N-苯基-双环[2.2.1]庚-5-烯-2,3-二甲酰亚胺的热聚合反应

以核磁共振波谱和溴加成法分析N-苯基-双环[2.2.1]庚-5-烯-2,3-二甲酰亚胺的聚合物的化学结构。聚合物分子具有含内、外式双环[2.2.1]庚-5-烯双键和环戊烯双键的结构单元。半定量地测定了各类双键的含量。分子的饱和链段有5,7-位相连的外式构型和5,6-位相连的内式构型的双环[2.2.1]庚烷的结构单元。结果表明,聚合过程中有构型的转变,重排反应,以及不同的链增长途径。     

近临界水中己二腈的水解

在间歇式反应器中成功地实现了己二腈(ADN)在近临界水中的水解。考察了m(ADN)/m(水)比、温度、时间、m(ADN)/m(添加物)比、添加物种类以及压力对每种产物产率的影响。通过高效液相色谱检测,己二腈在近临界水中水解主要生成五种产物,分别为5-氰基戊酰胺、己二酰胺、5-酰胺己戊酸、己二酸和微量的5-氰基戊酸。实验结果表明,ADN浓度和时间的改变对己二酰胺、5-酰胺基戊酸和己二酸的产率有明显的影响;时间是影响5-氰基戊酸产率的重要因素;5-氰基戊酰胺产率主要取决于ADN的浓度。     

外式双环[2.2.1]庚烷(庚-5-烯)-2,3-二甲酸酐膦二肽衍生物的合成

选择有机磷基团对斑蝥素的结构骨架进行修饰改造,以外式双环[2.2.1]庚-5-烯-2,3-二甲酸酐为原料,设计合成了一系列斑蝥素类似物。化合物的结构经1HNMR,MS及元素分析确证。     

低价钛还原环化δ-酮腈成环戊酮

四氯化钛-锌粉还原环化δ-酮腈是合成环戊酮的一种简便方法。在同样条件下, 由4-甲基-4-乙酰基庚二腈得到1,5-二甲基双环-[3.3.0]-2,8-辛二酮。     

1,4-二氮杂双环[2.2.2]辛烷催化双环邻-氨基腈衍生物的合成（英文）

报道了1,4-二氮杂双环[2.2.2]辛烷(DABCO)催化下的三组分一锅法合成双环邻-氨基腈衍生物,在该催化体系下,21种双环邻-氨基腈衍生物以68%～96%的收率制备得到.该方法于室温下即可顺利完成,反应时间短,目标化合物产率高.重要的是目标产物通过简单的过滤和乙醇洗涤即可获得     

7-氧杂双环[2.2.1]庚-2,3-二甲酸衍生物的合成及其抗HIV活性

以呋喃和顺丁烯二酸酐为原料,经环化反应制得7-氧杂双环[2.2.1]庚-5-烯-2,3-二甲酸酐(3);打开3的酸酐五元环,选择性地进行单酯化反应,合成了一系列7-氧杂双环[2.2.1]庚-3-烷氧羰基-2-甲酸(4a～4d),其结构经1H NMR和MS表征.初步探讨了4的抗HIV构效关系,其中4a的治疗指数与其先导化合物去甲基斑蝥素相当,毒性较之降低.     

低价钛还原环化σ-酮腈成环戊酮

四氯化钛-锌粉还原环化δ-酮腈是合成环戊酮的一种简便方法。在同样条件下,由4-甲基-4-乙酰基庚二腈得到1,5-二甲基双环-[3.3.0]-2,8-辛二酮。     

碘化钾在1,2-双(二溴甲基)苯及4位取代衍生物与反丁烯二腈反应中的作用

1,2-双(二溴甲基)苯及4位取代衍生物与反丁烯二腈在N,N-二甲基甲酰胺中反应12 h没有新的产物生成,在同样的条件下,加入碘化钾可使反应发生,主产物是2,3-二氰基萘及其6位取代衍生物,它的产率随加入的碘化钾的量不同而不同.当碘化钾的加入量相当于1,2-双(二溴甲基)苯及4位取代衍生物分子中溴的摩尔数,则1,2-双(二溴甲基)苯及其4位取代衍生物与反丁烯二腈基本作用完毕,反应产物主要是2,3-二氰基萘及其6位取代衍生物,产率87.1%.这个实验事实表明,碘化钾的作用机制不是传统意义上的催化剂而是一个反应试剂.据此,提出了上述反应的机理.     

