Combinations of alkyl radicals with alkyl and substituted allyl radicals

In contrast with expectations based upon simple collision theory, reactions of alkyl radicals with substituted allyl radicals yield cross-combination ratios of =2. Reactions of CH ₃ ^\ with some C₅ radicals give >2, in accordance with theory.

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, =2. CH₃ ^\ C₅ >2, .

     

Fluorine transfer to alkyl radicals

The development of new synthetic technologies for the selective fluorination of organic compounds has increased with the escalating importance of fluorine-containing pharmaceuticals. Traditional methods potentially applicable to drug synthesis rely on the use of ionic forms of fluorine (F(-) or F(+)). Radical methods, while potentially attractive as a complementary approach, are hindered by a paucity of safe sources of atomic fluorine (F(?)). A new approach to alkyl fluorination has been developed that utilizes the reagent N-fluorobenzenesulfonimide as a fluorine transfer agent to alkyl radicals. This approach is successful for a broad range of alkyl radicals, including primary, secondary, tertiary, benzylic, and heteroatom-stabilized radicals. Furthermore, calculations reveal that fluorine-containing ionic reagents are likely candidates for further expansion of this approach to polar reaction media. The use of these reagents in alkyl radical fluorination has the potential to enable powerful new transformations that otherwise would take multiple synthetic steps.     

Vibrational analysis of tertiary alkyl bromides

Infrared spectra have been obtained for 2-bromo-2-methylpentane and 3-bromo-3-methylpentane. Both compounds exist in T_HHH and T_CHH conformations. Normal coordinate calculations were made for these two compounds and for 2-bromo-2-methylbutane, using the 44-parameter modified valence force field that was used for tertiary chlorides. Fifteen force constants were adjusted to fit 169 frequencies below 1500 cm^?1 of six molecules (two each for the three named compounds) with an average error of 5.6 cm^?1. Vibrational assignments are presented.     

Vibrational analysis of tertiary alkyl chlorides

Vibrational spectra were obtained for 2-chloro-2-methylpentane, 3-chloro-3-methylpentane, 2-chloro-2-methylhexane, and 3-chloro-3-methylhexane. All four compounds exist in T_HHH and T_CHH conformations in the neat liquid, and the T_HHH' conformer of the last named compound also seems to be present. Only the T_HHH conformer is present in the crystalline state of the two pentanes, but the hexanes could not be made to crystallize and both conformers were present in the solid. A 44-parameter modified valence force field was used in normal coordinate calculations, with fifteen force constants being adjusted to fit 188 assigned frequencies below 1500 cm^?1 of six molecules (two conformers each of 2-chloro-2-methylbutane, 2-chloro-2-methylpentane, and 3-chloro-3-methylpentane). The resulting force constant values were used in zero-order calculations of the two hexanes as an aid in interpreting vibrational spectra for those compounds.     

Electron affinities of a homologous series of tertiary alkyl radicals and their C-H bond dissociation energies (BDEs)

Heats of formation have been derived from G3(MP2)//B3LYP and G3MP2B3(+) atomization energies for tert-butyl radical (6R), cubyl radical, bicyclooctyl radical (1R), and tricyclo[3.3.n.0^3,7]alk-3(7)-yl (n=0-3, 2R-5R) radicals, and their respective anions (1A-6A) and hydrocarbons (1H-6H). The electron affinity (EA) of 6R is estimated at 1.5±2 kcal/mol and tert-butyl anion (6A) is likely to be bound. In the homologous series 2R-5R the EAs range from 3.4±2 to 13.5±2 kcal/mol. The computed enthalpies of the acidities of the tricyclic hydrocarbons 1H-5H are in the range 407-411 kcal/mol. Their C-H bond dissociation energies (BDEs) are in the range 97-110 kcal/mol. The increase of the BDEs in the homologous series 2H-5H and the increase of EAs of 2A-5A is attributed to the enhanced pyramidalization induced in radicals 2R-5R by the shortening of the methylene chain connecting carbons C₃ and C₇.     

Applications of molecular mechanics to alkyl radicals

The MM2 force field has been extended to alkyl radicals. The known structures and conformational energy relationships are well reproduced for many simple radicals, and predictions were made for 1-butyl, 2-butyl, cyclopentyl, cyclohexyl and others. Heats of formation were also studied.     

Reaction kinetics of alkyl and alkylperoxide radicals

Rate constants for the reaction of alkyl and alkylperoxide radicals in solutions of cyclohexane and tridecane have been measured by flash photolysis and kinetic spectrophotometry methods, respectively.

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Reactions of BrCl with alkyl radicals.

It is demonstrated that photohalogenations of low reactivity substrates with BrCl occurs mainly with Cl· selectivity. With tertiary or benzylic hydrogens in the substrate, mainly Br· selectivity is observed. These observations are rationalized, taking into account the relative concentrations of halogen atoms and their respective rates of hydrogen abstractions. The resultant radicals react with BrCl to make (RBr/RCl) in ratios between 1 and 15.     

Disproportionation-combination ratios of large branched alkyl radicals

The disproportionation-combination reactions of radicals 4,4-dimethylpentyl-2 and 2,4-dimethylpentyl-2, produced by collisional stabilization of the respective chemically activated species, have been studied at 298°K, with and without getter radicals. Use of getters t-C₄H₉ and C₂H₅ with 4,4-dimethylpentyl-2, and of iso-C₃H₇ with 2,4-dimethylpentyl-2 yielded disproportionation-combination ratios ω for parent-getter and t-C₄H₉-C₂H₅ cross reactions, and for the mutual reaction of t-C₄H₉ radicals. The unstabilized hot radicals decompose, and these experiments also yielded values for the high-pressure rate constant k_a∞ of 1.70 × 10⁸sec^–1 and 2.11 × 10⁷sec^–1 for 4,4-dimethylpentyl-2 and 2,4-dimethylpentyl-2, respectively. The results, compared to those for other large alkyl radical systems obtained earlier, suggest that steric effects influence the accessibility of H atoms for transfer.