2-[1-(Hydroxyimino)ethyl]-2,5,5-trimethylperhydropyrimidine–butane-2,3-dione monooxime (1/1)

The title compound, C₉H₁₉N₃O·C₄H₇NO₂, displays strong intramolecular O—H⃛N [O⃛N 2.6743 (13) Å] and N—H⃛N [N⃛N 2.6791 (15) Å] hydrogen bonds, and strong intermolecular O—H⃛N [O⃛N 2.7949 (15) Å] and N—H⃛O [N⃛O 3.0924 (16) Å] hydrogen bonds. This creates chains of per­hydro­pyrimidine mol­ecules, linked by hydrogen bonds. Each chain is linked to a partner chain, through hydrogen bonds to two butane-2,3-dione monooxime mol­ecules, in a structure reminiscent of a ladder.     

Solid-state structures of 2-(4-hydroxyphenyl)-substituted phenalene-1,3-dione and indan-1,3-dione

The structure of 2-(4-hydroxyphenyl)-substituted indan-1,3-dione and phenalene-1,3-dione is investigated using a combination of solid-state NMR, single crystal X-ray analyses and quantum chemical calculations. It is shown that 2-(4-hydroxyphenyl)-1,3-indandione exists as a diketo tautomer while 2-(4-hydroxyphenyl)-1,3-phenalenedione exists in the enol form.     

1—N—（6—硝基苯并咪唑—1—乙酰基）—4—苯基氨基硫脲及其过渡金属配合物

以新配体１－Ｎ－（６－硝基苯并咪唑－１－乙酰基）－４－苯基氨基硫脲（ＮＢＰＭＳ）合成了Ｍｎ（Ⅱ）、Ｃｕ（Ⅱ）、Ｃｏ（Ⅱ）、Ｚｎ（Ⅱ）、Ｃｄ（Ⅱ）、Ｎｉ（Ⅱ）、Ｐｂ（Ⅱ）等金属离子的配合物，并进行了表征。这些化合物的红外光谱表明，配体以四齿方式通过烯醇式羰基氧原子，烯醇式硫羰基硫原子，以及Ｃ＝Ｎ↑１、Ｃ＝Ｎ↑２的红外光谱表明，配体以四齿方式通过烯醇式羰基氧原子，烯醇式硫羰基硫原子，以及Ｃ＝Ｎ↑１、Ｃ     

Molecular and crystal structure of 4-trifluoro-2-[2-(4-fluorophenyl)hydrazine-1-ylidene]-1-(thiophen -2-yl)butane-1,3-dione

Single crystal X-ray diffraction is used to determine the crystal and molecular structure of 4-trifluoro-2-[2-(4-fluorophenyl)hydrazine-1-ylidene]-1-(thiophen-2-yl)butane-1,3-dione. Crystallographic data for C₁₄H₈F₄N₂O₂S are as follows: a = 8.2723(6) ?, b = 9.3009(7) ?, c = 9.9895(7) ?; α = 79.224(2)°, β = 75.851(2)°, γ = 72.337(2)°. Triclinic crystal system, P-1 space group, d _x = 1.622 g/cm³, V = 704.83(9) ?³, μ = 0.286 mm⁻¹, crystal size 0.30×0.20×0.20 mm, R1 = 0.0891, wR2 = 0.1989.     

Antioxidant,Antimicrobial and Antitumor Studies of Transition Metal Complexes Derived from N-(2-Aminoethyl)-1,3-Propanediamine with DFT Calculations and Molecular Docking Investigation

New expected biologically active complexes for some of the first (Mn (II), Ni (II), Cu (II) and Zn (II)) and second (Rh (III) and Cd (II)) transitional metals rows with N-(2-Aminoethyl)-1,3-propanediamine as a ligand (AEPD)have been synthesized. All synthesized complexes were formed with 1:1 (metal: AEPD) stoichiometry except Ni (II) 1:2 (Ni: AEPD). The compounds were characterized by different analysis tools such as; elemental analysis, Fourier transform infrared (FTIR), ¹H-NMR, mass spectra, thermal analysis, electronic spectra, magnetic measurement and molar conductance techniques. AEPD ligand interacted with all metal ions as tridentate ligand by using the nitrogen atoms. On the other hand, density functional theory (DFT) calculations have been performed to confirm the optimized geometrical structures for both AEPD and its complexes. Furthermore, coordination compounds were screened for their potential antibacterial activities against six pathogenic bacteria as well as one kind of fungi in comparison to standard antibiotics by agar well diffusion method. The results show that most of the complexes exhibit antibacterial and antifungal activities against these organisms. Rh (III)-AEPD complex exhibited the strongest antibacterial effect followed by the Cd (II) complex but as antifungal agents Cd (II) was the first and the second was Rh (III). Also, the anticancer activity was screened for these metal complexes against growth of human liver cancer HEPG2 tumor cell line and this inhibition activity of Cd (II) chelate was noticed to be more active with lowest IC₅₀ than that of all other synthesized complexes. Unfortunately, Mn (II) and Rh (III) chelates lacked anticancer activity. The docking active sites interactions were evaluated using the selected protein for anticancer activity. Finally, antioxidant activity was studied. Mn (AEPD) showed maximum activity followed by complex of Rh (III).     

