Alcohols chelation

Intramolecular H bond Polyvalent alcohols Chelation 3600-3500 (s) 3200-2500 Sharper than dimeric band above Broad and occasionally weak the lower the frequency, the stronger the intramolecular bond... 

The capability of the highly oxygenated carbohydrate auxiliaries to coordinate the counter-ion of the enolate allows the formation of chiral chelate complexes with a restricted flexibility of the enolate moiety. The cation complexation also increases the tendency of the carbohydrate to react as a leaving group. It has been found [153] that the enolate 204 generated by deprotonation of the carbohydrate linked ester 203 with LDA underwent an elimination of the carbohydrate moiety generating the alcohol chelate complex 205 and the ketene 206 (Scheme 10.67). 

The first identified complexes of unsubstituted thiazole were described by Erlenmeyer and Schmid (461) they were obtained by dissolution in absolute alcohol of both thiazole and an anhydrous cobalt(II) salt (Table 1-62). Heating the a-CoCri 2Th complex in chloroform gives the 0 isomer, which on standirtg at room temperature reverses back to the a form. According to Hant2sch (462), these isomers correspond to a cis-trans isomerism. Several complexes of 2,2 -(183) and 4,4 -dithiazolyl (184) were also prepared and found similar to pyridyl analogs (185) (Table 1-63). Zn(II), Fe(II), Co(II), Ni(II) and Cu(II) chelates of 2.4-/>is(2-pyridyl)thiazole (186) and (2-pyridylamino)-4-(2-pyridy])thiazole (187) have been investigated. The formation constants for species MLr, and ML -" (L = 186 or 187) have been calculated from data obtained by potentiometric, spectrophotometric, and partition techniques. 

Nickel halide complexes with amines give mixtures of linear polymer and cychc trimers (30). Nickel chelates give up to 40% of linear polymer (31). When heated with ammonia over cadmium calcium phosphate catalysts, propargyl alcohol gives a mixture of pyridines (32). 

Formulated metal poHshes consist of fine abrasives similar to those involved in industrial buffing operations, ie, pumice, tripoH, kaolin, rouge and crocus iron oxides, and lime. Other ingredients include surfactants (qv), eg, sodium oleate [143-19-1] or sodium dodecylben2enesulfonate [25155-30-0], chelating agents (qv), eg, citric acid [77-92-9], and solvents, eg, alcohols or aUphatic hydrocarbons. 

Enols and alkoxides give chelates with elimination of alcohol. For example, in the reaction of the enol form of acetylacetone [123-54-6] all four alkoxide groups attached to zirconium can be replaced, but only two of the four attached to titanium (Fig. 3). Acetoacetic esters react similarly. 

R SiH and CH2= CHR interact with both PtL and PtL 1. Complexing or chelating ligands such as phosphines and sulfur complexes are exceUent inhibitors, but often form such stable complexes that they act as poisons and prevent cute even at elevated temperatures. Unsaturated organic compounds are preferred, such as acetylenic alcohols, acetylene dicarboxylates, maleates, fumarates, eneynes, and azo compounds (178—189). An alternative concept has been the encapsulation of the platinum catalysts with either cyclodextrin or in thermoplastics or siUcones (190—192). 

Chelated titanates are made simply by mixing the chelating agent with TYZOR TPT or another alkoxide. The Hberated alcohol is usually left in the product to maintain the products fluidity. It may, however, be removed by distillation if desirable. Organic titanates are normally shipped in 208-L dmms, totes, cylinders, or tank tmcks. Most titanates are moisture-sensitive and must be handled with care, preferably under dry nitrogen. 

Where the glycol contains one or two secondary or tertiary hydroxyls, the products are more soluble and some are even monomeric cycHc chelates (65,66). Three compounds are obtained from 2-meth5lpentane-2,4-diol, depending on the mole ratio (67—70). Stmcture (3) represents an isolable but labile alcoholate of (2)... 

P-Diketone Chelates. P-Diketones, reacting as enols, readily form chelates with titanium alkoxides, Hberating in the process one mole of an alcohol. TYZOR AA [17927-72-9] (6) is the product mixture from TYZOR TPT and two moles of acetylacetone (acac) reacting in the enol form. The isopropyl alcohol is left in the product (87). The dotted bonds of stmcture (6) indicate electron... 

