Halides carboxylation

Similar additions have been successfully carried out with carboxylic acids, anhydrides, acyl halides, carboxylic esters, nitriles, and other types of compounds. These reactions are not successful when the alkene contains electron-withdrawing groups such as halo or carbonyl groups. A free-radical initiator is required, usually peroxides or UV light. The mechanism is illustrated for aldehydes but is similar for the other compounds ... 

Ionic compounds such as halides, carboxylates or polyoxoanions, dissolved in (generally aqueous) solution can generate electrostatic stabilization. The adsorption of these compounds and their related counter ions on the metallic surface will generate an electrical double-layer around the particles (Fig. 1). The result is a coulombic repulsion between the particles. If the electric potential associated with the double layer is high enough, then the electrostatic repulsion will prevent particle aggregation [27,30]. 

The principal developments in hydrostannation during the past decade are in the use of hydrides R2SnXH, where X is an electronegative group such as halide, carboxylate, or sulfonate, and in the use of the hydrides complexed to a transition metal, particularly palladium. 

Attempts to increase conversion by variation of the solvent, hydrogen pressure, or the catalyst and substrate concentration were unsuccessful. Coordinating solvents and additives such as amines, or coordinating anions such as halides, carboxylates. 

Hydrolytic reactions can also be applied in the synthesis of aldehydes or ketones via the corresponding 1,3-oxazine derivatives. The anion formed from 3-methyl-2-(4-pyridyl)tetrahydro-l,3-oxazine 155 on treatment with BuLi proved to react with various electrophiles (alkyl halides, carboxylic esters, acid chlorides, or aldehydes) exclusively at position 2 of the 1,3-oxazine ring and not at the pyridine nitrogen atom. The readily formed 2,2-disubstituted-l,3-oxazine... 

Carbon Disulfide under Sulfur Compounds Carbon Monoxide under Carbon Compounds Carbon Tetrachloride under Saturated Alkyl Halides Carbon Tetrafluoride under Saturated Alkyl Halides Carboxylic Acids Carboxylic Acids and Derivatives Carboxylic Acids with Other Functional Groups Cesium... 

Halogenations with dihalotriphenylphosphoranes have been reviewed briefly by Fieser and Fieser.4 Dibromotriphenylphos-phorane appears to have been studied somewhat more than the dichloro compound, but both reagents effectively convert alcohols to alkyl halides, carboxylic acids and esters to acid halides, etc. The reaction of 1,2-epoxycyclohexane with dibromotriphenylphos-phorane under conditions similar to those described here gives a mixture of cis- and trans-1,2-dibromocyclohexanes. A reagent prepared from triphenylphosphine and carbon tetrachloride has been used for similar transformations.5... 

Similar additions have been successfully carried out with carboxylic acids, anhydrides,561 acyl halides, carboxylic esters, nitriles, and other types of compounds.562... 

Adducts of triazoles with transition metal salts are usually prepared by direct reactions between the two components involved and frequently precipitate or crystallize spontaneously from the reaction mixture (55,172,194, 202). Complexes containing triazolate anions can usually be obtained from the corresponding transition metal halide, carboxylate, nitrate, or perchlorate complex and an alkali metal (146, 147, 172) or thallium(I) triazolate salt (33). Other routes to triazolate complexes include the direct reactions of metal halides with triazoles in the presence of a base (201) and the treatment of triazole/metal halide... 

Amides can be obtained from acyl halides, carboxylic anhydrides, or esters with amines or ammonia. The mechanisms of these reactions are very similar to the corresponding reactions of alcohols ... 

The original reaction procedures have steadily been extended and improved, and an overwhelming number of catalyst systems are now known. Besides aryl halides, many additional substrates, for example aryl triflates, diazonium salts, sulfonyl and aroyl halides, carboxylic and phosphonic acids, and even arenes have been used as... 

Most compounds with triple and quadruple bonds are formed by Re, Cr, Mo, and W. The ligands in such compounds are in general relatively hard Lewis bases such as halides, carboxylic acids, and amines. Nevertheless, in some cases n-acceptor ligands such as carbonyl, phosphines and nitrile are also present. 

In scientific and patent literature on diene polymerization the following Nd(III)-salts are most often cited as catalyst precursors halides, carboxylates, alcoholates, phosphates, phosphonates, allyl compounds, cyclopentadienyl derivatives, amides, boranes and acetylacetonates. The catalyst systems based on these Nd-sources are reviewed in the following subsections. 

Nucleophilic substitutions reactions are those reactions in which the substitution of one nucleophile for another is involved. Alkyl halides, carboxylic acids, and carboxylic acid derivatives undergo nucleophilic substitution. However, the mechanisms involved for alkyl halides are quite different from those involved for carboxylic acids and their derivatives. The reaction of a methoxide ion with ethanoyl chloride is a nucleophilic substitution reaction (Following fig.). In it one nucleophile (the methoxide ion) substitutes another nucleophile Cl. ... 

This chapter deals with the carboxylic acids, carbonyl halides, carboxylic esters, carbonitriles, carbaldehydes, and ketone of 1,8-naphthyridine. 

To Diorgano Tellurium Dihalides/Pseudo halides/ Carboxylates... 

Acemoglu L, Williams JMJ (2002) Synthetic Scope of the Tsuji-Trost Reaction with Allylic Halides, Carboxylates, Ethers, and Related Oxygen Nucleophiles as Starting Compounds. In Negishi E, de Meijere A (eds) Handbook of Organopalladium Chemistry for Organic Synthesis. Wiley, New York, p 1689... 

Certain carboxylates R3Sn02CR (e.g. R = H, C=CR, CH2=CH, or CeFs) can be decarboxylated to RsSuR (equation 101). Other reactions include halide/carboxylate exchanges (equation 102). 

As mentioned above, the oxidative addition of allyl halides, carboxylates, ethers, and sulfides to Ru(0) complexes is a powerful tool for synthesizing jt-allylrutheni-um(II) complexes (Eqs. 5.7 and 5.8) [15, 16]. 

II-I9 Carboxylation With Carbonyl Halides Carboxylation or Carboxy-de-hydrogenation... 

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