Selective Hydrogenation of Butyne-1,4-diol to Butane-1,4-diol over Ni/Al_2O_3-SiO_2 Catalysts

Ni/Al_2O_3-SiO_2 catalysts were synthesized via one-step method employing SiO_2 as an additive for the selective hydrogenation of butyne-1,4-diol(B_3D) to butane-1,4-diol(B1D). The prepared catalysts were evaluated by a series of characterization techniques including BET, XRD, SEM, EDX-mapping, TEM, H_2-TPR, XPS, NH_3-TPD and Py-FTIR. Compared to Ni/Al_2O_3 catalyst, the SiO_2-doped samples exhibited better B_3D conversion. SiO_2 could help to form a strong interaction between NiO with the support, which inhibited Ni agglomeration at high temperature, improved the Ni dispersion, and enhanced the hydrogenation activity. B_1D selectivity was mainly influenced by the quantity of Lewis acid sites in addition to the Ni dispersion. The catalyst with a silica loading of 6.4% demonstrated an excellent selectivity of 75.18%(by 13% higher than the contrastive Ni/Al_2O_3 catalyst), which was attributed to the larger amount of Lewis acid sites and the moderate interaction between NiO with the support, which could facilitate the nickel dispersion on a preferable surface area of 176.3 m^2/g of support.

Synthesis and spectral studies of macrocyclic Pb(Ⅱ),Zn(Ⅱ),Cd(Ⅱ)and La(Ⅲ) complexes derived from 1,4-bis(3-aminopropoxy)butane with metal nitrate and salicylaldehyde derivatives

Eight new macrocyclic complexes were synthesized by template reaction of 1,4-bis（3-aminopropoxy）butane with metal nitrate and 1,3-bis（2-formylphenyl）propane or 1,4-bis（2-formylphenyl）butane and their structures were proposed on the basis of elemental analysis, FTIR, UV-vis, molar conductivity measurements, ^1H NMR and mass spectra. The metals to ligand molar ratios of the complexes were found to be 1： 1. The complexes are 1：2 electrolytes for Pb（II）, Zn（II） and Cd（II） complexes and 1：3 electrolytes for La（III） as shown by their molar conductivities （Am） in DMSO at 10^-3 mol L^-1. Due to the existence of free ions in these complexes, such complexes are electrically conductive. The configurations of La（III） and Pb（II） were proposed to probably octahedral and Zn（II） and Cd（II） complexes were proposed to probably tetrahedral.

Synthesis,Crystal Structure and Theoretical Calculations of a Cadmium Complex Containing 3-Hydroxybenzoic Acid and 1,4-Bis(imidazol-1-yl)-butane

A new complex [Cd（hba）2（bib）]n·nH2O（1,Hhba = 3-hydroxybenzoic acid,bib = 1,4-bis（imidazol-1-yl）-butane） has been hydrothermally synthesized and characterized by elemental analysis,IR spectrum,thermogravimetric analysis,fluorescence spectrum,and singlecrystal X-ray diffraction.Yellow crystal crystallizes in the orthorhombic system,space group Pbca with a = 16.220（5）,b = 14.980（5）,c = 20.521（5） ？,V = 4986（3） ？~3,C（24）H（26）CdN4O7,Mr = 594.89,Dc = 1.585 g/cm^3,μ（Mo Kα） = 0.927 mm^（-1）,F（000） = 2416,Z = 8,the final R = 0.0242 and w R = 0.0589 for 4076 observed reflections（I 〉 2s（I））.In 1,the Cd（Ⅱ） ion takes a six-coordination mode,and bib ligand bridges adjacent Cd（Ⅱ） ions to generate 1D zigzag chains; these neighboring chains are connected by O–H···O hydrogen bonding interactions,producing a 2D folded layered structure.Furthermore,by O–H···O hydrogen bonding between layers and layers,a 3D supramolecular architecture is formed.In addition,we analyzed Natural Bond Orbital（NBO） in using the PBE0/LANL2 DZ method built in Gaussian 03 Program.The calculation results indicated obvious covalent interaction between the coordinated atoms and Cd（Ⅱ） ion.

