α,β,γ,δ-四-{4-[3-(9-(4-(3-(9-(4-(2-(5,5-二酰氧基甲基-1,3-二噁烷基))))苯基-2,4,8,10-四氧杂螺[5.5]十一烷基)))苯基-2,4,8,10-四氧杂螺[5.5] 十一烷基]}苯基卟啉星形化合物的合成

以对苯二甲醛、丙二腈、季戊四醇和吡咯为原料, 合成了含有螺环结构单元的中间体3-[4-(2,2-二氰基)乙烯基]苯基-9-(4-甲酰基)苯基-2,4,8,10-四氧杂螺[5.5]十一烷(3)和α,β,γ,δ-四-(4-甲酰基苯基)卟啉(4). 4与过量的季戊四醇反应, 得到α,β,γ,δ-四-{4-[2-(5,5-二羟甲基-1,3-二噁烷基)]}苯基卟啉(5), 5与3的反应产物经10% NaOH 处理后, 再与过量的季戊四醇反应, 得到α,β,γ,δ-四-{4-[3-(9-(4-(3-(9-(4-(2-(5,5-二羟甲基-1,3-二噁烷基))))苯基-2,4,8,10-四氧杂螺[5.5]十一烷基)))苯基-2,4,8,10-四氧杂螺[5.5]十一烷基]}苯基卟啉(6), 6与乙酐、丙酐、苯甲酰氯反应, 得到α,β,γ,δ-四-{4-[3-(9-(4-(3- (9-(4-(2-(5,5-二乙酰氧基甲基-1,3-二噁烷基))))苯基-2,4,8,10-四氧杂螺[5.5]十一烷基)))苯基-2,4,8,10-四氧杂螺[5.5]十一烷基]}苯基卟啉(7), α,β,γ,δ-四-{4-[3-(9-(4-(3-(9-(4-(2-(5,5-二丙酰氧基甲基-1,3-二噁烷基))))苯基-2,4,8,10-四氧杂螺[5.5]十一烷基)))苯基-2,4,8,10-四氧杂螺[5.5]十一烷基]}苯基卟啉(8)和α,β,γ,δ-四-{4-[3-(9-(4-(3-(9-(4-(2-(5,5-二苯甲酰氧基甲基-1,3-二噁烷基))))苯基-2,4,8,10-四氧杂螺[5.5]十一烷基)))苯基-2,4,8,10-四氧杂螺[5.5]十一烷基]}苯基卟啉(9)等三种卟啉星形化合物. 中间体1～6和星形化合物7～9均进行了IR, ¹H NMR, MS和元素分析等结构表征. 对影响反应的诸因素进行了讨论.      

α,β,γ,δ-四-{4-13-(9-(4-(3-(9-(4-(2-(5,5-二酰氧基甲基-1,3-二噁烷基))))苯基-2,4,8,10-四氧杂螺[5.5]十一烷基)))苯基-2,4,8,10-四氧杂螺[5.5]十一烷基]}苯基卟啉星形化合物的合成

以对苯二甲醛、丙二腈、季戊四醇和毗咯为原料,合成了含有螺环结构单元的中间体3-[4-(2,2-二氰基)乙烯基]苯基-9-(4-甲酰基)苯基-2,4,8,10-四氧杂螺[5.5]十一烷(3)和α,β,γ,δ-四-(4-甲酰基苯基)卟啉(4).4与过量的季戊四醇反应,得到α,β,γ,δ-四-{4-[2-(5,5-二羟甲基-1,3-二噁烷基)]}苯基卟啉(5),5与3的反应产物经10%NaOH处理后,再与过量的季戊四醇反应,得到α,β,γ,δ-四-{4-[3-(9-(4-(3-(9-(4-(2-(5,5-二羟甲基-1,3-二噁烷基))))苯基一2,4,8,10.四氧杂螺[5.5]十一烷基)))苯基-2,4,8,10-四氧杂螺[5.5]十一烷基]]苯基卟啉(6),6与乙酐、丙酐、苯甲酰氯反应,得到α,β,γ,δ-四-{4-[3-(9-(4-(3-(9-(4-(2-(5,5-二乙酰氧基甲基-1,3-二噁烷基))))苯基-2,4,8,10-四氧杂螺[5.5]十一烷基)))苯基-2,4,8,10-四氧杂螺[5.5]十一烷基])苯基卟啉(7),α,β,γ,δ-四-{4-[3-(9-(4-(3-(9-(4-(2-(5,5-二丙酰氧基甲基-1,3-二噁烷基))))苯基.2,4,8,10-四氧杂螺[5.5]十一烷基)))苯基-2,4,8,10-四氧杂螺[5.5]十一烷基]}苯基卟啉(8)和α,β,γ,δ-四-{4-[3-(9-(4-(3-(9-(4-(2-(5,5-二苯甲酰氧基甲基-1,3-二噁烷基))))苯基-2,4,8,10-四氧杂螺[5.5]十一烷基)))苯基-2,4,8,10-四氧杂螺[5.5]十一烷基]}苯基卟啉(9)等三种卟啉星形化合物.中间体1～6和星形化合物7～9均进行了IR,1H NMR,MS和元素分析等结构表征.对影响反应的诸因素进行了讨论.     

