Diaminomaleonitrile Research Articles

The syntheses of pteridin‐2‐one derivatives from diaminomaleonitrile (DAMN)

Abstract1,3‐Dimethyl‐4‐iminopteridin‐2‐one, 1,3‐dimethylpteridine‐2,4‐dione, 1‐methylpteridine‐2,4‐dione, 4‐alkoxy‐1‐methylpteridin‐2‐one, and 4‐alkylamino‐1‐methylpteridin‐2‐one were synthesized from diaminomaleonitrile (DAMN) through pyrazine‐2,3‐dicarbonitrile. The synthetic procedures consist of the condensation of DAMN with glyoxal, the nucleophilic substitution of pyrazine‐2,3‐dicarbonitrile with methylamine, the reaction of 3‐methylaminopyrazine‐2‐carbonitrile with electrophiles such as methyl isocyanate and methyl chloroformate in the presence of sodium hydride, and the transformation of 3‐(methoxycarbonylmethyl)aminopyrazine‐2‐carbonitrile into the pteridine derivatives.

The adsorption and reaction of adenine nucleotides on montmorillonite.

The binding of AMP to Zn(2+)-montmorillonite was investigated in the presence of buffers and salts. Good's buffers, piperazine-N,N'-bis(2-ethanesulfonate) [PIPES] and morpholine-N-2-ethanesulfonate [MES], perturbed the exchangeable cations to a lesser extent (only 9% of Zn2+ displaced by 0.2 M buffer) than was observed with imidazole and lutidine buffers or NaCl and KCl salts (up to 80% of Zn2+ displaced). AMP adsorption isotherms measured in the presence of 0.2 M PIPES, MES, or Na2SO4 exhibited normal Langmuir-type behavior. The adsorption coefficient, KL, is 3-fold greater in the presence of HEPES or PIPES than it is in the absence of buffers. Basal spacings measured by X-ray diffraction for Zn(2+)-montmorillonite are 13 and 15 angstroms in the presence of PIPES, while a value of 12.8 angstroms was determined in the absence of PIPES. These data are interpreted in a model in which the adsorption of AMP is mediated by a Zn2+ complex of PIPES in different orientations in the interlamellar region of the montmorillonite. The type of exchangeable cation does not affect the ability of the lattice-bound Fe3+ in the montmorillonite to oxidize diaminomaleonitrile (DAMN). Exchangeable Cu2+ oxidizes DAMN, but exchangeable Fe3+ is nearly ineffective as an oxidant. The addition of DISN to 3'-AMP bound to Zn(2+)-montmorillonite in the presence of 0.2 M PIPES resulted in a higher yield of 2',3'-cAMP than is observed with a comparable concentration of Zn2+, a result which inplicates surface catalysis by the montmorillonite.

Liberation of hydrogen cyanide from diaminomaleonitrile by Trichoderma sp. MB 519.

A fugus which utilizes diaminomaleonitrile (DAMN) as a source of nitrogen was isolated from soil, and identified as a strain belonging to the genus Trichoderma. The strain degraded DAMN and accumulated several fluorescent metabolites. The intact mycelia and a cell-free extract of the strain formed hydrogen cyanide and ammonia from DAMN, besides the same fluorescent compounds, as metabolites. The enzyme catalyzing the liberation of hydrogen cyanide from DAMN was partially purified and its properties were investigated. From the results, the enzyme was found to catalyze the liberation of hydrogen cyanide from DAMN but not the formation of ammonia from DAMN, and its substrate specificity was very narrow; it reacts only with DAMN of the compounds so far examined.

The prebiotic chemistry of nucleotides.

Diiminosuccinonitrile (DISN), formed by the oxidation of diaminomaleonitrile (DAMN), has been investigated as a potential prebiotic phosphorylating agent. DISN effects the cyclization of 3'-adenosine monophosphate to adenosine 2', 3'-cyclic phosphate in up to 39% yield. The mechanism of this reaction was investigated. The DISN-mediated phosphorylation of uridine to uridine monophosphate does not proceed efficiently in aqueous solution. The reaction of DISN with uridine-5'-phosphate and uridine results in the formation of 2,2'-anhydronucleotides and 2,2'-anhydronucleosides respectively, and other reaction products resulting from an initial reaction at the 2'- and 3'- hydroxyl groups. The clay mineral catalysis of the cyclization of adenosine-3'-phosphate was investigated using homoionic montmorillonites.

