吩噻嗪基查尔酮的合成及其Michael反应研究
发布时间：2018-09-17 12:36
【摘要】：在碱性条件下,α,β-不饱和酮与活泼性亚甲基化合物,进行亲核1,4-共轭加成,该类反应为Michael加成反应。此类反应是生成C-C单键中最简单而有效的途径之一。吩噻嗪又称为硫代二苯胺、硫氮杂蒽,是多功能活性大分子,将其引入查尔酮中,可得吩噻嗪基查尔酮,其反应及生物活性相当可观,可以在多个领域中予以重用。本课题设计合成不同类型的1-吩噻嗪基-3-芳基-丙烯酮,将其与不同活泼亚甲基类化合物发生Michael反应,从而增长化合物体系中的分子链,共轭体系也随之增大。(1)10-乙酰基吩噻嗪的合成。以吩噻嗪为初始原料,乙酰氯作酰化剂,苯作溶剂,合成得10-乙酰基吩噻嗪。并用FT-IR、~1H NMR等对所得化合物结构进行表征。(2)1-吩噻嗪基-3-芳基-丙烯酮的合成。以10-乙酰基吩噻嗪与12种芳香醛作原料,于甲醇溶剂中,NaOH催化下,发生Aldol反应,从而可得目标化合物。其包括:1-吩噻嗪基-3-苯基-丙烯酮,1-吩噻嗪基-3-(4-氟苯基)-丙烯酮,1-吩噻嗪基-3-(4-氯苯基)-丙烯酮,1-吩噻嗪基-3-(4-溴苯基)-丙烯酮,1-吩噻嗪基-3-(4-二甲氨基苯基)-丙烯酮,1-吩噻嗪基-3-(4-甲基苯基)-丙烯酮,1-吩噻嗪基-3-(4-甲氧基苯基)-丙烯酮,1-吩噻嗪基-3-(4-硝基苯基)-丙烯酮,1-吩噻嗪基-3-(3-硝基苯基)-丙烯酮,1-吩噻嗪基-3-(2-吡啶基)-丙烯酮,1-吩噻嗪基-3-(2-噻吩基)-丙烯酮,1-吩噻嗪基-3-(2-呋喃基)-丙烯酮。并用FT-IR、~1H NMR等对其结构进行表征;同时用单因素实验法,探讨摩尔比(10-乙酰基吩噻嗪/芳香醛),催化剂种类,反应温度,取代基团不同等因素对所得化合物产率的影响,得吩噻嗪基查尔酮的最佳合成条件为:摩尔比(10-乙酰基吩噻嗪/芳醛)为1:1.1,反应温度70℃,NaOH颗粒作催化剂,反应时间为30min,产率高达85%以上。(3)含吩噻嗪基查尔酮的Michael反应研究。将1-吩噻嗪基-3-芳基-丙烯酮分别与乙酰丙酮、巴比妥酸、环己酮、乙酰乙酸乙酯、硫代巴比妥酸、CH2(CN)2、CH3NO2、CH3CN,以溶剂法与无溶剂固相研磨法分别进行Michael加成反应,得最终产物;并用FT-IR、~1H NMR、~(13)C NMR等对其结构予以表征。在固相研磨法中,经单因素实验法探索优化Michael反应的反应条件,得最佳反应条件为:摩尔比(吩噻嗪基查尔酮/活泼亚甲基类化合物)为1:1.3,室温,研磨时间为35min,最终产物的产率可达80%以上。
[Abstract]:In alkaline condition, 伪, 尾 -unsaturated ketones and active methylene compounds were added with nucleophilic 1 + 4-conjugated adduct. The reaction was Michael addition reaction. This kind of reaction is one of the simplest and most effective ways to form C-C single bond. Phenothiazine, also known as thiodiphenylamine, is a multifunctional active macromolecule. Phenothiazide can be obtained by introducing it into chalcone. Its reaction and biological activity are considerable and can be reused in many fields. In this paper, different types of 1-phenothiazinyl-3-aryl-propenone were designed and synthesized, and Michael reaction took place with different active methylene compounds, thus increasing the molecular chain in the compound system. The conjugated system also increased. (1) Synthesis of 10-acetyl phenothiazine. 10-acetyl phenothiazine was synthesized from phenothiazine, acetyl chloride as acylation agent and benzene as solvent. The structures of the compounds were characterized by FT-IR,~1H NMR et al. (2) Synthesis of 1-phenothiazinyl -3-aryl-propenone. Using 10-acetylphenothiazine and 12 aromatic aldehydes as raw materials, the target compounds can be obtained by Aldol reaction in methanol solvent catalyzed by NaOH. It includes: 1-phenothiazinyl -3-phenyl-propenone 1-phenothiazinyl -3- (4-fluorophenyl) -3- (4-phenothiazinyl) -3- (4-bromophenyl) -propenone 1-phenothiazinyl -3- (4-dimethylaminophenyl) -propylene ketone 1-phenothiazinyl -3- (4-methylphenyl) -propenone 1-phenothiazinyl-3- (4-methoxyphenyl) -1-phenothiazinyl -3- (4-nitrophenyl) -propenone 1-phenothiazinyl -3- (3-nitrophenyl) -propenone 1-phenothiazine-3- (2-pyridyl) -propylene ketone 1-phenothiazinyl -3- (2-thiophenyl) -propenone and 1-phenothiazinyl -3- (2-furyl) -propenone. The structure was characterized by FT-IR,~1H NMR, and the effects of molar ratio (10-acetylphenothiazine / aromatic aldehyde), type of catalyst, reaction temperature and different substituent groups on the yield of the compounds were investigated by single factor experiment. The optimum conditions for the synthesis of phenothiazinyl chalcone were as follows: molar ratio of 10-acetylphenothiazine / aromatic aldehyde was 1: 1.1, reaction temperature was 70 鈩，
本文编号：2245944
[Abstract]:In alkaline condition, 伪, 尾 -unsaturated ketones and active methylene compounds were added with nucleophilic 1 + 4-conjugated adduct. The reaction was Michael addition reaction. This kind of reaction is one of the simplest and most effective ways to form C-C single bond. Phenothiazine, also known as thiodiphenylamine, is a multifunctional active macromolecule. Phenothiazide can be obtained by introducing it into chalcone. Its reaction and biological activity are considerable and can be reused in many fields. In this paper, different types of 1-phenothiazinyl-3-aryl-propenone were designed and synthesized, and Michael reaction took place with different active methylene compounds, thus increasing the molecular chain in the compound system. The conjugated system also increased. (1) Synthesis of 10-acetyl phenothiazine. 10-acetyl phenothiazine was synthesized from phenothiazine, acetyl chloride as acylation agent and benzene as solvent. The structures of the compounds were characterized by FT-IR,~1H NMR et al. (2) Synthesis of 1-phenothiazinyl -3-aryl-propenone. Using 10-acetylphenothiazine and 12 aromatic aldehydes as raw materials, the target compounds can be obtained by Aldol reaction in methanol solvent catalyzed by NaOH. It includes: 1-phenothiazinyl -3-phenyl-propenone 1-phenothiazinyl -3- (4-fluorophenyl) -3- (4-phenothiazinyl) -3- (4-bromophenyl) -propenone 1-phenothiazinyl -3- (4-dimethylaminophenyl) -propylene ketone 1-phenothiazinyl -3- (4-methylphenyl) -propenone 1-phenothiazinyl-3- (4-methoxyphenyl) -1-phenothiazinyl -3- (4-nitrophenyl) -propenone 1-phenothiazinyl -3- (3-nitrophenyl) -propenone 1-phenothiazine-3- (2-pyridyl) -propylene ketone 1-phenothiazinyl -3- (2-thiophenyl) -propenone and 1-phenothiazinyl -3- (2-furyl) -propenone. The structure was characterized by FT-IR,~1H NMR, and the effects of molar ratio (10-acetylphenothiazine / aromatic aldehyde), type of catalyst, reaction temperature and different substituent groups on the yield of the compounds were investigated by single factor experiment. The optimum conditions for the synthesis of phenothiazinyl chalcone were as follows: molar ratio of 10-acetylphenothiazine / aromatic aldehyde was 1: 1.1, reaction temperature was 70 鈩，
本文编号：2245944
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