5-二氰亚甲基-4-二环丙亚甲基-3-[1-(2, 5-二甲基-3-呋喃基)亚乙基]四氢呋喃-2-酮的合成

报道俘精酸酐类化合物(E/Z)4-二环丙亚甲基-3-[1-(2, 5-二甲基-3-呋喃基)亚乙基]四氢呋喃-2, 5-酮的拆分, 及(E)和(Z)-5-二氰亚甲基-4-二环丙亚甲基-3-[1-(2, 5-二甲基-3-呋喃基)亚乙基]四氢呋喃-2-酮 4(E)和4(Z)的合成, 并对它们的光致变色特性进行了初步研究。     

2-(1,2-亚乙/1,3-亚丙二硫)亚甲基-3-羰基丁酰氯的制备及其与芳烃的酰化反应

制备了较稳定的2-(1,2-亚乙/1,3-亚丙二硫)亚甲基-3-羰基丁酰氯,并实现了其与芳烃的酰化反应,为1-芳基-2-(1,2-亚乙/1,3-亚丙二硫)亚甲基-1,3-丁二酮的合成提供了一条新途径.     

α—羰基烯酮式环二硫代缩醛类化合物的制备

从具有α-亚甲基的酮出发,利用溶液稀释的方法,提高了用Dieter法合成α-羰基烯酮式环二硫代缩醛类化合物的产率,并用改进方法合成了4个该类化合物。     

(4-甲基-1,3-二噻烷-2-亚甲基)-1,7-二芳基-1,6-二烯-3,5-二酮的合成

从2,4-戊二酮和1,2,3-三溴丙烷出发合成了一类新的α-羰基二硫缩烯酮类化合物,并以其为底物合成了(4-甲基-1,3-二噻烷-2-亚甲基)-1,7-二芳基-1,6-二烯-3,5-二酮类化合物,通过IR和1H NMR方法对其进行了表征.     

3-亚甲基六氢苯并呋喃-2(3H)-酮的简便合成

以氧化环己烯为原料,在正丁基锂作用下与乙腈经开环反应制得2-羟基环己基乙腈(2);2依次经水解、内酯化、二甲胺甲基化、甲基化和Hofmann降解反应合成了α-亚甲基-γ-丁内酯类化合物--3-亚甲基六氢苯并呋喃-2(3H)-酮,总收率30.4%,其结构经¹H NMR,¹³C NMR和HR-MS(EI)确证。     

5-二氰亚甲基-4-二环丙亚甲基-3-[1-(2,5-二甲基-3-呋喃基)亚乙基]四氢呋喃-2-酮的合成

报道俘精酸酐类化合物(E/Z)4-二环丙亚甲基-3-[1-(2,5-二甲基-3-呋喃基)亚乙基]四氢呋喃-2,5-酮的拆分,及(E)和(Z)-5-二氰亚甲基-4-二环丙亚甲基-3-[1-(2,5-二甲基-3-呋喃基)亚乙基]四氢呋喃-2-酮4(E)和4(Z)的合成,并对它们的光致变色特性进行了初步研究。     

亚甲基烯酮与5-亚甲基-1,3-二噁烷-4,6-二酮反应机理的研究

利用半经验分子轨道理论AM1方法，研究了5-亚甲基-1，3-二噁烷-4，6-二酮与亚甲基烯酮的2，3-位C＝C，3，4-位C＝O和1，2-位C＝O三种双键位置上的环加成反应的反应机理．采用Berny梯度法优化得到反应的过渡态，并进行了振动分析确认．计算结果表明，环加成反应是按照协同的非同步途径进行的，经过一个扭曲的六员环过渡态，前线轨道分析表明反应机理为［4＋2］机理．根据AM1优化得到的产物反应物及过渡态的生成热可知三个反应的活化焓分别为27．07kJ·mol-1，32．41kJ·mol-1和137．96kJ·mol-1，2，3-位C＝C双键上的环加成反应的活化焓最低，这与实验中只观察到2，3－位C＝C双键上环加成产物的结论是一致的．     

（3′→5′）亚甲基缩醛连接的二聚和三聚体脱氧核苷的另法合成

3′-O－（甲硫甲基）缩醛的脱氧核苷（1）与N－碘代丁二酰亚胺（NIS）和二苯基次膦酸反应得到相应的3′-O－（二苯膦酰氧）甲基缩醛（2）。在三甲基硅三氟甲磺酸酯(TMSOTf)的条件下,后与3′-位保护的脱氧核苷（5）缩合,得到（3′→5′)亚甲基缩醛连接的二聚体d[(B1-m-B2)](m=次甲基）（6）。同样的,2（B＝T或B＝C）与3′-位保护的二聚体9（T-m-T或C-m-T）缩合,可得到相应的三聚体10(T-m-T-m-T,C-m-T-m-T和T-m-C-m-T）。     

