http://www.chxb.cn ISSN 0253-9837 CN 21-1195/O6 CODEN THHPD3
催 化 学 报 CHINESE JOURNAL OF CATALYSIS
Chinese Journal of Catalysis 2014 主编
林励吾
Editor-in-Chief
Vol. 35 No. 3
LIN Liwu
March 2014 Vol. 35 No. 3 pages 279 - 452
中 国 化 学 会 催 化 学 会 会 刊
Transaction of the Catalysis Society of China
2014
2014年 第35卷 第3期
CHINESE JOURNAL OF CATALYSIS
Vol. 35 No. 3
In This Issue
封面: 范晓强等发现镍钼氧化物前驱体的制备方法影响其氮化物催化 剂的物理化学性质, 进而影响其丙烷氨氧化性能, 氮化物中的活性氮物种对 丙烷氨氧化反应中丙烯腈的选择性起重要作用. 见本期第 286–293 页. Cover: Fan and coworkers in their Article on pages 286–293 show that the physico-chemical properties and catalytic performance of propane ammoxidation over Ni-Mo nitride catalysts is strongly dependent on the preparation methods of the oxide precursors. The nitrogen species in Ni-Mo nitride play an important role in the selectivity of acrylonitrile for propane ammoxidation.
About the Journal Chinese Journal of Catalysis is an international journal published monthly by Chinese Chemical Society, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, and Elsevier. The journal publishes original, rigorous, and scholarly contributions in the fields of heterogeneous and homogeneous catalysis in English or in both English and Chinese. The scope of the journal includes: New trends in catalysis for applications in energy production, environmental protection, and production of new materials, petroleum chemicals, and fine chemicals; Scientific foundation for the preparation and activation of catalysts of commercial interest or their representative models; Spectroscopic methods for structural characterization, especially methods for in situ characterization; New theoretical methods of potential practical interest and impact in the science and applications of catalysis and catalytic reaction; Relationship between homogeneous and heterogeneous catalysis; Theoretical studies on the structure and reactivity of catalysts. The journal also accepts contributions dealing with photo-catalysis, bio-catalysis, and surface science and chemical kinetics issues related to catalysis. Types of Contributions
Impact Factor
Reviews deal with topics of current interest in the areas covered by this journal. Re-
2012 SCI Impact Factor: 1.304 2012 SCI 5-Year Impact Factor: 1.011 2012 ISTIC Impact Factor: 1.198
views are surveys, with entire, systematic, and important information, of recent progress in important topics of catalysis. Rather than an assemblage of detailed information or a complete literature survey, a critically selected treatment of the material is desired. Unsolved problems and possible developments should also be discussed. Authors should have published articles in the field. Reviews should have more than 80 references. Communications rapidly report studies with significant innovation and major academic value. They are limited to four Journal pages. After publication, their full-text papers can also be submitted to this or other journals. Articles are original full-text reports on innovative, systematic and completed research on catalysis. Research Perspectives describe the results of original research in general in some area, with a view to highlighting the progress, analyzing the major problems, and commenting the possible research target and direction in the future. Research Highlights describe and comment on very important new results in the original research of a third person with a view to highlight their significance. The results should be presented clearly and concisely without the comprehensive details required for an original article. Academic Arguments can discuss, express a different opinion or query the idea, concept, data, data processing method, characterization method, computational method, or the conclusion of published articles. The objective of an academic argument should be to enliven the academic atmosphere.
Abstracting and Indexing Abstract Journals (VINITI) Cambridge Scientific Abstracts (CIG) Catalysts & Catalysed Reactions (RSC) Current Contents/Engineering, Computing and Technology (Thomson ISI) Chemical Abstract Service/SciFinder (CAS) Chemistry Citation Index (Thomson ISI) Japan Information Center of Science and Technology Journal Citation Reports/Science Edition (Thomson ISI) Science Citation Index Expanded (Thomson ISI) SCOPUS (Elsevier) Web of Science (Thomson ISI)
2014年 第35卷 第3期
月刊 SCI 收录 1980 年 3 月创刊 中国化学会催化学会会刊 2014年3月20日出版
2014 Vol. 35 No. 3
CHINESE JOURNA OF CATALYSIS 《催化学报》第四届编辑委员会
The Fourth Editorial Board of Chinese Journal of Catalysis 顾问 (Advisors)
主管 中国科学院 主办 中国化学会 中国科学院大连化学物理研究所 主编 林励吾 编辑 《催化学报》编辑委员会 出版
蔡启瑞 (CAI Qirui) 闵恩泽 (MIN Enze) 彭少逸 (PENG Shaoyi) 宋春山 (SONG Chunshan, 美国)
辛 勤 (XIN Qin) 胥诲熊 (XU Huixiong) Jürgen CARO (德国) Michel CHE (法国)
Bernard DELMON (比利时) Gerhard ERTL (德国) Masaru ICHIKAWA (日本)
主编 (Editor-in-Chief) 林励吾 (LIN Liwu)
国内统一连续出版物号 CN 21-1195/O6 国际标准连续出版物号 ISSN 0253-9837 CODEN THHPD3 广告经营许可证号 2013003
