新型氟代缺联吡啶环蕃的合成

以1,3-二溴甲基-5-氟苯为原料,在低温条件下利用模板效应制得"联吡啶环蕃化合物"(1);1经过连续萃取及离子交换合成了新型氟代缺电子联吡啶环蕃单体——环蕃F-CPQT,收率7.6%,其结构经1H NMR和13C NMR表征。     

氟醚链的合成及超分子性能研究

以2,3,5,6-四氟-1,4-苯二甲醇为原料,经选择性单醚化、溴代及酯化反应合成了一种新型的氟醚链(Ⅰ),通过IR、MS、1H NMR对目标化合物和中间体结构进行了确证.以此作为富π电子供体和缺π电子联吡啶大环化合物环双(百草枯-亚苯基)四阳离子环蕃(CPQT)自组装形成新型准轮烷Ⅱ(I-CPOT),并利用1HNMR化学位移变化跟踪该准轮烷在温度调控下的分子开关功能.     

三聚联苯醚类大环化合物的合成

在温和条件下, 以3,3 -二溴-4,4 -联苯二酚和1,2-二溴乙烷或1,4-二溴丁烷为原料, 经过两步反应方便地合成了三聚联苯醚类大环化合物4a和4b, 并通过¹H NMR, ¹³C NMR, HRMS对中间体和目标化合物的结构进行了表征.     

2,3,5,6-四氟苯甲醇的合成

经氟代、水解脱羧、酯化、还原等步骤合成了杀虫剂四氟苯菊酯的重要中间体2,3,5,6-四氟苯甲醇, 改进了氟代反应的无水操作和反应条件, 产物四氟对苯二甲腈纯度高达98.3%, 通过加入水参与反应改进了水解反应, 使水解和脱羧由两步反应变为一步, 且产物为只脱一个羧基的2,3,5,6-四氟苯甲酸, 收率可以高达92.5%, 用相对价廉的NaBH₄/I₂体系还原2,3,5,6-四氟苯甲酸甲酯以52.3%的收率得到了目标产物, 总收率29.6%.     

3,9-二氮杂四星烷类化合物的合成研究

对3,9-二氮杂四星烷(3,9-二氮杂六环[6.4.0.0^2,7.0^4,11.0^5,10]十二烷)的合成进行了系统地研究. 以1,4-二氢吡啶为原料, 研究了溶剂、溶液浓度、光源、照射波长及光照时间等因素对[2＋2]环加成反应的影响, 得到了一系列3,9-二氮杂四星烷化合物, 并用IR, ¹H NMR, ¹³C NMR, MS和HRMS对其结构进行了表征.     

新型含硫代乙酸酯缺电子环蕃的合成

以3,5-二甲基苯酚为原料,经4步反应合成了1,1’-【{5-[3-(乙酰硫基)丙氧基]-1,3-亚苯基}双(亚甲基)】双{[(4,4’-联吡啶)-1-鎓]}二六氟磷酸盐(4);4与1,4-二溴甲基苯和萘模板在低温反应制得含硫代乙酸酯的缺电子环蕃(5);5经连续萃取及离子交换除去萘模板合成了新型含硫代乙酸缺电子环蕃——5,13,20,27-四氮杂七环[25,2,2,22,5,17,11,213,16,217,20,222,25]四十-9-(1-丙基硫代乙酸酯)氧-1(28),2,4,7,9,12,14,16,18,21,23,26,29,31,33,35,37,39-十八烯四六氟磷酸盐(6),其结构经1H NMR和13C NMR表征。     

1,4-二氢-4-芳基-3,5-吡啶二羧酸酯的合成及表征

基于二氢吡啶化合物的构效关系, 设计了一系列1,4-二氢-4-芳基-3,5-吡啶二羧酸酯新化合物. 含有易于水解基团的1,4-二氢-4-芳基-3,5-吡啶二羧酸酯类化合物在碱性条件下水解合成了重要中间体1,4-二氢-4-芳基-3,5-吡啶二羧酸单酯, 收率93%～99.8%. 该二羧酸单酯与α-溴代芳基乙酮在相转移剂催化下反应合成目标化合物, 收率74%～99%. 中间体和目标化合物经¹H NMR, ¹³C NMR, IR, MS和元素分析等确证.     

