3,5-二甲基-4-溴碘苯和2,6-二甲基-4-溴碘苯的合成

二甲基对溴碘代苯是带有两种不同卤素基团的芳香族有机合成中间体。2,6-二甲基苯胺在过碳酸钠作用下,于45~50℃与碘反应1 h,得到2,6-二甲基-4-碘苯胺,收率42.5%。2,6-二甲基-4-碘苯胺在-5~0℃下进行重氮化,进一步与溴化亚铜发生Sandm eyer反应,得到3,5-二甲基-4-溴碘苯,收率31.5%。2,6-二甲基苯胺室温下与六亚甲基四胺溴络合物反应30 m in,得到2,6-二甲基-4-溴苯胺,收率62.0%。2,6-二甲基-4-溴苯胺在-5~0℃进行重氮化,与K I反应,得到2,6-二甲基-4-溴碘苯,收率33.1%。通过熔点、红外光谱和核磁共振氢谱对中间体2,6-二甲基-4-碘苯胺、2,6-二甲基-4-溴苯胺以及最终产物3,5-二甲基-4-溴碘苯和2,6-二甲基-4-溴碘苯进行了表征。     

N—取代邻苯二甲酰亚胺衍生物的合成

合成了12种N-取代邻苯二甲酰亚胺衍生物。以邻苯二甲酰亚胺为母体,38%甲醛-95%乙醇为溶剂,分别与脂肪胺和芳香胺加热回流,合成了12种N-Mannich 碱。所制得化合物的熔点敏锐。元素分析和红外光谱分析表明,12种化合物均为首次合成的新化合物。     

稀土铽三元有机配合物合成及荧光性能研究

合成了7种铽的稀土荧光有机材料——铽三元有机配合物,通过荧光光谱的测定,比较了第一配体的改变对配合物发光性能,尤其是发光强度的影响。实验表明,在以邻菲啉为第二配体的情况下,第一配体对铽三元配合物荧光强度影响顺序依次是:磺基水杨酸对甲基苯甲酸水杨酸苯甲酸对氨基苯甲酸乙酰丙酮,其磺基水杨酸为第一配体的铽三元有机配合物荧光强度最大,其相对强度为20000。     

pH值对苯甲酸类正辛醇／水分配系数的影响

苯甲酸类化合物是自然水体中的常见有机污染物,属于有机酸。为了考察水相的pH值对该类化合物正辛醇／水分配系数的影响,采用摇瓶法测定了苯甲酸、邻氯基苯甲酸、间硝基苯甲酸和对甲基苯甲酸在不同pH值下的正辛醇／水分配系数,测定结果表明,4种化合物的正辛醇／水分配系数随pH值的升高而降低,且pH值在3～5范围内变化显著。     

Synthesis of polyelectrolyte-modified ordered nanoporous carbon for removal of aromatic organic acids from purified terephthalic acid wastewater

In this work polyelectrolyte (polydiallyldimethylammonium chloride) modified ordered mesoporous carbon (CMK-1/PDDA) has been synthesized and has been employed in removal of major aromatic compounds present in purified terephthalic acid wastewater, such as p-toluic acid, benzoic acid, 4-carboxybenzaldehyde, phthalic acid and terephthalic. The adsorption behavior of these acidic impurities has been studied through batch experiments and using UV-spectrophotometric technique. The results show that CMK-1/PDDA is very effective in selective removal of acidic compounds from PTA-waste aqueous solutions. The electrostatic interaction was considered to be the main mechanism for the adsorption of acidic compounds. The effects of chemical modification, contact time, initial concentrations, adsorbent dose, agitation speed, solution pH and reaction temperature have been optimized. The sorption equilibrium was reached within 5 min. The sorption of acidic compounds on the CMK-1/PDDA slightly decreases with increasing pH, and temperature, indicating an exothermic process. The experimental isotherm data were analyzed using the Langmuir and Freundlich equations. The equilibrium data were best represented by the Langmuir isotherm.     

The influence of methyl groups on the colour and dyeing properties of acid dyes derived from 1-amino-4-bromo-anthraquinone-2-sulphonic acid and arylamines

Four blue acid dyes were synthesized by condensation of bromamine acid with aniline, 2,4-dimethylaniline, 2,6-dimethylaniline and 2,4,6-trimethylaniline. It was found that the number and orientation of the methyl groups on the 4-phenylamino substituent affected both the colour and dyeing properties of the dyes. The more methyl groups present, the higher was the dye uptake and the better the fastness to wet treatments. When a methyl group is present in the ortho position of the phenylamino group, the hue of the dyes is hypsochromically shifted.     

