1,3-苯并噻嗪酮类衍生物合成方法的研究进展

1,3-苯并噻嗪酮类衍生物具有广泛的生物学活性,因此这类衍生物的合成方法备受关注.从引入硫原子的方式及反应机理的角度,归纳总结了以苯硫酚类衍生物、二硫化物、同碳上连有胺基和巯基类衍生物、异硫氰酸酯类衍生物与小分子硫源等为原料合成1,3-苯并噻嗪酮类衍生物的方法.     

2-胺基苯并噁唑衍生物合成的研究进展

2-胺基苯并噁唑衍生物是一类重要的杂环化合物,在医药、生物和材料科学方面具有较好的用途,因此其合成方法备受关注.近年来,文献报道了在过渡金属或非金属催化下等一系列高效、绿色的合成2-胺基苯并噁唑衍生物方法.按照不同的反应原料和合成方法进行分类,综述了近年来2-胺基苯并噁唑衍生物合成研究的新进展.     

2-取代苯并噁唑衍生物的合成及生物活性

疏基苯并噁唑;2-取代苯并噁唑衍生物的合成及生物活性     

新型苯并噻二唑-7-羧酸衍生物的合成

以2,3-二氯硝基苯和异丙硫醇为原料,设计并合成了3个新型的苯并噻二唑-7-羧酸衍生物,其结构经1H NMR,IR和元素分析表征.     

2,3-二氢-1,4-苯并噁嗪衍生物的合成研究进展

综述了2,3-二氢-1,4-苯并噁嗪衍生物的合成研究进展,并对其发展趋势、应用前景作了进一步的展望。     

1,5-苯并硫氮杂卓-α-恶唑烷酮-β-内酰胺衍生物的光谱研究(Ⅱ)

苯并硫氮杂卓-β-内酰胺化合物是目前广泛用于临床的广谱抗生素药物.它的抗生素生理活性与其结构有着密切联系,为使该类化合物更具生理活性和优良药效,合成了五种新的1,5-苯并硫氮杂卓-α-恶唑烷酮-β-内酰胺衍生物,并用核磁共振(NMR)、质谱(MS)、红外光谱(1R)及元素分析确定了其衍生物结构,分析和讨论了该类衍生物的光谱特征及其规律,确定了该类衍生物结构的分析判据.     

2-叠氮基-1,1-二硝基乙基取代苯衍生物的合成

详细研究了2-叠氮基-1,1-二硝基乙基取代苯衍生物的合成方法。由苯基二硝基甲烷钾盐经羟甲基化,磺酰酯化和叠氮化得到目标化合物:3-硝基-(2-叠氮基-1,1-二硝基乙基)苯(4b),4-硝基-(2-叠氮基-1,1-二硝基乙基)苯(4c),m-二(2-叠氮基-1,1-二硝基乙基)苯(10)和p-二(2-叠氮基-1,1-二硝基乙基)苯(15)。     

2-叠氮基-1,1-二硝基乙基取代苯衍生物的合成

详细研究了2-叠氮基-1,1-二硝基乙基取代苯衍生物的合成方法。由苯基二硝基甲烷钾盐经羟甲基化，磺酰酯化和叠氮化得到目标化合物：3-硝基-(2-叠氮基-1,1-二硝基乙基)苯(4b)，4-硝基-(2-叠氮基-1,1-二硝基乙基)苯(4c)，m-二(2-叠氮基-1,1-二硝基乙基)苯(10)和p-二(2-叠氮基-1,1-二硝基乙基)苯(15)。     

手性双苯并噁嗪-2-酮二酚衍生物的高效合成及其在不对称催化中的应用

探索了手性苯并噁嗪-2-酮二酚衍生物的高效合成,以甲氧基取代的2-羟基苯甲醛衍生物和手性环己二胺为起始原料合成手性双亚胺,后经低价钛促进下还原、偶联与固体光气作用,构建了含有甲氧基的手性苯并噁嗪-2-酮衍生物,通过官能团转化,利用三溴化硼还原得到相应的手性苯并噁嗪-2-酮二酚衍生物.在此基础上,考察了手性苯并噁嗪-2-酮二酚催化剂在醛与二乙基锌不对称加成中的应用.此方法为合成手性苯并噁嗪-2-酮二酚衍生物提供了一条有效途径.     

