Stereoselective Synthesis and Characterization of (Z)-(−)-4-(1′-Alkoxyl-1′-alkyloxycarbonyl-methylidene)-5(R)-[(1R)-menthyloxy]-γ-butyrolactones

Abstract

A series of enantiomerically pure (Z)-(?)-4-(1′-alkyloxy-1′-alkyloxycarbonyl-methylidene)-5(R)-[(1R)-menthyloxy]-γ-butyrolactones were synthesized and characterized in good to excellent yields via O-alkylation of (4R,5R)-(?)-4-ethoxyoxalyl-5-[(1R)-menthyloxy]-γ-butyrolactone with alkyl halides in the presence of K₂CO₃ in acetone at room temperature.     

Transition metal(II) complexes of 1-(α-hydroxynaphthyl)-2-(3′-methyl-5′-mercapto-1′,2′,4′-triazole)-2-aza-ethane

Summary Binuclear metal complexes of the type [M(HMTE)-(H₂O)₂]₂, where HMTE=1-(-hydroxynaphthyl)-2-(3-methyl-5-mercapto-1,2,4-triazolc)2-aza-ethane and M-Cu^II, Co^II, Ni^II and Mn^II have been prepared and characterized. An octahedral geometry around the metals is proposed. The complexes have been screened as possible fungicides.     

1,10-双(1′-苯基-3′-甲基-5′-氧代吡唑-4′-基)癸二酮-(1,10)萃取钪

本文研究了1,10-双(1-苯基-3’-甲基-5’-氧代吡唑-4’-基)癸二酮-〔1,10〕从硝酸溶液中对Sc、Y、La的萃取分离。测定了固态萃合物的溶解性、摩尔电导、热稳定性及UV、IR、~1H NMR谱,讨论了萃合物的可能结构。     

Abnormal Reaction of 1-(2′-Methoxybenzoyl)-1-(2′-hydroxy-5′-methoxycarbonylbenzoyl)methane Treated with Etyyl Orthoformate and Acetic Anhydride

邻羟基二苯甲酰基甲烷与Ａｃ２Ｏ和ＨＣ（ＯＥｔ）３反应通常是ＨＣ（ＯＥｔ）３作为酰化剂，得到３－苯甲酰基色酮。本文报道５－甲氧羰基－２－羟基苯甲酰基－（２′－甲氧苯甲酰基）甲烷与Ａｃ２Ｏ和ＨＣ（ＯＥｔ）３反应时，是Ａｃ２Ｏ而不是ＨＣ（ＯＥｔ）３作为酰化剂，生成３－苯甲酰基－２－甲基色酮。其结构经ＮＭＲ、ＭＳ、ＩＲ和ＥＡ证实。并对其反应机理作了讨论。     

Synthesis of (−)-(1′S,4aS,8aR)- and (+)-(1′S,4aR,8aS)-4a-ethyl-1-(1′-phenylethyl)-octahydroquinolin-7-ones

A synthesis of the enamine (−)-(1′S)-5-ethyl-1-(1′-phenylethyl)-1,2,3,4-tetrahydropyridine 4 and its application in a synthesis of (−)-(1′S,4aS,8aR)- and (+)-(1′S,4aR,8aS)-4a-ethyl-1-(1′-phenylethyl)-octahydroquinolin-7-ones 5 and 6 is described. In addition, an X-ray study of 6 is reported. Finally, the preparation of (+)-(4aS,8aR)-4a-ethyl-octahydroquinolin-7-one 7 is described.     

1-(5′-溴-2′-吡啶基)-5-4′-硝基苯基)-3-(2′-呋喃基)甲(月朁)的合成及其与锌显色反应的研究

甲■类试剂是有色金属离子的优良显色剂。它们的各种取代衍生物,有许多作为分析试剂已被研究。近年来,为了改善该类试剂的分析性能,在甲(?)骨架上接上吡啶、噻唑、眯唑及呋喃等杂环基团,合成了一系列不对称型的杂环甲(?)。 本文报导5-Br-PNPFF试剂的合成和提纯方法。研究了它与锌显色反应的条件,用     

Photochemical Synthesis of 5-Ethynyl-5′-(1-Propynyl)-2.2′-Bithiophene

The synthesis of the title compound is described. The key-step is the photochemical coupling between 5-iodo-2-thienylcarbaldehyde and 2-bromothio-phene to give 5-bromo-2,2′-bithienyl-5′-carbaldehyde.     

