Please wait a minute...
 
最新公告: 重要提醒:骗子冒充编辑部要求加作者微信,谨防上当!   关于暑假、寒假期间版面费发票及期刊样刊延迟邮寄的通知    
现代化工  2022, Vol. 42 Issue (S2): 71-75    DOI: 10.16606/j.cnki.issn0253-4320.2022.S2.017
  科研与开发 本期目录 | 过刊浏览 | 高级检索 |
单取代三苯基膦配体在催化氢甲酰化中的应用
卢锦龙1,2, 李存耀3, 余林1, 汪文龙2
1. 广东工业大学轻工化工学院, 广东 广州 510006;
2. 东莞理工学院材料科学与工程学院, 广东 东莞 523808;
3. 中国科学院大连化学物理研究所化石能源与应用催化研究部, 辽宁 大连 116023
Application of monosubstituted triphenylphosphine ligands in catalytic hydroformylation
LU Jin-long1,2, LI Cun-yao3, YU Lin1, WANG Wen-long2
1. School of Chemical Engineering and Light Industry, Guangdong University of Technology, Guangzhou 510006, China;
2. School of Materials Science and Engineering, Dongguan University of Technology, Dongguan 523808, China;
3. Division of Fossil Energy Conversion, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China
下载:  PDF (1844KB) 
输出:  BibTeX | EndNote (RIS)      
摘要 考察了不同取代基团在三苯基膦(PPh3)中一个苯环的邻位或者对位上进行单取代后配体的1-己烯氢甲酰化反应性能。结果表明,邻位基团会显著增强膦配体的位阻效应,一方面大概率弱化了催化活性,另一方面则提升了氢甲酰化产物醛的区域选择性;对位取代的基团在不影响活性的基础上会大概率对配体的化学选择性(主产物醛的选择性)有正向的提升。综合评价表明,最好的配体是对位醛基单取代的PPh3配体,转化率为99%,醛选择性高达80%,正异比达到2.48,对位基团的存在优化了配体的电子和空间性质。
服务
把本文推荐给朋友
加入引用管理器
E-mail Alert
RSS
作者相关文章
卢锦龙
李存耀
余林
汪文龙
关键词:  三苯基膦  氢甲酰化  位阻效应  电子效应  化学选择性  区域选择性    
Abstract: The performance of the 1-hexene hydroformylation reaction is investigated over the ligands that are formed through monosubstitution of different substituent groups at the ortho or para position of one of the benzene rings of triphenylphosphine.The results show that ortho-substituted group significantly enhances the steric effect of phosphine ligand,which on the one hand weakens the catalytic activity and on the other hand enhances the regioselectivity of the hydroformylation product aldehyde.Para-substituted group positively enhances the chemoselectivity of the ligand (selectivity of main product aldehyde) without affecting the activity.It is identified through overall evaluation that the best ligand is the triphenylphosphine ligand with monosubstituted aldehyde group at the para position,which leads to a 99% of conversion,an 80% of aldehyde selectivity and a 2.48 ratio of linear to branch.It is believed that the presence of group at para position optimizes the electronic and steric properties of the ligand.
Key words:  triphenylphosphine    hydroformylation    steric effect    electronic effect    chemical selectivity    regioselectivity
收稿日期:  2022-03-23      修回日期:  2022-06-01          
ZTFLH:  TQ224  
基金资助: 国家自然科学基金项目(21972018,22002152)
通讯作者:  汪文龙(1985-),男,博士,研究员,研究方向为金属有机催化,通讯联系人,wangwl@dgut.edu.cn    E-mail:  wangwl@dgut.edu.cn
作者简介:  卢锦龙(1997-),男,硕士生,研究方向为有机催化,ljl06168@126.com
引用本文:    
卢锦龙, 李存耀, 余林, 汪文龙. 单取代三苯基膦配体在催化氢甲酰化中的应用[J]. 现代化工, 2022, 42(S2): 71-75.
LU Jin-long, LI Cun-yao, YU Lin, WANG Wen-long. Application of monosubstituted triphenylphosphine ligands in catalytic hydroformylation. Modern Chemical Industry, 2022, 42(S2): 71-75.
链接本文:  
https://www.xdhg.com.cn/CN/10.16606/j.cnki.issn0253-4320.2022.S2.017  或          https://www.xdhg.com.cn/CN/Y2022/V42/IS2/71
[1] Franke R,Selent D,B erner A.Applied hydroformylation[J].Chem Rev,2012,112:5675-5732.
[2] Bohnen H W,Cornils B.Hydroformylation of alkenes:An industrial view of the status and importance[J].Adv Catal,2002,47:1-64.
[3] Zapirtan V I,Mojet B L,Van Ommen J G,et al.Gas phase hydroformylation of ethylene using organometallic Rh-complexes as heterogeneous catalysts[J].Catal Lett,2005,101:43-47.
