CN102189000B - Preparation method for bifunctional proline ionic liquid catalyst - Google Patents
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- 239000002608 ionic liquid Substances 0.000 title claims abstract description 40
- ONIBWKKTOPOVIA-BYPYZUCNSA-N L-Proline Chemical compound OC(=O)[C@@H]1CCCN1 ONIBWKKTOPOVIA-BYPYZUCNSA-N 0.000 title claims abstract description 36
- ONIBWKKTOPOVIA-UHFFFAOYSA-N Proline Natural products OC(=O)C1CCCN1 ONIBWKKTOPOVIA-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 239000003054 catalyst Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 230000001588 bifunctional effect Effects 0.000 title abstract description 18
- 229960002429 proline Drugs 0.000 claims abstract description 37
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 239000002253 acid Substances 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 7
- 238000001291 vacuum drying Methods 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229930182821 L-proline Natural products 0.000 claims abstract description 4
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims abstract description 3
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims abstract description 3
- 239000002841 Lewis acid Substances 0.000 claims description 11
- 150000007517 lewis acids Chemical class 0.000 claims description 11
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical group COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 10
- 238000006555 catalytic reaction Methods 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 6
- 150000003973 alkyl amines Chemical class 0.000 claims description 5
- -1 halogen acids Chemical class 0.000 claims description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 2
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 claims description 2
- 230000005611 electricity Effects 0.000 claims 3
- 238000006845 Michael addition reaction Methods 0.000 claims 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims 2
- XYOVOXDWRFGKEX-UHFFFAOYSA-N azepine Chemical compound N1C=CC=CC=C1 XYOVOXDWRFGKEX-UHFFFAOYSA-N 0.000 claims 2
- 229910052736 halogen Inorganic materials 0.000 claims 2
- BQJCRHHNABKAKU-KBQPJGBKSA-N morphine Chemical compound O([C@H]1[C@H](C=C[C@H]23)O)C4=C5[C@@]12CCN(C)[C@@H]3CC5=CC=C4O BQJCRHHNABKAKU-KBQPJGBKSA-N 0.000 claims 2
- 229960005181 morphine Drugs 0.000 claims 1
- 150000003053 piperidines Chemical class 0.000 claims 1
- 238000010025 steaming Methods 0.000 claims 1
- 238000005303 weighing Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 4
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 3
- 238000005966 aza-Michael addition reaction Methods 0.000 description 3
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 239000012429 reaction media Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 238000005102 attenuated total reflection Methods 0.000 description 2
- 239000007809 chemical reaction catalyst Substances 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- FBVVGPMIPAZFAW-RZVRUWJTSA-N (2S)-pyrrolidine-2-carboxylic acid Chemical compound OC(=O)[C@@H]1CCCN1.OC(=O)[C@@H]1CCCN1 FBVVGPMIPAZFAW-RZVRUWJTSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 238000006957 Michael reaction Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229940071870 hydroiodic acid Drugs 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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Abstract
本发明公开了一种双功能脯氨酸离子液催化剂的制备方法。属于有机化学合成领域，称取一定摩尔比的L-脯氨酸和氢卤酸，在室温下持续搅拌反应2小时，减压蒸去水和氢卤酸，再将其置于真空干燥箱，真空80℃下加热1-2小时，得到的产物分别与CuI、ZnCl2、FeCl3、CuCl2或MgCl2按摩尔比1:2～2:1混合均匀，再在真空80℃下加热干燥1.5～2h，得到分散均匀的双功能脯氨酸离子液催化剂。本发明制得的离子液催化剂，具有较高的稳定性和活性，且所用试剂价格均非常低廉，可以在反应中重复回收使用而性能保持不变。
The invention discloses a preparation method of a bifunctional proline ionic liquid catalyst. Belonging to the field of organic chemical synthesis, weigh a certain molar ratio of L-proline and hydrohalic acid, continue to stir and react at room temperature for 2 hours, evaporate water and hydrohalic acid under reduced pressure, and then place it in a vacuum drying oven. Heating under vacuum at 80°C for 1-2 hours, the obtained product was mixed with CuI, ZnCl 2 , FeCl 3 , CuCl 2 or MgCl 2 in a molar ratio of 1:2 to 2:1, and then heated and dried at 80°C for 1.5 ~2h to obtain a uniformly dispersed bifunctional proline ionic liquid catalyst. The ionic liquid catalyst prepared by the invention has high stability and activity, and the price of the used reagents is very low, and can be recycled and used repeatedly in the reaction without changing the performance.
