The Mechanism of the Reaction of C-Nitroso-compounds with Alkenes

Kogan, L. M.

doi:10.1070/rc1986v055n12abeh003249

Cited by 8 publications

(6 citation statements)

References 2 publications

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“…We were not able to intercept the nitrosoarene derived from 1 a by addition of a conjugated diene to the reaction mixture. However, this is not surprising because of the high reactivity of nitrosoarenes with olefins [40] and the higher rate of intra ‐molecular reactions with respect to inter ‐molecular ones. As a matter of fact, all previous attempt to obtain o ‐nitrosostyrenes met with failure [3d,41] …”

Section: Resultsmentioning

confidence: 99%

Synthesis of Indoles by Reductive Cyclization of Nitro Compounds Using Formate Esters as CO Surrogates

et al. 2021

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Alkyl and aryl formate esters were evaluated as CO sources in the Pd‐ and Pd/Ru‐catalyzed reductive cyclization of 2‐nitrostyrenes to give indoles. Whereas the use of alkyl formates requires the presence of a ruthenium catalyst such as Ru3(CO)12, the reaction with phenyl formate can be performed by using a Pd/phenanthroline complex alone. Phenyl formate was found to be the most effective CO source and the desired products were obtained in excellent yields, often higher than those previously reported using pressurized CO. The reaction tolerates many functional groups, including sensitive ones like a free aldehydic group or a pendant pyrrole. Detailed experiments and kinetic studies allow to conclude that the activation of phenyl formate is base‐catalyzed and that the metal doesn't play a role in the decarbonylation step. The reactions can be performed in a single thick‐walled glass tube with as little as 0.2 mol‐% palladium catalyst and even on a 2 g scale. The same protocol can be extended to other nitro compounds, affording different heterocycles.

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Section: Resultsmentioning

confidence: 99%

Synthesis of Indoles by Reductive Cyclization of Nitro Compounds Using Formate Esters as CO Surrogates

et al. 2021

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“…In particular, poly( trans -1,4-phenyleneazo- N , N ′-dioxide) has been used as a photosensitive resin and is widely employed as a vulcanizing agent in the cross-linking of rubber by nitroso–ene reactions . The generally accepted mechanism for cross-linking first involves thermolysis of the polymer to regenerate 1,4-dinitrosobenzene, followed by a nitroso–ene reaction and final dehydration of the resulting hydroxylamine. − …”

Section: Aromatic Dinitroso and Polynitroso Compoundsmentioning

confidence: 99%

Dimerization of Aromatic C-Nitroso Compounds

2016

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Aromatic C-nitroso compounds (Ar-N═O) and related species have a rich chemical history, and they continue to interest researchers in many fields. Among the most distinctive and puzzling properties of these compounds is their ability to dimerize reversibly to form azodioxy compounds. The present review subjects this intriguing phenomenon to comprehensive analysis. All aspects of the subject are examined in detail, including the structures of monomeric and dimeric forms, the mechanism of dimerization, features that favor or disfavor dimerization, thermodynamic and kinetic factors, dimerization under specific conditions (including in solution, in the solid state, and on surfaces), and the special associative behavior of dinitroso and polynitroso compounds. By summarizing the current state of knowledge, the review promises to spur further advances in the evergreen field of C-nitroso chemistry, including the discovery of new ways to exploit the reversible dimerization of nitrosoarenes.

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“…However, the data obtained from the IR spectra were not enough to determine the exact structure of the product of Stage A. Considering the references about the vulcanization of rubber with PDNB and the pathway of ene reaction, we proposed the chemical structure in Figure 8 as the most favorable structure for the crosslinking of the pre‐polymer 20–27…”

Section: Resultsmentioning

confidence: 99%

“…The first trial was to react PDNB with excess SO; however, the reaction rate was slower and considerable amount of SO remained unreacted. SO/PDNB ratios of 1/1, 1/1.3, and 1/1.5 were chosen 20–27…”

Section: Resultsmentioning

confidence: 99%

Synthesis and characterization of polymers from soybean oil and p‐dinitrosobenzene

Mutlu

Küsefoǧlu

2009

J of Applied Polymer Sci

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In this study, rubbery, bio-based thermoset polymers were synthesized from soybean oil (SO) and pdinitrosobenzene (DNB) via an ene reaction. Polymeric pdinitrosobenzene (PDNB) was synthesized from p-quinone dioxime and was thermally depolymerized in the presence of SO. SO/PDNB polymers were synthesized by a twostage polymerization. During the reaction, the role of different parameters such as mol ratio of SO and PDNB, preheating temperature of SO, polymerization time, and temperature were examined. Polymerization was followed by IR spectroscopy, and the polymers obtained were characterized by dynamic mechanical analysis, thermogravimetric analysis, and differential scanning calorimetry. The polymers have glass transition temperature ranging from À51.5 C to À46.3 C, whereas their storage moduli are between 430 and 210 MPa at À60C. Thermogravimetric analysis reveals that all of the polymers have temperatures of maximum degradation around 500 C. The crosslinked network structure of the polymers was investigated by swelling behavior and surface hardness test. Methyl oleate was used as a model compound to examine the chemical structure of the products.

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The Mechanism of the Reaction of C-Nitroso-compounds with Alkenes

Cited by 8 publications

References 2 publications

Synthesis of Indoles by Reductive Cyclization of Nitro Compounds Using Formate Esters as CO Surrogates

Synthesis of Indoles by Reductive Cyclization of Nitro Compounds Using Formate Esters as CO Surrogates

Dimerization of Aromatic C-Nitroso Compounds

Synthesis and characterization of polymers from soybean oil and p‐dinitrosobenzene

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