Methyl Isocyanide

Schuster, Ronald E.; Scott, J. E.; Casanova, Joseph

doi:10.1002/0471264180.os046.23

Cited by 18 publications

(18 citation statements)

References 4 publications

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“…This molecule, in its liquid form is much less stable than its isomer CH 3 CN. CH 3 NC was prepared using the synthesis of Schuster et al (1973) but with trioctylamine instead quinoline as the base, and had to be kept under nitrogen at low temperature (<273 K) and protected from light. It is therefore important to verify whether the product we introduced in the vacuum chamber is solely CH 3 NC or if the molecule was partially degraded or isomerized to CH 3 CN or CH 2 CNH during the deposition or the warming up.…”

Section: Methodsmentioning

confidence: 99%

Nitrile versus isonitrile adsorption at interstellar grains surfaces

Bertin

Doronin

Fillion

et al. 2017

A&A

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Context. Almost 20% of the ∼200 different species detected in the interstellar and circumstellar media present a carbon atom linked to nitrogen by a triple bond. Among these 37 molecules, 30 are nitrile R-CN compounds, the remaining seven belonging to the isonitrile R-NC family. How these species behave in presence of the grain surfaces is still an open question. Aims. In this contribution we investigate whether the difference between nitrile and isonitrile functional groups may induce differences in the adsorption energies of the related isomers at the surfaces of interstellar grains of different nature and morphologies. Methods. The question was addressed by means of a concerted experimental and theoretical study of the adsorption energies of CH 3 CN and CH 3 NC on the surface water ice and silica. The experimental determination of the molecule -surface interaction energies was carried out using temperature programmed desorption (TPD) under an ultra-high vacuum (UHV) between 70 and 160 K. Theoretically, the question was addressed using first principle periodic density functional theory (DFT) to represent the organized solid support. Results. The most stable isomer (CH 3 CN) interacts more efficiently with the solid support than the higher energy isomer (CH 3 NC) for water ice and silica. Comparing with the HCN and HNC pair of isomers, the simulations show an opposite behaviour, in which isonitrile HNC are more strongly adsorbed than nitrile HCN provided that hydrogen bonds are compatible with the nature of the model surface.Conclusions. The present study confirms that the strength of the molecule surface interaction between isomers is not related to their intrinsic stability but instead to their respective ability to generate different types of hydrogen bonds. Coupling TPD to first principle simulations is a powerful method for investigating the possible role of interstellar surfaces in the release of organic species from grains, depending on the environment.

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Section: Methodsmentioning

confidence: 99%

Nitrile versus isonitrile adsorption at interstellar grains surfaces

Bertin

Doronin

Fillion

et al. 2017

A&A

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“…1 70 and methyl isocyanide 71 were prepared following the procedures adapted from the literature. All solvents were purified and dried prior to use.…”

Section: General Considerationsmentioning

confidence: 99%

Binuclear complexes of Ni(i) from 4-terphenyldithiophenol

et al. 2015

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Binuclear complexes of Ni(i) have been prepared from a 4-terphenyldithiophenol ligand. Steric effects were found to determine the formation of coordination isomeric structures that differ in the nature of metal-to-ligand bonding. Coordination of spatially demanding phosphine ligands PR3, R = C6H6, C6H11, at nickel sites results in a butterfly shaped thiolate-bridged Ni2(μ-S)2 motif. For smaller PMe3, the central π-system of the 4-terphenyl backbone adopts a bis-allyl like μ-syn-η(3):η(3)-C6H4 structure due to significant d-π* Ni(i)-to-ligand charge transfer. Delocalisation indices δ(Ni-Ni) derived from DFT calculations provide a metric to assess the strength of electronic coupling of the Ni sites based on solid state structural data, and indicated less strong electronic coupling for the bis-allyl like structure with δ(Ni-Ni) = 0.225 as compared to 0.548 for the Ni2(μ-S)2 structural motif. A qualitative reactivity study toward CNCH3 as an auxiliary ligand has provided the first insight into the chemical properties of the bimetallic complexes presented.

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“…In an attempt to lower the steric demands of the 2° amides found in substrates 2b‐g and encourage transamidation for the desired 2‐indolinones, we turned our attention to methyl isocyanide35a and the preparation of aniline precursor 2h (Table 2). Methyl isocyanide was synthesized on a 50 g quantity using a dehydratative distillation procedure 35b. With 2h in hand, the cyclization for 2‐indolinones using Lewis/Brønsted acids and a variety of solvents under the influence of microwave irradiation was attempted (Table 2).…”

Section: Resultsmentioning

confidence: 99%

Synthesis of 3‐Substituted 2‐Indolinones by a Multicomponent Coupling Isocyanide‐Dependent Microwave‐Assisted Intramolecular Transamidation Process

Maddirala

Andreana

2015

Eur J Org Chem

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A small‐molecule library synthesis of 3‐substituted 2‐indolinones using methyl isocyanide and a microwave‐assisted intramolecular transamidation process with 10 % TFA in dichloroethane has been achieved in 3 steps. A modified Fe0 Bechamp‐type reduction of a substituted bifunctional substrate, o‐nitrobenzaldehyde, renders 3‐substituted 2‐indolinones in yields ranging from 76–91 % (21 examples). Furthermore, it has been determined that symmetrical 2o N‐alkyl or aryl substituents, as a component of the amine starting material, suppresses 3‐substituted 2‐indolinone rotameric mixtures and allows for facile compound 1H NMR characterization. In the absence of methyl isocyanide, 3,4‐dihydroquinazolines or transamidation products predominate under both Brønsted or Lewis acid conditions in reasonable yields.

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Methyl Isocyanide

Abstract: Methyl isocyanide product: Methyl isocyanide reactant: Quinoline, practical grade product: methyl (50%), ethyl (45%), s‐butyl (35%) and cyclobutyl (24%) isocyanides

Cited by 18 publications

References 4 publications

Nitrile versus isonitrile adsorption at interstellar grains surfaces

Nitrile versus isonitrile adsorption at interstellar grains surfaces

Binuclear complexes of Ni(i) from 4-terphenyldithiophenol

Synthesis of 3‐Substituted 2‐Indolinones by a Multicomponent Coupling Isocyanide‐Dependent Microwave‐Assisted Intramolecular Transamidation Process

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Methyl Isocyanide

Abstract: Methyl isocyanide product: Methyl isocyanide reactant: Quinoline, practical grade product: methyl (50%), ethyl (45%), s‐butyl (35%) and cyclobutyl (24%) isocyanides

Cited by 18 publications

References 4 publications

Nitrile versus isonitrile adsorption at interstellar grains surfaces

Nitrile versus isonitrile adsorption at interstellar grains surfaces

Binuclear complexes of Ni(i) from 4-terphenyldithiophenol

Synthesis of 3‐Substituted 2‐Indol­inones by a Multicomponent Coupling Isocyanide‐Dependent Microwave‐Assisted Intramolecular Transamidation Process

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Synthesis of 3‐Substituted 2‐Indolinones by a Multicomponent Coupling Isocyanide‐Dependent Microwave‐Assisted Intramolecular Transamidation Process