Of oxalic acids

Certain aliphatic compounds are oxidised by concentrated nitric acid, the carbon atoms being split off in pairs, with the formation of oxalic acid. This disruptive oxidation is shown by many carbohydrates, e.g., cane sugar, where the chains of secondary alcohol groups, -CH(OH)-CH(OH)-CH(OH)CH(OH)-, present in the molecule break down particularly readily to give oxalic acid. 

The oxalate is prepared in a similar way, using a solution of 1 2 g. of oxalic acid in about 15 ml. of water. On stirring the mixed solutions with a rod, the oxalate crystallises out. 

Sulphuric add test. To 0-5 g. of oxalic acid or of an oxalate, add I ml. of cone. H2SO4 and warm CO and COg are evolved (cf. formic acid). The CO burns with a blue flame. Detect the COg by passing the mixed gases evolved into lime-water. It is essential to test for the COj in a separate reaction, or (if the same test-tube is used) before testing for CO. 

Reduction of acid permanganate. Add a few ml. of dil. HgSO to 1 ml. of a solution of oxalic acid or of an oxalate. Warm gently and add a dilute solution of KMn04 drop by drop and note the decolorisation. 

It follows that liquids of high boiling point should not be distilled from drying agent systems which have appreciable vapour pressures. An extreme case of this action is the dehydration of oxalic acid dihydrate by distillation over toluene or over carbon tetrachloride. 

Urea oxalate is also sparingly soluble in amyl alcohol and since urea is soluble in this alcohol, the property may be utilised in separating urea from mixtures. An aqueous extract of the mixture is rendered slightly alkaline with sodium hydroxide solution and extracted with ether this removes all the basic components, but not urea. The residual aqueous solution is extracted with amyl alcohol (to remove the urea) upon adding this extract to a solution of oxalic acid in amyl alcohol crystalline urea oxalate is precipitated. 

J-unsaturated ester is formed from a terminal alkyne by the reaction of alkyl formate and oxalate. The linear a, /J-unsaturated ester 5 is obtained from the terminal alkyne using dppb as a ligand by the reaction of alkyl formate under CO pressure. On the other hand, a branehed ester, t-butyl atropate (6), is obtained exclusively by the carbonylation of phenylacetylene in t-BuOH even by using dppb[10]. Reaction of alkynes and oxalate under CO pressure also gives linear a, /J-unsaturated esters 7 and dialkynes. The use of dppb is essen-tial[l 1]. Carbonylation of 1-octyne in the presence of oxalic acid or formic acid using PhiP-dppb (2 I) and Pd on carbon affords the branched q, /J-unsatu-rated acid 8 as the main product. Formic acid is regarded as a source of H and OH in the carboxylic acids[l2]. 

A balanced chemical reaction indicates the quantitative relationships between the moles of reactants and products. These stoichiometric relationships provide the basis for many analytical calculations. Consider, for example, the problem of determining the amount of oxalic acid, H2C2O4, in rhubarb. One method for this analysis uses the following reaction in which we oxidize oxalic acid to CO2. 

The balanced chemical reaction provides the stoichiometric relationship between the moles of Fe used and the moles of oxalic acid in the sample being analyzed— specifically, one mole of oxalic acid reacts with two moles of Fe. As shown in Example 2.6, the balanced chemical reaction can be used to determine the amount of oxalic acid in a sample, provided that information about the number of moles of Fe is known. 

The amount of oxalic acid in a sample of rhubarb was determined by reacting with Fe as outlined in reaction 2.2. In a typical analysis, the oxalic acid in 10.62 g of rhubarb was extracted with a suitable solvent. The complete oxidation of the oxalic acid to CO2 required 36.44 mb of 0.0130 M Fe. What is the weight percent of oxalic acid in the sample of rhubarb ... 

The moles of oxalic acid reacting with the Fe, therefore, is... 

Converting moles of oxalic acid to grams of oxalic acid... 

Note that the moles of oxalic acid are multiplied by 2 since there are two carbon atoms, each of which undergoes a 1-electron oxidation. 

Table 1. Physical and Thermochemical Properties of Oxalic Acid and its Dihydrate...

Table 2. Specific Gravities of Various Aqueous Solutions of Oxalic Acid Dihydrate...

Table 4. Supply and Demand of Oxalic Acid in tbe World Market in 1992, tons...

Uses of oxalic acid ia each region are summarized in Table 5 (58). The demand for agrochemical/pharmaceutical production and for separation/recovery of rare-earth elements in each region has been increasing. The use for marble polishing in western Europe is unique to the region. 

