Showing papers on "Triazene published in 1992"
TL;DR: Cross-linkers containing 3,3-dialkyl-1-phenylenetriazene (-C 6 H 4 N=NNMe 2 ) end groupq have been prepared by diazotization of aromatic diamines and subsequent reaction of the diazotsized products with an amine as mentioned in this paper.
Abstract: Cross-linkers containing 3,3-dialkyl-1-phenylenetriazene (-C 6 H 4 N=NNMe 2 ) end groupq have been prepared by diazotization of aromatic diamines and subsequent reaction of the diazotized products with an amine. Differential scanning calorimetry (DSC) of these cross-linkers exhibits decomposition peak temperatures (T d ) from 180 to 350°C. Fluorinated polyimides and other aromatic polymers cross-linked with these cross-linkers at 400°C exhibit high gel contant, increased T g , improved resistance to organic solvents and improved thermal stability
30 citations
15 citations
TL;DR: In this paper, the behavior of 1-morpholinocyclohexene and tetraethyldiamidophosphazidoarenes was investigated and the triazene group migrated from the phosphorus atom to the carbon atom of the cyclohexenyl ring.
Abstract: Phosphorylation of a relatively simple enamine with phosphorus (III) halides was first exemplified by the behavior of 1-morpholinocyclohexene. Novel types of functionalized P(III) derivatives have now been obtained and studied. The hydrolysis of (2-morpholino-1-cyclohexenyl) tetraethyldiamidophosphazidoarenes was found to be accompanied by the migration of the triazene group from the phosphorus atom to the carbon atom of the cyclohexene ring.
13 citations
Patent•
09 Sep 1992TL;DR: In this article, the authors define a composition having the structure "STR1" where each node is independently selected from the group consisting of C 1 -C 6 alkyl or hydroxyalkyl moieties and aryl moieties, and n is 1 or 2.
Abstract: A composition having the structure ##STR1## wherein --R' is --F or --Cl, each --R", which may be the same or different, is independently selected from the group consisting of C 1 -C 6 alkyl or hydroxyalkyl moieties and aryl moieties, and n is 1 or 2. These compositions are useful as co-monomers or end-cappers for the introduction of thermally reactive cross-linking sites into polymers.
10 citations
9 citations
Journal Article•
9 citations
TL;DR: In this paper, the X-ray crystal structure of the title compound was determined and cyclic voltammery measurements showed that the oxidation potentials of the high-spin, pseudo-octahedral cobalt(II) complexes of triazene-loxides are ca 0.1-0.2 V higher than those found for low-spin and square-planar cobalt bis-chelates thereof.
8 citations
TL;DR: In this paper, a common product was identified by means of ESR- and ENDOR-spectroscopy: the 2,7-dimethoxy-5,10-dimethyl-5-10-dihydrophenazine radical cation, confirming the postulated cleavage between nitrogen atoms N(2) and N(3) in oxidized triazene intermediates.
8 citations
TL;DR: The molecular structures of the title compounds have been determined by X-ray crystallographic methods and revealed differences in the geometry, and by inference the bond delocalization in these two triazenes owing to the presence in the 1-oxide structure of an N-O bond
Abstract: The molecular structures of the title compounds have been determined by X-ray crystallographic methods. The analyses revealed differences in the geometry, and by inference the bond delocalization in these two triazenes owing to the presence in the 1-oxide structure of an N-O bond. The geometries are compared to the crystal structures of the isomeric 3-oxides [Kuroda & Wilman (1985). Acta Cryst. C41, 1543-1545; Neidle, Webster, Kuroda & Wilman (1987). Acta Cryst. C43, 674-676] which shows the dominance of an alternative tautomeric equilibrium for the triazene groups.
7 citations
TL;DR: In this paper, the title compounds (azido acid derivatives) and cyclisation in situ can be used to obtain the desired lactam or unexpected acyl triazene 4 depending on the reaction conditions.
7 citations
TL;DR: 1-(4-Nitrophenyl)-3-(2-quinolyl)triazene has been synthesized, and used as an extremely sensitive reagent for the spectrophotometric determination of mercury by the decrease in the absorbance of the reagent at 490 nm and pH 9.0-10.8 in the presence of cetylpyridinium bromide.
TL;DR: In this article, high-spin five-coordinate Lewis-base adducts of cobalt triazene 1-oxide complexes have been prepared and their reactivity in reversible dioxygen binding studied.
