2-(4-硝基苯基)吡啶衍生物的合成研究

以对硝基苯胺和合成得到的2-溴-4-硝基苯胺为原料, 采用Gomberg-Bachmann芳基偶联反应,合成了两种电致磷光材料的关键中间体2-(4-硝基苯基)吡啶和2-(2-溴-4-硝基苯基)吡啶,并通过1HNMR确证了产物结构.研究结果表明,该合成方法简单、可行,芳基偶联产物2-(4-硝基苯基)吡啶和2-(2-溴-4-硝基苯基)吡啶的产率分别达到了22.5%和5.9%,其中前者超过文献报道水平,后者未见文献报道.     

FeCl3·6H2O/C催化水合肼还原制备2,2-二(4-羟基-3-氨基)苯基丙烷

以ω(Fe)=5%的FeCl3·6H2O/C为催化剂,用ω (NH2NH2)=80%的水合肼,在乙醇溶剂中将2,2-二(4-羟基-3-硝基)苯基丙烷还原成为阻燃剂的中间体2,2-二(4-羟基-3-氨基)苯基丙烷.实验条件:用0.3 g的催化剂(每10 mmol反应物),反应物与水合肼的摩尔比为1∶4.5,控制反应温度为70℃,反应时间为3.5 h,目标产物的产率为93.0%,纯度为98.5%,考察9种金属离子对催化活性的影响.结果表明:Pb2 会引起催化剂中毒;Mg2 、Cu2 和Zn2 钝化了催化剂的催化活性;Ba2 和Cr3 对反应几乎不影响;只有Al3 、Ni2 、Ti4 3种离子能活化催化剂,从而使反应速度加快,但这3种金属离子单独作为催化剂时都没有催化活性.     

2,2-二(3-溴-4-羟基-5-硝基苯基)丙烷的合成及结构表征

以双酚A为起始原料,经过硝化、溴代反应,合成了2,2-二(3-溴-4-羟基-5-硝基苯基)丙烷,产率为83.1%.由IR、1HNMR、13CNMR和MS对目标产物的结构进行表征,所得数据与产物结构相符.     

3-(2'-羟基亚苄基)诺蒎酮的合成、表征及其酸碱指示性能研究

以β-蒎烯为原料,先经氧化反应合成诺蒎酮,诺蒎酮与水杨醛进一步经羟醛缩合反应合成了3-(2'-羟基亚苄基)诺蒎酮,通过单因素和正交试验优化了缩合反应的工艺条件。结果表明:缩合反应的优化工艺条件为:诺蒎酮1.43 g,以30 m L叔丁醇为溶剂,2.5 g叔丁醇钾为催化剂,n(诺蒎酮)∶n(水杨醛)为1.0∶1.2,回流反应2 h,产物得率为79.46%。采用MS、IR、NMR、X射线单晶衍射等对3-(2'-羟基亚苄基)诺蒎酮的结构进行了表征,确认了化合物的结构,该化合物的晶体属单斜晶系,P212121空间群。对3-(2'-羟基亚苄基)诺蒎酮的酸碱指示性能进行了研究,结果表明:该化合物滴定0.257 4 mol/L盐酸标准溶液时,指示颜色为橘黄色,测定的盐酸浓度为0.259 6 mol/L,RSD为0.089%,滴定的灵敏度高、偏差小,效果优于酚酞指示剂。     

2α-羟基齐墩果酸与2α-羟基熊果酸的分离及其EI-MS(+)差异性的研究

采用半制备高效液相法从枇杷叶中分离了2α-羟基齐墩果酸与2α-羟基熊果酸,通过UV、电子电离质谱(EI-MS)、NMR、IR对其结构进行了确认。并对其电子电离质谱正离子(EI-MS(+))裂解途径进行了研究,通过比较不同离子碎片的稳定性,提出了利用EI-MS中m/z248、203和133这3个特征离子碎片丰度差异鉴别这两种物质的方法。     

