Ethylenediamine reaction

The desired long spacer necessary to allow multiple branch construction, was obtained with commercial tetra(ethylene glycol) which was readily modified into aminoacetal 21 in five steps (Scheme 8). Using 21 as an amine source, poly(amidoamine) (PAMAM) dendrons were prepared according to published protocol using reiterative cycles of methyl acrylate and ethylenediamine reactions. The terminal amines of each generation (G = 1, G = 2 and G = 3, 22a-c) were obtained quantitatively from each of the half generation methyl ester precursors. 

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. 

In 1937 I.G.-Farbenindustrie patented a method for the preparation of polyaminoacetonitriles, corresponding acids and their derivatives . The process, known as the hydrogen cyanide process, utilizes sodium cyanide in acid solution. The cyanomethylation takes place by treatment of the amine with formaldehyde and hydrogen cyanide. In the case of ethylenediamine reaction (2) takes place ethylenediaminetetraacetonitrile (1) is isolated to ensure that the resulting tetrasodium salt, after hydrolysis, is not contaminated by by-products. This synthesis can be performed as a continuous process and is also used to obtain other complexones. The use of hydrogen cyanide and of an acid medium gives rise to corrosion and safety problems. 

Lei,X.P, Lewis, D.M., 1990. Modification ofcotton to improve its dyeability. Part3—polyamide-epichlorohydrin resins and their ethylenediamine reaction products. J. Soc. Dyers Color. 106 (11), 352-356. 

Cuprous acetate ethylenediamine Reactions of cuprous acetate with halides Dimerization of halides... 

Currently around lOOOkton/year of numerous other C2-based building blocks are utilized. Some of the vital examples are acetic acid, dichloroethane (formed by the chlorination of ethane), vinylchloride (formed by the dehydrochlorination of dichloroethane), ethylene oxide (oxidation of ethylene), and ethylenediamine (reaction of 1,2-dichloroethane and ammonia Jong, 2012). 

There are a few documented examples of studies of ligand effects on hydrolysis reactions. Angelici et al." investigated the effect of a number of multidentate ligands on the copper(II) ion-catalysed hydrolysis of coordinated amino acid esters. The equilibrium constant for binding of the ester and the rate constant for the hydrolysis of the resulting complex both decrease in the presence of ligands. Similar conclusions have been reached by Hay and Morris, who studied the effect of ethylenediamine... 

In contrast, investigation of the effect of ligands on the endo-exo selectivity of the Diels-Alder reaction of 3.8c with 3.9 demonstrated that this selectivity is not significantly influenced by the presence of ligands. The effects of ethylenediamine, 2,2 -bipyridine, 1,10-phenanthroline, glycine, L-tryptophan and L-abrine have been studied. The endo-exo ratio observed for the copper(II)-catalysed reaction in the presence of these ligands never deviated more than 2% from the endo-exo ratio of 93-7 obtained for catalysis by copper aquo ion. 

The expression template reaction indicates mostly a reaction in which a complexed me) ion holds reactive groups in the correct orientation to allow selective multi-step reactions. T1 template effect of the metal is twofold (i) polymerization reactions are suppressed, since th local concentration of reactants around the metal ion is very high (ii) multi-step reactions are possible, since the metal holds the reactants together. In the following one-step synthesis eleven molecules (three ethylenediamine — en , six formaldehyde, and two ammonia molecules) react with each other to form one single compound in a reported yield of 95%. It is ob vious that such a reaction is dictated by the organizing power of the metal ion (I.I. Creasei 1977),... 

PoIya.mines are condensation polymers containing nitrogen they are made by a variety of synthetic routes. Most of the commercial polyamines are made by reaction of epichlorohydrin with amines such as methylamine [25988-97-0] or dimethylamine [39660-17-8] (18,19). Branching can be increased by a dding small amounts of diamines such as ethylenediamine [42751-79-1]. A typical stmcture of this type of polyamine is stmcture (9). 

Aluminum chloride [7446-70-0] is a useful catalyst in the reaction of aromatic amines with ethyleneknine (76). SoHd catalysts promote the reaction of ethyleneknine with ammonia in the gas phase to give ethylenediamine (77). Not only ammonia and amines, but also hydrazine [302-01-2] (78), hydrazoic acid [7782-79-8] (79—82), alkyl azidoformates (83), and acid amides, eg, sulfonamides (84) or 2,4-dioxopyrimidines (85), have been used as ring-opening reagents for ethyleneknine with nitrogen being the nucleophilic center (1). The 2-oxopiperazine skeleton has been synthesized from a-amino acid esters and ethyleneknine (86—89). 

Lithium Acetylide. Lithium acetyhde—ethylenediamine complex [50475-76-8], LiCM7H -112X01120112X112, is obtained as colodess-to-light-tan, free-flowing crystals from the reaction of /V-lithoethylenediamine and acetylene in an appropriate solvent (131). The complex decomposes slowly above 40°O to lithium carbide and ethylenediamine. Lithium acetyhde—ethylenediamine is very soluble in primary amines, ethylenediamine, and dimethyl sulfoxide. It is slightly soluble in ether, THF, and secondary and tertiary amines, and is insoluble in hydrocarbons. 

