Chlorine+methyl radical

The authors of primary Reference 80 present their own and selected literature values for the R—NO bond enthalpies for the hydrocarbyl cases of Me, Et, t-Bu, allyl and benzyl, as well as mixed fluorinated, chlorinated methyl radicals. We now wish to compare nitroso species with the corresponding amino and nitro compounds. Choosing what we consider the most reliable and relevant nitroso compound data, and accompanying them with the corresponding radical data, we derive enthalpies of formation of gaseous nitrosomethane, 2-methyl-2-nitrosopropane and o -nitrosotoluene81 to be 65 2, —29 4 and 174 7 kJmol-1. (By comparison, the earlier values recommended8 for nitrosomethane and 2-methyl-2-nitrosopropane were 70 and —42 kJmol-1 respectively.)... 

Examine the structures of the two transition states (chlorine atom+methane and chlorine+methyl radical). For each, characterize the transition state as early (close to the geometry of the reactants) or as late (close to the geometry of the products) In light of the thermodynamics of the individual steps, are your results anticipated by the Hammond Postulate Explain. 

Computations on the FCH, FjCH, and FjC radicals indicate successively greater pyramidalization. Chlorinated methyl radicals and mixed chlorofluoro radicals show the same trend toward increasing pyramidalization, as illustrated in Figure 11.5. 

D. Brault, C. Bizet, P. Morliere, M. Rougee, E.J. Land, R. Santus, and A.J. Swallow, One-Electron Reduction of Ferrideuteroporphyrin IX and Reaction of the Oxidized and Reduced Forms with Chlorinated Methyl Radicals, J. Am. Chem. Soc., 102 (1980) 1015. 

Like carbocations most free radicals are exceedingly reactive species—too reac tive to be isolated but capable of being formed as transient intermediates m chemical reactions Methyl radical as we shall see m the following section is an intermediate m the chlorination of methane... 

Chlorine atom Methane Hydrogen chloride Methyl radical... 

Step 3 Reaction of methyl radical with molecular chlorine... 

Combination of a methyl radical with a chlorine atom... 

Termination steps are m general less likely to occur than the propagation steps Each of the termination steps requires two free radicals to encounter each other m a medium that contains far greater quantities of other materials (methane and chlorine mol ecules) with which they can react Although some chloromethane undoubtedly arises via direct combination of methyl radicals with chlorine atoms most of it is formed by the propagation sequence shown m Figure 4 21... 

Chlorine atoms obtained from the dissociation of chlorine molecules by thermal, photochemical, or chemically initiated processes react with a methane molecule to form hydrogen chloride and a methyl-free radical. The methyl radical reacts with an undissociated chlorine molecule to give methyl chloride and a new chlorine radical necessary to continue the reaction. Other more highly chlorinated products are formed in a similar manner. Chain terrnination may proceed by way of several of the examples cited in equations 6, 7, and 8. The initial radical-producing catalytic process is inhibited by oxygen to an extent that only a few ppm of oxygen can drastically decrease the reaction rate. In some commercial processes, small amounts of air are dehberately added to inhibit chlorination beyond the monochloro stage. 

Chlorination of Methane. Methane can be chlorinated thermally, photochemicaHy, or catalyticaHy. Thermal chlorination, the most difficult method, may be carried out in the absence of light or catalysts. It is a free-radical chain reaction limited by the presence of oxygen and other free-radical inhibitors. The first step in the reaction is the thermal dissociation of the chlorine molecules for which the activation energy is about 84 kj/mol (20 kcal/mol), which is 33 kJ (8 kcal) higher than for catalytic chlorination. This dissociation occurs sufficiendy rapidly in the 400 to 500°C temperature range. The chlorine atoms react with methane to form hydrogen chloride and a methyl radical. The methyl radical in turn reacts with a chlorine molecule to form methyl chloride and another chlorine atom that can continue the reaction. The methane raw material may be natural gas, coke oven gas, or gas from petroleum refining. 

Fig. 1. Examples of temperature dependence of the rate constant for the reactions in which the low-temperature rate-constant limit has been observed 1. hydrogen transfer in the excited singlet state of the molecule represented by (6.16) 2. molecular reorientation in methane crystal 3. internal rotation of CHj group in radical (6.25) 4. inversion of radical (6.40) 5. hydrogen transfer in halved molecule (6.16) 6. isomerization of molecule (6.17) in excited triplet state 7. tautomerization in the ground state of 7-azoindole dimer (6.1) 8. polymerization of formaldehyde in reaction (6.44) 9. limiting stage (6.45) of (a) chain hydrobromination, (b) chlorination and (c) bromination of ethylene 10. isomerization of radical (6.18) 11. abstraction of H atom by methyl radical from methanol matrix [reaction (6.19)] 12. radical pair isomerization in dimethylglyoxime crystals [Toriyama et al. 1977].

Methyl radical Chlorine atom Combination of two methyl radicals ... 

The resulting methyl radical abstracts a chlorine atom from CI2, leading to product and generation of another chlorine atom. 

