Cyanate ions

The most stable Lewis structure for cyanate ion is F because the negative charge is on its oxygen... 

Organosulfur Compounds. These compounds, Hsted in Table 8, are used in a variety of appHcations, including cooling water, paint, and metalworking. Methylenebisthiocyanate hydroly2es rapidly at a pH above 8 to cyanate ion which complexes with ferric iron to poison the cytochrome systems (36). 

Similar differences are found for organic azides (e.g. MeN3). In ionic azides (p. 417) the N3 ion is both linear and symmetrical (both N-N distances being 116 pm) as befits a 16-electron species isoelectronic with CO2 (cf. also the cyanamide ion NCN, the cyanate ion NCO, the fulminate ion CNO and the nitronium ion N02 ). 

Alkyl halides or sulfuric or sulfonic esters can be heated with sodium or potassium thiocyanate to give alkyl thiocyanates, though the attack by the analogous cyanate ion (10-66) gives exclusive N-alkylation. Primary amines can be converted to thiocyanates by the Katritzky pyrylium-pyridinium method (pp. 447, 489). "... 

When the reagent is the thiocyanate ion, S-alkylation is an important side reaction (10-43), but the cyanate ion practically always gives exclusive N-alkylation. ° Primary alkyl halides have been converted to isocyanates by treatment with sodium nitrocyanamide (NaNCNN02) and m-chloroperoxybenzoic acid, followed by heating of the initially produced RN(N02)CN. ° When alkyl halides are treated with NCO in the presence of ethanol, carbamates can be prepared directly (see 16-7). ° Acyl halides give the corresponding acyl isocyanates and isothiocyanates. For the formation of isocyanides, see 10-111. 

C09-0108. Carbon, nitrogen, and oxygen form two different polyatomic ions cyanate ion, NCO, and isocyanate ion, CNO". Write Lewis stmctures for each anion, including near-equivalent resonance structures and indicating formal charges. 

Now that we have determined that structure I is correct for the cyanate ion, we still need to consider resonance structures. In keeping with the rules given earlier, the acceptable resonance structures that can be devised are... 

An additional example of the use of bond energies will be considered. Earlier in this chapter, we considered the structure of the cyanate ion, OCN-. Suppose the structures being considered are... 

Recently, the solvolyses of l-chloro-l,3,3-triarylallenes 10 (andof 1-butyl-3,3-diphenyl-allenyl chloride) were carried out in the presence of thiocyanate and o-ethyl dithiocar-bonate anions as nucleophiles and found to give the corresponding allenyl derivatives 11 and 12 in good yield (equation 3)18. However, when potassium cyanate was used as a nucleophile, the cyanate ion attacked at the /-position to give the propargyl amines 14 after decarboxylation of the unstable intermediate 13 (equation 4). 

Efflox A process for destroying cyanide wastes in hydiometallurgical effluents by the use of Caro s acid. The cyanide ion is oxidized to cyanate ion. 

Now we will apply this formal-charge concept to the cyanate ion OCN We chose this example because many students incorrectly write the formula as CNO , and then try to use this as the atomic arrangement in the Lewis structure. Based on the number of electrons needed, the carbon should be the central atom. We will work this example using both the incorrect atom arrangement and the correct atom arrangement. Notice that in both structures all atoms have a complete octet. 

A phase-transfer catalysed nucleophilic displacement reaction on chloro-acetanilides by cyanate ions, followed by ring-closure (Scheme 5.10), provides a simple and viable synthesis of hydantoins [41], The formation of the hydantoins is inhibited by substituents in the orf/to-position of the aryl ring, but the addition of potassium iodide, or tetra-n-butylammonium iodide, generally increases the overall rate of formation of the cyclic compounds, presumably by facilitating the initial nucleophilic substitution step. 

Autoxidation of secondary acetonitriles under phase-transfer catalytic conditions [2] avoids the use of hazardous and/or expensive materials required for the classical conversion of the nitriles into ketones. In the course of C-alkylation of secondary acetonitriles (see Chapter 6), it had been noted that oxidative cleavage of the nitrile group frequently occurred (Scheme 10.7) [3]. In both cases, oxidation of the anionic intermediate presumably proceeds via the peroxy derivative with the extrusion of the cyanate ion [2], Advantage of the direct oxidation reaction has been made in the synthesis of aryl ketones [3], particularly of benzoylheteroarenes. The cyanomethylheteroarenes, obtained by a photochemically induced reaction of halo-heteroarenes with phenylacetonitrile, are oxidized by air under the basic conditions. Oxidative coupling of bromoacetonitriles under basic catalytic conditions has been also observed (see Chapter 6). 

No reaction of excited 1-nitroazulene with hydroxide and cyanate ions or p nidine could be detected... 

Again, a hnear relationship of and [CNS] i shows a bimolecular reaction between the excited triplet state of 1 and the nucleophile to take place. The triplet lifetime of la is 4.7 X 10 s in water and 1.2xl0 8s in aqueous 10 2M solutions of potassium cyanide as determined from quenching studies The nitro group in 7 a is likewise replaced photochemically by methoxide and cyanate ions. 

The structures of lithium and sodium cyanates and isocyanates and their related ion-pair 5n2 reactions have been examined by using quantum mechanics at the Hartree-Fock (HF)/6-31G V/HF/6-31G level. (The cyanate ion is NCO the isocyanate ion is CNO. ) The isocyanate ion pairs are the most stable monomeric forms the lowest energy dimers are planar eight-membered rings. For the ionic 5 n2 reaction of cyanate ion with MeF or MeCl, methyl isocyanate is the predicted major product. Predictions about the 5ivr2 reactions of the ion pairs were also made. 

For synthetic purposes the cyanate ion is a promising reagent leading to amines in water and to carbamates in dcohol (Hartsuiker et al., 1971). Alkyl-lithium reagents may also function in nucleophilic photosubstitutions with aromatic partners containing suitable leaving groups (Shapiro and Tomer, 1968). 

In acidic solutions the cyanate ion rapidly hydrolyzes according to ... 

Isocyanides have been oxidized to isocyanates with HgO and with Oj, as well as with a halogen and dimethyl sulfoxide (or pyridine N-oxide).428 In the latter case the oxidizing agent is the halogen, which converts the isocyanide to R—N=CCI which is hydrolyzed to the isocyanate.429 Cyanide ion has been oxidized to cyanate ion with many oxidizing agents. 

Owing to the rapid decomposition of the cyanate ion in water, the use of aprotic solvents was necessary for the preparation of the Ag(NCO)J ion. Since alkali cyanates are poorly soluble in aprotic solvents, the cyanate salts used were the tetraethylammonium, tetramethylammonium and tetraphenylarsonium cyanates. Either dry acetone or acetonitrile could be used as solvent as silver isocyanate was reasonably soluble in both. Once prepared the silver salts were found to be light- and moisture-sensitive.136-137... 

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