Hydrogen cyanide chemistry. IV. Diiminosuccinonitrile reactions with nucleophiles, acyl halides, and carbonyl compounds

Begland, Robert W.; Hartter, Donald R.

doi:10.1021/jo00798a038

Cited by 67 publications

(10 citation statements)

References 10 publications

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“…14 The reaction conditions provide an overall dehydrogenating and oxygenating environ-ment. For the formation of the main products 9a-d, an initial didehydrogenation of the starting materials 8a-d to the fully unsaturated 2H-pyrrolo [3,4-b]quinoxalines 12 seems to be most logical.…”

Section: Resultsmentioning

confidence: 99%

Novel dicyanomethylene compounds from the reaction of 2-aryl-2,3-dihydro-1H-pyrrolo[3,4-b]quinoxalines with ethenetetracarbonitrile

Hassan¹,

El‐Shaieb²,

Döpp³

2005

Arkivoc

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Section: Resultsmentioning

confidence: 99%

Novel dicyanomethylene compounds from the reaction of 2-aryl-2,3-dihydro-1H-pyrrolo[3,4-b]quinoxalines with ethenetetracarbonitrile

Hassan¹,

El‐Shaieb²,

Döpp³

2005

Arkivoc

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“…[35] 2,3-Dicyanoquinoxaline was synthesized by condensation of DISN and o-phenylenediamine according to ref. [36] 2,3-Dicyanoquinoxaline (1 g, 5.6 mmol) was added to solution of n-butanol (50 mL) with dissolved magnesium (140 mg, 5.8 mmol) (dissolution was initiated by iodine crystal) and the stirred mixture was refluxed for 6 h. Solvent was evaporated under reduced pressure. After this the obtained Mg II complex was demetallated by dissolution in CF 3 COOH (15 mL).…”

Section: Synthesismentioning

confidence: 99%

Molecular Structure, Optical and Magnetic Properties of Iron Tetra(2,3-quinoxalino)porphyrazine [(N-MeIm)2FeI{T(2,3-Q)Pz}•3-]}•2- Radical Dianions

Faraonov¹,

Romanenko²,

Kuźmin³

et al. 2019

MHC

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Iron(II) tetra(2,3-quinoxalino)porphyrazine, Fe II T(2,3-Q)Pz, was obtained using diaminomaleonitrile and o-phenylenediamine as starting materials. Reduction of Fe II T(2,3-Q)Pz by sodium fluorenone ketyl in the presence of cryptand[2.2.2] and N-methylimidazole followed by precipitation of crystals leads to crystalline salt {cryptand[2.2.2](Na +)} 2 ⋅[(N-MeIm) 2 Fe I {T(2,3-Q)Pz} •3-] •2-⋅3C 6 H 4 Cl 2 ⋅2H 2 O (1). Molecular structure and properties of the [(N-MeIm) 2 Fe I {T(2,3-Q)Pz} •3-] •2radical dianions have been studied. Reduction of Fe II T(2,3-Q)Pz is accompanied by strong blue shift of Soret band in spectrum of 1 but Q-band has close position to that in the spectrum of neutral macrocycle. There is an alternation of the C-N meso bonds in the macrocycle in 1, the difference between short and long C-N meso bonds of 0.017 Ȧ supports the formation of radical trianionic T(2,3-Q)Pz •3macrocycle. Coordination of N-methylimidazole molecules to iron (I) atoms with the Fe-N(imidazole) distance of 1.999(7) Ȧ is observed. Both Fe I atom and radical trianionic {T(2,3-Q)Pz} 3•macrocycle contribute to the EPR signal of 1, which is well interpreted as the superposition of Lorentzian shaped lines with g 1 = 2.0917, g 2 = 2.0679, g 3 = 2.0292, g 4 = 1.9991 and g 5 = 1.9922. The lines with higher g-factor (g 1 and g 2) value can be attributed to low spin (S = 1/2) Fe I whereas the lines with lower g-factor (g 4 and g 5) values can be attributed to the radical trianionic {T(2,3-Q)Pz} •3macrocycle. The line with intermediate g-factor value (g 3) can originate from the contribution of both components. The value of effective magnetic moment at 300 K (2.32 µ B) indicates a contribution of two non-interacting S = 1/2 spins from iron(I) atoms and radical trianionic {T(2,3-Q)Pz} •3macrocycle. These spins weakly antiferromagnetically interact with Weiss temperature of-3 K.

