SYNTHESIS AND SPECTROSCOPIC STUDIES OF SOME NEW REDOX-ACTIVE BENZYLAMINE COMPLEXES OF COPPER(II) AND ESR STUDIES OF THEIR OXIDATIONREDUCTION PRODUCTS

Abstract

New Cu(II) complexes Cu(L′_x)₂, where L′_x=L′₁, L′₂, L′₃, L′₄ are monoanion of unsubstituted, 5-Cl, 5-Br and 3,5-di-Br-substituted 2-hydroxybenzylamines of redox-active N-(3,5-di-tert-butyl-1-hydroxyphenyl)-2-hydroxybenzylamines were synthesized. Each compound of L′_xH and Cu(L′_x)2 as well as products of their oxidation and reduction by PbO2 and PPh3, respectively, was characterized by IR, UV-visible and ESR spectroscopy. ESR results showed that one-electron oxidation of mononuclear tetrahedrally distorted Cu(L′_x)2 chelates with PbO2, via C-C coupling of the Cu(II)-stabilized ligand radical intermediates and by the oxidative dehydrogenation of amine-chelates, produce new Cu(II) complexes with square-planar geometry. The powder ESR spectra of these new Cu(II) complexes exhibit a triplet-state type pattern with the zero-field splitting due to interaction between the copper(II) pairs. Interaction of Cu(L′_x)2 with PPh3 via intramolecular ligand-metal electron transfer results in the formation of radical species and reduction of the metal center. All radical intermediates were characterized by ESR parameters.     

INTERMEDIATES IN THE ROOM TEMPERATURE FLASH PHOTOLYSIS OF ADENINE AND SOME OF ITS DERIVATIVES

The transient absorption spectra of aqueous solutions of adenine, 2′-deoxyadenosine, 2′-deoxyadenosine-5′-phosphate and 2′-deoxyadenylyl-(3′-5′)-2′-deoxyadenosine have been determinated at different pH values using conventional flash photolysis. Reactives intermediates produced in the flash photolysis of these adenine derivatives present similar absorption regions: two higher intensity bands in the UV and 560–720 nm wavelength region and a third weaker band at 420–560 nm. On the basis of the effects produced by triplet quenchers and/or electron scavengers the bands have been assigned to hydrated electrons, radical cations, radical anions and/or neutral radicals resulting from neutralization reactions of the charged radicals. The results indicate that the bases photoionize via a triplet state under these conditions.     

ONE POT SYNTHESIS OF ARYL THIOPHOSPHORAMIDATE DERIVATIVES OF AZT

ABSTRACT

Novel aryl thiophosphoramidate derivatives of the anti-HIV nucleoside analogue 3′-azido-3′-deoxythymidine (AZT) have been prepared by the thiophosphorochloridate chemistry. These materials were designed to act as membrane-soluble prodrugs of the bioactive free nucleotides.     

THE CHEMISTRY OF SOME UREIDOBENZENESULFONYL CHLORIDES

Abstract

o-Methoxyphenyl-, N-phenyl-N′,N′-dimethyl, and N-3-acetylphenyl-urea with chlorosulfonic acid gave 4-methoxy-3-ureido, 4-(N′,N′-dimethylureido)-, and N-3-acetylureido-benzenesulfonyl chlorides respectively.

However, attempts to chlorosulfonate phenylthiourea were unsuccessful; the product was the zwitterionic sulfonic acid which did not give the sulfonyl chloride with phosphorus pentachloride.

N-Phenyl-N′-p-tolyl urea by reaction with chlorosulfonic acid afforded the corresponding 4-sulfonyl chloride. N-Phenyl-N′-2-pyridyl- and N-phenyl-N′-2-thiazolyl thioureas reacted similarly. In contrast, N-phenyl-N′-2′-pyridylurea only gave the bis-sulfonyl chloride.

Selected ureido-sulfonyl chlorides have been condensed with hydrazine and sodium azide and some reactions of the sulfonyl azides examined.

