- Insights into the synthesis of hexaaminobenzene hydrochloride: An entry to hexaazatriphenylenes
-
Polycyclic N-heteroaromatic systems and particularly, the dipyrazino[2,3-f:2′,3′-h]quinoxaline also known as 1,4,5,8,9,12-hexaazatriphenylene (HAT) displays very useful optoelectronic properties. Its synthesis through condensation of functionalized 1,2-diketones and hexaaminobenzene is often applied on laboratory scale. Hexaaminobenzene could be prepared from 4-nitroaniline but, despite its many applications, the experimental protocol is not trivial and should by carefully controlled in each step. In this work, we presented an efficient and reproducible 4 steps synthesis of hexaaminobenzene hydrochloride and a comprehensive analysis of reactions conditions and products formed in all synthetic steps. As evidence, this aromatic polyamine was effectively condensed with 1,2-di(4-bromophenyl)-1,2-ethanedione affording a synthetically versatile HAT derivative for the application in the design of organic materials.
- Comba, María Betina,Libonatti, Bernardo,Mangione, María Inés,Spanevello, Rolando A.,Vázquez, Darián
-
-
- Ultrathin two-dimensional π-d conjugated coordination polymer Co3(hexaaminobenzene)2 nanosheets for highly efficient oxygen evolution
-
Organic two-dimensional (2D) materials with unique optic-electronic properties are attracting great interest for application in functional electronic devices. However, low electronic conductivity and poor stability still are major defects of 2D organic systems. Herein, we demonstrated ultrathin 2D conductive cobalt-hexaaminobenzene metal-organic coordination polymer nanosheets (Co-HAB-NSs) with a thickness of ~4.5 nm. The as-prepared Co-HAB-NSs exhibit a low overpotential (310 mV @ 10 mA cm-2) and high durability in 1 M KOH. The experimental and computational results show that the high electrocatalytic activity is ascribed to the enhanced electrochemically active surface area as well as the dense and stable catalytic active sites of Co-HAB-NSs.
- Li, Chun,Shi, Lingling,Zhang, Lili,Chen, Peng,Zhu, Junwu,Wang, Xin,Fu, Yongsheng
-
p. 369 - 379
(2019/12/26)
-
- Signature of metallic behavior in the metal-organic frameworks M3(hexaiminobenzene)2 (M = Ni, Cu)
-
The two-dimensionally connected metal- organic frameworks (MOFs) Ni3(HIB)2 and Cu3(HIB)2 (HIB = hexaiminobenzene) are bulk electrical conductors and exhibit ultraviolet-photoelectron spectroscopy (UPS) signatures expected of metallic solids. Electronic band structure calculations confirm that in both materials the Fermi energy lies in a partially filled delocalized band. Together with additional structural characterization and microscopy data, these results represent the first report of metallic behavior and permanent porosity coexisting within a metal-organic framework.
- Dou, Jin-Hu,Sun, Lei,Ge, Yicong,Li, Wenbin,Hendon, Christopher H.,Li, Ju,Gul, Sheraz,Yano, Junko,Stach, Eric A.,Dincǎ, Mircea
-
supporting information
p. 13608 - 13611
(2017/11/07)
-
- Erratum: Hexaaminobenzene as a building block for a family of 2D coordination polymers (Journal of the American Chemical Society (2017) 139 (19-22) DOI: 10.1021/jacs.6b09889)
-
Supporting Information, page S2. We regret that we inadvertently omitted a safety note stating that 2,4,6-trinitroaniline (TNA) and 1,3,5-triamino-2,4,6-trinitrobenzene (TATB) are very sensitive and highly explosive. They should be handled with extreme caution. An updated Supporting Information file with this note in place is provided.
- -
-
supporting information
p. 2119 - 2119
(2017/02/15)
-
- Hexaaminobenzene as a building block for a family of 2D coordination polymers
-
A family of 2D coordination polymers were successfully synthesized through "bottom-up" techniques using Ni2+, Cu2+, Co2+, and hexaaminobenzene. Liquidliquid and air-liquid interfacial reactions were used to realize thick (~1-2 μm) and thin (10 nm) stacked layers of nanosheet, respectively. Atomic-force microscopy and scanning electron microscopy both revealed the smooth and flat nature of the nanosheets. Selected area diffraction was used to elucidate the hexagonal crystal structure of the framework. Electronic devices were fabricated on thin samples of the Ni analogue and they were found to be mildly conducting and also showed back gate dependent conductance.