副主编 (Associate Editors-in-Chief) 包信和 (BAO Xinhe) 高 滋 (GAO Zi)
寇 元 (KOU Yuan) 刘宇新 (LIU Yuxin)
张
涛 (ZHANG Tao)
李 灿 (LI Can) 李大东 (LI Dadong) 李微雪 (LI Weixue) 林励吾 (LIN Liwu) 刘昌俊 (LIU Changjun) 刘宇新 (LIU Yuxin) 刘中民 (LIU Zhongmin) 卢冠忠 (LU Guanzhong) 罗锡辉 (LUO Xihui) 沈俭一 (SHEN Jianyi) 沈师孔 (SHEN Shikong) 沈之荃 (SHEN Zhiquan) 申文杰 (SHEN Wenjie) 苏宝连 (SU Baolian, 比利时) 孙予罕 (SUN Yuhan) 万惠霖 (WAN Huilin) 万 颖 (WAN Ying) 王德峥 (WANG Dezheng) 王国祯 (WANG Guozhen) 王建国 (WANG Jianguo)
王祥生 (WANG Xiangsheng) 吴 凯 (WU Kai) 吴通好 (WU Tonghao) 夏春谷 (XIA Chungu) 肖丰收 (XIAO Fengshou) 谢在库 (XIE Zaiku) 熊国兴 (XIONG Guoxing) 徐柏庆 (XU Boqing) 许建和 (XU Jianhe) 徐 杰 (XU Jie) 徐龙伢 (XU Longya) 严玉山 (YAN Yushan, 美国) 杨启华 (YANG Qihua) 杨维慎 (YANG Weishen) 杨向光 (YANG Xiangguang) 余 林 (YU Lin) 袁友珠 (YUAN Youzhu) 张 涛 (ZHANG Tao) 赵进才 (ZHAO Jincai) 郑小明 (ZHENG Xiaoming)
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Publication Monthly (12 issues) Started in March 1980 Transaction of the Catalysis Society of China Superintended by Chinese Academy of Sciences Sponsored by Chinese Chemical Society and Dalian Institute of Chemical Physics of CAS Editor-in-Chief LIN Liwu Edited by Editorial Board of Chinese Journal of Catalysis Published by Science Press
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安立敦 (AN Lidun) 包信和 (BAO Xinhe) 陈 德 (CHEN De, 挪威) 陈经广 (CHEN Jingguang,美国) 陈庆龄 (CHEN Qingling) 陈诵英 (CHEN Songying) 陈耀强 (CHEN Yaoqiang) 陈 懿 (CHEN Yi) 椿范立 (Noritatsu TSUBAKI, 日本) 邓友全 (DENG Youquan) 方佑龄 (FANG Youling) 伏义路 (FU Yilu) 高 滋 (GAO Zi) 关乃佳 (GUAN Naijia) 郭新闻 (GUO Xinwen) 何鸣元 (HE Mingyuan) 贺鹤勇 (HE Heyong) 胡友良 (HU Youliang) 贾继飞 (JIA Jifei, 美国) 寇 元 (KOU Yuan)
编辑部成员 (Editorial Office Staff) 主任 (Managing Editor) 资深编辑 (Senior Editor) 编辑 (Editor) 编辑 (Editor)
尹红梅 (YIN Hongmei) 刘宇新 (LIU Yuxin) 初人合 (CHU Renhe) 张 艳 (ZHANG Yan)
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(CUIHUA XUEBAO)
CHINESE JOURNAL OF CATALYSIS 中国科学院科学出版基金资助出版
月刊
SCI 收录
2014 年 3 月 第 35 卷 第 3 期
目 快
讯
279 (英/中) 环己烷氧化反应: 有机小分子的催化作用 张义成, 戴卫理, 武光军, 关乃佳, 李兰冬
研究论文 286 (英/封面文章) Ni-Mo 氮化物催化剂: 合成及其丙烷氨氧化催化性能 范晓强, 张惠民, 李建梅, 赵震, 徐春明, 刘坚, 段爱军, 姜桂元, 韦岳长 294 (英) 原位漫反射傅里叶变换红外光谱研究锰铁基催化剂上低温选 择性催化还原反应机理 陈婷, 管斌, 林赫, 朱霖 302 (英) Ni/SiO2-ZrO2 催化剂焙烧温度对其催化愈创木酚加氢脱氧性 能的影响 张兴华, 张琦, 陈伦刚, 徐莹, 王铁军, 马隆龙
次 351 (英) 由蛋壳为原料制备的纳米氧化钙用于高效催化合成吡喃并 [4,3-b]吡喃 Elaheh Mosaddegh, Asadollah Hassankhani 357 (英) 纯水中有氧条件下 Pd/C 催化的无配体 Suzuki 反应 饶小峰, 刘春, 张义霞, 高占明, 金子林 362 (英) 无溶剂条件下勃姆石纳米粒子一锅催化多组分合成 3,4-二 氢嘧啶-2-(1H) 酮 Ali Keivanloo, Mahdi Mirzaee, Mohammad Bakherad, Atena Soozani 368 (英) ZnAl2O4@SiO2 纳米复合催化剂用于无溶剂条件下乙酸酐与 醇、酚和胺的乙酰化反应 Saeed Farhadi, Kosar Jahanara
310 (英/中) Mg-Al 水滑石催化甘油与碳酸二甲酯的酯交换反应 郑丽萍, 夏水鑫, 侯召同, 张梦媛, 侯昭胤
376 (英) 绿色可磁性分离二氧化硅包裹镍铁尖晶石负载硫酸氢铁纳 米粒子催化剂用于合成 1,8-二氧十氢吖啶合成 Amir Khojastehnezhad, Mohammad Rahimizadeh, Hossein Eshghi, Farid Moeinpour, Mehdi Bakavoli
319 (英) 铜催化异噁唑还原开环清洁高效合成 1-氨基-2-乙酰基蒽醌 赵忠奎, 李仁志, 李宇
383 (英) 以方沸石负载 Ni(II) 催化剂修饰的电极电氧化甲醇 Seyed Naser Azizi, Shahram Ghasemi, Neda Salek Gilani
324 (英) 有氧条件下聚(氯乙烯)负载 Pd(II) 配合物高效催化 Heck 和 无铜 Sonogashira 反应 Mohammad Bakherad, Ali Keivanloo, Shahrzad Samangooei
391 (英) 以淀粉溶液为催化剂一锅三组分法合成四氢苯并 [b] 吡喃和 3,4-二氢吡喃并[c]苯并吡喃衍生物 Nourallah Hazeri, Malek Taher Maghsoodlou, Fatemeh Mir, Mehrnoosh Kangani, Hamideh Saravani, Ebrahim Molashahi
329 (英) 聚乙烯基吡啶高氯酸盐作为高效固定酸催化剂在无溶剂条 件下催化醛化学选择性制备二乙酸盐 Nader Ghaffari Khaligh
396 (英/中) 酸性离子液体催化油酸酯化合成生物柴油 李颖, 胡双岚, 程建华, 娄文勇
335 (英/中) 锰负载量对活性炭载锰氧化物的结构及催化分解臭氧性能 的影响 王鸣晓, 张彭义, 李金格, 姜传佳
407 (英) Pt/Ce0.6Zr0.4O2 催化剂催化氧化碳烟过程中活性氧对 NO-NO2 循环及表面含氧物种的分解作用 刘爽, 吴晓东, 林雨, 李敏, 翁端
342 (英/中) 以钴羰基簇合物为前驱体制备的钴基催化剂上 F-T 反应性能 李雪芬, 白凤华, 苏海全
416 (英) 水对甲醇在 Rutile-TiO2(110)-(1 × 1) 表面光催化解离的影响 徐晨彪, 杨文紹, 郭庆, 戴东旭, 陈茂笃, 杨学明
423 (英) 用聚(L-蛋氨酸)/纳米金修饰玻碳电极同时灵敏检测多巴胺和 尿酸 Reza Ojani, Jahan-Bakhsh Raoof, Ali Asghar Maleki, Saeid Safshekan
444 (英) 高效可回收的非均相催化剂 SiO2-Cu2O 催化伯胺和仲胺苄 基化反应 Manjulla Gupta, Satya Paul, Rajive Gupta
相关信息
430 (英) 混合气体中 SAPO-34 上单个物种的表面浓度 Yasukazu Kobayashi, 李玉新, 王垚, 王德峥
451
437 (英) La(OH)3 和 La2O2CO3 纳 米 棒 的 合 成 及 其 催 化 ClaisenSchmidt 缩合反应性能 王非, 塔娜, 李勇, 申文杰
英文全文电子版(国际版)由Elsevier出版社在ScienceDirect上出版 http://www.sciencedirect.com/science/journal/18722067 http://www.elsevier.com/locate/chnjc http://www.chxb.cn
作者索引
Chinese Journal of Catalysis Vol. 35, No. 3, March 2014
催化学报 2014年 第35卷 第3期 | www.chxb.cn
a v a i l a b l e a t w w w. s c i e n c e d i r e c t . c o m
j o u r n a l h o m e p a g e : w w w . e l s e v i e r. c o m / l o c a t e / c h n j c
Chinese Journal of Catalysis Graphical Contents
Communication Chin. J. Catal., 2014, 35: 279–285 doi: 10.1016/S1872‐2067(14)60024‐3 Cyclohexane oxidation: small organic molecules as catalysts R1OCH2R2
Yicheng Zhang, Weili Dai, Guangjun Wu, Naijia Guan, Landong Li * Nankai University
H H
H
O2
R1OCH2R2
H
H
H
R1OCHR2
O O H
N‐ or O‐containing small organic molecules were used as catalysts for cyclohexane oxidation. The polarity, α‐H activity, strength of the hydrogen bond formed with cyclohexane and the radical scavenging capability of these molecules determine their catalytic activity.