Prebiotic synthesis and reactions of nucleosides and nucleotides

Diiminosuccinonitrile (DISN) has been investigated as a potential prebiotic phosphorylating agent. It is formed readily by the oxidation of diaminomaleonitrile (DAMN), a tetramer of HCN, DISN effects the cyclization of 3′-adenosine monophosphate to adenosine 2′,3′-cyclic phosphate in up to 40% yield. The DISN-mediated phosphorylation of uridine to uridine monophosphate does not proceed efficiently in aqueous solution. The reaction of DISN and BrCN with uridine-5′-phosphate and uridine results in the formation of 2,2′-anhydronucleotides and 2,2′-anhydronucleosides respectively, and other reaction products resulting from an initial reaction at the 2′- and 3′-hydroxyl groups. The clay mineral catalysis of the cyclization of adenosine-3′-phosphate was investigated using homoionic montmorillonites.

Chemical evolution 40. Clay-mediated oxidation of diaminomaleonitrile.

The previously reported inhibition of the oligomerization of HCN by montmorillonite clays was investigated. The inhibition is due to the oxidation of diaminomaleonitrile (DAMN) by the Fe3+ in the clay lattice. Fe2+ and oxalic acid were shown to be the reaction products. From these reaction products and the previous report that two equivalents of HCN are formed per equivalent ofDAMN, it was established that diiminosuccinonitrile (DISN) is the initial reaction product, which is rapidly hydrolyzed to oxalic acid and HCN. The same oxidative transformations are effected by Fe3+ bound to Dowex 50, Fe3+ in solution and Ni(NH3)62+. The rate of reaction of DAMN decreased in the order Fe3+ > Fe3+-Dowex > montmorillonite, indicating no catalytic role for the clay in the oxidation of DAMN. Little reaction of DAMN was observed with montmorillonite in which the bulk of the iron was in the Fe2+ oxidation state. The possible significance of these redox reactions to chemical evolution is discussed.

ChemInform Abstract: GENERAL SYNTHESIS OF IMIDAZOLE C‐NUCLEOSIDES FROM CARBOHYDRATE ADDUCTS OF DIAMINOMALEONITRILE

AbstractAus den Maleonitrilen (I) erhält man die Imidazole (II), von denen (IIa) zu (III) cyclisiert wird.

Synthesis of pyrazinedicarboximides from diaminomaleonitrile.

Synthesis of pyrazinedicarboximides from diaminomaleonitrile.

The effect of clays on the oligomerization of HCN

The reaction of 0.1 M HCN and dilute solutions of diaminomaleonitrile (DAMN) at pH 8--9 and 25 degrees C in the presence of suspensions of montmorillonite (bentonite) clays were investigated. Montmorillonite clays inhibit the oligomerization of aqueous solutions of HCN. Yields of colored oligomers, ura, and DAMN, are all diminished by clays, but the rate of loss of cyanide is not significantly decreased. The inhibition of oligomer formation is due to the clay-catalyzed decomposition of DAMN. The absence of strong binding of DAMN to clays was suggested by our failure to detect DAMN when a clay that had been incubated with DAMN was washed with spermidine (6 x 10(-3) g/liter). It was established that DAMN does not simply bind to the clays by the observation that the bulk of the radioactivity was recovered from the supernatant in the reaction of 14C-DAMN with montmorillonite. The clay-catalyzed decomposition of DAMN was observed when montmorillonite from two different sources was used and with a variety of homoinic montmorillonites and bentonites. A modification of the established procedure for using the cyanide electrode for cyanide analyses was used to follow the release of HCN from DAMN. This new method can be used in both the acidic and basic pH range and it does not result in the destruction of DAMN by the reagents used for the analysis. Quantitative analyses of the reaction solution from the clay-catalyzed decomposition of DAMN revealed the formation of 1--2 equivalents of HCN per mole of DAMN. The possible significance of these clay-catalyzed reactions in chemical evolution is discussed.

Chemistry of diaminomaleonitrile. 5. Dihydropyrazine synthesis

Chemistry of diaminomaleonitrile. 5. Dihydropyrazine synthesis

Studies on the polymerization of vinyl compounds in the presence of metal salts, 13. Polymerization of methyl methacrylate initiated by diaminomaleonitrile (DAMN)/copper ion/carbon tetrachloride

AbstractThe polymerization of methyl methacrylate initiated by the system diaminomaleonitrile (DAMN)/copper ion/carbon tetrachloride was investigated. The polymerization requires the presence of these three components, and both the cupric and the cuprous ion are suitable. The initial rate of polymerization with the cuprous ion is greater than that with the cupric ion. The cuprous ion was detected in both systems. It is considered that the cupric ion is reduced to the cuprous ion by DAMN, and the cuprous ion takes part in the initiation of the polymerization.

