Acoustical and Viscometric Studies of CdCl2 and KCl in Aqueous-Acetone Co-Solvent Between 25 and 45°C

Abstract

Ultrasonic velocity of CdCl₂ and KCl in co-solvent of Acetone and Water is measured at different concentrations from 298.15 K to 318.15 K using single crystal interferometer; operating at frequency of 2 MHz. Various acoustical parameters such as adiabatic compressibility (β_s), specific impedance (Z), apparent molar compressibility (Ø_K), relative association (R _A), Rao's molar sound function (R), molar compressibility (W), free volume (V _f) have been calculated. Results throw light on the solute-solvent and solute-solute interactions. Effect of temperature variation on these interactions has also been discussed.     

Isolation,structural elucidation and cytotoxicity evaluation of a new pentahydroxy-pimarane diterpenoid along with other chemical constituents from Aerva lanata

Aervalanata possesses various useful medicinal and pharmaceutical activities. Phytochemical investigation of the plant has now led to the isolation of a new 2α,3α,15,16,19-pentahydroxy pimar-8(14)-ene diterpenoid (1) together with 12 other known compounds identified as β-sitosterol (2), β-sitosterol-3-O-β-D-glucoside (3), canthin-6-one (4), 10-hydroxycanthin-6-one (aervine, 5), 10-methoxycanthin-6-one (methylaervine, 6), β-carboline-1-propionic acid (7), 1-O-β-D-glucopyranosyl-(2S,3R,8E)-2-[(2′R)-2-hydroxylpalmitoylamino]-8-octadecene-1,3-diol (8), 1-O-(β-D-glucopyranosyl)-(2S,3S,4R,8Z)-2-[(2′R)-2′-hydroxytetracosanoylamino]-8(Z)-octadene-1,3,4-triol (9), (2S,3S,4R,10E)-2-[(2′R)-2′-hydroxytetracosanoylamino]-10-octadecene-1,3,4-triol (10), 6′-O-(4″-hydroxy-trans-cinnamoyl)-kaempferol-3-O-β-D-glucopyranoside (tribuloside, 11), 3-cinnamoyltribuloside (12) and sulfonoquinovosyldiacylglyceride (13). Among these, six compounds (8–13) are reported for the first time from this plant. Cytotoxicity evaluation of the compounds against five cancer cell lines (CHO, HepG2, HeLa, A-431 and MCF-7) shows promising IC₅₀ values for compounds 4, 6 and 12.     

Acoustical study on ternary mixture of dimethyl acetamide (DMAC) in diethyl ether and isobutyl methyl ketone at different frequencies

The experimental density (ρ) and the velocity (U) for ternary mixture of dimethyl acetamide diethyl ether and isobutyl methyl ketone at different frequencies (2, 4, 6 and 8 MH_Z) have been measured at a constant temperature of 308 K. These data have been used to compute acoustic impedance (Z), adiabatic compressibility (K _s), intermolecular free length (L_f ), molar volume (V_m ), molar sound velocity (R), molar compressibility (B), available volume (V _a), Lennard-Jones potential repulsive term exponent (n), relative association (R _A), interaction parameter (X) and excess values of some of the above parameters for entire range of mole fraction and are interpreted to explain molecular interaction occurring in the liquid mixture.     

Solid state structures of the chiral heterobimetallic complexes [Cu(dach)2][Pt(CN)4] · 2H2O, [Ni(dach)3][Pt(CN)4] · 2DMF · H2O,and [Pd(dach)2][Pt(CN)4] · H2O (dach = 1 R , 2 R -diaminocyclohexane)

The chiral dinuclear heterometallic complexes [Cu(dach)₂][Pt(CN)₄]?·?2H₂O (1), [Ni(dach)₃][Pt(CN)₄]?·?2DMF?·?H₂O (2), and [Pd(dach)₄][Pt(CN)₄]?·?H₂O (3) (dach?=?1R,2R-cyclohexanediamine) have been prepared and characterized by X-ray diffraction analysis. Crystal data: 1, monoclinic, P2₁, a?=?8.108(3), b?=?15.552(6), c?=?9.914(4)?Å, β?=?110.931(6)°, V?=?1167.6(8)?ų, Z?=?2, R ₁?=?0.0420, wR ₂?=?0.1122; 2, monoclinic, P2₁, a?=?13.264(11), b?=?9.285(7), c?=?16.211(13)?Å, β?=?111.640(9)°, V?=?1856(3)?ų, Z?=?2, R ₁?=?0.0276, wR ₂?=?0.0698; 3, monoclinic, P2₁, a?=?6.887(2), b?=?12.809(4), c?=?12.975(4)?Å, β?=?94.865(4)°, V?=?1140.6(6)?ų, Z?=?2, R ₁?=?0.057, wR ₂?=?0.156. In complex 1, the Pt and Cu atoms are linked by a CN bridge that presents a very bent C=N–Cu angle [136.8(8)°].     

