4-甲氧基-3-[3-(吗啉-4-基)丙氧基]苯甲腈的合成研究

以3-羟基-4-甲氧基苯甲醛为原料,在甲酸、甲酸钠、盐酸羟胺作用下,将醛基转化为氰基,在含有碳酸钾的DMF中,所得化合物与N-(3-氯丙基)吗啉反应得目标化合物,总收率为87.5%。产物结构由1HNMR表征。本方法具有操作简单、易于纯化、收率高等特点,为工业化生产提供实验基础。     

两种4’-对甲苯磺酰基异黄酮衍生物的合成及抗氧化性质研究

摘要 合成了未见文献报道的脂溶性较好的7-甲氧基-4’-对甲苯磺酰基异黄酮（L1）和7-氧乙酸乙酯-4’-对甲苯磺酰基异黄酮（L2）,并得到了L1的单晶结构,采用IR、1H NMR、元素分析和X射线单晶衍射对L1进行了结构表征. 利用紫外分光光度法研究了化合物L1和L2对DPPH•自由基的清除作用,并采用量子化学半经验法（AM1）和Hartree-Fock 从头算的方法,计算了化合物分子中相关原子的电荷密度,探讨了它们与DPPH•自由基反应的可能活性位点. 获得了理论计算和光谱实验相一致的结果. 晶体结构测定表明, L1晶体属单斜晶系,P2 (1)/c点群, a=20.041(5)Å ,b=6.0876(17)Å ,c=16.516(4)Å. 理论推断和光谱实验表明,L2对DPPH自由基的清除效果好于L1.     

3-芳基磺酰氧基(取代)异噻唑的合成及除草活性

通过3-羟基异噻唑和4-氰基-5-甲硫基-3-羟基异噻唑与芳基磺酰氯在碱性条件下缩合,合成了3-芳基磺酰氧基异噻唑和3-芳基磺酰氧基-4-氰基-5-甲硫基-异噻唑.对所合成的化合物进行了除草活性的测定.     

合成4-叔丁基-4′-甲氧基二苯甲酰甲烷的新方法

对叔丁基苯甲醛与对甲氧基苯乙酮在甲醇钠作用下缩合生成1-(4-甲氧基苯基)-3-(4-叔丁基苯基)-2-丙烯-1-酮(1,收率91%);1经溴加成,甲醇钠脱溴合成4-叔丁基4′-甲氧基二苯甲酰甲烷(收率89%),总收率81%,其结构经UV-Vis和1H NMR表征.     

聚丙烯酸[2,5-双(对甲氧基苯甲酰氧基)苄酯]及聚甲基丙烯酸[2,5-双(对甲氧基苯甲酰氧基)苄酯]的合成

周其凤等曾报道聚丙烯酸［２,５－双（对甲氧基苯甲酰氧基）节酯］［１］和聚甲基丙烯酸［２,５－双（对甲氧基苯甲酰氧基）苄酯］［２］的合成．但后来的研究发现,在合成单体的条件下出现的一种未见报道的异常反应［３］使产物成分复杂化,因此当时报道的聚合物可能不是聚丙烯酸［２,５－双－（对甲氧基苯甲酰氧基）苄酯］或聚甲基丙烯酸［２,５－双（对甲氧基苯甲酰氧基）苄酯］,而可能是共聚物．针对这一问题,我们重新设计了合成路线以避免发生上述副反应,成功地合成了丙烯酸或ａ－甲基丙烯酸［２,５－双－（对甲氧基苯甲酰氧基…     

4-芳氧乙(丙)酰氨基苯磺酰胺的合成与除草活性

芳氧羧酸;4-芳氧乙(丙)酰氨基苯磺酰胺的合成与除草活性     

2-[3-(4-甲氧基苯氧基)丙基]-1,3-二乙酰硫基丙烷的合成

自组装单层膜(SAMs)技术是自20世纪80年代以来快速发展起来的一个新型有机成膜技术,它是通过表面活性剂的头基与基底之间产生化学吸附,在界面上自发形成的有序的单分子层[1].     

荧光性的二(邻苯二甲酸异丙酯酰氧基)-丙烯酰氧基铝及其聚合物的合成、表征与性质

合成了螯合物二(邻苯二甲酸异丙酯酰氧基)-丙烯酰氧基铝(DIAA);以DIAA为单体进行游离基聚合合成了聚合物PDIAA.用元素分析、VPO、MS、ICP、IR、~1H-NMR和~(27)Al-NMR对其结构进行了表征,主要研究了它们在空气中的水解稳定性、热稳定性及其在溶剂中的荧光性质.     

