Cyanamide, aqueous solution

Specifications and Analysis. Cyanamide is sold as anhydrous, aqueous 50%, and calcium cyanamide. Aqueous 50% cyanamide solutions contain a buffer additive, usually 2% NaH2P04, to stabilize the pH and prevent formation of dicyandiamide and urea. Calcium cyanamide is stable under dry conditions. Table 2 gives a typical analysis of the three commercial forms. 

The checkers used 16.8 g. of Eastman Kodak Company cyanamide (P1995) without further purification. A convenient method of preparing cyanamide from commercial calcium cyan-amide has been described. According to the submitters, an aqueous solution of crude cyanamide is satisfactory in the present synthesis and is obtained by adapting this published procedure as follows. 

Somewhat above their melting points the aminothiatriazoles decompose more or less violently. When they are heated in aqueous solution nitrogen and sulfur are formed together with a cyanamide (isolated by Freund and Schwarz as the trimeric melamines) [Eq. (18)]. With the unsubstituted 5-aminothiatriazole the reaction... 

An aqueous solution of amitrole can decompose in the following free radical systems Fenton s reagent, UV irradiation, and riboflavin-sensitized photodecomposition (Plimmer et al, 1967). Amitrole-5- C reacted with Fenton s reagent to give radiolabeled carbon dioxide, unlabeled urea, and unlabeled cyanamide. Significant degradation of amitrole was observed when an aqueous solution was irradiated by a sunlamp (L = 280-310 nm). In addition to ring compounds, it was postulated that other products may have formed from the polymerization of amitrole free radicals (Plimmer et al., 1967). 

According to equation (19) decomposition also occurs on boiling nitroguanidine in an aqueous solution of ammonium carbonate, with liberation of nitrous oxide and ammonia. The latter combines with the cyanamide also resulting from reaction (19) and guanidine carbonate is formed in almost quantitative yield. 

Chretien and Woringer [34] described the preparation of silver cyanamide from calcium cyanamide by the action of silver nitrate and also described its explosive properties. Montagu-Pollock [35] described a method for growing large crystals of the salt from its aqueous solution in the presence of ammonium nitrate, ammonia and a surface active agent. Bowden and Montagu-Pollock [36] and Montagu-Pollock [35] studied the slow decomposition of the crystals when heated at temperatures from 150 to 360°C. The course of decomposition was studied by electron microscope. 

An autoclave (7) is supplied with an aqueous solution that contains 600 g of ammonium nitrate and 40 g of ammonia per litre. Calcium cyanamide in the ratio of 500 g CaCN2 to every litre of solution is then added from container (2) after being weighed at (3). The autoclave is closed, carbon dioxide is introduced, while the contents are cooled with water so that the temperature does not exceed 100°C. When no more carbon dioxide is absorbed, the supply is stopped, and so is the inflow of cooling water. The reaction mixture is now steam heated to 160°C. Afterwards a communicating valve joining the autoclave (7) with a second autoclave (75) is opened. The other vessel (75) is filled with ammonium nitrate solution prepared for the next charge. In this way the major part of the ammonia passes from autoclave (7) over to autoclave (75). After the reaction is finished the mixture is raised from the auto-... 

Cyanamide itself is not a suitable raw material for the preparation of guanidine salts, for it is difficult to prepare and to purify, and it polymerizes on keeping. The evaporation of an aqueous solution of cyanamide yields the dimer, dicyandiamide, and the heating, or even the long keeping, of the dry substance produces the trimer, melamine. 

Cyanamide, colorless crystals, m.p. 40°, is readily soluble in water, alcohol, and ether. An aqueous solution of cyanamide gives a black precipitate of copper cyanamide with ammoniacal copper sulfate solution, and a yellow precipitate of silver cyanamide with ammoniacal silver nitrate. The precipitates are almost unique among the compounds of copper and silver in the respect that they are insoluble in ammonia water. 