Ozonolyse von Olefinen,III: Säurekatalysierte Ozonolyse von 3-Hexen-1,6-und 2-Penten-1,5-dicarbonylderivaten

Summary The ozonolysis of mono-unsaturated compounds containing the structural element =CH-CH₂-R [R=COOH, COOCH₃, CH(OCH₃)₂] was investigated. Reductive ozonolysis of (E)-3-hexene-1,6-dioic acid gives methyl 3,3-dimethoxypropanoate (2), whereas ozonolysis of dimethyl (E)-3-hexene-1,6-dioate (1a) and (Z)-1,1,6,6-tetramethoxy-3-hexene (1b) in a methanolic solution of HCl leads to a mixture of2, dimethyl malonate (3 a) and 1,1,3,3-tetramethoxypropane (3 b). The homologuos derivatives, dimethyl glutaconate (4 a) and 1,1,5,5-tetramethoxy-2-pentene (4 b), were ozonized to give mixtures of2, 3, dimethyl oxalate (5), methyl 2,2-dimethoxyacetate (6 a), and 1,1,2,2-tetramethoxyethane (6 b). The ratios of the various reaction products were determined by gas chromatography. In each case the formation of the bifunctional derivatives2 and6 a was favoured.

     

Thermodynamic studies of some 1,2,4-triazole derivatives in DMF and THF solutions at 308.15 K

Some new 1,2,4-triazole derivatives have been synthesized and characterized by TLC, IR, NMR and mass spectra. Densities, viscosities and ultrasonic velocities of these compounds have been measured over the wide composition range at 308.15?K in dimethyl formamide (DMF) and tetrahydro furan (THF). From these data, various acoustical and thermodynamic parameters (C.V. Suryanarayana, J. Kuppuswamy. J. Acoust. Soc. Ind., 4, 75 (1976); H. Erying, M.S. John, Significance of Liquid Structures, Wiley, New York (1969); G.K. Johri, R.C. Misra. Acustica, 56, 66 (1989)) were evaluated. Some of these parameters are isentropic compressibility (κ_s), intermolecular free length (L _f), relaxation strength (r), relative association (R _A), Rao's molar constant (R _m), van der Waal's constant (b), molar compressibility (W), internal pressure (π), free volume (V _f), solvation number (S _n) etc. The behavior of solutions of these compounds in DMF and THF are explained from the evaluated parameters.     

Syntheses,Characterization and x-ray Structures of Gold(III) Complexes Obtained by Addition of Bases to Gold(III)(2-Pyridinecarboxaldehyde)

Reaction of potassium tetrachloroaurate(III), KAuCl₄, with 2-pyridinecarboxaldehyde (2CHO-py) have been examined in protic HX (X=OH, OMe, OEt, OCH₂CH₂CH₂, OCH₂CH₂CH₂CH₃, OCH₂CF₃) solvents. Compounds in which the pyridine ligand is N or N-O coordinated in a newly carbonyl hydrated or in semi- and acetal-forms, derived by addition of one or two hydroxylic molecules, have been isolated; these include dichloro[pyridine-2(α-hydroxymethanolato)]gold(III) (1), dichloro[pyridine-2(α-ethoxymethanolato)] gold(III) (2), dichloro[pyridine-2[α-(2,2,2-trifluoroethoxymethanolato)]gold(III) (3), trichloro(2-pyridinecarboxaldehyde dimethyl acetal)gold(III) (4), trichloro(2-pyridinecarboxaldehyde diethyl acetal)gold(III) (5), trichloro(2-pyridinecarboxaldehyde di-1-propyl acetal)gold(III) (6) and trichloro(2-pyridinecarboxaldehyde di-1-butyl acetal)gold(III) (7). The crystal and molecular structures of (2), (5) and (7) have been determined by X-ray methods. Compound (2) crystallizes in space group Pna2₁ with Z=4, a=7.8914(4), b=17.3660(4) and c=8.3873(5)Å; (5) crystallizes in space group P&1macr; with Z=2, a=7.7779(3), b=8.2878(2) and c=13.3202(6)Å, α=96.975(2), β=95.096(2), γ=115.027(2)°; (7) crystallizes in space group P2₁/a with Z=4, a=14.5438(12), b=8.9865(7) and c=15.0362(11)Å.     

