Showing papers on "Triazene published in 2006"

Triazenes as a Stable Diazonium Source for Use in Functionalizing Carbon Nanotubes in Aqueous Suspensions

Abstract: Organic triazene compounds are stable precursors to diazonium salts for functionalizing single-wall carbon nanotubes (SWNTs) in aqueous media. This method is particularly useful when a target molecule has functionality that will not tolerate diazotization conditions. We illustrate this by detailing the synthesis of a biotin-containing triazene followed by reaction with SWNTs.

Synthesis and characterization of triazenide and triazene complexes of ruthenium and osmium.

Abstract: Triazenide [M(η2-1,3-ArNNNAr)P4]BPh4 [M = Ru, Os; Ar = Ph, p-tolyl; P = P(OMe)3, P(OEt)3, PPh(OEt)2] complexes were prepared by allowing triflate [M(κ2-OTf)P4]OTf species to react first with 1,3-Ar...

Synthesis and properties of new photosensitive triazene polyacrylates

Abstract: 1-(Phenyl)-3-(2-acryloyloxyethyl)-3-methyl triazene-1 (M1) and 1-(p-nitrophenyl)-3-(2-acryloyloxyethyl)-3-methyl triazene-1 (M2) were synthesized to study the substituent effect of the triazene unit on the copolymerization with methyl methacrylate (MMA). From the 1H NMR spectra of the resulting copolymers, their compositions were determined to be 1:3.18 M1/MMA and 1:2.45 M2/MMA, respectively. The polymers were examined with respect to their structure, thermal properties, and surface morphology. The influence of the triazene structure on the photosensitive properties of the copolymers exposed to ultraviolet/laser irradiation was also investigated and compared with that of the parent derivatives. The copolymer containing the phenyl triazene chromophore as the photochemically most active group exhibited a low threshold of ablation and a high etching rate for fluences under 400 mJ cm−2. Scanning electron microscopy images confirm the formation of ablated craters more clearly in the copolymer made with M1, for which the thermal effects of the ablation mechanism were visible only with 2500× magnification. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5271–5282, 2006

Crystal Structure of Triazene-1,3-di(2-methoxyphenyl)

Abstract: their interesting structural, anticancer, and reactivity properties. They have been used in medicinal, combinatorial chemistry, in natural synthesis and as organometalic ligands.1 Triazenes compounds, characterized by having a diazoamino group (–N=N–N<), commonly adopt a trans configuration in the ground state.2,3 In this paper, we show the crystal structure of a new triazene ligand (triazene 1,3-di(2-methoxyphenyl) (Fig. 1). The compound was prepared by the following method: A 1 liter flask was charged with 100 g of ice and 150 ml of water and then cooled to 0 ̊C in an ice-bath. To this was added 12.30 g (0.10 mol) of o-anisidine and 13 g (0.13 mol) of hydrochloric acid (d = 1.18 g/ml). To this solution was added a solution of NaNO2 containing 4.10 g (0.06 mol) in 25 ml of water during a 15 min period. After mixing for 15 min a solution containing 14.76 g (0.18 mol) of sodium acetate in 45 ml of water was added. After mixing for 45 min the brown product was filtered and dissolved in Et2O, and was crystallized in a freezer. Yield, 50% (6.85 g). Recrystallization from Et2O afforded the product as an orange crystalline material. M. P. 95 – 97 ̊C. The crystal structure of triazene-1,3-di(2-methoxyphenyl) was solved by direct methods and refined by full-matrix least squares using the program SHELXTL-98.4 The H atoms were refined isotropically. The molecular structure of crystalline triazene-1,3-di(2-methoxyphenyl) is presented in Fig. 2. The N(1)–N(2)–N(3) bond angle and the C(8)–N(1)–N(2)–N(3) dihedral angle in this compound are 112.47 and 179.82, x79 ANALYTICAL SCIENCES 2006, VOL. 22

Multivalent Complex Salts of Copper: Synthesis and X-Ray Structural Analysis of [CuII(en)3][CuI4{(NNNPh)2C6H4}3] (en = ethylendiamine), an anionic Tris-1,3-bis(phenyltriazenide)benzene Complex of Tetrakis-Copper(I)

Abstract: An ethanolic solution of CuCl / ethylendiamine reacts with 1.3-bis- (phenyltriazene)benzene in THF leading to the deprotonation of the bis triazene ligand to give orange crystals of [CuII(en)3][CuI4{(NNN-Ph)2C6H4}3], an example of a rare complex salt of copper with mixed valence states. In the anion complex [CuI4{(NNNPh)2C6H4}3]2− the copper(I) ions are disposed linearly as single, bridged pairs in the two extremes of an axis, each of them presenting a trigonal bipyramidal alike coordination arrangement.

