Metal derivatives of 1,3-bis(2-pyridyl)-1,3-propanedione and N,N′-dimethyl-1,3-bis(2-pyridyl)-1,3-propanedione

Complexes of transition metal ions with the oxygen-nitrogen containing ligand 1,3-bis(2-pyridyl)-1,3-propanedione (bpypH) have been synthesized. These present stoichiometries which do not conform with the usual tendency manifested by β-diketones, since molecular formulas with the composition M(bpyp)X are found. A nitrogen methylated ligand N,N′-dimethyl-1,3-bis(2-pyridyl)-1,3-propanedione methyl sulphate [dimebpypH] (MeSO₄)₂ has also been synthesized and its complexes with transition metal ions studied. The stoichiometries now, resemble those of typical β-diketones, namely [dimepyp]₂MX₄ with four anions because of the dicationic nature of the original ligand. This, together with IR evidence suggests a dual type of coordination by bpip via the β-diketone and the pyridyl moieties.     

β-diketone interactions: Part 4. The structures and properties of 1,3-diphenyl-2-methylpropane-1,3-dione,C16H14O2, and 1,3-diphenyl-2-(4-methoxyphenyl)propane-1,3-dione,C22H18O3

The X-ray crystal structures of 1,3-diphenyl-2-methylpropane-1,3-dione and 1,3-diphenyl-2-(4-methoxyphenyl)propane-1,3-dione show them both to adopt cis-diketo (Z,Z) conformations with carbonyl—carbonyl dihedral angles of 89.0(3)° (2-methyl derivative), and 85.5(4)° and 77.7(4)° for the two molecules in the asymmetric unit of the 2-(4-methoxyphenyl) derivative. These are the first acyclic β-diketones with an α-hydrogen to be reported which do not have an enol configuration in the solid state.     

Hydrochlorination of δ2-1,3-oxazolines and 1,3-oxazolidines

The compounds 2-(ethoxycarbonylmethyl)-²-l,3-oxazoline and 1-methyl-2-(methoxycarbonylmethylene)-1,3-oxazolidine are hydrochlorinated at the C=N or C= C bond, respectively, with subsequent opening of the oxazolidine ring. Depending on the reaction conditions, this occurs regioselectively to form various products.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 684–686, May, 1992     

Antimicrobial effects of bis(Δ2-2-imidazolinyl)-5,5′-dioxime and its mono- and tri-nuclear complexes

Bis(Δ²-2-imidazolinyl)-5,5′-dioxime (H₂L) and its nickel, cobalt, zinc, cadmium and mercury complexes have been prepared and tested in vitro against different microorganisms in order to assess their antimicrobial properties. We used Bacillus subtilis RSKK 244, Micrococcus flavus, Streptococcus faecalis RSKK 500, Staphylococcus aureus RSKK 490 from Gram-positive bacteria; Pseudomonas aeruginosa RSKK 356, Salmonella typhimurium RSKK 1017, Escherichia coli RSKK 550, Enterobacter aerogenes RSKK 720 from Gram-negative bacteria, Candida tropicalis RSKK 665 and Penicillium raciborskii IMI 40568. This revised version was published online in June 2006 with corrections to the Cover Date.     

Synthesis,Dimer Crystal Structure and Herbicidal Activity of 2-（4-Ethoxybenzoyl）cyclopentane-1,3-dione

The title compound 2-(4-ethoxybenzoyl)cyclopentane-1,3-dione(C14H14O4) was synthesized, and its crystal structure was studied. It crystallized in the triclinic system, space group P1 with a = 8.980(2), b = 9.080(2), c = 15.482(3) , α = 93.49(3), β = 93.84(3), γ = 107.27(3)°, Dc = 1.365 g/cm3, Z = 4, λ = 0.71073, μ(MoKα) = 2.769 mm-1, Mr = 246.25, V = 1198.5(4)3, F(000) = 520, the final R = 0.0559 and wR = 0.1278 for 2301 observed reflections with I 2σ(I). In the crystalline state, the molecular skeleton contains one enol grouping, which is intramolecularly hydrogen bonded to a neighboring keto O atom. Preliminary bioassay result showed that this compound provided 93.8% and 87.2% control of B. campestris and A. retroflexus at post-emergence at 375 g/hm2.     

