芸苔素甾醇类物质的研究进展

芸苔素甾醇类物质（Ｂｒａｓｓｉｎｏｓｔｅｒｏｉｄｓ，简称ＢＲｓ）是广泛存在于植物界的一类新的植物生长物质。ＢＲｓ表现的调节植物生长的生理活性及作用机理与其它的植物激素不同。这类新型的植物生长物质已被广泛应用于农业生产。本文综述了国内外多年来有关ＢＲｓ的生理功能、构效关系及合成等方面的研究进展。     

柱前衍生-高效液相色谱法测定肥料中芸苔素内酯异构体

建立了以苯硼酸为衍生试剂,柱前衍生-高效液相色谱测定肥料中24-表芸苔素内酯(24-EBL)和28-高芸苔素内酯(28-HBR)的方法。样品采用甲醇作为提取溶剂,常温条件下用苯硼酸衍生30 min,乙腈/水(85/15, V/V)为流动相,在222 nm波长下进行分析。结果表明：在0～1250 mg/kg范围内线性关系良好,相关系数(r²)≥0.999。24-EBL和28-HBR的检出限分别为0.46和0.51 mg/kg。样品加标回收率为67.1%～128.5%,批间相对标准偏差为0.09%～2.4%。该方法满足2种芸苔素内酯异构体在肥料内定量分析的要求。     

青蒿素及其一类物结构和合成的研究——Ⅺ.环氧青蒿酸的分离和鉴定

青蒿亦称黄花蒿(Artemisia annua L.),为菊科植物,我国民间用于治疗疟疾。据报道,该植物的主要成分为挥发油、烯炔和倍半萜内酯。倍半萜内酯有青蒿素、青蒿甲素、青蒿乙素及青蒿丙素(脱氧青蒿素)。此外,还有青蒿酸、香豆素及黄酮等。我们由山东七、八月所产青蒿提取物中分到青蒿素、青蒿甲素、青蒿乙素、青蒿丙     

高效液相色谱-质谱法鉴定总合草苔虫中的草苔虫内酯成分

采用高效液相色谱分离与质谱检测的联用技术,对总合草苔虫中的草苔虫内酯成分进行定性分析。在以体积比为80∶20的甲醇-水溶液为流动相、采用ODS柱进行分离的色谱条件下,10种草苔虫内酯成分均可获得良好的分离。分析结果表明：深圳大亚湾产地的总合草苔虫中共含有9种已知和1种未知的草苔虫内酯成分。已知成分分别是bryostatin 4,5,6(9),7,8,10,16,17,18,其中bryostatin 7和17是首次从中国海域总合草苔虫中发现的2种痕量草苔虫内酯。该方法简便、准确、灵敏度高,可以很好的对总合草     

长苞铁杉中两个新的重排羊毛甾烷型三萜

从中国特有植物长苞铁杉树枝的甲醇提物中分离得到2个新的重排羊毛甾烷型三萜,命名为铁杉内酯素A(1)和铁杉内酯素B(2),其结构通过HR-ESIMS,1D和2D NMR等光谱技术确定,铁杉内酯素A(1)的构型进一步通过X单晶衍射确认.     

合理利用甾体皂苷元资源的研究 I: 具有油菜甾醇内酯A/B环结构单元的甾体皂苷元的合成

本文提出用薯蓣皂苷元合成油菜甾醇内酯及其类似物的新思想, 从薯蓣皂苷元合成了具有油菜甾醇内酯A/B环结构单元的新甾体皂苷元。作为进一步合成油菜甾醇内酯的重要中间体, 它本身也显示促进植物生长的作用。     

合理利用甾体皂苷元资源的研究 I: 具有油菜甾醇内酯A/B环结构单元的甾体皂苷元的合成

本文提出用薯蓣皂苷元合成油菜甾醇内酯及其类似物的新思想, 从薯蓣皂苷元合成了具有油菜甾醇内酯A/B环结构单元的新甾体皂苷元。作为进一步合成油菜甾醇内酯的重要中间体, 它本身也显示促进植物生长的作用。     

几种芳烃化合物对诸葛菜染色体形态影响的研究

几种芳烃化合物对诸葛菜染色体形态影响的研究肖龙，李峰（四川大学生物工程系成都６１００６４）关键词芳烃化合物，诸葛菜染色体，形态诸葛菜是十字花科芸苔诸葛菜属植物￣［１］，是一种具有极大开发价值的优质油料作物种源￣［２，３，４］。它的染色体形态研究县分类...     

合理利用甾体皂苷元资源的研究 Ⅰ.具有油菜甾醇内酯A/B环结构单元的甾体皂苷元的合成

本文提出用薯蓣皂苷元合成油菜甾醇内酯及其类似物的新思想。从薯蓣皂苷元合成了具有油菜甾醇内酯A/B环结构单元的新甾体皂苷元3.3作为进一步合成油菜甾醇内酯的重要中间体,它本身也显示促进植物生长的作用。     

新法构建25-羟基油菜甾体的侧链

油菜甾体例如油菜甾醇内酯(1a)和24-表油菜甾醇内酯(2a)是一族新型的甾体植物生长激素(植物生长调节剂).它们具有提高植物生长调节和应变的活性并具有农作物增产效果,已愈益受到国际上的广泛重视[1].     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%.     

CoFe2O4自形成磁性液体场致结构化对磁化的影响

The Langevin paramagnetic theory can’t describe the relation between magnetization of ferrofluids and applied magnetic field. The structuralization of ferrofluids, which is considered the main influence factor of the magnetization, is regarded. The part of magnetization works is deposited when the structure is forming. This action influences the magnetization of ferrofluids directly or indirectly. On the base of the “compressing” model, the Langevin function that usually describes the magnetization of ferrofluid is modified, and a well-fitted curve is obtained. An equation of the relation between the equivalent volume fraction after being “compressed” and the intensity of magnetic field is discovered, which approximately describes the process of magnetization. The relation between the approximate initial susceptibility and the volume fraction can be obtained from modified formula.     

