CN103804105A - A kind of synthetic method of biphenyl compound - Google Patents
A kind of synthetic method of biphenyl compound Download PDFInfo
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Abstract
本发明涉及有机合成领域,公开了一种联苯类化合物的合成方法,方法如下:在无机碱存在条件下,在乙醇和水的混合溶剂中,加入芳基硼酸、卤代芳烃、非均相催化剂ZrO2-Pd(OAc)2,控制温度为60-120℃,反应30-180min,反应液冷却至室温后经过滤、洗涤回收催化剂,向滤液加入NaOH水溶液,经萃取、干燥、浓缩得到高纯度联苯类化合物。本方法首次利用高催化活性并可重复使用的非均相催化剂ZrO2-Pd(OAc)2并以绿色无毒性的乙醇和水为溶剂在温和的条件下实现了卤代芳烃和芳基硼酸的快速偶联,后用NaOH水溶液去除过量芳基硼酸即可得高纯度联苯类化合物。本方法催化效果好、操作简单,对环境友好。The invention relates to the field of organic synthesis, and discloses a synthesis method of biphenyl compounds. The method is as follows: in the presence of an inorganic base, in a mixed solvent of ethanol and water, add arylboronic acid, halogenated aromatic hydrocarbons, heterogeneous Catalyst ZrO 2 -Pd(OAc) 2 , control the temperature at 60-120°C, react for 30-180 minutes, filter and wash the reaction solution to recover the catalyst after cooling to room temperature, add NaOH aqueous solution to the filtrate, extract, dry and concentrate to obtain high Purity biphenyl compounds. For the first time, this method utilizes the highly active and reusable heterogeneous catalyst ZrO 2 -Pd(OAc) 2 to realize the synthesis of halogenated aromatic hydrocarbons and arylboronic acids under mild conditions using green non-toxic ethanol and water as solvents. Rapid coupling, and then use NaOH aqueous solution to remove excess aryl boronic acid to obtain high-purity biphenyl compounds. The method has the advantages of good catalytic effect, simple operation and environmental friendliness.
Description
技术领域technical field
本发明涉及有机合成领域,尤其涉及了一种联苯类化合物的合成方法。The invention relates to the field of organic synthesis, in particular to a method for synthesizing biphenyl compounds.
背景技术Background technique
联苯类化合物是一类非常重要的化合物,被广泛地应用于医药、染料、先进性功能材料等领域,开发其绿色、低成本以及操作简单的合成方法是有机合成的研究热点。Pd催化的卤代芳烃和芳基硼酸的偶联反应——Suzuki反应是合成联苯类化合物的有效方法之一。经典的Suzuki反应以钯为催化剂,在配体和碱的存在下,卤代芳烃和芳基硼酸于均相体系中进行偶联得到联芳基化合物。均相Suzuki反应虽然具有催化活性高和反应选择性好等优点,但是存在催化剂与产物不能分离,催化剂不易回收利用以及对产品造成金属污染等缺点。同时,Pd催化的均相Suzuki反应所用的配体通常结构复杂、价格昂贵、对水和空气敏感,所用的溶剂通常为毒性较大的极性溶剂,反应过程中通常需要惰性气体保护。这些局限性在很大程度上制约了均相Suzuki反应在工业上的应用。Biphenyl compounds are a very important class of compounds, which are widely used in medicine, dyes, advanced functional materials and other fields. The development of green, low-cost and easy-to-operate synthesis methods is a research hotspot in organic synthesis. The Pd-catalyzed coupling reaction of haloarenes and arylboronic acids—Suzuki reaction is one of the effective methods for the synthesis of biphenyls. The classic Suzuki reaction uses palladium as a catalyst, and in the presence of ligands and bases, halogenated aromatic hydrocarbons and arylboronic acids are coupled in a homogeneous system to obtain biaryl compounds. Although the homogeneous Suzuki reaction has the advantages of high catalytic activity and good reaction selectivity, it has the disadvantages that the catalyst and the product cannot be separated, the catalyst is not easy to recycle, and it causes metal pollution to the product. At the same time, the ligands used in the homogeneous Suzuki reaction catalyzed by Pd are usually complex in structure, expensive, and sensitive to water and air. The solvents used are usually highly toxic polar solvents, and inert gas protection is usually required during the reaction process. These limitations largely restrict the industrial application of the homogeneous Suzuki reaction.
