AN EFFICIENT SYNTHESIS OF PROPARGYLIC PHOSPHONIUM SALTS

Alkylated propargyl bromides react with phosphiaes in acidic tetrahydrofuran solution to give propargylic phosphonium salts in good yield.

Synthesis, Characterization and Performance of a New Type of Alkylene Triphenyl Double Quaternary Phosphonium Salt

ByBimolecular Nucleophilic Substitution, four new types of alkylene triphenyl double quaternary phosphonium salt were synthesized respectively by using triphenylphosphine, 1,3-dibromopropane, 1,6-dibromohexane,1,10-dibromo- decane, 1,12-dibromododecane as raw materials and using DMAC as the solvent, under a certain temperature and reac- tion time. The productivity is 58% - 83%. The molecular structures of the products were characterized by IR, NMR and elemental analysis. The sterilizing effect of 1,6-hexylidene triphenyl double phosphonium bromide(HTDPB) and 1,12- dodecylidene triphenyl double phosphonium bromide(DoTDPB) was evaluated by using extinct dilution method.The experimental result shows that the sterilizing effect of DoTDPB is better than the effect of HTDPB under the same drug concentration and contact time. When the concentration of DoTDPB was 20 mg/L and the contact time was 0.5 h, the sterilizing rate of DoTDPB used to kill saprophytic bacteria (TGB), sulfate-reducing bacteria (SRB) and iron bacteria (IB) was 95.56%, 84% and 99.58% respectively.

Synthesis and Antibacterial Performance of Quaternary Phosphonium Salts with Reactive Hydroxyl Group

Quaternary phosphonium salts (QPS) with reactive groups used as antibacterial agents are promising which could be covalently linked to inert polymer surfaces by in situ polymerization. In this work, two kinds of quaternary phosphonium salts with hydroxyl groups were synthesized successfully. Characterization of these two quaternary phosphonium salts was performed by the Fourier transform infrared spectroscopy (FT-IR) and nuclear magnetic resonance (NMR) spectrometry. The thermal stability and antibacterial activity of antibacterial agents were also investigated by using thermo-gravimetric analysis, differential scanning calorimetry (TG-DSC) and agar diffusion method. The test results showed that these two QPS exhibited good thermal stability and excellent antibacterial activity against both bacteria: Staphylococcus aureus and Escherichia coli.

POLYMER-SUPPORTED SINGLE AND MIXED AMMONIUM AND PHOSPHONIUM SALTS AS CATALYSTS FOR PHASE-TRANSFER REACTIONS

In this study was to investigate, by phase-transfer catalysis, the activity of single and mixed ammonium and phosphonium salts grafted on a 揼el-type?styrene-7% divinylbenzene copolymer in the oxidation of benzyl alcohol with hydrogen peroxide. A wide variety of catalysts with different quaternary groups and different quaternary chain length substituents were examined. The activity of single 搊nium?salts increases as a consequence of the association of ammonium and phosphonium salts grafted on the same polymeric support. The activity of polymer-supported ammonium and phosphonium salts increases with the number of carbon atoms contained in the alkyl radicals of the onium and of the functionalization degree with phosphonium groups.

ANTIBACTERIAL ACTIVITY OF SINGLE AND MIXED AMMONIUM AND PHOSPHONIUM SALTS GRAFTED ON "GEL-TYPE" STYRENE-DIVINYLBENZENE COPOLYMERS

A systematic study on the synthesis and antibacterial activity of the quaternary "onium" salts grafted on an insoluble "gel-type" styrene-7% divinylbenzene copolymer by polymer-analogous reactions is showed. Antibacterial activity of quaternary ammonium and/or phosphonium salts grafted on polymer-supports has been studied against Staphylococcus aureus and Escherichia coli. A wide variety of "onium" salts bound to macromolecular supports with different quaternary groups and different quaternary chain length substituents were examined. The antibacterial activity of mixed "onium" salts increases as a consequence of the association of ammonium and phosphonium salts grafted on the same polymeric support.

Charge transfer complex enabled photoreduction of ether phosphonium salts for the selective oxyalkylation of enamides

A charge transfer complex(CTC)-enabled photoreduction of ether phosphonium salts for the generation of oxyalkyl radicals was described.The photoreduction provides a convenient method to achieve selective oxyalkylation of enamides with broad substrate scope.The method features operational simplicity,mild and inherent green conditions.

