降冰片二烯衍生物的染料敏化电子转移光异构化反应的研究

降冰片二烯及其衍生物的光异构化反应已有广泛的研究,反应生成的四环烷衍生物是储能的重要化合物。由于降冰片二烯及其衍生物的吸收波长大多都在紫外区,所以,为了有效地实现太阳能的储存和转换,人们除了利用直接光异物化的途径外,更感兴趣的是用敏化光异构化的办法实现这种转换。到目前为止,已报道的降冰片二烯衍生物的敏化光异构化反应大多是通过较高三重态能量的敏化剂的三重态能量传递位降冰片二烯衍生物发生异构     

对-双(双环[2.2.1]-2,5-庚二烯-2-甲酰胺基)苯的合成

降冰片二烯(即双环[2.2.1]-2,5-庚二烯)及其衍生物,在光照下异构化为四环庚烷,在热或催化剂作用下,又恢复为原先的双烯结构,过程中伴随着释放热能。因此,降冰片二烯系列是将光能转成热能的具有开发价值的体系之一。     

降冰片二烯衍生物的光异构化 Ⅱ.2-萘胺甲酰基-2,5-[2.2.1]-双环庚二烯的光异构化

合成了降冰片二烯衍生物——2-萘胺甲酰基-2,5-[2.2.1]-双环庚二烯(B)。研究了它在太阳光直接照射下的光异构化反应。(?) 此外,还确定了化合物(B)和(C)的分子结构。它们都是文献中未曾报道过的新化合物。     

具分子内氮硼配键的10,9-硼氧杂菲螯合物的合成与性质

10,9-硼氧杂菲的四配位硼化合物很少见报道。我们曾报道10-羟基-10,9-硼氧杂菲与β-二酮反应可生成两种类型的四配位硼化合物。本文将报道10-羟基-10,9-硼氧杂菲与脂肪族β-氨基醇(氨基乙醇、氨基丁醇、羟乙基乙二胺和二甲胺基乙醇)和喹啉的取代衍生物(8-羟基喹啉、5,7-二溴-8-羟基喹啉和喹哪啶酸)反应,得到7种新的10,9-硼氧杂菲含氮衍生物。其合成路线如下:     

杂环光化学Ⅴ.烯类与1,3-二甲基-6-氮杂胸腺嘧啶的光环合加成反应

1974年Sweeton等人首先报道了这一反应^[1]。1981年樊美公等报道了1,3-二甲基-6-氮杂胸腺嘧啶(A)与庚烯-1的反应^[2],1986年又相继报道了含有极性基团的烯类与A的反应。本文通过这类反应合成了新化合物:1,2,4-三氮杂-2,4,6,7-四甲基-3,5-二氧-8-正丁基双环[4,2,0]辛烷(Ⅰ)和1,2,4-三氮杂-2,4,6-三甲基-3,5-二氧叁环[6,4,0,0^7,12]十二烷甲基衍生物(Ⅱ)。     

用二茂锆配合物一锅法合成1,1’-二取代联烯

二氯二茂锆(Cp_2ZrCl_2)与乙基溴化镁(EtMgBr)反应生成二乙基二茂锆(Cp_2ZrEt_2),再与1,4-二烷氧基-2-丁炔反应形成锆杂环戊烯,经过烷氧基在锆原子上的消除直接得到1,1′-二取代联烯(端联烯)。或者Cp_2ZrCl_2与正丁基锂(n-BuLi)反应生成二丁基二茂锆(Cp_2ZrBu_2),再与α-烯烃反应形成锆杂环戊烷,然后与1,4-二烷氧基-2-丁炔反应形成锆杂环戊烯,经过烷氧基在锆原子上的消除得到端联烯。上述反应合成端联烯的收率都比较高,这为构造端联烯衍生物提供了一种简单实用的方法。     

相转移催化合成7-氧杂双环[2.2.1]-庚-5-烯-2,3-二酰亚胺N-烃基衍生物

7-氧杂双环[2.2.1)-庚-5-烯-2,3-二酰亚胺的N-烃基衍生物是一类有生物活性的化合物。刘纪云等用相应的酸酐和各种胺类化合物在水或醇中反应合成了上述化合物,但收率较低。聚乙二醇(PEG)作为一种新的相转移催化剂在合成中广有应用。实验证明PEG     