If it is warmed in aqueous solution, the nitrosoamide breaks down into water and nitrogen, and the cyanamide polymerizes to dicy-andiamide. The evaporation of the solution yields crystals of the latter substance. A cold aqueous solution of nitrosoguanidine acidified with hydrochloric acid yields nitrous acid, and may be used for the introduction of a nitroso group into dimethylaniline or some similar. substance which is soluble in the acidified aqueous liquid. 

Dicyandiamide, which is readily obtainable from calcium cyanamide and is a stable commercial product, may be converted into guanidine nitrate by the action of ammonium nitrate, either in concentrated aqueous solution under pressure12,13 or by a fusion reaction.13-16 The latter procedure gives a very pure product and is to be preferred for laboratory practice. Directions for its use are given under procedure A. 

Cyanamide is also acted upon directly by ammonium salts in aqueous and non-aqueous solutions.17-20 Since it is of decided advantage to avoid the isolation of pure cyanamide, methods have been developed in which aqueous solutions of cyanamide are prepared from calcium cyanamide and are then permitted to react with ammonium salts. However, guanidine nitrate may also be prepared directly from commercial calcium cyanamide by the action of ammonium nitrate. This reaction takes place readily in the fused state, in concentrated aqueous solution,21 or by direct admixture of solid ammonium nitrate with calcium cyanamide and subsequent heating to 100°C.22 The latter procedure is to be preferred, since better yields are obtainable and the hazard of fusion with ammonium nitrate is obviated. The directions given for procedure B require the use of a fairly good grade of unoiled calcium cyanamide containing approximately 65 per cent CaNCN. 

Melamine, a white powder, was discovered and identified by Liebig in 1834 but commercial manufacture came only in 1939, by Cyanamid Company of America with dicyandiamide as raw material. Melamine is 2,4,6-triamino-l,3,5-triazine with a structure as shown in Figure 53. On reaction with formaldehyde in aqueous solution the melamine powder dissolves rapidly on heating to form various methylol melamines, as in Figure 54. After further heating and the elimination of water the methylol melamines condense to form resinous polymers. 

It is made by dimerizing cyanamide in basic aqueous solution, and is a colorless solid melting at 208°C. Dicyandiamide is soluble in polar solvents, but at room temperature is insoluble in bisphenol A epoxy resins. It can be made into a very fine powder and milled into epoxy resins to form stable dispersions. Because the dicy is insoluble in the epoxy, the only possible reaction sites are at the particle surfaces. Although some reaction certainly occurs over a short time, the adhesives easily can have a useful shelf life of six months. On heating to about 150°C, the dicyandiamide becomes soluble in the epoxy resin, and the adhesive polymerizes rapidly. Cure can be accelerated by incorporation of tertiary aromatic amines or substituted ureas. 

The earliest method of this type was the old Marckwald synthesis (1] in which a suitable a-aminocarbonyl compound is cyclized with cyanate, thiocyanate or isothiocyanatc. More recent modifications have employed the acetals of the a-amino aldehyde or ketone or an a-amino acid ester. The two-carbon fragment can also be provided by cyanamide, a thioxamate, a carbodiimidc or an imidic ester. When cyanates, thiocyanates or isothiocyanates are used, the imidazolin-2-ones or -2-thiones (1) are formed initially, but they can be converted into 2-unsubstituted imidazoles quite readily by oxidative or dehydrogenative means (Scheme 4.1.1). The chief limitations of the method arc the difficulty of making some a-aminocarbonyls and the very limited range of 2 substituents which are possible in the eventual imidazole products. The method is nonetheless valuable and widely used, and typically condenses the hydrochloride of an a-amino aldehyde or ketone (or the acetals or ketals), or an a-amino-)6-ketoester with the salt of a cyanic or thiocyanic acid. Usually the aminocarbonyl hydrochloride is warmed in aqueous solution with one equivalent of sodium or potassium cyanate or thiocyanate. An alkyl or aryl isocyanate or isothiocyanate will give an A-substituted imidazole product (2), as will a substituted aminocarbonyl compound (Scheme 4.1.1) [2-4]. 

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