2-乙酰基吡咯和1-甲基-2-乙酰基吡咯的合成

以吡咯为原料，经Vilsmeier—Haeeh反应合成2-乙酰基吡咯，再用碘甲烷进行甲基化得到1-甲基-2-乙酰基吡咯。所得产物的化学结构经红外光谱，核磁共振氢谱得到了证实。此合成方法操作简便，收率较高。     

3-辛酰基吡咯的合成与表征

吡咯和对甲苯磺酰氯在金属钾的催化作用下合成N-甲苯磺酰基吡咯,它与辛酰氯在无水AlCl3催化下进行傅一克酰基化反应合成了,N-甲苯磺酰基-3-辛酰基吡咯(2)。在NaOH水溶液中,回流条件下,2进行碱式水解可得到目标产物。通过^1HNMR、IR及元素分析对产物的结构进行了表征。     

二乙酰基吡咯的合成

吡咯转化为吡咯钾与对甲基苯磺酰氯反应,得1 对甲基苯磺酰基吡咯(Ⅰ),产率61 0%,熔点105～106℃;n(Ⅰ)∶n(乙酸酐)=1 0∶1 15,在室温下反应2h,得1 对甲基苯磺酰基 2 乙酰基吡咯(Ⅱ),产率80 5%,熔点110～111℃;Ⅱ在碱性溶液中水解,得2 乙酰基吡咯(Ⅲ),产率为94 4%,熔点89～90℃;Ⅲ与冰乙酸在室温下反应14d,得2,5 二乙酰基吡咯(产率16 2%,熔点158～159℃)和2,4 二乙酰基吡咯(产率45 1%,熔点137～138℃)。通过核磁共振、红外光谱和元素分析验证了产品的结构。     

溴代2-三氯乙酰基吡咯的合成和表征

以四氯化碳为溶剂,在室温下2-三氯乙酰基吡咯与溴进行溴代反应,通过控制反应物的物质的量比,方便地合成了4-溴-2-三氯乙酰基吡咯和4,5-二溴-2-三氯乙酰基吡咯等4种溴代产物,产率为90．5％～92．6％。以^1HNMR、IR、MS和元素分析对目标产物的结构进行了表征。     

吡咯-3-羧酸的合成

以吡咯为原料,经苯磺酰氯保护、傅-克酰基化、溴仿反应和去保护等反应制备了吡咯-3-羧酸,总产率48.8%。并对溴仿反应的工艺条件进行了优化,最佳溴仿反应条件是:Br2∶底物=4∶1(摩尔比),反应温度0℃,反应时间2 h,收率可达82%。     

噻酮布洛芬的合成研究

设计了噻酮布洛芬的新合成路线,该路线原料易得,除酰化反应一步产率尚需提高外,其它各步反应都已证明可行。     

聚3-乙酰基吡咯的合成、表征及其三阶非线性光学效应研究

以吡咯为原料,通过4步反应合成了一种大π共轭高分子———聚3 乙酰基吡咯(PAPY)。利用1HNMR、FTIR和UV-Vis-NIR对反应中间产物及聚合物PAPY进行了结构表征。热重分析表明PAPY可耐330℃的高温。通过碘掺杂和w(H2SO4)=98%的浓硫酸掺杂处理,PAPY的电导率提高了3个数量级,分别为0 86和0 28S/cm。用721型分光光度计对PAPY在可见光区的透过率进行了测量,计算结果表明,PAPY的光学禁带宽度Eg=1 435eV,属窄能隙聚合物。采用标准后向简并四波混频(DFWM)系统对PAPY的三阶非线性光学效应进行了测量。结果表明,在532nm处PAPY的三阶非线性极化率为8 6×10-10esu。     

3,4-二-O-乙酰基-D-鼠李糖的合成

标题化合物作为一种重要的有机合成中间体,在有机合成活性较高的天然产物中具有重要意义。以三-O-乙酰基-D-己烯糖作为起始原料,经脱乙酰基反应、磺酰化反应、乙酰化反应、亲核取代反应和还原反应合成目标产物。其中间体及目标产物的结构均经IR、~1HNMR和MS进行表征。对提高目标产物收率进行深入探索,结果表明,适当的反应时间、温度及投料的物质的量比分别能够有效提高乙酰化反应、亲核取代反应和还原反应的产品收率,总收率为63%。     

