棉田除草剂溴嘧氯草醚的中试合成及杂质鉴定

为研究棉田除草剂溴嘧氯草醚(开发代号SIOC0426,化学名称为N-[2-氯-6-(4,6-二甲氧基-2-嘧啶氧基)苄基]-4-溴苯胺)的中试合成工艺,以2-氟-6-氯苯甲醛为起始原料,通过水解、缩合、还原和亲核取代反应在公斤级规模上合成了溴嘧氯草醚,用高效液相色谱外标法测定了原药含量,通过三维高效液相色谱-质谱联用(HPLC-DAD-MS)技术对原药中的杂质结构进行了鉴定。结果表明,反应总收率高于80%,原药含量大于98%,主要杂质为未反应完全的中间体2-[(4-溴苯氨基)甲基]-3-氯苯酚和溴嘧氯草醚Smiles重排产物。该工艺反应条件温和,反应收率高,原药含量高,"三废"排放较少,较适合工业化放大生产。     

农药中间体2-氯烟酸的绿色合成工艺

以N,N-二甲基甲酰胺、光气或双(三氯甲基)碳酸酯和丁基乙烯醚为原料合成了3-二甲氨基丙烯醛,再和氰基乙酸乙酯反应,合成2-氰基-5-二甲氨基-2,4-戊二烯酸乙酯,经过环合、水解,合成2-氯烟酸,总收率70. 8%。该工艺反应条件温和,收率高、生产成本低,适合于工业化生产的新工艺。     

噻虫胺的合成

以2,3-二氯丙烯和硫氰酸钠为起始原料,首先生成中间体2-氯丙烯硫代异氰酸酯（1）,（1）经过氯化反应得到2-氯-5-氯甲基-1,3-噻唑（2）;（2）与1-甲基-2-硝基亚胺基-5-苄基-六氢-1,3,5-三嗪反应得到1-（2-氯噻唑-5-甲基）-2-硝基亚胺基-3-甲基-5-苄基-六氢-1,3,5-三嗪（3）;（3）在乙醇溶剂中,催化合成了产物噻虫胺。合成总收率达到51.38%。该工艺可以有效降低生产成本,经济效益和社会效益显著,具有很好的推广应用价值。     

含取代吡啶基的不对称硫代磷(膦)酸酯的合成及杀菌活性研究

从二硫代磷酸二乙酯钠盐或O,O-二乙基硫代磷酰氯出发 ,经酯化、去烷基化反应得到相应的硫代或二硫代铵盐 ,分别与 2 -氯 - 5 -氯甲基吡啶反应得产物 2 a～ 2 c。从 O-乙基硫代磷酰二氯或苯基硫代膦酰二氯出发 ,先与取代苯酚或甲胺反应 ,然后与 2 -氯 - 5 -羟甲基吡啶反应得到产物 2 d～ 2 k和 2 m～ 2 u。O-乙基 - S-丙基二硫代磷酰氯、O-乙基硫代磷酰二氯和苯基硫代膦酰二氯与 2 -氯 - 5 -羟甲基吡啶反应分别得产物 2 l、2 v和 2 w。所合成的 2 3个新化合物对9种植物病菌的离体及活体杀菌活性测试表明 ,其中一些化合物对水稻稻瘟病和水稻纹枯病有一定活性 ,个别化合物活性很好 ,但对其它病菌的活性均较低     

