Synthesis,Structure and Reactivity of [1, 2‐Bis(diphenylphosphinite)ethane]bromotricarbonylmanganese(I) with Reactions of Phosphites,Phosphonites. and Phosphinites

The manganese carbonyl complex [MnBr(CO)₃ L ] ( 1 ), where L = Ph₂POCH₂CH₂OPPh₂, was prepared by reacting [MnBr(CO)₅] with the bidentate ligand 1, 2‐Bis(diphenylphosphinite)ethane. From this compound and the appropriate phosphite, phosphinite or phosphonite ligands were synthesized the complexes [MnBr(CO)₂ LL ′], where L ′ = P(OMe)₃ ( 2 ) or P(OEt)₃ ( 3 ) and [MnBr(CO)₃ L ′₂], where L ′ =PPh(OEt)₂ ( 4 ) or PPh₂(OEt) ( 5 ). The obtained compounds have been characterized by elemental analysis, mass spectrometry, IR and NMR (¹H, ¹³C and ³¹P) spectroscopies and X‐ray diffractometry for the complexes 1 , 4 and 5 .     

双席夫碱类化合物的合成及晶体结构

以2-苯基-1,2,3-三唑基-4-甲醛、喹喔啉基-2-甲醛等杂环醛和苯甲酰丙酮为原料,用乙醇作溶剂与(1S,2S)-(一)-1,2-环己二胺和1,1'-联萘-2,2'-二胺反应,合成了一系列席夫碱类化合物4a～4f,5a～5c,5f.目标化合物的结构经元素分析,IR,1HNMR,13CNMR确证.并测定了化合物4b,4f,5f的晶体结构.     

新型双席夫碱类化合物的合成及晶体结构

用2-苯基-1,2,3-三唑基-4-甲醛、喹喔啉基-2-甲醛和2-(4-溴苯基)-1,2,3-三唑基-4-甲醛为原料, 在冰醋酸的条件下分别与二胺反应, 合成了一系列新的双席夫碱5a～5d, 6a～6d和7a～7d. 目标化合物的结构经元素分析, IR, 1H NMR, MS, X射线确证. 同时测定了化合物6c的晶体结构. 其属于单斜晶系, C2/c空间群, 晶胞参数 a＝1.7670(4) nm, b＝0.48001(10) nm, c＝1.1751(2) nm, α＝90.00°, β＝94.42(3)°, γ＝90.00°, V＝0.9937(4) nm3, Dc＝1.399 g/cm3, Z＝2, F(000)＝436, μ＝0.089 mm－1, R＝0.0413, wR＝0.1067. 初步生物活性筛选结果表明, 目标化合物6b在Vero细胞上有抗疱疹病毒I型活性.     

Chiral Gold(III) Complexes: Synthesis,Structure, and Potential Applications

Since the beginning of the 2000’s, homogeneous gold catalysis has emerged as a powerful tool to promote the cyclization of unsaturated substrates with excellent regioselectivity allowing the synthesis of elaborated organic scaffolds. An important goal to achieve in gold catalysis is the possibility to induce enantioselective transformations by the assistance of chiral complexes. Unfortunately, the linear geometry of coordination for gold usually encountered in complexes at the +1 oxidation states renders this goal very challenging. In consequence, the interest toward the synthesis of chiral gold(III) complexes is steadily growing. Indeed, the square planar geometry of the gold(III) cation appears more suitable to promote chiral induction. Beside catalysis, gold(III) complexes have also shown promising potential in the field of pharmacology. Herein, syntheses and applications of well-defined gold(III) complexes reported over the last fifteen years are summarized.     

First Trifluoromethylated Phenanthrolinediamides: Synthesis,Structure, Stereodynamics and Complexation with Ln(III)

The first examples of 1,10-phenanthroline-2,9-diamides bearing CF₃-groups on the side amide substituents were synthesized. Due to stereoisomerism and amide rotation, such complexes have complicated behavior in solutions. Using advanced NMR techniques and X-ray analysis, their structures were completely elucidated. The possibility of the formation of complex compounds with lanthanoids nitrates was shown, and the constants of their stability are quantified. The results obtained are explained in terms of quantum-chemical calculations.     