2-(1,3-亚丙二硫)亚甲基-3-羰基丁酸作为硫醇替代试剂在缩硫醛/酮化反应中的应用

探讨了以2-(1,3-亚丙二硫)亚甲基-3-羰基丁酸作为硫醇替代试剂,乙醇作溶剂的缩硫醛/酮化反应.实验结果表明,该硫醇替代试剂能与各类醛、酮化合物快速、顺利地进行缩硫醛/酮化反应,以较高的产率生成相应的1,3-二噻烷类化合物.同时,该缩硫醛/酮化反应对不同的醛、酮化合物具有较高的化学选择性.     

二茂铁甲醛与含活性亚甲基化合物的水相反应研究

二茂铁甲醛与具有活性亚甲基的化合物巴比妥酸 ( 2a)、硫代巴比妥酸 ( 2b)、2 ,2 二甲基 1,3 二烷 4,6 二酮 ( 2c)、1 苯基 3 甲基 5 吡唑啉酮 ( 2d)、氰乙酸乙酯 ( 2e)、2 ,4 戊二酮 ( 2f)、环己酮 ( 2g)及环戊酮 ( 2h)在水相中进行缩合反应 ,高产率简便地得到α 二茂铁亚甲基酮 .产物结构经1 HNMR ,1 3 CNMR ,IR及元素分析进行了表征 .     

Synthesis and characterization of octa- and hexanuclear polyoxomolybdate wheels: role of the inorganic template and of the counterion

Eight new compounds based on [O3PCH2PO3]4- ligands and {MoV2O4} dimeric units have been synthesized and structurally characterized. Octanuclear wheels encapsulating various guests have been isolated with different counterions. With NH4+, a single wheel was obtained, as expected, with the planar CO32- guest, (NH4)12[(MoV2O4)4(O3PCH2PO3)4(CO3)2].24H2O (1a), while with the pyramidal SO32- guest, only the syn isomer (NH4)12[(MoV2O4)4(O3PCH2PO3)4(SO3)2].26H2O (2a) was characterized. The corresponding anti isomer was obtained with Na+ as counterions, Na12[(MoV2O4)4(O3PCH2PO3)4(SO3)2]39H2O (2b), and with mixed Na+ and NH4(+) counterions, Na+(NH4)11[(MoV2O4)4(O3PCH2PO3)4(SO3)2].13H2O (2d). With [O3PCH2PO3]4- extra ligands, the octanuclear wheel Li12(NH4)2[(MoV2O4)4(O3PCH2PO3)4(HO3PCH2PO3)2].31H2O (4a) was isolated with Li+ and NH4+ counterions and Li14[(MoV2O4)4(O3PCH2PO3)4(HO3PCH2PO3)2].34H2O (4c) as a pure Li+ salt. A new rectangular anion, formed by connecting two MoV dimers and two MoVI octahedra via methylenediphosphonato ligands with NH4+ as counterions, (NH4)10[(MoV2O4)2(MoVIO3)2(O3PCH2PO3)2(HO3PCH2PO3)2].15H2)O (3a), and Li9(NH4)2Cl[(MoV2O4)2(MoVIO3)2(O3PCH2PO3)2]. 22H2O (3d) as a mixed NH4+ and Li+ salt have also been synthesized. The structural characterization of the compounds, combined with a study of their behavior in solution, investigated by 31P NMR, has allowed a discussion on the influence of the counterions on the structure of the anions and their stability. Density functional theory calculations carried out on both isomers of the [(MoV2O4)4(O3PCH2PO3)4(SO3)2]12- anion (2), either assumed isolated or embedded in a continuum solvent model, suggest that the anti form is favored by approximately 2 kcal mol(-1). Explicit insertion of two solvated counterions in the molecular cavity reverses this energy difference and reduces it to less than 1 kcal mol(-1), therefore accounting for the observed structural versatility.     