高分子体系中降冰片二烯的光异构化反应

本文合成了降冰片二烯和咔唑为侧基的甲基丙烯酸酯共聚物,并与仅带有降冰片二烯侧基的聚甲基丙烯酸酯进行了光异构化反应的对比研究。实验结果表明,当入射光波长小于350nm时,两种降冰片二烯聚合物均发生了光异构化反应;当入射光波长大于350nm时,只有共聚物的降冰片二烯侧基能够异构化为相应的四环烷。利用荧光猝灭实验及化学诱导动态核极化(CIDNP)等研究了咔唑的敏化机理,利用三氟乙酸作催化剂实现了四环烷的反向异构化。     

2-β-二酮-1,3,2-二苯并[d,f]和二萘并(α,β)[d,f]-二氧硼杂环庚二烯的合成与结构

本文报道1,3,2-二苯并[d,f]二氧硼杂环庚二烯和1,3,2-二萘并(α,β)[d,f]二氧硼杂环庚二烯的制备及其β-二酮衍生物—以硼为螺原子的螺环[6,5]化合物的合成与性质. 8个标题化合物均为新化合物, 具有与10-β-二酮-10, 9-硼氧杂菲类似的结构.     

降冰片二烯衍生物的染料敏化电子转移光异构化反应的研究

降冰片二烯及其衍生物的光异构化反应已有广泛的研究, 反应生成的四环烷衍生物是储能的重要化合物, 为了更好地利用太阳能, 并进一步提高光敏化异构化反应的量子效率, 本文选用了具有强荧光的吖啶染料为敏化剂, 利用它们的单重态电子转移来引发反应, 在这类染料的光敏作用下异构化成为四环烷储能化合物。     

1-(2-Quinoxalyl)-, 1-[3,5-Di(trifluoromethyl)phenyl]-, 1-(2-Carboxyphenyl)-, and 1-Ethoxycarbonyl-4-oxo-4,5,6,7-tetrahydroindazoles

The corresponding 1-(2-quinoxalyl)-, 1-[3,5-di(trifluoromethyl)phenyl]-, and 1-ethoxycarbonyl-3-methyl-4-oxo-4,5,6,7-tetrahydroindazoles have been obtained from reactions of 2-acetyl-1,3-cyclohexanedione, its 5,5-dimethyl and 5-(2-furyl) derivatives, with 2-hydrazinoquinoxaline, 3,5-di(trifluoromethyl)phenylhydrazine, and ethoxycarbonylhydrazine. On interaction with ethoxycarbonylhydrazine the intermediate 2-[1-(-ethoxycarbonyl)hydrazino]ethylidene-1,3-cyclohexanediones were also isolated. From the potassium salt of 2-formyldimedone and 2-carboxyphenylhydrazine hydrochloride, 2-(2-carboxyphenyl)hydrazinomethylene-5,5-dimethyl-1,3-cyclohexanedione was obtained, the cyclization of which in ethanol in the presence of HCl led to 1-(2-carboxyphenyl)- and 1-(2-ethoxycarbonylphenyl)-6,6-dimethyl-4-oxo-4,5,6,7-tetrahydroindazole.     

Reactions of 3-(4-Aryl-2-thiazolyl)- and 3-(2-Benzothiazolyl)-2-iminocoumarins with N-Nucleophiles

The reaction of 3-(4-aryl-2-thiazolyl)- and 3-(2-benzothiazolyl)-2-iminocoumarins with N-nucleophiles was studied. This reaction gives 2-N-substituted 3-(4-aryl-2-thiazolyl)- and 3-(2-benzothiazolyl)iminocourmarins. N-Nucleophiles such as arylamines, heterocyclic amines, and hydrazine derivatives undergo this reaction.     

3-(2-Quinolyl)- and 3-(5-carbethoxyfuryl-2)coumarins

3-(2-Quinolyl)- and 3-(5-carbethoxyfuryl-2)coumarins were prepared by reaction of substituted salicylaldehydes and hetarylacetonitriles. Alkylation and acylation of 3-hetaryl-7-hydroxycoumarins were studied. __________ Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 432–434, September–October, 2005.     

Synthesis of （S）-2-（3-Arylacrylamido）-3-{4-[2-（5-methyl-2-phenyloxazol-4-yl）ethoxy]phenyl}propanoic Acids

The synthesis of （S）-2-（3-arylacrylamido）-3-{4-[2-（5-methyl-2-phenyloxazol-4-yl）etho- xy]phenyl}propanoic acids is described. Their structures were confirmed by ^1H-NMR.     

