芳香胺和酚溴化的新工艺

研究了在室温下,N-溴丁二酰亚胺对芳香胺和酚的溴化工艺,在CHCl3、EtOH或EtOH/CHCl3溶剂中,用等摩尔的N-溴丁二酰亚胺可将某些芳香胺和酚(考察了5种反应底物)选择性地一溴化,产率92%~98%,N-溴丁二酰亚胺和反应底物摩尔比为2∶1;某些芳香胺和酚被专一地二溴化(考察了5种反应底物),产率90%~97%。 反应无须催化剂,投料后室温搅拌,反应条件温和,产品只需过滤洗涤即可纯化,操作简便。     

2,4,4,6-Tetrabromo-2,5-cyclohexadienone (TABCO), N-Bromosuccinimide (NBS) and Bromine as Efficient Catalysts for Dithioacetalization and Oxathioacetalization of Carbonyl Compounds and Transdithioacetalization Reactions

The use of 2,4,4,6-tetrabromo-2,5-cyclohexadienone (TABCO), N-bromosuccinimide (NBS), and bromine as efficient catalysts for conversion of carbonyl compounds to their cyclic and acyclic dithioacetals and 1,3-oxathiolanes under mild reaction conditions are described. These catalysts are also used for efficient transdithioacetalization of acetals, diacetals, ketals, acylals, enamines, hydrazones, and oximes with high yields in the presence of thiols.     

A new approach to the synthesis of diacetals（diketals） pentaerythritol catalyzed by SO3H-functionalized ionic liquids

<正>In this article,an efficient,simple and environmentally friendly approach to the synthesis of diacetals(diketals) pentaerythritol using SO_3H-functionalized ionic liquids(ILs) as catalysts was reported.The ILs show high catalytic activity and reusability with good to excellent yields of the desired products.Hammett method has been used to determine the acidity order of these ionic liquids and the results are consistent with the catalytic activities observed in acetalization reaction.Maximum product yield of 93%was observed on using[PSPy][OTf]as catalyst and it can be reused at least 8 times without obvious activity loss.     

新手性双-(三氟甲磺酰)亚胺基硫代缩酮基硅烷的合成及其不对称催化Diels-Alder反应

合成了数个新手性双-(三氟甲磺酰)亚胺基二硫代缩酮基硅路易斯酸2～4, 并研究了它们对环戊二烯和丙烯酸衍生物11a～11c的Diels-Alder反应的催化活性. 结果表明催化剂活性高, 环加成反应的产率高达89%～96%, 并且获得较高的非对映选择性和中等对映选择性, 当催化剂为2b时, 反应的对映选择性达到最高, 为48% ee.     

环钯化二茂铁亚胺-三苯基膦配合物的合成、表征及催化Suzuki反应研究

为筛选高效催化Suzuki反应的催化剂, 合成了3种新的环钯化二茂铁亚胺-三苯基膦配合物2~4, 经元素分析(或HRMS)、 红外光谱和核磁共振谱对其结构进行了表征, 并通过X射线单晶衍射测定了化合物3的晶体结构. 这些化合物容易合成, 在空气和溶液中稳定, 可用作芳基溴及杂芳基溴与苯基硼酸偶联的Suzuki反应催化剂. 使用摩尔分数为0.01%的催化剂3, 以2倍量的K3PO4为碱, 于110 ℃下, 在甲苯中反应5~15 h, 使具有不同电子和位阻效应的取代芳基溴及杂芳基溴能以较高的产率与苯基硼酸反应生成偶联产物; 与溴苯相比, 带吸电子基的溴苯反应活性较高, 催化剂的摩尔分数降低至0.001%时, 仍能得到较高产率, 而带强给电子基的溴苯如4-溴苯甲醚及带邻位取代基的溴苯在其它条件相同时, 需要延长反应时间才能得到较高的产率.     

