盐酸决奈达隆合成新工艺

设计了一条全新的盐酸决奈达隆(1)的合成路线, 该路线以价廉易得的对氨基苯酚(2)为起始原料, 经N-甲磺酰化、 氧化得到对甲磺酰亚氨基苯醌(4)后, 再与3-氧代庚酸甲酯缩合、 环化制得关键中间体2-丁基-5-甲磺酰胺基苯并呋喃-3-甲酸甲酯(6), 然后经水解、 酰氯化, 继而与1-苯氧基-3-二正丁胺基丙烷盐酸盐进行傅-克酰基化反应, 成盐后即得化合物1, 总收率达33%.     

硫酸酯型氟表面活性剂的合成与表面活性

以4-全氟壬烯氧基苯磺酰氯和2-甲氨基乙醇为主要原料,经酰胺化、酯化和中和反应制备了硫酸2-（N-甲基-4-全氟壬烯氧基苯磺酰胺基）乙酯钠（I）,用红外光谱和19F NMR,1H NMR对中间体和产物分子结构进行了表征,借助正交试验法优化了反应条件。酰胺化反应较佳工艺条件：n（4-全氟壬烯氧基苯磺酰氯）: n（2-甲氨基乙醇）＝1.0 : 2.0,以三乙胺为缚酸剂,在THF溶剂中,室温下搅拌反应3.0 h,收率93.4 ％;酯化反应较佳工艺条件：n（ N-羟乙基-N-甲基-4-全氟壬烯氧基苯磺酰胺）: n（氯磺酸）＝1.0 : 2.0,在THF溶剂中,室温下反应0.5 h,收率97.1 ％。硫酸2-（N-甲基-4-全氟壬烯氧基苯磺酰胺基）乙酯钠表面活性剂的临界胶束浓度 8.0×10-4mol/L,γcmc 23.1 mN/m (25℃)。     

N-糖基-N＇-酰氨基硫脲及其环合产物的合成

以L-α-氨基酸为起始原料，经酯化、氨基保护、肼解制得N-对甲苯磺酰基-L—α-氨基酸酰肼2，再与糖基异硫氰酸酯3～5反应，得到9种新型N-糖基-N＇-酰氨基硫脲6～8，然后在Hg（OAc）2／EtOH条件下关环，合成了一系列新的2-对甲苯磺酰氨基烃基-5-糖氨基-1，3，4-噁二唑类化合物9～11．所有新化合物的结构均经IR，^1H NMR，MS谱和元素分析确证．     

苯嘧磺草胺的新合成方法

设计并完成苯嘧磺草胺及其关键中间体的合成工艺路线,使其具备工业化生产潜力。采用氯磺酰异氰酸酯、叔丁醇、N-甲基-N-异丙基胺等作为起始原料,制备了关键中间体N-甲基-N-异丙基氨基磺酰胺,3步反应总收率~75%;采用2-氯-4-氟苯甲酸为原料,经过硝化、酰氯化、缩合、催化氢化还原、氨酯交换、甲基化反应制备了苯嘧磺草胺。共计8步反应制备得到苯嘧磺草胺,总收率为48.6%,纯度98.6%,产物与中间体经NMR、MS等进行了表征。     

4,4′-二（4-氯甲酰苯氧基）二苯砜的合成

以DMF作溶剂,在四丁基氟化铵 （TBAF）存在下,对甲基苯基三甲硅基醚（1）和4,4＇-二氯二苯砜（2）于100 ℃反应1 h,合成了4,4＇-二（4-甲基苯氧基）二苯砜（3）,产率为92%;加入催化量的N-溴代丁二酰亚胺（NBS）并在光照条件下,与氧气反应得到中间体-4,4＇-二（4-羧基苯氧基）二苯砜（4）,其产率达90%;将化合物4与二氯亚砜反应合成目标产物4,4＇-二（4-氯甲酰基苯氧基）二苯砜（5）,总收率为74.5%（以对甲基苯基三甲硅基醚为基准计算）.     

三氟甲基嘧啶磺酰脲的合成与除草活性

以三氟乙酰乙酸乙酯和盐酸胍为原料,经环合、氯化、甲氧基化、胺化反应合成了4种2-氨基-4-取代-6-三氟甲基嘧啶中间体(Ⅰa~Ⅰd),Ⅰ与邻甲氧羰基苯磺酰异氰酸酯亲核加成,合成了3种含不同取代嘧啶环的磺酰脲化合物(Ⅱb~Ⅱd)。其中2-氨基-4-二甲胺基-6-三氟甲基嘧啶(Ⅰd)和N[-2-(′4-二甲胺基-6-三氟甲基)嘧啶基]-2-甲氧羰基苯磺酰脲(Ⅱd)为新化合物,结构经1H NMR和MS表征。初步除草活性测定结果表明,N-[2-′(4-甲氧基-6-三氟甲基)嘧啶基]-2-甲氧羰基苯磺酰脲(Ⅱc)在浓度为200 ga.i./ha时对稗草和马唐的防效分别为70%和50%。     

合成盐酸氨溴索的新方法

以邻氨基苯甲酸甲酯（1）为起始原料,与溴素发生溴化反应制得2-氨基-3,5-二溴苯甲酸甲酯（2）。2经红铝试剂还原制得2-氨基-3,5-二溴苯甲醛（3）; 3经还原胺化制得氨溴索（4）; 4盐酸化得到盐酸氨溴索（5）,总收率60.8%,其结构经¹H NMR确证。     

