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可见光催化二氧化碳参与非活化烯烃1,3-双羧基化反应
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作者 肖汉至 于博 +6 位作者 颜思顺 章炜 李茜茜 鲍莹 罗书平 叶剑衡 余达刚 《Chinese Journal of Catalysis》 SCIE EI CAS CSCD 2023年第7期222-228,共7页
二氧化碳(CO_(2))具有储量丰富、廉价易得、无毒可再生的特点,是一种理想的碳一合成子.在CO_(2)参与的众多转化中,合成应用广泛、易于衍生的羧酸化学品具有较高的研究价值.其中,有机二元羧酸是一种重要的化学品,广泛应用于材料加工、有... 二氧化碳(CO_(2))具有储量丰富、廉价易得、无毒可再生的特点,是一种理想的碳一合成子.在CO_(2)参与的众多转化中,合成应用广泛、易于衍生的羧酸化学品具有较高的研究价值.其中,有机二元羧酸是一种重要的化学品,广泛应用于材料加工、有机合成和生物医药等领域.尽管目前CO_(2)参与的单羧基化反应研究取得了较大进展,但CO_(2)参与构建的区域选择性二羧基化反应方法仍然亟待发展.近年来,可见光化学因其具有绿色温和、官能团兼容性较好等特点已成为利用CO_(2)构建二羧基化反应的有力策略.目前虽已发展了不同策略实现了烯烃1,1-, 1,2-, 1,6-和1,7-双羧基化等不同的区域选择性,但现有策略还未能完成烯烃1,3-双羧基化的区域选择性.另外,现有策略仅能构建两个C–C键.本文利用可见光催化策略,基于1,2-芳基迁移过程,在温和条件下实现了CO_(2)参与非活化烯烃1,3-双羧基化反应,实现了双羧基化领域尚未实现的区域选择性.反应过程涉及一个C–C单键断裂和三个C–C单键形成,可合成一系列新型戊二酸类产物,并且产物易于衍生为杂环结构.一系列给电子、吸电子取代基以及杂芳环取代基均能兼容于反应体系.机理实验结果表明,反应中可原位产生二氧化碳自由基阴离子(CO_(2)^(-)),随后经历自由基加成、1,2-芳基迁移、单电子还原和亲核进攻CO_(2)等过程产生二元羧酸产物.综上,本文为可见光催化CO_(2)参与二羧基化反应方法提供了重要的区域选择性补充,并可同时构建多个C–C键,具有应用前景. 展开更多
关键词 二氧化碳 可见光催化 1 3-双羧基化 活化烯烃 1 2-芳基迁移
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辅酶NADH模型物BNAH与活化烯烃在氧气饱和混合溶剂中的反应机理研究
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作者 王珏玉 冯乙巳 《安徽化工》 CAS 2011年第4期34-35,38,共3页
在氧气饱和的混合溶剂中,随着反应时间的延长,在辅酶NADH模型物BNAH与活化烯烃的反应中,氧化产物与还原产物的比例逐渐变小,但总产率越来越大。
关键词 辅酶NADH模型物 活化烯烃 混合溶剂 反应机理
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自由基介导的未活化烯烃的官能团向远端迁移反应研究进展
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作者 秦一洲 《有机化学研究》 2022年第1期1-17,共17页
自由基介导的烯烃1,2-双官能化大大拓展了烯烃的应用范围,近年来已成为热门研究领域。通常,烯烃的应用范围主要局限于活化的烯烃。然而,一类用于未活化的烯烃的官能化的通用策略已经开发出来。本文总结了分子内官能团向远端迁移的策略... 自由基介导的烯烃1,2-双官能化大大拓展了烯烃的应用范围,近年来已成为热门研究领域。通常,烯烃的应用范围主要局限于活化的烯烃。然而,一类用于未活化的烯烃的官能化的通用策略已经开发出来。本文总结了分子内官能团向远端迁移的策略的最新进展,该策略已经有效地应用于自由基介导的未活化烯烃的双官能化,包括芳基,氰基,杂芳基,亚氨基,羰基,炔基和烯基在内的官能团。 展开更多
关键词 自由基 活化烯烃 官能团远程迁移
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可见光诱导的二氧化碳对活化烯烃的脱碳羧基化反应
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作者 段东森 马媛 +3 位作者 刘宇博 程富 朱道勇 王少华 《有机化学》 SCIE CAS CSCD 北大核心 2024年第5期1675-1685,共11页
报道了一种高效的可见光促进的活化烯烃脱碳羧化的方法,与传统的烯烃羧化相比,该方法条件温和,收率最高可达96%,对多种官能团具有很好的兼容性,为芳基乙酸的合成及后续转化提供了新方法.机理研究表明,该反应是通过对烯烃碳碳双键的置换... 报道了一种高效的可见光促进的活化烯烃脱碳羧化的方法,与传统的烯烃羧化相比,该方法条件温和,收率最高可达96%,对多种官能团具有很好的兼容性,为芳基乙酸的合成及后续转化提供了新方法.机理研究表明,该反应是通过对烯烃碳碳双键的置换,实现了表观碳数不变的对应羧酸的合成. 展开更多
关键词 可见光诱导 二氧化碳 活化烯烃 羧基化反应
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无金属催化非活化烯烃的多氯甲基化/芳基化自由基反应合成含多氯甲基吲哚啉(英文) 被引量:3
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作者 李文兰 孙一茼 +4 位作者 姚永超 许颖 李鹏 刘颖杰 梁德强 《有机化学》 SCIE CAS CSCD 北大核心 2019年第6期1727-1734,共8页
N-烯丙基芳胺在非金属催化条件下,发生多氯甲基化/环化串联反应生成多氯甲基取代的吲哚啉.该反应以非活化的烯烃为自由基受体,过氧化二异丙苯(DCP)为引发剂,廉价的二氯甲烷、氯仿、四氯化碳溶剂作为二氯甲基化或三氯甲基化试剂,且具有... N-烯丙基芳胺在非金属催化条件下,发生多氯甲基化/环化串联反应生成多氯甲基取代的吲哚啉.该反应以非活化的烯烃为自由基受体,过氧化二异丙苯(DCP)为引发剂,廉价的二氯甲烷、氯仿、四氯化碳溶剂作为二氯甲基化或三氯甲基化试剂,且具有操作简单、条件温和、成本低、底物适用范围广等优点. 展开更多
关键词 活化烯烃 多氯甲基化 吲哚啉 自由基反应
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Methanol-to-olefin induction reaction over SAPO-34 被引量:4
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作者 You Zhou Liang Qi +3 位作者 Yingxu Wei Cuiyu Yuan Mozhi Zhang Zhongmin Liu 《Chinese Journal of Catalysis》 SCIE EI CAS CSCD 北大核心 2016年第9期1496-1501,共6页
The methanol-to-olefin induction reaction over the SAPO-34 was performed using a fluidized-bed system.We found that the whole induction period could be divided into three reaction stages.Further investigation of the r... The methanol-to-olefin induction reaction over the SAPO-34 was performed using a fluidized-bed system.We found that the whole induction period could be divided into three reaction stages.Further investigation of the reaction kinetics revealed that this induction reaction behavior was different from that over H-ZSM-5 catalyst.Compared with the H-ZSM-5,the generation of initial active centers is easier over SAPO-34 because of its limited diffusivity and the spatial confinement effect of the cages.However,the autocatalysis reaction stage is difficult over SAPO-34 because of the continuous formation of inactive methyladamantanes. 展开更多
