可见光诱导玫瑰红催化喹喔啉-2(1H)-酮的C3-H烷基化反应

建立了一种简单、实用的光诱导一锅法高选择性N-甲基喹喔啉酮类化合物和苯乙酮类化合物合成一系列3-烷基化喹唑啉-2(1H)-酮类化合物的方法。该方法在室温条件下,以玫瑰红作为光催化剂,在18 W 460nm的蓝色LED下照射8 h,通过直接C3-H活化的方案,较好收率获得一系列相应的3-烷基化喹喔啉-2(1H)-酮类化合物,最高产率可达到76%。反应体系具有经济实用性和底物适用范围广的特点,为3-烷基化喹喔啉-2(1H)-酮类化合物类化合物的合成提供了一种简便经济的方法。     

硝酸镧高效催化合成3,4-二氢嘧啶-2(1H)-(硫)酮

报道了以La(NO3)3催化芳香醛、β-酮酯和脲或硫脲-锅法合成3,4-二氢嘧啶-2(1H)-(硫)酮的简单、有效方法.与经典Biginelli反应条件相比,它具有产率高、反应时间短和操作简单等优点.所有目标化合物的结构经元素分析、IR、13C NMR和1H NMR确证.     

(+)-(1S,2S,5R)-8-联苯薄荷醇的合成

以(R)-( )-pu legone为起始原料,经1,4-加成,还原两步反应合成了手性辅助试剂( )-(1S,2S,5R)-8-联苯薄荷醇及其差向异构体(-)-(1R,2S,5R)-8-联苯薄荷醇,总产率95%。其结构经1H NMR,13C NMR,IR,MS和X-射线衍射仪表征。     

3-亚烷基(亚芳基)异苯并呋喃-1(3H)-酮及其衍生物的合成研究

报道了3-亚烷基(亚芳基)异苯并呋喃-1(3H)-酮及其衍生物的简易而且高效的合成方法.其特点是原料易得、价格低廉、反应条件温和、收率高.该方法以异苯并呋喃-1(3H)-酮(苯酞)及其衍生物为原料,经过自由基溴代合成了3-溴异苯并呋喃-1(3H)-酮及其衍生物,随后与三苯基膦发生亲核取代反应,接着在三乙胺的作用下发生消除反应生成Wittig试剂,最后与脂肪族醛或者芳香族醛发生Wittig反应得到目标化合物.目标产物及其中间体有13个是新化合物.     

4-(N-乙酰氨基)-3-(4-芳基噻唑-2-氨基)苯甲酸乙酯的合成与生物活性

以3-氨基-4-乙酰氨基苯甲酸乙酯为原料设计合成了18种4-(N-乙酰氨基)-3-(4-芳基噻唑-2-基)-苯甲酸乙酯新化合物.化合物结构经质谱,元素分析,1H NMR和13C NMR确证.生物活性实验结果表明,化合物3d,3h,3p(40μg/mL)对神经氨酸酶(NA)的抑制率分别为36.02%,33.40%,42.05%;化合物3g,3h(500mg/L)对纹枯病菌的抑制率为50%.     

CoH生成热力学函数的量子力学计算

用B3LYP/SDD密度泛函方法计算了CoH的微观性质、CoH(g)、CoD(g)和CoT(g)的能量(E)和熵(S),进而计算Co与H2、D2、T2反应的△H(-)、△G(-)、△S(-).CoH分子的基电子状态为三重态,Re、D(-)0、ωe分别为1.52nm、277.84 kJ/mol和1321 cm-1,与实验值基本一致.在固态分子的E和S的计算中,以气态分子计算得到的总能量中的振动能Ev代替固态能量,以总熵中的电子振动熵SEv代替固态熵.导出了Co与氢同位素气体反应的△H(-)、△G(-)、△S(-)及平衡氢压力与温度的关系.CoH的室温下平衡离解压力很低,表明CoH是一种稳定的氢化物,这与CoH分子的D(-)0很大的实验事实一致.     

(R)-4-氰基-3-羟基丁酸乙酯的合成

研究了一条新的路线用于他汀类药物的重要中间体(R)-4-氰基-3-羟基丁酸乙酯的合成. 以廉价、易得的L-(－)-苹果酸为起始原料, 经酯化、还原、溴代和氰化四步反应得到目标化合物(R)-4-氰基-3-羟基丁酸乙酯, 合成总收率为56.7%. 所有中间体和最终产物均由ESI-MS, 1H NMR和13C NMR光谱及比旋光度表征并与文献值比较. 该方法原料易得、操作简便、收率良好, 产物容易分离纯化, 是一条适合大规模制备(R)-4-氰基-3-羟基丁酸乙酯的新合成工艺路线.     

4-(1H)-喹诺酮及甲氧基和溴代衍生物的合成研究

提出了一种4-(1H)-喹诺酮衍生物合成方法.以3,3-二乙氧基丙酸乙酯和苯胺为原料,生成中间体3-(苯基亚氨基)丙酸乙酯,再经热环化或微波促进环化两步反应制备4-(1H)-喹诺酮,并以此方法合成了7个溴代或甲氧基取代的4-(1H)-喹诺酮衍生物.     