1,4-二(苯并噁唑-1,3-基-2)苯及其5,5′-二取代衍生物的合成和光性能

合成了1,4-二(苯并噁唑-1,3-基-2) 苯及其5,5′-二取代衍生物共10个化合物,测定了它们的熔点、紫外吸收光谱、荧光发射光谱、红外光谱、荧光量子产率和激光性能.     

STUDIES OF HETEROCYCLIC COMPOUNDS: VI1 THE MASS SPECTRA OF SOME 2-THIOPHENEMERCURIC DERIVATIVES

Abstract

The mass spectra of some 2-thiophenemercuric derivatives are determined and the fragmentation interpretations are based on mechanistic analogy and supported in some cases by metastable peaks and low energy mass spectra. They all fragment ultimately to the 2-thienyl cation formed either through a two-step process, by cleavage of Hg[sbnd]X bond to give the 2-thienylmercuric cation, followed by extrusion of mercury, or by a one-step process through cleavage of carbon-mercury bond. Their base peaks being the C₃H₃ ⁺ion (m/e 39).     

几个新型二茂铁衍生物的合成

二茂铁及其衍生物作为油类消烟剂、燃速催化剂等已得到应用,在药物、合成材料等方面亦具有应用前景。文献曾报道含二茂铁基β-二酮的合成及以它为配体的金属配合物。此类配合物均含两个以上金属原子,它们在有机合成中具有独特的催化活性。 我们将二茂铁甲酰丙酮分别与水扬酰肼、异菸肼、乙二胺及硫代氨基脲在甲醇或甲醇-水介质中进行缩合反应,合成了4个新型二茂铁衍生物,它们含有三个或四个配位功能基团,可作为多齿配体用于金属有机配合物的合成。衍生物的合成路线如下:     

某些1-酰基苯并咪唑及1-酰基咪唑衍生物的合成

2-取代的苯氧甲基苯并咪唑、咪唑分别与酰氯在缚酸剂存在下反应,制备了24个新的1-酰基2-苯氧甲基苯并咪唑及1-苯氧乙酰咪唑衍生物.后者容易吸水,转变成相应的铵盐.所制得的化合物中某些经小麦垂直生长法测定表现出一定的促进或抑制生长活性.     

THE TRIPLET AND RADICAL SPECIES OF HAEMATOPORPHYRIN AND SOME OF ITS DERIVATIVES

Abstract— Nanosecond laser flash photolysis and pulse radiolysis have been used to generate and characterise the triplet state, and semioxidised and semireduced radicals of haematoporphyrin, and three 0 -acyl compounds derived from it (the monoacetate, the diacetate and the disuccinate).
After 347 nm irradiation in water containing 2% Triton X-100, haematoporphyrin forms the triplet state (φ_T= 0.92) and photoionises monophotonically (φ_I= 0.03). For the O -acyl derivatives, φ_T approaches unity and photoionisation is reduced. In acetone the triplet yield of all four compounds are close to unity. The difference and corrected spectra for the triplet species are presented and decay rates ( k ₁˜10⁴s^-1) and oxygen quenching constants ( k _Q˜1.5times10⁹ M ^-1s^-1) for the triplet state have been measured. The difference and corrected spectra for the semi-reduced species in methanol and semi-oxidised species in aqueous Triton X-100 are presented.
The photophysical characteristics in fluid solution of haematoporphyrin and its 0 -acyl derivatives are rather similar to those previously recorded for other photosensitising porphyrins.     

SYNTHESIS OF SOME SULFUR-CONTAINING SPIROINDOLE DERIVATIVES

Abstract

The synthesis of some new sulfur-containing spiroindole derivatives is reported. Fluorinated 3′-aryl-2′-phenylimino-spiro[3H-indole-3,6′[4,5′-pyrazolin][4,3-d]thiazolo]2(1H)-ones were prepared by the reaction of 5-(2-oxo-3-indolinylidene)-3-aryl-2-phenylimino-4-thiazolidinones with hydrazine hydrate. The compounds have been characterized on the basis of elemental and spectral studies.     