Acetylation of phenylurea gave only the N-(3-acetyl)- or the S-acetyl derivative depending on the conditions. Contrary to previous work, it is not considered that the N-(l-acetyl) phenylthiourea is formed.     

空间因素对敏化剂性质的影响

本文介绍了一种新的敏化剂cis-(NCS)₂-bis(2,2′-bipyridyl-3,3′-dicar-boxylate)ruthenium(Ⅱ)的合成,测定了它的吸收光谱及氧化还原电位,并将这种染料吸附到具有大比表面的TiO₂纳晶电极上测量它的光电转换效率。另外,参照文献分别合成出cis-(NCS)₂-bis(2,2′-bipyrdyl-4,4′-or 5,5′-dicarboxylate)Ru(Ⅱ)染料,测定它们的光电及光物理性质并以此为依据讨论了空间因素对敏化剂性质的影响。     

SYNTHESIS OF NOVEL AMINOPHOSPHONIC DERIVATIVES OF BENZO-15-CROWN-5 ETHER

Synthesis of new aminomethylphosphonic acids containing benzo-15-crown-5 ether, is described. These compounds were obtained from the 4′-formylbenzo-15-crown-5 by a sequence of reactions, which afforded 4′-(aminomethylphosphono)-benzo-15-crown-5 and its N-benzyl derivative in high yields.     

INTERACTION OF 2,4,6-TRINITROTOLUENE AND ITS ANALOGUES WITH ALDEHYDES. SYNTHESIS OF BENZOANNELATED HETEROCYCLES FROM THE PRODUCTS OF CONDENSATION

ABSTRACT

2,4,6-Trinitrotoluene (TNT) and its sulfonyl analogue 2-isobutylsulphonyl-4,6-dinitrotoluene undergo smooth condensation with chloral and fluoral to give 2-R-4,6-dinitrophenyl-1-(trihalomethyl)ethanols which easily cyclize to give 4-R-6-nitro-2-trihalomethyl-2,3-dihydrobenzo[b]furans (R=NO₂, i-Bu; halogen = F or Cl) in the presence of K₂CO₃. 2-R′-sulphonyl-4,6-dinitrotoluenes, prepared from TNT, condense with aromatic aldehydes to form 1-(2-R′-sulphonyl-4,6-dinitro)-2-arylethenes in which the ortho-nitro group, upon interaction with NaN₃ was selectively substituted by the azido group. Thermolysis of the obtained azides gave 2-aryl-4-R′-sulphonyl-6-nitroindoles (R′ = Ph, i-Bu, PhCH₂). Such N-methylated indole (R′ = i-Bu) was regioselectively aminated.     

SYNTHESIS AND CHEMISTRY OF SOME NEW 2-MERCAPTOIMIDAZOLE DERIVATIVES OF POSSIBLE ANTIMICROBIAL ACTIVITY

4,5-Diaryl-2,3-dihydro-2-mercaptoimidazoles (2a–e) were synthesized. They reacted with chloroacetic acid in gl. acetic acid/Ac ₂ O in presence of anhyd. sodium acetate afforded 5,6-diaryl-2,3-dihydro-imidazo[2,1-b]thiazol-3-ones (3a–d). Also these compounds were prepared by the action of chloroacetyl chloride on compounds (2) in pyridine. Compounds (3a–d) on condensation with aromatic aldehydes yield 2-arylmethylene-5,6-diaryl-2,3-dihydroimidazo[2,1-b]-thiazol-3-ones (4a–q). The latter compounds were prepared directly by the reaction of (2) with chloroacetic acid and the aromatic aldehydes. Compounds (3a–d) coupled with aryldiazonium salts in pyridine to give 2-arylhydrazono-5,6-diaryl-2,3-dihydroimidazo[2,1-b]thiazol-3-ones (5a–r). Also compounds (2) when reacted with 2 or 3-bromopropionic acid afford 2,3-di-hydro-5,6-diaryl-2-methylimidazo[2,1-b]thiazol-3-ones (6a–d) and 2,3-di-hydro-6,7-diaryl imidazo-[2,1-b]-1,3-thiazin-4-ones (7a–d), respectively. Compounds (3, 6, and 7) have been cleaved by aromatic amines to give the corresponding 2-(4′,5′-diaryl-2′,3′-dihydroimidazol-2′-yl)thioacetanilide (8a–f), 2-(2′,3′-dihydro-4′,5′-diaryl imidazol-2′-yl)thiopropionamide (9a–c), and 3-(2′,3′-dihydro-4′,5′-diaryl-imidazol-2′-yl)thiopropionamide (10a–d) respectively. All the prepared compounds show considerable antimicrobial activity against bacteria, yeast, and fungi.     

