具有生物活性有机硅化合物的研究(XIV)──含硅四配位双(单)硫代磷酸酯化合物的研究

共合成了13个含硅四配位二硫代磷酸酯和2个含硅四配位单硫代磷酸酯的新化合物,经元素分析、IR、¹HNMR、MS确定了新化合物结构,对部分化合物进行了生物活性的测定,结果表明个别化合物有较好的生物活性。     

2个新颖的(3,4,6)和(3,6)连接的多核金属有机骨架化合物的合成、结构与性质

在水热和溶剂热条件下合成了2个新颖的金属有机骨架化合物{[Cu_3(BCPBA)_2(bpmp)(H_2O)]·2DMF}n(1)和{Zn3(BCPBA)_2(bip)(H_2O)_2}n(2)[H3BCPBA=3,5-双(4-羧基-苯氧基)苯甲酸;bpmp=1,4-二(吡啶-4-亚甲基)哌嗪;bip=1,3-二(咪唑基)丙烷].通过单晶及粉末X射线衍射、红外光谱、元素分析和热重分析对这2个化合物进行了表征.结果表明,化合物1属于单斜晶系,C2/m空间群,是由羧酸连接3个二级结构单元[Cu_2(CO_2)4]形成的具有自穿插结构的三维骨架结构,其骨架拓扑符号为(4·8~2)(8~6)(4~2·6~8·8~3·9·10);化合物2属于三斜晶系,P1空间群,其骨架是由1个新颖的二级结构单元组成的拓扑结构为(4~2·6)_2(4~4·6~2·8~8·10)的三维超分子网络.     

碱催化降解法制备抗癌活性化合物20(S)-原人参二醇

通过碱催化降解制备了与植物体内结构一致且具有抗癌活性的人参皂苷元--20(S)-原人参二醇,并对其进行分离及结构表征. 将西洋参茎叶总皂苷和强碱溶于高沸点有机溶剂中,在常压和高温条件下进行降解. 通过正交试验确定了制备20(S)-原人参二醇的最佳降解条件,并将降解物经萃取、 柱层析及重结晶等方法分离得到20(S)-原人参二醇. 按西洋参茎叶总皂苷计,20(S)-原人参二醇产率为5.01%,纯度为98.56% . 通过理化性质和光谱分析可确认该化合物为20(S)-原人参二醇. 所制备的20(S)-原人参二醇具有产率和纯度高及成本低等特点.     

青藤碱N-四氮唑和N-噁二唑杂环衍生物的设计与合成

建立了两个新的合成路线,在青藤碱D环的N原子上构建了N-四氮唑和N-1,3,4-噁二唑取代的杂环衍生物,共获得了34个新的青藤碱杂环衍生物.以青藤碱为原料,通过溴化氰取代生成N-CN青藤碱,再与叠氮化钠通过1,3-偶极环加成反应,生成了N-四氮唑青藤碱.苄氯类试剂与四氮唑发生取代反应生成青藤碱N-四氮唑杂环衍生物;酰氯类试剂与四氮唑通过酰化反应和惠思根重排反应生成青藤碱N-1,3,4-噁二唑杂环衍生物.方法简单,条件温和,产率优良.此工作为天然产物结构修饰提供了新的方法,扩大了青藤碱衍生物库,为潜在的青藤碱药物活性研究提供了药物分子设计方法.     

盐酸青藤碱在铅笔芯电极上的电化学性质及应用

研究了盐酸青藤碱在1B、2B、4B铅笔芯电极上的电化学行为,发现盐酸青藤碱在2B铅笔芯电极上具有良好的电化学行为。通过考察pH、底液、温度、静置时间等对盐酸青藤碱在2B铅笔芯电极上的电化学行为的影响,建立了以2B铅笔芯电极为工作电极测定盐酸青藤碱的电化学分析新方法。该方法氧化峰电流与盐酸青藤碱在0.146~36.585mg/L范围内呈良好的线性关系,相关系数r=0.9948,检出限为0.049mg/L,可应用于测定盐酸青藤碱肠溶片中盐酸青藤碱含量。进一步探讨了盐酸青藤碱在2B铅笔芯电极上的电化学反应机理。     

(±)-迷迭香酸(Rosmarinic acid)的全合成

以藜芦醛为起始原料,经Erlenmeyer反应、水解开环、还原、羧基保护、酯化缩合、Kunz-Waldmann转化、脱甲基7步反应,完成了(±)-迷迭香酸(Rosmarinic acid)的全合成,并重点对甲醚化迷迭香酸脱甲醚方法进行了研究,探索出一条原料便宜易得、高收率的(±)-迷迭香酸合成路线.     