关键词 METHANOL-TO-OLEFIN Activation energy SAPO-34 Hydrocarbon pool Induction period
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Effect of Aminoaromatic Acids as Additives on the Activity and Selectivity of the Platinum-catalyzed Hydrosilylation of Alkenes 被引量:1
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作者 白赢 彭家建 +3 位作者 胡应乾 厉嘉云 邱化玉 来国桥 《Chinese Journal of Chemical Engineering》 SCIE EI CAS CSCD 2009年第6期1038-1042,共5页
A series of aromatic acids has been tested as additives for the platinum-catalyzed hydrosilylation of styrene with triethoxysilane. Both excellent conversion of styrene and selectivity in favor of the ,β-adduct were ... A series of aromatic acids has been tested as additives for the platinum-catalyzed hydrosilylation of styrene with triethoxysilane. Both excellent conversion of styrene and selectivity in favor of the ,β-adduct were achieved using aminobenzoic acids as additive. Moreover, the use of 4-aminobenzoic acid led to significantly superior enhancement in both catalytic activity and selectivity among the tested aminobenzoic acids. Indeed, 100% conversion of styrene and 98.4% selectivity in favor of the β-adduct were obtained. Additionally, hydrosilylations of various alkenes with a variety of platinum catalysts have also been tested, and in each case the conversion of substrate and the selectivity of the β-adduct were promoted by using 4-aminobenzoic acid as additive. 展开更多
关键词 HYDROSILYLATION platinum catalyst aminoaromatic acid additive
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Development and CommercialApplication of RSDS-II Technology for Selective Hydrodesulfurization of FCC Naphtha 被引量:6
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作者 Qu Jinhua Xi Yuanbing +4 位作者 Li Mingfeng Pan Guangcheng Jin Xin Gao Xiaodong Nie Hong 《China Petroleum Processing & Petrochemical Technology》 SCIE CAS 2013年第3期1-6,共6页
The FCC naphtha selective hydrodesulfurization technology(RSDS-II)has been tested with different feedstocks in pilot scale.The results show that RSDS-II technology is viable in terms of its adaptability to different f... The FCC naphtha selective hydrodesulfurization technology(RSDS-II)has been tested with different feedstocks in pilot scale.The results show that RSDS-II technology is viable in terms of its adaptability to different feedstocks.To produce gasoline with a sulfur content of less than 50μg/g by the RSDS-II technology,the gasoline RON loss is less than 1.8,0.9and 0.2 units,respectively,upon processing the conventional high-sulfur and high-olefin FCC naphtha,the high-sulfur MIP naphtha,and the medium-sulfur or low-sulfur MIP naphtha.Upon using the naphtha produced from pre-hydrotreated FCC feedstock as the RSDS-II feedstock to manufacture gasoline with a sulfur content of lower than 10μg/g,the RON loss does not exceed 1.0 unit.The RSDS-II technology has been commercialized successfully at many refineries.The result of operating commercial RSDS-II unit at the Shanghai Petrochemical Company has revealed that upon processing a feedstock containing 38.7 v% —43.3 v% of olefins and 250—470 mg/g of sulfur,the sulfur content in the treated gasoline ranges from 33μg/g to 46μg/g and the RON loss is equal to only 0.3—0.6 units.Till now this RSDS-II unit has been operating smoothly over 30 months.Thanks to its high HDS activity and good selectivity,the RSDS-II technology can meet the refinery’s needs for adequate upgrading of gasoline. 展开更多
关键词 FCC naphtha selective HYDRODESULFURIZATION commercial application
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Conversion of n-Pentanol and n-Butanol over Cu/AC Catalyst
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作者 Falah Iip Izul Triyono Triyono 《Journal of Chemistry and Chemical Engineering》 2010年第6期22-28,共7页
