Carboxylic acids alkoxylation

POE monoesters can be produced by direct interaction of carboxylic acid and ethylene oxide but they contain a large quantity of PEG as by-product [7, 8]. Principally, the carboxylic acid alkoxylation is applied for the monoester production such as glycol stearate and propylene glycol stearate (VI) that show good performance as oil-soluble emulsifiers, emollients and opacifiers in cosmetics. 

All the 7,8-secoberbines incorporate an JV-methyltetrahydroisoquinoline moiety with two or three oxygenated substituents at C-l, C-2, and C-3. The lower aromatic ring possesses four substituents in a vicinal arrangement of which two are alkoxyls and the third the berbine bridge carbon. The latter may occur in different oxidation states as an aldehyde (in 1 and 2), an alcohol (3-6, 8, 9), or a carboxylic acid (7). 

No analogous reactions take place with carboxylic acid esters. Cristol and his co-workers [49] therefore suggest that initially an alkoxyl ion is formed and afterwards the corresponding alcohol and nitrate ion are produced ... 

Phenol has been hydroxylated nearly quantitatively to hydroquinone 2 3 9 Most alkoxylations or hydroxylations of aromatics however either lead to anodic addition products (see Sect. 10.1) or to side chain substitution (see below). Specific side-chain hydroxylation is difficult to achieve because the alcohols formed as primary products are further oxidized to aldehydes, ketones and/or carboxylic acids. 

Ligand incorporation was achieved by facile alkoxylation of 4-chloro-substituted ter-pyridine by a hydroxy-terminated carboxylic acid followed by divergent dendrimer con-... 

Marlowet 45 Series Alkyl-(aryl)-alkoxylated carboxylic acids... 

Acid chlorides and esters are derivatives of carboxylic acids. In such acid derivatives, the —OH group of a carboxylic acid is replaced by other electron-withdrawing groups. In acid chlorides, the hydroxyl group of the acid is replaced by a chlorine atom. In esters, the hydroxyl group is replaced by an alkoxyl (—O—R) group. 

Alcohols containing heterocyclic nuclei, halo, and alkoxyl groups as well as double bonds may be prepared. Without doubt, this is the best general procedure for the formation of the primary alcohol grouping from compounds at the oxidation level of a carboxylic acid. Reductions by this reagent were reviewed in 1951. °°... 

Table 6 Acyloxylation and Alkoxylation of o -Hetero-Siibstituted Carboxylic Acids... 

Electrolysis of a-sulfenyl carboxylic acids in protic solvents gives ketones, presumably via replacement of the carboxyl group with alkoxyl or acetoxyl groups and a subsequent two-electron oxidation of the sulfenyl moiety [Eq. (32)]. (This discussion is postponed to Sec. IV.D.)... 

Koester, Behler, Neuss, Schmid, Eisner Cognis Hand dishwashing liquid comprising an alkoxylated carboxylic acid ester Contains an alkoxylated carboxylic acid ester... 

Hydrocarboxylation is the formal addition of hydrogen and a carboxylic group to double or triple bonds to form carboxylic acids or their derivatives. It is achieved by transition metal catalyzed conversion of unsaturated substrates with carbon monoxide in the presence of water, alcohols, or other acidic reagents. Ester formation is also called hydroesterification or hydrocarb(o)alkoxylation . The transition metal catalyst precursors are nickel, iron or cobalt carbonyls or salts of nickel, iron, cobalt, rhodium, palladium, platinum, or other metals4 5. 

R = FL, alkyl, alkoxyl, halo, amino, cyano, nitro, carboxylic acid... 

Pyridinecarboxylates (99) give photosubstitution products on irradiation with alcohols the products have alkyl or alkoxy substituents, and the product ratios depend on the absence or presence of added mineral acid. A mechanistic rationalization is presented, based on the involvement of a triplet excited state located largely on C==0 or a triplet located largely on the ring (for alkylation), and a singlet excited state (for alkoxylation). The reaction of pyridinecarboxylic acids in the presence of transition-metal ions is reported pyridine-2-carboxylic acid gives pyridine and 2,2 -bipyridyl with iron(iii), but 2-pyridone with copper(ii) pyridine-3-carboxylic acid (100) with Fe gives a dehydrodimer without decarboxylation. 

