Reaction of Tris(2-hydroxyethyl)amine with Iron(III) and Manganese(II) Salts

Russian Journal of General Chemistry - The reaction of tris(2-hydroxyethyl)amine with Fe(III) and Mn(II) carboxylates was studied for the first time. The complexes formation was confirmed by the IR...     

含三(2-吡啶甲基)胺识别体的荧光化学敏感器核磁共振谱分析

采用二维核磁共振谱技术对新型丹磺酰胺和1,8-萘酰亚胺荧光化学敏感器的结构进行了测定。应用'H—'HCOSY、HSQC、HMBC等二维相关核磁谱对化合物的C和H进行了正确的归属。     

Nitrogen-NMR Studies on the Protonation of 2-(Aminomethyl)pyridine and Tris[(2-pyridyl)methyl]amine

¹⁴N- and ¹⁵N-NMR spectra have been recorded for 2-(aminomethyl)pyridine ( 1 ), tris[(2-pyridyl)methyl]amine ( 2 ), and some of their protonated forms. For 1 , the most basic site is the aliphatic N-atom, whereas for 2 the pyridine N-atoms are more basic, in contrast to what might be expected for a tertiary aliphatic amine.     

Preparations of Tris(Triphenylphospnine)copper and Tris(triphenylphosphine)silver Complexes of Phenalenone,Diphenylcyclopropenone and Tropone

The tris(triphenylphosphine)copper and tris(triphenylphosphine)silver complexes of phenalenone 4 , diphenylcyclopropenone 5 and tropone 6 were prepared by treating tris(triphenylphosphine)copper tetrafloroborate 2 and tris(triphenylphosphine)silver tetrafluoroborate 3 with basic ketones 4, 5 and 6 in high yields. All these complexes are stable in either air or moisture, and soluble in common organic solvents such as dichloromethane and chloroform.     

Tris(trimethylsilyl)silylamin und seine lithiierten und silylierten Derivate — Kristallstruktur des dimeren Lithium-trimethylsilyl-[tris(trimethylsilyl)silyl]amids

Tris(trimethylsilyl)silylamine and the lithiated and silylated Derivatives — X-Ray Structure of the dimeric Lithium Trimethylsilyl-[tris(trimethylsilyl)silyl]amide The ammonolysis of the chlor, brom or trifluormethanesulfonyl tris(trimethylsilyl)silane yields the colorless tris(trimethylsilyl)silylamine, destillable at 51°C and 0.02 Torr. The subsequent lithiation, reaction with chlor trimethylsilane and repeated lithiation lead to the formation of lithium tris(trimethylsilyl)silylamide, trimethylsilyl-[tris(trimethylsilyl)silyl]amine and finally lithium trimethylsilyl-[tris(trimethylsilyl)silyl]amide, which crystallizes in the monoclinic space group P2₁/n with a = 1 386.7(2); b = 2 040.2(3); c = 1 609.6(2) pm; β = 96.95(1)° and Z = 4 dimeric molecules. The cyclic Li₂N₂ moiety with Li? N bond distances displays a short transannular Li …? Li contact of 229 pm. The dimeric molecule shows nearly C₂-symmetry, so that one lithium atom forms agostic bonds to both the trimethylsilyl groups, the other one to the tris(trimethylsilyl)silyl substituents. However, the ⁷Li{¹H}-NMR spectrum displays a high field shifted singlet at —1.71 ppm. The lithiation of trimethylsilyl-[tris(trimethylsilyl)silyl]amine leads to a high field shift of the ²⁹Si{¹H} resonance of about 12 ppm for the Me₃SiN group, whereas the parameters of the tris(trimethylsilyl)silyl ligand remain nearly unaffected.     

Salze der Tris[1,2-äthandiolato(2-)]- und der Tris[2,3-butandiolato(2-)]arsensäure

Salts of the Tris[1.2-ethanediolato(2-)]- and of the Tris[2.3-butanediolato(2-)] Arsenic Acid Salts of tris[1.2-ethanediolato(2-)]arsenic acid and of tris[2,3-butanediolato(2-)]-arsenic acid are obtained by ester interchange of As(OCH₃)₅ with 1.2-diols in the presence of various amines.     

