聚硒醚催化环己烯氧化制备1,2-环己二醇

doi:10.6023/cjoc202008032

摘要/Abstract

开发了一种一步合成聚硒醚的新方法, 该材料可用于催化环己烯二羟化合成重要的化工中间体环己二醇, 是一种高效并可回收的催化剂. 有趣的是, 该材料在分子层面的独特结构, 使得相关反应以自由基机理进行, 并可使用分子氧作为部分氧化剂, 这与之前许多报道的硒催化反应有所不同.

关键词: 硒, 聚硒醚, 环己烯, 1,2-环己二醇, 绿色氧化

A new method for one-step synthesis of polyselenide was developed. The material was found to be an efficient and recyclable catalyst for the dihydroxylation of cyclohexene to produce 1,2-cyclohexanediol, which was an important inter- mediate for the synthesis of many fine chemicals. Interestingly, the unique structure of the catalyst at molecular level resulted in a novel free-radical reaction methanism allowing the utilization of O₂ as the supplementary oxidant, which was quite different from most of the reported organoselenium-catalyzed reactions.

Key words: selenium, polyselenide, cyclohexene, 1,2-cyclohexanediol, green oxidation

引用此文

黄杰军, 钱蓉蓉, 王爽, 曹洪恩. 聚硒醚催化环己烯氧化制备1,2-环己二醇[J]. 有机化学, 2021, 41(4): 1639-1645.

Jiejun Huang, Rongrong Qian, Shuang Wang, Hong'en Cao. Polyselenide-Catalyzed Cyclohexene Oxidation to Produce 1,2-Cyclohexanediol[J]. Chinese Journal of Organic Chemistry, 2021, 41(4): 1639-1645.

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图/表 8

Scheme 1. Synthesis of the polystyrene-supported selenic acid catalyst for cyclohexene dihydroxylation

Figure 1. (a) Preparation steps and (b) element mapping of the polyselenide being synthesized from 1,4-bis(chloromethyl)ben- zene

Entry	Oxidant/Additive	Conversion/%^c	Yield/%^d
1	90 mol% H₂O₂, O₂/—	88	86
2	O₂/—	6	5
3	O₂/200 mol% H₂O	17	16
4	80 mol% H₂O₂, O₂/—	77	76
5	90 mol% H₂O₂, O₂/—	80	79
6	90 mol% H₂O₂, O₂/—	72	70
7	90 mol% H₂O₂, O₂/—	76	74

Table 1. Parallel experiments of the polyselenide-catalyzed dihydroxylation reactions of cyclohexenea

Figure 2. Catalyst recycle and reuse (a) and the SEM images of the polyselenide before (b) and after (c) the 5th cycle of reaction

Entry	Ref.	Consumed weight of starting ma- terials vs. product/(mg?mmol^–1)
1	[14]	493.0
2	[16]	149.8
3	This work	142.9

Table 2. Comparison of the work with reported references on atom economy

Entry	Oxidant/additve	t/h	Conversion/%	Yield^c/%
1	90 mol% H₂O₂, O₂/ TEMPO (100 mol%)	48	0	0
2	90 mol% H₂O₂, O₂/Hy- droquinone (100 mol%)	48	0	0
3	90 mol% H₂O₂, O₂/ AIBN (100 mol%)	24	88	78
4	90 mol% H₂O₂, O₂	24	67	66
5	100 mol% H₂O₂, N₂	48	81	79
6	N₂/200 mol% H₂O^d	48	42	38

Table 3. Control experiments for mechanism studya,b

Figure 3. (a) XPS spectrum of the used catalyst, (b) IR spectra of the polyselenide before and after the reaction and (c) hydroxyl radical capture by salicylic acid via UV-Vis detection

Scheme 2. Plausible mechanism of the Se-polymer-catalyzed oxidation of cyclohexene

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