Description
技术领域: Technical field:
本发明属于有机化学合成领域，具体涉及一种双功能脯氨酸离子液催化剂的制备方法。 The invention belongs to the field of organic chemical synthesis, and in particular relates to a preparation method of a bifunctional proline ionic liquid catalyst.
背景技术： Background technique:
化学工业在推动人类社会飞速发展的同时，也成为环境污染的主要来源。近年来，“绿色化学”引起科学界越来越多的关注，对化学反应催化剂和溶剂的优化成为绿色化学中最为重要的一环。绿色化学的兴起直接促进了离子液体研究热潮的出现，离子液体（ionic liquid）作为一种新的化学反应溶剂，被誉为21世纪清洁绿色工业中最理想的反应介质之一，由于其具有不同于分子溶剂的特性，在化学反应中呈现出独特的优点，在提高反应速率和选择性以及优化催化剂的循环利用等方面具有明显的优势，已经被广泛地用来取代传统分子溶剂而成为新的反应介质。近年来，离子液体又在催化领域显示出巨大的潜力，以离子液体催化剂替代其他有机催化剂的一些反应，具有反应产率高、易于分离且循环使用多次而催化活性依然很好的特性。因此，离子液体作为一种新型的反应媒介和催化剂，越来越受到人们的重视。 While promoting the rapid development of human society, the chemical industry has also become a major source of environmental pollution. In recent years, "green chemistry" has attracted more and more attention from the scientific community, and the optimization of chemical reaction catalysts and solvents has become the most important part of green chemistry. The rise of green chemistry has directly promoted the emergence of an upsurge in ionic liquid research. As a new chemical reaction solvent, ionic liquid is known as one of the most ideal reaction media in the clean and green industry in the 21st century. Due to the characteristics of molecular solvents, it presents unique advantages in chemical reactions. It has obvious advantages in improving reaction rate and selectivity and optimizing the recycling of catalysts. It has been widely used to replace traditional molecular solvents and become a new reaction medium. In recent years, ionic liquids have shown great potential in the field of catalysis. The use of ionic liquid catalysts to replace some reactions of other organic catalysts has the characteristics of high reaction yield, easy separation and repeated use, while the catalytic activity is still very good. Therefore, as a new type of reaction medium and catalyst, ionic liquids have attracted more and more attention.
发明内容: Invention content:
本发明的第一方面目的在于提供一种双功能脯氨酸离子液催化剂的制备方法。 The purpose of the first aspect of the present invention is to provide a method for preparing a bifunctional proline ionic liquid catalyst.
本发明为实现上述目的采取的技术方案如下， The technical scheme that the present invention takes for realizing the above object is as follows,
一种双功能脯氨酸离子液催化剂的制备方法，其特征在于，包括以下步骤：称取一定摩尔比的L-脯氨酸和氢卤酸，在室温下持续搅拌反应2小时，减压蒸去水和氢卤酸，再将其置于真空干燥箱，真空80℃下加热1-2小时，得到脯氨酸离子液, 将脯氨酸离子液与路易斯酸混合均匀，再在真空80℃下加热干燥1.5～2h，得到分散均匀的双功能脯氨酸离子液催化剂。 A kind of preparation method of bifunctional proline ionic liquid catalyst, it is characterized in that, comprises the following steps: weigh the L-proline and hydrohalic acid of certain molar ratio, keep stirring reaction at room temperature for 2 hours, evaporate under reduced pressure Remove water and hydrohalic acid, then place it in a vacuum drying oven, heat it at 80°C for 1-2 hours to obtain proline ionic liquid, mix the proline ionic liquid and Lewis acid evenly, and then heat it under vacuum at 80°C Heating and drying at low temperature for 1.5-2 hours to obtain a uniformly dispersed bifunctional proline ionic liquid catalyst.
