【摘要】：在堿性條件下,α,β-不飽和酮與活潑性亞甲基化合物,進行親核1,4-共軛加成,該類反應為Michael加成反應。此類反應是生成C-C單鍵中最簡單而有效的途徑之一。吩噻嗪又稱為硫代二苯胺、硫氮雜蒽,是多功能活性大分子,將其引入查爾酮中,可得吩噻嗪基查爾酮,其反應及生物活性相當可觀,可以在多個領域中予以重用。本課題設計合成不同類型的1-吩噻嗪基-3-芳基-丙烯酮,將其與不同活潑亞甲基類化合物發(fā)生Michael反應,從而增長化合物體系中的分子鏈,共軛體系也隨之增大。(1)10-乙酰基吩噻嗪的合成。以吩噻嗪為初始原料,乙酰氯作酰化劑,苯作溶劑,合成得10-乙�；脏玎骸２⒂肍T-IR、~1H NMR等對所得化合物結構進行表征。(2)1-吩噻嗪基-3-芳基-丙烯酮的合成。以10-乙�；脏玎号c12種芳香醛作原料,于甲醇溶劑中,NaOH催化下,發(fā)生Aldol反應,從而可得目標化合物。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等對其結構進行表征;同時用單因素實驗法,探討摩爾比(10-乙酰基吩噻嗪/芳香醛),催化劑種類,反應溫度,取代基團不同等因素對所得化合物產(chǎn)率的影響,得吩噻嗪基查爾酮的最佳合成條件為:摩爾比(10-乙�；脏玎�/芳醛)為1:1.1,反應溫度70℃,NaOH顆粒作催化劑,反應時間為30min,產(chǎn)率高達85%以上。(3)含吩噻嗪基查爾酮的Michael反應研究。將1-吩噻嗪基-3-芳基-丙烯酮分別與乙酰丙酮、巴比妥酸、環(huán)己酮、乙酰乙酸乙酯、硫代巴比妥酸、CH2(CN)2、CH3NO2、CH3CN,以溶劑法與無溶劑固相研磨法分別進行Michael加成反應,得最終產(chǎn)物;并用FT-IR、~1H NMR、~(13)C NMR等對其結構予以表征。在固相研磨法中,經(jīng)單因素實驗法探索優(yōu)化Michael反應的反應條件,得最佳反應條件為:摩爾比(吩噻嗪基查爾酮/活潑亞甲基類化合物)為1:1.3,室溫,研磨時間為35min,最終產(chǎn)物的產(chǎn)率可達80%以上。
[Abstract]:In alkaline condition, 偽, 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，

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