Synthesis,structure and biological activity of new 6,6‐dimethyl‐2‐oxo‐4‐{2‐[5‐organylsilyl(germyl)]furan(thiophen)‐2‐yl}vinyl‐5,6‐dihydro‐2H‐pyran‐3‐carbonitriles

New 6,6‐dimethyl‐2‐oxo‐4‐{2‐[5‐alkylsilyl(germyl)]furan(thiophen)‐2‐yl}vinyl‐5,6‐dihydro‐2H‐pyran‐3‐carbonitriles (IC₅₀: 1–6 µg ml^?1) have been prepared by the condensation of corresponding silicon‐ and germanium‐containing furyl(thienyl)‐2‐carbaldehydes with 3‐cyano‐4,6,6‐trimethyl‐5,6‐dihydropyran‐2‐one using piperidine acetate as a catalyst. The obtained carbonitriles were identified using NMR (¹H, ¹³C and ²⁹Si) spectroscopy and GC‐MS. The structure of 6,6‐dimethyl‐2‐oxo‐4‐[2‐(5‐trimethylsilyl)thiophen‐2‐yl]‐5,6‐dihydro‐2H‐pyran‐3‐carbonitrile was studied using X‐ray diffractometry. The influences of the heterocycle and the structure of the organoelement substituent on cytotoxicity and on matrix metalloproteinase inhibition have been studied. Copyright © 2015 John Wiley & Sons, Ltd.     

N-(4-甲基苯甲酰氨基) N’-[5-(2-三氟甲基苯基)-2-呋喃甲酰硫脲的合成、晶体结构测定与生物活性测定

本文首次合成标题化合物N-(4-甲基苯甲酰氨基)-N’-[5-(2-三氟甲基苯基)-2-呋喃甲酰硫脲。化合物(C21H16F3N3O3S, Mr = 447.43)单晶经测定为单斜晶体,空间群为P -1。在晶体中,存在一些分子内和分子间的相互作用,分子间还有C—H···π 的相互作用,这可能导致晶体更稳定的原因。目标产物的结构经IR, H NMR和元素分析测定确证。初步生物活性测试表明,部分化合物对棉花枯萎病、黄瓜灰霉病、苹果轮纹病和棉花炭疽病有较好的选择性杀菌活性;部分目标化合物有较好的除草活性。     

EPR Spectroscopy of 4, 4′‐Bis(tert‐butyl)‐2, 2′‐bipyridine‐1, 2‐dithiolatocuprates(II) in Host Lattices with Different Coordination Geometries

A series of new heteroleptic MN₂S₂ transition metal complexes with M = Cu²⁺ for EPR measurements and as diamagnetic hosts Ni²⁺, Zn²⁺, and Pd²⁺ were synthesized and characterized. The ligands are N₂ = 4, 4′‐bis(tert‐butyl)‐2, 2′‐bipyridine (tBu₂bpy) and S₂ =1, 2‐dithiooxalate, (dto), 1, 2‐dithiosquarate, (dtsq), maleonitrile‐1, 2‐dithiolate, or 1, 2‐dicyanoethene‐1, 2‐dithiolate, (mnt). The Cu^II complexes were studied by EPR in solution and as powders, diamagnetically diluted in the isostructural planar [Ni^II(tBu₂bpy)(S₂)] or[Pd^II(tBu₂bpy)(S₂)] as well as in tetrahedrally coordinated[Zn^II(tBu₂bpy)(S₂)] host structures to put steric stress on the coordination geometry of the central CuN₂S₂ unit. The spin density contributions for different geometries calculated from experimental parameters are compared with the electronic situation in the frontier orbital, namely in the semi‐occupied molecular orbital (SOMO) of the copper complex, derived from quantum chemical calculations on different levels (EHT and DFT). One of the hosts, [Ni^II(tBu₂bpy)(mnt)], is characterized by X‐ray structure analysis to prove the coordination geometry. The complex crystallizes in a square‐planar coordination mode in the monoclinic space group P2₁/a with Z = 4 and the unit cell parameters a = 10.4508(10) Å, b = 18.266(2) Å, c = 12.6566(12) Å, β = 112.095(7)°. Oxidation and reductions potentials of one of the host complexes, [Ni(tBu₂bpy)(mnt)], were obtained by cyclovoltammetric measurements.     