Synthesis and Characterization of New Schiff Bases 2-(2-(2-(Aryl)Methyleneamino)Phenylthio) Ethylthio)-N-((aryl)Methylene)Benzeneamine

A series of Schiff bases containing four to six coordination sites N₂S₂ X₂(X = O,N) 2-(2-(2-(aryl)methyleneamino)phenylthio)ethylthio)-N-((aryl)methylene)benzeneamine (2c–f) were prepared from the reaction of 1,2-di(2-aminophenylthio)ethane (1) with aromatic aldehydes. All compounds were characterized by means IR, mass, ¹H and ¹³C NMR spectroscopy, and elemental analysis, and in the case of 2b with a single crystal X-ray diffraction. The X-ray crystal structure of 2b showed that the resonance occurs between aromatic rings, through the C=N bonds of the molecule.

Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file.     

Selective Spectrophotometric Determination of Palladium (II) With 2-(5-Bromo-2-Pyridylazo)-5-(Diethylamino)-Phenol

Abstract

A spectrophotometric study of the Pd(II) complex of a reagent 2-(5-Bromo-2-Pyridylazo)-5-(diethylamino)-Phenol (5-Br-PADAP) is presented. A violet complex is formed at pH 3.53, and shows maximal absorbance at 585 nm with molar absorptivity of 3.86 × 10⁴ 1. mol^?1 cm^?1. Beer's law is obeyed up to 50 μ of Pd(II). The method offers the advantages of simplicity, high precision, requires no extraction and is very selective, where 5.0 mg Pt(VI) and 0.3 mg Au(III) ions do not interfere.     

(E)-N-芳基-3-[2-(8-羟基喹啉基)-乙烯基]咔唑的合成、抗氧化活性及促进鼠骨髓间质干细胞增殖的研究

设计合成了3-[2-(8-羟基喹啉基)-乙烯基]-N-对甲苯基咔唑(8)和3-[2-(8-羟基喹啉基)-乙烯基]-N-对甲氧苯基咔唑(9)两个新的化合物, 用IR, MS, 1H NMR和元素分析确认其结构. 并利用DPPH•方法, 超氧阴离子自由基( )法, 羟基自由基HO•法和噻唑蓝比色法(MTT法)分别测定了目标产物的抗氧化活性和调控鼠骨髓间质干细胞(MSCs)的作用. 结果表明, 这两种化合物对DPPH•自由基、超氧阴离子自由基和羟基自由基具有较强的抗氧化活性, 化合物9在低浓度时对鼠骨髓间质干细胞增殖有很好的促进作用.     

Synthese und Struktur des Kupferkomplexes 2-(2-Hydroxy-5-methylphenyl)-6-(2-hydroxyphenyl)pyridinato(2−)-dipyridin-kupfer(II) und des freien Liganden

Synthesis and Structure of the Copper Complex 2-(2-Hydroxy-5-methylphenyl)-6-(2-hydroxyphenyl)pyridinato(2?)dipyridin-copper(II) and of the free Ligand The tridentate diacidic ligand 2-(2-hydroxy-5-methyl)-6-phenyl-6-(2-hydroxyphenyl)pyridine 4a was synthesized and characterized by X-ray structural analysis. The compound forms a copper complex, 2-(2-Hydroxy-5-methyl-phenyl)-6-(2-hydroxyphenyl)pyridinato(2?)-dipyridine copper(II), which was crystallized from pyridine solution. The coordination number of the central atom copper ist five.     

Synthesis and Molecular Structure of (E)-1-(Morpholino)-2-(thiomethyl)-2-phenylvinylphosphonate

1 INTRODUCTION Phosphorus-containing vinyl compounds havebeen widely studied due to their versatile physiolo-gical activities and applications in transition metalchemistry, asymmetric catalysis and photorearrange-ment[1～4]. In our previous papers, we have reportedthe syntheses of 2,2,4,5-tetrasubstituted-1,3-dithio-les[5] and 2,5-bis(morpholino)-3,4-bis-(p-chloro-phe-nyl)thiophenes[6] by the reactions of α-thioaroyl-thiofor-mamide with trimethyl phosphite at room tempera-ture and in refl…     

DIASTEREOSELECTIVE SYNTHESIS AND STEREOCHEMISTRY OF (Z)-1-[3-ARYL-2-(PHENYLSULFANYL)-2-OXIRANYL]-1-ETHANONES

Diastereoselective synthesis of a series of (Z)-1-[3-aryl-2-(phenylsulfanyl)-2-oxiranyl]-1-ethanones was effected from the reaction of (Z)-4-aryl-3-(phenylsulfanyl)-3-buten-2-ones with alkaline hydrogen peroxide in tetrahydrofuran. The stereochemistry of the oxiranes has been deduced from two-dimensional NOESY spectrum.