1,6,9,13-四氧双螺[4.2.4.2]十四烷-2,10-二酮的晶体结构测定

1,6,9,13-Tetraoxadispiro[4.2.4.2]tetradecane-2,10-dione,C_(10)H_(12)O_6,are colourless transparent crystal,and belonges to monoclinic system with space groupP2_1/n.The unit cell parameters are:a=9.051(1)(?),b=6.051(2)(?),c=10.098(1)(?),β=112.57(1)°,Z=2.A four-circle diffractmeter has been used to observe the diffrac-tion intensities.The crystal structure has been determined by direct method and its para-meters refined by the block-matrix least-squares method.The final agreement factor isR=0.065.The result shows that two saturated γ-lactone ring are connected to the dioxanering in dispiro arrangement.     

9,9-(′1,4-亚苯基)十四氢-二-吖啶-1,1,′8,8′-四酮缩双季戊四醇的合成

利用1,3-环己二酮和1,4-苯二甲醛为原料,在微酸介质中通过羟醛缩合和脱水反应,合成了9,9′-(1,4-亚苯基)-2H,2′H,3H,3′H,4H,4′H,5H,5H,′6H,6′H,7H,7′H,9H,9′H-十四氢-二-吖啶-1,1,′8,8′-四酮(化合物Ⅰ)。提出了化合物Ⅰ生成的反应机理。将化合物Ⅰ与季戊四醇在I2催化下反应,生成了目标化合物9,9-(′1,4-亚苯基)-2H,2′H,3H,3′H,4H,4′H,5H,5H,′6H,6′H,7H,7′H,9H,9′H-十四氢-二-吖啶-1,1,′8,8′-四酮缩双季戊四醇(化合物Ⅱ),收率为40%。产物和中间体用IR1、H NMR、MS和元素分析进行了结构表征。在含有螺环单元的化合物Ⅱ1H NMR中,亚甲基中的8个氢由于受手性轴和苯环的影响而裂分成8重峰。对影响反应的因素特别是副产物生成的原因进行了探讨     

氰基亚胺与亚甲基二氢苯并呋喃二酮类化合物的[3+2]环加成反应:螺吡唑类化合物的合成

采用具有环外双键的二氢苯并呋喃二酮类化合物和氰基亚胺的[3+2]环加成反应,在温和条件下,以高产率(78%~94%)和高非对映选择性(>20∶1dr)构建了一系列具有螺环结构的吡唑类化合物.     

9,9''''-(1,4-亚苯基)十四氢-二-吖啶-1,1'''',8,8''''-四酮缩双季戊四醇的合成

利用1,3-环己二酮和1,4-苯二甲醛为原料,在微酸介质中通过羟醛缩合和脱水反应,合成了9,9'-(1,4-亚苯基)-2H,2'H,3H,3'H,4H,4'H,5H,5H',6H, 6'H,7H,7'H,9H,9'H-十四氢-二-吖啶-1,1',8,8'-四酮(化合物Ⅰ). 提出了化合物Ⅰ生成的反应机理. 将化合物Ⅰ与季戊四醇在I2催化下反应,生成了目标化合物9,9'-(1,4-亚苯基)-2H,2'H,3H,3'H,4H, 4'H,5H,5H',6H,6'H,7H,7'H,9H,9'H-十四氢-二-吖啶-1,1',8,8'-四酮缩双季戊四醇(化合物Ⅱ),收率为40%. 产物和中间体用IR、1H NMR、MS和元素分析进行了结构表征. 在含有螺环单元的化合物Ⅱ1H NMR中,亚甲基中的8个氢由于受手性轴和苯环的影响而裂分成8重峰.对影响反应的因素特别是副产物生成的原因进行了探讨     

光学活性螺-环丙烷双内酯化合物的合成

描述了5-(l-孟氧基)-3-溴-2(5H)-呋喃酮新手性试剂1与氮亲核试剂发生的串联不对称双Michael加成/分子内亲核取代反应,一举生成4个新手性中心。报道了含有叔胺官能团的螺-环丙烷双内酯化合物4a-4d的合成方法以及结构测定。     

