聚-2-氨基吡啶电化学合成及性质

报导了在 0.43 mol•dm－3 C6H6N2和0.01 mol•dm－3 NaOH中用循环伏安法合成聚-2-氨基吡啶. 聚-2-氨基吡啶在1.0 mol•dm－3 ZnCl2(pH=4.99)溶液中的循环伏安图上有三对氧化-还原峰.旋转环-盘实验的结果表明,在 2-氨基吡啶聚合的初期有中间体生成.由红外光谱可知，聚-2-氨基吡啶具有头-尾相接的结构.聚-2-氨基吡啶平均粒子大小约893 nm， 平均粒子间距约 255 nm. 由聚-2-氨基吡啶正极和锌负极及2.5 mol•dm－3 ZnCl2溶液和 3.0 mol•dm－3 NH4Cl (pH=5.5) 溶液构成的电池，其放电曲线类似于Li-SOCl2, 放电曲线的中间区域非常平稳.     

O-烷基-O-芳基-N-烷基-N-[(二烷氨基羰基)甲基]硫代磷酰胺酯的合成性质和杀螨活性

我们曾报道了关于 O,O-二烷基-N-烷基-N-[(二烷氨基羰基)甲基]硫代磷酰胺酯类化合物的合成及其生物活性。通过生物活性测试发现两个新化合物比 Tarpai 等发现的RA-17[(C_2H_5O)_2-P(S)N(Et)CH_2CONPr_2~n]具有更高的杀螨活性。为了进一步研究此类含磷     

烷基芳基环聚硅烷[RArSi)n,n=5,6]的合成及其波谱性质

半个多世纪前 Kipping 最先报道了二芳基环聚硅烷(Ar_2Si)(?)的合成,其中 Ar=Ph,p-MeC_6H_4,n=4,5,6。但是直到四十年后,它们的结构才由 Gilman 证明。迄今研究最     

Regioselective Synthesis and Inclusion Properties of distal-Bis[(2-pyridylmethyl) oxy]tetrathiacalix[4]arenes

Regioselective synthesis of bis[(2-pyridylmethyl)oxy]tetrathiacalix[4]arenes was accomplished by a protection–deprotection method using benzyl groups as a protecting group. The conformational studies of distal-bis[(2-pyridylmethyl)oxy]thiacalix[4]arenes in solution and solid state are described. The two-phase solvent extraction data indicated that bis[(2-pyridylmethyl)oxy]tetrathiacalix[4]arenes show strong Ag⁺ (E%, 97%) affinity. In contrast, no significant E% is observed for K⁺. A good Job plots proves 1:1 coordination of 1,3-alternate -3 with Ag⁺ cation. ¹H-NMR Titration of 1,3-alternate- 3 with AgSO₃CF₃ also clearly demonstrates that a 1:1 complex is formed with retention of the original symmetry. The conformational changes of pyridine moiety from the original outward orientation of the ring nitrogen to the inside orientation toward the thiacalixarene cavity were observed in the process of Ag⁺ complexation. The down-field shifts of the benzene protons of the benzyl group were also observed and attributed to the conformational deviation from the original face to face overlapping.     

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…     

5-[(偶氮苯基)偶氮]-8-氨基喹啉的合成、性质及其应用的研究

本文报道了新试剂5-[(偶氮苯基)偶氯]-8氨基喹啉的合成方法。研究了该试剂的理化性质,分析性能及其与钯显色反应的条件。从而拟定了直接分光光度法测定微量钯的新方法,结果满意。     

聚γ-巯丙基硅氧烷钯(0)配合物的合成及催化性能研究

γ－巯丙基三乙氧基硅烷依次与气相法二氧化硅，氯化钯作用，然后用水合肼还原，合成了新配合物聚γ－巯丙基硅氧烷钯。该配合物是丙烯酰胺及丙烯酸丁酯的Ｈｅｃｋ芳基化反应的有效催化剂，为立体选择性地２Ｅ－不饱酰胺及不饱和酯提供了简便且实用的方法。     

