6—硫杂—13—氮杂二环（9.3.0）—3,8—二炔十四烷的合成及核磁共振鉴定

以３，４－二（４′－甲磺酰氧－２′－丁炔基）四氢呋喃或６－硫杂－３，８－二炔－１，１１－二羟甲基环十一烷为原料合成了二环化合物６－硫杂－１３－氧杂二环（９．３．０）－３，８－二炔十四烷，通过＾１ＨＮＭＲ＾１３ＣＮＭＲ，ＩＲ及ＭＳ进行结构鉴定。     

新杂环化合物6,20-二硫杂-13,27-二氧杂三环[23,3,0,011,15]-3,8,17,22-四炔-二十八烷的合成及NMR结构鉴定

近年来,科学家先后从细菌分泌物中分离出几种含有环状"烯-二炔”的Calicheamicinγ1I[1～4]Esperamicin A1[5～7],Dynemicin A1[8]Neocarzinostatin 发色团[9～11],Kedarcidin发色团[12～13]等新型抗癌抗菌素,我们已做过评述[14].它们的"1,5-二炔-3-烯”部分经生物还原生成1,4-脱氢苯双自由基,从癌细胞DNA糖磷酯骨架上夺取氢原子,引起癌细胞DNA氧化断裂,杀灭癌细胞,因而有广泛的应用前景. 标题化合物是"烯-二炔”前体,以3,4-二(4′-甲磺酰氧-2′-丁炔基)四氢呋喃(1)为原料,在硫化钠作用下关环,得到了新杂环化合物(2).通过元素分析,红外光谱,质谱进行了分析,又进一步进行了1H NMR和13C NMR谱测定,并对其谱线进行归属,确证了结构.     

"烯-二炔"模型化合物前体--6-硫杂-13-氧杂双环[9.3.0]-3,8-十四二炔的合成(Ⅱ)

以顺-1,2,3,6-四氢邻苯二甲酸酐为原料,经还原、环化、臭氧化、Wittig羰基烯化、酯化、二醇化和硫化等8步反应,合成了新型抗癌抗菌素"烯-二炔"的双环前体:6-硫杂-13-氧杂双环[9.3.0]-3,8-十四二炔.该合成路线步骤少,收率高,反应条件温和.6个新化合物4-9的结构均经元素分析、核磁共振、红外光谱和质谱确证.     

包公藤甲素全合成的研究(Ⅱ)——中间体8-甲基-2β-羟基-8-氮二环[3.2.1]辛烷-6-exo-腈的合成

研究了Ｎ－甲基－３－羟基吡啶盐与丙烯腈的１，３－偶极环加成反应．由环合产物经过氢化，还原得包公藤甲素的中间体８－甲基－２β－羟基－８－氮二环［３．２．１］辛烷－６－ｅｘｏ－腈．本合成路线具有高立体选择性．     

3-吡唑基-6-取代均三唑并[3,4-b]-1,3,4-噻二唑的合成及生物活性

以１－甲基－３－乙基（－４－氯）－５－吡唑甲酰肼作原料，经两步得到４－氨基－３－（１－甲基－３－乙基（－４－氯）－５－吡唑基）－１，２，４－三唑－５－硫酮（３），３再与取代羧酸反应，得到一系列３－（１－甲基－３－乙基（－４－氯）－５－吡唑基）－６－取代均三唑并［３，４－ｂ］－１，３，４－噻二唑（４、５、６）．元素分析、１ＨＮＭＲ、ＩＲ和ＭＳ确定了它们的结构．初步生测结果表明：３具有植物生长调节活性，４ｂ、４ｄ、６具有杀菌活性．     

1-(3-氨基丙基)-2,8,9-三氧杂-5-氮杂-1-硅杂双环[3,3,3]十一烷衍生物的合成及其抗肿瘤活性研究

通过1-(3-氨基丙基)-2,8,9-三氧杂-5-氮杂-1-硅杂双环[3,3,3]十一烷与酸反应或1-(3-氯丙基)-2,8,9-三氧杂-5-氮杂-1-硅杂双环[3,3,3]十一烷与胺反应,合成了14种1-(3-氨基丙基)-2,8,9-三氧杂-5-氮杂-1-硅杂双环[3,3,3]十一烷衍生物.体外细胞培养试验结果表明,某些1-(3-氨基丙基)-2,8,9-三氧杂-5-氮杂-1-硅杂双环[3,3,3]十一烷衍生物对艾氏腹水癌细胞具有较好的杀伤活性.     