Synthesis and Reactivity of Trifluoromethylthiophosphonium Salts

This article described an unprecedented synthesis of trifluoromethylthiophosphonium salts from allyl trifluoromethyl sulfoxide and phosphines in the presence of trimethylsilyl trifluoromethanesulfonate(TMSOTf)through Mislow-Evans-type rearrangement.The resulting trifluoromethylthiophosphonium salts were firstly isolated and fully characterized.These fluoroalkylphosphonium salts,as exemplified by trifluoromethylthio triphenylphosphonium salt(6a),exhibited unique and versatile reaction with nucleophiles and deoxygenative trifluoromethylthiolation reaction of carboxylic acids.Furthermore,the photoredox catalytic tunable radical hydrotrifluoromethylation and hydrotrifluoromethythiolation of unactivated alkenes with 6a was successfully.

Highly stereoselective construction of polycyclic benzofused tropane scaffolds and their latent bioactivities: bifunctional phosphonium salt-enabled cyclodearomatization process

Structurally fused heterocycles encompassing a centerpiece of benzotropane are significant scaffolds with a plethora of promising biological activities,but such molecular architectures pose a long-standing daunting synthetic challenge.Herein,we reported a highly efficient asymmetric cyclodearomatization of 2-nitrobenzofurans with cyclic azomethine ylides by employing bifunctional phosphonium salts as phase-transfer catalysts.Under optimized reaction conditions,a diverse array of polycyclic benzofused tropane derivatives with four contiguous 4°/3°stereocenters were readily synthesized in both high yields and diastereoselectivities with up to>99%ee.The practicality and utility of this protocol were further demonstrated by the scaled-up reaction and facile elaborations.Moreover,preliminary investigations into their antitumor activities were also presented.

A facile preparation of a novel nonleaching antimicrobial waterborne polyurethane leather coating functionalized by quaternary phosphonium salt

The aim of this research is to develop a novel non-leaching antimicrobial waterborne polyurethane(WPU)leather coating material with covalently attached quaternary phosphonium salt(QPS).The structure of the QPS-bearing WPU has been identified,and their thermal stability,mechanical property,and antimicrobial performance have been investigated.The results reveal that the incorporation of QPS slightly reduces the thermal stability of WPU material but would not affects its usability as leather coating.Despite the presence of hydrophobic benzene in QPS structure,the strong hydration of its cationic groups leads to the increased surface contact angle(SCA)and water absorption rate(WAR)of the films,suggesting that the water resistance of the films needs to be improved for the purpose of leather coatings.Antibacterial tests demonstrate that when the QPS content is 20 wt%,QPS-bearing WPU shows effective antimicrobial activity against bacteria.The WPU containing QPS prepared in this study is a non-leaching antimicrobial material and has great potential application as leather coating.

Novel Stereoselective Synthesis of (E)-a,b-Unsaturated Esters by the Tandem Reaction of Deprotonation-Oxidation-Wittig Reaction from Phosphonium and Arsonium Salt

Phosphonium or arsonium salt 1 can undergo the tandem reaction of deprotonation -oxidation-Wittig reaction with alcohol 2 in the presence of sodium hydroxide and manganese dioxide, which affords a general simplified method for the stereoselective synthesis of (E)- a, b-unsaturated esters 3.

Functionalized COFs with Quaternary Phosphonium Salt for Versatilely Catalyzing Chemical Transformations of CO_(2)

Currently,it encounters great challenges to accomplish catalyzing various kinds of carbon dioxide(CO_(2))conversion reactions efficiently with single catalyst,let alone control the interplay among catalytic efficiency and selectivity evenly.Here,we prepared a functional covalent organic framework,[PTPP]X%-TD-COF[PTPP=3-bromopropyltriphenylphosphonium;TD=1,3,5-tri(4-aminophenyl)benzene-1,4-diformylbenzene],by immobilizing the quaternary phosphonium salt onto the skeleton of COFs through a post-synthesis strategy for versatilely catalyzing reduction of CO_(2) and CO_(2) fixation on epoxide and aziridine facilely.With the typical features of COFs(such as porosity and ordered structure)and catalytic activity of the quaternary phosphonium salt,[PTPP]X%-TD-COF possesses an intensely synergistic effect for catalyzing the chemical transformations of CO_(2).Noteworthily,the quaternary phosphonium salt functionalized COFs catalyze the CO_(2) reduction reaction with amine and phenylsilane to produce formylated and methylated products under gentle reaction conditions with high selectivity and efficiency.Furthermore,[PTPP]_(X%)-TD-COF shows high catalytic ability in CO_(2) chemical fixation reactions.

