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Nitrosation of Enols01:19

Nitrosation of Enols

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The nitrosation reaction is one of the methods of preparing 1,2-diketones. The enol tautomer of the starting ketone reacts with sodium nitrite in hydrochloric acid, generating the 1,2-diketone after hydrolysis.
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The presence of electron-donating, electron-withdrawing, or conjugating groups adjacent to a radical center, imparts electronic stabilization to the radicals. Examples of such electronically-stabilized radicals are triphenylmethyl, tetramethylpiperidine‐N‐oxide, and 2,2‐diphenyl‐1‐picrylhydrazyl. These radicals are remarkably stable and are known as persistent radicals. Some of the persistent radicals can even be isolated and purified.
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Insensitive Nuclei Enhanced by Polarization Transfer (INEPT) is an advanced Nuclear Magnetic Resonance (NMR) technique specifically designed to detect and enhance the signals of low-abundance nuclei, such as carbon-13 and nitrogen-15, in small molecules. The fundamental principle behind INEPT is the transfer of polarization from a more abundant and highly polarizable nucleus, typically hydrogen-1, to the low-abundance nucleus of interest. This process effectively boosts the NMR signal of the...
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Nitrous acid is a relatively weak and unstable acid prepared in situ by the reaction of sodium nitrite and cold, dilute hydrochloric acid. In an acidic solution, the nitrous acid undergoes protonation when it loses water to form a nitrosonium ion—an electrophile. Nitrous acid reacts with primary amines to give diazonium salts. The reaction is called diazotization of primary amines.
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Many organic, inorganic, and biological molecules contain spin-half nuclei such as nitrogen-15, fluorine-19, and phosphorus-31. As a result, NMR studies of these nuclei have found extensive applications in chemical and biological research.
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Ziegler–Natta polymerization is another form of addition or chain‐growth polymerization used for synthesizing linear polymers over branched polymers. The catalyst used for polymerization is the Ziegler–Natta catalyst, named after Karl Ziegler and Giulio Natta, who developed it in 1953. This catalyst is an organometallic complex of titanium tetrachloride and triethyl aluminum, with the active form of the catalyst being an alkyl titanium compound. Using the Ziegler–Natta...
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Pressure-induced nitrogen-rich GeN20 with pentazolate units.

Lulu Liu1,2, Shoutao Zhang3, Dinghui Wang4

  • 1School of Electronic Engineering, Nanjing Xiaozhuang University, Nanjing 211171, China.

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|May 15, 2025
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Researchers discovered Ge(N5)4, a novel high-energy material. This germanium-nitrogen compound exhibits exceptional stability and energy density, comparable to TNT, with environmentally friendly detonation products.

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Area of Science:

  • Materials Science
  • Computational Chemistry
  • Inorganic Chemistry

Background:

  • Polynitride compounds are of significant interest due to their unique nitrogen structures and high energy densities.
  • Metal-bearing nitrogen-rich compounds, particularly those containing the pentazolate anion (cyclo-N5-), are highly sought after for research and applications.

Purpose of the Study:

  • To explore the germanium-nitrogen system under high pressure using computational methods.
  • To design and identify novel, stable, high-energy density materials based on nitrogen-rich compounds.

Main Methods:

  • Comprehensive first-principles structure search simulations were employed to investigate the germanium-nitrogen system at high pressure (49 GPa).
  • The stability of the predicted material was assessed through dynamic, mechanical, and thermal stability analyses.

Main Results:

  • A previously unknown unconventional stoichiometric material, GeN20, was identified, predicted to be stable at 49 GPa.
  • The compound Ge(N5)4, featuring the cyclo-N5- anion, was discovered, stabilized by strong covalent N-N bonds and charge transfer from Ge to N.
  • Ge(N5)4 exhibits high energy density (4.1 kJ g-1), high detonation pressure (619 kbar), and high explosion velocity (11.42 km s-1), surpassing TNT, with environmentally friendly detonation products. It also possesses an indirect bandgap of 3.0 eV, indicating potential optical properties.

Conclusions:

  • The computational discovery of Ge(N5)4 demonstrates the feasibility of synthesizing novel, high-performance energetic materials through rational design.
  • The predicted stability and superior energetic properties of Ge(N5)4 suggest its potential for future applications.
  • These findings provide valuable insights for the design and synthesis of advanced nitrogen-based functional materials.