CN101948365A - Preparation method of 1,4-diaryl-1,3-butadiyne - Google Patents
Preparation method of 1,4-diaryl-1,3-butadiyne Download PDFInfo
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- CN101948365A CN101948365A CN 201010276567 CN201010276567A CN101948365A CN 101948365 A CN101948365 A CN 101948365A CN 201010276567 CN201010276567 CN 201010276567 CN 201010276567 A CN201010276567 A CN 201010276567A CN 101948365 A CN101948365 A CN 101948365A
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Abstract
The invention belongs to the technical field of organic synthesis midbody, medicine, pesticide and liquid crystal materials, in particular to a preparation method of 1,4-diaryl-1,3-butadiyne. In the invention, the easily obtained beta, beta-dibromo arylethylene is served as a raw material, under the catalytic action of cuprous iodide, no ligand is added to the raw material and the 1,4-diaryl-1,3-butadiyne compound is efficiently synthesized in dimethylsulfoxide solvent in the presence of 1,8-dual nitrogen heterocyclic ring hendecene. The 1,4-diaryl-1,3-butadiyne synthesized by the invention can be served as the synthesis midbody of the medicine, the pesticide and the liquid crystal. Compared with the existing synthesis method of noble metal palladium, the method of the invention has the characteristics of easily obtained raw materials, low cost, simple operation, and mild reaction conditions, is easy to be industrialized, and has wide application prospect.
Description
Technical field
The invention belongs to organic synthesis intermediate, medicine, agricultural chemicals and liquid crystal material field, be specifically related to a kind of 1,4-diaryl-1, the preparation method of 3-diacetylene.
Background technology
1,3-diacetylene compound is the very important organic compound of a class, and they are widely used in fields such as organic synthesis intermediate, medicine, agricultural chemicals and liquid crystal material.As conjugation linker important in the organic synthesis, 1,3-diacetylene compound is known as the omnipotent module that makes up molecule, can be used in macromolecular compound such as annulene synthetic, also can be used for synthetic organometallics and derivatives of porphyrin etc. (Li, C.Langmuir 2007,23,6754).1,3-diacetylene compound also is the structural unit (Shi Shun, A.L.K.Angew.Chem.Int.Ed.2006,45,1034) of natural product, antifungal drug.Because it has natural photosensitivity; 1; the 3-diacetylene is used to photo-activation pesticide; to the Culex quinquefasciatus instar larvae have stronger photoactivation poisoning effect (Wan Shuqing. insect journal .2000; 43,264), to the growth of barnyard grass grass roots and stem have the photoactivation restraining effect (Wan Shuqing. plant protection journal .2004; 31,299).Based on 1,3-diacetylene compound has the photoelectron performance of regulating molecule, the effect of induced fluorescence enhanced, thereby they also are used as the liquid crystal material use.As seen 1,3-diacetylene compound has crucial effect in fields such as organic synthesis, medicine, agricultural chemicals and liquid crystal material.
Bibliographical information is arranged, institute of the present invention synthetic 1,4-diaryl-1,3-diacetylene compounds be a kind of novel, efficient, low toxicity, low residue photo-activation pesticide (Wu Renhai. the journal .2008 of Agricultural University Of South China, 29,44), under the artificial light irradiation of daylight or specific wavelength, show strong insecticidal activity, thereby this insecticides is expected to become the surrogate of traditional chemical sterilant.Experimental results show that, in 1 of 100 μ g/mL mass concentrations, 4-phenylbenzene-1,3-diacetylene and 1,4-two (3, the 4-methylene-dioxy) phenyl-1, under the effect of 3-diacetylene, the mortality ratio of Aedes albopictus is 100%, and visible 1,4-diaryl-1,3-diacetylene compounds has stronger photoactivation poisoning effect to Aedes albopictus.
Usually preparation 1,4-diaryl-1, the method for 3-diacetylene is in the presence of transition metal copper or palladium, under the fellowship effect of containing n-donor ligand, terminal alkyne takes place to obtain (Adimurthy, S.J.Org.Chem.2009,74,5648 from linked reaction; Yin, W.Org.Lett.2009,11,709).Palladium catalyst cost an arm and a leg and toxicity bigger, very sensitivity and price are not low to air for containing n-donor ligand.
β, beta-2-dibrom vinyl compound are the multi-functional organic synthesis intermediates of a class, are widely used in the starting raw material of organic synthesis.People such as Yan have reported in the presence of potassium tert.-butoxide, in toluene solvant, β, beta-2-dibrom ethene takes place to obtain 1 of higher yields from linked reaction, 4-two replaces-1,3-diacetylene compound, but reaction conditions is gentle inadequately, need carry out (Yan under 120 ℃ of temperature, J.Synth.Commun, 2005,35,2333).