发明内容Contents of the invention
本发明针对现有技术中钯催化的卤代芳烃和芳基硼酸均相偶联反应存在需要使用昂贵的不稳定的配体,Pd不能回收利用以及大量使用毒性较大的有机溶剂等缺点,提供了一种联苯类化合物的合成方法,本方法是利用高催化活性并可重复使用的非均相催化剂ZrO2-Pd(OAc)2并以绿色无毒性的乙醇和水为溶剂在温和的条件下对卤代芳烃和芳基硼酸进行快速偶联,后用NaOH水溶液进行简单处理即可得高纯度联苯类化合物。本方法催化效果好、操作简单,对环境友好。The present invention aims at the disadvantages of palladium-catalyzed homogeneous coupling reaction of halogenated aromatic hydrocarbons and aryl boronic acids in the prior art that expensive and unstable ligands need to be used, Pd cannot be recycled, and a large amount of toxic organic solvents are used, etc., and provides A synthesis method of biphenyl compounds is proposed. This method utilizes a highly catalytically active and reusable heterogeneous catalyst ZrO 2 -Pd(OAc) 2 and uses green non-toxic ethanol and water as solvents under mild conditions. High-purity biphenyl compounds can be obtained by quickly coupling halogenated aromatic hydrocarbons and arylboronic acids, and then simply treating them with NaOH aqueous solution. The method has the advantages of good catalytic effect, simple operation and environmental friendliness.
为了解决上述技术问题,本发明通过下述技术方案得以解决:In order to solve the above technical problems, the present invention is solved through the following technical solutions:
一种如式(I)所示的联苯类化合物的合成方法,方法如下:A kind of synthetic method of the biphenyl compound shown in formula (I), the method is as follows:
在无机碱存在条件下,在乙醇和水的混合溶剂中,加入芳基硼酸、卤代芳烃、非均相催化剂ZrO2-Pd(OAc)2,控制温度为60-120,℃反应30-180min,反应液冷却至室温后经过滤、洗涤回收催化剂,向滤液加入NaOH水溶液,经萃取、干燥、浓缩后得到高纯度联苯类化合物;其反应式如下:In the presence of inorganic bases, add aryl boronic acid, halogenated aromatic hydrocarbons, and heterogeneous catalyst ZrO 2 -Pd(OAc) 2 in a mixed solvent of ethanol and water, control the temperature at 60-120, and react at ℃ for 30-180 minutes , after the reaction solution is cooled to room temperature, the catalyst is recovered by filtration and washing, and NaOH aqueous solution is added to the filtrate to obtain high-purity biphenyl compounds after extraction, drying and concentration; its reaction formula is as follows:
其中,X=I或Br,R1=H、F、C2H5或CHO,R2=CH3、C2H5、COCH3、OCH3、CN或CHO。Wherein, X=I or Br, R 1 =H, F, C 2 H 5 or CHO, R 2 =CH 3 , C 2 H 5 , COCH 3 , OCH 3 , CN or CHO.
作为优选,所述的ZrO2-Pd(OAc)2催化剂的制备方法如下:将介孔ZrO2分散于四氢呋喃中,加入一定量的Pd(OAc)2,室温下搅拌3小时后,用旋转蒸发仪减压浓缩,在50℃的温度下真空干燥即得到催化剂ZrO2-Pd(OAc)2。催化剂ZrO2-Pd(OAc)2在使用过程中的Pd(OAc)2质量百分含量以Pd(OAc)2的理论百分含量计算。As a preference, the preparation method of the ZrO 2 -Pd(OAc) 2 catalyst is as follows: disperse the mesoporous ZrO 2 in tetrahydrofuran, add a certain amount of Pd(OAc) 2 , stir at room temperature for 3 hours, and then use rotary evaporation Concentrate under reduced pressure, and dry under vacuum at a temperature of 50°C to obtain the catalyst ZrO 2 -Pd(OAc) 2 . The mass percentage of Pd(OAc) 2 in the catalyst ZrO 2 -Pd(OAc) 2 during use is calculated based on the theoretical percentage of Pd(OAc) 2 .
作为优选,所述的Pd(OAc)2与介孔ZrO2的质量比为1:(40-100)。Pd(OAc)2被分散在介孔金属氧化物ZrO2中,可防止Pd在反应过程中的团聚,从而可保持其催化活性。Preferably, the mass ratio of Pd(OAc) 2 to mesoporous ZrO 2 is 1:(40-100). Pd(OAc) 2 is dispersed in mesoporous metal oxide ZrO 2 , which prevents the agglomeration of Pd during the reaction and thus maintains its catalytic activity.