3,9—二羟乙基—3‘,9’—二苯甲基—1,5,7,11—四氧杂螺环[5,5]十一烷的合…

从丙二酸二乙酯、氯乙酸乙酯和氯苄出发，经ＬｉＡｌＨ４还原，合成新的二元醇，进而合成新的螺环化合物：３，９－二羟乙基－３′，９′－二苯甲基－１，５，７，１１－四氧杂螺〔５，５〕十一烷。该化合物的结构由它的氢和碳－１３核磁共振谱。红外光谱和元素分析得到证明。该单体在三氟化硼乙醚络合物的作用下进行开环聚合反应。由于环上四个取代基的稳定作用，聚合物的收率比较低。通过对聚合物的结构分析，提出了这一单体的阳离     

螺[1-溴-4-甲氧基-5-氧杂-6-氧代双环[3.1.0]己烷-2,2¢-(3-{α-[二(乙氧基)膦酸酯基]苄氧基}-4-甲氧基-5-氧杂-1-氧代环戊烷)]的合成、 结构及抗肿瘤活性的研究

α-羟基取代膦酸酯和5-甲氧基-3-溴-2(5H)-呋喃酮通过不对称串联反应, 得到螺环-膦酸酯类化合物的非对映异构体5和6. 目标分子5和6经IR, 1H NMR, 13C NMR, MS, 元素分析进行了结构表征, 其中非对映异构体5c和6c的立体化学结构通过X射线晶体分析得到了确认. 此研究结果为某些复杂的有机磷化合物提供了新的合成策略.     

新型树形化合物1,3,5-三-[7-(7-甲基-2,2-二-(2,2-二羟甲基-3-羟基丙氧基羰基)-6,8-二氧杂螺[3.5]-壬基)]苯的合成

以丙酮和甲酸乙酯为原料, 在醇钠的作用下合成了1,3,5-三乙酰基苯(1). 1与二溴新戊二醇在酸的作用下发生缩酮化反应, 制成1,3,5-三-(1-甲基-2,6-二氧杂-4,4-二溴甲基环己基)苯(2). 2与5,5-二甲基-4,6-二氧杂-1,3-环己二酮在乙醇钠的作用下合成了1,3,5-三-[7-(7-甲基-2,2-二-乙氧羰基-6,8-二氧杂螺[3.5]-壬基)]苯(3). 将3在氯仿中与季戊四醇进行酯交换反应得到产物1,3,5-三-[7-(7-甲基-2,2-二-(2,2-二羟甲基-3-羟基丙氧基羰基)-6,8-二氧杂螺[3.5]-壬基)]苯(4). 收率为47.7%. 标题化合物及中间产物使用IR, ¹H NMR和MS或元素分析进行了表征.     

Synthesis and Properties of Brominated 6,6'-Dimethyl-[2,2'-bi-1H-indene]-3,3'-diethyl-3,3'-dihydroxy-1,1 '-diones

Photochromic 6‐bromomethyl‐6′‐methyl‐[2,2′‐bi‐1H‐indene]‐3,3′‐diethyl‐3,3′‐dihydroxy‐1,1′‐dione ( 2 ), 6,6′‐ bis(bromomethyl)‐[2,2′‐bi‐1H‐indene]‐3,3′‐diethyl‐3,3′‐dihydroxy‐1,1′‐dione ( 3 ) and 6,6′‐bis(dibromomethyl)‐[2,2′‐ bi‐1H‐indene]‐3,3′‐diethyl‐3,3′‐dihydroxy‐1,1′‐dione ( 4 ) have been synthesized from 6,6′‐dimethyl‐[2,2′‐bi‐1H‐ indene]‐3,3′‐diethyl‐3,3′‐dihydroxy‐1,1′‐dione ( 1 ). The single crystal of 4 was obtained and its crystal structure was analyzed. The results indicate that in crystal 4 , molecular arrangement is defective tightness compared with its precursor 1 . Besides, UV‐Vis absorption spectra in CH₂Cl₂ solution, photochromic and photomagnetic properties in solid state of 2 , 3 and 4 were also investigated. The results demonstrate that when the hydrogen atoms in the methyl group on the benzene rings of biindenylidenedione were substituted by bromines, its properties could be affected considerably.     

Synthesis and Crystal Structure of 3,3-Dimethyl-7,11-di（thiophene- 2-yl）-2,4-dioxyspiro[5. 5]undecane- 1,5,9-trione

The title compound （C19H18O5S2） has been synthesized by the reaction of thio- phene-2-carboxaldehyde, isopropylidene malonate and 4-chloroaniline using [bmim]Br as solvent, and characterized by IR, ^1H NMR and X-ray single-crystal diffraction. The crystal belongs to monoclinic, space group P21/n with a = 9.4872（15）, b = 9.5148（13）, c = 20.634（3）A, β= 92.209（2）°, V= 1861.2（4）A^3, Mr= 390.45, Z = 4, Dc = 1.393 g/cm^3,μ（MoKα） = 0.313 mm^-1, F（000） = 816, the final R = 0.0685 and wR = 0.1685. X-ray analysis reveals that two six-membered rings adopt chair and planar conformations, respectively.     