3,3',5,5'-tetramethyl benzidine derivative and its preparation method and uses

Abstract: The present invention discloses bi(2-benzothiazolyl diazo amino)-3, 3', 5, 5'-tetramethyl biphenyl (BBTDTMB) as one kind of 3, 3', 5, 5'-tetramethyl benzidine derivative. The derivative is prepared through diazotization of 2-amino benzothiazole and subsequent coupling with 3, 3', 5, 5'-tetramethyl benzidine. As one kind of fluorescent reagent, BBTDTMB has heterocyclic triazene structure capable of conjugating with silver ion in alkaline medium to quench its fluorescence, and one new fluorescent analysis method for testing Ag with BBTDTMB is thus established. The fluorescent analysis BBTDTMB method is used in testing silver ion in human hair and tea, and satisfactory result has been obtained. In addition, BBTDTMB may be also used as developer.

1,4,8,11-Tetra[2-aryl-1-diazenyl]-1,4,8,11-tetraazacyclotetradecanes — Synthesis, characterization, and X-ray crystallography of the first tetrakistriazenes to be reported

Abstract: The reactions of a series of arene diazonium salts with 1,4,8,11-tetraazacyclotetradecane (cyclam) afford the novel compounds, the 1,4,8,11-tetra[2-aryl-1-diazenyl]-1,4,8,11-tetraazacyclotetradecanes (1a–1f), which are the first examples of tetrakistriazenes to be reported. The tetrakistriazenes were characterized by IR spectroscopy, proton and carbon NMR, elemental analysis, high resolution electrospray mass spectrometry, and X-ray crystallography. The analogous reaction of a diazonium salt with 1,4,7-triazacyclononane or 1,5,9-triazacyclododecane yields the tristriazenes 2, 3a, and 3b. The structures of compounds 1c and 1e were solved by X-ray crystallography at low temperature (150 K). Both molecules display a conformation where the four phenyltriazenyl groups point alternately upwards and downwards with respect to the mean macrocyclic plane.Key words: triazene, tetrakistriazene, cyclam, tetraazacyclotetradecane, X-ray, NMR, cyclic polyamines.

1-[2-(p-Tolyl)-1-diazenyl]-3-({3-[2-(p-tolyl)-1-diazenyl] perhydrobenzo[d]imidazol-1-yl}methyl)perhydrobenzo[d]imidazole: synthesis,characterization and X-ray crystal structure

Abstract: 1-[2-(p-Tolyl)-1-diazenyl]-3-({3-[2-(p-tolyl)-1-diazenyl]perhydrobenzo[d]imidazol-1-yl}methyl)perhydrobenzo[d]imidazole(1) has been synthesized by reactionof a mixture of 1,2-diaminocyclohexane and formaldehyde withp-toluene diazonium chloride inaqueous solution. The product has been characterized by IR and NMRspectroscopy and elemental analysis. A crystal grown from solution ina mixed solvent system of ethyl acetate and hexanes was analyzed byX-ray crystallography. The solution of the crystal structure of(1) is important in establishing theconnectivity of this molecule and other compounds of similarstructure. The crystal structure of (1) is compared with the previously reportedstructure of the p-cyano analogue(2). Compounds (1) and (2)differ principally in the relative orientation of the heterocyclicrings; in (1), the molecule has adistinct V-shape, whereas compound (2) adopts a more extended conformation.Significant conjugation within the triazene moieties is evident inboth (1) and (2), as manifested in the N465=N andN–N bond lengths. The conjugation is greater in (2) due to the extended conjugation through tothe nitrile group. The title compound (1){C29H40N8}crystallizes in the monoclinic, space group C2/c, with lattice constants: a = 30.532(6) A,b =5.9050(12) A, c= 15.463(3) A, α = 90°,β = 99.94(3)°, γ = 90°,V =2746.0(10) A3, Z = 4, D c =1.209 mg m−3,F(000) = 1076, R 1 = 0.0785,wR 2= 0.1877.

Triazene derivatives of (1,x-)diazacycloalkanes. Part VI. 3-({5,5-Dimethyl-3-[2-aryl-1-diazenyl]-1-imidazolidinyl}methyl)-4,4-dimethyl-1-[2-aryl-1-diazenyl]imidazolidines — Synthesis, characterization, and X-ray crystal structure

Abstract: Reaction of a series of diazonium salts with a mixture of formaldehyde and 1,2-diamino-2-methylpropane affords the 3-({5,5-dimethyl-3-[2-aryl-1-diazenyl]-1-imidazolidinyl}methyl)-4,4-dimethyl-1-[2-...