氮杂类聚合大环化合物的合成

以间苯二甲酰氯为原料, 分别与二(4-氨基苯基)甲烷、二(4-氨基苯基)醚及二(4-氨基苯基)砜通过一步反应合成了3种新的[3＋3]氮杂类聚合大环化合物, 产率分别为41%, 40%和36%; 并通过元素分析, IR, 1H NMR,13C NMR和MS对其结构进行了表征.     

基于稳定的膦叶立德合成2(5H)-呋喃酮和2(5H)-吡咯酮作为细菌群体感应抑制剂的研究

利用稳定的乙酸乙酯基膦叶立德与含羰基化合物反应,合成了不同的2(5H)-呋喃酮,然后将获得的部分2(5H)-呋喃酮与醋酸铵反应转化为2(5H)-吡咯酮类化合物.所合成化合物均经1H NMR、13C NMR和MS等确认.通过测定所得到的化合物对于绿脓杆菌的最低抑菌浓度(MIC)来检验其抑菌活性;利用细莆生物膜染色实验来检测所得到的化合物对细菌群体感应系统和细菌生物膜的影响.活性实验结果表明,所得到的2(5H)-呋喃酮类化合物和2(5H)-吡咯酮类化合物均具有一定的抑制细菌群体感应的能力.     

手性二噁唑啉吡啶铁和镍配合物的制备与表征

Tridentate bis(oxazolinylpyridine)(1) reacted with nickel chloride or ferrous chloride in anhydrous ethanol to form bis(oxazolinylpyridine) Nickel(Ⅱ) and Iron(Ⅱ) complexes. The stable solid complexes were characterized with IR， UV， MS， XPS and elemental analysis. No stable complexes were formed with bidentate bis(oxazoline)(2) ins- tead of bis(oxazolinylpyridine).     

Asymmetric Synthesis of (R)-and (S)-Moprolol

A simple and effective procedure for the enantioselective synthesis of (R)-and (S)-moprolol was described.The key step was the asymmetric synthesis of enantiopure (R)-and (S)-guaifenesin,which were synthesized from enantioenriched (R)-3-chloro-1,2-propanediol and (S)-epichlorohydrin via kinetics of hydrolysis resolution of racemic epichlorohydrin by chiral Salen-CoIIII complex.The e.e.values of both the optical compounds were above 98%,and the chemical structures of the target compounds were confirmed by 1H NMR,13C NMR,IR,and MS.     

(Phosphine)gold(I) Complexes of Benzenedithioles. Crystal structures of 1,2-benzenedithiolato-bis[triphenyl-phosphinegold(I)] and bis(triethylphosphine)gold(I) bis(1,2-benzenedithiolato)gold(III)

The reaction of 1,2- and 1,3-benzenedithiol C₆H₄(SH)₂ with chloro(phosphine)gold(I) complexes R₃PAuCl (R = Et, Ph) in the presence of triethylamine in tetrahydrofuran gives stable gold(I) complexes 1,2-C₆H₄(SAuPR₃)₂ [R = Et ( 1 ) and Ph ( 2 )] or 1,3-C₆H₄(SAuPPh₃)₂ ( 3 ), respectively, in high yield. The compounds have been characterized by analytical and NMR spectroscopic data. From the reaction of 1,2-C₆H(SH)₂ with Et₃P? AuCl a by-product [(Et₃P)₂Au]⁺ [Au(1,2? C₆H₄S₂)₂]^? ( 4 ) has also been isolated in low yield. The crystal structures of compounds 2 and 4 have been determined by single crystal X-ray diffraction. The gold(I) atoms in complex 2 are two-coordinate with bond angles S? Au? P of 175.2(1) and 159.5(1)°, Au? S bond distances of 2.304(1) and 2.321(1) å, and a short Au…?Au contact of 3.145(1) Å. The gold(I) atom in the cation of complex 4 is also linearly two-coordinate with a P? Au? P angle of 170.1(1) Å and Au? P distances of 2.296(3) and 2.298(3) Å. The geometry of the anion in 4 shows a square-planar coordination of gold(III) by two chelating 1,2-benzenedithiolate ligands with Au? S distances between 2.299(3) and 2.312(3) Å (for two crystallographically independent, centrosymmetrical anions in the unit cell).     

Rhodium(III), palladium(II) and platinum(II) complexes of Bis(o-aminobenzenesulfonyl)ethylenediamine

New complexes of the formulae K₃[RhL ₃]·2 H₂O, [PdL]·H₂O and [M(LH₂)Cl₂] [whereM = Pd, Pt andLH₂ = bis(o-aminobenzenesulfonyl)ethylenediamine] have been prepared and characterized by conductivity measurements, thermogravimetric analysis, X-ray powder patterns and IR, Ligand Field and¹H-NMR spectroscopy.