Highly regioselective Buchwald–Hartwig amination at C-2 of 2,4-dichloropyridine enabling a novel approach to 2,4-bisanilinopyridine (BAPyd) libraries

The highly regioselective Buchwald–Hartwig amination at C-2 of the cheap and readily accessible reagent, 2,4-dichloropyridine with a range of anilines and heterocyclic amines is described. This new methodology is robust and provides a facile access to 4-chloro-N-phenylpyridin-2-amines on 0.25 mol scale. These intermediates undergo a further Buchwald–Hartwig amination at higher temperature to enable rapid exploration of the chemical space at C-4 and to provide a library of 2,4-bisaminopyridines.     

Sulfur-directed metal-free and regiospecific methyl C(sp3)–H imidation of thioanisoles

Regiospecific and direct imidation of the methyl C(sp³)–H bond of thioanisoles is realized under mild and metal-free conditions with N-fluorobis(benzenesulfonyl)imide as an oxidant and nitrogen source. Proposed mechanism suggests that thionium ion intermediates and a Pummerer-type reaction are involved. The imidation has advantages such as high step-economy, excellent functionality tolerance, and regiospecificity, giving structurally diverse imidation products.     

Selective syntheses of 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones via temperature-dependent Rh(II)-carbenoid-mediated 2H-azirine-ring expansion

The Rh(II)-catalyzed reaction of 2-carbonyl-substituted 2H-azirines with ethyl 2-cyano-2-diazoacetate or 2-diazo-3,3,3-trifluoropropionate provides an easy access to 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones. These compounds can be selectively prepared from the same starting material using temperature as the only varied parameter. The 2-azabuta-1,3-diene intermediate, a common precursor for both heterocyclic products, isomerizes into 2H-1,3-oxazine under kinetic control, while 1H-pyrrol-3(2H)-one is the sole product of the reaction at elevated temperatures. According to DFT-calculations a one-atom oxazine ring contraction involving ring-opening to a 2-azabuta-1,3-diene intermediate, followed by a 1,5- and 1,2-prototropic shift leads to the consecutive formation of imidoylketene and azomethine ylide, which then further undergo cyclization to the pyrrole derivative.     

Copper catalyzed/mediated synthetic methodology for ebselen and related isoselenazolones

Scope of the copper catalyzed/mediated selenium-nitrogen coupling reaction has been studied for the synthesis of isoselenazolones. It is noticed that the 2-chloro, 2-bromo-, and 2-iodo-aryl amides substrates can be exploited in the selenium-nitrogen coupling reaction by employing 25-100 mol % of CuI/1,10-phenanthroline (L) and potassium carbonate as a base in DMF. Furthermore, electron rich 2-chloro-arylamides also underwent selenium-nitrogen coupling reaction to give biologically important selenium-nitrogen heterocycles. Also, copper-catalyzed selenium-nitrogen coupling reaction has been meticulously applied for the synthesis of diaryl diselenides having methoxy, amine, and amide functionality from respective aryl iodides in the presence of stoichiometric amount of succinimide as an external Se-N coupling partner.     

Knoevenagel condensation catalyzed by novel Nmm-based ionic liquids in water

A series of novel N-methyl morpholine (Nmm) based ionic liquids with 1,2-propanediol group were synthesized and used as catalysts for Knoevenagel condensation at room temperature in water. Under the effect of the catalyst, various aldehydes or aliphatic ketones could react with a wide range of activated methylene compounds well, including malononitrile, alkyl cyanoacetate, cyanoacetamide, β-diketone, barbituric acid, 2-arylacetonitrile and thiazolidinedione. Furthermore, most of the products could be separated just by filtrating and washing with water. Additionally, the catalyst is recyclable and applicable for the large-scale synthesis.     

Construction of polyheterocyclic spirotetrahydrothiophene derivatives via sulfa-Michael/aldol cascade reaction

A series of polyheterocyclic spirotetrahydrothiophene derivatives were obtained in moderate to excellent yields via a catalyst-free sulfa-Michael/aldol cascade reaction of chalcones 1 and commercially available 1,4-dithiane-2,5-diol 2 under mild conditions. We also present the first asymmetric sulfa-Michael/aldol cascade reaction of chalcones 1 and commercially available 1,4-dithiane-2,5-diol 2 with moderate to good enantioselectivities catalyzed by readily available chiral phase-transfer catalysts (PTCs).     

Suzuki-Miyaura reactions of the soluble guanylate cyclase inhibitor NS2028: a non-product specific route to C-8 substituted analogues

Both soluble guanylate cyclase (sGC) inhibitors ODQ 1 and NS2028 2 are synthesized via improved protocols. In the former case treating 3,4-dihydroquinoxalin-2(1H)-one oxime 8, which can be prepared in two steps from 1,2-benzenediamine, with 1,1′-carbonyldiimidazole (CDI) gives the dihydro-ODQ 10 that in the presence of KMnO₄ oxidises to give ODQ 1 in an overall yield of 46% starting from 1,2-benzenediamine. In the latter case, the synthesis affords NS2028 2 from 2-amino-4-bromophenol 3 in three steps with an overall yield of 85% and avoids the need for chromatography. Furthermore, Suzuki-Miyaura reaction conditions are described that enable the preparation of 8-aryl and 8-heteroaryl derivatives of NS2028 directly from NS2028 2. Finally, demethylation of the 8-(methoxyphenyl) substituted analogues afforded the 8-(hydroxyphenyl) derivatives 40-42. All new products are fully characterised.