2,6-二羟基苯甲酸合成工艺研究

为提高2,6-二羟基苯甲酸的合成收率,采用有机溶剂法制备了2,6-二羟基苯甲酸。探讨了溶剂种类,催化剂种类及用量,反应温度,反应压力及反应时间对产品收率的影响。确定以N,N-二甲基甲酰胺（DMF）为溶剂、K2CO3为催化剂,在140℃、10 atm压力下反应6 h,2,6-二羟基苯甲酸的单程收率可达35%以上,产品纯度95%以上。     

难降解芳烃化合物在超临界水中氧化的COD去除率的研究

Some aromatic compounds, phenol, aniline and nitrobenzene, were oxidized in supercritical water. It was experimentally found that the chemical oxygen demand (COD) removal efficiency of these organic compounds can achieve a high level more than 90% in a short residence time at temperatures high enough. As temperature, pressure and residence time increase, the COD removal efficiencies of the organic compounds would all increase. It is also found that temperature and residence time offer greater influences on the oxidation process than pressure. The difficulty in oxidizing these three compounds is in the order of nitrobenzene > aniline > phenol. In addition, it is extremely difficult to oxidize aniline and nitrobenzene to CO2 and H2O at the temperature lower than 873.15 K and 923.15 K, respectively. Only at the temperature higher than 873.15 K and 923.15 K, respectively, the COD removal efficiencies of 90% of aniline and nitrobenzene can be achieved.     

The mechanism and kinetics of the electrochemical cleavage of azo bond of 2-hydroxy-5-sulfophenyl-azo-benzoic acids

The electrochemical reduction of 2-hydroxy-5-[(4-sulfophenyl)azo]benzoic acid, 2-hydroxy-5-[(3-sulfophenyl)azo]benzoic acid, 2-hydroxy-5-[(2-sulfophenyl)azo]benzoic acid and 2-hydroxy-5-azo-benzoic acid has been carried out in aqueous solutions at glassy carbon electrode using cyclic voltammetry and chronoamperometry. The position of sulfo substituent relative to azo bridge as well as pH of the solution have significant impact on the electrochemical behavior of these compounds. It has been proposed that these compounds are reduced predominantly as hydrazone tautomers resulting in corresponding hydrazo compounds. The overall electrochemical reduction follows DISP2 mechanism, ultimately leading to the 5-amino salicylic acid and sulfanilic acid. The rate determining step is the homogenous redox reaction between intermediate hydrazo compound and 5-amino salicylic acid quinoneimine. The mechanism is proposed in which activated complex of 5-amino salicylic acid quinoneimine and intermediate hydrazo compound is formed with the simultaneous loss of one proton.     

Electrochemical Oxidation of Benzoic Acid Derivatives on Boron Doped Diamond: Voltammetric Study and Galvanostatic Electrolyses

The electrochemical oxidation of aqueous wastes polluted with benzoic and salicylic acids and phthalic anhydride on boron‐doped diamond electrodes has been studied. The complete mineralization of the organic waste has been obtained in each case regardless of the nature of the compound, composition of the solution, and current density. Different voltammetric behaviors between benzoic acid, salicylic acid, and phthalic anhydride were obtained in the voltammetric study, but no differences in the electrochemical oxidation of the three compounds seems to exist in the bulk electrolyses study. The total mineralization of the three compounds at different current densities confirms that the oxidation must occur directly on the electrode surface and/or by hydroxyl radicals generated by decomposition of water and/or by other oxidants electro‐generated from the sulfate oxidation.     

