Dithiooxamide, reaction with

In addition to stabilizing organic products by reaction with metal-exchanged clays, as indicated above, aluminosilicate minerals may enable the preparation of metal organic complexes that cannot be formed in solution. Thus a complex of Cu(II) with rubeanic acid (dithiooxamide) could be prepared by soaking Cu montmorillonite in an acetone solution of rubeanic acid (93). The intercalated complex was monomeric, aligned with Its molecular plane parallel to the interlamellar surfaces, and had a metal ligand ratio of 1 2 despite the tetradentate nature of the rubeanic acid. 

Heating of dithiooxamide (26) with primary amines yields the corresponding iV-alkyl derivatives (27) the reaction is catalyzed by acid with even CO2 being effective (equation 15). ... 

Diaminofurazan (DAF) (24) is a starting material for the synthesis of many nitro-substituted furazans and is readily prepared from the cyclization of 1,2-diaminoglyoxime (23) in the presence of aqueous base under pressure at 180 °C the latter prepared from the reaction of glyoxal/ glyoxime/ cyanogen or dithiooxamide with hydroxylamine. 

The only recorded complex is the product of composition UF4 SC3N2H2 which results from the reaction of UF6 with dithiooxamide.137... 

The reaction of dithiooxamide and its tetramethyl and tetraethyl derivatives with zinc, cadmium and mercury halides leads to complexes of stoichiometry MLX2 (M = Zn, Cd or Hg X = C1, Br or I).900,9 1 M—S bonding is involved IR spectra show that the zinc and mercury complexes are four-coordinate, while the cadmium complexes are octahedral with halogen bridges. 

The condensation product of dithiooxamide with benzaldehyde has been shown to be 2,5-diphenylthiazolo[5,4-d]thiazole (equation 75) (60JA2719). Its formation involves dehydration of the reactants and further dehydrogenation. The reaction is comparable in scope with condensations such as the Perkin reaction, and many 2,5-diarylthiazolo[5,4-c ]thiazoles have been prepared from a variety of aryl aldehydes. Condensation products were not obtained from simple aliphatic aldehydes (71JMC743). 

Preparation of polymers from dithiooxamide 22 In a three-necked 100 mL flask, equipped with a reflux condenser and a glass inlet tube, a mixture of cobalt chloride hexahydrate (2.38 g, 0.01 mol) in 20 mL ethanol and dithiooxamide 22 (1.2 g, 0.01 mol) in 20 mL ethanol and 5 mL DMSO were added and stirred at 70-80 °C, under a thin stream of nitrogen gas, for 24 h. At the end of the reaction, the mixture was poured into 300 mL of distilled water. The dark powdery precipitated polymer complex was filtered by suction in a Buchner funnel, washed thoroughly five times with hot distilled water, twiee with diethyl ether and then dried under vacuum at 40 °C for 24 h. The light-brown polymerie eobalt complexes were obtained in a yield of 87%. IR (KBr) -1300-1390 (C-N), -1080-1170 (C=S) cm". ... 

Hglj dissolved in dimethylformamide reacts with triphenylphosphine and, according to the spectrophotometric experiments, at least three different complexes are formed. Similarly complex formation was observed with o-phenantroline, dipyridyl, 8-hydroxyquinoline and dithiooxamide. The quantitative study of these reactions is in progress. 

A few examples of early coordination polymerizations are noted here to provide a flavor for this work. The reaction of Cu(II) with dithiooxamides, reported by Kanda in 1962, gives a three-dimensional (3D) insoluble material (10) that has the catana-p, -(A(Ar -disubstituted dithiooxamido)copper stmcture." ... 

A structure containing four-membered chelate rings [7] was first proposed for these polymers 15), but was soon discarded by subsequent workers 11, 22) who favored the five-ring structure [8]. The most recent work on the structure of copper rubeanate indicates that it possesses a three-dimensional structure 16, 30). A solid-solid reaction between dithiooxamide and copper(II) bis(8-hydroxyquinolinate) yielded a product that was fractionated into several different crystalline fractions. A detailed study of the infrared, magnetic and electrical properties of these products supported structures [11] and [12], They differ in that [11] has copper atoms in both directions, whereas, the copper atoms of [12] are all in one plane. The reaction of copper with rubeanic acid has been patented as the basis of a photocopying process 13). 

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