α-松油烯为原料的单萜衍生物合成及其构造解析

把α-松油烯与马来酸酐的分子间Diels-Alder环加成反应产物1-甲基-4-（1-甲基乙基）-双环[2．2．2]-5-辛烯-2,3-二酸酐（1）,在甲醇溶剂中,用Raney Ni为催化剂进行加氢,获得了加氢产物1-甲基-4-（1-甲基乙基）-双环[2．2．2]辛烷-2,3-二酸酐（2）,然后,对化合物1和2分别进行加水分解反应获得了二羧酸化合物1-甲基-4-（1-甲基乙基）-双环[2．2.2]-5-辛烯-2,3-二羧酸（3）和-个新化合物1-甲基-4-（1-甲基乙基）-双环[2．2．2]辛烷-2,3-二羧酸（4）。用^1HNMR（^1H-^1H Cosy）以及^13CNMR（DEPT,HMQC,HMBC,NNE,INADEQUATE）高分解能核磁共振测定手法对化合物1～4进行了详细的解析和化学位鹈的归属．     

5，7-二甲基-1，2，4-三唑并[1，5-a]嘧啶-2-羧（磺）酸酯类化合物的合成及生物活性

以2-羟基-5,7-二甲基-1,2,4-三唑并[1,5-a]嘧啶为原料,与杂环和苯环取代的（磺）酰氯化合物进行酯化反应,制备得到三唑并嘧啶类羧（磺）酸酯类化合物ZJUT-7。化合物ZJUT-7经^1H NMR和MS确定,并对其进行了初步生物活性测试。     

合成8-氯-10，11-二氢-4-氮杂-5H-二苯并[a，d]-5-环庚酮研究进展

介绍了氯雷他定的重要中间体8-氯-10,11-二氢-4-氮杂-5H-二苯并[a,d]-5-环庚酮的基本性质和用途,叙述了以2-溴-3-甲基吡啶、2-[（叔丁基氨基）]-3-甲基吡啶、3-甲基吡啶甲酸和3-吡啶甲酸乙酯为原料出发的合成方法。     

2-{[5-（取代吡唑-5-基）-1，3，4-噁二唑-2-基]甲巯基）-5，7-二甲基-1，2，4-三唑[1，5-a]嘧啶类化合物合成及生物活性

设计并合成了七个2-{[5-（取代吡唑-5-基）-1,3,4-噁二唑-2-基]甲巯基）-5,7-二甲基-1,2,4-三唑[1,5-a]嘧啶类化合物,均为未见文献报道的新化合物。目标产物的结构经元素分析、IR、MS和^1H NMR测定确证,初步生物活性测试表明标题化合物具有一定的除草活性。     

2-氯-6，7-二氢喹啉-8（5H）-酮的合成研究

2-氯-6,7-二氢喹啉培（5H）-酮是四氢喹啉是一个重要的含氮杂环化合物。文章以2-氯-5,6,7,8-四氢喹啉为原料,经氧化、酯化、水解反应后得到2．氯-5,6,7,8-四氢喹啉-8-醇,再经Anelli氧化后得到总收率为57,8％的目标产物。所得化合物的结构均经核磁和质谱确证。     

3,6-亚甲基桥-4,5-二(4-氯化苯甲酰基)环己烯的合成及表征

以顺丁烯二酸酐、氯苯经 Friedle- Crafts反应合成了 1 ,2 -二 (4-氯化苯甲酰基 )乙烯。经 Diels- Alder反应 ,以环戊二烯环合成了含环己烯结构的双氯双酮化合物 :3,6 -亚甲基桥 - 4 ,5 -二 (4-氯化苯甲酰基 )环己烯。并用质谱、红外光谱、氢核磁共振谱、碳核磁共振谱及 Dept1 35谱等方法对化合物进行了表征 ,证明了化合物的结构。该化合物具有不饱和双键结构 ,是制备聚芳醚酮功能高分子材料的理想单体。     

3-氯-4-（2-溴甲基-4-甲基-1，3-二恶戍烷-2-基）苯基-4’-氯苯基醚的合成

3-氯-4-（2-溴甲基-4-甲基-1，3-二恶戍烷-2-基）苯基-4’-氯苯基醚是杀菌剂苯醚甲环唑的一个重要中间体。以2-氯-4-（4-氯苯氧基）-苯乙酮为起始原料，采用溴化和合环同时进行的合成工艺制得该化合物，收率90％．产品含量95％。优化了反应条件，简化了操作。     

4，4’-（4，4’-砜基二苯氧基）二苯甲酰氯（SODBC）的合成

以对甲基苯酚、4,4’-二氯二苯砜为原料，通过亲核取代反应合成了4，4’-二（4-甲基苯氧基）二苯砜，用高锰酸钾将甲基氧化得到4，4’-（4，4’-砜基二苯氧基）二苯甲酸（SoDBA），后者在二氯亚砜和路易斯碱的催化下合成了4，4’-（4，4’-砜基二苯氧基）二苯甲酰氯（SoDBC）白色固体。用FT-IR、H—NMR、3C—NMR、DSC等对其进行了表征，实验证明该化合物具有预期的结构和较高的纯度。     

