Synthesis and Antibacterial Activities of 4—Amino—3—（1—aryl—5—methyl—1,2,3—triazol—4—yl）—5—mercapto—1,2,4—triazoles／2—Amino—5—（1—aryl—5—methyl—1,2,3—triazol—4—yl）—1,3,4—

Treatment of 4-amino-3-(1-aryl-5-methyl-1,2,3-triazol-4-yl)-5-mercapto-1,2,4-triazoles/2-amino-5-(1-aryl-5-methyl-1,2,3-triazole-4-yl)-1,3,4-thiadiazoles with benzaldehyde,acetone and ω-bromoacetophenone was tested and compared.The title compounds Schiff bases,amides,imidazolo [2,1-b]-1,3,4-thiadiazoles and 7H-s-triazolo[3,4-b]-1,3,4-thiadiazines have been confirmed by elemental analyses,^1H NMR,IR and MS spectra.All the compounds have also been screened for their antibacterial activities against B.subtilis,S.aureus and E.coli.     

3,3—二甲基—9—（5,5—二甲基—3—羟基—2—环己烯—1—酮—2—基）—1—氧代—2 …

标题化合物Ｃ２３Ｈ２６Ｏ４是水杨醛与５，６－二甲基－１，３－环己二酮在Ｎ，Ｎ－二甲基甲酰胺中反应而得。结果通过单晶Ｘ－射线衍射法确定，其晶体属于单斜晶系，空间群Ｐ２１／ｃ，ａ＝７．０５６，ｂ＝２０．２６３，ｃ＝１３．６６５Ａ，β＝９３．３２，Ｖ＝１９５０．７Ａ＾３，Ｍｒ＝３６６．４６，Ｄｃ＝１．２４８ｇ／ｃｍ＾３，Ｚ＝４，μ（ＭＯＫα）＝０．８４ｃｍ＾－１，Ｆ（０００）＝７８４。晶体结构用直接法解     

1—芳基—2—苯基—3—甲基—3—异丙基—2—氧代—1,4,2—二氮磷杂？…

利用取代苯基脲与苯基二氮化膦和３－甲基－２－丁酮进行的类Ｍａｎｎｉｃｈ反应合成了１５种新的１,４,２－二氮磷杂环戊－５－酮类化合物（２ａ－２ｏ）,其结构经＾１Ｈ ＮＭＲ,ＩＲ,ＭＳ和元素分析证实,根据ＮＭＲ谱分析,反应主要生成顺式几何异构体,除草活性测试表明,目标化合物对阔叶杂草具有很好的选择性草活性,并对其结构与除草活性关系进行了讨论。     

Synthesis of 3—Biaryl—1—ferrocenyl—2—propene—1—ones

The novel structures of organometallic compounds 3-biaryl-1-ferrocenyl-2-propene-1-ones 5 were synthesized for nonlinear optical chromophores by Suzuki cross-coupling reaction.Their structures were determined with elemental analyses,^1H NMR spectra and ^13C NMR spectra.     

Crystal and Molecular Structure of N—Phenyl 1—Methoxycarbonylmethyl—3—benzyl—1,2,3,4—tetrahydro—4—oxo—1,3,2—benzodiazaphosphorin—2—thiocarboxamide 2—Oxide

1 INTRODUCTIONOrganophosphorus compounds are ubiquitous in nature and they have broad applications in the fields of agriculture and medicine. During the past two decades, (-ketophosphonates and their derivatives containing sulfur have attracted considerable attention because these compounds are endowed with special physical, chemical and pharmacological properties due to the proximity of the carbonyl and the phosphoryl groups[1～8]. In the study on new pharmacenticals and agrochemicals, th…     

