Arenediazonium tetrafluoroborates

The preparation of an aryl fluoride—e.g. fluorobenzene 3—starting from an aryl amine—e.g. aniline 1—via an intermediate arenediazonium tetrafluoroborate 2, is called the Schiemann reaction (also called the Balz-Schiemann reaction) The diazotization of aniline 1 in the presence of tetrafluoroborate leads to formation of a benzenediazonium tetrafluoroborate 2 that can be converted into fluorobenzene 3 by thermolysis. 

Doyle and Bryker (1979) reported high yields of arenediazonium tetrafluoroborates when aromatic amines were reacted with tert-butyl nitrite and trifluoroboro etherate in CH2C12. It is likely that nitrosyl fluoride is formed as nitrosating reagent by fluoride-alkoxy exchange. 

All these results are consistent with the hypothesis that aryl cations react in aqueous media at diffusion-controlled rates with all nucleophiles that are available in the immediate neighbourhood of the diazonium ion. On this basis Romsted and coworkers (Chaudhuri et al., 1993a, 1993b) used dediazoniation reactions as probes of the interfacial composition of association colloids. These authors determined product yields from dediazoniation of two arenediazonium tetrafluoroborates containing ft-hexadecyl residues (8.15 and 8.16) and the corresponding diazonium salts with methyl groups instead of Ci6H33 chains. ... 

On the basis of these redox potentials it seems likely that direct electron release to the benzenediazonium ion takes place only with iodide. This corresponds well with experience in organic synthesis iodo-de-diazoniations are possible without catalysts, light, or other special procedures (Sec. 10.6). For bromo- and chloro-de-di-azoniations, catalysis by cuprous salts (Sandmeyer reaction, Sec. 10.5) is necessary. For fluorination the Balz-Schiemann reaction of arenediazonium tetrafluoroborates in the solid state (thermolysis) or in special solvents must be chosen (see Sec. 10.4). With astatide (211At-), the heaviest of the halide ions, Meyer et al. (1979) found higher yields for astato-de-diazoniation than for iodo-de-diazoniation, a result consistent with the position of At in the Periodic System. It has to be emphasized, however, that in investigations based on measuring yields of final products (Ar-Hal), the possibility that part of the yield may be due to heterolytic dediazoniation is very difficult to quantify. 

Shono et al. (1979) describe a method for hydro-de-diazoniations which is simple, gives excellent yields, and is claimed to show no unfavorable substituent effects (14 examples). It consists of the addition of thiophenol (7 equiv.) to a suspension of an arenediazonium tetrafluoroborate in a mixture of water and pentane (10 1) at room temperature. After the completion of N2 evolution, excess thiophenol is removed by addition of Na2C03. The usual work-up gave the corresponding hydrocarbon in 84-100% yield and diphenylsulfide. The deuterated compounds are obtained if one uses C6H5SD and D20. 

As the classical Balz-Schiemann reaction is carried out in the solid state, the structures of the arenediazonium tetrafluoroborates as determined by X-ray crystallography must be the starting point for mechanistic investigations, as pointed out by Gougoutas (1979) in the context of his work on the X-ray structures of 3-carboxy-2-naphthalenediazonium bromide and iodide (see Secs. 4.2 and 10.6). 

Cyano-de-diazoniations of the Sandmeyer type have been used for the synthesis of aromatic nitriles for many decades (example Clarke and Reed, 1964), as cyanide ions are comparable to bromide and iodide in many respects. A homolytic cyano-de-diazo-niation that does not use metal ions as reductant or ligand transfer reagent was described by Petrillo et al. (1987). They showed that substituted diazosulfides (XC6H4 — N2 — SC6H5), either isolated or generated in situ from arenediazonium tetrafluoroborates and sodium benzenethiolate, react with tetrabutylammonium cyanide in dimethylsulfoxide under photon stimulation, leading to nitriles (XC6H4CN). The method worked well with eleven benzenediazonium ions substituted in the 3- or 4-position, and was also used for the synthesis of phthalo-, isophthalo-, and tere-... 

Recently Keumi et al. (1989) found that arenediazonium tetrafluoroborates readily decompose in the presence of azidotrimethylsilane in DMF solution to afford the corresponding aryl azides. 

The Pd°-catalyzed arylations using arenediazonium tetrafluoroborates are limited to those diazonium salts that can be manipulated at room temperature. The reaction can, if necessary, be performed at temperatures up to 50 °C by using a mixture of an arylamine and tert-butyl nitrite in chloroacetic acid or in a mixture of chloroacetic and acetic acid (Kikukawa et al., 1981a). Styrene reacted with fourteen arylamines in the presence of 5 mol-% Pd(dba)2 to give the corresponding substituted stilbenes in yields of 46-97%. It is important for good yields to carry out these reactions in an acidic system. Without acid the yield was low (11%), and diazo tars were also formed. 

