CN103214328B - Synthesis method for alpha-bromo-aromatic ketone compounds - Google Patents
Synthesis method for alpha-bromo-aromatic ketone compounds Download PDFInfo
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- 238000001308 synthesis method Methods 0.000 title description 6
- -1 ketone compound Chemical class 0.000 claims abstract description 57
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000010189 synthetic method Methods 0.000 claims abstract description 28
- 239000003054 catalyst Substances 0.000 claims abstract description 24
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 20
- 150000002576 ketones Chemical class 0.000 claims abstract description 18
- 230000031709 bromination Effects 0.000 claims abstract description 17
- 238000005893 bromination reaction Methods 0.000 claims abstract description 17
- 239000011259 mixed solution Substances 0.000 claims abstract description 12
- 239000012141 concentrate Substances 0.000 claims abstract description 11
- 239000003480 eluent Substances 0.000 claims abstract description 11
- 239000003208 petroleum Substances 0.000 claims abstract description 11
- 238000000746 purification Methods 0.000 claims abstract description 9
- 238000000926 separation method Methods 0.000 claims abstract description 9
- 238000010898 silica gel chromatography Methods 0.000 claims abstract description 9
- 239000003960 organic solvent Substances 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims description 41
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 24
- HJUGFYREWKUQJT-UHFFFAOYSA-N tetrabromomethane Chemical group BrC(Br)(Br)Br HJUGFYREWKUQJT-UHFFFAOYSA-N 0.000 claims description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 11
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 11
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 10
- JFJNVIPVOCESGZ-UHFFFAOYSA-N 2,3-dipyridin-2-ylpyridine Chemical group N1=CC=CC=C1C1=CC=CN=C1C1=CC=CC=N1 JFJNVIPVOCESGZ-UHFFFAOYSA-N 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 8
- 229910001509 metal bromide Inorganic materials 0.000 claims description 7
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 6
- 150000008365 aromatic ketones Chemical class 0.000 claims description 3
- GIKVBRPARHQMMK-UHFFFAOYSA-M [Ru+]=O.[Cl-] Chemical compound [Ru+]=O.[Cl-] GIKVBRPARHQMMK-UHFFFAOYSA-M 0.000 claims description 2
- CTPLJPLKYKCNAY-UHFFFAOYSA-N 2-(4-methoxyphenyl)-3-(4-nitrophenyl)oxirane Chemical compound C1=CC(OC)=CC=C1C1C(C=2C=CC(=CC=2)[N+]([O-])=O)O1 CTPLJPLKYKCNAY-UHFFFAOYSA-N 0.000 claims 1
- ZKZNUVVMVYSOFM-UHFFFAOYSA-N 2-(4-methoxyphenyl)-3-phenyloxirane Chemical compound C1=CC(OC)=CC=C1C1C(C=2C=CC=CC=2)O1 ZKZNUVVMVYSOFM-UHFFFAOYSA-N 0.000 claims 1
- YUWWNQUBHDXKMT-UHFFFAOYSA-N Epoxyanethole Chemical compound C1=CC(OC)=CC=C1C1C(C)O1 YUWWNQUBHDXKMT-UHFFFAOYSA-N 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- VLSGACWGKWLNCR-UHFFFAOYSA-N ethyl 3-(4-methoxyphenyl)oxirane-2-carboxylate Chemical compound CCOC(=O)C1OC1C1=CC=C(OC)C=C1 VLSGACWGKWLNCR-UHFFFAOYSA-N 0.000 claims 1
- IEMGDBAQQAUBCA-UHFFFAOYSA-M lithium;bromide;hydrobromide Chemical compound [Li+].Br.[Br-] IEMGDBAQQAUBCA-UHFFFAOYSA-M 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 16
- 238000005481 NMR spectroscopy Methods 0.000 description 9
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 8
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 8
- 239000000758 substrate Substances 0.000 description 6
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 4
- HIJBTEQTPNSNOY-UHFFFAOYSA-N 1-bromo-1-(4-methoxyphenyl)propan-2-one Chemical compound COC1=CC=C(C(Br)C(C)=O)C=C1 HIJBTEQTPNSNOY-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical compound BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 238000001311 chemical methods and process Methods 0.000 description 3
- 125000004185 ester group Chemical group 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 125000000468 ketone group Chemical group 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000011941 photocatalyst Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- PYQQRMAHBJULNP-UHFFFAOYSA-N C(CC)(=O)O.C1CO1 Chemical compound C(CC)(=O)O.C1CO1 PYQQRMAHBJULNP-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 238000013375 chromatographic separation Methods 0.000 description 1
- 238000011097 chromatography purification Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/582—Recycling of unreacted starting or intermediate materials
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
一种α-溴代芳香酮类化合物的合成方法，本发明涉及一种α-溴代芳香酮类化合物的合成方法，本发明是要解决现有α-溴代芳香酮类化合物的合成方法对环境有污染、无选择性并且产率低问题，具体方法为：向芳香环氧乙烷类化合物中加入溴化试剂和光反应催化剂，然后在可见光照射下，在有机溶剂中室温反应6～12h，然后进行过滤浓缩，再以体积比为(10～16)∶1的石油醚∶乙酸乙酯的混合溶液作为洗脱剂，进行硅胶柱层析纯化分离，得到α-溴代芳香酮类化合物，即完成α-溴代芳香酮类化合物的合成方法。本发明应用于化工领域。A kind of synthetic method of α-bromoaromatic ketone compound, the present invention relates to a kind of synthetic method of α-bromoaromatic ketone compound, the present invention is to solve the synthetic method of existing α-bromoaromatic ketone compound The environment has the problems of pollution, non-selectivity and low yield. The specific method is: add bromination reagent and photoreaction catalyst to aromatic oxirane compounds, and then react in an organic solvent at room temperature for 6 to 12 hours under visible light irradiation. Then filter and concentrate, and then use the volume ratio of (10-16): 1 petroleum ether: ethyl acetate mixed solution as eluent, carry out silica gel column chromatography purification and separation to obtain α-bromoaromatic ketone compounds, That is to complete the synthetic method of α-bromoaromatic ketones. The invention is applied in the field of chemical industry.