新型水溶性聚[(3-辛酰基吡咯-2,5-二)对二甲氨基苯甲烯]的合成、表征及性能研究

合成一种新型含推-拉电子基团的大π共轭高分子聚[(3-辛酰基吡咯-2,5-二)对二甲氨基苯甲烯](POPDMABE).用氢核磁共振谱、傅里叶红外光谱、紫外-可见光谱等分析手段对聚合物POPDMABE进行了结构表征.该聚合物易溶于多种极性有机溶剂和酸性水溶液,易于加工.热重分析表明,POPDMABE可耐180℃的高温.通过X射线衍射和透射电镜研究表明,POPDMABE以晶态和无定形态共存.光致发光光谱表明,在360nm的紫外光激发下,POPDMABE能发出蓝色荧光.     

Synthesis, Conformational Studies and Inclusion Properties of Tetrakis[(2-pyridylmethyl)oxy]thiacalix[4]arenes

An attempted O-alkylation of the flexible macrocycle 1with 2-(chloromethyl)pyridine in the presence of Cs₂CO₃ under THF reflux afforded a mixture of twoconformers of tetra-O-alkylated product 4a in a ratio of 91:9 (cone-4a:1,2-alternate-4a)in 70% yield, while other possible isomers were not observed. In the case of Na₂CO₃, there was no reaction product,only the starting compound 1, whereasonly monoalkylated compound 3 was obtained when usingK₂CO₃ as the base. The distribution of cone conformer decreased in the case of O-alkylation of tetraol 1with 4-(chloromethyl)pyridine or benzyl bromide in the presence of Cs₂CO₃ in comparison with that ofO-alkylation with 2-(chloromethyl)pyridine, while the 1,2-alternate conformer increased in the same sequence. The larger Cs⁺might increase the contribution of the metal template effect, which can hold the 2-pyridylmethyl group(s) and theoxide group(s) on the same side of the tetrathiacalix[4]arene 1 through the cation-O^- and -N-interaction in the caseof O-alkylation of tetraol 1 with 2-(chloromethyl)pyridine.Only when the template metal can hold the 2-pyridyl group(s) andthe oxide group(s) on the same side of the tetrathiacalix[4]arene is the conformation immobilized to thecone. The template effect of the cesium cation plays an important role in this alkylation reaction. The structuralcharacterization of these products is also discussed.The two-phase solvent extraction data indicated thattetrakis[(2-pyridylmethyl)oxy]thiacalix[4]arenes 4a show strong Ag⁺ affinity and a high Ag⁺ selectivity wasobserved for cone-4a. A good Job plot proves 1:1 coordination of cone-4a with Ag⁺ cation.¹H-NMR titration of cone-4a with AgSO₃CF₃ also clearly demonstrates that a 1:1complex is formed with retention of the original symmetry. In contrast, the 1,2-alternate-4a can form a 2:1 metal/thiacalix[4]arene complex and the two metal-binding sites display positive allostericity. The conformational changes ofpyridine moiety from the original outward orientation of the ring nitrogen to the inside orientation toward thethiacalixarene cavity were observed in the processof Ag⁺ complexation.     

Synthesis of (difluoroamino)tetrazoles and [(difluoroamino)alkyl]tetrazoles

(Difluoroamino)tetrazoles were obtained by direct fluorination of 5-aminotetrazoles with gaseous fluorine. Reactions of 2-(oxoalkyl)- and 2-(hydroxyalkyl)tetrazoles with difluoroamine yielded [(difluoroamino)alkyl]tetrazoles. Deceased Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 950–952, May, 2000.     

聚-4-氧杂-6,7-二甲硒基庚基硅氧烷钯(0)配合物的合成及其催化性能研究

4 氧杂 6,7 二氯庚基三甲氧基硅烷依次与气相法二氧化硅、甲硒基钠、氯化钯作用 ,然后用水合肼还原 ,合成了二氧化硅负载的聚 4 氧杂 6,7 二甲硒基庚基硅氧烷钯 ( 0 )配合物 .该配合物是苯乙烯及丙烯酸的Heck芳基化反应的有效催化剂 ,为立体选择性地合成各种取代的反式 1,2 二苯乙烯及反式肉桂酸提供了简便且实用的新方法 .     