木薯淀粉接枝共聚物对钢在羟基乙酸溶液中的缓蚀性能

用丙烯酰胺(AA)单体对木薯淀粉(CS)进行接枝共聚化学改性,合成了木薯淀粉接枝共聚物(CSGC),采用失重法和电化学法研究了CSGC对冷轧钢在羟基乙酸溶液中的缓蚀性能。结果表明:CSGC能有效抑制冷轧钢在羟基乙酸中的腐蚀;缓蚀率随CSGC添加量的增大而不断上升,缓蚀率会随着温度的上升和浸泡时间的延长而下降,缓蚀率随着羟基乙酸质量浓度的增加呈先上升后下降的趋势。20℃时100 mg/L CSGC在0.3 mol/L羟基乙酸中浸泡24 h缓蚀率(失重法)高达92.1%,浸泡时间延长至72 h缓蚀率可达到89.13%。20~50℃时CSGC在0.3 mol/L羟基乙酸中的钢表面吸附符合Langmuir等温式,吸附焓(ΔH~Θ)为-23.8 k J/mol、吸附Gibbs自由能(ΔG~Θ)为-28.3~-28.9 k J/mol、吸附熵(ΔS~Θ)为15.4~16.8 J/(mol·K)。羟基乙酸中CSGC在钢表面发生物理吸附/化学吸附的混合吸附,且吸附伴随熵增加的放热过程。在0.3 mol/L羟基乙酸中CSGC为符合"几何覆盖效应"机理的混合抑制型缓蚀剂;由Nyquist图谱显示,钢/羟基乙酸界面上存在H_2O、H~+、HOCH_2COO~-和CSGC的吸附/脱附过程,CSGC通过挤走水分子发生吸附。     

HSPAF的合成及分光光度法测定微量钯的应用

1,5-二(2-羟基-5-磺酸基苯基)-3-乙酰基甲月 (无无)/(白)(HSPAF),是一种新的显色剂.以2-氨基-4-磺酸基苯酚和NaNO2为原料,经重氮化,偶合,在pH=5的溶液中,加丙酮析出,经多次提纯,干燥,用元素分析验证了HSPAF的组成.该试剂与Pd2+有显色反应,研究结果表明:在酸性溶液中,能形成稳定的红色络合物,其组成为n(Pd2+)∶n(HSPAF)＝1∶1,最大吸收波长为532 nm,表观摩尔吸光系数为2.8×104 L.mol-1cm-1,Pd2+的浓度在0～70 μg/25 mL范围内符合比耳定律.该试剂测定Pd2+具有较高的灵敏度和选择性,操作简便.还研究了共存离子的影响,测定了Pd-C催化剂中微量钯的含量,结果令人满意.     

-羟基熊果酸

在单因素试验的基础上,采用正交试验法对2α-羟基熊果酸的提取工艺进行优选,选用L9(34)进行正交试验,以2α-羟基熊果酸的得率为指标,考察常温(25℃)下超高压压力、保压时间、乙醇体积分数及其固液比(g∶mL)对2α-羟基熊果酸得率的影响。得到的最佳工艺条件为超高压压力300 MPa,保压时间5 min,乙醇体积分数90%,固液比1∶15,提取3次。2α-羟基熊果酸的提取得率可达0.415%。     

三氟化硼催化合成2,3,4,4'-四羟基二苯甲酮新方法研究

以高沸程石油醚代替1,1,2,2-四氯乙烷为溶剂,对焦性没食子酸合成2,3,4,4'-四羟基二苯甲酮的经典方法——三氟化硼催化法进行改进。在常温下快速搅拌和加热,使原料和溶剂体系由混悬液转变成棕色油状溶液,一定时间后瞬间产生大量黄色油性结晶产物沉淀,完成合成反应。采用正交试验法优化反应条件为:焦性没食子酸0.05 mol、对羟基苯甲酸用量0.055 mol、催化剂用量0.16 mol(20 mL)、反应温度110℃、反应时间1 h,在此条件下,2,3,4,4'-四羟基二苯甲酮产率达83.24%,产品纯度为97.83%。该方法与传统方法的产率相近,生产过程中比1,1,2,2-四氯乙烷的毒性小、成本低,改进的合成反应还具有时间短、后处理简便、催化剂可回收等优点。对提纯到99.53%的产物,通过红外吸收光谱、核磁共振谱、质谱等方法进行鉴定和表征,确定了产物为2,3,4,4'-四羟基二苯甲酮。     

N-(邻羟基苯甲基)脱氢枞胺的合成及在盐酸溶液中对碳钢的缓蚀性能

由脱氢枞胺与水杨醛制备脱氢枞胺水杨醛希夫碱(DAS),经硼氢化钠还原得到N-(邻羟基苯甲基)脱氢枞胺(DARS).采用红外光谱、紫外光谱、1H NMR对DARS进行结构表征,并通过静态失重法、电化学方法考察DARS在盐酸溶液中对A3钢的缓蚀性能.结果表明,DARS含有仲胺官能团,在盐酸溶液中的溶解性和稳定性大于DAS,...     

