主链型阳离子表面活性剂聚季铵盐的制备

以N,N-二甲基-1,3-丙二胺、尿素及1,4-二氯丁烷为原料,通过共缩聚反应两步法制备了一种新的主链型的水溶性聚季铵盐.采用正交试验获得了制备聚季铵盐的最佳条件：N,N-二甲基-1,3-丙二胺与尿素的物质的量比为2∶1,反应温度为135℃,反应时间为11h,得到中间体双[3-（N,N-二甲基丙胺基）]丙脲,产率高达99％;中间体与1,4-二氯丁烷的物质的量比为1∶1,于90℃下反应6h.采用红外光谱和核磁氢谱对产物结构进行表征,测定了其热稳定性和特性粘数.     

一种新型甜菜碱两性表面活性剂的合成及其性能

N,N-二甲基-1,3-丙二胺(1)与丙烯酸甲酯经Michael加成反应制得N,N-二甲基-N′-甲氧酰丙基-1,3-丙二胺(2); 2经胺基保护、季铵盐化及水解反应合成了一种新型的甜菜碱两性表面活性剂(6),其结构经¹H NMR, IR和ESI-MS表征。通过电导率法测得6的CMC为1.48×10^-4mol·L^-1,滴体积法测得γ_CMC为39.99 mN·m^-1, Krafft点小于0 ℃。乳化与泡沫性能研究结果表明：6具有较好的表面活性,且乳化性和泡沫性能优良。     

新型N-取代苯基-苯磺酰脲类化合物的合成

以4-氟苯磺酰氯或4-三氟甲基苯磺酰氯为原料,经氨化反应制得4-氟苯磺酰胺（2a）和4-三氟甲基苯磺酰胺（2n）;不同取代苯胺分别与三光气（BTC）反应制得一系列取代苯基异氰酸酯（4a~4m, 4t和4I）; 2分别与4经缩合反应合成了27个新型的N-取代苯基-4-氟（或三氟甲基）苯磺酰脲类化合物,其结构经1H NMR, IR和ESI-MS表征。     

尼达尼布的合成新方法

以N-甲基-4-硝基苯胺作为起始原料,依次经氯乙酰化、取代及氢化还原反应制得关键中间体N-(4-氨基苯基)-甲基-2-(4-甲基-1-哌嗪基)乙酰胺（4）;以4-氯-3-硝基苯甲酸为原料,依次经酯化、取代、氢化还原及环合反应制得6-甲氧羰基-2-吲哚酮（8）; 8与原苯甲酸三乙酯和乙酸酐经“一锅煮”反应制得中间体1-乙酰基-3-甲氧基(苯基)亚甲烯基-2-氧代吲哚环-6-羧酸甲酯（9）; 4和9进行取代反应的同时脱除保护,经“一锅煮”反应合成尼达尼布,总收率57.2%,其结构经¹H NMR,¹³C NMR和MS(ESI)确证。     

4-(N-乙基-3-甲基苯胺基）丁酸甲酯的合成

以γ-丁内酯为起始原料,经开环氯化和醇解反应合成4-氯丁酸甲酯（2）; 2与N-乙基间甲苯胺经亲核取代反应合成了4-(N-乙基-3-甲基苯胺基）丁酸甲酯,纯度97.5%,总收率75.3%,其结构经¹H NMR确证。     

低分子量N,O-羧甲基壳聚糖的合成及吸湿保湿性能

采用不同反应温度、反应时间和低分子量壳聚糖与氯乙酸摩尔比,在非均相反应体系中合成了不同取代度的低分子量N,O-羧甲基壳聚糖。当反应温度为60°C,反应时间为4h,低分子量壳聚糖与氯乙酸投料比为1∶1.5时,目标产物的取代度可达71%。吸湿保湿性能测定表明:取代度越大,低分子量N,O-羧甲基壳聚糖的吸湿保湿性越好,在相对湿度为81%,取代度从27%增大到71%时,其吸湿性从32.14%增大到37.27%,保湿性从310.72%增大到348.69%。     