1,4-二叠氮-2,3-二叠氮甲基-2,3-二硝基丁烷的合成

以硝基甲烷为原料合成了1,4-二叠氮-2,3-二叠氮甲基-2,3-二硝基丁烷,总收率为37.8%。采用1HNMR﹑IR和MS对目标产物及中间体的结构进行了表征。在三羟甲基硝基甲烷的合成中,结合反应机理确定了氢氧化钙的用量为:n(CH3NO2)n(Ca(OH)2)=1001;通过对催化剂浓硫酸﹑三氟化硼—乙醚络合物和对甲苯磺酸的比较,得出对甲苯磺酸为中间体2,2-二甲基-5-羟甲基-5-硝基-1,3-二氧杂环己烷合成的较优催化剂;分别采用2,3-二羟甲基-2,3-二硝基-1,4-丁二醇四硝酸酯和2,3-二羟甲基-2,3-二硝基-1,4-丁二醇四对甲苯磺酸酯与NaN3反应,发现磺酸酯基易离去,叠氮化反应更易进行,收率较高;叠氮化反应的较优溶剂为DMSO。DSC分析表明,1,4-二叠氮-2,3-二叠氮甲基-2,3-二硝基丁烷的分解峰温为223.46℃。

高柔性线型配体1,4-双(2-甲基-8-喹啉氧基)-丁烷的合成与表征

2-甲基-8-羟基喹啉和二溴丁烷在正丁基锂的存在下反应,生成标题化合物(C24H24N2O2, Mr = 372.46)。X-射线单晶结构分析表明此晶体属于单斜晶系,空间群P21/c, a = 5.7002(5), b = 12.186(1), c = 14.312(1) , b = 92.503(2), V = 993.2(2) 3, Z = 2, m = 0.080 mm-1, Dc = 1.245 g/cm3, F(000) = 396, R = 0.0505, wR = 0.0705. 结果表明,该化合物的2个配位端基2-甲基-8-羟基-喹啉基处于间隔基团-(CH2)4-的两侧,整个分子呈现中心对称的反式构象。此外,通过分子间的p…p 堆积作用和 CH…p 作用,使分子堆积成三维网络结构。

Syntheses, Structures and Characteristics of Two New Cu(II) Coordination Polymers Based on 4-tert-butyl-phthalate and Different Bis(1,2,4-triazol-1-yl) Co-Ligands

Two new Cu（Ⅱ） coordination polymers, [Cu2（tbph）2（btb）2]n （1） and {[Cu2（tbph）2- （bth）2]·H2O}n （2）, （H2tbph = 4-tert-butyl-phthalic acid, btb = 1,4-bis（1,2,4-triazol-1- yl）butane, bth = 1,6-bis（1,2,4-triazol-l-yl）hexane）, have been synthesized and characterized by elemental analysis, FT-IR and X-ray single-crystal diffraction. Complex 1 has a 2D sql layer. Complex 2 shows a （3,4）-connected 2D sheet with a （4.6^4.8）（4.8^2） topology. The thermal behavior of the two cor- responding complexes has briefly been investigated.

1,4-丁二醇生产技术及国内外市场分析

介绍了1,4-丁二醇的生产方法及其进展,包括雷珀(Reppe)法、丁二烯法、环氧丙烷法和正丁烷/顺酐法等;分析了国内外1,4-丁二醇的生产消费现状及发展前景。2011年我国1,4-丁二醇的总生产能力约为504 kt/a,消费量约为367 kt/a;预计到2015年总需求量将达到约600 kt/a,而届时的生产能力将超过1 500 kt/a,产能大大过剩,未来市场竞争将十分激烈。国内相关企业今后应该慎重新建装置,同时不断开发新技术,调整产品结构,拓宽用途,以确保该行业健康快速发展。

固态1,4-二-(4-羧基吡啶基)丁烷锰(Ⅱ)配位化合物中的二维互相穿插和三维互锁结构(英文)

利用1,4-二-(4-羧基吡啶基)丁烷(L)合成了两种锰的新配位化合物{[MnL_2(H_2O)_4]·2H_2O·2ClO_4}_n(1)和{[MnL(H_2O)_3]·H_2O·2Cl}_2(2)。单晶X-射线衍射结构分析表明,1是由氢键所连接而成的二维互相交织的结构,2呈现出二重互锁的三维结构。结果显示在固体中反离子形成氢键的能力对1和2的结构起关键作用。

Syntheses, Structures, and Properties of Three Coordination Polymers: [Cd_2(bpp)_(1.5)(Hbpp)(phen)_2]_n, [Mn_3(Htptc)_2(phen)_2(H_2O)_2]_n, and {[Cu(btc)_(0.5)(1,4-bib)]·2H_2O}_n