Carbohydrate based chiral iodoarene catalysts for enantioselective dearomative spirocyclization

Organocatalysis using chiral iodoarenes enables many different enantioselective chemical reactions with cheap, easily accessible and robust catalysts. Carbohydrates have often been used as starting materials for the synthesis of chiral ligands for transition metal catalysts. Here, we now present the synthesis of the first carbohydrate based iodoarene catalysts which can be synthesized in one step starting from known compounds. These catalysts were used for oxidative spriolactonization of 3-(1-hydroxynaphthalen-2-yl)propanoic acid to afford the corresponding spirolactone in yields up to 77% and enantiomeric ratios er up to 80:20.     

基于配合共保护策略合成γ-L-谷氨酰二肽的新方法

提出了一种采用谷氨酸席夫碱Ni(II)配合物共保护L-谷氨酸的α-氨基和α-羧基合成γ-L-谷氨酰二肽的新方法. 首先由手性助剂——2-[N-(N-苄基-脯氨酰)氨基]二苯甲酮(1)、六水合氯化镍和L-谷氨酸反应, 得到谷氨酸席夫碱Ni(II)配合物2, 产率为98.2%; 进而采用二异丙基碳二亚胺(DIC)/1-羟基-苯并三唑(HOBt)复合缩合剂法分别与L-氨基酸3a～3h反应, 得到相应的γ-L-谷氨酰二肽席夫碱Ni(II)配合物4a～4h, 产率为93.1%～99.0%; 最后稀酸水解配合物, 得到γ-L-谷氨酰二肽5a～5h, 产率为73.0%～86.4%, 高收率(92.2%～97.4%)回收手性助剂. 中间产物和终产物的结构经由旋光, 1H NMR, 13C NMR和HRMS表征.     

选择性合成双[噻吩并[2,3-d]嘧啶-4(3H)-酮]

以2-氨基-4-三氟甲基-5-甲基-噻吩-3-羧酸乙酯(1)为起始原料制得膦亚胺2.在碳酸钾的催化下,膦亚胺2与芳基异氰酸酯和伯二胺的氮杂Wittig反应制得嘧啶环上2,2’取代的双[噻吩并[2,3-d]嘧啶-4(3H)-酮]3;膦亚胺2与烷基异氰酸酯和伯二胺的氮杂Wittig反应制得嘧啶环上3,3’取代的双[噻吩并[2,3-d]嘧啶-4(3H)-酮]4.化合物3的核磁共振氢谱表明关环反应在嘧啶环的2,2’位;化合物4的核磁共振氢谱表明关环反应在嘧啶环的3,3’位.对合成反应机理的推导及目标产物核磁共振氢谱数据的分析解释了此合成反应的选择性.     

3-(2-卓二唑啉基) - 色酮类化合物的合成研究

报道了取代的邻羟基苯乙酮(1a～1e)经Vilsmeier-Haack反应一步制得3－醛基色酮(2a～2e),2a～2e与取代的芳酰肼(3a～3c)缩合制得15个酰腙类化合物(4a～4o),4a～4o在醋酸酐作用下关环得15个3-(2-卓二唑啉基)-色酮(5a～5o),并通过元素分析,IR,^1^HNMR和MS谱数据确证了上述化合物的结构。     

3,3-二{2,2-二[4-(N,N-二取代氨基)苯基]乙烯基}-4,5,6,7-四氯-2-苯并[c]呋喃酮的合成

在对甲苯磺酸存在下，采用1,1-二[4-(N,N-二取代氨基)苯基]乙烯(3)和四氯苯酐在乙酸酐溶液中的缩合反应合成了3,3-二{2,2-二[4-(N,N-二取代氨基)苯基]乙烯基}-4,5,6,7-四氯-2-苯并[c]呋喃酮(4)，产率89～93%。3由4,4'-二(N,N-二取代氨基)二苯甲酮(1)与甲基碘化镁进行Grignard反应的产物经水解再脱水制得，产率85%～88.5%(以1为基准)。     

Fe,Cu-codoped metal-nitrogen-carbon catalysts with high selectivity and stability for the oxygen reduction reaction