Abstract: High-spin five-co-ordinate Lewis-base adducts of cobalt(II) triazene 1-oxide complexes have been prepared and their reactivity in reversible dioxygen binding studied. Monoclinic spin-Hamiltonian parameters are reported for the dioxygen complexes. An X-ray structure analysis of high-spin bis[3-(4-chlorophenyl)-1-methyltriazen-1-olato]cobalt(II)–pyridine (1/1) has been performed. The adduct crystallizes in the monoclinic system, space group P2/c, with a= 18.39(2), b= 12.553(9), c= 9.827(8)A, β= 105.65(7)° and Z= 4. The co-ordination about the cobalt atom is distorted trigonal bipyramidal.
TL;DR: In this paper, a new synthesis of 4-imino-4,5-dihydro-1,2,3-triazole 1-oxides and 4-amino-1 2, 2, 3 triazolines was proposed.
Patent•
15 Dec 1992TL;DR: In this article, the authors proposed a new process for Diazotisation and coupling in the presence of acid-binding agent, which avoids these drawbacks and is economical and environmentally friendly.
Abstract: Prodn. of triazene and triazatrimethine dyestuffs of the formula D-N=N-Z (I) comprises reacting an aromatic or heterocyclic diazo component of formula D-NH2 (II) with a (het)arylamine of formula H-Z1 in aq. medium in the presence of a HNO2 precursor (IV) and CO2 at 5-100 bar at 0-125 deg.C. D = the radical of an aromatic or heterocyclic diazo component; Z = arylamino or a heterocyclylimino gp. of the formula -N=Het; Het = a heterocyclic diradical; Z2 = (het)arylamino. USE/ADVANTAGE - Diazotisation and coupling take place simultaneously if the CO2 pressure is over 5 bar. Diazotisation in mineral acid soln. and coupling in the presence of acid-binding agent leads to the formation of inorganic salts, which pollute the waste liquor and must be removed by costly methods, e.g. pressure permeation or reverse osmosis, to produce stable (I) solns. The new process avoids these drawbacks and is economical and environmentally friendly. Cationic (quaternised) (I) are useful for dyeing e.g. polyacrylonitrile.
TL;DR: In this article, the reaction of S4N4 with dicyclohexylaminophenyl-(2-aminopyridyl)phosphine in MeCN at room temperature leads to the formation of the novel compound Ph(cycloHex2 N)PS2 N3.
Abstract: The reaction of S4N4 with dicyclohexylaminophenyl-(2-aminopyridyl)phosphine in MeCN at room temperature leads to the formation of the novel compound Ph(cycloHex2 N)PS2 N3. An X-Ray structure determination confirms that this, compound consists of a six-membered PSN-ring with two different substituents at phosphorus.
TL;DR: In this paper, 1,3-Diaryltriazene 1-oxides formed stable (1 : 1) charge transfer complexes with tetracyanoethylene in different solvents, which were studied spectrophotometrically.
Abstract: 1,3-Diaryltriazene 1-oxides formed stable (1 : 1) charge-transfer complexes with tetracyanoethylene in different solvents, which were studied spectrophotometrically. The stability constants of the complexes were affected by substituents and solvent polarities. Likewise the thermodynamic properties ΔG, ΔH, and ΔS depend on the solvent polarities.
TL;DR: In this article, the catalytic rate constants of 3-Alkyl-3-hydroxymethyl-1-aryltriazenes were analyzed in a six-membered transition state involving the NCH2-OH group of the triazene and the N−H of the base and in which proton transfer from the hydroxy group to the nitrogen atom of the catalyst is extensive.
Abstract: 3-Alkyl-3-hydroxymethyl-1-aryltriazenes are stable in aprotic solvents, but decompose in non-aqueous protic solvents to the corresponding 3-alkyl-1-aryltriazenes. The reactions are catalysed by the presence of bases, and the catalytic activity of the base depends upon its aqueous pKa. A Bronsted plot of the catalytic rate constant, kB, versus base pKa gives rise to a Bronsted β value of 1.1. Tertiary bases have no catalytic effect. The deuterium isotope effect for the piperidine catalysed reaction is ca. 1.4. The catalytic rate constants kB depend upon the triazene structures, increasing with the size of the 3-alkyl group (Pr > Et > Me) and with electron-withdrawing ability of the substituent in the 1-aryl group (Cl > H > MeO). The observations are rationalised in terms of a six-membered transition state involving the N–CH2–OH group of the triazene and the N–H of the base and in which proton transfer from the hydroxy group to the nitrogen atom of the catalyst is extensive. In mixed aqueous–ethanol solvents tertiary bases also have a catalytic effect. A Bronsted β value of 0.67 and a solvent deuterium isotope effect of 1.18 identify the proton as ca. 70% transferred to the base in the transition state. In no reaction was aminomethylation of the base observed.