较优的是： The better ones are:
所述的路易斯酸选自CuI、ZnCl2、FeCl3、CuCl2或MgCl2。 The Lewis acid is selected from CuI, ZnCl 2 , FeCl 3 , CuCl 2 or MgCl 2 .
所述的脯氨酸离子液和路易斯酸按摩尔比1:2～2:1混合。 The proline ionic liquid and Lewis acid are mixed in a molar ratio of 1:2 to 2:1.
本发明的反应路线如下： The reaction scheme of the present invention is as follows:
采用上述方法制得的双功能脯氨酸离子液催化剂，由于同时具有Br?nsted和Lewis酸性中心，具有较高的稳定性和活性，且所用试剂价格均非常低廉，可以在反应中重复回收使用而性能保持不变。 The bifunctional proline ionic liquid catalyst prepared by the above method has high stability and activity due to having both Brönsted and Lewis acid centers, and the reagents used are very cheap and can be recycled and used repeatedly in the reaction And the performance remains the same.
本发明的另一方面目的在于提供一种上述制备的双功能脯氨酸离子液催化剂，在催化由缺电子烯烃和烷基胺进行氮杂Michael加成反应中的应用，其特征在于，使用上述方法制备得到的双功能脯氨酸离子液催化剂进行催化，所述的缺电子烯烃为丙烯酸甲酯、丙烯酸丁酯或甲基丙烯酸甲酯；烷基胺为二乙胺、吗啡啉、哌啶或异丙胺。 Another object of the present invention is to provide a kind of bifunctional proline ionic liquid catalyst prepared above, in catalyzing the application in carrying out aza-Michael addition reaction by electron-deficient olefin and alkylamine, it is characterized in that, using the above-mentioned The bifunctional proline ionic liquid catalyst prepared by the method is catalyzed, and the electron-deficient olefin is methyl acrylate, butyl acrylate or methyl methacrylate; the alkylamine is diethylamine, morpholine, piperidine or Isopropylamine.
催化反应方程式如下： The catalytic reaction equation is as follows:
。 .
本发明的双功能脯氨酸离子液催化剂，在催化上述反应时，具有较高的稳定性和活性，而且在多次循环催化反应后，双功能脯氨酸离子液催化剂的催化活性无明显降低，具有绿色、环保、可循环使用的优点。 The bifunctional proline ionic liquid catalyst of the present invention has higher stability and activity when catalyzing the above reaction, and after multiple cycles of catalytic reactions, the catalytic activity of the bifunctional proline ionic liquid catalyst has no obvious reduction , has the advantages of being green, environmentally friendly and recyclable.
以下结合附图和具体实施方式对本发明作进一步说明。 The present invention will be further described below in conjunction with the accompanying drawings and specific embodiments.
附图说明： Description of drawings:
图1为本发明实施例1的双功能脯氨酸离子液的红外图谱（FT-IR 5DX 型红外光谱仪（美国Nicolet公司），衰减全反射（ATR））；
Fig. 1 is the infrared spectrum of the bifunctional proline ionic liquid of
图2为本发明实施例3中路易斯酸为CuI的双功能离子液催化反应的产物气相色谱图（岛津GC-14CPTF气相色谱仪，Rtx-1 30mx0.25mmX0.25um）； Fig. 2 is the product gas chromatogram (Shimadzu GC-14CPTF gas chromatograph, Rtx-1 30mx0.25mmX0.25um) of the product gas chromatogram (Shimadzu GC-14CPTF gas chromatograph, Rtx-1 30mx0.25mmX0.25um) that Lewis acid is the bifunctional ionic liquid catalytic reaction of CuI in the embodiment of the present invention 3;
图3为本发明实施例1的双功能脯氨酸离子液在循环使用对Michael反应的影响。 Fig. 3 is the influence of the bifunctional proline ionic liquid of Example 1 of the present invention on the Michael reaction during recycling.