BIOLOGICAL PROPERTIES OF SOME BENZOPSORALEN DERIVATIVES

Abstract— The biological activity of some benzopsoralen derivatives, prepared with the aim of obtaining new drugs for photochemotherapy, has been studied. The more interesting compounds are 4-hydroxy-methyl-4',5'-benzopsoralen and 4-hydroxymethyl-4',5'-tetrahydro-benzopsoralen, which were found to be active in the dark also: DNA and RNA synthesis were both inhibited in Ehrlich cells, even if in a partially reversible fashion, while protein synthesis remained unaffected. In Chinese hamster ovary cells cultured in vitro , the clonal growth was strongly inhibited by incubation in the dark with both drugs, while a number of chromosomal aberrations was observed in the fraction of growing cells. Using alkaline elution, DNA strand breaks were detected. In addition, in the presence of aphidicolin, a specific inhibitor of DNA polymerase, the clonal growing capacity was completely restored; in contrast, the number of DNA strand breaks remained unchanged. All these results suggest that DNA topoisomerases are probably the target of these two benzopsoralens. These compounds are also good sensitizers; by UV-A irradiation they have a good capacity to produce singlet oxygen, but they appeared to be unable to induce erythemas on guinea-pig skin. Under UV-A light, they induced a strong inhibition of DNA synthesis in Ehrlich cells. Thus, benzopsoralens appear to be capable of inducing strong antiproliferative effects by two different mechanisms, by UV-A irradiation and in the dark.     

SOME PHOSPHORYLATED DERIVATIVES OF 1- AND 2-ADAMANTANOLS AND 1-ADAMANTYLAMINE

Abstract

The phosphorylation of 1- and 2-adamantanols and of 1-adamantylamine with POCl₃, PSCl₃, PhOP(O)Cl₂, 4-ClC₆H₄OP(O)Cl₂, and PCl₃ is described and the conversion of the obtained phosphorochloridates into a number of derivatives such as phenylhydrazides, diamidates, hydrazides, hydrazones and azides is reported.     

几种常见药物的高分子衍生物的合成

小分子药物高分子化能延长药效,减小副作用,是改进现有药物的重要方法之一。目前研究的高分子药物大致有两类:(1)高分子本身有药效;(2)高分子本身无药效,但可释放出小分子药物。例如,Vogl等合成的5-乙烯基水杨酸甲酯聚合物本身有抗紫外辐射功能,李福绵等合成的聚甲基丙烯酸-β-(乙酰水杨酰氧)乙酯等本身虽不是药,但可释放出阿斯匹林。我们希望合成出兼有以上两类特点的高分子药物,为此合成了几种常见药物的高分子衍生物:聚甲基丙烯酸水杨酸酯(PSAMA),聚甲基丙烯酸对乙酰胺基苯酯(PAPMA),聚甲基丙烯酸磺胺嘧啶酰胺(PSDMA)和聚甲基丙烯酸乳酸酯(PLAMA)。     

STUDIES IN THE HETEROCYCLIC COMPOUNDS V1. SOME REACTIONS OF 5-CHLORO-2-THIOPHENESULFONYL DERIVATIVES

Abstract

The reactions of 5-chloro-2-thiophenesulfonyl chloride are described. Treatment of the sulfonyl chloride with ammonia, hydrazine hydrate, sodium azide, indole and imidazole gave the sulfonamides (5), sulfonohydrazide (4), sulfonyl azide (3), 1-(5-chloro-2-thiophenesulfonyl)indole (27) and 1-(5-chloro-2-thiophenesulfonyl)-imidazole (26), respectively. The sulfonyl chloride was reacted further with 20 aryl-and cycloalkyl-amines to give the corresponding sulfonamides (6)-(25). Attempted chlorination of the sulfonyl chloride (2) with sulfuryl chloride or bromination of the sulfonyl azide (3) with pyridinium bromide perbromide failed. However, nitration of the sulfonyl chloride (2) with fuming nitric acid gave the 4-nitro-sulfonyl chloride (28), which with sodium azide afforded the 5-chloro-4-nitro-sulfonyl azide (29). The sulfonyl azides, (3) and (29), have been reacted with triphenylphosphine, triethylphosphite, norbornene and cyclohexene. The azides reacted further with indole and 1-methylindole to give the 2-sulfonyl-iminoindolines (34)-(36). The infra-red spectra and mass spectra of some of the substituted thiophenesulfonyl derivatives are discussed.