CHEMISTRY OF BIOLOGICALLY ACTIVE SULFUR COMPOUNDS

Abstract

All living organisms require sulfur for various metabolic processes. Sulfur occurs in enzymes, in structural proteins of cells, and in a wide variety of naturally occurring compounds which often play key roles in metabolism. The chemistry and biochemistry of sulfur compounds has been reviewed.^1–3.     

THE SULFUR FUNCTIONALIZATION OF ACTIVE METHYLENE COMPOUNDS

Abstract

Thiolsulfonates 1 are reagents which can sulfenylate simple aliphatic ketones and other active methylene compounds under remarkably mild conditions. The reported synthesis of 1 ¹ has been improved considerably.     

THE CHEMISTRY OF HETEROARYLPHOSPHORUS COMPOUNDS. PART XII.1 THE DIFFERENTIAL-PULSE POLAROGRAPHIC REDUCTION OF HETEROARYL-AND HETEROARYLMETHYLPHOSPHONIUM SALTS

Abstract

The polarographic reduction of series of heteroaryl- and heteroarylmethylphosphonium salts has been studied using a differential pulse polarographic technique, this having a number of advantages over classical dc polarography. For the salts Ar₃P⁺CH₂PhBr^-, the observed order of ease of reduction correlates with the electron-withdrawing ability of the heteroaryl group (i.e. Ar = 2-furyl > 2-thienyl > phenyl > 1-methylpyrrol-2-yl). In contrast, for the salts Ph₃P⁺CH₂ArBr^- (Ar = 2-furyl, 2-thienyl, phenyl, 1-methylpyrrol-2-yl, 3-thienyl and 3-furyl), the ease of reduction correlates best with the order of stability of the forming carbanions as established in earlier studies of the alkaline hydrolysis of these salts.     

旋光性聚甲基丙烯酸三苯甲酯的合成

<正> 旋光性聚甲基丙烯酸三苯甲酯(PTrMA,A)是一种新型旋光聚合物,其旋光性不是来自结构单元中的手性原子或基因,而是刚性的分子链呈长程单向螺旋构象,使分子链获得手征性的结果.自70年代末问世以来,在改进其合成方法和作为色谱固定相直接拆分手性化合物的应用方面受到人们注意,由于独特的结构,可以设想,如果将它带上特殊     

氨基硫脲及其相关化合物的化学

本文综述了氨基硫脲及其相关化合的合成、波谱和化学性质以及在药物、工业、农业等方面的应用。     

SYNTHESIS OF DIOLS BEARING PHOSPHONATE GROUPS PART III. THIOLS USED AS STARTING MATERIALS

This article describes the synthesis of diols bearing a phosphonated group. The method used is the monoaddition of a thiol on unsaturated compounds. Two ways are possible depending on the species bearing either the phosphonated group or the diol function. First we added a thiol bearing a diol function onto dialkylallylphosphonates. Then a thiol bearing phosphonated groups was added onto an allylic diol. On the other hand we compared radical and UV additions. We also compared the reactivity of similar phosphonated compounds (dimethyl and diethyl phosphonates). All the reactions gave very good yields and the different products have been analyzed by NMR studies. Finally, we succeeded in the synthesis of the corresponding phosphonic diacids by the bromosilane method.     

PHOSPHONYLATION BY A SPIROPHOSPHORANE: APPLICATION OF THE RIBOZYME CHEMISTRY IN THE BIOORGANIC SYNTHESIS

The phosphonylation by oxirane/phosphorous acid is characterized by formation of spirophosphorane, which provides the active intermediate in the reaction, β-hydroxyalkyl alkylene phosphite. Here, we demonstrate that a well-known and readily accessible spirophosphorane, 2λ⁵-2,2′spirobi[1,3,2-benzodioxaphosphole] can be used as convenient and effective phosphonylating agent in similar reaction. The easily detectable primary 3-phenylpropyl H-phosphonate, as well as 5′-O-tritylthymidyl, 4-N-benzoyl-5′-O-trityl-deoxycytidyl, 5′-O-trityl-deoxycytidyl, 6-N-benzoyl-5′-O-trityl- deoxyadenosyl 5′-O-trityluridyl, and 2′,3′-isopropylidene-uridyl H-phosphonates were prepared using a simple and straightforward procedure. Our results provide an interesting example of the potential and the limitations of a synthetic approach utilising reaction of leaving of diol system.     

