Ethylenediamine, reaction with sulfur

The synthesis and biological testing of the pyrazine compound 123 was described by Wang et al. [34], The same benzoin intermediate 22 was formed as described in Scheme 2. A three-step reaction was then performed to obtain the desired pyrazine 123, shown in Scheme 31 (i) oxidation of Q1SO4 in aqueous pyridine, (ii) reaction with ethylenediamine in EtOH, and (iii) aromatization in the presence of elemental sulfur. 

The synthesis of 1,2,5-thiadiazoles from a-diamines was studied as early as 1897 when Michaelis attempted the preparation of the parent compound by reaction of ethylenediamine with sulfur dioxide. The product, however, was bissulfimic acid (28) which readily lost sulfur dioxide to form the betaine (28a). Later Shew reported that 3,4-dicyano-l,2,5-thiadiazole (30) results from the reaction of cis-diaminomaleonitrile (29, HCN tetramer) with thionyl chloride, a reaction which is analogous to 2,1,3-benzothiadiazole formation from o-phenylenediamines. The synthesis of the parent 1,2,5-thiadiazole and some alkyl analogs (32) was accomplished by reaction of salts of... 

The diisocyanate derivative of ethylenediamine was treated with sulfur-containing diamines or glycols in THF to form macrocycles containing sulfur, nitrogen, and in some cases, oxygen atoms in the ring (method Z-16) (Ishii et al., 1988). No specific details for these reactions were given in the patent. 

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. 

A review has appeared on the synthesis and reactivity of (sUylamino) and (silyl-anilino)phosphines. The S5mthesis, derivatisation and coordination behaviour of the morpholine (69) and piperazine (70) derivatives have been described. They are formed from the appropriate amine with diphenylchlorophosphine, and both react with sulfur or selenium to give the chalcogenide, whilst reaction of (69) with paraformaldehyde leads to insertion of methylene into the P N bond to give the phosphine oxide. The reaction between ethylenediamine and diphenylchlorophosphine can lead to the bis-, tris- and tetrakis(diphenylphosphino)ethylene-diamines, depending upon the stoichiometry. The first two are oxidised in situ whist the latter, (71), is stable. A nickel complex of (71) has been shown to be active as a catalyst for ethylene pol5nnerisation. ... 

Quite a number of mixed sulfur-nitrogen macrocycles have been prepared, but these have largely been by the methods outlined in Chaps. 4 and 5 for the respective heteroatoms. An alternative method, involves the formation of a Schiff base, followed by reduction to the fully saturated system, if desired. An interesting example of the Schiff base formation is found in the reaction formulated in (6.12). Dialdehyde 14 is added to ethylenediamine in a solution containing ferrous ions. Although fully characterized, the yield for the reaction is not recorded. To avoid confusion with the original literature, we note the claim that the dialdehyde [14] was readily prepared in good yield by reaction of the disodium salt of 3-thiapentane-l, 5-diol . The latter must be the dithiol rather than the diol. 

The amount of ammonia volatilized was determined from the amount of standard sulfuric acid consumed in the traps. Ethylenediamine was determined by the salicylaldehyde method (14). The sample for cobalt(II) determination was made slightly acidic with hydrochloric acid immediately upon removal of the sample from the reaction flask, in order to prevent further oxidation of the cobalt (18). The carbon was removed by filtration, and the cobalt (II) concentration was determined spectrophotometrically as the cobalt-ammonium thiocyanate complex, (NH4)2Co(NCS)4 (28). 

Macrocycles with 2 nitrogen and 3 sulfur donors have been prepared (14) by a template synthesis in which the dialdehyde (XCI) is condensed with primary diamines, e.g., ethylenediamine gives XCII in boiling acetonitrile containing Fe(II) perchlorate. The reaction is typical of template condensation between carbonyl compounds and primary amines. An unusual monanionic macrocyclic ligand was produced (2) when formaldehyde was condensed with the hydrazine (XCIII) instead of a primary amine in the presence of Ni(II) salts, and complexes XCIV have been characterized. 

A few reports involving copper-mediated substitution of selenophenes with heteroatoms (N, S) have appeared. The preparation of 2-amidoselenophenes (e.g., 48) was accomplished by treating 45 with amides in the presence of copper(l) iodide and ethylenediamine <2006JOC1552>. A similar copper-mediated reaction involving thiols was utilized to prepare sulfur-substituted selenophenes (e.g., 49) <2005TL2647>. 

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