On the other hand, Hartman and Biffar (1977) observed that the decomposition of several arenediazonium tetrafluoroborates in methylene chloride was catalyzed by the addition of 10 mol% of dicyclohexane-18-crown-6 and powdered copper, but not by copper alone nor by the crown ether and powdered glass. 

Aromatic diazo compounds can be reduced in water via a radical process (Scheme 11.5).108 The reduction mechanism of arenediazo-nium salts by hydroquinone was studied in detail.109 Arenediazonium tetrafluoroborate salts undergo facile electron-transfer reactions with hydroquinone in aqueous phosphate-buffered solution containing the hydrogen donor solvent acetonitrile. Reaction rates are first order in a... 

The thermal decomposition of arenediazonium tetrafluoroborates is slowed down when the salt is complexed by 18-crown-6 (Bartsch et al., 1976). The kinetic data obtained for the 4-t-butylbenzenediazonium salt at 50°C in 1,2-dichloroethane revealed that the rate of complexed to uncomplexed salt is more than 100. Other crown ethers such as dibenzo-18-crown-6 and dicyclohexyl-18-crown-6 exhibited the same effect but smaller molecules such as 15-crown-5 did not influence the rate at all. It is not only the rate of the Schiemann reaction that is affected by the crown ether nucleophilic aromatic substitutions by halide ions (Cl-, Br-) at the 4-positions in arenediazonium salts are retarded or even entirely inhibited when 18-crown-6 is added. This is attributed to the attenuation of the positive charge at the diazonio group in the complex (Gokel et al., 1977). 

On the other hand, Hartman and Biffar (1977) reported that decomposition of arenediazonium tetrafluoroborates in dichloromethane in the presence of copper metal is catalysed by dicyclohexyl- 18-crown-6. Electron-withdrawing substituents in the aryl ring enhance the rate of the reaction. The main function of the crown ether is probably to solubilize the salt. The effect of the complexation on the rate was not investigated in detail. Similar enhanced solubilization of diazonium salts in apolar solvents was reported and used by Martin and Bloch (1971) in pyrolysis experiments aimed at the generation of the dehydrocyclopentadienyl anion. 

Aldehydes can also be prepared by the carbonylation of aryl and alkenyl halides and triflate, and benzyl and allyl chlorides using tin hydride as a hydride source and Pd(Ph P)4 as a catalyst[377], Hydrosilancs arc used as another hydride source[378]. The arenediazonium tetrafluoroborate 515 is converted into a benzaldehyde derivative rapidly in a good yield by using Et.SiH or PH MS as the hydride source[379]. 

Due to the corrosive and toxic nature of volatile hydrogen fluoride, the fluorodediazoniation of aromatic and heteroaromatic amines in anhydrous hydrogen fluoride (see Section 26.1.2.), though very efficient, inexpensive and easy to scale up, needs special apparatus and safety measures which are not always available in every laboratory. Thus, the Balz-Schiemann reaction remains the most popular way to substitute aromatic amino groups for fluorine on a laboratory scale. Moreover, special techniques have been developed during the last decade to control formation, storage and decomposition of arenediazonium tetrafluoroborates on a large scale. 

The story of the Balz-Schiemann reaction began with Bart102 who reported in 1913 on the insolubility of arenediazonium tetrafluoroborates which he found insensitive to shocks and friction and could isolate and dry. Then, in 1927, Balz and Schiemann observed that these solids can be thermally decomposed to aryl fluorides with loss of boron trifluoride.103 This paper was the starting point of intensive research which led, before the 1940s, to almost all the still-valid principles governing this method.104-119 Thus, Roe was able to provide, as early as 1949, a splendid detailed review1 which is still beneficial nowadays. Two other updated reviews were published in the 1960s (see Houben-Weyl, Vol. 5/3, pp 213-246).3... 

The basic Balz-Schiemann reaction involves the preparation of an insoluble arenediazonium tetrafluoroborate 1, either by direct diazotization of arylamines in aqueous tetra-fluoroboric acid, or by addition of tetrafluoroboric acid or alkaline tetrafluoroborates to an aqueous solution of another arenediazonium salt. After filtration and air-drying, this solid diazonium tetrafluoroborate is decomposed either neat or suspended in an inert solvent. 

Arenediazonium tetrafluoroborates 3 arc formed from aromatic amines 1 either by precipitation (shown schematically as a dropping arrow) of the diazonium tetrafluoroborate from an aqueous solution of another soluble diazonium salt 2 or through direct diazotization in aqueous tet-rafluoroboric acid. 

Side Reactions During the Synthesis of Arenediazonium Tetrafluoroborates... 

