(±)-脱落酸的合成

以β-紫罗兰酮为起始原料,经环氧化、开环、烯丙位氧化、Wittig反应、碱性水解5步反应,以39％的总收率合成了植物激素3-甲基-5-(1-羟基-4-氧代-2,6,6-三甲基-2-环己烯基)-2,4-戊二烯酸(脱落酸),用IR、¹H NMR、MS及元素分析等测试技术表征了产物的结构。     

Crystal structure of <Emphasis Type="Italic">N</Emphasis>-(3-hydroxypropyl)-β-alanine and Bis(<Emphasis Type="Italic">N</Emphasis>-(3-hydroxypropyl)-β-alaninato)dicopper(II) [Cu<Subscript>2</Subscript> (Pro-ala)<Subscript>2</Subscript>]

N-(3-Hydroxypropyl)-β-alanine was synthesized by the reacti on of 3-aminopropanol with acrylic acid. From this ligand and basic copper carbonate, bis(N-(3-hydroxypropyl)-β-alaninato)dicopper(II) [Cu₂ (C₆H₁₁NO₃)₂] was obtained. The structures of the chelating agent and the copper complex were studied by X-ray diffraction. The Cu(II) coordination polyhedron is a distorted square pyramid. Each ligand forms six-membered β-alaninate and propanolamine chelate rings. The propoxy group functions as a bridge. In the crystal structure, the molecules form intermolecular coordination bonds C=O→Cu, which are perpendicular to the layers. The EPR signal typical of dimeric copper complexes is not observed due to low occupancy of the excited paramagnetic triplet state. The weak paramagnetic signal from monomeric copper complex allowed recording of the ¹H NMR spectrum of [Cu₂ (Pro-ala) ₂] with characteristic line broadening and contact shift. It follows from the obtained data that on dissolution, the complex dissociates by 40% to give monomeric copper complexes.     

新型手性<i>β</i>-烷氨基-<i>γ</i>-(<i>l</i>-孟氧基)丁内酯的合成

脂肪族伯胺作为亲核试剂与手性合成子5(R)-(l-孟氧基)-2(5H)-呋喃酮(4)发生不对称Michael加成反应, 得到一系列新的手性β-烷氨基-γ-(l-孟氧基)丁内酯类化合物6(产率34～81%, de≥98%). 通过IR, ¹H NMR, ¹³C NMR, MS, 元素分析及单晶X射线衍射分析, 确认了它们的化学结构、立体化学和绝对构型. 此结果为某些具有生物活性化合物及复杂分子的合成提供了新的途径.     

新型环状聚(ε-己内酯-co-γ-三乙基硅氧基-ε-己内酯)的合成

设计合成了具有精确分子结构的聚合物对深入了解其结构与性能之间的关系起着至关重要的作用。研究了一种合成带有三乙基硅氧侧基的环状无规共聚酯的新方法。功能性单体γ-三乙基硅氧基-ε-己内酯(γ-Et3SiOεCL)和ε-己内酯(ε-CL)在环状引发剂2,2-二丁基-2-锡-1,3-二氧环庚烷(DSDOP)的作用下,进行活性开环聚合反应以制备活性环状无规共聚酯(LCP(εCLcoγEt3SiOεCL))前体,当单体完全转化后,以该活性环状前体作为大分子引发剂,引发反应性单体α-(1-丙烯酰氧乙基)-ε-己内酯(αAEεCL)进行嵌段聚合反应,合成了在活性中心附近带有不饱和双键的功能性环状嵌段共聚酯,即活性环状聚(ε-己内酯-co-γ-三乙基硅氧基-ε-己内酯)-b-(α-(1-丙烯酰氧乙基)-ε-己内酯)。最后该活性环状嵌段共聚酯在紫外光照射下,反应性单体结构单元中的双键发生分子内交联反应,从而制得稳定的不含有机锡的新型环状无规共聚酯cP(εCLcoγEt3SiOεCL)(Mn,NMR=28500)。采用SEC、1H NMR以及DSC等技术手段对聚合物的结构和性能进行表征。该方法的突出特点是能够高效地合成带有功能性侧基的高相对分子质量的环状无规共聚酯。     

(Z)-2-苯氧(硫)基甲基-2-戊烯-γ-内酯和(Z)-2-苯氧(硫)亚甲基-γ-戊内酯的简便合成

以3-苯氧(硫)基丙炔(1)为原料,经5步反应合成(Z)-2-苯氧(硫)基甲基-2-戊烯-γ-内酯(8)和(Z)-2-苯硫亚甲基-γ-戊内酯(9).合成关键步骤为TMSCl/NaI/H2O/CH3CN体系中化合物(3)的碘氢化和去共轭.     