Stereochemistry of the asymmetric reduction of (1′s)-1,3-dimethyl-4(1′-phenylethylimino)piperidine

The stereochemistry of the asymmetric reduction of the imine obtained from 1,3-dimethylpiperidin-4-one and (S)--phenylethylamine has been studied. It is shown that hydride reduction of imine 1 by sodium borohydride in methanol is asymmetric and gives the cis and trans diastereomeric pair 1,3-dimethyl-4-(-phenyl-ethylamino) piperidine in the ratio 3:1. Using sodium in isopropanol gives only one trans diastereomeric pair.¹H NMR has been used to identify the stereochemical structure and diastereomer excess of the cis and trans isomers of 1,3-dimethyl-4-(-phenylethylamino)piperidine which had been separated by column chromatography.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 219–221, February, 1996.     

Synthesis and applications of (R)- and (S)-7,7′-dimethoxy-2,2′-bis(diphenylphosphino)-1,1′-binaphthalene

The synthesis of (R)- and (S)-7,7′-dimethoxy-2,2′-bis(diphenylphosphino)-1,1′-binaphthalene 5a and 5b is described. The phosphorus atoms in (S)-(−)-5b are shown to be slightly more basic than the phosphorus atoms in (S)-BINAP by comparing the magnitude of the ¹J (³¹P–⁷⁷Se) coupling constant in their respective diselenide derivatives. (S)-(−)-5b behaved similarly to (S)-BINAP in asymmetric Heck reactions.     

A Facile Synthesis of an Advanced Glycosylation Endproduct 2-(2′-furoyl)-4(5)-(2′-furanyl)-1H-imidazole

Abstract: A three step synthesis of the advanced glycosylation endproduct 2-(2′-furoyl)-4(5)-(2′-furanyl)-1H-imidazole (4, FFI) has been achieved from 2-acetylfuran. The key step in the synthesis was the rearrangement of the hydrazinium bromide 3 in refluxing methanol.     

Molecular and crystal structure of 2,3-dimethyl-5-(2′-methylprop-1′-enyl)-6-(morpholyl-4′-carbonyl)-cyclohex-3-en-1-carboxylic acid

An X-ray structural examination is carried out for 2,3-dimethyl-5-(2′-methylprop-1′-enyl)-6-(morpholyl-4′-carbonyl)-cyclohex-3-en-1-carboxlic acid that is one of the products of the Diels-Alder reaction of an acyclic monoterpene alloocimene with maleic and citraconic anhydrides followed by the ring opening of adducts with morpholine to corresponding amides. The crystals are triclinic; a = 10.619(1) ?, b = 12.784(2) ?, c = 14.328(2) ?; α = 65.752(1)°, β = 87.932(1)°, γ = 78.120(1)°; V = 1733.0(3) ?³, P-1 space group, Z = 4 (two independent molecules). In both molecules, the anti-conformation of the carboxylic group is observed, the conformation being stabilized by an intramolecular hydrogen bond involving the carboxylic hydrogen atom and ketonic oxygen.     

5′-鸟嘌呤核苷三磷酸(5′-GTP)和5′-尿嘧啶核苷三磷酸(5′-UTP)二钠盐的制备

前言核苷三磷酸是含有两个高能磷酸键的高能化合物。除了参与核糖核酸合成外,在生物体内的生命活动中起着重要的作用。ATP 主要用于供给合成细胞的物质所需要的能量,也是被称为“第二信使”的环化AMP(3′5′-cyclicAMP)的前体。而后者已知与多种生化过程有关。CTP 参与重要磷脂类的合成。GTP 在蛋白质合成中是必不可少的。UTP 是肝脏中重要解毒剂尿二磷葡萄糖醛酸(UDPG)的前体,与肝糖元、酸性粘多糖的合成密切相关。根据已知的生理功能有些兄弟研究单位作了一些临床应用试验,还值得进一步探讨。     

Synthesis of (Z)-(2′R)-1-O-(2′-methoxynonadec-10′-enyl)-sn-glycerol,a new analog of bioactive ether lipids

An unsaturated 2-methoxy-substituted 1-O-alkylglycerol, (Z)-(2′R)-1-O-(2′-methoxynonadec-10′-enyl)-sn-glycerol, a new analog of bioactive ether lipids, was synthesized from oleic acid and 2,3-isopropylidene-sn-glycerol. The two key steps of this synthesis were the conversion of oleyl aldehyde to a monounsaturated epoxide using Matteson’s method followed by hydrolytic kinetic resolution and a nucleophilic epoxide opening by 2,3-isopropylidene-sn-glycerol in the presence of potassium tert-butoxide in anhydrous DMF, which appeared to be a good reagent for this purpose. Furthermore, the diol by-product of the HKR process was also easily converted back to the starting epoxide thus almost doubling the amount of target molecule.     