3-溴-1-(3-氯-2-吡啶基)-1H-吡唑-5-甲酸的合成工艺研究

旨在优化合成氯虫苯甲酰胺的重要中间体3-溴-1-(3-氯-2-吡啶基)-1H-吡唑-5甲酸,并寻找一条适用于工业化生产的工艺路线。以2,3-二氯吡啶为原料,首先经过肼解反应,生成3-氯-2-肼基吡啶,然后3-氯-2-肼基吡啶经过环合,得到2-(3-氯吡啶-2-基)-5-羟基吡唑-3-甲酸乙酯,2-(3-氯吡啶-2-基)-5-羟基吡唑-3-甲酸乙酯经过溴化,得到3-溴-1-(3-氯吡啶-2-基)4,5-二氢-1H-吡唑-5-甲酸乙酯,再氧化3-溴-1-(3-氯吡啶-2-基)4,5-二氢-1H-吡唑-5-甲酸乙酯,生成3-溴-1-(3-氯吡啶-2-基)-1H-吡唑-5-甲酸乙酯,最后3-溴-1-(3-氯吡啶-2-基)-1H-吡唑-5-甲酸乙酯水解,得到目标中间体3-溴-1-(3-氯-2-吡啶基)-1H-吡唑-5甲酸。在优化的条件下,反应总收率为44.44%,纯度为99.2%,所有中间体及产物经过1H NMR、IR进行表征。该路线条件温和、操作简便,为工业化生产奠定了基础。     

放射性同位素碳-14标记氯虫苯甲酰胺的合成与分析

以[14C]碳酸钡为放射性同位素原料,通过格氏反应、亲核取代、胺化和缩合等8步放化反应制备了2种放射性同位素碳-14标记的氯虫苯甲酰胺粗品,经反相高效液相色谱(RPHPLC)纯化获得标记物纯品14C-氯虫苯甲酰胺[3-溴-N-[4-氯-2-甲基-6-(甲氨基[羰基-14C]甲酰基)苯基]-1-(3-氯-2-吡啶基)-1H-吡唑-5-甲酰胺(2,55.6 mCi)和3-溴-N-[4-氯-2-甲基-6-(甲氨基甲酰基)苯基]-1-(3-氯-2-吡啶基)-1H-吡唑-5-[羰基-14C]甲酰胺(3,58.6 mCi)]。以[14C]碳酸钡计,两种标记物的总放化收率分别为32%和52%。其结构经核磁共振氢谱、质谱和在线放射性高效液相色谱(HPLC-FSA)分析确认。放射性薄层成像分析(TLC-IIA)、离线放射性高效液相色谱分析(HPLC-LSC)、在线放射性高效液相色谱-二极管阵列检测器/质谱联用(HPLCFSA/PDA/MS)和LSC分析表明,两种14C-氯虫苯甲酰胺的放化纯度分别为99.8%和99.6%,化学纯度分别为99.1%和98.4%,比活度分别为52.45 mCi/mmol和52.30 mCi/mmol。这2种标记物可作为放射性示踪剂,可满足氯虫苯甲酰胺在中国的登记代谢试验研究的需要。     

N-羟基-N-2-[N-(4-氯苯基)-3-吡唑氧基甲基]-苯胺的合成

高效低成本合成N-羟基-N-2-[N-(4-氯苯基)-3-吡唑氧基甲基]-苯胺。以2-[(N-4-氯苯基)-1H-吡唑-3-基氧甲基]硝基苯和碳酸氢钠为原材料,5%Pt/C为催化剂,通入氢气还原得N-羟基-N-2-[N-(4-氯苯基)-3-吡唑氧基甲基]-苯胺,并对不同条件下的试验结果进行了分析。优化条件为氢气进气压力为0.2Mpa,5%Pt/C催化剂与2-[(N-4-氯苯基)-1H-吡唑-3-基氧甲基]硝基苯的配比为5∶60,温度为30℃,反应时间为4h。该反应条件下产物反应收率≥97%,含量≥97%,生产成本低、操作简便非常适合工业化生产。     

连续法生产2-甲基-2-甲硫基丙醛技术研究

本文介绍了以异丁醛为原料，经过氯代反应，甲硫基化反应，合成2-甲基-2-甲硫基丙醛的连续法生产工艺，两步反应收率分别为97％、95％，粗品蒸馏后可以得到98％的产品。     

2-氰基-3-[(6-氯)-3-吡啶甲基]氨基-3-脂肪氨基丙烯酸乙酯的合成

以3-氨甲基吡啶和2-氯-5-氨甲基吡啶为原料先与2-氰基-3,3-二甲硫基丙烯酸乙酯反应得到中间体2a和2b,不经分离,直接与脂肪胺反应,合成了7个未见文献报道的开环类吡虫啉结构化合物3.所有目标化合物(包括2a和2b)均经元素分析和1H NMR确证,并对其构型进行了讨论.     