作为优选,所述的加入的催化剂中Pd(OAc)2的摩尔质量为卤代芳烃摩尔质量的0.1-1%。本发明方法即联苯类化合物的合成过程无需配体参与,无需惰性气体保护。催化剂ZrO2-Pd(OAc)2催化活性高,回收简单,可重复使用而不降低其催化活性,有效节约合成成本。As a preference, the molar mass of Pd(OAc) in the added catalyst is 0.1-1% of the molar mass of halogenated aromatic hydrocarbons. The method of the present invention, that is, the synthesis process of the biphenyl compounds does not require the participation of ligands and the protection of inert gases. The catalyst ZrO 2 -Pd(OAc) 2 has high catalytic activity, is easy to recycle, can be reused without reducing its catalytic activity, and effectively saves synthesis cost.
作为优选,所述的混合溶剂中乙醇与水的体积比为3:(1-3)。使用的溶剂为绿色无毒性的乙醇和水,对环境友好。As a preference, the volume ratio of ethanol to water in the mixed solvent is 3:(1-3). The solvent used is green non-toxic ethanol and water, which is friendly to the environment.
作为优选,所述的无机碱为K2CO3。Preferably, the inorganic base is K 2 CO 3 .
作为优选,所述的经冷却后的反应液经过滤回收催化剂后,向滤液加入NaOH水溶液进行处理,并用有机溶剂萃取,有机层依次用饱和NaCl水溶液洗涤、无水Na2SO4干燥、经减压浓缩后得到高纯度的联苯类化合物。用NaOH水溶液去除反应剩余的芳基硼酸,方法简单且效果非常好。As a preference, after the cooled reaction solution is filtered to recover the catalyst, NaOH aqueous solution is added to the filtrate for treatment, and then extracted with an organic solvent, the organic layer is sequentially washed with a saturated NaCl aqueous solution, dried over anhydrous Na 2 SO 4 , High-purity biphenyl compounds were obtained after concentrated under pressure. Use NaOH aqueous solution to remove the remaining aryl boronic acid in the reaction, the method is simple and the effect is very good.
作为优选,所述的卤代芳烃为对碘甲苯、对碘苯甲醚、对碘苯甲腈、邻碘苯甲醚、对溴甲苯、间溴甲苯、间溴苯甲醚、间溴苯乙酮、对甲碘苯、对甲碘苯中任一种。Preferably, the halogenated aromatic hydrocarbons are p-iodotoluene, p-iodoanisole, p-iodobenzonitrile, o-iodoanisole, p-bromotoluene, m-bromotoluene, m-bromoanisole, m-bromophenethyl Any of ketone, p-methyl iodobenzene, p-methyl iodobenzene.
本发明由于采用了以上技术方案,具有显著的技术效果:The present invention has remarkable technical effect owing to adopted above technical scheme:
1、Pd(OAc)2被分散在介孔金属氧化物ZrO2中,可防止Pd在反应过程中的团聚,从而可保持其催化活性。1. Pd(OAc) 2 is dispersed in the mesoporous metal oxide ZrO 2 , which can prevent the agglomeration of Pd during the reaction, thereby maintaining its catalytic activity.
2、联苯类化合物的合成过程无需配体参与,无需惰性气体保护。催化剂ZrO2-Pd(OAc)2催化活性高(Pd的摩尔质量低至卤代芳烃摩尔质量的0.1%),回收简单,可重复使用而不降低其催化活性,有效节约合成成本。2. The synthesis process of biphenyl compounds does not require ligand participation and inert gas protection. The catalyst ZrO 2 -Pd(OAc) 2 has high catalytic activity (the molar mass of Pd is as low as 0.1% of the molar mass of halogenated aromatic hydrocarbons), is easy to recover, can be reused without reducing its catalytic activity, and effectively saves synthesis costs.
3、本发明方法后续处理过程用NaOH水溶液去除反应剩余的芳基硼酸,该处理方法简单、成本低、效果好。3. In the subsequent treatment process of the method of the present invention, NaOH aqueous solution is used to remove the remaining arylboronic acid from the reaction. The treatment method is simple, low in cost and good in effect.