A new alkylbenzoquinone from Embelia rowlandii Gilg. (Myrsinaceae)

A new alkylbenzoquinone named embeliquinone (1) together with five known compounds, lupeol (2), 3-O-[6′-O-palmitoyl-β-d-glucosyl]-spinasta-7,22(23)-diene (3), quercetin (4), (2S,3S,4R,8E)-2-[(2′R)-2′-hydroxy-heneicosanoylamino]-heneicosane-1,3,4-triol-8-ene (5), and β-sitosterol-3-O-β-d-glucopyranoside (6) were isolated from the MeOH leaf extract of Embelia rowlandii by using repeated open column chromatography techniques. The structure of the new compound was characterized by analyses of 1D- and 2D-NMR, and MS data. Embeliquinone (1) had moderate anti-cell proliferation activity against A549 cell line with the IC₅₀ value of 21.8 μM. In addition, 1 exhibited weak antibacterial activities against Klebsiella pneumoniae and Staphylococcus aureus with an MIC value of 206.0 μM in both cases.     

Synthesis,structure and characterization of copper(II) and zinc(II) complexes based on 3-carboxyl-1,2,4-triazole

Two complexes [CuL₂(H₂O)₂] (1) and [ZnL₂(H₂O)₂] (2) (L?=?3-carboxyl-1,2,4-triazole (L)) have been synthesized and characterized by single-crystal X-ray diffraction analysis. Compound 1 crystallizes in the monoclinic space group P ₂(1)/n, a?=?8.632(8)?Å, b?=?9.153(8)?Å, c?=?6.991(7)?Å, β?=?94.279(12)°, Z?=?2, R ₁?=?0.0296, wR ₂?=?0.0918. Compound 2 also crystallizes in the monoclinic space group P ₂(1)/n, a?=?4.937(3)?Å, b?=?18.107(10)?Å, c?=?6.344(4)?Å, β?=?106.839(7)°, Z?=?2, R ₁?=?0.0230, wR ₂?=?0.0556. Extensive intermolecular hydrogen bonds assemble 1 and 2 into three-dimensional (3D) supramolecular architectures, with eight-member H-bonded synthons. Compounds 1 and 2 were also characterized by element analysis, FT–IR, luminescence and EPR studies.     

SYNTHESES,CRYSTAL STRUCTURES AND ELECTRONIC SPECTRA OF MIXED-LIGAND ZINC(II) COMPLEXES WITH DIIMINES AND DITHIOLATES

Abstract

Three zinc(II) complexes, [Zn(bipy)(dmit)]₂ (1), [Zn(phen)(dmit)]₂ (2) and Zn(py)(mnt) (3), where bipy = 2,2′-bipyridine, phen = 1,10-phenanthroline, py = pyridine, H₂dmit = 4,5-dimer-capto-1,3-dithiol-2-thione, mnt = maleonitriledithiolate, have been synthesized and their crystal structures determined. Complex 1 is monoclinic, space group P2₁/c, with a = 11.570(3), b = 9.137(3), c = 15.051(6)Å, β = 109.56(2)°, Z = 2 and was refined to R ₁ = 0.039. Complex 2 is monoclinic, space group P2₁/n, with a = 9.363(2), b = 13.732(3), c = 12.767(3), β = 94.06(3)°, Z = 2 and was refined to R ₁ = 0.038. Complex 3 is orthorhombic, space group P2₁2₁2₁, with a = 8.621(3), b = 10.546(4), c = 16.848(2), Z = 4 and was refined to R ₁ = 0.040. IR and electronic absorption spectra were investigated.     

