Carboxylic acids aliphatic: derivatives

Syntheses of Aliphatic Carboxylic Acids and Derivatives. Alkenes are carbonylated in the presence of acid catalysts at 75-100°C and under pressures of 60—90 MPa (600—900 atm) to give carboxyUc acids (186). 

Specific biological activity of carboxylic acids peroxide derivatives in compaiison with their oxidation ability and ionization degree in aqueous solutions has been considered. Peroxyoctanoic, diperoxynonandioic and diperoxydecandioic acids give the most intense bactericidal effect among researched cai boxylic acids peroxide derivatives. The perspectives of use of the aliphatic middle-chain peracid C8-C9 as anti-infective agents have been discussed. 

The reaction of sulfur tetrafluoride with carboxylic acids (aliphatic, aromatic, and heterocyclic) is of particular importance as the most general and simplest route to trifluorotnethyl derivatives. The reaction proceeds in two steps, the first step gives acyl or aroyl fluorides 1, and then catalysis in the second step by hydrogen fluoride released in the first step results in the tri-fluoromethyl derivatives 2.41... 

All six of the chlorophenyl-substituted carboxylic acids are derived from acid chlorides of long-chain aliphatic half esters. To prepare these uncommon intermediates in sufficient amounts, practicable preparative methods had to be developed. Methods are given for converting appropriate ,co-dicarboxylic acids to the corresponding acid chloride half esters. 

The most water-like of this class of solvents is methanol, for it maintains much the same nice balance of basic and acidic properties found in water. Its autoprotolysis constant is smaller than that of water (Table 3.3.4) because of its lower dielectric constant. Medium effects for transfer of ionisation equilibria from water to methanol are approximately constant for closely related acids. For six cation acids, the pyri-dinium ion and five methyl derivatives, the average medium ejffect is 0.06 0.02, small because the ionisation of these cations creates no new charge field. For phenol and thirteen of its derivatives the medium effect is 4.32 0.09 smaller values are obtained for nitrophenols, possibly because the anions are stabilised by dispersion interactions with methanol. For 23 carboxylic acids, aliphatic and aromatic, the average medium effect is 4.87 0.15. Values of the medium effect for individual acids are collected in Appendix 3.5.5. 

Thallium(m) acetate effects a one-step synthesis of aliphatic a-acyloxy-carboxylic acids (Scheme 28) the transition state (92) is proposed. a-Aminoesters are readily oxidized to the corresponding a-diazoesters by isoamyl nitrite in the presence of acetic acid. A review has been published on the radical addition of carboxylic acids and derivatives to unsaturated linkages. ... 

Amino Aliphatic Carboxylic Acids. 3,5-Dinitrobenzoyl derivatives (p. 381), Benzoyl derivatives (p. 382), Sulphonyl derivatives (p. 382). 

Bromocresol green (3.8...5.4) aliphatic carboxylic acids[103,187 — 204] triiodobenzoic acid [205], derivatives of barbituric acid [206] amphetamine derivatives [207, 208] phenazones, morazone [209] alkaloids [91, 209] nephopam [210] phenyramidol metabolites [211] diethylalkylacetamide derivatives [212] zipeprol (Mirsol) [213] thalidomide and hydrolysis products [214] cyclohexylamine derivatives [215] herbicide residues [216]... 

Bromophenol blue (3.0...4.6) aliphatic carboxylic acids [225 — 228] malonic and lactic acids [229] palmitic and lactic acids [230] malonic, glycolic, malic, citric, tartaric, ketoglutaric, galacturonic and oxalic acids [196] dicarboxylic acids, succinic acid [231] indoleacetic acid, trichloroacetic acid [232] palmitic acid, palmityl- and stearyllactic acid [223] benzoic, sorbic and salicylic acid [234] metabolites of ascorbic acid [235] chloropropionic acid [236] oligogalacturonic acids [237] amino acids, hydrocarbons, mono-, di- and triglycerides [238] xylobiose, xylose, glucose and derivatives [239] sugar alcohols [91] toxaphene [240]... 