新型含吡啶环席夫碱的合成及其晶体结构

[N,N'-(2-胺基苯基)-2,6-二甲酰亚胺]吡啶分别与苯甲酰丙酮和4-甲氧基水杨醛通过缩合反应合成了新型含吡啶环席夫碱(1a和1b),其结构经X-射线单晶衍射,1H NMR,IR和元素分析表征.1a属三斜晶系,空间群P-1,晶体参数a=11.895(4)(A),b=12.584(4)(A),c=13.191(4)...     

Comprehensive Review of Recent Advances in Chiral A-Ring Flavonoid Containing Compounds: Structure,Bioactivities, and Synthesis

Flavonoids are a group of natural polyphenolic substances that are abundant in vegetables, fruits, grains, and tea. Chiral A-ring-containing flavonoids are an important group of natural flavonoid derivatives applicable in a wide range of biological activities such as, cytotoxic, anti-inflammatory, anti-microbial, antioxidant, and enzyme inhibition. The desirable development of chiral A-ring-containing flavonoids by isolation, semi-synthesis or total synthesis in a short duration proves their great value in medicinal chemistry research. In this review, the research progress of chiral A-ring-containing flavonoids, including isolation and extraction, structural identification, pharmacological activities, and synthetic methods, is comprehensively and systematically summarized. Furthermore, we provide suggestions for future research on the synthesis and biomedical applications of flavonoids.     

Bis(oxofluorenediyl)oxacyclophanes: Synthesis,Crystal Structure and Complexation with Paraquat in the Gas Phase

The first three representatives of the new family of oxacyclophanes incorporating two 2,7‐dioxyfluorenone fragments, connected by [‐CH₂CH₂O‐]_m spacers (m=2–4), have been synthesized. The yield of the smallest oxacyclophane (m=2) is considerably higher with respect to the larger ones (m=3 and m=4), which are formed in comparable yields. Molecular modeling and NMR spectra analysis of the model compounds suggest that an essential difference in oxacyclophanes yields is caused by formation of quasi‐cyclic intermediates, which are preorganized for macrocyclization owing to intramolecular π–π stacking interactions between the fluorenone units. The solid‐state structures of these oxacyclophanes exhibit intra‐ and intermolecular π–π stacking interactions that dictate their rectangular shape in the fluorenone backbone and crystal packing of the molecules with the parallel or T‐shape arrangement. The crystal packing in all cases is also sustained by weak C? H ??? O hydrogen bonds. FAB mass spectral analysis of mixtures of the larger oxacyclophanes (m=3 and m=4) and a paraquat moiety revealed peaks corresponding to the loss of one and two PF₆^? counterions from the 1:1 complexes formed. However, no signals were observed for complexes of the paraquat moiety with the smaller oxacyclophane (m=2). Computer molecular modeling of complexes revealed a pseudorotaxane‐like incorporation of the paraquat unit, sandwiched within a macrocyclic cavity between the almost parallel‐aligned fluorenone rings of the larger oxacyclophanes (m=3 and m=4). In contrast to this, only external complexes of the smallest oxacyclophane (m=2) with a paraquat unit have been found in the energy window of 10 kcal mol^?1.     

Synthesis, Metal Complexation and Spectroscopic Characterization of Three New Azo Compounds

The synthesis of azo compounds [4-(N'-2-thiazol-2-ylsulfanyl)-4'-hydroxyazo benzene (1), 4-(N'-2-thiazol-2-ylsulfanyl)-2'-hydroxy-5-tert-butylazobenzene (2), 7-[4-(N'-2-thiazol-2-ylsulfanyl)phenylazo-8-hydroxy quinoline (3)] have been carried out by reacting phenol, 4-tert-butyl phenol and 8-hydroxy quinoline with N'-2-thiazol-2-ylsulfanylamide as coupling component. The resulting ligands (2 and 3) were treated with two transition metal salts (e.g., CuCl₂2H₂O andNiCl₂6H₂O). Cu(II) and Ni(II) complexes of the azo derivative ofphenol were obtained and characterised by IR, UV-Vis, ¹H NMR, spectroscopic and elemental analysis techniques. All the complexes have a metal : ligand ratio of 1 : 2 and are square-planar.     

Synthesis,Structure and Properties of C(X)NHP(Y) Fragment Containing Compounds

Abstract

N-(thio)carbonyl(thio)amidophosphate, their open-chain and crown-containing analogues with a C (X) NHP (Y) fragments are associated with intermolecular hydrogen bonds as C=X…H-N and P=Y…H-N or intramolecular hydrogen bonds of N-H…O(macrocycle). These compounds easily enter into alkylation reaction, are added according to C=N bonds of activated imines, take part in O → S and S → O exchanging reactions.     

