3，4-二氢嘧啶-2（1H）-酮的合成与理论研究
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摘要
1893年,Biginelli首次报道了芳香醛、脲和乙酰乙酸乙酯在浓盐酸催化下发生缩合反应生成3,4-二氢嘧啶-2(1H)-酮衍生物(DHPMs)。自20世纪90年代以来,研究发现DHPMs具有广泛的药理活性,因此DHPMs的合成及分子性质研究成为生物活性有机杂环化合物研究的热点之一。
本论文主要包括实验和理论计算两方面的内容:实验部分,系统探讨了三氯化锑(SbCl3)作为催化剂参与的Biginelli反应;理论计算部分,用量子化学方法研究了DHPMs的分子性质、Biginelli反应机理,并用从头算及变分过渡态理论研究了尿素和甲醛的反应。研究取得了以下几个方面的成果:
1、使用SbCl3作为催化剂,无溶剂条件下合成一系列DHPMs。反应的最佳条件为:芳香醛、β-二羰基化合物和尿素的摩尔比为1:1:1.5,催化剂用量为芳香醛的10%,反应最佳温度为70℃。此改进方法具有反应时间短、收率高、操作简便等优点,为DHPMs的制备提供了一条方便、快捷、有效的合成方法。
2、在6-31G(d)或6-311G基组水平上,用B3LYP、HF和MP2三种方法对四种DHPMs进行了几何全优化,并对其电荷分布、前线分子轨道、成键情况以及自然键轨道(NBO)进行了分析。DHPMs的氮原子和氧原子以及与氢原子相连的碳原子,带负电荷;而非氢原子中正电荷主要分布在与氮原子和氧原子相连的碳原子上;DHPMs中嘧啶环为船式构象;DHPMs的前线轨道能级差较小,表明它们的稳定性较差,可能具有很好的生物活性;在DHPMs中,嘧啶环上两个氮原子的孤对电子都与相邻键有较强的相互作用。
3、用密度泛函理论在B3LYP/6-31G(d) , B3LYP/6-31+G(d,p)和B3LYP/6-311+G(3df,2p)//B3LYP/6-31+G(d,p)水平,研究了Biginelli反应机理,计算了反应的平衡常数。经典Biginelli反应机理为:在酸的作用下醛和脲首先生成中间体酰基亚胺正离子,然后与乙酰乙酸乙酯发生缩合反应得到一个开链的酰脲,后者进一步环化、脱水得到相应的DHPMs,反应平衡常数为70.80。合成二氢嘧啶硫酮反应机理与经典Biginelli反应机理类似,反应平衡常数为947.73。
4、作为Biginelli反应机理第一步反应的拓展,用MP2方法研究了尿素和甲醛反应的机理,用变分过渡态理论加小曲率隧道效应计算了200~3000K温度范围内尿素和甲醛反应的速率常数。脲与甲醛的反应是比较简单的加成反应,反应的基元过程主要是氮氢键的断裂和氧氢键的生成。在MP2/6-31+G(d)理论水平下,反应的势垒高度为32.83 kcal/mol。计算的速率常数展示出较强的非Arrhenius行为,速-温关系用三参数公式拟合为: k (T ) = (3.32×10~(-43) )T 8.32exp( -9027.8/ T) cm3·molecule-1·s-1。
In 1893, Biginelli reported the the synthesis of 3,4-dihydropyrimidin-2(1H)-ones (DHPMs) by one-pot condensation of benzaldehyde, urea and ethyl acetoacetate under strongly acidic conditions. Since 1990s, Biginelli reactions are ranked as one of the most powerful tools for the facile synthesis of complex heterocyclic scaffolds due to their wide range of therapeutical and pharmacological properties. So the synthesis and molecular properties of DHPMs have attracted considerable attentions.
This dissertation includes experiment and theoretical studies. In the experimental part, Biginelli reaction was extensively investigated in the presence of antimony trichloride (SbCl3) as a Lewis acid. In the theoretical calculation part, the molecular properties of DHPMs and the mechanisms of Biginelli reaction were studied by quantum chemistry methods. Furthermore, mechanism and dynamics for the reaction of urea with formaldehyde were studied using the canonical variational transtition state theory with the small-curvature tunneling correction method. Major valuable results are listed as follows:
1. An efficient synthesis of DHPMs using SbCl3 as the catalyst under solvent-free conditions is described. The optimum conditions are: the molar ratio of aldehyde,β-dicarbonyl compound and urea is 1:1:1.5, the amount of catalyst is 10 mol% of aldehydes and the best reaction temperature is 70℃. The advantages of this condensation reaction include the simple work-up procedure, high product yields, short reaction time and free solvent. Therefore, this is an important alternative to the synthesis of DHPMs.
