Reaction with silver carboxylates

In the reaction of sulfenyl chlorides with silver carboxylates mixed anhydrides are formed they are known as sulfenyl carboxylates 90, 130) ... 

Reaction of [PdCl2(diene)] with silver carboxylates yields complexes [Pd2(/u -... 

Silver nitrate test The compound to be tested is treated with a few drops of 1% alcoholic silver nitrate. A white precipitate indicates a positive reaction. This could be due to either silver chloride (reaction with a reactive alkyl halide), silver alkynide (reaction with a terminal alkyne), or the silver salt of a carboxylic acid (reaction with a carboxylic acid). 

The classical Hunsdiecker reaction (equation 18), involving the reaction of silver carboxylates with halogens, and the various associated side reactions, has been reviewed several times. Optimum yields are obtained with bromine, followed by chlorine. Iodine gives acceptable yields provid that the correct stoichiometry of 1 1 is used. The reaction is most frequently carried out in tetrachloromethane at reflux. From a practical point of view, one drawback is the difficulty encountered in the preparation of dry silver carboxylates the reaction of silver oxide on the acyl chloride in tetrachloromeAane at reflux has been employed to circumvent this problem. Evidently the use of molecular bromine limits the range of functional groups compatible with the reaction the different reaction pathways followed by the silver salts of electron poor (equation 19) and electron rich (equation 20) aryl carboxylates illustrate this point well. 

The Hunsdiecker reaction is the reaction of silver carboxylate 1 with bromine to give bromide 2 at elevated temperature.1The reaction also works for making chlorides and iodides. It is also known as the Hunsdiecker-Borodin reaction. 

The first step of the Hunsdiecker reaction is quite straightforward. The reaction between silver carboxylate 1 and bromine gives rise to insoluble silver bromide along with acyl hypobromite 3. The unstable acyl hypobromite 3 undergoes a homolytic cleavage of the O-Br bond to provide carboxyl radical 4. Carboxyl radical 4 then decomposes via radical decarboxylation to release carbon dioxide and alkyl radical 5, which subsequently reacts with another molecule of acyl hypobromite 3 to deliver alkyl bromide 2, along with regeneration of carboxyl radical 4. Because of the radical pathway, chirality is often lost for the chiral carbon atom immediately adjacent to the carboxylic acid. 

Mark and Rechnitz [3] systematized a vast amount of experimental material that can be used directly in KGCM. Some data are presented here that show the wide differences in organic compounds with regard to their kinetic characteristics. Table 2.1 [14] gives the relative rates of reaction of olefins with perbenzoic acid and Table 2.2 summarizes the rates of the etherification reaction of carboxylic acids with diphenyldiazomethane [15]. The tabulated data are indicative of large differences in organic compounds as far as their reactivity is concerned. The rates of reaction of some isomers differ so widely that one can, for example, analyse secondary and tertiary alkyl bromides in the presence of primary alkyl bromides in a reaction with silver nitrate [16]. It is possible to differentiate between CIS and trans isomers of 1,3-dienes by their reaction with dienophils (e.g., chloromethylene anhydride) because the cis isomer reacts much more slowly than the trans isomer [17]. 

The greater reactivity of the P-X bond compared with the P-F bond is also evident from metathetical reactions with silver pseudohalides 105, 274) and silver salts of perfluorinated carboxylic acids 105), e.g.,... 

Scheme 3.10 Synthesis of various sulfur-bridged silver clusters by reactions of silver carboxylates with silylated sulfur compounds in the presence of tertiary phosphanes.

Further oxidation reactions of trimethylsilyl enol ethers have been reported. For example, Mo02(acac)2 and Bu OOH can be used very effectively to cleave these systems to carbonyl compounds. This procedure is quoted as being more convenient and certainly more selective than the alternative ozonolysis method (Scheme 7). Trimethylsilyl enol ethers also react with silver carboxylate-iodine... 

The carboxyl group, in the presence of hydroxyls, may be differentiated by reaction with silver trifluoracetate [Eq. (27) Ref. 7, p. 76] or with trifluoroanhydride [Eqs. 

Heterobimetallic complexes in which a half-sandwich complex of rhodium ill) is cormected by three bromo-bridges to Re(CO)3 were prepared from metathesis reactions of [Cp RhBr2]2 and [Re( -Br)(C0)3(C4H80)]2- The crystal structure of Cp Rh(/t-Br)3Re(CO)3 was determined by X-ray analysis. The treatment of a mixture of [(rf-CjH8)RuCl2]2 and [Cp RhCl2]2 with silver carboxylates and subsequent hydrogenation afforded mixed metal... 

