Co⁃NC⁃900 Catalyzed Oxidation of Alkenes Synthesis of Esters via Unsaturated C=C Cleavage

doi:10.12422/j.issn.1006-396X.2023.04.006

Abstract

Abstract:

A new method for the synthesis of esters by C=C bond breaking in olefins has been realised using cobalt nanoparticles (Co?NC?900) as catalysts and oxygen as oxidant.The catalytic system has a wide range of substrate applications and functional group compatibility.A diverse set of mono? and multi?substituted aromatic and aliphatic alkenes could be effectively cleaved and converted into the corresponding esters by C=C bond cleavage. In addition, the catalyst can be recycled up to six times without significant loss of activity.Characterization analysis revealed nanostructured nitrogen?doped graphene?layer coated cobalt nanoparticleis possibly responsible for excellent catalytic activity.Mechanistic studies revealed that alcohols or ketones derived from olefins under oxidative conditions are formed as intermediates,which subsequently are converted to esters through a tandem sequential process.

Key words: Oxidative cleavage, Alkenes, C=C, Esters, Cobalt catalyst

摘要：

以钴纳米颗粒（Co?NC?900）为催化剂、氧气为氧化剂，使烯烃中C=C断裂，合成了酯类化合物。该催化体系具有广泛的底物适用范围以及官能团兼容性，多种单取代或多取代的芳香族和脂肪族烯烃可以顺利地通过C=C断裂转化为相应的酯。此外，催化剂经过6次回收利用，无明显活性损失。通过表征发现，纳米结构的氮掺杂石墨烯层包覆的钴纳米颗粒具有优异的催化活性。机理研究结果表明，在氧化条件下，当烯烃生成的醇或酮作为中间体时，醇和酮可以通过串联的氧化过程转化为酯。

关键词: 氧化断裂, 烯烃, C=C, 酯, 钴催化剂

CLC Number:

TQ138.1

Yujing Li, He Wang, Yang Chen, Lei Li. Co⁃NC⁃900 Catalyzed Oxidation of Alkenes Synthesis of Esters via Unsaturated C=C Cleavage[J]. Journal of Petrochemical Universities, 2023, 36(4): 40-46.

李愉景, 王贺, 陈阳, 李蕾. Co⁃NC⁃900催化氧化烯烃C=C断裂合成酯[J]. 石油化工高等学校学报, 2023, 36(4): 40-46.

Figures/Tables 11

Fig.1 Equation for the reaction of styrene

Table 1 Screening of catalysts and optimization of reaction conditions

序号	催化剂	转化率/%	产率/%
1	-	-	-
2	Co⁃NC⁃700	99	47
3	Co⁃NC⁃800	99	77
4	Co⁃NC⁃900	99	98
5	NC⁃900	49	24
6	Co(OAc)₂•4H₂O/1,10⁃phen^d	77	1
7	Co(phen) _x @SiO₂⁃900	16	3
8^a	Co⁃NC⁃900	-	-
9^b	Co⁃NC⁃900	-	-
10^c	Co⁃NC⁃900	>99	79

Fig.2 Substrate scope of alkenes

Fig.3 Recycling of Co?NC?900 for aerobic oxidation of alkenes

Fig.4 The XRD spectra of the Co?NC?900 catalyst before and after six cycles of reaction

Fig.5 TEM image and HRTEM image of the Co?NC?900 catalyst after six cycles of reaction

Fig.6 Experimental results of free radical capture

Fig.7 The isotopic labeling experiment

Fig.8 The reaction of CD3OD as solvent

Fig.9 Kinetic reaction equation

Fig.10 Results of kinetic experiments and control experiments

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