聚-4-氧杂0-6，7-二甲硒基庚基硅氧烷钯（0）配合物的合成及其催化性能研究

4-氧杂-6，7-二氯庚基三甲氧基硅烷依次与气相法二氧化硅、甲硒基钠、氯化 钯作用，然后用水合肼还原，合成了二氧化硅负载的聚-4-氧杂，6，7-二甲硒基庚 基硅氧烷钯(O)配合物．该配合物是苯乙烯及丙烯酸的Heck芳基化反应的有效催化 剂，为立体选择性地合成各种取代的反式-1，2-二苯乙烯及反式肉桂酸提供了简便 且实用的新方法     

二(三甲硅亚甲基)锡二芳香羧酸酯的合成和结构表征

用二(三甲硅亚甲基)二氯化锡与芳香酸按1∶2的摩尔比进行反应, 合成了11个新的含硅有机锡化合物二(三甲硅亚甲基)锡二芳香羧酸酯. 通过IR, ¹H NMR, ¹³C NMR, MS以及元素分析对这些化合物的结构进行了表征. 部分化合物生物活性的初步测定结果表明, 该类化合物对肺癌细胞SPC-A-1具有较好的体外抗癌活性.     

Synthesis of N-methyl-N-[(1S)-1-[(3R)-pyrrolidin-3-yl]ethyl]amine

N-Methyl-N-[(1S)-1-[(3R)-pyrrolidin-3-yl]ethyl]amine (1)(1) is a key intermediate in the preparation of premafloxacin (2), which was under development as an antibiotic for use against pathogens of veterinary importance. This paper describes the development of a practical, efficient, and stereoselective process for the preparation of 1 from isobutyl (3S)-3-[methyl[(1S)-1-phenylethyl]amino]butanoate (5c). The key steps in the synthetic sequence are an asymmetric Michael addition, which yields 5c, and a stereoselective alkylation, which yields (3S,4S)-3-allyl-1,4-dimethylazetidin-2-one (17).     

Synthesis and Characterization of Poly-[2-methoxy-4,6-di(2,7-Naphthyloxy)-s-triazine]

Abstract

Poly[2-methoxy-4,6-di (2,7-naphthyloxy)-s-triazine] was synthesized by interfacial polycondensation of 2-methoxy-4,6-dichloro-s-triazine with 2,7-dihydroxy-naphthalene. The polymer was characterized by IR and UV spectra, dynamic mechanical analysis, differential scanning calorimetry, and thermogravimetric analysis. The polymer was fractionated by the fractional precipitation method and the fractions were characterized by viscometry and membrane osmometry. The polymer has a T^g of 175°C and is found to be stable up to 300°C in air. The polymer sample is found to degrade in air in two steps, and the energy of activation for the first step is around 25 kcal/mol.     

Porphyrin-[(E)-1,2-Diethynylethene] Scaffolding: Synthesis and Optical and Electrochemical Properties of Multinanometer-Sized Porphyrin Arrays

