CN105152922A - Method for synthesizing benzoic acid with thioxanthone catalyst under condition of illumination - Google Patents
Method for synthesizing benzoic acid with thioxanthone catalyst under condition of illumination Download PDFInfo
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- CN105152922A CN105152922A CN201510425696.7A CN201510425696A CN105152922A CN 105152922 A CN105152922 A CN 105152922A CN 201510425696 A CN201510425696 A CN 201510425696A CN 105152922 A CN105152922 A CN 105152922A
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- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 35
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 238000005286 illumination Methods 0.000 title claims description 4
- 239000005711 Benzoic acid Substances 0.000 title abstract description 22
- 235000010233 benzoic acid Nutrition 0.000 title abstract description 22
- 239000003054 catalyst Substances 0.000 title abstract description 17
- 230000002194 synthesizing effect Effects 0.000 title abstract description 5
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 64
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- 239000002904 solvent Substances 0.000 claims abstract description 21
- 239000002994 raw material Substances 0.000 claims abstract description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 24
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 21
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 11
- 239000011521 glass Substances 0.000 claims description 11
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 230000003647 oxidation Effects 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 4
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 claims description 4
- 238000013019 agitation Methods 0.000 claims 1
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 abstract description 4
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 230000003749 cleanliness Effects 0.000 abstract description 2
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- 238000003760 magnetic stirring Methods 0.000 abstract description 2
- 239000002243 precursor Substances 0.000 abstract description 2
- 238000001308 synthesis method Methods 0.000 abstract description 2
- 231100000331 toxic Toxicity 0.000 abstract description 2
- 230000002588 toxic effect Effects 0.000 abstract description 2
- 238000004440 column chromatography Methods 0.000 description 7
- 238000004128 high performance liquid chromatography Methods 0.000 description 7
- 238000000746 purification Methods 0.000 description 7
- 238000002390 rotary evaporation Methods 0.000 description 7
- 238000000926 separation method Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 4
- 229910001385 heavy metal Inorganic materials 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 235000019249 food preservative Nutrition 0.000 description 2
- 239000005452 food preservative Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- SLRMQYXOBQWXCR-UHFFFAOYSA-N 2154-56-5 Chemical compound [CH2]C1=CC=CC=C1 SLRMQYXOBQWXCR-UHFFFAOYSA-N 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/255—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of compounds containing six-membered aromatic rings without ring-splitting
- C07C51/265—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of compounds containing six-membered aromatic rings without ring-splitting having alkyl side chains which are oxidised to carboxyl groups
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0215—Sulfur-containing compounds
- B01J31/0229—Sulfur-containing compounds also containing elements or functional groups covered by B01J31/0201 - B01J31/0214
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明属于化工技术领域，具体涉及一种以光照为条件噻吨酮催化合成苯甲酸的方法。本发明步骤为：将原料甲苯、噻吨酮催化剂及溶剂加入反应器中；空气氛中磁力搅拌反应；反应温度25-100℃；在可见光光照条件下反应1-100h。本发明方法避免了传统合成方法中使用高腐蚀性，高毒，易制毒试剂，提高了工业合成反应的清洁性，降低了环境污染，降低了能耗。本发明方法采用正丁醇作为反应的催化剂，降低了成本。本发明方法一步完成，使用的原料种类单一，提高了工艺的经济性。The invention belongs to the technical field of chemical industry, and in particular relates to a method for catalytically synthesizing benzoic acid with thioxanthone under the condition of light. The steps of the invention are as follows: adding raw materials toluene, thioxanthone catalyst and solvent into a reactor; magnetic stirring reaction in an air atmosphere; reaction temperature of 25-100 DEG C; and reaction for 1-100 hours under the condition of visible light. The method of the invention avoids the use of highly corrosive, highly toxic and precursor reagents in the traditional synthesis method, improves the cleanliness of industrial synthesis reactions, reduces environmental pollution, and reduces energy consumption. The method of the invention adopts n-butanol as the catalyst of the reaction, which reduces the cost. The method of the invention is completed in one step, and the types of raw materials used are single, thereby improving the economical efficiency of the process.
Description
技术领域 technical field
本发明属于化工技术领域，具体涉及一种合成苯甲酸的方法，尤其是涉及一种以光照为条件噻吨酮催化合成苯甲酸的方法。 The invention belongs to the technical field of chemical industry, and in particular relates to a method for synthesizing benzoic acid, in particular to a method for catalyzing the synthesizing of benzoic acid with thioxanthone under the condition of light.