某些内-双环[2.2.2]辛烯(或辛烷)基-2-甲醛缩醛的合成及香气

合成了16个内-双环[2.2.2]辛烯(或辛烷)基-层-甲醛缩醛类化合物。用Ms, IR和HNMR测定了它们的结构。双环[2.2.2]辛烯基缩醛的质谱断裂途径被确定了, 对这些化合物的香气进行了评定, 讨论了香气和结构的关系。     

内-α,α-二取代双环[2.2.1]-5-庚烯-2-甲醇的合成及其香气

文献[1]报道了一系列a-甲基-a-取代双环[2.2.1]-5-庚烯-2-甲醇类化合物的合成,并评定了它们的香气。我们以环戊二烯和丙烯酸甲酯为原料,经Diels-Alder反应和Grignard反应,合成了九个标题化合物(2a～i)。除2a外,其余均为新化合物。     

Heterogenous Oxidation of [2.2.1] Bridged Bicyclic Alkenes with KMnO4-CuSO4.5H2O: An Alternative Ozonolysis

Seven [2.2.1] bridged alkenes were cleaved to the corresponding dialdehyde products by neutral heterogenous oxidation with KMnO₄-CuSO₄.5H₂O. While endo, endo-dimethyl bicyclo[2.2.2]oct-5-ene-2,3-dicarboxylate, [2.2.2] bridged alkene, gave the corresponding α-hydroxy ketone, endo, endo-dimethyl bicyclo[3.2.2]non-8-ene-6,7-dicarboxylate afforded a diketone product.     

N-Substituted Aminomethoxybicyclo[2.2.1]heptanols and Their Antimicrobial Activity in Lubricating Fluids and Oils

Aminomethylation of bicyclo[2.2.1]heptane-2,3-diol, as well as of its O-allyl- and 5-vinyl derivatives, afforded a series of N-substituted 2-hydroxy(or allyloxy)-3-(aminomethoxy)bicyclo[2.2.1]heptanes which showed high bactericidal and fungicidal activity in lubricating oils.     

Mechanism of interaction of substituents in bicycloalkane compounds

The mechanism of interaction of substituents in the 4-substituted bicyclo[2.2.2]oct-1-ylfluorides and bicyclo[2.2.1]hept-1-ylfluorides based on the inductive effect and the positive charge effect was studied.     

Regioselective Electrophilic Additions of Bicyclo[2.2.n]alk-2-enes Controlled by Remote Epoxide Functions

The electrophilic additions of 2-nitrobenzenesulfenyl chloride to (1RS,2SR,4RS)-spiro[bicyclo[2.2.1]hept-5-ene-2,2′-oxirane] ( 12 ) and (1RS,2SR,4RS)-spiro[bicyclo[2.2.2]oct-5-ene-2,2′-oxirane] ( 14 ) were not regioselective under condition of kinetic control. However, good regioselectivity was observed for the addition of 2-nitro-benzenesulfenyl chloride to (1RS,2RS,4RS)-spiro[bicyclo[2.2.1]hept-5-ene-2,2′-oxirane] ( 13 ), giving (1RS,2SR,4SR,5RS,6RS)-6-exo-(2-nitrophenylthio)spiro[bicyclo[2.2.1]heptane-2.2′-oxirane]-5-endo-yl chloride ( 24 ) and for the exo addition to (1RS,2RS.4RS)-spiro[bicyclo[2.2.2]oct05-ene-2,2′-oxirane] ( 15 ), giving preferntially (1RS,2SR,4SR,5RS,6 RS)-6-exo-(2-nitrophenylthio) spiro[bicyxlo[2.2.2]octane-2,2′-oxirane]-5-endo-yl chloride ( 30 ). The facial selectivity (electrophilic exo vs. endo attack on the bucyclic alkene) depended on the relative configuration of the spiroepoxide ring in the bicyclo[2.2.2]octenes 14 and 15 . The exo-epoxide 14 was attacked preferentially (6:1) on the endo face by sulfenyl whereas exo attack was preferred (7:2) in the case of the endo-epoxide 15 . No products resulting from transannular ring expansion of the spiro-epoxide moieties could be detected.     