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Rhodium(III), Palladium(II)- und Platin(II)-Komplexe mit Bis(o-aminobenzolosulfonyl)ethylendiamin (Kurze Mitteilung)

Zusammenfassung Neue Komplexe der allgemeinen Formeln K₃[RhL ₃]·2H₂O, [PdL]·H₂O und [M(LH₂)Cl₂] mitM = Pd, Pt undLH₂ = Bis(o-aminobenzolosulfonyl)ethylendiamin wurden dargestellt und mit Konduktionsmessungen, thermogravimetrischen Analysen, Röntgenstrukturanalysen, IR, Ligandfeld- und¹H-NMR-Spektroskopie charakterisiert.

     

界面缩聚法合成双(烯基环戊二烯基)钛(锆)聚醚的研究

本文通过界面缩聚法利用双(烯基环戊二烯基)钛(锆)二氯化物与二酚反应,制成了16个新的高分子化合物,对它们进行了IR、TGA和分子量的测定。文中还对反应条件与分子量的关系进行了讨论。     

Molecular structure of (3,5-diallylisocyanuratomethyl)bis(chloromethyl)phosphine oxide. Synthesis of (3,5-diallylisocyanuratomethyl)phosphine sulfides

X-Ray study of the (3,5-diallylisocyanuratomethyl)bis(chloromethyl)phosphine oxide showed that the phosphorylmethyl group is bonded to the nitrogen atom of the cycle. Reaction of the tris(chloromethyl)phosphine sulfide with sodium diallylisocyanurate gave (3,5-diallylisocyanuratomethyl)bis(chloromethyl)phosphine sulfide, and treatment of the tris(3,5-diallylisocyanuratomethyl)phosphine oxide with phosphorus pentasulfide gave a tris(3,5-diallylisocyanuratomethyl)bis(chloromethyl)phosphine sulfide.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1446–1448, August, 1993.     

以氯醌酸二价阴离子为桥联配体的Fe(Ⅲ)-Fe(Ⅲ)和Mn(Ⅱ)-Mn(Ⅱ)双核配合物的合成与磁性

基于铁和锰的双核配合物在生物氧化还原过程中的重要作用及在化学的氧化还原过程中可能做为催化剂的应用前景,本文合成了两个新的以氯醌酸二价阴离子为桥联配体的Fe(Ⅲ)双核和Mn(Ⅱ)双核配合物:[Fe_2(phen)_4(μ-CA)](ClO_4)_4·2H_2O(1)和[Mn_2(phen)_4(μ-CA)](ClO_4)_2·3H_2O(2)(phen=1,10菲咯啉;CA=氯醌酸二价阴离子)。经元素分析、IR、电子光谱及磁性等测定,对两配合物进行了表征。     

Synthesis of (diorgano)chloro(4-chlorobutoxy)silanes

Some novel (diorgano)chloro(4-chlorobutoxy)silanes were obtained by the reaction of dichlorodiorganosilanes with tetra hydrofuran in the presence of chloroplatinic acid.Translated fromIzvestiva Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 943–945, April, 1996.     

Synthesis and Crystal Structure of 4-Chloro-N- （2-（2-nitrophenyl）acetoxy）-N-（m-tolyl）benzamide

The new title compound 4-chloro-N-(2-(2-nitrophenyl)acetoxy)-N-(m-tolyl)benzamide(C22H17ClN2O5, Mr = 424.82) has been synthesized via the reaction of 4-chloro-N-hydroxy-N-(m-tolyl)benzamide with 2-(2-nitrophenyl)acetyl chloride. The structure of the product was confirmed by 1H NMR, 13 C NMR, IR, HRMS(ESI) and single-crystal X-ray diffraction. The title compound crystallizes in the monoclinic system, space group P21/c with a = 13.0269(10), b = 6.7251(6), c = 23.9313(16) , β = 99.931(6)o, V = 2065.1(3) 3, Z = 4, Dc = 1.366 g/cm3, F(000) = 880, μ = 0.221 mm-1, the final R = 0.0600 and wR = 0.1754 for 1981 observed reflections(I 2σ(I)). X-ray analysis indicates that the chloro-phenyl ring(C(10)~C(15)) and the methyl-substituted benzene ring(C(16)~C(21)) are not coplanar with the nitro-substituted benzene ring(C(1)~C(6)), with the dihedral angle to be 70.78° and 63.72°, respectively. Hydrogen bonds C(2)–H(2)···O(2) and C(7)–H(7B)···O(5) are observed.     

草酸根桥联的不对称双核铜(Ⅱ)和铜(Ⅱ)-锌(Ⅱ)配合物的合成与磁性

本文合成了一组新的不对称的双核配合物,[Cu_2(C_2O_4)_2terp]和〔Cu Zn(C_2O_4)_2terp〕(图1),terp表示联三吡啶。配合物〔Cu_2(C_2O_4)2terp〕的变温磁化率已测,其数值已用最小二乘法与Bleaney-Bowers方程拟合,求得交换积分J=-47.20cm~(-1)。文中还用Kahn理论解释了这种较弱的反铁磁自旋交换作用。