四氮杂环蕃衍生物的合成

在不同的条件下用二茂铁磺酰氯对1,6,16,21-四氮杂[6.1.6.1]对环蕃进行了修饰, 分别得到单取代和四取代产物. 用双官能团化合物溴乙酰溴对1,6,16,21-四氮杂[6.1.6.1]对环蕃进行了修饰, 得到1,6,16,21-四(2-溴乙酰基)-1,6,16,21-四氮杂[6.1.6.1]对环蕃, 然后将苯并咪唑基团引入四氮杂环蕃. 合成了带有生物活性基团的四氮杂环蕃衍生物. 用¹H NMR, IR和元素分析对新化合物进行了表征.     

烃基硅铜酸盐与2-芳基-2-环烯酮1,4-加成反应的立体选择性及2-取代- 3-硅基环烷酮的合成

研究了烷基苯基硅铜酸盐与2-环烯酮的1,4-加成反应的立体选择性, 并合成了一系列新的2-取代-3-硅基环烷酮. 结果表明, 在0 ℃下用饱和NH₄Cl溶液处理, 烷基苯基硅铜酸盐与2-芳基-2-环烯酮的1,4-加成反应的立体选择性不同程度地受芳基和环的大小影响, 得到顺、反两种产物; 并首次发现室温下用甲醇处理反应时, 其立体选择性不受或者很少受环大小、芳基的性质以及与硅原子相连的取代基的影响, 只得到反式产物. 芳基溴甲烷与由烷基苯基硅铜酸盐与2-环烯酮1,4-加成所得的烯醇盐反应时, 只得到反式产物. 合成产物的结构用IR, ¹H NMR, ¹³C NMR, MS和HRMS等进行了表征.     

含丁三醇端基富电子醚链与阳离子环蕃超分子准轮烷的表征和性能研究

以4-(2-(4-(苄氧基)苯氧基)乙氧基)-1,2,3-丁三醇(C)为富电子供体的醚链,与缺电子联吡啶大环化合物环双(百草枯-亚苯基)四阳离子环蕃(CPQT)和四氟取代环蕃(4FCPQT)自组装形成超分子准轮烷C(CPQT)和C(4FCPQT),并利用1HNMR的化学位移变化来研究两种不同准轮烷在温度变化时它们的相互作用。实验结果表明,由于富电子供体的一端含有3个羟基,易和缺电子联吡啶大环形成氢键,因此醚链的丁三醇端不能进入大环;缺电子联吡啶大环的一个苯环上的氢被氟取代后,由于电场力的作用,使富电子供体进入大环的概率相对降低,并使富电子醚链供体穿入大环的位置发生"偏心"作用。     

2,3-二羟甲基-2,3-二硝基-1,4-丁二醇四硝酸酯的合成、晶体结构及性能研究

以硝基甲烷为起始原料,经缩合、环化、氧化耦合、脱缩酮及硝化等5步反应合成了2,3-二羟甲基-2,3-二硝基-1,4-丁二醇四硝酸酯(BHDBT),总收率为36.1％,并采用核磁共振谱、红外光谱以及元素分析等进行了结构表征.用浓盐酸代替氯化氢气体,改进了关键中间体2,3-二羟甲基-2,3-二硝基-1,4-丁二醇(BHDB)的合成方法,并确定最佳反应条件为:刀(浓盐酸):n(BDND)=1.1∶1,反应温度55℃,时间4h,收率为94.8％.首次发现了BHDB和BHDBT的亚甲基质子具有磁不等价性,并从理论上分析其产生的原因.培养了BHDBT单晶,四元衍射晶体结构解析表明:BHDBT属于单斜晶系,空间群P2(1)/n,晶胞参数:a=0.81944(11) nm,b=2.3365(3) nm,c=0.85838(11) nm,a=90°,β=113.501(2)°,y=90°,V=1.5072(3) nm3,Z=4,Dc=1.852 g·cm-3,μ=0.189 mm-1,F(000)=856.BHDBT熔点为86.37℃,分解峰温度为185.79℃(DSC),摩擦感度为100％ (3.92 MPa,90°),特性落高H50为10.0 cm(5 kg).     