Hydrothermal reactions of three aromatic polycarboxylic acids and the transitional metal cations in the presence of phen and 1,4-bib afford three new coordination polymers： [Cd2（bpp）1.5（Hbpp）（phen）2]n （1）, [Mn3（Htptc）2（phen）2（H2O）2]n （2）, and {[Cu（btc）0.5（1,4- bib）]·2H2O}n（3） （H2bpp = 2,6-bis（4＇-carboxyphenyl）-4-phenylpyridine, H4tptc = terphenyl-2,5,2＇,5＇-tetracar- boxylic acid, H4btc =biphenyl-2,2＇,4,4＇-tetracarboxylic acid, phen =1,10-phenanthroline, and 1,4-bib = 1,4-bis（1H-imidazol-1-yl）benzene）. Their structures have been determined by single- crystal X-ray diffraction analyses, elemental analyses, IR spectra, and powder X-ray diffraction （PXRD） analyses. In compound 1, the CdII cations are linked by bpp2- to form one ladder structure, based on which a 3D network is constructed with the help of non-covalent interactions. The topology of 2 is a 3D （3,4,5）-connected framework with the Point Schl？fli symbol of （42.6）2（43.62.8）（45.64.8）2. Compound 3 shows an unprecedented 3D （4,4）-connected framework with the Point Schl？fli symbol of （64.82）2（65.8）. Moreover, the luminescent property of 1 has been investigated.

2-丁亚砜-1,4-萘醌诱导人恶性黑色素瘤A375细胞凋亡及其机制

目的:探究2-丁亚砜-1,4-萘醌(BSNQ)对人恶性黑色素瘤A375细胞的诱导凋亡作用,阐明其诱导凋亡的机制.方法:MTT比色法检测BSNQ对人黑色素瘤A375细胞的杀伤作用.Annexin V-FITC/PI双染法与流式细胞术检测BSNQ对人黑色素瘤A375细胞的诱导凋亡作用.Western blotting法检测Akt信号通路相关蛋白的表达情况.流式细胞术检测BSNQ对A375细胞内ROS的调控作用.结果:BSNQ处理A375细胞其存活率逐渐降低.BSNQ能够显著诱导A375细胞发生凋亡.抗凋亡蛋白p-Akt和Bcl-2表达量逐渐降低,pro-caspase-3表达量逐渐降低,促凋亡蛋白Bad和cleaved-caspase-3表达量逐渐升高(P<0.05).BSNQ能够显著增加细胞内ROS水平.同时,BSNQ与NAC共同处理后,能够显著降低BSNQ诱导的细胞凋亡程度.结论:BSNQ通过上调细胞内ROS水平,下调Akt信号通路的活性,诱导人黑色素瘤A375细胞凋亡.

4-(环己基氨基)-1-丁烷磺酸的制备

以1,4-丁烷磺内酯和环己胺为原料制备4-(环己基氨基)-1-丁烷磺酸,优化的工艺条件为:n(环己胺)∶n(1,4-丁烷磺内酯)=1.5,以1,4-二氧六环为溶剂,回流条件下反应,反应时间8h,产物经丙酮洗涤、干燥后制得。此工艺条件下制备的4-(环己基氨基)-1-丁烷磺酸,收率为93%,纯度≥98%。

1,4-二氯甲氧基丁烷的制备及应用

以1,4-丁二醇、多聚甲醛和干燥的氯化氢气体为原料,合成了氯甲基化试剂1,4-二氯甲氧基丁烷(BCMB),并对白球进行氯甲基化。并采用红外光谱对它们的结构进行了表征。研究了物料配比,溶剂用量,反应温度及反应时间对标题化合物收率的影响。通过正交实验得优化工艺条件为n(1,4-丁二醇)∶n(多聚甲醛)=1∶2,溶剂40 mL,温度6～10℃,反应时间9 h。此条件下,标题化合物收率达到86.73%。

毛细管气相色谱法测定磺丁基醚-β-环糊精中杂质1,4-丁烷磺内酯

目的建立磺丁基醚-β-环糊精(SBE_7-β-CD)中的杂质1,4-丁烷磺内酯(1,4-BS)的测定方法。方法采用气相色谱法。色谱柱:DB1701 (30 m×0.32 mm,0.25μm);氢火焰离子化检测器;载气为氮气(纯度99.999%),燃气为氢气,助燃气为空气;载气流速30 ml/min;进样口温度为200℃;柱温为程序升温:初始温度100℃,以10℃/min的升温速率升到200℃,恒温0 min,再以30℃/min的升温速率升到260℃,恒温3 min;检测器温度为270℃;柱前压为9.9 psi;分流比为10∶1;进样1μl。采用二乙砜作为内标。结果二乙砜与1,4-BS的保留时间分别为6.131 min和8.615 min;1,4-BS的检测限为0.112 6 ng,定量限为0.259 9 ng;1,4-BS在2.984~8.952μg/ml范围内线性关系良好(r=0.998 9);高、中、低3种浓度的加样回收率分别为101.5%、99.3%、100.3%,精密度分别为1.6%、1.2%、1.2%;1,4-BS高、中、低3种浓度的平均萃取率分别为81.6%、73.0%、71.8%,RSD分别为14.3%、5.4%、6.3%;二乙砜高、中、低3种浓度的平均萃取率分别为59.0%、62.4%、50.5%,RSD分别为10.9%、7.6%、10.2%。结论本实验所建立的方法简单、快速、准确,灵敏度可满足检测要求,避免了美国药典论坛(PF)规定的标准加入法的繁琐计算,可作为SBE_7-β-CD中的杂质1,4-BS的有效检测方法。