光学活性甲苄菊酯的合成及其结构与活性关系的研究

本文改进了Goffinet方法,完成了(±)-trans菊酸的拆分;改进了Campbel?方法,只用一种拆分剂(奎宁)完成了对(±)-cis菊酸的拆分。用IR、~1HNMR、旋光度测定等方法确定了各甲苄菊酯光学异构体的结构。生物试验表明结构与活性有如下关系:1,各异构体中以1R-酯的杀虫活性为高,尤其(-)-(1R,3R)-trans甲苄菊酯对全部测试昆虫均显示较高的杀虫活性;2,昆虫不同,各异构体的活性次序也略有差异。     

THE MASS SPECTRA OF PHOSPHONYL COMPOUNDS PART 21 PHOSPHONYL DIHALIDES

Abstract

The mass spectra of two series of alkane- and substituted-methanephosphonyl dichlorides have been studied together with the spectrum of benzenephosphonyl dichloride. The molecular ions are of low abundance. Ions corresponding to hydrocarbon or halomethyl groups, which occur by cleavage of the P–C bond, are usually abundant, producing the base peaks in most of the spectra.     

THE PHENOMENON OF CONGLOMERATE CRYSTALLIZATION. PART 53. THE CRYSTALLIZATION BEHAVIOR OF TWO COBALT(III) CARBONATO AMINE COMPOUNDS

Abstract

Two new cobalt(III) carbonato amine compounds were synthesized, and their crystal structures were determined.

Compound (I), Na₂[Co(tren)(CO₃)]₂(CIO₄)₄·3H₂O, Co₂C₁₄CI₄H₄₂N₈Na₂O 25, crystallized as a racemate in the orthorhombic system, space group Pcab (No. 61). The cell dimensions, obtained from the centering of 25 reflections, are a = 10.684(5)å, b = 18.559(8)å, c = 37.528(10)å, V= 7441(5)å³. FW= 1028.18, Z= 8, F(000) = 4203.87, dc = 1.836 Mg·m^?3, μ = 1.30 mm^?3, λ = 0.70930å. A total of 3457 data were collected over the range of 4° ≤2θ ≤40°; of these, 2377 (independent and I≥2.5σ(I)) were used in the structural analysis. The final RF and Rw residuals were 0.055 and 0.064.

Compound (II), [cis-β-Co(trien)(CO₃)](HCO₃)· H₂O, CoC₈H₂₁N₄O₇, crystallized as a conglomerate in the orthorhombic system, space group P2₁2₁2₁ (No. 19). The cell dimensions, obtained from the centering of 25 reflections, are a = 8.869(4)å, b = 12.032(8)å, c = 12.522(7)å, V = 1336(1)å³. FW = 344.20, Z = 4, F(000) = 713.62, dc = 1.701 Mg·m^?3, μ = 1.32mm^?1, λ = 0.70930å. A total of 3504 data were collected over the range of 4° ≤2θ ≤40°; of these, 2497 (independent and I≥ 2.5σ(I)) were used in the structural analysis. The final RF and Rw residuals were 0.049 and 0.059.     

催化裂化汽油中类型硫含量分布

利用催化裂化汽油中各类硫化物的系统分析方法,对催化裂化(FCC)汽油和重油催化裂化(RFCC)汽油中各类型硫进行了分析测定,碱洗后FCC汽油和RFCC汽油中类型硫的布规律为:硫醇硫和二硫化物硫的含量较少,硫醚硫含量中等,而噻吩类硫的含量最多,占总硫含量的60%以上.     

SYNTHESIS OF OPTICALLY ACTIVE POLY (N-VINYLCARBAZOLE)S

The organic salts as initiators [A~+B~-:Ph_3C~+ClO_4~-, Ph_3C~+SbCl_6~-, (-)Sp~+ClO_4~- and(-)(Sp)_2~(+3)(ClO_4)_3] and catalysts [A~+B~-:(+)CSA, A~+B~-:Ph_3C~+(+)CSA~- and(-)Sp~+(+)CSA] are prepared and characterized by specific rotation. The asymme-trically stereoselective induction of the initiators and catalysts in the polymerization ofN-vinylcarbazole is in an order of A~+B~->A~+B~->A~+B~-. The specific rotations ofobtained poly (N-vinylcarbazole ) (PVCZ) generally are in accordance with mentioned order.     

光学活性两亲性嵌段共聚物的合成与表征

以溴封端聚乙二醇单甲醚(MPEG-Br)为大分子引发剂,三(2-二甲氨基乙基)胺(Me6TREN)/溴化亚铜(CuBr)为催化体系,通过原子转移自由基聚合(ATRP)反应制备了不同嵌段比例且分子量分布较窄的光学活性聚乙二醇单甲醚嵌段聚(N-甲基丙烯酰-L-亮氨酸甲酯)(MPEG-b-PMALM)聚合物.以1H-NMR表征了其化学结构以及两嵌段的比例.通过热重分析(TGA)和示差扫描量热仪(DSC)研究了嵌段共聚物的热学性能.相对于单体的旋光度,共聚物在聚合过程中旋光度发生了反转,其旋光度的绝对值显著增加,且随着PMALM嵌段含量的增加而增加.圆二色谱法(CD)结果表明,嵌段共聚物分子主链形成了一种无规卷曲的二级构象结构,其光学活性亦随PMALM含量的增加而增强.     