Synthesis and Fungicidal Activity of (E)‐5‐[1‐(2‐Oxo‐1‐oxaspiro[4,5]dec/non‐3‐en‐3‐yl)ethylidene]‐2‐aminoimidazolin‐4‐one Derivatives

The novel fungicidal agents, (E )‐5‐[1‐(2‐oxo‐1‐oxaspiro[4,5]dec/non‐3‐en‐3‐yl)ethylidene]‐2‐aminoimidazolin‐ 4‐one derivatives, were designed and synthesized in moderate to excellent yields in four steps using α ‐hydroxyketone and diketene as raw materials and characterized by HR‐ESI‐MS , ¹H NMR and X‐ray diffraction. The preliminary bioassay showed that some of these compounds, such as 5e , 6a , 6e , and 7 h exhibit 87.8%, 91.3%, 89.9% and 87.8% inhibition rates against Sclerotinia scleotiorum , 3b , 3c , 4c and 7 h exhibit 96.4%, 92.5%, 90.3% and 76.9% inhibition rates against Phytophthora capsici at the concentration of 50 µg/mL , respectively. These compounds exhibited significant fungicidal activities against S. scleotiorum and P. capsici with EC₅₀ values of 2.56–11.60 µg/mL , and compounds 6e and 7 h exhibited weak inhibition against the spore germination of S. scleotiorum , while the spore germination of P. capsici was strongly inhibited by compound 7 h solution. Scanning electron microscopy (SEM ) and transmission electron microscopy (TEM ) observation indicated that compound 7 h had a significant impact on the structure and function of the hyphal cell wall of P. capsici mycelium.     

Formation and Molecular Structure of an Ion Pair Iron (II) Compound Derived from 2,6‐Bis‐ [1‐(2,6‐dibromophenylimino) ‐ethyl] pyridine and 2‐Acetyl‐6‐[1‐(2, 6‐dibromophenylimino)‐ethyl] pyridine

Two novel tridentate ligands of 2,6‐bis‐[l‐(2,6‐dibromophenylimino) ethyl] pyridine (L₁) and2‐acetyl‐6‐[1‐(2,6‐dibromophenylimino) ethyl] pyridine (L2) have been synthesized. The iron(II) complex of L₁ and L₂ has been characterized with the crystal structure of [Fe(L₁)(L₂)]²⁺ [FeCl₄]² CH₂Cl₂ [monoclinic, P2₁ (#11), a = 1.0562(4), b = 2.0928(4), c = 1.2914(2) nm, β = 100.12°, V = 2.810(1) nm³ D_c = 1.879 g/cm³ and Z = 2].     

Synthesis, Structure and Biological Activities of S-[α-（ 4-Methoxyphenylcarbonyl ）-2-（1,2,4-triazole-l-yl） ethyl-N, N-dime-thyldithiocarbamate

The title compound was prepared by reaction of N, N‐dimethyldithiocarbamate sodium with l‐bromo‐l‐(4‐methoxyphenylcarbonyl)‐2‐(1, 2, 4‐triazole‐l‐yl) ethane. Its crystal structure has been determined by X‐ray diffraction analysis. The crystal belongs to triclinic with space group Pī, a = 0.7339(2) nm, b = 1.1032(2) nm, c = 1.1203(2) nm, a = 90.27(3)°, β = 102.03(3)°, γ = 104.91(3)°, Z=2, V = 0.8556(3) nm³, D_c = 1.360 g/cm³, μ =0.325 mm^?1, F(000)=368, final R₁ =0.0475. The planes of 4‐methoxybenzyl group and triazole ring are nearly perpendicular to each other. The dihedral angle is 83.97°. There is an obvious π‐π stacking interaction between the molecules in the crystal lattice. The results of biological test show that the title compound has fungicidal and plant growth regulating activities.     