2，4-二氯-5-溴甲基噻唑的合成

2-氯丙酸和硫脲在浓盐酸的作用下关环反应得到5-甲基-2，4-噻唑烷二酮，其进-步在四甲基氯化铵的催化作用下与三氯氧磷反应生成2，4-二氯-5-甲基噻唑。2，4-二氯-5-甲基噻唑在溴代丁二酰亚胺的作用进行溴代反应得到标题化合物2，4-二氯-5-溴甲基噻唑，总收率为20．5％，所有的化合物的结构经过1HNMR和元素分析证实。     

5-甲基-N-芳基-1，2，4-三唑[1，5-a]嘧啶-2-磺酰胺的合成

以4个N-芳基-5-氨基-1,2,4-三唑-3-磺酰胺为原料,分别与4,4-二甲氧基-2-丁酮在碱性水溶液中环合,制得4个5-甲基-N-芳基-1,2,4-三唑[1,5-a]嘧啶-2-磺酰胺衍生物,并比较了4,4-二甲氧基-2-丁酮的合成路线,所有目标产物的结构均经IR和1HNMR谱验证.     

3-三氟甲基-4-[（4-甲基哌嗪-1-基）甲基]苯胺的核磁共振研究

通过1H-1H COSY、HSQC和HMBC等2D NMR技术对3-三氟甲基-4-[（4-甲基哌嗪-1-基）甲基]苯胺的1H NMR和13C NMR谱进行了全归属,给出了相应的耦合常数。     

新型含联萘骨架的手性Brφnsted酸催化剂的合成

近年来,手性磷酸被广泛应用于催化不对称反应。通过以手性(R)-BINOL为原料,在联萘骨架的3,3’-位上通过醚化、取代、磷酸化等制备得到喹啉取代的新型含联萘骨架的手性Brnsted酸催化剂。所有化合物的结构用核磁碳谱、氢谱对进行了标征鉴定。我们并对目标化合物的刚性结构进行了讨论。     

Characterization of epoxidized natural rubber by 2D NMR spectroscopy

Assignment of signals in aliphatic region of ¹H NMR spectrum for epoxidized natural rubber was carried out through NMR spectroscopy. The epoxidized natural rubber was prepared by epoxidation of purified natural rubber with peracetic acid in latex stage followed by degradation with propanal and ammonium persulfate. The resulting liquid epoxidized natural rubber was characterized through 1D- and 2D-NMR spectroscopy. The unknown signals in the aliphatic region of the ¹H NMR spectrum were assigned through ¹³C NMR and two-dimensional heteronuclear shift correlation (HETCOR) measurement. The assignments were proved by two-dimensional inverse detected heteronuclear long-range shift correlation (HMBC) and two-dimensional homonuclear shift correlation (COSY) measurements, and they were supported with epoxidized squalene as a model compound through NMR spectroscopy.     

Chiral oligomers of spiro-salencobalt(III)X for catalytic asymmetric cycloaddition of epoxides with CO2

Several new chiral oligomers of spiro-salenCo(III)X (spiro = 1.1′-spirobiindane-7.7′-diol) complexes have been designed, synthesized, and characterized by nuclear magnetic resonance (NMR), infrared (IR), and elemental analyses, in which, the chiral spiro moieties are first introduced into a scaffold of chiral salenCo catalysts. They were used to catalyze the asymmetric cycloaddition of epoxides with carbon dioxide. Under very mild reaction conditions, a kinetic resolution of racemic epoxides with CO₂ was smoothly initiated by these chiral oligomer catalysts with good enantioselectivities, which can be attributed to the match effect between chiral backbones of salen and spiro. High stability and easy recyclability are their major advantages.     

磷杂螺环化合物的合成及表征

合成了双（４ 甲撑 ２，６，７ 三氧杂 １ 磷杂双环［２，２，２］辛烷）磷酸三聚氰胺盐（Ⅲ）及２，６，７ 三氧杂 １ 磷杂双环［２，２，２］辛烷甲醇（Ⅰ）、双（４ 甲撑 ２，６，７ 三氧杂 １ 磷杂双环［２，２，２］辛烷）氯代磷酸酯（Ⅱ），三者的得率分别为７２７％、９００％及５７３％；同时对化合物（Ⅰ）、（Ⅱ）及（Ⅲ）的核磁共振碳谱和红外光谱谱图进行了归属和解析，并得到元素分析的证实     