X-Ray crystal structure determination of a series of 1-aryl- 2-[3-(3-[2-aryl-1-diazenyl]-1,3-diazepan-1-ylmethyl)-1, 3-diazepan-1-yl]-1-diazenes obtained from the reaction of diazonium salts with mixtures of formaldehyde and 1,4-diaminobutane

Abstract: A new series of bis-triazenes, the 1-aryl-2-[3-(3-[2-aryl-1-diazenyl]-1,3-diazepan-1-ylmethyl)-1,3-diazepan-1-yl]-1-diazenes has been synthesized from the reaction of diazonium salts with a mixture of 1,4-diaminobutane and formaldehyde The structures of 1-(p-bromophenyl)-2-[3-{3-[2-(p-bromophenyl)-1-diazenyl]-1,3-diazepan-1-ylmethyl}-1,3-diazepan-1-yl]-1-diazene(1), 1-(p-cyanophenyl)-2-[3-{3-[2-(p-cyanophenyl)-1-diazenyl]-1,3-di azepan-1-ylmethyl}-1,3-diazepan-1-yl]-1-diazene(2), and 1-(p-methoxyphenyl)-2-[3-{3-[2-(p-methoxy-phenyl)-1-diazenyl]-1,3-diazepan-1-ylmethyl}-1,3-diazepan-1-yl]-1 diazene(3) have been unequivocally determined by X-ray crystallography The new bis-triazenes are important since the structure contains the novel saturated heterocycle, 1,3-diazepane The general conclusion of this study is that alkanediamines with 3 or 4 carbon atoms in the spacer link between the nitrogen atoms give rise to the linear bicyclic molecules of type 5, in contrast to the case of ethylenediamine (spacer link 2 carbon atoms), which affords molecules of type 6, which exemplify the general cage structure of type 4 The crystal structures of 1, 2 and 3 are compared with the previously reported structure of the hexahydropyrimidine analogue 8a(X=CN); compounds 2 and 8a(X=CN) are homologous with respect to the alkane spacer moiety The structures of 2 and 8a(X=CN) are very different in one respect; in 2 the aryldiazenyl-1,3-diazepanyl groups are in the s-trans orientation around the central methylene group whereas in 8a(X=CN) the arrangement of the aryldiazenyl-hexahydropyrimidinyl groups is the s-cis orientation Crystal data: 1 C23H30N8Br2, triclinic, space group P-1, a=83979(2), b=107828(3), c=144692(5) A, α=83670(1), β=78662(1), γ=78758(1)°, V=125648(6) A3, for Z=2 2 C25H30N10, monoclinic, space group P2 1 /n, a=134046(6), b=94482(4), c=106913(4)A, β=103239(2)°, V=24905(2) A3, for Z=4 3 C25H36N8O2, triclinic, space group P-1, a=85223(3), b=106913(4), c=144034(7)A, α=85657(2), β=78731(2), γ=80153(1)°, V=126688(9) A3, for Z=2

Triazene Formation via Reaction of Imidazol-2-ylidenes with Azides.

Abstract: Treatment of N-heterocyclic carbenes (as their free carbenes or generated in situ) with alkyl, aryl, acyl or tosyl azides afforded the respective substituted triazenes in excellent yields.

Triazene derivatives of (1,x)-diazacycloalkanes. Part VII. Synthesis of a series of 1-aryl-2-[3-(3-[2-aryl-1-diazenyl]-1,3-diazepan-1-ylmethyl)-1,3-diazepan-1-yl]-1-diazenes from the reaction of diazonium salts with mixtures of formaldehyde and 1,4-diaminobutane

Abstract: A new series of bistriazenes, the 1-aryl-2-[3-(3-[2-aryl-1-diazenyl]-1,3-diazepan-1-ylmethyl)-1,3-diazepan-1-yl]-1-diazenes (8), has been synthesized from the reaction of diazonium salts with a mix...

Ultra Microanalysis of Ferric Ion Using Triazene and Capillary Electrophoresis

Abstract: The triazene compound {2,2′-[3-(4-methoxyphenyl)triaz-2-ene-1,1-diyl]diethanol} was utilized for the high sensitive and quantitative detection of ferric ion.