Abstract Progress in the field of metal-catalyzed redox-neutral additions of oxygen nucleophiles (water, alcohols, carboxylic acids, and others) to alkenes, alkynes, and allenes between 2001 and 2009 is critically reviewed. Major advances in reaction chemistry include development of chiral Lewis acid catalyzed asymmetric oxa-Michael additions and Lewis-acid catalyzed hydro-alkoxylations of nonacti-vated olefins, as well as further development of Markovnikov-selective cationic gold complex-catalyzed additions of alcohols or water to alkynes and allenes. 

The oxidative thermal stability is markedly affected by the concentration of both carboxylic and basic end groups. Carboxylic acid groups initiate the homolytic decomposition of 6-hydroperoxy-6-hexanelactam. Thus, alkoxyl and hydroxyl radicals are formed as intermediates. Eventually, the monoamide of adipic acid is formed. PAs with carboxylic end groups are oxidized in a similar way. The rate of oxidization increases with the content of carboxylic groups. ... 

First of a family of alkoxylated linear alcohol carboxylic acid adduct sodium salts. These are low-foaming surfactants with moderately high caustic solubility. Their excellent sequestering ability makes them unique among surfactants and truly multifunctional in character. Applications include laundry detergents, tub and tile cleaners, metal cleaners and alkaline hard surface cleaners. These surfactants can eliminate or minimize the need for builders in a formulation. 

Necine bases are esterified by different carboxylic acids. With the exception of acetic acid, these acids have 5 10 carbon atoms and include mono- and dicarboxylic acids with branched chains substituted with hydroxyl, methoxyl (other alkoxyl), epoxy, carboxy and acetoxy groups. Necines with two hydroxyls, such as 7,9-necinediol, may be esterified with carboxyhc acids in positions C-7 and C-9 or in both positions. Esterification with dicarboxyhc acids produces macrocyclic alkaloids with 11 to 14-membered rings. Depending on the ester type, the following alkaloids can be recognised ... 

N,N-dimethyl(3-myristoylaminopropyl)ammonio]propanesulfon-ate (Amidosulfobetaine-14) l-(3-Sulfopropyl)pyridinium betaine 3-Dodecyldimethylammoniopropane-l-sulfonate 3-[(3-cholamidopropyl)dimethylammonio]-l-propanesulfonate Lauryl betaine Cocamidopropyl betaine n-d odecyl-N,N-d imethylglycine Tallowglycine Perfluorooctanesulfonate Perfluorinated carboxylic acids Perfluorooctanoic acid Fluorinated telomere alcohols Acetylene diols Acetylene diol alkoxylates Acetylene glycols... 

Hydroperoxides decompose relatively slowly at ambient temperatures in the dark, but in light they are readily photolysed to free radicals, (Scheme 1.1, reaction d). Consequently, the rate of photo-oxidation of the hydrocarbon polymers is orders of magnitude higher than thermal oxidation. In addition, small amounts of transition metal compounds, notably iron, cobalt, manganese and copper, have a powerful catalytic effect on radical formation from hydroperoxides [14], leading to rapid molecular weight reduction by breakdown of the intermediate alkoxyl radical and the formation of carboxylic acids and esters as oxidation end products (see Scheme 1.2) [15]. 

Usually the above method may be applied to substances with a free phenolic hydroxyl group and a free para position or a para position that is substituted by a halogen, hydroxyl or alkoxyl, sulphonic acid or carboxylic acid group since in general these substances give a positive reaction. 

In polyethylene the proportion of vicinal hydroperoxides is lower than in PP and random chain scission is initially the dominant process. However, a variety of low molar mass oxidation products are formed via vicinal hydroperoxides (Scheme 1). The alkoxyl radicals formed by decomposition of the hydroperoxides contain weak carbon-carbon bonds in the a positions to the hydroperoxide groups which lead to the formation of low molecular weight aldehydes and alcohols that further oxidise rapidly to abiotically stable carboxylic acids. These are biodegradable species, similar to those formed by hydrolysis of aliphatic polyesters and they provide an environment for rapid biofilm formation (Section 5.5). 

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