Hydrogen atoms tertiary

Figure 7.15 Top the mechanism of metabolic oxidation of primary and secondary alcohols to aldehydes and ketones. Bottom the mechanism requires that the carbon with the hydroxyl group is also bonded to at least one hydrogen atom. Tertiary alcohols therefore do not undergo metabolic oxidation by this mechanism. The primary alcohol resulting from co-oxidation of ibuprofen is oxidized by alcohol dehydrogenase to an aldehyde. This is rapidly metabolized further to a carboxylic acid.

Polybutadiene and polyunsaturated fats, which contain aHyUc hydrogen atoms, oxidize more readily than polypropylene, which contains tertiary hydrogen atoms. A linear hydrocarbon such as polyethylene, which has secondary hydrogens, is the most stable of these substrates. 

A refined grade of MTBE is used ia the solvents and pharmaceutical iadustries. The main advantage over other ethers is its uniquely stable stmctural framework that contains no secondary or tertiary hydrogen atoms, which makes it very resistive to oxidation and peroxide formation. In addition, its higher autoignition temperature and narrower flammabihty range also make it relatively safer to use compared to other ethers (see Table 3). 

Figure 18.17 Two-dimensional NMR spectnim of the C-terminal domain of a cellulase. The peaks along the diagonal correspond to the spectrum shown in Figure 18.16b. The off-diagonal peaks in this NOE spectrum represent interactions between hydrogen atoms that are closer than 5 A to each other in space. From such a spectrum one can obtain information on both the secondary and tertiary structures of the protein. (Courtesy of Per Kraulis, Uppsala.)...

Another convenient method for the preparation of tertiary enamines involves the dehydrogenation of saturated bases with mercuric acetate (111-116). A trans-1,2 elimination occurs, which requires an antiperi-planar position of the nitrogen-free electron pair and the eliminated atom. A preferential elimination of the hydrogen atom from the tertiary carbon atom is supposed. Overoxidation can be avoided by adding disodium ethyl-enediaminotetraacetate to the reaction mixture (117). 

Free radicals may also react with a hydrocarbon molecule from the feed by abstracting a hydrogen atom. In this case the attacking radical is terminated, and a new free radical is formed. Abstraction of a hydrogen atom can occur at any position along the chain. However, the rate of hydrogen abstraction is faster from a tertiary position than from a secondary, which is faster than from a primary position. 

Alpha-scission is not favored thermodynamically but does occur. Alpha-scission produces a methyl radical, which can extract a hydrogen atom from a neutral hydrocarbon molecule. The hydrogen extraction produces methane and a secondary or tertiary free radical (Equation 4-3). 

Identify the hydrogen atoms on the compounds shown in Problem 3.8 as primary, secondary, or tertiary. 

Draw a skeletal structure of the following carbocation. Identify it as primary, secondary, or tertiary, and identify the hydrogen atoms that have the proper orienta- tion for hyperconjugation in the conformation shown. 

The key features of Curran s productive and elegant tandem radical cyclization strategy are illustrated in a retrosynthetic analysis for hirsutene (1) (see Scheme 27). The final synthetic event was projected to be an intermolecular transfer of a hydrogen atom from tri-rc-butyltin hydride to the transitory tricyclic vinyl radical 131. The latter can then be traced to bicyclic tertiary radical 132 and thence to monocyclic primary radical 133 through successive hex-5-enyl-like radical cyclizations. It was anticipated that the initial radical 133 could be generated through the abstraction of the iodine atom from... 

However, the situation is not as clear-cut as it might at first seem since a variety of other factors may also contribute to the above-mentioned trend. Abuin et a/.141 pointed out that the transition state for addition is sterically more demanding than that for hydrogen-atom abstraction. Within a given series (alkyl or alkoxy), the more nucleophilic radicals are generally the more bulky (i.e. steric factors favor the same trends). It can also be seen from Tabic 1.6 that, for alkyl radicals, the values of D decrease in the series primary>secondary>tertiary (i.e. relative bond strengths favor the same trend). 

Amines are ammonia derivatives in which one or more hydrogen atoms have been replaced by an organic radical. Amines are sometimes called nitrogen bases. Basic chemistries include fatty amines (as primary, secondary, tertiary, and polyamines), amine salts, quaternary ammonium compounds, amine oxides, and amides. 

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