具有六重穿插非中心对称金刚石网络结构的Cd(Ⅱ)和Zn(Ⅱ)的配位高聚物(英)

利用1，4-二-(4-羧基吡啶基)丁烷(L)合成了两个新的三维配位聚合物{(CdL₂)·4H₂O·2ClO₄}_n 1和{(ZnL₂)·4H₂O·2ClO₄}_n 2。单晶X-射线结构分析表明，1和2具有相同的计量式，但其晶体属于不同的空间群(1属于P4n2，2属于P4₂22)。两种配合物中，每个金属离子分别由配体与四个相邻的金属离子连接，从而形成具有六重穿插的金刚石网络结构，其网络中大的空腔被高氯酸根离子和(H₂O)₄分子簇所占据。     

极弱酸(碱)的交流示波滴定——二次微分法

本文采用交流示波滴定二次微分技术(d~2E/dt~2～E)发现了5种新的碱性范围内的示波中和滴定指示剂。在水溶液中直接滴定了有机弱酸及有机弱碱的盐类药物。     

含有4,5-二氮芴-9-酮锌(Ⅱ)、钴(Ⅱ)化合物的合成和晶体结构

Two compound crystals of (Hdafo)₂[ZnCl₄]·2H₂O (1) and (Hdafo)₂[CoCl₄]·2H₂O (2) were obtained when we tried synthesizing the mixed ligand compounds of Zinc (Ⅱ) and Cobalt(Ⅱ) with 4,5-diazafluorene-9-one(dafo) and o-phthalic acid, respectively. Their structure was determined by single crystal X-ray diffraction. The crystals all belong to monoclinic system, C2/c space group with crystallographic data:(Hdafo)₂[ZnCl₄]·2H₂O, a=1.6768(5)nm, b=1.2052(3)nm, c=1.3888(4)nm, β=116.793(3), V=2.5053(12)nm³, Z=4, F(000)=1232, M_r=609.57, D_c=1.616g·cm^-3, μ(MoKα)=1.444mm^-1, R₁=0.0373, wR₂=0.0765; (Hdafo)₂[CoCl₄]·2H₂O, a=1.6787(4)nm, b=1.2078(3)nm, c=1.3911(4)nm, β=116.665(3)°, V=2.5204(11)nm³, Z=4, F(000)=1220, M_r=603.13, D_c=1.589g·cm^-3, μ(MoKα)=1.142mm^-1, R₁=0.0257, wR₂=0.0654. The constitutes of the two compounds were proved by elemental, IR Spectra and thermal analyses. CCDC: 1, 198516; 2, 198517.     

天然产物(－)-Patriscabrol和(＋)-Isopatriscabrol的全合成研究

以反丁烯二酰氯和薄荷醇为起始原料, 经十四步反应, 得到光活的(－)-patriscabrol和(＋)-isopatriscabrol, 总收率约为4.6%. 化合物的结构经¹H NMR, MS, NOE差谱, HMBC, HMQC确定.     

Design,Synthesis, Biological Evaluation and Silico Prediction of Novel Sinomenine Derivatives

Sinomenine is a morphinan alkaloid with a variety of biological activities. Its derivatives have shown significant cytotoxic activity against different cancer cell lines in many studies. In this study, two series of sinomenine derivatives were designed and synthesized by modifying the active positions C₁ and C₄ on the A ring of sinomenine. Twenty-three compounds were synthesized and characterized by spectroscopy (IR, ¹H-NMR, ¹³C-NMR, and HRMS). They were further evaluated for their cytotoxic activity against five cancer cell lines, MCF-7, Hela, HepG2, SW480 and A549, and a normal cell line, Hek293, using MTT and CCK8 methods. The chlorine-containing compounds exhibited significant cytotoxic activity compared to the nucleus structure of sinomenine. Furthermore, we searched for cancer-related core targets and verified their interaction with derivatives through molecular docking. The chlorine-containing compounds 5g, 5i, 5j, 6a, 6d, 6e, and 6g exhibited the best against four core targets AKT1, EGFR, HARS and KARS. The molecular docking results were consistent with the cytotoxic results. Overall, results indicate that chlorine-containing derivatives might be a promising lead for the development of new anticancer agents.     

