- Syntheses and crystal structures of two unsymmetrical 1,2,4, 5-tetrazine derivatives
-
Two unsymmetrical 1,2,4,5-tetrazine derivatives, (6-(3,5-dimethyl-1H- pyrazol-1-yl)-1,2,4,5-tetrazin-3-ylamino) methanol (C9H 13N7O, 3) and 4-(6-(3,5-dimethyl-1H-pyrazol- 1-yl)-1,2,4,5-tetrazin-3-yl) morpholine (C11H15N 7O, 4), were synthesized from 3,6-bis(3,5-dimethyl-1H-pyrazol-1- yl)-1,2,4,5-tetrazine and the corresponding aliphatic amine (2-aminoethanol and morpholine, respectively), there structureswere confirmed by single-crystalX-ray diffractionmethods. Both molecules have very similar bond length and angle patterns, The crystal structures show that compound 3 is stabilized by intermolecular O-H-N, N-H-O hydrogen bonds and p-p interactions, while compound 4 is stabilized by π- π interactions. The structure analyses establish that compound 3 belongs to the monoclinic system, space group P2(1)/c, with crystal data a = 6.979(2) A, b = 9.563(3) A, c = 16.542(5) A, V = 1084.4(5) A3, Z = 4, F(000) = 496, R1 = 0.0488, wR2 = 0.1063. Compound 4 belongs to the orthorhombic system, space group P2(1)2(1)2(1), with crystal data a = 6.544(14) A, b = 12.085(3) A, c = 15.753(4) A, V = 1245.7(5) A3, Z = 4, F(000) = 552, R1 = 0.0403, wR2 = 0.0913. Springer Science+Business Media, LLC 2012.
- Xu, Feng,Yang, Zhen-Zhen,Jiang, Jun-Rong,Ke, Zhong-Lu
-
-
Read Online
- Proposed Proton-Transfer Mechanism for the Initial Decomposition Steps of BTATz
-
The first steps in the gas-phase decomposition mechanism of N3,N6-bis (1H-tetrazol-5-yl)-1,2,4,5-tetrazine-3,6-diamine, BTATz, anions and the kinetic isotope effects in these processes were studied using combined multi-stage mass spectrometry (MS/MS) and computational techniques. Two major fragmenta-tion processes, the exergonic loss of nitrogen molecules and the endergonic loss of hydrazoic acid, were identified. The observation of a primary isotope effect supported by calculations, suggests that the loss of a nitrogen molecule from the tetrazole ring involves proton migration, either to, or within the terazole ring, as a rate-determining step. The fragmentation of a hydrazoic acid occurs through an asymmetrical retro pericyclic reaction. Calculations show the relevance of these mechanisms to neutral BTATz. Our findings may contribute to the understanding of decomposition routes in these nitrogen-rich energetic materials and allow tailoring their reactivity and decomposition pathways for better control of performance.
- Parvari, Galit,Levi, Moran,Preshel Zlatsin, Maya,Panz, Larisa,Grinstein, Dan,Gottlieb, Levi,Denekamp, Chagit,Eichen, Yoav
-
-
Read Online
- Single-molecule magnet behaviour in a tetranuclear DyIII complex formed from a novel tetrazine-centered hydrazone Schiff base ligand
-
Two analogous tetranuclear lanthanide complexes have been synthesized with the general formula [Ln4(vht)4(MeOH)8](NO3)4·aMeOH·bH2O, where H2vht = (3,6-bis(vanillidenehydrazinyl)-1,2,4,5-tetrazine) and Ln = DyIII (1), GdIII (2). These complexes are characterized by several techniques; including single-crystal X-ray diffraction, SQUID magnetometry and single-crystal micro-SQUID hysteresis loop measurements. Elucidation of the crystal structure of the complexes shows that the lanthanide ions are bridged by a tetrazine ring, a rare bridging moiety for lanthanide ions. Magnetic studies reveal that both 1 and 2 exhibit weak ferromagnetic exchange interactions between Ln ions, and 1 displaying Single-Molecule Magnet (SMM) behaviour with a magnetisation reversal barrier of Ueff = 158 K (τ0 = 1.06 × 10?7 s).
