Mono halogen substitution products

Methyl Halides.— The mono-halogen substitution products of methane, of which we have been speaking, are known by this new system of names as methyl compounds so that we have the two sets of names for the same substances, both of which are correct and either of which expresses the relationship to methane. 

This reaction is entirely different from that of phosphorus penta-chloride on alcohol, in which the hydroxyl of the alcohol is replaced by one chlorine, and the mono-halogen substitution product of the hydrocarbon results (p. 81). If our ideas in regard to the constitution of aldehyde are correct, this reaction must mean, that, in the di-chlor ethane formed in this way, the two chlorine atoms are linked to the same carbon atom. Such a structure represents a compound which is plainly unsymmetricaL... 

The simpler mono substitution products of these hydrocarbons a) Halogen substitution products. 

The ethylidene, or unsymmetrical di-halogen substitution products of ethane, are not of much importance, because they do not easily undergo reaction. They are prepared by the reactions just described, viz., from aldehyde by the action of phosphorus penta-chloride, -bromide, or -iodide. Also by the action of phosphorus chlor-bromide, PCl3Br2, or of carbonyl chloride (phosgene), COCI2. They may also be made by the further halogenation of the mono-halogen ethanes ... 

Phenols react with halogens to yield mono-, di-, or tri-substituted products, depending on reaction conditions. For example, an aqueous bromine solution brominates all ortho and para positions on the ring. 

The photostimulated reactions of thiolate anions with 2-halo-2 -nitropropane derivatives yield both oc-nitrosulphides via an S l pathway and disulphides (equation 71a)282 284. In contrast with the case of the oxidative dimerisation products of the mono-enolates, the disulphides are formed via an ionic mechanism nucleophilic attack by the thiolate anion on the a-halogen and subsequent reaction of a second thiolate with the sulphenyl halide. As expected for such a process, disulphide formation is favoured (and thus a-nitrosulphide formation is disfavoured) the more nucleophilic the thiolate (i.e. derived from a less acidic thiol) and the easier the abstraction of the halo-substituent (i.e. I > Br > Cl). Use of the protic solvent methanol instead of the usual dipolar aprotic solvents for the reaction of equation 71a is detrimental to the yield of the S l substitution products exclusively disulphides are formed285 (equation 71b). Methanol solvation probably retards the dissociation of the radical anion intermediate in the SRN reaction, into radical and anion, and hence retards the chain reaction relative to the ionic reaction. The non-nucleophilic methylsulphinate ion gives only an S l reaction product with 2-bromo-2-nitropropane286. 

The halogenation reaction proceeds in darkness and is reasonably considered as ionic. It has been shown that if chlorine gives primarily free radical addition on mono- and di-substituted alkenes, it gives ionic substitution products with tri- and tetra-substituted alkenes [73], A model compound study, together with NMR analysis of commercial chloro and bromobutyl samples, confirmed that the reaction on isoprenyl unit leads predominantly to the exomethylene-substituted structure A, and this is explained by steric hindrance due to the tetra-substituted carbon in f3-position which favors proton elimination rather than the nucleophilic attack of halide counter ion in the second phase of addition (Fig. 11, Table 1) [74,75]. 

Isomerism of Di-chlor Ethanes.—When, however, we study the constitution of the poly-halogen ethanes we find that isomerism occurs just as in the case of the propyl iodides and of the hydrocarbons above propane. In the case of ethane it is a fact that only one mono-substitution product of any type is known, thereby proving the symmetry of the ethane molecule and the like character of all six of the hydrogen atoms. When two hydrogen atoms are substituted by two chlorine atoms two dif event compounds are produced both having the composition C2H4CI2. From the constitution of the ethane molecule, that has been established by its synthesis from methane (p. 16), we can readily see how this may be explained as we may have two hydrogen atoms replaced by two chlorine atoms in two different ways, as follows ... 

Synthesis.—We have shown that the alkyl halides are mono-substitution products of the hydrocarbons, i.e., one hydrogen of the hydrocarbon has been substituted by a halogen, e.g., methyl iodide, CH3—I. Now when methyl iodide is treated with ammonia a new compound is formed having the composition CHsN and the other product of the reaction is hydrogen iodide. 

Isomerism.— As all of the second group, in which substitution occurs in the side chain, considered as benzene derivatives, are mono-substituted benzenes, they do not exist in isomeric forms, and only one compound of each formula is known. The first group, however, in which halogen substitution occurs in the ring, are all poly-substitution products of benzene, since toluene itself is a mono-substituted benzene. Mono-chlor toluene is, therefore, a di-substituted benzene, and occurs in the three forms, as follows ... 

---