Ethylenediamine, carbon dioxide

Experiment 1. Effect of Carbon Catalyst on Oxidation of Cobalt(ll) to Cobalt (III) and Formation of Ethylenediamine and Effect of Cobalt on Formation of Ethylenediamine. Carbon dioxide-free air was bubbled through the reaction mixture. Nine determinations each of the amounts of ammonia volatilized, the ethylenediamine concentration, and the cobalt (II) concentration were made over a period of 18 hours. The results are shown in Figure 1. 

Add 40 ml. of ethyl alcohol to 21 -5 g. of 70 per cent, ethylenediamine solution (0 -25 mol) dissolve 36 -5 g. of adipic acid (0 -25 mol) in 50 ml. of a 6 1 mixture of ethyl alcohol and water. Mix the two solutions, stir and cool. Filter off the resulting salt and recrystalliae it from 60 ml. of a 6 1 ethyl alcohol - water mixture, and dry the salt in the air. Heat the salt in an atmosphere of oxygen-free nitrogen or of carbon dioxide in an oil bath until it melts (ca. 160°) the product will sohdify after a short time. Reduce the pressure to 15 mm. of mercury or less and raise the temperature of the oil bath until the product remelts (about 290°) and continue the heating for 4r-5 hours. Upon coohng, a nylon type polymer is obtained. 

In an interesting reaction, pyrrolysis of the urethane leads to extrusion of carbon dioxide and formation of 23, propiomazine Although this agent contains the ethylenediamine side chain, its main use is as a sedative. 

Ethylenediamine (15 g, 0 5 mol) was added dropwise to 100 ml 9B-100% formic acid in a two-necked 500 ml flask, fitted with an addition tube and reflux condenser with drying tube, cooled in an ice-bath. After complete addition of the base, 53 g of benzaldehyde (0.5 mol) was added in one lot. The ice-bath was removed and the flask was heated to the refluxing temperature. The initial rate of carbon dioxide evolution was too rapid to measure. After twenty minutes, the rate was circa 100 ml per minute and decreased rapidly to B ml per minute in one hour. Heating at reflux was continued for 35 hours. 

Figure 2 Formation of carbon dioxide during the deprotection of CBz protected phenylalanine (with and without ethylenediamine) in the presence of 5%Pd/C.

I believed that when the bacteria ate away an ethylenediamine molecule that nitrogen and carbon dioxide would escape and that would be that. But the bacteria are much more complex, and they convert the ethylenediamine into an amino... 

Experiment 3. Rates of Formation of Ethylenediamine and Ammonia vs. Rate of Disappearance of Cobalt (II). Carbon dioxide-free air was bubbled through the solution. Ammonia, ethylenediamine, and cobalt (II) were determined periodically over a total reaction time of 5 hours. The results of this experiment are collected in Table I and plotted in Figure 3. The ammonia measured was actually the ammonia volatilized during the reaction, but it was calculated as moles per liter of solution in order to be consistent with the ethylenediamine and cobalt (II) results. 

Ethylenediamine (en) [15] Among the impurities are water, carbon dioxide, ammonia and polyethylene amines (e.g. diethylenetriamine and triethylenetetra-mine). In the recommended purification method, commercial product (98%) is shaken for about 12h with activated molecular sieves (5A, 70 gl-1), the supernatant is decanted and shaken for about 12 h with a mixture of CaO (50 gl-1) and... 

Reaction with Nitrogen Nucleophiles. The acid-catalyzed reaction of primary, secondary, and tertiary amines with ethyleneimine yields asymmetrically substituted ethylenediamines (71). Steric effects dominate basicity in the relative reactivity of various amines in the ring-opening reaction with ethyleneimine (72). The use of carbon dioxide as catalyst in the aminoethylation of aliphatic amines, for which a patent application has been filed (73), has two advantages. First, the corrosive salts produced when mineral acids are used as catalysts (74,75) are no longer formed, and second, the reaction proceeds with good yields under atmospheric pressure. 

In the following, a series of preparations of dianionobis(ethyl-enediamine)cobalt(III) compounds, all starting with (carbonato)-bis(ethylenediamine)cobalt(III) chloride are given. (Carbonato )bis-(ethylenediamine)cobalt(III) chloride has been prepared with a high yield (80%) by a new method based upon the use of cobalt(II) chloride and the equivalent amount of (2-aminoethyl)-carbamic acid. The carbonato compound is easily converted into a number of dianionobis(ethylenediamine)cobalt(III) compounds with high yields. In some of the following procedures it was possible to use the carbon dioxide-ethylenediamine reaction mixture directly. 

The following procedure is based on the reaction of an aqueous solution of cobalt(II) chloride with the equivalent amount of (2-aminoethyl)carbamic acid, followed by oxidation with hydrogen peroxide and the subsequent formation of bis(ethylene-diamine)cobalt(III) ions. The bis(ethylenediamine)cobalt(lII) species are converted to the carbonato complex by reaction with lithium hydroxide and carbon dioxide. During the entire preparation a vigorous stream of carbon dioxide is bubbled through the reaction mixture. This procedure appears to be essential in order to minimize the formation of tris(ethylenediamine)cobalt(III) chloride as a by-product. However, the formation of a negligible amount of the tris salt cannot be avoided. The crude salts have a purity suitable for preparative purposes. The pure salts are obtained by recrystallization from aqueous solution. 

