聚对苯二甲酰十碳二胺的制备和非等温结晶动力学研究

以对苯二甲酸和癸二胺为原料,经成盐,预聚合和固相聚合三个步骤合成了新型长碳链和较高相对分子质量的半芳香尼龙聚对苯二甲酰十碳二胺,由红外光谱和核磁共振对其结构进行了确认。用DSC方法研究了聚对苯二甲酰十碳二胺的非等温结晶动力学,用莫志深提出的R～f法对非等温结晶动力学进行了分析,由R～t法得到α值在0.70～0．81之间。利用Kissinger方法求得了半芳香尼龙的非等温结晶活化能,△E=-297．08kJ／mol。     

Salen型铜(Ⅱ)和镍(Ⅱ)配合物的合成与电化学性质

合成了2种salen型配体及其具有N2O2配位模式的salen型铜、镍金属配合物ML1和ML2[M=Cu,Ni;salen型配体L1=N,N'-双(4-羟基-邻羟苯亚甲基)-2,2'-联苯二胺;L2=N,N'-双(3,5-二叔丁基-邻羟苯亚甲基)-2,2'-联苯二胺];并通过核磁共振波谱(1H NMR)、电喷雾质谱(ESI-MS)、红外光谱(FT-IR)、紫外-可见光谱(UV-Vis)和元素分析等对配体及目标金属配合物进行了表征。循环伏安法电化学研究发现,在-1.5~+1.5 V电势扫描中,CuL2和NiL1只有一组单电子准可逆氧化还原过程,而NiL2发生了两次氧化还原反应。     

化学计量学和红外光谱研究3,5-二氨基-1,2,4-三唑合成机理

通过红外光谱在线监测3,5-二氨基-1,2,4-三唑(DAT)的合成过程,应用多元曲线分辨-交替最小二乘法(MCR-ALS)对过程中获得的光谱数据矩阵进行解析,推导出合理的反应机理.反应以水为背景,依次加入二氰二胺与二盐酸肼固体,用红外探头监测反应全过程.用MCR-ALS法对所得光谱数据进行解析,得到反应物、中间体和产...     

Bola型表面活性剂N,N′-二苯丙氨酸酰基-1,8-辛二胺的合成及性质研究

以L-苯丙氨酸为亲水部分和1,8-辛二胺为疏水部分,通过酯化生成酰胺和HCl脱去BOC保护基两步反应,合成一种新型Bola型表面活性剂N,N′-二苯丙氨酸酰基-1,8-辛二胺(DAOPh),采用IR、质谱和~1H NMR对其结构进行了表征.应用酸碱滴定法测得其pKa,采用电导率法、表面张力和芘荧光探针法测定了DAOPh水溶液的临界胶束浓度(CMC),进而预测其在水溶液中的聚集行为,探讨其作为药物载体的潜在优势.     

[N,N-二-(2-氯乙基)]-O-[O′,O′-二烷基膦酰甲基]-N′,N′-二烷基磷酰二胺的合成及性质研究

合成了6种含有氮芥结构及膦酰甲基取代基的磷酰二胺。其结构经~1H NMR、MS和元素分析确定,讨论了它们的性质,并对部分化合物的抗癌活性进行了初步试验。     

含哒嗪环聚酰亚胺的合成及性能表征

以马来酸酐为原料与水合肼反应得到哒嗪酮,再与三氯氧磷反应制备3,6-二氯哒嗪中间体,哒嗪中间体与间氨基苯酚通过亲核取代反应合成了一种新的二胺单体——3,6-二(3-氨基苯氧基)哒嗪.通过1HNMR,FTIR及HPLC-MS确证了哒嗪二胺及中间体的结构.这种哒嗪二胺单体与6种芳香二酐单体——均苯四甲酸二酐(PMDA)、3,3',4,4'-联苯四甲酸二酐(BPDA)、4,4-六氟异丙基邻苯二甲酸酐(6FDA)、3,3',4,4'-二苯甲酮四甲酸二酐(BTDA)、3,3',4,4'-二苯醚四甲酸二酐(ODPA)和双酚A型二醚二酐(BPADA)通过两步法聚合制备了一系列的聚酰亚胺,并对其结构和性能进行了研究.结果表明,聚酰胺酸的比浓对数黏度为0.37~0.50 dL/g,该系列聚酰亚胺膜具有良好的热稳定性和机械性能,玻璃化温度(Tg)为188~241℃,氮气氛围下5%和10%热失重分别为421~448℃和447~473℃,拉伸强度(TS)高达102 MPa,断裂伸长率(EB)为2.0%~6.5%.紫外可见光谱测试得到的截止波长(λcut-off)为367~389 nm.     

