1,4,7,10—四氮杂环十二烷的制备

N,N′,N″—三(对—甲苯磺酰基)二亚乙基三胺与氢化钠反应生成二钠盐,然后与N,O,O'—三(对—甲苯磺酰基)双(2—羟乙基)胺进行缩合环化反应,得N—对甲苯磺酰化的四氮杂环十二烷。在浓H_2SO_4作用下,脱去对—甲苯磺酰基,最后得到了1,4,7,10—四氮杂环十二烷,总得率为44％。     

N,N′,N″—三(对—甲苯磺酰基)二亚乙基三胺的合成

二亚乙基三胺与对—甲苯磺酰氯在碳酸钾存在下,发生对甲苯磺酰化反应,生成N,N′,N″-三(对—甲苯磺酰基)二亚乙基三胺,产率96％。考察影响反应的几个因素。     

N,N′—二(芳磺酰)磺酰亚胺—S—(2—苯并咪唑)钠、银盐的合成及应用

芳磺酰氯胺钠是一类化学活性很强的物质,由它们参予的许多反应已引起化学工作者浓厚的兴趣。Boberg,Koide和Bruchmann等在这方面做了很多工作。Bruchmann用2—巯基吡啶酮与二分子芳磺酰氯胺钠(氯胺T,氯胺Cl,氯胺N,氯胺B和氯胺M)合成了相应的N,N′—二(芳磺酰)磺酰亚胺—S—(2—吡啶)钠盐化合物。众所周知2—巯基苯并咪     

4-N-{2-[4-(2-巯基乙氧基)苯氧基]乙基}-1-N-对甲苯磺酰基哌嗪的合成

以对苄氧基苯酚为原料,经三步反应合成了2-[4-(2-溴乙氧基)苯氧基]乙醇(3); 3与1-对甲苯磺酰基哌嗪反应制得4-N-{2-[4-(2-羟乙氧基)苯氧基]乙基}-1-N-对甲苯磺酰基哌嗪(5);在5上引入乙酰巯基后再经碱性水解,合成了新化合物4-N-{2-[4-(2-巯基乙氧基)苯氧基]乙基}-1-N-对甲苯磺...     

含吡啶环大环多胺的合成及其与Cu(Ⅱ)的络合行为

本文以2,6-二溴甲基吡啶和对甲苯磺酰胺钠盐合成含吡啶环大环多胺,得到了尚未见文献报道的含四个吡啶环的三十二环胺. 2,6-二溴甲基-吡啶与甲苯磺酰胺钠盐在无水乙醇回流温度下得到1,9,17,25-四甲苯磺酰基大环多胺.用浓硫酸脱去N-甲苯磺酰基化合物的甲苯磺酰基, 生成标题大环多胺化合物. 配体与Cu(Ⅱ)的络合由紫外吸收光谱测定. 实验结果表明配体确与Cu^2^+以1:2络合成为双核络合物.     

N-(2-苦胺基乙基)单氮杂冠醚的合成

研究并比较了氮支套索型生色冠醚1a和1b两条不同的合成路线, 结果表明, 由N-苦基乙二胺(2)与1,11-二碘-3,6,9-三氧杂十一烷进行N-烷基化环化反应, 可方便地制备N-(2-苦胺基乙基)单氮杂-12-冠-4(1a), 但按此法未能获得更大环的-15-冠-5(1b);若从N-对甲苯磺酰基乙二胺(6)或N-(2-对甲苯磺酰胺基乙基)二乙醇胺(7)出发, 经环化, 脱除对甲苯磺酰基而制得的N-(2-氨基乙基)单氮杂冠醚5a和5b分别与苦基氯反应, 则可获得高产率的生色生色冠醚11a和1b.     