Synthesis,characterization, and optimum reaction conditions of oligo‐2‐[(pyridine‐2‐yl‐methylene) amino] phenol

The reaction conditions of the oxidative polycondensation of 2‐[(pyridine‐2‐yl‐methylene) amino] phenol (2‐PMAP) with air O₂, H₂O₂, and NaOCl were studied in an aqueous alkaline medium between 60 and 90 °C. Oligo‐2‐[(pyridine‐2‐yl‐methylene) amino] phenol (O‐2‐PMAP) was characterized with ¹H NMR, Fourier transform infrared, ultraviolet–visible, size exclusion chromatography (SEC), and elemental analysis techniques. Moreover, solubility testing of the oligomer was performed in polar and nonpolar organic solvents. With the NaOCl, H₂O₂, and air O₂ oxidants, the conversions of 2‐PMAP into O‐2‐PMAP were 98, 87, and 62%, respectively, in an aqueous alkaline medium. According to SEC, the number‐average molecular weight, weight‐average molecular weight, and polydispersity index of O‐2‐PMAP were 2262 g mol^?1, 2809 g mol^?1, and 1.24 with NaOCl, 3045 g mol^?1, 3861 g mol^?1, and 1.27 with air O₂, and 1427 g mol^?1, 1648 g mol^?1, and 1.16 with air H₂O₂, respectively. Also, thermogravimetric analysis showed that O‐2‐PMAP was stable against thermooxidative decomposition. The weight loss of O‐2‐PMAP was 96.68% at 900 °C. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2717–2724, 2004     

Syntheses,and Crystal Structures of Indium Complexes with η2‐Piperidinyldithiocarbamate and η2‐Pyridine‐2‐Thionate Containing Ligands: Structures of [In(η2‐S2CNC5H10)3] and [In(η2‐pyS)3]

The η²‐thio‐indium complexes [In(η²‐thio)₃] (thio = S₂CNC₅H₁₀, 2 ; SNC₄H₄, (pyridine‐2‐thionate, pyS, 3 ) and [In(η²‐pyS)₂(η²‐acac)], 4 , (acac: acetylacetonate) are prepared by reacting the tris(η²‐acac)indium complex [In(η²‐acac)₃], 1 with HS₂CNC₅H₁₀, pySH, and pySH with ratios of 1:3, 1:3, and 1:2 in dichloromethane at room temperature, respectively. All of these complexes are identified by spectroscopic methods and complexes 2 and 3 are determined by single‐crystal X‐ray diffraction. Crystal data for 2 : space group, C2/c with a = 13.5489(8) Å, b = 12.1821(7) Å, c = 16.0893(10) Å, β = 101.654(1)°, V = 2600.9(3) ų, and Z = 4. The structure was refined to R = 0.033 and Rw = 0.086; Crystal data for 3 : space group, P2₁ with a = 8.8064 (6) Å, b = 11.7047 (8) Å, c = 9.4046 (7) Å, β = 114.78 (1)°, V = 880.13(11) ų, and Z = 2. The structure was refined to R = 0.030 and Rw = 0.061. The geometry around the metal atom of the two complexes is a trigonal prismatic coordination. The piperidinyldithiocarbamate and pyridine‐2‐thionate ligands, respectively, coordinate to the indium metal center through the two sulfur atoms and one sulfur and one nitrogen atoms, respectively. The short C‐N bond length in the range of 1.322(4)–1.381(6) Å in 2 and C‐S bond length in the range of 1.715(2)–1.753(6) Å in 2 and 3 , respectively, indicate considerable partial double bond character.     

Anion‐directed Silver(I) Coordination Assemblies Based on 1‐(2‐Pyridyl)‐2‐(4‐pyridyl)‐1,2,4‐triazolewith Diverse Supramolecular Networks and Dichromate Removal Capabilities

A series of silver(I) supramolecular complexes, namely, {[Ag(L²⁴)](NO₃)}_n ( 1 ), [Ag₂(L²⁴)(NO₂)₂]_n ( 2 ), and {[Ag_1.25(L²⁴)(DMF)](PF₆)_1.25}_n ( 3 ) were prepared by the reactions of 1‐(2‐pyridyl)‐2‐(4‐pyridyl)‐1,2,4‐triazole (L²⁴) and silver(I) salts with different anions (AgNO₃, AgNO₂, AgPF₆). Single‐crystal X‐ray diffraction indicates that 1 – 3 display diverse supramolecular networks. The structure of dinuclear complex 1 is composed of a six‐membered Ag₂N₄ ring with the Ag ··· Ag distance of 4.4137(3) Å. In complex 2 , the adjacent Ag^I centers are interlinked by L²⁴ ligands into a 1D chain, the adjacent of which are further extended by the bridged nitrites to construct a 2D coordination architecture. Complex 3 shows a 3D (3,4)‐connected framework, which is generated by the linkage of L²⁴ ligands. All complexes were characterized by IR spectra, elemental analysis, and powder X‐ray diffraction. Notably, a structural comparison of the complexes demonstrates that their structures are predominated by the nature of anions. Additionally, 1 and 2 show efficient dichromate (Cr₂O₇^2–) capture in water system, which can be ascribed to the anion‐exchange.     

