联苯对甲苯磺酰腙参与的偶联反应构建C-X键研究

发布时间：2018-03-26 17:00

本文选题：联苯　切入点：对甲苯磺酰腙　出处：《石河子大学》2017年硕士论文

【摘要】：近几十年来,过渡金属催化的偶联反应一直是构建C-X(X=C,O,N等)键最有效的方法之一,被广泛应用于功能性药物、光电材料、热记录材料、染料、以及日用化工产品的合成中。基于该方法的重要性,过渡金属催化的偶联反应(如:Suzuki、Ullmann、Glaser等)得到了高速发展与广泛地应用。然而,发展更高效、绿色的催化体系来构建C-X键仍然是有机合成中的热点之一。在本文中,通过钯催化的Suzuki偶联反应,以对溴苯乙酮(或对溴苯甲醛)与芳基硼酸为反应原料合成一系列联苯羰基化合物;并利用合成出的联苯羰基化合物与对甲苯磺酰肼反应制备相应的对甲苯磺酰腙。本论文主要内容包括以下三个部分:首先,在无金属参与的情况下,选用4-乙酰基联苯制备的对甲苯磺酰腙与苯酚或苄醇还原偶联反应构建C-O键,并合成了一系列联苯醚类化合物,在有机合成中具有重要意义。我们选用K2CO3作为碱,甲苯作为溶剂,在110°C条件下反应24 h,获得相应产物产率在38%-83%之间。同时,该反应体系可以放大到克级规模反应,使用联苯对甲苯磺酰腙3a 1.83 g(5.0 mmol),苯酚1.60 g(17mmol),反应能顺利进行合成出相应目标产物1.07 g,获得78%的优良产率。更重要的是,该反应体系具有原料廉价易得,官能团兼容性强,底物适用性广等特点。其次,我们通过联苯对甲苯磺酰腙与叠氮化钠在无金属催化的条件下,以K2CO3作为碱,四丁基溴化铵作为相转移催化剂,甲苯作为溶剂,在130°C条件下,反应29 h,合成了一系列新的4-(1-叠氮乙基)-1,1'-联苯类衍生物,其相应产物产率在34%-74%之间。同时,利用合成出的联苯叠氮化合物与末端炔烃在Salen-Cu(II)配合物催化下发生环加成反应,反应温度控制在70°C,反应时间7 h,水相中合成了一系列1,4-二取代的1,2,3-三氮唑类衍生物,其相应产物产率在27%-94%之间。该催化体系具有催化效率高,底物适用性广,而且水相中就能顺利反应。再次,通过钯催化的交叉偶联反应以羰基联苯化合物,对甲苯磺酰肼,溴代芳烃(或苄基卤)为模型反应,合成了一系列二取代的芳基烯烃类化合物。通过实验我们筛选出最优反应条件:4-乙酰基联苯(0.5 mmol),对甲苯磺酰肼(0.55 mmol),对溴甲苯(1.0 mmol),四(三苯基膦)钯(5 mol%),叔丁醇锂(1.0 mmol),在T1=100°C(t1=2 h)和T2=100°C(t2=12 h)条件下,1,4-二氧六环(3 mL),氮气保护。在最优反应条件下,我们利用一锅、两步的方法进行了底物适用性研究,合成了一系列1,1-二芳基取代的烯烃化合物,其相应产物产率在23%-96%之间。最后,我们采用一锅、两步的方法对联苯甲醛与苄基溴的反应进行了考察,得到了一系列1,2-二芳基取代的烯烃化合物,其相应产物产率在37%-85%之间。该反应体系是在四(三苯基膦)钯,叔丁醇锂共同作用下,以羰基联苯类化合物为原料,与对甲苯磺酰肼,芳基溴化物(或苄基卤)通过一锅、两步加料的方法合成一系列二取代芳基烯烃化合物。
[Abstract]:In recent decades, the transition metal-catalyzed coupling reaction has been one of the most effective methods to construct C-XTX (C) O (N) bonds. It has been widely used in functional drugs, optoelectronic materials, thermal recording materials, dyes, etc. Because of the importance of this method, transition metal-catalyzed coupling reactions (such as: Suzukien Ullmann Glaser, etc.) have been developed at a high speed and widely used. However, the development of transition metal-catalyzed coupling reactions is more efficient. The green catalytic system to construct C-X bond is still one of the hot spots in organic synthesis. In this paper, palladium catalyzed Suzuki coupling reaction, A series of biphenyl carbonyl compounds were synthesized from p-bromoacetophenone (or p-bromobenzaldehyde) and aryl boric acid. The corresponding p-toluenesulfonyl hydrazone was prepared by the reaction of the synthesized biphenyl carbonyl compounds with p-toluene sulfonyl hydrazide. The main contents of this thesis are as follows: first, without metal participation, A series of diphenyl ethers were synthesized from p-toluenesulfonyl Hydrazone by reductive coupling reaction with phenol or benzyl alcohol, and a series of diphenyl ethers were synthesized, which are of great significance in organic synthesis. When toluene was used as solvent, under 110 掳C for 24 h, the yield of the product was between 38% and 83%. The corresponding target product 1.07 g was successfully synthesized by using 3a 1.83 g N 5.0 mmol / L of phenol and 1.60 g / L phenol with 3a 1.83 g of diphenyl sulfonyl Hydrazone, and 78% yield was obtained. More importantly, the reaction system was cheap and easy to obtain, and the functional group compatibility was strong. Secondly, K2CO3 was used as base, tetra#china_person0# ammonium bromide as phase transfer catalyst, toluene as solvent, and toluene as solvent at 130 掳C under the condition of no metal catalyzed by biphenyl p-toluene sulfonylhydrazone and sodium azide, using K2CO3 as base, tetra#china_person0# ammonium bromide as phase transfer catalyst and toluene as solvent. In the 29 h reaction, a series of new derivatives of 4-N-1-azidoethyl-1-azo-1-triphenyl were synthesized. The yields of the corresponding derivatives ranged from 34% to 74%. At the same time, the cycloaddition reaction of the synthesized biphenyl azide with terminal alkynes was catalyzed by the Salen-CuN II complex. Under the conditions of 70 掳C reaction temperature and 7 h reaction time, a series of 1o _ 4-disubstituted 1o _ 2o _ 3-triazole derivatives were synthesized in water phase. The yields of the corresponding products ranged from 27% to 94%. The catalyst system had high catalytic efficiency and wide applicability of substrate, and the reaction temperature was 70 掳C and the reaction time was 7 h, and the reaction temperature was 70 掳C, and the reaction time was 7 h. And the reaction was smooth in the water phase. Thirdly, the palladium catalyzed cross-coupling reaction was modeled on carbonyl biphenyls, p-toluenesulfonyl hydrazide, bromoaromatic hydrocarbons (or benzyl halides). A series of disubstituted aryl olefin compounds were synthesized. The optimum reaction conditions were selected as follows: 1: 4-acetylbiphenyl (0.5 mmol), p-toluene sulfonyl hydrazide (0.55 mmol / L), p-bromotoluene (1.0 mmol / L), tetra- (triphenylphosphine) palladium (5 mol / L), lithium tert-butanol. 1. 0 mmol 路mol ~ (-1) and T _ (1) O _ (100 掳C(t1=2 ~ (h)) and T _ (2) O _ (100 掳C(t2=12 ~ (-1)), N ~ (2 +) protection. We used a one-pot, two-step method to study the suitability of the substrate, and we synthesized a series of 1-diarylsubstituted olefin compounds with yields ranging from 23- 96%. Finally, we used one pot. The reaction of benzaldehyde with benzyl bromide was investigated by a two-step method. A series of alkenes with 1 (2-diaryl) substituted alkenes were obtained. The yields of the corresponding products ranged from 37% to 85%. The reaction was carried out in the presence of tetra- (triphenylphosphine) palladium. A series of disubstituted aryl olefin compounds were synthesized from carbonyl biphenyls with p-toluenesulfonyl hydrazide aryl bromide (or benzyl halogen) by one-pot two-step feeding under the interaction of lithium tert butanol and carbonyl biphenyls.
【学位授予单位】：石河子大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O621.251

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