3-烷基/芳基-6-(2', 4'-二氯苯基)-7H-1, 2, 4-三唑[3, 4-b]- 1, 3, 4-噻二 嗪的合成及波谱性质

以间二氯苯与氯乙酰氯反应,生成ω-氯代-2,4-二氯苯乙酮(1),再使之分别与3-烷基/芳基-4-氨基-5-巯基-1,2,4-三唑(2a～2l)反应,合成了12种新的3-烷基/芳基-6-(2',4'-二氯苯基)-7H-1,2,4-三唑并[3,4-b]1,3,4-噻二嗪(4a～4l)。利用EA,IR,^1HNMR确定了其结构,并提出该反应的可能机制。     

Self-assembly and redox modulation of the cavity size of an unusual rectangular iron thiolate aryldiisocyanide metallocyclophane

The decarbonylation reaction of ferric carbonyl dicationic [Cp(2)Fe(2)(μ-SEt)(2)(CO)(2)](BF(4))(2) [1(BF(4))(2)] carried out in refluxing acetonitrile affords a binuclear iron-sulfur core complex [Cp(2)Fe(2)(μ-SEt)(2)(CH(3)CN)(2)](BF(4))(2) [2(BF(4))(2)] containing two acetonitrile coordinated ligands. The treatment of 2(BF(4))(2) with 2 equiv of the 1,4-diisocyanobenzene (1,4-CNC(6)H(4)NC) results in the formation of the diisocyanide complex [Cp(2)Fe(2)(μ-SEt)(2)(1,4-CNC(6)H(4)NC)(2)](BF(4))(2) [3(BF(4))(2)]. The rectangular tetranuclear iron thiolate aryldiisocyanide metallocyclophane complex [Cp(4)Fe(4)(μ-SEt)(4)(μ-1,4-CNC(6)H(4)NC)(2)](BF(4))(4) [4(BF(4))(4)] has been synthesized by a self-assembly reaction between equimolar amounts of 2(BF(4))(2) and 1,4-diisocyanobenzene or by a stepwise route involving mixing of a 1:1 molar ratio of complexes 2(BF(4))(2) and 3(BF(4))(2). Chemical reduction of 4(BF(4))(4) by KC(8) was observed to produce the reduction product 4(BF(4))(2). The spectroscopic and electrochemical properties of the iron-sulfur core complexes 1(PF(6))(2), 3(BF(4))(2), 4(BF(4))(4), and 4(BF(4))(2) were determined. Finally, differences between the redox control cavities of rectangular tetranuclear iron thiolate aryldiisocyanide complexes are revealed by a comparison of the X-ray crystallographically determined structures of complexes 4(BF(4))(4) and 4(BF(4))(2).     

A Novel Fused Phosphorus Heterocycle: 4-(1'''',2'''',3'''',4-Tetrahydro-1, 3, 2-benzodiazaphosphorin-2''''-sulfide)-3, 4b, 4a-thiazphosphaphenanthridine Derivative

Organophosphorus compounds are ubiquitous in nature and they have broad applications in the fields of agriculture and medicine1-4. There has been a considerably growing interest in heterocyclic compounds due to their pharmaceutical importance and extensive application in organic synthesis, and the application of heterocycles is suggested to enhance the biological activity and/or offer other diverse properties5-7. In the previous work8, we have reported that 11-ethoxycarbonylmethyl-6-oxo-3, 4…     

Synthesis and pharmacological activity of 4-amino-5-chloro-2-methoxy-N-[(2S,4S)-1-ethyl-2-hydroxymethyl-4- pyrrolidinyl]benzamide (TKS159) and its optical isomers

Of 4-amino-5-chloro-2-methoxy-N-(1-ethyl-2-hydroxymethyl-4- pyrrolidinyl)benzamide, four optical isomers, (2S,4S)-1 (TKS159), (2S,4R)-25, (2R,4S)-26 and (2R,4R)-27, were prepared from optically active 4-amino-1-ethyl-2-hydroxymethylpyrrolidine di-p-toluenesulfonate [(2S,4S)-14, (2S,4R)-17, (2R,4S)-20 and (2R,4R)-23, respectively]. The requisites, (2S,4S)-14, (2S,4R)-17, (2R,4S)-20 and (2R,4R)-23, were prepared from a commercially available trans-4-hydroxy-L-proline. The absolute configurations of (2S,4S)-1 (TKS159), (2S,4R)-25, (2R,4S)-26 and (2R,4R)-27 were spectroscopically determined. Of the benzamide derivatives, four optical isomers, (2S,4S)-1, (2S,4R)-25, (2R,4S)-26 and (2R,4R)-27, showed a relatively potent affinity for 5-hydroxytryptamine 4 (5-HT4) receptors in a radioligand binding assay ([3H]GR113808). The activities of 25-27 were less effective than that of 1 for the gastric emptying of a phenol red semisolid meal in rats. All this suggests that the most potent of the isomers was 4-amino-5-chloro-2-methoxy-N-[(2S,4S)-1-ethyl-2- hydroxymethyl-4-pyrrolidinyl]benzamide (1).     