1,5-二氮杂双环[4,3,0]壬碳-5-烯与全氟炔酸酯的反应及其产物的核磁共振研究

1，5—二氮杂双环[4，3，0]壬碳—5—烯(DBN)与全氟炔酸酯反应生成成环化合物。通过对成环产物的^1HNMR、^13C NMR及相关的2D NMR谱的分析，确证了该类化合物的结构，并讨论了其化学位移及J-偶合特征。同时提出了整个反应可能的历程和机理。     

1—硫代—1磷杂—2，6，7—三氧杂双环[2,2,2]亲烷—4—甲撑烷氧基硫代磷酰胺的合成

以三氯硫磷、高位阻醇A等为材料，通过三步反应合成了化合物1－硫代－1磷杂－2，6，7－三氧杂双环[2,2,2]亲烷－4－甲撑烷氧基硫代磷酰胺。研究了化合物的^31P NMR和MSo产物的结构经元素分析和核磁共振等证实。     

7-氮杂-3,6-二氧杂-二环[3.3.0]辛-2-酮类化合物合成的新方法

5-甲氧基-2-（5H）-呋喃酮与氮酸硅烷基酯通过1，3-偶极环加成反应可以为7-氮杂-4-甲氧基-3，6-二氧杂-二环[3.3.0]辛-2-酮类化合物提供新的合成途径。通过元素分析、IR、^1HNMR、^13CNMR、MS等波谱分析进行了结构表征。     

3,6—二芳基—1,2,4—三唑并[3,4,b]—1,3,4—噻二唑化合物的合成

３－芳基－４－氨基－５－巯基－１，２，４－三唑与芳酸在三氯氧磷的作用下合成了１０个标题化合物，通过元素分析、红外光谱、核磁共振氢谱和质谱确证了它们的结构．对反应条件作了简略的讨论．部分化合物具有较强的生物活性．     

Analysis of the 1H and 13C NMR spectra of bicyclo[6.2.1]undecane ring systems

A detailed NMR analysis with full assignment of the ¹H and ¹³C spectral data for two polycyclic compounds is described. These compounds are derivatives of the product obtained from the pericyclic reaction between cyclopentadiene and tropone. Peculiar intriguing conformational features of these molecules are discussed. Copyright © 2003 John Wiley & Sons, Ltd.     

1H NMR spectroscopic study of the interaction between cyclodextrins and bicyclo[3.3.1]nonanes

The formation and structure of inclusion complexes of 2,6- and 2,9-substituted bicyclo[3.3.1]nonanes with- and-cyclodextrin (CD) has been investigated by high-resolution¹H NMR spectroscopy.- and-CD were found to form 1:1 inclusion complexes and the binding constants were estimated from titration studies. 2D ROESY experiments provided insight into the structure of the complexes.Presented in part at the 8th International Cyclodextrin Symposium, Budapest, March 30–April 2, 1996.     

Ethylene addition to group-6 transition metal oxo complexes - A theoretical study

Quantum chemical calculations using density functional theory (B3LYP) were carried out to elucidate the reaction pathways for ethylene addition to the chromium and molybdenum complexes CrO(CH₃)₂(CH₂) (Cr1) and MoO(CH₃)₂(CH₂) (Mo1). The results are compared with previously published results of the analogous tungsten system WO(CH₃)₂(CH₂) (W1). The comparison of the group-6 elements shows that the molybdenum and tungsten compounds Mo1 and W1 have a similar reactivity while the chromium compound has a more complex reactivity pattern. The kinetically most favorable reaction pathway for ethylene addition to Mo1 is the [2+2]_Mo,C addition across the MoCH₂ double bond which has an activation barrier of only 8.4 kcal/mol. The reaction is slightly exothermic with ΔE_R = −0.6 kcal/mol. The [2+2]_Mo,O addition across the MoO double bond and the [3+2]_C,O addition have much higher barriers and are strongly endothermic. The thermodynamically mostly favored reaction is the [1+2]_Mo addition of ethylene to the metal atom which takes place after prior rearrangement of the Mo(VI) compound Mo1 to the Mo(IV) isomer Mo1g. The reaction is −19.2 kcal/mol exothermic but it has a large barrier of 34.5 kcal/mol. The kinetically and thermodynamically most favorable reaction pathway for ethylene addition to the chromium homologue Cr1 is the multiple-step process with initial rearrangements Cr1 → Cr1c → Cr1g which are followed by a [1+2]_Cr addition yielding an ethylene π complex Cr1g + C₂H₄ → Cr1g-1. The highest barrier comes from the first step Cr1 → Cr1c which has an activation energy of 14.2 kcal/mol. The overall reaction is exothermic by −26.3 kcal/mol.     

