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化学工业与工程 2014, Vol. 31 Issue (2) :7-12    DOI: 10.13353/j.issn.1004.9533.2014.02.002
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3,5-二溴-2,6-双(2’-噁唑啉基)苯基钯(Ⅱ)钳型物的合成及其催化Suzuki反应
 刘芳, 彭秒, 王洪星
(天津大学理学院,天津 300072)
Synthesis of 3, 5-Dibromo-2, 6-bis(2’-oxazolinyl)phenylpalladium(II)  Chloride and Its Catalytic Activity in Suzuki Coupling
 LIU  Fang, PENG  Miao, WANG  Hong-Xing
(School of Science, Tianjin University, Tianjin 300072, China)

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摘要 以4,6-二溴间苯二甲酸为起始原料,经过酰化、氨解、氯化以及成环反应生成配体4,6二溴-1,3-双(2’-噁唑啉基)苯。后者先与醋酸钯作用后经离子交换最终得到对应的钳形化合物氯化[3,5-二溴-2,6-双(2’-噁唑啉基)]苯基钯(Ⅱ)。考察了该钳形化合物催化取代芳氯与苯硼酸的偶合反应。结果表明:除对氯苯胺外,其余各取代芳氯与苯硼酸的偶合均得到较高偶合收率,且带供电子基团的氯苯与苯硼酸的偶合收率要高于吸电子基团氯苯的偶合收率,这可能与钳形化合物中溴的吸电子性能有关。
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刘芳
彭秒
王洪星
关键词噁唑啉   环金属化   钳型化合物   碳-碳偶联反应     
Abstract: The ligand 4,6-dibromo-1,3-bis(2’-oxazolinyl)benzene was synthesized from starting material 4,6-dibromoisophthalic acid after a series of reactions including acylation, amination, chlorination as well as ring closure. Treatment of this bisoxazoline with palladium acetate(II) and then ion exchanging with lithium chloride resulted in the corresponding pincer complex,[3,5-dibromo-2,6-bis (2’-oxazolinyl)phenyl]palladium(Ⅱ) chloride. The catalytic activity of this pincer complex in Suzuki coupling between aryl chlorides and phenylboronic acid was assessed. Experimental results demonstrate that the Suzuki coupling between series aryl chlorides and phenylboronic acid all give out the expected products in high yields except the case of p-chloroaniline. In addition, the product yields in the coupling of aryl chlorides bearing electron-donating groups catalyzed by palladium pincer are higher than those of aryl chlorides containing electron-withdrawing substituents probably because of the character of electron-withdrawing of bromines at 3,5-positions in this pincer complex.
Keywordsoxazoline   cyclometalation   pincer complex   carbon-carbon cross coupling     
Received 2012-12-11;
Corresponding Authors: 王洪星,E-mail:hongxing_wang@tju.edu.cn。     Email: hongxing_wang@tju.edu.cn
About author: 刘芳(1988-),女,硕士研究生,现从事金属有机合成方面的研究。
引用本文:   
刘芳, 彭秒, 王洪星.3,5-二溴-2,6-双(2’-噁唑啉基)苯基钯(Ⅱ)钳型物的合成及其催化Suzuki反应[J].  化学工业与工程, 2014,31(2): 7-12
LIU Fang, PENG Miao, WANG Hong-Xing.Synthesis of 3, 5-Dibromo-2, 6-bis(2’-oxazolinyl)phenylpalladium(II)  Chloride and Its Catalytic Activity in Suzuki Coupling[J].  Chemcial Industry and Engineering, 2014,31(2): 7-12
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