两亲型羧甲基壳聚糖衍生物的合成及体外药物释放

通过羧甲基壳聚糖与醛和乳糖反应制得N-烷基乳糖基-O,N-羧甲基壳聚糖,并以戊二醛为交联剂制成水凝胶;以人血清蛋白作为模型药物,初步探讨了该水凝胶对蛋白类药物的释放规律。结果表明:该水凝胶具有亲水-疏水两亲性和不同于壳聚糖的pH敏感性,有望应用于蛋白类药物的控制释放。     

羟丙基壳聚糖的制备

用环氧丙烷改性壳聚糖得羟丙基壳聚糖 ,确定制备的最佳条件为 :壳聚糖 2 .5 g,环氧丙烷 3 0mL ,反应时间 4h,反应温度 60℃～ 70℃。所得羟丙基壳聚糖的特性粘度可低至 2 5mL·g-1,3 0℃溶解度为 7g·(H2 O1 0 0mL) -1。     

甲磺酸洛美他派的合成工艺改进

以9-芴甲酸为起始原料经亲核取代反应和N-酰基化反应制得N-(2,2,2-三氟乙基)-9-(4-溴丁基)-9H-芴基-9-甲酰胺(4);4'-(三氟甲基)-[1,1'-联苯]-2-羧酸与N-叔丁氧羰基-4-氨基哌啶反应制得中间体N-(1-叔丁氧羰基哌啶-4-基)-4'-(三氟甲基)-[1,1'-联苯]-2-甲酰胺(7);7在4 mol·L-1HCl二噁烷溶液中脱除保护基制得N-(哌啶-4-基)-4'-(三氟甲基)-[1,1'-联苯]-2-甲酰胺盐酸盐(8);8与4在K2CO3作用下反应制得洛美他派(9);9与甲磺酸经成盐反应合成了甲磺酸洛美他派,总收率36.4%,其结构经1H NMR,IR和HR-ESIMS确证。     

高取代度羧甲基壳聚糖的制备

用非质子溶剂法,以DMSO-H2O为溶剂,在碱性条件下壳聚糖(CTS)与氯乙酸反应,制得取代度为1.93的羧甲基壳聚糖(CMC)。较适宜的反应条件为:CTS 1 g,m(氯乙酸)∶m(CTS)=5∶1,w(NaOH)=35%(以CTS质量计算),w(十六烷基三甲基溴化铵)=5%(以CTS质量计算),于50℃反应6 h。用XRD和IR对CMC进行表征,结果表明CTS的-OH参与了羧甲基化反应,-NH2没有参与反应。     

羟丙基三甲基氯化铵壳聚糖的制备及其吸湿、保湿性能

抑菌活性;羟丙基三甲基氯化铵壳聚糖的制备及其吸湿、保湿性能     

新型双苯基型季铵盐Gemini表面活性剂的合成及其表面活性

以水杨醛和1,2-二溴乙烷为原料,经Williamson反应、氧化反应、酰氯化反应和酰胺化反应制得酰胺化合物（3）; 3与溴代正癸烷经季胺化反应合成了新型双苯基型季铵盐Gemini表面活性剂（4）,其结构经¹H NMR和IR表征。表面活性测试结果表明：4具有优异的抗酸、抗盐性能。在0.1 mol·L^-1NaCl溶液中, γ＝36.8 mN·m^-1, CMC＝0.20 mmol·L^-1;在HCl（pH 1）溶液中, γ＝32．5 mN·m^-1, CMC＝0.16 mmol·L^-1。     

