Dissolving metals carboxylic acids

Complexing agent Solubilize dissolved metals Amino acids (glycine, etc.), carboxylic acids (citric acid, etc.) America and Babu (2004), Gopal et al. (2006)... 

Calcon carboxylic acid [3-hydroxy-4-(2-hydroxy-4-sulfo-l-napbtbylazo)napbtbalene-2-carboxylic acid] [3737-95-9] M 428.4, m 300°, X,max 560nm, pKj 1.2, pK2 3.8, PK3 9.26, PK4 13.14. Purified through its p-toluidinium salt. The dye was dissolved in warm 20% aq MeOH and treated with p-toluidine to ppte the salt after cooling. Finally recrystd from hot water. [Itoh and Ueno Analyst (London) 95 583 1970.] Patton and Reeder (Anal Chem 28 1026 1956) indicator and complexes with Ca in presence of Mg and other metal ions. 

Ion exchange, in which cation and/or anion resins are used to replace undesirable anionic species in liquid solutions with nonhazardous ions. For example, cation-exchange resins may contain nonhazardous, mobile, positive ions (e g., sodium, hydrogen) which are attached to immobile acid groups (e.g., sulfonic or carboxylic). Similarly, anion-exchange resins may include nonhazardous, mobile, negative ions (e.g., hydroxyl or chloride) attached to immobile basic ions (e.g., amine). These resins can be used to eliminate various species from wastewater, such as dissolved metals, sulfides, cyanides, amines, phenols, and halides. 

Guo et al. [70,71,73] recently attempted to hydrogenate NBR in emulsion form using Ru-PCy complexes. However, successful hydrogenation can only be obtained when the emulsion is dissolved in a ketone solvent (2-butanone). A variety of Ru-phosphine complexes have been studied. Crosslinking of the polymer could not be avoided during the reaction. The use of carboxylic acids or first row transition metal salts as additives minimized the gel formation. The reactions under these conditions require a very high catalyst concentration for a desirable rate of hydrogenation. 

Both organic and inorganic ligands such as Cl and dissolved organic carbon (fulvie acid and carboxylic acids) decrease metal adsorption. In the arid soils with higher pH, folic acids increase the solubility of metals such as Cu and Zn. The interaction between the transition of heavy metals and silicate surfaces was reviewed by McBride (1991). 

Dissolved metals and metal-containing surfaces play an important role in the transformation of organic contaminants in the subsurface environment. Metal ions can catalyze hydrolysis in a way similar to acid catalysis. Organic hydrolyzable compounds susceptible to metal ion catalysis include carboxylic acids, esters, amides, anilides, and phosphate-containing esters. Metal ions and protons... 

Dissolving metal reductions of the benzene rings are especially important with functional derivatives of benzene such as phenols, phenol ethers and carboxylic acids (pp. 80, 82,93 and 140). 

The difference is pronounced. In an alcohol solution a minimum of approximately six water molecules are required per soap to bring it into solution. A liquid carboxylic acid will dissolve the soap without water to a soap/acld molecular ratio of 1/2. It appears reasonable to evaluate these differences from terms of intermolecular forces. These forces, the strong hydrogen bonds and ligand bonds to the metal ion will be treated in the following section. 

The carboxylic acids are considerably stronger acids than the phenols. They turn litmus red, and yield alkali metal salts which are neutral to litmus. They do not turn Congo red paper blue, however at best only a violet coloration is formed. In contrast to the phenols, the carboxylic acids dissolve even in bicarbonate solutions, and very easily in carbonate and ammonia solutions. The free acids are regenerated from their salts by strong mineral acids. 

Carbonates are one plausible sohd source for metal ions which display similar dissolution/complexation barriers for various ions (that is, different COj salts, e.g. of Fe(II), Mg, Cu, Zn or Mn(II), are similarly soluble in water (pKs 11 Mizerski 1997)) and form mixed crystals among each other. In addition, the products of chemical evolution, with HCOOH, many higher carboxylic acids with or without amino groups being prominent in yields (Lemmon 1970), are usually acidic and thus would dissolve carbonates readily. Contrary to carbonates, other kinds of minerals like phosphates. 

