Carboxylic halides

Fluonnated alkoxides, obtamed by addition of the fluonde anion to a carboxylic halide group, are weak nucleophiles, which can be alkylated [d5,36] (equanons 31 and 32)... 

Keywords sodium carboxylate, halide, layered double hydroxide, carboxylate alkylation, microwave irradiation... 

This synthesis also gives a small glimpse at the chemistry of heterocyclic compounds. Most active compounds in today s pharmaceuticals or agrochemicals include heterocycles, as well as most vitamins and natural products. The chemistry of heterocycles is thus very important and lectures or textbooks should be consulted.6 Formation of amide bonds also plays a large role in this problem. It was demonstrated that the strong amide bond can be formed from an amine and a carboxylic acid only after the acid has been activated. This can be done by transformation into the carboxylic halide or imidazolide or by application of an activating agent developed for peptide synthesis. 

Diorgano Tellurium Carboxylate Halides/Oximate Chlorides... 

The final part of the synthesis and properties section of this review addresses other alkaline-earth complexes containing mono-, bi-, or polydentate ligands and anionic ligands such as carboxylates, halides, thiocyanates, or nitrates, where the low degree of oligomerization may result in sufficient volatility for CVD. We have not attempted to be comprehensive in this section, but rather to present examples of the different types of compounds formed by these anionic ligands. More comprehensive coverage of this area can be found elsewhere.74170 223 224... 

A few examples of the 3 3 carboxylate halide complexes Re2(02CR)3X3 have been obtained. One such example is Re2(02CCMe3)3Cl3 which is formed during the thermal decomposition of... 

Cupric salts have not proven to be particularly useful in hydrocarbon oxidation. They do, however, exhibit interesting characteristics. Cupric ion has a singular ability to compete with oxygen for carbon-centered radicals in autoxidation (compare eq. (32), where X can be carboxylate, halide, etc., with eq. (3)) ... 

In 1898 Solomina [1] reported that sulfur dioxide reacted with allyl alcohol, allyl methyl ether, and allyl ethyl ether [1]. Solomina reported that carboxyl, halide, and ester groups inhibited the reaction [1]. In 1935 Ryden and Marvel [26] reported that sulfur dioxide did not copolymerize with allyl cyanide or 2-allyl-/i-cresol when peroxide-paraldehyde was used but did polymerize when ascaridole was added [62]. In a later publication Kharasch and Steinfeld reported that allyl chloride copolymerized with sulfur dioxide in the presence of ascaridole and aqueous hydrochloric acid [63]. 

Carboxylic acids 61Chr, 87Bau2, 88Jac, 90Ali Carboxylic halides 61Chr, 80Del... 

The conversion of an aliphatic carboxylic acid into the a-bromo- (or a-chloro ) acid by treatment with bromine (or chlorine) in the presence of a catal3rtic amount of phosphorus tribromide (or trichloride) or of red phosphorus is known as the Hell-Volhard-Zelinsky reaction. The procedure probably involves the intermediate formation of the acyl halide, since it is known that halogens react more rapidly with acyl haUdes than with the acids themselves ... 

The conversion of carboxylic acid derivatives (halides, esters and lactones, tertiary amides and lactams, nitriles) into aldehydes can be achieved with bulky aluminum hydrides (e.g. DIBAL = diisobutylaluminum hydride, lithium trialkoxyalanates). Simple addition of three equivalents of an alcohol to LiAlH, in THF solution produces those deactivated and selective reagents, e.g. lithium triisopropoxyalanate, LiAlH(OPr )j (J. Malek, 1972). 

Diene carboxylates can be prepared by the reaction of alkenyl halides with acrylates[34]. For example, pellitorine (30) is prepared by the reaction of I-heptenyl iodide (29) with an acrylate[35]. Enol triflates are reactive pseudo-halides derived from carbonyl compounds, and are utilized extensively for novel transformations. The 3,5-dien-3-ol triflate 31 derived from a 4,5-unsaturated 3-keto steroid is converted into the triene 32 by the reaction of methyl acrylate[36]. 

Formation of carboxylic acids ami their derivatives. Aryl and alkenyl halides undergo Pd-catalyzed carbonylation under mild conditions, offering useful synthetic methods for carbonyl compounds. The facile CO insertion into aryl- or alkenylpalladium complexes, followed by the nucleophilic attack of alcohol or water affords esters or carboxylic acids. Aromatic and a,/ -unsaturated carboxylic acids or esters are prepared by the carbonylation of aryl and alkenyl halides in water or alcohols[30l-305]. 

Carboxylate ion (RC—O ) An ester IS formed when the negatively charged oxygen of a carboxylate re places the halogen of an alkyl halide... 

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