Crystal Structure of 1,3-Bis(4-nitrophenyl)triazenido- κ2N1N3]-bis(triphenylphosphine)copper(I), [Cu(O2NC6H4NNNC6H4NO2)(C18H15P)2]

Abstract: The reaction between [CuCl(PPh3)3] and 1,3-bis(4-nitrophenyl)triazene deprotonated with metallic sodium in methanol yields crystalline [Cu(O2NC6H4NNNC6H4NO2)(C18H15P)2], the first mononuclear triazenide complex of Cu(I) including a [Cu(PPh3)2]+ fragment. The crystals belong to the monoclinic system, space group P21/c with the cell dimensions a = 15.8852(3), b = 11.9539(3), c = 23.2094(6)A, β = 94.646(1)°, V = 4392.75(18)A3, Z = 4. The crystal structure reveals a bidimensional assembling of complex molecules linked through intermolecular non-classical C-H…O hydrogen bonds.

Formation of Benzylamines from Triazene Compounds via a 1,2‐Proton Shift.

Abstract: A new approach to benzylamines using triazene compounds has been developed that is facilitated by the lithiation of aryltriazenes followed by treatment with an electrophile The regioselectivity of the reaction can be controlled by means of the substituents in the aryl group The reaction contains the following steps: intramolecular carbon–carbon bond formation involving lithiation of an alkyl group on a 3-nitrogen atom; a 1,2-proton shift; and the subsequent release of nitrogen gas Through the use of a deuterated triazene, we were able to determine that the reaction proceeds through a 1,2-proton shift

Synthesis and Crystal Structure of cis-Bis[1,3-bis(4-nitrophenyl)-triazenido κ2N1N3]bis(pyridine-κN)cadmium(II), [Cd(O2NC6H4NNNC6H4NO2)2(C5H5N)2]

Abstract: The title complex was prepared by reaction of 1,3-bis(4-nitrophenyl)triazene with Cd(II) acetate in methanol/NaOH. Single crystals were obtained from pyridine and belong to the monoclinic space group C2/c with the lattice constants a = 20.086(1), b = 16.600(1), c = 11.250(1)A, β = 102.122(1)°. The crystal structure consists of discrete mononuclear complexes of C2 symmetry, in which the Cd(II) ions have a distorted octahedral coordination environment. Two deprotonated 1,3-bis(4-nitrophenyl)triazenide ions act as N11-η1, N13-η1 bidentate ligands. Two neutral pyridine molecules in the cis position complete the coordination sphere of the metal ion. The complexes are linked to chains via intermolecular non-classical C-H…O hydrogen bonds.

Crystal Structure of 1,3-Bis(2-trifluoromethylphenyl)triazene

Abstract: alkyl group), characterized by X-ray analysis, show always a trans stereochemistry about the N=N double bond. On the other hand, hydrogen bonds play an important role on geometrical aspects of molecules in the solid state. From this point of view, the diazoamino moiety of 1,3-disubstituted triazenes, N=N–N(H), provides intra and intermolecular interactions through hydrogen bonds with polarizable acceptor atoms included on the terminal aryl substituents. A review of the literature showed that no X-ray crystal data have been reported of free 1,3-diaryltriazenes including trifluoromethyl fragments attached to terminal aryl substituents. In this work, we report on the crystal structure of the title molecule, (I), (Fig. 1) based on a single-crystal X-ray structural analysis. The synthesis of the title complex included reagents of reagent grade, which were used without further purification. Methanol was treated with metallic sodium and distilled over an argonium atmosphere. A solution of o-trifluoromethylaniline (2.0 g, 12.3 mmol) and isopentyl nitrite (0.7 g, 6.0 mmol) in 40 mL anhydrous methanol was stirred 1 h at room temperature. The yellow precipitate of 1,3-bis(2-trifluoromethylphenyl)triazene was separated by filtration and dried over P2O5 under vacuum. The product was recrystallized from an acetone/pyridine/ethyl acetate/methanol mixture (1:1:1:1). Vitreous yellow bar-shaped crystals of (I), suitable for X-ray analysis, were obtained by slow evaporation of the solvent mixture. Yield 90% (1.78 g, 5.6 mmol) based on o-trifluoromethylaniline, m.p. 175 – 177 ̊C. IR (KBr pellet, cm–1) 3354.8 (νas N–H) s; 1428.8 (νs N=N) vs; 1334.0 (νas C–F) vs; 1193.7 (νs N–N) vs (IR data: vs, very strong; s, strong). Data were collected with a Bruker APEX II CCD areadetector diffractometer and graphite-monochromatized Mo-Kα radiation (λ = 0.71073 Å). The crystal and experimental data are listed in Table 1. The structure was solved by direct methods using SIR2004.1 The non-hydrogen atoms were refined anisotropically by the full-matrix least-square method x295 ANALYTICAL SCIENCES 2006, VOL. 22