乙酰基二茂铁的合成

以三氯化铝为催化剂,乙酰氯为酰化剂,在二氯乙烷中对二茂铁酰化得到了产率较高的乙酰基二茂铁。研究了反应温度、加料方式和反应物摩尔比对反应的影响。     

5-甲基-3-乙基-4-乙酰基-2-甲氧羰基吡咯的合成

以乙酰丙酮和丙酰乙酸甲酯为主要原料,经过亚硝化、还原和Knorr成环等反应步骤,合成了多取代吡咯化合物5-甲基-3-乙基-4-乙酰基-2-甲氧羰基吡咯。研究了乙酰丙酮用量,亚硝化反应温度以及亚硝酸钠用量等反应条件对目标化合物产率的影响,确定了最佳的合成反应条件为:乙酰丙酮和丙酰乙酸甲酯摩尔比为1.8∶1.0,亚硝化反应温度为5℃,亚硝酸钠和丙酰乙酸甲酯摩尔比为1.3∶1.0。在给定的最佳合成反应条件下目标化合物的产率可达55%。通过熔点测定、IR和1H NMR等光谱分析手段对化合物进行了表征。     

加压下FeCl_3催化Friedel-Crafts酰化反应合成二苯甲酮

研究了在加压和催化量 Fe Cl3存在的条件下 ,苯甲酰氯和苯发生 Friedel- Crafts酰化反应合成二苯甲酮的工艺。 3 1 5 .2 g苯、1 43 .4g苯甲酰氯和 14.4g Fe Cl3混合于 2 L的高压釜中 ,在压力为 1 .6× 1 0 6～ 1 .8× 1 0 6Pa、温度为 1 80～ 2 0 0°C的条件下反应 8h,经纯化处理得到二甲苯酮 1 49.3 g,收率为 82 .1 %,纯度为 99.8%( GC分析 )     

二茂铁酰化反应研究

以二茂铁为起始原料,分别与乙酸酐、酰氯、氯乙酰氯,在质子酸或Lew is酸作用下发生Friedel-Crafts酰基化反应生成乙酰基二茂铁,二乙酰基二茂铁,氯乙酰基二茂铁(2 a~2 c),在制备的过程中我们对(2 a~2 c)合成工艺进行优化,以68.9%~98.6%的收率得到三种常见的酰化产物,与文献相比收率都有所提高。     

Chemoselective Cascade Synthesis of N‐Fused Heterocycles via Silver(I) Triflate‐Catalyzed Friedel–Crafts/N‐C Bond Formation Sequence

An efficient cascade methodology toward chemoselective synthesis of N‐fused heterocycles including 9H‐pyrrolo[1,2‐a]indole, 3H‐pyrrolo[1,2‐a]indole and 1H‐pyrrolo[1,2‐a]indole derivatives has been developed. This transformation proceeds via a silver(I) triflate‐catalyzed consecutive Friedel–Crafts reaction/N C bond formation sequence between readily available propargyl alcohols and 3‐substituted 1H‐indoles. Not only is excellent chemoselectivity observed according to the substitution patterns of propargyl alcohols, but also the Lewis acid‐catalyzed N C bond formation process can be carried out under base‐ and ligand‐free conditions.     

4,4'-二氟-二苯甲酮(高熔点)合成的实验研究

辽宁省阜新市是含氟芳香族化合物的重要生产基地,本文介绍了4,4'-二氟-二苯甲酮的合成方法,通过实验, 找到了最佳的合成路线及实验数据,完成了小试和中试的生产过程。现在,该路线已用于工业化大生产。     

Performance of combined use of chlorosilanes and AlCl3 in the carboxylation of toluene with CO2

Carboxylation of toluene with CO₂ for the production of p‐toluic acid was shown to be promoted by the addition of Me₂PhSiCl, Ph₂SiCl₂, Ph₃SiH, or Ph₃SiCl into the AlCl₃ activated system, and the reaction activity was in the increasing order of Ph₂SiCl₂ < Me₂PhSiCl < Ph₃SiH < Ph₃SiCl. The spectrum of IR indicated that CO₂ could be effectively activated by AlCl₃ or Ph₃SiCl independently. DFT calculation was carried out to estimate the electrophilic potentials of the chlorine bridged AlCl₃···chlorosilane complex in the form of the APT atomic charges of Si and Al. The much higher activity of Ph₃Si‐Cl···AlCl₃ over AlCl₃‐AlCl₃ was considered due to its higher valences of Si and Al which are +2.107 and +1.833 compared with the +1.814 of Al in the latter. The mechanism of CO₂ activation under the action of double Lewis acid sites of Si and Al and the subsequent carboxylation of toluene was consequently proposed. © 2016 American Institute of Chemical Engineers AIChE J, 63: 185–191, 2017     

