Sodium methoxide, reaction with aryl halides

The generally accepted mechanism for nucleophilic aromatic substitution m nitro substituted aryl halides illustrated for the reaction of p fluoromtrobenzene with sodium methoxide is outlined m Figure 23 3 It is a two step addition-elimination mechanism, m which addition of the nucleophile to the aryl halide is followed by elimination of the halide leaving group Figure 23 4 shows the structure of the key intermediate The mech anism is consistent with the following experimental observations... 

The most common types of aryl halides in nucleophilic aromatic substitutions are those that bear- o- or p-nitro substituents. Among other classes of reactive aryl halides, a few merit special consideration. One class includes highly fluorinated aromatic compounds such as hexafluorobenzene, which undergoes substitution of one of its fluorines on reaction with nucleophiles such as sodium methoxide. 

Aryl halides can undergo photostimulated polycarbonylation catalysed by Co2(CO)8 in aqueous sodium hydroxide solution or in methanol containing sodium methoxide (equation 193)752-754. Such reactions have been performed with chloro-, bromo- and dichloro-... 

Discrete copper compounds can also be used as catalysts for the synthesis of arylamines (Scheme 3.52) [58]. Venkataraman used a neocuproine-ligated copper(I) species to promote the coupling of aryl halides with secondary amines. A practical advantage to this chemistry was that only air-stable materials were needed to construct the catalyst needed for the cross-coupling. A base was needed to promote the reaction, and potassium tert-butoxide was found to be more effective in the cross-coupling than other common bases including potassium phosphate, sodium methoxide, or cesium carbonate. Curiously, cesium carbonate was not as active in this chemistry, but it was quite effective in the preparation of diaryl ethers. Several aryl halides were screened for activity, and aryl bromides and iodides afforded moderate to good yields of the arylamines. It should be noted that an electron-neutral aryl chloride was converted into the triarylamine, albeit in lower yield (49%). 

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