Thermal stability and long-acting antibacterial activity of phosphonium montmorillonites

Na-montruorillonite (Na-MMT) was exchanged with three quaternary alkylphosphonium salts: decyl tributylphosphonium bromide (DTBPBr), dodecyl tributylphosphonium bromide (DDTBPBr) and hexadecyl tributylphosphonium bromide (HDTBPBr), to investigate the effects of phosphonium salts species and relative molecular mass on the characteristics, morphology, thermal stability and long-acting antibacterial property of phosphonium montmorillonites. The resulting modified montmorillonites were characterized by the FTIR, XRD, TEM, and TG/DTG techniques. And minimum inhibitory concentration (MIC) was used to investigate antibacterial activity. The results show that the phosphonium salts are intercalated into Na-MMT, and the basal spacing of P-MMTs is enlarged with the increase of phosphonium salt content or the growth of alkyl chain length. DDTBP-MMT-3 with 19.83% (mass fraction) of dodecyl tributylphosphonium salts, displays excellent thermal stability and long-acting antibacterial activity.

不同凝聚态季膦盐改性蒙脱土对PP性能的影响

为了改善聚丙烯(PP)的性能,分别以液态的十四烷基三己基氯化磷(THTDP)改性蒙脱土(THTDPMMT)、固态的十六烷基苄基氯化磷改性蒙脱土(BCQPMMT)为添加剂制备PP复合材料,着重考察改性剂凝聚态及结构对PP复合材料性能的影响。通过傅里叶变换红外光谱、热重分析、X射线衍射(XRD)、透射电子显微镜(TEM)和扫描电子显微镜进行表征。结果表明,THTDP较BCQP更易插入蒙脱土层间,更易扩大蒙脱土(001)面的片层间距,使蒙脱土颗粒更蓬松,更有利于PP分子链插入MMT层间。XRD和TEM结果表明,PP/THTDPMMT复合材料较PP/BCQPMMT复合材料中MMT (001)面的片层间距更大,MMT在PP基体中的分布分散更好。差示扫描量热分析结果表明,PP/THTDPMMT复合材料较PP/BCQPMMT复合材料具有更高的结晶温度和熔融温度,且均高于纯PP。动态力学分析结果表明,PP/THTDPMMT复合材料较PP/BCQPMMT复合材料具有更高的储能模量,且均高于纯PP。力学性能测试表明,PP/THTDPMMT复合材料较PP/BCQPMMT复合材料具有更优异的拉伸强度、冲击强度、弯曲强度和弯曲弹性模量,且均高于纯PP。

一种新型硅胶固载季鏻盐杀菌剂的制备和性能研究

用γ-胺丙基-三乙氧基硅烷(KH550)和卤代烷基三苯基膦溴化物反应,制得硅胶固载季鏻盐杀菌剂。此反应是伯胺的双分子亲核取代反应(SN2反应),研究表明:KH550与溴代烷基三苯基膦溴化物摩尔比为2:1,无水乙醇为溶剂,在此条件下,首先用无水乙醇溶解溴代烷基三苯基膦溴化物,再逐滴加入,产物的产率较高。生产的季鏻化硅烷偶联剂的结构组成通过红外光谱和核磁共振手段进行表征,验证了各步反应的进行并确认其结构。杀菌性测试表明杀菌剂用量为10mg·mL-1时,40min后对异养菌的杀菌率可达100%,重复杀菌4次后杀菌性能减到75%左右,再生后杀菌性能可恢复到96%以上。

抗菌防霉剂的研究进展及其在纺织品中的应用

介绍了国内外无机、有机、天然抗菌防霉剂的研究进展以及其在纺织品上的应用。具体包括金属离子型抗菌剂,TiO2等光催化氧化型抗菌剂,金属离子光催化氧化物型复合纳米抗菌剂,有机无机复合抗菌剂,双胍类、卤代胺类、苯酚、季铵盐类、季鏻盐类等有机抗菌剂,壳聚糖及其衍生物等天然抗菌剂。着重介绍了季铵和季鏻盐类有机抗菌剂。对纤维和纺织品抗菌处理方法进行了分类,有共混纺丝法、纤维化学改性法、复合纺丝法、纤维整理法、纺织品后整理法。对抗菌防霉性及安全性检测方法进行了概述,并对抗菌剂的发展进行了展望。