芳烃的氰甲基化

以三氯化铝为催化剂使对甲苯磺酰氧基乙腈乙芳香族化合物发生Ｆｒｉｅｄｅｌ－Ｃｒａｆｔｓ反应成芳乙腈，产率３２％－６９％。     

Hypercrosslinked functionalized lignosulfonates prepared via Friedel–Crafts alkylation reaction for enhancing Pb(Ⅱ) removal from aqueous

ABSTRACT

Hypercrosslinked functionalized lignosulfonates (CLS) were prepared by Friedel–Crafts alkylation reaction. The structure of CLS without introducing any functional groups and the according adsorption behaviors of Pb(II) were characterized and studied, respectively. Due to increase of specific surface area and abundance exposure of binding sites, the maximum adsorption capacity of CLS was found to be as high as 74.45 mg/g, which was about seven times that of raw lignin. The results provide a new feasible synthesis method for preparing lignin-based materials with porous structures and promising application for the removal of heavy metal ions from wastewater.     

The Synthesis of Covalent Triazine-Based Frameworks via Friedel–Crafts Reactions of Cyanuric Chloride with Thienyl and Carbazolyl Derivatives for Fluorescence Sensing to Picric Acid,Iodine and Capturing Iodine

A multifunctional thiophene-based covalent triazine framework (TTPATTh) with triphenylamine as core is synthesized by Friedel–Crafts reaction of cyanuric chloride with thienyl derivative for the first time. The yield of TTPATTh (99.59%) is far higher than that of the carbazole-based CTF (TTPATCz, 47.03%). TTPATTh and TTPATCz possess high BET surface areas with 1235 and 2501 m² g^–1 as well as high pore volumes with 1.60 and 2.23 cm³ g^–1, respectively. TTPATTh and TTPATCz have high thermal stability with high thermal decomposition temperatures of 514 and 598 °C in nitrogen atmosphere. With the introduction of triazine rings, the fluorescence sensing sensitivities of TTPATTh and TTPATCz to picric acid and iodine are improved significantly. Especially for TTPATTh, the K_sv values reach 5.95 × 10⁵ and 1.61 × 10⁴ L mol^–1, and LODs reach 1.02 × 10^–12 and 1.86 × 10^–12 mol L^–1. To the best of the knowledge, this is the most sensitive value among thiophene-based porous organic polymers to PA and I₂. Furthermore, TTPATTh and TTPATCz can also adsorb iodine in vapor phase, cyclohexane solution and aqueous solution, and release iodine by heating or in ethanol solution. The efficiency of controlling the release of iodine is higher than that in ethanol.     

4-羟基-4'-氯二苯甲酮的合成研究

4-羟基-4'-氯二苯甲酮是一种合成降血脂药物非诺贝特等的重要中间体,具有广泛的用途。参考了国内有关4-羟基-4'-氯二苯甲酮合成的文献,综述了我国4-羟基-4'-氯二苯甲酮的合成研究,比较了各种方法的优缺点,提出了今后的研究发展方向,展望了离子液体在该领域中的应用前景。     

对甲苯磺酸催化漆酚铝螯合物固化行为及其膜性能的研究

本文利用漆酚与AlCl3合成漆酚铝螯合物,再以对甲苯磺酸为催化剂制备漆酚铝螯合固化膜,用FT-IR,TG等手段对固化膜的结构与性能进行表征。结果表明,漆酚的酚羟基先与Al3+发生作用,形成漆酚铝螯合物,然后在对甲苯磺酸的催化作用下,漆酚铝螯合物的不饱和侧链与漆酚上的苯环发生Friedel-Crafts烷基化反应及未螯合的酚羟基发生缩合反应,形成漆酚铝固化膜。该固化膜具有优良的物理机械性能和耐热性能。