2-氰基-3- 氨基-3-脂肪氨基丙烯酸乙酯的合成

以3-氨甲基吡啶和2-氯-5-氨甲基吡啶为原料先与2-氰基-3,3-二甲硫基丙烯酸乙酯反应得到中间体 2a和2b, 不经分离,直接与脂肪胺反应,合成了7个未见文献报道的开环类吡虫啉结构化合物 3 。所有目标化合物(包括 2a和2b )均经元素分析和1H NMR确证,并对其构型进行了讨论。     

不同施肥配比对宁夏盐碱土壤油用向日葵产量的影响

研究了不同施肥配比对宁夏盐碱土壤向日葵产量的影响,建立了一元二次肥料效应函数方程.结果表明:对碱化土壤施氮量达到10.56 kg/667m2时,产量达到最大值183.2 kg/667m2;当施磷量达到5.71 kg/667m2时,产量达到最大值156.9 kg/667m2;最高产量施肥配方氮磷钾配比为10.56∶5.7...     

基于农用地分等成果的武功县耕地生产能力分析

为了充分利用农用地分等成果测算耕地生产能力,合理开发农用地生产潜力,建立了农用地产能核算技术方案体系,并据此以武功县为例,计算了该县农用地自然生产潜力、利用生产潜力和现实生产能力.通过各分等单元的自然质量等级指数和利用等级指数分别乘以单元面积并累加得到自然生产潜力和利用生产潜力,并利用Logistic模型拟合标准粮产量和利用等指数之间的关系来计算现实生产能力。结果表明,武功县自然生产潜力和利用生产潜力分别为107.42×10⁴ t和70.05×10⁴ t,单位面积自然生产潜力和利用生产潜力分别为39.22 t·hm^-2和25.58 t·hm^-2,现实生产能力为28.49×10⁴ t,单位面积现实生产能力为10.40 t·hm^-2。武功县耕地生产能力在空间上差异明显,粮食单产有从东南向西北递减的趋势,单位面积现实产能最高和最低的分别为普集镇和游风镇,为13.53 t·hm^-2和8.66 t·hm^-2,未来西北台塬区的乡镇是粮食增产的重点区域。     

Ca2+,Mn2+等8种金属离子对软腐欧文氏菌一些致病因子的影响

 在离体试验中,不同金属离子对马铃薯软腐欧文氏菌(Erwinia carotovora subsp.carotovora)菌株StEcc-12生长,产生胞外酶和胞外酶活性具有不同的影响。在含果胶酸钠的培养液中,Ca²⁺促进生长,并使培养液中的果胶裂解酶(PL)、果胶水解酶(PG)和蛋白酶3种胞外酶分别提高1.4~23.4倍,0.3~2.9倍和0.7~6.5倍。Mn²⁺对StEcc-12生长及产生3种胞外酶的影响与Ca²⁺相似。Ni²⁺显著抑制细菌的生长,但在含Ni²⁺培养液中3种胞外酶的单位活性比对照高1.7倍以上。在酶粗提液中分别加入上述3种离子对PL酶的活性均有抑制作用。Zn²⁺对细菌生长没有显著影响,高浓度Al³⁺抑制细菌生长,这2种离子均能促进3种胞外酶的产生。随着Fe²⁺和K⁺浓度的增高,细菌生长减少,两种果胶酶产量降低,蛋白酶产量增加,粗提液中PL酶活性下降。Mg²⁺对细菌生长和胞外PG产生没有明显影响,提高Mg²⁺浓度有利于PL的产生。酶粗提液中加入Mg²⁺后PL活性增高。所有以上离子都能使聚半乳糖醛酸发生不同程度的凝聚,但只有Ca²⁺和Mg²⁺的有效凝聚浓度与薯块的实际浓度接近。     