Metal-nitrogen-carbon materials(M-N-C) are non-noble-metal-based alternatives to platinum-based catalysts and have attracted tremendous attention due to their low-cost,high abundance,and efficient catalytic performance towards the oxygen reduction reaction(ORR).Among them,Fe-based materials show remarkable ORR activity,but they are limited by low selectivity and low stability.To address these issues,herein,we have synthesized FeCu-based M-N-C catalysts,inspired by the bimetal center of cytochrome c oxidase(CcO).In acidic media,the selectivity was notably improved compared with Febased materials,with peroxide yields less than 1.2%(<1/3 of the hydrogen peroxide yields of Fe-N-C catalysts).In addition to Cu-N-C catalysts which can catalytically reduce hydrogen peroxide,the reduction current of hydrogen peroxide using FeCu-N-C-20 exceeded that of Fe-N-C by about 6% when the potential was greater than 0.4 V.Furthermore,FeCu-based M-N-C catalysts suffered from only a15 mV attenuation in their half-wave potentials after 10,000 cycles of accelerated degradation tests(ADT),while there was a 30 mV negative shift for Fe-N-C.Therefore,we propose that the H₂O₂ released from Fe-Nx sites or N-doped carbon sites would be reduced by adjacent Cu-Nx sites,re sulting in low H₂O₂ yields and high stability.     

2-取代-4(3H)-喹唑啉酮在Br(o)nsted酸性功能化离子液体中的微波合成

以N-甲基咪唑、吡啶为起始原料,合成了二种新型Br(o)nsted酸性功能化离子液体:1-(4-磺酸基)苄基-3-甲基咪唑硫酸氢根盐(3a),N-(4-磺酸基)苄基吡啶硫酸氢根盐(3b),以其作为反应介质与催化剂,研究了2-取代-4(3H)-喹唑啉酮的三组分、一锅法微波合成.结果表明,当n(2-氨基苯甲酸):n(酰氯):n(乙酸铵):n(3a或3b)=1:1.2:1.5:0.1时,反应6 min即可完成,产率81%～95%.离子液体经减压蒸馏、真空干燥可重复使用3次,催化活性基本保持不变.     

Ni ion-containing immobilized ionic liquid on magnetic Fe3O4 nanoparticles: An effective catalyst for the Heck reaction

In this work, we synthesized Ni²⁺-containing 1-methyl-3-(3-trimethoxysilylpropyl) imidazolium chloride ionic liquid on magnetic Fe₃O₄ nanoparticles. The catalytic activity of these novel nanocomposites was finally evaluated for the Heck reaction at 100 °C, and can be reused after washing without loss in activity. The immobilized ionic liquid catalysts proved to be effective and easily separated from the reaction media by applying an external magnetic field. This procedure has many obvious advantages compared to those reported in the previous literature, including avoidance of the use of the expensive Pd catalysts, mild reaction conditions, high yields, and simplicity of the methodology.     

卤代萘与三氧化硫的磺化反应

卤代萘与三氧化硫的磺化反应林静,邹友思（厦门大学化学系,厦门,３６１００５）关键词磺化反应,三氧化硫,卤代萘甲基和甲氧基萘用三氧化硫进行的磺化反应已有报道［１～３］,而卤代萘的磺化反应迄今未见报道．本文研究了６种卤代茶在非极性溶剂二氯甲烷中用三氧化硫...     