H2O
CHR2 R1O
H O
H O
H
Articles Chin. J. Catal., 2014, 35: 286–293 doi: 10.1016/S1872‐2067(14)60015‐2 Ni‐Mo nitride catalysts: synthesis and application in the ammoxidation of propane Xiaoqiang Fan, Huimin Zhang, Jianmei Li, Zhen Zhao *, Chunming Xu, Jian Liu *, Aijun Duan, Guiyuan Jiang, Yuechang Wei China University of Petroleum; Shenhua Group Corporation Ltd
NiMoON NiMoN
Precursor preparation methods affect the structure and properties of nitrides. Lattice nitrogen species participate in propane ammoxida‐ tion reaction. The mechanism for propane ammoxidation over the Ni‐Mo nitride is analogous to the Mars‐van Krevelen mechanism.
vi
Graphical Contents / Chinese Journal of Catalysis Vol. 35, No. 3, 2014
Chin. J. Catal., 2014, 35: 294–301 doi: 10.1016/S1872‐2067(12)60730‐X In situ DRIFTS study of the mechanism of low temperature selective catalytic reduction over manganese‐iron oxides Ting Chen, Bin Guan, He Lin *, Lin Zhu Shanghai Jiao Tong University
Langmuir–Hinshelwood mechanism
N2+H2O NO *-O-NO2[NH3]2
NO+O2
NO2
NH3(ad)
*-O-NO2
NH3 *-O-NO2[NH4]+2
NH4+
NO N2+H2O
*:active metal ions
Selective catalytic reduction reactions over Ti0.9Mn0.05Fe0.05O2‐δ catalysts possibly proceed according to both Langmuir‐Hinshelwood and Eley‐Rideal mechanisms, but NO more likely reacts as an adsorbed species. Chin. J. Catal., 2014, 35: 302–309 doi: 10.1016/S1872‐2067(12)60733‐5 Effect of calcination temperature of Ni/SiO2‐ZrO2 catalysts on its hydrodeoxygenation of guaiacol
Activation of C-O bond OH
Xingua Zhang, Qi Zhang, Lungang Chen, Ying Xu, Tiejun Wang *, Longlong Ma * Guangzhou Institute of Energy Conversion, Chinese Academy of Sciences
OH OH
acidic site
OH
OH
Cyclohexane was obtained with high selectivity by the hydrodeox‐ ygenation of guaiacol over a bifunctional Ni/SiO2‐ZrO2 catalyst. The catalytic performance was influenced significantly by the calcina‐ tion temperature of the catalyst.
CH3
O
O
Ni/SiO2-ZrO2
H2
Chin. J. Catal., 2014, 35: 310–318 doi: 10.1016/S1872‐2067(12)60738‐4 Transesterification of glycerol with dimethyl carbonate over Mg‐Al hydrotalcite Liping Zheng, Shuixin Xia, Zhaotong Hou, Mengyuan Zhang, Zhaoyin Hou * Zhejiang University; Jiangsu Changlong Chemical Co. O
O
OH HO
OH
Glycerol
+ MeO
O HO
OMe
Dimethyl carbonate
OH OH
O
Glycerol carbonate
OH
OH
Layered solid base Mg-Al-O HLT The transesterification of glycerol with dimethyl carbonate was catalyzed by a series of Mg‐Al hydrotalcites with different Mg/Al ratios (0.5–6) under mild conditions. The hydrotalcite with Mg/Al = 2 is the most active catalyst for this reaction.
Graphical Contents / Chinese Journal of Catalysis Vol. 35, No. 3, 2014
vii
Chin. J. Catal., 2014, 35: 319–323 doi: 10.1016/S1872‐2067(12)60743‐8 NH2NH2∙H2O
Highly efficient and clean synthesis of 1‐amino‐2‐acetylanthraquinone by copper‐catalyzed reductive cleavage of isoxazole motif Zhongkui Zhao *, Renzhi Li, Yu Li Dalian University of Technology
Trace copper in water
A trace‐copper‐catalyzed reductive isoxazole‐ring‐cleavage strategy for clean and highly efficient production of 1‐amino‐2‐acetylanthraquinone under mild reaction conditions was presented.
Only N2 is released
Chin. J. Catal., 2014, 35: 324–328 doi: 10.1016/S1872‐2067(12)60746‐3 Poly(vinyl chloride)‐supported Pd(II) complex as an efficient catalyst for Heck and Cu‐free Sonogashira reactions under aerobic conditions Mohammad Bakherad *, Ali Keivanloo, Shahrzad Samangooei Shahrood University of Technology, Iran PVC
S N
PhHN N
N Ph Pd
Cl Cl PVC-dtz-Pd(II) complex R2
R1
X +
PVC-dtz-Pd(II) o
Et3N, 70 C
X +
R
CO2Me
R1
PVC-dtz-Pd(II) R
Et3N, r.t.
Y
Y
A novel poly(vinyl chloride)‐supported palladium complex was found to be highly active in the Heck and Sonogashira reactions of aryl halides under aerobic conditions. The complex is thermally stable and can be easily recovered and reused for five runs without apprecia‐ ble loss of catalytic activity. Chin. J. Catal., 2014, 35: 329–334 doi: 10.1016/S1872‐2067(12)60750‐5 Poly(4‐vinylpyridinium) perchlorate as an efficient solid acid catalyst for the chemoselective preparation of 1,1‐diacetates from aldehydes under solvent‐free conditions Nader Ghaffari Khaligh * House Research of Professor Reza, Iran
O
O R
H
+
Me
O
O O
P(4-VPH)ClO4 Me
Solvent-free, r.t.
Me
O R
R = Alkyl or aryl
H
O O
Me
Poly(4‐vinylpyridinium) perchlorate was used as a catalyst for the acetylation of aliphatic and aromatic aldehydes under solvent‐free conditions. Ketones were unaffected by the reaction conditions and the catalyst could be reused several times without any loss in activity.
viii
Graphical Contents / Chinese Journal of Catalysis Vol. 35, No. 3, 2014
Chin. J. Catal., 2014, 35: 335–341 doi: 10.1016/S1872‐2067(12)60756‐6 The effects of Mn loading on the structure and ozone decompo‐ sition activity of MnOx supported on activated carbon Mingxiao Wang, Pengyi Zhang *, Jinge Li, Chuanjia Jiang Tsinghua University The 1.1% MnOx/AC (AC: activated carbon) catalyst gave the highest activity for ozone decomposition, which was mainly due to its porous structure, while 11% MnOx/AC with the thickest MnOx layer showed the lowest activity because of its compact morphology.
Chin. J. Catal., 2014, 35: 342–350 doi: 10.1016/S1872‐2067(12)60757‐8 Cobalt‐based catalysts derived from cobalt carbonyl clusters for Fischer‐Tropsch synthesis
CO conversion(%)
Xuefen Li, Fenghua Bai, Haiquan Su * Inner Mongolia University
Al2O3
100 90 80 70 60 50 40 30 20 10 0 100
Co2/-Al2O3 Co3/-Al2O3 Co4/-Al2O3 Co(N)/-Al2O3 10 20 30 40 50 60 70 Time (h)
H2/CO = 2
C5+ selectivity (%)
90 80 70 60 50 40 30 20 10
Co2/-Al2O3 Co3/-Al2O3 Co4/-Al2O3 Co(N)/-Al2O3
0
10 20 30 40 50 60 70 Time (h)
A series of Co‐based catalysts supported on γ‐Al2O3 prepared using cobalt carbonyl clusters showed higher CO conversion and C5+ selec‐ tivity in F‐T synthesis than a reference catalyst prepared using Co(NO3)2. Chin. J. Catal., 2014, 35: 351–356 doi: 10.1016/S1872‐2067(12)60755‐4 Preparation and characterization of nano‐CaO based on eggshell waste: novel and green catalytic approach to highly efficient synthesis of pyrano[4,3‐b]pyrans Elaheh Mosaddegh *, Asadollah Hassankhani Graduate University of Advanced Technology, Iran
Eggshell
Nano eggshell waste (Nano-CaO) ∆, solvent-free
Calcination
The ball‐mill‐assisted preparation by thermal decomposition of nano‐CaO derived from chicken eggshell waste was reported as a novel, bioactive, and heterogeneous catalyst with high catalytic activity and reusability in the green synthesis of pyrano[4,3‐b]pyrans.
