Synthesis and characterization of octakis(4,5-bis{2-[2-(1-naphthyloxy)ethoxy]ethoxy})- substituted metal-free and metallophthalocyanines

The synthesis of octakis(4,5-bis{2-[2-(1-naphthyloxy)ethoxy]ethoxy}) metal-free (4) and metallophthalocyanines (5–8) were carried out by the cyclotetramerization of a 4,5-bis{2-[2-(1-naphthyloxy)ethoxy]ethoxy}phthalonitrile (3). Newly substituted octakisphthalocyanines showed enhanced solubility in organic solvents. The new compounds were characterized by IR, ¹H-NMR, ¹³C-NMR, UV-Vis, and MS spectral data.     

Halocyclization of 2-(2-{4-[allylamino(thioxo)methyl]piperazin-1-yl}ethyl)-1<Emphasis Type="Italic">H</Emphasis>-benzo[<Emphasis Type="Italic">de</Emphasis>]isoquinoline-1,3(2<Emphasis Type="Italic">H</Emphasis>)-dione

Cyclization of 2-(2-{4-[allylamino(thioxo)methyl]piperazin-1-yl}ethyl)-1H-benzo[de]isoquinoline-1,3(2H)-dione by the action of iodine, bromine, or sulfuryl chloride gave 2-(2-{4-[4,5-dihydro-5-(halomethyl)-thiazol-2-yl]piperazin-1-yl}ethyl)-1H-benzo[de]isoquinoline-1,3(2H)-dione hydrohalides which were converted into 2-{2-[4-(5-methylthiazol-2-yl)piperazin-1-yl]ethyl}-1H-benzo[de]isoquinoline-1,3(2H)-dione.     

Solvent-Free Synthesis of Novel Highly Functionalized Dihydroanthra[1,2-b]furan-6,11-dione Derivatives

A convenient and environmentally friendly solvent-free procedure has been developed to react 1,5-dihydroxyanthraquinone with dialkyl acetylenedicarboxylates in the presence of triphenylphosphine in one pot to afford novel dialkyl (E)-2-{1,5-dihydroxy-6-[3-methoxy-1-(methoxycarbonyl)-3-oxo-2-(triphenyl-λ ⁵-phosphanylidene)propyl]-9,10-dioxo-9,10-dihydro-2-anthracenyl}-2-butanedioate 3a–c. As a result of intramolecular nucleophilic attack at 90 °C, novel dialkyl (E)-2–{2,7-dihydroxy-3-[2-methoxy-2-oxo-1-(triphenyl-λ ⁵ phosphanylidene)ethyl]-6,11-dioxo-6,11-dihydroanthra[1,2-b]furan-8-yl}-2-butanedioates 4a–c were produced in good yield.     

EPR studies on H-abstractions/spin-trapping reactions of new 'magic blue' reagents with alcohols

The H-abstractions/spin-trapping reactions with primary, secondary and tertiary alcohols of new 'magic blue' reagents, namely, the blue F113 (CClF₂CCl₂F) solution containing bis{perfluoro[1-(2-fluorosulfonyl)ethoxy]ethyl} nitroxide (2) and perfluoro[1-nitroso-1-(2-fluorosulfonyl)ethoxy]ethane (3) both generated in the reaction of perfluoro[2-(2-fluorosulfonyl)ethoxy]propionyl peroxide (1) with sodium nitrite in F113 at room temperature, were studied by EPR. Based on the interpretation of the EPR spectra of the spin adducts, nitroxides, the region-selectivity of H-abstraction has been disclosed and the possible mechanistic paths of H-abstraction have also been discussed. EPR of H-abstraction by using 'magic blue' reagents can also be used for producing various hydroxyalkyl radicals from common alcohols.     

