Catalytic Systems Based on the Metal Complexes of 1-Alkyl-4-Aza-1-Azoniabicyclo[2.2.2]Octane Bromides

Kinetics and Catalysis - The catalytic activity of supramolecular systems based on the complexes of 1-alkyl-4-aza-1-azoniabicyclo[2.2.2]octane bromide (Alk = CnH2n+ 1, n = 16, 18) with lanthanum...     

Metallomicellar Systems Based on the Complexes of 1-Hexadecyl-4-aza-1-azoniabicyclo[2.2.2]octane Bromide with Transition Metal Nitrates

Potentiometry, fluorimetry, dynamic light scattering, and transmission electron microscopy were used to study the aggregation properties of the complexes 1-hexadecyl-4-aza-1-azoniabicyclo[2.2.2]octane bromide with transition metal nitrates [Cu(II), Ni(II), Co(II), and La(III)]. The critical micelle concentrations, aggregation numbers, the degree of counterion binding to micelles, the size of aggregates, and electrokinetic potentials were determined. The complexes exhibited a high antimicrobial activity, and some of them proved to be more potent than the reference drugs.     

Metallomicellar Complex of 1-Hexadecyl-4-aza-1-azoniabicyclo-[2.2.2]octane Bromide with Copper Dibromide for Solubilization of Nitrofurantoin

Associates of amphiphilic 1-hexadecyl-4-aza-1-azoniabicyclo[2.2.2]octane bromide–copper dibromide complex solubilize nitrofurantoin (furadonin). The solubilizing capacity of premicellar aggregates with respect to nitrofurantoin is 15 times higher than that of micelles and is considerably higher (by a factor of 5–16) than the solubilizing effect of micellar solutions of the complex, ligand, and conventional cationic surfactants with respect to Orange OT.     

1,4-二氮杂双环[2.2.2]辛烷催化的有机化学反应

综述了有机小分子催化剂1,4-二氮杂双环[2.2.2]辛烷(DABCO)在有机合成反应中的应用与发展。这种有机小分子催化的反应大多数条件温和、操作简单;相对过渡金属而言,对环境友好;在一定条件下,这种催化剂可以回收再利用。     

Complexes of 1-alkyl-4-aza-1-azoniabicyclo[2.2.2]octane bromides with lanthanum nitrate. Micelle-forming and adsorption properties

Novel organometallic surfactants were synthesized from monoquaternized 1,4-diazabicyclo[2.2.2]-octanes of varied hydrophobicity [Alk = C _n H_2n+1, n = 14, 18] and lanthanum nitrates. The spectral, micelleforming, and adsorption properties of the synthesized compounds were studied by IR, ¹Н NMR and electronic spectroscopy, tensiometry, conductometry, and potentiometry. The critical micelle concentrations, counterionic micellar binding constants, and adsorption parameters at the water–air interface were determined and compared with the respective characteristics of the ligands and conventional amphiphiles.     

Cationic polymerization of 1-phenyl-4-ethyl-2,6,7-trioxabicyclo[2.2.2]octane

Cationic polymerization of bicyclo ortho ester, 1-phenyl-4-ethyl-2,6,7-trioxabicyclo[2.2.2]octane, was carried out with Lewis acids and cation sources to obtain the polyether containing ester group in the side chain. It was found that boron trifluoride etherate was the most active initiator in the Lewis acids. Magnesium perchlorate and triphenylcarbenium tetrafluoroborate, which have lower nucleophilic counter ions, initiated effectively the polymerization of bicyclo ortho ester.     

Calix[4]arene stabilized Transition Metal Imido Complexes

The usage of calix[n]arenes as ancillary poly(phenolate) ligands is a rapidly developing area in coordination chemistry. This article focuses on the synthesis, structure and reactivity of calix[4]arene‐ and calix[4]arene ether‐stabilized imido complexes of group 4 — 6 transition metals as well as on the comparison of calix[4]arene dialkyl ethers in particular with other widely employed related ligand systems such as salenes, porphyrins and tetraazaannulenes. Contrary to these nitrogen containing systems, it is much easier to control the charge of the ligand system through the degree of alkylation of the calixarene's lower rim without a major change in the geometry of the resulting metal complex. This could lead to isoelectronic and structurally closely related transition metal complex fragments for metals in neighboring groups of the periodic table or for metals in different oxidation states. The “intrinsic” reactivity of metal imido linkages might therefore be explored using calix[4]arenes and calix[4]arene ethers and first results are summarized in this research report.     

1-氮杂环[2.2.2]辛烷的高效合成

将4-（2-羟乙基）哌啶蒸汽在425 ℃下通过CNM-3型固体酸催化剂进行分子内脱水反应,一步合成了目的产物1-氮杂环[2.2.2]辛烷（奎宁环）,4 h内25 g 4-（2-羟乙基）哌啶蒸汽单程收率可达76.8%,最高收率84.3%。 该方法原料易得,适合于奎宁环的工业化制备。     

Supramolecular systems based on 1-alkyl-4-aza-1-azoniabicyclo[2.2.2]octane bromides

The aggregation in aqueous solutions of alkylated 1,4-diazabicyclo[2.2.2]octanes of various hydrophobicity and their adsorption at the water-air interface were studied by tensiometry, conductometry, potentiometry, viscosimetry, and ESR spectroscopy. The parameters of adsorption, critical micelle concentrations, concentrations of free counterions (bromide ions), and degree of binding of the counterions with micelles were determined. The intensification of the micelle formation ability of the surfactants with an elongation of the alkyl fragment was shown. The effective radii of ensembles of the hexadecyl and octadecyl derivatives were determined by the dynamic light scattering method. A relationship between the concentration dependences of the size of micelles and their shape was established.     

