Oxidative cyanation

Figure 2. Redox potential history of cyanide and cyanate oxidation...

Further, Tyler (22) and some subsequent workers (5) postulate a cyanate oxidation to the release of carbon dioxide and nitrogen ... 

Thousands of compounds of the actinide elements have been prepared, and the properties of some of the important binary compounds are summarized in Table 8 (13,17,18,22). The binary compounds with carbon, boron, nitrogen, siUcon, and sulfur are not included these are of interest, however, because of their stabiUty at high temperatures. A large number of ternary compounds, including numerous oxyhaUdes, and more compHcated compounds have been synthesized and characterized. These include many intermediate (nonstoichiometric) oxides, and besides the nitrates, sulfates, peroxides, and carbonates, compounds such as phosphates, arsenates, cyanides, cyanates, thiocyanates, selenocyanates, sulfites, selenates, selenites, teUurates, tellurites, selenides, and teUurides. 

Isocyanates are derivatives of isocyanic acid, HN=C=0, ia which alkyl or aryl groups, as weU as a host of other substrates, are direcdy linked to the NCO moiety via the nitrogen atom. StmcturaHy, isocyanates (imides of carbonic acid) are isomeric to cyanates, ROCMSI (nitriles of carbonic acid), and nitrile oxides, RCMSI—>0 (derivatives of carboxyUc acid). 

For example, 5,6-acenaphthenedicarboximide (44) can be prepared in 84% yield by the reaction of acenaphthene with excess sodium cyanate in anhydrous HF (78). The intermediate can be oxidized to the tetracarboxyhc acid. 

Unpiotonated hydioxylamine is oxidized rapidly by ozone, / = 2.1 X 10 (39). The reaction of ozone with the lower oxides of nitrogen (NO and NO2) is also rapid and quantitative the end product is nitrogen pentoxide, which is also a catalyst for the decomposition of ozone (45). Nitrous oxide, however, reacts slowly (k < 10 ) (39). Nitrogen-containing anions, eg, nitrite and cyanide, also ate oxidized by ozone (39). Nitrite is oxidized to nitrate (fc = 3.7 X 10 and cyanide is oxidized rapidly to cyanate (fc = 2.6 X 10 (46) and 10 -10 (39)). Cyanate, however, is oxidized slowly. 

Cyanide destmction by alkaline chlorination is a widely used process. With alkaline chlorination, cyanide is first converted to cyanate with hypochlorite [7681-52-9] at a pH greater than 10. A high pH is required to prevent the formation of cyanogen chloride [506-77-4] which is toxic and may evolve in gaseous form at a lower pH. With additional hypochlorite, cyanate is then oxidized to bicarbonate, nitrogen gas, and chloride. The pH for this second stage is 7—9.5 (6). 

Ozone can be used to completely oxidize low concentrations of organics in aqueous streams or partially degrade compounds that are refractory or difficult to treat by other methods. Compounds that can be treated with ozone include alkanes, alcohols, ketones, aldehydes, phenols, benzene and its derivatives, and cyanide. Ozone readHy oxidizes cyanide to cyanate, however, further oxidation of the cyanate by ozone proceeds rather slowly and may require other oxidation treatment like alkaline chlorination to complete the degradation process. 

Ethyl carbamate, C2HyN02, is developed naturally during the fermentation of alcohoHc beverages. It also appears in foods such as bread and yogurt. Since ethyl carbamate is not easily distilled, its formation most likely involves a distillable precursor. The mechanism of ethyl carbamate formation probably involves cyanate produced from the oxidation of cyanide or from urea-based compounds in the beer. Cyanate reacts with alcohol to form ethyl carbamate as follows ... 

Cyanate can be further oxidized by HOCl to nitrogen and bicarbonate along with small amounts of N2O and NCl. Hypochlorous acid reacts with peroxide with evolution of oxygen by the postulated intermediate formation of peroxyhypochlorous acid (99). 