Synthesis and characterization of poly(phenylacetylene)s carrying oligo(ethylene oxide) pendants

A group of new amphiphilic poly(phenylacetylene)s bearing polar oligo(ethylene oxide) pendants, poly{4‐[2‐(2‐hydroxyethoxy)ethoxy]phenylacetylene} ( 1 ), poly(4‐{2‐[2‐(2‐hydroxyethoxy)‐ethoxy]ethoxy}phenylacetylene) ( 2p ), poly(3‐{2‐[2‐(2‐hydroxyethoxy)ethoxy]ethoxy}phenylacetylene) ( 2m ), poly(4‐{2‐[2‐(2‐methanesulfonyloxyethoxy)ethoxy]ethoxy}phenylacetylene) ( 3 ), poly(4‐{2‐[2‐(p‐toluenesulfonyloxyethoxy)ethoxy]ethoxy}phenylacetylene) ( 4 ), poly(4‐{2‐[2‐(2‐trimethylsilyloxy‐ethoxy)ethoxy] ethoxy}phenylacetylene) ( 5 ), and poly(4‐{2‐[2‐(2‐chloroethoxy)ethoxy]ethoxy}phenylacetylene) ( 6 ), were synthesized with organorhodium complexes as the polymerization catalysts. The structures and properties of the polymers were characterized with IR, UV, NMR, and thermogravimetric analysis. 1 , 2p , and 2m , the three polymers containing pendants with hydroxyl groups, were oligomeric or insoluble. The organorhodium complexes worked well for the polymerization of the monomers without hydroxyl groups, giving soluble polymers 3 – 6 with a weight‐average molecular weight up to ～160 × 10³ and a yield up to 99%. Z‐rich polymers 3 – 6 could be prepared by judicious selections of the catalyst under optimal conditions. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 1153–1167, 2006     

The synthesis and characterization of a new (E,E)-dioxime containing 18-membered dithiadiazadioxamacrocyclic moieties and its mononuclear complexes

A new (E,E)-dioxime, (21Z,22Z)-6,7,9,10,12,13-hexahydro-16H- benzo[h][1,4,7,16,10,13][1, 4,7,16,10,13]dioxadithiadiazacyclooctadecine-21,22(20H,23H)-dione dioxime (H ₂ L) has been synthesized by reacting cyanogen-di-N-oxide (2) with (2-{[2-(2-{2-[(7-aminocyclohepta-1,4,6-trien-1-yl)thio]ethoxy}ethoxy)ethyl]thio}phenyl)amine. Mononuclear complexes of this ligand have been synthesized by reacting the vic-dioxime (H₂L) with CuCl₂, NiCl₂.6H₂O and CoCl₂.6H₂O respectively. The BF₂⁺ capped Ni(II) and Co(III) complexes of the dioxime have been synthesized from. The new compounds were characterized by a combination of elemental analysis, ¹H- and ¹³C-n.m.r, I.R. and m.s. spectral data.     

Synthesis of 3-pyrrol-3′-yloxindoles with a carbamate function

By the reaction of methyl {4(3)-[2-(2-oxo-1,2-dihydro-3H-indol-3-ylidene)acetyl]phenyl} carbamates with ethyl 3-aminocrotonate at boiling in the mixture toluene-anhydrous ethanol, 2: 1, ethyl 5-{3(4)-[(methoxycarbonyl)amino]phenyl}-2-methyl-4-(2-oxo-2,3-dihydro-1H-indol-3-yl)-1H-pyrrole-3-carboxylates were obtained. The condensation of methyl {3(4)-[2-(2-oxo-1,2-dihydro-3H-indol-3-ylidene)acetyl] phenyl}carbamates with ethyl acetoacetate in the presence of ammonium acetate and 20 mol% of 1-methyl-3-butylimidazolium chloride or 1-methyl-3-octylimidazolium tetrafluoroborate at boiling in anhydrous ethanol led to the formation of the corresponding 3-pyrrol-3′-yloxindoles with a carbamate function.     