Synthesis and Some Properties of Transition Metal Complexes with Octa(sulfophenyl)tetrapyrazinoporphyrazine

Sulfonation of metal complexes of octaphenyltetrapyrazinoporphyrazine gave water-soluble octasulfoderivatives. The complexes synthesized were studied by EPR, ¹H NMR, electronic, and IR spectroscopy. It was found that, unlike complexes of other porphyrins and porphyrazines, this nickel complex is paramagnetic, whereas the cobalt complex gives no EPR signal. The cobalt complex can reversibly bind an oxygen molecule.__________Translated from Koordinatsionnaya Khimiya, Vol. 31, No. 5, 2005, pp. 545–549.Original Russian Text Copyright © 2005 by Shishkin, Kudrik, Shaposhnikov.     

Reactivity of 2-(Hydroxyimino)-1-pyridylbutane-1,3-diones in the Synthesis of p-Nitrosophenols

Russian Journal of Organic Chemistry - Completely substituted p-nitrosophenols were synthesized by cyclocondensation of dimethyl 3-oxopentanedioate with 2-(hydroxyimino)-1-pyridylbutane-1,3-diones....     

Nickel(II) complex with 4,4,4-trifluoro-1-(2-thienyl)butane-1,3-dione and dimethyl sulfoxide: Crystal and molecular structures

A nickel(II) complex with 4,4,4-trifluoro-1-(2-thienyl)butane-1,3-dione and dimethyl sulfoxide, [Ni(C₈H₄F₃O₂S)₂(C₂H₆OS)₂], was obtained and examined by X-ray diffraction. The crystals are monoclinic: a = 7.557(2) Å, b = 17.854(3) Å, c = 10.470(2) Å, β = 106.412(3)°, V = 1355.1(4) ų, ρ_calcd = 1.611 g/cm³, Z = 2, space group P2₁, R = 0.032. The coordination polyhedron of the nickel atom is a distorted octahedron consisting of four equatorial O atoms of two β-diketonate ligands and two axial O atoms of DMSO. The average Ni-O_ax and Ni-O_eq distances are 2.083(2) and 2.019(2)Å, respectively. The crystal structure is built from the discrete mononuclear complexes [Ni(C₈H₄F₃O₂S)₂(C₂H₆OS)₂] linked only by van der Waals contacts.     

从2-(2-吡啶)-1,3-丙二醇衍生出的一些新的吡啶化合物

本文报道了2-(2-吡啶)-1,3-丙二醇及其衍生物的一些新的反应,以此得到了一系列新的1,3-二取代2-(2-吡啶)丙烷和3-取代2-(2-吡啶)丙烯-1化合物,并讨论了这些化合物的光谱数据。     

Novel Synthesis of Isoquinoline Derivatives Derived from (Z)-4-(1,3-Diphenylpyrazol-4-yl)isochromene-1,3-dione

A series of isoquinoline derivatives were synthesized via the reaction of the (Z)-4-(1,3-diphenylpyrazol-4-yl)isochromene-1,3-dione with different hydrazides, primary amines, diamines, 2-aminothiophenol, 2-aminobenzoic acid, p-aminoacetophenone, and ethyl 2-amino-4,5,6,7-tetrahydrobenzo-[b]thiophene-3-carboxylate. All the synthesized compounds were characterized by infrared, ¹H NMR, and mass spectra besides the analytical data.     

The Synthesis and Spectroscopic Characterization of Heterobimetallic Bu2Sn(IV) Complexes Derived from Some Chelating Ligands

The interaction of Bu₂Sn(OPrⁱ)₂ with a trifunctional tetradentate Schiff base (LH₃) (where H₃L = HOC₆H₄CH═NCH₃C(CH₂OH)₂) yields the precursor complex Bu₂Sn(LH) 1, which, on equimolar reactions with different metal alkoxides [Al(OPrⁱ)₃, Bu₃Sn(OPrⁱ), Ge(OEt)₄]; Al(Medea)(OPrⁱ) (where Medea = CH₃N- (CH₂CH₂O)₂); and Me₃SiCl in the presence of Et₃N], affords, respectively, the complexes Bu₂Sn(L)Al(OPrⁱ)₂ 2, Bu₂Sn(L)Al(Medea) 3, Bu₂Sn(L)Bu₃Sn 4, Bu₂Sn(L)Ge(OEt)₃ 5, and Bu₂Sn(L)SiMe₃ 6. The reactions of 2 with 2,5-dimethyl-2,5-hexanediol in a 1:1 ratio and with acetylacetone (acacH) in a 1:2 molar ratio afforded derivatives Bu₂Sn(L)Al(OC(CH₃)₂CH₂CH₂C(CH₃)₂ O) 7 and Bu₂Sn(L)Al(acac)₂ 8, respectively. All of the derivatives 1– 8 have been characterized by elemental analyses, molecular weight measurements, and spectroscopic [IR and NMR (¹H, ¹¹⁹Sn, ²⁹Si, and ²⁷Al)] studies.     

