOOH, respectively. In the last case, ionized tropidine is formed. Concomitant losses of ethylene and hydrogen radical lead again to the /V-methylpyridinium ion (cf. Route A). 

We saw earlier that when benzophenone is photoreduced in the presence of optically active 2-butanol, the alcohol recovered from the reaction loses no optical activity/541 This was presented as evidence that there could be no appreciable reversibility of the initial hydrogen abstraction since this should lead to racemization of the unreacted alcohol. However, if one uses relabeled benzhydrol and examines the initially produced benzpinacol for the presence of the label, one finds that the product pinacol contains no 14C. This would indicate that there must be some type of rapid transfer of the hydrogen radical from the ketyl radical produced upon abstraction from benzhydrol,... 

This product probably arises from initial abstraction of a hydrogen radical from the isopropanol, followed by radical coupling ... 

Hydrogen Radical Elimination from Ionized Ethylene... 

The early studies of the chemical effects of ultrasound have been thoroughly reviewed (5-7). Only the most important and most recent research is mentioned here as needed to provide a perspective on sonochemical reactivity patterns. The sonolysis of water is the earliest and most exhaustively studied (3,93,96,98-105). The first observations on the experimental parameters which influence sonochemistry come from these reports. The primary products are H202 and H2, and various data supported their formation from the intermediacy of hydroxyl radicals and hydrogen radicals ... 

Molecular hydrogen is rather unreactive at ambient conditions, but many transition and lanthanide metal ions are able to bind and therefore activate H2, which results in transformation into H (hydride) 11 (hydrogen radical) or H+ (proton), and subsequent transfer of these forms of hydrogen to the substrate.7,8 In this context, not only metal hydride but also dihydrogen complexes of transition metal ions, play a key role,9 10 especially since the first structural characterization of one of these species in 1984 by Kubas.11... 

FIGURE 6 Speculative mechanism of Crl hydrocarbon biosynthesis from fatty acid hydroperoxides in algae. Homolytic cleavage of the hydroperoxide is assumed to give an allyl radical, which cyclizes to the thermolabile (1S,2R)-cyclopropane. The sequence is terminated by transfer of a hydrogen radical from C(16) to the -X-0 function. The cyclopropane rearranges to (6S)-ectocarpene as shown in Figure 4. 

In the past this was referred to as a homolytic reaction [23], It is clear that it would be highly unlikely that dihydrogen would be split into a metal hydride and a highly energetic hydrogen radical in this sense the term homolytic splitting is misleading. 

Hydrogen Radical Transfer Catalyzed by a Coenzyme Bn-Dependent Mutase... 

Fig. 6-3S. Potential energy curves for water adsorption on metal surface in the states of molecules and hydrozjd radicals c = energy r = reaction coordinate solid curve = adsorption as water molecules and as partially dissociated hydroxj4 and hydrogen radicals broken curve = adsorption of completely dissociated oxygen and hydrogen radicals.

Cleavage of a bond without immediate dissociation of the precursor radical ion is one way for the generating distonic ions. Isomerization of molecular ions by hydrogen radical shift frequently leads to distonic ions prior to fragmentation and. 

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