- Lacelle,Brunet,Pialat,Holmberg,Lan,Gabidullin,Korobkov,Wernsdorfer,Murugesu
-
-
Read Online
- The crystal structure and synthesis mechanism of 3,6-Bis(3,5- dimethylpyrazol-1-yl)-1,4-dihydro-1,2,4,5-tetrazine (BDT): A key precursor of s-tetrazine
-
The single crystal structure of 1,1′-bis (3,5-dimethyl-pyrazole) methenehydrazine (BDM) was determined by X-ray single crystal diffraction for the first time. The obtained experimental results indicated that BDM was the intermediate of 3,6-bis(3,5-dimethylpyrazol-1-yl)-1,4-dihydro-1,2,4,5-tetrazine (BDT), which was the key precursor of s-tetrazine. By this evidence, the preparation mechanism of BDT was proved: At 318.15 K, triaminoguanidine and pentanedione reacted to achieve the intermediate (BDM) by molecular nucleophilic addition and intramolecular nucleophilic substitution; when heated to 363.15 K, BDT was then generated by two molecules of BDM with nucleophilic substitution reaction. Furthermore, the thermal decomposition properties and also the non-isothermal kinetic parameters have been investigated in the present work.
- Zhang, Jian-Guo,Wu, Jin-Ting,Sun, Mou,Feng, Jin-Ling,Zhang, Tong-Lai,Zhou, Zun-Ning
-
-
Read Online
- A one-pot, three-component synthesis of 3-(1 H -pyrazol-1-yl)-4 H,7 H -[1,2,4,5]tetraazino[6,1- b ][1,3]benzoxazin-7-ones under solvent-free conditions
-
A one-pot, three-component synthesis of 3-(1H-pyrazol-1-yl)-4H,7H-[1,2,4,5]tetraazino[6,1-b][1,3]benzoxazin-7-ones is described which involves heating a mixture of 1,2-dihydro-3,6-bis(3,5-dimethyl-1H-pyrazol-1-yl)-1,2,4,5-tetrazine, aldehydes, and dimedon
- Adib, Mehdi,Soheilizad, Mehdi,Zhu, Long-Guan,Wu, Jing
-
-
Read Online
- Nucleophilic Attack on Nitrogen in Tetrazines by Silyl-Enol Ethers
-
The nucleophilic addition of silyl-enol ethers to nitrogen in 3-monosubstituted s-tetrazines mediated by BF3 is reported. The preference for this azaphilic addition over the usually observed inverse electron demand Diels-Alder reactions was evaluated theoretically and corroborated by experiments. The substrate dependency of this unusual reaction was rationalized by determination of the activation barriers and on the basis of the activation strain model by employing density functional theory.
- Schnell, Simon D.,Schilling, Mauro,Sklyaruk, Jan,Linden, Anthony,Luber, Sandra,Gademann, Karl
-
supporting information
p. 2426 - 2430
(2021/04/05)
-
- s-Tetrazines as a New Electrode-Active Material for Secondary Batteries
-
Because of the limitations of conventional metal-oxide-based electrodes, studies on organic redox-active materials as alternative electrodes for secondary batteries are emerging. However, reported organic electrode materials are still limited to a few kinds of organic redox groups. Therefore, the development of new redox-active groups for high-performance electrode materials is indispensable. Here, we evaluate s-tetrazine derivatives as a new electrode material in Li-ion batteries and study their charge/discharge mechanisms by ex situ XPS measurements. The porous carbon CMK-3 was introduced to encapsulate the s-tetrazines, which allowed 100 % utilization of the theoretical capacity and stable cycle performance of the s-tetrazines by preventing dissolution of the molecules into the electrolytes. This new class of redox-active group can pave the way for the next-generation of energy storage systems.
