N—丁基—2—乙氧基硫代吖啶酮的光化学反应机理

采用荧光光谱研究了N－丁基－2－乙氧基硫代吖啶酮的光化学反应机理。结果表明：在Xe灯光照下，N－丁基－2－乙氧基硫代吖啶酮转变成了相应的吖啶酮，用紫外－可见光谱和质谱证实了吖啶酮的存在；生成的吖啶酮可被二苯基碘翁盐猝灭，它们之间的荧光猝灭遵循电子转移的反应机理，实验又证明了由硫代吖啶酮、二苯基碘翁盐和硫代水杨酸三者组成的光聚合引发体系的引发效果最好。     

四种1-乙氧基-1-烷硫基丙烷类化合物的合成

丙醛二乙缩醛分别与丁硫醇、仲丁硫醇、戊硫醇和糖硫醇在四氯化碳中，常温搅拌20min，减压下蒸出溶剂（丙醛二乙缩醛与戊硫醇反应，常压蒸出溶剂），再次减压馏收集产物，可分别得到1－乙氧基－1－丁硫基丙烷、1－乙氧基－1仲丁硫基丙烷、1－乙氧基－1－戊硫基丙烷和1－乙氧基－1－糖硫基丙烷、产率分别为40％、23％、37％、60％。此方法收集的产品中不易含有缩充醛。经红外光谱、色－质联机、核磁共振谱检测及硫元素含量分析，确证了产物结构。     

新型防污剂3-（1-吲哚基）-N-（4-乙氧基丙基）丙酰胺的合成

以吲哚与N,N’-二乙基丙基二硫代二丙酰胺为原料,经迈克尔加成反应,合成了3-（1-吲哚基）-N-（4-乙氧基丙基）丙酰胺,总收率为41．6％。其结构经’HNMR和IR确认。最佳制备条件为：吲哚和氢化钠的反应摩尔比1：1．8、反应温度0℃、反应时间3h,反应溶剂为THF（四氢呋喃）。     

2-硫代-3-芳基-5-苯基亚甲基-4-咪唑啉二酮衍生物的有效合成新方法

研究了应用烯基膦亚胺与二硫化碳、芳伯胺的串联aza-Wittig反应,来合成2-硫代-3-芳基-5-苯基亚甲基-4-咪唑啉二酮衍生物的有效新方法。提出了可能的环化反应机理,探讨了所合成化合物的成环反应条件和波谱性质。生成的环化产物均为新的化合物,其结构经元素分析、IR、^1HNMR和MS确证。     

直接胺化缩合制备葡萄糖胺为化合物

在催化剂存在条件下，通过对葡萄糖与一乙醇胺或乙二胺的直接胺化缩合反应的研究，制备了N－葡萄糖基－乙醇胺和N，N′－双葡萄糖基－乙二胺，考察了反应温度，时间及催化剂用量对该类反应产物产率的影响。     

2-溴-3-{4-[2-(5-乙基-2-吡啶基)-乙氧基]苯基}丙烯酸甲酯的合成

以5－乙基－2吡啶基乙醇为起始原料,与对氟硝基苯缩合,Pd/C催化加氢,得4－[2－（5－乙基－2－吡啶基）－乙氧基]苯胺,再经重氮化和桑德迈尔反应,制得2－溴－3－{4－[2－（5－乙基－2－吡啶基）－乙氧基]苯基}丙烯酸甲酯,总收率为65．6％,最终产物经IR和NMR结构确证。     

N，N—二甲基—N′—月酰基—1，3—丙二胺的合成

以月桂酸和N,N－二甲基－1,3－丙二受为原料,合成了N,N－二甲基－N′－月桂酰基－1,3－丙二胺,通过改变反应温度,酸胺的量比和投料方式,探索反应的优化条件。结果显示,当反应温度为160℃,n(月桂酸）：n（N,N－二基－1,3－丙二胺）＝1．00：1．10,N,N－二甲基－1,3丙二胺按40min连续滴加时,产物的游离酸值最低,为5．54mg/g。产品的红外光谱与标准样品的谱图相符。     

2-(2-氯乙氧基)乙酰胺合成研究

以氯乙醇与溴乙酸乙酯为原料、以碳酸钾为缚酸剂、DMF为溶剂,经缩合反应制得氯乙氧基乙酸乙酯,氯乙氧基乙酸乙酯在乙醇氨溶液中胺化得2-(2-氯乙氧基)乙酰胺,考察了反应条件的影响。结果表明,反应最优条件为:氯乙醇与溴乙酸乙酯的摩尔比为1.2:1.0,缚酸剂为碳酸钾,胺化试剂为20%～24%氨乙醇溶液;总收率为52.2%,产物经GC-MS分析证明结构正确。     

新型防污剂3-(1-吲哚基)-N-(4-乙氧基丙基)丙酰胺的合成

以吲哚与N,N'-二乙基丙基二硫代二丙酰胺为原料,经迈克尔加成反应,合成了3-(1-吲哚基)-N-(4-乙氧基丙基)丙酰胺,总收率为41.6%.其结构经1HNMR和IR确认.最佳制备条件为:吲哚和氢化钠的反应摩尔比1:1.8、反应温度0℃、反应时间3 h,反应溶剂为THF(四氢呋喃).     

