Synthesis and characterization of zirconium silicalite-1

Zirconium silicalite-1 (ZS-1) catalysts with MFI structure were prepared using a hydrothermal synthesis method. XRD, SEM, IR,²⁹Si MAS NMR, UV-VIS DRS, physical adsorption of nitrogen, and elemental analysis were then performed to evaluate its physico-chemical properties, and evidences of Zr⁴⁺ incorporation into the zeolite framework were provided : The unit cell volume of zirconium silicalite-1 increased linearly with increases in zirconium content, and the characteristic framework i.r. spectra shifted to lower frequencies as Zr⁴⁺ was incorporated into the silicalite-1 lattice. For its catalytic reaction test, liquid phase 2-butanol oxidation using hydrogen peroxide as an oxidant was carried out. All of the zirconium silicalite-1 samples synthesized were active for the 2-butanol oxidation, but activities obtained using ZS-1 catalysts were lower than TS-1 catalyst. Zirconium in the zeolite frameworkwas found to be the active site for the 2-butanol oxidation.     

1,1’-过氧化双环己胺合成及表征

重点介绍 1,1’ 过氧化双环己胺的合成方法 ,利用质谱、红外光谱、核磁共振等测试方法对它进行了分子表征 ,确定所合成的物质为目标产物。并得到了 1,1’ -过氧化双环己胺的质谱、红外光谱和核磁共振谱图。     

不敏感炸药1-甲基-2,4,5-三硝基咪唑的合成

以咪唑为原料,通过两步硝化制得1,4-二硝基咪唑,然后在氯苯中热重排得2,4-二硝基咪唑,将2,4-二硝基咪唑进一步硝化并制得2,4,5-三硝基咪唑的钾盐,最后将钾盐甲基化,得到1-甲基-2,4,5-三硝基咪唑.采用红外光谱、元素分析、核磁的方法对其结构进行表征.用DSC进行了热分解研究.同时优化了2,4-二硝基咪唑的重排工艺:反应温度为120℃～125℃.反应时间为4h,1,4-二硝基咪唑和氯苯的物质的量比为1:30.对2,4,5-三硝基咪唑不稳定性进行了分析.     

5-氯-1-萘磺酰丙氨酸的合成及表征

以5－氯－1萘磺酰为原料合成了5－氯－1萘磺酰丙氨酸,并通过元素分析、红外光谱、核磁共振等进行了证实。经初步实验证明,此化合物对巨噬细胞释放肿瘤因子（TNF）具有抑制释放的作用。     

1-溴-4-乙氧基-2,3-二氟苯的合成及性能表征

以2,3-二氟苯乙醚、溴素为原料,还原铁粉为催化剂,合成了1-溴-4-乙氧基-2,3-二氟苯。考察了反应温度、溴素与还原铁粉的物质的量及反应时间对合成反应的影响,确定了最佳工艺条件为:反应温度为-2~-8℃,溴素用量为1.04 mol,还原铁粉用量为0.017 5 mol,反应时间为3 h。最后通过重结晶,得到了含量大于99%的白色晶体状产品,收率为93%。并对产物用GC-MS,IR和DSC进行了表征。     

1,1–二甲基–1–烷基胺–2–辛酰亚胺的合成与表征

以偏二甲肼、溴代(十二、十四、十八)烷和辛酰氯为原料,合成了3种脂肪族胺基酰亚胺。分别采用FT–IR和1H–NMR表征了产物的结构,以DSC法分别测试了各产物的熔点和热分解温度,最后探讨了各步反应的最佳条件。结果表明:烷基化最佳反应温度为35~40℃,反应时间为120 min;酰基化最佳反应温度为80~85℃,反应时间为120 min;脱氢反应最佳温度为10~30℃,反应时间为180 min。3种胺基酰亚胺的熔点和热分解温度随胺基碳链的增长而升高。     

1-氨丙基-2-甲基咪唑的合成与表征

以1-氰乙基-2-甲基咪唑(2MZCN)为原料催化氢化制备1-氨丙基-2-甲基咪唑,考察了反应过程中合成工艺参数对产物的影响,确定较为适宜的工艺条件为:温度100℃,压力5 MPa,转速624 r/min,时间4 h,溶剂是氨的饱和乙醇溶液(与原料质量比是2∶1),雷尼镍为催化剂(占原料质量的18.9%),氢氧化钾为助催化剂,原料的转化率可达99.7%,产率可达94.2%。采用红外光谱(FTIR)和核磁共振氢谱(1HNMR)及气质联用(GC-MS)对产物进行了表征。     

Synthesis, characterization and surface properties of 1-N-l-tryptophan-glycerol-ether surfactants

A novel homologous series of 1-N-l-tryptophanglycerol-ether surfactants was synthesized and characterized. The precursor compounds, 3-alkyloxy-1-chloropropan-2-ols, were prepared from epichlorohydrin and aliphatic alcohols with alkyl chain lengths of 9–16 carbon atoms. Tryptophan was then attached to the monosubstituted glycerol backbone from its α-amino group through an α-NH-C bond. Structural assignment of the new compounds was made on the basis of elemental analysis and spectroscopic data. Critical micelle concentrations of the new surfactants, as well as the negative logs of the surfactant concentrations required to reduce the surface tension of the solvent by 20 mN/m (pC ₂₀) and the interfacial areas occupied by the surfactant molecules, were calculated from aqueous surface tension measurements using the Wilhelmy plate technique.     

