【作者】 冯晓琴；

【导师】 程原；

【作者基本信息】 中北大学 ， 应用化学， 2010， 硕士

【摘要】 脒类化合物广泛用作抗生素、消炎药、驱虫剂和杀菌剂等，随着其用途的扩大，对其合成方法的研究也引起了越来越多科学工作者的重视。目前Pinner法合成丙烷脒的工艺路线中，由于在反应结束后需要对外排出产物10倍以上的氯化氢和氨气，对环境造成了严重的污染，致使无法进行生产。本研究对Pinner法合成丙烷脒的反应机理进行了深入探讨，提出了用对位含有吸电子基的苯甲腈为起始原料，先进行脒基化反应，然后进行醚化反应的新的合成路线。用对硝基苯甲腈和对氟苯甲腈在不使用氯化氢和氨气的条件下，合成了对硝基苯甲脒和对氟苯甲脒，并用红外谱图对其结构进行了表征。通过正交实验和单因素实验研究了原料物质的量之比、反应温度、反应时间对产率的影响，得到脒基化反应的最佳反应条件。实验结果表明：对硝基苯甲腈和对氟苯甲腈可以在较温和的反应条件下进行脒基化反应，并得到较高的产率。以对硝基苯甲腈为原料，甲醇钠为催化剂，乙酸铵为氨化剂，采用改进的Pinner法合成对硝基苯甲脒。通过正交实验和单因素实验研究得到最佳的反应条件为：n(对硝基苯腈): n(甲醇钠): n(乙酸铵) =1:1:1.1，加成反应时间为3h，反应温度为45℃；胺化反应时间为18h，反应温度为40℃，产率可达90%左右。此合成工艺比较稳定，反应条件温和，同时对环境友好。以对氟苯甲腈为原料，N-乙酰半胱氨酸为催化剂，氨基甲酸铵为氨化剂，采用催化合成法合成对氟苯甲脒。通过单因素实验研究得到最佳的反应条件为：n(对氟苯腈): n(N-乙酰半胱氨酸): n(氨基甲酸铵) = 1:1:0.55，加成反应时间为20h，反应温度为50℃，；胺化反应时间为24h，反应温度为50℃，产率可以达到92%，反应条件温和，对环境友好。更多还原

【Abstract】 Amidine compounds are widely used as antibiotics, anti-inflammatory drugs, insectrepellents and fungicides et al. With the expansion of its use, its method of synthesis alsoattracts more and more attention of scientific workers.At present, the synthesis route of Propamidine employs Pinner method and the reactionemits more than 10 times of hydrogen chloride gas and ammonia than products toenvironment. The reaction causes serious pollution and can not be used for industrialproduction. The mechanism of the Pinner reaction which was used to synthesize Propamidinewas investigated in this thesis. New synthesis route that using benzonitrile as raw material toconduct amidine reaction firstly, then conduct etherification reaction was proposed.P-nitrophenyl formamidine and p-fluorophenyl formamidine were synthesized byp-nitrobenzonitrile and p-fluorobenzonitrile without the use of hydrogen chloride andammonia, and their structures were characterized by IR. The influences of reactiontemperature, reaction time, the mole ratio of the raw material were investigated. The bestprescription was found after a series of orthogonal tests and single factor tests. The resultsshow that: high amidine production rate was obtained under the mild experimental conditionwhen p-nitrobenzonitrile and p-fluorobenzonitrile were used as the raw materials.P-nitrophenyl formamidine was synthesized with p-nitrobenzonitrile as raw material,sodium methoxide as catalyst, ammonium acetate as amination agent, and improved Pinnermethod as its synthesis method. The influences of these factors were analyzed after a series oforthogonal and single factor experiments, and its most apt reaction conditions are as follows:the ratio of p-nitrobenzonitrile, sodium methylate and ammonium acetate is 1:1:1.1, thereaction time and reaction temperature of the addition reaction are 3h and 45℃; the reactiontime and reaction temperature of the amido reaction are 18h and 40℃respectively. The yield of p-nitrophenyl formamidine can reach 90%. The synthesis process is mild andenvironmentally feiendly.P-fluorophenyl formamidine was synthesized with p-fluorobenzonitrile as raw material,n-acetyl-cysteine as catalyst, ammonium carbamate as amination agent, catalytic synthesismethod as its synthesis method. The influences of these factors were analyzed after a series ofsingle factor experiments, and its most apt reaction conditions are as follows: the ratio ofp-fluorobenzonitrile and n-acetyl-cysteine and ammonium carbamate is 1:1:0.55; the reactiontime and reaction temperature of the addition reaction are 20h and 50℃; the reaction time andreaction temperature of the amido reaction are 24h and 50℃respectively. The yield ofp-fluorophenyl formamidine can reach 92% and the synthesis process is mild andenvironmentally friendly.更多还原