一步法合成N-(1-乙基丙基)-3,4-二甲基苯胺

以自制的Pd－Pt/C为加氢催化剂，有机酸为助催化剂，3，4－二甲基硝基苯和3－戊酮为原料，通过硝基加氢、酮胺加成、脱水与碳氮双键加氢一系列反应一步法合成了N－（1－乙基丙基）－3，4－二甲基苯胺。考察了不同加氢催化剂、助催化剂和反应温度对该反应的影响：在较佳的反应工艺条件下，四步反应的总收率达98．6％，比文献值收率提高10％。     

季铵化硅烷的合成与应用

利用γ-氯丙基三甲氧基硅烷与N，N-二甲基十八胺反应，合成了N，N-二甲基-N-十八烷基氨丙基三甲氧基硅烷季铵盐(BFS)，对其抑菌性能及与氨基硅微乳同浴使用的效果进行了测定和研究。结果表明：BFS用量为10g／L条件下，能使整理后的棉织物对金黄色葡萄球菌、大肠杆菌的抑菌率分别达到99．82％和99．12％；而与氨基硅微乳同浴使用，所整理的织物不仅抑菌效果显著，柔软性良好，而且具有舒适的手感；另外，弱酸性使用条件有助于BFS和氨基硅微乳的协同效应，表现出最佳的整理效果。     

N-芳基-N-异丙基-2-羟基乙酰胺的合成

以 4个不同结构的芳胺为原料 ,经过N 烷基化 ,N 氯乙酰化 ,酯化 ,酯交换反应合成了 4个 2 羟基乙酰胺类化合物 ,它们都是重要的农药中间体。其中N (4 三氟甲基苯基 ) N 异丙基 2 羟基乙酰胺的合成 :控制温度在 10～ 2 0℃ ,向 4 三氟甲基苯胺 ,冰醋酸与丙酮的混合液中慢慢加入硼氢化钾 ,加完后 2 0℃反应 2h得到产品N 异丙基 4 三氟甲基苯胺 ,产率 86 .0 %。升温至40℃ ,向N 异丙基 4 三氟甲基苯胺、甲苯混合液中滴加氯乙酰氯 ,滴完后升温至 75℃ ,通氮气反应 2h得到产品N (4 三氟甲基苯基 ) N 异丙基 2 氯乙酰胺 ,产率 92 .9%。N (4 三氟甲基苯基 ) N 异丙基 2 氯乙酰胺 ,甲醇 ,醋酸钾 ,三乙胺 ,碳酸钾 ,回流反应 17h ,得到产品N (4 三氟甲基苯基 ) N 异丙基 2 羟基乙酰胺 ,产率 88.2 % ,总收率为 70 .5 %。产品结构经质谱和核磁确定     

The effect of delaying autumn incorporation of green manure crop on N mineralization and spring wheat (Triticum aestivum L.) performance

The use of legumes as green manuring crops does involve a potential riskof N leaching losses over the winter period. The susceptibility of cropresidue-derived N to losses and the pre-crop value of a green manuring crop canbe manipulated by proper timing of incorporation into soil. In this study,mineralization of C and N was investigated in a range of low temperatures,including thawing and freezing, that are characteristic to autumn green manureincorporation and its decomposition. The pre-crop effect of green manuring wasfurther tested with spring wheat under field conditions. We hypothesized thatdelaying green manure incorporation in the autumn would reduce the risk of Nlosses from the field and maximize the N transfer to a successive spring wheatcrop. To test the hypothesis, N mineralization was followed in alaboratory experiment where red clover (Trifoliumpratense L.) shoots were incubated at 4–8 °Cfor 40–80 days to simulate early autumn, delayed autumn and late autumnincorporation of a green manuring crop, followed by an incubation at–2 °C or at –2 °C to+4 °C for 25 days to simulate winter conditions. In asimultaneous field experiment, we measured the effect ofdelayed autumn incorporation of common vetch (Vicia sativaL.) green fallow on spring wheat performance. In the laboratoryexperiment, significant N mineralization during incubation wasdetected when simulating both early autumn and delayed autumn incorporation. Incontrast, no net N mineralization was detected when simulating lateincorporation. In the field experiment, the N supply fromsoil to spring wheat was higher in the late and delayed incorporationtreatmentsthan in early or spring incorporation of green manure. Late incorporationalso produced most wheat grain. We conclude that different amounts of N becomeavailable to wheat, depending on the time of incorporation of green manureresidues in soil. This difference is due to temperature. Late or delayedincorporation of green manure residues has the potential to reduce thesusceptibility of mineral N to leaching and yields more N available to asubsequent crop.     