Synthesis of 1,4-diazabicyclo[2.2.2]octane

Double intramolecular cyclization of N,N-bis(2-chloroethyl)-N-N-bis(2-cyanoethyl)ethylenediamine leads to 1,4-bis(2-cyanoethyl)-1,4-diazoniabicyclo[2.2.2]octane dichloride, which undergoes decyanoethylation to 1,4-diazabicyclo[2.2.2]octane when it is heated. The structures of the compounds were confirmed by their IR and PMR spectra.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 548–550, April, 1978.     

Complexation of 1-hexadecyl-4-aza-1-azoniabicyclo[2.2.2]octane bromide with nickel nitrate in acetone

The complexation of 1-hexadecyl-4-aza-1-azoniabicyclo[2.2.2]octane bromide with Ni(II) nitrate in acetone is studied by means of spectrophotometry (the Job–Ostromisslensky technique and molar ratios). The formation of 3: 1 and 1: 1 ligand: metal complexes is established and confirmed by mathematical modeling. The stability constants of the complexes and the change in the Gibbs free energy are determined.     

Organic reactions catalyzed by 1, 4-diazabicyclo [2.2.2] octane (DABCO)

The organic reactions catalyzed by 1, 4-diazabicyclo [2.2.2] octane (DABCO) are reviewed. Most of the reactions start conveniently from available substrate and proceed under mild conditions. The reactions are environmentally friendly and the catalyst can be recycled in some cases. The perspectives on DABCO-catalyzed reactions are pointed out. __________ Translated from Chemistry online, 2007, 70(10): 759–765 [译自: 化学通报]     

Complexes of 1-hexadecyl-4-aza-1-azoniabicyclo[2.2.2]octane bromide with transition metal nitrates. Micelle-forming,solubilizing, and adsorption properties

Amphiphilic complexes of 1-hexadecyl-4-aza-1-azoniabicyclo[2.2.2]octane bromide (D-16) with nitrates of transition metals (La³⁺, Cu²⁺, Ni²⁺, and Co²⁺) have been synthesized and characterized. Absorption spectrophotometry in the UV, visible, and IR regions, as well as ¹Н NMR spectroscopy, have been employed to study their spectral properties in water and organic media. Adsorption properties and micelleforming and solubilizing abilities of the amphiphilic complexes have been investigated in aqueous solutions by the methods of tensiometry and conductometry, as well as by solubilization of a water-insoluble dye (Orange OT). The values of the critical micelle concentration, adsorption parameters at a water/air interface, and solubilization capacity S of complex micelles have been determined. It has been shown that the most pronounced decrease in the critical micelle concentration (as large as two to three times) and differences in the adsorption characteristics and the S values as compared with those of ligand D-16 are observed for complexes of copper and lanthanum. The S values for these complexes are 1.3?2.5 and 3?6.5 times higher than those for D-16 and cetyltrimethylammonium bromide, respectively.     

Synthesis of crownophane with the bicyclo[2.2.2]octane core

Russian Chemical Bulletin -     

Transition Metal Complexes of p-Sulfonatocalix[5]arene

The X-ray crystal structure of the p-sulfonatocalix[5]arene(5)(-) anion (1b) in the form of the dimeric hydrate Na(10)[p-sulfonatocalix[5]arene](2).33.5H(2)O (2) is reported. The reactions of 1b with a number of transition metal salts to form transition metal bridged bis(calixarene) inclusion complexes have also been investigated. The X-ray crystal structure of the "Co(H(2)O)(4)(2+)" bridged species Na(8)[Co(H(2)O)(4)(p-sulfonatocalix[5]arene)(2)].2CH(3)C(O)N(CH(3))(2).37H(2)O (3) which incorporates a "supercavity" large enough to encompass 2 N,N-dimethylacetamide (dma) guest molecules as well as ca. 15 water molecules and Na(+) ions is reported. Crystal data are as follows: for 2, monoclinic space group P2(1)/c, Z = 4, a = 22.0644(4), b = 19.1180(3), c = 27.7834(4) ?, beta = 91.780(1), V = 11714.1(5) ?(3); complex 3, orthorhombic space group Pnma, Z = 4, a = 22.2271(5), b = 30.1693(6), c = 18.8503(4) ?, V = 12640.6(5) ?(3).     

Catalytic properties of micellar systems based on 4-aza-1-alkyl-1-azoniabicyclo[2.2.2]octane bromides

The catalytic effect of micellar systems based on alkylated 1,4-diazabicyclo[2.2.2]octanes on the alkaline hydrolysis of butyl chloromethyl 4-nitrophenyl phosphonate is reported. The catalytic effect is due to the reactants concentrating in the micellar phase. It increases with an increase in the hydrophobicity of the surfactant. The bicyclic surfactant manifests the higher efficiency than its cyclic and noncyclic analogues. The micellization properties of alkylated 1,4-diazabicyclo[2.2.2]octanes in aqueous solutions have been investigated by the NMR method. An increase in the hydrophobicity of the surfactant decreases the critical micelle concentration and increases the hydrodynamic radius and aggregation numbers of the micelles.     

Synthesis of novel spiro-cyclohexene bicyclo[2.2.2]octane derivatives

A methodology for the synthesis of novel spiro-cyclohexene bicyclo[2.2.2]octane derivatives, including Claisen rearrangement and ring-closing metathesis (RCM) as key synthetic steps, is described.