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An Efficient and Concise Synthesis of Heteroaryldipyrromethanes, Tetrapyrazolylporphyrins and Metalloporphyrins 杂芳基二吡咯烷、四吡唑啉和金属卟啉的高效简明合成
Pub Date : 2009-11-12 DOI: 10.2174/1874095200903010042
Farhanullah, V. Ram
One pot synthesis of terpyrromethanes (3a) and (di(1H-pyrrol-2-yl)methyl)heteroarenes (3b-m) has been de- lineated by Amberlyst 15 catalyzed condensation of pyrrole and heterocyclic aldehydes (2), not reported earlier. The com- pounds 3a and 3b have been formylated to 5-(di(5-formyl-1H-pyrrol-2-yl)methyl)-1H-pyrrole-2-carbaldehyde (4a) and 5- ((5-formyl-1H-pyrrol-2-yl)(3-pyridinyl)methyl)-1H-pyrrole-2-carbaldehyde (4b), by using a mixture of POCl 3 and DMF as formylating agent. Similarly, 5-alkyl-1H-pyrrole-2-carbaldehyde (8) has also been prepared from 2-alkyl-1H-pyrroles (6), obtainable by acylation followed by Wolf-Kishner reduction. Amberlyst 15 / TFA catalyzed the condensation of 8 with pyrrole which gave 3a instead of expected product 10, due to an unusual cleavage of alkyl substituent at position 5 in 8. CS 2 addition to 6 followed by methylation provided methyl 5-alkyl-1H-pyrrole-2-carbodithioates (7), which on reaction with hydrazine hydrate yielded 5-alkyl-1H-pyrrole-2-carbothiohydrazide (9). Tetrapyrazolylporphyrins (12) have been synthesized directly by condensation of pyrrole with 3-aryl-4-formyl-1-phenylpyrazole (11) in propionic acid. These por- phyrins were transformed to metalloporphyrins (13) from reaction with zinc and copper acetate separately.
用Amberlyst 15催化吡咯和杂环醛缩合制备了三吡咯甲烷(3a)和(二(1h -吡咯-2-基)甲基)杂芳烃(3b-m),这在以前没有报道过。以pocl3和DMF为甲酰化剂,合成了5-(二(5-甲酰基- 1h -吡咯-2-基)甲基)- 1h -吡咯-2-醛(4a)和5-((5-甲酰基- 1h -吡咯-2-基)(3-吡啶基)甲基)- 1h -吡咯-2-醛(4b)。同样,2-烷基- 1h -吡咯(6)也可以通过酰化和Wolf-Kishner还原得到5-烷基- 1h -吡咯-2-乙醛(8)。Amberlyst 15 / TFA催化了8与吡咯的缩合反应,由于8中5位烷基取代基的异常裂解,得到了3a而不是预期的产物10。将cs2加入到6中,然后甲基化得到5-烷基- 1h -吡咯-2-碳二硫代酸甲酯(7),与水合肼反应得到5-烷基- 1h -吡咯-2-碳硫代肼(9)。吡咯与3-芳基-4-甲酰-1-苯基吡唑(11)在丙酸中缩合,直接合成了四吡唑卟啉(12)。这些卟啉分别与锌和醋酸铜反应转化为金属卟啉(13)。
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引用次数: 0
Smiles Rearrangement in the Synthesis of Di- and Triiodinated 5- (Acylamino)-1,3-Benzenedicarboxamides 二和三碘化5-(酰基氨基)-1,3-苯二羧基酰胺合成中的Smiles重排
Pub Date : 2009-04-03 DOI: 10.2174/1874095200903010035
P. Anelli, M. Brocchetta, E. Cappelletti, V. Vincenzi
Both the number and the position of iodine atoms on the aromatic ring of polyiodinated N,N'-bis(2,3- dihydroxypropyl)-5-(2-methylamino-2-oxoethoxy)-1,3-benzenedicarboxamides are crucial to define the structure of the product obtained by treatment with aqueous NaOH. The 2,6-diiodo and the 2,4,6-triiodo derivatives give the correspond- ing Smiles rearrangement products in 77 and 96% yields, respectively. Conversely, under the same conditions, the 2,4- diiodo isomer predominantly undergoes hydrolysis of the phenoxyacetamide moiety.