4、本发明方法使用的溶剂为绿色无毒性的乙醇和水,对环境友好。4. The solvent used in the method of the present invention is green nontoxic ethanol and water, which is environmentally friendly.
具体实施方式Detailed ways
下面结合具体实施例对本发明作进一步详细描述:The present invention is described in further detail below in conjunction with specific embodiment:
实施例1Example 1
在100mL耐压反应管中,依次加入磁子、对碘甲苯(5mmol)、苯硼酸(7.5mmol)、ZrO2-Pd(OAc)2催化剂(280mg,含2.8mg醋酸钯,0.25mol%)、K2CO3(10mmol)、水(5mL)和乙醇(15mL)。反应管用硅橡胶垫密封后在100℃的油浴加热0.5小时,经气相检测反应完全,并用过滤的方法将催化剂回收。催化剂用依次水(4mL×2)、乙酸乙酯(100mL×2)洗涤。将滤液合并后加入NaOH水溶液并分去水层。有机层依次用饱和NaCl水溶液洗涤、无水Na2SO4干燥,减压浓缩后经1H-NMR检测确定为高纯度的偶联产物,产率为97%,结构如下:In a 100mL pressure-resistant reaction tube, add magneton, p-iodotoluene (5mmol), phenylboronic acid (7.5mmol), ZrO 2 -Pd(OAc) 2 catalyst (280mg, containing 2.8mg palladium acetate, 0.25mol%), K 2 CO 3 (10 mmol), water (5 mL) and ethanol (15 mL). The reaction tube was sealed with a silicone rubber gasket and heated in an oil bath at 100° C. for 0.5 hour. The reaction was complete by gas phase detection, and the catalyst was recovered by filtration. The catalyst was washed successively with water (4 mL×2), ethyl acetate (100 mL×2). After the filtrates were combined, NaOH aqueous solution was added and the aqueous layer was separated. The organic layer was washed successively with saturated NaCl aqueous solution, dried over anhydrous Na 2 SO 4 , concentrated under reduced pressure and determined to be a high-purity coupling product by 1 H-NMR detection with a yield of 97%, and the structure is as follows:
实施例2-5Example 2-5
在100mL耐压反应管中,依次加入磁子、对碘甲苯(5mmol)、苯硼酸(7.5mmol)、实施例1中回收的全部ZrO2-Pd(OAc)2催化剂、K2CO3(10mmol)、水(5mL)和乙醇(15mL)。反应管用硅橡胶垫密封后在100℃的油浴加热0.5小时,经气相检测反应完全,并用过滤的方法将催化剂回收。催化剂用依次水(4mL×2)、乙酸乙酯(100mL×2)洗涤。将滤液合并后加入NaOH水溶液并分去水层。有机层依次用饱和NaCl水溶液洗涤、无水Na2SO4干燥,减压浓缩后经1H-NMR检测确定为高纯度的偶联产物。将回收所得的催化剂进行重复实验,结果见表一。In a 100mL pressure-resistant reaction tube, add magnetons, p-iodotoluene (5mmol), phenylboronic acid (7.5mmol), all ZrO 2 -Pd(OAc) 2 catalysts recovered in Example 1, K 2 CO 3 (10mmol ), water (5mL) and ethanol (15mL). The reaction tube was sealed with a silicone rubber gasket and heated in an oil bath at 100° C. for 0.5 hour. The reaction was complete by gas phase detection, and the catalyst was recovered by filtration. The catalyst was washed successively with water (4 mL×2), ethyl acetate (100 mL×2). After the filtrates were combined, NaOH aqueous solution was added and the aqueous layer was separated. The organic layer was washed successively with saturated NaCl aqueous solution, dried over anhydrous Na 2 SO 4 , concentrated under reduced pressure and determined to be a high-purity coupling product by 1 H-NMR detection. The recovered catalyst was subjected to repeated experiments, and the results are shown in Table 1.