甲壳素类液晶高分子的研究Ⅵ.邻苯二甲酰化壳聚糖中酰胺酸取代度对液晶性的影响

通过控制不同反应时间和邻苯二甲酸酐 壳聚糖的摩尔比制备不同取代度的邻苯二甲酰化壳聚糖(PHCS) .用FTIR研究了反应机理和产物结构 ,观察到PHCS含两类取代即酰胺酸取代和酰亚胺取代 .反应时间较短时主要为前者 ,取代度表示为DS1 ;反应时间较长时主要为后者 ,取代度表示为DS2 .对PHCS在二氯乙酸 (DCA)中的液晶行为观察 ,结果表明 ,PHCS的临界浓度随DS1 的增加而显著增加 .DS1 对PHCS临界浓度的影响明显大于DS2 的影响 .基本上为酰胺酸取代的PHCS的临界浓度高于溶解度 ,以至于观察不到     

Synthesis,Characterization and Antioxidant Activity of Quaternized Carboxymethyl Chitosan Oligosaccharides

In order to determine the effect of quaternary ammonium groups and carboxymethyl groups of chitosan on antioxidant activity, nine quaternized carboxymethyl chitosan oligosaccharides (QCMCOs) were prepared from chitosan with chloroacetic acid and 2,3-epoxypropyltrimethyl ammoniumchloride as the modifying agent under microwave irradiation. The structures of QCMCOs were characterized by FT-IR, NMR, XRD and their Mw were detected by gel permeation chromatography (GPC). The thermal stability was evaluated by thermal gravimetric analysis (TGA), and their antioxidant activities were investigated including scavenging activity of superoxide and hydroxyl radical, reducing power and metal chelating ability. The results revealed that the introduction of quaternary ammonium groups and carboxymethyl groups decreased the crystallinity and the thermal stability of chitosan oligosaccharide (COS), and their antioxidant activities were closely related to the degree of substitution of quaternary ammonium groups and the carboxymethyl groups. This study provides important guidelines for developing new antioxidant agents.     

Cellulosic polyelectrolytes: synthetic pathways to regioselectively substituted ammonium and phosphonium derivatives

Cationic polysaccharide polyelectrolytes are important synthetic targets for drug and gene delivery, especially by encapsulation of nucleic acids and proteins through electrostatic interactions. They also have potential as paracellular permeability enhancers that may increase transport across the gastrointestinal (GI) epithelium, especially for therapeutic hydrophilic macromolecules. Semisynthetic chitosan has been more heavily investigated as a cationic polysaccharide polyelectrolyte. This study explores the synthetic conditions needed to produce ammonio and phosphonio cellulose derivatives regioselectively by halogen displacement at C-6 while maximizing the degree of substitution (DS) of cationic substituent. Regioselective substitution was successful, however there were found to be some limitations to the DS and solubility of ammonium derivatives prepared in this way (highest DS 0.43); conversely, water-soluble 6-phosphonio-6-deoxycellulose derivatives were produced with DS > 0.5, with highest DS of 0.73. The repulsion between accumulating positive charges was confirmed as a likely source of DS limitation since high DS (0.9) of 6-triethylamino cellulose was synthesized under comparable conditions. Further reaction of 6-ammonio-co-6-bromo derivatives with a thiol produced 6-ammonio-co-6-thiolated products with improved aqueous solubility. The thiol DS of 0.68 determined by elemental analysis confirmed substitution of residual bromide from low DS (0.30) ammonium products to give essentially complete substitution at C-6.     

4，5-环氧-α-紫罗兰酮的合成研究

研究以H2O2为氧化剂,钨酸钠／磷酸／十六烷基氯化毗啶原位合成的过氧钨配合物催化α-紫罗兰酮合成4,5-环氧-α-紫罗兰酮的反应,考察了催化剂用量、反应温度、反应时间、pH值、溶剂及季铵盐等因素对反应的影响。结果表明,以1,2-二氯乙烷作溶剂,nα-紫罗兰酮：n钨酸钠：n磷酸：n十六烷基氯化吡啶：n过氧化氢=100：0.3：0．1：0．2：120,pH值为4．0,65℃的条件下反应6h,收率可达85％,其结构通过MS、^1H-NMR、IR、EA等检测技术进行表征。     