四甲基吡嗪多元醇及其乙酸酯的合成

四甲基吡嗪经溴代和酯化反应得到2,3,5-三乙酰氧甲基-6-甲基吡嗪(4)和2,3,5,6-四乙酰氧甲基吡嗪(5);4和5分别经水解得2,3,5-三羟甲基-6-甲基吡嗪和2,3,5,6-四羟甲基吡嗪。其结构经UV,1H NMR,13C NMR,IR和MS表征。     

Coordination networks with fluorinated backbones

Fluorine-containing ligands 2,3,5,6-tetrafluoro-1,4-bis(imidazol-1-yl-methyl)benzene (1) and 2,3,5,6-tetrafluoro-1,4-bis(2-methylimidazol-1-yl-methyl)benzene (2) were prepared and coordinated with AgNO3, Co(ClO4)2 x 6 H2O, and Cd(NO3)2 x 4 H2O, respectively, to form the following structures: 3D channel polymer [Ag2(1)2(NO3)2 x H2O x MeOH]n (3), 2D sheet polymer [Co(1)3(ClO4)2]n (4), 1D chain polymer [Cd(1)3(NO3)2 x 4 H2O]n (5), and a 2D herringbone sheet polymer [Ag(2)NO3 x 1.5 MeOH]n (6). The solid-state crystal structures of 3-6 were studied by single-crystal X-ray crystallography.     

Synthesis of tetrachloroisophthalic and-terephthalic aldehydes and stable bis(nitrile oxides) based on them

A new route for the synthesis of 2,4,5,6-tetrachloroisophthalic and 2,3,5,6-tetrachloroterephthalic aldehydes from the corresponding tetrachlorobenzenes was developed. The method involves dichloromethylation of the initial compounds with chloroform in the presence of aluminum chloride and subsequent hydrolysis of the resulting 1,3-bis(dichloromethyl)-2,4,5,6-tetrachlorobenzene and 1,4-bis(dichloromethyl)-2,3,5,6-tetrachlorobenzene. Stable 2,4,5,6-tetrachlorobenzene-1,3-dicarbonitrile oxide and 2,3,5,6-tetrachlorobenzene-1,4-dicarbonitrile oxide were obtained for the first time from the above aldehydesvia the corresponding oximes. The products were characterized by IR and¹³C NMR spectra, and were converted into substituted 1,3- and 1,4-phenylenebis(isoxazolines) using 1,3-dipolar cycloaddition with styrene. Translated fromIzvestiya Akademit Nauk. Seriya Khimicheskaya, No. 1, pp. 106–109, January. 1997.     

7-氯-[1，2，3，4]-四氢吩嗪-[2，3]-并富勒烯[60]的合成

60富勒烯及其衍生物因其结构的特殊性,在有机超导、分子磁性、有机发光材料、分子器件、非线性光学活性、能量代谢和生物活性等[1]方面表现出独特的性能和潜在的应用前景,是非常活跃的研究领域之一.     

Synthesis of benzoquinone derivatives containing benzotriazole fragments

2,3,5,6-Tetrakis(1H-benzotriazol-1-yl)-1,4-benzoquinone was synthesized in 85% yield by reaction of 2,3,5,6-tetrachloro-1,4-benzoquinone with 1H-benzotriazole in pyridine at room temperature. Treatment of 2,3,5,6-tetrakis(1H-benzotriazol-1-yl)-1,4-benzoquinone with piperidine, ω-amino acids, and aromatic amines gave the corresponding 2,5-diamino-3,6-bis(1H-benzotriazol-1-yl)-1,4-benzoquinones.     