Synthesis,Crystal Structure and Thermal Behavior of 4,5‐Diacetoxyl‐2‐(dinitromethylene)‐imidazolidine

A new energetic material, 4,5‐diacetoxyl‐2‐(dinitromethylene)‐imidazolidine (DADNI), was synthesized by the reaction of 4,5‐dihydroxyl‐2‐(dinitromethylene)‐imidazolidine (DDNI) and acetic anhydride, and characterized by single crystal X‐ray diffraction. Crystal data for DADNI are monoclinic, space group C2/c, a=15.9167(3) Å, b=8.6816(4) Å, c=8.5209(3) Å, β=103.294(9)°, V=1145.9(3) ų, Z=4, µ=0.150 mm⁻¹, F(000)=600, D_c=1.682 g·cm⁻³, R₁=0.0565 and wR₂=0.1649. Thermal decomposition behavior of DADNI was studied and an intensely exothermic process was observed. The kinetic equation of the decomposition reaction is: dα/dT=(10^16.64/β)×4α^3/4exp(−1.582×10⁵/RT). The critical temperature of thermal explosion is 163.76°C. The specific heat capacity of DADNI was studied with micro‐DSC method and theoretical calculation method. The molar heat capacity is 343.30 J·mol⁻¹·K⁻¹ at 298.15 K. The adiabatic time‐to‐explosion of DADNI was calculated to be 87.7 s.     

Thermal Behaviors of 2‐(Dinitromethylene)‐1,3‐diazacycloheptane (DNDH)

2‐(Dinitromethylene)‐1,3‐diazacycloheptane (DNDH) was prepared by the reaction of 1,1‐diamino‐2,2‐dinitroethylene (FOX‐7) with 1,4‐diaminoethane in NMP. Thermal decomposition behavior of DNDH was studied under the non‐isothermal conditions with DSC method, and presents only one intensely exothermic decomposition process. The kinetic equation of the decomposition reaction is dα/dT=10^33.88×3α^2/3exp(−3.353×10⁵/RT)/β. The critical temperature of thermal explosion is 215.97°C. Specific heat capacity of DNDH was studied with micro‐DSC method and theoretical calculation method, and the molar heat capacity is 215.40 J·mol⁻¹·K⁻¹ at 298.15 K. Adiabatic time‐to‐explosion was calculated to be 92.07 s. DNDH has same thermal stability to FOX‐7.     

1‐[(E)‐2‐Arylethenyl]‐2,2‐diphenylcyclopropanes: Kinetics and Mechanism of Rearrangement to Cyclopentenes

Kinetic measurements for the thermal rearrangement of 2,2‐diphenyl‐1‐[(E)‐styryl]cyclopropane ( 22a ) to 3,4,4‐triphenylcyclopent‐1‐ene ( 23a ) in decalin furnished ΔH =31.0±1.2 kcal mol^?1 and ΔS =?6.0±2.6 e.u. The lowering of ΔH^≠ by 20 kcal mol^?1, compared with the rearrangement of the vinylcyclopropane parent, is ascribed to the stabilization of a transition structure (TS) with allylic diradical character. The racemization of (+)‐(S)‐ 22a proceeds with ΔH =28.2±0.8 kcal mol^?1 and ΔS =?5±2 e.u., and is at 150° 106 times faster than the rearrangement. Seven further 1‐(2‐arylethenyl)‐2,2‐diphenylcyclopropanes 22 , (E)‐ and (Z)‐isomers, were synthesized and characterized. The (E)‐compounds showed only modest substituent influence in their k_rac (at 119.4°) and k_isom (at 159.3°) values. The lack of solvent dependence of rate opposes charge separation in the TS, but a linear relation of log k_rac with log p.r.f., i.e., partial rate factors of radical phenylations of ArH, agrees with a diradical TS. The ring‐opening of the preponderant s‐trans‐conformation of 22 gives rise to the 1‐exo‐phenylallyl radical 26 that bears the diphenylethyl radical in 3‐exo‐position, and is responsible for racemization. The 1‐exo‐3‐endo‐substituted allylic diradical 27 arises from the minor s‐gauche‐conformation of 22 and is capable of closing the three‐ or the five‐membered ring, 22 or 23 , respectively. The discussion centers on the question whether the allylic diradical is an intermediate or merely a TS. Quantum‐chemical calculations by Houk et al. (1997) for the parent vinylcyclopropane reveal the lack of an intermediate. Can the conjugation of the allylic diradical with three Ph groups carve the well of an intermediate?     