4—取代苯基—6—甲基—5—硫代—1,2,4—三嗪—3—酮的合成

合成了一系列新的４，６－二取代－５－硫代－１，２，４－三嗪－３－酮类化合物，并用元素分析、ＩＲ、＾１Ｈ ＮＭＲ及ＭＳ对其结构进行了表征。     

聚酰亚胺／聚N－乙烯吡咯烷酮分子复合物的合成和表征

由原位缩聚制备了刚性高分子聚酰亚胺（ＰＩ）和柔性基体聚Ｎ－乙烯吡咯烷附（ＰＶＰ）的分子复合物，并由实验证明了中间体聚酰胺酸（ＰＡ）和聚乙烯吡咯烷酮大分子之间存在的酸一碱相互作用．这种相互作用促进了混容性，使聚酰亚胺能以分子水平或接近分子水平分散在聚毗咯烷酮的基体之中．聚酰亚胺／聚Ｎ－乙烯吡咯烷团分子复合物的薄膜呈透明性，在整个组成范围内只有一个Ｔｇ，显示单相行为。当ＰＩ含量＜２０％时，ＳＥＭ相片呈现均相形貌，看不到ＰＩ微晶．广角Ｘ－ｒａｙ衍射图表明ＰＩ特征结晶峰消失，和无定形的ＰＶＰ完全混容．当ＰＩ含量＞４０％，ＳＥＭ显示有均匀分布的、棒状ＰＩ微晶存在．通过分子复合，即使ＰＩ含量为１０％，聚Ｎ－乙烯吡咯烷酮不再溶于乙醇，耐热性也有提高．     

THE BEHAVIOR OF N-PHENYLIMINOPHOSPHORANE TOWARDS o- AND p-QUINONES. NEW SYNTHESIS OF DIOXAZOLE AND OXADIAZOLE DERIVATIVES

ABSTRACT

N-Phenyliminophosphorane (1) reacts with 9,10-phenanthrenequinone (2a) to give the new products 2-phenylphenanthro[9,10-d][1,3,2]dioxazole (4a) and (10Z)-10-(phenylimino)-9(10H) phenanthrenone (4b). The reaction of 1 with 1,2-naphthoquinone (2b) afforded both the dioxazole derivative 5a and the known 2-anilino-naphthoquinone-1,4-anil (5b). On the other hand, 2,6-di-tert-butyl-2,3-diphenyl-2,3-dihydro-1,2,3-benzoxadiazole (6) was obtained from the reaction of (2c) with phosphinimine (1). Application of reagent 1 on 2d and 2e renders (6E)-2,3,4,5-tetrahalogeno-6-(phenylimino)-2,4-cyclohexadien-1-one 7a and 7b, respectively. Moreover, p-quinones (3a–3c) react with phosphinimine (1) to yield products 8, 9 and 10, respectively. Mechanisms accounting for the formation of the new products are discussed and the probable structures of the products are presented based on analytical and spectroscopic data.     

DISCOVERY OF SPECIAL PREDOMINANCE OF VANADYL PORPHYRIN AND HIGH ABUNDANCE OF Di-DPEP IN NONMARINE STRATA

By means of TLC, UV-Vis, HPLC and MS analyses, the types, structure and fingerprint distribution of porphyrin compounds in the nonmarine strata of China have been studied herein. It is revealed that the predominance of vanadyl porphyrin in lacustrine sediments of the Ordos Basin resulted from the high maturity, while the abnormal high content of Di-DPEP in the boghead-cannel coal from Guizhou Province was probably related to its abundant source input, the weakly oxidizing condition during the early diagenesis and the consequent reducing environment.     

