A shaped binderless ZSM-11 zeolite catalyst for direct amination of isobutene to tert-butylamine

A shaped binderless and two binder‐containing ZSM‐11 zeolite catalysts were prepared and characterized by powder X‐ray diffraction, N2 adsorption‐desorption, and pyridine adsorption‐infrared measurements. The binderless catalyst was synthesized using a dry‐gel conversion technique, inwhich 1,6‐hexanediamine and tetrabutylammonium bromide were used as structure‐directingagents and no other alkaline materials were added. The catalytic performance of the zeolites in the direct amination of isobutene to tert‐butylamine was evaluated in a fixed‐bed reactor. By virtue of its high crystallinity as well as its good mechanical strength, the shaped binderless ZSM‐11 catalyst showed a higher rate of formation of tert‐butylamine than did the binder‐containing catalysts.

Carbamate Synthesis from Aromatic Amines and Dimethyl Carbonate Using Lead Acetate as Catalyst

Carbamates are important intermediates in the syntheses of pesticides, herbicides, drugs, polyurethane-based polymers, and other fine and commodity chemicals.

A Novel Synthesis of N-Methyl-N-aryl Carbamates from Aromatic Amines and Dimethyl Carbonate Catalyzed by K_2CO_3/Bu_4NBr

A facile synthesis of N-methyl-N-aryl carbamates from aromatic amines and dimethyl carbonate (DMC) has been achieved with high yields in the presence of potassium carbonate (K2CO3)and tetrabutylammonium bromide (Bu4NBr) under solvent-free conditions.

Synthesis, Crystal Structure and Antitumor Activity of (E)-4-tert-Butyl-N-(2,4-dichlorobenzylidene)-5-(1,2,4-triazol-1-yl)-thiazol-2-amine

The title compound （E）-4-tert-butyl-N-（2,4-dichlorobenzylidene）-5-（1,2,4-triazol-1-yl）-thiazol-2-amine was synthesized by the reaction of 4-tert-butyl-5-（1,2,4-triazol-1-yl）-thiazol-2-amine with 2,4-dichlorobenzaldehyde, and its crystal structure was determined by singlecrystal X-ray diffraction. The crystal belongs to the triclinic system, space group P1 with a = 7.9748（4）, b = 10.1803（5）, c = 11.4603（6）, α = 102.882（1）, β = 100.253（1）, γ = 104.457（1）°, V = 850.95（7）3, Z = 2, F（000） = 392, C16H15Cl2N5S, Mr = 380.29, Dc = 1.484 g/cm3, S = 1.095, μ = 0.512 mm-1, the final R = 0.0301 and wR = 0.0965 for 3334 observed reflections （I 〉 2σ（I））. The preliminary antitumor activity shows that for the title compound the IC50 of Hela is 0.175 μmol/mL and that of Bel7402 is 0.156 μmol/mL.

Synthesis, Crystal Structure and Antitumor Activity of 4-tert-Butyl-N-(2-fluorophenyl)-5- (1H-1,2,4-triazol-1-yl)-thiazol-2-amine

The title compound has been synthesized by the reaction of 1-bromo-3,3-dime- thyl- 1 - （1 H- 1,2,4-triazol- 1 -yl）butan-2-one with 1 -（2-fluorophenyl）thiourea, and its crystal struc- ture was determined by single-crystal X-ray diffraction. The crystal belongs to the orthorhombic system, space group Pbca with a = 15.2568（6）, b = 12.1533（5）, c = 16.7307（7） A, Z = 8, V = 3102.2（2） A3, Mr = 317.39, Dc = 1.359 g/cm3, S = 1.05, μ = 0.223 mm-1, F（000） = 1328, the final R = 0.034 and wR = 0.097 for 2590 observed reflections （I 〉 2σ（I））. X-ray crystal structure presents the intramolecular N-H…N hydrogen bond, which plays an important role in stabilizing the crystal structure. In addition, the preliminary biological test on the title compound shows good antitumor activity, with IC50 of 0.122 μmol/mL against the Hela cell line.