Synthesis and crystal structure of the Ag(I) complex with a cyclic β-diketone, 2-(diphenylacetyl)indan-1,3-dione (L), and the HL molecule

An Ag(I) complex with HL (I), AgL (AgC₂₃H₁₅O₃, II), has been synthesized. Compounds I and II have been studied by X-ray diffraction. The crystals are monoclinic, I: space group P2₁/n, a = 10.459(2) Å, b = 12.354(2) Å, c = 13.390(3) Å, β = 96.67(3)°, Z = 4; II: space group P2₁/c, a = 10.764(2) Å, b = 10.683(2) Å, c = 15.939(3) Å, β = 101.57(3)°, Z = 4. The structural units of the crystal of I are neutral molecules with intramolecular hydrogen bonds. In structure II, the Ag₂O₆ dimeric groups and the ligands form infinite openwork layers perpendicular to the x axis and containing cavities. The layers are penetrated by channels with an oblong cross section. In the crystal of II, all intermolecular distances exceed the sums of the van der Waals radii of the corresponding atoms.     

Reactions of 1,3-bis(ω-bromoalkyl)-6-methyluracils with 2-(dialkylamino)ethylphosphonates and 2-(dialkylamino)ethyl phosphates

1,3-Bis(4-bromobutyl)-6-methyluracil reacts with diethyl 2-(dimethylamino)ethylphosphonate to form a bisquaternary ammonium salt, whereas the reaction of 1,3-bis-(6-bromohexyl)-6-methyluracil with diethyl 2-(diethylamino)ethyl phosphate gives 1,3-bis-[(6-diethoxyphosphoryloxy)hexyl]-6-methyluracil and 1,1,4,4-tetraethylpiperazinium dibromide. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1130–1132, June, 2000.     

Synthesis and Crystal Structure of 3,6-Bis（4,4,4- trifluorobutane- 1,3-dione）-9-n-butylcarbazole

A novel bis（β-diketonate） derivate, 3,6-bis（4,4,4-trifluorobutane-1,3-dione）-9-n- butylcarbazole 1, was synthesized and structurally characterized by single-crystal X-ray diffrac- tion. The crystal belongs to the monoclinic system, space group P2 1/c with a = 10.961（6）, b = 22.942（13）, c = 9.408（6）A, α = 90, β = 109.663（9）, y = 90°, V = 2228（2）A^3, Z = 4, Dc = 1.489 g/cm^3, C24H19F6NO4, Mr = 499.40, F（000） = 1024 and μ = 0.134 mm^-1. The structure was refined to the final R = 0.0699 and wR = 0.1627 for 3744 independent reflections （Rint = 0.1288） and 1349 observed reflections （I 〉 2σ（I））. Compound 1 consists of carbazole unit and two terminal diketonate groups, in which carbazole and its two adjacent diketonate rings are almost coplanar. Moreover, compound 1 was characterized with IR, elemental analysis, IH NMR, MS, electronic absorption, and single-photon fluorescence.     

Ion Channel Behavior of a Supported Bilayer Lipid Membrane Composed of 5,5-Ditetradecyl-2-(2-trimethyl-ammonioethyl)-1,3-dioxane Bromide Modified Glassy Carbon Electrode

A synthetic cationic surfactant, 5, 5-ditetradecyl-2-(2-trimethyl-ammonioethyl)-1, 3-dioxane bromide (DTDB), was used toconstruct a supported bilayer lipid membrane (s-BLM) coatedon an underlying glassy carbon electrode (GCE). Electrochem-ical impedance spectroscopy (EIS), small-angle X-ray diffrac-tion (SAXD) and cyclic voltammetry were used to characterizethe s-BLM. Both EIS and SAXD data indicated that the syn-thetic lipid exists as a well-oriented bilayer in the membrane.     