N-(2,6-二甲苯基)-N-酰基丙氨酸甲酯类化合物的合成及生物活性研究

以α-氯丙酸为起始原料,甲酯化后得α-氯丙酸甲酯;在碘化钾催化下,α-氯丙酸甲酯与2,6-二甲基苯胺缩合获得中间体N-(2,6-二甲苯基)丙氨酸甲酯,再在室温下以吡啶作缚酸剂,与系列羧酸酰氯反应15 h,合成了12个新型N-(2,6-二甲苯基)-N-酰基丙氨酸甲酯类目标化合物。目标化合物的结构经GC-MS、FTIR和元素分析确认。对目标化合物进行了杀菌、杀虫、除草生物活性测定,结果表明,各化合物均具有不同程度的杀菌生物活性。     

裂解气相色谱法研究聚对苯二甲酰对苯二胺纤维热分解

采用裂解气相色谱质谱法研究了在400￣700℃之间聚对苯二甲酰对苯二胺纤维(PPTA)的裂解产物组成。400℃时裂解,仅检测到8种裂解产物。随裂解温度上升,裂解产物急剧增加。在700℃时,检测到45种裂解产物,主要特征裂解产物为苯、氰苯、苯胺、苯甲酸、1,4-对苯二胺、苯甲酸N2-苯肼等。聚对苯二甲酰对苯二胺裂解过程中,发生链剪切作用,由聚合物链断裂成单体,经重排、环化、次级反应等形成了各种裂解产物。作出了PPTA裂解过程示意图。     

几种芳香化合物电化学性质的研究

采用循环伏安法考察了苯胺在铂电极上不同浓度、pH值和不同扫描速率等条件下的电化学反应特性。结果表明:在中性条件下,苯胺未出现明显的氧化还原峰,氯苯、苯甲酸分别出现了2个氧化峰和1个还原峰;随着硫酸浓度的增大,氯苯和苯甲酸峰电流密度呈减小趋势,而苯胺峰电流密度增大,这可能与氨基、氯、羧基的Hammet常数和溶液的pH值有关,Hammet常数越小易于发生亲电攻击;苯胺的氧化峰和还原峰相比大约为1,接近于可逆反应,苯胺的可逆性最强。     

Synthesis and characterization of surface-active compounds derived from cholesterol derivatives and glucose

The synthesis and characterization of surface-active compounds based on various steroid derivatives and glucose are presented. The hydrophobic and hydrophilic parts of the compounds were linked via glucosidic bonds. All compounds were found to have very low water solubility and only limited solubility in various organic solvents. The compounds were investigated according to their ability to interact with an anionic surfactant, sodium dodecylsulfate (SDS), in order to induce a decrease in the critical micelle concentration (CMC) of the surfactants. This synergistic effect was pronounced for cholestanol-6-on-β-D-glucopyranoside and for cholestan-3,6-diol-β-D-glucopyranoside. These two compounds lowered the CMC from 8 to 6 and 0.6 mM, respectively, for water solutions of SDS/glucoside with a molar ratio of 92∶8. Furthermore, the ability of the compounds to stabilize lipid membranes, in liposomes, at varying concentrations of Ca²⁺, was studied. The compounds were, as expected, found to induced stabilization similar to that of cholesterol.     

三氟乙基苯胺衍生物合成的研究

三氟乙基苯胺衍生物是重要的有机合成中间体和生命活性物质。其合成一般是以苯胺和六氟丙酮为起始原料,经过亲电加成、酰化和还原三步反应。本文研究了这三步反应。     

旋光性N-(2,6-二甲苯基)-N-酰基丙氨酸甲酯类化合物的合成及生物活性研究

以α-氯丙酸、甲醇、2,6-二甲基苯胺为起始原料,合成了N-(2,6-二甲苯基)丙氨酸甲酯。以S(-)-α-甲基苄胺为化学拆分剂,利用非对映异构体在不同溶剂中溶解度的差异,分离得到了R(+)、S(-)-N-(2,6-二甲苯基)-丙氨酸的两个旋光异构体和反-R(+)、反-S(-)、顺-R(+)和顺-S(-)-二氯菊酸的4个旋光异构体。两个N-(2,6-二甲苯基)-丙氨酸旋光异构体与甲醇反应得到两种N-(2,6-二甲苯基)丙氨酸甲酯的旋光异构体。最后N-(2,6-二甲苯基)-丙氨酸甲酯的旋光异构体与二氯菊酰氯的7个异构体进行反应,合成了19个N-(2,6-二甲苯基)-N-酰基丙氨酸甲酯类化合物,其中18个具有旋光性。这些化合物的结构经GC-MS、FTIR测定后确认。对19个标题化合物进行了杀菌、杀虫生物活性实验,结果表明,部分化合物显示出较高的杀虫、杀菌活性。     