A zinc(II) complex with tris(2-( N -methyl)benzimidazlylmethyl)amine and salicylate: synthesis,crystal structure,and DNA-binding

A five-coordinate zinc complex with tris(2-(N-methyl)benzimidazylmethyl)amine (Mentb) and salicylate, with composition [Zn(Mentb)(salicylate)](NO₃), was synthesized and characterized by elemental analysis, IR and UV-Vis spectral measurements. The crystal structure of the zinc complex shows that Zn(II) is bonded to tris(2-(N-methyl)benzimidazylmethyl)amine (Mentb) and a salicylate through four nitrogens and one oxygen, and the coordination geometry is best described as distorted trigonal-bipyramid. The DNA-binding of the Zn(II) complex and Mentb were investigated by spectrophotometric methods and viscosity measurements, and the results suggest that the Zn(II) complex binds to DNA via intercalation; the binding affinity of the Zn(II) complex to DNA is greater than Mentb. Additionally, Zn(II) complex exhibited potential to scavenge hydroxyl radical in vitro.     

Tris(2-chloroethyl)amine isomerization and subsequent spectrophotometric determination using sulfonephthaleins

In a polar environment, tris(2-chloroethyl)amine molecule undergoes isomerization when forming N,N-bis(2-chloroethyl)aziridinium cation as a reactive intermediate. New methods were developed to spectrophotometrically determine tris(2-chloroethyl)amine in the form of aziridinium cation extraction using 4 sulfonephthaleins—bromothymol blue, thymol blue, bromoxylenol blue, and bromocresol green. The developed methods, reflecting potent electrophilic properties of the analyte, are based on the formation of extractable ion pairs between the aziridinium cation and a quinoid anion form of a sulfonephthalein. Chloroform was used as the solvent for extraction from the water phase. The conditions of the methods were optimised by determining the suitable pH (8.5) of a buffer and the concentration of sulfonephthaleins as reagents. The dependence of the reaction time in the water phase was found to be 10 min. The composition of the ion pairs was found to be 1:1 by in all cases and the conditional extraction constant of the complexes were calculated. The detection and determination limits of separate procedures were ascertained. Best results (detection limit 3.5 µg ml^?1 and determination limit 11.6 µg ml^?1) were obtained using bromothymol blue. The methods were empirically compared with a group spectrophotometric method to determine alkyl halides using the alkalized water–ethanol solution of thymolphthalein. Relatively low interferences of other nitrogen mustards and sulfur mustard were recorded. The interaction mechanism—ion association—was validated.     

Chloromethylated polystyrene reaction with tris(2-hydroxyethyl)amine. I. Crosslinked polymers prepared by chloromethylated polystyrene with tris(2-hydroxyethyl)amine

A multifunctional crosslinked polymer resulted from a chloromethylated polystyrene reaction with tris(2-hydroxyethyl)amine. A benzyl chloride reaction (chosen as a structural unit model) with tris(2-hydroxyethyl)amine was investigated to explain the reasons for the crosslinking. Amino-ethers and tris(2-hydroxyethyl)amine hydrochloride in addition to ammonium quaternary salt were isolated from this reaction. The formation of amino-ethers proved that an ammonium quaternary salt rearrangement also takes place during the quaternization reaction. This rearrangement leads to chloromethylated polystyrene during its reaction with tris(2-hydroxyethyl)amine.     

Synthesis of Immunoactive Tris(2-hydroxyethyl)ammonium 1-R-Indol-3-ylsulfanyl(sulfonyl)acetates

Difficultly accessible 1-R-indol-3-ylsulfanyl(sulfonyl)acetic acids 1-R-IndYCH₂CO₂H (R = H, Me, Bn; Y = S, SO₂) 1a–Id were prepared. Their reaction with tris(2-hydroxyethyl)amine yielded tris(2-hydroxyethyl) ammonium 1-R-indol-3-ylsulfanyl(sulfonyl)aceetates (protatranes) 2a–2d. The immunoactive properties of 2a–2d were studied. Protatranes 2a, 2c, and 2d proved to be effective immunosuppressive agents (up to 99.5% inhibition of mice splenocyte proliferation in vitro).     

Tris(porphyrinyl-oxinato)Ga Complexes as a Photosynthetic Antenna Miniature

Two oxinylporphyrins, 5-(8-hydroxy-5-quinolinyl)-10,15,20-( p -tolyl)- porphyrin ( 1 ) and 5,15-bis(8-hydroxy-5-quinolinyl)-10,20-bis( n -heptyl)-porphyrin ( 2 ), were prepared and coordinated with Ga(III) to afford tris(oxinato) complex 3 and poly(oxinato) complex 4 , respectively. The structure of 3 was analyzed by variable temperature NMR study with referring to tris(8-hydroxy-5-quinolinyl)Ga(III) complex 5 to be in a meridional form. Oxinato ligands of 3 and 5 were exchanged with one another, with keeping the meridional structure. UV-Vis and fluorescence spectra of tris(oxinato)complex 3 and poly(oxinato)complex 4 were compared with each monomeric compound 1 and 2 . The absorption spectra showed only a slight broadening of the Soret band, suggesting trivial electronic and excitonic interactions. The fluorescence intensity was increased significantly compared with each monomeric compound 1 and 2 . At the same time, efficient excitation energy transfer among three porphyrins has been observed.     