New metallomesogenic polymers built by self-assembly of non-mesomorphic stilbazole dimers and CF3SO3Ag through coordination bonds

Supramolecular liquid-crystalline main-chain polymers have been obtained by self-assembly of non-mesomorphic bifunctional ligands and a transition metal ion. Stibazole dimers, bis[2-(2-{4-[2-(4-pyridyl)vinyl]phenoxy}ethoxy)ethyl] ether (1) and 1,2-bis[2-(2-{4-[2-(4-pyridyl)vinyl]phenoxy}ethoxy)ethoxy]benzene (2) have been synthesized and complexed with silver trifluoromethanesulfonate (CF₃SO₃Ag). The metallomesogenic polymeric complexes formed by coordination bonds between the pyridyl groups of the stilbazole dimers and the silver ion exhibit smectic phases.     

Synthesis,crystal structure and catalytic performance of bis (imino)pyridyl nickel complexes

Two new Ni(II) complexes of 2,6-bis[1-(2,6-diethylphenylimino)ethyl]pyridine (L¹), 2,6-bis[1-(4-methylphenylimino)ethyl]pyridine (L² ) have been synthesized and structurally characterized. Complex Ni(L¹)Cl₂?·?CH₃CN (1), exhibits a distorted trigonal bipyramidal geometry, whereas complex Ni(L¹)(CH₃CN)Cl₂ (2), is six-coordinate with a geometry that can best be described as distorted octahedral. The catalytic activities of complexes 1, 2, Ni{2,6-bis[1-(2,6-diisopropyl-phenylimino)ethyl]pyridine} Cl₂?·?CH₃CN (3), and Ni{2,6-bis[1-(2,6-dimethylphenylimino) ethyl]pyridine}Cl₂?·?CH₃CN (4), for ethylene polymerization were studied under activation with MAO.     

Synthesis and characterization of silver(I) and heterometallic Cr(III)–Na compounds with the tripodal ligand <Emphasis Type="Italic">N</Emphasis>-(carbamoylmethyl)-iminodiacetatic acid

Using the tripodal ligand N-(carbamoylmethyl)-iminodiacetatic acid (H₂ADA), a two dimensional Ag^I coordination polymer [Ag(HADA)] _n (1) and a mononuclear complex [Cr^III(ADA)₂](H₂O)(H₃O) (2) have been isolated. Using 2 as a precursor, a novel 3D heterometallic compound (3) was obtained. In 1 the singly deprotonated HADA⁻ ligand adopts a novel asymmetrical η₁,η₁,η₂,μ₄-tetradentate coordination mode while in 3 four different coordination modes of ADA²⁻ are observed. The solid-state fluorescence spectrum of 1 shows a maximum at 615 nm whereas no fluorescence emission band was observed for free H₂ADA. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Coordination behavior of chromone Schiff bases towards the [ReVO]3+ and [ReI(CO)3]+ cores

Herein, we describe the coordination behavior of chromone Schiff bases towards [Re^VO]³⁺ and [Re^I(CO)₃]⁺. The reaction between 2-(2-thiolphenyliminomethyl)-4H-chromen-4-one (Htch) and [Re(CO)₅Cl] led to fac-[Re(CO)₃(bsch)Cl] (1) (bsch = 2-benzothiazole-4H-chromen-4-one). The square pyramidal [ReO(Hns)] (2) {H₂ns=bis-[(2-phenylthiolate)iminomethyl]-methyl-1-(2-hydroxyphenyl)prop-2-en-1-one} and octahedral [ReO(OCH₃)(PPh₃)(Huch)] (3) complexes were isolated from reactions of trans-[Re^VOBr₃(PPh₃)₂] with Htch and H₃uch [(5Z)-5-((4-hydroxy-2-methoxy-2H-chromen-3-yl)methyleneamino)-6-amino-1,3-dimethylpyrimidine-2,4(1H, 3H)-dione], respectively. The chromone Schiff bases and their metal complexes were fully characterized via NMR-, IR- and UV–Vis spectroscopy, single crystal XRD analysis and conductivity measurements. In addition, DFT studies were conducted to compare selected optimized and experimental parameters of the complexes.     