Synthesis,characterization, and application for addition polymerization of norbornene of novel acetylacetonate bis(anilines) palladium (II) complexes

New acetylacetonate bis(aniline) palladium (II) complexes were synthesized by nitrile substitution of [Pd(acac)(MeCN)₂]BF₄ with L (L = o-toluidine, p-toluidine, 2,6-dimethylaniline, 2,6-diisopropylaniline) which yielded [Pd(acac)(L)₂]BF₄ as a mononuclear species with chelating acac ligand. Preliminary investigations into the polymerization of norbornene in the presence of BF₃·OEt₂ were performed. An X-ray diffraction study of [Pd(acac){NH₂(2,6-Me₂C₆H₃)}₂]BF₄ establishes the presence of hydrogen bonding between the 2,6-dimethylaniline ligand and [BF₄]⁻ anion.     

Removal of Trace Levels of Aromatic Amines from Aqueous Solution by Foam Flotation

Abstract

Aromatic amines, including 4-(t-butyl)pyridine, 4-(n-butyl)aniline, benzylamine, 4-aminobiphenyl, 1- and 2-aminonaphthalene, and 2,6-xylidine, were effectively removed from water by foam flotation with the anionic surfactant sodium dodecylsufate (SDS). With initial amine concentrations of 10 mg/L or less, residual amine concentrations of less than 0.1 mg/L were generally obtained after 10–30 min of flotation. The SDS concentration and flotation time are directly related to the amount of amine removed. Amine removal is most efficient at pH values low enough so that the amine is protonated (usually about 3), and at low ionic strength. Alcohols up to 10% by volume do not appreciably affect amine removal. The mechanism of removal is dominated by ion-ion attraction between the surfactant and the protonated amine; there is also apparently some contribution from ion-dipole attraction. Benzidine is not removed effectively; evidently it is insufficiently hydrophobic.     

Fe(Ⅱ)/亚硫酸盐体系活化溶解氧降解苯胺

研究了Fe（Ⅱ）/亚硫酸盐体系活化溶解氧氧化降解苯胺的工艺并探索了氧化过程中的主要活性物种。结果表明,溶解氧是苯胺氧化的氧化剂,pH=4.0以及亚硫酸盐与Fe（Ⅱ）物质的量之比为10：1的体系对苯胺的催化效果最佳,苯胺去除率可达70%。Fe（Ⅱ）在体系中发挥着重要作用,只存在亚硫酸盐的情况下,苯胺去除效果下降至30%以下,且反应时间由90 min延长至40 h。在Fe（Ⅱ）/亚硫酸盐体系中,pH=3.0条件下Fe（Ⅱ）全部被氧化成Fe（Ⅲ）,而在其它pH值条件下,Fe（Ⅱ）与Fe（Ⅲ）主要以络合物形式存在。叔丁醇与甲醇的自由基掩蔽实验进一步证实了SO₄^·-是氧化过程中的主要氧化物种,而SO₅^·-是次要氧化物种。实验结果丰富了Fe（Ⅱ）/亚硫酸盐体系催化溶解氧降解有机污染物的研究,表明其在有机工业废水处理方面具有很好的应用前景。     

Synthesis of some new spiroheterocyclic pyrylium salts related to 1-oxa-4-thiaspiro[4.4] nonan-2-one and/or [4.5]decan-2-one as antimicrobial agents

1-Oxa-4-thiaspiro[4.4]nonan-2-one ( 1a ) and/or 1-oxa-4-thiaspiro[4.5] decan-2-one ( 1b ) were reacted with aniline and/or p-chloroaniline to afford the corresponding spirothiazolidinones ( 2a–d ). Reaction of 2a–d with chalcones gave 2-(α – paracylbenzyl)-4-aryl-1-thia-4-azaspiro[4.4]nonan-3-one and 2-(α-aracylbenzyl)-4-aryl-1-thia-4-azaspiro[4.5]decan-3-one ( 3a–p ) respectively. Compounds 3a–p were reacted with acetic anhydride and perchloric acid to yield the spiropyrano[2,3-d]thiazol[4]ium perchlorate derivatives 4a–p . The structures of the synthesized compounds were elucidated by elemental and spectroscopic ( IR and ¹H-NMR) analysis. All the prepared compounds were tested for their antimicrobial activities in comparison with tetracyclic as a reference compound.