背景技术 Background technique
苯甲酸为具有苯或甲醛的气味的鳞片状或针状结晶。熔点122.13℃，沸点249℃，微溶于水，易溶于乙醇、乙醚等有机溶剂。苯甲酸用于医药、染料载体、增塑剂、香料和食品防腐剂等的生产，也用于醇酸树脂涂料的性能改进。苯甲酸是重要的酸型食品防腐剂。其分子式为C7H6O2，相对分子质量为122.1214。苯甲酸的结构式为： Benzoic acid is scaly or needle-like crystals with the smell of benzene or formaldehyde. Melting point 122.13°C, boiling point 249°C, slightly soluble in water, easily soluble in organic solvents such as ethanol and ether. Benzoic acid is used in the production of medicines, dye carriers, plasticizers, spices and food preservatives, and is also used in the performance improvement of alkyd resin coatings. Benzoic acid is an important acid-type food preservative. Its molecular formula is C 7 H 6 O 2 , and its relative molecular mass is 122.1214. The structural formula of benzoic acid is:
目前，全球普遍采用的是甲苯热氧化法制备苯甲酸的生产工艺。该法利用重金属盐钴或锰作为催化剂，在高温高压的条件下，实现对甲苯的进行氧化，并最终合成苯甲酸。该法为美国Allied化学公司率先研发成功，后经意大利SNIA粘胶公司加以改进，并于1983年大规模投产。之后，各国只是在催化剂组成，产品精制以及环保方面进行了一些改进。整体生产工艺一直延用至今。我国现在主要采用的就是这种方法。该方法需要采用重金属钴或锰作为催化剂。在造成了重金属污染的同时，还增加了成本。 At present, the production process of preparing benzoic acid by thermal oxidation of toluene is widely used in the world. The method utilizes heavy metal salt cobalt or manganese as a catalyst to oxidize p-toluene under high temperature and high pressure conditions, and finally synthesize benzoic acid. The method was first successfully developed by Allied Chemical Company of the United States, then improved by SNIA Viscose Company of Italy, and put into large-scale production in 1983. After that, countries only made some improvements in terms of catalyst composition, product refining and environmental protection. The overall production process has been used to this day. This method is mainly adopted in our country now. This method requires the use of heavy metals cobalt or manganese as catalysts. While causing heavy metal pollution, it also increases the cost.
随着环境经济的发展，苯甲酸的传统的生产方法所暴露出来的不具有可持续发展性的弊端，亟需被环境更友好的方法所取代。 With the development of environmental economy, the disadvantages of unsustainable development exposed by traditional production methods of benzoic acid urgently need to be replaced by more environmentally friendly methods.
光化学作为一门新兴学科，在欧美国家已经得到了较为系统的发展。其中，有机光化学的基本理论体系已经建立起来了。但在中国，有机光化学的发展还比较落后。光照而引发的自由基反应，往往可以在很低的温度下进行，此时很多副反应已不能发生，另外很多官能团在光照下并不是活性很高或根本不参与光反应，因此该反应的官能团容忍性将会很好，更利于在全合成的工作中发挥作用。将光化学的方法用于很多反应，将不再需要苛刻的无水无氧条件，操作更加容易。此外，光能比加热更清洁，并节约能源，降低成本，同时可以减少金属试剂带来的污染和降低成本。 As a new subject, photochemistry has been developed systematically in European and American countries. Among them, the basic theoretical system of organic photochemistry has been established. But in China, the development of organic photochemistry is still relatively backward. The free radical reaction induced by light can often be carried out at a very low temperature. At this time, many side reactions can no longer occur. In addition, many functional groups are not very active or do not participate in the photoreaction under light. Therefore, the functional groups of this reaction It will be well tolerated and better suited for fully synthetic work. Using photochemical methods for many reactions will no longer require harsh anhydrous and oxygen-free conditions, and the operation will be easier. In addition, light energy is cleaner than heating, saves energy, reduces costs, and can reduce pollution caused by metal reagents and reduce costs.
发明内容 Contents of the invention
本发明的目的在于提供一种能够降低重金属污染，减少生产成本的以光照为条件噻吨酮催化合成苯甲酸的方法。 The object of the present invention is to provide a kind of method that can reduce heavy metal pollution, reduce the method for the catalyzed synthesis of benzoic acid with thioxanthone under the condition of light irradiation.
