Synthesis of 1,2,4,5-Tetrakis(1,2,4-Triazolyl) Benzene and 1,2,4,5-Tetrakis(1,3,4-Oxadiazolyl) Benzene Derivatives

Abstract

A series of 1,2,4,5-tetrakis(1,2,4-triazolyl)benzenes and 1,2,4,5-tetrakis(1,3,4-oxadiazolyl)benzenes was synthesized by nucleophilic addition of sodium salts of 4-phenyl-2,4-dihydro-3H-1,2,4-triazole-3-thiones and 1,3,4-oxadiazole-2(3H)-thiones to 1,2,4,5-tetrakis(bromomethyl)benzene. The structure of the newly synthesized compounds was confirmed by elemental analysis, IR and ¹H and ¹³C NMR spectra.

Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements for the following free supplemental resource: 1H and 13C NMR spectra of products (Figures S1-S24).     

1,2,4,5-Tetrakis(tetramethylguanidino)-3,6-diethynyl-benzenes: Fluorescent Probes,Redox-Active Ligands and Strong Organic Electron Donors

In this work, the change of reactivity induced by the introduction of two para-ethynyl substituents (CCSi(iPr)₃ or CCH) to the organic electron-donor 1,2,4,5-tetrakis(tetramethylguanidino)-benzene is evaluated. The redox-properties and redox-state dependent fluorescence are evaluated, and dinuclear Cu^I and Cu^II complexes synthesized. The Lewis-acidic B(C₆F₅)₃ substitutes the proton of the ethynyl −CCH groups to give new anionic −CCB(C₆F₅)₃⁻ substituents, leading eventually to a novel dianionic strong electron donor in its diprotonated form. Its two-electron oxidation with dioxygen in the presence of a copper catalyst yields the first redox-active guanidine that is neutral (instead of cationic) in its oxidized form.     

树枝形分子1,2,4,5-四芳基苯的合成、荧光性质和电存储效应

采用钯催化条件下多位点Heck偶联反应,以芳香八碘代物1,2,4,5-四{4-[N,N-二(4-碘苯基)氨基]苯乙烯基}苯(TPAB-I)和4-(N,N-二苯基)氨基苯乙烯为反应物,合成了一种新型荧光树枝分子1,2,4,5-四{4-{N,N-二{4-[4-(N,N-二苯基氨基)苯乙烯基]苯基}氨基}苯乙烯基}苯(TPAB-TPA).目标化合物的结构经过红外光谱、核磁共振谱、高分辨质谱确认.树枝分子TPAB-TPA在甲苯、乙酸乙酯、四氢呋喃、二氯甲烷和N,N-二甲基甲酰胺(DMF)溶液中的最大荧光发射峰分别位于483,457,497,531,505 nm.量子产率分别为0.48,0.28,0.23,0.49,0.18,在二氯甲烷和四氢呋喃(THF)中的荧光寿命分别为1.48和1.53 ns.用循环伏安法测定TPAB-TPA的HOMO能级和LUMO能级分别为-5.16和-2.64 eV.制备了ITO/TPAB-TPA/Al三明治型电存储器件,ON/OFF电流比大于104,在1 V的读取电压下,持续时间达到1000 s.     

1,2,4,5‐Tetrakis(diazidomethyl)benzene

The molecule of the title compound, C₁₀H₆N₂₄, lies on a crystallographic inversion centre located in the middle of the benzene ring. Steric overcrowding by the bulky N₃ groups is avoided by the tendency of four azide entities to be arranged parallel to the benzene ring and the other four azide groups to be arranged alternately above and below the benzene plane in a skeletal C_i symmetry. The compound is of interest for high‐energy research and as a precursor for the synthesis of carbon nanotubes, nanospheres or high‐nitrogen carbon nitrides with great potential for biological and technological applications.     

peri-Naphthalenediamines: XXXIV. 1,4,5,8-Tetrakis(dimethylamino)naphthalene: Alternative Approaches to Synthesis

New methods were proposed for synthesizing 1,4,5,8-tetrakis(dimethylamino)naphthalene with an overall yield of 4 to 12% to replace the known procedure ensuring an overall yield of 2%. Catalytic hydrogenation was shown to be inapplicable for preparation of polyaminonaphthalenes from nitro compounds having 3 or 4 nitro gruops in the -positions. Nucleophilic amination of 1,5-dinitronaphthalene in the system NH₂OH/NaOH/MeOH yields 1-amino-4-nitronaphthalene. The nitration of 1,5-bis(p-tolylsulfonylamino)naphthalene leads to formation of 2,6-dinitro rather than 4,8-dinitro derivative, as it was believed formerly. This was confirmed by transformation of the latter into 1,2,5,6-tetrakis(dimethylamino)naphthalene. 3-Nitro, 2,6-dinitro, 2,6-diamino, and 2,4,6,8-tetranitro derivatives of 1,5-bis(dimethylamino)naphthalene, nitro and amino derivatives of 1,4,5-tris(dimethylamino)naphthalene, and 4,5-diamino-1,8-bis(methylamino)naphthalene were synthesized. By treatment with perchloric acid 1,4,5,8-tetrakis(dimethylamino)naphthalene was oxidized to 2,3-dihydroperimidinium salt.     