People such as Hitomi have reported in the presence of cuprous iodide and potassiumiodide are common, β, beta-2-dibrom vinylbenzene is by obtaining 1 from linked reaction, 4-phenylbenzene-1, the synthetic method of 3-diacetylene, the consumption of cuprous iodide is not a catalytic amount for the chemistry amount in this method, thereby consumption is big, cost height (Suzuki, H.Synthesis., 1988,236).
People such as Regis are with β, beta-2-dibrom vinylbenzene is raw material, with the nickelous acetate is catalyzer, does in the presence of the part preparation 1 at sodium hydride and two pyridines, 4-phenylbenzene-1,3-diacetylene, but big (Regis, V.Tetrahedron Lett.1986 of the toxicity of catalyzer and part in this method, 27,3517).
Therefore, the present invention is with β, and the beta-2-dibrom aromatic ethylene is a raw material, is catalyzer with CuI, does not need to add any part, preparation 1,4-diaryl-1,3-diacetylene compound.This method has advantages such as raw material is easy to get, with low cost, simple to operate, reaction conditions gentleness, is easy to industrialization, has broad application prospects.
Summary of the invention
The object of the present invention is to provide a kind of 1,4-diaryl-1, the preparation method of 3-diacetylene.
1 of the present invention's proposition, 4-diaryl-1, the preparation method of 3-diine, its reaction equation is as follows:
Wherein, R is H, to methyl, to methoxyl group, meta-methoxy, 3, the 4-dimethoxy, to benzyloxy, to amino, 1, in 2-methylene-dioxy or the naphthalene any.
Concrete steps are as follows:
In reactor, add methyl-sulphoxide, β, beta-2-dibrom aromatic ethylene, alkali and cuprous iodide, stirring reaction is 8 hours under 80 ℃ of temperature.Add distilled water after reaction is finished, again with ethyl acetate extraction, organic layer is behind saturated common salt water washing, anhydrous sodium sulfate drying, underpressure distillation is removed solvent and is obtained thick product, and thick product obtains final product 1 through column chromatography for separation, 4-diaryl-1, the 3-diacetylene.Wherein, cuprous iodide and β, the mol ratio of beta-2-dibrom aromatic ethylene is 0.05: 1-0.3: 1; Alkali and β, the mol ratio of beta-2-dibrom aromatic ethylene is 1.5: 1-3: 1.
Among the present invention, it is eluent that described column chromatography adopts ethyl acetate and sherwood oil.
Among the present invention, described alkali is 1,8-diazacyclo hendecene (DBU).
Utilize that the inventive method obtains 1,4-diaryl-1, the 3-dialkyne, its general formula is:
Wherein, R is H, to methyl, to methoxyl group, meta-methoxy, 3, the 4-dimethoxy, to benzyloxy, to amino, 1, in 2-methylene-dioxy or the naphthalene any.
Further, utilize that the inventive method obtains 1,4-diaryl-1,3-diacetylene compound, its structural formula are following any:
Synthetic 1 of the present invention, 4-diaryl-1, the 3-diacetylene can be used as the synthetic intermediate of medicine, agricultural chemicals and liquid crystal material.Compare with existing precious metal palladium process for catalytic synthesis, the inventive method has characteristics such as raw material is easy to get, with low cost, simple to operate, reaction conditions gentleness, is easy to industrialization, has broad application prospects.
Embodiment
Further specify the inventive method below by embodiment, but can not limit content of the present invention.
Embodiment 1:1,4-two (4-p-methoxy-phenyl)-1,3-diacetylene synthetic
In the 60mL tube sealing, add 3mL methyl-sulphoxide, 2-(4-p-methoxy-phenyl)-1, the 1-sym-dibromoethane (146mg, 0.5mmol), DBU (115mg, 0.75mmol), (4.75mg, 0.025mmol), stirring reaction is 8 hours under 80 ℃ of temperature for cuprous iodide.After reaction finishes, in reaction solution, add 3mL distilled water, use ethyl acetate extraction, organic layer is behind saturated common salt water washing, anhydrous sodium sulfate drying, and underpressure distillation is removed solvent and obtained thick product, and thick product separates through column chromatography (ethyl acetate/petroleum ether=1/30～1/5), get faint yellow solid 1,4-two (4-p-methoxy-phenyl)-1,3-diacetylene 38mg, yield 57%.Characterization data is as follows:
1H NMR (500MHz, CDCl
3): δ=3.82 (6H, s), 6.85 (4H, d, J=9.0Hz), 7.46 (4H, d, J=9.0Hz).