本发明提供的以光照为条件噻吨酮催化合成苯甲酸的方法，是采用有机光化学方法，甲苯在被光照激发的噻吨酮催化剂的催化作用下，脱除一个氢原子，生成相应的苄基自由基中间体，随后苄基自由基在空气的氧化作用下氧化成苯甲醛，苯甲醛进一步被空气氧化成苯甲酸。本发明也提供了一种在光照条件下，碳氢键断裂以及高选择性氧化的方法。 The method for catalyzing the synthesis of benzoic acid with thioxanthone under the condition of light provided by the invention adopts an organic photochemical method, and toluene removes a hydrogen atom under the catalysis of the thioxanthone catalyst excited by light to generate the corresponding benzyl The free radical intermediate is subsequently oxidized by the benzyl radical to benzaldehyde under the oxidation of air, which is further oxidized by air to benzoic acid. The invention also provides a method for carbon-hydrogen bond breaking and highly selective oxidation under light conditions.
本发明提供的以光照为条件噻吨酮催化合成苯甲酸的方法，具体步骤为：将原料甲苯、噻吨酮催化剂及溶剂加入反应器中；空气气氛中磁力搅拌反应；反应温度25-100℃；在可见光光照条件下反应1-100h，其中：噻吨酮催化剂用量为甲苯质量分数的0.1%-5%，优选2-4%，溶剂的用量为甲苯体积的1-5倍， The method for catalyzing and synthesizing benzoic acid with thioxanthone under the condition of light provided by the invention comprises the following steps: adding raw materials toluene, thioxanthone catalyst and solvent into a reactor; magnetic stirring reaction in air atmosphere; reaction temperature 25-100°C ; Reaction 1-100h under visible light illumination conditions, wherein: the consumption of thioxanthone catalyst is 0.1%-5% of the mass fraction of toluene, preferably 2-4%, and the consumption of solvent is 1-5 times of the volume of toluene,
本发明中，噻吨酮催化剂用量为甲苯质量分数的2-4%。 In the present invention, the dosage of thioxanthone catalyst is 2-4% of the mass fraction of toluene.
本发明中，溶剂的用量为甲苯体积的2-3倍。 In the present invention, the consumption of solvent is 2-3 times of the volume of toluene.
本发明中，所述的反应器为玻璃反应器，反应器压力为常压。 In the present invention, the reactor is a glass reactor, and the reactor pressure is normal pressure.
本发明中，所述的反应器与球型冷凝管相连接，让反应在空气的氧化下进行。 In the present invention, the reactor is connected with a spherical condenser so that the reaction can be carried out under the oxidation of air.
本发明中，所述的催化剂为噻吨酮。使用催化剂可以提高反应速度、产率和选择性。 In the present invention, the catalyst is thioxanthone. The use of catalysts can increase reaction rate, yield and selectivity.
本发明中，所述的溶剂选用二氯甲烷、DMSO、THF、苯、乙腈或硝基甲烷中一种，或其中几种的混合物。优选乙腈和苯。 In the present invention, the solvent is selected from one of dichloromethane, DMSO, THF, benzene, acetonitrile or nitromethane, or a mixture of several of them. Acetonitrile and benzene are preferred.
本发明中，优选的技术方案是：在反应器中通入含氧气体，加入催化剂，加入溶剂，所用的催化剂为噻吨酮，所选溶剂为二氯甲烷、DMSO、THF、苯、乙腈、硝基甲烷中一种或几种混合物。 Among the present invention, preferred technical scheme is: pass into oxygen-containing gas in reactor, add catalyst, add solvent, and used catalyst is thioxanthone, and selected solvent is dichloromethane, DMSO, THF, benzene, acetonitrile, One or more mixtures of nitromethane.
本发明中，进一步优选的技术方案是：以玻璃反应瓶为反应容器，空气为氧化剂，反应温度为室温，催化剂选用噻吨酮，溶剂选择乙腈或苯。 In the present invention, a further preferred technical solution is: use a glass reaction bottle as the reaction vessel, air as the oxidant, the reaction temperature at room temperature, thioxanthone as the catalyst, and acetonitrile or benzene as the solvent.
本发明典型的合成步骤如下：用有机溶剂溶解甲苯，再加入适量催化剂，通入空气，在常温、常压下在光照条件下搅拌反应1-100h。经高效液相色谱确定，原料甲苯已经反应完全，真空旋转蒸发，柱层析分离纯化，计算苯甲醛和苯甲酸各自组分含量。 The typical synthesis steps of the present invention are as follows: dissolving toluene with an organic solvent, adding an appropriate amount of catalyst, introducing air, stirring and reacting for 1-100 hours at normal temperature and pressure under light conditions. It was determined by high-performance liquid chromatography that the raw material toluene had been completely reacted, vacuum rotary evaporation, separation and purification by column chromatography, and the respective component contents of benzaldehyde and benzoic acid were calculated.
本发明方法与传统工艺相比有着显著的优点： Compared with traditional technology, the inventive method has significant advantages:
（1）新方法采用了可见光为能量来源，为工业上制备各种精细化学品提供了一种全新的思路。 (1) The new method uses visible light as the energy source, which provides a new idea for the industrial preparation of various fine chemicals.