TL;DR: In this paper, Les deux structures adoptent une forme tautomere de l'oxyde lie a N. 3 O 3 cristallise dans P2 1 /c avec a=12,963, b=8,1716, c=11,212A, β=110,85°, Z=4; affinement jusqu'a R=0,070.
Abstract: (1) C 10 H 13 N 3 O 3 cristallise dan sP2 1 /c avec a=5,5055, b=25,2007, c=8,1241A, β=100,434°, Z=4; affinement jusqu'a R=0,044. (2) C 10 H 13 N 3 O 3 cristallise dans P2 1 /c avec a=12,963, b=8,1716, c=11,212A, β=110,85°, Z=4; affinement jusqu'a R=0,070. Les deux structures adoptent une forme tautomere de l'oxyde lie a N.
TL;DR: In this paper, a new method was proposed for the synthesis of O,N-disubstituted hydroxylamines and ketoxime esters that is based on the reaction of triazene 1-oxides containing strong electron-withdrawing substitutents with bases.
Abstract: A new method has been put forward for the synthesis of O,N-disubstituted hydroxylamines and ketoxime esters that is based on the reaction of triazene 1-oxides containing strong electron-withdrawing substitutents with bases.
TL;DR: In this article, a method for the synthesis of triazene 1-oxides based upon reaction of 1,1-disubstituted hydrazines with bromine in the presence of aryl- and heteroarylnitroso compounds in acid media is presented.
Abstract: We have worked out a method for the synthesis of 1,3,3-trisubstituted triazene 1-oxides based upon reaction of 1,1-disubstituted hydrazines with bromine in the presence of aryl- and heteroarylnitroso compounds in acid media. Obtained are a broad range of triazene 1-oxides, among which hitherto unknown compounds of the series of pyrazole and 3,3-dialkyltriazene 1-oxides that contain functional groups at the alkyl part of the molecule. We propose a reaction scheme which includes in situ formation of diazenium cations and reaction of them with nitroso compounds that are present in the system. By means of PMR,13C, and14N NMR spectroscopy, and mass spectroscopy, it has been shown that in all the prepared compounds the oxidated nitrogen atom is at the N1 position of the triazene N-oxide group.
TL;DR: The reaction of aryl diazonium salts containing electron-withdrawing substituents in the aromatic ring with acetone oxime leads to the formation of nitrogen-containing products instead of the expected functional derivatives of 1-alkyl-3-aryltriazene 1-oxides as discussed by the authors.
Abstract: The reaction of aryl diazonium salts containing electron-withdrawing substituents in the aromatic ring with acetone oxime leads to the formation of nitrogen-containing products instead of the expected functional derivatives of 1-alkyl-3-aryltriazene 1-oxides. The structure of these products is a function of the number and chemical nature of the substituents in the diazo component.
TL;DR: In this paper, a high-yielding method leading to a novel family of sugars: the sugar triazene N-oxides was described, and the anticonvulsant effect of one of these compounds was tested.
Abstract: In this paper we describe a high-yielding method leading to a novel family of sugars: the sugar triazene N-oxides. The anticonvulsant effect of one of these compounds was tested. It showed a promising activity indicating the potential therapeutic usefulness of this class of carbohydrate derivatives.
TL;DR: The hydrosoluble triazene derivatives of phenylacetic, phenylbutyric and cinnamic acid have been synthesized and their logP and pKa values were simultaneously determined according to a multiparametric fitting of potentiometric data.
Abstract: The hydrosoluble triazene derivatives of phenylacetic, phenylbutyric and cinnamic acid have been synthesized and their logP and pKa values were simultaneously determined according to a multiparametric fitting of potentiometric data. The antitumor activity caused by the synthesized compounds in mice bearing either Lewis lung carcinoma or TLX5 lymphoma was evaluated and discussed in comparison with the parent compound (p-(3,3-dimethyl-1-triazeno)benzoic acid potassium salt (DM-COOK, CAS 70055-49-1). The tested compounds were at least as active as DM-COOK, the cinnamic and the phenylacetic derivatives being the more active compounds in mice bearing TLX5 lymphoma and Lewis lung carcinoma, respectively.