Kinetics of Oxidation of L-Valine by a Copper(III) Periodate Complex in Alkaline Medium

The kinetics of oxidation of L-valine by a copper(III) periodate complex was studied spectrophotometrically. The inverse second-order dependency on [OH⁻] was due to the formation of the protonated diperiodatocuprate(III) complex ([Cu(H₃IO₆)₂]⁻) from [Cu(H₂IO₆)₂]³⁻. The retarding effect of initially added periodate suggests that the dissociation of copper(III) periodate complex occurs in a pre-equilibrium step in which it loses one periodate ligand. Among the various forms of copper(III) periodate complex occurring in alkaline solutions, the monoperiodatocuprate(III) appears to be the active form of copper(III) periodate complex. The observed second-order dependency of [L-valine] on the rate of reaction appears to result from formation of a complex with monoperiodatocuprate(III) followed by oxidation in a slow step. A suitable mechanism consistent with experimental results was proposed. The rate law was derived as:

Reaction of 2-{[2-(ethenyloxy)ethoxy]methyl}oxirane with oxazolidin-2-ones

Reactions of 2-{[2-(ethenyloxy)ethoxy]methyl}oxirane with N-unsubstituted oxazolidin-2-ones give mixtures of isomeric 3-{3-[2-(ethenyloxy)ethoxy]-2-hydroxypropyl}- and 5-{[2-(ethenyloxy)ethoxy]- methyl}-3-(2-hydroxyalkyl)oxazolidin-2-ones. If the initial oxazolidin-2-one contains two alkyl groups on C⁴, 3-{3-[2-(ethenyloxy)ethoxy]-2-hydroxypropyl}oxazolidin-2-ones are selectively formed.     

Organotellurium Ligands & Their Metal Complexes: Recent Developments

Abstract

The ligand chemistry of telluroethers, halotellurium ligands, and polytellurides has received good attention in the last decade. Tellurium-containing species have been used to design clusters. In the recent past the ligation of di and tri-telluroethers (including bis(4-methoxyphenyltelluro)methane) has been studied. Hybrid organotellurium ligands, N-[2-(4-methoxyphenyltelluro)propyl]phthalimid (L ¹ ), 2-(4-ethoxyphenyltelluromethyl)-tetrahydro-2H-pyran (L ² ), 2-(2-{4-ethoxyphenyl} telluroethyl)-1,3-dioxane (L ³ ), N-{2-(4-methoxyphenyltelluro)ethyl}morpholine (L ⁴ ), N-{2-(4-methoxyphenyltelluro)ethyl}-pyrrolidine (L ⁵ ), bis{2-(pyrrolidine-N-yl)ethyl}telluride (L ⁶ ), 1-(4-methoxyphenyltelluro)-2-[3-(6-methyl-2-pyridyl) propoxy]ethane (L ⁷ ), and 2-[2-(4-methoxyphenyltelluro)ethyl]thiophene (L ⁸ ) have been designed recently and studied for their complexation reactions. The (Te, N) and (N, Te, N) ligands, L ⁵ and L ⁶ , coordinate with Hg(II) through Te and N both, but the bonding with N is some what weak. The morpholine nitrogen of L ⁴ does not coordinate with Pd(II) or Pt(II) along with Te. The L ⁷ behaving as a (Te, N) ligand has formed 20-membered metallomacrocycle ring with Pt(II). Tellurated Schiff bases 4-MeOC₆H₄TeCH₂CH₂N═C(CH₃)C₆H₄-2-OH (L ⁹ ) and 2-HO-C₆H₄-(CH₃)C═NCH₂CH₂TeCH₂CH₂N═C(CH₃)C₆H₄-2-OH (L ¹⁰ ) and their reduction products 4-MeOC₆H₄TeCH₂CH₂NHCH(CH₃)C₆H₄-2-OH (L ¹¹ ) and 2-HO-C₆H₄-(CH₃)CHNHCH₂CH₂TeCH₂CH₂NHCH(CH₃)C₆H₄-2-OH (L ¹² ) respectively have been synthesized and studied for ligation behaviour. The L ⁹ on reaction with the [Ru(p-cymene)Cl₂]₂ results in [Ru(p-cymene)(4-MeOC₆H₄TeCH₂CH₂NH₂)Cl]Cl · H₂O whereas in the reaction of L ¹⁰ with [Ru(p-cymene) Cl₂]₂, p-cymene ligand is lost resulting in [RuCl(L ¹⁰ -H)]. The recent developments, particularly designing of L ¹ to L ¹² and their ligand chemistry, are reviewed in the present paper.     

