Kinetics and mechanism of the 1,3-dipolar cycloaddition of phenyl azides to methyl 3-pyrrolidinoacrylate

Al-Sader, Basil H.; Kadri, M.

doi:10.1016/s0040-4039(00)98779-3

Cited by 10 publications

(9 citation statements)

References 16 publications

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“…An alternative approach is the use of the [3 + 2] cycloaddition reaction of the azide groups with appropriate dipolarophiles. Azides are 1,3‐dipolar compounds and readily undergo a cycloaddition with olefinic or acetylene esters and amides to yield a five‐membered heterocyclic ring (i.e., 1,2,3‐triazoline or 1,2,3‐triazole) 7, 8. Such additions are always cis and usually regiospecific 9, 10.…”

Section: Introductionmentioning

confidence: 99%

Curing and thermal behavior of poly(allyl azide) and bismaleimides

Varma

Choudhary

Gaur

et al. 2006

J of Applied Polymer Sci

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ABSTRACT:The reaction of poly(allyl azide) (PAA; number-average molecular weight ϭ 1800 g/mol) with N-phenyl maleimide, 4,4Ј-bis(maleimidodiphenyl) ether, 4,4Ј-(bismaleimidodiphenyl) sulfone, and 1,6-bismaleimido hexane is described in this article. As indicated by Fourier transform infrared studies, the azido group reacted with the highly electron-deficient olefinic bond of N-phenyl maleimide or bismaleimides in a 3 ϩ 2 cycloaddition reaction under mild reaction conditions. The curing of PAA with bismaleimides (10 -30 phr) was monitored with differential scanning calorimetry. In freshly prepared samples of PAA and bismaleimides, a broad exothermic transition was observed in the temperature range of 150 -280°C and could be attributed to the loss of N 2 from PAA and the curing of bismaleimides. The heat of the exothermic reaction (⌬H) depended on the structure and composition and was in the range of 800 -1413 J/g. Isothermal heating in an air oven at 40°C (2 days) followed by 60°C (5-6 days) resulted in the conversion of a sticky, viscous liquid into an elastic, nonsticky material. No significant difference in the ⌬H values of uncured and cured samples was observed, and this indicated the reaction of fewer azido groups with the bismaleimides (dipolarophiles). In the thermogravimetry traces, a mass loss was indicated in the temperature range of 130 -280°C due to the loss of nitrogen from the azido group.

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Section: Introductionmentioning

confidence: 99%

Curing and thermal behavior of poly(allyl azide) and bismaleimides

Varma

Choudhary

Gaur

et al. 2006

J of Applied Polymer Sci

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“…Our postulate was believed to be supported by cis-stereospecific aziridine formation from thermolysis of 2-BTA in (2)-or (E)-but-Zene. We subsequently showed 2b that on thermolysis in diethyl-or dimethyl-amine both 2-BTA and 3-azidobenzothiophene (3-BTA) afforded the appropriate 2-amino-3-(dialkylamino)benzothiophene (6) in good yield. The ortho-diamine compounds (6) were envisaged as resulting from trapping of, respectively, the ring-cleavage product (2) and the tricyclic azirine (7), the valence tautomer of 3-nitrenobenzothiophene, by the dialkylamine present.…”

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confidence: 99%

Thermal reactivity of 2-azido- and 3-azido-benzo[b]thiophene with alkenes

Funicello¹,

Spagnolo²,

Zanirato³

1990

J. Chem. Soc., Perkin Trans. 1

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“…The comparison of the reactions 1a + 1b and 2a + 2b allows investigating the influence of the nature of the substituents on the stereoisomerism of the products. 15 We studied the reaction using the semiempirical PM6 Hamiltonian 16 to determine energy and forces driving the dynamics of the system. This choice offers a reasonably good compromise between computational cost and qualitative description of the process, allowing identifying and properly characterizing the main structural motifs of the reaction.…”

Section: Scheme 1 (A) Huisgen Cycloaddition In the Gas Phase (B) Reac...mentioning

confidence: 99%

“…In the post-processing analysis, to keep into account the effect of these external potentials together with the deposited bias, we used the reweighting procedure, as explained in ref. 15.…”

Section: B Computational Detailsmentioning

confidence: 99%

The reaction mechanism of the azide–alkyne Huisgen cycloaddition

Danese

Bon

Piccini

et al. 2019

Phys. Chem. Chem. Phys.

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The azide-alkyne Huisgen cycloaddition has a key role in click chemistry and configures as powerful tool in pharmaceutical and medicinal chemistry. Although this reaction has already been largely studied, there is an ongoing debate about its mechanism. In this work we study the dynamical aspects of the process using metadynamics computer simulation. We focus on the conformational aspects that determine the course of the reaction and characterize the free energy landscape of the process. To properly capture the thermodynamics of the process we select optimal collective variables using harmonic linear discriminant analysis. The results confirm the experimental evidence qualitatively and give insight on the role of the substituents and the possible transition mechanisms. on a semi-empirical potential energy surface suggest the stepwise mechanism. 8,9 The latter outcome, however, might be affected by the neglect of closed shell diatomic overlap. 4

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Kinetics and mechanism of the 1,3-dipolar cycloaddition of phenyl azides to methyl 3-pyrrolidinoacrylate

Cited by 10 publications

References 16 publications

Curing and thermal behavior of poly(allyl azide) and bismaleimides

Curing and thermal behavior of poly(allyl azide) and bismaleimides

Thermal reactivity of 2-azido- and 3-azido-benzo[b]thiophene with alkenes

The reaction mechanism of the azide–alkyne Huisgen cycloaddition

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