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.     

新型芳香性螺双内酯聚合物的合成

以间二甲苯和多聚甲醛为原料合成了芳香性螺双内酯单体———５ ,５′ 二甲酰氯 ７ ,７′ 二氧 ２ ,２′ 螺双（ 苯并四氢呋喃） ,并通过常温溶液缩聚和界面缩聚合成了一系列聚酰胺和聚酯．研究了聚合物的核磁、红外光谱及其溶解性、热性能和聚酰胺薄膜的力学性能．含芳香性螺双内酯的聚酰胺在极性溶剂中具有良好的溶解性、高的热稳定性和一定的力学性能．     

超细粉体二硫纶·取代菲咯啉铁(Ⅱ)配合物的光敏性研究

报道了新近合成的二硫纶·取代菲咯啉铁 (Ⅱ )配合物FeLL′(L =mnt2 - ,1 ,2 二氰基乙烯 1 ,2 二硫醇离子 ,L′ =phen 5,6 dione,1 ,1 0 菲咯啉 5,6 二酮 ;5 NO2 phen ,5 硝基 1 ,1 0 菲咯啉 )的电子吸收光谱、电子发射光谱及对CdS的光敏性 ,研究了FeLL′对CdS的光敏化作用与其电子光谱间的关系     

锰(Ⅱ)呋喃甲醛Schiff碱催化苯乙烯环氧化的研究

自1979年Groves首先以金属卟啉模拟细胞色素P－450,实现烯烃的环氧化^[1]以来,仿单加氧酶催化环氧化烯烃就成为仿酶催化领域里的一个非常活跃的研究课题^[2-5],但在这些报道中所用的模型化合物均为金属卟啉及其衍生物或Mn-Salen及其衍生物,这些化合物高昂的价格极大地限制了其应用前景。呋喃甲醛（俗称糠醛）取之于米糠或玉米芯,价格便宜且非石化产品,用它取代水杨醛不仅可降低成本,而且符合绿色化学要求。为此,本文选取了五种锰呋喃甲醛Schiff碱配合物作为模型化合物,以NaOCI为氧化剂,催化苯乙烯环氧化。讨论了配体结构、氧化物的pH值、轴配体、反应时间对催化环氧化反应的影响。     