铽(Ⅲ)-1,4-双(1′-苯基-3′-甲基-5′-氧代吡唑-4′-基)丁二酮-[1,4]体系荧光性质的研究及应用

本文研究了Tb(Ⅲ)-1,4-双(′-苯基-3′-甲基-5′-氧代吡唑-4′-基)丁二酮-[1,4](BPMPBD)-溴化十六烷基三甲胺(CTMAB)体系的荧光性质,探讨了响影体系荧光性质的诸因素,确定了最佳实验条件。该体系中Tb(Ⅲ)浓度以2.0×10~(-5)～1.0×10~(-10)mol/L范围内与其荧光强度呈线性关系,检测限可达到5.0×10~(-11)mol/L。应用于合成样品中微量Tb(Ⅲ)的分析,结果令人满意。     

Synthesis and Crystal Structure of 1′-Methyl-4′- (4-chlorophenyl)-1H-indole-3-spiro-2′-pyrrolidine- 3′-spiro-4'-(2'-phenyloxazole)-2,5'(3H,4'H)-dione

The title compound (C26H20ClN3O3) has been synthesized by 1,3-dipolar cycloaddition reaction from isatin, sarcosine and (Z)-4-(4-chlorobenzylidene)-2-phenyloxazol-5(4H)-one through a one-pot procedure, and its structure was confirmed by IR, 1H NMR, elemental analysis and single-crystal X-ray diffraction analysis. The crystal belongs to the triclinic system, space group P1, with a = 9.3903(19), b = 11.398(2), c = 12.603(3) , α = 83.495(3), β = 68.988(3), γ = 67.178(3)°, V = 1160.1(4) 3, Z = 2, Mr = 457.90, Dc = 1.311 g/cm3, μ = 0.198 mm-1, F(000) = 476, the final R = 0.0489 and wR = 0.1144 for 3109 observed reflections with I > 2σ(I).     

1，4-双(1′-苯基-3′-甲基-5′-氧代吡唑-4′-基)丁二酮-(1，4)合双铜(Ⅱ)配合物的合成、表征、非等温热分解反应动力学及电化学性质

The paper reported the synthetic procedure and character of Copper(Ⅱ) binuclear coordination compound of 1,4-bis-(1′-phenyl-3′-methyl-5′-pyrazolone-4′)-1,4-butanedione. The non-isothermal kinetic of the thermal decomposition of the complex has been studied from the TG-DTG curves by means of the Achar et al and Coats-Redfern methods. The electrochemical characterization of the complex were studied by means of powder microelectrodes technique.     

3,4-双(3,′5′-二硝基苯-1′-基)氧化呋咱的合成

设计并合成了新化合物3,4-双（3′,5′-二硝基苯-1′-基）氧化呋咱（4）。以苯甲腈为起始原料,经加成、重氮化、分子间二聚得到3,4-二苯基氧化呋咱（3）,3经HNO3／H2SO。硝化合成了4,其结构经^1H NMR,IR和元素分析表征;初步考察了加成、重氮化、缩合环化、硝化等反应的主要影响因素,确定了适宜的反应条件。     

Novel 2′-(pyridin-4-yl)-5′-(pyridin-2-yl)-1′-(pyridin-2-yl)methylpyrrolidinyl[60]fullerene-hydroxyoxo(5,10,15,20-tetraphenyl-21H,23H-porphynato) molybdenum(V) dyads

Interaction between hydroxyoxo(5,10,15,20-tetraphenylporphyrinato)molybdenum(V) and 2′-(pyridin-4-yl)-5′-(pyridin-2-yl)-1′-(pyridin-2-yl)methylpyrrolidinyl[60]fullerene in toluene has been studied by means of spectrophotometry. The reaction proceeds via two stages: rapidly established equilibrium between the reactants and their molecular complex 1: 1 [K = (1.97 ± 0.52) × 10⁴ L/mol] followed by slow irreversible displacement of hydroxy group into the second coordination sphere to form cationic outer sphere complex (k = 0.26 L s^?1 mol^?1). The effect of fullerene fragment on pyridine fragments coordination has been considered.     

1-(2′-苯基-1′,2′,3′-三唑-4′-甲酰基)-4-芳基氨基硫脲及其环化产物的合成

以2-苯基-1,2,3-三唑-4甲酰肼为原料合成了几种新的1-(2′-苯基-1′,2′,3′-三唑-4′-甲酰基)-4芳基氨基硫脲,在不同条件下环化,制得一系列新的1,3,4-噻二唑、1,3,4- 二唑和1,2,4-均三唑衍生物.化合物的结构经元素分析、IR、1HMR和MS确证,并对其波谱性质进行了讨论.