本文關(guān)鍵詞：呋蟲胺水解機(jī)理的理論研究　出處：《重慶師范大學(xué)》2017年碩士論文　論文類型：學(xué)位論文

  更多相關(guān)文章： 呋蟲胺 水解 溶劑效應(yīng) M06-2X B3LYP MP2 CPCM模型

【摘要】：呋蟲胺作為第三代新煙堿類殺蟲劑為現(xiàn)代農(nóng)業(yè)作出了重大貢獻(xiàn),具有殺蟲廣譜,極強(qiáng)的吸收效果,高效的殺蟲活性和獨(dú)特的生物化學(xué)性。由于其廣泛和頻繁的應(yīng)用,隨著呋蟲胺在農(nóng)作物和水中的不斷積累將對人類和動物造成潛在危害并且會破壞作物的正常生長。呋蟲胺不含氯原子和芳香環(huán),這點(diǎn)與其他已經(jīng)存在的殺蟲劑有很大的不同,因此為確保其安全性應(yīng)該特別關(guān)注呋蟲胺在環(huán)境中的降解機(jī)理。相關(guān)報道指出呋蟲胺能夠溶解在如甲醇和甲苯等有機(jī)溶劑中甚至可以達(dá)到37g/L,水解反應(yīng)是呋蟲胺在環(huán)境中的主要降解途徑之一。據(jù)我們所知,近幾年有部分關(guān)于呋蟲胺水解的實(shí)驗(yàn)研究,然而對于呋蟲胺的水解機(jī)理的研究很少并且其水解反應(yīng)機(jī)理仍不清楚,因而對呋蟲胺的水解機(jī)理進(jìn)行理論研究具有很重要的意義。水溶液的酸堿性是呋蟲胺在水溶液環(huán)境中降解的重要影響因素之一。在整篇文章中我們對呋蟲胺在堿性、中性和酸性條件下的水解機(jī)理進(jìn)行系統(tǒng)研究,主要采用M06-2X,B3LYP的方法并結(jié)合6-311++G(d,p)基組和MP2的方法結(jié)合6-311+G(d,p)基組進(jìn)行計算。在氣相條件當(dāng)中,我們運(yùn)用M06-2X以及B3LYP的方法分別對不同酸堿性條件下反應(yīng)路徑中的過渡態(tài)(TS)、反應(yīng)物(RC)、中間體(INT)及產(chǎn)物(PC)的分子構(gòu)型進(jìn)行了全優(yōu)化,同時也經(jīng)過對虛頻進(jìn)行分析得出對應(yīng)過渡態(tài)的準(zhǔn)確性。此外,反應(yīng)是在水溶液中進(jìn)行的,因此我們也考慮了溶劑化效應(yīng)對整個理論研究的影響,本研究對所有的穩(wěn)定結(jié)構(gòu)運(yùn)用CPCM模型在M06-2X方法基礎(chǔ)上進(jìn)一步進(jìn)行優(yōu)化。數(shù)據(jù)顯示,不管是在水溶液條件下還是在氣相條件下,呋蟲胺在堿性環(huán)境下的水解的活化能壘都是最低的,在堿性條件下反應(yīng)最迅速,因而得出呋蟲胺的水解為堿性水解。呋蟲胺在堿性條件下的Path A是反應(yīng)的最優(yōu)路徑,即呋蟲胺陰離子中羥基上的H6原子遷移至N2原子上的反應(yīng)路徑。本論文對呋蟲胺的水解理論計算進(jìn)行了細(xì)致地論述,這能夠?yàn)閷?shí)驗(yàn)探究作出進(jìn)一步驗(yàn)證,同時還可以為呋蟲胺的進(jìn)一步實(shí)驗(yàn)作出相應(yīng)的預(yù)測,從而提高實(shí)驗(yàn)探究能力和效率。我們的研究也能夠?yàn)轭愃频睦碚撗芯刻峁└嗟膮⒖純r值。
[Abstract]:Furoxime as the third generation of new nicotinic insecticides has made a great contribution to modern agriculture, has a broad spectrum of insecticidal, very strong absorption effect. Highly effective insecticidal activity and unique biochemistry. Due to its extensive and frequent application. Furosemide, which contains no chlorine atoms and aromatic rings, can cause potential harm to humans and animals and damage the normal growth of crops as furfuramide accumulates in crops and water. This is very different from other pesticides that already exist. Therefore, in order to ensure its safety, we should pay special attention to the degradation mechanism of furosemide in the environment. It has been reported that furosemide can be dissolved in organic solvents such as methanol and toluene even up to 37 g / L. Hydrolysis is one of the major degradation pathways of furosemide in the environment. As far as we know, there have been some experimental studies on the hydrolysis of furosemide in recent years. However, there are few studies on the hydrolysis mechanism of furosemide and the mechanism of its hydrolysis is still unclear. Therefore, it is of great significance to study the hydrolysis mechanism of furosemide. The acidity and alkalinity of aqueous solution is one of the important factors that affect the degradation of furosemide in aqueous solution. Sex. The hydrolysis mechanism under neutral and acidic conditions was studied systematically. The method of M06-2XPB3LYP combined with 6-311 GTD was used. The p-) basis group and MP2 method were combined with the 6-311 G ~ (+) ~ (-) G ~ (2 +) base set to calculate in the gas phase condition. We have used M06-2X and B3LYP methods to study the transition state of TSN, the reactant RCin, in different reaction paths under different acid-base conditions, respectively. The molecular configuration of the intermediate (INT) and its product (PCC) were optimized, and the accuracy of the corresponding transition states was obtained through the analysis of the virtual frequency. In addition, the reaction was carried out in aqueous solution. Therefore, we also consider the solvation effect on the whole theoretical study. In this study, all stable structures are further optimized by using CPCM model based on M06-2X method. Whether in aqueous solution or in gas phase, the activation energy barrier of hydrolysis of furoxime in alkaline environment is the lowest, and the reaction is the most rapid in alkaline condition. It is concluded that the hydrolysis of furosemide is alkaline, and the Path A of furosemide in alkaline condition is the optimal route. In this paper, the theoretical calculation of the hydrolysis of furosemide is discussed in detail, which can be further verified for the experiment. At the same time, it can also make corresponding prediction for furoxime further experiments, so as to improve the ability and efficiency of experimental inquiry, and our research can also provide more reference value for similar theoretical research.
【學(xué)位授予單位】：重慶師范大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：X592