[4] Hebrard F,Kalck P.Cobalt-catalyzed hydroformylation of alkenes:Generation and recycling of the carbonyl species,and catalytic cycle[J].Chem Rev,2009,109:4272-4282.
[5] Osborn J A,Wilkinson G.Tris (triphenylphosphine) halorhodium (I)[J].Inorg Synth,1967,10:67-71.
[6] Sharma S K,Jasra R V.Aqueous phase catalytic hydroformylation reactions of alkenes[J].Catal Today,2005,101:43-47.
[7] Jiang M,Yan L,Ding Y J,et al.Ultrastable 3V-PPh3 polymers supported single Rh sites for fixed-bed hydroformylation of olefins[J].J Mol Catal A-Chem,2015,404:211-217.
[8] Li C,Yan L,Lu L,et al.Single atom dispersed Rh-biphephos&PPh3@porous organic copolymers:Highly efficient catalysts for continuous fixed-bed hydroformylation of propene[J].Green Chem,2016,18:2995-3005.
[9] Wang W,Li C,Zhang H,et al.Enhancing the activity,selectivity,and recyclability of Rh/PPh3 system-catalyzed hydroformylation reactions through the development of a PPh3-derived quasi-porous organic cage as a ligand[J].Chin J Catal,2021,42:1216-1226.
[10] Tolman C A.Steric effects of phosphorus ligands in organometallic chemistry and homogeneous catalysis[J].Chem Rev,1977,77:313-348.
[11] Tolman C A.Phosphorus ligand exchange equilibriums on zerovalent nickel.Dominant role for steric effects[J].J Am Chem Soc,1970,92:2956-2965.
[12] Kühl O.Predicting the net donating ability of phosphines-Do we need sophisticated theoretical methods?[J].Coord Chem Rev,2005,249:693-704.
[13] Diebolt O,Tricas H,Freixa Z,et al.Strong π-acceptor ligands in rhodium-catalyzed hydroformylation of ethene and 1-octene:Operando catalysis[J].ACS Catal,2013,3:128-137.
[14] Carmona D,Lamata M P,Pardo P,et al.Arene-ruthenium chemistry and Brønsted acid catalysis of a chiral phosphane-hydroxyl ligand[J].Organometallics,2014,33:616-619.
[15] Evans D,Yagupsky G,Wilkinson G.The reaction of hydridocarbonyltris (triphenylphosphine) rhodium with carbon monoxide,and of the reaction products,hydridodicarbonylbis (triphenylphosphine) rhodium and dimeric species,with hydrogen[J].J Chem Soc A,1968,2660-2665.
[16] Brown C K,Wilkinson G.Homogeneous hydroformylation of alkenes with hydridocarbonyltris (triphenylphosphine) rhodium (I) as catalyst[J].J Chem Soc A,1970,2753-2764.
[17] 李存耀.含P多孔有机聚合物自负载型催化剂的合成及其在烯烃氢甲酰化和CO2转化中的应用[D].北京:中国科学院大学大连化学物理研究所,2016.
[18] 李升平,刘金尧,刘殿求.铑膦络合物催化丙烯氢甲酰化反应的研究[J].天然气化工,1988,(5):15-21.
[19] 浙江微通催化新材料有限公司.一种基于氢气还原合成羧酸铑二聚体的方法:CN 20211108396.X[P].2021-12-21.
[20] 丁成.含羧酸配体的配位化合物的合成、结构与性能研究[D].哈尔滨:哈尔滨工业大学,2016.
[1] 雷帅, 王兴永, 傅送保, 张卉. 国产新型配体的氢甲酰化催化性能研究[J]. 现代化工, 2022, 42(3): 189-192,198.
[2] 高照华, 宋华兴, 颜晓瑞, 魏海生, 王文华, 任万忠. 不同金属改性剂对Rh/FePO4催化剂氢甲酰化性能的影响[J]. 现代化工, 2022, 42(2): 136-141.
[3] 何璇, 贺友, 赵明, 孙環, 张谦温, 孙锦昌. 烯烃氢甲酰化研究进展[J]. 现代化工, 2022, 42(1): 80-84.
[4] 田敬浩, 魏海生, 王文华, 陈乐乐, 任万忠. MOF衍生Rh/ZrO2@C催化剂的制备及氢甲酰化性能研究[J]. 现代化工, 2019, 39(5): 119-122.
[5] 胡嵩霜, 郑明芳. 铑催化剂在1-辛烯氢甲酰化反应中的应用[J]. 现代化工, 2018, 38(7): 172-175.
[6] 刘倩, 刘伯潭. 新型Rh-Ni@MOF-5催化剂催化烯烃氢甲酰化反应的研究[J]. 现代化工, 2017, 37(5): 71-75.
[7] 曾群英,白玉洁,孟锐,杨春基,肖海成. 一步法制备丙烯氢甲酰化制丁醛铑膦络合催化剂研究[J]. , 2011, 31(11): 0-0.
[8] 赵宙兴,李政. 1,1,3,3-四溴-2-(4-氯苯基)-丙烯的合成研究[J]. , 2010, 30(9): 0-0.
[9] 王淑波,王利生. 三苯基膦及其衍生物的合成及应用[J]. , 2006, 26(6): 0-0.
[10] 谭波,蒋景阳,金子林. 羰基合成高碳醇工艺研究进展[J]. , 2006, 26(1): 0-0.
[11] 王俐. 国外工业氢甲酰化的现状和发展[J]. , 2002, 22(8): 0-0.
No Suggested Reading articles found!
Viewed
Full text


Abstract

Cited

  Shared   
  Discussed   
京ICP备09035943号-37
版权所有 © 《现代化工》编辑部
本系统由北京玛格泰克科技发展有限公司设计开发 技术支持:support@magtech.com.cn