Ultrasonic study on some monosaccharides in aqueous media at 298.15 K

The ultrasonic velocity (U), density (ρ) and viscosity (η) at 298.15 K have been measured in the binary systems of monosaccharides (glucose, fructose and galactose) in aqueous medium. The acoustical parameters such as adiabatic compressibility (β), free length (L_f), free volume (V_f), internal pressure (π_i), acoustical impedance (Z), relative association (R_A), molar sound velocity (R) and molar sound compressibility (W) are calculated. The results are interpreted in terms of molecular interaction between the components of the mixtures.     

三苯基咪唑类化合物的合成及其紫外、荧光性质研究

设计合成了四种三苯基咪唑类化合物:4,5-二苯基-2-对甲酰基苯基咪唑(2a),4,5-二(2-硝基苯基)-2-对甲酰基苯基咪唑(2b),N-苄基-4,5-二苯基-2-对甲酰基苯基咪唑(2c)和N-苄基-4,5-二(2-硝基苯基)-2-对甲酰基苯基咪唑(2d),并用FT-IR,NMR和MS进行结构表征.在乙酸乙酯-石油醚溶液中获得了2c的单晶,用X射线单晶衍射法测定了其晶体结构,晶体属于三斜晶系,空间群P1,晶胞参数a=0.73796(15)nm,b=0.90136(18)nm,c=1.6644(3)nm,α=86.87(3)°,β=78.25(3)°,γ=89.94(3)°,V=1.0822(4)nm3,Dc=1.272g/cm3,Z=2,F(000)=436,μ=0.077mm-1,R1=0.0459,wR2=0.1303.研究了四种化合物的紫外与荧光性质,发现官能团硝基与苄基的引入,对其吸收峰和发射峰均有不同程度的影响:在紫外光谱中两种官能团均使吸收峰蓝移;在荧光光谱中苄基使发射峰蓝移而硝基使发射峰红移.测定了2a和2c在不同溶剂中的荧光寿命,其中2a在DMSO中寿命最长,为3.18ns.这些光谱性质为研究其双光子吸收、双光子荧光和非线性光学性质奠定了理论和实验基础.     

1-(2,6-二氯-4-三氟甲基苯基)-3-氰基-5-氨基吡唑及其酰胺、二酰亚胺的合成及晶体结构

2,6-二氯-4-三氟甲基苯胺经重氮化后与2,3-二氰基丙酸酯反应合成了1-(2,6-二氯-4-三氟甲基苯基)-3-氰基-5-氨基吡唑(1), 1与乙酸酐、顺丁烯二酸酐、苯甲酰氯反应得到1的乙酰胺2a、顺丁烯酰亚胺2b和苯甲酰胺2c. 通过元素分析、红外光谱、核磁共振氢谱、核磁共振碳谱、质谱等手段对其结构进行了表征. 用X射线单晶衍射测定了化合物2a, 2b和2c的晶体结构. 2a属于单斜晶系, C2/c空间群, 晶胞参数a＝1.88282(6) nm, b＝0.86541(3) nm, c＝1.90766(6) nm, β＝95.5830(10)°, V＝3.09362 nm³, Z＝8, R＝0.064, wR＝0.170. 2b属于单斜晶系, P2₁/n空间群, 晶胞参数 a＝1.28261(10) nm, b＝0.89942(7) nm, c＝1.46896(12) nm, β＝104.217(1)°, V＝1.6427(2) nm³, Z＝4, R＝0.055, wR＝0.165. 2c属于三斜晶系, P-1空间群, 晶胞参数a＝0.84613(11) nm, b＝0.98923(13) nm, c＝1.14305(15) nm, β＝96.002(2)°, V＝0.9326 nm³, Z＝2, R＝0.0684, wR＝0.1795.     