（2）本发明方法避免了传统合成方法中使用高腐蚀性，高毒，易制毒试剂，提高了工业合成反应的清洁性，降低了环境污染，降低了能耗。 (2) The method of the present invention avoids the use of highly corrosive, highly toxic, and precursor reagents in traditional synthesis methods, improves the cleanliness of industrial synthesis reactions, reduces environmental pollution, and reduces energy consumption.
（3）本发明方法采用正丁醇作为反应的催化剂，降低了成本。 (3) The inventive method adopts n-butanol as the catalyst of the reaction, which reduces the cost.
（4）本发明方法一步完成，使用的原料种类单一，提高了工艺的经济性。 (4) The method of the present invention is completed in one step, and the types of raw materials used are single, which improves the economy of the process.
（5）本发明方法可选择在常温、常压下完成反应。在常温、常压下反应可以降低对反应设备的要求，降低反应设备制造成本及反应过程成本，提高反应的安全性。 (5) The method of the present invention can be selected to complete the reaction at normal temperature and pressure. The reaction at normal temperature and normal pressure can reduce the requirements for the reaction equipment, reduce the manufacturing cost of the reaction equipment and the cost of the reaction process, and improve the safety of the reaction.
（6）本发明采用空气作为氧化剂来源，进一步节约了成本。 (6) The present invention uses air as the source of oxidant, further saving costs.
（7）本发明方法提供了一种碳氢键高效断裂，以及高选择性氧化的新方法。 (7) The method of the present invention provides a new method for efficient breaking of carbon-hydrogen bonds and highly selective oxidation.
反应器在实验室可以使用玻璃反应器，工业生产时可以使用带有玻璃片的釜式反应器或管式反应器等。 The reactor can use a glass reactor in the laboratory, and a tank reactor or a tubular reactor with a glass sheet can be used in industrial production.
具体实施方式 Detailed ways
以下结合具体实施例，对本发明进行详细说明。 The present invention will be described in detail below in conjunction with specific embodiments.
实施例1Example 1
在50mL玻璃反应瓶中，加入92mg甲苯，3倍体积的溶剂乙腈，5%质量分数的噻吨酮，空气氛中磁力搅拌，在25℃温度，可见光光照下反应100小时。反应时间达到后，经高效液相色谱分析，只有单一的产物苯甲酸生成。真空旋转蒸发，柱层析分离纯化，产物质量为68mg，产率为50%。 In a 50mL glass reaction vial, add 92mg of toluene, 3 times the volume of solvent acetonitrile, 5% mass fraction of thioxanthone, stir magnetically in an air atmosphere, and react for 100 hours at 25°C under visible light. After the reaction time was up, only a single product, benzoic acid, was generated through high-performance liquid chromatography analysis. Rotary evaporation in vacuum, separation and purification by column chromatography, the product quality was 68 mg, and the yield was 50%.
实施例2Example 2
在50mL玻璃反应瓶中，加入92mg甲苯，5倍体积的溶剂DMSO，0.1%质量分数的噻吨酮，空气氛中磁力搅拌，在70℃温度，可将光光照下反应50小时。反应时间达到后，经高效液相色谱分析，只有单一的产物苯甲酸生成。真空旋转蒸发，柱层析分离纯化，产物质量为80mg，产率为66%。 In a 50mL glass reaction bottle, add 92mg of toluene, 5 times the volume of solvent DMSO, 0.1% mass fraction of thioxanthone, magnetically stir in an air atmosphere, and react under light for 50 hours at a temperature of 70°C. After the reaction time was up, only a single product, benzoic acid, was generated through high-performance liquid chromatography analysis. Rotary evaporation in vacuum, separation and purification by column chromatography, the product quality was 80 mg, and the yield was 66%.
实施例3Example 3
在50mL玻璃反应瓶中，加入92mg甲苯，3倍体积的溶剂苯，2%质量分数的噻吨酮，空气氛中磁力搅拌，在100℃温度，可见光光照下反应1小时。反应时间达到后，经高效液相色谱分析，只有单一的产物苯甲酸生成。真空旋转蒸发，柱层析分离纯化，产物质量为122mg，产率为100%。 In a 50 mL glass reaction vial, add 92 mg of toluene, 3 times the volume of solvent benzene, and 2% mass fraction of thioxanthone, stir magnetically in an air atmosphere, and react for 1 hour at a temperature of 100 ° C under visible light. After the reaction time was up, only a single product, benzoic acid, was generated through high-performance liquid chromatography analysis. Rotary evaporation in vacuum, separation and purification by column chromatography, the product quality was 122 mg, and the yield was 100%.