表一:ZrO2-Pd(OAc)2催化剂的循环使用实验Table 1: Recycling experiment of ZrO 2 -Pd(OAc) 2 catalyst
实施例6Example 6
在10mL耐压反应管中,依次加入磁子、对碘苯甲醚(1mmol)、苯硼酸(1.5mmol)、ZrO2-Pd(OAc)2催化剂(56mg,含0.56mg醋酸钯,0.25mol%)、K2CO3(2mmol)、水(1mL)和乙醇(3mL)。反应管用硅橡胶垫密封后在100℃的油浴加热0.5小时,经气相检测反应完全,并用过滤的方法将催化剂回收。催化剂用依次水(2mL×2)、乙酸乙酯(50mL×2)洗涤。将滤液合并后加入NaOH水溶液并分去水层。有机层依次用饱和NaCl水溶液洗涤、无水Na2SO4干燥,经减压浓缩后得到高纯度的偶联产物,产率为97%,经1H-NMR检测,结构如下:In a 10mL pressure-resistant reaction tube, add magneton, p-iodoanisole (1mmol), phenylboronic acid (1.5mmol), ZrO 2 -Pd(OAc) 2 catalyst (56mg, containing 0.56mg palladium acetate, 0.25mol% ), K 2 CO 3 (2 mmol), water (1 mL) and ethanol (3 mL). The reaction tube was sealed with a silicone rubber gasket and heated in an oil bath at 100° C. for 0.5 hour. The reaction was complete by gas phase detection, and the catalyst was recovered by filtration. The catalyst was washed successively with water (2 mL×2), ethyl acetate (50 mL×2). After the filtrates were combined, NaOH aqueous solution was added and the aqueous layer was separated. The organic layer was washed successively with saturated NaCl aqueous solution, dried over anhydrous Na 2 SO 4 , and concentrated under reduced pressure to obtain a high-purity coupling product with a yield of 97%. The structure was as follows detected by 1 H-NMR:
实施例7Example 7
在10mL耐压反应管中,依次加入磁子、对碘苯甲腈(1mmol)、苯硼酸(1.5mmol)、ZrO2-Pd(OAc)2催化剂(56mg,含0.56mg醋酸钯,0.25mol%)、K2CO3(2mmol)、水(1mL)和乙醇(3mL)。反应管密封后在100℃的油浴加热0.5小时,经气相检测反应完全,并用过滤的方法将催化剂回收。催化剂用依次水(2mL×2)、乙酸乙酯(50mL×2)洗涤。将滤液合并后加入NaOH水溶液并分去水层。有机层依次用饱和NaCl水溶液洗涤、无水Na2SO4干燥,经减压浓缩后得到高纯度的偶联产物,产率为99%,经1H-NMR检测,结构如下:In a 10mL pressure-resistant reaction tube, add magneton, p-iodobenzonitrile (1mmol), phenylboronic acid (1.5mmol), ZrO 2 -Pd(OAc) 2 catalyst (56mg, containing 0.56mg palladium acetate, 0.25mol% ), K 2 CO 3 (2 mmol), water (1 mL) and ethanol (3 mL). After the reaction tube was sealed, it was heated in an oil bath at 100° C. for 0.5 hour, and the reaction was detected by the gas phase, and the catalyst was recovered by filtration. The catalyst was washed successively with water (2 mL×2), ethyl acetate (50 mL×2). After the filtrates were combined, NaOH aqueous solution was added and the aqueous layer was separated. The organic layer was washed successively with saturated NaCl aqueous solution, dried over anhydrous Na 2 SO 4 , and concentrated under reduced pressure to obtain a high-purity coupling product with a yield of 99%. The structure was as follows detected by 1 H-NMR:
实施例8Example 8
在10mL耐压反应管中,依次加入磁子、邻碘苯甲醚(1mmol)、苯硼酸(1.5mmol)、ZrO2-Pd(OAc)2催化剂(56mg,含0.56mg醋酸钯,0.25mol%)、K2CO3(2mmol)、水(1mL)和乙醇(3mL)。反应管密封后在100℃的油浴加热1小时,经气相检测反应完全,并用过滤的方法将催化剂回收。催化剂用依次水(2mL×2)、乙酸乙酯(50mL×2)洗涤。将滤液合并后加入NaOH水溶液并分去水层。