具体实施方式: Detailed ways:
实施例1： Example 1:
称取L-脯氨酸（Proline）11.5g（0.1mol）和40%氢溴酸21g（0.11mol），室温搅拌下缓慢滴加40%氢溴酸，30分钟滴完。在室温下继续搅拌反应2小时，减压蒸去水和氢溴酸得到淡黄色液体，再将其置于真空干燥箱，真空加热(80℃)1-2小时，将得到的脯氨酸离子液与9.5g CuI以2:1的摩尔比混合均匀，呈土黄色粘稠液，再真空80℃加热干燥1.5-2h，得到分散均匀的双功能脯氨酸离子液（CuI/Proline（1:2）离子液）。将制得的CuI/Proline（1:2）离子液进行红外图谱分析，CuI/Proline（1:2）离子液的红外图谱显示如图1所示，图中：1460 cm-1是吡啶吸附在Lewis酸上，而在1630，1640 cm-1处的弯曲振动吸收峰是吸附在Br?nsted酸上，说明该催化剂的结构中包含Lewis酸和Br?nsted酸。 Weigh 11.5 g (0.1 mol) of L-proline (Proline) and 21 g (0.11 mol) of 40% hydrobromic acid, slowly add 40% hydrobromic acid dropwise with stirring at room temperature, and drop it in 30 minutes. Continue to stir and react at room temperature for 2 hours, evaporate water and hydrobromic acid under reduced pressure to obtain a light yellow liquid, then place it in a vacuum drying oven, and heat it in vacuum (80°C) for 1-2 hours to obtain the proline ion solution and 9.5g CuI were mixed evenly at a molar ratio of 2:1, and it was an earthy yellow viscous liquid, and then heated and dried in vacuum at 80°C for 1.5-2h to obtain a uniformly dispersed bifunctional proline ionic liquid (CuI/Proline (1: 2) ionic liquid). The prepared CuI/Proline (1:2) ionic liquid was analyzed by infrared spectrum, the infrared spectrum of CuI/Proline (1:2) ionic liquid is shown in Figure 1, in the figure: 1460 cm -1 is pyridine adsorbed on Lewis acid, and the bending vibration absorption peaks at 1630, 1640 cm -1 are adsorbed on Br?nsted acid, indicating that the structure of the catalyst contains both Lewis acid and Br?nsted acid.
实施例2： Example 2:
称取L-脯氨酸11.5 g（0. 1mol）和氢碘酸14 g（0.11mol），室温搅拌下缓慢滴加氢碘酸，10分钟滴完。在室温下继续搅拌反应2小时，减压蒸去水和氢碘酸得到淡黄色液体，再将其置于真空干燥箱，真空加热(80℃)1-2小时，将得到的脯氨酸离子液与19g CuI以1:1的摩尔比混合均匀，呈土黄色粘稠液，再真空80℃加热干燥1.5-2h，得到分散均匀的双功能脯氨酸离子液。 Weigh 11.5 g (0.1 mol) of L-proline and 14 g (0.11 mol) of hydriodic acid, slowly add hydriodic acid dropwise with stirring at room temperature, and finish dropping in 10 minutes. Continue to stir the reaction at room temperature for 2 hours, evaporate water and hydroiodic acid under reduced pressure to obtain a light yellow liquid, then place it in a vacuum drying oven, and heat it in vacuum (80°C) for 1-2 hours, and the obtained proline ion Liquid and 19g CuI were mixed evenly at a molar ratio of 1:1, and it was an earthy yellow viscous liquid, and then heated and dried at 80°C for 1.5-2h in vacuum to obtain a uniformly dispersed bifunctional proline ionic liquid.
