Glutarate complexes

Miscellaneous Derivatives. Fimehc acid is used as an intermediate in some pharmaceuticals and in aroma chemicals ethylene brassylate is a synthetic musk (114). Salts of the diacids have shown utUity as surfactants and as corrosion inhibitors. The alkaline, ammonium, or organoamine salts of glutaric acid (115) or C-5—C-16 diacids (116) are useflil as noncorrosive components for antifreeze formulations, as are methylene azelaic acid and its alkah metal salt (117). Salts derived from C-21 diacids are used primarily as surfactants and find apphcation in detergents, fabric softeners, metal working fluids, and lubricants (118). The salts of the unsaturated C-20 diacid also exhibit anticorrosion properties, and the sodium salts of the branched C-20 diacids have the abUity to complex heavy metals from dilute aqueous solutions (88). 

Hexaammonium macrocycles [32]aneN6 and [38]aneN6 were designed as selective ditopic receptor molecules for dicarboxylates -02C—R—C02- such as succinate, glutarate, or adipate 51). Highest stability of the complex corresponds to the best fit between the substrate R length and the site separation of the receptor II. 

The aromatic spacer group of the model receptors prevent the formation of intramolecular hydrogen bonds between the opposing carboxyls yet these functions are ideally positioned for intermolecular hydrogen bonds of the sort indicated in 32. The acridine derivatives do indeed form stoichiometric complexes with oxalic, malonic (and C-substituted malonic acids) as well as maleic and phthalic acids, Fumaric, succinic or glutaric acids did not form such complexes. Though protonation appears to be a necessary element in the recognition of these diacids, the receptor has more to... 

Soluble polymer-bound catalysts for epoxidation reactions have also been explored, with a complete study into the nature of the polymeric backbone performed by Janda [70]. Chiral (salen)-Mn complexes were appended to MeO-PEG, NCPS, Jan-daJeF and Merrifield resin via a glutarate spacer. It was found that for the Jacobsen epoxidation of ds-/ -mefhylstyrene, the enantioselectivities for each polymer-supported catalyst were comparable (86-90%) to commercially available Jacobsen catalyst (88%). Both soluble polymer-supported catalysts could be used twice before a decline in yield and enantioselectivity was observed. However, neither soluble polymer support proved as suitable as the insoluble JandaJel-supported (salen)-Mn complex for the epoxidation because residual impurities during precipitation and leaching of Mn from the complex, resulted in lowered yields. 

The equilibrium formation constants for the 1 1 complexes of Hf with glycine and serine in solutions of pH 2 have been determined as 31 and 18, respectively, and the HfO -amygdalic acid complex, [HfO PhCH(0)- 02)2] , has been obtained in aqueous solutions of pH 7—10.5. The stability constants of the 1 1 complexes of ZrO with iVh/ -ethylenediamine-bis(succinic acid) and Nh/ -ethylenediaminebis(glutaric acid) have been determined. ... 

The stepwise stability constants for V complexes with glutamic, aspartic, W -ethylenediaminedisuccinic, and W -ethylenediamine-bis-(a-glutaric acid) have been reported.The 1 1 oxovanadium(iv) complex of 5-nitrosalicylic acid has been characterized = 710 nm), and the mixed species formed between vanadium(iv) with protocatechuic acid (H3L ) or gallic acid (H L ) and 4-aminoantipyrine (aant) have been identified spectroscopically as the 1 1 1 and 1 2 2 HL (HL ) aant complexes. The species present in solutions of and tartaric acid below pH 2 have been identified as [VO-... 

Figure 11.2 shows a cyclohexane oxidation reactor. The further oxidation of the ketone and alcohol to adipic acid is very complex but occurs in good yield, 94%, despite some succinic and glutaric acid by-products being formed because the adipic acid can be preferentially crystallized and centrifuged. 

In the last few years, Hamilton has published reports of a series of open chain or cyclic receptors featuring 2-acylaminopyridine units as combined H-bond donor and acceptor groups [30]. The simple terephthaloyl derivative 22 forms stable complexes with dicarboxylic acids of appropriate chain length, like adipic and glutaric acid, in CDCI3 [31]. Additionally, complexation influences the s-cis s-trans ratio of the amide bond in acylprolines [32]. 

Complexes with succinate, glutarate and adipate have subnormal magnetic properties that indicate V-v-V interactions. Oxalato, malonato and maleato 1 1 complexes appeal monomeric as indicated by v(V=0) and and ease of formation, stability constants anc decrease in v(V=Q) follow the order oxalate>malonate>maleate. For the 1 2 complexes... 

Figure 11.26 X-ray crystal structure of the 2 2 complex of 11.41 with glutaric acid showing the matching of the guest and host hydrogen-bonding binding sites.37...

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