2,2'-联吡啶参与的分子梭合成与1H NMR研究

2-{2-[4-苯基-二(4-特丁基苯基)甲基]苯氧基}乙氧乙醇磺酸酯(1)与4,4'-联吡啶在乙腈中回流36 h, 随后通过阴离子交换得到N-{2-{2-[4-苯基-二(4-特丁基苯基)甲基]苯氧基}乙氧乙基}-4,4'-联吡啶六氟磷酸盐(3), 产率为93.4%. 3与4,4'-二(溴甲基)-2,2'-联吡啶在乙腈中、70 ℃下反应72 h, 生成哑铃型化合物5, 产率为45%. 5与冠醚BPP34C10在55 ℃下搅拌5 d, 得到分子梭6和7, 产率分别为42.3%和27.3%. ¹H NMR数据表明, 富电子冠醚BPP34C10与哑铃型组分上贫电子4,4'-联吡啶的非键作用使4,4'-联吡啶上氢的化学位移向高场有较大移动.     

Pharmacological evaluation of isochromen-1-ones and their thioanalogues derived from anti-inflammatory drug ketoprofen

The 3-[1-(3-benzoylphenyl)ethyl]-1H-isochromen-1-one, 2 and their thio-analogues 3-[1-(3-benzoylphenyl)ethyl]-1H-isochromen-1-thione, 3 and 3-{1-[3-(benzothioyl) phenyl]ethyl}-1H-isochromen-1-one, 5 were successfully obtained in good yield and purity from anti-inflammatory drug ketoprofen, 1 and its thio analogue, 4. The compounds were successfully characterized by FT-IR, MASS, ¹HNMR and ¹³CNMR spectral techniques. The in vitro anti-inflammatory and anti-oxidant screening revealed that 3-[1-(3-benzoylphenyl) ethyl]-1H-isochromen-1-one, 2 possesses better anti-oxidant and anti-inflammatory activity whereas 3-(1-(3-benzoylphenyl)ethyl)-1H-isochromene-1-thione, 3 and 3-(1-(3-benzothioyl) phenyl] ethyl}-1H-isochromen-1-one, 5 showed moderate anti-oxidant activity in comparison to ketoprofen.     

Novel Compounds with a Viologen Skeleton and N‐Heterocycles on the Peripheries: Electrochemical and Spectroscopic Properties

The present article deals with novel compounds comprising a redox‐active group as core and a nucleobase in the peripheries, linked covalently via a spacer. The new derivatives 1,1′,1″‐(benzene‐1,3,5‐triyltrimethanediyl)tris{1′‐[3‐(3,4‐dihydro‐5‐methyl‐2,4‐dioxopyrimidin‐1(2H)‐yl)propyl]‐4,4′‐bipyridinium} hexafluorophosphate ( 1 ), 1,1′,1″‐(benzene‐1,3,5‐triyltrimethanediyl)tris{1′‐[2‐(4‐chloro‐7H‐pyrrolo[2,3‐d]pyrimidine‐7‐yl)ethyl]‐4,4′‐bipyridinium} hexachloride ( 2a ) 1

1 The numbering of the pyrrolo[2,3‐d]pyrimidine system follows the IUPAC rules and is different from that of the purine ring system.