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“…The competing hydrolysis [ 15] and self-condensation [ t 4, 39] of DISN would have to have been suppressed if it effected the condensation of nucleotides on the primitive Earth. This may have occured by the constant synthesis of a low concentration of DISN in an environment where the nucleotide concentration was comparable to or greater than that of water.…”

Section: Disn and Prebiotic Synthesismentioning

confidence: 99%

“…The rapid reaction of DISN with nucleophiles [15] suggests that its reaction with phosphate and carboxylate derivatives would yield 1 and 3 respectively (Scheme I), imino analogs of mixed anhydrides, compounds that would condense readily with amino or hydroxyl groups to give phosphodiester (_2), peptide (4_) and pyrophosphate links. The present study describes our initial experiments which test this hypothesis.…”

Section: Introductionmentioning

confidence: 99%

The investigation of the hcn derivative diiminosuccinonitrile as a prebiotic condensing agent. The formation of phosphate esters

Ferris

Yanagawa

Dudgeon

et al. 1984

Origins Life Evol Biosphere

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Diiminosuccinonitrile (DISN) is formed readily by the Fe3+ oxidation of diaminomaleonitrile, a tetramer of HCN. DISN effects the phosphorylation of uridine in 13% yield to a mixture of the isomers of UMP when the reaction is performed in dimethylformamide solution. A 4% yield of the UMP isomers is obtained in neutral aqueous solution using 2 times the DISN concentration and 7 times the phosphate concentration used in DMF. DISN did not effect the conversion of adenosine to AMP or 5'-AMP to 5'-ADP in aqueous solution. The cyclization of 3'-AMP and 3'-UMP to the corresponding 2'-3'-cyclic phosphates proceeds in yields as high as 40-50% at 60 degrees C in pH 6 aqueous solutions in the presence of divalent metal ions. Lower yields of the cyclic phosphate are observed when 2'-AMP is the starting material. Substitution of acetate buffer for imidazole buffer results in a decrease in the yield of cyclic phosphate, the extent of which depends on the metal ion used in the reaction. No 3'5'-cyclic AMP was detected as a reaction product with either 5'-AMP or 3'-AMP as the starting material except for a 2.4% yield from 3'-AMP in the presence of Zn2+. BrCN effects the conversion of 3'-AMP to the 2'-3'-cyclic AMP in 37-65% yield depending on the divalent cation used as catalyst. A mechanism has been proposed for these cyclization reactions and their potential significance to the prebiotic synthesis of ribonucleic acid derivatives is discussed.

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Hydrogen cyanide chemistry. IV. Diiminosuccinonitrile reactions with nucleophiles, acyl halides, and carbonyl compounds

Cited by 67 publications

References 10 publications

Novel dicyanomethylene compounds from the reaction of 2-aryl-2,3-dihydro-1H-pyrrolo[3,4-b]quinoxalines with ethenetetracarbonitrile

Novel dicyanomethylene compounds from the reaction of 2-aryl-2,3-dihydro-1H-pyrrolo[3,4-b]quinoxalines with ethenetetracarbonitrile

Molecular Structure, Optical and Magnetic Properties of Iron Tetra(2,3-quinoxalino)porphyrazine [(N-MeIm)2FeI{T(2,3-Q)Pz}•3-]}•2- Radical Dianions

The investigation of the hcn derivative diiminosuccinonitrile as a prebiotic condensing agent. The formation of phosphate esters

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