Oxalic acid synthesis

Lapeyrie, F., Chilvers, G. A. Bhem, C. A. (1987). Oxalic acid synthesis by the mycorrhizal fungus Paxillus involutus (Batsch.ex fr.). New Phytologist, 106, 139-46. 

In general, imines are too reactive to be used to protect carbonyl groups. In a synthesis of juncusol, however, a bromo- and an iodocyclohexylimine of two identical aromatic aldehydes were coupled by an Ullman coupling reaction modi-fied by Ziegler. The imines were cleaved by acidic hydrolysis (aq. oxalic acid, THF, 20°, 1 h, 95% yield). Imines of aromatic aldehydes have also been prepared... 

Synthesis of 9-oxo-11 CH,1 Sol-bis-(2-tetrahydropyranytoxy)-16,16-dimethyl-prosta-trans-2, trans-13-dienoicacid 4gof ethyl 9a-hydroxy-1 la,1 5a-bis-(2-tetrahydropyranyloxy )-16,16-dimethyl-prosta-trans-2,trans-13-dienoate were dissolved In 130 ml of a mixture of ethanol-water (3 1), mixed with 3.9 g of potassium hydroxide and stirred at 25°C for 2 hours. The reaction mixture was acidified with aqueous solution of oxalic acid to pH 5, and diluted with 100 ml of water, extracted with ethyl acetate. The extracts were washed with water, dried over sodium sulfate and concentrated under reduced pressure to obtain 3,88 g of 90 -hydroxy-11a,15a-bis-(2-tetrahydropyranyloxy)-16,16-dimethyl-prosta-trans-2,trans-13-dienoic acid. 

The acidic catalysts used for these reactions include formic acid, HX (X = F, Cl, Br), oxalic acid, phosphoric acid, sulfuric acid, sulfamic acid, and p-toluenesulfonic acid.4 Oxalic acid is preferred since resins with low color can be obtained. Oxalic acid also decomposes at high temperatures (>180°C) to C02, CO, and water, which facilitates the removal of this catalyst thermally. Typically, 1-6 wt % catalyst is used. Hydrochloric acid results in corrosive materials and reportedly releases carcinogenic chloromethyl ether by-products during resin synthesis.2... 

Halide (3) is available, but could be made by bromination of (4) or methylation of (5). In the synthesis, oxalic acid (6) was used as the dehydrating agent. This is a reasonably strong acid (pKa 1.23) and is conveniently solid. 

From a prachcal standpoint, formic acid or its salts are the least valuable reaction products. The energy content of formic acid upon its reverse oxidation to CO2 is insignificant, and its separation from the solutions is a labor-consuming process. At present, maximum effort goes into the search for conditions that would ensure purposeful (with high faradaic yields) synthesis of methanol, hydrocarbons, oxalic acid, and other valuable products. 

Procedures for pretreatment of soil samples and synthesis of sample benzene for 14C analysis had been described in Chen et al. (2002b). Sample benzene was often left for 3-4 weeks to allow any radon with half-life of 3.82 days that may be present to decay. 14C activity of the CgFL was then determined using a 1220-QUANTULUS ultralow-level liquid scintillation spectrometer manufactured by WALLAC Company, Sweden. The 14C analyses were conducted at the Guangzhou Institute of Geochemistry, CAS. Results are reported as A14C, in parts per thousand of the 14C/12C ratio from that of the standard (oxalic acid decay corrected to 1950) (Stuiver and Po-lach 1977), and corrected for bomb 14C (Chen et al. 2002b), where ... 

It was observed that glutamate and aspartate are diverted predominantly to the synthesis of cell substance rather than to the formation of oxalate. It is not inconsistent to see oc-ketoglutarate being formed from glutamate, while no oxaloacetic acid can be detected in the medium containing aspartate, as the oxaloacetic acid is known to be extremely unstable (2), (62), (Hi). The relatively low yields of oxalic acid, derived... 

A typical example is the synthesis of oxalic acid. Electrochemical synthesis of oxalic acid by reduction of C02 in aprotic media with a Zn sacrificial anode was brought to pilot scale by the Dechema Institute some years ago (1981) [177]... 

Robertson, J. M., and J. Woodward The Structure of the Carboxyl Group. A Quantitative Investigation of Oxalic Acid Dihydrate by Fourier-Synthesis from the X-Ray Crystal Data. J. chem. Soc. London 1936, 1817-.— — Trans. Faraday Soc. 36, 913 (1940). 

Having the electrophile 95 to hand, the synthesis proceeded by metallation of the SAMP hydrazone 96 followed by alkylation with the iodide affording the a-alkylated hydrazone 97 with diastereomeric excess de = 9S% (Scheme 1.2.21). The removal of the auxiliary proceeded smoothly with oxalic acid, leading to 98 in good yield (80%, two steps) and no epimerization without deprotection of the amino group. 

The mechanism of toxicity of ethylene glycol involves metabolism, but unlike previous examples, this does not involve metabolic activation to a reactive metabolite. Thus, ethylene glycol is metabolized by several oxidation steps eventually to yield oxalic acid (Fig. 7.84). The first step is catalyzed by the enzyme alcohol dehydrogenase, and herein lies the key to treatment of poisoning. The result of each of the metabolic steps is the production of NADH. The imbalance in the level of this in the body is adjusted by oxidation to NAD coupled to the production of lactate. There is thus an increase in the level of lactate, and lactic acidosis may result. Also, the intermediate metabolites of ethylene glycol have metabolic effects such as the inhibition of oxidative phosphorylation, glucose metabolism, Krebs cycle, protein synthesis, RNA synthesis, and DNA replication. 

A similar pathway was followed in the synthesis of siccanochromenes (e.g., 17), where the aldehyde was condensed with the lithio derivative of a protected resorcinol. Treatment with oxalic acid gave directly the chromcne in 45% yield.220... 

A variation of this synthesis involving enamines is the condensation of cyclohexenyl-pyrrolidine (301) with styrene oxide (reflux DMF) to give compound 311 (R2 = Ph) by distillation of the intermediate perhydro derivative 312 from oxalic acid.720... 

Dialkyl Oxalates. Oxalic acid gives various esters, Dialkyl esters ROOC—COOR, are industrially useful, but monoalkyl esters, ROOC— COOH, are not The dialkyl esters are characterized by good solvent properties and serve as starting materials in the synthesis of many organic compounds, such as pharmaceuticals, agrochemicals, and fine chemicals (qv). Among die dieslers, dimethyl, diediyl. and di-n-butyloxalates are industrially important. 

Oxalvl Chloride. This diacid chloride is produced by the reaction of anhydrous oxalic acid and phosphorus pentachloride. The compound vigorously reacts with water, alcohols, and amines, and is employed for tile synthesis of agrochemicals, pharmaceuticals, and fine chemicals. 

There are two principal synthetic routes to dicarboxylate complexes. One of these uses an aqueous solution of the alkali metal dicarboxylate and the corresponding metal halide,93 while the other depends upon the dicarboxylic acid reduction of higher oxidation state metals. This reductive property of oxalic acid results in its ready dissolution of iron oxides and hence a cleaning utility in nuclear power plants.94 Mention must also be made of the successful ligand exchange synthesis of molybdenum dicarboxylates, Mo(dicarboxylate)2 H2 O, from the corresponding acetate complex. Unfortunately the polymeric, amorphous and insoluble nature of these complexes has restricted the study of these systems, which may well provide examples of multiple M—M bonding in dicarboxylate coordination chemistry.95... 

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