新型1-取代-2-(1′,3′-二氧五环-4′-基)苯并咪唑的合成

以地沟油水解副产物甘油和多聚甲醛为原料,经醇醛缩合和次氯酸钠催化氧化反应制得1,3-二氧杂环戊-4-酸(DIC); DIC与邻苯二胺或其衍生物进行酰胺化-环化反应高效地合成了3种新型的1-取代-2-(1′,3′-二氧五环-4′-基)苯并咪唑类化合物,其结构经UV-Vis, ¹H NMR, ¹³C NMR, IR和GC-MS表征。     

Platinum(II) and platinum(IV) chloro complexes with (<Emphasis Type="Italic">RS</Emphasis>)-1-(4-chlorophenyl)-4,4-dimethyl-3-(1Н-1,2,4-triazol-1-ylmethyl)pentan-3-ol

Platinum(II) and platinum(IV) chloro complexes with (RS)-1-(4-chlorophenyl)-4,4-dimethyl-3-(1Н-1,2,4-triazol-1-ylmethyl)pentan-3-ol (L), namely, cis-[PtCl₂L₂], trans-[PtCl₂L₂], and trans-[PtCl₄L₂], were synthesized. The structures of their coordination cores and the coordination mode of the reagent to the metal ions via the N(4) atom of the triazole ring were determined by electronic, IR, and NMR ¹H and ¹³C spectroscopy. The ratio between treo and erythro diastereomers and the conformation of reagent L in the complexes were established from the complete assignment of signals in their NMR spectra.     

Experimental and theoretical studies on bis[<Emphasis Type="Italic">μ</Emphasis>-2-methoxy-<Emphasis Type="Italic">N</Emphasis>′-(2-oxidobenzoyl)benzohydrazidato(3-)]dipyridinetricopper(II)

A novel homotrinuclear pyridine Schiff base copper(II) compound, [Cu₃(C₁₅H₁₁N₂O₄)₂(C₅H₅N)₂], has been synthesized and characterized by elemental analysis and X-ray single crystal deterimination. X-ray structural determination reveals that each copper(II) ion has a distorted square-planar geometry. The central copper ion is coordinated by two O and two N atoms from two Schiff base ligands, while each terminal copper ion is coordinated by one N and two O atoms of one Schiff base ligand and by one N atom of a pyridine molecule. Density funcational theory (DFT) method calculations of the structure, atomic charges distribution and natural bond orbital (NBO) analyses have been performed. The coordinate stabilization energies show that the trinuclear copper(II) compound is very stable.     

Effective synthesis and X-ray investigation of (±)-2<Emphasis Type="Italic">S</Emphasis>-2-(2-chlorophenyl)-3-acetyl-1,3-oxazolidine

The crystal and molecular structure of (±)-2S-2-(2-chlorophenyl)-3-acetyl-1,3-oxazolidine was determined by X-ray diffraction analysis. Orthorhombic crystal with unit cell parameters a = 6.7419(8) Å, b = 10.3797(12) Å, c = 14.9233(18) Å; space group P2₁2₁2₁, Z = 4, ρ _calc = 1.436 g/cm³, composition C₁₁H₁₂ClNO₂. The deviation of the chlorine atom from the mean square plane of the phenyl cycle is ?0.010(5) Å. The five-membered oxazolidine cycle has an envelope conformation, which is typical for this class of compounds; the cycle is rotated at the C-C bond with respect to the phenyl fragment (the dihedral angle is 79.7(1)°). The spatial structure of the C2 chiral center lying in the plane of the 2-chlorophenyl fragment may be described as a distorted tetrahedron with an S configuration of the sp ³ hybridized carbon atom. Analysis of torsion angles and deviation of the nitrogen atom from the surrounding three-angle plane by ?0.017(3) Å allows one to speak about a tendency toward a pyramidal structure for the trisubstituted nitrogen atom. The 3D crystal structure is formed by intermolecular hydrogen bonds of C-H...O type and a strong intermolecular contact of 3.164(3) Å between the chlorine atom and the carbonyl oxygen of the acyl group.     