偏钛酸型锂离子交换剂表面性质与选择吸附性研究

本文采用Li渗入于TiO2经高温热力学重结晶制备偏钛酸型锂离子交换剂,其对碱金属、碱土金属溶液中的Li+ 具有特殊选择吸附性,其次序为Li+>Mg2+>Ca2+>Na+,K+。对交换剂表面性质以及Li+ 在固-液界面的选择吸附特性进行了研究。通过对某气田卤水提锂实验表明:该交换剂对低Li+ 含量卤水中Li+ 的选择性吸附效果显著,对Mg2+、Ca2+、Na+、K+ 的分离效果好,Li+ 的富集倍数达9倍,并具有较好的循环稳定性。     

火试金法测定锡阳极中金量和银量

锡阳极是锡冶炼过程中的一种中间产物,其中含有大量的金银贵金属。准确测定锡中金银含量有很重要的现实意义。采用火试金法能实现锡中金、银连测,该方法准确度高,精密度好,金银回收率在97.47～101.66％之间,能很好的满足锡阳极中高品位金银的测定。     

THE PHOTOTOXIC EFFECT OF BENOXAPROFEN AND ITS ANALOGS ON HUMAN ERYTHROCYTES AND RAT PERITONEAL MAST CELLS

Abstract— Benoxaprofen [2-(4-chlorophenyl)-α-methyl-5-benzoxazoleacetic acid] is a phototoxic non-steroidal anti-inflammatory agent. Irradiation of human erythrocytes in the presence of benoxaprofen (8 μ M ) and oxygen resulted in rapid cell lysis which began after 10 min and was complete within 30 min. While photohemolysis was also observed under anerobic conditions, its onset was delayed for more than 20 min and it took nearly 100 min for complete lysis to occur. Photohemolysis was also delayed by butylated hydroxyanisole but was unaffected by reduced glutathione. 1,4-diazabicyclo[2.2.2]octane, D₂O. β-carotene, or superoxide dismutase. The main photoproduct of benoxaprofen, 2-(4-chlorophenyl)-5-ethylbenzoxazole, was almost as effective in causing photohemolysis as benoxaprofen itself. In the presence of UV irradiation, benoxaprofen (10 (μ M ) caused the degranulation of rat peritoneal mast cells and the release of histamine. The release of mast cell histamine may provide a reasonable explanation for the urticarial response to benoxaprofen and irradiation seen in human subjects.     

KINETICS OF FORMATION AND STABILITY CONSTANTS OF MONO AND BIS l-TYROSINE COMPLEXES OF Cu(II), Co(II), AND Ni(II)

Abstract

The kinetics and stability constants of l-tyrosine complexation with copper(II), cobalt(II) and nickel(II) have been studied in aqueous solution at 25° and ionic strength 0.1 M. The reactions are of the type M(HL)^(3-n)+ _n-1 + HL- ? M(HL)^(2-n)+_n(k_n, forward rate constant; k_-n, reverse rate constant); where M=Cu, Co or Ni, HL^? refers to the anionic form of the ligand in which the hydroxyl group is protonated, and n=1 or 2. The stability constants (K_n=k_n/k_-n) of the mono and bis complexes of Cu²⁺, Co²⁺ and Ni²⁺ with l-tyrosine, determined by potentiometric pH titration are: Cu²⁺, log K₁=7.90 ± 0.02, log K₂=7.27 ± 0.03; Co²⁺, log K₁=4.05 ± 0.02, log K₂=3.78 ± 0.04; Ni²⁺, log K₁=5.14 ± 0.02, log K₂=4.41 ± 0.01. Kinetic measurements were made using the temperature-jump relaxation technique. The rate constants are: Cu²⁺, k₁=(1.1 ± 0.1) × 10⁹ M ^?1 sec^?1, k_-1=(14 ± 3) sec^?1, k₂=(3.1 ± 0.6) × 10⁸ M ^?1 sec^?1, k^?2=(16 ± 4) sec^?1; Co²⁺, k₁=(1.3 ± 0.2) × 10⁶ M ^?1 sec^?1, k_-1=(1.1 ± 0.2) × 10² sec^?1, k₂=(1.5 ± 0.2) × 10⁶ M ^?1 sec^?1, k_-2=(2.5 ± 0.6) × 10² sec^?1; Ni²⁺, k₁=(1.4 ± 0.2) × 10⁴ M ^?1 sec^?1, k_-1=(0.10 ± 0.02) sec^?1, k₂=(2.4 ± 0.3) × 10⁴ M ^?1 sec^?1, k_-2=(0.94 ± 0.17) sec^?1. It is concluded that l-tyrosine substitution reactions are normal. The presence of the phenyl hydroxyl group in l-tyrosine has no primary detectable influence on the forward rate constant, while its influence on the reverse rate constant is partially attributed to substituent effects on the basicity of the amine terminus.     