For most cases, common fluoroacyl derivatives are sufficiently reactive and selective Thus conversion of perfluoroglutaric dichloride to a monomethyl ester by methanol proceeds smoothly under the appropriate reaction conditions [17] (equation 9) Perfluorosuccinic acid monoester fluoride, on the other hand, is prepared most conveniently from perfluorobutyrolacetone (equation 10) Owing to the strong acidity of a fluorinated carboxylic acids, Fischer esten-ficaiton with most aliphatic alcohols proceeds autocatalytically [79 20]... 

By application of the Schmidt reaction, the conversion of a carboxylic acid into an amine that has one carbon atom less than the carboxylic acid, can be achieved in one step. This may be of advantage when compared to the Curtius reaction or the Hofmann rearrangement, however the reaction conditions are more drastic. With long-chain, aliphatic carboxylic acids yields are generally good, while with aryl derivatives yields are often low. 

Notable examples of general synthetic procedures in Volume 47 include the synthesis of aromatic aldehydes (from dichloro-methyl methyl ether), aliphatic aldehydes (from alkyl halides and trimethylamine oxide and by oxidation of alcohols using dimethyl sulfoxide, dicyclohexylcarbodiimide, and pyridinum trifluoro-acetate the latter method is particularly useful since the conditions are so mild), carbethoxycycloalkanones (from sodium hydride, diethyl carbonate, and the cycloalkanone), m-dialkylbenzenes (from the />-isomer by isomerization with hydrogen fluoride and boron trifluoride), and the deamination of amines (by conversion to the nitrosoamide and thermolysis to the ester). Other general methods are represented by the synthesis of 1 J-difluoroolefins (from sodium chlorodifluoroacetate, triphenyl phosphine, and an aldehyde or ketone), the nitration of aromatic rings (with ni-tronium tetrafluoroborate), the reductive methylation of aromatic nitro compounds (with formaldehyde and hydrogen), the synthesis of dialkyl ketones (from carboxylic acids and iron powder), and the preparation of 1-substituted cyclopropanols (from the condensation of a 1,3-dichloro-2-propanol derivative and ethyl-... 

Habid and Malek49 who studied the activity of metal derivatives in the catalyzed esterification of aromatic carboxylic acids with aliphatic glycols found a reaction order of 0.5 relative to the catalyst for Ti(OBu)4, tin(II) oxalate and lead(II) oxide. As we have already mentioned in connection with other examples, it appears that the activation enthalpies of the esterifications carried out in the presence of Ti, Sn and Pb derivatives are very close to those reported by Hartman et al.207,208 for the acid-catalyzed esterification of benzoic and substituted benzoic acids with cyclohexanol. These enthalpies also approach those reported by Matsuzaki and Mitani268 for the esterification of benzoic acids with 1,2-ethanediol in the absence of a catalyst. On the other hand, when activation entropies are considered, a difference exists between the esterification of benzoic acid with 1,2-ethanediol catalyzed by Ti, Sn and Pb derivatives and the non-catalyzed reaction268. Thus, activation enthalpies are nearly the same for metal ion-catalyzed and non-catalyzed reactions whereas the activation entropy of the metal ion-catalyzed reaction is much lower than that of the non-catalyzed reaction. 

In 1983, Yamada et al. developed an efficient method for the racemization of amino acids using a catalytic amount of an aliphatic or an aromatic aldehyde [50]. This method has been used in the D KR of amino acids. Figure 4.25 shows the mechanism of the racemization of a carboxylic acid derivative catalyzed by pyridoxal. Racemization takes place through the formation of Schiff-base intermediates. 

Terminal aliphatic alkynes (e.g., 1-octyne) react with iron(III) halides (FeCls and FeBrs) to give the corresponding 2-halovinyl derivatives (route A, Scheme 10). The moderate yields were remarkably improved upon addition of stoichiometric amounts of carboxylic acids. 