有机层依次用饱和NaCl水溶液洗涤、无水Na2SO4干燥,经减压浓缩后得到高纯度的偶联产物,产率为98%,经1H-NMR检测,结构如下:In a 10mL pressure-resistant reaction tube, add magneton, o-iodoanisole (1mmol), phenylboronic acid (1.5mmol), ZrO 2 -Pd(OAc) 2 catalyst (56mg, containing 0.56mg palladium acetate, 0.25mol% ), K 2 CO 3 (2 mmol), water (1 mL) and ethanol (3 mL). After the reaction tube was sealed, it was heated in an oil bath at 100° C. for 1 hour, and the reaction was detected by the gas phase, and the catalyst was recovered by filtration. The catalyst was washed successively with water (2 mL×2), ethyl acetate (50 mL×2). After the filtrates were combined, NaOH aqueous solution was added and the aqueous layer was separated. The organic layer was washed successively with saturated NaCl aqueous solution, dried over anhydrous Na 2 SO 4 , and concentrated under reduced pressure to obtain a high-purity coupling product with a yield of 98%. The structure was as follows detected by 1 H-NMR:
实施例9Example 9
在10mL耐压反应管中,依次加入磁子、对溴甲苯(1mmol)、苯硼酸(1.5mmol)、ZrO2-Pd(OAc)2催化剂(56mg,含0.56mg醋酸钯,0.25mol%)、K2CO3(2mmol)、水(1mL)和乙醇(3mL)。反应管密封后在100℃的油浴加热3小时,经气相检测反应完全,并用过滤的方法将催化剂回收。催化剂用依次水(2mL×2)、乙酸乙酯(50mL×2)洗涤。将滤液合并后加入NaOH水溶液并分去水层。有机层依次用饱和NaCl水溶液洗涤、无水Na2SO4干燥,经减压浓缩后得到高纯度的偶联产物,产率为97%,经1H-NMR检测,结构如下:In a 10mL pressure-resistant reaction tube, add magneton, p-bromotoluene (1mmol), phenylboronic acid (1.5mmol), ZrO 2 -Pd(OAc) 2 catalyst (56mg, containing 0.56mg palladium acetate, 0.25mol%), K 2 CO 3 (2 mmol), water (1 mL) and ethanol (3 mL). After the reaction tube was sealed, it was heated in an oil bath at 100° C. for 3 hours, and the reaction was complete by gas phase detection, and the catalyst was recovered by filtration. The catalyst was washed successively with water (2 mL×2), ethyl acetate (50 mL×2). After the filtrates were combined, NaOH aqueous solution was added and the aqueous layer was separated. The organic layer was washed successively with saturated NaCl aqueous solution, dried over anhydrous Na 2 SO 4 , and concentrated under reduced pressure to obtain a high-purity coupling product with a yield of 97%. The structure was as follows detected by 1 H-NMR:
实施例10Example 10
在10mL耐压反应管中,依次加入磁子、间溴甲苯(1mmol)、苯硼酸(1.5mmol)、ZrO2-Pd(OAc)2催化剂(56mg,含0.56mg醋酸钯,0.25mol%)、K2CO3(2mmol)、水(1mL)和乙醇(3mL)。反应管密封后在100℃的油浴加热3小时,经气相检测反应完全,并用过滤的方法将催化剂回收。催化剂用依次水(2mL×2)、乙酸乙酯(50mL×2)洗涤。将滤液合并后加入NaOH水溶液并分去水层。有机层依次用饱和NaCl水溶液洗涤、无水Na2SO4干燥,经减压浓缩后得到高纯度的偶联产物,产率为91%,经1H-NMR检测,结构如下:In a 10mL pressure-resistant reaction tube, add magneton, m-bromotoluene (1mmol), phenylboronic acid (1.5mmol), ZrO 2 -Pd(OAc) 2 catalyst (56mg, containing 0.56mg palladium acetate, 0.25mol%), K 2 CO 3 (2 mmol), water (1 mL) and ethanol (3 mL). After the reaction tube was sealed, it was heated in an oil bath at 100° C. for 3 hours, and the reaction was complete by gas phase detection, and the catalyst was recovered by filtration. The catalyst was washed successively with water (2 mL×2), ethyl acetate (50 mL×2). After the filtrates were combined, NaOH aqueous solution was added and the aqueous layer was separated. The organic layer was washed successively with saturated NaCl aqueous solution, dried over anhydrous Na 2 SO 4 , and concentrated under reduced pressure to obtain a high-purity coupling product with a yield of 91%. The structure was as follows detected by 1 H-NMR:
实施例11Example 11