芳醚砜二胺、芳醚砜双马来酰亚胺的合成及共聚树脂的性能研究

通过在三种不同的溶剂一碱体系中合成芳醚砜二胺的研究，确定了最佳的合成路线。用酸碱法对产物进行了纯化，进而合成了芳醚砜双马来酰亚胺。热重分析表明，芳醚砜双马来酰亚胺／芳醚砜二胺共聚树脂具有较高的热和热氧稳定性。     

双水杨醛缩环己二胺类西佛碱及其配合物的合成、性质研究

合成了两种双水杨醛缩环已二胺类西佛碱N，N’-(二羟苯次甲基)环已二胺(1)和N，N’-二(3，5-二叔丁基-2-羟苯次甲基)环已二胺(2)，以及它们的金属锌配合物(3)和(4)，通过核磁共振、元素分析和红外光谱确定了四种物质的结构，研究了它们的紫外吸收光谱、荧光光谱，测定了(3)和(4)的荧光量子效率．(4)中四个叔丁基的存在使其荧光量子效率提高．此类双西佛碱金属配合物可以应用于有机电致发光材料中．     

硼化合物研究(ⅩⅣ)——含硼双(π-芳烃)铁(Ⅱ)化合物的合成与性质

合成了13个新的双(π-芳烃)铁(Ⅱ)化合物,对它们进行了元素分析和红外光谱测定,部分化合物还做了质谱和~1H核磁共振谱的鉴定。通过DTATG法,研究了化合物的热行为。     

邻菲罗啉聚西佛碱金属配合物的合成及磁性能研究

以5,6-二胺-1,10-菲罗啉与2,6-吡啶二甲酸缩聚合成得到一种新的含邻菲罗啉结构的聚西佛碱,并制备了其相应的与过渡金属离子Ni2+和Fe2+以及稀土离子Nd3+的配合物,通过红外光谱,核磁共振和元素分析等手段对聚合物及其金属配合物的结构进行了表征,并分析和讨论了它们的磁学性能.结果表明,这一类金属配合物在低温区,...     

Sulfur-containing polymers. II. Preparation and properties of polycarbamoylsulfenamides

Polycarbamoylsulfenamides have been prepared by interfacial and solution polycondensation of chlorocarbonylsulfenyl chloride with diamines. In preparing the polycarbamoylsulfenamides, the following types of diamines were used: primary aliphatic diamines, a mixed primary-secondary aliphatic diamine, primary aromatic diamines, and secondary aromatic diamines. The properties of the resulting polymers depended primarily on the kind of diamines used. Transparent, tough films were obtained from the polymer based on N,N′-dimethyl-4,4′-diaminodiphenylmethane. The photochemical decomposition of the polymers has been studied.     

Microwave assisted cyclocondensation of dialdehydes with chiral diamines forming calixsalen type macrocycles

Microwave irradiation of various dialdehydes and chiral diamines afforded chiral macrocyclic imines in moderate to good yields. Linked dialdehydes predominantly form [2+2] macrocycles whereas dialdehydes without linkers yield [3+3] macrocycles. This is the first report of template-free synthesis of calixsalen-type macrocycles formed in shorter reaction times under microwave conditions. In all the reactions, the salts of chiral diamines were used in contrast to the free diamines normally employed.     

