Twelve novel carane-3,4-diol derivatives were designed, synthesized, and evaluated for their herbicidal activities against Lolium multiflorum Lam. and Brassica campestris for the first time. The relationships between the chemical structural factors, including types, the number or the carbon chain length of functional groups, associated with the lipophilicity and the herbicidal activity of the tested compounds were also discussed. The results showed that most of newly synthesized compounds had a dose-dependent, herbicidal activity against the root and shoot growths of Lolium multiflorum Lam. and Brassica campestris. Compared to carane-3,4-diol, most of the target derivatives possessed improved lipophilicity and certain solubilities in representative solvents with different polarities. Particularly, ester derivatives 3a-3b and 3e can be dissolved or dispersed in water, but also displayed higher herbicidal activity against Lolium multiflorum Lam. and Brassica campestris than other ester derivatives. The 50 % inhibitory concentration (IC50) value of compound 3e against shoot growth of Brassica campestris (0.485 mmol/L) was superior to that of commercial herbicide glyphosate (1.14 mmol/L), indicating that the potential application as a water-based herbicide for Brassica campestris control.

Twelve novel omega-aminomethyl longifolene amide derivatives (6 a-6 l) were synthesized and characterized. The intermolecular contacts and the relationship of structure-property for the synthesized compounds were performed with the use of two-dimensional fingerprint plots and Hirshfeld surface method. Moreover, the chemical reactivity and geometrical characteristics of target compounds were investigated using density functional theory (DFT) method. Molecular docking studies were performed to investigate the interactions between compounds 6 a-6 l and sortase A (SrtA) from S. aureus, the carboxy terminal domain of colicin E5 (E5-CRD) and Serine/Threonine phosphatase Z1 (PPZ1) from C. albicans, respectively, and together with their biological activities. The docking results of the synthesized compounds 6 a-6 l showed different binding efficiencies and inhibitory effects on S. aureus, E. coli and C. albicans. Furthermore, preliminary antimicrobial activity assay showed that compounds 6 f, 6 i and 6 k exhibited comparable or superior antibacterial activity against S. aureus, B. subtilis and K. pneumoniae compared to rifampicin with minimum inhibitory concentration (MIC) values from 0.488 to 0.977 mu g/mL. In addition, the absorption, distribution, metabolism and excretion (ADME) and drug-likeness properties of the synthesized derivatives were evaluated as well.

Twelve novel longifolene-derived primary amine carboxylates were synthesized and evaluated for herbicidal activity. The structures of title compounds were confirmed by Fourier-transform infrared spectroscopy, H-1 nuclear magnetic resonance (NMR), C-13 NMR, and high-resolution mass spectrometry. The results showed that all the synthesized compounds exhibited higher herbicidal activity than the corresponding carboxylic acids involved in the reaction and the commercial herbicide glyphosate; some of them even possessed inhibition rates of 100% against Lolium multiflorum Lam. and Brassica campestris at low concentrations (0.039-0.313 mmol/L). Moreover, structural factors, including types of carboxylates and carbon chain length, had a great influence on the herbicidal performance. The herbicidal activity of dicarboxylates was similar to or much higher than that of corresponding monocarboxylates and glyphosate. Furthermore, compound 5l was found to be the most active candidate against the root and shoot growth of L. multiflorum Lam. and B. campestris with half maximal inhibitory concentrations (IC50) of around 0.010 and 0.023 mmol/L. The present work indicated that those prepared compounds have great potential to serve as high-performance botanical herbicides used at low doses.

采用平皿培养法考察蒈烷-3,4-二醇在水溶液中对一年生黑麦草和油菜根、茎伸长的抑制作用,探讨其作为水基除草剂的应用潜力.结果表明:蒈烷-3,4-二醇微溶于水,可在少量亲水性有机溶剂和表面活性剂作用下配制成浓度大于20 mmol/L水乳液,能够抑制黑麦草和油菜根、茎的伸长,表现与浓度相关的除草活性,对黑麦草的根、茎伸长的半数抑制浓度(IC50)分别达到1.12和1.73 mmol/L,而对油菜根、茎伸长的IC50分别达到1.23和2.12 mmol/L.其除草活性明显高于天然单萜二醇对孟烷-3,8-二醇,而稍低于商业除草剂草甘膦,有望进一步研究开发作为水基植物源除草剂.

传统林产化学工艺学实验教学项目"松脂加工"以常压饱和水蒸气作为解吸介质,在仪器设备、实验操作步骤方面与目前松脂加工企业生产实际存在较大差别,不利于学生认识与理解水蒸气蒸馏法松脂加工理论、加强工程意识.通过增加简单易行、安全的水蒸气过热器及操作步骤,设计建立以常压过热水蒸气为解吸介质的松脂加工实验教学项目,使实验教学项目内容贴近工业生产实际,取得了良好的教学效果.