Description
技术领域technical field
本发明涉及一种α-溴代芳香酮类化合物的合成方法。The invention relates to a method for synthesizing α-bromoaromatic ketones.
背景技术Background technique
α-溴代芳香酮类化合物是医药和农药等精细有机合成化学品的重要中间体。由于其具有高反应活性，在作为前体片段构筑复杂分子方面吸引了越来越多的关注，人们也更加重视其合成方法的研究。α-Bromoaromatic ketones are important intermediates of fine organic synthetic chemicals such as pharmaceuticals and pesticides. Due to its high reactivity, it has attracted more and more attention in the construction of complex molecules as precursor fragments, and more attention has been paid to the study of its synthetic methods.
α-溴代芳香酮类化合物的合成方法很多，其中大多数方法是采用液溴或溴化氢作为溴化试剂对相应芳香酮的α-位进行溴代。然而，该类溴化试剂的使用却日益受到限制，这是由于其毒性、强挥发性和刺激性、对设备的腐蚀性、生产和运输上的安全性问题及产生大量酸性废气会对环境产生极大的污染和破坏，不可避免地会威胁到人类社会的和谐发展，产率仅为50％左右，并且会同时生成一溴取代和二溴取代产物，反应的选择性差。因此，使用低毒无污染的溴化试剂，寻求到一种绿色环保、操作简单并具有选择性、高产率的α-溴代芳香酮类化合物的合成方法是合乎人们需求的。There are many synthetic methods for α-bromoaromatic ketones, most of which use liquid bromine or hydrogen bromide as bromination reagents to bromine the α-position of the corresponding aromatic ketones. However, the use of such brominated reagents is increasingly limited because of its toxicity, strong volatility and irritation, corrosion to equipment, safety issues in production and transportation, and the generation of a large amount of acidic waste gas that will cause environmental damage. Great pollution and destruction will inevitably threaten the harmonious development of human society. The yield is only about 50%, and monobromine and dibromine substitution products will be produced at the same time, and the selectivity of the reaction is poor. Therefore, it is desirable to seek a synthetic method of α-bromoaromatic ketones with low toxicity and pollution-free bromination reagents, which is environmentally friendly, simple to operate, selective and high in yield.
发明内容Contents of the invention
本发明是要解决现有α-溴代芳香酮类化合物的合成方法对环境有污染、选择性差并且产率低问题，提供了一种α-溴代芳香酮类化合物的合成方法。The invention aims to solve the problems of environmental pollution, poor selectivity and low yield in the prior synthesis method of α-bromoaromatic ketones, and provides a synthesis method of α-bromoaromatic ketones.
本发明一种α-溴代芳香酮类化合物的合成方法，通过以下步骤进行：向芳香环氧乙烷类化合物中加入溴化试剂和光反应催化剂，然后在可见光照射下，在有机溶剂中室温反应6～12h，然后进行过滤并浓缩反应液至干，再以体积比为(10～16)∶1的石油醚∶乙酸乙酯的混合溶液作为洗脱剂，进行硅胶柱层析纯化分离，得到α-溴代芳香酮类化合物，即完成α-溴代芳香酮类化合物的合成方法，其中溴化试剂为四溴化碳或金属溴化物，光反应催化剂为三联吡啶氯化钌；其中芳香环氧乙烷类化合物与溴化试剂的摩尔比为1∶(1.1～1.5)，芳香环氧乙烷类化合物与光反应催化剂的摩尔比为1∶(0.01～0.05)。The synthesis method of a kind of α-bromoaromatic ketone compound of the present invention is carried out through the following steps: add bromination reagent and photoreaction catalyst to aromatic oxirane compound, then under visible light irradiation, react in organic solvent at room temperature 6-12h, then filter and concentrate the reaction solution to dryness, then use the mixed solution of petroleum ether: ethyl acetate with a volume ratio of (10-16): 1 as eluent, carry out purification and separation by silica gel column chromatography, and obtain α-Bromoaromatic ketone compound, that is to complete the synthesis method of α-bromoaromatic ketone compound, wherein the bromination reagent is carbon tetrabromide or metal bromide, and the photoreaction catalyst is terpyridyl ruthenium chloride; wherein the aromatic ring The molar ratio of the oxirane compound to the bromination reagent is 1: (1.1-1.5), and the molar ratio of the aromatic oxirane compound to the photoreaction catalyst is 1: (0.01-0.05).