实施例3： Example 3:
将丙烯酸甲酯(0.12 mol)、二乙胺(0.1mol)和双功能脯氨酸离子液体(1% mol)（脯氨酸离子液与路易斯酸摩尔比为2:1），在室温下搅拌反应1-5分钟，进行氮杂Michael加成反应，其实验数据见下表。 Methyl acrylate (0.12 mol), diethylamine (0.1 mol) and bifunctional proline ionic liquid (1% mol) (the molar ratio of proline ionic liquid to Lewis acid is 2:1) were stirred at room temperature React for 1-5 minutes to carry out aza-Michael addition reaction, and the experimental data are shown in the table below.
表1 不同催化剂在不同反应时间下的催化反应效果 Table 1 Catalytic reaction effects of different catalysts at different reaction times
实施例3中CuI/Proline（1:2）离子液体的催化效果进行气相色谱分析如图2所示，图2中：3.1分钟左右的峰为过量的丙烯酸甲酯，而5.9分钟左右的峰为产物的色谱峰。 Gas chromatographic analysis of the catalytic effect of CuI/Proline (1:2) ionic liquid in Example 3 is shown in Figure 2, in Figure 2: the peak at about 3.1 minutes is excess methyl acrylate, and the peak at about 5.9 minutes is The chromatographic peak of the product.
实施例4： Example 4:
将实施例1中制备得到的离子液催化剂，一次使用后，通过离心分液进行分离，用丙酮（5mL）洗涤后减压蒸馏回收后，循环催化二乙胺和丙烯酸甲酯（1: 1.2）的氮杂Michael加成反应，催化活性无明显降低，其催化效果如图3所示。 After the ionic liquid catalyst prepared in Example 1 is used once, it is separated by centrifugation, washed with acetone (5mL) and recovered by distillation under reduced pressure, and then recycled to catalyze diethylamine and methyl acrylate (1: 1.2) The aza-Michael addition reaction did not significantly reduce the catalytic activity, and its catalytic effect is shown in Figure 3.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1621152A (en) * | 2004-10-11 | 2005-06-01 | 北京大学 | Ion liquid of amino acid ester cation and its preparation method |
| CN1631539A (en) * | 2004-12-03 | 2005-06-29 | 北京大学 | Amino acid salt ionic liquid and preparation method thereof |
| CN101050196A (en) * | 2007-05-15 | 2007-10-10 | 武汉大学 | Bronsted acidic compound of containing L- proline radical, preparation method, and application |
| CN101050195A (en) * | 2007-05-15 | 2007-10-10 | 武汉大学 | Compound of containing cation radical of L - proline, preparation method, and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1621152A (en) * | 2004-10-11 | 2005-06-01 | 北京大学 | Ion liquid of amino acid ester cation and its preparation method |
| CN1631539A (en) * | 2004-12-03 | 2005-06-29 | 北京大学 | Amino acid salt ionic liquid and preparation method thereof |
| CN101050196A (en) * | 2007-05-15 | 2007-10-10 | 武汉大学 | Bronsted acidic compound of containing L- proline radical, preparation method, and application |
| CN101050195A (en) * | 2007-05-15 | 2007-10-10 | 武汉大学 | Compound of containing cation radical of L - proline, preparation method, and application |
Non-Patent Citations (2)
| Title |
|---|
| 柳文敏 等，."L_脯氨酸离子液催化苹果酯的合成".《南阳师范学院学报》.2010,第9卷(第9期),第27-30页. |
| 柳文敏 等,."L_脯氨酸离子液催化苹果酯的合成".《南阳师范学院学报》.2010,第9卷(第9期),第27-30页. * |
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