β-环糊精的双官能化

通过两条路线对β-环糊精进行双官能化合成了3个带双官能团的β-环糊精--叠氮基对甲苯磺酰基β-环糊精(3), 二对甲苯磺酰基β-环糊精(4)和二叠氮基β-环糊精(5).对甲苯磺酰基β-环糊精(1)的对甲苯磺酰基被叠氮基取代制得单叠氮基β-环糊精(2);2与对甲苯磺酰咪唑反应得到3.1先与对甲苯磺酰咪唑反应生成4;4的对甲苯磺酰基被叠氮基取代得到5.3～5的结构经1H NMR, IR和元素分析表征.     

N-(2-对甲苯磺酰胺基乙基)单氮杂冠醚的合成及其晶体结构

N-对甲苯磺酰基乙二胺分别与1,11-二碘-3,6,9-三氧杂十一烷和1,14-二碘-3,6,9,12-四氧杂十四烷反应,制得N-(2-对甲苯磺酰胺基乙基)单氮杂-12-冠-4或15-冠-5;当用N-(2-对甲苯磺酰胺基乙基)二乙醇胺与1,11-二对甲苯磺酸酯-3,6,9-三氧杂十一烷反应时,才能获得N-(2-对甲苯磺酰胺基乙基)单氮杂-18-冠-6.从甲醇溶液中培养得N-(2-对甲苯磺酰胺基乙基)单氮杂-12-冠-4单晶,属单斜晶系,P2₁/a空间群;a=1.4229(1)nm,b=0.9595(2)nm,c=1.4564(1)nm,β=102.20(1)°,V=1.9435nm³,Z=4.最终偏离因子R=0.043.     

Synthesis of Novel Bis(mesocyclic) polyamines

介绍了带羟基桥连双－（中环多胺）的合成。首先利用Ｎ－对甲苯磺酰基－３－羟基－１，５－二氮杂环庚烷与５种双官能基化合物在Ｎ２气氛下于无水乙腈中反应，得到５种带对甲苯磺酰基的中环多胺，然后利用ＨＢｒ／ＨＯＡｃ脱去保护基团，得到桥连双－（中环多胺）的氢溴酸盐。所有新化合物的结构均经ＩＲ、１ＨＮＭＲ、ＭＳ或元素分析证实。     

N,N-二(2-羟乙基)对甲苯磺酰胺与氯化亚砜的反应

N,N-二(2-羟乙基)对甲苯磺酰胺(1)与SOCl_2反应,通常得化合物2. 文献报道采用过量SOCl_2作溶剂在130～140℃进行反应,但后处理较麻烦,且SOCl_2用量也较大.我们改用二甲苯作溶剂,并减少SOCl_2的用量及采用分次加入的方法,收到了较好的效果.在此反应过程中,意外地获得了一无色针状结晶,根据IR,~1H NMR,MS及元素分析证明此化合物为3.上述反应如控制反应条件可使1全部转化得3.     

Reaction of phenyltrifluorosilane and phenyl(hydrocarbyl)difluorosilanes with bis(2-hydroxyethyl)-and tris(2-hydroxyethyl)amine and their N-methyl and O-trimethylsilyl derivatives. A novel route to quasisilatranes

Reaction of phenyltrifluorosilane, diphenyldifluorosilane, and methylphenyldifluorosilane with bis(2-hydroxyethyl)amine, methyl-bis(2-hydroxyethyl)amine, methyl-bis(2-trimethylsiloxyethyl)amine, leads to 1,3-dioxa-6-aza-2-silacyclooctane derivatives, (N → Si) quasisilatranes: 1,1-difluoroquasisilatrane, 1-phenyl-1-fluoro-5-methylquasisilatrane, or 1-methyl-1-fluoroquasisilatrane, containing the donor-acceptor bond N → Si and pentacoordinate silicon atom. 1-Phenylsilatrane was found to be the product of the reaction of phenyltrifluorosilane with tris(2-trimethylsiloxyethyl)amine, whereas with tris(2-hydroxyethyl)amine 1-phenylsilatrane and 1-fluorosilatrane were formed in the molar ratio of 3:1. The structure of the synthesized compounds was proved by ¹H, ¹³C, ¹⁵N, ¹⁹F, ²⁹Si NMR and IR spectroscopy.     