2-(3,4,5-三甲氧基苯基)-1,3-二噻茂烷的合成工艺研究

以3,4,5-三甲氧基苯甲醛为原料与1,2-乙二硫醇进行硫缩醛反应合成2-(3,4,5-三甲氧基苯基)-1,3-二噻茂烷,产物结构通过FT-IR、GC-MS等进行表征。并通过单因素试验对化合物的合成工艺条件进行优化,优化条件后产物得率达98%以上。     

2-(2-Phenylethyl)chromone derivatives from Chinese agarwood induced by artificial holing

Three new 2-(2-phenylethyl)chromone derivatives (1–3), together with thirteen known ones (4–16), were isolated from the EtOAc extract of Chinese agarwood induced by artificial holing, originating from Aquilaria sinensis (Lour.) Gilg (Thymelaeaceae). The chemical structures of the new compounds were identified by spectroscopic techniques (UV, IR, MS, 1D and 2D NMR). Compounds 1, 6, 15 and 16 exhibited inhibitory effects on Staphylococcus aureus, and compounds 15 and 16 showed inhibitory effects on Ralstonia solanacearum. Compounds 1–3, 7, 9, 11, 12, 15 and 16 exhibited acetylcholinesterase inhibitory activity. A possible biogenetic pathway of compounds 1–16 was proposed to show the relationships between diepoxy-tetrahydro-2-(2-phenylethyl)chromones, epoxy-tetrahydro-2-(2-phenylethyl) chromones, tetrahydro-2-(2-phenylethyl)chromones, and 2-(2-phenylethyl)chromones of the flidersia type, the four main types of 2-(2-phenylethyl)chromones found in agarwood, on the basis of their appearances in different stage of agarwood formation.     

SZW(S)10-2.5-M型废料锅炉的研制

随着木材工业的发展,我国木材综合利用企业生产能力达到年产6 0×104～1 0×105 企业不断增多,在建厂初期企业就考虑到木材综合利用原料中有10%～20%的废料(腐朽木、树皮、砂光粉等)是不能利用的废弃物,如何利用这部分废料减轻环境污染,企业的首选方法是利用废料作为燃料使用,这样既解决了废料的污染问题,又节约了企业燃料费支出,企业可在节约燃料费上得到经济效益。木材加工企业购进及改造废料锅炉应根据生产中产生的废料量确定锅炉的容量,根据废料的种类确定锅炉的燃烧方式。1木材加工企业废料量中密度纤维板厂、刨花板厂等木材加工企业…     

Bioactivities of caffeic acid methyl ester (methyl-(E)-3-(3,4-dihydroxyphenyl)prop-2-enoate): a hydroxycinnamic acid derivative from Solanum melongena L. fruits

Feeding deterrent and growth inhibitory effects of caffeic acid methyl ester (CME) isolated from the fruit extract of eggplant, Solanum melongena L. along with two known phenolic acids, caffeic acid (CA) and chlorogenic acid (CG) and azadirachtin (taken as active control), were evaluated against Spodoptera litura Fab. and Achaea janata L. (Lep., Noctuidae). The structure of CME was determined on the basis of extensive spectroscopic (UV, FTIR, ¹H, and ¹³C NMR) data analysis. CME has exhibited strong feeding deterrent activity against S. litura and A. janata larvae with ED₅₀ values of 52.02 and 41.02 μg/cm² leaf area, respectively. CA and CG were relatively less effective compounds when compared with CME. The results also revealed that the isolated compound CME caused marked larval growth inhibition in S. litura and A. janata larvae after 7 days of feeding on a treated diet. The effect on growth of larvae was concomitant with the reduced feeding and digestibility of ingested food. So the activities of digestive proteases within the midgut of larvae were examined using specific substrates to understand the digestive physiology in the larval guts. The bulk of the activity was associated with serine proteases comprising trypsin-, chymotrypsin-, and elastase-like enzymes, which decreased in diets containing CME, whereas, interestingly increased with CG. From the results, we conclude that CME isolated from S. melongena fruit extract shows feeding deterrent and larval development inhibitory activities that may prove useful in the management of S. litura and A. janata larvae.     

Robert Hartig (1839-1901)

Ohne Zusammenfassung     

Physiologische Reaktionen der Fichte (Picea abies) auf komplexen SO2- und Trockenstreß

Physiological reactions of spruce (Picea abies) on complex SO₂- and drought-induced stress. Part 3. Responses of SO₂-stressed spruces to subsequent drought-induced stress. SO₂-stressed spruces under drought-stress showed less reduced water content, less increased osmotical potential and less restricted photosynthesis compared to spruces without preceding SO₂-stress and thus seemed to be in a better physiological situation. Their ability to retain water (in cut-off twigs) as well as their ability to withstand a quick and strong water-loss in the needle-tissue without cell-damage were reduced. Reasons for the temporarily favourable effect of a pre-going SO₂-stress in surviving a drought-stress are discussed.     

高SO4^2-离子腐蚀区钻孔灌注桩防腐措施

在受污染地区进行基础建设时，需考虑结构防腐问题，国内外曾发生过多起由于防腐处理不好而造成结构报废的重大事故。介绍了济南顺河高架桥施工过程中的砼防腐技术。