1-苯氧基(或对甲氧基苯氧基)-1-氟乙烯的合成

氟溴乙酸乙酯分别与苯酚或对甲氧基苯酚经取代反应得1-(苯氧基)-1-氟乙酸乙酯(3a)或1-(对甲氧基苯氧基)-1-氟乙酸乙酯(3b);3经Na2BH4还原后,将其羟基转化成溴原子,然后通过消除反应合成了两个新化合物——1-苯氧基-1-氟乙烯和对甲氧基苯氧基-1-氟乙烯,其结构经1H NMR和19F NMR表征。     

N'-取代苯基-4-甲氧基苯磺酰脲类化合物的合成及其对Cdc25B抑制活性研究

以苯甲醚为原料,经氯磺化、氨化反应制得4-甲氧基苯磺酰胺3;取代苯胺与三光气反应制得取代苯基异氰酸酯5a~5q;5分别与3经缩合反应合成了17个新型的N'-取代苯基-4-甲氧基苯磺酰脲类化合物6a~6q,其结构经MS、IR和1H NMR表征确证。通过抗肿瘤活性初步测试,其中有5个化合物对Cdc25B具有一定的抑制作用。     

奥希替尼的合成工艺改进

以2-甲氧基-4-氟苯胺(2)为原料,用硝酸铵代替硝酸钾进行硝化反应得2-氟-4-甲氧基-5-硝基苯胺(3),进而与丙烯酰氯进行酰胺化反应得N-(2-氟-4-甲氧基-5-硝基)苯基-2-丙烯酰胺(4).4与N,N,N-三甲基乙二胺进行亲核取代反应时,加入阻聚剂对羟基苯甲醚,成功地降低了副反应Michael加成反应的发生...     

艾拉莫德关键中间体的合成工艺改进

以3-硝基-4-苯氧基苯甲醚（2）为起始原料,甲酸铵为氢源,氢氧化钯碳为催化剂,经还原反应得到3-氨基-4-苯氧基苯甲醚（3）,再经过甲磺酰化反应得到3-甲基磺酰氨基-4-苯氧基苯甲醚（4）,最后通过盖特曼-科赫反应得到2-氨基-1-(2-甲氧基-4-甲磺酰胺基-5-苯氧基苯基)乙酮盐酸盐（1）。目标产物结构均经1H-NMR、MS等确证,改进后的还原工艺,避开了污染重、压力大等落后工艺,收率高至95.6%,具有较高的商业化价值。     

KBr催化剂上DMC与苯酚甲基化合成苯甲醚的反应机理研究

结合原位FT-IR,热力学分析及反应规律研究了KBr催化剂上碳酸二甲酯（DMC）氧位甲基化苯酚合成苯甲醚的反应机理。FT-IR显示KBr催化剂高于100℃活化苯酚生成酚盐,但至200℃也不活化DMC。共吸附的FT-IR及反应数据均显示苯甲醚高于150℃时生成。反应中检测到少量羰基甲氧基化产物苯基甲基碳酸酯（MPC）先于苯甲醚而生成,结合热力学计算及MPC分解转化的实验结果分析,生成MPC的反应是与生成苯甲醚的甲基化反应并行的可逆副反应。甲基化反应的机理为苯酚先被去质子化而形成酚盐,高于150℃时,酚盐的酚氧负离子亲核进攻DMC的甲基碳而生成苯甲醚。     

蒽基修饰的新型铂基大环化合物的合成

以3,5-二溴苯甲醚为起始原料,通过Suzuki偶联反应制得3,5-二吡啶苯甲醚(3); 3经三溴化硼脱保护得到3,5-二吡啶苯酚(4); 4进一步发生亲核取代反应得到化合物5;化合物6与5组装得到新型铂基超分子大环,其结构经¹H NMR和³¹P NMR表征。     

