摘要
室温下,以0.3 mmol苄基醇(1-苯基乙醇,Ⅰa)为反应底物、空气中的氧气为氧化剂、FeCl_(3)为光催化剂,光诱导催化合成苯乙酮。考察了不同催化剂及用量、反应溶剂、光源(10 W)波长和反应时间对苯乙酮(Ⅱa)产率的影响,探究了在最佳反应条件下制备醛、酮类化合物的底物适用性。产物经^(1)HNMR和^(13)CNMR确认。对反应机理进行了推测。结果表明,在以FeCl_(3)为催化剂(用量为Ⅰa物质的量的10%)、1 mL乙腈为溶剂、400 nm波长光源(10 W)照射12 h的最佳反应条件下,Ⅱa的产率为88%。该反应条件适用于其他8种醛、酮类化合物(二苯甲酮、苯甲醛、对甲基苯甲醛、对羟基苯甲醛、2-氨基苯甲醛、1-萘甲醛、2-吡啶甲醛、2-噻吩甲醛)的合成,产率为16%~76%。芳环取代基上的电子效应对反应有重要影响,Fe(Ⅲ)催化剂(FeCl_(3))和光照是苄基醇氧化合成醛、酮类化合物的必要条件,苄基醇与Fe(Ⅲ)进行配位形成的配合物在光照条件下发生配体到金属电荷转移的活化过程是反应的关键。
Acetophenone was synthesized through photo induced catalysis at room temperature using 0.3 mmol benzyl alcohol(1-phenylethanol,Ⅰa)as substrate,oxygen in the air as oxidant and FeCl_(3) as photocatalyst.The effects of catalyst type as well as dosage,reaction solvent,light source wavelength(10 W)and reaction time on the yield of acetophenone(Ⅱa)were analyzed.The suitability of substrates for preparation of aldehydes and ketones under the optimal reaction conditions was evaluated,with the product confirmed by ^(1)HNMR as well as ^(13)CNMR,and the reaction mechanism was speculated.The results showed that under the optimal conditions of FeCl_(3) as catalyst(10%of the amount of substance ofⅠa),1 mL acetonitrile as solvent and irradiation with 400 nm wavelength light source(10 W)for 12 h,the yield of productⅡa was 88%.This reaction condition was suitable for the synthesis of other 8 aldehydes and ketones(benzophenone,benzaldehyde,p-methylbenzaldehyde,p-hydroxybenzaldehyde,2-aminobenzaldehyde,1-naphthalene formaldehyde,2-pyridinaldehyde,2-thiophenaldehyde),and the yields were ranging 16%~76%.Fe(Ⅲ)catalyst(FeCl_(3))and light were the necessary conditions for the synthesis of aldehydes and ketones by oxidation of benzyl alcohols.The activation process of ligand to metal charge transfer of the complexes formed by the coordination of benzyl alcohols and Fe(Ⅲ)under light irradiation was the key to the reaction.
作者
徐文耀
杨士磊
于晓强
石文华
XU Wenyao;YANG Shilei;YU Xiaoqiang;SHI Wenhua(State Key Laboratory of Fine Chemicals,Dalian University of Technology,Dalian 116023,Liaoning,China;Guangdong Nantian Institute of Forensic Science,Shenzhen 518026,Guangdong,China)
出处
《精细化工》
北大核心
2025年第3期692-696,共5页
Fine Chemicals
基金
国家自然科学基金项目(22271039)
中央高校基本科研业务费专项资金项目(DUT23LAB611)
国家重点研发计划项目(2022YFB3806500)。
关键词
空气
光催化
铁催化
醇氧化
绿色合成
精细化工中间体
air
photocatalysis
iron catalysts
oxidation of alcohols
green synthesis
fine chemical intermediates