Diaminomaleonitrile (DAMN) に関する研究

These experiments were carried out to study the properties of a plant growth regulator, Diaminomaleonitrile (DAMN).(1) It was apparently recognized that the growth of herbaceous cutting of chrysanthemum was stimulated by treatmant of 24 hourss at 50 to 100 ppmw water solution of DAMN, for such a kind of Gay Anne (American potmum species). And, under conditions both of water cultivation and propagation bed, such as vermiculite plus river sand, the growth effect was shown to be the same as β-IAA or α-NAA, on the root numbers, rooted stamp numbers, root length, root weight and leaf fresh weight.(2) The most adequate concentrations due to the treatment for 24 hours of DAMN water solution for many kinds of chrysanthemum were 25 to 100 ppmw to Gay Anne, Otomezakura (lemon yellow) and Beniotome (violet), 25 ppmw to Ryunotama, 50 to 100 ppmw to Soannoaki, Otomezakura (white) and Shimizunokagayaki, 50 ppmw to Unzen and 100 ppmw to Whitealps.(3) When the talc formulation is treated for chrysanthemum herbaceous cutting, the most effective DAMN concentration is 0.25 to 0.5 percent in active ingredient.(4) The root growth of chrysanthemum herbaceous cutting accelerated particularly in several propagation beds. And the descending order of the effect among them was shown as river sand=Kanuma soil>vermiculite>river sand plus vermiculite.(5) The root growth of chrysanthemum herbaceous cutting was examined by using many DAMN formulations. The most adequate carrier were zeeklite, clay (comercial name is Fubasami clay) and talc. Besides, the formulations of perlite and kaolin were fairly good.(6) When the root of chrysanthemum herbaceous cutting was grown by DAMN talc formulation, the most effective treatment length was the range of 1 to 2cm from cutting section.(7) The chrysanthemum herbaceous cutting treated by DAMN talc formulation, begins the rooting 10 days after treatment. It was assumed that the adequate transplanting time is on the 27 to 34 days after placing in propagation bed.

青酸化学最近の進歩 ＤＡＭＮの化学とその利用

Contents ;1. The Structure and Reactivity.The stability of DAMN (diaminomaleonitrile) and its derivatives was discussed from the conjugation between the nitrogene lone pairs and the π-electron systems. The reactivity of these compounds was explained in terms of the product stability.2. The Synthesis of Derivatives.2.1. Open-chain compounds. 2.2. Imidazole derivatives.2.3. Pyrazine derivatives. 2.4. Diazepine derivatives.2.5. Purine derivatives. 2.6. Other heterocycles.

Reaction of diaminomaleonitrile with acetaldehyde

Reaction of diaminomaleonitrile with acetaldehyde

Polymers from intermediates obtained from hydrogen cyanide

AbstractThe recent demonstration of an easy synthesis of diiminosuccinonitrile (DISN) from hydrogen cyanide and cyanogen, the reduction of DISN to diaminomaleonitrile (DAMN), and the use of these compounds to form difunctional heterocycles has made several new polyamide intermediates accessible. The 1‐ and 2‐methyl‐1,2,3‐triazole‐4,5‐dicarbonyl chlorides have been polymerized interfacially to form high‐melting polyamides of good heat stability. Interfacial polymerization of 1‐methylimidazole‐4,5‐dicarbonyl chloride and trans‐2,5‐dimethylpiperazine has given a polyamide that is water‐soluble. The 2,6‐ and 2,3‐pyrazinedicarbonyl chlorides have been similarly converted to high‐melting polyamides. 2,6‐Dicyano‐3,5‐dipiperazinylpyrazine has been prepared from tetracyanopyrazine and piperazine and reacted with toluene diisocyanate to form a strong, stiff polyurea. Polyamides were also made from 2,3‐diaminoquinoxaline, 1,4,5,6‐tetrahydro‐5,6‐dioxo‐2,3‐pyrazinedicarbonitrile, and DAMN.

Synthesis ofN-Substituted Diiminosuccinonitrile (DISN) and Diaminomaleonitrile (DAMN) Derivatives

Synthesis of<i>N</i>-Substituted Diiminosuccinonitrile (DISN) and Diaminomaleonitrile (DAMN) Derivatives

Complexes of diaminomaleonitrile with nickel, palladium and platinum, and the crystal structure of bis-(diaminomaleonitrile)dichloropalladium

Diaminomaleonitrile (DMN) reacts with Pd II and Pt II in acidic solution to give the complexes [ M(DMN) 2Cl 2], ( M = Pd, Pt). A single crystal X-ray study has been made of the Pd complex. The crystals are monoclinic with unit cell parameters, a = 7·41, b = 7·89, c = 12·25 A ̊ , β = 102·8° . The spacegroup is P2 1 a and there are two centrosymmetric molecules per cell. The complex has the expected square planar geometry, with monodentate DMN ligands coordinating through one amine group. The possibility of further interaction between the metal atom d orbitals and the ligand π-system is discussed. In basic or neutral solutions, DMN react with Ni II, Pd II and Pt II to give the highly coloured complexes [ M(C 4H 2N 4) 2]. With [Pt 0(Ph 3P) 4], DMN forms the complex [Pt(Ph 3P) 2C 4H 2N 4]. The structures of these complexes are discussed.