2. The structures of four DHPMs were fully optimized by B3LYP, HF and MP2 methods at 6-31G(d) or 6-311G level. The charge distribution, frontier molecular orbital, bond formations and natural bond orbital (NBO) were also analysed. The pyridine ring in DHPMs adopts boat conformation. In DHPMs, nitrogen atoms, oxygen atoms and carbon atoms which connected with hydrogen atoms carry negative electronics. The positive charges are mainly carried by the carbon atoms which linked to nitrogen atom or oxygen atom. The energy difference between frontier molecular orbitals is lower. DHPMs may have good biological activities because of hard stability. In DHPMs, the lone pair electrons of the two nitrogen atoms in the pyridine ring both have strong interactions with neighboring bonds.
3. The mechanisms of Biginelli reaction were investigated at B3LYP/6-31G(d), B3LYP/6-31+G(d,p) and B3LYP/6-311+G(3df,2p)//B3LYP/6-31+G(d,p) levels. The equilibrium constants of the reactions were also computed. Mechanism of the classical Biginelli reaction is described as follows: The first step of the reaction is the acid-catalyzed formation of a N-acyliminium ion intermediate from aldehyde and urea. Interception of the iminium ion by ethyl acetoacetate through its enol tautomer, produces an open-chain ureide which subsequently cyclizes to dihydropyrimidine. The calculated equilibrium constant is 70.80 . The mechanism of synthesis of 3,4-dihydropyrimidin-2(1H)-thiones is similar with the classical Biginelli reaction’s. The calculated equilibrium constant is 947.73 .
4. As expansion to the first step of the classical Biginelli reaction, the reaction mechanism of urea with formaldehyde was investigated by MP2 method. Reaction rate of urea and formaldehyde between 200~3000K has been studied using the canonical variational transtition state theory with the small-curvature tunneling correction method. The reaction of urea with formaldehyde is a simple addition reaction. The elementary processes of this reaction are the breaking of nitrogen-hydrogen bond and the formation of oxygen-hydrogen bond. The forward potential barrier at MP2/6-31+G(d) level is 32.83 kcal/mol. The reasult shows that the calculated CVT/SCT rate constants exhibit typical non-Arrhenius behavior. The relativity of rate-temperature can be described as follows: k (T ) = (3.32×10 ?43 )T 8.32exp( ? 9027.8/ T) cm3·molecule-1·s-1.
本论文主要包括实验和理论计算两方面的内容:实验部分,系统探讨了三氯化锑(SbCl3)作为催化剂参与的Biginelli反应;理论计算部分,用量子化学方法研究了DHPMs的分子性质、Biginelli反应机理,并用从头算及变分过渡态理论研究了尿素和甲醛的反应。研究取得了以下几个方面的成果:
1、使用SbCl3作为催化剂,无溶剂条件下合成一系列DHPMs。反应的最佳条件为:芳香醛、β-二羰基化合物和尿素的摩尔比为1:1:1.5,催化剂用量为芳香醛的10%,反应最佳温度为70℃。此改进方法具有反应时间短、收率高、操作简便等优点,为DHPMs的制备提供了一条方便、快捷、有效的合成方法。
2、在6-31G(d)或6-311G基组水平上,用B3LYP、HF和MP2三种方法对四种DHPMs进行了几何全优化,并对其电荷分布、前线分子轨道、成键情况以及自然键轨道(NBO)进行了分析。DHPMs的氮原子和氧原子以及与氢原子相连的碳原子,带负电荷;而非氢原子中正电荷主要分布在与氮原子和氧原子相连的碳原子上;DHPMs中嘧啶环为船式构象;DHPMs的前线轨道能级差较小,表明它们的稳定性较差,可能具有很好的生物活性;在DHPMs中,嘧啶环上两个氮原子的孤对电子都与相邻键有较强的相互作用。
3、用密度泛函理论在B3LYP/6-31G(d) , B3LYP/6-31+G(d,p)和B3LYP/6-311+G(3df,2p)//B3LYP/6-31+G(d,p)水平,研究了Biginelli反应机理,计算了反应的平衡常数。经典Biginelli反应机理为:在酸的作用下醛和脲首先生成中间体酰基亚胺正离子,然后与乙酰乙酸乙酯发生缩合反应得到一个开链的酰脲,后者进一步环化、脱水得到相应的DHPMs,反应平衡常数为70.80。合成二氢嘧啶硫酮反应机理与经典Biginelli反应机理类似,反应平衡常数为947.73。
4、作为Biginelli反应机理第一步反应的拓展,用MP2方法研究了尿素和甲醛反应的机理,用变分过渡态理论加小曲率隧道效应计算了200~3000K温度范围内尿素和甲醛反应的速率常数。脲与甲醛的反应是比较简单的加成反应,反应的基元过程主要是氮氢键的断裂和氧氢键的生成。在MP2/6-31+G(d)理论水平下,反应的势垒高度为32.83 kcal/mol。计算的速率常数展示出较强的非Arrhenius行为,速-温关系用三参数公式拟合为: k (T ) = (3.32×10~(-43) )T 8.32exp( -9027.8/ T) cm3·molecule-1·s-1。
In 1893, Biginelli reported the the synthesis of 3,4-dihydropyrimidin-2(1H)-ones (DHPMs) by one-pot condensation of benzaldehyde, urea and ethyl acetoacetate under strongly acidic conditions. Since 1990s, Biginelli reactions are ranked as one of the most powerful tools for the facile synthesis of complex heterocyclic scaffolds due to their wide range of therapeutical and pharmacological properties. So the synthesis and molecular properties of DHPMs have attracted considerable attentions.