本发明在常温常压下即可反应，反应条件温和，无需严格的除水处理及惰性气体保护，加料顺序任意，操作简单方便。反应采用清洁、易得的可见光作为能量来源，家用的白炽灯、LED灯以及太阳光均可作为光源，清洁无污染；采用的溴化试剂为低毒的四溴化碳或金属溴化物，廉价易得，易于加料，辅助催化剂过硫酸钠便宜易得且无污染；光催化剂用量少且能够回收再利用。并且本发明的反应底物的适用范围广，可以利用不同的芳香环氧乙烷类底物实现反应的高产率，例如烷基、酮基、酯基和芳香基团等。本发明的产率和选择性均较高，部分反应收率可高达90％以上，而且生成单一溴代产物，无二溴取代的产物生成；；整个反应安全环保，成本低，经济效益高，属于绿色化学工艺。The invention can react at normal temperature and pressure, has mild reaction conditions, does not need strict water removal treatment and inert gas protection, has arbitrary feeding sequence, and is simple and convenient to operate. The reaction uses clean and easily available visible light as the energy source. Household incandescent lamps, LED lamps and sunlight can be used as light sources, clean and pollution-free; the bromination reagent used is low-toxic carbon tetrabromide or metal bromide, which is cheap Easy to obtain, easy to add materials, the auxiliary catalyst sodium persulfate is cheap and easy to obtain and has no pollution; the amount of photocatalyst is small and can be recycled and reused. Moreover, the reaction substrate of the present invention has a wide range of applications, and can utilize different aromatic oxirane substrates to achieve high yields of the reaction, such as alkyl groups, ketone groups, ester groups, and aromatic groups. The yield and selectivity of the present invention are high, and the partial reaction yield can be as high as more than 90%, and a single brominated product is generated, and no dibrominated product is generated; the whole reaction is safe and environmentally friendly, with low cost and high economic benefit. It belongs to the green chemical process.
具体实施方式Detailed ways
具体实施方式一：本实施方式一种α-溴代芳香酮类化合物的合成方法，通过以下步骤进行：向芳香环氧乙烷类化合物中加入溴化试剂和光反应催化剂，然后在可见光照射下，在有机溶剂中室温反应6～12h，然后进行过滤并浓缩反应液至干，再以体积比为(10～16)∶1的石油醚∶乙酸乙酯的混合溶液作为洗脱剂，进行硅胶柱层析纯化分离，得到α-溴代芳香酮类化合物，即完成α-溴代芳香酮类化合物的合成方法，其中溴化试剂为四溴化碳或金属溴化物，光反应催化剂为三联吡啶氯化钌；其中芳香环氧乙烷类化合物与溴化试剂的摩尔比为1∶(1.1～1.5)，芳香环氧乙烷类化合物与光反应催化剂的摩尔比为1∶(0.01～0.05)。Specific Embodiment 1: In this embodiment, a method for synthesizing α-brominated aromatic ketones is carried out through the following steps: adding bromination reagents and photoreaction catalysts to aromatic oxirane compounds, and then irradiating with visible light, React in an organic solvent at room temperature for 6-12 hours, then filter and concentrate the reaction solution to dryness, then use a mixed solution of petroleum ether: ethyl acetate with a volume ratio of (10-16): 1 as an eluent, and carry out a silica gel column Chromatographic purification and separation to obtain α-bromoaromatic ketone compounds, that is, to complete the synthesis method of α-bromoaromatic ketone compounds, wherein the bromination reagent is carbon tetrabromide or metal bromide, and the photoreaction catalyst is terpyridine chloride Ruthenium oxide; wherein the molar ratio of the aromatic oxirane compound to the bromination reagent is 1: (1.1-1.5), and the molar ratio of the aromatic oxirane compound to the photoreaction catalyst is 1: (0.01-0.05).
本实施方式的反应式为：The reaction formula of this embodiment is:
本实施方式适用所有芳香环氧乙烷类化合物。This embodiment is applicable to all aromatic oxirane compounds.
本实施方式在常温常压下即可反应，反应条件温和，无需严格的除水处理及惰性气体保护，加料顺序任意，操作简单方便。反应采用清洁、易得的可见光作为能量来源，家用的白炽灯、LED灯以及太阳光均可作为光源，清洁无污染；采用的溴化试剂为低毒的四溴化碳或金属溴化物，廉价易得，易于加料，辅助催化剂过硫酸钠便宜易得且无污染；光催化剂用量少且能够回收再利用。并且本实施方式的反应底物的适用范围广，可以利用不同的芳香环氧乙烷类底物实现反应的高产率，例如烷基、酮基、酯基和芳香基团等。本实施方式的产率和选择性均较高，部分反应收率可高达90％以上，而且生成单一溴代产物，无二溴取代的产物生成；整个反应安全环保，成本低，经济效益高，属于绿色化学工艺。This embodiment can be reacted at normal temperature and pressure, the reaction conditions are mild, no strict water removal treatment and inert gas protection are required, the order of feeding is arbitrary, and the operation is simple and convenient. The reaction uses clean and easily available visible light as the energy source. Household incandescent lamps, LED lamps and sunlight can be used as light sources, clean and pollution-free; the bromination reagent used is low-toxic carbon tetrabromide or metal bromide, which is cheap Easy to obtain, easy to add materials, the auxiliary catalyst sodium persulfate is cheap and easy to obtain and has no pollution; the amount of photocatalyst is small and can be recycled and reused. Moreover, the reaction substrate of this embodiment has a wide range of applications, and high yields of the reaction can be achieved by using different aromatic oxirane substrates, such as alkyl groups, ketone groups, ester groups, and aromatic groups. The yield and selectivity of this embodiment are high, and the partial reaction yield can be as high as more than 90%, and a single brominated product is generated, and no dibrominated product is generated; the whole reaction is safe and environmentally friendly, with low cost and high economic benefit. It belongs to the green chemical process.