Liquid-liquid extraction of phosphorus from sulfuric acid solution using benzyl dimethyl amine

This study addresses the liquid-liquid extraction behavior of phosphorus from a sulfuric acid solution using benzyl dimethyl amine(BDMA)in kerosene.The extraction equilibria investigated with varied BDMA concentrations could reveal the formation of 3[BDMA]·[H_(3)PO_(4)]^(-)complex in the organic phase.The thermodynamic properties determined at various temperatures indicated that the process was exothermic with a calculated enthalpy(△H^(Θ))of−24.0 kJ·mol^(−1).The organic-to-aqueous phase(O/A)volume ratio was varied to elucidate the quantitative extraction of phosphorus.The McCabe-Thiele diagram plotted for the extraction isotherm was validated for the requirement of three counter-current stages in the extraction at an O/A volume ratio of 2.0/3.5.The back-extraction of phosphorus from the loaded organic phase was quantitatively achieved by contacting 4.0 mol·L−1 H2SO4 solution in three stages of counter-current contact at an O/A volume ratio of 3/2.This study can be applied to remove phosphorus from the sulfuric acid leach solutions of monazite processing,and many other solutions.

Synthesis, Crystal Structure and Antitumor Activity of 4-(tert-butyl)-5-(1H-1,2,4-triazol-1-yl)-N-(2-hydroxy-3,5-diiodinebenzyl)-thiazol-2-amine

The title compound, 4-（tert-butyl）-5-（1 H- 1,2,4-triazol- 1 -yl）-N-（2-hydroxy-3,5-diio- dinebenzyl）thiazol-2-amine, was synthesized via the reduction of 4-（tert-butyl）-5-（1H-l,2,4- triazol-l-yl）-N-benzylidene-thiazol-2-amine with NaBH4, and its crystal structure was determined by single-crystal X-ray diffraction. The compound crystallizes in monoclinic system, space group P21/c with a = 7.91944（19）, b = 10.5250（3）, c = 24.4985（6） A, Z = 4, V = 2041.66（9） A3, Mr = 599.22, Dc = 1,949 Mg/m3, S = 1.120, p = 3.203 mm-1, F（000） = 1152, the final R = 0.0283 and wR = 0.0592 for 3490 observed reflections （I 〉 2σ（I））. X-ray analysis displays that the crystal water takes part in three intermolecular hydrogen bonds of O（2）-H（2A）…O（1）, O（2）-H（2B）…N（I） and N（5）-H（5）…O（2）, and an octatomic ring R^（8） is formed via intramolecular hydrogen bond of O（I）-H（IA）…N（4）. Furthermore, the I…I contacts are involved in stabilizing the overall three-dimensional network structure. The preliminary biological test shows the title compound has good antitumor activity with the IC50 value of 26 μM against the Hela cell line.

Kinetics of Reaction of Bromo-epoxy Resin with Oleic Acid catalyzed by Dimethyl benzyl amine

The kinetics of reaction of bromo-epoxy resin with oleic acid in the presence of dimethylbenzylamine catalyst was studied. The reaction is a zero order reaction with respect to oleic acid, first order with respect to epoxy group and 0. 74 order with respect to dimethylbenzylamine. The reaction rate constants at various temperatures and activation energy were determined. The mechanism of this reaction was discussed. Keywords Tetrabromobisphenol-A, Bromo-epoxy resin, Oleic acid kinetics, Reaction mechanism

4-(7-Methoxy-2,2-dimethyl-2,3-dihydrobenzo-furan-5-yl)-N-(pyridin-2-yl)thiazol-2-amine: Chiral Crystal from Achiral Molecule

The title compound 4-（7-methoxy-2,2-dimethyl-2,3-dihydrobenzofuran-5-yl）-N- （pyridin-2-yl） thiazol-2-amine was synthesized by reacting 2-bromo-1-（7-methoxy-2,2-dime- thyl-2,3-dihydrobenzofuran-5-yl）ethanone with 1-（pyridine-2-yl）thiourea, and its crystal was determined by single-crystal X-ray diffraction. The crystal belongs to the monoclinic system, chiral space group C2 with a = 18.1328（14）, b = 5.5969（5）, c = 19.2195（15） A, β= 115.5420（10）°, V= 1759.9（2）A3, Z = 4, F（000） = 744, C19H19N3O2S, Mr= 353.43, Dc= 1.334 g/cm3, S = 1.15, μ = 0.201 mm-1, the final R = 0.035 and wR = 0.111 for 2307 observed reflections （I 〉 2σ（I））. The Flack parameter is -0.03（10）. The preliminary bioassay result indicated that the title compound exhibits strong insecticidal activity （93.75% mortality） against Mythimna separate at the concentration of 1.000 g/L.

