A Study of the Thermal Decomposition of 2-Azidoethanol and 2-Azidoethyl Acetate by Ultraviolet Photoelectron Spectroscopy and Matrix Isolation Infrared Spectroscopy

Hooper, N.; Beeching, Levi; Dyke, John M.; Morris, Alan; Ogden, J. S.; Dias, Ângela; Costa, M.L.; Barros, M. Teresa; Cabral, Mónica; Moutinho, A.M.C.

doi:10.1021/jp020625e

Cited by 51 publications

(62 citation statements)

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“…Detailed kinetic models on decomposition of EA included these species [23,24]. (CH 2 =NH) is the simplest imine compound, it has been observed in the pyrolysis of methylamine, ethylamine (amines in general), and azides as a reactive intermediate [25][26][27][28][29][30][31][32][33]. A great deal of research has been carried out to assign the microwave, infrared, and electronic spectrum of this moiety [25][26][27][28][29][30][31][32][33][34][35][36][37][38][39][40][41][42][43].…”

Section: Introductionmentioning

confidence: 99%

“…(CH 2 =NH) is the simplest imine compound, it has been observed in the pyrolysis of methylamine, ethylamine (amines in general), and azides as a reactive intermediate [25][26][27][28][29][30][31][32][33]. A great deal of research has been carried out to assign the microwave, infrared, and electronic spectrum of this moiety [25][26][27][28][29][30][31][32][33][34][35][36][37][38][39][40][41][42][43]. As a reactive species, MI can dissociate by 1,2-elimination of H 2 which has been studied both experimentally and theoretically [44][45][46][47][48][49][50][51][52][53][54][55].…”

Section: Introductionmentioning

confidence: 99%

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Computational study for the second-stage cracking of the pyrolysis of ethylamine: Decomposition of methanimine, ethenamine, and ethanimine

Almatarneh

Barhoumi

Al-Tayyem

et al. 2016

Computational and Theoretical Chemistry

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Accepted ManuscriptThis is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain. AbstractThe mechanism that accounts for the observed experimental activation energy for the decomposition of ethylamine (EA) is still unknown. This paper reports the first detailed study of possible mechanisms for the pyrolysis of second-stage cracking product of ethylamine: the decomposition reaction of methanimine, ethanimine, and aminoethylene. Investigated reactions charactarise either H 2 elimination or 1,3-proton shift. These pathways result in the removal of H 2 , CH 4 , and NH 3 ; and the formation of hydrogen cyanide, acetylene, acetonitrile, ethynamine, and ketenimine. The IRC analysis was carried out for all transition state structures to obtain the complete reaction pathways. The stationary points were fully optimized at B3LYP and MP2 levels of theory using the 6-31G(d), 6-31G(2df,p), and 6-31++G(3df,3dp) basis sets. Based on comparing energetic requirements, we find 1,3-proton shift is the most probable pathway for the decomposition of ethanimine. The decomposition reaction of ethenamine was the most plausible reaction with an activation energy of 297 kJ mol −1 calculated at the composite method of G4MP2.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Computational study for the second-stage cracking of the pyrolysis of ethylamine: Decomposition of methanimine, ethenamine, and ethanimine

Almatarneh

Barhoumi

Al-Tayyem

et al. 2016

Computational and Theoretical Chemistry

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“…Recent studies [1][2][3] on the thermal decomposition on organic azides by photoelectron spectroscopy (PES) and infrared matrix isolation spectroscopy have shown that two distinct decomposition pathways must be invoked to account for the experimental observations.…”

Section: Introductionmentioning

confidence: 99%

“…It was first recognised in the decomposition of azidoacetic acid [1] (Scheme 2) and has subsequently also been found to occur in the pyrolysis of ethyl azidoacetate. [3] In both these molecules, "Type 1" behavior is also possible, but is evidently less favorable.…”

Section: Introductionmentioning

confidence: 99%

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Contrasting Behavior in Azide Pyrolyses: An Investigation of the Thermal Decompositions of Methyl Azidoformate, Ethyl Azidoformate and 2‐Azido‐N, N‐dimethylacetamide by Ultraviolet Photoelectron Spectroscopy and Matrix Isolation Infrared Spectroscopy

Dyke¹,

Levita²,

Morris³

et al. 2005

Chemistry A European J

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The thermal decompositions of methyl azidoformate (N3COOMe), ethyl azidoformate (N3COOEt) and 2-azido-N,N-dimethylacetamide (N3CH2CONMe2) have been studied by matrix isolation infrared spectroscopy and real-time ultraviolet photoelectron spectroscopy. N2 appears as an initial pyrolysis product in all systems, and the principal interest lies in the fate of the accompanying organic fragment. For methyl azidoformate, four accompanying products were observed: HNCO, H2CO, CH2NH and CO2, and these are believed to arise as a result of two competing decomposition routes of a four-membered cyclic intermediate. Ethyl azidoformate pyrolysis yields four corresponding products: HNCO, MeCHO, MeCHNH and CO2, together with the five-membered-ring compound 2-oxazolidone. In contrast, the initial pyrolysis of 2-azido-N,N-dimethyl acetamide, yields the novel imine intermediate Me2NCOCH=NH, which subsequently decomposes into dimethyl formamide (HCONMe2), CO, Me2NH and HCN. This intermediate was detected by matrix isolation IR spectroscopy, and its identity confirmed both by a molecular orbital calculation of its IR spectrum, and by the temperature dependence and distribution of products in the PES and IR studies. Mechanisms are proposed for the formation and decomposition of all the products observed in these three systems, based on the experimental evidence and the results of supporting molecular orbital calculations.

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Polyurethane nanocomposites with click‐coupled nanodiamonds exhibiting enhanced mechanical and shape memory effects

Yoo

Lee

Mahapatra

et al. 2017

J of Applied Polymer Sci

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Poly(ɛ‐caprolactone)diol (PCL)–functionalized nanodiamonds (f‐NDs) were synthesized using a click chemistry reaction between the azide‐moiety PCL and alkyne‐moiety NDs and were incorporated into shape memory polyurethane (PU) at f‐ND concentrations of 0, 0.5, 1, and 2 wt % to produce high‐performance shape memory nanocomposites. The PU/f‐ND nanocomposites exhibited better shape recovery, shape recovery stress, and breaking stresses than pure PU. Shape recovery of greater than 95% was demonstrated for all the nanocomposites in the third cycle, and the shape recovery stresses increased significantly with the f‐ND content. These enhanced mechanical and shape recovery properties are ascribed to increased interactions between the f‐NDs and PU matrix due to incorporation of click‐coupled f‐NDs. The click‐coupled NDs can be used as nanofillers to enhance the mechanical and shape memory properties of polymers. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 45465.

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A Study of the Thermal Decomposition of 2-Azidoethanol and 2-Azidoethyl Acetate by Ultraviolet Photoelectron Spectroscopy and Matrix Isolation Infrared Spectroscopy

Cited by 51 publications

References 32 publications

Computational study for the second-stage cracking of the pyrolysis of ethylamine: Decomposition of methanimine, ethenamine, and ethanimine

Computational study for the second-stage cracking of the pyrolysis of ethylamine: Decomposition of methanimine, ethenamine, and ethanimine

Contrasting Behavior in Azide Pyrolyses: An Investigation of the Thermal Decompositions of Methyl Azidoformate, Ethyl Azidoformate and 2‐Azido‐N, N‐dimethylacetamide by Ultraviolet Photoelectron Spectroscopy and Matrix Isolation Infrared Spectroscopy

Polyurethane nanocomposites with click‐coupled nanodiamonds exhibiting enhanced mechanical and shape memory effects

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