具体实施方式二：本实施方式与具体实施方式一不同的是溴化试剂为金属溴化物时，向芳香环氧乙烷类化合物中添加辅助催化剂过硫酸钠，其中芳香环氧乙烷类化合物与过硫酸钠的摩尔比为1∶(1～2)。其他步骤和参数与具体实施方式一相同。Specific embodiment two: the difference between this embodiment and specific embodiment one is that when the bromination reagent is a metal bromide, an auxiliary catalyst sodium persulfate is added to the aromatic oxirane compound, wherein the aromatic oxirane compound and The molar ratio of sodium persulfate is 1: (1-2). Other steps and parameters are the same as those in the first embodiment.
具体实施方式三：本实施方式与具体实施方式一或二不同的是芳香环氧乙烷类化合物与溴化试剂的摩尔比为1∶(1.1～1.2)。其他步骤和参数与具体实施方式一或二相同。Embodiment 3: The difference between this embodiment and Embodiment 1 or 2 is that the molar ratio of the aromatic oxirane compound to the bromination reagent is 1: (1.1-1.2). Other steps and parameters are the same as those in Embodiment 1 or 2.
具体实施方式四：本实施方式与具体实施方式一至三之一不同的是芳香环氧乙烷类化合物与光反应催化剂的摩尔比为1∶(0.02～0.04)。其他步骤和参数与具体实施方式一至三之一相同。Embodiment 4: This embodiment differs from Embodiments 1 to 3 in that the molar ratio of the aromatic oxirane compound to the photoreaction catalyst is 1: (0.02-0.04). Other steps and parameters are the same as those in the first to third specific embodiments.
具体实施方式五：本实施方式与具体实施方式一至四之一不同的是有机溶剂为乙腈、甲醇或N，N-二甲基甲酰胺，用量为每毫摩尔芳香环氧乙烷类化合物使用5-10毫升的有机溶剂。其他步骤和参数与具体实施方式一至四之一相同。Specific embodiment five: the difference between this embodiment and one of specific embodiments one to four is that the organic solvent is acetonitrile, methanol or N, N-dimethylformamide, and the consumption is 5 per millimole of aromatic oxirane compounds. - 10 ml of organic solvent. Other steps and parameters are the same as one of the specific embodiments 1 to 4.
具体实施方式六：本实施方式与具体实施方式一至五之一不同的是可见光为白炽灯、LED灯或太阳光。其他步骤和参数与具体实施方式一至五之一相同。Embodiment 6: This embodiment is different from Embodiment 1 to Embodiment 5 in that the visible light is incandescent lamp, LED lamp or sunlight. Other steps and parameters are the same as one of the specific embodiments 1 to 5.
通过以下试验验证本发明的有益效果：Prove the beneficial effect of the present invention by following test:
试验1、一种α-溴代芳香酮类化合物的合成方法，通过以下步骤进行：向反应瓶中加入45.3mg2-(4-甲氧基苯基)-3-苯基环氧乙烷、99.5mg四溴化碳和7.5mg三联吡啶氯化钌催化剂，然后用注射器吸取2mL乙腈加入到反应瓶中，塞上插有针头的橡胶塞后置于可见光照射下，室温反应7h，然后进行过滤并浓缩反应液至干，再以体积比为10∶1的石油醚∶乙酸乙酯的混合溶液作为洗脱剂，进行硅胶柱层析纯化分离，得到2-溴-2-(4-甲氧基苯基)-1-苯乙酮，即完成α-溴代芳香酮类化合物的合成方法。其中2-溴-2-(4-甲氧基苯基)-1-苯乙酮的结构式为：Test 1, a kind of synthetic method of α-bromoaromatic ketone compound, carry out by following steps: add 45.3mg2-(4-methoxyphenyl)-3-phenyloxirane, 99.5 mg carbon tetrabromide and 7.5 mg terpyridine ruthenium chloride catalyst, then draw 2 mL of acetonitrile with a syringe and add it to the reaction bottle, put a rubber stopper with a needle on it and place it under visible light irradiation, react at room temperature for 7 h, then filter and Concentrate the reaction solution to dryness, and then use a mixed solution of petroleum ether: ethyl acetate with a volume ratio of 10:1 as an eluent to carry out purification and separation by silica gel column chromatography to obtain 2-bromo-2-(4-methoxy Phenyl)-1-acetophenone, promptly completes the synthetic method of α-bromoaromatic ketone compound. Wherein the structural formula of 2-bromo-2-(4-methoxyphenyl)-1-acetophenone is:
本试验合成的2-溴-2-(4-甲氧基苯基)-1-苯乙酮为浅黄色固体，产率为92％，其核磁数据为：1H NMR(400MHz，CDCl3)：δ7.98(d，J＝7.8Hz，2H)，7.56(t，J＝7.4Hz，1H)，7.49-7.42(m，4H)，6.89(d，J＝8.7Hz，2H)，6.40(s，1H)，3.80(s，3H).13C NMR(100MHz，CDCl3)：δ191.2，160.3，134.3，133.7，130.6，129.2，128.9，127.9，114.6，55.4，51.4。The 2-bromo-2-(4-methoxyphenyl)-1-acetophenone synthesized in this test is a light yellow solid with a yield of 92%. The nuclear magnetic data is: 1 H NMR (400MHz, CDCl 3 ) : δ7.98(d, J=7.8Hz, 2H), 7.56(t, J=7.4Hz, 1H), 7.49-7.42(m, 4H), 6.89(d, J=8.7Hz, 2H), 6.40( s, 1H), 3.80 (s, 3H). 13 C NMR (100 MHz, CDCl 3 ): δ 191.2, 160.3, 134.3, 133.7, 130.6, 129.2, 128.9, 127.9, 114.6, 55.4, 51.4.