Two series of linearly conjugated hybrid materials, consisting of (E)-1,2-diethynylethene (DEE; hex-3-ene-1,5-diyne) and Zn^II porphyrin components, were prepared by Pd⁰-catalyzed cross-coupling reactions. In one series, one or two DEE substituents were introduced into the meso-positions of the Zn^II porphyrins, leading from 5 ⋅ Zn , to 9 and 1 (Scheme 1). The second series contains the linearly π-conjugated molecular rods 1 – 3 that span a length range from 23 Å ( 1 ) to 53 Å ( 3 ) (Fig. 1). The larger rods 2 and 3 consist of two or three porphyrin moieties, respectively, that are bridged at the meso-positions by trans-enediynediyl (hex-3-ene-1,5-diyne-1,6-diyl) linkers (Scheme 2). The UV/VIS spectra in the series 5 ⋅ Zn , 9 , and 1 (Fig. 2) showed a strong bathochromic shift of both Soret and Q bands of the Zn^II porphyrin as a result of the addition of DEE substituents. Upon changing from 1 to 2 (Fig. 3), the Q band was further bathochromically shifted, whereas the Soret band remained nearly at the same position but became broadened and displayed a shoulder on the lower-wavelength edge as a result of excitonic coupling. The close resemblance between the UV/VIS spectra of 2 and 3 suggests that saturation of the optical properties in the oligomeric series already occurs at the stage of dimeric 2 . Stationary voltammetric investigations showed that the DEE substituents act as strong electron acceptors which induce large anodic shifts in the first reduction potential upon changing from 5 ⋅ Zn to 9 (ΔE=190 mV) and to 1 (ΔE=340 mV). Increasing the number of porphyrin moieties upon changing from 1 to 2 had no effect on the first reduction potential yet the first oxidation potential was substantially lowered (ΔE=110 mV). Large differences in the potentials for one-electron oxidation of the two porphyrin moieties in 2 (ΔE=200 mV) confirmed the existence of substantial electronic communication between the two macrocycles across the trans-enediynediyl bridge.     

1,3,5-三[(4’-乙炔基苯基)乙炔基]苯的合成

设计了多种合成路线制备芳香炔基树枝状化合物中间体1,3,5-三[(4’-乙炔基苯基)乙炔基]苯,通过一系列的合成路线和反应条件的对比,发现多官能团的端基炔化合物与芳基溴化合物之间发生多重Sonogashira反应时,常会生成不同取代程度的极性相似化合物,因而难以分离.采用多官能团的端基炔化合物与芳基碘化合物反应可以避免这种情况.最终确定以1,3,5-三溴苯和2-甲基-3-丁炔-2-醇为原料,制得中间产物1,3,5-三乙炔基苯;再以对碘苯胺和三甲基硅乙炔为原料,经重氮化化、卤代反应制得4-三甲基硅乙炔基碘苯;后者与1,3,5-三乙炔苯经Sonogashira反应、裂解去保护反应,制得化合物1,3,5-三[(4’-乙炔基苯基)乙炔基]苯.用1H NMR,13C NMR,元素分析等表征手段确认了中间体及最终产物的结构.     

Synthesis of [(thiazol-2-ylamino)-methylene]bisphosphonic acids

A method for the synthesis of [(thiazol-2-ylamino)methylene]bisphosphonic acids from (aminomethylene)-bisphosphonic acid through 3-N-unsubstituted (thioureidomethylene)bisphosphonic acid was proposed.     

Synthesis of 3-[(1-aryl)aminomethyl]indoles

We report the novel synthesis of various highly functionalized 3-arylaminomethyl indoles. This synthetic approach makes use of the directing ability of a bulky tert-butyldimethylsilyl-protecting group, which directs the condensation of an array of aromatic tosylaldimines specifically into the 3-position of the indole nucleus. The reactions, which occur under relatively mild conditions, afford the desired products in moderate yields. Prior to selective cleavage of the protecting group, the functionalized protected indoles also serve as attractive substrates for many future organic transformations.     

Synthesis and electrical and optoelectronic properties of poly[(N-benzyldiphenylamino)methane]

Poly[(N-benzyldiphenylamino)methane] was synthesized by the condensation polymerization of benzyldiphenylamine and formalin (30% HCOH in water) and examined for electrical and optoelectronic properties. Dark conductivity and photoconductivity of the polymer film were investigated by steady-state measurements. Current-voltage characteristics and intrinsic photoconduction of the polymer in the visible wavelength range were studied. A superlinear current increase is tentatively explained in the light of the Poole-Frenkel effect. Dielectric constant and dielectric loss parameters of the polymer are independent of frequency (50 Hz–10 kHz) and temperature (273–323 K), respectively. The growth and decay rates of the photocurrent depend on the applied voltage, and the photocurrent varies directly with the light intensity. The activation energies for dark conductivity and photoconductivity are 1.16 eV and 1.05 eV, respectively, and the optical energy band gap as evaluated from absorption coefficient spectra is 2.86 eV.