MECHANISMS OF QUENCHING OF THE FLUORESCENCE OF A BENZO[a]PYRENE TETRAOL METABOLITE MODEL COMPOUND BY 2'-DEOXYNUCLEOSIDES

Abstract— The hydrophobic interactions of bulky polycyclic aromatic hydrocarbons with nucleic acid bases and the formation of noncovalent complexes with DNA are important in the expressions of the mutagenic and carcinogenic potentials of this class of compounds. The fluorescence of the polycyclic aromatic residues can be employed as a probe of these interactions. In this work, the interactions of the (+)-trans stereoisomer of the tetraol 7,8,9,10-tetrahydroxytetrahydrobenzo[a]pyrene (BPT), a hydrolysis product of a highly mutagenic and carcinogenic diol epoxide derivative of benzo[a]pyrene, were studied with 2′-deoxynucleosides in aqueous solution by fluorescence and UV spectroscopic techniques. Ground-state complexes between BPT and the purine derivatives 2′-deoxyguanosine (dG), 2′-deoxyadenosine (dA), and 2′-deoxyinosine (dI) are formed with association constants in the range of ～40–130 M^?1 Complex formation with the pyrimidine derivatives 2′-deoxythymidine (dT), 2′-deoxycytidine (dC), and 2′-deoxyuridine (dU) is significantly weaker. Whereas dG is a strong quencher of the fluorescence of BPT by both static and dynamic mechanisms (dynamic quenching rate constant k_dyn= [2.5 ± 0.41 × 10⁹M¹ s ¹, which is close to the estimated diffusion-controlled value of ～ 5 × 10⁹M^{? 1} s^?1), both dA and dI are weak quenchers and form fluorescenceemitting complexes with BPT. The pyrimidine derivatives dC, dU, and dT are efficient dynamic fluorescence quenchers (K_dyn～ [1.5–3.0] × 10⁹M^?1 s^?1), with a small static quenching component due to complex formation evident only in the case of dT. None of the four nucleosidcs dG, dA, dC and dT are dynamic quenchers of BPT in the triplet excited state; the observed lower yields of triplets are attributed to the quenching of single excited states of BPT by 2′-deoxynucleosides without passing through the triplet manifold of BPT. Possible fluorescence quenching mechanisms involving photoinduced electron transfer are discussed. The strong quenching of the fluorescence of BPT by dG, dC and dT accounts for the low fluorescence yields of BPT-native DNA and of pyrene-DNA complexes.     

PREPARATION AND CHARACTERIZATION OF SCHIFF BASE POLYMERS DERIVED FROM 4,4′-METHYLENEBIS(CINNAMALDEHYDE)

New Schiff base polymers poly[4,4＇-methylenebis（cinnamaldehyde）ethylenediimine] （PMBCen）, poly[4,4＇- methylenebis（cinnamaldehyde）1,2-propylenediimine] （PMBCPn）, poly[4,4＇-methylenebis（cinnamaldehyde）1,3-propylenediimine] （PMBCPR）, poly[4,4＇-methylenebis（cinnamaldehyde） 1,2-phenylenediimine] （PMBCPh）, poly[4,4＇-methylenebis（cinnamaldehyde）meso-stilbenediimine] （PMBCS）, poly[4,4＇-methylenebis（cinnamaldehyde）urea] （PMBCUR）, poly[4,4＇- methylenebis（cinnamaldehyde）semicarbazone] （PMBCSc）, poly[4,4＇-methylenebis（cinnamaldehyde）thiosemicarbazone] （PMBCTSc） and poly[4,4＇-methylenebis（cinnamaldehyde）hydrazone] （PMBCH） were formed by polycondensation of 4,4＇- methylenebis（cinnamaldehyde） with ethylenediamine, 1,2-propylenediamine, 1,3-propylenediamine, 1,2-phenylenediamine, meso-stilbenediamine, urea, semicarbazide, thiosemicarbazide and hydrazine, respectively. The dialdehyde and polymers have been characterized through elemental micro-analysis, IR, UV-Vis and ^1H-NMR spectroscopic techniques. Thermoanalytical studies and viscous flow of dilute solutions of dialdehyde and its polymers have been examined and compared.     

A NEW EFFICIENT PROTOCOL FOR THE PREPARATION OF CHIRAL BISPHOSPHINES OF THE BICP FAMILY

A new procedure for the synthesis of chiral BICP ligands is described. The protocol involves the reaction of sodium diarylphosphide–borane complex with chiral 2,2′-bisbenzenesulfonyl-1,1′-dicyclopentane in toluene, followed by HBF₄·OMe₂-mediated BH₃ decomplexation.     

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.     