A variety of substituted alkanolamines (Table 2) can also be made by reaction of oxide with the appropriate amine. Aminoethylethanolamine is made from the reaction of ethylenediamine [107-15-3J and ethylene oxide. Methyldiethanolamine is made from the reaction of ethylene oxide and methylamine [74-89-5J. Diethylethanolamine is made by the reaction of diethylamine [109-87-7] and ethylene oxide. 

Bisamides. Methylenebisamides are prepared by the reaction of the primary fatty amide and formaldehyde in the presence of an acid catalyst. AijAT-Methylenebisoleamide has been made via this route without the use of refluxing solvent (55). Polymethylenebisamides can be made from fatty acid, esters, or acid haUdes with diamines while producing water, alcohol, or mineral acid by-products. Eatty acids and diamines, typically ethylenediamine, have been condensed in the presence of NaBH and NaH2P02 to yield bisamides (56). When stearic acid, ethylenediamine, and methyl acetate react for 6 h at... 

Ethyleneurea Resins. One of the most widely used resins during the 1950s and 1960s was based on dimethylolethyleneurea [136-84-5] (l,3-bis(hydroxymethyl)-2-imidazohdinone) commonly known as ethyleneurea resin. This resin [28906-87-8] is most convenientiy prepared from urea, ethylenediamine, and formaldehyde. 2-Imidazohdinone [120-93-4] (ethyleneurea) is first prepared by the reaction of excess ethylenediamine [107-15-3] wiih. urea (38) in an aqueous medium at about 116°C. 

Ethylenediamine Alkoxylates. The reaction 1,2-alkylene oxides with ethylenediamine forms the basis of a series of surfactants of the following general stmcture ... 

Nitrite can be deterrnined by reaction with sulfanilamide to form the diazo compound, which couples with /V-(1-naphthyl)ethylenediamine dihydrochloride to form an intensely colored red azo dye. Nitrate can be deterrnined in a similar manner after reduction to nitrite. Suitable reducing agents are cadmium filings or hydrazine. This method is useful at a nitrogen concentration of 10 -lO " M. 

Analogous reactions form sodiummethyldithiocarbamate [137-42-8] from methylamine, and disodiumethylenebis(dithiocarbamate) [142-59-6] from ethylenediamine. Iron, manganese, and 2iac salts can be prepared from the sodium salts heavy metals form characteristically colored compounds with dithio c arb amate s. 

Ammonium acetate and sodium methoxide are effective catalysts for the ammonolysis of soybean oil (49). Polyfunctional amines and amino alcohols such as ethylenediamine, ethanolamine, and diethanolamine react to give useful intermediates. Ethylenediamine can form either a monoamide or a diamide depending on the mole ratio of reactants. With an equimolar ratio of reactants and a temperature of >250° C, a cyclization reaction occurs to give imidazolines with ethylenediamine (48) ... 

Direct reaction of formaldehyde cyanohydrin and ethylenediamine in the presence of a sulfuric acid catalyst gives ethylenediarninetetraacetonitrile [5766-67-6], hydrolysis of which leads to ethylenediarninetetraacetic acid [60-00-4] (EDTA), a widely used sequestering agent (26). 

A kind of modification of the Polonovski-Boon synthesis is the reaction of 5,6-dihalopyrimidines with ethylenediamine derivatives. Depending on the bulkiness of the amino substituents a more or less regiospecific condensation may proceed (71CB780), as shown recently in the reaction of 5-bromo-6-chloro-l,3-dimethyluracil (279) with 2-methyl-amino- -propylamine to form l,3,5,6-tetramethyl-5,6,7,8-tetrahydrolumazine (280 equation 99) (80Ba3385). 

In a 2-1. round-bottomed flask are placed 120 g. (1.83 moles) of 92% ethylenediamine (Note 1), 300 ml. of 95% ethanol, and 300 ml. of water. The flask is attached to an efficient reflux condenser, and 121 ml. of carbon disulfide is placed in a separatory funnel attached to the top of the condenser by means of a notched cork. About 15 to 20 ml. of the carbon disulfide is added, and the flask is shaken to mix the contents. A vigorous reaction takes place (Note 2), and it may be necessary to cool the flask. After the reaction has started, a water bath at 60° is placed under the flask and the balance of the carbon disulfide is added at such a rate that the vapors reflux about one-third the way up the condenser. About 2 hours are required for the addition of the carbon disulfide. At this time the bath temperature is raised to about 100°, and the mixture is allowed to reflux for 1 hour. Then 15 ml. of concentrated hydrochloric acid is added, and the mixture is refluxed under a good hood (bath at 100°) for 9 to 10 hours. The mixture is cooled in an ice bath, and the product is filtered by suction on a Buchner funnel and washed with 200-300 ml. of cold acetone (Note 3). A yield of 156-167 g. (83-89%) of white crystals is obtained melting at 197-198° (Note 4). 

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