- Lahiri, Nabajit,Lotfizadeh, Neda,Tsuchikawa, Ryuichi,Deshpande, Vikram V.,Louie, Janis
-
supporting information
p. 19 - 22
(2017/05/16)
-
- A Stable Hexakis(guanidino)benzene: Realization of the Strongest Neutral Organic Four-Electron Donor
-
The growing demand for efficient batteries has stimulated the search for redox-active organic compounds with multistage redox behavior, as materials with large charge capacity. Herein we report the synthesis and properties of the first hexakis(guanidino)benzene derivative: a strong neutral organic electron donor with reversible multistage redox behavior and a record low redox potential for donation of four electrons. Detailed structural and spectroscopic characterization of three redox states (0, +2, and +4) reveal its unique electronic features. Despite its nitrogen richness, the compound is thermally robust and can be readily purified by sublimation.
- Eberle, Benjamin,Kaifer, Elisabeth,Himmel, Hans-J?rg
-
supporting information
p. 3360 - 3363
(2017/03/17)
-
- Method of synt hesizing Hexaaminobenzene
-
The present invention relates to a synthesis method for hexaaminobenzene trihydrochloride. The present invention solves existing problems that large-scale production is impossible due to instability of hexaaminobenzene by converting hexaaminobenzene into hexaaminobenzene hydrochloride and enables large-scale production of stable high-purity hexaaminobenzene with improved processing efficiency. Additionally, the present invention is able to be applied to various fields since HAB synthesized according to the present invention is able to be an excellent intermediate for discotic liquid crystal, a compound with low resistance to the transfer of hole and electron to be used in organic electron fields, a marcrocyclic compound, a hexaazatriphenylene based donor-acceptor molecule, an electron deficiency electron extension system, a ferromagnetism organic salt and cadmium (II) for a fluorescent sensor.
- -
-
Paragraph 0039-0043
(2016/10/17)
-
- A novel N-N bond cleavage in 1,5-diaminotetrazole: Synthesis and characterization of 5-picrylamino-1,2,3,4-tetrazole (PAT)
-
The reaction of 1,5-diaminotetrazole with picryl chloride (PiCl) forms 5-picrylamino-1,2,3,4-tetrazole (PAT) rather than the expected 1-picrylamino-5-amino-1,2,3,4-tetrazole or 5-picrylamino-1-amino-1,2,3,4- tetrazole. The structure of PAT was confirmed by single-crystal X-ray diffraction. Some of the energetic properties of the synthesized compound were also studied.
- Tang, Yongxing,Yang, Hongwei,Ju, Xuehai,Huang, Hui,Lu, Chunxu,Cheng, Guangbin
-
p. 4127 - 4131
(2014/03/21)
-
- Scalable synthesis of pure and stable hexaaminobenzene trihydrochloride
-
Synthesis of hexaaminobenzene (HAB) in pure and stable form has remained as an important challenge for a long time, since it is a fascinating synthon for the synthesis of aromatic nitrogenous compounds having many interesting applications. Here, we report an improved synthesis of pure and stable HAB form using modified catalytic hydrogenation in aqueous acidic medium. The structure of needle-shaped HAB crystals was confirmed by single-crystal X-ray diffraction study. The synthetic protocol could thus be a simple, but efficient for the large-scale synthesis of highly pure and stable HAB. Georg Thieme Verlag Stuttgart New York.
- Mahmood, Javeed,Kim, Dongwook,Jeon, In-Yup,Lah, Myoung Soo,Baek, Jong-Beom
-
p. 246 - 248
(2013/02/25)
-
- Synthesis of N-(5,7-diamino-3-phenyl-quinoxalin-2-yl)-3,4,5-substituted anilines and N-[4[(5,7-diamino-3-phenylquinoxalin-2-yl)amino]benzoyl]-l-glutamic acid diethyl ester: Evaluation of in vitro anti-cancer and anti-folate activities
-
Several diamino quinoxalines were designed, synthesized and evaluated as anti-tumor agents. Two compounds showed the most potent cytotoxic activities against the leukemia CCRF-CEM cell line (GI50 50 = 0.03 μM), respectively, with comparable/better activities than Methotrexate (MTX). Docking calculations of the complexes of hDHFR with the most active compounds identified the binding mode of the described molecules with respect to MTX.
- Corona, Paola,Loriga, Mario,Costi, M. Paola,Ferrari, Stefania,Paglietti, Giuseppe
-
p. 189 - 203
(2008/09/17)
-
- Synthesis and purification of 1,3,5-triamino-2,4,6-trinitrobenzene (TATB)
-
A method to convert surplus nitroarene explosives (picric acid, ammonium picrate,) into TATB is described. The process comprises three major steps: conversion of picric acid/ammonium picrate into picramide; conversion of picramide to TATB through vicarious nucleophilic substitution (VNS) of hydrogen chemistry; and purification of TATB.