Ruthenium(II) carbonyl complexes of P,P and P,O donor diphosphine ligands,Ph2P(CH2)nPPh2 and Ph2P(CH2)nP(O)Ph2, n = 2, 3 and their activities in catalytic transfer hydrogenation reactions

The polymeric precursor [RuCl₂(CO)₂]_n reacts with the ligands, P∩P (a, b) and P∩O (c, d), in 1:1 M ratio to generate six-coordinate complexes [RuCl₂(CO)₂(?²-P∩P)] (1a, 1b) and [RuCl₂(CO)₂(?²-P∩O)] (1c, 1d), where P∩P: Ph₂P(CH₂)_nPPh₂, n = 2(a), 3(b); P∩O: Ph₂P(CH₂)_nP(O)Ph₂, n = 2(c), 3(d). The complexes are characterized by elemental analyses, mass spectrometry, thermal studies, IR, and NMR spectroscopy. 1a–1d are active in catalyzed transfer hydrogenation of acetophenone and its derivatives to corresponding alcohols with turnover frequency (TOF) of 75–290 h^?1. The complexes exhibit higher yield of hydrogenation products than catalyzed by RuCl₃ itself. Among 1a–1d, the Ru(II) complexes of bidentate phosphine (1a, 1b) show higher efficiency than their monoxide analogs (1c, 1d). However, the recycling experiments with the catalysts for hydrogenation of 4-nitroacetophenone exhibit a different trend in which the catalytic activities of 1a, 1b, and 1d decrease considerably, while 1c shows similar activity during the second run.     

Synthesis of Fused Isolated Azoles and N-Heteroaryl Derivatives Based on 2-Methyl-3,4-dihydrothieno[3,4-d]pyrimidin-5-amine

In this work, we report the synthesis and characterization of new compounds derived from thieno[d]pyrimidines. The formation of isolated and fused thieno[d]pyrimidine derivatives was achieved via reacting 5-amino-(2-methyl)thieno[3,4-d]pyrimidin-4(3H)-one (3) with some selected reagents. The starting compound (2) was prepared in a quantitative yield using a modified procedure by conversion of the cyano group in 1 to the amide via hydrolysis using concentrated H₂SO₄. Methylthieno[3,4-d]pyrimidin-5-yl (8, 9, and 18), 3-phenylthieno[3,4-e][1,2,4]triazolo[4,3-c]pyrimidines (11–15) and tetrazolo[1,5-c]thieno[3,4-e]pyrimidine (16) have been synthesized in excellent isolated yield. The interaction of N-acetyl derivative 19 with benzaldehyde and/or some nitroso compounds afforded the chalcones and Schiff's bases derivatives 20 and 26a and c respectively. The latter compounds were used as key intermediates in the synthesis of N-acetylpyrazol-3-yl (21a and 21b), 6-phenylpyrimidine-2-(one)thione (22a and b), pyrazolo-1-carbothioamide (25), and thiazolidinone andβ β-lactam derivatives 28a and 28c and 30a and 30c respectively. The structures of these compounds were established by elemental analysis, infrared (IR), mass spectrometry (MS), and NMR spectral analysis.     

Two helical coordination polymers constructed from V-shaped and chelate ligands

The synthesis and X-ray characterization of two supramolecular isomers, [Co(oba)(2,2′-bpy)] _n (1 and 2) (oba?=?4,4′-oxybis(benzoate), 2,2′-bpy?=?2,2′-bipyridine) are reported. Crystal data for 1: a?=?12.026(2), b?=?15.120(3), c?=?11.361(2)?Å, β?=?91.46(3)°, Z?=?4, R ₁?=?0.0330, wR ₂?=?0.0949. Crystal data for 2: a?=?16.171(3), b?=?19.162(4), c?=?22.914(5)?Å, α?=?107.66(3), β?=?91.46(3), γ?=?98.99(3)°, Z?=?2, R ₁?=?0.0388, wR ₂?=?0.0456. They are conformational supramolecular isomers without solvent molecules in the structures, and exhibit different one-dimensional helical structures that are further assembled into distinct two-dimensional layers via π–π stacking interactions. The results indicate that the geometry of ligand is one of the most important factors for the construction of a helical motif.     

Insecticidal and α-glucosidase inhibitory activities of chemical constituents from Viburnum fordiae Hance

