Isocyanic acids

HNCO isocyanic acid H2PHO3 phosphonic acid... 

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). 

More recently, other nonphosgene routes for the preparation of aUphatic isocyanates have been reported. For example, American Cyanamid has disclosed the reaction of diisopropenylben2ene with HCl and isocyanic acid [75-13-8] to yield tetramethyixylylene diisocyanates (57). 

C rb myl tion. Modification of the amino-terminal groups of hemoglobin (Hb) by the carbamylation reaction using isocyanic acid [75-13-8]... 

Carbamic acid [463-77-4] NH2COOH, is the hydrated form of isocyanic acid [75-13-8] H—N=C=0. It is not known in the free state hydrolysis rapidly gives ammonia and carbon dioxide. 

Alkyl carbamates (urethanes) ate formed from reaction of alcohols with isocyanic acid or urea (see Urettpane polymers). 

With excess isocyanic acid, stable aUopbanates aie formed (see Cyanuric AND ISOCYANURIC acids). 

Cyanuiic acid is an ododess, white, ciystalline solid that does not melt up to 330°C at higher temperatures it sublimes and dissociates to isocyanic acid (HNCO) [75-13-8],... 

Although much weaker than the parent compound isocyanic acid (pK = 3.7), CA is sufftciendy acidic to form salts. Many inorganic and organic salts of CA have been reported (11). Lead and 2iuc cyanurates are usehil as corrosion inhibitors (20). The 1 1 adduct, melamine cyanurate [37640-57-6] has achieved commercial importance. 

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. 

If the addition is too rapid the odor of isocyanic acid (remindful of that of sulfur dioxide) becomes strong and the yield is diminished. 

The hydroxyl derivative of X-CN is cyanic acid HO-CN it cannot be prepared pure due to rapid decomposition but it is probably present to the extent of about 3% when its tautomer, isocyanic acid (HNCO) is prepared from sodium cyanate and HCI. HNCO rapidly trimerizes to cyanuric acid (Fig. 8.25) from which it can be regenerated by pyrolysis. It is a fairly strong acid (Ka 1.2 x 10 at 0°) freezing at —86.8° and boiling at 23.5°C. Thermolysis of urea is an alternative route to HNCO and (HNCO)3 the reverse reaction, involving the isomerization of ammonium cyanate, is the clas.sic synthesis of urea by F. Wohler (1828) ... 

Reaction of the glycol, 70, affords an oxazolidinone rather than the expected carbamate (71) on fusion with urea. It has been postulated that the urea is in fact the first product formed. This compound then undergoes 0 to N migration with loss of carbon dioxide reaction of the amino alcohol with the isocyanic acid known to result from thermal decomposition of urea affords the observed product, mephenoxolone (74) this compound shows activity quite similar to that of the carbamate. An analogous reaction on the glyceryl ether, 75, affords metaxa-lone (76). 

Fusion of an all cyclic ring onto the piperidine so as to form a perhydroisoquinoline is apparently consistent with analgesic activity. Synthesis of this agent, ciprefadol (68), starts with the Michael addition of the anion from cyclohexanone 56 onto acrylonitrile (57). Saponification of the nitrile to the corresponding acid ( ) followed by Curtius rearrangement leads to isocyanate Acid... 

Iso-crotonsaure, /. isocrotonic acid, -cumarin, n. isocoumarin, isocumarin. -cyansaure, /. isocyanic acid, -cyanursaure, /. isocyanuric add. 

The structures of these ylide polymers were determined and confirmed by IR and NMR spectra. These were the first stable sulfonium ylide polymers reported in the literature. They are very important for such industrial uses as ion-exchange resins, polymer supports, peptide synthesis, polymeric reagent, and polyelectrolytes. Also in 1977, Hass and Moreau [60] found that when poly(4-vinylpyridine) was quaternized with bromomalonamide, two polymeric quaternary salts resulted. These polyelectrolyte products were subjected to thermal decyana-tion at 7200°C to give isocyanic acid or its isomer, cyanic acid. The addition of base to the solution of polyelectro-lyte in water gave a yellow polymeric ylide. 

ISOCYANIC ACID, ANHYDRIDE WITH CHIO ROACETIC ACID, 46, 16 ISOCYANIC ACID, ANHYDRIDF WITH CHLOROSULPONIC ACID, 46, 23 Isocyanides, preparation of volatile, 46, 77... 