一类含多氟烷基侧链的螺环化合物的合成及结构表征

A series of spiro compounds have been synthesized via several steps.The structure of these compounds wereconfirmed by ~1H NMR,~(13)C NMR,IR,MS spectra and X-ray diffraction analysis.The possible mechanism to formthese products was also proposed.     

Efficient Synthesis of Spiro[furan‐3,3′‐indoline] Derivatives via Reactions of Pyridinium Salts with Isatinylidene Acetoacetates

An efficient synthetic procedure for the functionalized spiro[furan‐3,3′‐indoline] derivatives was successfully developed by domino reactions of N‐phenacylpyridinium bromides or N‐ethoxycarbonylmethylenepyridinium bromide with isatinylidene acetoacetate in the presence of triethylamine in ethanol at room temperature. The mechanism included sequential Michael addition of the in situ generated pyridinium ylide and intramolecular substitution of enolate.     

Convenient Synthesis of Spiro[benzo[d]pyrrolo[2,1‐b]thiazole‐3,2′‐indenes] Derivatives via Three‐Component Reaction

The three‐component reaction of N‐phenacylbenzothiazolium bromides, aromatic aldehydes and indane‐1,3‐dione in ethanol at room temperature in the presence of triethylamine as base afforded functionalized spiro[benzo[d]pyrrolo[2,1‐b]thiazole‐3,2′‐indenes] in good yields and with high diastereoselectivity. The ¹H NMR data and single crystal structure clearly indicated that the obtained spiro compounds predominately have one diastereoisomer.     

Efficient Synthesis of the Functionalized Spiro[indoline‐3,4′‐pyridine] via Four‐component Reaction

An efficient synthetic procedure for the functionalized spiro[indoline‐3,4′‐pyridine] was developed via the four‐component reactions of arylamines, acetylenedicarboxylates, isatins and malononitrile with triethylamine as the base catalyst. The advantages of this reaction are using common starting material, mild reaction conditions, broad scope of reactants and operational simplicity.     

Solid‐Phase Synthesis of a Seventh‐Generation Inverse Poly(amidoamine) Dendrimer: Importance of the Loading Ratio on the Resin

Here, this study overcomes the current barriers to efficient solid‐phase synthesis of high‐generation dendrimers by decreasing the loading ratio on the resin. G7 inverse poly(amidoamine) dendrimer is now prepared, for the first time, through a solid‐phase synthesis using only 50% of the available reactive sites and by choosing a large resin. This preparation takes only 15 d to afford highly pure product in 80% yield with precipitation being the only purification procedure used. The results clearly show the amount of the initial monomer loaded on the resin to be a vital factor for the ability to use solid‐phase synthesis to produce large dendrimers. This finding also sets stage for the applications of solid‐phase synthesis for the preparation of other macromolecules.

     

螺环倍半萜(±)-α-花柏烯和(±)-β-花柏烯的全合成

以萜品油烯 ( terpinolene)与 2 ,4 -二氧代戊酸甲酯的 de Mayo反应得到加成产物为起始原料 ,经反 aldol重排 ,再环合成具有螺 [5 ,5 ]十一烷结构的基本碳骨架 ,通过官能团的化学修饰 ,完成了 (± ) -α-花柏烯和 (± ) -β-花柏烯的全合成     

新型螺{二氢吲哚-3,2'-[1,3,4]噁二唑}-2-酮类似物的合成

靛红及其衍生物与丙二腈缩合得中间体2-(2-氧代吲哚-3-叉基)丙二腈及其衍生物(2l~2t);苯甲酸及其衍生物与水合肼缩合得苯甲酰肼及其衍生物(4a~4l);2和4分别经环合反应合成了20个螺{二氢吲哚-3,2'-[1,3,4]噁二唑}-2-酮类似物(5a~5t),其中5b~5t为新化合物,其结构经1H NMR和ESI-MS表征。     

新型螺[氧化吲哚-3,3′-吡唑]-5′-二氟甲基-4′-甲酸酯类化合物的合成

以原位生成的二氟甲基重氮甲烷（CF₂HCHN₂）与靛红衍生的3-烯基氧化吲哚为原料,通过[3+2]环加成反应和1,3-H迁移过程,合成了3种结构新型的螺[氧化吲哚 3,3′-吡唑]-5′-二氟甲基-4′-甲酸酯类化合物,收率41~68%, dr 91: 9~99 : 1,其结构经¹H NMR, ¹³C NMR, ¹⁹F NMR和HR-MS(ESI-TOF)表征。并通过单晶X-射线单晶衍射确定其相对构型。