Two different one‐dimensional supramolecular chains formed from the reaction of 2‐[1‐(pyridin‐4‐ylmethyl)‐1H‐benzimidazol‐2‐yl]quinoline with two different precursors,Co(NO3)2 and CoCl2

Two different one‐dimensional supramolecular chains with Co^II cations have been synthesized based on the semi‐rigid ligand 2‐[1‐(pyridin‐4‐ylmethyl)‐1H‐benzimidazol‐2‐yl]quinoline (L), obtained by condensation of 2‐(1H‐benzimidazol‐2‐yl)quinoline and 4‐(chloromethyl)pyridine hydrochloride. Starting from different Co^II salts, two new compounds have been obtained, viz. catena‐poly[[[dinitratocobalt(II)]‐μ‐2‐[1‐(pyridin‐4‐ylmethyl)‐1H‐benzimidazol‐2‐yl]quinoline] dichloromethane monosolvate acetonitrile monosolvate], {[Co(NO₃)₂(C₂₂H₁₆N₄)]·CH₂Cl₂·CH₃CN}_n, (I) and catena‐poly[[[dichloridocobalt(II)]‐μ‐2‐[1‐(pyridin‐4‐ylmethyl)‐1H‐benzimidazol‐2‐yl]quinoline] methanol disolvate], {[CoCl₂(C₂₂H₁₆N₄)]·2CH₃OH}_n, (II). In (I), the Co^II centres lie in a distorted octahedral [CoN₃O₃] coordination environment. {Co(NO₃)₂L}_n units form one‐dimensional helical chains, where the L ligand has different directions of twist. The helical chains stack together via interchain π–π interactions to form a two‐dimensional sheet, and another type of π–π interaction further connects neighbouring sheets into a three‐dimensional framework with hexagonal channels, in which the acetonitrile molecules and disordered dichloromethane molecules are located. In (II), the Co^II centres lie in a distorted trigonal–bipyramidal [CoCl₂N₃] coordination environment. {CoCl₂L}_n units form one‐dimensional chains. The chains interact via C—H...π and C—H...Cl interactions. The result is that two‐dimensional sheets are generated, which are further linked into a three‐dimensional framework via interlayer C—H...Cl interactions. When viewed down the crystallographic b axis, the methanol solvent molecules are located in an orderly manner in wave‐like channels.     

Novel 5‐Methyl‐2‐[(un)substituted phenyl]‐4‐{4,5‐dihydro‐ 3‐[(un)substituted phenyl]‐5‐(1,2,3,4‐tetrahydroisoquinoline‐2‐yl)pyrazol‐1‐yl}‐oxazole Derivatives: Synthesis and Anticancer Activity

Eleven novel 5‐methyl‐2‐[(un)substituted phenyl]‐4‐{4,5‐dihydro‐3‐[(un)substituted phenyl]‐5‐(1,2,3,4‐tetrahydroisoquinoline‐2‐yl)pyrazol‐1‐yl}‐oxazole derivatives were synthesized and characterized by elemental analysis, ESI‐MS, ¹H NMR and ¹³C NMR. All of the compounds have been screened for their antiproliferative activities against PC‐3 cell (human prostate cancer) and A431 cell (human epidermoid carcinoma cancer) lines in vitro. The results revealed that compounds 4g , 4j and 4k exhibited the strong inhibitory activities against the PC‐3 cell lines (with IC₅₀ values of 2.8±0.11, 3.1±0.10 and 3.0±0.06 μg/mL, respectively).     

