Synthesis and reactions of azidopolybromopyridines

Moshchitskii, S. D.; Zeikan, A. A.; Pavlenko, A. F.; Kukhar, V. P.

doi:10.1007/bf00471431

Cited by 6 publications

(7 citation statements)

References 3 publications

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“…Nevertheless, it was found that the anisotropy of g-tensor is negligibly small in the EPR spectra of these molecules. [9][10][11][12][13][14] Typical value of the isotropic g-factor is close to g e . In the bromine-containing high spin molecules Q-1, Q-2, and S-1, the SOC-term is large in comparison with that in organic high-spin molecules studied previously.…”

Section: B Dft Calculationsmentioning

confidence: 84%

High-spin organic molecules with dominant spin-orbit contribution and unprecedentedly large magnetic anisotropy

Misochko

Акимов

Masitov

et al. 2012

The Journal of Chemical Physics

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High-spin organic molecules with dominant spin-orbit contribution to magnetic anisotropy are reported. Quintet 4-azido-3,5-dibromopyridyl-2,6-dinitrene (Q-1), quintet 2-azido-3,5-dibromopyridyl-4,6-dinitrene (Q-2), and septet 3,5-dibromopyridyl-2,4,6-trinitrene (S-1) were generated in solid argon matrices by ultraviolet irradiation of 2,4,6-triazido-3,5-dibromopyridine. The zero-field splitting (ZFS) parameters, derived from electron spin resonance spectra, show unprecedentedly large magnitudes of the parameters D: ∣D(Q1)∣ = 0.289, ∣D(Q2)∣ = 0.373, and ∣D(S1)∣ = 0.297 cm(-1). The experimental ZFS parameters were successfully reproduced by density functional theory calculations, confirming that magnetic anisotropy of high-spin organic molecules can considerably be enhanced by the "heavy atom effect." In bromine-containing high-spin nitrenes, the spin-orbit term is dominant and governs both the magnitude and the sign of magnetic anisotropy. The largest negative value of D among septet trinitrenes is predicted for 1,3,5-trinitrenobenzene bearing three heavy atoms (Br) in positions 2, 4, and 6 of the benzene ring.

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Section: B Dft Calculationsmentioning

confidence: 84%

High-spin organic molecules with dominant spin-orbit contribution and unprecedentedly large magnetic anisotropy

Misochko

Акимов

Masitov

et al. 2012

The Journal of Chemical Physics

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“…2,4,6-Triazido-3,5-dibromopyridine ( 55a ) was the first triazidopyridine, obtained by Moshchitskii and co-workers in 1979, using the reaction of pentabromopyridine ( 54a ) with sodium azide (Scheme 12) [88]. The reaction was carried out in DMSO at room temperature for 15 h and gave triazide 55a (a brown solid with a melting point 85–86 °C) in 97% yield.…”

Section: Triazidopyridinesmentioning

confidence: 99%

Six-Membered Aromatic Polyazides: Synthesis and Application

Чапышев

2015

Molecules

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Aromatic polyazides are widely used as starting materials in organic synthesis and photochemical studies, as well as photoresists in microelectronics and as cross-linking agents in polymer chemistry. Some aromatic polyazides possess high antitumor activity, while many others are of considerable interest as high-energy materials and precursors of high-spin nitrenes and C3N4 carbon nitride nanomaterials. The use of aromatic polyazides in click-reactions may be a new promising direction in the design of various supramolecular systems possessing interesting chemical, physical and biological properties. This review is devoted to the synthesis, properties and applications of six-membered aromatic compounds containing three and more azido groups in the ring.

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“…The results show that two strong electron‐donating R 3 PN substituents in positions 4 and 6 of the pyridine ring substantially increase the nucleophilicity of the ring nitrogen atom, thus favoring the partial transformation of 14 into 15 . At the same time, about 50% of the bis‐phosphorylated adduct of triazide 10 is present in the form of azide 14 and can be further phosphorylated till the corresponding tris‐adduct described in the literature . A similar tris‐adduct is also obtained on boiling of diazide 9 with an excess of triphenylphosphine in benzene .…”

Section: Resultsmentioning

confidence: 68%

“…Similar selective reactions are also typical for many other 2,4,6‐triazidopyridines . The only exception of this rule was the reaction of 2,4,6‐triazido‐3,5‐dibromopyridine ( 10 ) with an excess of triethyl phosphite, leading to the formation of 2,4,6‐tris(triethoxyphosphorimino)‐3,5‐dibromopyridine . It was postulated that this reaction involves the initial addition of two molecules of triethyl phosphite to the α‐azido groups of triazide 10 , and only then, to its γ‐azido group.…”

Section: Introductionmentioning

confidence: 74%

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Chemoselective Staudinger‐Phosphite Reaction on the Azido Groups of 2,4,6‐Triazido‐3,5‐dibromopyridine

Чапышев

Chernyak

Yakushchenko

2015

Journal of Heterocyclic Chem

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2,4,6‐Triazido‐3,5‐dibromopyridine reacts with an equimolar amount of triethyl phosphite in ether at room temperature chemoselectively on the γ‐azido group to form 2,6‐diazido‐3,5‐dibromo‐4‐triethoxyphosphoriminopyridine as a single product. The latter adds another molecule of triethyl phosphite to give a mixture of 6‐azido‐2,4‐bis(triethoxyphosphorimino)‐3,5‐dibromopyridine and its tetrazolo[1,5‐a]pyridine isomer, the acidic hydrolysis of which affords 6‐azido‐2,4‐bis(diethoxyphosphoramino)‐3,5‐dibromopyridine. The study shows that the Staudinger‐phosphite reactions with heterocyclic polyazides occur selectively on the most electron‐deficient azido groups, opening up new prospects for preparation of new polyfunctional heterocyclic compounds.

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Synthesis and reactions of azidopolybromopyridines

Cited by 6 publications

References 3 publications

High-spin organic molecules with dominant spin-orbit contribution and unprecedentedly large magnetic anisotropy

High-spin organic molecules with dominant spin-orbit contribution and unprecedentedly large magnetic anisotropy

Six-Membered Aromatic Polyazides: Synthesis and Application

Chemoselective Staudinger‐Phosphite Reaction on the Azido Groups of 2,4,6‐Triazido‐3,5‐dibromopyridine

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