Synthesis,characterization, optical and anti-bacterial properties of benzothiazole Schiff bases and their lanthanide (III) complexes

Two new Schiff base ligands comprising benzothiazole derivatives, namely (N,N′,E,N,N′E)-N,N′-(1,3-phenylenebis(methanylylidene))bis(5-nitrobenzo[d]thiazoL2-amine (L1) and (N,N′,E,N,N′E)-N,N′-(1,3-phenylene-bis(methanylylidene))bis(5-methylthiazo-L2-amine (L2), have been synthesized and thoroughly characterized using FTIR, ¹H NMR, mass UV/vis and fluorescence spectral techniques. Further, L1 and L2 lead to the formation of lanthanide complexes 1–6 with Ce(III), Nd(III), and Pr(III) ions in 1:2 (metal:ligand) stoichiometry. UV/vis spectra of L1, L2 and 1–6 exhibit characteristic ligand centered absorptions in the range of 230–350 nm. Besides, both ligands and complexes show significant emissions and good anti-bacterial activity against pathogenic bacteria. Ligands and complexes display anti-bacterial activity against bacteria Staphylococcus aureus (S. aureus) (MTCC 1144) causing skin infection and food poisoning and pimple-causing bacteria propionic bacteria acnes (P. acnes) (MTCC 1951).     

Bis(difluorphosphoryl)amin und einige N-Derivate

Bis(difluorophoryl)amine and Some N-Derivatives Preparation and chemical and physical properties of bis(difluorophosphoryl)-amine, its lithium salt and of the N methyl and N trimethylsilyl derivatives are described. The chemical shifts δ(³¹P), δ(¹⁹F), δ(¹H) and numerous coupling constants are tabulated and discussed.     

Synthesis,structure, and photoluminescence properties of molecular complexes of bis(4-formyl-3-methyl-1-phenyl-1<Emphasis Type="Italic">H</Emphasis>-pyrazol-5-olato)cadmium(II) with aminoquinolines and 1-aminoisoquinoline

Molecular complexes of bis(4-formyl-3-methyl-1-phenyl-1H-pyrazol-5-olato)cadmium(II) with isoquinolin-1-amine, quinolin-3-amine, 4,6-dimethylquinolin-5-amine, and quinolin-6-amine have been synthesized, and their structure was studied by IR, UV, ¹H NMR, and X-ray absorption spectroscopy. Photoluminescence properties of the complexes have also been examined.     

Reaction of tetrafluorosilane with tris(2-hydroxyethyl)amine, tris(2-trimethylsiloxyethyl)amine and bis(2-trimethylsiloxyethyl)amine and its N-methyl derivative. 1,1-difluoroquasisilatranes

Reaction of tetrafluorosilane with tris(2-hydroxyethyl)-and tris(2-trimethylsiloxyethyl)amine results in formation of 1-fluorosilatrane and fluorosilatrane in 75 and 53% yield, respectively. Reaction of tetrafluorosilane with bis(2-trimethylsiloxyethyl)amine and its N-methyl derivative leads to the hitherto unknown 1,1-difluoroquasisilatranes (N → Si) F₂Si(OCH₂CH₂)₂NR (R = H, Me) containing donor-acceptor bond N → Si and pentacoordinate silicon atom. The structure of the synthesized compounds was proved by ¹H, ¹³C, ¹⁵N, ¹⁹F, ²⁹Si NMR and IR spectroscopy.     