对甲苯磺酰β-丙氨酸稀土(La,Ho)配合物的合成及晶体结构

合成了LaⅢ和HoⅢ离子与对甲苯磺酰β-丙氨酸的配合物,并进行了元素分析、红外等表征,测定了两个配合物的晶体结构.配合物组成为[Ln2(Ts-β-AlaH)6 (H2O)4]n·4nH2O (Ln=La(1),Ho(2),Ts-β-AlaH=N-对甲苯磺酰β-丙氨酸),配合物均属单斜晶系,P21/n空间群,晶胞参数: 配合物(1) a=0.9563(2) nm,b=1.9113(3) nm,c=2.2933(4) nm,β=100.04(2)°,Z=4,Mr=937.77,Dc=1.509 kg·m-3,F(000)=1912,R1=0.0367,wR2=0.0944;配合物(2) a=0.9545(2) nm,b=1.8971(4) nm,c=2.2930(6) nm,β=100.19(2)°,Z=4,Mr=963.79,Dc=1.566 kg·m-3,F(000)=1952,R1=0.0363,wR2=0.0991.配合物(1)和(2)均为一维链状结构,但链中羧基桥连方式不同;同时两个金属离子一个是9配位,一个是8配位.     

Synthesis and reactions of 2-hydroxy-4-oxo-4-(2,3,5,6-tetrafluoro-4-methoxyphenyl)-but-2-enoic acid methyl ester

2-Hydroxy-4-oxo-4-(2,3,5,6-tetrafluoro-4-methoxyphenyl)-but-2-enoic acid methyl ester (1) was synthesized by the reaction of pentafluoroacetophenone with dimethyl oxalate in the presence of sodium methylate. Subsequently, reactions of compound 1 with aniline, o-phenylenediamine, and o-aminophenol were investigated. In addition, the thermal cyclization of ester 1 was studied and led to the formation of 5,6,8-trifluoro-7-methoxy-4-oxo-4H-chromene-2-carboxylic acid methyl ester (6) due to nucleophilic substitution of the 3-fluoro group. Hydrolysis of compound 1 and subsequent cyclization by treatment with SOCl₂ gave 5-(2,3,5,6-tetrafluoro-4-methoxyphenyl)-furan-2,3-dione (3). Thermal decarbonylation of compound 3 under mild conditions resulted in the formation of 3-(2,3,5,6-tetrafluoro-4-methoxyphenyl)-propene-1,3-dione (4) which dimerized to pyranone 5.     

Synthesis of （S）-2-（3-Arylacrylamido）-3-{4-[2-（5-methyl-2-phenyloxazol-4-yl）ethoxy]phenyl}propanoic Acids

The synthesis of （S）-2-（3-arylacrylamido）-3-{4-[2-（5-methyl-2-phenyloxazol-4-yl）etho- xy]phenyl}propanoic acids is described. Their structures were confirmed by ^1H-NMR.     

Synthesis of 1-aryl-3-（3,4-dihydro-2H-chromen-5-yl） ureas as TNF-α inhibitors

A new series of compounds,1-aryl-3-(3,4-dihydro-2H-chromen-5-yl) ureas,have been synthesized and their structures were confirmed by FAB-MS and ~1H NMR.The preliminary pharmacological screening showed that these compounds inhibited TNF-αproduction in lipopolysaccharide (LPS)-stimulated THP-1 cells.     

A new ytterbium(III) PVC membrane electrode based on 6-methy-4-{[1-(1H-pyrrol-2-yl)methylidene]amino}-3-thioxo-3,4dihydro-1,2,4-triazin-5(2H)-one

This study presents the development of an original electrode, employing 6-methy-4-{[1-(1H-pyrrol-2-yl)methylidene]amino}-3-thioxo-3,4dihydro-1,2,4-triazin-5(2H)-one (PMTO) as a suitable ionophore. Interestingly, the electrode performance provided a very good response for Yb³⁺ in a wide concentration range (from 1.0 × 10⁻⁶ to 1.0 × 10⁻¹ mol L⁻¹) with a detection limit of 4.6 × 10⁻⁷ mol L⁻¹ and a slope of 19.5 ± 0.3 mV per decade of Yb³⁺ concentration. Furthermore, it possessed a fast response time of about 10 s and it functioned in the pH range of 3.3-8.0 with a usage of at least 2 months without observing any deviations. Noticeably, the proposed electrode revealed an excellent selectivity for Yb³⁺ over a broad variety of alkali, alkaline earth, transition and heavy metal ions. The practical applicability of the electrode was demonstrated by its utilization as an indicator electrode in the potentiometric titration of Yb³⁺ ions with EDTA and in the determination of F⁻ in mouth wash samples. Additionally, it was also applied for the determination of Yb³⁺ ions in binary mixtures.     