Synthesis of 2-Ferrocenyl-2-(Dialkyl Hydroxymethyl)D-1,3-Dithianes

The reactions of lithiated 2-ferrocenyl-1,3-dithiane with alkyl carbonyl compounds are studied. Fifteen of title compounds which are new ferrocene derivatives were synthesized and structurally characterized by elemental analysis, IR and 1H NMR spectra. The 1H NMR spectra of the dithiane compounds are briefly discussed.     

Synthesis and anti-inflammatory activity of N′-substituted 2-[2-(diarylmethylene)hydrazinyl]-5,5-dimethyl-4-oxohex-2-enehydrazides

New N′-substituted 2-(2-(diarylmethylene)hydrazinyl)-5,5-dimethyl-4-oxohex-2-enehydrazides were synthesized by the ring opening reaction of 3-diarylmethylenehydrazono-5-tert-butyl-3H-furan-2-ones under the action of aliphatic, aromatic, and heterocyclic acid hydrazides. The structures of the obtained compounds were confirmed by ¹H and ¹³C NMR spectroscopy, IR spectroscopy, and elemental analysis. Their anti-inflammatory activity was studied.

     

Montmorillonite K-10 clay catalyzed solvent-free synthesis of bis-indolylindane-1,3-dione, 2-(1′,3′-dihydro-1H-[2,3′]biindolyl-2′-ylidene)-indan-1,3-dione and bisindolylindeno[1,2-b]quinoxaline under microwave irradiation

An environmentally benign protocol has been described for the synthesis of novel 2-(1′,3′-dihydro-1H-[2,3′]biindolyl-2′-ylidene)-indan-1,3-diones/bis-indolylindane-1,3-diones from ninhydrin and 3-substituted/unsubstituted indoles. It uses montmorillonite K-10 as catalyst in a solvent-free condition under microwave irradiation. The method was also used for the synthesis of novel bisindolylindeno[1,2-b]quinoxaline derivatives.     

One-pot synthesis of α-bromoacetals of ketones from secondary alcohols and 1,3-dibromo-5,5-dimethylhydantoin (DBDMH) in ethylene glycol

α-Bromoacetals of ketones were prepared from various secondary alcohols with 1,3-dibromo-5,5-dimethylhydantoin (DBDMH) and ethylene glycol through oxidation, bromination, and acetalization in one pot without the use of other catalysts under mild conditions. The effects of DBDMH, the solvent, and N-bromosuccinimide on the reaction were investigated. Under the optimal conditions, most α-bromoacetals of ketones were obtain in 90–98% yields.     

Crystal and Molecular Structure of Ethyl 2-[（4-Hydroxy-phenyl）hydrazono]-3-oxobutanoate

The title compound,C 12 N 2 O 4 H 14 (M r=250.3),crystallizes in triclinic P1 space group with a=7.7709(9),b=8.7534(11),c=9.6958(12),α=77.103(2),β=80.496(2),γ=86.726(2)o,V=633.9(1) 3,Z=2,F(000)=264,D c=1.311 Mg/m 3,μ(MoKα)=0.1 mm-1,the final R=0.056,and wR=0.15 for 2239 observed reflections (I > 2σ(Ⅰ)).The molecules in the crystal are linked through O-H···O type of hydrogen bonding interaction forming an infinite chainlike structure.The phenylhydrazone ring and oxobutanoate groups are almost planar.The keto hydrazo group adopts a Z-configuration in the molecule and the torsion angle is-177.6(2)°.     

Synthesis and Structural Determination of (2R,4S,SS)-( )-Threo-5-(2,2-dichloroacetamido)-4-(4-nitrophenyl)-2-aryl-1,3-dioxanes

Acetalscanbesynthesizedinanumberofways.Themainproblemintheacetalformationinacidicmediumistoshifttheequilibriumtotherightbyremovalofthewaterformedduringthereactionl.Wesynthesized(2R,4S,SS)-( )-threo-5-(2,2-dich(4-nitrophenyl)-2-aryl-1,3-dioxanesbyacet...     