Though safer than the decomposition of pure, solid diazonium tetrafluoroborates, dediazoni-ation of these compounds mixed with inert solid salts cannot be scaled up to a large extent since heat exchange through large quantities of powdered solids rapidly becomes difficult. Thus, dediazoniation of arenediazonium tetrafluoroborates suspended in inert fluids is an alternative proposition.13105 141 175-219 220 In addition to the safety improvement, lower quantities of tar are formed using this technique. The inert fluid can be ligroin,143 petroleum ether,147 Decalin,3 or simple aromatic compounds,1-3,5,131-221 such as toluene, xylene, biphenyl, nitrobenzene,177 or quinoline. Simple esters have also been used as solvents in the dediazoniation... 

The decomposition of arenediazonium tetrafluoroborates in the resulting fluoroarene as solvent has also been utilized.179 This method is very fruitful in the synthesis of fluorobenzene (96% yield) or fluorotoluenes (85-88% yield for the three isomers) but fails with substrates such as anisolediazonium tetrafluoroborates which probably arylate the reactive fluoroaromatic solvent. In contrast, perfluorinated tertiary amines (EF-L 174, F-C 40), perfluorinated alkyl tetrahydropyran (EF-L 102), perfluorodecahydronaphthalene (Flutec PP7) or other per-fluorocycloalkanes (Flutec s) are claimed to be the best media for fluorodediazoniation of all types of diazonium tetrafluoroborates.224 These media seem to be more efficient, at least in the synthesis of 1,2-difluorobenzene, than silicone oil which has also been claimed to improve fluorodediazoniation.225... 

When arenediazonium tetrafluoroborates 7 are not isolated but decomposed in water or aqueous tetrafluoroboric acid, water competes with the tetrafluoroborate anion as nucleophile so that phenols 8 are formed (30- 50 % yield) together with the fluoroarenes 1 (40-55 % yield).179... 

However, as these two types of compounds are readily separated in basic media, dediazoniation, in an aqueous medium, of nonisolated arenediazonium tetrafluoroborates has been claimed as advantageous since 5 hours only are sufficient for the preparation of fluorobenzene and fluorotoluene by this method, while the Schiemann s procedure requires two days. In the case of aryl fluorides with the polar OMe and N02 substituents, the yields which are achieved are in practice not worse than the yield obtained in the decomposition of the dry salt .179... 

Concerning electrophilic side reactions, intramolecular Friedel-Crafts condensations have been reported for example, fluorenone is formed from 2-benzoylbenzenediazonium tetrafluorobo-rate.241 The strong Lewis acid boron trifluoride can also be responsible for side reactions, such as the extensive formation of tars from nitro-substituted arenediazonium tetrafluorobor-ates or the acidic hydrolysis of ester substituents, especially in the case of 2-(ethoxycar-bonyl)benzenediazonium tetrafluoroborate.105,242... 

Most of the side reactions have already been discussed in Section 26.1.3.3. (dediazoniation in organic solvents). Chlorinated aliphatic solvents, such as 1,2-dichloroethane and dichloro-methane, lead to an extensive formation of chloroaromatics, and aromatic solvents, even halogenated examples, can be arylated to some extent by arenediazonium tetrafluoroborates (vide supra). For example, during dediazoniation of benzenediazonium tetrafluoroborate in toluene, chlorobenzene, bromobenzene or anisole, 3-5 % of substituted biphenyls Ph-C6H4-X (X = Me, Cl, Br, OMe) are formed together with 0.5-0.8% of fluorobiphenyls.5 Fluorobiphenyls are formed through an ionic pathway (only 2- and 4-isomers are formed) whereas chlorobiphenyls result from a radical process (X = Cl, 2-/3-/4-isomer 26 47 27).243... 

Nitromethane also reacts with arenediazonium tetrafluoroborates to give phenol, arene and benzoxazole derivatives,244 whereas radical-chain hydrodediazoniation occurs in dioxane when atmospheric oxygen is not strictly excluded.245... 

The decomposition of arenediazonium tetrafluoroborates RC6H4N2 + BF4 (R = Me, OMe, Cl, Br, N02, C02R, OPh) in aqueous solutions (pH 1-7) which gives phenols and phenyl-diazenylphenols is first order with respect to the concentration of the diazonium salt.246 At lower pH, the rates (k) are constant but above a certain pH value, k increases with pH linearly. Correlations with the Hammett constants er have been proposed. 

As mentioned in the preceding section, several side reactions occur during the thermal decomposition of diazonium tetrafluoroborates, especially with derivatives reluctant to react which require high temperature levels. Thus, it can be imagined that the required energy could be supplied in a form other than heat. Indeed, photochemical decomposition as well as sonication of arenediazonium tetrafluoroborates has been proposed. 

The initial experiments were performed on crystalline films of arenediazonium tetrafluoroborates which decomposed into fluoroarenes at room temperature (or below 30 C) under UV irradiation (350 nm).247 In some cases, the result is even better than under Balz-Schiemann conditions, e.g. formation of 1 the diazonium tetrafluoroborates, particularly those bearing substituents known to favor competitive hydrodediazoniation, such as dialkylamino, do not deliver reduced products under photochemical conditions. 

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