【參考文獻(xiàn)】

相關(guān)期刊論文 前6條

1 ;Theoretical study on the hydrolysis mechanism of N,N-dimethyl-N′-(2′,3′-dideoxy-3′-thiacytidine)formamidine[J];Science in China(Series B:Chemistry);2008年10期

2 ;SHRIMP zircon U-Pb dating of the intrusives in the Tongling metallogenic cluster and its dynamic setting[J];Science in China(Series D:Earth Sciences);2008年07期

3 張嫦;薛英;;N,N-二甲基-N′-(2′,3′-二脫氧-3′-硫代胞苷)甲脒水解機(jī)理的理論研究[J];中國科學(xué)(B輯:化學(xué));2008年05期

4 謝國紅;劉國光;孫德智;鄭立慶;;啶蟲脒水解動力學(xué)研究[J];安徽農(nóng)業(yè)科學(xué);2007年30期

5 何冰;薛英;郭勇;鄢國森;;2',3'-二脫氧-2',3'-二去氫鳥嘌呤核苷構(gòu)象穩(wěn)定性的理論研究[J];化學(xué)學(xué)報;2007年06期

6 徐昕，王南欽，呂鑫，，張乾二;量子化學(xué)的研究現(xiàn)狀、發(fā)展趨勢與展望[J];化學(xué)進(jìn)展;1996年01期

相關(guān)博士學(xué)位論文 前1條

1 任慧;量子化學(xué)理論在現(xiàn)代化學(xué)中應(yīng)用的研究[D];北京化工大學(xué);2008年

相關(guān)碩士學(xué)位論文 前1條

1 張磊磊;呋蟲胺的水解和光化學(xué)降解研究[D];河南師范大學(xué);2014年

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