Chalcogen Effect of Atom Substitution on the Properties of Tris(2,4,6-trichlorophenyl)methyl(TTM) Radical

Luminescent open-shell organic radicals have recently been regarded as one of the most potential materials in organic light-emitting diodes(OLEDs). Herein, we have synthesized two new organic radicals, namely tris{4-[4-(tert-butyl)phenoxy]-2,6- dichlorophenyl}methane radical(TTM-O) and tris(4-{[4-(tert-butyl)- phenyl]thio}-2,6-dichlorophenyl)methane radical(TTM-S), by the substitution of chalcogen atom elements at the para position of conventional tris(2,4,6-trichlorophenyl)methyl(TTM) radical moiety. Interestingly, both TTM-O and TTM-S exhibited significantly enhanced photostability compared with the unsubstituted TTM radical parent. Moreover, the chalcogen atom also had a crucial impact on the photoluminescence quantum yield(PLQY) of the radicals, i.e., the PLQY of TTM-S was greatly enhanced compared to TTM radical while TTM-O was nearly non-emissive. Particularly, TTM-S showed intense PLQY of 37.54% and 185-fold longer photostability than that in cyclohexane solution of TTM.     

Tris(2-hydroxyethyl)ammonium salts: 2,8,9-Trihydroprotatranes

New method of synthesis of tris(2-hydroxyethyl)ammonium salts, 2,8,9-trihydroprotatranes X-[HN(CH₂CH₂OH)₃]⁺, based on the reaction of tris(2-hydroxyethyl)amine (triethanolamine) with ammonium salts NH₄X (X = F, Cl, Br, I, NO₃, ClO₄) was developed. ¹H, ¹³C, ¹⁵N NMR and IR spectra of these protatranes were investigated, as well as those of their analogs with X = RCH₂COO (R = H; 2-MeC₆H₄O; 2-Me-4ClC₆H₃O; 2-MeC₆H₄S; 4-ClC₆H₄S; 4-ClC₆H₄SO₂; 3-IndS; 3-(PhCH₂-IndS) prepared from the corresponding acids RCH₂COOH and triethanolamine. The parameters of IR and NMR spectra of the studied protatranes were governed by the nature of substituent X, which also determined the character of the intra and intermolecular hydrogen bonds NH⋯O and OH⋯O in the protatrane framework.     

相转移催化与微波辐射合成三(2-氰乙基)胺

将微波辐射与相转移催化技术相结合,在加压密闭容器中,以氨水和丙烯腈合成了配位中间体三(2-氰乙基)胺,产率为61.2%,合成时间比传统方法缩短了8倍;在微波辐射下,产率为67.2%,合成时间缩短约90倍.对产物进行了元素分析,IR,¹H-NMR,ES-MS,及TG-DTA表征.     

Rhodium, palladium and platinum complexes of tris(pyridylalkyl)amine and tris(benzimidazolylmethyl)amine N4-tripodal ligands

To investigate the influence of a potentially N4-tripodal amine ligand on the structure and internal exchange processes of its complexes with late transition metals, five rhodium, six palladium and two platinum complexes have been prepared from seven alkyl-bridged N-heterocyclic amine tripodal ligands: tris(2-pyridylmethyl)amine, (2-(2-pyridylethyl))bis(2-pyridylmethyl)amine, bis(2-(2-pyridylethyl))-2-pyridylmethylamine, bis(2-(2-pyridylethyl))amine, ((6-(hydroxymethyl)-2-pyridyl)methyl)bis(2-pyridylmethyl)amine, tris(2-benzimidazolylmethyl)amine (tbima) and tris(3-ethyl-2-benzimidazolylmethyl)amine. Single-crystal X-ray diffraction studies were completed for ten complexes: the d6-rhodium(III) complexes are octahedral with kappa 4 N-bound ligands, whereas the d8-palladium(II) and d8-platinum(II) complexes are square planar, kappa 3 N-bound by the tripodal ligand with a dangling N-donor leg, except for the unusual [Pd2(tbima)2Cl2]Cl2 dimer in which each palladium(II) ion is square planar and bound by two benzimidazole legs from one tbima ligand, one leg from the other tbima ligand and a chloride ancillary ligand. Cation bilayers are a common structural motif in the crystal structures. Variable-temperature 1H NMR studies reveal exchange occurs between the coordinated and dangling N-donor legs in the palladium and platinum complexes. Exchange free energy (Delta G++ c) values have been calculated and some general rules governing the favoured complex structures and exchange pathways elucidated. The palladium(II) and platinum(II) complexes of a ligand with an pyridylethyl leg are unstable with respect to elimination of vinylpyridine.     