P-Ketoester Chelates. p-Ketoesters react in a fashion similar to the p-diketones. TYZOR DC [27858-32-8] is the hght-yeUow Hquid from TYZOR TPT and two moles of ethyl acetoacetate (eaa) after removal of the isopropyl alcohol. TYZOR BEAT, the bis-ethylacetoacetate [20753-28-0] derived from the tetra- -butyl titanate, and TYZOR IBAY [83877-91-2] the isobutoxy analogue, perform similarly to TYZOR DC. Both, however, have better cold-storage stabiHty. 

Partial hydrolysis of TYZOR DC or the monoethylacetoacetate ester chelate, followed by removal of the isopropyl alcohol by-product, gives a dimeric )J.-oxo chelate (8), which also has improved cold-temperature-storage stabiUty (98). 

Titanium Phosphorous Containing Chelates. The reaction of a mixture of mono (alkyl) diacid orthophosphate, di(alkyl)monoacid orthophosphate, and TiCl in a high boiling hydrocarbon solvent such as heptane, with nitrogen-assisted evolution of Hberated HCl, gives a mixture of titanium tetra(mixed alkylphosphate)esters, (H0)(R0)0=P0) Ti(0P=0(0R)2)4 in heptane solution (100). A similar mixture can be prepared by the addition of two moles of P2O5 to mole of TiCl in the presence of six moles of alcohol ... 

The bonding properties of (Ti02) have been used for size-reinforcing of glass fibers so that they adhere to asphalt or to a PTEE—polysulfide mixture to impart enhanced flex endurance (434—436). Poly(vinyl alcohol) (PVA) solutions mixed with sucrose can be cross-linked with the lactic acid chelate and used generally for glass-fiber sizing (437). 

In acidic solution, the degradation results in the formation of furfural, furfuryl alcohol, 2-furoic acid, 3-hydroxyfurfural, furoin, 2-methyl-3,8-dihydroxychroman, ethylglyoxal, and several condensation products (36). Many metals, especially copper, cataly2e the oxidation of L-ascorbic acid. Oxalic acid and copper form a chelate complex which prevents the ascorbic acid-copper-complex formation and therefore oxalic acid inhibits effectively the oxidation of L-ascorbic acid. L-Ascorbic acid can also be stabilized with metaphosphoric acid, amino acids, 8-hydroxyquinoline, glycols, sugars, and trichloracetic acid (38). Another catalytic reaction which accounts for loss of L-ascorbic acid occurs with enzymes, eg, L-ascorbic acid oxidase, a copper protein-containing enzyme. 

Deprotonation of enols of P-diketones, not considered unusual at moderate pH because of their acidity, is faciUtated at lower pH by chelate formation. Chelation can lead to the dissociation of a proton from as weak an acid as an aUphatic amino alcohol in aqueous alkaU. Coordination of the O atom of triethanolamine to Fe(III) is an example of this effect and results in the sequestration of iron in 1 to 18% sodium hydroxide solution (Fig. 7). Even more striking is the loss of a proton from the amino group of a gold chelate of ethylenediamine in aqueous solution (17). 

Other developments in chelating resins include fibers made from poly(ethylene glycol) and poly(vinyl alcohol) to which EDA was attached with epichl orohydrin (281) and a styrene—divinylbenzene resin with pendant EDTA or DETPA groups (282). 

Molecular Interactions. Various polysaccharides readily associate with other substances, including bile acids and cholesterol, proteins, small organic molecules, inorganic salts, and ions. Anionic polysaccharides form salts and chelate complexes with cations some neutral polysaccharides form complexes with inorganic salts and some interactions are stmcture specific. Starch amylose and the linear branches of amylopectin form inclusion complexes with several classes of polar molecules, including fatty acids, glycerides, alcohols, esters, ketones, and iodine/iodide. The absorbed molecule occupies the cavity of the amylose helix, which has the capacity to expand somewhat to accommodate larger molecules. The starch—Hpid complex is important in food systems. Whether similar inclusion complexes can form with any of the dietary fiber components is not known. 

Another method for slowing oxidation of rubber adhesives is to add a compound which destroys the hydroperoxides formed in step 3, before they can decompose into radicals and start the degradation of new polymer chains. These materials are called hydroperoxide decomposers, preventive antioxidants or secondary antioxidants. Phosphites (phosphite esters, organophosphite chelators, dibasic lead phosphite) and sulphides (i.e. thiopropionate esters, metal dithiolates) are typical secondary antioxidants. Phosphite esters decompose hydroperoxides to yield phosphates and alcohols. Sulphur compounds, however, decompose hydroperoxides catalytically. 

Its acidity is considerably enhanced by chelation with polyhydric alcohols (e.g. glycerol, mannitol) and this forms the basis of its use in analytical chemistry e.g. with mannitol p T drops to 5.15,... 

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