本文選題：聯(lián)苯　切入點：對甲苯磺酰腙　出處：《石河子大學》2017年碩士論文

【摘要】：近幾十年來,過渡金屬催化的偶聯(lián)反應一直是構建C-X(X=C,O,N等)鍵最有效的方法之一,被廣泛應用于功能性藥物、光電材料、熱記錄材料、染料、以及日用化工產(chǎn)品的合成中�；谠摲椒ǖ闹匾�,過渡金屬催化的偶聯(lián)反應(如:Suzuki、Ullmann、Glaser等)得到了高速發(fā)展與廣泛地應用。然而,發(fā)展更高效、綠色的催化體系來構建C-X鍵仍然是有機合成中的熱點之一。在本文中,通過鈀催化的Suzuki偶聯(lián)反應,以對溴苯乙酮(或?qū)︿灞郊兹?與芳基硼酸為反應原料合成一系列聯(lián)苯羰基化合物;并利用合成出的聯(lián)苯羰基化合物與對甲苯磺酰肼反應制備相應的對甲苯磺酰腙。本論文主要內(nèi)容包括以下三個部分:首先,在無金屬參與的情況下,選用4-乙�；�(lián)苯制備的對甲苯磺酰腙與苯酚或芐醇還原偶聯(lián)反應構建C-O鍵,并合成了一系列聯(lián)苯醚類化合物,在有機合成中具有重要意義。我們選用K2CO3作為堿,甲苯作為溶劑,在110°C條件下反應24 h,獲得相應產(chǎn)物產(chǎn)率在38%-83%之間。同時,該反應體系可以放大到克級規(guī)模反應,使用聯(lián)苯對甲苯磺酰腙3a 1.83 g(5.0 mmol),苯酚1.60 g(17mmol),反應能順利進行合成出相應目標產(chǎn)物1.07 g,獲得78%的優(yōu)良產(chǎn)率。更重要的是,該反應體系具有原料廉價易得,官能團兼容性強,底物適用性廣等特點。其次,我們通過聯(lián)苯對甲苯磺酰腙與疊氮化鈉在無金屬催化的條件下,以K2CO3作為堿,四丁基溴化銨作為相轉(zhuǎn)移催化劑,甲苯作為溶劑,在130°C條件下,反應29 h,合成了一系列新的4-(1-疊氮乙基)-1,1'-聯(lián)苯類衍生物,其相應產(chǎn)物產(chǎn)率在34%-74%之間。同時,利用合成出的聯(lián)苯疊氮化合物與末端炔烴在Salen-Cu(II)配合物催化下發(fā)生環(huán)加成反應,反應溫度控制在70°C,反應時間7 h,水相中合成了一系列1,4-二取代的1,2,3-三氮唑類衍生物,其相應產(chǎn)物產(chǎn)率在27%-94%之間。該催化體系具有催化效率高,底物適用性廣,而且水相中就能順利反應。再次,通過鈀催化的交叉偶聯(lián)反應以羰基聯(lián)苯化合物,對甲苯磺酰肼,溴代芳烴(或芐基鹵)為模型反應,合成了一系列二取代的芳基烯烴類化合物。通過實驗我們篩選出最優(yōu)反應條件:4-乙�；�(lián)苯(0.5 mmol),對甲苯磺酰肼(0.55 mmol),對溴甲苯(1.0 mmol),四(三苯基膦)鈀(5 mol%),叔丁醇鋰(1.0 mmol),在T1=100°C(t1=2 h)和T2=100°C(t2=12 h)條件下,1,4-二氧六環(huán)(3 mL),氮氣保護。在最優(yōu)反應條件下,我們利用一鍋、兩步的方法進行了底物適用性研究,合成了一系列1,1-二芳基取代的烯烴化合物,其相應產(chǎn)物產(chǎn)率在23%-96%之間。最后,我們采用一鍋、兩步的方法對聯(lián)苯甲醛與芐基溴的反應進行了考察,得到了一系列1,2-二芳基取代的烯烴化合物,其相應產(chǎn)物產(chǎn)率在37%-85%之間。該反應體系是在四(三苯基膦)鈀,叔丁醇鋰共同作用下,以羰基聯(lián)苯類化合物為原料,與對甲苯磺酰肼,芳基溴化物(或芐基鹵)通過一鍋、兩步加料的方法合成一系列二取代芳基烯烴化合物。
[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 擄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 擄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 擄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 擄C and the reaction time was 7 h, and the reaction temperature was 70 擄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 擄C(t1=2 ~ (h)) and T _ (2) O _ (100 擄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.
【學位授予單位】：石河子大學
【學位級別】：碩士
【學位授予年份】：2017
【分類號】：O621.251

【參考文獻】

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1 劉振興;張艷;王劍波;;過渡金屬催化的對甲苯磺酰腙的偶聯(lián)反應[J];有機化學;2013年04期

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本文編號：1668747