Nitrogen concentration in cottonseed as an indicator of N availability

Research on corn and winter wheat has shown that a critical N concentration in the grain exists above which a yield response to N fertilizer is unlikely. This indicator can be used for post-harvest evaluation of N sufficiency and for mapping N availability in the field, which may be helpful for making future N fertilizer decisions. The purpose of this study was to determine if a critical N concentration in the seed exists for cotton. The study was conducted in the Georgia Coastal Plain during 1998, 1999, and 2001, using a different variety of cotton in each year. In 1998, 12 N fertilizer rates ranging from 38 to 203 kg ha^–1 were applied to Delta Pineland 90 at three locations within one field that differed in soil organic matter and clay concentration, and in 1999 and 2001, 6 N fertilizer rates ranging from 22 to 179 kg ha^–1 were applied to Stoneville 474 and Delta Pineland 458 in a different field. At all locations, the N concentration in the cottonseed increased linearly with increasing N fertilizer rates. Maximum yields were obtained at less than maximum seed N concentration. Lower seed N concentrations indicated some degree of N deficiency. Based on these results, it appears that a critical N concentration of 35 g kg^–1 exists for cottonseeds, above which no yield response to N fertilizer is likely. Information on the spatial distribution of cottonseed N concentrations could therefore help to evaluate the adequacy of N fertilization for cotton, thereby providing a basis for adjustment of N fertilization rates in future crops.     

Rational nitrogen fertilization in intensive cropping systems

The objective of a rational N fertilization program is to account for the sources and fate of N while estimating crop N needs. Efficiency of N use will vary with cropping systems and N sources. Management technologies that affect N use efficiency include the amount of N applied, timing and placement of N fertilizer, and use of inhibitors. One of the main problems in making a fertilizer N recommendation is to account for the contribution of N mineralization to plant available N. Most laboratory procedures do not account for the environmental factors that affect N mineralization and only estimate the size of the mineralizable N pool. However, changes in soil moisture and temperature can dramatically affect the amount and rate of release of mineralized N. Field and modeling techniques are two possible techniques to estimate N mineralization. Field techniques can be divided into soil and plant approaches. Soil incubations in the field provide a quantitative approach while soil nitrate tests during the growing season provide a qualitative approach to estimating N mineralization. The plant is the ultimate integrator of N mineralization. Plant N uptake by an unfertilized crop can provide a quantitative approach with certain precautions. This approach may be costly, labor intensive, and site specific. Crop N uptake during the growing season can be estimated by measuring the tissue N content or using a chlorophyll meter. The chlorophyll meter measures the greenness of the plant and has been shown to be positively correlated to plant N status. Modeling may provide another option by including the factors that affect the rate of N mineralization from a known pool. The two most important variables include soil moisture and temperature. Realistic yield expectations and accounting for existing and projected amounts of available N can improve the accuracy of N recommendations.     

Extraction of Uranium(VI) and Thorium(IV) from Nitric Acid Solution by N,N,N′,N′ – Tetraoctylglutaricamide

Synthesis and characterization of N,N,N′,N′-tetraoctylglutaricamide (TOGA) was carried out and used for extraction of U(VI) and Th(IV) from nitric acid solutions. The processes of extraction were determined by the slope analysis and by analyzing a function that allows the simultaneous treatment of all the experimental points obtained in different conditions. The different factors affecting the extraction distribution ratio(D) of U(VI) and Th(IV) (extraction concentration, concentrations of nitric acid, salting-out agent NaNO₃ concentration, equilibration time, temperature, and types of diluents) were investigated. The results obtained indicated that the extraction species of U(VI) and Th(IV) are mainly extracted as UO₂(NO₃)₂·1.0TOGA and Th(NO₃)₄·1.5TOGA. The apparent equilibrium constant of U(VI) and Th(IV) extraction determined are 3.35 ± 0.03 L³/mol³ and 1.87 ± 0.01 L⁵/mol⁵ at 298 ± 1 K. Thermodynamic parameters such as the free energy(ΔG), enthalpy(ΔH), and entropy(ΔS) changes associated with the extraction processes could be evaluated. Back-extraction of U(VI) and Th(IV) from organic phases was also studied.     