Poly(sulphopropylbetaines): 1. Synthesis and characterization

The synthesis of aromatic and aliphatic poly(sulphopropylbetaines) is described within the series of vinylpyridines and tertiary amino-methacrylates. Two complementary strategies were used: (a) preparation and free radical polymerization in aqueous solution (60°C, 4,4'-azobiscyanovaleric acid) of the monomers; (b) heterogeneous quaternization of preformed poly(vinylpyridines) and poly(tertiary amino-methacrylates) by 1,3-propanesultone in propylene carbonate or tetramethylene sulphone solution (120°C). The high molecular weight poly (zwitterions) ($\text{10}{}^5\text{<}\text{M}\text{?}{}_{\mathrm{W}}\text{< 5 × 10}{}^6$) were characterized by ultra-violet and ¹H nuclear magnetic resonance spectroscopy, and their water affinity at 20°C was estimated by water vapour absorption measurements.     

4-溴-4,4-二硝基丁酸乙酯的合成及表征

以溴代二硝基甲烷钾盐和丙烯酸乙酯为原料,在相转移催化剂四丁基溴化铵的作用下通过Michael加成反应得到4-溴-4,4-二硝基丁酸乙酯。通过单因素实验,探讨了反应物料摩尔比、反应温度、反应时间及催化剂用量对产物产率的影响,得到的最佳工艺条件为:反应温度30℃,n(丙烯酸乙酯)∶n(溴代二硝基甲烷钾盐)=2∶1,反应时间30 min,四丁基溴化铵用量为溴代二硝基甲烷钾盐物质的量的20%,在该条件下产物产率可达52%;并用UV-vis、FTIR、1HNMR、MS以及元素分析等方法表征了产物的结构。     

Synthesis,characterization, properties,and derivatives of poly(starch-g-(1-amidoethylene)). I. Synthesis and characterization

Poly(starch-g-(1-amidoethylene)) can be formed by aqueous, free radical polymerization of 2-propenamide on lintnerized, potato starch. Initiation is by attack of cerium ions (+IV) on the D -glucopyranosyl units of starch. The reaction produces a water-soluble thickener with molecular properties of the product controlled, in part, by the gel effect induced in virtually all syntheses. Yield of product varies from 38 to 100% with yields of 90–100% being common. Products containing less than 50 wt % sidechain were found to be difficult to dissolve once they were recovered from the synthesis mixture. A sample with a design molecular weight of 0.8 × 10⁶ and 4 grafts per backbone formed 3.9 wt % of a water-insoluble solid in the reaction mixture. The solid, which had a composition similar to that of the reaction mixture, may be the result of selective reaction within the distribution of backbone molecules.     

两种新型1-烷基咪唑类双膦酸的合成与表征

分别以1-乙基咪唑和1-丁基咪唑为原料,经过羟甲基化、溴代、氰解、酸性水解、膦酰化5步反应,合成了两种新型的唑来膦酸衍生物,通过元素分析、IR、MS和1HNMR测定对目的产物进行了结构确认.     

1-丁基-3-甲基咪唑四氟硼酸盐离子液体的合成与表征

以N-甲基咪唑和1-溴代正丁烷为原料,两步合成法制备了离子液体[bmim]BF4。考察了反应时间、反应温度、原料配比对中间体1-丁基-3-甲基咪唑溴盐[bmim]Br收率的影响和离子交换时间和离子交换温度对目标产物[bmim]BF4产率的影响。结果表明:①合成中间体[bmim]Br的最佳条件为:反应温度65℃,反应时间16 h,N-甲基咪唑与1-溴代正丁烷的摩尔比为1∶1.1,产品收率可达94.8%;②合成离子液体的最佳条件为:反应温度65℃,反应时间24 h。     

1-乙基-3-甲基咪唑四氟硼酸盐[Emim]BF_4离子液体的制备和表征

以N-甲基咪唑、溴乙烷和四氟硼酸钠为原料,按照两步法制备了离子液体1-乙基-3-甲基咪唑四氟硼酸盐([Emim]BF4),考察了反应时间、温度、溶剂等对中间体[Emim]Br以及离子液体[Emim]BF4产率的影响,结果表明,反应物N-甲基咪唑与溴乙烷的摩尔比1∶1.5,温度70℃,反应8 h,中间体产率为87.4%;中间体中加入等摩尔NaBF4,25℃下反应10 h,离子液体产率为91.1%。     