聚酯催化剂乙二醇锑的合成及光谱分析

以过量的乙二醇与三氧化二锑进行脱水水反应,用甲苯带水剂将生成的水带出,再进行真空减压除水合成了聚酯催化剂乙二醇锑,并研究了反应物摩尔配比、反应温度对产品收率的影响。采用了元素分析、FT-IR,^1HMR,^13NMR等分析手段表征了目标化合物的分子结构,并对化合物红外光谱及核磁共振谱带进行了归属分析。     

Chiral diphosphine and monodentate phosphorus ligands on a spiro scaffold for transition-metal-catalyzed asymmetric reactions

The preparation of chiral compounds in enantiomerically pure form is a challenging goal in modern organic synthesis. The use of chiral metal complex catalysis is a powerful, economically feasible tool for the preparation of optically active organic compounds on both laboratory and industrial scales. In particular, the metals coordinated by one or more chiral phosphorus ligands exhibit amazing enantioselectivity and reactivity. Many chiral phosphorus ligands have been synthesized and used in transition-metal-catalyzed asymmetric reactions in past decades. However, a large number of reactions still lack effective chiral ligands, and the enantioselectivities in many reactions are substrate-dependent. The development of effective chiral phosphorus ligands, especially ligands having novel chiral backbones, is still an important task in the area of asymmetric catalysis. Molecules containing a spirocyclic framework are ubiquitous in nature. The synthesis of molecules with this spiro structure can be traced back to 100 years ago. However, the use of this spirocyclic framework to construct chiral phosphorus ligands is a recent event. This Account outlines the design and synthesis of a new family of chiral spiro phosphorus ligands including spiro diphosphines and spiro monodentate phosphorus ligands with 1,1'-spirobiindane and 9,9'-spirobifluorene backbone and their applications in transition-metal-catalyzed asymmetric hydrogenation and carbon-carbon bond formation reactions. The chiral spiro diphosphine lgands SDP with a 1,1'-spirobiindane backbone and SFDP with a 9,9'-spirobifluorene backbone, and the spiro monophosphorus ligands including phosphoramidites, phosphites, phosphonites, and phospholane with a 1,1'-spirobiindane backbone were synthesized in good yields from enantiomerically pure 1,1'-spirobiindane-7,7'-diol and 9,9'-spirobifluoren-1,1'-diol. The ruthenium complexes of chiral spiro diphosphine ligands proved to be very effective catalysts for asymmetric hydrogenations of ketones, alpha-arylaldehydes and alpha,beta-unsaturated acids. The rhodium complexes of chiral spiro monophosphorus ligands are highly enantioselective for the asymmetric hydrogenations of alpha- and beta-dehydroamino acid derivatives, alpha-arylethenyl acetamides and non- N-acyl enamines. The spiro monophosphorus ligands were demonstrated to be highly efficient for the Rh-catalyzed asymmetric addition of arylboronic acids to aldehydes and N-tosylarylimines, Pd-catalyzed asymmetric allylation of aldehydes with allylic alcohols, Cu-catalyzed asymmetric ring opening reactions with Grignard reagents, and Ni-catalyzed asymmetric hydrovinylation of styrene derivatives with ethylene. The chiral spiro phosphorus ligands show high enantioselectivities for a wide range of transition-metal-catalyzed asymmetric reactions. In most of these transformations, the enantioselectivities of spiro phosphorus ligands are superior to those obtained by using the corresponding phosphorus ligands with other backbones. These results arise from the intriguing chiral inducement of spiro structures of the ligands.     

线型聚苯乙烯支载手性咪唑烷酮的制备

以N-叔丁氧羰基-L-酪氨酸乙酯为原料,经系列反应制备(S)-4-[4′-(对乙烯基苄氧基)苄基]-1-苯基-2-咪唑烷酮手性单体,用AIBN作引发剂,与苯乙烯溶液聚合制备线型聚苯乙烯支载的手性咪唑烷酮,用IR、1H-NMR、13C-NMR及元素分析对其结构进行表征,所得数据与其结构相吻合。     

基于拼合原理的具有姜黄素药效团的asperphenamate衍生物的合成

开发了具有崭新抗肿瘤作用机制的天然产物姜黄素及asperphenamate的全新骨架结构。以拼合原理为基础,将两种天然产物中的活性片段进行对接以拓宽其结构类型。以光学活性的苯丙氨酸为原料,经还原、酰化、缩合、脱保护及氢解等步骤得到目标产物。所得目标产物结构均经核磁共振氢谱及高分辨质谱表征。     

依卡倍特钠的核磁共振数据解析

依卡倍特钠是日本田边公司生产的一种具有覆盖作用的抗胃炎、胃溃疡的新型药物。笔者对依卡倍特钠进行了1H NMR、13C NMR检测,并通过DEPT、gCOSY、gHMQC、gHMBC等2DNMR技术对其NMR数据进行较为详细的解析和NMR信号全归属,为今后的分析鉴定工作提供完善的NMR数据。