- -
-
Page/Page column 3
(2008/06/13)
-
- Nucleophilic aromatic substitution for heteroatoms: An oxidative electrochemical approach
-
The nucleophilic aromatic substitution for heteroatom through electrochemical oxidation of the intermediate σ-complexes (Meisenheimer complexes) in simple nitroaromatic compounds is reported for the first time (NASX process). The studies have been carried out with hydride, cyanide, fluoride, methoxy, and ethanethiolate anions and n-butylamine as a nucleophile, at the cyclic voltammetry (CV) and preparative electrolysis level. The cyclic voltammetry experiments allow for detection and characterization of the σ-complexes and they have led us to a proposal for the mechanism of the oxidation step. Furthermore, the power of the CV technique in the analysis of the reaction mixture throughout the whole chemical and electrochemical process is described.
- Gallardo, Iluminada,Guirado, Gonzalo,Marquet, Jordi
-
p. 2548 - 2555
(2007/10/03)
-
- Electrochemical synthesis of nitroanilines
-
Alkylamines and amides are readily prepared by nucleophilic aromatic substitution of hydrogen in nitroarenes by electrochemical oxidation. Useful yields (15-85%) are achieved in a simple direct and regioselective amination process. The synthetic method has been examined in the absence and presence of external bases, used to promote the first step of the nucleophilic aromatic substitution reaction, i.e. the nucleophilic attack. In both cases, good results were obtained. The unreacted starting material can easily be recovered at the end of the electrochemical oxidation process. This new method represents an environmentally favourable route to amino- and amido-substituted nitroaromatic compounds.
- Gallardo, Iluminada,Guirado, Gonzalo,Marquet, Jordi
-
p. 251 - 259
(2007/10/03)
-
- Nitroanilinodinitrobenzofuroxans - Synthesis, characterisation, thermal stability and explosive properties
-
Three new derivatives of 4,6-dinitrobenzofuroxan: 7-(4-nitrophenylamino)-4,6-dinitrobenzofuroxan, 7-(3,5-dinitrophenylamino)-4,6-dinitrobenzofuroxan and 7-(2,4,6-trinitrophenylamino)-4,6-dinitrobenzofuroxan, have been synthesised by condensing 4-nitroaniline, 3,5-dinitroaniline and 2,4,6-trinitroaniline with 7-chloro-4,6-dinitrobenzofuroxan, respectively. The characterisation of the compounds by IR, 1H-NMR, mass spectrometry and elemental analysis is described along with some of the evaluated preliminary explosive properties. The compounds were found to exhibit acceptable hazards properties. Furthermore, the thermal stability measurements indicated acceptable stability.
- Mehilal,Sikder,Salunke,Sikder
-
p. 1549 - 1552
(2007/10/03)
-
- AROMATIC NUCLEOPHILIC SUBSTITUTION REACTIONS OF ACTIVATED N-ARYLPYRAZOLES WITH FORMAMIDES
-
Different activated N-arylpyrazoles, as N-(2',4'-dinitrophenyl)-3,5-dimethylpyrazole, N-picryl-3,5-dimethylpyrazole etc., can react with excess formamides, as formamide N-methylformamide and N,N-dimethylformamide, at 165-175 deg C, for 5-6 hours, resulting amines in high yieds.This reaction is influenced by steric hindrance.
- Chiriac, Constantin I.,Lupu, Viorel,Chiriac, Florentina,Ropot, Radu,Tibirna, Mihaela,Truscan, Ion
-
p. 549 - 553
(2007/10/03)
-
- SULFENAMIDES AND SULFINAMIDES VII. REACTIONS OF ARYL SULFINAMIDES WITH DIPHENYLPICRYLHYDRAZYL FREE RADICAL
-
In common with the sulfenamides, hydrogen abstraction is postulated as the first step in reactions of aryl sulfinamides with the stable diphenylpicrylhydrazyl free radical.However, marked differences between the reations of the two classes are established, with rates and extents of reaction controlled by the oxidation level of the sulfur atom.Reversibility of the sulfinamide reaction is discussed.
- Clarke, Victor,Cole, Edward R.,Southwell-Keely, Peter T.
-
p. 237 - 243
(2007/10/02)
-
- A Comparison of the Reactions of Some Ethyl N-Arylcarbamates with Those of the Corresponding Acetanilides. I. Nitration
-
The reactions of some ethyl N-arylcarbamates and of the corresponding acetanilides towards 1 equiv. of sodium nitrate in concentrated sulfuric acid at 0-5 deg have been compared with one another and have been found to exhibit significant differences.Except in the case of the unsubstituted analogues, nitration of the carbamates was found to occur significantly more quickly than that of the acetanilides as shown by (i) a representative competitive nitration, and (ii) the fact the carbamates containing a nitro group are nitrated smoothly whereas the corresponding nitroacetanilides are slow to react.On the basis of competitive reactions, it is suggested that this difference in reactivity is due to steric factors.