以厚壁透明高硼硅玻璃耐压瓶、便携卡式炉液化丁烷气瓶、冰箱为主要设备及器材,设计制作了小型亚临界流体丁烷萃取实验装置.实践表明,该装置具有造价低、占地面积小、操作简单易行、安全可控能控、实验过程直观可视等特点,可应用于实验教学和科研工作,在培养学生动手能力与科研思维,增强学生的工程知识学习,改善实验条件和提高实验教学效果等方面具有积极作用.

A series of novel quaternary ammonium salts (QASs) (4a-4n) comprising a camphene moiety were synthesized for the first time. Fourteen examples were prepared from camphene through Prins reaction, halogenation, and quaternarization, successively. The structures of the synthesized QASs were analyzed by Fourier transform infrared spectroscopy, 1H NMR, 13C NMR and high-resolution mass spectrometry. Surface-active properties, emulsifying abilities, and foaming properties of the investigated compounds were then studied. The antimicrobial activities of these QASs against Gram-positive bacteria (Staphylococcus aureus and Bacillus subtilis), Gram-negative bacteria (Escherichia coli and Klebsiella pneumoniae), and fungi species (Candida albicans, Candida tropicalis, and Aspergillus niger) were determined by the microdilution method. The results showed that the chemical structural factors, including types of substitutes and alkyl chain length, might be correlated with the lipid-water partition coefficient (cLog P), which played a critical role in the antimicrobial process. Compounds with alkyl chain lengths (N) in the range of 10-14 were relatively more active, while compounds bearing pyridinium, benzyl, methylimidazolium groups, or varied alkyl chain lengths (N < 5 and N > 16) were almost inactive. Compound 4k possessing a dodecyl group exhibited the most effective and broad-spectrum antimicrobial activity against almost all tested bacteria and fungi with the minimal inhibitory concentration values ranging from 0.24 to 0.98 μg/mL.

The target compound of ω-aminomethyl longifolene( 5) was synthesized from ω-chloromethyl longifolene( 3) by Gabriel synthesis via intermediate N-substituted phthalimide derivative( 4). The structures of compounds 4 and 5 were confirmed by high resolution mass spectrum(HRMS), Fourier transform infrared(FT-IR), 1H nuclear magnetic resonance(1H NMR), 13C nuclear magnetic resonance(13C NMR) and single-crystal X-ray diffraction(SC-XRD). The absolute configuration of compound 5 was inferred from the crystal structure of the synthesized compound 4. In the hydrolysis reaction of compound 4, the yield of compound 5 could be improved and the separation and purification process could be simplified by adding sodium hydroxide and heating reflux hydrazinolysis conditions under solvent-free. The results of single-factor experiment showed that under the optimum hydrazine hydrolysis conditions of n(hydrazine hydrate): n(compound 4)=23:1, 5 g 10% sodium hydroxide solution, and 6 h reaction time at reaction temperature of 120 ℃, the yield and purity of compound 5 could be reached 94.1% and 99.98%, respectively. The results of antibacterial activity assay in vitro showed that compound 5 could significantly inhibit the growth of four bacteria( Staphylococcus aureus, Bacillus subtilis, Escherichia coli and Klebsiella pneumoniae) and three fungi( Candida albicans, Candida tropicalis and Aspergillus niger). The minimum inhibitory concentrations(MIC) were 1.95, 1.95, 7.81, 3.91, 3.91, 1.95 and 15.63 mg/L, respectively. Among them, compound 5 showed stronger inhibitory activities against C. albicans and C. tropicalis than positive control ketoconazole.

研究ω-氯甲基长叶烯与不同硫氰酸盐的取代反应,选择性合成了含长叶烯结构的ω-硫氰甲基长叶烯和ω-异硫氰甲基长叶烯,采用FTIR、UPLC-QTOF/MS、1H NMR和13C NMR对产物进行结构表征.结果 表明,硫氰酸盐类型和反应体系对产物的选择性有较大影响.在60℃加热搅拌条件下,硬酸型阳离子K+、Na+和NH4+的硫氰酸盐,在以水或正己烷为溶剂的反应体系中,主要产物是ω-硫氰甲基长叶烯,选择性大于75.0％,而在室温无溶剂研磨反应体系中主要产物没有生成;软酸型阳离子Ag+和交界酸型阳离子Pb2+的硫氰酸盐,在以水为溶剂和室温无溶剂研磨两种反应体系中,主要产物为ω-硫氰甲基长叶烯,选择性均大于80.0％,而在以正己烷为溶剂反应体系中,主要产物为ω-异硫氰甲基长叶烯,选择性大于70.0％.