Response to N-fertilizer of Italian ryegrass grown alone and in mixture with berseem clover under continental irrigated mediterranean conditions

In a field experiment over three growing seasons, the potential benefits of planting berseem clover (Trifolium alexandrinum L) with Westerwold Italian ryegrass (Lolium multiflorum Lam.) were examined under irrigated continental Mediterranean conditions.Similar N rates (0, 30, 60, 90 and 120 kg N ha^–1 cut^–1) were applied to both pure Italian ryegrass stands and mixtures, each given three successive cuts. One previously unfertilized cut was performed in late winter. Species in the mixture were established at 50:50 seed ratio but the mean proportion of berseem clover was 14%. Mean winter survival of berseem was 87% but 88% of the plants had leaves damaged by the frost. Forage production varied with both N rate and cutting sequence in both the pure stand and the mixture but differences between the two types of swards were significant only at low levels of fertilizer N. Total DM production over the four cuts in plots with N applications of 0,90, 180, 270 and 360 kg N ha^–1 a^–1 were 7.14, 9.51, 11.66, 13.91 and 14.36 t DM ha^–1 a^–1 in pure stand, respectively. Corresponding values for the mixture were 8.80, 10.94, 12.90, 14.05 and 13.64 t DM ha^–1 a^–1. The mean response of Italian ryegrass in the range of 0–360 kg N ha^–1 a^–1 was 20 kg DM per kg N applied. The corresponding value for the mixture was 13 kg DM per kg N applied. At the berseem clover proportions reached in this work, N equivalence showed values of about 80 kg N ha^–1 a^–1. As rates of N increased from 0 to 120 kg N ha^–1 cut^–1, nitrogen concentration increased by 78%. In the applied range of N fertilizers, N0₃-N was not affected.

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Résumé Dans un essai réalisé au cours de trois saisons agricoles, on a étudié le potentiel de 1'association du bersim avec le raygrass italien. Les cultures ont été emenées et irrigué dans des conditions continentales méditerranéennes. On a appliqué, aussi bien pour la culture pure du raygrass que pour l'association, une fertilisation azotée avec les doses suivantes (0, 30, 60, 90 et 120 kg N/ha/coupe) après chacune des trois coupes successives. Une autre coupe avant fertilisation a été faite à la fin de 1'hiver. Les proportions du bersim et du raygrass dans le mélange de graines étaient de 50:50. Cependant, dans la culture en association, les plantes du bersim n'étaient préentés qu'avec un 14 pourcent. 87% des plantes du bersim ont pu survivre en hiver, dont 88% avaient des feuilles endommagées par les gelées. La production d'herbe a été proportionnelle aux doses de fertilisation pour la culture pure et l'association. Néanmoins, différence entre les rendements de chacune de ces dernières était d'autant plus nette que les doses d'azote incorporées dans le sol étaient faibles. La production de la MS pour les quatre coupes dans les parcelles avec les applications de 0, 90, 180, 270 et 360 kg N ha^–1 a^–1 étaient de 7.14, 9.51, 11.66, 13.51, 14.36 tMS ha^–1 a^–1. Le rendement moyen du raygrass italien dans un intervalle de 0-360 kg N ha^–1 a^–1 a été de 20 kg MS par kg de N de fertilisation. Concernant le bersim, les valeurs équivalentes de N étaient de 1'ordre de 80 kg N ha^–1 a^–1. Au fur et à mesure que les doses de fertilisation azotée augmente de 0 à 120 kg ha^–1 coupe, la concentration en azote augmente de 78%. Dans l'intervalle de la fertilisation azotée appliqué NO₃ -N n'a pas été affectée.

     

正丁基脒合成工艺的改进

以N、N，N-二丁基戊酰胺和三氟甲磺酸酐为原料，合成正丁基脒。以物料比、反应温度、反应时间为考察因素，采用正交化实验方法筛选最优工艺条件。结果表明，当N、N，N-二丁基戊酰胺与Tf20的投料比为1：2，反应温度0℃，反应时间2h时，产品收率达45％。采用。HNMR和IR对产品结构进行了表征。     

N,N-二乙基-氨丙基甲基二甲氧基硅烷的合成及结构表征

以γ-氯丙基甲基二甲氧基硅烷和二乙胺为原料，经过胺化反应制得N，N-二乙基-氨丙基甲基二甲氧基硅烷，确定最佳反应条件为温度110℃。二乙胺与γ-氯丙基甲基二甲氧基硅烷的量之比4：1，反应时间20h，产品产率可达80%以上；并通过IR，^1HNMR光谱对产品结构进行了表征。应用HF/6-31G*量子化学从头算方法计算了分子构型。     

长链烷基酰胺丙基季铵盐的合成及性能

长碳链烷基酰胺丙基二甲基胺是合成有关阳离子及两性表面活性剂的中间体，其分子中独特的长碳链及酰胺基使其制成的表面活性剂具有更优异的特性。本文以不同的长碳链脂肪酸，N，N-二甲基丙二胺为原料，合成了三种烷基酰胺丙基二甲基胺及其阳离子季铵盐表面活性剂，并对其合成条件进行了研究和探索。