2-苯甲酰基嘧啶类化合物的合成与生物活性

2-嘧啶氧基-N-芳基苄胺类化合物结构经过两次骨架结构优化后得到2-苯甲酰基嘧啶类化合物二次先导结构.在二次先导结构基础上,共设计并合成了36个化合物,所有化合物结构经1H NMR、13C NMR、HRMS确认,并进行了室内杀菌活性筛选,对各部位取代基进行了逐次优化.结果表明2-苯甲酰基嘧啶类化合物中R1取代基以2位卤素或烷基取代的苯环或杂环活性最好;中间苯环6位引入氟原子活性保持;嘧啶环4,6位甲氧基取代活性较好,5位甲基取代活性大大降低;羰基被还原为羟基后活性消失.其中2,3-二氯-N-[2-(4,6-二甲氧基嘧啶-2-甲酰基)苯氧基]-N-甲基苯甲酰胺(4AHl)、2,5-二氯-N-[2-(4,6-二甲氧基嘧啶-2-甲酰基)苯氧基]-N-甲基苯甲酰胺(4AHn)及N-[2-(4,6-二甲氧基嘧啶-2-甲酰基)-3-氟苯氧基]-N,2-二甲基苯甲酰胺(4AFd)对黄瓜白粉病的杀菌活性与对照样苯菌酮相当.     

氧化铝负载催化剂作用下以甲醇为烷基化试剂的苯酚气相转化制备苯甲醚(英文)

苯甲醚作为重要的化学品和医药中间体而广泛应用于香料、调味剂及有机合成.液相法是传统的苯甲醚制备工艺,例如在碱性环境下,通过酚钠与硫酸二甲酯反应,溴苯与甲醇反应,酚钠与氯代甲烷反应均可制得苯甲醚.然而,这些方法具有环境处理负担较重和所用原料毒性较强等不足而备受限制.因此,环境友好的绿色苯甲醚合成工艺的开发成为必然,苯酚的气相烷基化工艺由此提出.其中,以碳酸二甲酯(DMC)为烷基化试剂的苯酚气相转化苯甲醚制备方法最受关注.DMC是常用的绿色高效烷基化试剂,但其价格相对较高,在一定程度上增加了苯甲醚制备工艺的复杂性和产品成本.鉴于DMC可由甲醇经氧化羰基化制得,因此以甲醇为烷基化试剂的苯酚气相烷基化转化制备苯甲醚方法成为另一研究热点.然而,与DMC的烷基化性能相比,以甲醇为烷基化试剂的反应产物分布较为复杂,作为苯酚O-烷基化(在苯酚的羟基氧原子上发生的烷基化)产物的苯甲醚相对较难获得,而苯酚的C-烷基化(在苯酚的芳环上发生的烷基化)产物甲基酚产率更易提高.总体而言,与DMC烷基化方法相比,以甲醇为烷基化试剂的苯酚气相转化制备苯甲醚方法有待改善,相关反应机理也更欠明晰,因此具有重要的研究价值.本文研究了γ-Al_2O_3(AA)负载型催化剂上以甲醇为烷基化试剂的苯酚气相转化制备苯甲醚方法,考察了反应温度、气体空速、苯酚与甲醇配比以及催化剂中K负载量和焙烧温度等对反应性能的影响,并分析了该体系中的反应机理.研究表明,在AA上负载的8种化合物(NaCl,MgCl_2,Fe_2(SO_4)_3,Co(NO_3)_2,ZnCl_2,La(NO_3)_3,Ce(NO_3)_3和KH_2PO_4)的催化剂中,KH_2PO_4/AA的催化性能最佳,相应催化剂中K离子负载量为7.53 wt%,于700 oC焙烧8 h.苯酚与甲醇气相反应过程中,苯甲醚最大收率出现在400–450 oC,且随甲醇与苯酚的摩尔比升高而增加,但随空速的提高而降低.另外,在KH_2PO_4/AA催化剂的高K含量,以及低温、高空速、低甲醇含量的物料配比的条件下,对苯酚的O-烷基化过程有利.产物除主产物苯甲醚以外,还有少量甲基苯酚、甲基苯甲醚以及二甲基苯酚等副产物.在K含量为7.53 wt%的KH_2PO_4/AA催化剂作用下,苯甲醚收率最高时反应条件为400–450 oC,空速小于0.18 h儃1,甲醇与苯酚摩尔配比为5.本文所开发的催化剂制备方法简单,反应条件温和,产物收率较高,因此具有较好的应用前景.X射线衍射结果显示,经高温焙烧及固相反应后,KH_2PO_4/AA催化剂中产生了K_3Al_2(PO_4)_3新物相.推测该反应机理是酸性氧化铝促进甲醇脱羟基负离子以及K离子促进酚羟基脱氢质子,所形成的甲基正离子进一步与苯氧基负离子结合得到苯甲醚的"钾离子-酸"双功能催化作用过程     