实施例4Example 4
在50mL玻璃反应瓶中，加入92mg甲苯，1倍体积的溶剂二氯甲烷，5%质量分数的噻吨酮，空气氛中磁力搅拌，在45℃温度，可见光光照下反应40小时。反应时间达到后，经高效液相色谱分析，只有单一的产物苯甲酸生成。真空旋转蒸发，柱层析分离纯化，产物质量为60mg，产率为45%。 In a 50mL glass reaction vial, add 92mg of toluene, 1 volume of dichloromethane as a solvent, and 5% by mass of thioxanthone, stir magnetically in an air atmosphere, and react for 40 hours at a temperature of 45°C under visible light. After the reaction time was up, only a single product, benzoic acid, was generated through high-performance liquid chromatography analysis. Vacuum rotary evaporation, separation and purification by column chromatography, the product quality is 60 mg, and the yield is 45%.
实施例5Example 5
在50mL玻璃反应瓶中，加入92mg甲苯，4倍体积的溶剂THF，3%质量分数的噻吨酮，空气氛中磁力搅拌，在80℃温度，可将光光照下反应90小时。反应时间达到后，经高效液相色谱分析，只有单一的产物苯甲酸生成。真空旋转蒸发，柱层析分离纯化，产物质量为70mg，产率为60%。 In a 50mL glass reaction bottle, add 92mg of toluene, 4 times the volume of solvent THF, and 3% mass fraction of thioxanthone, stir magnetically in an air atmosphere, and react under light for 90 hours at a temperature of 80°C. After the reaction time was up, only a single product, benzoic acid, was generated through high-performance liquid chromatography analysis. Vacuum rotary evaporation, separation and purification by column chromatography, the product quality is 70 mg, and the yield is 60%.
实施例6Example 6
在50mL玻璃反应瓶中，加入92mg甲苯，1倍体积的溶剂THF，1倍体积的溶剂硝基甲烷，1倍体积的溶剂乙腈，1倍体积的溶剂苯，2%质量分数的噻吨酮，空气氛中磁力搅拌，在30℃温度，可将光光照下反应50小时。反应时间达到后，经高效液相色谱分析，只有单一的产物苯甲酸生成。真空旋转蒸发，柱层析分离纯化，产物质量为77mg，产率为65%。 In a 50mL glass reaction vial, add 92mg of toluene, 1 volume of solvent THF, 1 volume of solvent nitromethane, 1 volume of solvent acetonitrile, 1 volume of solvent benzene, 2% mass fraction of thioxanthone, Stir magnetically in an air atmosphere, and react under light for 50 hours at a temperature of 30°C. After the reaction time was up, only a single product, benzoic acid, was generated through high-performance liquid chromatography analysis. Rotary evaporation in vacuum, separation and purification by column chromatography, the product quality was 77 mg, and the yield was 65%.
应当理解的是，对本领域普通技术人员来说，可以根据上述说明加以改进或变换，而所有这些改进和变换都应属于本发明所附权利要求的保护范围。 It should be understood that those skilled in the art can make improvements or changes based on the above description, and all these improvements and changes should belong to the protection scope of the appended claims of the present invention.
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| CN107805194A (en) * | 2017-10-26 | 2018-03-16 | 复旦大学 | A kind of preparation method of the benzoic acid of 9 thiophene ketone compound for catalysis |
| CN107805195A (en) * | 2017-10-26 | 2018-03-16 | 复旦大学 | The preparation method of benzoic acid under a kind of illumination condition |
| CN107805196A (en) * | 2017-10-26 | 2018-03-16 | 复旦大学 | A kind of synthetic method of benzoic acid of the visible ray according under |
| CN107814695A (en) * | 2017-10-26 | 2018-03-20 | 复旦大学 | A kind of synthetic method of benzoic acid under 9 thiophene ketone compound for catalysis |
| CN107814696A (en) * | 2017-10-26 | 2018-03-20 | 复旦大学 | A kind of preparation method of benzoic acid |
| CN107827731A (en) * | 2017-10-26 | 2018-03-23 | 复旦大学 | The synthetic method of oxidation generation benzoic acid under a kind of illumination condition |
| CN107879923A (en) * | 2017-10-26 | 2018-04-06 | 复旦大学 | The synthetic method of the benzoic acid of 9 thiophene ketone compound for catalysis under a kind of visible light conditions |
| CN107879924A (en) * | 2017-10-26 | 2018-04-06 | 复旦大学 | The synthetic method of benzoic acid under a kind of illumination condition |
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