新方法合成（Z）-5-氟-2-甲基-1-[（4-甲基亚磺酰苯基）亚甲基]-1H-茚-3-乙酸及其X-单晶衍射分析

以对甲亚磺酰基苄溴为原料，通过4步反应合成得到立体专一性的Z式构型产物（Z）-5-氟-2-甲基-1-[（4-甲基亚磺酰苯基）亚甲基]-1H-茚-3-乙酸（Sulindac舒林酸）。X-单晶衍射分析舒林酸分子中共存有强和弱的分子间氢键。     

苯嘧磺草胺的新合成方法

设计并完成苯嘧磺草胺及其关键中间体的合成工艺路线,使其具备工业化生产潜力。采用氯磺酰异氰酸酯、叔丁醇、N-异丙基甲胺等作为起始原料,制备了关键中间体N-甲基-N-异丙基氨基磺酰胺,3步反应总收率约75%。再以2-氯-4-氟苯甲酸为原料,经过硝化、酰氯化、缩合、催化氢化还原、氨酯交换、甲基化反应制备了苯嘧磺草胺。8步反应的总收率为48. 6%,纯度98. 6%,产物与中间体经NMR、MS等确证。     

2-氨基乙基磺酰胺盐酸盐合成研究

以羟乙基磺酸钠为原料,与氯化亚砜反应制备2-氯乙基磺酰氯;然后采用2-氯乙基磺酰氯与邻苯二甲酰亚胺钾盐反应制备N-(2-邻苯二甲酰亚氨基乙磺酰基)邻苯二甲酰亚胺(中间体1);中间体1经硼氢化钠还原、盐酸酸化得到2-氨基乙基磺酰胺盐酸盐,总收率为80.26%,与文献报道方法相比总收率提高了33.34%。通过熔点、红外光谱、气相色谱-质谱联用、高分辨质谱和核磁共振氢谱对中间体和产品进行了表征。     

利用手持技术改进测定乙醇分子结构实验

利用压强传感器代替排水集气法,改进测定乙醇分子结构实验的仪器装置,并探索最佳反应条件。另外,设计两个空白实验,结合压强变化曲线对实验误差进行相关讨论。     

光谱仪测试范围的扩展

由于石化行业的生产需要，其材质的使用具有多样性和广泛性，经常会出现顾客委托的测试样品的一个或几个元素跨越光谱仪现有测试程序测量范围的情况。本法通过对光谱仪测试原理的认识，根据光谱仪的测试能力及标样的采集，实现了一个或几个元素测量范围的扩展，并对其测量的影响因素进行了研究。     

Influence of viscosity of medium on processes of oxygen quenching of excited states of mesoporphyrin

The oxygen quenching rate constants for singlet and triplet excited states of the dimethyl ester of mesoporphyrin IX increase with decreasing viscosity of the medium and reach a maximum at a viscosity of approximately 0.4 mPa·sec, after which the rate constants begin to decrease. The drop in rate constant with increasing fluidity of the medium may be related to a nonequilibrium character of the elementary act in the interaction of the reactants in the solvent cage. In viscous media such as isopropyl alcohol, isobutyl alcohol, and isoamyl alcohol, the reaction radius is greater than the sum of the radii of the reacting particles. The long-range character of these processes is due to the relatively weak dependence of the quenching probability on distance.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 25, No. 2, pp. 161–167, March–April, 1989.     

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.     

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.

     

物质分配系数的测定实验改进

实验教学目的是从解决实际问题出发,以实验技术训练和实验设计思想培养为目标。介绍了将单一的物质分配系数测定实验改进为综合实验,提高了实验效果及实验资源利用率。     

Neutral diterpenoids of oleoresins of five species of conifers of Transcarpathia

The compositions of the neutral diterpenoids of the oleoresins of five species of conifers growing in the Transcarpathia have been studied. It has been found that the oleoresins ofAbies alba M.,Larix decidua M., andPicea excelsa L. contain more than 50% of neutral diterpenoids. The group and qualitative compositions of the oxygen-containing diterpenoids have been determined. In the oleoresins ofAbies alba,Picea excelsa, andPicea abies tertiary alcohols — cis-abienol and isocembrol — predominate, while inLarix decidua the main component is the hydroxy ester larixyl acetate. Primary alcohols related to the resin acids have been found in all the oleoresins investigated. Features of the distribution of diterpenoids according to the species of conifers have been revealed. The results obtained are necessary for the chemotaxonomy of conifers of the family Pinceae.Novosibirsk Institute of Organic Chemistry, Siberian Branch, Academy of Sciences of the USSR. Translated from Khimiya Prirodynkh Soedinenii, No. 6, pp. 812–816, November–December, 1988.     

Calculation of enthalpies of hydrogenation of hydrocarbons

Sets of hydrogen molecule equivalents have been developed which permit the calculation of hydrogenation of different types of carbon-carbon bonds from ab initio total energies (3-21G and 6-31G* basis sets, and, to a more limited extent, for MP2/6-31G* data) of reactants and products. The calculated enthalpies of hydrogenation are in good agreement with experiment for unstrained molecules, with average errors on the order of 2 kcal/mol. The 6-31G* equivalents allow the enthalpies for strained molecules to be calculated accurately, but the 3-21G equivalents do not. The equivalents for both basis sets have been tested by calculating the enthalpies of hydrogenation of carbon-carbon bonds in nitrogen- and oxygen-containing organic molecules, free radicals, and classical carbocations. The results are in good agreement with experiment in most cases.     

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。