Sterically encumbered systems for two low-coordinate phosphorus centers

Tetraarylphenyls of the form 2,3,5,6-Ar4C6 (Ar = p-tert-butylphenyl) are investigated as sterically demanding ligands for the syntheses of compounds having two p-phenylene-bridged phosphorus centers. The precursor to such materials, 1,4-diiodo-2,3,5,6-tetrakis(p-tert-butylphenyl)benzene (1), is readily obtained via a one-pot procedure in 68% yield. Compound 1 is then used to provide the bis(dichlorophosphine) 1,4-bis(dichlorophosphino)-2,3,5,6-tetrakis(p-tert-butylphenyl)benzene (2) and the derived bis(phosphine) 1,4-bis(phosphino)-2,3,5,6-tetrakis(p-tert-butylphenyl)benzene (3) in yields of 56 and 94% respectively. These materials provide access to novel materials containing two low-coordinate phosphorus centers bridged by a sterically encumbered phenylene unit. Compound 2 reacts with benzaldehyde and 2,6-dichlorobenzaldehyde in the presence of excess trimethylphosphine and zinc to produce the new pale yellow crystalline bis(phosphaalkenes) (E,E)-PhC(H)=PAr4C6P=C(H)Ph (4a; 42%) and (E,E)-Ar'C(H)=PAr4C6P=C(H)Ar' (4b; 46%; Ar' = 2,6-dichlorophenyl). The crystal structure of 4a shows a P=C bond length of 1.676(5) A. Compound 2 is also used to provide the unusual red-orange bis(diphosphene) DmpP=PAr4C6P=PDmp (5; 55%; Dmp = 2,6-Mes2C6H3). Compound 5 is structurally characterized, and a P=P bond length of 2.008(2) A is ascertained.     

2，6-双（3’-溴甲基-1’-吡唑基）-4-溴吡啶的合成与表征

以2,6-双（3’-甲基-1’-吡唑基）4-氨基吡啶为原料,经重氮化,溴化合成了新型时间分辨荧光免疫分析双功能螯合剂中间体2,6-双（3＇-溴甲基-1’-吡唑基）4-溴吡啶．结构通过IR,MS,^1HNMR和元素分析进行了表征,对合成条件进行了探讨．     

Pd2L2 metallacycles as molecular containers for small molecules

M(2)L(2) type metallacyclic complexes, [Pd(2)(L1)(2)Cl(4)]·1.5CH(2)Cl(2) (1), [Pd(2)(L1)(2)Cl(4)]·2CHCl(3) (2), [Pd(2)(L2)(2)Cl(4)]·2CH(2)Cl(2)·2CH(3)CN (3), [Pd(2)(L2)(2)Cl(4)]·2CHCl(3)·2CH(3)CN (4) and [Pd(2)(L3)(2)Cl(4)]·CH(2)Cl(2)·2CH(3)CN (5), have been prepared from three semi-rigid benzimidazol or benzotriazol ligands, 1,4-bis(benzimidazol-1-ylmethyl)-2,3,5,6-tetramethylbenzene (L1), 1,4-bis(5,6-dimethylbenzimidazol-1-ylmethyl)-2,3,5,6-tetramethylbenzene (L2) and 1,4-bis(benzotriazol-1-ylmethyl)-2,3,5,6-tetramethylbenzene (L3). All the complexes were structurally characterized by single-crystal X-ray diffraction and the phase purity was confirmed by powder X-ray diffraction (PXRD) measurements. The solution structure of representative complex 1 was studied by (1)H NMR titration and ESI mass spectroscopy. The thermal stability and guest-exchange properties of 1, 3 and 4 were investigated, revealing that the Pd(2)L(2) metallacycles can act as a selective receptor for CH(2)Cl(2) or CHCl(3) guest molecules. The catalytic activity of 1 in Suzuki-Miyaura coupling reaction was also studied and 1 could be recycled at least 5 times under heterogeneous conditions, indicative of a potential self-supported catalyst.