- Min, Dong Joo,Miomandre, Fabien,Audebert, Pierre,Kwon, Ji Eon,Park, Soo Young
-
p. 503 - 510
(2019/01/04)
-
- Hydrogen sulfide fluorescent probe as well as preparation method and application thereof
-
The invention provides a series of hydrogen sulfide fluorescent probe compounds and a preparation method thereof. A fluorescent probe can be used for detecting hydrogen sulfide and has very good selectivity for the hydrogen sulfide; when being mixed in a water solution or a buffer solution, the fluorescent probe can be used for detecting in vitro hydrogen sulfide. The fluorescent probe compounds can autonomously penetrate cell membranes into cells, and can be used for intracellular hydrogen sulfide imaging.
- -
-
Paragraph 0024; 0054-0057
(2017/10/31)
-
- Synthesis of a tetrazine-based catecholamide derivative and its evaluation as a chelating agent for removal of Cd(II), Co(II), and Cu(II)
-
The synthesis and structural characterization of a tetrazine-based catecholamide (CAM) ligand, N,N′-bis(N″-(aminoethyl)-2,3-bis(hydroxy)benzamide)-1,2,4,5-tetrazine-3,6-diamine (5), were investigated. All compounds were characterized by 1H NMR spectroscopy, 13C NMR spectroscopy, and FTIR spectroscopy. The protonation equilibria of 5 and complexation capacities (log βpqr) of Cd2+, Co2 +, and Cu2+ complexes of 5 were evaluated through potentiometric titration and spectrophotometric titration, respectively. Species independent pM value (=?log [M]free) was used to compare metal affinities with the final sequence Cu2+?>?Cd2+?>?Co2+. Results show that 5 has potential for heavy metal removal.
- Lei, Shan,Jin, Bo,Peng, Rufang,Zhang, Qingchun,Chu, Shijin
-
p. 2384 - 2392
(2017/08/02)
-
- Chemical modification of single walled carbon nanotubes with tetrazine-tethered gold nanoparticles via a Diels-Alder reaction
-
A versatile methodology for the modification of single walled carbon nanotubes (SWCNTs) through an inverse electron demand Diels-Alder reaction with tetrazine-AuNPs (1-AuNPs) under ambient conditions is described. A robust covalently bonded hybrid nanocomposite is formed.
- Zhu, Jun,Hiltz, Jonathan,Lennox, R. Bruce,Schirrmacher, Ralf
-
supporting information
p. 10275 - 10277
(2013/10/22)
-
- A tetrazine templated method for the synthesis of ternary conjugates
-
Conjugation is an important reaction that enables coupling of molecules. Many protocols exist for the synthesis of binary conjugates from two different molecules or for the polyvalent display of a single molecule. There aren't many methods for the synthesis of ternary conjugates. However, methods for ternary conjugation are important for understanding the interplay of interactions between three biomolecules (or any three molecules per se). A strategy for ternary bioconjugation using inverse electron demand Diels-Alder reaction with tetrazine is studied. Ternary conjugation was demonstrated by the reaction of a model glyco-peptide binary conjugate with a fluorescent tagged olefin. The Royal Society of Chemistry 2013.
- Venkateswara Rao, Boddu,Dhokale, Snehal,Rajamohanan, Pattuparambil R.,Hotha, Srinivas
-
supporting information
p. 10808 - 10810
(2013/11/06)
-
- Reactions of 3,6-bis(3,5-dimethyl-4-r-pyrazol-1-yl)-1,2,4,5-tetrazines with indole and 1,3,3-trimethyl-2-methyleneindoline
-
It has been found that 3,6-bis(3,5-dimethyl-4-R-pyrazol-1-yl)-1,2,4,5- tetrazines react with indole and 1,3,3-trimethyl-2-methyleneindoline to give pyridazines as [4+2]cycloaddition products. 1,3,3-Trimethyl-2-methyleneindoline has been shown to act as C-nucleophile in the substitution of pyrazolyl group as well as in the reactions of tetrazine ring expansion in [1,2,4]triazolo[4,3-b] [1,2,4,5]tetrazine derivatives.
- Ishmetova, Rashida I.,Ignatenko, Nina K.,Ganebnykh, Ilya N.,Tolshchina, Svetlana G.,Slepukhin, Pavel A.,Rusinov, Gennady L.