- Rosevear, Judi,Wilshire, John F. K.
-
p. 723 - 733
(2007/10/02)
-
- Synthesis of Polynitrobenzenes. Oxidation of Polynitroanilines and Their N-Hydroxy, N-Methoxy, and N-Acetyl Derivatives
-
Nitro-substituted arylhydroxylamines and alkyloxyamines have been oxidized to polynitroaryl compounds by utilizing ozone.Polynitroanilines have been oxidized to polynitroaromatics by peroxydisulfuric acid generated in situ from SO3 and ozone.Thus N-hydroxy-2,4,6-trinitroaniline (1a) or N-methoxy-2,4,6-trinitroaniline (1b) was cleanly oxidized to 1,2,3,5-tetranitrobenzene (2) by reaction with ozone in methylene chloride.Weakly basic amines such as pentanitroaniline (10) can conveniently be oxidized to hexanitrobenzene (11) in high yields by simply dissolving the amine in oleum and introducing ozone.A variety of substituted arylamines have been oxidized to polynitroaromatic compounds by using these two oxidation techniques.
- Atkins, Ronald L.,Nielsen, Arnold T.,Bergens, Cynthia,Wilson, William S.
-
p. 503 - 507
(2007/10/02)
-
- Products of reaction between styrene and some radicals with 2,2-diphenyl-1-picrylhydrazyl
-
Addition of 2,2-diphenyl-1-picrylhydrazyl DPPH to styrene at 75 deg C results in little change in the amounts of cis- and trans-1,2-diphenylcyclobutane and 1,2,3,4-tetrahydro-1-phenylnaphthalene, in a slightly smaller amount of 1-phenylnaphthalene, and in a considerable increase in the amount of 1,2-dihydro-1-phenylnaphthalene that are formed.Formation of the styrene trimer 1,2,3,4-tetrahydro-1-phenyl-4-(1-phenylethyl)naphthalene is eliminated completely.Products derived from DPPH are 1-(4-nitrophenyl)-1-phenyl-2-picrylhydrazine 9 and 1--2,2-diphenylhydrazine, 10.DPPH intercepts the thermally formed Diels-Alder dimer of styrene as soon as it is formed to give the 1,2,3,4-tetrahydro-4-phenyl-1-naphthyl radical.Thermolysis of bis(1,2,3,4-tetrahydro-4-phenyl-1-naphthyl)diazene in the presence of DPPH yields 20percent of 10, 10percent of 1--2-(4-nitrophenyl)-2-phenylhydrazine and 9 while thermolysis of 1,2-bis(1-phenylethyl)diazene in the presence of DPPH yields 9 and 44percent of 1--2,2-diphenylhydrazine showing that substituted benzyl radicals efficiently displace the 4-nitro group of DPPH.The nitro group is transferred to an unsubstituted phenyl group of DPPH.
- Kopecky, Karl R.,Hall, Michael C.
-
p. 3095 - 3104
(2007/10/02)
-
- AMBIPHILIC FUROXAN RING. BENZOFUROXAN OXIDATION BY PERACID AND REDUCTION BY COPPER
-
Monopersulfuric acid, trifluoroperacetic acid and hydrogen peroxide in polyphosphonic acid, or with selenium dioxide in t-butyl alcohol, or in tetramethylene sulfone have each oxidized benzofuroxan into o-dinitrobenzene.Monopersulfuric acid oxidized 4-nitrobenzofuroxan into 1,2,3-trinitrobenzene (80percent) and 4,6-dinitrobenzofuroxan into 1,2,3,5-tetranitrobenzene (99percent); hydrogen peroxide in polyphosphoric acid was moderately efficient for the latter oxidation.Copper in acidified ethanol transformed 4,6-dinitrobenzofuroxan into picramide quantitatively.
- Boyer, Joseph H.,Huang, Chrongbao
-
p. 1233 - 1240
(2007/10/02)
-
- Succinimido azo dyestuffs
-
The invention relates to water-insoluble azo dyestuffs of the formula SPC1 In which A represents the residue of a diazo component of the azobenzene series, R1 a hydrogen atom or an alkyl group which may be substituted which may be substituted, R2 an alkyl group which may be substituted, R3 represents a divalent organic residue which together with the grouping EQU1 may form a 5- to 7-membered heterocycle, and X represents a hydrogen atom or an alkyl, alkoxy, aryloxy or arylmercapto group. The dyestuffs dye polyester fibre in orange, red or blue shades with good fastness: the use of such succinimido containing azo dyestuffs in imparting blue to red color to fibers or fabrics of wool, cellulose triacetate, polyamides and polyesters. The dyeings display excellent fastness to light, sublimation and abrasion on polyester fibers.
- -
-
-