It is already well known that availability of petroleum oil, as a world energy source, is running low. Much work has been done by experts to produce renewable energy, especially using vegetable oil as a raw material. ... It is already well known that availability of petroleum oil, as a world energy source, is running low. Much work has been done by experts to produce renewable energy, especially using vegetable oil as a raw material. Accordingly, this paper presents preparation and activity test of Cu catalyst using coconut shell activated carbon (AC) as a support, for conversion of n-pentanol and n-butanol to their alkenes as the first step of conversion of ethanol to biogasoline. This conversion is interesting due to any agriculture product containing sugar or starch can be converted to ethanol. Activated carbon was used as a catalyst support because this material is inert; hence, it would not yield unexpected side product, and pollution of environment with the used catalyst can be prevented because the used catalytic metal can easily be recovered. Results of the work showed that coconut shell carbon contained some metals, which disturbed in preparation catalyst by cation exchange process. Washing the carbon with ammonium acetate or HCI solution could reduce the metals content more compared to using water, with optimum concentration for ammonium acetate solution was 1.25 M. Application of Cu/AC in converting n-pentanol and n-butanol, based on qualitative analysis to the products using GLC, GC-MS, and FTIR, when n-pentanol and nitrogen gas were flowed into a reactor filled with Cu/AC catalyst, it could be converted to n-pentene with 200 ℃ as the optimal temperature. While when n-butanol and nitrogen gas were flowed into a reactor filled with more Cu/AC catalyst, the product was supposed to contain its aldehyde and butyl vinyl ether. 展开更多
关键词 CATALYST Cu/AC n-pentanol N-BUTANOL conversion.
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基于(—)-Sparteine的不对称碳锂化反应研究进展 被引量:1
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作者 田丽霞 杜文斌 +1 位作者 张扬 唐寿初 《有机化学》 SCIE CAS CSCD 北大核心 2014年第3期507-514,共8页
以非活化烯烃为底物,利用(-)-sparteine诱导的分子间-分子内不对称碳锂化反应构建高区域选择性和立体选择性的碳碳新键,合成了一系列手性化合物.综述了近十几年基于(-)-sparteine的不对称碳锂化反应最新研究成果.
关键词 活化烯烃 分子间分子内 (-)-sparteine 对映选择性 碳锂化反应
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Enantioselective epoxidation of nonfunctionalized alkenes catalyzed by recyclable new homochiral bis-diamine-bridged bi-Mn(salen) complexes
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作者 HUANG XueMei FU XiangKai +2 位作者 JIA ZiYong MIAO Qiang WANG GuoMing 《Science China Chemistry》 SCIE EI CAS 2013年第5期604-611,共8页
Three new homochiral bis-diamine-bridged bi-Mn(salen) complexes were synthesized. Their catalysis on asymmetric epoxidation of a-methylstyrene, styrene and indene was studied with NaC10 and m-CPBA as oxidants respec... Three new homochiral bis-diamine-bridged bi-Mn(salen) complexes were synthesized. Their catalysis on asymmetric epoxidation of a-methylstyrene, styrene and indene was studied with NaC10 and m-CPBA as oxidants respectively. This homogeneous catalyst exhibited comparable catalytic activity and enantioselectivity to the Jacobsen's catalyst in the asymmetric epoxidation of unfunctionalized olefins. Furthermore, the catalyst could be conveniently recovered and reused at least five times without significant losses of both activity and enantioselectivity. Specially, it also could be efficiently used in large-scale reactions with superior catalytic disposition being maintained at the same level, which provided the potential for the applications in industry. The effect of axial bases, temperature and solvent on activity and enantioselectivity of the catalytic system were also studied. 展开更多
关键词 homochiral bi-Mn(salen) complex ENANTIOSELECTIVE asymmetric epoxidation unfunctionalized olefins
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