CHLOROSULFONATION OF SOME COMPOUNDS CONTAINING TWO PHENYL RINGS

Abstract

Diphenylmethane (1) and dibenzyl (17) reacted with chlorosulphonic acid to give the corresponding p,p′-disulphonyl chlorides (2,18). However, attempted chlorosulfonations of α-chloro-, αα′-dichlorodiphenylmethane, stilbene and 1,4-diphenylbutadiene were unsuccessful.

Diphenylacetic acid reacted with chlorosulfonic acid to give a mixture of 4,4′-dichlorosulfonyl-benzophenone (40) and α-chlorodiphenylmethane-4,4′-disulfonyl chloride (39). Benzilic acid (41) afforded 9-chlorofluorene-2,7-disulfonyl chloride (42), which with amines gave 3 different products according to the reaction conditions. Fluorene (53) and the 9-carboxylic acid (43) have been treated with chlorosulfonic acid. The various sulfonyl chlorides were converted into 43 derivatives for biocidal evaluation. Mechanistic interpretations for the reactions are included.     

超拉伸聚乙烯的弹性模量和导热性能

为了揭示聚合物分子链伸展、取向的本征特性，发展了两个新的测量方法和实验装置，用于研究拉伸比高达２００的超拉伸聚乙烯凝胶的弹性性能、传热性能和聚合物结构的关系．应用激光脉冲热致超声法给出材料拉伸方向和横向杨氏模量，应用激光脉冲光热辐射法给出拉伸方向，横向和厚度方向的导热系数．随拉伸比λ的增加，轴向杨氏模量急剧的增加，而横向的仅有少许减小．导热系数具有相似的特性．本文发现当λ＝２００时，这种拉伸取向聚乙烯的轴向模量可达钢的８０％，而导热系数甚至可达２倍，直至成为热的良导体，这是由于在高拉伸比时形成了相当数量的伸展分子链构成的针状晶体———晶桥．本文提出晶桥作为短纤维分散相的取向聚合物的结构模型，对于超拉伸聚乙烯的上述特性可以进行统一描述和定量化分析，和实验结果很好符合．     

PREPARATION AND CHARACTERIZATION OF COBALT(III) COMPLEXES WITH SARCOSINE AND SOME TETRADENTATE LIGANDS OF THE EDDA TYPE

Abstract

Meridional geometrical isomers of cobalt(III) complexes with sarcosine (N-methylglycine) and tetradentate ligands edda (ethylenediamine-N,N′-diacetate ion), eddp (ethylenediamine-N,N′-di-3-propionate ion) and 1,3-pdda (1,3-propylenediamine-N,N′-diacetate ion) have been prepared. The edda and eddp cobalt(III) complexes were made by the reaction of sarcosine and sodium ethylenediamine-N,N′-diacetato(carbonato)cobaltate(III), and sodium uns-cis-(ethylenediamine-N,N′-di-3-propionato)(carbonato)cobaltate(III) dihydrate, respectively. The previously synthesized pdda-cobalt(III) complex with sarcosine was obtained by a new route by direct synthesis of cobalt(II) chloride hexahydrate with sarcosine and 1,3-pdda in the presents of lead(IV) oxide. Complexes were isolated chromatographically and characterized by elemental analysis, electron absorption spectra, infrared spectra and ¹H NMR spectroscopy.     

BINUCLEAR METAL CHELATES OF BISACETYLACETONE BIPHENYLDIHYDRAZONE

Abstract

Reaction of bihenyl-4,4′-tetrazonium ion with 2,4-pentanedione leads to 3,3′-(4,4′-biphenyldihydrazoni)bis-(2,4-pentanedione).The compound exists in the intramolecularly hydrogen bonded dihydrazone state. Copper(II), nickel(II) and palladium(II) complexes having the composition M₂L₂ have been synthesised and characterised. Ir, ¹H and ¹³C nmr and mass spectroscopic data clearly indicate the binucleating nature of the chelates in which the hydrogen bonded carbonyls and one of the hydrazono nitrogens of each pentanedione group are involved in bonding with the metal ion.