Domino ring-opening metathesis-ring-closing metathesis of bicyclo[2.2.2]octene derivatives: scope and limitations

Domino metathesis involving ring-opening metathesis-ring-closing metathesis (ROM-RCM) of a bicyclo[2.2.2]octene derivative having an appropriate alkene chain, expected to produce a 7/6 fused bicyclic system, provided a decalin system in contrast to ROM-RCM of the corresponding bicyclo[2.2.1]heptene analogues, which as expected produced the 7/5 fused bicycles. The expected 6/7 bicyclic system could, however, be made through RCM of the elusive ROM product prepared from the same bicyclo[2.2.2]octene analogue by a nonmetathetic route. A rationale to explain the difference in reactivity pattern between these two systems toward ROM-RCM has been forwarded.     

L'importance de la presence de l'oxygene en position-7 dans les reactions des alkylmagnesiens secondaires avec les anhydrides tricycliques pontes.

The reaction of secondary alkylmagnesium bromides with endo and exo bicyclo-[2.2.1]hept-5-ene-2,3-dicarboxylic anhydrides lead at the corresponding ketoacids whereas with the 7-oxa exo bicyclo[2.2.1]hept-5-ene-2,3 dicarboxylic anhydride produced only the monosubstituted lactones.     

A New Route to the Synthesis of 7-Functionalised Bicyclo[2.2.1]Heptane Derivatives

A new route to the synthesis of 7-functionalised bicyclo[2.2.1]heptane derivatives having a bridgehead alkoxy group is described involving Wolff rearrangement of α-diazo ketone in a bicyclo[2.2.2]octane derivative.     

Experimental and computational bridgehead C-H bond dissociation enthalpies

Bridgehead C-H bond dissociation enthalpies of 105.7 ± 2.0, 102.9 ± 1.7, and 102.4 ± 1.9 kcal mol(-1) for bicyclo[2.2.1]heptane, bicyclo[2.2.2]octane, and adamantane, respectively, were determined in the gas phase by making use of a thermodynamic cycle (i.e., BDE(R-H) = ΔH°(acid)(H-X) - IE(H(·)) + EA(X(·))). These results are in good accord with high-level G3 theory calculations, and the experimental values along with G3 predictions for bicyclo[1.1.1]pentane, bicyclo[2.1.1]hexane, bicyclo[3.1.1]heptane, and bicyclo[4.2.1]nonane were found to correlate with the flexibility of the ring system. Rare examples of alkyl anions in the gas phase are also provided.     

Pyrolysis of cyclo-aromatic diesters

Studies on the pyrolysis of cyclo-aromatic diesters derivatives of 3-phenylprop-2-en-1-ol are presented. The diesters are obtained during catalyzed esterification process of a stoichiometric ratio of 3-phenylprop-2-en-1-ol with suitable cycloaliphatic or aromatic acid anhydride in the solvent-free medium. As an acid anhydrides cyclohexane-1,2-dicarboxylic anhydride, cis-4-cyclohexene-1,2-dicarboxylic anhydride, bicyclo[2.2.1]-5-heptene-2,3-dicarboxylic anhydride, and phthalic anhydride were applied. The thermal properties of obtained compounds under inert atmosphere were tested by means of differential scanning calorimetry and thermogravimetry coupled with FTIR analysis. The pyrolysis products were determined and the probable mechanism of their decomposition was proposed.     

Barriers to inversion at nitrogen in bicyclic amines and hydrazines

Nitrogen inversion barriers have been measured for 7-chloro-1,7-diazabicyclo-[2.2.1] heptane and [2.2.2]octane; the unusual nature of the bridging nitrogen in bicyclo [2.2.11 systems is discussed.