Synthesis of 4-(2-chloroethyl)-2,3-dihydro[1,4]oxazino[2,3-b]quinoline and 4-(2-chloroethyl)2,3-dihydropyrido[2,3-b][1,4]oxazine

The title compounds were synthesized from 3-[bis(2-hydroxyethyl)amino]quinolin-2(1H)-one 11a and 3-[bis(2-hydroxyethyl)amino]pyridin-2(1H)-one 18 respectively. The preparation involved a tandem chlorination/cyclization reaction.     

A Facile Synthesis of 5-N,N-Bis(2-Hydroxyethyl)Amino-2-Thiophenecarboxaldehyde

Amination of 5-bromo-2-thiophenecarboxaldehyde with an acyclic secondary amine - bis(2-methoxyethyl)amine was effected by using weak base sodium bicarbonate. The resulting 5-N,N-bis(2-methoxyethyl)amino-2-thiophenecarboxaldehyde was treated with boron tribromide to give 5-N,N-bis(2-hydroxyethyl)amino-2-thiophenecarbox- aldehyde.     

Enhancing the Crystallization Performance of Poly(L-lactide) by Intramolecular Hybridizing with Tunable Self-assembly-type Oxalamide Segments

In this work, hydroxyl-terminated oxalamide compounds N~1,N~2-bis(2-hydroxyethyl)oxalamide(OXA1) and N~1,N~(1′)-(ethane-1,2-diyl)bis(N2-(2-hydroxyethyl)oxalamide(OXA2) were synthesized to initiate the ring-opening polymerization of L-lactide for preparation of oxalamide-hybridized poly(L-lactide)(PLA_(OXA)), i.e., PLA_(OXA1) and PLA_(OXA2). The crystallization properties of PLA were improved by the self-assembly of the oxalamide segments in PLA_(OXA) which served as the initial heterogeneous nuclei. The crystal growth kinetics was studied by HoffmanLauritzen theory and it revealed that the nucleation energy barrier of PLA_(OXA1) and PLA_(OXA2) was lower than that of PLA. Consequently, PLA_(OXA) could crystallize much faster than PLA, accompanied with a decrease in spherulite size and half-life crystallization time by 74.8% and 86.5%(T=125 ℃), respectively. In addition, the final crystallinity of PLA_(OXA1) and PLA_(OXA2) was 6 and 8 times higher, respectively, in comparison with that of neat PLA under a controlled cooling rate of 10 ℃/min. The results demonstrate that the hybridization of oxalamide segments in PLA backbone will serve as the self-heteronucleation for promoting the crystallization rate. The higher the content of oxalamide segments(PLA_(OXA2) compared with PLA_(OXA1)) is, the stronger the promotion effect will be. Therefore, this study may provide a universal approach by hybridizing macromolecular structure to facilitate the crystallization of semi-crystalline polymer materials.     

Complex of tris(2-hydroxyethyl)amine with zinc bis(2-methylphenoxyacetate) as an inhibitor of the acid lipase of the aortic intima

The previously unknown ability of Zitrimin, the complex of tris(2-hydroxyethyl)amine with zinc(ii) bis(2-methylphenoxyacetate), to affect the activity of acid lipase of the aortic intima was studied. Daily administration of an aqueous solution of the tris(2-hydroxyethyl)amine complex with zinc bis(2-methylphenoxyacetate) in a dose of 10 mg kg^?1 for 3 months to rabbilts with experimental atherosclerosis was found to decrease the cholesterol and total lipid levels in the aortic tissue and to decrease the degree of aortic damage with atherosclerotic plaques. According to the results of enzymatic analysis, development of atherosclerosis is accompanied by 68% increase in the activity of acid lipase in the intima of the aorta compared to the control.

     

Inhibition of acid phospholipase A1 activity by the complex of tris(2-hydroxyethyl)amine with zinc bis(2-methylphenoxyacetate)

Russian Chemical Bulletin - Studies in the atherosclerosis model in rabbits showed that the complex of tris(2-hydroxyethyl)amine with zinc bis(2-methylphenoxyacetate) (zincatrane) modulates lipid...