Self-assembly and interconversion of tetranuclear copper(II) complexes

The ligand 1,2-bis(benzimidazol-2-yl)-1,2-ethanediol (H2bzimed, 1) and its N-methylated analogue (H2mbzimed, 2) form a variety of polynuclear complexes with copper(II), all of which contain a planar Cu2O2 lozenge as a central element and in which the bridging oxygen belongs to an alkoxo group of the ligand. Syntheses are reported for dinuclear [Cu2(Hmbzimed)2](ClO4)2 x 1.5H2O, Cu(2)2(2), and the tetranuclear species [Cu4(Hbzimed)4(ClO4)2](NO3)2 x 4H2O, Cu(4)1(4), [Cu4(Hmbzimed)2(mbzimed)Cl2](ClO4)2 x 2H2O x C2H5OH, Cu(4)2(3), and rac-[Cu4(H2bzimed)4(bzimed)(ClO4)2](ClO4)4 x 1.5H2O x 3.5C2H5OH, Cu(4)1(5). Crystal structures are reported for the tetranuclear species. Cu(4)1(4) shows a cubane structure, Cu(4)2(3) a stepped cubane structure, and rac-Cu(4)1(5) a novel structure in which one doubly deprotonated ligand lies between the two Cu2O2 units. Magnetic susceptibility measurements indicate that all complexes show antiferromagnetic coupling in the solid state. Studies in solution (ESI-MS, CD, NMR) show that Cu(2)2(2) and Cu(4)2(3) persist in solution but that Cu(4)1(4) dissociates partially and rac-Cu(4)1(5) completely. The six coordination modes of the ligands are discussed together with the effect of the N-methylation on the ligand conformation.     

4-Methoxy- and 4-cyano-substituted lithium aryloxides: electronic effects of substituents on aggregation

The para-substituted lithium aryloxides [{4-NC-C6H4OLi.(Pyr)2}2.Pyr] 1a, [{4-NC-C6H4OLi.(THF)2}2] 1b, [{4-MeO-C6H4OLi.Pyr}4] 2a, [4-MeO-C6H4OLi.(THF)n] 2b, [{4-NC-2,6-(t-Bu)2-C6H2OLi.(Pyr)2}infinity] 3a, [{4-NC-2,6-(t-Bu)2-C6H2OLi.(THF)2}infinity] 3b, [{4-MeO-2,6-(t-Bu)2-C6H2OLi.Pyr}2.(Pyr)2] 4a, and [4-MeO-2,6-(t-Bu)2-C6H2OLi.(THF)n] 4b were prepared by the direct deprotonation of the corresponding phenol with an alkyllithium base (BuLi or MeLi) in the appropriate solvent, either pyridine or THF. All compounds were characterized by 1H and 13C NMR spectroscopy, and the crystal structures of 1a, 1b, 2a, 3a, 3b and 4a were elucidated. The cyano derivatives 1a and 1b adopt discrete tetrasolvated Li2O2 ring dimers whereas the methoxy analogue 2a crystallizes as a tetrasolvated molecular tetramer with a pseudo cubic Li4O4 core. The sterically encumbered cyano derivatives 3a and 3b form isostructural 1D polymeric chains of monomers via bridging of the phenolate ligands through Li...NC and Li-O contacts. In comparison, the crystal structure of the methoxy counterpart 4a is a disolvated molecular Li2O2 ring dimer. Solution NMR spectroscopic studies of 1-4 in d5-pyridine and d8-THF indicate that the methoxy complexes are more highly aggregated than the cyano derivatives, consistent with the solid-state studies. Ab initio molecular orbital calculations at the HF/6-31G* level of theory indicate that the origin of the aggregation state variations between the cyano and methoxy complexes is due to electronic effects.     

