Use of phenylselenyl chloride in the preparation of methyl 11-phenylseleno-10-acetamido- and ethyl phenylselenoethoxy fatty alkanoates

Reaction of methyl 10-undecenoate (I) with phenylselenyl chloride in acetonitrile furnished methyl 11-phenylseleno-10-acetamido-undecanoate (II) as a major product, and a similar reaction of I with phenylselenyl chloride in absolute ethanol gave ethyl 11-phenylseleno-10-ethoxy-undecanoate (III) as a sole product. A similar reaction of methyl octadec-cis-9-enoate (IV; oleate) with phenylselenyl chloride in absolute ethanol was conducted and resulted in the formation of ethyl 10(9)-phenylseleno-9(10)-ethoxy-octadecanoate (V).     

合成醇醚羧酸的Pt/C催化剂催化活性研究及表征

通过浸渍法结合液相还原法将金属Pt,Ni和Sn负载在活性炭上制备了多组分Pt/C催化剂,并应用于催化氧化直接制备醇醚羧酸的反应中,考察了催化剂组分不同对脂肪醇聚氧乙烯醚(AEO9)氧化法制备醇醚羧酸(AE9C)过程中催化性能的影响;采用TEM,XRD和XPS对催化剂进行了表征。结果表明,在Pt/C催化剂中加入Ni和Sn后,Pt的颗粒粒径变小,分散性更好,Pt0的含量增加,从而提高了催化剂的活性。多组分Pt/C催化剂与单一组分Pt/C催化剂相比,AE9C产率提高了27.54百分点。     

Degradation of poly(vinyl chloride) in the presence of 9-(2,3-epoxypropane)carbazole studied by means of TGA/FTIR

Blends containing poly(vinyl chloride) and 9-(2,3-epoxypropane)carbazole in different weight ratios were subjected to investigations using thermogravimetric analysis coupled with Fourier transform infrared spectroscopy. The effect of additive on the polymer degradation process was studied. It was found that 9-(2,3-epoxypropane)carbazole causes an increase in the onset temperature of hydrogen chloride emission by about 20–25°C. Finally, the mechanisms of stabilization were proposed. © 1995 John Wiley & Sons, Inc.     

磷钨酸铝催化合成9-苯甲酰蒽

为合成功能高分子中间体9-苯甲酰蒽,考察了以杂多酸型催化剂磷钨酸铝(AlPW12O40)催化蒽和苯甲酰氯的Friedel-Crafts酰基化反应,提纯得到w(9-苯甲酰蒽)=96.3,用GC/MS、FTIR和1HNMR等确认了其结构;考察了各反应条件对9-苯甲酰蒽产率和选择性的影响,得到9-苯甲酰蒽的优化合成条件为:反应温度90℃,反应时间5h,n(蒽):n(苯甲酰氯)=1.0:1.5,w(催化剂)=4.5,溶剂为环己烷。在上述条件下,9-苯甲酰蒽的产率和选择性分别可达47.4和91.8。证明AlPWO对目标产物选择性高、无环境污染,可以回收利用。     

Lewis Acid Induced Additions to Unsaturated Fatty Compounds III: Alkylaluminium Halide Induced Friedel-Crafts Acylations of Unsaturated Fatty Compounds

Alkylaluminium halide induced Friedel-Crafts acylations of unsaturated fatty compounds with acyl chlorides give the corresponding β,γ-unsaturated ketones. Acylation of oleic acid and 10-undecenoic acid with acetyl chloride yields (E)-9(10)-acetyloctadec-10(8)-enoic acid and 12-oxo-tridec-9-enoic acid, respectively. Acylation of 10-undecenoic acid with heptanoyl chloride followed by NaBH₄-reduction gives ricinelaidic acid. The very interesting β,γ-unsaturated ketodicarboxylic acid (E)-9(10)-(1-oxo-3-carboxy-propyl)octadec-10(8)-enoic acid is obtained by acylation of oleic acid with succinic anhydride.     