以正己烷为溶剂,在加热回流条件下,ω-氯甲基长叶烯(Ia)与硫氰酸铅进行取代反应,选择性合成具有低刺激性气味的ω-异硫氰甲基长叶烯(Ib).采用高分辨率质谱、傅里叶红外吸收光谱、紫外吸收光谱、1 H与13 C核磁共振谱对目标化合物的化学结构进行表征确证.高分辨质谱确定了其分子式为C17 H25 NS,傅里叶红外吸收光谱、紫外-可光吸收光谱、1 H NMR与13 C NMR分别证实了N=C=S结构和长叶烯结构的存在.化合物Ib兼具长叶烯和异硫氰酸甲酯的分子结构,可归属于异硫氰酸烯丙酯类化合物.通过96孔板二倍稀释法抑藻活性试验的评价,得到化合物Ib能够抑制斜生栅藻和中肋骨条藻的生长,其最小抑制质量浓度分别为62.5和31.25 mg/L左右,抑藻活性明显优于化合物Ia、长叶烯和异硫氰酸甲酯.

有机化学实验是高等学校化学相关专业重要的一门实践课程,传统的教学与考核方式多为动手操作或笔试考核为主,方式单一,不利于学生综合能力的培养与提升.为拓宽教学途径,有效提高有机化学实验的教学质量,采用"演讲评"综合考核模式应用于该课程的教学环节中,该模式对调动学生学习的积极性与主动性,巩固专业知识、提高专业技能素质、培养创新精神与团队协作意识有良好的助推作用.

以丙烯酰胺(AM)为单体、马来松香丙烯酸乙二醇酯(EGMRA)为交联剂在6063铝合金上热合成了一种共聚膜.采用傅里叶变换红外光谱、扫描电镜分别对共聚膜的结构及形貌进行了研究.结果 表明在6063铝合金上已合成了AM与EGMRA的共聚膜.在NaCl质量分数3.5％的溶液中测试了不同EGMRA浓度下合成的聚合膜的电化学性能,结果表明,EGMRA的浓度为0.04～0.06 mol./L时,共聚膜显示出较高的防腐蚀性能.制备的共聚膜对铝合金的保护效率达95.2％.同时也比较了单独的AM聚合膜与共聚膜的防腐蚀性能,结果表明共聚膜能更高效地保护铝合金.

以ω-乙酰氧甲基莰烯、乙酰氯、无水乙醇为原料,通过卤代反应,合成 ω-氯甲基莰烯,通过 FT-IR、1 H NMR、13 C NMR 和 LC-HRMS 等对产物进行了结构表征.研究结果表明:反应时间、反应物料比对卤代反应有较大的影响,在温度为30 ℃、n(ω-乙酰氧甲基莰烯)∶n(乙酰氯)∶n(无水乙醇)为1∶2∶2的条件下反应5 min,ω-乙酰氧甲基莰烯的转化率和ω-氯甲基莰烯产率分别高达97.5％和95.2％.微量肉汤二倍稀释法抑菌活性实验结果表明:ω-氯甲基莰烯能抑制细菌和真菌的生长,对4种细菌(大肠杆菌、肺炎克雷伯菌、金黄色葡萄球菌、枯草芽孢杆菌)的最低抑菌质量浓度(MIC)分别为125、62.5、15.63、250 mg/L,对3种真菌(白色念珠菌、热带念珠菌、黑曲霉)的MIC均为31.25 mg/L,抑菌活性明显高于莰烯、ω-乙酰氧甲基莰烯和ω-羟甲基莰烯,对白色念珠菌的抑菌活性与阳性对照品酮康唑相当.

The title compound (E)-2-(2-(4,8,8-trimethyldecahydro-1,4-methanoazulen-9-ylidene)ethyl)benzoldlisothiazol-3(2H)-one (Ic) was synthesized from longifolene and 1,2-benzoisothiazolinone (short as BIT) through Prins, halogenation and nitro-alkylation reaction and structurally identified by means of FIRMS, IR, H-1-NMR, C-13-NMR and single-crystal X-ray diffraction. The crystal of compound Ic is of bi-molecular structure and belongs to orthorhombic system, P2(1)2(1)2(1) space group with a = 7.5715(7), b = 16.8824(9), c = 31.1926(14) angstrom, V = 3987.2(5) angstrom(3), M-r = 367.53, D-c = 1.225 mg/m(3), Z = 8, mu = 0.174 mm(-1) and F(000) = 1584. A total of 17045 reflections were collected, of which 7306 were unique (R-int = 0.0566). The structure was refined to R = 0.0967 and wR = 0.1998 for 7306 observed reflections with I > 2 sigma(I). 1D chain along the a-axis is formed by two types of pi-pi interactions between benzene rings from adjacent molecules. Especially, compound Ic shows improved solubility in nonpolar organic solvents and higher antimicrobial activity than longifolene and BIT against bacteria and fungi. The minimum inhibition concentration (MIC) of Ic against two Gram-positive bacteria (S. aureus and B. subtili), two Gram-negative bacteria (E. coli and K. pneumoniae) and three fungi (C. albicans, C. tropicalis and A. niger) are 0.242, 0.242, 15.6, 15.6, 1.95, 1.95 and 1.95 mu g/mL, respectively.