SYNTHESIS AND REACTIONS OF TRIPHENYLPHOSPHONIMINOGLYOXALIC ACID ANILIDE ARYLHYDRAZONES

Abstract

A series of α-azidoglyoxatic acid anilide arylhydrazones 2 were prepared and converted to the corresponding phosphonimines 6 by reaction with triphenylphosphine. Treatment of the latter with acyl chlorides yielded the phosphonium salts 9 which afforded, upon treatment with triethylamine, 1, 5-disubstituted 1H-1, 2, 4-triazole-3-carboxylic acid anilides 11. Acid hydrolysis of 6 yielded the amidrazones 8.     

COMPLEXES OF HEXATERTIARY PHOSPHINES AND ARSINES AND THEIR REACTION WITH SMALL MOLECULES

Abstract

The synthesis of a new sexadentate ligand, P,P,P′,P′-tetrakis(2-diphenylarsinoethyl)α, α′-diphospha-p-xylene (TDADX) and the preparation of its iridium(I), rhodium(I) and ruthenium (II) complexes are described. When M=Ir and Rh, MCl(CO)(PPh₃)₂ reacts in benzene solution with the ligand TDADX to yield the complexes, [Ir(TDADX)] Cl and Rh₂ Cl₂ (TDADX). RuCl(CO)(PPh₃)₃ Cl reacts with this ligand to yield [RuCl(TDADX)]Cl. Complexes of P,P,P′,P′-tetrakis(2-diphenylphosphinoethyl-α,α-diphospha-p-xylene(TDDX) were also studied for comparison. Molecular hydrogen reacts with the complexes Ir₂ Cl₂ (TDDX), [Ir(TDADX)] Cl and [RuCl(TDADX)] Cl to form the corresponding hydrido complexes. Reaction of molecular oxygen with Rh₂ Cl₂ (TDADX) resulted in the formation of the dioxygen complex. Ir(I), Rh(I) and Ru(II) complexes of TDDX and TDADX react with carbonmonoxide to give mixed ligand carbonyl complexes. The complexes Ir₂ Cl₂ (TDDX), [Ir(TDADX)] Cl, and [RuCl(TDADX)] Cl react with nitric oxide to yield nitrosyl complexes. Infrared spectral data are provided for adducts formed with hydrogen, oxygen, carbon monoxide and nitric oxide.     

天然氨基酸水溶液中聚吡咯的电化学合成及其表征

报道了各种天然α-氨基酸水溶液中电化学聚合吡咯获得氨基酸掺杂的聚吡咯.实验表明吡咯在酸性氨基酸电解质中的氧化聚合电位较低,速度较快;而在碱性氨基酸水溶液中几乎无法进行电化学聚合.在电化学聚合过程中,氨基酸既作为支持电解质,又作为对离子被掺杂到聚合物中.该聚吡咯的电导率被测定为0.3～1.0 S/cm,在酸性氨基酸溶液中得到的聚合物电导率明显高于酸性较弱的氨基酸溶液中得到的聚合物,同时聚合物还具有良好的电化学活性和电化学稳定性,在-0.5 V到+0.5 V区间有一对氧化还原峰,该氧化还原峰的形状和特性在100次循环后基本保持不变.通过扫描电镜和透射电镜照片可以看出,不同种氨基酸的掺杂对聚吡咯的形貌具有影响,由于氨基酸的软模板效应,在数种氨基酸水溶液中能制得具有纳米纤维结构的聚吡咯.