Alkanes reactions with halogens

Reactions with halogens give boron halides. While reaction with chlorine can be explosive with diborane, it is slow with bromine. Diborane reacts with alkanes forming alkylboranes. Reactions with aromatics give arylboranes. 

Neutral formyl complexes which contain ligating CO often decompose by decarbonylation however, several exceptions exist. For instance, the osmium formyl hydride Os(H)(CO)2(PPh3)2(CHO) evolves H2(54). Although the data are preliminary, the cationic iridium formyl hydride 49 [Eq. (14)] may also decompose by H2 evolution (67). These reactions have some precedent in earlier studies by Norton (87), who obtained evidence for rapid alkane elimination from osmium acyl hydride intermediates Os(H)(CO)3(L)(COR) [L = PPh3, P(C2H5)3], Additional neutral formyls which do not give detectable metal hydride decomposition products have been noted (57, 65) however, in certain cases this can be attributed to the instability of the anticipated hydride under the reaction conditions (H2 loss or reaction with halogenated solvents). 

Alkanes are fuels they burn in air if ignited. Complete combustion gives carbon dioxide and water less complete combustion gives carbon monoxide or other less oxidized forms of carbon. Alkanes react with halogens (chlorine or bromine) in a reaction initiated by heat or light. One or more hydrogens can be replaced by halogens. This substitution reaction occurs by a free-radical chain mechanism. 

Alkenes are similar to alkanes in structure and also undergo combustion. However, they are much more likely to undergo addition reactions with halogens, rather than substitution. Addition reactions occur with a wide variety of reagents. 

Alkynes undergo addition reactions with halogens (CI2, Br2) to produce tetrahalo alkanes. To saturate each allqme molecule, two halogen molecules are needed. Alkynes decolorize aqueous Br2 solution, as alkenes do. 

Hydroalumination of alkenes. Hydroalumination of alkynes is a well-known reaction, but hydroalumination of alkenes has been achieved only recently under catalysis by TiCU or ZrCU, (8, 288). As expected hydroalumination affords a convenient, high-yield route to primary alkanes (by hydrolysis), terminal primary alcohols (by oxygenation), and primary alkyl halides (reaction with halogens, N-halosuccinimides, or CuXa). ... 

In the presence of light or heat, alkanes react with halogens to form alkyl halides. Haiogenation is a radical substitution reaction, because a halogen atom X replaces a hydrogen via a mechanism that involves radical intermediates. 

Alkanes are rather inert chemically. Aside from burning in air or oxygen to produce carbon dioxide and water (or carbon monoxide and water), the most characteristic reaction they undergo is reaction with halogen molecules, initiated with light. For example. 

Addition reactions with halogens, hydrogen halides, and water hydrogenation to yield alkanes... 

In ultraviolet light, chlorine or bromine react with alkanes to form chloroalkanes or bromoalkanes (the general term is halogenoalkanes). The reaction with halogens is called halt enation and, since it takes place in the presence of light, it is termed a photochemical reaction. 

Alkanes and cycloalkanes are quite unreactive toward most reagents, a behavior consistent with the fact that they are nonpolar compounds and contain only strong sigma bonds. Under certain conditions, however, alkanes and cycloalkanes do react with O2 and with the halogens CI2 and Br2. At this point, we present only their combustion with oxygen. We discuss their reaction with halogens in Chapter 8. 

The alkanes will undergo substitution reactions with halogens in sunlight. For example ... 

The reactivity of the halogens decreases m the order F2 > CI2 > Br2 > I2 Fluo rme is an extremely aggressive oxidizing agent and its reaction with alkanes is strongly exothermic and difficult to control Direct fluonnation of alkanes requires special equip ment and techniques is not a reaction of general applicability and will not be discussed further... 

Chlorination of alkanes is less exothermic than fluonnation and bromination less exothermic than chlorination Iodine is unique among the halogens m that its reaction with alkanes is endothermic and alkyl iodides are never prepared by lodmation of alkanes... 

Strong oxidizers and strong acids are incompatible with nikanolamines. Reactions, generating temperature and/or pressure increases, may occur with halogenated organic compounds. Alkan olamines are corrosive to copper and brass and may react. Contact with aluminum by alkan olamines, particularly when wet or at elevated temperatures (60°C), should be avoided. 

This method is also used with alcohols of the stmcture Cl(CH2) OH (114). HaloaLkyl chlorosulfates are likewise obtained from the reaction of halogenated alkanes with sulfur trioxide or from the chlorination of cycHc sulfites (115,116). Chlorosilanes form chlorosulfate esters when treated with sulfur trioxide or chlorosulfuric acid (117). Another approach to halosulfates is based on the addition of chlorosulfuric or fluorosulfuric acid to alkenes in nonpolar solvents (118). 

Simple alkyl halides can be prepared by radical halogenation of alkanes, but mixtures of products usually result. The reactivity order of alkanes toward halogenation is identical to the stability order of radicals R3C- > R2CH- > RCH2-. Alkyl halides can also be prepared from alkenes by reaction with /V-bromo-succinimide (NBS) to give the product of allylic bromination. The NBS bromi-nation of alkenes takes place through an intermediate allylic radical, which is stabilized by resonance. 

This type of polyhalo alkane adds to halogenated alkenes in the presence of AICI3 by an electrophilic mechanism. This is called the Prins reaction (not to be confused with the other Prins reaction, 16-53). ... 

Such a molecule, containing alternating single and double bonds, would be expected to be quite reactive. Actually, benzene is quite unreactive, and its chemical properties resemble those of the alkanes much more than those of the unsaturated hydrocarbons. For example, the characteristic reaction of benzene with halogens resembles that of the reaction of the alkanes ... 

Alkenes undergo addition reactions with hydrogen to form alkanes, with halogens to form dihaloalkanes, with hydrogen halides to form monohaloalkanes and with water to form alcohols. For example ... 

Halogenation reactions of alkanes provide good examples of radical processes, and may also be used to illustrate the steps constituting a radical chain reaction. Alkanes react with chlorine in the presence of light to give alkyl chlorides, e.g. for cyclohexane the product is cyclohexyl chloride. 

As discussed in Chapter 6, group additivity approaches have been developed for estimating the rate constants for the reactions of a variety of species such as OH with organics. DeMore (1996) has applied a similar approach for estimating the rate constants for the reaction of OH with halogenated alkanes. The rate constant per hydrogen atom at 298 K is calculated using Eq. (D) ... 

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