蒙脱石-氯化铁的红外光谱分析

通过吡啶吸附红外光谱分析了蒙脱石 (EC1)、蒙脱石 -氯化铁 (EC4 ( )、EC4 ( )、EC7、EC9)特征吸收峰的相对强度。在 EC4 ( )、EC4 ( )、EC7、EC9中 ,B酸 1 540 cm-1吸收增强 ,而 L酸在1 44 0 cm-1吸收所占总酸量的比例下降。对于苯与氯化苄的反应 ,L酸 1 44 0 cm-1附近吸收所占总酸量的比例越小 ,催化剂的催化性能越强     

肠衣废水气浮预处理泥渣脱水性能研究

针对肠衣废水处理过程中气浮池排出的泥渣含水率高、比阻大的特点,以三氯化铁(FeCl3)、聚合氯化铝(PAC)、阳离子聚丙烯酰胺(CPAM)为脱水剂,通过单因素实验预处理肠衣加工生产浮渣,结果表明:无机脱水剂中三氯化铁效果更佳,有机脱水剂为阳离子聚丙烯酰胺,投加量分别为干污泥质量的8%和0.25%,处理后的污泥比阻分别为0.2468×10^9 s^2/g和0.2706×10^9 s^2/g。通过双因素实验预处理肠衣加工生产浮渣,结果表明:当三氯化铁和阳离子聚丙烯酰胺的投加量分别为干污泥质量的4%和0.125%,脱水效果达到最佳,处理后的污泥比阻为0.2468×10^9s^2/g;在此实验加药条件下,某污水处理厂通过板框压滤机对气浮池产生的泥渣进行脱水性能实验,使其处理后肠衣水浮渣的含水率达到60%以下。     

1-(并二甲硫基)甲基-4-甲氧基苯的合成

０．１５ｍｏｌ茴香醛和０．６ｍｏｌ甲硫醇在９ｍｍｏｌ对甲苯磺酸催化下发生反应，合成了相应的缩硫醛，产率８３．７％。通过红外光谱、元素分析、核磁共振检测对产物结构进行了确证。此外，浓硫酸、氯化锌也是反应的催化剂。     

Some New Heterocyclic Sulphonates with potential antimicrobial activity

4-(Phenylhydrazono-4′-benzenesulphonato)-3-methyl-2-pyrazolin-5-one ( 2 ) was prepared by treating 4-(4′-hydroxyphenylhydrazono)-3-methyl-2-pyrazolin-5-one ( 1 ) with benzenesulphonyl chloride. Heating 2 with acetic anhydride, chloroacetyl chloride and benzenesulphonyl chloride afforded the N-acetyl ( 3 ), N-chloroacetyl ( 4 ) and O-benzenesulphonyl ( 5 ) derivatives, respectively. 2 reacted with benzenesulphonyl chloride under cooling conditions to give the N-benzenesulphonyl derivative ( 6 ). 2 undergoes Mannich reaction to give the N-Mannich base ( 7 ). Reaction of 2 with formaldehyde in methanol afforded the N-hydroxymethyl derivative ( 8 ) which undergoes condensation with ethyl acetoacetate, ethyl cyanoacetate and malononitrile to give compounds 9 , 10 and 11 respectively. The antimicrobial activity of these products against gram-positive (+ve), gram-negative (−ve) bacteria and fungi was screened. They showed potential bactericidal activity and some of them exhibited high fungicidal activity.     

Mechanochemical synthesis and characterization of poly(vinyl chloride)-block-poly(vinyl alcohol) copolymers by ultrasonic irradiation

Mechanical degradation and mechanochemical reaction in heterogeneous systems of the solid poly(vinyl chloride)-poly(vinyl alcohol) aqueous solutions have been studied by ultrasonic irradiation at 30 °C. The rate of decrease in the viscosity-average degree of polymerization of the degraded poly(vinyl chloride) was much faster than that of the degraded poly(vinyl alcohol). Mechanochemical reaction occurred by free radicals produced from the chain scissions of both polymers by ultrasonic waves. The copolymer was obtained and the molar ratio of the vinyl chloride and the vinyl alcohol units in its copolymer can be determined. In addition, the changes in the composition of the total block copolymer, the unreacted poly(vinyl chloride), and the unreacted poly(vinyl alcohol) were obtained. Received: 1 October 1998/Revised version: 9 January 1999/Accepted: 13 January 1999     