试验2、一种α-溴代芳香酮类化合物的合成方法，通过以下步骤进行：向反应瓶中加入32.8mg2-(4-甲氧基苯基)-3-甲基环氧乙烷、26mg溴化锂、90mg过硫酸钠和7.5mg三联吡啶氯化钌催化剂，然后用注射器吸取2mL乙腈加入到反应瓶中，塞上插有针头的橡胶塞后置于可见光照射下，室温反应8h，然后进行过滤并浓缩反应液至干，再以体积比为16∶1的石油醚∶乙酸乙酯的混合溶液作为洗脱剂，进行硅胶柱层析纯化分离，得到1-溴-1-(4-甲氧基苯基)-2-丙酮，即完成α-溴代芳香酮类化合物的合成方法，其中1-溴-1-(4-甲氧基苯基)-2-丙酮的结构式为：Test 2, a kind of synthetic method of α-bromoaromatic ketone compound, carry out by following steps: add 32.8mg2-(4-methoxyphenyl)-3-methyloxirane, 26mg Lithium bromide, 90 mg sodium persulfate and 7.5 mg terpyridyl ruthenium chloride catalyst, and then use a syringe to draw 2 mL of acetonitrile into the reaction bottle, plug the rubber stopper with a needle, place it under visible light, react at room temperature for 8 hours, and then filter And concentrate the reaction solution to dryness, then use the mixed solution of petroleum ether:ethyl acetate with a volume ratio of 16:1 as the eluent, carry out purification and separation by silica gel column chromatography, and obtain 1-bromo-1-(4-methoxy phenyl)-2-propanone, promptly completes the synthetic method of α-bromoaromatic ketone compound, wherein the structural formula of 1-bromo-1-(4-methoxyphenyl)-2-propanone is:
本试验合成的1-溴-1-(4-甲氧基苯基)-2-丙酮为白色固体，产率为88％，其核磁数据为：1HNMR(400MHz，CDCl3)：δ7.35(d，J＝8.7Hz，2H)，6.89(d，J＝8.7Hz，2H)，5.43(s，1H)，3.80(s，3H)，2.29(s，3H).13C NMR(100MHz，CDCl3)：δ199.3，160.3，130.2，127.2，114.6，56.4，55.5，26.4.The synthetic 1-bromo-1-(4-methoxyphenyl)-2-propanone of this test is white solid, and productive rate is 88%, and its NMR data is: 1HNMR (400MHz, CDCl ): δ7.35(d , J=8.7Hz, 2H), 6.89(d, J=8.7Hz, 2H), 5.43(s, 1H), 3.80(s, 3H), 2.29(s, 3H).13C NMR (100MHz, CDCl3): δ199.3, 160.3, 130.2, 127.2, 114.6, 56.4, 55.5, 26.4.
试验3、一种α-溴代芳香酮类化合物的合成方法，通过以下步骤进行：向反应瓶中加入44.4mg3-(4-甲氧基苯基)环氧乙烷-2-羧酸乙酯、99.5mg四溴化碳和7.5mg三联吡啶氯化钌催化剂，然后用注射器吸取2mL乙腈加入到反应瓶中，塞上插有针头的橡胶塞后置于可见光照射下，室温反应9h，然后进行过滤并浓缩反应液至干，再以体积比为16∶1的石油醚∶乙酸乙酯的混合溶液作为洗脱剂，进行硅胶柱层析纯化分离，得到3-溴-3-(4-甲氧基苯基)-丙酮酸乙酯，即完成α-溴代芳香酮类化合物的合成方法，其中3-溴-3-(4-甲氧基苯基)-丙酮酸乙酯的结构式为：Test 3, a kind of synthetic method of α-bromoaromatic ketone compound, carry out by the following steps: add 44.4mg3-(4-methoxyphenyl) oxirane-2-ethyl carboxylate in reaction bottle , 99.5mg of carbon tetrabromide and 7.5mg of terpyridine ruthenium chloride catalyst, then draw 2mL of acetonitrile into the reaction bottle with a syringe, put the rubber stopper with a needle on it and put it under visible light irradiation, react at room temperature for 9h, and then carry out Filter and concentrate the reaction solution to dryness, then use a mixed solution of petroleum ether:ethyl acetate with a volume ratio of 16:1 as the eluent, perform silica gel column chromatography purification and separation to obtain 3-bromo-3-(4-methyl Oxyphenyl)-pyruvate ethyl ester, promptly completes the synthetic method of α-bromoaromatic ketone compound, wherein the structural formula of 3-bromo-3-(4-methoxyphenyl)-pyruvate ethyl ester is:
本试验合成的3-溴-3-(4-甲氧基苯基)-丙酮酸乙酯为淡黄色液体，产率为67％，其核磁数据为：1HNMR(400MHz，CDCl3)：δ7.39(d，J＝8.7Hz，2H)，6.90(d，J＝8.7Hz，2H)，6.22(s，1H)，4.32(qd，J＝7.2，3.7Hz，2H)，3.81(s，3H)，1.33(t，J＝7.2Hz，3H).13C NMR(100MHz，CDCl3)：δ184.0，160.7，160.3，131.2，125.0，114.6，63.3，55.5，50.1，14.0.The synthetic 3-bromo-3-(4-methoxyphenyl)-pyruvate ethyl ester of this test is pale yellow liquid, and productive rate is 67%, and its NMR data is: 1HNMR (400MHz, CDCl ): δ7.39 (d, J=8.7Hz, 2H), 6.90(d, J=8.7Hz, 2H), 6.22(s, 1H), 4.32(qd, J=7.2, 3.7Hz, 2H), 3.81(s, 3H) , 1.33 (t, J=7.2Hz, 3H).13C NMR (100MHz, CDCl3): δ184.0, 160.7, 160.3, 131.2, 125.0, 114.6, 63.3, 55.5, 50.1, 14.0.