化工生产实习是高等学校化学化工学科本科教学的重要组成部分.为有效提高化工生产实习的教学质量,顺应新时代化工人才培养的需求,将"演讲评"综合考核模式应用于生产实习教学环节中.该模式对调动实习生积极性与主动性,巩固专业理论知识,增强实际工作能力,提升综合素质,具有良好的促进作用.

The chemosynthesis and potential as green herbicides of the derivatives of (3R,4R)-4,7,7-trimethyl-6-oxabicyclo [3.2.1]octane-3,4-diol (compound 2) were emphatically addressed in this work. First, the ester and ether derivatives of (3R,4R)-4,7,7-trimethyl-6- oxabicyclo[3.2.1]octane-3,4-diol (compound 2) were synthesized and structurally characterized by infrared spectroscopy, high-resolution mass spectrometer, and proton nuclear magnetic resonance. Then, the post-emergence herbicidal activities of these compounds against Lolium multi-florum Lam. (annual ryegrass) and Raphanus sativus L. (radish) were evaluated. All the compounds exhibited remarkable herbicidal activity. The IC50 of these compounds against the root and shoot growths of annual ryegrass and radish were in the range of 0.11-1.34 mmol L-1. Both the ester and ether derivatives displayed much stronger herbicidal activities than compound 2. Some of these compounds showed comparable herbicidal activities to the commercial herbicide glyphosate. The herbicidal activities of 3b, 3c, and 3d against ryegrass shoot growths were 272.7%, 173.3%, and 241.7% higher than that of glyphosate, respectively. Furthermore, comparing the herbicidal activities between the ester derivatives and the ether derivatives, no strong relationship was observed. The results indicated that these compounds could be environmentally acceptable herbicides.

Four mono-fatty acid esters (Ia similar to d) were synthesized via the esterification of (3R,4R)-4,7,7-trimethyl-6-oxabicyclo[3.2.1]octane-3,4-diol (I) with fatty acid chlorides (CH3(CH2)(n) COC1, n = 0, 2, 4, 6) and structurally characterized by means of H RMS, IR, H-1-1-NMR, C-13-NMR and X-ray diffraction. Compounds Ia similar to d all belong to monoclinic system, P2(1/c) space group. Intermolecular O(2)-H(2)center dot center dot center dot O(1) hydrogen bonds, intramolecular O(2)-H(2)center dot center dot center dot O(3) hydrogen bonds and van der Waals' interaction between fatty acid ester groups link each of the mono-fatty acid ester molecules into a bilayer structure similar to liposome with the exposed hydrophobic moiety and the sandwiched lipophilic moiety. Especially, compounds Ia similar to d could be dissoluble or scattered in aqueous solution and showed hydrophilic/lipophilic property-dependent herbicidal activity against the dicotyledon plant rape (Brassica campestris) and the monocotyledon plant barnyard grass (Echinochloa crus galli). At the concentration of 10 mmol.L-1, the inhibition rates of compounds Ia-d against the root growth of rape are 31.9, 90.8, 99.5 and 100%, respectively and the inhibition rates against the shoot elongation of barnyard grass are 19.3, 50.0, 80.2 and 100%, respectively.

(1S,4R)-4,7,7-trimethyl-6-oxabicyclo[3.2.1] octane-1,4-diol(2) was synthesized from terpinolene by using hexadecyl pyridinium peroxo heteropolyoxomolybdotungstate( HPP) as redox-acid bifunctional catalyst and 30％( mass fraction) H2 O2 as oxidant.The optimal conditions for the reaction were terpinolene 4 mmol, HPP catalyst 7.35％( calculated by the mass of terpinolene), solvent chloroform 0.8 mL, the reaction material ratio(molar ratio of H2O2 and terpinolene) 3, reaction temperature 35℃, reaction time 6 h.Under these conditions, the conversion rate of terpinolene reached 100％and the yield of compound 2 reached 29％.The molecular structure was identified by means of IR, NMR and single crystal X-ray diffraction. The preliminary herbicidal activity assay indicated that compound 2 showed excellent inhibitory effect against the root growth and shoot elongation of ryegrass(Lolium rigidum);the inhibition rates against the root growth and shoot elongation were up to 91.8％and 80.7％, respectively, at the concentration of 120 mmol/L.Compared with the reported 1, 8-cineole, compound 2 had better inhibitory effect on ryegrass.