The ethanolic extract of the stems of Viburnum fordiae Hance showed insecticidal and α-glucosidase inhibitory activities and then was fractionated by bioactivity-guided fractionation to obtain a rare C₁₃-norisoprenoid (1), together with a new phenolic glycoside (2), and seven known compounds, alangionoside C (3), pisumionoside (4), koaburaside (5), 3,5-dimethoxy-benzyl alcohol 4-O-β-d-glucopyranoside (6), 3,4,5-trimethoxybenzyl-β-d-glucopyranoside (7), arbutin (8), and salidroside (9). The previously undescribed compounds were elucidated as (3R,9R)-3-hydroxy-7,8-didehydro-β-ionyl 9-O-α-d-arabinopyranosyl-(1→6)-β-d-glucopyranoside (1) and 2-(4-O-β-d-glucopyranosyl)syringylpropane-1,3-diol (2) by spectroscopic data (¹H and ¹³C NMR, HSQC, HMBC, ¹H-¹H COSY, HSQC-TOCSY, HRESIMS, IR and ORD) and chemical methods. Compound 1 showed potent insecticidal effect against Mythimna separata with LD₅₀ value of 140 μg g^?1. Compounds 2, 5, 6, 8 and 9 showed varying α-glucosidase inhibitory activity with IC₅₀ values ranging from 148.2 to 230.9 μM.     

Das Carotinoidspektrum der Hagebutten von Rosa pomifera: Nachweis von (5Z)-Neurosporin; Synthese von (3R, 15Z)-Rubixanthin

Carotenoids from Hips of Rosa pomifera: Discovery of (5Z)-Neurosporene; Synthesis of (3R, 15Z)-Rubixanthin Extensive chromatographic separations of the mixture of carotenoids from ripe hips of R. pomifera have led to the identification of 43 individual compounds, namely (Scheme 2): (15 Z)-phytoene (1) , (15 Z)-phytofluene (2) , all-(E)-phytofluene (2a) , ξ-carotene (3) , two mono-(Z)-ξ-carotenes ( 3a and 3b ), (6 R)-?, ψ-carotene (4) , a mono-(Z)-?, ψ-carotene (4a) , β, ψ-carotene (5) , a mono-(Z)-β, ψ-carotene (5a) , neurosporene (6) , (5 Z)-neurosporene (6a) , a mono-(Z)-neurosporene (6b) , lycopene (7) , five (Z)-lycopenes (7a–7e) , β, β-carotene (8) , two mono-(Z)-β, β-carotenes (probably (9 Z)-β, β-carotene (8a) and (13 Z)-β, β-carotene (8b) ), β-cryptoxanthin (9) , three (Z)-β-cryptoxanthins (9a–9c) , rubixanthin (10) , (5′ Z)-rubixanthin (=gazaniaxanthin; 10a ), (9′ Z)-rubixanthin (10b) , (13′ Z)- and (13 Z)-rubixanthin (10c and 10d , resp.), (5′ Z, 13′ Z)- or (5′ Z, 13 Z)-rubixanthin (10e) , lutein (11) , zeaxanthin (12) , (13 Z)-zeaxanthin (12b) , a mono-(Z)-zeaxanthin (probably (9 Z)-zeaxanthin (12a) ), (8 R)-mutatoxanthin (13) , (8 S)-mutatoxanthin (14) , neoxanthin (15) , (8′ R)-neochrome (16) , (8′ S)-neochrome (17) , a tetrahydroxycarotenoid (18?) , a tetrahydroxy-epoxy-carotenoid (19?) , and a trihydroxycarotenoid of unknown structure. Rubixanthin (10) and (5′ Z)-rubixanthin (10a) can easily be distinguished by HPLC. separation and CD. spectra at low temperature. The synthesis of (3 R, 15 Z)-rubixanthin (29) is described. The isolation of (5 Z)-neurosporene (6a) supports the hypothesis that the ?-end group arises by enzymatic cyclization of precursors having a (5 Z)- or (5′ Z)-configuration.     

New flavonoid glycosides and other chemical constituents from Clerodendrum phlomidis leaves: isolation and characterisation

Phytochemical investigation of the plant Clerodendrum phlomidis Linn. F. (Lamiaceae) has now led to the isolation of two new flavonoid glycosides (1, 2) together with six known compounds identified as pectolinaringenin (3), pectolinaringenin-7-O-β-d-glucopyranoside (4), 24β-ethylcholesta-5,22E,25-triene-3β-ol (5), 24β-ethylcholesta-5,22E,25-triene-3β-O-β-D-glucopyranoside (6), (2S,3S,4R,10E)-2-[(2′R)-2′-hydroxytetracosanoylamino]-10-octadecene-1,3,4-triol (7) and andrographolide (8) mainly by spectroscopic analysis. Compounds 4 and 6–8 are reported for the first time from C. phlomidis.