四氯合钴(Ⅱ)-4-氯苄基吡啶季铵盐的制备及其晶体结构和抗菌性能

合成了1种含四氯合钴配阴离子的4-氯苄基吡啶季铵盐[4-ClBzPy]2[CoCl4];利用元素分析仪、X射线单晶衍射仪以及紫外光谱仪和红外光谱仪等分析了其组成、晶体结构及光谱学性质;利用电导仪测定了[4-ClBzPy]2[CoCl4]的电导,并检测了其对金黄色葡萄球菌和大肠杆菌的抗菌活性.结果表明,合成的[4-ClBzPy]2[CoCl4]季铵盐为单斜晶系,P2(1)/c空间群,晶胞参数为a=0.769 5(13)nm,b=1.895 1(3)nm,c=0.946 3(15)nm,β=93.183(2)°,V=1.378 0(4)nm3,Z=2,Dc=1.470g/cm3,GOOF=1.007,R1=0.041 8,wR2=0.100 2.与此同时,季铵盐[4-ClBzPy]2[CoCl4]对金黄色葡萄球菌和大肠杆菌均具有较好的抗菌活性.     

阳离子改性壳聚糖的合成工艺

弱碱性条件下,在壳聚糖（CTS）上引入2-羟丙基三甲基氯化铵（CTA）基团,使其阳离子化。采用正交试验通过测定合成产物的取代度确定其最佳合成条件,再用红外光谱对产物结构进行表征。结果表明：CTS/CTA质量比=1∶5,溶胀时间60 min,碱化温度35℃,反应温度60℃,反应时间9 h为该工艺的优化条件,在此条件下合成...     

在苯-乙醇介质中生成的羧甲基纤维素取代基分布的研究

以三组份两相液体苯 乙醇 水为介质合成羧甲基纤维素（ＣＭＣ），应用１Ｈ ＮＭＲ谱图分析了ＣＭＣ中羧甲基在葡萄糖单元（ＡＧＵ）的Ｃ２、Ｃ３及Ｃ６位上对羟基的取代分布．结果表明，取代基的分布顺序是Ｃ６＞Ｃ２＞Ｃ３；当取代度（ＤＳ）低于１０时，Ｃ２∶Ｃ３∶Ｃ６近似于１４５∶１∶２１５；ＤＳ高于１０以后，分布趋于相同，通过对ＣＭＣ的Ｘ 衍射分析解释了取代基分布规律．同时研究了苯的影响，证实相同取代度下，在苯 乙醇 水中生成的ＣＭＣ试样，其Ｃ６位取代基分布多于在乙醇 水中生成的试样．     

Binding cellulose and chitosan via click chemistry: Synthesis,characterization, and formation of some hollow tubes

A novel cellulose‐click‐chitosan polymer was prepared successfully in three steps: (1) propargyl cellulose with degrees of substitution (DS) from 0.25 to 1.24 was synthesized by etherification of bamboo Phyllostachys bambusoide cellulose with propargyl chloride in DMA/LiCl in the presence of NaH. The regioselectivity of propargylation on anhydrous glucose unit determined by GC‐MS was in the order of 2 >> 6 > 3; (2) the functional azide groups were introduced onto the chitosan chains by reacting chitosan with 4‐azidobenzoic acid in [Amim]Cl/DMF and the DS ranged from 0.02 to 0.46; (3) thus, the cellulose‐click‐chitosan polymer was obtained via click reaction, that is, the Cu(I)‐catalyzed Huisgen 1,3‐dipolar cycloaddition reaction, between the terminal alkyne groups of cellulose and the azide groups on the chitosan backbone at room temperature. The successful binding of cellulose and chitosan was confirmed and characterized by FTIR and CP/MAS ¹³C NMR spectroscopy. TGA analyses indicated that the cellulose‐click‐chitosan polymer had a higher thermal stability than that of cellulose and chitosan as well as cellulose–chitosan complex. More interestingly, some hollow tubes with near millimeter length were also observed by SEM. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012