超氧自由基在三环唑防治稻瘟病中的作用

 研究了三环唑对水稻超氧自由基(O₂^{· -})产生的影响及其在病害防治中的意义,结果表明三环唑能刺激药剂-植物-病菌互作过程中O₂^{· -}的产生。O₂^{· -}清除剂甘露醇和抗坏血酸对稻瘟病菌菌丝生长有一定的抑制作用,于接种后处理却对三环唑表现拮抗作用。外源H₂O₂和O₂^{· -}及从经三环唑预处理并接种的植株获得的叶片泌出液都对稻瘟病菌孢子萌发有直接的抑制作用,且三环唑对这种抑制作用表现明显的增效。说明刺激寄主产生O₂^{· -}和降低病菌的抗氧化能力可能是三环唑防治稻瘟病的作用机制之一     

Regulation of elicitin-induced ethylene production in suspension-cultured tobacco BY-2 cells

INF1 elicitin, a proteinaceous elicitor produced by Phytophthora infestans, induces a hypersensitive response in tobacco BY-2 cells. In response to elicitin, tobacco cells produce both reactive oxygen species (ROS) and ethylene (ET). To investigate the regulation of elicitin-induced ET production, we pharmacologically analyzed the effects of several chemicals on ET production. Inhibitors of ROS generation or ROS chelators efficiently inhibited ET production, whereas simultaneous treatment of a superoxide anion-generating system with salicylhydroxamic acid recovered ET production. In an in vitro experiment, superoxide anion was necessary and sufficient for conversion of 1-aminocyclopropane-1-carboxylate (ACC) to ET because ET was produced from ACC solely in the presence of the superoxide-generating chemical KO₂. ET production was also inhibited by lipoxygenase (LOX) inhibitors, indicating a possible involvement of LOX-mediated generation of superoxide anion and ET production itself. Furthermore, elicitin-induced ET production was completely inhibited by the protein synthesis inhibitor cycloheximide but recovered after exogenous application of ACC, indicating that de novo protein synthesis is required for ACC accumulation, leading to ET production. We also investigated the effects of several phytohormones on elicitor-induced ET production and discuss their role in the defense response.     

Modelling the impact of climate change on rangeland forage production using a generalized regression neural network: a case study in Isfahan Province,Central Iran

Monitoring of rangeland forage production at specified spatial and temporal scales is necessary for grazing management and also for implementation of rehabilitation projects in rangelands. This study focused on the capability of a generalized regression neural network(GRNN) model combined with GIS techniques to explore the impact of climate change on rangeland forage production. Specifically, a dataset of 115 monitored records of forage production were collected from 16 rangeland sites during the period 1998–2007 in Isfahan Province, Central Iran. Neural network models were designed using the monitored forage production values and available environmental data(including climate and topography data), and the performance of each network model was assessed using the mean estimation error(MEE), model efficiency factor(MEF), and correlation coefficient(r). The best neural network model was then selected and further applied to predict the forage production of rangelands in the future(in 2030 and 2080) under A1 B climate change scenario using Hadley Centre coupled model. The present and future forage production maps were also produced. Rangeland forage production exhibited strong correlations with environmental factors, such as slope, elevation, aspect and annual temperature. The present forage production in the study area varied from 25.6 to 574.1 kg/hm~2. Under climate change scenario, the annual temperature was predicted to increase and the annual precipitation was predicted to decrease. The prediction maps of forage production in the future indicated that the area with low level of forage production(0–100 kg/hm~2) will increase while the areas with moderate, moderately high and high levels of forage production(≥100 kg/hm~2) will decrease both in 2030 and in 2080, which may be attributable to the increasing annual temperature and decreasing annual precipitation. It was predicted that forage production of rangelands will decrease in the next couple of decades, especially in the western and southern parts of Isfahan Province. These changes are more pronounced in elevations between 2200 and 2900 m. Therefore, rangeland managers have to cope with these changes by holistic management approaches through mitigation and human adaptations.     