Graphical Contents / Chinese Journal of Catalysis Vol. 35, No. 3, 2014
ix
Chin. J. Catal., 2014, 35: 357–361 doi: 10.1016/S1872‐2067(12)60754‐2 Pd/C‐catalyzed ligand‐free and aerobic Suzuki reaction in water Xiaofeng Rao, Chun Liu *, Yixia Zhang, Zhanming Gao, Zilin Jin Dalian University of Technology
A highly efficient and recyclable catalytic system for the Pd/C‐catalyzed, ligand‐free Suzuki reaction was developed; a wide range of aryl bromides were tolerated, and the reaction proceeded without any additives in water. Chin. J. Catal., 2014, 35: 362–367 doi: 10.1016/S1872‐2067(12)60759‐1 Boehmite nanoparticle catalyst for the one‐pot multicom‐ ponent synthesis of 3,4‐dihydropyrimidin‐2‐(1H)‐ones and thiones under solvent‐free conditions Ali Keivanloo *, Mahdi Mirzaee, Mohammad Bakherad, Atena Soozani Shahrood University of Technology, Iran Boehmite nanoparticles are a highly active and green catalyst for the synthesis of highly substituted 3,4‐dihydropyrimidin‐2‐(1H)‐ ones and thiones under solvent‐free conditions. Chin. J. Catal., 2014, 35: 368–375 doi: 10.1016/S1872‐2067(12)60758‐X ZnAl2O4@SiO2 nanocomposite catalyst for the acetylation of alcohols, phenols and amines with acetic anhydride under solvent‐free conditions Saeed Farhadi *, Kosar Jahanara Lorestan University, Iran
ZnAl2O4/SiO2 nanocomposite
-
Acetic anhydride, R.T., Solvent-free conditions
ROAc ArOAc RNHAc Yeilds: 80% 96% Time: 3 50 min -
ROH ArOH RNH2
A ZnAl2O4@SiO2 nanocomposite fabricated by a sol‐gel process was a good and recyclable catalyst for the efficient acetylation of alcohols, phenols and amines with acetic anhydride under solvent‐free conditions.
x
Graphical Contents / Chinese Journal of Catalysis Vol. 35, No. 3, 2014
Chin. J. Catal., 2014, 35: 376–382 doi: 10.1016/S1872‐2067(14)60001‐2 Ferric hydrogen sulfate supported on silica‐coated nickel ferrite nanoparticles as new and green magnetically separable catalyst for 1,8‐dioxodecahydroacridine synthesis Amir Khojastehnezhad *, Mohammad Rahimizadeh, Hossein Eshghi, Farid Moeinpour, Mehdi Bakavoli Ferdowsi University of Mashhad, Iran; Islamic Azad University‐Bandar Abbas Branch, Iran
M A G N E T
Magnetic nano supported catalyst
Catalyst loading: 1.0 mol% Reaction condition: solvent free Yields: 86%–94%
A new magnetically separable catalyst consisting of ferric hydrogen sulfate supported on silica‐coated nickel ferrite nanoparticles was prepared and was shown to be an efficient heterogeneous catalyst for the synthesis of 1,8‐dioxodecahydroacridines under solvent‐free conditions. The catalyst was readily recovered by simple magnetic decantation and was recycled several times with no significant loss of catalytic activity. Chin. J. Catal., 2014, 35: 383–390 doi: 10.1016/S1872‐2067(14)60002‐4 An electrode with Ni(II) loaded analcime zeolite catalyst for the electrooxidation of methanol
10
Seyed Naser Azizi *, Shahram Ghasemi, Neda Salek Gilani University of Mazandaran, Iran
J/(mA cm-2 )
Ni/ANACPE
5
Ni/CPE ANACPE CPE
0 0
0.5
1
1.5
E /V vs Ag|AgCl|KCl (3 mol/L)
-5
Ni loaded analcime zeolite was used as the catalyst for the electro‐ chemical oxidation of methanol.
Chin. J. Catal., 2014, 35: 391–395 doi: 10.1016/S1872‐2067(14)60003‐6 An efficient one‐pot three‐component synthesis of tetrahydrobenzo[b]pyran and 3,4‐dihydropyrano[c]chromene derivatives using starch solution as catalyst Nourallah Hazeri *, Malek Taher Maghsoodlou, Fatemeh Mir, Mehrnoosh Kangani, Hamideh Saravani, Ebrahim Molashahi The University of Sistan and Baluchestan, Iran OH
O NC
O
CN
O
Ar
O
O
CN
Ar
O
NH2
Ar
H
O
CN
O Starch solution
O
O NC
H
Ar CN
Starch solution
O
NH2
Tetrahydrobenzo[b]pyran and 3,4‐dihydropyrano[c]chromene derivatives were synthesized via one‐pot three‐component condensation of aromatic aldehydes with malononitrile and dimedone or 4‐hydroxycoumarin in excellent yields in the presence starch solution as a highly efficient homogenous catalyst. The use of a nontoxic and biodegradable catalyst, simple work‐up procedure, and short reaction time are advantages of this method.
Graphical Contents / Chinese Journal of Catalysis Vol. 35, No. 3, 2014
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Chin. J. Catal., 2014, 35: 396–406 doi: 10.1016/S1872‐2067(14)60005‐X Acidic ionic liquid‐catalyzed esterification of oleic acid for biodiesel synthesis
CH3(CH2)7CH=CH(CH2)7COOH
Ying Li, Shuanglan Hu, Jianhua Cheng *, Wenyong Lou * South China University of Technology
+
The esterification of oleic acid with methanol was success‐ fully conducted with acidic ionic liquids as catalysts. [BHSO3MIM]HSO4 exhibited the best results and could also efficiently catalyze the conversion of waste oils to biodiesel.
Ionic Liquid
CH3OH
CH3(CH2)7CH=CH(CH2)7COCH3 + H2O
Chin. J. Catal., 2014, 35: 407–415 doi: 10.1016/S1872‐2067(14)60004‐8 Active oxygen‐assisted NO‐NO2 recycling and decomposition of surface oxygenated species in diesel soot when employing a Pt/Ce0.6Zr0.4O2 Shuang Liu, Xiaodong Wu *, Yu Lin, Min Li, Duan Weng Tsinghua University
Pt/Al2O3
Pt/Ce0.6Zr0.4O2
CO2 O O O NO2 NO O2 Soot Pt
CO2
Al2O3
O
O O2 Pt
O O NO2 Soot
NO Pt
O Ce0.6Zr0.4O2
O
The synergistic effect between Pt and CeZr increases the availability of active oxygen which in turn accelerates NO ↔ NO2 recycling and the oxidation of SOCs, resulting in enhanced catalytic activity during soot oxidation. Chin. J. Catal., 2014, 35: 416–422 doi: 10.1016/S1872‐2067(14)60006‐1 The role of water in photocatalytic dissociation of methanol on rutile TiO2(110)‐(1 × 1) Chenbiao Xu, Wenshao Yang, Qing Guo *, Dongxu Dai, Maodu Chen, Xueming Yang * Dalian University of Technology; Dalian Institute of Chemical Physics, Chinese Academy of Sciences
H2O
CH3OH
m/z = 31 (CH3O+) 0.3 ML CH3OH 0.3 ML CH3OH + 0.2 ML H2O 0.3 ML CH3OH + 0.4 ML H2O
H
CH2O H2O
Total TPD signals (a.u.)
1.0
0.9
0.8
0.7
0.6
0.5
0
10
20
30
40
50
60
Irradiation time (min) Coadsorbed water on methanol covered TiO2(110)‐(1 × 1) surface has nearly no effect on methanol photodissociation.
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Graphical Contents / Chinese Journal of Catalysis Vol. 35, No. 3, 2014
Chin. J. Catal., 2014, 35: 423–429 doi: 10.1016/S1872‐2067(14)60022‐X Simultaneous and sensitive detection of dopamine and uric acid using a poly(L‐methionine)/gold nanoparticle‐modified glassy carbon electrode Reza Ojani *, Jahan‐Bakhsh Raoof, Ali Asghar Maleki, Saeid Safshekan University of Mazandaran, Iran S
S
S S
OH NH2
S S
S
S
HAuCl4·4H2O
S
S
Electropolymerization
S
S
Electrodeposition
S S
S S
S
S SH S
S S
S
S S
S
S
S
GCE
H3C
GCE
GCE
O
S
S
S
S
S S
S
S S
S S
S
S
S
S S
A glassy carbon electrode modified with gold nanoparticles and poly(L‐methionine) exhibited high electrocatalytic activity towards the oxidation of dopamine and uric acid. This electrode allowed sensitive and selective determination of dopamine and uric acid at nanomo‐ lar levels. Chin. J. Catal., 2014, 35: 430–436 doi: 10.1016/S1872‐2067(14)60007‐3
Yasukazu Kobayashi, Yuxin Li, Yao Wang, Dezheng Wang * Tsinghua University
Methanol has a larger adsorption capacity than dimethyl ether (DME) on SAPO‐34, which caused DME coverage to decrease with increasing pressure of a gas mixture. Ideal adsorbed solution the‐ ory calculations showed this but the Langmuir isotherm for com‐ petitive adsorption did not.