Transition metal complexes with 1,3-bis-(2-hydroxyphenyl)-1,3-propanedione—I : Mononuclear complexes

Reaction of 1,3-(2-hydroxyphenyl)-1,3-propanedione (BhPPH₃), a ligand with three possible sites of coordination acting as a chelating agent, with metal acetates results in the formation of mononuclear species M(BhPPH₂)₂S,S′ (M=Mn, Fe, Co, Ni, Zn; S,S′=CH₃OH, C₂H₅OH or H₂O); M′(BhPPH₂)₂ (M′=Cu, Pd), and M″(BhPPH₂)₃S,S′ (M″= Fe, Al). The complexes have been studied by ¹H-NMR when possible, and IR spectra. The position of the methine proton (=CH-) at 6.88 ppm in Zn(BhPPH₂)₂S,S′ indicates that BhPPH₃ behaves in mononuclear complexes as a common β-diketone. Most of the complexes lose S,S′ molecules on heating but a crystal structure of Zn(BhPPH₂)₂ · 2C₂H₅)OH indicates that the C₂H₅OH molecules are oxygen bonded to the metal centre.     

1－N－（苯并咪唑－1－乙酰基）－4－苯基－3－氨基硫脲金属配合物的合成及结构表征

合成了新配体１－Ｎ－（苯并咪唑－１－乙酰基）－４－苯基－３－氨基硫脲（ＢＰＭＳ），将其与Ｍｎ（Ⅱ）、Ｃｏ（Ⅱ）、Ｎｉ（Ⅱ）、Ｃｕ（Ⅱ）、Ｃｄ（Ⅱ）、Ｚｎ（Ⅱ）、ＵＯ２（Ⅱ）等金属的醋酸盐反应，合成了７个新配合物。所有化合物均经元素分析、ＩＲ、１ＨＮＭＲ和热重分析等表征。红外光谱表明，配体以四齿方式通过烯醇式羰基氧原子、烯醇式硫羰基硫原子以及Ｃ＝Ｎ１和Ｃ＝Ｎ２的氮原子与金属配位     

Synthesis and Properties of Macroheterocycles Derived from an Indane-1,3-dione Analog

Heterocycles with 5,7-diimino-2,5,6,7-tetrahydro-1H-cyclopenta[cd]phenalene, diphenyl sulfone, diphenylbenzanilide, and diphenyl sulfide fragments were synthesized. The heterocycles were cyclized to obtain symmetrical heterocycles.     

Synthesis of Boron-containing Complexes of 1-(2-hydroxyphenyl)-3-phenyl-2-propen-1-one

Condensation of o-hydroxyacetophenone with benzaldehyde in alcohol in the presence of a triple excess of a sodium hydroxide solution leads to 2'-hydroxychalcone sodium salt. The latter was heated with boron trifluoride etherate in toluene to a 2'-hydroxychalcone boron fluoride complex in which the boron atom is coordinated to the carbonyl oxygen atom. The same complex was obtained by boiling of the o-hydroxyacetophenone boron fluoride complex with benzaldehyde in acetic anhydride.     

Thermodynamic functions of thermotropic polyethers based on the semiflexible mesogen 1-(4-hydroxyphenyl)-2-(2-methyl-4-hydroxyphenyl)ethane

Heat capacities of a series of thermotropic polyethers consisting of a semiflexible mesogen [1-(4-hydroxyphenyl) - 2 - (2 - methyl - 4 - hydroxyphenyl)ethane], with n methylene flexible spacers (n = 4–12) (MBPE-n) have been measured by DSC and fitted at low temperature to an approximate frequency spectrum, as well as at high temperature to a general equation for the liquid MBPE-n. The latter equation is: C_p = n(17.33 + 0.04551T) + (280.9 + 0.3839T) where n is the number of methylenes in the polyether spacer. The calculated vibration-only heat capacities start to show deviations from the measured heat capacities below the melting temperature, reflecting contributions from conformational disorder and motion in methylene spacers. It is suggested that part of this increase in heat capacity can be looked upon as a glass transition of the partially conformationally disordered crystals. Solid state ¹³C–NMR studies showed similarly that over the range of temperature some of the C? C bonds in the spacer are in a rotational state similar to that in the melt. The equilibrium heats of fusion (ΔH) and the changes of heat capacity (ΔC_p) for the amorphous polymer at the glass transition temperature, T_g, were determined by WAXD and DSC. Based on the discrepancy of ΔC_p it is concluded that these phenylene containing polyethers have a certain amount of rigid amorphous polymer. Thermodynamic functions H, S and G for all of the polyethers have been established.