含酚醚中心功能基的大二环型穴醚的合成及配位性能

4-氯-2, 6-二羟基苯甲醚(2)与氯乙酸钠缩合, 制得4-氯-2, 6-二(羟甲氧基甲基)苯甲醚(4), 由4经酰氯化生成4-氯-2, 6-二(3-氯甲酰基-2-氧杂丙基)苯甲醚(5)后, 再与相应的二氮杂冠醚3a, 3b和3c反应制备标题化合物1a~1c。用1^H NMR法研究了1a~1c对碱金属离子的配位性能, 讨论了分子内的中心功能基和底环大小对其IR, 1^H NMR和配位行为的影响。     

高效液相色谱-串联质谱法测定兔尿中溴氰菊酯及其毒性生物标志物

建立了一种应用高效液相色谱-串联质谱（HPLC-MS/MS）测定兔尿中与溴氰菊酯毒性相关的多种生物标志物的检测方法。分析物包括溴氰菊酯及其代谢产物1R,3R-二溴菊酸、3-苯氧基苯甲酸,以及5种生物标志物5-羟色胺、5-羟基吲哚乙酸、3-硝基丙酸、8-羟基脱氧鸟苷和6-甲氧基鸟嘌呤。样品经硅藻土基质固相分散萃取、三氯乙酸沉淀蛋白质和HLB固相萃取小柱净化,使用电喷雾离子源,在多反应监测模式下正负切换采集测定,其中溴氰菊酯、5-羟色胺、5-羟基吲哚乙酸、8-羟基脱氧鸟苷和6-甲氧基鸟嘌呤采用正离子模式,1R,3R-二溴菊酸、3-苯氧基苯甲酸和3-硝基丙酸采用负离子模式。基质校准曲线外标法定量。结果表明,7种生物标志物在各自的浓度范围内线性关系良好（R²不小于0.9914）,5-羟基吲哚乙酸的检出限和定量限分别为20 μg/L和50 μg/L,其余化合物的检出限和定量限分别为0.2~5.0 μg/L和0.5~10 μg/L;在兔尿中3个不同添加水平的平均回收率为74.2%~98.7%,相对标准偏差（RSD）不大于12%,方法简单、快速、准确、灵敏,可作为溴氰菊酯暴露评估的检测方法。     

Dichroism of absorption and polarization of phosphorescence of molecules of the closed form of nitrobenzospirothiopyran

The spectral-polarization characteristics of absorption and phosphorescence of molecules of the initial form of nitro-substituted indolinospirobenzothiopyran were studied in oriented polyethylene films and in solutions with different polarity. An oscillator model of the electron transitions responsible for the formation of absorption and luminescence spectra was suggested. It was established that the principal differences in the spectral and photophysical properties of the compound studied and its oxygen-containing analog are associated with the fact that the electronegativity of the S atom is lower than that of the O atom. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1143–1146, June, 1997.     

非那雄胺合成工艺改进

非那雄胺能抑制5α-还原酶的活性,明显降低二氢睾酮水平,是一种治疗良性前列腺增生的有效药品。该合成工艺以甾烯酮酸为原料,将其与氯化亚砜反应,无须分离即与叔丁胺反应得17β-酰胺化合物,再氧化开环,环合,氢化,脱氢合成了非那雄胺。经元素分析、IR、1HNMR、13CNMR、MS分析表征了其结构。该法无须使用昂贵的2,2-二吡啶二硫化物和剧毒药品苯亚硒酸酐,且以乙酸铵代替氨气,降低了对设备的要求和腐蚀,更适用于工业生产。     

Determination of heats of detonation and influence of components of composite explosives on heats of detonation of high explosives

The heats of detonation of 20 simple high explosives and explosive mixtures were determined by means of an adiabatic detonation calorimeter designed by the authors. The results indicated that the performance of the instrument was reliable and the experimental data were very accurate. For explosive mixtures, there was a linear accumulative relationship between the heats of detonation of the explosive mixture and its components. Accordingly, the heats of detonation of explosive mixtures could be calculated directly from the heats of detonation of simple explosives and the characteristic heats of other components. The experiments showed that the gold or brass shell of the cylindrical charge could be substituted by a thick-walled porcelain shell, which had the advantage of cheapness.