试验4、一种α-溴代芳香酮类化合物的合成方法，通过以下步骤进行：向反应瓶中加入54.2mg2-(4-甲氧基苯基)-3-(4-硝基苯基)环氧乙烷、26mg溴化锂、90mg过硫酸钠和7.5mg三联吡啶氯化钌催化剂，然后用注射器吸取2mL乙腈加入到反应瓶中，塞上插有针头的橡胶塞后置于可见光照射下，室温反应8h，然后进行过滤并浓缩反应液至干，再以体积比为10∶1的石油醚∶乙酸乙酯的混合溶液作为洗脱剂，进行硅胶柱层析纯化分离，得到2-溴-2-(4-甲氧基苯基)-1-(4-硝基苯基)乙酮，即完成α-溴代芳香酮类化合物的合成方法，其中2-溴-2-(4-甲氧基苯基)-1-(4-硝基苯基)乙酮的结构式为：Test 4, a synthetic method of α-bromoaromatic ketones, carried out by the following steps: add 54.2mg 2-(4-methoxyphenyl)-3-(4-nitrophenyl) to the reaction flask Ethylene oxide, 26mg lithium bromide, 90mg sodium persulfate and 7.5mg terpyridine ruthenium chloride catalyst, then draw 2mL of acetonitrile with a syringe and add to the reaction bottle, plug the rubber stopper with a needle and place it under visible light irradiation, room temperature React for 8h, then filter and concentrate the reaction solution to dryness, then use a volume ratio of 10:1 petroleum ether: ethyl acetate mixed solution as eluent, carry out silica gel column chromatography purification and separation to obtain 2-bromo-2 -(4-methoxyphenyl)-1-(4-nitrophenyl)ethanone, that is, to complete the synthetic method of α-bromoaromatic ketones, wherein 2-bromo-2-(4-methoxy The structural formula of phenyl)-1-(4-nitrophenyl)ethanone is:
本试验合成的2-溴-2-(4-甲氧基苯基)-1-(4-硝基苯基)乙酮为淡黄色液体，产率为72％，其核磁数据为：1HNMR(400MHz，CDCl3)：δ8.27(d，J＝8.7Hz，2H)，8.12(d，J＝8.7Hz，2H)，7.44(d，J＝8.6Hz，2H)，6.90(d，J＝8.6Hz，2H)，6.33(s，1H)，3.80(s，3H).13CNMR(100MHz，CDCl3)：δ189.8，160.6，150.5，139.1，130.7，130.3，126.7，124.0，114.8，55.5，51.1.The synthetic 2-bromo-2-(4-methoxyphenyl)-1-(4-nitrophenyl)ethanone of this test is light yellow liquid, and productive rate is 72%, and its NMR data is: 1HNMR ( 400MHz, CDCl3): δ8.27(d, J=8.7Hz, 2H), 8.12(d, J=8.7Hz, 2H), 7.44(d, J=8.6Hz, 2H), 6.90(d, J=8.6 Hz, 2H), 6.33(s, 1H), 3.80(s, 3H).13CNMR(100MHz, CDCl3): δ189.8, 160.6, 150.5, 139.1, 130.7, 130.3, 126.7, 124.0, 114.8, 55.5, 51.1.