Salen Mn（Ⅲ）配合物的合成及其在离子液体中对苯乙烯环氧化反应的催化性能

合成了在5,5’位上分别含羟基叔胺基和酯基叔胺基取代基的新型手性水杨醛Schiff碱的Salen Mn（Ⅲ）配合物1～4．在CH2Cl2／H2O反应体系中,以吡啶氮氧化物（PyNO）为助催化剂,NaCl0为氧化剂,考察了配合物1—4对苯乙烯环氧化的催化性能．以氯化-双[3-（叔丁基）-5-（N,N-二（乙醇基）氨基亚甲基）水杨醛]缩（1r,2R）-二苯基乙二胺[N,N’,O,O’]锰（Ⅲ）2和氯化-双[3-（叔丁基）-5-（N,N-二（乙酰乙酯基）氨基亚甲基）水杨醛]缩（1R,2R）-二苯基乙二胺[N,N’,O,O’]锰（11I）4为例,研究了不同的离子液体[BMIM]PF6和[BMIM]BF4对苯乙烯环氧化反应的影响．结果显示,两种离子液体的加入均能使催化剂循环使用,在离子液体[BMIM]PF。中,配合物2和4催化得到的环氧化物ee％值分别为53．2％和55．8％,且催化剂可以重复使用四次,效果好于在离子液体[BMIM]BF4中对苯乙烯的催化的影响．     

磷钨杂多酸及其铯盐上的常温正戊烷异构化反应

制备了一系列用于正戊烷异构化的磷钨杂多酸及其铯盐催化剂,并对它们进行了详细的物性表征。实验结果表明, Cs含量对催化剂的比表面、孔结构、热稳定性和表面酸量有显著的影响。考察了所制备的催化剂上常温下正戊烷异构化反应的活性和选择性。利用催化剂表征结果讨论了活化温度和Cs含量等因素对催化性能的影响。磷钨杂多酸及其铯酸式盐属固体超强酸。根据35℃时正戊烷异构化反应速率常数估测H~3PW~1~2O~4~0和Cs~2~.~2~5H~0~.~7~5PW~1~2O~4~0的酸强度H~0约在-13～-12.4之间。     

功能化离子液体为载体液相合成二氢吡啶酮衍生物

在微波辐照条件下, 以甲基咪唑、氯乙醇和四氟硼酸钠为原料制备了含羟基功能化离子液体1-(2-羟乙基)-3-甲基咪唑四氟硼酸盐([2-hydemim][BF₄]), 并以其为液态载体, 首先与乙酰乙酸乙酯反应, 得到的中间体再分别和Meldrum酸、醋酸铵以及各种芳香醛反应, 最后在温和的条件下用甲醇钠进行切割反应, 得到了一系列产率和纯度较高的3,4-二氢吡啶酮衍生物, 目标化合物不需要进一步的色谱纯化处理, 纯度为95%～98%, 产率为83%～93%. 回收得到的功能化离子液体可以重复套用至少6次也不影响其活性. 表明该方法是一种高效的3,4-二氢吡啶酮衍生物的组合化学合成方法.     

微波辐射条件下季戊四醇双缩醛和双缩酮化合物的合成

微波辐射硫酸锆-硅胶催化季戊四醇与醛、酮缩合反应,高收率制得了双缩醛和双缩酮化合物.该方法操作简便,收率高,催化剂可重复使用,是一种环境友好型催化反应.     

The electrochemical fluorination of N-(ω-chloroalkyl)pipecolines and N-(ω-chloroalkyl)hexamethyleneimines

Electrochemical fluorinations of six kinds of N-(ω-chloroalkyl)pipecolines [N-(2-chloroethyl)-2-, N-(3-chloropropyl)-2-, N-(2-chloroethyl)-3-, N-(3-chloropropyl)-3-, N-(2-chloroethyl)4- and N-(3-chloropropyl)-4-pipecolines] and two kinds of N-(ω- chloroalkyl)-substituted hexamethyleneimines [N-(2-chloroethyl)- and N-(3-chloropropyl)hexamethyleneimines] were conducted. From these starting materials, corresponding chlorine-retained fully fluorinated amines together with ring isomerized products were formed in yields of 7.6～14.8% from the former and 5.4～5.5% from the latter, respectively. New chloropolyfluoroamines obtained in the present investigation have been isolated and characterized by spectroscopic (infrared, ¹⁹F nmr and mass) and elemental analysis.     

UNSUPPORTED PRECIPITATED Fe-Cu-K CATALYSTS USED FOR THE SLURRY FISCHER-TROPSCH SYNTHESIS

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