在10mL耐压反应管中,依次加入磁子、间溴苯甲醚(1mmol)、苯硼酸(1.5mmol)、ZrO2-Pd(OAc)2催化剂(56mg,含0.56mg醋酸钯,0.25mol%)、K2CO3(2mmol)、水(1mL)和乙醇(3mL)。反应管密封后在100℃的油浴加热3小时,经气相检测反应完全,并用过滤的方法将催化剂回收。催化剂用依次水(2mL×2)、乙酸乙酯(50mL×2)洗涤。将滤液合并后加入NaOH水溶液并分去水层。有机层依次用饱和NaCl水溶液洗涤、无水Na2SO4干燥,经减压浓缩后得到高纯度的偶联产物,产率为98%,经1H-NMR检测,结构如下:In a 10mL pressure-resistant reaction tube, add magneton, m-bromoanisole (1mmol), phenylboronic acid (1.5mmol), ZrO 2 -Pd(OAc) 2 catalyst (56mg, containing 0.56mg palladium acetate, 0.25mol% ), K 2 CO 3 (2 mmol), water (1 mL) and ethanol (3 mL). After the reaction tube was sealed, it was heated in an oil bath at 100° C. for 3 hours, and the reaction was complete by gas phase detection, and the catalyst was recovered by filtration. The catalyst was washed successively with water (2 mL×2), ethyl acetate (50 mL×2). After the filtrates were combined, NaOH aqueous solution was added and the aqueous layer was separated. The organic layer was washed successively with saturated NaCl aqueous solution, dried over anhydrous Na 2 SO 4 , and concentrated under reduced pressure to obtain a high-purity coupling product with a yield of 98%. The structure was as follows detected by 1 H-NMR:
实施例12Example 12
在10mL耐压反应管中,依次加入磁子、间溴苯乙酮(1mmol)、苯硼酸(1.5mmol)、ZrO2-Pd(OAc)2催化剂(56mg,含0.56mg醋酸钯,0.25mol%)、K2CO3(2mmol)、水(1mL)和乙醇(3mL)。反应管密封后在100℃的油浴加热3小时,经气相检测反应完全,并用过滤的方法将催化剂回收。催化剂用依次水(2mL×2)、乙酸乙酯(50mL×2)洗涤。将滤液合并后加入NaOH水溶液并分去水层。有机层依次用饱和NaCl水溶液洗涤、无水Na2SO4干燥,经减压浓缩后得到高纯度的偶联产物,产率为97%,经1H-NMR检测,结构如下:In a 10mL pressure-resistant reaction tube, add magneton, m-bromoacetophenone (1mmol), phenylboronic acid (1.5mmol), ZrO 2 -Pd(OAc) 2 catalyst (56mg, containing 0.56mg palladium acetate, 0.25mol% ), K 2 CO 3 (2 mmol), water (1 mL) and ethanol (3 mL). After the reaction tube was sealed, it was heated in an oil bath at 100° C. for 3 hours, and the reaction was complete by gas phase detection, and the catalyst was recovered by filtration. The catalyst was washed successively with water (2 mL×2), ethyl acetate (50 mL×2). After the filtrates were combined, NaOH aqueous solution was added and the aqueous layer was separated. The organic layer was washed successively with saturated NaCl aqueous solution, dried over anhydrous Na 2 SO 4 , and concentrated under reduced pressure to obtain a high-purity coupling product with a yield of 97%. The structure was as follows detected by 1H-NMR:
实施例13Example 13
在10mL耐压反应管中,依次加入磁子、对甲碘苯(1mmol)、4-氟苯硼酸(1.5mmol)、ZrO2-Pd(OAc)2催化剂(56mg,含0.56mg醋酸钯,0.25mol%)、K2CO3(2mmol)、水(1mL)和乙醇(3mL)。反应管密封后在100℃的油浴加热0.5小时,经气相检测反应完全,并用过滤的方法将催化剂回收。催化剂用依次水(2mL×2)、乙酸乙酯(50mL×2)洗涤。将滤液合并后加入NaOH水溶液并分去水层。有机层依次用饱和NaCl水溶液洗涤、无水Na2SO4干燥,经减压浓缩后得到高纯度的偶联产物,产率为99%,经1H-NMR检测,结构如下:In a 10mL pressure-resistant reaction tube, add magneton, p-methyliodobenzene (1mmol), 4-fluorophenylboronic acid (1.5mmol), ZrO 2 -Pd(OAc) 2 catalyst (56mg, containing 0.56mg palladium acetate, 0.25 mol%), K 2 CO 3 (2 mmol), water (1 mL) and ethanol (3 mL). After the reaction tube was sealed, it was heated in an oil bath at 100° C. for 0.5 hour, and the reaction was detected by the gas phase, and the catalyst was recovered by filtration. The catalyst was washed successively with water (2 mL×2), ethyl acetate (50 mL×2). After the filtrates were combined, NaOH aqueous solution was added and the aqueous layer was separated. The organic layer was washed successively with saturated NaCl aqueous solution, dried over anhydrous Na 2 SO 4 , and concentrated under reduced pressure to obtain a high-purity coupling product with a yield of 99%. The structure was as follows detected by 1 H-NMR:
实施例14Example 14
在10mL耐压反应管中,依次加入磁子、对甲碘苯(1mmol)、4-甲酰基苯硼酸(1.5mmol)、ZrO2-Pd(OAc)2催化剂(56mg,含0.56mg醋酸钯,0.25mol%)、K2CO3(2mmol)、水(1mL)和乙醇(3mL)。反应管密封后在100℃的油浴加热40分钟,经气相检测反应完全,并用过滤的方法将催化剂回收。催化剂用依次水(2mL×2)、乙酸乙酯(50mL×2)洗涤。将滤液合并后加入NaOH水溶液并分去水层。有机层依次用饱和NaCl水溶液洗涤、无水Na2SO4干燥,经减压浓缩后得到高纯度的偶联产物,产率为91%,经1H-NMR检测,结构如下:In a 10mL pressure-resistant reaction tube, add magneton, p-methyliodobenzene (1mmol), 4-formylphenylboronic acid (1.5mmol), ZrO 2 -Pd(OAc) 2 catalyst (56mg, containing 0.56mg palladium acetate, 0.25 mol%), K 2 CO 3 (2 mmol), water (1 mL) and ethanol (3 mL). After the reaction tube was sealed, it was heated in an oil bath at 100° C. for 40 minutes, and the reaction was detected by the gas phase, and the catalyst was recovered by filtration. The catalyst was washed successively with water (2 mL×2), ethyl acetate (50 mL×2). After the filtrates were combined, NaOH aqueous solution was added and the aqueous layer was separated. The organic layer was washed successively with saturated NaCl aqueous solution, dried over anhydrous Na 2 SO 4 , and concentrated under reduced pressure to obtain a high-purity coupling product with a yield of 91%. The structure was as follows detected by 1 H-NMR:
实施例15Example 15
在10mL耐压反应管中,依次加入磁子、对甲碘苯(1mmol)、4-乙基苯硼酸(1.5mmol)、ZrO2-Pd(OAc)2催化剂(56mg,含0.56mg醋酸钯,0.25mol%)、K2CO3(2mmol)、水(1mL)和乙醇(3mL)。反应管密封后在100℃的油浴加热0.5小时,经气相检测反应完全,并用过滤的方法将催化剂回收。催化剂用依次水(2mL×2)、乙酸乙酯(50mL×2)洗涤。将滤液合并后加入NaOH水溶液并分去水层。有机层依次用饱和NaCl水溶液洗涤、无水Na2SO4干燥,经减压浓缩后得到高纯度的偶联产物,产率为99%,经1H-NMR检测,结构如下:In a 10mL pressure-resistant reaction tube, add magneton, p-methyliodobenzene (1mmol), 4-ethylphenylboronic acid (1.5mmol), ZrO 2 -Pd(OAc) 2 catalyst (56mg, containing 0.56mg palladium acetate, 0.25 mol%), K 2 CO 3 (2 mmol), water (1 mL) and ethanol (3 mL). After the reaction tube was sealed, it was heated in an oil bath at 100° C. for 0.5 hour, and the reaction was detected by the gas phase, and the catalyst was recovered by filtration. The catalyst was washed successively with water (2 mL×2), ethyl acetate (50 mL×2). After the filtrates were combined, NaOH aqueous solution was added and the aqueous layer was separated. The organic layer was washed successively with saturated NaCl aqueous solution, dried over anhydrous Na 2 SO 4 , and concentrated under reduced pressure to obtain a high-purity coupling product with a yield of 99%. The structure was as follows detected by 1 H-NMR:
总之,以上所述仅为本发明的较佳实施例,凡依本发明申请专利范围所作的均等变化与修饰,皆应属本发明专利的涵盖范围。In a word, the above descriptions are only preferred embodiments of the present invention, and all equivalent changes and modifications made according to the scope of the patent application of the present invention shall fall within the scope of the patent of the present invention.
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