试验5、一种α-溴代芳香酮类化合物的合成方法，通过以下步骤进行：向反应瓶中加入61.0mg2-(4-溴基苯基)-3-(4-甲氧基苯基)环氧乙烷、99.5mg四溴化碳和7.5mg三联吡啶氯化钌催化剂，然后用注射器吸取2mL乙腈加入到反应瓶中，塞上插有针头的橡胶塞后置于可见光照射下，室温反应10h，然后进行过滤并浓缩反应液至干，再以体积比为12∶1的石油醚∶乙酸乙酯的混合溶液作为洗脱剂，进行硅胶柱层析纯化分离，得到2-溴-1-(4-溴基苯基)-2-(4-甲氧基苯基)乙酮，即完成α-溴代芳香酮类化合物的合成方法，其中2-溴-1-(4-溴基苯基)-2-(4-甲氧基苯基)乙酮的结构式为：Test 5, a synthetic method of α-bromoaromatic ketones, carried out by the following steps: add 61.0mg 2-(4-bromophenyl)-3-(4-methoxyphenyl) to the reaction flask Ethylene oxide, 99.5mg of carbon tetrabromide and 7.5mg of terpyridine ruthenium chloride catalyst, then draw 2mL of acetonitrile into the reaction bottle with a syringe, put the rubber stopper with a needle on it, place it under visible light irradiation, and react at room temperature 10h, then filter and concentrate the reaction solution to dryness, then use the mixed solution of petroleum ether:ethyl acetate with a volume ratio of 12:1 as eluent, carry out purification and separation by silica gel column chromatography, and obtain 2-bromo-1- (4-bromophenyl)-2-(4-methoxyphenyl)ethanone, that is, to complete the synthetic method of α-bromoaromatic ketones, wherein 2-bromo-1-(4-bromophenyl The structural formula of -2-(4-methoxyphenyl)ethanone is:
本试验合成的2-溴-1-(4-溴基苯基)-2-(4-甲氧基苯基)乙酮为淡黄色固体，产率为86％，其核磁数据为：1H NMR(400MHz，CDCl3)：δ7.83(d，J＝8.6Hz，2H)，7.56(d，J＝8.6Hz，2H)，7.43(d，J＝8.7Hz，2H)，6.88(d，J＝8.7Hz，2H)，6.32(s，1H)，3.78(s，3H).13CNMR(100MHz，CDCl3)：δ190.2，160.4，133.0，132.2，130.7，130.6，129.0，127.5，114.6，55.4，51.2.The 2-bromo-1-(4-bromophenyl)-2-(4-methoxyphenyl)ethanone synthesized in this test is a pale yellow solid with a yield of 86%, and its NMR data is: 1 H NMR (400MHz, CDCl 3 ): δ7.83(d, J=8.6Hz, 2H), 7.56(d, J=8.6Hz, 2H), 7.43(d, J=8.7Hz, 2H), 6.88(d, J=8.7Hz, 2H), 6.32(s, 1H), 3.78(s, 3H). 13 CNMR (100MHz, CDCl 3 ): δ190.2, 160.4, 133.0, 132.2, 130.7, 130.6, 129.0, 127.5, 114.6 , 55.4, 51.2.
试验6、一种α-溴代芳香酮类化合物的合成方法，通过以下步骤进行：向反应瓶中加入72.1mg(2-苄氧基苯基)(3-(4-甲氧基苯基)环氧乙烷-2-基)甲酮、26mg溴化锂、90mg过硫酸钠和7.5mg三联吡啶氯化钌催化剂，然后加入用注射器吸取2mL甲醇到反应瓶中，塞上插有针头的橡胶塞后置于可见光照射下，室温反应11h，然后进行过滤并浓缩反应液至干，再以体积比为16∶1的石油醚∶乙酸乙酯的混合溶液作为洗脱剂，进行硅胶柱层析纯化分离，得到3-溴-1-(2-苄氧基苯基)-3-(4-甲氧基苯基)丙烷-1，2-二酮，即完成α-溴代芳香酮类化合物的合成方法，其中3-溴-1-(2-苄氧基苯基)-3-(4-甲氧基苯基)丙烷-1，2-二酮的结构式为： Test 6, a synthetic method of α-bromoaromatic ketones, carried out by the following steps: add 72.1mg (2-benzyloxyphenyl) (3-(4-methoxyphenyl) Oxirane-2-yl) ketone, 26mg lithium bromide, 90mg sodium persulfate and 7.5mg terpyridine ruthenium chloride catalyst were then added and the syringe was used to draw 2mL of methanol into the reaction bottle, and the rubber stopper with the needle was inserted on the stopper Place under visible light irradiation, react at room temperature for 11 h, then filter and concentrate the reaction solution to dryness, and then use a mixed solution of petroleum ether:ethyl acetate with a volume ratio of 16:1 as an eluent to carry out purification and separation by silica gel column chromatography , to obtain 3-bromo-1-(2-benzyloxyphenyl)-3-(4-methoxyphenyl)propane-1,2-dione, which completes the synthesis of α-bromoaryl ketones Method, wherein the structural formula of 3-bromo-1-(2-benzyloxyphenyl)-3-(4-methoxyphenyl)propane-1,2-dione is:
本试验合成的3-溴-1-(2-苄氧基苯基)-3-(4-甲氧基苯基)丙烷-1，2-二酮为淡黄色液体，产率为68％，其核磁数据为：1H NMR(400MHz，CDCl3)：δ7.89(d，J＝7.8Hz，1H)，7.55(t，J＝7.8Hz，1H)，7.48-7.39(m，5H)，7.19(d，J＝8.6Hz，2H)，7.08(t，J＝7.5Hz，1H)，7.01(d，J＝8.5Hz，1H)，6.79(d，J＝8.6Hz，2H)，5.72(s，1H)，5.14(d，J＝2.7Hz，2H)，3.77(s，3H).13CNMR(100MHz，CDCl3)：δ193.0，192.5，1602，159.4，136.5，135.3，131.1，129.0，128.7，128.3，127.1，122.9，121.6，114.3，113.3，71.4，55.4，51.3.The 3-bromo-1-(2-benzyloxyphenyl)-3-(4-methoxyphenyl)propane-1,2-dione synthesized in this test is a light yellow liquid with a yield of 68%. Its NMR data are: 1H NMR (400MHz, CDCl3): δ7.89(d, J=7.8Hz, 1H), 7.55(t, J=7.8Hz, 1H), 7.48-7.39(m, 5H), 7.19( d, J=8.6Hz, 2H), 7.08(t, J=7.5Hz, 1H), 7.01(d, J=8.5Hz, 1H), 6.79(d, J=8.6Hz, 2H), 5.72(s, 1H), 5.14(d, J=2.7Hz, 2H), 3.77(s, 3H).13CNMR(100MHz, CDCl3): δ193.0, 192.5, 1602, 159.4, 136.5, 135.3, 131.1, 129.0, 128.7, 128.3 , 127.1, 122.9, 121.6, 114.3, 113.3, 71.4, 55.4, 51.3.
