Diazonium salts, aryl iodination

One of the best methods for the introduction of iodine into aromatic rings is the reaction of diazonium salts with iodide ions. Analogous reactions with chloride, bromide, and fluoride ions give poorer results, and 14-25 and 13-20 are preferred for the preparation of aryl chlorides, bromides, and fluorides. However, when other diazonium reactions are carried out in the presence of these ions, halides are usually side products. Aniline has also been converted to fluorobenzene by treatment with t-BuONO and Sip4 followed by heating. A related reaction between PhN=N—N C4Hg and iodine gave iodobenzene. ... 

Let us now consider the formation of aryl iodides from aryl diazonium salts and potassium iodide in methanol (Singh and Kumar 1972a, 1972b). Electron-donor substituents decelerate the process as compared with benzene diazonium (the substituent is hydrogen), whereas electron acceptor substituents accelerate it. Oxygen inhibits the reaction, and photoirradiation speeds it up. As the authors pointed out, in the case of 4-nitrobenzene diazonium, the reaction leads not only to 4-iodonitrobenzene but also to nitrobenzene, elemental iodine, and formaldehyde. All of these facts support the following sequence of events ... 

These reactions are related to the reaction of aryl diazonium salts with iodide yielding iodoaryls, the mechanism of which seems to be a one-electron transfer (radical) reaction and not a nucleophilic displacement. Just as iodide is easily oxi- zed to iodine by the aryl diazonium cation, 2.4.6-triphenyl-X -phosphorin is oxidized to the radical cation 58. 

Keywords solid diazonium salt, potassium iodide, iodination, solid-solid reaction, aryl iodide... 

Aryl iodides.1 DMSO is a particularly useful solvent for decomposition of aryl diazonium salts. Decomposition in the presence of KI (and I2 to minimize formation of iodinated biphenyls) results in aryl iodides in > 85% yield. 

Alkyl iodides have been widely used for selective alkylation of heteroaromatic bases. The method is based on rapid iodine abstraction by aryl radicals (obtained from benzoyl peroxide or diazonium salts) or by a methyl radical (obtained from MeCOOH, t-BuOH, t-BuOOH, (t-BuO)2, (MeCOO)2, MeS0Me/H202, or MeC0Me/H202) [2]. An example is depicted in Eq. (14) of Table 3. 

Because aryl diazonium salts are reasonably stable, other nucleophiles may be introduced to capture the aryl cation when the diazonium salt is heated. Among these, iodide ion is important as it allows the preparation of aryl iodides in good yield. These compounds are not so easy to make by electrophilic substitution (Chapter 22) as aryl chlorides or bromides because iodine is not reactive enough to attack benzene rings. Aryl iodides are useful in the more modern palladium chemistry of the Heck reaction, which you will meet in Chapter 48. 

A diazonium salt reacts with. sodium or potassium iodide to form an aryl iodide. This, too, is a useful reaction because aryl iodides cannot be produced by direct iodination with I2 and a Lewis acid catalyst, as Ig reacts too slowly (Section 18.3). 

As it is well known, nucleophilic substitution of a C-X bond, one of the key synthetic reactions with aliphatic compounds is severely limited with aromatic derivatives, where it occurs thermally only with electron-withdrawing substituted compounds and/or under severe conditions. Alternatives include time honored reactions involving the phenyl radical generated by decomposition of diazonium salts after a reductive step, such as the Meerwein and the Gomberg-Bachmann reactions, as well as the (often photoinitiated) SrnI reaction, where a (usually weak, e.g. carbon-iodine) bond is cleaved after monoelectronic reduction to give an aryl radical as the active inter-mediate that adds to an enolate, cyanide or other nucleophiles (and thus again with an aryl radical as the key intermediate. Scheme S). ... 

The preparation of / -diiodobenzene given as an example above showed that iodine can be very easily substituted for a diazonium group by means of hydriodic acid without addition of a copper(i) salt. A little urea is added to the diazotized solution (to remove residual HN02), which is usually prepared in hydrochloric or sulfuric acid, followed by a cold iodide solution (1-2 moles of alkali iodide per mole of diazotized amine) or the solution of the diazonium salt in mineral acid is added to a cold iodide solution. Evolution of nitrogen ceases after storage for several hours or, if necessary, subsequent warming on a wather-bath. Phenols can be expected as by-products and may be removed by basification before isolation of the aryl iodide the latter is obtained then by distillation in steam, extraction in ether, CHC13, benzene, or toluene, or filtration. Biaryls and azo compounds are not formed, because the mechanism... 

Aryl diazonium ions are converted to iodides in high yield by reaction with iodide salts. This reaction is initiated by reduction of the diazonium ion by iodide. The aryl radical then abstracts iodine from either I2 or I3. A chain mechanism then proceeds... 

Conversion of diazonium compounds to aryl chlorides, bromides, or cyanides is usually accomplished using cuprous salts, and is known as the Sandmeyer reaction. Since a CN group is easily converted to a CO2H group (eq. 10.13), this provides another route to aromatic carboxylic acids. The reaction with KI gives aryl iodides, usually not easily accessible by direct electrophilic iodination. Similarly, direct aromatic fluorination is difficult, but aromatic fluorides can be prepared from diazonium compounds and tetrafluoroboric acid, HBF4. 

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