Synthesis, Crystal Structure and Quantum Chemical Investigation of Bis-Schiff Base Compounds Derived from2-phenyl-1,2,3-triazole-4-carboxaldehyde with Diamine

Two new schiff base N,N＇-bis（（2-phenyl-2H-1,2,3-triazol-4-yl）methylene）-1,3-propanediamine （1） and N,N＇-bis（（2-phenyl-2H-1,2,3-triazol-4-yl）methylene） -1,4-butanediamine （2） were synthesized by condensation of 2-phenyl-1,2,3-triazole-4-carboxaldehyde with diamine, and characterized by elemental analysis, IR, IH NMR and MS spectra. Their crystal structures were determined by X-ray single crystal diffraction. Both crystals belong to the monoclinic system, space group P21/c. For compound 1（C21H20N8, Mr=384.45）： a = 16.314（3）, b =5.7168（11）, c = 21.316（4） A, β = 105.3（2）°, Z = 4, V = 1917.6（7） A^3, De =1.332 g/cm^3, F（000） = 808,μ = 0.086 mm 1, R = 0.0533 and wR = 0.1460; for compound 2 （C22H22N8, Mr=398.48）： a = 8.6156（17）, b = 5.2964（11）, c = 22.665（5）A, β = 100.54（3）°, Z = 2, V = 1016.8（4） A^3, De= 1.302 g/cm^3, F （000） = 420, μ = 0.083 mm^-1, R = 0.0373 and wR = 0.1155. Based on the crystal data, quantum chemistry calculation was performed on the two title compounds by means of Gaussian 98 program. The molecular orbital energies and atomic net charges population were obtained. Furthermore, we antilyzed their active atoms. The investigation can serve as a theoretical guide to study the synthesis and activity of the title compounds.     

含L－氨基酸结构的手性液晶化合物的合成及其相变行为

合成了９种具Ｌ－氨基酸衍生物结构的介晶化合物（Ｉ－Ⅲ，Ⅳａｂ，Ⅴａ，ｂ，Ⅵａ，ｂ）、４种氨基酸衍生物（Ａ１－４）和６种介晶化合物（Ｍ１－６）．新化合物（Ⅰ－Ⅲ，Ⅳａ，ｂ，Ⅴａ，ｂ，Ⅵａ，ｂ，Ａ４，Ｍ３－６）的化学结构通过ＩＲ、１ＨＮＭＲ和元素分析证实；并用偏光显微观察和ＤＳＣ分析研究了其相变行为，结果表明有８种化合物（Ｍ３－６，Ⅵａ，ｂ，Ⅴｂ，Ⅵｂ）呈现液晶相变。测定了它们的比旋光度。通过Ｘ射线衍射研究了化合物Ⅵｈ１２０～１３０℃和Ⅵｂ１７０～１８０℃的近晶结构，Ⅵｂ显，Ⅵｂ呈。测定了化合物Ⅳｂ的电滞回线，证明其具铁电性。     

Some 4(1h) Pyridylidene Compounds II Synthesis and Structure of N,N-Conjugated-4-Pyridine Compounds

The reaction of 4-methylpyridine and its methiodide with p-N, N-dimethylamino-benzaldehyde gave 4-p-N, N-dimethylaminostyrylpyridine (I) and 4-p-N, N-dimethylaminostyrylpyridine methiodide (II), respectively, II was also prepared by methylation of I with methyl iodide in methanol. The pyridylidene structure of II, N-benzyl-4-(p-N, N-dimethylaminophenyl) pyridinium chloride (IV_a) and its methiodide (V_a) was discussed in terms of UV, NMR and mass spectra.     

