The Trimerization of Nitriles at High Pressures

Cairns, T. L.; Larchar, A. W.; McKusick, B. C.

doi:10.1021/ja01142a028

Cited by 76 publications

(20 citation statements)

References 3 publications

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“…It is known that the s ‐triazine structure can be formed by cyclotrimerization of the nitrile groups at high temperature (>350 °C) and high pressure (35,000–50,000 atm. ), or simply in molten ZnCl 2 at 400 °C in a sealed tube . Also, it has been shown under thermosetting conditions that aromatic nitrile can readily engage in a Diels‐Alders reaction at lower temperatures with a reactive dienophile such as o ‐quinodimethane generated from benzocyclobutene at ∼200–250 °C .…”

Section: Resultsmentioning

confidence: 99%

Synthesis and characterization of high nitrile content polyimides as dielectric films for electrical energy storage

Wang

Kurish

Treufeld

et al. 2014

J. Polym. Sci. Part A: Polym. Chem.

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Three new isomeric diamines containing three, oxylinked benzonitriles (3BCN), one of which is asymmetric (meta, para, or m, p), are synthesized in a 3-step sequence. Polycondensation of these diamines and four common dianhydrides (6FDA, OPDA, BTDA, and PMDA) in N,N-dimethylacetamide via poly(amic acid) precursors and thermal curing at temperatures up to 300 C lead to three series of tough, creasable polyimide (PI) films (tensile moduli 5 1.63 2 2.86 GPa). Among these PIs, two PMDA-based PIs possess relatively high crystallinity and two OPDA-based PIs, low crystallinity, whereas all 6FDA-and BTDA-based PIs, and m,m-3BCN-OPDA-PI are amorphous, readily soluble in common polar aprotic solvents. Thermally stable and having high T g (216 2 341 C), these PIs lose 5% weight around 493-503 C in air and 463-492 C in nitrogen. Dielectric properties have been evaluated by broadband dielec-tric spectroscopy (BDS) and electric displacement-electric-field (D-E) loop measurements. D-E loop results show an increase in high temperature permittivity (at 190 C/1 kHz) from 2.9 (for parent PI CP2 with no nitrile group) to as high as 4.9 for these PIs, while keeping their dielectric loss relatively low. Thus, an increase in dipole moment density by the presence of three neighboring CN per repeat unit can increase the overall permittivity, which could be further enhanced by sub-T g mobility of para-phenylene linkages (BDS results). Published 2014. † J. Polym. Sci., Part A: Polym. Chem. 2015, 53, 422-436

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Section: Resultsmentioning

confidence: 99%

Synthesis and characterization of high nitrile content polyimides as dielectric films for electrical energy storage

Wang

Kurish

Treufeld

et al. 2014

J. Polym. Sci. Part A: Polym. Chem.

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“…The first literature reference to the latter compound is over 106 years old;13 however, to the best of our knowledge, it has never been prepared. It is possible that 3 could be formed from NCNO 2 in a manner analogous to the known trimerization of other nitriles 14. Compound 3 has previously been predicted to be a powerful HEDM with a density of 1.99 g cm −3 15.…”

Section: Fundamental Vibrational Modes Of Nitryl Cyanidementioning

confidence: 99%

Nitryl Cyanide, NCNO₂

2014

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The elusive nitryl cyanide, NCNO2, has been synthesized and characterized. It was prepared in good yield, isolated by fractional condensation, characterized by NMR and vibrational spectroscopy, and studied by theoretical calculations. Nitryl cyanide holds promise as a high energy density material (HEDM) and might also prove useful as a HEDM building block. The simplicity and inherent stability of nitryl cyanide, together with the known multitude of nitriles in interstellar space, suggest that the compound might also be a potential candidate for observations in atmospheric and interstellar chemistry.

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“…A trimerization process involving three cyanide groups from different dicyanamide ions to form a tricyanomelaminate ring was reported in some nitride compounds [72][73][74]. The behavior of LiN(CN) 2 under high pressure was studied by Raman spectroscopy, infrared spectroscopy and XRD [75].…”

Section: Cyanidementioning

confidence: 99%

“…(f) Neutron PDF (G(r)) of K3Fe(CN)6 recovered from different pressures. (g) Phase transition and chemical reaction process of K3Fe(CN)6 under high pressure [71].A trimerization process involving three cyanide groups from different dicyanamide ions to form a tricyanomelaminate ring was reported in some nitride compounds[73][74][75]. The behavior of LiN(CN)2 under high pressure was studied by Raman spectroscopy, infrared spectroscopy and XRD…”

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confidence: 99%

From Molecules to Carbon Materials—High Pressure Induced Polymerization and Bonding Mechanisms of Unsaturated Compounds

Yang

Wang

et al. 2019

Crystals

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With the development of high-pressure apparatus, in situ characterization methods and theoretical calculations, high-pressure technology becomes a more and more important method to synthesize new compounds with unusual structures and properties. By compressing compounds containing unsaturated carbon atoms, novel poly-ionic polymers, graphanes and carbon nanothreads were obtained. Their compositions and structures were carefully studied by combining multiple cutting-edge technologies, like the in situ high-pressure X-ray and neutron diffraction, transmission electron microscopy, pair distribution function, solid-state nuclear magnetic resonance and gas chromatography-mass spectroscopy. The reaction mechanisms were investigated based on the crystal structure at the reaction threshold pressure (the pressure just before the reaction taking place), the long-range and short-range structure of the product, molecular structure of the intermediates, as well as the theoretical calculation. In this review, we will summarize the synthesis of carbon materials by compressing the unsaturated compounds and its reaction characteristics under extreme conditions. The topochemical reaction mechanism and related characterization methods of the molecular system will be highlighted. This review will provide a reference for designing chemical reaction and exploring novel carbon materials under high-pressure condition.

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The Trimerization of Nitriles at High Pressures

Cited by 76 publications

References 3 publications

Synthesis and characterization of high nitrile content polyimides as dielectric films for electrical energy storage

Synthesis and characterization of high nitrile content polyimides as dielectric films for electrical energy storage

Nitryl Cyanide, NCNO₂

From Molecules to Carbon Materials—High Pressure Induced Polymerization and Bonding Mechanisms of Unsaturated Compounds

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The Trimerization of Nitriles at High Pressures

Cited by 76 publications

References 3 publications

Synthesis and characterization of high nitrile content polyimides as dielectric films for electrical energy storage

Synthesis and characterization of high nitrile content polyimides as dielectric films for electrical energy storage

Nitryl Cyanide, NCNO2

From Molecules to Carbon Materials—High Pressure Induced Polymerization and Bonding Mechanisms of Unsaturated Compounds

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Nitryl Cyanide, NCNO₂