试验7、一种α-溴代芳香酮类化合物的合成方法，通过以下步骤进行：向57.7mg(4-氯基苯基)(3-(4-甲氧基苯基)环氧乙烷-2-基)甲酮中加入26mg溴化锂、90mg过硫酸钠和7.5mg三联吡啶氯化钌催化剂，然后用注射器吸取2mLN，N-二甲基甲酰胺加入到反应瓶中，塞上插有针头的橡胶塞后置于可见光照射下，室温反应10h，然后进行过滤并浓缩反应液至干，再以体积比为10∶1的石油醚∶乙酸乙酯的混合溶液作为洗脱剂，进行硅胶柱层析纯化分离，得到3-溴-1-(4-氯基苯基)-3-(4-甲氧基苯基)丙烷-1，2-二酮，即完成α-溴代芳香酮类化合物的合成方法，其中3-溴-1-(4-氯基苯基)-3-(4-甲氧基苯基)丙烷-1，2-二酮的结构式为：Test 7, a synthetic method of α-bromoaromatic ketones, carried out through the following steps: To 57.7mg (4-chlorophenyl) (3-(4-methoxyphenyl) oxirane- Add 26mg lithium bromide, 90mg sodium persulfate and 7.5mg terpyridine ruthenium chloride catalyst in 2-base) ketone, draw 2mLN with syringe then, N-dimethylformamide joins in the reaction flask, the plug with needle Put the rubber stopper under visible light irradiation, react at room temperature for 10 h, then filter and concentrate the reaction solution to dryness, and then use a mixed solution of petroleum ether:ethyl acetate with a volume ratio of 10:1 as an eluent to conduct a silica gel column layer Purify and separate to obtain 3-bromo-1-(4-chlorophenyl)-3-(4-methoxyphenyl)propane-1,2-dione, which is the completion of α-bromoaromatic ketones The synthetic method of wherein 3-bromo-1-(4-chlorophenyl)-3-(4-methoxyphenyl) propane-1, the structural formula of 2-dione is:
本试验合成的3-溴-1-(4-氯基苯基)-3-(4-甲氧基苯基)丙烷-1，2-二酮为淡黄色固体，产率为75％，其核磁数据为：1H NMR(400MHz，CDCl3)：δ7.97(d，J＝8.5Hz，2H)，7.48(d，J＝8.2Hz，2H)，6.91(d，J＝9.5Hz，2H)，6.37(s，1H)，3.82(s，3H).13C NMR(100MHz，CDCl3)：δ189.9，189.4，160.8，141.9，131.8，131.4，130.7，129.5，124.8，114.6，55.5，49.8。The 3-bromo-1-(4-chlorophenyl)-3-(4-methoxyphenyl)propane-1,2-dione synthesized in this test is a light yellow solid with a yield of 75%. NMR data: 1H NMR (400MHz, CDCl3): δ7.97 (d, J = 8.5Hz, 2H), 7.48 (d, J = 8.2Hz, 2H), 6.91 (d, J = 9.5Hz, 2H), 6.37(s, 1H), 3.82(s, 3H).13C NMR (100MHz, CDCl3): δ189.9, 189.4, 160.8, 141.9, 131.8, 131.4, 130.7, 129.5, 124.8, 114.6, 55.5, 49.8.
由试验1～试验7可知，本试验反应条件温和，无需严格的除水处理及惰性气体保护，加料顺序任意，操作简单方便。反应采用清洁、易得的可见光作为能量来源，家用的白炽灯、LED灯以及太阳光均可作为光源，清洁无污染；采用的溴化试剂为低毒的四溴化碳或金属溴化物，廉价易得，易于加料，辅助催化剂过硫酸钠便宜易得且无污染；光催化剂用量少且能够回收再利用。并且本试验的反应底物的适用范围广，可以利用不同的芳香环氧乙烷类底物实现反应的高产率，例如烷基、酮基、酯基和芳香基团等。本试验的产率和选择性均较高，部分反应收率可高达90％以上，而且生成单一溴代产物，无二溴取代的产物生成；；整个反应安全环保，成本低，经济效益高，属于绿色化学工艺。From Test 1 to Test 7, it can be seen that the reaction conditions of this test are mild, no strict water removal treatment and inert gas protection are required, the order of feeding is arbitrary, and the operation is simple and convenient. The reaction uses clean and easily available visible light as the energy source. Household incandescent lamps, LED lamps and sunlight can be used as light sources, clean and pollution-free; the bromination reagent used is low-toxic carbon tetrabromide or metal bromide, which is cheap Easy to obtain, easy to add materials, the auxiliary catalyst sodium persulfate is cheap and easy to obtain and has no pollution; the amount of photocatalyst is small and can be recycled and reused. Moreover, the reaction substrates of this test have a wide range of applications, and different aromatic oxirane substrates can be used to achieve high yields of the reaction, such as alkyl groups, ketone groups, ester groups, and aromatic groups. The yield and selectivity of this test are all high, and the yield of some reactions can be as high as more than 90%, and a single brominated product is generated, and no dibrominated product is generated; the whole reaction is safe and environmentally friendly, with low cost and high economic benefit. It belongs to the green chemical process.
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