Nitroureas 1. Synthesis,scale-up and characterization of K-6

The synthesis and characterization of 2-oxo-1,3,5-trinitro-1,3,5-triazacyclohexane (K-6), a cyclic dinitrourea, is described. The laboratory synthesis was scaled-up to provide 1.6 kilograms of crystalline K-6 which was used for performance testing. K-6 was formulated with 5% Viton A and pressed to 96.5% theoretical maximum density (TMD). Performance measurements in the form of front surface velocity measurements (tantalum plate push) and 1-inch cylinder expansion experiments indicate K-6 will out-perform HMX by 4% at early volume expansions. Thermal response and shock sensitivity experiments on K-6 are also described.     

N-乙酰基-1-氧杂-4-氮杂-螺[4,5]癸烷的合成与表征

用乙醇胺和环己酮为原料,脱水缩合得到1-氧杂-4-氮杂-螺[4,5]癸烷,再经过与乙酰氯的酰化反应制得标题化合物,产率分别为69.1%和63.5%.产物的结构经1HNMR、IR和元素分析表征.     

1-硝氨基-2,3-二硝酰氧基丙烷(NG-N1)合成、表征及性能研究

以氨基甘油和氯甲酸乙酯为原料,通过取代、硝化、碱解三步合成了1-硝氨基-2,3-二硝酰氧基丙烷(NG-N1),并利用元素分析、核磁共振、红外光谱等鉴定其结构;优化了碱解反应条件,采用KOH作为碱解试剂,最优工艺条件为:n(KOH)∶n(II)为4∶1～5∶1,常温反应5 min;利用TG-DSC对化合物进行了热分析,其熔点为62.1℃,分解点为182.3℃。采用NASA-CEA软件,在标准条件(p_c∶p_o=70∶1)下计算了含NG-N1的改性双基推进剂(CMDB)的能量性能,当NG-N1的含量为30%时,推进剂的能量性能最优,理论比冲I_(sp)最大为2 578.3 N·s/kg,较基础配方提高了50.5 N·s/kg,特征速度C~*最大为1 576 m/s,较基础配方增加了48 m/s。     

1-硝氨基-2,3-二硝酰氧基丙烷(NG-N1)合成、表征及性能研究

以氨基甘油和氯甲酸乙酯为原料,通过取代、硝化、碱解三步合成了1-硝氨基-2,3-二硝酰氧基丙烷(NG-N1),并利用元素分析、核磁共振、红外光谱等鉴定其结构;优化了碱解反应条件,采用KOH作为碱解试剂,最优工艺条件为:n(KOH)∶n(II)为4∶1～5∶1,常温反应5 min;利用TG-DSC对化合物进行了热分析,其熔点为62.1℃,分解点为182.3℃。采用NASA-CEA软件,在标准条件(p_c∶p_o=70∶1)下计算了含NG-N1的改性双基推进剂(CMDB)的能量性能,当NG-N1的含量为30%时,推进剂的能量性能最优,理论比冲I_(sp)最大为2 578.3 N·s/kg,较基础配方提高了50.5 N·s/kg,特征速度C^*最大为1 576 m/s,较基础配方增加了48 m/s。     

桥联茂金属催化1-癸烯聚合及其产物结构与性能

采用桥联茂金属催化体系rac-Et(1-Ind)₂ZrCl₂/Al(ⁱBu)₃/[Me₂NHPh]⁺[B(C₆F₅)₄]^-催化1-癸烯聚合,考察了茂金属浓度、Al/Zr摩尔比、B/Zr摩尔比、温度、反应时间对反应转化率、黏度和摩尔质量的影响.当反应条件为1-癸烯20mL、甲苯20mL、Zr/烯摩尔比8×10^-5、Al/Zr摩尔比80、B/Zr摩尔比1.5、温度80℃、反应时间1h时,转化率达到96.2%.采用¹³C NMR和¹H NMR表征了产物的结构,优化条件下所得的聚合产物具有高黏度指数(259)和低分子量分布(2.088),可作为理想的润滑油基础油的原料.     

3,5-双-O-苯甲酰基-2-脱氧-2,2-二氟-1-氧代-D-呋喃核糖的合成与表征

以N,N-二甲基-4-氨基吡啶为催化剂,用3R,3S-2-脱氧-2,2-二氟-1-氧代-D-呋喃核糖和苯甲酰氯反应,合成了药物Gemcitabine的关键中间体3,5-双-O-苯甲酰基-2-脱氧-2,2-二氟-1-氧代-D-呋喃核糖,用元素分析、IR与1H NMR对其结构进行了表征。用异丙醇作溶剂进行重结晶,分离出非对映异构体产物。讨论了不同催化剂、反应温度和反应物比对反应的影响。