季鏻盐改性蒙脱土的制备及性能

采用离子交换法将不同的季鏻盐交换到钠基蒙脱土的层间得到改性蒙脱土,并对改性蒙脱土的结构和性能进行了研究。热重量法和X射线衍射分析的结果表明,季鏻盐已插入蒙脱土的层间,并且季鏻盐改性蒙脱土中有机物的热分解起始温度比季铵盐改性蒙脱土的热分解起始温度提高30℃;解吸试验的结果表明,改性蒙脱土中的季鏻盐在水和0.9%NaCl溶液中都很稳定。钠基蒙脱土对金黄色葡萄球菌(S.aereus)和大肠杆菌(E.coli)的最低抑菌浓度均大于2 g/L,而当插入季鏻盐后,其最低抑菌浓度大幅度降低,如十四烷基三丁基季鏻盐改性蒙脱土对S.aereus和E.coli的最低抑菌浓度分别为12.5 mg/L和200.0 mg/L。随着季鏻盐改性蒙脱土浓度的增加和接触时间的延长,改性蒙脱土的抗菌性能增强。

有机抗菌剂研究的新进展

按照构效关系综述了双委铵盐、季铵盐和含氮杂环的盐化合物及具有高效、快速、广谱抗菌性的季盐阳离子表面活性剂型抗菌剂以及聚氮阳离子、聚磷阳离子抗菌剂。相似结构的聚季盐较聚季铵盐有更佳的抗菌性。水不溶性聚合物抗菌剂较之水溶性抗菌剂具有更优异的性能。它有望成为水处理抗菌剂的发展方向之一。

壳聚糖/烯丙基三苯基氯化磷抗菌材料的制备

以硝酸铈铵为氧化还原引发剂,在氮气保护下,研究了壳聚糖(CTS)与烯丙基三苯基氯化磷在2%的乙酸溶液中的接枝共聚反应,制备出具有较好抗菌性能的CTS/烯丙基三苯基氯化磷抗菌材料。重点讨论了反应时间、反应温度、引发剂浓度和烯丙基三苯基氯化磷用量对接枝共聚反应的影响。结果表明,当反应温度为60℃、反应时间为5.0h、引发剂用量为3.5mL(Ce4+质量浓度为0.01g/mL)、烯丙基三苯基氯化磷用量为0.5g、CTS用量为0.2g时,接枝率最高,可达48.2%。与CTS相比,CTS/烯丙基三苯基氯化磷的亲水性和热稳定性都得到了提高,且其对大肠杆菌和金黄色葡萄球菌有较高的抗菌活性。

THP盐与双氰胺原位结合鞣研究

确定了四羟甲基氯化鏻(THPC)与皮粉的最佳作用条件,研究了THPC单独用作鞣剂及其与双氰胺原位结合鞣时pH、用量对鞣革收缩温度(Ts)的影响,并对四羟甲基鏻盐(THP盐)鞣革性能进行了分析。实验结果表明,THPC与皮粉的最佳作用条件为pH=10.0,w(THPC)=60%(以皮粉质量计),温度40℃,时间1.5 h;THPC单独用作鞣剂时,pH=6.0时,Ts=75.5℃;在与双氰胺结合鞣时,四羟甲基硫酸鏻(THPS)的鞣制效果优于THPC;THP盐与双氰胺最佳摩尔比为n(THPS)∶n(双氰胺)=0.41∶1,n(THPC)∶n(双氰胺)=1.76∶1;THPS与双氰胺结合鞣革的抗张强度和撕裂强度分别为11.45 MPa、20.76 N/mm,氧指数为34.7%,有一定的阻燃性。

蒙脱土表面改性研究进展

蒙脱土(MMT)是一种制备纳米复合材料常用的层状硅酸盐。本文从MMT的结构出发,首先介绍了MMT的改性机理、改性剂在MMT层间的构象、排列和分布;重点阐述了季铵盐、季膦盐、咪唑盐、过渡金属离子及功能性单体等改性蒙脱土,并对改性蒙脱土的结构、性能和应用加以介绍。