-
experimental part
p. 1363 - 1370
(2011/07/06)
-
- Antimalarial 3-arylamino-6-benzylamino-1,2,4,5-tetrazines
-
We report on novel 3-arylamino-6-benzylamino-1,2,4,5-tetrazines with potent activity against Plasmodium falciparum.
- Nhu, Duong,Duffy, Sandra,Avery, Vicky M.,Hughes, Andrew,Baell, Jonathan B.
-
supporting information; experimental part
p. 4496 - 4498
(2010/10/02)
-
- Hydrolytic stability of nitrogenous-heteroaryltrifluoroborates under aqueous conditions at near neutral pH
-
The hydrolytic stability of heteroaryltrifluoroborates under physiological conditions has been analyzed by 19F NMR spectroscopy and is found to be greatly enhanced by the presence of endocyclic ring nitrogens. Stability is further enhanced by the presence of exocyclic electron withdrawing substituents. As with aryltrifluoroborates, NMR analysis suggests that the hydrolysis proceeds via single rate-determining step reflecting loss of the first fluoride atom. The stability of these complexes is significant both in terms of metal catalyzed cross-coupling reactions as well as the potential for generating boronic acid based 18F-PET imaging agents.
- Li, Ying,Asadi, Ali,Perrin, David M.
-
experimental part
p. 377 - 382
(2009/12/04)
-
- Synthesis and physical chemistry of s-tetrazines: Which ones are fluorescent and why?
-
New fluorescent tetrazines have been prepared and their electrochemistry and fluorescence efficiency evaluated. The occurrence of fluorescence as well as the wavelength were found to be strongly dependent on the substituents, which have to be electronegative heteroatoms. This has been rationalized through a computational study that showed that the crucial factor is the nature of the HOMO, which determines the existence or not: of fluorescence. Wiley-VCH Verlag GmbH & Co. KGaA.
- Gong, Yong-Hua,Miomandre, Fabien,Meallet-Renault, Rachel,Badre, Sophie,Galmiche, Laurent,Tang, Jie,Audebert, Pierre,Clavier, Gilles
-
supporting information; experimental part
p. 6121 - 6128
(2010/03/24)
-
- The azaphilic addition of organometallic reagents on tetrazines: Scope and limitations
-
A series of tetrazines were reacted with organometallic reagents. Depending on the nature of the metal azaphilic addition, reduction of the tetrazine or simple complex formation was the predominant transformation and usually high selectivity was observed.
- Faragó, János,Novák, Zoltán,Schlosser, Gitta,Csámpai, Antal,Kotschy, András
-
p. 1991 - 1996
(2007/10/03)
-
- [4+2]-cycloaddition of 3,6-bis(3,5-dimethyl-4-R-pyrazol-1-yl)-1,2,4,5-tetrazines with alkenes
-
A number of 1,4-dihydropyridazines and pyridazines were prepared by the Diels-Alder reaction with an inverse electron demand from cyclic heterodienc systems, 3,6-bis(3,5-dimethyl-4-R-pyrazol-1-yl)-1,2,4,5-tetrazines, and some enamines as well as from 4-vi
- Rusinov,Ishmetova,Lalosh,Ganebnych,Chupakhin,Potemkin
-
p. 355 - 362
(2007/10/03)
-
- An Improved Synthesis of 3,6-Diamino-1,2,4,5-tetrazine. II. From Triaminoquanidine and 2,4-Pentanedione
-
A new synthesis for the title compound that gives an 80percent overall yield was developed.Treatment of triaminoguanidine monohydrochloride (1) with 2,4-pentanedione (2) gave 3,6-bis(3,5-dimethylpyrazol-1-yl)-1,2-dihydro-1,2,4,5-tetrazine (3) in 80-85percent yield.Oxidation of 3 with nitric oxide or nitrogen dioxide to 3,6-bis(3,5-dimethylpyrazol-1-yl)-1,2,4,5-tetrazine (4) followed by ammonolysis of 4 gave 3,6-diamino-1,2,4,5-tetrazine (5) in quantitatively yields
- Coburn, M.D.,Buntain, G.A.,Harris, B.W.,Hiskey, M.A.,Lee, K.-Y.,Ott, D.G.
-
p. 2049 - 2050
(2007/10/02)
-