In reality all carbon atoms share equally the pool of electrons which constitute the double bonds and benzene resists addition across the double bonds which would otherwise destroy its unique structure and stability. Single or multiple hydrogen atoms can be substituted to form a host of derivatives containing similar functional groups to those above, e.g. saturated and unsaturated aliphatic chains, amino, carboxylic acidic, halogeno, nitro, and sulphonic acid groups as shown in Table 3.6. 

A dispersant that can be used in drilling fluids, spacer fluids, cement slurries, completion fluids, and mixtures of drilling fluids and cement slurries controls the rheologic properties of and enhances the filtrate control in these fluids. The dispersant consists of polymers derived from monomeric residues, including low-molecular-weight olefins that may be sulfonated or phosphonated, unsaturated dicarboxylic acids, ethylenically unsaturated anhydrides, unsaturated aliphatic monocarboxylic acids, vinyl alcohols and diols, and sulfonated or phosphonated styrene. The sulfonic acid, phosphonic acid, and carboxylic acid groups on the polymers may be present in neutralized form as alkali metal or ammonium salts [192,193]. 

The classes of compounds that are conveniently considered together as derivatives of carboxylic acids include the acyl chlorides, carboxylic acid anhydrides, esters, and amides. In the case of simple aliphatic and aromatic acids, synthetic transformations... 

More than just a few parameters have to be considered when modelling chemical reactivity in a broader perspective than for the well-defined but restricted reaction sets of the preceding section. Here, however, not enough statistically well-balanced, quantitative, experimental data are available to allow multilinear regression analysis (MLRA). An additional complicating factor derives from comparison of various reactions, where data of quite different types are encountered. For example, how can product distributions for electrophilic aromatic substitutions be compared with acidity constants of aliphatic carboxylic acids And on the side of the parameters how can the influence on chemical reactivity of both bond dissociation energies and bond polarities be simultaneously handled when only limited data are available ... 

The commercial extractants currently used fall into the following categories 297 a-hydroxy-ketox-imes, phenolic-oximes,298 dialkylsulfides, esters of pyridine mono and di-carboxylic acids,299- 1 alkyl derivatives of 8-hydroxyquinoline,79,302,303 trialkylamines,304,305 alkyl derivatives of aniline,306 aliphatic ethers, and ketones.307-309... 

Kwakman et al. [65] described the synthesis of a new dansyl derivative for carboxylic acids. The label, N- (bromoacetyl)-A -[5-(dimethylamino)naphthalene-l-sulfonyl]-piperazine, reacted with both aliphatic and aromatic carboxylic acids in less than 30 min. Excess reagent was converted to a relatively polar compound and subsequently separated from the derivatives on a silica cartridge. A separation of carboxylic acid enantiomers was performed after labeling with either of three chiral labels and the applicability of the method was demonstrated by determinations of racemic ibuprofen in rat plasma and human urine [66], Other examples of labels used to derivatize carboxylic acids are 3-aminoperylene [67], various coumarin compounds [68], 9-anthracenemethanol [69], 6,7-dimethoxy-l-methyl-2(lH)-quinoxalinone-3-propionylcarboxylic acid hydrazide (quinoxalinone) [70], and a quinolizinocoumarin derivative termed Lumarin 4 [71],... 

Ligand-free catalysts have been prepared from the following types of nickel(II) compounds nickel salts of long-chain aliphatic or aromatic carboxylic acids (10, 11) or of sulfonic acids (11), nickel enolates of /3-diketones (11) [e.g., nickel acetylacetonate (4, 12)] or their imino derivatives (11, 13), nickel phenolates (11), dithiocarbamates (14), and mer-captides (15). 

Where acetic is the starting acid (eq. 1), homologation selectively yields the corresponding C3+ aliphatic carboxylic acids. Since acetic acid is itself a "syngas" chemical derived from methanol via carbonylation (2,3), this means the higher MW carboxylic acids generated by this technique could also be built exclusively from C0/H2 and would thereby be in-depent of any petroleum-derived coreactant. 

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