Octyl iodide, reduction

The occurrence of a radical intermediate is also indicated in the reduction of 2-octyl iodide by LiAlD4 since, in contrast to the chloride or bromide, extensive racemization accompanies reduction. 

Reactions of formyl complexes with alkylating agents can be more complex than the reductions in Eqs. (15-22). Some examples of simple hydride transfer exist. For instance, (CO)4Fe(CHO) (22) reduces octyl iodide to octane (75%) (27, 28) (C2H5)4N + 25 (Table I) reacts with heptyl iodide (overnight, room temperature, THF) to give heptane (71%) and (CO)4[(ArO)3P]Fe (37, 42) c/.s-(CO)5ReRe(CO)4(CHO) (19) converts octyl iodide to octane (68%) (47). 

Yoon and Kim have prepared potassium triphenylborohydride (KPhjBH) and examined the reducing ability toward alkyl halides. n-Octyl iodide is reduced within 1 h at 0 °C, whereas n-octyl bromide takes 24 h for complete reduction. Secondary bromides are inert under these conditions. 

Table III. The Reduction and Alkylation of Illinois No. 6 Coal with Methyl, Butyl, and Octyl Iodide ...

Hindered di-t-alkylamines RNHBu1 (R = t-Bu, t-octyl or 1-adamantyl) have been synthesized from t-alkylamines as follows. Reaction with peracetic acid gave the nitrosoalkanes RNO, which were treated with t-butyl radicals, generated from t-butylhydrazine and lead(IV) oxide, to yield t-butyloxyhydroxylamines. Reduction with sodium naphthalide in THF gave the products (equation 12). The di-t-alkyl-amines are inert to methyl iodide and dimethyl sulphate but can be alkylated by methyl fluorosulphonate42. 

For secondary alkyl iodides, the two one-electron polarographic waves are more separated. Reduction of 2-iodooctane at the potential of the first wave alfords the dialkylmercury and 7,8-dimethyl-tetradecane by reactions of the sec-octyl radical. At the potential of the second wave only octane and octenes are isolated [37]. 2-Bromooctane shows only one polarographic wave and yields octane and octene on reduction at any potential [37]. Radicals generated by reduction of primary and secondary iodoalkanes will react with other cathode materials including tin, lead and thallium to form metal alkyls [48,49],... 

Another convenient procedure for the reductive removal of the mesylate or tosylate group is through reaction with a Nal/Zn system The iodide intermediate which is formed in the reaction is reduced to the alkane with zinc powder. Following this procedure 2-octyl tosylate could be reduced to n-octane in high yield (equation... 

The cathodic peak current is diffusion controlled, and the reduction potentials in the case of alkaline iodides are close to those already measured with the platinum interfaces. Also with TAAX salts, palladium shows a behavior similar to platinum. TMAX (X = halide) displays a quasi-reversible system. Contrarily, bulky TAA+ cations considerably enlarge the irreversibility of the charge-discharge process. Thns, while the potential difference AE between the cathodic and anodic peaks is abont 0.7 V when the cation is tetramethylammonium, it reaches almost 1.8 V when the cation is a tetra-n-octyl salt (Table 2.6). 

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