Arylations silver® nitrate

Alkyl aryl ketones can be converted to arylacetic acid derivatives in an entirely different manner. The reaction consists of treatment of the substrate with silver nitrate and I2 or Br2, ° or with thallium nitrate, MeOH, and trimethyl orthoformate adsorbed on Montmorillonite K-10 clay, an acidic clay. ... 

Alkyl halides are often used as substrates instead of alcohols. In such cases the salt of the inorganic acid is usually used and the mechanism is nucleophilic substitution at the carbon atom. An important example is the treatment of alkyl halides with silver nitrate to form alkyl nitrates. This is used as a test for alkyl halides. In some cases there is competition from the central atom. Thus nitrite ion is an ambident nucleophile that can give nitrites or nitro compounds (see 0-60).731 Dialkyl or aryl alkyl ethers can be cleaved with anhydrous sulfonic acids.732... 

Methyla-arylacetates. These esters have been obtained by oxidative rearrangement of alkyl aryl ketones with thallium(III) nitrate in acidic methanol or trimethyl orthoformate (4,496 5, 656 7, 362). A new method, which avoids the toxic TTN, is based on the Woodward version of the Prevost reaction. Thus, treatment of the ketone with iodine (or bromine) and silver nitrate (2 equiv.) in refluxing methanol containing trimethyl orthoformate results in methyl a-arylacetates in 90% yield from simple substrates. Yields are lowered by electron-withdrawing substituents on the aromatic group and by a-branching in the alkyl group.2... 

During their work on the arylation of aromatic compounds by substitution, Fujiwara, et al. observed biaryl formation when aromatic compounds were placed in the presence of olefin-palladium complexes and silver nitrate.80 Developing this reaction as a method for biphenyl synthesis, these authors showed that the more stable the olefin-palladium complex was, the lower the yield. Ethylene dichloropalladium proved to be the best choice, when used with silver nitrate. However, the reaction required stoichiometric amounts of both catalysts (Scheme 10.47). Benzene derivatives substituted by electron-donating or -withdrawing groups reacted as well, but a mixture of regioisomers was produced, except for nitrobenzene, which only gave m,m -dinitrobiphenyl. 

In 2005 and 2006, Mori et al. reported the arylation of heterocycles with aryl iodides using palladium dichloride complexes as catalysts and silver nitrate or fluoride as activators (Scheme 10.50). The best coupling conditions were obtained with a combination of silver nitrate and potassium fluoride.82... 

The silver-catalyzed cycloisomerization of allenic carboxylic acids to butenolides was also reported by Marshall and co-workers.329 Starting from the enantiomerically enriched propargyl mesylate 390, palladium-catalyzed hydroxycarbonylation led to the chiral allenecarboxylates 391 which afforded the butenolides 392 upon treatment with silver nitrate (Scheme 114). Unfortunately, partial racemization could not be avoided in this two-step sequence. In a related study, Ma and Shi330 have shown that the combination of Pd(PPh3)4 and Ag2C03 promotes the cyclization of allenecarboxylates to the corresponding butenolides, accompanied by the introduction of aryl or alkenyl groups at C3. 

We have seen (Sec. 14.24) that an alkyl halide is conveniently detected by the precipitation of insoluble silver halide when it is warmed with alcoholic silver nitrate. The reaction occurs nearly instantaneously with tertiary, allyl, and benzyl bromides, and within five minutes or so with primary and secondary bromides. Compounds containing halogen joined directly to an aromatic ring or to a doubly-bonded carbon, however, do not yield silver halide under these conditions. Bromo-benzene or vinyl bromide can be heated with alcoholic AgN03 for days without the slightest trace of AgBr being detected. In a similar way, attempts to convert aryl... 

Aryl halides are distinguished from aromatic hydrocarbons by the presence of halogen, as shown by elemental analysis. Aryl halides are distinguished from most alkyl halides by their inertness toward silver nitrate in this respect they resemble vinyl halides (Sec. 25.5). 

Examples of the successful application of this method are the use of cop-per(II) acetate for the preparation of neutral complexes [Cu(SR)] (R = aryl, alkyl no base needed) (46), and the use of copper(II) nitrate for the synthesis of anionic species [Cu4(SPh))6]2 and [Cu5(SPh)7]2- (47, 48), as well as of the cationic species [Cu,(SC5H4NH)3]+ (49). The latter complex is interesting in that each thiolate ligand is neutral due to protonation of the pyridine nitrogen atom. Similarly, silver nitrate has been used to prepare several neutral alkyl-thiolato silver complexes (33). The use of copper(I) oxide was reported in the synthesis of a family of copper(I) arenethiolates containing intramolecularly... 

Adducts of the l,2-dithiole-3-thione with silver nitrate and copper dichloride have been described, and for various l,2-dithiole-3-thiones, adducts containing iron, cobalt, nickel, and copper have been studied in more detail. The ligands (L) used are either unsubstituted l,2-dithiole-3-thione or its methyl- or aryl-substituted derivatives. If X represents a halogen atom, the following types of coordination compounds have been characterized CuXLj and CuXLa, FeXjLj, CoXaL, and NiX Lj. Complexes of titanium(III), tin(IV), antimony(III) and (V), and bismuth(III) have also been studied. ... 

It was only in 1972 that pure, uncomplexed phenylsilver was isolated for the first time . The method used by Beverwijk and Van der Kerk employs the very slow addition of a solution of silver nitrate in ethanol to a solution of a large excess of trialkylphenyltin or tiialkylphenyllead compounds in the same solvent. Although this route affords pure, stable PhAg as a colourless solid, it is cumbersome and restricted to small-scale preparations. These problems are overcome when diarylzinc compounds are used as arylating... 

Nitric acid (70 %) or the mixture of nitric acid and sulfuric acid or other mixed acids with catalytic function can nitrate secondary nitroalkanes directly into gem-inal dinitroalkane [8]. With the sodium alkoxide and tetranitromethane, primary nitroalkanes can be nitrated into dinitroalkanes and trinitroalkanes [9]. In a neutral or basic solvent, primary, secondary nitroalkane salts can be nitrated, step by step, into gem-dinitroalkanes by silver nitrate and sodium nitrite [10]. Alkali metal salts of aryl nitroalkanes can be nitrated, step by step, into dinitroalkanes and trinitroalkanes by dinitrogen tetroxide [11]. 

Reaction with alcoholic silver nitrate has been used as a qualitative test for the ditin linkage, and a variety of compounds, including aryl derivatives, have been shown to deposit a silver mirror on treatment with the reagent (195, 198, 200, 215, 244). Potassium permanganate is also reduced readily (200,265). Hexaphenylditin has been shown to react virtually quantitatively to produce triphenyltin hydroxide when subjected to the action of potassium permanganate in acetone solution (265). 

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