氯化肉碱腈的化学制备

研究了三甲胺盐酸盐与环氧氯丙烷在乙醇水溶液中催化反应生成氯化3 氯 2 羟丙基三甲铵(CHPTMA),再经氰化反应生成氯化3 氰 2 羟丙基三甲铵(氯化肉碱腈)的工艺。通过正交实验得到了催化反应最佳工艺条件:反应液pH=8～9、反应温度35℃、n(环氧氯丙烷)/n(三甲胺盐酸盐)=0 95、反应时间1h,在此实验条件下进行合成,产率93%。氰化反应最佳工艺条件:反应温度40～45℃、反应时间1 5h、n(氰化钠)/n(CHPTMA)=1 05,在此条件下,产率为78 8%。     

Studies on the ozonization of methyl oleate

The ozonides of methyl 9-octadecenoate, 9-octadecene and methyl 9-octadecendioate (along with pelargonyl aldehyde, methyl azelaaldehydate and a fraction which appears to consist mainly of hydroperoxy-ozonides) were isolated from ozonizations of methyl oleate in pentane and methylene chloride at −65C. The relative amounts of these compounds were determined in ozonizations of methyl oleate in pentane, methylene chloride and ethyl acetate. Present concepts of the mechanism of the reaction are elaborated on the light of new information on the products of the ozonization of methyl oleate and related compounds under various conditions. Supported in part by Grant no. AM-05018, U. S. Public Health Service, National Institutes of Health. Presented at the AOCS meeting in Atlanta, 1963.     

无味透明软质医用PVC-LMW／PVC-HMW共混物的研究

以医用通用级聚氯乙烯（PVC-LMW）、高相对分子质量聚氯乙烯（PVC-HMW）、邻苯二甲酸二辛酯（DOP）和酯基有机锡热稳定剂等为原料，使用Brabender塑化仪和HAA转矩流变仪，通过熔融共混制备了软质PVC-LMW／PVC-HMW共混物，研究了其力学、光学等性能。结果表明，在PVC-LMW中加入一定量的PVG-HMW，可提高共混物的弹性，透明性能略有改进。选择适宜的加工温度，共混物的力学性能有明显改善，拉伸强度为14．1MPa，断裂伸长率为431．88％，回弹性为9．5％。当去味吸收剂含量为0．3～0．5份（质量份，下同）时可以除去共混物中的味道。     

香料丁酸糠醇酯的合成与表征

由丁酰氯和糠醇反应,以廉价的氧化钙和碳酸钠为复合束酸剂,合成了香料丁酸糠醇酯,并用IR、GC等进行了表征。优化条件为:n(丁酰氯)/n(糠醇)=1 2;0 1mol糠醇溶剂用量为60mL、束酸剂用量为18g,回流时间为4h。丁酸糠醇酯的收率为87 2%,产品质量分数为99 9%。     

含氯介质超临界水氧化过程中几种镍基合金腐蚀的实验研究

超临界水氧化过程中,含氯化合物水溶液对普通不锈钢具有极强的腐蚀性. 使用超临界水氧化反应装置,研究了4种镍基合金不锈钢试样(1Cr18Ni9Ti, 316L, 0Cr18Ni12Ti和QLC12)在超临界水氧化过程中(400~620℃, 28~32 MPa)处理含氯废水时的腐蚀情况. 经过30 d的实验,用金相光学显微镜和扫描电子显微镜观测试样腐蚀的形貌. 结果表明,4种合金在15%(w)含氯水溶液中经过超临界水氧化反应均存在腐蚀. 对腐蚀速率进行了测试,其中1Cr18Ni9Ti和316L腐蚀速率较大,而QLC12腐蚀速率最小,为0.06 mm/a, 可用于制造反应器. 实验发现0Cr18Ni12Ti存在晶间腐蚀现象. 同时对腐蚀机理进行了分析.     

Organoselenium-mediated cyclization of hydroxyolefinic fatty acids and m-CPBA oxidation of selenium-containing 1,4-epoxy acids

Chlorophenylselenenylation methodology is shown to cause cyclization of naturally occurring β- and γ-hydroxyolefinic acids. The phenylseleno-substituted 1,4-epoxides (tetrahydrofurans) thus obtained are oxidized by m-chloroperbenzoic acid (m-CPBA). Reaction of phenylselenenyl chloride with methyl 12-hydroxyoctadec-cis-9-enoate (methyl ricinoleate) gave methyl 9,12-epoxy-10-phenylselenenyloctadecanoate in useful yields. A similar reaction of phenylselenenyl chloride with methyl 9-hydroxyoctadec-cis-12-enoate afforded a quantitative yield of methyl 9,12-epoxy-13-phenylselenenyloctadecanoate. Oxidation of selenium-containing 1,4-epoxy esters by m-chloroperbenzoic acid (1 equivalent) yielded the respective olefinic 1,4-epoxy esters, while 5 equivalent m-CPBA afforded the corresponding oxirane esters of epoxytetrahydrofurans in high yields. The structure of the individual reaction products have been established from analytical and spectral data and corroborated by a study of their mass spectra.     