多碘化N,N'-双(2,3-二羟丙基)-5-(2-甲基氨基-2-氧乙氧基)-1,3-苯二羧基酰胺芳香环上碘原子的数目和位置对于确定水溶液氢氧化钠处理后产物的结构至关重要。2,6-二碘和2,4,6-三碘衍生物分别以77%和96%的收率得到相应的Smiles重排产物。相反,在相同条件下,2,4-二碘异构体主要发生苯氧乙酰胺部分的水解。
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引用次数: 2
Synthesis of Pyrene-Anthracene Conjugated Molecular Rods 芘-蒽共轭分子棒的合成
Pub Date : 2009-01-26 DOI: 10.2174/1874095200903010011
J. Chávez, S. Ortega, M. Martínez-García
Fully conjugated pyrene-anthracene-based molecular rods were synthesized by the Horner-Wadsworth- Emmons reaction utilizing potassium tert-butoxide in dry THF. The synthesized rods, which have butylene groups as solubility spacers in the main chain, exhibited good solubility in polar solvents. The solutions of the synthesized pyrene- containing molecular rods exhibited a blue shift in the UV-vis from the absorption maximum due to the presence of the pyrene group in comparison with the dialdehydes. The chemical structure and purity of the synthesized rods were con- firmed by 1 H and 13 C NMR, FAB+, MALDI-TOF, electrospray mass spectra and elemental analysis. The presence of charge-transfer reaction centers in mac- romolecules depends on factors as the composition, the sepa- ration in the interchromophore, the overall dynamical and supramolecular reorganization, and the electronic coupling (1). The synthesis of artificial charge-transfer model systems in which the introduction of simple molecular changes is used to control and tune the magnitude of the electron- transfer parameters became a theme of great interest in the last years. The molecular chains or bridges inside the mole- cule provide endless opportunities, since they determine the structural features and the size of the electronic coupling between the donor and acceptor fragments (2). The modifica- tion of the spacer gives the possibility to introduce a system- atic alteration of separation, orientation, and overlap without affecting the electronic nature of the donor-acceptor pair, for which the coupling is proportional to the overlap of their electronic clouds (3). The electron-transfer processes depend on molecular size and structure, as well as the temperature and the free-energy difference between the donor and accep- tor in donor-bridge-acceptor systems. Currently, monodis- perse and soluble  -conjugated systems with a well-defined length and composition are receiving a growing interest for the design of molecular wires (4) and rods (5), since they can be used as tunable building blocks (6) for nanoscale chemi-
以叔丁二氧化钾为原料,采用Horner-Wadsworth- Emmons反应,在干燥四氢呋喃中合成了全共轭芘-蒽基分子棒。合成的棒材在极性溶剂中具有良好的溶解度,其主链上有丁烯基团作为溶解度间隔。由于芘基团的存在,合成的含芘分子棒溶液在紫外-可见光谱中与二醛相比出现了蓝移。通过1h和13c NMR、FAB+、MALDI-TOF、电喷雾质谱和元素分析对合成棒的化学结构和纯度进行了证实。高分子分子中电荷转移反应中心的存在取决于组成、间色团的分离、整体动力学和超分子重组以及电子耦合等因素(1)。人工电荷转移模型系统的合成,其中引入简单的分子变化来控制和调节电子转移参数的大小,已成为近年来人们非常感兴趣的主题。分子链或分子桥提供了无限的机会,因为它们决定了给体和受体片段之间的结构特征和电子耦合的大小(2)。修饰间隔层使得在不影响给体-受体对的电子性质的情况下,引入分离、取向和重叠的系统改变成为可能。其耦合与它们的电子云的重叠成正比(3)。电子转移过程取决于分子的大小和结构,以及供体-桥-受体系统中供体和受体之间的温度和自由能差。目前,具有明确长度和组成的单一多样和可溶性共轭体系正受到越来越多的人的兴趣,用于设计分子线(4)和分子棒(5),因为它们可以用作纳米级化学的可调构建块(6)
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引用次数: 9