Although Smh is more chemoselective than traditional dissolving metal reagents, it does react with sulfoxides, epoxides, the conjugated double bonds of unsaturated ketones, aldehydes and esters, alkyl bromides, iodides and p-toluenesulfonates. It does not, however, reduce carboxylic acids, esters, phosphine oxides or alkyl chlorides. In common with most dissolving metal systems, ketones with an a-hetero substituent suffer loss of the substituent rather than reduction of the carbonyl group. ... 

Several related reactions involve reduction of cyclic carboxylic acid derivatives to masked aldehydes which resist further reduction but can be converted into the required aldehydes by acid hydrolysis. In a series of papers, it was established that carboxylic acids could be converted into dihydro-1,3-thiazines or dihydro-1,3-oxazines which could be reduced by NaBH4 in weakly acidic ethanol. Thus, as shown in Scheme 20, dihydro-1,3-thiazines (41) were reduced to tetrahydro-1,3-thiazines (42) in yields of 66-84%. The resulting tetrahydro compounds could be hydrolyzed to aldehydes by aqueous acid. - In a later publication, these workers showed that there was little evidence for ring opening during reduction and that other methods of reduction e.g. hydrogenation over Pt, Pd or Rh or use of dissolving metals such as Zn, Sn or Na) were totally unsuccessful. In closely similar work, reduction of 5,6-dihydro-4W-... 

Aromatic acids are reduced by metal-ammonia solutions very much more readily than simple hydrocarbons and ethers. In contrast to the normal requirements for the latter derivatives, it is often possible to achieve reduction with close to stoichiometric quantities of metal. The addition of aromatic carboxylic acids to liquid ammonia (or vice versa) results in the immediate precipitation of the ammonium salt. As the metal is added, however, the precipitate usually dissolves as reduction proceeds, especially if lithium is used. If reduction is carried out in carefully dried, redistilled ammonia, as little as 2.2 mol of lithium are consumed in some cAses, thereby demonstrating that the substrate is reduced much more readily than the ammonium ions, which instead react with the intermediates from reduction of the substrate. However, protonation by NH4 is not essential since reduction proceeds equally well on preformed metal car-boxylates (although low solubility is then often a problem). The addition of an alcohol is not necessary, but it may serve as a useful buffer and can often improve solubility. The presence of alcohol can nevertheless be deleterious, since it facilitates isomerization of the initially formed 1,4-dihydro isomer to the 3,4-isomer and in this way affords the possibility of further reduction. ... 

Many other examples of chemoselective enone reduction in the presence of other reducible functionalities have been reported. For instance, the C—S bonds of many sulfides and thioketals are readily cleaved by dissolving metals. " Yet, there are examples of conjugate reduction of enones in the presence of a thioalkyl ether group." " Selective enone reduction in the presence of a reducible nitrile group was illustrated with another steroidal enone. While carboxylic acids, because of salt formation, are not reduced by dissolving metals, esters" and amides are easily reduced to saturated alcohols and aldehydes or alcohols, respectively. However, metal-ammonia reduction of enones is faster than that of either esters or amides. This allows selective enone reduction in the presence of esters"" and amides - -" using short reaction times and limited amounts of lithium in ammonia. 

Apart from catalytic hydrogenation and dissolving metal methods, very few other techniques exist for the reduction of the pyrrole ring. However, one example is the improved use of hypophosphorus acid that has been described by Scott and coworkers in a reduction of pyrrole-2-carboxylic acid to the prolyl hydroxylase inhibitor (5)-3,4-dehydroproline (after resolution) (equation 10). r,—A i, HI, AcOH, H3PO2... 

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