Amount adsorbed (mmol/g)
Species surface concentrations on a SAPO‐34 catalyst exposed to a gas mixture
2.0
Experiment Methanol DME
1.5
IAST Methanol DME
1.0
Langmuir theory Methanol DME
0.5 0.0
0
5 10 15 Total pressure (kPa)
20
Chin. J. Catal., 2014, 35: 437–443 doi: 10.1016/S1872‐2067(14)60008‐5 La(OH)3 and La2O2CO3 nanorod catalysts for Claisen‐Schmidt condensation Fei Wang, Na Ta, Yong Li, Wenjie Shen * Dalian Institute of Chemical Physics, Chinese Academy of Sciences The basicity of La2O2CO3 nanorods increased with increasing as‐ pect ratio, and their catalytic activity for Claisen‐Schmidt conden‐ sation was associated with the La3+−O2− sites on the (110) facets.
Graphical Contents / Chinese Journal of Catalysis Vol. 35, No. 3, 2014
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Chin. J. Catal., 2014, 35: 444–450 doi: 10.1016/S1872‐2067(14)60009‐7 SiO2‐Cu2O: An efficient and recyclable heterogeneous catalyst for N‐benzylation of primary and secondary amines Manjulla Gupta, Satya Paul *, Rajive Gupta University of Jammu, India Glucose Solution
Fehling Solution
Cu2O
SiO2-Cu2O
SILICA C6H5
N
C6H5
C6H5 +
NH
(1) C6H 5CH 2Cl (2) K 2CO 3
NH2
Silica‐supported Cu2O was prepared in situ using inexpensive and widely available starting materials and used as a catalyst for N‐benzylation and N,N‐dibenzylation of primary and secondary amines.
Chinese Journal of Catalysis 35 (2014) 444–450
催化学报 2014年 第35卷 第3期 | www.chxb.cn
available at www.sciencedirect.com
journal homepage: www.elsevier.com/locate/chnjc
Article
SiO2‐Cu2O: An efficient and recyclable heterogeneous catalyst for N‐benzylation of primary and secondary amines Manjulla Gupta, Satya Paul *, Rajive Gupta Department of Chemistry, University of Jammu, Jammu‐180 006, India
A R T I C L E I N F O
A B S T R A C T
Article history: Received 16 September 2013 Accepted 24 December 2013 Published 20 March 2014
Keywords: Silica supported copper(I) oxide Benzylation Substituted amine Recyclability Heterogeneous catalysis
A mild, effective, and selective procedure is reported for the mono N‐benzylation and N,N‐ diben‐ zylation of primary amines as well as mono N‐benzylation of secondary amines using sili‐ ca‐supported copper(I) oxide in water. The silica‐supported Cu2O was generated in situ by the reac‐ tion of Fehling solution and glucose at 100 °C onto activated silica. The catalyst was filtered, washed with water, and oven‐dried, and was characterized by Fourier transform infrared spectroscopy, thermogravimetric analysis, scanning electron microscopy, transmission electron microscopy, and atomic absorption spectroscopy. The prepared Cu2O‐SiO2 was found to be thermally stable up to 325 °C. The copper was uniformly distributed onto the surface of the silica, and the mean particle diameter was 7 nm. The catalyst served as a selective heterogenous catalyst for the N‐benzylation of primary and secondary amines. The catalyst is recyclable and was used effectively upto fifth run without a significant loss of catalytic activity. Various reaction solvents including water, acetonitrile, and toluene were screened for N‐benzylation of amines, and the success of the aqueous system highlights the low environmental impact of the procedure. © 2014, Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by Elsevier B.V. All rights reserved.
1. Introduction In recent years, there has been growing interest in reactions designed to form carbon–nitrogen bonds, which is a useful strategy in synthetic organic chemistry. In the past few dec‐ ades, the synthesis of amines has attracted considerable atten‐ tion because of their industrial and commercial importance [1,2] and also for the synthesis of various dyes. The traditional synthetic approach to N‐substituted amines is direct N‐ alkyla‐ tion [3], but this procedure is problematic owing to over‐ alkyl‐ ation, the toxic nature of many alkyl halides [4], and poor selec‐ tivity [5]. Furthermore, various bases including NaOH [6], ce‐ sium hydroxide [7], PhN(n‐Pr)2 [8], and Hunig’s base [9] have been used for synthesis of N‐substituted amines, but they re‐ quire harsh reaction conditions. Transition metal catalysis has proved useful in selective and
atom‐economical transformations. Although C–N couplings using palladium [10,11], ruthenium [4], iridium [12,13], and platinum [14,15] catalysts have been explored, copper‐cata‐ lyzed C–N bond formation has gained more attention because of its low cost, non‐toxic nature, and excellent selectivity [16–20]. Heterogenous catalysts have recently gained much importance because they are more selective, stable at high temperature, easily separated from the reaction mixture at the end of the process, and can be reused. These factors favor the cost effectiveness of what can be regarded as a “green reac‐ tion”. Among the alkylations of amines, benzylation continues to be one of the most commonly used reactions in pharmaceu‐ tical chemistry [21,22] because of the medicinal importance of N‐benzylated amines. Here we report a selective procedure for mono N‐benzylation and N,N‐dibenzylation of anilines (Scheme 1) and N‐benzylation of secondary amines (Scheme 2) using
* Corresponding author. Tel: +91‐191‐2453969; Fax: +91‐191‐2431365; E‐mail:
[email protected] DOI: 10.1016/S1872‐2067(14)60009‐7 | http://www.sciencedirect.com/science/journal/18722067 | Chin. J. Catal., Vol. 35, No. 3, March 2014
Manjulla Gupta et al. / Chinese Journal of Catalysis 35 (2014) 444–450
Cl
NH2
SiO2-Cu2O, K2CO3
+
HN
C 6 H5
N
C6H5
Scheme 1. N‐Benzylation and N,N‐dibenzylation of amines with benzyl chloride in water.
Cl R
H N
R'
+
SiO2-Cu2O, K2CO3
silica gel with ethyl acetate/petroleum ether. 2.3. General procedure for N‐benzylation of secondary amines using SiO2‐Cu2O
+
H2O, 30 oC or 100 oC
R
C6H5
445
C6H5
H2O, TBAB, 100 oC
R
N
R'
Scheme 2. N‐Benzylation of secondary amines with benzyl chloride in water.
silica‐supported copper(I) oxide in aqueous media.
A mixture of secondary amine (0.5 mmol), benzyl chloride (0.127 g, 1 mmol), K2CO3 (0.139 g, 1 mmol), TBAB (0.082 g, 0.25 mmol), and SiO2‐Cu2O (0.2 g, 5 mol% Cu) in water (5 mL) in a round‐bottom flask (50 mL) was stirred at 100 °C. On com‐ pletion of the reaction (monitored by TLC), the flask was cooled to room temperature and the mixture filtered. The residue was washed with water followed by ethyl acetate (3 × 10 mL). The combined organic extracts were washed with water (3 × 100 mL) and dried over anhydrous Na2SO4. The solvent was re‐ moved under reduced pressure, and the product was obtained by crystallization from petroleum ether or ethyl acetate/ petro‐ leum ether, or by eluting the crude product through a column of silica gel with ethyl acetate/petroleum ether.