Effects of crop management practices on Echinochloa crus-galli and Chenopodium album seed production in a maize/soyabean rotation

Seed production of residual weed populations needs to be taken into account when estimating the long-term impact of low-input agronomic practices. The objective of this study was to measure the effects and interactions of crop, weed control, tillage practice and nutrient source on the seed production of the dominant residual weed species in a maize/soyabean rotation at two sites: Echinochloa crus-galli (L.) Beauv. on a Sainte-Rosalie clay and Chenopodium album L. on a Duravin clay loam. Seed production per unit area was estimated in each experimental unit. Weed seed production was greater under mechanical weed control compared with chemical weed control. In 1997, E. crus-galli seed production reached over 326 000 seeds m^–2 in mechanical weed control treatments, but averaged less than 500 seeds m^–2 in the chemical weed control treatments. Chenopodium album produced in the range of 766 000 and 73 000 seeds m^–2 in mechanical and chemical weed control treatments respectively. Very few or no weed seeds were produced in soyabean under chemical control. Tillage intensity and nutrient source did not affect seed production of either weed species, with the exception that E. crus-galli produced more seeds in chisel than in mouldboard plough tillage in soyabean. Weed control method had more impact on seed production than tillage intensity and nutrient source in a maize/soyabean rotation.     

东北商品粮基地县粮食安全情景模拟——以德惠市为例

基于寻求粮食主产区粮食安全理想方案的目标,以德惠市为例,定量刻画了影响粮食生产的关键要素之间以及要素与粮食生产之间的作用关系,构建了粮食生产系统的SD模型.根据最初拟设的4种情景,模拟了单要素变化下粮食生产能力的变动趋势,并结合多个单要素情景模拟结果,提出了更符合实际需求的多要素变化情景(综合情景).根据模型运行结果,提出了保障区域粮食安全的政策建议:(1)保障水资源供给能力;(2)德惠中长期粮食安全目标是保持总量在200万吨左右;(3)水田比例应以不超过35％为宜;(4)城市化年均增长率应以1个百分点为上限.     

Early Events During Quiescent Infection Development by Colletotrichum gloeosporioides in Unripe Avocado Fruits

Inoculation of avocado pericarp tissue with Colletotrichum gloeospori-oides and treatment of avocado cell cultures with the cell wall elicitor of C. gloeosporioidesboth increased the production of reactive oxygen species (ROS). However, whereas the production of ROS could be detected within minutes in avocado cell suspensions, it was detected only after 2 h following inoculation of pericarp tissue. Protein kinase inhibitors such as K-252a and staurosporine and the phosphatase inhibitor microcystin-LR inhibited the release of H(2)O(2) from avocado cell suspensions. When 1 mM H(2)O(2) was exogenously applied to pericarp tissue, it enhanced ROS, phenyl-alanine ammonia lyase (PAL) activity, and epicatechin levels. But, when H(2)O(2) treatment was applied following staurosporine treatment, PAL activity was no longer induced. The uninduced ROS production in pericarp tissue of freshly harvested, unripe, resistant fruit was twice as high as in ripe, susceptible fruit. Challenge inoculation of resistant fruit further increased the ROS level; however, this increase did not occur in susceptible fruits. The current findings are consistent with the hypothesis that production of ROS is induced by fungal infection of unripe fruits and, consequently, may modulate resistance, resulting in the inhibition of fungal development and quiescence.     

水氮管理及打顶时间对烤烟品质及产值产量的影响

为探究水氮打顶配合对烤烟化学品质及产值产量的影响,以烤烟红花大金元为研究对象,通过设置不同的土壤田间持水量、施氮量和打顶时间采取完全随机试验设计方案进行盆栽试验。结果表明:(1)不同田间持水量、施氮量和打顶时间配合对烤烟化学品质影响显著;当土壤田间持水量为65%、施氮量为5 kg·666.7 m~(-2)与烤烟打顶时间为初花后7天时,各烟叶化学成分综合评分均达到最高值,上部烟叶的可用性增加,对改善烟叶化学成分的协调性具有显著效果;(2)水氮打顶配合条件下,可以实现最优的产量配合处理为A2B3C1,产量达到145.51 kg·666.7 m~(-2);最优的产值配合处理为A2B2C2,产值为1 924.95元·666.7 m~(-2),其中水氮配合对烟叶的产量产生极显著性影响,不同土壤田间持水量、施氮量和打顶时间的配合对烤烟产值具有显著的影响;产值最大时烟叶化学成分协调性综合评分最高,印证了烟草品质与产值的关系。因此,适宜土壤田间持水量、施氮量和适时的打顶时间配合,将改善烟叶的化学成分,提高烟叶的品质,增大烤烟产值。