A Rapid HPLC Determination of C2–C7 Aliphatic Diamines by Precolumn Derivatization with Acetylacetone in Methanol-Water

A rapid reversed-phase high performance liquid chromatographic analysis for the determination of seven aliphatic diamines in water is described. Precolumn derivatization with acetylacetone is used for traces of aliphatic diamines in water-methanol (10:1 v/v) medium. The acetylacetone derivatives obtained after 15 min were extracted with an octadecylsilane functionalized silica cartridge, and then injected into the HPLC system. The HPLC system consisted of a reversed-phase column, and a spectrophotometric detector adjusted to 310 nm as elution solvent a methanol-tetrahydrofuran-water (55:3:42 v/v) mixture was used. The acetylacetone derivatives of the C2-C7 diamines were separated with a good resolution in 23 min. The detection limits achieved for each diamine were between 0.18-0.72 ng/ml for a 100 ml water sample. The recovery of diamine derivatives from river and seawater was 88-101%, with relative standard deviations of 2.2-4.0%, and 82-93%, with relative standard deviations of 2.8-4.6%, respectively. Aliphatic diamines are widely used as chemical reagents, occur as metabolic in biomedical studies and are used as chelating agents in analytical chemistry. As they are soluble in water, their use results in their ultimate release to the environment. The need for a sensitive, selective and rapid determination of aliphatic diamines in environmental samples thus has become important. Dobberpuhl et al. [1] have described a highly sensitive pulsed electrochemical detection for aliphatic monoamines and diamines following their chromatographic separation. Although, it is a sensitive method the determination has to be carried out in alkaline conditions. The most common method for the determination of aliphatic amines is high performance liquid chromatography (HPLC), using different derivatives with either fluorescence [2-5] or UV-visible detection [6-11]. The fluorescence detection method most often relies on post-column derivatization, which requires a second pump to deliver the reagent. Acetylacetone is soluble to some degree in water, and has been used as a pre-column derivatization reagent [12]. The reaction only is effective with diamines, and results in UV-active acetylacetone derivatives known as Schiff bases. But acetylacetone requires a long reaction time in water, which makes it rather unsuitable for routine analysis. In this paper an optimized reversed-phase HPLC determination procedure for C2-C7 aliphatic diamines at low ng/ml levels in water is described.     

Ab Initio Quantum Mechanical Study on the Origin of the pK(a) Differences of the Proton Sponges 1,8-Bis(dimethylamino)naphthalene, 1,8-Bis(dimethylamino)-2,7-dimethoxynaphthalene, 1,6-Dimethyl-1,6-diazacyclodecane, and 1,6-Diazabicyclo[4.4.4]tetradecane

Ab initio quantum mechanical calculations were used in studying the origin of the exceptionally high basicities of four diamines (13-16) with pK(a1) values ranging from 12.1 to 25. The computational approach involved the calculation of the gas-phase proton affinities of the molecules studied at the MP2/6-31G//HF/6-31G level and the solvation energies with the polarizable continuum model at the HF/6-31G level. The calculated gas-phase and aqueous-phase proton affinities of a structurally diverse series of amines were compared with the corresponding experimental gas-phase proton affinities and pK(a1) values. The calculated values were found to be in reasonable agreement with the experimental ones. The high basicities of the studied diamines were found to originate from the nitrogen lone-pair repulsion, solvation effects, and strong intramolecular hydrogen bonds. Each of these factors were found to be able to increase the pK(a1) values of the high-basicity diamines by 2-6 pK(a) units. The relative contributions of the factors varied between the compounds. The nitrogen lone-pair repulsion was estimated to be the most important factor in increasing the pK(a1) values. In addition, barriers for proton transfers between the nitrogens of selected diamines were calculated, and comparison was made between the barrier heights and the geometries of the diamines.     

