Alkyl halides Compounds with halogen

Alkyl organo tellurium compounds, prepared from alkane- or arenetellurolates and alkyl halides, react with butyl lithium,. 9ec-butyl lithium, /ert.-butyl lithium, or phenyl lithium. The alkyl group bonded to the tellurium atom is cleaved from the tellurium and is present in solution as the alkyl lithium that can be used for further reactions. This tellurium-lithium exchange reaction is synthetically useful, whenever the alkyl halides cannot be converted to alkyl lithiums by other, more conventional halogen exchange reactions. The following exchange reactions were successfully carried out ... 

In this and the next chapter, we ll be discussing the chemistry of alkyl halides—compounds that have a halogen atom bonded to a saturated, s/> -hybridized carbon atom. We ll begin in this chapter with a look at how to name and prepare alkyl halides, and we ll see several of their reactions. Then in the following chapter, we ll make a detailed study of the substitution and elimination reactions of alkyl halides—two of the most important and well-studied reaction types in organic chemistry. 

The reactivity of the normal alkyl halides varies with the halogen and with the alkyl group the more reactive are those with the smaller number of carbon atoms. The iodides are the most reactive, the chlorides the most inert. Methyl iodide is much used in organic syntheses, as it reacts readily with many substances and serves as a means of introducing the methyl group into such compounds. An alcoholic solution of methyl iodide reacts with a similar solution of silver nitrate in the cold, and silver iodide is formed. With ethyl iodide the reaction proceeds much more slowly, and with the higher alkyl iodides the application of heat is necessary to bring about reaction. 

In the previous chapters the preparation and properties of certain important classes of compounds have been discussed, and the principles which are illustrated in their transformations into one another have been emphasized. These principles are of wide application and can be employed in the preparation of compounds of more complex structure than any met with so far. For example, the method of preparing an alcohol by the treatment of an alkyl halide with water or an alkali, is very general in its application. The reaction consists in the replacement of a halogen atom by a hydroxyl group, and such replacement takes place not only with alkyl halides, but with other compounds which contain halogen. Thus, chloroacetic acid can be transformed into hydroxyacetic acid by water —... 

A key step in the reaction mechanism appears to be nucleophilic attack on the alkyl halide by the negatively charged copper atom but the details of the mechanism are not well understood Indeed there is probably more than one mechanism by which cuprates react with organic halogen compounds Vinyl halides and aryl halides are known to be very unreactive toward nucleophilic attack yet react with lithium dialkylcuprates... 

These compounds generally exist in carbonyl forms. The oxygen function can be converted into halogen by phosphorus halides. Reactions with electrophiles are quite complex. Thus urazole (511) reacts with diazomethane quickly to yield (512), which is more slowly converted into (513). 1-Phenylurazole gives (514) however, 4-phenylurazole yields (515). Oxadiazolinones of type (516) can be alkylated at both O- and N-atoms. 

B. Reactions with Organic Halogen Compounds 1. Alkyl Halides... 

The haloalkanes (also called alkyl halides) are alkanes in which at least one hydrogen atom has been replaced by a halogen atom. Although they have important uses, many haloalkanes are highly toxic and a threat to the environment. The haloalkane 1,2-dichlorofluoroethane, CHC1FCH2C1, is an example of a chlorofluorocarbon (CFC), one of the compounds held responsible for the depletion of the ozone layer (see Box 13.3). Many pesticides are aromatic compounds with several halogen atoms. 

It seems likely that the mechanism of the Wurtz reaction consists of two basic steps. The first is halogen-metal exchange to give an organometallic compound (RX -(- M —+ RM), which in many cases can be isolated (12-36). Following this, the organometallic compound reacts with a second molecule of alkyl halide (RX + RM —> RR). This reaction and its mechanism are considered in the next section (10-94). 

---