2. Experimental 2.1. Preparation of silica‐supported copper(I) oxide (SiO2‐Cu2O) To a round‐bottom flask containing activated silica (10 g), Fehling solution (50 mL) was added and the reaction mixture was stirred at 100 °C. After every interval of 30 min, 2 mL of glucose solution (0.5 g in 96 mL of water) was added up to 24 h. Then the catalyst was filtered off, washed with water until the washings were colorless, and dried in an oven at 110 °C. To remove excess glucose, the catalyst was refluxed in water at 120 °C for 6 h (3 × 2 h). Then the catalyst was dried at 110 °C for 5 h in an oven. The general preparation procedure for silica‐supported nano copper(I) oxide (SiO2‐Cu2O) is shown in Scheme 3. 2.2. General procedure for mono N‐benzylation and N,N‐dibenzylation of anilines in the presence of SiO2‐Cu2O A mixture of aniline (0.5 mmol), benzyl chloride (0.5 mmol for mono N‐benzylation and 2 mmol for N,N‐dibenzylation), K2CO3 (0.5 mmol for mono N‐benzylation and 1 mmol for N,N‐dibenzylation), SiO2‐Cu2O (0.1 g, 2.5 mol% Cu for mono N‐benzylation and 0.2 g, 5 mol% Cu for N,N‐dibenzylation), and tetra‐n‐butylammonium bromide (TBAB, 0.082 g, 0.25 mmol, only in the case of N,N‐dibenzylation) in water (5 mL) in a round‐bottom flask (50 mL) was stirred at 30 °C for mono N‐benzylation and 100 °C for N,N‐dibenzylation. On completion of the reaction monitored by thin‐layer chromatography (TLC), the reaction mixture was filtered, and the residue was washed with water followed by ethyl acetate (3 × 10 mL). The com‐ bined organic extracts were washed with water (3 × 100 mL) and dried over anhydrous Na2SO4. The solvent was removed under reduced pressure, and the product was obtained by crystallization from petroleum ether or ethyl acetate/petrole‐ um ether, or by eluting the crude product through a column of SiO
2
OH Glucose OH + Fehling solution 100 oC, reflux, 24 h OH
Cu2O Cu2O OHOHOH SiO2 SiO 2
Scheme 3. General procedure for the preparation of SiO2‐Cu2O.
2.4. Selected spectral data N‐Benzyl‐3‐methoxyaniline (Table 3). IR (υmax in cm−1, KBr): 1042 (C–O–C symm. str.), 1582 (aromatic C=C str.), 3029 (aro‐ matic C–H str.), 3422 (NH str.). 1H NMR (CDCl3): δ 3.82 (s, 3H, OCH3), 4.0 (bs, 1H, NH), 4.33 (s, 2H, CH2Ph), 6.85–7.0 (m, 4H, Ar–H), 7.16–7.32 (m, 5H, Ar–H). MS: m/z 213 (M+). N‐Benzyl‐4‐methylaniline (Table 3). IR (υmax in cm−1, KBr): 1575 (aromatic C=C str.), 2918 (C–H str.), 3021 (aromatic C–H str.), 3427 (N–H str.). 1H NMR (CDCl3): δ 2.27 (s, 3H, CH3), 4.02 (bs, 1H, NH), 4.37 (s, 2H, CH2Ph), 6.86–6.96 (d, 2H, Ar–H), 7.06–7.17 (d, 2H, Ar–H), 7.33–7.46 (m, 5H, Ar–H). MS: m/z 197 (M+). N‐Benzyl‐4‐chloroaniline (Table 3). IR (υmax in cm−1, KBr): 740 (C–Cl str.), 1580 (aromatic C=C str.), 3029 (aromatic C–H str.), 3420 (N–H str.). 1H NMR (CDCl3): δ 4.13 (bs, 1H, NH), 4.29 (s, 2H, CH2Ph), 6.89–6.97 (d, 2H, Ar–H), 7.21–7.34 (m, 5H, Ar–H), 7.50–7.58 (d, 2H, Ar–H). MS: m/z 217 (M+), 219 (M+2). N‐Benzyl‐4‐nitroaniline (Table 3). IR (υmax in cm−1, KBr): 865 (C–NO2 str.), 1530 (NO2 str.), 1585 (aromatic C=C str.), 3039 (aromatic C–H str.), 3460 (N–H str.). 1H NMR (CDCl3): δ 4.10 (bs, 1H, NH), 4.25 (s, 2H, CH2Ph), 6.94–7.03 (d, 2H, Ar–H), 7.46–7.59 (m, 5H, Ar–H), 8.01–8.12 (d, 2H, Ar–H). MS: m/z 228 (M+). N,N‐Dibenzyl‐3‐methoxyaniline (Table 3). IR (υmax in cm−1, KBr): 1052 (C–O–C symm. str.), 1579 (aromatic C=C str.), 3029 (aromatic C–H str.). 1H NMR (CDCl3): δ 3.83 (s, 3H, OCH3), 4.35 (s, 4H, 2 × CH2Ph), 6.87–7.20 (m, 4H, Ar–H), 7.29–7.34 (m, 10H, Ar–H). MS: m/z 303 (M+). N,N‐Dibenzyl‐4‐methylaniline (Table 3). IR (υmax in cm−1, KBr): 1572 (aromatic C=C str.), 2925 (C–H str.), 3017 (aromatic C–H str.). 1H NMR (CDCl3): δ 2.28 (s, 3H, CH3), 4.42 (s, 4H, 2 × CH2Ph), 6.89–6.97 (d, 2H, Ar–H), 7.08–7.18 (d, 2H, Ar–H), 7.29–7.46 (m, 10H, Ar–H). MS: m/z 287 (M+). N,N‐Dibenzyl‐4‐chloroaniline (Table 3). IR (υmax in cm−1, KBr): 743 (C–Cl str.), 1582 (aromatic C=C str.), 3030 (aromatic C–H str.), 3422 (N–H str.). 1H NMR (CDCl3): δ 4.13 (s, 4H, 2 × CH2Ph), 6.93–7.02 (d, 2H, Ar–H), 7.25–7.40 (m, 10H, Ar–H),
Manjulla Gupta et al. / Chinese Journal of Catalysis 35 (2014) 444–450
3.1. Characterization of SiO2‐Cu2O Prepared SiO2‐Cu2O was characterized by Fourier transform infrared (FTIR) spectroscopy, thermogravimetric analysis (TGA), X‐ray diffractometry (XRD), X‐ray photoelectron spec‐ troscopy (XPS), scanning electron microscopy (SEM), transmis‐ sion electron microscopy (TEM), and atomic absorption spec‐ troscopy (AAS). In the FTIR spectra, the activated silica showed absorption peaks at 459, 800, 964, 1344, 1384, 1400, 1598, 2341, 2362, 2856, and 2929 cm−1, and wide absorption bands were observed at 1078 and 3396 cm−1 (Fig. 1). For SiO2‐Cu2O, an additional peak observed at 669 cm−1 was attributed to Cu2O (Fig. 2). The stability of the SiO2‐Cu2O was determined by TGA (Fig. 3). The curve showed an initial weight loss up to 116 °C, which was attributed to the loss of residual water trapped onto the surface of the silica. This was followed by a slight weight loss up to 325 °C, which was considered to be caused by the loss of unreacted glucose or components of Fehling solution. Further continuous weight loss occurred up to 648 °C. This indicates that the catalyst is stable up to 325 °C and is safe to use in reac‐ tions at 100 °C. The XRD diffraction patterns for SiO2‐Cu2O showed peaks that were indexed on the basis of crystallographic data for the known structure of silica. In addition, reflection patterns were
0.6 0.5 0.4 0.3
1099.43 958.62 798.53 669.30 460.99
0.7
2362.80 2341.58
3396.64
0.8
1598.99 1400.32
2929.87 2856.58
0.9
0.2 3750
3250
2750 2250 1750 1250 Wavenumber (cm1)
750
Fig. 2. FTIR spectrum of SiO2‐Cu2O. 50
2 0 25.2 o C -0.7%
40 30 20 10
Heat flow (smoothed)
-2 dM-rel (%)
3. Results and discussion
1.0
Transmittance
7.48–7.57 (d, 2H, Ar–H). MS: m/z 307 (M+), 309 (M+2). N,N‐Dibenzyl‐3‐nitroaniline (Table 3). IR (υmax in cm−1, KBr): 860 (C–NO2 str.), 1530 (NO2 str.), 1585 (aromatic C=C str.), 3047 (aromatic C–H str.). 1H NMR (CDCl3): δ 4.33 (s, 4H, 2 × CH2Ph), 7.13–7.21 (m, 2H, Ar–H), 7.53–7.63 (m, 10H, Ar–H), 8.16–8.27 (m, 2H, Ar–H). MS: m/z 318 (M+). N‐Benzylmorpholine (Entry 1, Table 4). IR (υmax in cm−1, KBr): 1050 (C–O–C str.), 1340 (C–N str.), 1565 (C=C aromatic str.), 3070 (C–H symm. str.). 1H NMR (CDCl3): δ 2.43 (t, 4H, CH2), 4.92 (s, 2H, CH2Ph), 3.70 (t, 4H, CH2), 7.04–7.16 (m, 5H, Ar–H). MS: m/z 177 (M+). N‐Benzylpiperidine (Entry 2, Table 4). IR (υmax in cm−1, KBr): 1310 (C–N str.), 1560 (C=C aromatic str.), 3085 (C–H aromatic str.). 1H NMR (CDCl3): δ 1.40 (m, 6H, CH2), 2.24 (m, 4H, CH2), 4.90 (s, 2H, CH2Ph), 7.12–7.23 (m, 5H, Ar–H). MS: m/z 175 (M+).