过渡金属簇合物合成化学

本文以与催化作用紧密相关的金属羰基簇合物的合成和与化学仿生相关的铁硫和钼铁硫簇合物的合成为例,评述了过渡金属簇合物合成化学的发展概况,给出了金属-金属间键合的两条通则(低氧化态金属间容易成键和同一族元素中重金属具有较大的成键倾向)和三类簇合物的主要合成路线。     

气相色谱法测定合成气中硫化合物

建立了气相色谱法测定合成气中硫化合物的方法。采用能自动进样的六通阀和对硫磷有选择性的FPD检测器,色谱峰面积与硫化合物含量存在很好的双对数线性关系。对H2S,COS及CS2三种气体的线性相关系数依次为0．9995,0．9997及0．9997。     

CIRCULAR DICHROISM OF BIS(DIMETHYLGLYOXIMATO)COBALT(III) COMPLEXES CONTAINING OPTICALLY ACTIVE AMINES

Abstract

The preparations and circular dichroism (CD) spectra of a series of bis(dimethylglyoximato)cobalt(III) complexes, each containing two asymmetric unidentate amines in trans positions, are reported. Tentative spectral assignments are made for the d-d region on the basis of effective D_4h molecular symmetry. In all cases the rotational strengths observed for the aromatic amine complexes are larger than those observed for the alkyl amine complexes.     

甲基丙烯酸三苯基甲酯与甲基丙烯酸甲酯光学活性共聚物的结构特征

采用１３Ｃ－ＮＭＲ，ＩＲ及ＷＡＸＳ表征了甲基丙烯酸三苯基甲酯（ＴｒＭＡ）与甲基丙烯酸甲酯（ＭＭＡ）光学活性共聚物结构．阐明了具有单向螺旋链的光学活性共聚物组成的非均一性及其光学活性随组成变化呈ｓ型曲线的特征．     

有机锡化合物光解活泼自由基的ESR研究

本文用自旋捕捉技术与ESR相结合的方法,研究了六种有机锡化合物的光解反应历程。结果表明:有机锡化合物紫外光照时,碳-锡键发生均裂,产生碳中心和锡中心自由基。其中碳中心自由基易被捕捉剂α-苯基-N-特丁基氮氧化物(PBN)或2,3,5,6-四甲基亚硝基苯(ND)所捕获;而锡中心自由基可与菲醌形成稳定的环状加合物。由于环状加合物中配体的不同,产生的空间效应也不同,从而导致加合物中的未偶电子云密度发生变化,给出相异的ESR信号。     

STUDIES IN THE HETEROCYCLIC SERIES. XIV. THE CHEMISTRY AND BIOLOGICAL ACTIVITY OF NEW AZA- AND THIA-PHENOTHIAZINES,AND RELATED DIBENZOTHIAZEPINES

Abstract

Owing to increasing demand for phenothiazine compounds both in medicine and industry, novel rings in these series have been prepared and evaluated. The benzene rings have been replaced with pyrrole, pyrazole, pyridine, pyridazine, pyrimidine, pyrazine, thiazine and triazine rings or their combinations leading to twelve new polyaza- and thia-phenothiazines. Expansion of the central thiazine ring in these systems has also been carried out. This article therefore provides a survey of the chemistry and applications of new polyaza- and thia-phenothiazine systems and their related thiazepines and thiazocines.     

连苯三酚缩二乙烯基苯树脂活性醚化物的合成与成像应用

通过乙烯基乙醚和连苯三酚缩二乙烯基苯树脂( PDVB resin)的羟基加成,合成了具有缩醛结构的活性醚化物,并对该活性醚化物的合成条件进行优化.这种具有缩醛结构的活性醚化物具有常温酸解和热解性能,作为阻溶促溶剂可用于常温化学增幅阳图感光成像和阳图热敏成像中.用于阳图热敏CTP感热成像配方中,使得版材具有高感度、高抗碱性、高稳定性;用于阳图CTcP感光成像配方中,使得该版材的综合成像性能优良;用于正性光致抗蚀剂成像配方中,使得该正性光致抗蚀剂具有高感度和高分辨率.