Reactions of Alkynyl Aryl Phosphine Oxide with Oxalyl Bromide

doi:10.6023/cjoc202405014

Chinese Journal of Organic Chemistry ›› 2024, Vol. 44 ›› Issue (12): 3753-3760.DOI: 10.6023/cjoc202405014 Previous Articles Next Articles

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炔基芳基磷氧化物与草酰溴的反应研究

赵鹏^a, 甘贞洁^b, 李卓^a, 王丽丽^a^,^*(), 段征^a^,^*()

a 郑州大学化学学院国际磷化学实验室郑州 450001
b 河南工程学院化工与印染工程学院郑州 450007

收稿日期:2024-07-06 修回日期:2024-07-25 发布日期:2024-08-16
基金资助:
国家自然科学基金(22101262); 国家自然科学基金(22171245); 河南省科技攻关(242102230166)

Reactions of Alkynyl Aryl Phosphine Oxide with Oxalyl Bromide

Peng Zhao^a, Zhenjie Gan^b, Zhuo Li^a, Lili Wang^a^,^*(), Zheng Duan^a^,^*()

a International Phosphorus Laboratory, College of Chemistry, Zhengzhou University, Zhengzhou 450001
b College of Printing and Dyeing Chemical Engineering, Henan University of Engineering, Zhengzhou 450007

Received:2024-07-06 Revised:2024-07-25 Published:2024-08-16
Contact: *E-mail:wanglili@zzu.edu.cn;duanzheng@zzu.edu.cn
Supported by:
National Natural Science Foundation of China(22101262); National Natural Science Foundation of China(22171245); Key Scientific and Technological Project of Henan Province(242102230166)

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Abstract

Tertiary phosphines and their oxides react with oxalyl bromide to generate corresponding quaternary phosphonium salts, which can be further transformed as active intermediates to facilitate the bromination of alcohols and the dibromination of unsaturated hydrocarbons. This chemical process carries substantial research significance in the field of organic synthesis. In this study, two types of triaryl phosphine oxides and benzyl diaryl phosphine oxides containing alkyne groups were designed and synthesized. These compounds were then subjected to reaction with oxalyl bromide, resulting in the formation of novel benzophosphonium tribromides and trans-phosphoryl dibromoalkenes, respectively. These findings demonstrate variations from their reactions with oxalyl chloride. Furthermore, the benzophosphonium tribromide obtained can act as an alternative reagent for bromine, enabling the direct bromination of aromatics compounds, olefin, alkyne and acetophenone derivatives.

Key words: aryl phosphine oxide, benzyl phosphine oxide, oxalyl bromide, quaternary phosphonium salt, alkyne

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Peng Zhao, Zhenjie Gan, Zhuo Li, Lili Wang, Zheng Duan. Reactions of Alkynyl Aryl Phosphine Oxide with Oxalyl Bromide[J]. Chinese Journal of Organic Chemistry, 2024, 44(12): 3753-3760.

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Fig. & Tab. 6

Scheme 1. Reactions of phosphine oxides with oxalyl chloride and oxalyl bromide

Scheme 2. Proposed mechanism for the formation of the benzophosphonium tribromide 2a

Scheme 3. Reactions of benzyl phosphine oxides 1 with (COBr)2 Reaction conditions: 1 (1.0 mmol), (COBr)2 (2.0 mmol), toluene (5.0 mL), room temperature for 30 min, then 100 ℃ for 5 h, and a powdery precipitate was generated. Wash the precipitate with toluene, and then ether for twice to obtain a yellow solid. All yields were isolated.

Scheme 4. Proposed mechanism for the formation of the dibromoalkene 4c

Scheme 5. Synthesis of phosphoryl dibromoalkenes 4 Reaction conditions: 3 (0.5 mmol), (COBr)2 (1.0 mmol), toluene (5.0 mL), room temperature for 30 min, then 100 ℃ for 3 h, finally stirred in air for 10 min. All yields were isolated by column chromatography.

Scheme 6. Bromination reactions Reaction conditions: (a) 5 (0.3 mmol), 2a (0.3 mmol), CH2Cl2 (2.0 mL), 40 ℃ for 5 h; (b) 8 (0.3 mmol), 2a (0.3 mmol), CH2Cl2 (2.0 mL), 40 ℃ for 5 h, subsequently, Et3N (0.3 mmol), room temperature for 30 min; (c) 10 (0.2 mmol), 2a (0.2 mmol), THF＋MeOH (2.0 mL＋0.5 mL), Et3N (0.2 mmol), 60 ℃ for 5 h; (d) 12 (0.2 mmol), 2a (0.4 mmol), CH2Cl2＋MeOH (2.0 mL＋0.5 mL), Et3N (0.4 mmol), 40 ℃ for 5 h; (e) 14 (0.2 mmol), 2a (0.4 mmol), THF＋MeOH (2.0 mL＋0.5 mL), Et3N (0.4 mmol), 60 ℃ for 5 h. All yields were isolated by column chromatography

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炔基芳基磷氧化物与草酰溴的反应研究

Reactions of Alkynyl Aryl Phosphine Oxide with Oxalyl Bromide

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