A Novel Synthesis of 2-Amino-2-deoxy-D-gluconic Acid and Its Complexation with Cu（Ⅱ） in Alkaline Medium

A novel synthesis of the functional carbohydrate 2-amino-2-deoxy-D-gluconic acid was introduced and itscomplex formation with Cu(Ⅱ)was investigated to obtain the stability constant for its further applications to thefood and pharmaceutical industries.The equilibrium was investigated by spectrophotometric measurements andprocessed by dual-series linear regression method.Results:the yield of 2-amino-2-deoxy-D-gluconic acid is 70%.The complexation molar ratio is 1:2,the molar apsorptivity of the complex is 39.906 L·mol~(-1)·cm~(-1) at 630 nm,and the stability constant β_n is 6.24×10~5.     

Synthesis and Characterization of Two Formyl 2‐Tetrazenes

The synthesis of two formyl 2‐tetrazenes, namely, (E)‐1‐formyl‐1,4,4‐trimethyl‐2‐tetrazene ( 2 ) and (E)‐1,4‐diformyl‐1,4‐dimethyl‐2‐tetrazene ( 3 ), by oxidation of (E)‐1,1,4,4‐tetramethyl‐2‐tetrazene ( 1 ) using potassium permanganate in acetone solution is presented. Compound 3 was also synthesized in an improved yield from the oxidation of 1‐formyl‐1‐methylhydrazine ( 4a ) using potassium permanganate in acetone. Both compounds 2 and 3 were characterized by analytical (elemental analysis, GC‐MS) and spectroscopic methods (¹H, ¹³C, and ¹⁵N NMR spectroscopy, and IR and Raman spectroscopy). In addition, the solid‐state structures of the compounds were confirmed by low‐temperature X‐ray analysis. (Compound 2 : triclinic; space group P‐1; a=5.997(1) Å, b=8.714(1) Å, c=13.830(2) Å; α=107.35(1)°, β=90.53(1)°, γ=103.33(1)°; V_UC=668.9(2) ų; Z=4; ρ_calc=1.292 cm^?3. Compound 3 : monoclinic; space group P2₁/c; a=5.840(2) Å, b=7.414(3) Å, c=8.061(2) Å; β=100.75(3)°; V_UC=342(2) ų; Z=2; ρ_calc=1.396 g cm^?3.) The vibrational frequencies of compounds 2 and 3 were calculated using the B3LYP method with a 6‐311+G(d,p) basis set. We also computed the natural bond orbital (NBO) charges using the rMP2/aug‐cc‐pVDZ method and the heats of formation were determined on the basis of their electronic energies. Furthermore, the thermal stabilities of these compounds, as well as their sensitivity towards classical stimuli, were also assessed by differential scanning calorimetry and standard BAM tests, respectively. Lastly, the attempted synthesis of (E)‐1,2,3,4‐tetraformyl‐2‐tetrazene ( 6 ) is also discussed.     

A Novel and Efficient Synthesis of 3‐[(4,5‐Dihydro‐1H‐pyrrol‐3‐yl)carbonyl]‐2H‐chromen‐2‐ones (=3‐[(4,5‐Dihydro‐1H‐pyrrol‐3‐yl)carbonyl]‐2H‐1‐benzopyran‐2‐ones)

An efficient one‐pot synthesis of 3‐[(4,5‐dihydro‐1H‐pyrrol‐3‐yl)carbonyl]‐2H‐chromen‐2‐one (=3‐[(4,5‐dihydro‐1H‐pyrrol‐3yl)carbonyl]‐2H‐1‐benzopyran‐2‐one) derivatives 4 by a four‐component reaction of a salicylaldehyde 1 , 4‐hydroxy‐6‐methyl‐2H‐pyran‐2‐one, a benzylamine 2 , and a diaroylacetylene (=1,4‐diarylbut‐2‐yne‐1,4‐dione) 3 in EtOH is reported. This new protocol has the advantages of high yields (Table), and convenient operation. The structures of these coumarin (=2H‐1‐benzopyran‐2‐one) derivatives, which are important compounds in organic chemistry, were confirmed spectroscopically (IR, ¹H‐ and ¹³C‐NMR, and EI‐MS) and by elemental analyses. A plausible mechanism for this reaction is proposed (Scheme 2).     