正丁烷氧化、氢化制备1,4-丁二醇、γ-丁内酯和四氢呋喃

从工艺流程、原料价格、操作参数和反应结果等方面阐明正丁烷氧化、氢化制备1,4-丁二醇、γ-丁内酯和四氢呋喃是当前最有发展前途的原料路线.

相转移催化合成1,4-双(咪唑-1-基)丁烷的研究

以四丁基氢氧化铵作为相转移催化剂制备了1,4-双(咪唑-1-基)丁烷。通过单因素实验得到了合成该产物的最佳条件:氢氧化钾浓度90%,催化剂用量0.3 mmol,反应温度60℃,反应物摩尔比2.2,反应时间6 h。通过核磁共振波谱、红外光谱对所得产物进行了结构表征。

聚丙烯催化剂内给电子体环戊基-1,1-二甲醇二甲醚的合成

以丙二酸二乙酯和1,4-二溴丁烷为起始原料,经烷基化、酯还原和醚化反应合成环戊基-1,1-二甲醇二甲醚,分别考察关键因素对3步合成反应的影响。适宜的工艺条件为:①烷基化反应时,n(丙二酸二乙酯)∶n(CsOH)∶n(1,4-二溴丁烷)=1.0∶2.2∶1.4,CsOH为催化剂,环戊基-1,1-二甲酸二乙酯的收率为93.0%;②酯还原反应时,以无水ZnCl2为催化剂,n(环戊基-1,1-二甲酸二乙酯)∶n(KBH4)=2.0∶1.0,环戊基-1,1-二甲醇的收率为88.1%;③醚化反应时,以四丁基溴化铵为催化剂,n(环戊基-1,1-二甲醇)∶n(NaOH)∶n(碳酸二甲酯)=1.0∶8.0∶2.4,环戊基-1,1-二甲醇二甲醚的收率为61.2%。

“一锅法”简便合成1,4-双(2,4-二羟基苯基)-丁二酮-1,4(英文)

１，４－双（２，４－二羟基苯基）丁二酮－１，４－是Ｐｒａｋａｓｈ等从买麻藤属龈（ＧｅｎｅｈｕｍＵＬａ）中分离得到的一种微量组分。文中报道了以丁二腈和间苯二酚为原料，“一锅法”简便合成了此化合物。

双烯交联剂1,4-二(4′-乙烯苯氧基)丁烷的新合成方法

以对羟基苯乙酮为原料,经与1,4-二溴丁烷醚化,得到1,4-二(4′-乙酰苯氧基)丁烷,将其羰基还原得到中间体1,4-二(4′-羟乙基苯氧基)丁烷,脱水成烯就得到双烯交联剂1,4-二(4′-乙烯苯氧基)丁烷;用此方法合成的标题化合物作交联剂与苯乙烯聚合,可得到具有特殊溶胀性能的聚苯乙烯树脂。

1,4-双(2,3-环氧丙氧基)丁烷端基极性改性 溶聚丁苯橡胶的制备及性能研究

以正丁基锂为引发剂、环己烷为溶剂,采用醚类结构调节剂,以阴离子聚合法制备溶聚丁苯橡胶(SSBR),然后用1,4-双(2,3-环氧丙氧基)丁烷封端极性改性SSBR,考察SSBR的优化合成条件和优化改性条件。结果表明:当单体苯乙烯/丁二烯质量比为25/75、单体质量分数为9.3%、每千克溶剂中四氢呋喃用量为300 mg和醚类结构调节剂用量为135 mg、反应温度为60~65℃时,制得适用于轮胎胎面胶的分子中1,2-丁二烯结构质量分数为62%~67%的SSBR;1,4-双(2,3-环氧丙氧基)丁烷/正丁基锂物质的量比为0.5/1~0.7/1、改性温度为56.0~65.0℃时,SSBR的改性效果较好。1,4-双(2,3-环氧丙氧基)丁烷端基改性SSBR胶料各项性能达到国外同类SSBR胶料水平,与未改性SSBR胶料相比,其抗湿滑性能提升,滚动阻力降低。