Heterocyclic Analogs of 5,12-Naphthacenequinone. 1. Synthesis of Heterocyclic Analogs Starting from 2,3-Diaminoquinizarine

The amination of 2-nitroquinizarine using hydroxylamine gives 2-amino-3-nitroquinizarine, which, upon reduction, gives previously unreported 2,3-diaminoquinizarine, a key intermediate in the synthesis of heterocyclic analogs of 5,12-naphthacenequinone, namely, 4,11-dihydroxyanthra[2,3-d]imidazole-5,10-dione (imidazoloquinizarine), 4,11-dihydroxyanthra[2,3-d][1,2,3]triazole-5,10-dione (triazoloquinizarine), and 5,12-dihydroxynaphtho[2,3-g]quinoxaline-6,11-dione (pyrazinoquinizarine). __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 1081–1088, July, 2005.     

（＋）-Talaumidin的全合成

以(S)4-苯基-3-戊烯酰基-2-噁唑烷酮为起始原料.以不对称的Aldol反式羟醛缩合反应和付-克反应为关键步骤,合成了( )-Talaumidin,其结构经1H NMR,13C NMR和ESI-MS表征.     

雌舞毒蛾引诱剂: (＋)-(7R,8S)-7,8-环氧-2-甲基十八烷的不对称全合成

由雌舞毒蛾释放的性引诱剂由于在害虫防治方面的需求不断增加, 已有许多文献对其合成方法进行报道. 以正十一醛和环戊酮为起始原料, 用L-脯氨酸催化的不对称羟醛缩合反应构筑手性中心, 后经拜耶-维利格氧化, 维梯希烯化等步骤, 为雌舞毒蛾性引诱剂(＋)-(7R,8S)-7,8-环氧-2-甲基十八烷提供了一条简便高效的不对称合成新途径, 总收率为37.8%.     

Synthesis of enantiomericcis-homocaronic acids from (+)-3-carene

The syntheses of the dimethyl ester of (-)-(1R)-cis-homocaronic acid (7 steps, overall yield 43 %) and its antipode, the dimethyl ester of (+)-(1S)-cis-homocaronic acid (5 steps, overall yield 27 %), were performed starting from (+)-3-carene and its derivatives, (+)-4-acetyl-2-carene and (+)-4-acetoxymethyl-2-carene. Oxidative cleavage in the key stages was carried out by ozonization.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 314–318, February, 1995.     

(+)-(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。     

Synthesis of the Juvenoid (S)-(+)-Hydroprene from L-(-)-Menthol

The versatile chiral synthon methyl (R)-5,5-dimethoxy-3-methylpentanoate has been prepared for the first time via ozonolytic decyclization of (R)-4-menthenone, which is available from L-(-)-menthol. The optically pure juvenoid (S)-(+)-hydroprene can be prepared from the synthon     

手性亚砜法合成粉 虫性信息素

5-氯-2-戊酮(2)经四步反应制得(R)-(+)-4-甲基-3-戊烯基对甲苯基亚砜(6), 化合物6与乙醛进行不对称加成反应得手性醇(7), 7经兰尼镍还原性脱硫反应即合成出目标产物粉 虫性信息素(1), 其光学纯度可达45%。     

Synthesis of (+)-lagerstronolide from (+)-sclareol

The γ-acetoxybutenolide (+)-lagerstronolide was synthesized from (+)-sclareol, with an overall yield of 10%. The absolute stereochemistry for the natural compound (−)-lagerstronolide has been correctly established.     

左旋异松蒎酮的合成

研究了以(－)-α-蒎烯为原料合成(－)-异松蒎酮的反应. 以四氢呋喃为溶剂, 硼氢化钠与三氟化硼乙醚溶液生成的硼烷不经分离直接与α-蒎烯发生反马氏加成反应, 生成二异松蒎烷基硼; 采用四水合过硼酸钠或NaOH-H₂O₂氧化硼氢化物得到(＋)-异松蒎醇, 产率为89.5%, 纯度97.4%, 熔点为55～56 ℃, 比旋光度 ＋28.31 (c 5.55, CH₃OH). 以钒磷氧化物为催化剂、双氧水作氧化剂, 将(＋)-异松蒎醇氧化得到(－)-异松蒎酮, 产率88% 以上, 纯度96.0%, 比旋光度为 －10.58 (c 5.51, CH₃OH). 采用IR, MS, ¹H NMR, ¹³C NMR等对(＋)-异松蒎醇和(－)-异松蒎酮结构进行了表征.