双烷基及双（β－烷氧羰乙基）锡聚胺的合成及性质的研究

利用界面缩聚技术，将二烷基或二（烷氧羰已基）二氯化锡与有机二胺反应，制成了５８种有机锡聚胺大分子化合物，研究了部分聚胺对ＰＶＣ树脂热稳定性的影响，取得了有意义的结果。     

Novel tricyclic diamines 2. Synthesis of 1,7-diazaisoadamantane, 1,5-diazaisoadamantane and 1,6-diazahomobrendane

Three novel tricyclic diamines (1,7-diazaisoadamantane, 1,5-diazaisoadamantane and 1,6-diazahomobrendane) were prepared. A flexible synthetic strategy was employed which used flat, aromatic azaindoles as the starting materials. The requisite azaindoles were prepared by a tandem Sonogashira coupling/intramolecular cyclization reaction. Ring saturation, appropriate functionalization and intramolecular alkylation provided the three novel tricyclic diamines cores.     

Synthesis of C2-symmetrical chiral diamines: diastereoselective addition to bis(1,3-oxazolidinyl)alkanes with Grignard reagents

Asymmetric syntheses of C₂-symmetrical chiral 1,4- and 1,5-diamines with stereogenic centers adjacent to the nitrogen atom have been accomplished. Chiral diamines were prepared by diastereoselective alkylations of bisoxazolidine, which was derived from (R)-phenylglycinol. Methyl and phenyl Grignard reagents were employed as alkylating reagents. In addition, tertiary chiral diamines were readily converted to primary diamines in high yield.     

New poly(amide-imide) siloxane copolymers by polycondensation

Some new poly(amide-imide) siloxane copolymers have been synthesized by solution polycondensation of some aromatic diamines with siloxanic diacids having preformed imide rings. Two polycondensation techniques were used: polycondensation of aromatic diamines with diacid chlorides and direct polycondensation of aromatic diamines with diacids in the presence of organic phosphites, following the Yamazaki-Higashi phosphorylation technique. In all cases the reactions were carried out using equimolecular amounts of the two monomers, in polar aprotic solvents and inert atmosphere.The obtained compounds were characterized by elemental C, H and Si analysis, solubility tests, IR and ¹H-NMR spectrometry. Thermogravimetric curves were also recorded. All data agree with the proposed structures.     

Synthesis and antiviral activities of N-mono- and/or N,N'-di-carbamoyl and acyl derivatives of symmetrical diamines

N-carbamoyl and N-acyl diamine derivatives were synthesized from symmetrical diamines by their addition to iso(thio)cyanates, cleavage reaction of acid anhydride, or N-acylation by acyl chloride. (1R,2R)-1,2-Diaminocyclohexane [(1R,2R)-1], meso-1,2-diaminocyclohexane (meso-1), (1R,2R)-1,2-diphenylethylenediamine [(1R,2R)-3], or meso-1,2-diphenylethylenediamine (meso-3) were used as the starting symmetrical diamines. The target compounds synthesized herein were evaluated for antiviral activity with herpes simplex virus type 1 (HSV-1). A few derivatives of 1,2-diaminocyclohexane [(1R,2R)-7aa and cis-7b] with adamantyl group(s) showed significant antiviral activity (EC(50)=16.0, 27.0 microg/ml).     

Small diamines as modifiers for phosphatidylcholine/phosphatidylserine coatings in capillary electrochromatography

Greater stability of liposome coatings and improved resolution of model steroids in capillary electrochromatography (CEC) were sought by adding small diamines (ethylenediamine, diaminopropane, bis-tris-propane, or N-(2-hydroxyethyl)piperazine-N'-(2-ethanesulfonic acid, HEPES)) to the liposome solution before coating of fused silica capillaries. The phospholipid coatings consisted of 1 mM of 8:2 mol% phosphatidylcholine (PC)/phosphatidylserine (PS) and 5 mM of modifier in buffer solutions (acetate, phosphate, or Tris) at pH 4.0-7.4. The coating was based on a published procedure, and five steroids were used as neutral model analytes in evaluation of the coating. The results showed that under optimal conditions, the small linear diamines increased the packing density of anionic phospholipids, leading to improved separations. In addition, the choice of buffer for the liposome coating and separation appeared to influence the performance of the coatings. While buffers with amino groups take part in the phospholipid bilayer formation, buffers like phosphate may even have negative effect on coating formation. The factors affecting phospholipid coatings with diamines as modifiers are clarified.