, and 1,1′,1″‐(benzene‐1,3,5‐triyltrimethanediyl)tris{1′‐[2‐(2‐amino‐4‐chloro‐7H‐pyrrolo[2,3‐d]pyrimidine‐7‐yl)ethyl]‐4,4′‐bipyridinium} hexabromide ( 2b )¹) were synthesized by nucleobase‐anion alkylation and linked to the 4,4′‐bipyridinium core. UV and CV analyses of these compounds were performed and revealed significantly different properties.     

Solid-solute phase equilibria in aqueous solutions,VIII: The standard gibbs energy of La2(CO3)3·8H2O

The solubilities of lanthanum carbonate La₂(CO₃)₃·8H₂O in solutionsS ₀([H⁺]=H mol kg^–1, [Na⁺]=(I–H) mol kg^–1, [ClO ₄ ^– ]=I mol kg^–1) at various fixed partial pressures of CO₂ have been investigated at 25.0 °C. The hydrogen ion molality and the total molality of La(III) ion in equilibrium with the solid phase were determined by e.m.f. and analytical methods, respectively. The stoichiometric solubility constants

Facile synthesis and characterization of novel pyrido[3′,2′:4,5]thieno[3,2-d]pyrimidin-4(3H)-one and pyrido[2′,3′:3,4]pyrazolo[1,5-a]pyrimidine incorporating 1,3-diarylpyrazole moiety

4-(3-(4-Hydroxyphenyl)-1-phenyl-1H-pyrazol-4-yl)-6-phenyl-2-thioxo-1,2-di hydro-pyridine-3-carbonitrile (1) reacted with ethyl chloroacetate (2) in ethanolic sodium acetate solution to yield the corresponding ethyl (3-cyanopyridin-2-ylsulphanyl)acetate derivative 3. Intramolecular cyclization of compound 3 was achieved by its heating in DMF containing potassium carbonate to afford the corresponding ethyl 3-aminothieno[2,3-b]pyridine-2-carboxylate derivative 4 which reacted with hydrazine hydrate in refluxing pyridine to yield the starting material 3-aminothieno[2,3-b]pyridine-2-carbohydrazide derivative 7. Compound 7 reacted with different reagents such as triethylorthoformate, formic acid, acetic acid and acetic anhydride to afford the target molecules pyrido[3′,2′:4,5]thieno[3,2-d]pyrimidin-4(3H)-one derivatives 8–10, 12 and 13 in good to excellent yields. On the other hand, pyridine-2(1H)-thione derivative 1 reacted with hydrazine hydrate in refluxing pyridine to give the other starting material 3-amino-1H-pyrazolo[3,4-b]pyridine derivative 20 which reacted with acetylacetone under reflux to afford the target molecule pyrido[2′,3′:3,4]pyrazolo[1,5-a]-pyrimidine derivative 21 in a good yield. The structures of target molecules were elucidated using elemental analyses and spectral data.     

Synthesis of 2-{2-hydroxy-3-[2-(vinyloxy)ethoxy]propoxy}-benzaldehyde and Schiff bases derived therefrom

Base-catalyzed reaction of 2-hydroxybenzaldehyde with 2-{[2-(vinyloxy)ethoxy]methyl}oxirane gave 2-{2-hydroxy-3-[2-(vinyloxy)ethoxy]propoxy}benzaldehyde in 42% yield, and subsequent condensations of the product with thiosemicarbazide and primary aliphatic amines afforded the corresponding thiosemicarbazone (yield 86%) and 1-{2-[(alkylimino)methyl]phenoxy}-3-[2-(vinyloxy)ethoxy]propan-2-ols (74–81%).