This dissertation includes experiment and theoretical studies. In the experimental part, Biginelli reaction was extensively investigated in the presence of antimony trichloride (SbCl3) as a Lewis acid. In the theoretical calculation part, the molecular properties of DHPMs and the mechanisms of Biginelli reaction were studied by quantum chemistry methods. Furthermore, mechanism and dynamics for the reaction of urea with formaldehyde were studied using the canonical variational transtition state theory with the small-curvature tunneling correction method. Major valuable results are listed as follows:
1. An efficient synthesis of DHPMs using SbCl3 as the catalyst under solvent-free conditions is described. The optimum conditions are: the molar ratio of aldehyde,β-dicarbonyl compound and urea is 1:1:1.5, the amount of catalyst is 10 mol% of aldehydes and the best reaction temperature is 70℃. The advantages of this condensation reaction include the simple work-up procedure, high product yields, short reaction time and free solvent. Therefore, this is an important alternative to the synthesis of DHPMs.
2. The structures of four DHPMs were fully optimized by B3LYP, HF and MP2 methods at 6-31G(d) or 6-311G level. The charge distribution, frontier molecular orbital, bond formations and natural bond orbital (NBO) were also analysed. The pyridine ring in DHPMs adopts boat conformation. In DHPMs, nitrogen atoms, oxygen atoms and carbon atoms which connected with hydrogen atoms carry negative electronics. The positive charges are mainly carried by the carbon atoms which linked to nitrogen atom or oxygen atom. The energy difference between frontier molecular orbitals is lower. DHPMs may have good biological activities because of hard stability. In DHPMs, the lone pair electrons of the two nitrogen atoms in the pyridine ring both have strong interactions with neighboring bonds.
3. The mechanisms of Biginelli reaction were investigated at B3LYP/6-31G(d), B3LYP/6-31+G(d,p) and B3LYP/6-311+G(3df,2p)//B3LYP/6-31+G(d,p) levels. The equilibrium constants of the reactions were also computed. Mechanism of the classical Biginelli reaction is described as follows: The first step of the reaction is the acid-catalyzed formation of a N-acyliminium ion intermediate from aldehyde and urea. Interception of the iminium ion by ethyl acetoacetate through its enol tautomer, produces an open-chain ureide which subsequently cyclizes to dihydropyrimidine. The calculated equilibrium constant is 70.80 . The mechanism of synthesis of 3,4-dihydropyrimidin-2(1H)-thiones is similar with the classical Biginelli reaction’s. The calculated equilibrium constant is 947.73 .
4. As expansion to the first step of the classical Biginelli reaction, the reaction mechanism of urea with formaldehyde was investigated by MP2 method. Reaction rate of urea and formaldehyde between 200~3000K has been studied using the canonical variational transtition state theory with the small-curvature tunneling correction method. The reaction of urea with formaldehyde is a simple addition reaction. The elementary processes of this reaction are the breaking of nitrogen-hydrogen bond and the formation of oxygen-hydrogen bond. The forward potential barrier at MP2/6-31+G(d) level is 32.83 kcal/mol. The reasult shows that the calculated CVT/SCT rate constants exhibit typical non-Arrhenius behavior. The relativity of rate-temperature can be described as follows: k (T ) = (3.32×10 ?43 )T 8.32exp( ? 9027.8/ T) cm3·molecule-1·s-1.
引文
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