Synthesis of 3- Benzylidene, 5-Substituted 3-Benzylidene, 3- Hetarylmethylene and 5-Substituted Hetarylmethylene Derivatives of Indolin- 2-ones 吲哚啉- 2-酮的3-苄基、5-取代3-苄基、3-乙基亚甲基和5-取代乙基亚甲基衍生物的合成
Pub Date : 2009-01-23 DOI: 10.2174/1874095200903010001
Haribabu Ankati, S. K. Akubathini, S. Kamila, Chandrani Mukherjee, S. D’Mello, E. Biehl
A wide variety of titled compounds, several of which have neuro-protecting properties has been prepared in yields ranging between 70 to 90%. The compounds were identified by 1 HNMR, 13 C NMR, 1D and 2D NOE analysis, and HRMS. An investigation of the effect of certain 5-substitutuents on the E to Z ratios in DMSO-d6 was carried out. The 5- nitro and 5-acetyl substituents were not isomerized, whereas the 5-fluoro, 5-chloro and 5-bromo underwent significant isomerization. In the former cases resonance interaction of the lone pair electrons of NH group of the indolin-2-one with the 5-nitro or 5-acetyl of the indolin-2-one prevents rotation of the benzylidene C=C bond whereas in the case of the latter 5-halo substituent, the lone pair electrons on the NH group interacts with the benzylidene C=C bond giving rise to anionic C-C - bond in which rotation about this bond can occur.
各种各样的命名化合物,其中一些具有神经保护特性,其产量在70%到90%之间。通过1hnmr、13c NMR、1D、2D NOE和HRMS对化合物进行了鉴定。研究了某些5-取代基对DMSO-d6中E - Z比的影响。5-硝基和5-乙酰基取代基没有异构化,而5-氟、5-氯和5-溴的异构化明显。在前一种情况下,吲哚林-2- 1的NH基团的孤对电子与吲哚林-2- 1的5-硝基或5-乙酰基的共振相互作用阻止了苄基C=C键的旋转,而在后一种情况下,NH基团上的孤对电子与苄基C=C键相互作用产生阴离子C-C -键,该键可以发生旋转。
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引用次数: 9
Solid State and Solution Structure of an Unusual Compound Containing a CS7 Ring~!2008-04-06~!2008-11-16~!2008-12-03~! 一种含CS7环的特殊化合物的固溶结构
Pub Date : 2008-12-16 DOI: 10.2174/1874095200802010110
H. Offermanns, J. Martens, Martin Watzke, P. Albers, B. Hannebauer, M. Janik, A. Müller, K. Shankland, Charlotte K. Leech, S. Parker
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引用次数: 1
The First Synthesis of p-Cl- and p-F-Phenylverbenene 对cl -和对f -苯基马鞭烯的首次合成
Pub Date : 2008-11-17 DOI: 10.2174/1874095200801020100
Claudia A Contreras-Celedón, L. Chacón-García
The first synthesis of 4´-X-phenylverbenene (X = F and Cl) via reaction of myrtenal with 4� -X phenylmagne- sium bromide and Bi(NO3)3 is described. Verbenene is formed due to the electron-withdrawing effect of the 4� - electronegative group, either fluorine or a Cl-Bi complex.
报道了桃金娘醛与4′-X苯基溴化镁和硝酸铋反应首次合成4′-X-苯基马尾草烯(X = F和Cl)。马鞭草烯是由于电负性基团氟或Cl-Bi配合物的吸电子作用而形成的。
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引用次数: 0
Solvent-Free Synthesis of Fused Pyrazolo[1,5-a]pyrimidines by Reaction of 5-Amino-1H-pyrazoles and β -Triketones 5-氨基- 1h -吡唑与β -三酮反应无溶剂合成融合吡唑[1,5-a]嘧啶
Pub Date : 2008-11-12 DOI: 10.2174/1874095200801020092
J. Quiroga, J. Portilla, Silvia Cruz, R. Abonía, B. Insuasty, M. Nogueras, J. Cobo, M. Hursthouse
The solvent-free reaction between 5-amino-1H-pyrazoles and  -triketones (2-acetyldimedone and 2- acetylindandione) leads to the formation of new fused pyrazolo(1,5-a)pyrimidines in good yields. A possible mechanistic route is postulated on the basis of the isolation of the cyclization intermediate. The structures and regiospecificity of the reaction were determined on the basis of nmr measurements and X-ray diffraction.