The Cl atom attacks methane and forms a methyl free radical plus HCI. The methyl radical reacts in a subsequent step with a chlorine molecule, forming methyl chloride and a Cl atom ... 

Chlorine atoms (each of which has one unpaired electron) are highly reactive they attack methane molecules and extract a hydrogen atom, leaving a methyl radical behind ... 

Recall from Section 2.9 that most radicals are very reactive. Because one of the products is another radical, this reaction is a propagation step (a step in which one reactive radical intermediate produces another). In a second propagation step, the methyl radical may react with a chlorine molecule ... 

The stratosphere contains, however, only small amounts--a few tenths of a ppb-of chlorine free radicals of natural origin. They are produced by the decomposition of methyl chloride, CH3Q. The nitrogen oxides (NO and NO2) are more abundant and are produced in the stratosphere by the decomposition of nitrous oxide, N2O. Both CH3CI and N2O are of biological origin these compounds, released at the Earth s surface, are sufficiently stable to reach the stratosphere in significant amounts. 

After dosing methyl radicals and chlorine molecules onto CuaSi samples which were cooled to 180 K, mass spectrometry was used to identify the gas phase reaction products upon heating. The silane products have been identified by monitoring their characteristic ions, which include SiCU" " (m/e=168), CHaSiCla (m/e=148), SiCla" " (m/e=133), (CHa)2SiCl2+ (m/e=128), CHaSiCl2+ (m/e=113), (CHa)2SiCl+ (m/e=93), SKCHala" " (m/e=73). All of these ions are detected. On the other hand, no CHaCl (m/e=53) or SiH4+ (m/e=32) are observed. 

In all of the studies described above, the CuaSi samples were prepared by ion bombardment at 330 K followed by cooling of the surface to 180 K before adsorbing the methyl radicals and chlorine. AES studies as well as ion scattering results in the literature [7, 15] show that this procedure produces a surface that is enriched in silicon compared with the Cu3Si bulk stoicWometry. We have found that surfaces with less Si enrichment (possibly even copper enriched relative to the bulk stoichiometry) can be prepared by ion bombardment at temperatures below 300 K. Specifically, Cu(60 eV)/Si(92 eV) Auger peak ratios of 1.2 - 1.7 compared with a ratio of 0.5 at 400 K can be obteiined by sputtering at 180 K. 

The EPR spectrum shows, in accordance with the XPS results, no feature that can be attributed to Ti centers. What is the nature of the radical observed in the EPR spectrum It might be thought that methyl radicals are the most natural products in the reduction of a mixed titaniiun-chlorine-methyl species according to the following simple reaction scheme ... 

A chlorine atom abstracts a hydrogen This step produces a molecule of atom from a methane molucule. hydrogen chloride and a methyl radical. 

A methyl radical abstracts a This step produces a molecule of methyl chlorine atom from a chloride and a cholrine atom. The chlorine chlorine molecule. atom can now cause a repetition of Step 2. 

A chlorine free radical attacks an alkane molecule like methane to form hydrogen chloride and a methyl radical (see Figure 2-15). 

The polar effect was at first invoked to explain various directive effects observed in aliphatic systems. Methyl radicals attack propionic acid preferentially at the a-position, ka/kp = 7.8 (per hydrogen), whereas chlorine " prefers to attack at the /3-position, ka/kp = 0.03 (per hydrogen). In an investigation of f-butyl derivatives, a semiquanti-tative relationship was observed between the relative reactivity and the polar effect of the substituents, as evidenced by the pK, of the corresponding acid. In the case of meta- and / ara-substituted toluenes, it has been observed that a very small directive effect exists for some atoms or radicals. When treated by the Hammett relation it is observed that p = —0.1 for H , CeHs , P-CH3C6H4 and CHs . On the contrary, numerous radicals with an appreciable electron affinity show a pronounced polar effect in the reaction with the toluenes. Compilation of Hammett reaction constants and the type of substituent... 

Our choice was the two series of dendritic polymers 5 and 6, depicted in Figure 4, which have all their open-shell centers (or trivalent carbon atoms) sterically shielded by an encapsulation with six bulky chlorine atoms in order to increase their life expectancies and thermal and chemical stabilities. Indeed, it is very well known that the monoradical counterpart of both series of polyradicals, the perchlo-rotriphenyl methyl radical, shows an astonishing thermal and chemical stability for which the term of inert free radical was coined. The series of dendrimer polymers 5 and 6 differ in the nature and multiplicity (or branching) of their central core unit, N, as well as in their branch-juncture multiplicities, N Thus, series 5 has a hyperbranched topology with = 3 and = 4, while dendrimer series 6 has a lower level of branching with = 3 and = 2, and the topology of a three-coordinated Cayley tree. 

Propagation. In this step, the intermediate reacts with a stable molecule to produce another reactive intermediate and a product molecule. The propagation step yields a new electrophilic species, the methyl radical, which has an unpaired electron. In a second propagation step, the methyl radical abstracts a chlorine atom from a chloromethane molecule, and generates a chlorine radical. 

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