Embodiment 2:1,4-two (4-p-methoxy-phenyl)-1,3-diacetylene synthetic
In the 60mL tube sealing, add 3mL methyl-sulphoxide, 2-(4-p-methoxy-phenyl)-1, the 1-sym-dibromoethane (146mg, 0.5mmol), DBU (230mg, 1.5mmol), (19mg, 0.1mmol), stirring reaction is 8 hours under 80 ℃ of temperature for cuprous iodide.After reaction finishes, in reaction solution, add 3mL distilled water, use ethyl acetate extraction, organic layer is behind saturated common salt water washing, anhydrous sodium sulfate drying, and underpressure distillation is removed solvent and obtained thick product, and thick product separates through column chromatography (ethyl acetate/petroleum ether=1/30～1/5), get faint yellow solid 1,4-two (4-p-methoxy-phenyl)-1,3-diacetylene 59mg, yield 89%.Characterization data is as follows:
1H NMR (500MHz, CDCl
3): δ=3.82 (6H, s), 6.85 (4H, d, J=9.0Hz), 7.46 (4H, d, J=9.0Hz).
Embodiment 3:1,4-two (4-aminomethyl phenyl)-1,3-diacetylene synthetic
In the 60mL tube sealing, add 3mL methyl-sulphoxide, 2-(4-aminomethyl phenyl)-1, the 1-sym-dibromoethane (138mg, 0.5mmol), DBU (230mg, 1.5mmol), (19mg, 0.1mmol), stirring reaction is 8 hours under 80 ℃ of temperature for cuprous iodide.After reaction finishes, in reaction solution, add 3mL distilled water, use ethyl acetate extraction, organic layer is behind saturated common salt water washing, anhydrous sodium sulfate drying, underpressure distillation is removed solvent and is obtained thick product, thick product separates through column chromatography (ethyl acetate/petroleum ether=1/30～1/5), gets white solid 46mg, yield 81%.
Characterization data is as follows:
1H NMR (500MHz, CDCl
3): δ=2.35 (6H, s), 7.13 (4H, d, J=8.0Hz), 7.41 (4H, d, J=8.0Hz).
Embodiment 4:1,4-two (4-aminophenyl)-1,3-diacetylene synthetic
In the 60mL tube sealing, add the 3mL methyl-sulphoxide, 2-(4-aminophenyl)-1,1-sym-dibromoethane (138mg, 0.5mmol), DBU (230mg, 1.5mmol), cuprous iodide (19mg, 0.1mmol), stirring reaction is 8 hours under 80 ℃ of temperature, after reaction finishes, adds 3mL distilled water in reaction solution, use ethyl acetate extraction, organic layer is through the saturated common salt water washing, behind the anhydrous sodium sulfate drying, underpressure distillation is removed solvent and is obtained thick product, and thick product separates through column chromatography (ethyl acetate/petroleum ether=1/30～1/5), obtain orange solid chemical compound 1,4-two (4-aminophenyl)-1,3-diacetylene 42mg, yield 72%.Characterization data is as follows:
1H NMR (500MHz, DMSO-d
6): δ=5.71 (4H, br), 6.52 (4H, d, J=8.5Hz), 7.19 (4H, d, J=8.5Hz).
Embodiment 5:1,4-two (4-benzyloxy phenyl)-1,3-diacetylene synthetic
In the 60mL tube sealing, add the 3mL methyl-sulphoxide, 2-(4-benzyloxy phenyl)-1,1-sym-dibromoethane (184mg, 0.5mmol), DBU (230mg, 1.5mmol), cuprous iodide (19mg, 0.1mmol), stirring reaction is 8 hours under 80 ℃ of temperature, after reaction finishes, adds 3mL distilled water in reaction solution, use ethyl acetate extraction, organic layer is through the saturated common salt water washing, behind the anhydrous sodium sulfate drying, underpressure distillation is removed solvent and is obtained thick product, and thick product separates through column chromatography (ethyl acetate/petroleum ether=1/30～1/5), obtain 1,4-two (4-benzyloxy phenyl)-1,3-diacetylene 86mg, yield 83%.Characterization data is as follows:
1H NMR (500MHz, CDCl
3): δ=5.07 (4H, s), 6.90 (4H, d, J=8.8Hz), 7.33-7.44 (4H, m).
Claims (4)
1. 4-diaryl-1, the preparation method of 3-diine is characterized in that concrete steps are as follows:
In reactor, add methyl-sulphoxide, β, beta-2-dibrom aromatic ethylene, alkali and cuprous iodide, stirring reaction is 8 hours under 80 ℃ of temperature, adds distilled water after reaction is finished, again with ethyl acetate extraction, organic layer is behind saturated common salt water washing, anhydrous sodium sulfate drying, underpressure distillation is removed solvent and is obtained thick product, and thick product obtains final product 1 through column chromatography for separation, 4-diaryl-1, the 3-diine; Wherein, cuprous iodide and β, the mol ratio of beta-2-dibrom aromatic ethylene is 0.05: 1-0.3: 1; Alkali and β, the mol ratio of beta-2-dibrom aromatic ethylene is 1.5: 1-3: 1.