Ferrimagnetic Mixed-Valency and Mixed-Metal Tris(oxalato)iron(III) Compounds: Synthesis, Structure, and Magnetism

The synthesis and structural and magnetic characterization of 16 compounds AM(II)Fe(III)(C(2)O(4))(3) (A = N(n-C(3)H(7))(4), N(n-C(4)H(9))(4), N(n-C(5)H(11))(4), P(n-C(4)H(9))(4), P(C(6)H(5))(4), N(n-C(4)H(9))(3)(C(6)H(5)CH(2)), (C(6)H(5))(3)PNP(C(6)H(5))(3), As(C(6)H(5))(4); M(II) = Mn, Fe) are reported. X-ray powder diffraction profiles are indexed in R3c or its subgroup P6(5)22 or P6/mmm to derive unit cell constants. The structures of all the compounds consist of two-dimensional honeycomb networks [M(II)Fe(III)(C(2)O(4))(3)(-)](infinity). The M(II) = Fe compounds behave as ferrimagnets with T(c) between 33 and 48 K, but five exhibit a crossover from positive to negative magnetization near 30 K when cooled in a field of 10 mT. The compounds exhibiting this unusual magnetic behavior are those that have the highest T(c). Within the set N(n-C(n)()H(2)(n)()(+1))(4)Fe(II)Fe(III)(C(2)O(4))(3) (n = 3-5), T(c) increases with interlayer separation and the low-temperature magnetization changes from positive (n = 3) to negative (n = 4, 5). In the M = Mn(II) compounds, the in-plane cell parameter a(0) is approximately 0.03 ? greater than in the corresponding M = Fe(II) ones while the interlayer separation (c(0)/6) is on average 0.08 ? smaller. All members of the M(II) = Mn series have magnetic susceptibilities showing broad maxima at 55 K characteristic of two-dimensional antiferromagnetism, but the magnetization of several of the salts increases sharply below 27 K due to the onset of spin canting, the magnitude of which varies significantly with A.     

Stereoselective Synthesis and Complexation of a New Chiral Hybrid Phosphine-Phosphine Oxide Ligand from (S)-(+)-Prolinol

Abstract

The synthesis and the complex formation of chiral heterotopic ligands with two different binding sites each capable of bonding a different type of metal are described. The action of bis(dimethylamino) aryl phosphine on (S)-(+)-prolinol gives rise to the kinetic stereoisomer (2S,4S)-2-phenyl-1,3,2-oxazaphospholidine 1 and the thermodynamic stereoisomer (2R,4S)-2-phenyl-1,3,2-oxazaphospholidine 2. 1 is then totally converted into 2 at the end of the reaction. The Michaelis Arbuzov reaction of 2 with benzylbromide affords (R_p)-benzylaryl-(2-(S)-bromomethyl pyrrolidine-1-yl) phosphine oxide 3 in 80% yield. Compound 3 is an ideal chiral precursor for the synthesis of chiral hybrid phosphine-phosphine oxide ligands. The bromide atom is smoothly displaced by lithium diphenylphosphide to afford in 80% yield (R_p)-benzylaryl-(2-(S)-diphenylphosphinomethylpyrrolidine-1-yl) phosphine oxide 5. These reaction are proved to be totally stereoselective : the Michaelis Arbuzov reaction does not change the configuration at C2 in the proline ring. The relative configuration (R_p) of 5 (aryl = phenyl) was determinated by X-ray diffraction, from the known configuration of (S)-(+)-prolinol.     

Ferrocene Compounds. XXVII. Synthesis and Structure of 2-(Ferrocenylmethyl)propane-1,3-diol

The title compound was obtained by reduction of diethyl (ferrocenylmethyl)malonate with lithium aluminium hydride in diethyl ether. The structure of this novel ferrocene derivative was assigned by means of elemental analysis, IR, [¹H]NMR, and [¹³C]NMR spectroscopy. The structure was also confirmed by a single crystal X-ray study. The compound crystallizes in monoclinic P2₁/a space group with unit cell dimensions: a = 9.7360(6), b = 27.040(5), c = 14.767(3) Å, = 103.835(6)°, V = 3774.8(11) ų, Z = 12. The asymmetric unit contains three crystallographically independent molecules. In the ferrocenyl moieties, the Fe–C bond distance values are in the range 2.006(5)—2.051(3) Å and C–C distances in the range 1.366(7)–1.425(4) Å. The cyclopentadienyl rings in each of the molecules are mutually twisted by about 13° from the eclipsed conformation. The hydroxyl groups are involved in the intermolecular O–H...O hydrogen bond formation with O-O distances in the range 2.686(3)–2.801(4) Å forming infinite two-dimensional network in a [0 0 1] plane. The crystal structure is additionally stabilized by C–H-O weak intermolecular hydrogen bonds.     

N-Cyanoimines in the Synthesis of Heterocyclic Compounds. (Review)

Methods for the synthesis of N-cyanoimines in the period between 1959 and 2003 and their chemical properties are examined. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 963–973, July, 2005.