Tris(1-4-eta 4-anthracene)niobate(1-), the first polyaromatic hydrocarbon complex of niobium

The first tris(arene)niobium complex, [Nb(1-4-eta 4-anthracene)3]-, has been obtained by the sodium or potassium anthracene reduction of NbCl4(THF)2, structurally characterized by X-ray analysis and shown to undergo facile anthracene displacement reactions in the presence of excess CO, PF3, 1,3,5,7-cyclooctatetraene and P(OMe)3.     

Atom-Economic Synthesis of Tris[2-(organylthio)ethyl]phosphine Oxides from Phosphine and Vinyl Sulfides

Abstract

Phosphine, generated from elemental phosphorus in the system KOH-toluene-H₂O, reacts with vinyl sulfides under free radical conditions (AIBN, dioxane, 65–70°C, atmospheric pressure) to form regiospecifically tris[2-(organylthio)ethyl]phosphines, which are readily oxidized in air to corresponding tris[2-(organylthio)ethyl]phosphine oxides.     

Tris(2,2'-bipyridyl)ruthenium(II) chemiluminescence

This paper critically reviews analytical applications of the chemiluminescence from tris(2,2'-bipyridyl)ruthenium(II) and related compounds published in the open literature between mid-1998 and October 2005. Following the introduction, which summarises the reaction chemistry and reagent generation, the review divides into three major sections that focus on: (i) the techniques that utilise this type of detection chemistry, (ii) the range of analytes that can be determined, and (iii) analogues and derivatives of tris(2,2'-bipyridyl)ruthenium(II).     

Atom transfer radical addition (ATRA) catalyzed by copper complexes with tris[2-(dimethylamino)ethyl]amine (Me6TREN) ligand in the presence of free-radical diazo initiator AIBN

In this article, we focus on the evaluation of tris[2-(dimethylamino)ethyl]amine (Me(6)TREN) ligand in copper catalyzed ATRA in the presence of free-radical diazo initiator AIBN (2,2'-azobis(2-methylpropionitrile)). The addition of carbon tetrachloride to 1-hexene, 1-octene and cis-cyclooctene proceeded efficiently to yield 89, 85 and 85% of monoadduct, respectively, using the catalyst to alkene ratio of 1 : 2500. For alkenes that readily undergo free radical polymerization, such as methyl acrylate, catalyst loadings as high as 0.4 mol-% were required. Furthermore, modest yields of the monoadduct were obtained with less active alkyl halides (chloroform and bromoform) using 250 : 1 and 500 : 1 ratios of alkene to copper(II). Interestingly, the addition of carbon tetrachloride to cis-cyclooctene produced only 1-chloro-4-(trichloromethyl)-cyclooctene, while carbon tetrabromide yielded 1,2 and 1,4-regioisomers in 75 : 25 ratio. The activity of [Cu(II)(Me(6)TREN)X][X] (X = Br(-) and Cl(-)) complexes in ATRA in the presence of AIBN was additionally probed by adding excess free ligand, source of halide anions and triphenylphosphine. The results indicated that disproportionation is a likely cause for lower activity of Me(6)TREN as compared to TPMA (tris(2-pyridylmethyl)amine).     

Emission efficiency of diamine derivatives of tris[4,4,4-trifluoro-1-(2-thienyl)-1,3-butanediono]europium

Diamine derivatives of tris[4,4,4-trifluoro-1-(2-thienyl)-1,3-butanediono]europium were synthesized and characterized by NMR, IR and UV-vis spectroscopy. The emission efficiency and decay times of the produced Eu(III) coordination complexes in acetone solutions were measured upon ligand excitation. The effect of the amine ligands was studied and the relation between the emission and the structure of the synthesized compounds was discussed.