Because of the structural requirements of the bielectrophile, fully aromatized heterocycles are usually not readily available by this procedure. The dithiocarbamate (159) reacted with oxalyl chloride to give the substituted thiazolidine-4,5-dione (160) (see Chapter 4.19), and the same reagent reacted with iV-alkylbenzamidine (161) at 100-140 °C to give the 1 -alkyl-2-phenylimidazole-4,5-dione (162) (see Chapter 4.08). Iminochlorides of oxalic acid also react with iV,iV-disubstituted thioureas in this case the 2-dialkylaminothiazolidine-2,4-dione bis-imides are obtained. Thiobenzamide generally forms linear adducts, but 2-thiazolines will form under suitable conditions (70TL3781). Phenyliminooxalic acid dichloride, prepared from oxalic acid, phosphorus pentachloride and aniline in benzene, likewise yielded thiazolidine derivatives on reaction with thioureas (71KGS471). 

Organic Solids A few organic compounds decompose before melting, mostly nitrogen compounds azides, diazo compounds, and nitramines. The processes are exothermic, classed as explosions, and may follow an autocatalytic law. Temperature ranges of decomposition are mostly 100 to 200°C (212 to 392°F). Only spotty results have been obtained, with no coherent pattern. The decomposition of malonic acid has been measured for both the solid and the supercooled liquid. The first-order specific rates at 126.3°C (259.3°F) were 0.00025/min for solid and 0.00207 for liquid, a ratio of 8 at II0.8°C (23I.4°F), the values were 0.000021 and 0.00047, a ratio of 39. The decomposition of oxalic acid (m.p. I89°C) obeyed a zero-order law at 130 to I70°C (266 to 338°F). 

Dry air is blown through the solution to remove the excess of ammonia, and the solution is then dissolved in its own volume of absolute alcohol. A sample of this solution is titrated with standard oxalic acid, litmus being used as an outside indicator (Note 3). The amount of oxalic acid (Note 4) necessary to form the acid salt is placed in a large evaporating dish and dissolved in 4 1. of 95 per cent alcohol. The amine solution is then slowly run into the acid with constant stirring. During the addition of the last half of the amine solution, the container must be cooled in order to avoid the formation of the neutral oxalate,... 

The end point to litmus occurs when the neutral salt is formed. As the acid salt is desired, twice the amount of oxalic acid calculated above is used. This is usually between 230 and 260 g. 

Morpholine [110-91-8] M 87.1, f -4.9", b 128.9", d 1.0007, n 1.4540, n 5 1.4533, pK 8.33. Dried with KOH, fractionally distd, then refluxed with Na, and again fractionally distd. Dermer and Dermer [J Am Ghent Soc 59 1148 1937] ppted as the oxalate by adding slowly to slightly more than 1 molar equivalent of oxalic acid in EtOH. The ppte was filtered and recrystd twice from 60% EtOH. Addition of the oxalate to cone aq NaOH regenerated the base, which was separated and dried with solid KOH, then sodium, before being fractionally distd. 

Androst-4-ene-3,17-dione. Testosterone (0.58 g, 2 mmoles) is dissolved in a solution prepared from 3 ml of benzene, 3 ml of dimethyl sulfoxide, 0.16 ml (2 mmoles) of pyridine and 0.08 ml (1 mmole) of trifluoroacetic acid. After addition of 1.24 g (6 mmoles) of dicyclohexylcarbodiimide, the sealed reaction flask is kept overnight at room temperature. Ether (50 ml) is added followed by a solution of 0.54 g (6 mmoles) of oxalic acid in 5 ml of methanol. After gas evolution has ceased ( 30 min) 50 ml of water is added and the insoluble dicyclohexylurea is removed by filtration. The organic phase is then extracted twice with 5 % sodium bicarbonate and once with water, dried over sodium sulfate and evaporated to a crystalline residue (0.80 g) which still contains a little dicyclohexylurea. Direct crystallization from 5 ml of ethanol gives androst-4-ene-3,17-dione (0.53 g, 92%) in two crops, mp 169-170°. 

Example.—o ljiogram of oxalic acid gave 01055 gram of COj and o o68 giam of H2O. 

P-form long chains giving crystals that cleave into laths parallel to the chain Figure 3.9 Schematic representation of the two forms of oxalic acid, (-C02H)2. 

The first example (49) was obtained by Wohl in 1901 by reacting an aqueous solution of oxalic acid with the diethyl acetal of y-benzoylaminopropionaldehyde. 

Its disemicarbazone, CjgHjgNgOj, melts at 228° C. with decomposition.. The diketone regenerated by the action of oxalic acid on the disemicarbazone has the following properties —... 

Indol, in alcoholic solutions, turns a pine shaving, moistened with Tiydrochloric acid, a cherry-red colour. When shaken with a solution of oxalic acid, indol gives a red coloration. 

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