Complete assignments of 1H and 13C NMR resonances of oleanolic acid, 18α‐oleanolic acid,ursolic acid and their 11‐oxo derivatives

Complete assignments of ¹H and ¹³C NMR chemical shifts for oleanolic acid, 18α‐oleanolic acid, ursolic acid and their 11‐oxo derivatives based on ¹H, ¹³C, 2D DQF‐COSY, NOESY, HSQC, HMBC and HSQC‐TOCSY experiments were achieved. Copyright © 2003 John Wiley & Sons, Ltd.     

Substituent effects on 13C chemical shifts of alkyl-substituted 4-oxo-1,3-dioxolanes and 5-oxo-1,3-oxathiolanes

The 13C NMR chemical shifts for 4-oxo-1,3-dioxolane (1) and its all methyl-substituted derivatives (2-10) as well as for 5-oxo-1,3-oxathiolane (11) and its nine alkyl-substituted derivatives (12-20) are reported. The magnitude and variety of the substituent effects are in accordance with the envelope conformations in which the oxygen or sulfur atom locates at the tip of the envelope as postulated on the basis of earlier data.     

13C NMR spectra of polycyclic compounds. Bicyclo[2.2.1]heptadiene tetramers

Comparison of experimental and calculated chemical shifts of carbon atoms in¹³C NMR spectra of two isomeric dodecacyclo[14.9.1.1^4,13.1^7,10.0^2,15.0^3,14.0^5,12.0^6,11.0^17,25.0^18,24.0^19,21. 0^20,24]-octacos-8-enes, bicyclo[2.2.1]heptadiene tetramers, confirmed theirexo-trans-exo-trans-exo-endo-andexo-trans-exo-trans-exo-exo-configurations. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2545–2547, December, 1998.     

Complete 1H and 13C data assignments of two new guaianolides isolated from Ainsliaea fragrans

Two new guaianolides, 8alpha-hydroxy-11alpha,13-dihydroglucozaluzanin C and 11alpha,13-dihydroglucozaluzanin C, were isolated from Ainsliaea fragrans, along with two known guaianolides, 8alpha-hydroxy-11alpha,13-dihydrozaluzanin C and glucozaluzanin C. The structures of the new compounds were unambiguously established by HR-ESI-MS, one-dimensional (1D) (DEPT), two-dimensional (2D) ((1)H-(1)H COSY, HSQC, HMBC, ROESY) NMR experiments and by comparison with structurally related compounds. The known compounds were identified by comparison of spectral data with published references. Some NMR data of the known compounds were reported for the first time.     

Complete assignments of (1)H and (13)C NMR data for two 3beta,8beta-epoxymexicanolides from the fruit of a Chinese mangrove Xylocarpus granatum

Three 3beta,8beta-epoxymexicanolides, including xyloccensin K, 6-acetoxycedrodorin and a new one named xyloccensin W, were isolated from the fruit of a Chinese mangrove Xylocarpus granatum. Their structures were determined by spectroscopic analyses. The first complete assignment of (1)H and (13)C NMR data for xyloccensin W was achieved by means of 2D NMR techniques, including (1)H-(1)H COSY, HSQC, HMBC and NOESY spectra. In addition, the confusion of (1)H and (13)C NMR data previously reported for xyloccensin K was clarified.     

1H and 13C NMR spectra of C-6 and C-9 substituted 3-azabicyclco[3.3.1]nonanes

The 1H and 13C NMR data for 3-azabicyclo[3.3.1]nonanes with OH and OMe substituents at C-6 and C-9 were measured using 1D (DEPT) and 2D (COSY, HSQC, HMBC, NOESY) experiments. Comparison of this NMR data illustrates the effects of stereochemistry and substitution at these positions.     

Complete assignments of 1H and 13C NMR data for two new sesquiterpenes from Cyperus rotundus L.

Two new sesquiterpenes, epi‐guaidiol A (1) and sugebiol (3), together with four known sesquiterpenes, guaidiol A(2), sugetriol triacetate (4), cyperenoic acid (5), and cyperotundone (6) were isolated from the rhizomes of Cyperus rotundus L. Their structures were identified by MS and NMR experiments, and the complete assignments of ¹H and ¹³C NMR data for two new sesquiterpenes were obtained by the aid of two‐dimensional (2D) NMR techniques, including HSQC, HMBC, ¹H‐¹HCOSY and nuclear overhauser enhancement spectroscopy(NOESY). Copyright © 2009 John Wiley & Sons, Ltd.