含吡啶基四硫富瓦烯衍生物的合成、 结构和电化学性质

在乙酰乙酸乙酯和氧化亚铜共同催化下, 二-(1,3-二硫环戊烯-2-硫酮-4,5-二硫)合锌酸四乙基铵盐分别与2-碘吡啶(1a)、 3-碘吡啶(1b)和4-碘吡啶(1c)反应, 制得硫酮化合物2,3-二(2-吡啶硫基)-1,3-二硫环戊烯-2-硫酮(2a)、 2,3-二(3-吡啶硫基)-1,3-二硫环戊烯-2-硫酮(2b)和2,3-二(4-吡啶硫基)-1,3-二硫环戊烯-2-硫酮(2c). 在醋酸汞催化下, 硫酮化合物2a, 2b和2c分别被氧化为2,3-二(2-吡啶硫基)-1,3-二硫环戊烯-2-酮(3a)、 2,3-二(3-吡啶硫基)-1,3-二硫环戊烯-2-酮(3b)和2,3-二(4-吡啶硫基)-1,3-二硫环戊烯-2-酮(3c). 以亚磷酸三乙酯为偶联剂, 氧酮化合物3a, 3b和3c分别发生自偶联反应生成2,3,6,7-四(2-吡啶硫基)四硫富瓦烯(4a)、 2,3,6,7-四(3-吡啶硫基)四硫富瓦烯(4b)和2,3,6,7-四(4-吡啶硫基)四硫富瓦烯(4c). 采用核磁共振波谱(NMR)、 傅里叶变换红外光谱(FTIR)和质谱(MS)分析了所合成化合物的结构和组成, 通过X射线衍射分析确认了吡啶基四硫富瓦烯衍生物4b和4c的晶体结构. 循环伏安法研究结果表明, 化合物4a, 4b和4c呈现准可逆的两电子转移过程, 结合量子化学计算, 分析了不同位置取代的吡啶基对四硫富瓦烯电化学电势的影响.     

Synthesis and characterization of a novel functionalized azanonaborane cluster for boron neutron capture therapy

The reactivity of an azanonaborane cluster containing free amino groups {H2N(CH2)4H2NB8H11NH(CH2)4NH2} towards ketones and aldehydes is investigated. In a one step reaction, the reductive amination of some ketones and aldehydes (namely acetone, benzaldehyde, 3-hydroxybenzaldehyde, 4-hydroxybenzaldehyde, 4-nitrobenzaldehyde, 4-acetoxybenzaldehyde, and 4-acetamidobenzaldehyde) with an azanonaborane cluster in the presence of H3BNH2(CH2)4NH2 gives monoalkylamino derivatives of the azanonaborane cluster {RHN(CH2)4H2NB8H11NH(CH2)4NHR} where (R =(Me)2CH-, C6H5CH2-, 3-OHC6H4CH2-, 4-OHC6H4CH2-, 4-NO2C6H4CH2-, 4-MeOCOC6H4CH2-, or 4-NH2COC6H4CH2-). The functionalized derivatives of the {B8N} cluster can be used in boron neutron capture therapy for tumors (BNCT). Similarly, the reductive amination of 5-(4"-formylphenyl)-10,15,20-triphenylporphyrin with the {B8N} cluster gave a porphyrin bearing azanonaborane cluster, while a porphyrin dimer linked by an azanonaborane moiety was obtained following the same method, starting with a 2:1 molar ratio of porphyrin:{B8N} cluster. 5,10,15,20-Tetraformylphenylporphyrin gave the chance to increase the percentage of boron in the resulting boronated porphyrin, which is considered an important factor for a BNCT delivery agent. With these compounds, the cell toxicity using V79 cells was carried out to determine whether these compounds would have favorable biological properties.     

High-performance liquid chromatographic identification of disaccharides generated from heparan sulphate isomers using heparitinases

Specific heparan sulphate-lyases, heparitinases I and II, were used to identify unsaturated disaccharide constituents generated from heterogeneous heparan sulphate isomers. All determinations were made using high-performance liquid chromatography with a column containing a sulphonized styrene-divinylbenzene copolymer. Unsaturated disaccharides generated from variously sulphated heparan sulphate isomers after simultaneous digestion with heparitinases I and II facilitated separation of the individual disaccharides, based on sulphate groups at the specific position of the uronic acid and glucosamine residues. The simultaneous digestion with heparitinases I and II produces unsaturated disaccharides from heparan sulphate isomers with the structure of 4-deoxy-2-O-alpha-L-threo-hex-4-enepyranosyluronic acid (1----4)-2-amino-deoxy-D-glucose, 4-deoxy-2-O-alpha-L-threo-hex-4-enepyranosyluronic acid (1----4)-2-deoxy-2-sulphamido-D-glucose, 4-deoxy-2-O-alpha-L-threo-hex-4-enepyranosyluronic acid (1----4)-2-aminodeoxy-6-O-sulpho-D-glucose, 4-deoxy-2-O-alpha-L-threo-hex-4-enepyranosyluronic acid (1----4)-2-deoxy-2-sulphamido-6-O-sulpho-D-glucose, 4-deoxy-2-O-sulpho-alpha-L-threo-hex-4-enepyranosyluronic acid (1----4)-2-amino-2-deoxy-6-O-sulpho-D-glucose and 4-deoxy-2-O-sulpho-alpha-L-threo-hex-4-enepyranosyluronic acid (1----4)-2-deoxy-2-sulphamido-6-O-sulpho-D-glucose.