HPLC法拆分(-)-2(S)-苄基-4-酮-4-(顺式-全氢化异吲哚-2-基)丁酸钙对映体

目的：建立刺激胰岛素分泌的新型降糖药物(-)-2 (S)-苄基-4-酮-4-(顺式-全氢化异吲哚-2-基)丁酸钙对映体的HPLC拆分方法。方法：采用Sumichiral OA-3300手性柱(250 × 4.6 mm I.D., 5 μm), 柱温35℃,以0.05 mol·L-1醋酸铵的甲醇溶液为流动相,检测波长为210 nm。结果：本品两对映体在22分钟内实现良好分离,分离度达3以上,S－异构体分别在0.028 ~ 5.6 μg mL-1和0.03 ~ 6.0 μg mL-1范围内线性关系良好,回归方程分别为：Y=1.32×103x-2.54 (r=0.9997)和Y=1.15×103x-1.78 (r=0.9998),最低检测限分别为0.15 ng和0.10 ng,方法精密度RSD低于1.0% (n=5)。结论：建立的对映体分离方法可用于本品光学异构体的质量控制。     

Synthesis,characterization and antibacterial activity of 3‐(2‐methoxyphenyl)‐2‐sulfanylpropenoic acid and di‐isopropylammonium [3‐(2‐methoxyphenyl)‐2‐sulfanylpropenoato] triphenylstannate(IV). The crystal structure of [HQ][SnPh3(o‐mpspa)]

Reaction of 3‐(2‐methoxyphenyl)‐2‐sulfanylpropenoic acid [H₂(o‐mpspa)] with SnPh₃OH in the presence of di‐isopropylamine resulted in the formation of the complex [HQ][SnPh₃(o‐mpspa)] (where HQ = di‐isopropylammonium cation and o‐mpspa = 3‐(2‐methoxyphenyl)‐2‐sulfanylpropenoato), which was characterized by mass spectrometry and vibrational spectroscopy, as well as by ¹H, ¹³C and ¹¹⁹Sn NMR spectroscopy. The single‐crystal X‐ray structural analysis of the new complex shows a trigonal‐bipyramidal coordination geometry around the Sn atom where o‐mpspa behaves as a bidentate chelating ligand. Dimeric units arise from the existence of N? H…O hydrogen bonds between the NH₂ group of the di‐isopropylammonium cation and the oxygen atoms of the two neighbouring carboxylato groups. The bacteriostatic activity of the complex is also reported. Copyright © 2007 John Wiley & Sons, Ltd.     

Association of hydrophobically α,ω‐end‐capped poly(2‐methyl‐2‐oxazoline) in water

The α,ω‐end‐capped poly(2‐methyl‐2‐oxazoline) (C_n‐POXZ‐C_n) have been synthesized by a one‐pot process using cationic ring‐opening polymerization with an appropriate initiator and terminating agent. The polymers bearing different alkyl groups C₁₂ and C₁₈ have molecular weight in the range of 2.4 × 10³ to 14 × 10³ with a small polydispersity index. The solution behavior of the free chains has been analyzed in a nonselective solvent, dichloromethane, by small‐angle neutron scattering and dynamic light scattering. These amphiphilic polymers associate in water to form flower‐like micellar structures. Critical micelle concentrations, investigated by fluorescence technique, are in the range of 0.03–0.5 g L^?1 and are dependent on the hydrophilic/lipophilic balance. The structural properties of the aggregates have also been investigated by viscometry. Intrinsic viscosities of these polymers are in the same range as that of the precursors poly(2‐methyl‐2‐oxazoline) (POXZ) and mono‐functionalized polymers. Large viscosity increase corresponding to intermicellar bridging was observed in the vicinity of the micelle overlap concentration. Addition of hydroxypropyl β‐cyclodextrin (HβCD) has dissociated the aggregates and the intrinsic viscosities of the HβCD‐end‐capped chains have become comparable with the ones of POXZ precursor chains. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 2477–2485, 2010