Heat flow (smoothed) (mJ/s)
446
-4 -6 -8
0
-10
-10
-12
-20
-14
116.1 o C -7.8% dM-rel
325.5 o C -10.3% 471.1 o C -12.3% 648.9 o C -13.6%
100
200
300 400 Temperature (o C)
500
600
700
Fig. 3. TGA of SiO2‐Cu2O.
found corresponding to 2θ = 36.3° and 42.2°, which were at‐ tributed to Cu2O. The absence of a peak at 2θ = 38.7° excluded the possibility of CuO formation (Fig. 4). The oxidation state of copper in the SiO2‐Cu2O was deter‐ mined by measurements of binding energies using XPS. The spectrum of Cu 2p3/2 photoelectrons is shown in Fig. 5. The intense and broad peak at 933 eV corresponds to Cu(I) and is in accordance with the literature values [23,24]. The amount of copper loaded onto the silica surface was determined by AAS analysis. The catalyst was stirred in dilute HNO3 solution and then subjected to AAS analysis. The SiO2‐Cu2O contained 0.0158 g of copper per gram of catalyst. The microstructure and morphology of the SiO2‐Cu2O was studied by SEM and TEM. The SEM image revealed a fine ho‐
1.0
0.3 0.2 3750
3250
2750
2250
1250
1
Wavenumber (cm ) Fig. 1. FTIR spectrum of activated silica.
750
Intensity
1344.38 1750
459.00
0.4
1598.99 1400.32 1384.89
0.5
2929.87 2856.58
0.6
2362.80 2341.58
0.7
1078.21 964.41 800.46
0.8
3396.64
Transmittance
0.9
(111)
10
20
30
40
(200)
50
2/( ) o
Fig. 4. XRD pattern of SiO2‐Cu2O.
60
70
962.8
976
Cu 2p3/2
953.1
956.0 943.1
960 944 Binding energy (eV)
928
mogenous powder with a porous structure (Fig. 6). The TEM micrographs of the catalyst showed that copper was uniformly distributed on the surface of silica (Fig. 7). The mean particle diameter was found to be 7 nm. Furthermore, no bulk aggregation of the metal was observed, indicating that the copper was evenly dispersed onto the surface of the silica.
(b)
Fig. 6. SEM images of SiO2‐Cu2O. (a) 500; (b) 3500.
(a)
100 nm
(b)
6.67 nm 4.76 nm 10.3 nm
Solvent Yield a (%) Acetonitrile 90 Toluene b 60 Water 95 Reaction conditions: 4‐nitroaniline (0.069 g, 0.5 mmol), benzyl chloride (0.0635 g, 0.5 mmol), SiO2‐Cu2O (0.1 g, 2.5 mol% Cu), K2CO3 (0.069 g, 0.5 mmol), solvent (5 mL), 30 °C, 8 h, air atmosphere. a Based on separation by column chromatography. b Along with N‐benzyl‐4‐nitroaniline, N,N‐dibenzyl‐4‐nitroaniline was also formed together with unreacted amine.
3.2. Catalyst testing for selective N‐benzylation of primary and secondary amines
Fig. 5. XPS spectra of SiO2‐Cu2O.
(a)
The reaction conditions for selective mono N‐benzylation were optimized by using 4‐nitroaniline as the test substrate and benzyl chloride as the benzylating agent. The reaction was carried out under different conditions with respect to solvent, temperature, and molar ratios of SiO2‐Cu2O. After carrying out a series of reactions, 2.5 mol% of Cu in SiO2‐Cu2O was found to be sufficient to complete the reaction selectively and give maxi‐ mum yield of N‐benzyl‐4‐nitroaniline. Solvents of different polarities were also tried, and the results are presented in Ta‐ ble 1. The best results were obtained when water was used as solvent, with consideration to environmental impact, reaction time, yield, and selectivity. The reaction temperature also plays a crucial role in the N‐benzylation of anilines; therefore, the reaction of the test substrate was also conducted at different temperatures, and the yield of mono N‐benzyl‐4‐nitroaniline was determined (Table 2). For N,N‐dibenzylation, 4‐chloroaniline was selected as the test substrate, and benzyl chloride was used as the benzylating agent. At room temperature, no dibenzylated product was formed, so the reaction temperature was increased to 100 °C. The dibenzylated product formed as the major product with a small amount of mono benzylated product. Further addition of TBAB increased the amount of dibenzylated product. With 4‐toluidine, 2‐toluidine, 4‐chloroaniline, or 4‐bromoaniline as the substrates, the N,N‐dibenzylated product was formed ex‐ clusively. However, for 2‐chloroaniline and 2‐nitroaniline, only the N‐benzylated product was formed, and no N,N‐dibenzylated Table 2 Effect of temperature on the SiO2‐Cu2O catalyzed N‐benzylation of 4‐ nitroaniline in water.
5.76 nm
7.99 nm 4.70 nm
Yield a (%) Mono di 30 95 0 40 80 10 60 75 12 80 40 35 100 30 50 Reaction conditions: 4‐nitroaniline (0.069 g, 0.5 mmol), benzyl chloride (0.0635 g, 0.5 mmol), SiO2‐Cu2O (0.1 g, 2.5 mol% Cu), K2CO3 (0.069 g, 0.5 mmol), H2O (5 mL), 8 h, air atmosphere. a Based on separation by column chromatography. Temperature (°C)
5.27 nm
447
Table 1 Effect of solvent on the SiO2‐Cu2O catalyzed N‐benzylation of 4‐ nitroan‐ iline in water.
933.0
Cu 2p1/2
935.2
Manjulla Gupta et al. / Chinese Journal of Catalysis 35 (2014) 444–450
Intensity
5.30 nm 8.66 nm
4.25 nm
20 nm Fig. 7. TEM images of SiO2‐Cu2O.