The final solution should be checked for absence of free cyanide. The hypochlorite or CI2 + NaOH method is by far the most widely used commercially (45). However, other methods are oxidation to cyanate using hydrogen peroxide, o2one, permanganate, or chlorite electrolysis to CO2, NH, and cyanate hydrolysis at elevated temperatures to NH and salts of formic acid air or steam stripping at low pH biological decomposition to CO2 and N2 chromium... 

In the presence of a trace of iron or nickel oxide, rapid oxidation occurs when cyanide is heated in air, first to cyanate and then to carbonate ... 

Molten sodium cyanide reacts with strong oxidizing agents such as nitrates and chlorates with explosive violence. In aqueous solution, sodium cyanide is oxidized to sodium cyanate [917-61 -3] by oxidizing agents such as potassium permanganate or hypochlorous acid. The reaction with chlorine in alkaline solution is the basis for the treatment of industrial cyanide waste Hquors (45) ... 

Chemical Properties. Potassium cyanide is readily oxidized to potassium cyanate [590-28-3] by heating in the presence of oxygen or easily reduced oxides, such as those of lead or tin or manganese dioxide, and in aqueous solution by reaction with hypochlorites or hydrogen peroxide. 

Cyanuric acid can also be prepared from HNCO (100). Isocyanic acid [75-13-8] can be synthesized directiy by oxidation of HCN over a silver catalyst (101) or by reaction of H2, CO, and NO (60—75% yield) over palladium or iridium catalysts at 280—450°C (102). Ammonium cyanate and urea are by-products of the latter reaction. 

Despite all precautions, urethanes can be used most effectively within certain thermal and oxidation limits. Outside these parameters, other adhesives, such as certain epoxies, cyanate esters, and other high-temperature adhesives, should be considered. 

Cyanides are dangerously toxic materials that can cause instantaneous death. They occur in a number of industrial situations but are commonly associated with plating operations, and sludges and baths from such sources. Cyanide is extremely soluble and many cyanide compounds, when mixed with acid, release deadly hydrogen cyanide gas. Cyanide is sometimes formed during the combustion of various nitrile, cyanohydrin, and methacrylate compounds. Cyanides (CN ) are commonly treated by chlorine oxidation to the less toxic cyanate (CNO ) form, then acid hydrolyzed to COj and N. Obviously, care should be taken that the cyanide oxidation is complete prior to acid hydrolysis of the cyanate. 

Alkali metal cyanates are stable and readily obtained by mild oxidation of aqueous cyanide solutions using oxides of or Ptf. The commercial preparation of NaNCO is by reaction of urea with Na2C03. 

The mechanism of action of the cyanation reaction is considered to progress as follows an oxidative addition reaction occurs between the aryl halide and a palladium(O) species to form an arylpalladium halide complex which then undergoes a ligand exchange reaction with CuCN thus transforming to an arylpalladium cyanide. Reductive elimination of the arylpalladium cyanide then gives the aryl cyanide. 

For best results the commercial triethylamine (Matheson, b.p. 89-90°) should be purified to remove primary and secondary amines and water, either by distillation from acetic anhydride and then from barium oxide, or by reaction with phenyliso-cyanate.5 2 3 4... 

For this class of reactions, only a few examples which proceed with reasonable diastereoselectivity are known. Allylation of a-methoxycarbamate 1, easily obtained as a 1 1 mixture of isomers by anodic oxidation of protected threonine, produces an 83 17 mixture of enantiomers on treatment with trimethyl(2-propcnyl)silanel03. Cyanation with trimcthylsilyl cyanide proceeds less stereoselectively (67 33 93 % yield). 

These major routes to quinoxalmecarbonitriles have been covered already by primary synthesis (Chapter 1), by cyanalysis of halogenoquinoxalines (Section 3.2.5), by deoxidative cyanation of quinoxaline N-oxides (Section 4.6.2.2), by cyanolysis of nitroquinoxalines (Section 6.1.2.2), from primary quinoxalina-mines by a Sandmeyer-type reaction (Section 6.3.2.3), from quaternary ammonio-quinoxalines with cyanide ion (Section 6.3.2.4), and by dehydration of quinoxalinecarboxamides (Section 7.4.2). Those remaining preparative routes that have been used recently are illustrated in the following examples. 

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