Hydrogen tertiary

Varley D F and Dagdigian P J 1996 Product state resolved study of the Cl + (CH3)3 CD reaction comparison of the dynamics of abstraction of primary vs tertiary hydrogens J. Phys. Chem. 100 4365-74... 

A similar study of the chlorination of 2 methylpropane established that a tertiary hydrogen is removed 5 2 times faster than each primary hydrogen... 

Bromine reacts with alkanes by a free radical chain mechanism analogous to that of chlorine There is an important difference between chlorination and brommation how ever Brommation is highly selective for substitution of tertiary hydrogens The spread m reactivity among pnmary secondary and tertiary hydrogens is greater than 10 ... 

In practice this means that when an alkane contains primary secondary and tertiary hydrogens it is usually only the tertiary hydrogen that is replaced by bromine... 

The transfer of a tertiary hydrogen between the polymer chain and a monomer can account for the vinylidene group in the polymer ... 

Each isomer has its individual set of physical and chemical properties however, these properties are similar (Table 6). The fundamental chemical reactions for pentanes are sulfonation to form sulfonic acids, chlorination to form chlorides, nitration to form nitropentanes, oxidation to form various compounds, and cracking to form free radicals. Many of these reactions are used to produce intermediates for the manufacture of industrial chemicals. Generally the reactivity increases from a primary to a secondary to a tertiary hydrogen (37). Other properties available but not Hsted are given in equations for heat capacity and viscosity (34), and saturated Hquid density (36). 

The point at which two polymeric chains are joined together by a cross-linker such as divinylbenzene, or sites where tertiary hydrogens are located in the stmcture, are other locations for oxidative attack. In both cation- and anion-exchange resins, oxidative attack results in the removal of cross-linking. 

These reactions occur on the benzylic hydrogens because these hydrogens are much more reactive. Competition experiments show, for example, that at 40°C a benzylic hydrogen of toluene is 3.3 times as reactive toward bromine atoms as the tertiary hydrogen of an alkane and nearly 100 million times as reactive as a hydrogen of methane. 

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). 

Important differences are seen when the reactions of the other halogens are compared to bromination. In the case of chlorination, although the same chain mechanism is operative as for bromination, there is a key difference in the greatly diminished selectivity of the chlorination. For example, the pri sec selectivity in 2,3-dimethylbutane for chlorination is 1 3.6 in typical solvents. Because of the greater reactivity of the chlorine atom, abstractions of primary, secondary, and tertiary hydrogens are all exothermic. As a result of this exothermicity, the stability of the product radical has less influence on the activation energy. In terms of Hammond s postulate (Section 4.4.2), the transition state would be expected to be more reactant-like. As an example of the low selectivity, ethylbenzene is chlorinated at both the methyl and the methylene positions, despite the much greater stability of the benzyl radical ... 

Fluorination of aliphatic hydrocarbons with cobalt trifluoride gives complex mixtures Isobutane (2-methylpropane) fluorinated at 140-200 °C affords a mixture of 30 products of different degrees of fluorination and of isobutane as well as butane skeletons. The tertiary hydrogen is replaced preferentially Products containing 5-10 atoms of fluorine including a small amount of perfluoroisobutane were isolated [10]. 

The next major bonded phase project was the development of the GBR resin, which stands for modified glucose bonded on both the backbone and the ring of basic PDVB gels. The manufacture of this product was ultimately achieved, as outlined later. The gel is first brominated, which places bromine atoms on both tertiary hydrogens of the PDVB. The brominated gel is then reacted with chlorosulfonic acid, and a specially treated reduced D-glucosamine is coupled to the gel. This process has the potential to covalently bond up to three sugar residues to each available divinylbenzene residue in the PDVB polymer. The exact reaction conditions used are proprietary however, the surface of the finished product is believed to look similar to Figs. 13.11 and 13.12. 

The oxidation of amines by mercuric acetate is an old reaction (54) which up until recent years was employed primarily to modify alkaloid structures (55). A systemic study of the oxidizing action of mercuric acetate by Leonard and co-workers led to the development of a general method for the synthesis of enamines from cyclic tertiary amines. An observation made after a large number of compounds were oxidized, but which is worth noting at the onset, is that a tertiary hydrogen alpha to the nitrogen atom is removed preferentially to a secondary a-hydrogen. 

Isobutane, on the other hand, is a much more reactive compound due to the presence of a tertiary hydrogen. 

Table IV. Chemical Shifts of the Tertiary Hydrogens at C-2 and C-4 of Kasuganobiosamine N-Monoderivatives...

A similar calculation for the chlorination of 2-methylpropane indicates that each of the nine primary hydrogens accounts for 65% + 9 = 7.2% of the product, while the single tertiary hydrogen (R3CH) accounts for 35% of the product. 

Thus, a tertiary hydrogen is 35 gen toward chlorination. 7.2 = 5 times as reactive as a primary hydro- ... 

In contrast with alkane chlorination, alkane bromination is usually much more selective. In its reaction with 2-methylpropane, for example, bromine abstracts the tertiary hydrogen with greater than 99% selectivity, as opposed to the 35 65 mixture observed in the corresponding chlorination. 

Phenols, alkali225, and some other substances226-228 serve as initiators of these reactions. In the case of poly(acrylonitrile) this role is played by a tertiary hydrogen which is activated by the C=N group. 

This has also been accomplished with concentrated H2SO4 saturated with CO. Not surprisingly, only tertiary halides perform satisfactorily secondary halides give mostly rearrangement products. An analogous reaction takes place with alkanes possessing a tertiary hydrogen, for example. 

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