Reactions of 1,2,4,5-Tetrafluoro-3,6-bis(vinylsulfonyl)benzene with Cyclic Amines

Reactions of 1,2,4,5-tetrafluoro-3,6-bis(vinylsulfonyl)benzene with pyrrolidine, piperidine, and morpholine lead to formation of different products, depending mainly on the reactant ratio. In the presence of 2 equiv of cyclic amine, adducts at both vinylsulfonyl groups are formed, while in reactions with 4 equiv of cyclic amine, the addition at the double bonds is accompanied by nucleophilic replacement of one or two fluorine atoms in the benzene ring.     

New 1,2,4,5-tetrakis-(N-imidazoliniummethyl)benzene and 1,2,4,5-tetrakis-(N-benzimidazoliummethyl)benzene salts as N-heterocyclic tetracarbene precursors: synthesis and involvement in ruthenium-catalyzed allylation reactions

New tetraimidazolinium and tetrabenzimidazolium salts have been prepared. Upon reaction with ^tBuOK, they generate carbene ligands, which were associated in situ to [RuCp*(MeCN)₃]PF₆ to produce new ruthenium catalysts that are active for the substitution of allylic substrates by amines, phenols, and carbonucleophiles. The influence of the N-heterocyclic core as well as that of the N-substitutents at the periphery of the salts, on reactivity and regioselectivity have been examined.     

1,2,5,6-Tetrakis(guanidino)-Naphthalenes: Electron Donors,Fluorescent Probes and Redox-Active Ligands

New redox-active 1,2,5,6-tetrakis(guanidino)-naphthalene compounds, isolable and storable in the neutral and deep-green dicationic redox states and oxidisable further in two one-electron steps to the tetracations, are reported. Protonation switches on blue fluorescence, with the fluorescence intensity (quantum yield) increasing with the degree of protonation. Reactions with N-halogenosuccinimides or N-halogenophthalimides led to a series of new redox-active halogeno- and succinimido-/phthalimido-substituted derivatives. These highly selective reactions are proposed to proceed via the tri- or tetracationic state as the intermediate. The derivatives are oxidised reversibly at slightly higher potentials than that of the unsubstituted compounds to dications and further to tri- and tetracations. The integration of redox-active ligands in the transition-metal complexes shifts the redox potentials to higher values and also allows reversible oxidation in two potentially separated one-electron steps.     

Reactions of 1,2,4,5-Tetrafluoro-3,6-bis(vinylsulfonyl)benzene with Nucleophilic Reagents Containing a Mercapto Group

Addition of 2-aminoethanethiol and 2-mercaptoethanol at both vinylsulfonyl groups of 1,2,4,5-tetrafluoro-3,6-bis(vinylsulfonyl)benzene occurs through the thiol group of the reagent and yields the corresponding 3,6-bis[2-(2-aminoethylthio)ethylsulfonyl] and 3,6-bis[2-(2-hydroxyethylthio)ethylsulfonyl] derivatives. The reaction of the title compound with 1,2-ethanedithiol leads to formation of only polymeric addition products.     

A New Electron Donor: synthesis of 2,3,6,7-tetra(ethyltellurio)tetrathiafulvalene

A new tetratellurio substituted derivative of tetrathiafulvalene has been prepared via a direct one pot three step synthesis.     

Synthesis, structure and two-photon absorption properties of a new multi-branched compound, 1,2,4,5-tetrakis(4-pyridylvinyl)benzene

A conjugated and symmetric multi-branched compound, 1,2,4,5-tetrakis(4-pyridylvinyl)benzene (TKPVB), has been synthesized and the crystal structures of TKPVB and its intermediate, 1,2,4,5-tetrakis(dimethoxyphosphorylmethyl)benzene, were determined by diffraction method. TKPVB with four units of 4-vinylpyridine moieties attached to the central benzene core presents an A-π-A general framework, where A is a π-deficient pyridine ring. The single-photon and two-photon absorption and fluorescence properties in different solvents of varying polarity have been investigated. It is also found that the one- and two-photon-induced fluorescence spectra are quite similar, which indicate that the one- and two-photon allowed-excited states are the same.