Biuret

C2H4N2O3, NH2CONHCOOH. Unknown in the free state as it breaks down immediately to urea and COi- The NH4, Ba, Ca, K and Na salts are known and are prepared by treating ethyl allophanate with the appropriate hydroxide. The esters with alcohols and phenols are crystalline solids, sparingly soluble in water and alcohol. They are formed by passing cyanic acid into alcohols or a solution of an alcohol or phenol in benzene. The amide of allophanic acid is biuret. Alcohols are sometimes isolated and identified by means of their allophanates. 

Formation of Biuret., and Biuret reaction. Place 0 2 g. of urea in a dry test-tube, heat very gently just above the m.p. and note the production of ammonia. After 1-2 minutes the liquid suddenly solidifies with the formation of biuret ... 

Ltease test. The enzyme uretwe hydrolyses urea to ammonium carbonate (p. 519). The reaction is sp ific and is frequently used for solu tions of urea to which the biuret test cannot be applied. Add about 5 drops of phenohred to o 2 g. of urea dissolved in 5 ml. of water. To this yellow solution, add 0 2 g. of jack bean meal suspended in 2 ml. of water containing. also 5 drops of phenol-red. The colour changes to red as the solution becomes alkaline. 

Biuret test. Oxamide, having two CONHj groups, will give this test without any preliminary treatment (c/. urea). Shake o-i g. of oxamide with 1 ml, of 10% NaOH solution, add i drop of very dilute CuSO solution and mix well. A rose-pink coloration is produced. 

The reaction of 2-aminothiazole derivatives with the 1,3,5-oxadiazine 2,4.6-trione shown leads to biuret derivatives (126) (Scheme 83) (287). 

At atmospheric pressure and at its melting point, urea decomposes to ammonia, biuret (1), cyanuric acid (qv) (2), ammelide (3), and triuret (4). Biuret is the main and least desirable by-product present in commercial urea. An excessive amount (>wt%) of biuret in fertiliser-grade urea is detrimental to plant growth. 

Urea processes provide an aqueous solution containing 70—87% urea. This solution can be used directiy for nitrogen-fertilizer suspensions or solutions such as urea—ammonium nitrate solution, which has grown ia popularity recentiy (18). Urea solution can be concentrated by evaporation or crystallization for the preparation of granular compound fertilizers and other products. Concentrated urea is sohdified ia essentially pure form as prills, granules, flakes, or crystals. SoHd urea can be shipped, stored, distributed, and used mote economically than ia solution. Furthermore, ia the soHd form, urea is more stable and biuret formation less likely. 

Sohd urea containing 0.8—2.0 wt% biuret is primarily used for direct appHcation to the soil as a nitrogen-release fertilizer. Weak aqueous solutions of low biuret urea (0.3 wt% biuret max) are used as plant food appHed to foHage spray. 

Commercial urea generally contains a small amount of the compound biuret [108-15-0] NH2CONHCONH2. For fertilizer use other than foflar apphcation, biuret contents of about 1.5% or less are not harmful, and under usual production conditions it is not difficult to avoid higher biuret levels. For most fohar apphcation, however, the level should not exceed 0.1%, and special production modifications are usually requited to ensure such a low level. 

Further reaction of the active hydrogens on nitrogen in the urethane groups (3) can occur with additional isocyanate (1) at higher temperatures to cause formation of aHophanate stmctures. The active hydrogens in urea groups can also react with additional isocyanate to form disubstituted ureas which can stiU further react with isocyanate to form biurets (13). 

An excess of phosgene is used during the initial reaction of amine and phosgene to retard the formation of substituted ureas. Ureas are undesirable because they serve as a source for secondary product formation which adversely affects isocyanate stabiUty and performance. By-products, such as biurets (23) and triurets (24), are formed via the reaction of the labile hydrogens of the urea with excess isocyanate. Isocyanurates (25, R = phenyl, toluyl) may subsequendy be formed from the urea oligomers via ring closure. 

Some of these isocyanates are commercially available in derivatized form, such as biurets and carbodiimides, to provide materials having improved handling or processing characteristics. 

Ammonia reacts vigorously with phosgene. The products are urea, biuret, ammeUde (a polymer of urea), cyanuric acid, and sometimes cyameUde (a polymer of cyanic acid). The secondary products probably arise through the very reactive intermediate carbamyl chloride [463-72-9] NH2COCI (see... 

Cyanuric acid can also be prepared by pyrolysis of urea derivatives. Biuret and triuret give less aminotria ines due to reduced ammonia evolution. Urea cyanurate also provides a higher assay product. 

The water reaction evolves carbon dioxide and is to be avoided with solid elastomers but is important in the manufacture of foams. These reactions cause chain extension and by the formation of urea and urethane linkages they provide sites for cross-linking, since these groups can react with free isocyanate or terminal isocyanate groups to form biuret or allophanate linkages respectively (Figure 27.5). 

---