聚硅酸聚合氯化铝的制备及性能研究

以废酸和钙粉为原料,制备了聚硅酸聚合氯化铝复合型絮凝剂(PSAC),利用正交实验方法考察了聚铝(PAC)中铝含量、聚合硅酸含量、聚硅酸pH值、n(Al)/n(Si)及复合熟化时间对PSAC絮凝性能的影响。实验结果表明,当n(Al)/n(Si)=13:1,PAC中Al3+的含量(以Al2O3质量分数计)为9%,复合时间为1 h时,研制的PSAC对工业污水具有最佳处理效果,并具有较宽的pH值使用范围。     

荧光衍生化试剂2-(9-咔唑)乙酰氯的合成

以咔唑为起始原料,经氮烷基化、碱性水解、酰氯化反应,合成了荧光衍生化试剂2-(9-咔唑)乙酰氯,该试剂可用于胺、氨基酸、醇、多糖等的分析检测。以IR、FAB-MS和元素分析对目标产物进行了表征。     

Lewis acid induced additions to unsaturated fatty compounds IV: Synthesis of cyclopentenones from Friedel- Crafts acylation products of unsaturated fatty compounds with α,β-unsaturated acyl chlorides

The ethylaluminium dichloride induced Friedel- Crafts acylation of unsaturated fatty compounds such as oleic acid ( 1a ), methyl oleate ( 1b ) and 10-undecenoic acid ( 9b ) and furthermore of 1-octene ( 9a ) with α,β-unsaturated acyl chlorides e.g. crotonic acid chloride ( 2a ) and acrylic acid chloride ( 2b ) gave the corresponding allyl vinyl ketones. Nazarov cyclizations of the acylation products 3a/4a, 3b/4b, 10a and 10b afforded the alkyl substituted 2-cyclopentenones 5a/6a, 5b/6b, 11a/12a and 11b/12b . Catalytic hydrogenation of 5b/6b and 11b/12b gave the respective saturated cyclic products 7b/8b and 13b/14b as diastereomeric mixtures.     

Expression of SLC26A9 in Airways and Its Potential Role in Asthma

SLC26A9 is an epithelial anion transporter with a poorly defined function in airways. It is assumed to contribute to airway chloride secretion and airway surface hydration. However, immunohistochemistry showing precise localization of SLC26A9 in airways is missing. Some studies report localization near tight junctions, which is difficult to reconcile with a chloride secretory function of SLC26A9. We therefore performed immunocytochemistry of SLC26A9 in sections of human and porcine lungs. Obvious apical localization of SLC26A9 was detected in human and porcine superficial airway epithelia, whereas submucosal glands did not express SLC26A9. The anion transporter was located exclusively in ciliated epithelial cells. Highly differentiated BCi-NS1 human airway epithelial cells grown on permeable supports also expressed SLC26A9 in the apical membrane of ciliated epithelial cells. BCi-NS1 cells expressed the major Cl⁻ transporting proteins CFTR, TMEM16A and SLC26A9 in about equal proportions and produced short-circuit currents activated by increases in intracellular cAMP or Ca²⁺. Both CFTR and SLC26A9 contribute to basal chloride currents in non-stimulated BCi-NS1 airway epithelia, with CFTR being the dominating Cl⁻ conductance. In wtCFTR-expressing CFBE human airway epithelial cells, SLC26A9 was partially located in the plasma membrane, whereas CFBE cells expressing F508del-CFTR showed exclusive cytosolic localization of SLC26A9. Membrane localization of SLC26A9 and basal chloride currents were augmented by interleukin 13 in wild-type CFTR-expressing cells, but not in cells expressing the most common disease-causing mutant F508del-CFTR. The data suggest an upregulation of SLC26A9-dependent chloride secretion in asthma, but not in the presence of F508del-CFTR.