Carbamates (substituted urethanes) are prepared when isocyanates are treated with alcohols. This is an excellent reaction, of wide scope, and gives good yields. Isocyanic acid HNCO gives unsubstituted carbamates. Addition of a second mole of HNCO gives allophanates. 

Ammonia and primary and secondary amines can be added to isocyanates to give substituted ureas. Isothiocyanates give thioureas. This is an excellent method for the preparation of ureas and thioureas, and these compounds are often used as derivatives for primary and secondary amines. Isocyanic acid (HNCO) also gives the reaction usually its salts (e.g., NaNCO) are used. Wohler s famous synthesis of urea involved the addition of ammonia to a salt of this acid. "... 

Isocyanic acid, 2-(chIoroformyl)ethyl ester (8) Propanoyl chloride, 3-isocyanato- (9) (3729-19-9)... 

Trichloromethyl chloroformate has proven effective in the preparation of N-carboxy-a-amino acid anhydrides from amino acids, and various compounds having isocyanate, acid chloride, and chloroformate groups.For example, trichloromethyl chloroformate may be used instead of phosgene in the preparation of 2-tert-butoxycarbonyloxyimino-2-phenylacetonitrile. The use of this reagent is illustrated here by the synthesis of 3-isocyanato-propanoyl chloride from 3-aminopropanoic acid hydrochloride. 

Isocyanic acid from sodium cyanate Schering Plough Res. Inst. Giusto (1994)... 

For reasons of safety and toxicity, urea is the preferred selective reducing agent for mobile SCR applications. Under the hydrothermal conditions in the exhaust system, urea decomposes to ammonia which reduces the nitrogen oxides on the surface of the SCR catalyst [18,19], If urea is used instead of ammonia, the DeNO chemistry involves isocyanic acid as an important intermediate which will lead to a complication of the SCR chemistry [20],... 

Equimolar amounts of ammonia and isocyanic acid are thus formed. These two endothermic processes, which can be slightly accelerated by catalysts, partially occur already in the gas phase ahead of the SCR catalyst. Investigations of the selective non-catalytic reduction showed that the mixture of ammonia and isocyanic is stable up to 850°C [21]. 

The major problems with the substitution of the reducing agent ammonia for urea are on the one hand the homogeneous mixing of urea and exhaust gas and on the other hand the limited residence time in SCR systems for the different decomposition steps, i.e. the evaporation of water from the droplet, the thermolysis of urea to isocyanic acid and the following hydrolysis to ammonia [18]. 

Also the thermohydrolysis of the urea solution after the injection into the hot exhaust gas upstream of the SCR catalyst has been investigated at the diesel test rig. Urea solution was atomized about 3 m upstream of the SCR catalyst into the hot exhaust equivalent to a residence time in the pipe section of 0.1 s at 440°C. As expected for the thermolysis reaction, ammonia and isocyanic acid were found at the catalyst entrance at all temperatures (Figure 9.3). The 1 1 ratio of both components shows that only the thermolysis but not the hydrolysis is taking place in the gas phase. It can also be seen that the residence time of 0.1 s is not sufficient for the quantitative thermolysis of urea, as appreciable amounts of undecomposed urea were always found. The urea share even raises with lowering the flue gas temperature, although the residence time... 

Figure 9.3. Ammonia, isocyanic acid and urea at various temperatures at the catalyst entrance. Residence time urea injection-catalyst entrance 0.09 s at 440°C.

Moreover, triuret, ammeline, ammelide, melamine and other products may be formed from isocyanic acid, biuret and combinations of them. If urea is heated up very fast, these reactions are suppressed and the decomposition into ammonia and isocyanic acid is the preferred reaction. Due to the high reactivity of isocyanic acid, its primary formation may subsequently lead to the formation of the aforementioned compounds of higher molecular weight. In order to avoid the formation of by-products, the heating-up must be carried out fast. Only then ammonia and isocyanic acid are obtained as sole products. In any case, local undercooling of the gas duct should be avoided and rapid dilution of the thermolysis products in the exhaust gas has to be ensured in order to avoid locally high concentrations of reactive compounds. 

---