胺液脱硫系统顽固性发泡的原因及对策

为解决中国海油宁波大榭石化有限公司胺液脱硫系统存在顽固性发泡问题,对发泡原因进行了分析,并提出了相应的对策。结果表明:胺液中的大分子烃类和组成复杂的聚合物成分经长时间积累是形成顽固性发泡体系的主要原因;催化裂解干气和气柜气携带的柴油组分是大分子烃类的主要来源,来自上游催化裂解装置液化气中的1,3-丁二烯是聚合物主要来源。采用河北精致科技有限公司开发的减压蒸馏工艺,实现了胺液在线净化处理,净化后胺液的发泡高度不高于4 cm,消泡时间不长于5 s,油质量浓度不大于100 mg/L,胺液清澈透明,可将甲基叔丁基醚含硫量降至45μg/g以下。

Flotation of kaolinite and diaspore with hexadecyl dimethyl benzyl ammonium chloride

Tertiary amine was synthesized from fatty amine and formaldehyde. And then the synthesized tertiary amine was used to react with benzyl chloride to synthesize hexadecyl dimethyl benzyl ammonium chloride (1627) at ambient pressure. Using the synthesized 1627 as collector,the flotation properties of diaspore and kaolinite were investigated by single mineral and mixed mineral test. The flotation mechanism of diaspore,kaolinite and 1627 was discussed based on FTIR spectra. The results show that the mass ratio of aluminum to silicate achieves 15.02 and the recovery of alumina in concentrate is 43.07% using 1627 as a collector. The 1627 is found to be a more effective and a promising collector for reverse flotation to remove aluminum-silicate minerals from bauxite.

无金属、卤素、硫等杂元素的聚甲基丙烯酸甲酯纳米微球的合成

聚合物纳米微球可用于多孔催化剂的制备,但是来源于乳化剂、引发剂等的硫、卤素、碱金属等容易导致催化剂中毒。因此,文中以十二烷基二甲基氧化胺为乳化剂,过氧化氢/抗坏血酸氧化还原体系为引发剂,通过甲基丙烯酸甲酯乳液聚合,合成了仅含碳、氢、氧、氮4种元素的聚甲基丙烯酸甲酯纳米微球。研究了聚合工艺、引发剂用量与配比、乳化剂用量及单体浓度对单体转化率和微球粒径的影响。结果表明,搅拌速率、温度、引发剂配比及乳化剂用量对单体转化率的影响较大;微球粒径受聚合工艺、引发剂用量及配比的影响较小,微球粒径主要受乳化剂用量和单体浓度控制。

ZSM-5催化异丁烯胺化制叔丁胺的研究进展

综述了近年来异丁烯胺化制叔丁胺研究取得的进展,重点从ZSM-5分子筛催化剂的反应过程、改性、活性影响等方面介绍了异丁烯胺化制叔丁胺催化剂的研究进展,总结并展望了异丁烯胺化制叔丁胺的研究方向,为ZSM-5分子筛催化剂的优化和异丁烯胺化制叔丁胺工艺开发提供参考。

异硫氰酸酯的合成

异硫氰酸酯是一种重要的有机合成中间体,在合成取代硫脲类农药中有广泛应用。综述了以不同起始原料如叔醇、胺、腈氧化物及异腈化物等合成异硫氰酸酯的方法,并对某些反应机理进行探讨研究。介绍了由二硫代氨基甲酸盐制备异硫氰酸酯的方法,其中Boc酸酐的使用因副产物少、后处理简单而有很好的应用前景。而一些如微波等新技术的应用对异硫氰酸酯的制备将会起到很好的推动作用。