     

Synthesis of phenolic components of Grains of Paradise

Two vanilloids, (5E)-8-(4-hydroxy-3-methoxyphenyl)oct-5-en-4-one (1) and 4-[3-hydroxydecyl]-2-methoxyphenol (2), isolated from the dried seeds of Grains of Paradise (Aframomum melegueta), were synthesized; the latter compound was made as the S-enantiomer and the material derived from the seeds was found to be a 1:1.7 mixture of the R and S isomers. The synthetic route used should allow the preparation of analogs having extended alkyl chains and consequently different lipophilicity, and 3, a homolog of 2, was also prepared.     

Summary of development of the theory of stability of colloids and thin films

In this review, the research of the author in the field of colloidal systems is summarized. The factors influencing colloidal stability are systematized and analyzed. Examples are presented to illustrate the practical utilization of the theory of stability of colloids and thin films.This review was prepared on the basis of the works of the author, which were awarded the State Premium for 1991 in the field of science and technology, chemistry section.Institute of Physical Chemistry, Russian Academy of Sciences, 117915 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 8, pp. 1708–1717, August, 1992.     

Study of hydration of two cements of different strengths

Main hydration products of two cement pastes, i.e. CSH-gel, portlandite (P) (and specific surface S) were studied by static heating, and by SEM, TEM and XRD, as a function of cement strength (C-33 and C-43) hydration time (th) and subsequent hydration in water vapour.Total change in mass on hydration and air drying, M_o, increased with strength of cement paste and with hydration time. Content of water escaping at 110 to 220°C, defined as water bound with low energy, mainly interlayer and hydrate water, was independent on cement strength but its content increased with (th). Content of chemically bound (zeolitic) water in CSH-gel, escaping at 220-400°C, was slightly dependent on strength and increased with (th). It was possibly derived from the dehydroxylation of CSH-gel and AFm phase. Portlandite water, escaping at 400-500°C, was independent on cement strength and was higher on longer hydration. Large P crystals were formed in the weaker cement paste C-33. Smaller crystals were formed in C-43 but they increased with (th). Carbonate formated on contact with air (calcite, vaterite and aragonite), decomposed in cement at 600-700^oC. It was high in pastes C-33(1 month) and C-43(1 month), i.e. 5.7 and 3.3%, respectively; it was less than 1% after 6 hydration months (low sensitivity to carbonation) in agreement with the XRD study showing carbonates in the air dry paste (1month), and its absence on prolonged hydration (6 months) and on acetone treatment. Water vapour treatment of (6 months) pastes or wetting-drying increased this sensitivity.Nanosized P-crystals, detected by TEM, could contribute to the cement strength; carbonate was observed on the rims of gel clusters.This revised version was published online in November 2005 with corrections to the Cover Date.     

氯氧化镁生成热的研究

用氧化镁氯化镁水溶液制备了8水合氯氧化镁[nMg(OH)2·MgCl2·8H2O], 并测定了其在盐酸中的溶解热, 实验结果表明, 氯氧化镁溶解热与n值呈线性关系, 根据溶解热求出5Mg(OH)2·MgCl2·8H2O和3Mg(OH)2·MgCl2·8H2O的生成热分别为-7727.1和5888.1kJ·mol^1^-。     

Thermodynamics of the formation of oxosulfides of rare-earth elements

The enthalpies of solution of several oxosulfides of rare-earth elements and the high-temperature enthalpies of oxosulfides and oxosulfates of lanthanum and yttrium were measured using solution calorimetry and high-temperature microcalorimetry techniques. Standard enthalpies of formation and some thermodynamic properties of oxosulfides and oxosulfates were calculated. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2 pp. 294–297, February, 1997.     

探究“铁的锈蚀条件”实验创新设计

设计了铁的锈蚀实验,说明了铁钉的处理方法,增加了温度、酸、碱的影响条件,实现了铁跟蒸馏水及空气中氧气快速反应而生锈,使实验在5 min左右就能够得到准确的结果。