This methodology is illustrated by the synthesis of platinum carboxylates through the reaction of platinum bromide complexes with silver carboxylates in dichloromethane, Scheme 5.1 ... 

Constitution. When coniine is distilled with zinc dust or heated with silver acetate/ a new base, coiiyrine, CgH N, differing from coniine by six atoms of hydrogen, is formed. This on oxidation yields pyridine-2-carboxylic acid and, since it is not identical with 2-isopropylpyridine, must be 2-propylpyridine (I). When coniine is heated with hydriodic acid at 300° it yields w-octane (II). These and other observations due mainly to A. W. Hofmann, made it clear by 1885 that coniine was probably a-propylpiperidine (III), and this has been amply confirmed by other reactions of the alkaloid and by syntheses. Thus, Wolffenstein showed that on oxidation with hydrogen peroxide, coniine is converted into amino-w-propylvaleraldehyde (IV) ... 

Silver carboxylates 1 can be decarboxylated by treatment with bromine, to yield alkyl bromides 2 in the so-called Hunsdiecker reaction. ... 

The reaction is likely to proceed by a radical-chain mechanism, involving intermediate formation of carboxyl radicals, as in the related Kolbe electrolytic synthesis. Initially the bromine reacts with the silver carboxylate 1 to give an acyl hypobromite species 3 together with insoluble silver bromide, which precipitates from the reaction mixture. The unstable acyl hypobromite decomposes by homolytic cleavage of the O-Br bond, to give a bromo radical and the carboxyl radical 4. The latter decomposes further to carbon dioxide and the alkyl radical 5, which subsequently reacts with hypobromite 3 to yield the alkyl bromide 2 and the new carboxyl radical 4Z... 

The present procedure offers a convenient alternative to the Prevost reaction and the Woodward modification of the Prevost reaction in which silver carboxylates are used instead of thal-lium(I) carboxylates. Thallium(I) salts have the advantages of being generally stable crystalline solids that can be readily prepared in high yield by neutralization of the appropriate carboxylic acid with thallium(I) ethoxide. Silver salts, on the other hand, are frequently unstable and difficult to dry. Thallium and its compounds are, however, extremely toxic, and great care must therefore be taken in the use and disposal of thallium salts. ... 

Vicinal iodo carboxylates may also be prepared from the reaction of olefins either with iodine and potassium iodate in acetic acid/ or with N-iodosuccinimide and a carboxylic acid in chloroform. " A number of new procedures for effecting the hydroxylation or acyloxylation of olefins in a manner similar to the Prevost or Woodward-Prevost reactions include the following iodo acetoxylation with iodine and potassium chlorate in acetic acid followed by acetolysis with potassium acetate reaction with iV-bromoacetamide and silver acetate in acetic acid reaction with thallium(III) acetate in acetic acid and reaction with iodine tris(trifluoroacetate) in pentane. ... 

However, in a re-investigation of the reaction of benzyne with benzene 39>, it was shown that the original method of isolating benzene-diazonium-2-carboxylate resulted in the contamination of the zwitter-ion with silver salts 40>41). In the absence of silver ions biphenylene, and... 

When colloidal selenium was heated with mercuric trifluoroacetate or silver trifluoroacetate, bis(trifluoromethyl)diselenide was formed (43). Later work with selenium/silver carboxylate, RC02Ag (R = CF3, C2F5, or C3F7), mixtures at 280° C in a vacuum produced a mixture of the bis(perfluoroalkyl)selenide and the bis(perfluoroalkyl)diselenide (44). Formation of a polyselenium trifluoroacetate, which decarboxylates to produce the trifluoromethylselenides, was the proposed mechanism for R = CF3 (44). However, silver trifluoroacetate is a source of trifluoromethyl radicals when heated above 260° C (21), hence the trifluoromethylselenides may be formed by reaction of trifluoromethyl radicals with selenium, as in the reaction of CF3I with selenium [Eq. (34)] (45). 

Alkylation of the 1,2,4-triazole ring by alkyl radical species has been achieved reaction of 1-methyl-1,2,-4-triazole 37 with alkyl carboxylic acids in the presence of a silver catalyst gave the corresponding 2-alkylated triazoles 38a-e in moderate yields (Equation 9 and Table 1) <2001TL7353>. 

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