A stream of carbon dioxide is bubbled through a mixture of 133 ml. (1.64 moles) of ethylenediamine monohydrate and 133 ml. of water cooled in ice. The stream of carbon dioxide is maintained during the entire preparation. A solution of 195 g. (0.82 mole) of cobalt(II) chloride hexahydrate in 175 ml. of water at room temperature is added to the cold solution, which is continually stirred. The addition of the cobalt(II) salt causes a violent evolution of carbon dioxide gas, and the solution becomes red-violet. (Sometimes the mixture coagulates and becomes gel-like.) The cooling and the stirring are continued, and the mixture is oxidized by dropwise addition of 200 ml. of 30%... 

To 27.5 g. (0.1 mole) of crude (carbonato)bis(ethylenediamine)-cobalt(III) chloride is added 200 ml. of 1.00 N hydrochloric acid. The carbonato complex is dissolved with evolution of carbon dioxide gas and formation of a red solution consisting primarily of the corresponding cw-diaqua species. The solution is evaporated in the steam bath until an almost dry paste has been formed. The purple residue is filtered and washed with three 20-ml. portions of ice-cold water. Drying in air yields 19.5 g. of purple crystals of cu-dichlorobis(ethylenediamine)cobalt(III) chloride. The mother liquor and the washings are again evaporated almost to dryness to yield a second crop of crystals, 5.9 g. The total yield is 25.4 g. (84% based on (carbonato)bis(ethylenediamine)cobalt(III) chloride). The analysis and the visible absorption spectrum of the two fractions are identical. Anal. Calcd. for [Co(en)2Cl2 ] C1 H20 Co, 19.42 N, 18.46 C, 15.82 Cl, 35.05 H, 5.98. Found Co, 19.50 N, 18.57 C, 15.77 C1, 35.15 H, 6.01. 

The procedure described here is based on the observation that amine monohydroxo complexes of cobalt(III), rhodium(IIl), and iridium(III) react directly with carbon dioxide to form the corresponding carbonato complexes,2 3 without effect on the configuration of the amine ligands.4 The amine monoaqua complex is allowed to react with lithium carbonate or carbon dioxide gas at room temperature at pH 8.0 for a few minutes, and the carbonato complex is isolated by adding alcohol. The procedure has been used to prepare salts of the following cations pentaammine(carbonato)-cobalt(III),2 ds-ammine(carbonato)bis(ethylenediamine)cobalt(III),5 trans-... 

Radioactive sparteine (II) was incorporated in good yield when lysine (2-14C) and cadaverine (l 5-i4C) were administered to L. luteus and Sarothamnus scoparius L. When the alkaloid was degraded by chromic oxide oxidation it gave succinic acid and a mixture of amino acids. The Schmidt degradation of the former generated carbon dioxide and ethylenediamine. The amino acid mixture contained jS-alanine and y-aminobutyric acid, which was further degraded to carbon dioxide and trimethy lenediamine. 

The encapsulation of catalytically active species into porous solids is one of the possible strategies of particular interest. Thus, Bessel and Rolison (1997b,c) compared the electrocatalytic effect of zeolite Y-encapsulated Co(salen) (salen = N,N -bis(salicylidene)ethylenediamine) on the reaction between benzyl chloride and carbon dioxide in tetrahydrofuran/hexamethylphosphoramide, with that exerted by the same complex in solution. Using a large surface area reticulated vitreous carbon electrode immersed into suspensions of Co(salen) NaY in solutions of the reagents, the effective electrocatalytic turnover is ca. 3000 times that of homogeneous Co(salen) under comparable conditions. Remarkably, coulometric experiments indicated that only... 

Imidazolidinone. 2-lmidazolidone ethylene urea. C5H4NjO mol wt 86.10. C 41.85%, H 7.03%, N 32.54%, O 18.58%. Prepd from ethylenediamine and carbon dioxide under the influence of heal and pressure Mulvaney. Evans, Imf. Eng. Chem. 40, 393 (1948) from ethylenediamine and urea Schweitzer. J. Org. Chem. 15, 471 (1950). Systematic survey and bibliography Klaus Hofmann, Imidazole, Part I (Interscience, New York, 1953). 

Fig. 7.8. Chromatograms of separation of model mixture and elemental analysis of isolated peaks. I = Diethyl ether 11 = benzene III = methanol IV = ethylenediamine V = nitromethane 1 = nitrogen 2 = carbon dioxide 3 = water 4 = carbon monoxide. From ref. 144.

EXPLOSION and FIRE CONCERNS dangerous fire and explosion hazard extremely flammable liquid NFPA rating Health 3, Flammability 3, Reactivity 1 vigorous or explosive reaction above -70°C with alkyl aluminum chlorides and aromatic hydrocarbons violently exothermic polymerization reaction with aluminum chloride, boron trifluoride, sulfuric acid incompatible or reacts strongly with nitric acid, ethylene imine, ethylenediamine, chlorsulfonic acid, oleum, sodium hydroxide combustion will produce carbon dioxide, carbon monoxide, and hydrogen chloride use carbon dioxide, alcohol foam, or dry chemical for firefighting purposes. 

Similarly, the corresponding carbonatoethylenediamine complexes have been synthesized Originally solid material prepared by saturating ethylenediamine hydrate with carbon dioxide was used in order to realize a mild substitution at the first-step, but we now recommend ethylenediamine instead of such salt-like material, because of convenience in procedure and a good yield of K[Co(C03)2en] H20. Other familiar complexes, [CoC03(en)2]X and [Co(en)3]X3, are also accessible. 

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