(±)-3,5-二羟基-7,4′-二甲氧基二氢黄酮醇和(±)-3,5,7-三羟基-4′-甲氧基二氢黄酮醇的全合成

3,5 -二羟基 - 7,4′-二甲氧基二氢黄酮醇 ( 1 )从 Cephalanthus spathelliferus中分离得到后 [1] ,又在H aplopappus bayahuen[2 ] 和 L annea coromandelica[3] 等植物中被发现 ,在印度一直被用于治疗象皮病、阳痿、溃疡、阴道炎、口臭、痢疾和风湿病等 . 3,5 ,7-三羟基 - 4′-甲氧基二氢黄酮醇 ( 2 )首次从 Prunusdonestica[4 ] 中分离出来后 ,又从 Salix caprea L.,Brazilian propolis中得到 .研究表明 ,该化合物具有抗菌、抗肿瘤活性 .我们用与文献 [5 ]类似的方法以 2 ,4,6-三羟基苯乙酮和茴香醛为起始原料 ,经选择性保护、缩合、…     

4-alkylated 2-(2,3,5-tri-<Emphasis Type="Italic">O</Emphasis>-acyl-β-D-ribofuranosyl)- and 2-(2,3,4,6-tetra-<Emphasis Type="Italic">O</Emphasis>-acetyl-β-D-glucopyranosyl)-1,2,4-triazine-3,5-diones

The alkylation of 2-(2,3,5-tri-O-acyl-β-D-ribofuranosyl)- and 2-(2,3,4,6-tetra-O-acetyl-β-D-glucopyranosyl)- 1,2,4-triazine-3,5-diones with benzyl halides afforded the corresponding 4-benzyl derivatives whose structure was determined by spectral methods, including X-ray analysis. Some of the synthesized compounds were tested for antibacterial and antitumor activity.     

(±)-19-去甲基-4(18),8,11,13-四烯-松香烷-7-酮的全合成

以间异丙基溴苯1为起始原料,通过进攻环氧乙烷及溴代两步制得溴化物3.溴化物3与Hagemann′s酯发生偶联反应,水解后生成偶联产物5.再以路易斯酸BF3·Et2O催化化合物5进行分子内环化为关键步骤得到反式稠合中间体6,最后通过与三苯基膦碘甲烷季盐发生Wittig反应及氧化,合成了(±)-19-去甲基-4(18),8,11,13-四烯-松香烷-7-酮[19-nor-abieta-4(18),8,11,13-tetraen-7-one](8).     

Synthesis and steric structure of 2-[1-(3-chlorophenyl)-2,2,2-trifluoroethoxy]-3-(trichloromethyl)-6,7-benzo-1,4,2λ<Superscript>5</Superscript>-dioxaphosphepin-5-one 2-oxide

The reaction with chloral of 2-[1-(3-chlorophenyl)-2,2,2-trifluoroethoxy]-5,6-benzo-1,3,2-dioxaphosphorinan-4-one containing a chiral fluorinated exocyclic substituent on phosphorus leads to formation of 2-[1-(3-chlorophenyl)-2,2,2-trifluoroethoxy]-3-(trichloromethyl)-6,7-benzo-1,4,2⁵-dioxaphosphepin-5-one 2-oxide with a high regio- and stereoselectivity. The molecular and supramolecular structure of the isolated diastereomer was established by means of X-ray diffraction.Translated from Zhurnal Obshchei Khimii, Vol. 74, No. 12, 2004, pp. 1973–1980.Original Russian Text Copyright © 2004 by Gubaidullin, Burnaeva, Mironov, Litvinov, Kotorova, Ivkova, Goryunov, Konovalova, Mastryukova.This revised version was published online in April 2005 with a corrected cover date.     

β-胡萝卜素

本文从 β 胡萝卜素与维生素A的结构上分析 β 胡萝卜素与维生素A的关系 ;并联系生活实际阐明 β 胡萝卜素的性质、应用及防癌新功能。     

Synthesis and characteristics of <Emphasis Type="Italic">N</Emphasis>-(glyoxyldioxime)-<Emphasis Type="Italic">N</Emphasis>′-(2-hydroxybenzylidene)-1,4-diaminonaphthalene and its metal complexes

A new vic-dioxime, N-(glyoxyldioxime)-N′-(2-hydroxybenzylidene)-1,4-diaminonaphthalene, was synthesized proceeding from naphthalene. Its complexes of nickel, copper and cobalt were prepared. The vicdioxime and its complexes were charecterized by FT-IR, UV, ¹H NMR, mass spectrometry, elemental analysis, DTA/TG analysis techniques and conductometric measurements. Published in Russian in Zhurnal Obshchei Khimii, 2008, Vol. 78, No. 5, pp. 797–802. The text was submitted by authors in English.     