双烷链阳离子表面活性剂的合成与定量分析

以N ,N 二甲基烷基叔胺和α,ω 二溴烷烃为原料 ,无水乙醇为溶剂合成阳离子型Gemini表面活性剂。反应产物以混合溶剂乙酸乙酯 乙醇重结晶纯化后 ,用红外光谱和核磁共振进行结构分析 ;以溴酚蓝为指示剂、二氯乙烷为分散相的两相化学滴定法测定其含量。结果表明 :7种已合成的阳离子型Gemini的活性物含量均在 97.5

添加剂对碱性锌电极电化学行为的影响

本文采用电流 -时间曲线、电化学阻抗谱、极化曲线和扫描电子显微镜等方法 ,研究了二甲胺基环氧丙烷对锌在碱性锌酸盐溶液中电化学行为的影响 .研究结果表明 :添加剂对可充锌电极的枝晶生长有较好的抑制作用 ,且随着其含量的增加 ,抑制效果增强 ;在高阴极极化区 ,添加剂自电极表面脱附 。

有机胺催化制备聚碳酸酯二元醇

以碳酸二甲酯(DMC)和1,4-丁二醇(BDO)为原料,在三乙胺等有机胺类催化剂催化下,酯交换制备出聚碳酸酯二元醇(PCDL)。采用核磁共振和红外光谱等分析手段鉴定产物的结构;凝胶渗透色谱分析减压时间对PCDL分子量分布的影响。详细研究了原料摩尔比(DMC/BDO)、催化剂用量、减压时间等因素对反应过程的影响,优化了PCDL的合成工艺参数。实验结果表明,当DMC/BDO的摩尔比为1.2～1.25,催化剂用量占BDO的质量分数为0.5%,采用阶段控温方式制备出数均分子量在1600g/mol左右的PCDL。

HZSM-5分子筛催化剂表面酸性质对异丁烯直接胺化反应的影响

研究了以不同离子改性的HZSM-5分子筛催化剂对异丁烯直接胺化反应的催化活性,发现以铈改性的HZSM-5分子筛催化剂的催化活性最佳。在氨烯摩尔比2∶1、反应温度230℃、压力0.5M Pa、空速450h-1的条件下,异丁烯转化率可达平衡转化率的67.53%。以吡啶为探针分子的原位红外光谱(In-situ IR)研究表明,稀土元素铈的加入增加了表面B酸中心浓度。由In-situ IR及过渡应答吸附研究结果可推断,异丁烯胺化反应过程是经由化学吸附的氨与气相的异丁烯作用形成反应中间物种叔丁基正离子,叔丁基正离子进一步与气相或化学吸附的氨作用生成叔丁胺。

异丁烯直接胺化制叔丁胺

介绍了由石油原料出发制备叔丁胺的合成路线 ,着重讨论了近年来愈益引起重视的异丁烯直接胺化制叔丁胺工艺路线 ,介绍了国内外的最新研究。以热力学分析为基础 ,根据我国国情 ,阐述了在我国利用抽余丁二烯的混合 C4气作为原料直接胺化制叔丁胺的工艺路线是比较经济的。提出低温胺化催化剂的开发 。

甲基碳酸酯季铵盐的合成与表征

研究了碳酸二甲酯与长链烷基叔胺的季铵化反应。考察了反应温度、反应时间、物料摩尔比和溶剂用量等反应条件对十二烷基二甲基叔胺季铵化反应的影响,确定了优化条件:反应温度130℃、反应时间5h、n(碳酸二甲酯)/n(烷基叔胺)=5、甲醇质量分数(相对于反应原料的质量)10%。在该条件下,不同碳链长度的单烷基叔胺的季铵化率均达到98%以上,而双碳十和双碳十八叔胺的转化率较低,分别为88.09%和68.77%。说明空间位阻是影响季铵化反应进程的重要因素,与分子空间结构模拟的结果一致。通过增加反应时间,双碳十叔胺反应7h季铵化率为98.85%,双十八烷基甲基叔胺反应12h季铵化率为95.68%。采用1HNMR与IR对合成季铵盐的结构进行了表征,结果表明,成功合成了甲基碳酸酯季铵盐。