5-氨基- 1h -吡唑与-三酮(2-乙酰二酮和2-乙酰林丹二酮)进行无溶剂反应,生成新的融合吡唑(1,5-a)嘧啶,收率高。在分离环化中间体的基础上,提出了一种可能的机理路线。根据核磁共振测量和x射线衍射确定了反应的结构和区域特异性。
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引用次数: 4
Chromone-3-carboxaldehydes in Passerini Reactions Using TosMIC as the Isonitrile Component 用TosMIC作为异腈组分在路人甲反应中的铬-3-羧醛
Pub Date : 2008-08-24 DOI: 10.2174/1874095200801020088
Michael A. Terzidis, J. Stephanidou-Stephanatou, C. Tsoleridis
p-Toluenesulfonylmethyl isocyanide (TosMIC) is used as the isonitrile component in Passerini reactions with chromone-3-carboxaldehydes to yield chromenyl-amidoesters in good yields.
对甲苯磺酰基甲基异氰酸酯(TosMIC)作为异腈组分,用于与3-羟色胺酮反应,产率高。
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引用次数: 1
A Convenient Method for the Synthesis of 1,5-benzodiazepin-2-one 1,5-苯二氮杂平-2-酮的简便合成方法
Pub Date : 2008-08-08 DOI: 10.2174/1874095200801020083
M. Rida, H. E. Meslouhi, N. H. Ahabchane, B. Garrigues, N. Es‐Safi, E. Essassi
New 3-hydroxy-1,5-benzodiazepin-2-ones were synthesized through condensation between o- phenylenediamines with glycidic ester. Alkylation and oxidation of some of the obtained compounds were also explored in different conditions yielding various oxidized and alkylated benzodiazepines. The structural elucidation of the synthe- sized compounds was achieved by MS, NMR spectroscopy and also through X-ray diffraction analysis. The glycidic ester was thus shown to be an interesting synthon in the synthesis of new 1,5-benzodiazepines used in alkylation and oxidation reactions. Synthesis of 3-hydroxy -4-phenyl tetrahydro-1,5- benzodiazepin-2-one (4) and (5) A mixture of o-phenylenediamine 1 or its dimethylated derivative 2 (0.03 mole) and ethyl glycidate (0.03 mole) was refluxed in 80 mL of xylene during 48 hours. The obtained crude mixture was left at room temperature during one night. The trans diastereoisomers 4a or 5a which precipitate were filtered under reduced pressure.
通过邻苯二胺与甘二酸酯缩合反应,合成了新的3-羟基-1,5-苯二氮平-2-酮。对所得化合物在不同条件下的烷基化和氧化反应进行了探讨,得到了各种氧化和烷基化的苯二氮卓类化合物。通过质谱、核磁共振谱和x射线衍射分析对合成的化合物进行了结构分析。因此,在烷基化和氧化反应中使用的新型1,5-苯二氮卓类化合物的合成中,甘油脂酯是一种有趣的合成物。合成3-羟基-4-苯基四氢-1,5-苯二氮平-2- 1(4)和(5)将邻苯二胺1或其二甲基化衍生物2(0.03摩尔)和甘酸乙酯(0.03摩尔)的混合物在80 mL二甲苯中回流48小时。得到的粗混合物在室温下放置一晚。对析出的反式非对映异构体4a或5a进行减压过滤。
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引用次数: 5
Suzuki - Miyaura Reaction of 4-Silyl-bromobenzenes with Phenylboronic Acid under Thermal and Microwave Conditions~!2008-03-27~!2008-05-15~!2008-06-10~! 4-硅基溴苯与苯硼酸在热和微波条件下的Suzuki - Miyaura反应
Pub Date : 2008-06-13 DOI: 10.2174/1874095200802010065
I. Greiner, E. Hohmann, L. Vida, G. Keglevich
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引用次数: 0
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The Open Organic Chemistry Journal
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