Thermolysis of 4-(ω-hydroxyalkyl)-2,6-di-<Emphasis Type="Italic">tert</Emphasis>-butylphenols

The process of thermolysis of tert-butylated hydroxyalkyl phenols includes de-tert-butylation, etherification, and fragmentation of the hydroxyalkyl group. On the basis of the proposed schemes of the mechanism of thermal de-tert-butylation the path of the search for catalysts for the synthesis of 4-hydroxyalkylphenols is defined and transformations of the by-products into biologically active substances were considered.     

Features of reactions of (<Emphasis Type="Italic">E</Emphasis>)-1-(β-aroylvinyl)pyridinium bromides with binucleophiles

Regardless of pH and a solvent nature the reactions of (E)-1-(β-aroylvinyl)pyridinium bromides with hydrazine led to the formation of pyrazole derivatives. The salts reacted with thiourea via intermediate formation of 4-arylpyrimidine-2-thiol to give (Z)-2-[(β-aroylvinyl)sulfanyl]-4-arylpyrimidines. In the case of N,N'-diphenylthiourea the reaction provided 6-aryl-3-aroyl-1-phenylpyridinium bromides. Pyridine hydrobromide liberated in the reaction course has a major influence on the process chemoselectivity.     

Studies on Nucleophilic Ring-Opning Reaction of Ethylene Epoxide by (μ- CH3S)(μ-IMIgS) Fe2 (CO)6——Syntheais and Crystal Structure of (μ-Methylthio)- (μ- R -Hydroxylethylthio)hexacarbonyldiiron

A new type of Fe-S complex (C), (μ -CH₃S) (μ-HOCH₂CH₂S) Fe₂(CO)₆ which contains μ-β-hydroxyethyl, has been synthesized in high yield through ring-opening reaction of ethylene epoxide under uncleophilic attack of active complex (A), (μ-CH₃S)(μ-IMgS) Fe₂(CO)₆, followed byan alcoholysis of the intermediate (B). The crystal structure of (C) was determined by an X-ray diffraction technique. The crystal belongs to monoclinic system with space group of C₂/c. Cell parameters a= 15.784(3), b = 22.172(3), c=9.774(2)Å, β=119.53(2)°, V=2976.3ų. D_c = 1.80g cm^-3, Z=8, F(000)=1616 and final R=0.077.     

Stability of the Ion Pair Between Ca<Superscript>2+</Superscript> and 2-(Hydroxymethyl)-3-Deoxy-D-<Emphasis Type="Italic">erythro</Emphasis>-Pentonate (α-Isosaccharinate)

Ion-pair formation between Ca²⁺ and -isosaccharinate, Ca²⁺ + ISA^-CaISA⁺, was studied by two independent methods: an ion-exchange and a potentiometric method (Ca-selective electrode). The two methods gave similar values for the complexation constant, log K_CaISA+^o at I = 0, (22 ± 1)°C. The ion-exchange method gave a value of log K_o^CaISA+ = (1.8 ± 0.1) and the potentiometric method resulted in logK_CaISA+^o = (1.78 ± 0.04). These values are in good agreement with the estimated value, log K_CaISA+^o = 1.7, based on the formation of a Ca-gluconate ion pair.     

(Indenyl)iridacarborane (η<Superscript>5</Superscript>-indenyl)Ir(η-7,8-C<Subscript>2</Subscript>B<Subscript>9</Subscript>H<Subscript>11</Subscript>): synthesis,structure, and bonding

A reaction of iodide [(η⁵-indenyl)IrI₂]_n (1) with thallium dicarbollide Tl[Tl(η-7,8-C₂B₉H₁₁)] leads to (indenyl)iridacarborane (η⁵-indenyl)Ir(η-7,8-C₂B₉H₁₁) (2) in 32% yield. The X-ray diffraction study showed that in the structure of 2, the five-membered rings C₅ and C₂B₃ have a cisoid conformation, in which the bridgehead carbon atoms of the indenyl ligand are arranged opposite to the carborane cage carbon atoms. The DFT calculations showed that the Ir—indenyl bond in compound 2 is weaker than the Ir—Cp bond in the complex (η-7,8-C₂B₉H₁₁)IrCp.