The complex Eu(phen)L3��5CH2Cl2 (HL is 1,3-bis(1,3-dimethyl-1H-pyrazol-4-yl)propane-1,3-dione): synthesis, crystal structure, and luminescent properties

A reaction of Eu(NO₃)₃·6H₂O with the novel heterocyclic ligand 1,3-bis(1,3-dimethyl-1H-pyrazol-4-yl)propane-1,3-dione and 1,10-phenanthroline in the presence of NaOH gave the complex Eu(phen)L₃·5CH₂Cl₂. The crystal structure of the complex was determined by single-crystal X-ray diffraction. The coordination polyhedron {EuO₆N₂} is a tetragonal antiprism. The complex shows bright orange-red luminescence in both the solid state and solution.     

SYNTHESIS OF POLY(5,5-DIMETHYL-1,3-DIOXAN-2-ONE)BY LIPASE-CATALYZED RING-OPENING POLYMERIZATION

Porcine pancreas lipase (PPL) and PPL immobilized on narrow distributed micron-sized glass beads wereemployed successfully for the ring-opening polymerization of 5, 5-dimethyl-1, 3-dioxan-2-one (DTC) for the first time.Different polymerization conditions such as enzyme concentration and reaction temperature were studied. Immobilized PPLexhibits higher activity than native PPL. Along wth the increasing enzyme concentration, the molecular weigh of resultingPDTC decreases. PPL immobilized on narrow distributed micron-sized glass beads has outstanding recyclability. For thethird recycle time, immobilized PPL exhibits the highest catalytic activity and with high activity even after the fifth recyletime for the synthesis of PDTC. The ~1H-NMR spectra indicate that decarboxylation does not occur during the ring-openingpolymerization.     

Synthesis, Crystal Structure and Thermal Properties of N,N′-Bis(5,5-dimethyl-2-phospha-2-thio-1,3-dioxan-2-yl) Ethylene Diamine

The title compound N,N′-bis(5,5-dimethyl-2-phospha-2-thio-1,3-dioxan-2-yl) ethylene diamine (DPTDEDA, C12H26N2O4P2S2) was synthesized by the reaction of neopentyl glycol, phosphorus thio-chloride and 1,2-ethylenediamine, and characterized by elemental analysis, IR and 1H NMR spectra. Its crystal structure was determined by single-crystal X-ray diffraction analysis and the thermal property was analyzed by TG analysis. The crystal structure belongs to monoclinic, space group P21/c, with a = 14.557(16), b = 11.299(12), c = 12.163(13) , β = 98.707(19)°, Dc = 1.305 g/cm3, Z = 4, λ = 0.71073 , μ(MoKα) = 0.447 mm-1, Mr = 388.41, V = 1977(4) 3, F(000) = 824, S = 1.107, the final R = 0.0478 and wR = 0.0810 for 1738 observed reflections (I > 2σ(I)). X-ray analysis reveals that the crystal structure is centrosymmetrically distributed through 1,2-ethylenediamine to join two distorted six-membered rings. The weak N–H···S interactions are observed and link the molecules into sheets. TG analysis shows that the title compound has good thermal stability and char-forming capability, which are required for an excellent intumescent fire retardant.     

Synthesis of cis-(±)-2-Hydroxymethyl-5-(Cytosine-1'-yl)-1,3-Oxathiolane (BCH-189)

cis-BCH-189 are potent anti-HIV agents and have been synthesized from mannose1 galactose2 or glucose3 etc. Owing to so many synthetic steps, it is difficult and expensive to obtain a few grams. In this paper, we have designed new route and promoted the reaction conditions for the synthesis of this nucleoside cis- (+)- BCH-189 from cheap starting material via a four step route as shown in Scheme 1. By this method, a series of derivatives of title compound can be synthesized conviniently for…