2. according to claim 11,4-diaryl-1, the preparation method of 3-diacetylene is characterized in that described alkali is 1,8-diazacyclo hendecene.
3. according to claim 11,4-diaryl-1, the preparation method of 3-diine is characterized in that gained 1,4-diaryl-1, the general formula of 3-dialkyne is:
Wherein, R is H, to methyl, to methoxyl group, meta-methoxy, 3, the 4-dimethoxy, to benzyloxy, to amino, 1, in 2-methylene-dioxy or the naphthalene any.
4. described 1 according to claim 3,4-diaryl-1, the preparation method of 3-diacetylene is characterized in that gained 1,4-diaryl-1, following any of 3-diacetylene compound:
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102517036A (en) * | 2011-12-12 | 2012-06-27 | 北京科技大学 | Di(alkynylbenzene) liquid crystal compound and preparation method thereof |
| CN104710254A (en) * | 2015-01-23 | 2015-06-17 | 绍兴文理学院 | Preparation method of symmetric 1,4-disubstituted-1,3-diacetylene |
| CN105016947A (en) * | 2015-07-15 | 2015-11-04 | 河南师范大学 | Method for synthesizing 1,3-butadiyne compound by copper (II) carboxymethylcellulose catalysis of terminal alkyne compound |
| CN105085157A (en) * | 2015-08-31 | 2015-11-25 | 河南师范大学 | Synthesis method of 1,3-butadiyne compound |
| CN107513003A (en) * | 2017-08-16 | 2017-12-26 | 佛山煜新科技有限公司 | A kind of preparation method of 1,4 2 substitution, 1,3 diacetylene |
| CN108440228A (en) * | 2018-04-27 | 2018-08-24 | 郑州大学 | The complex-catalyzed molecular oxygen oxidation synthesis in water 1 of water-soluble transition metal, the method for 3- diacetylene class compounds |
-
2010
- 2010-09-09 CN CN 201010276567 patent/CN101948365A/en active Pending
Non-Patent Citations (4)
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| 《ORGANIC LETTERS》 20000808 Wang Shen et al Synthesis of 1,3-Diynes via Palladium-Catalyzed Reaction of 1,1-Dibromo-1-alkenes 2857-2860 1-4 第2卷, 第18期 2 * |
| 《Organometallics》 19831231 Vilmos Galamb et al Synthesis of Diynes, alpha,beta-Unsaturated Monoacids, and Dlacids by the Selective Palladium(0)-Catalyzed and Phase Transfer Catalyzed Reactions of Vinylic Dibromides 801-805 1-4 第2卷, 第7期 2 * |
| 《Synthetic Communications》 20051231 Jincan Yan et al First Example of Transition-Metal-Free Glaser-Type Coupling Reaction 2333-2338 1-4 , 2 * |
| 《华南农业大学学报》 20080131 吴仁海 等 芳基丁二炔类化合物的合成与光活化杀虫活性 44-47 1-4 第29卷, 第1期 2 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102517036A (en) * | 2011-12-12 | 2012-06-27 | 北京科技大学 | Di(alkynylbenzene) liquid crystal compound and preparation method thereof |
| CN102517036B (en) * | 2011-12-12 | 2014-06-18 | 北京科技大学 | Di(alkynylbenzene) liquid crystal compound and preparation method thereof |
| CN104710254A (en) * | 2015-01-23 | 2015-06-17 | 绍兴文理学院 | Preparation method of symmetric 1,4-disubstituted-1,3-diacetylene |
| CN105016947A (en) * | 2015-07-15 | 2015-11-04 | 河南师范大学 | Method for synthesizing 1,3-butadiyne compound by copper (II) carboxymethylcellulose catalysis of terminal alkyne compound |
| CN105016947B (en) * | 2015-07-15 | 2017-01-18 | 河南师范大学 | Method for synthesizing 1,3-butadiyne compound by copper (II) carboxymethylcellulose catalysis of terminal alkyne compound |
| CN105085157A (en) * | 2015-08-31 | 2015-11-25 | 河南师范大学 | Synthesis method of 1,3-butadiyne compound |
| CN105085157B (en) * | 2015-08-31 | 2018-06-19 | 河南师范大学 | A kind of synthetic method of 1,3- diacetylene class compound |
| CN107513003A (en) * | 2017-08-16 | 2017-12-26 | 佛山煜新科技有限公司 | A kind of preparation method of 1,4 2 substitution, 1,3 diacetylene |
| CN108440228A (en) * | 2018-04-27 | 2018-08-24 | 郑州大学 | The complex-catalyzed molecular oxygen oxidation synthesis in water 1 of water-soluble transition metal, the method for 3- diacetylene class compounds |
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