448
Manjulla Gupta et al. / Chinese Journal of Catalysis 35 (2014) 444–450
Table 3 SiO2‐Cu2O catalyzed selective N‐benzylation and N,N‐dibenzylation of anilines in water. N‐Benzylation of anilines a N,N‐Dibenzylation of anilines b Yield c (%) Yield c (%) Time (h) MP or BP/Ref. (°C) Time (h) MP or BP/Ref. (°C) Amine/Mono/Di Di/Mono 1 3‐Anisidine 40/50/0 5 Liq/183–187 [25] 80/14 17 55–56/56 [32] 2 2‐Anisidine 15/78/0 1.5 Oil/oil [26] — — — 97/0 10 62–63/63–64 [33] 3 4‐Toluidine 15/75/5 4 243–245/244–245 [27] 4 3‐Toluidine 15/55/10 15 166–168/160–170 [28] 82/11 17 74–75/75–76 [34] 5 2‐Toluidine — — — 97/0 9 42–43/42 [35] 6 4‐Fluoroaniline 0/60/30 4 36–38/38–39 [29] — — — 7 4‐Chloroaniline 0/80/10 3 46–47/46–48 [30] 96/0 11 104–106/104–105 [36] 8 2‐Chloroaniline d 20/75/0 12 38–40/38–39 [26] 0/96 1.5 38–39/38–39 [31] 93/0 16 124–125/124–126 [37] 9 4‐Bromoaniline 10/82/0 0.75 50–51/51–52 [30] 10 4‐Nitroaniline 0/95/0 8 73–74/72–74 [31] 65/20 17 86–87/84–86 [32] 11 3‐Nitroaniline 20/70/0 10 104–106/106–107 [29] 80/10 16 73–75/73–74 [38] 12 2‐Nitroaniline — — — 0/95 18 65–66/66–67 [39] a Reaction conditions: amine (0.5 mmol), benzyl chloride (0.0635 g, 0.5 mmol), SiO2‐Cu2O (0.1 g, 2.5 mol% Cu), K2CO3 (0.069 g, 0.5 mmol), H2O (5 mL), 30 °C. b Reaction conditions: amine (0.5 mmol), benzyl chloride (0.254 g, 2 mmol), TBAB (0.082 g, 0.25 mmol), K2CO3 (0.139 g, 1 mmol), SiO2‐Cu2O (0.2 g, 5 mol % Cu), water (5 mL), 100 °C. c Isolated yield based on separation through column chromatography or crystallization. d Benzyl chloride (0.127 g, 1 mmol) was used for for N,N‐dibenzylation of anilines. Entry
Amine
product was observed. For N‐benzylation of secondary amines, morpholine was used as the test substrate and benzyl chloride as the benzylating agent. After carrying out a series of reac‐ tions, 5 mol% of Cu in SiO2‐Cu2O was found to be sufficient to achieve good yields. Being benign and environmentally friend‐ ly, water was used as the solvent. Furthermore, the addition of base was found to have a profound effect on the rate of the reaction. Various bases were screened for the test reaction, and K2CO3 was selected because of its wide availability and low cost. A reaction temperature of 100 °C was found to be the op‐ timum reaction temperature. Addition of TBAB as phase trans‐ fer catalyst was also found to enhance the reaction rate. To study the generality of the developed protocol for mono N‐benzylation and N,N‐dibenzylation, various anilines substi‐ tuted with electron‐withdrawing and electron‐releasing groups were chosen. The results are presented in Table 3. For N‐benzylation of secondary amines, various secondary amines were chosen and products were obtained in almost quantita‐ tive yields (Table 4). To confirm the role of the catalyst for N‐benzylation of primary and secondary amines, the test reac‐ tion was also carried out with the test substrate in the absence Table 4 SiO2‐Cu2O catalyzed N‐benzylation of secondary amines in water at 100 °C. Entry Amine Time (h) Yield a (%) MP/Ref. (°C) 1 Morpholine 0.5 93 194–195/194 [40] 2 Piperidine 0.5 90 182–183/181–182 [41] 3 Diphenylamine b 12 80 85–87/86–87 [42] 4 Imidazole c 12 80 70–72/71–73 [43] Reaction conditions: amine (0.5 mmol), benzyl chloride (0.127 g, 1 mmol), K2CO3 (0.139 g, 1 mmol), TBAB (0.082 g, 0.25 mmol), SiO2‐Cu2O (0.2 g, 5 mol% Cu), water (5 mL), 100 °C. a Isolated yield. b Rest being the starting material. c Product was obtained after passing through column of silica gel and elution with ethyl acetate/petroleum ether.
of catalyst. The reaction was observed to proceed very slowly in the absence of catalyst, confirming the catalytic effect of SiO2‐Cu2O. The mechanism for the N‐benzylation of amines catalyzed by SiO2‐Cu2O is considered to proceed through a recyclable coordination process via oxidative addition followed by reduc‐ tive elimination (Scheme 4). First, the oxidative addition of amine to copper is thought to occur in the presence of base to give a copper complex (I), followed by the addition of benzyl chloride to form the second intermediate (II). Intermediate II then undergoes reductive elimination to give the product. 3.3. Recyclability of SiO2‐Cu2O for N‐benzylation of amines In the use of heterogeneous catalysts, the recyclability of the catalyst is an important factor. To determine the recyclability, a NH2 PhH2C
+ Base
SiO2-Cu(I)
NH
R Base-H
R
SiO2-Cu CH2Ph NH
II
SiO2-Cu NH
R R I Cl-
PhCH2Cl
Scheme 4. Proposed mechanism for N‐benzylation of amines using SiO2‐Cu2O.
Manjulla Gupta et al. / Chinese Journal of Catalysis 35 (2014) 444–450
60
the selective mono N‐benzylation and N,N‐dibenzylation of primary aromatic amines. The catalytic system has also been used for the N‐benzylation of secondary amines. The environ‐ mentally friendly nature of the reaction is underscored by the use of water as the reaction solvent.
40
Acknowledgements
20
We are grateful to Director, SAIF, Punjab University, Chandigarh for SEM, TEM, and XRD and also extend our sincere thanks to UGC, New Delhi for financial support to purchase FTIR; awarding Major Research Project (F 41‐281/2012 (SR)), and Prof. R. K. Bamezai, Department of Chemistry, University of Jammu for recording TGA.
Primary amine
100
Secondary amine
80 Yield (%)
449
0 1
2
3 Run
4
5
Fig. 8. Recyclability of SiO2‐Cu2O. Reaction conditions for primary amine: 2‐chloroaniline (0.5 mmol), benzyl chloride (0.127 g, 1 mmol), TBAB (0.082 g, 0.25 mmol), K2CO3 (0.139 g, 1 mmol), SiO2‐Cu2O (0.2 g, 5 mol% Cu), water (5 mL), 100 °C. Reaction conditions for secondary amine: morpholine (0.5 mmol), benzyl chloride (0.127 g, 1 mmol), K2CO3 (0.139 g, 1 mmol), TBAB (0.082 g, 0.25 mmol), SiO2‐Cu2O (0.2 g, 5 mol% Cu), water (5 mL), 100 °C.
(a)
References [1] [2] [3] [4]
(b)
[5] [6] [7] [8] [9] [10] [11]
Fig. 9. (a) Freshly prepared SiO2‐Cu2O; (b) SiO2‐Cu2O after 5th use.
series of five consecutive runs were carried out (reactions of entry 8, Table 3 and entry 1, Table 4). Almost no change was observed in the catalyst activity after the fifth use (Fig. 8). The catalyst after fifth use showed the presence of Cu(II), as indicated by magnetic moment measurements. A comparison of the fresh catalyst and that after a fifth use is shown in Fig. 9.
[12] [13] [14] [15]
4. Conclusions
[16] [17] [18] [19]
We have prepared an efficient and recyclable silica‐ sup‐ ported copper(I) oxide catalyst and studied its application for
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Graphical Abstract Chin. J. Catal., 2014, 35: 444–450 doi: 10.1016/S1872‐2067(14)60009‐7 Glucose Solution
SiO2‐Cu2O: An efficient and recyclable heterogeneous catalyst for N‐benzylation of primary and secondary amines Manjulla Gupta, Satya Paul *, Rajive Gupta University of Jammu, India Silica‐supported Cu2O was prepared in situ using inexpensive and widely available starting materials and used as a catalyst for N‐benzylation and N,N‐dibenzylation of primary and secondary amines.
Fehling Solution
Cu2O
SiO2-Cu2O
SILICA C6H5
N
C6H5
C6H5 +
NH
(1) C6H 5CH 2Cl (2) K 2CO 3
NH2
450
Manjulla Gupta et al. / Chinese Journal of Catalysis 35 (2014) 444–450
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