Synthesis and Crystal Structure of Ethyl 3-（4-Chlorophenyl）-3,4-dihydro-6-methyl-4-oxo-2- （pyrrolidin-1-yl）furo[2,3-d]pyrimidine-5-carboxylate

The crystal structure of the title compound ethyl 3-（4-chlorophenyl）-3,4-dihydro-6- methyl-4-oxo-2-（pyrrolidin-1-yl）furo[2,3-d]pyrimidine-5-carboxylate （C20H20ClN3O4, Mr= 401.84） has been prepared and determined by single-crystal X-ray diffraction. The crystal is of monoclinic, space group P21/n with a = 20.6215（9）, b = 8.5311（4）, c = 21.6886（9） A^°, β = 91.607（1）°, V = 3814.0（3）A^°^3, Z = 8, Dc = 1.400 g/cm^3, F（000） = 1680, μ = 0.233 mm^-1, R = 0.0718 and wR = 0.1545 for 6717 observed reflections with I 〉 2σ（I）. X-ray diffraction analysis reveals two crystallographically independent molecules in the asymmetric unit.     

Synthesis and Crystal Structure of Ethyl 2-(6-(1,3-Dioxo-4,5,6,7-tetrahydro-1H-isoindol-2(3H)-yl)-7-fluoro-3-oxo-2H-benzo[b][1,4]oxazin-4(3H)-yl) Butanoate

The title compound ethyl 2-(6-(1,3-dioxo-4,5,6,7-tetrahydro-1H-isoindol-2(3H)-yl)-7-fluoro-3-oxo-2H-benzo[b][1,4]oxazin-4(3H)-yl) butanoate 3 was synthesized by the reaction of ethyl 2-(6-amino-7-fluoro-3-oxo-2H-benzo[b][1,4]oxazin-4(3H)-yl) butanoate with 4,5,6,7-tetraydrophthalic anhydride,and its structure was determined by X-ray single-crystal diffraction.The crystal belongs to the monoclinic system,space group P21/n with a = 9.3469(2),b = 16.7715(5),c = 13.7153(4) ,β = 104.9680(10)°,μ = 0.107 mm-1,Mr = 430.42,V = 2077.08(10) 3,Z = 4,Dc = 1.376 g/cm3,F(000) = 904,T = 296(2) K,R = 0.0508 and wR = 0.1478.     

Synthesis and Crystal Structure of [2-Hydroxy- 5-（4-hydroxy-3-phenyliminomethylbenzyl）-benzylidene]-phenyl-amine

The title compound [2-hydroxy-5-（4-hydroxy-3-phenyliminomethyl-benzyl）-benzylidene]-phenyl-amine （C27H22N2O2, Mr = 406.47） was synthesized by 5,5′-methylene-bissalicylal- dehyde with aminobenezene, and its crystal structure was determined by single-crystal X-ray diffraction. The crystal belongs to the monoclinic system, space group C2/c with a = 4.4026（6）, b = 1.501（13）, c = 0.95818（12） nm, β = 90.868（2）°, V= 4.2813（9） nm^3, Z= 8, Dc= 1.292 g/cm^3,μ = 0.010, F（000） = 1744, R = 0.0576 and wR = 0.1450 for 3766 observed reflections with I 〉 2σ（I）. X-ray analysis reveals that the molecule has a pair of intramolecular OH…N hydrogen bonds.     

Synthesis and Antiviral Activity of 1-{[2-(Phenoxy)ethoxy]methyl}uracil Derivatives

The synthesis of novel 1-{[2-(phenoxy)ethoxy]methyl}uracil derivatives with different substituents in positions and 6 of the pyrimidine ring has been carried out. It has been shown that the alkylation of trimethylsilyl derivatives of uracil with 2-(4-chlorophenoxy)- and 2-(4-methylphenoxy)ethoxymethyl chloride under Hilbert-Johnson reaction conditions gives N₍₁₎-substitution products. It was found that the 1-{ [2-(phenoxy)ethoxy]methyl}uracil derivatives show viral inhibition properties relative to human immunodeficiency type 1 virus in vitro. The most active compounds are 5-bromo-6-methyluracil derivatives which suppress viral reproduction by 50% at 7.2 and 7.8 micromolar concentrations.__________Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 726–731, May, 2005.     

Synthesis and Crystal Structure of 1,4-Dimethyl-2,5-di{[2’-(3-pyridylmethylamino-formyl)phenoxyl]methyl}benzene Perchlorate

The title compound, 1,4-dimethyl-2,5-di{[2’-(3-pyridylmethylaminoformyl)phenoxyl]- methyl}benzene perchlorate (C36H36Cl2N4O12, Mr = 787.59), has been synthesized and structurally determined by single-crystal X-ray diffraction. The crystal crystallizes in the orthorhombic system, space group Pbca with a = 14.366(4), b = 15.159(4), c = 16.443(5), V = 3580.9(17)3, Z = 4, Dc = 1.461 g/cm3, μ = 0.253 mm-1, F(000) = 1640, R = 0.0618 and wR = 0.1525 for 1615 observed reflections (I > 2σ(I)). In the structure of the title compound, a two-dimensional supramolecular layer is formed via intermolecular hydrogen bonding interactions.