CN103724246A - Aryl elemental selenium compound synthesis method - Google Patents
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Abstract
An aryl elemental selenium compound synthesis method comprises the following steps: taking copper compound as a catalyst; under the existence of an oxidant and an organic ligand, allowing aryl group aryl boric acid compound to react with the elemental selenium in a reaction solvent; obtaining the aryl elemental selenium compound through further manufacturing. The synthesis method is simple in operation, good in catalysis efficiency, and relatively high in product purity, and has a great scientific research value and an excellent industrialization prospect.
Description
Technical field
The invention provides a kind of synthetic method of selenide compound, more specifically, provide a kind of synthetic method of aryl list selenide, belong to organic chemical synthesis field.
Background technology
As a kind of trace element, selenium is that multiple metabolism and the physiological activity in organism is necessary, and it has multiple special function to HUMAN HEALTH, is described as " kindling material of life " and " anticancer king ".
A large amount of scientific researches show, many organoselenium compounds not only have effect antiviral, antitumor and treatment neural system aspect disease, but also have biochemistry and the pharmacological actions such as anti-inflammatory, anti-ageing, prevention and cure of cardiovascular disease and prevention liver disease.For example Ebselen (ebselen) and Selenazofurin (Selenofurin) are two representative drugs of carrying out clinical study.In addition, organoselenium compounds also can be used as important intermediate, chiral ligand and the functional materials etc. in organic synthesis.Therefore, organoselenium compounds had become one of focus of current organic chemistry, pharmaceutical chemistry and Materials science research already.
At present, people have researched and developed the method for a large amount of synthetic single selenide compounds.
The people (" Eco-friendly cross-coupling of diaryl diselenides with aryl and alkyl bromides catalyzed by CuO nanopowder in ionic liquid " such as Devender Singh, Green Chem., 2009,11,1521-1524) aromatic bromide or alkyl bromide are disclosed under the catalysis of nanometer CuO powder and different ionic liquid, with diphenyl disenenide ether ((PhSe)
2) there is linked reaction, and obtain aryl list selenide.
The people (" Synthesis of diaryl selenides using electrophilic selenium species and nucleophilic boron regents in ionic liquids " such as Camilo S.Freitas, Green Chem., 2011,13,2931-2938) in Electron Affinities compd A r-Se-Cl (Br) and nucleophilicity compound aryl boric acid (Ar are disclosed
1-B (OH)
2) or aromatic yl acid salt (Ar
1-BF
3k) under ionic liquid-catalyzed, and obtain aryl list selenide compd A r-Se-Ar
1.
The people (" Microwave-assisted reaction of aryl diazonium fluoroborate and diaryl dichalcogenides in dimethyl carbonate:a general procedure for the synthesis of unsymmetrical diaryl chalcogenides " such as Debasish Kundu, Green Chem., 2012,14, diazotization fluoroborate (Ar is disclosed 2024-2030) under microwave-assisted and under Zn exists
1-N
2bF
4) and diaryl chalcogenide (Ar
2 2x
2, X=S, Se, Te) in methylcarbonate, react, thus obtain asymmetric diaryl chalcogenide Ar
1-X-Ar
2.
The people (" An efficient synthesis of alkynyl selenides and tellurides from terminal acetylenes and diorganyl diselenides or ditellurides catalyzed by recyclable copper oxide nanopowder " such as Marcelo Godoi, Tetrahedron, 2012,68,10426-10430) disclose the synthetic method containing the selenide compound of alkynyl, the method is alkine compounds R
1c ≡ CH and R
2seSeR
2under nano oxidized copper powder, DMSO and salt of wormwood effect, react and make R
1c ≡ CSe-R
2.
People (" Solvent-Controlled Hlao-Selective Selenylation of Aryl Halides Catalyzed by Cu (II) the Supported on Al such as Tanmay Chatterjee
2o
3.A General Protocol for the Synthesis of Unsymmetrical Organo Mono-and Bis-selenides ") disclose under the effect of Cu-aluminum oxide, (R is aryl, vinyl, heteroaryl to R-X; X is halogen) react with R '-Se-Se-R ' (R ' be aryl, alkyl, heteroaryl), can obtain R-Se-R '.
In Yunyun Liu (Zhejiang University's doctorate paper, in April, 2010), report Liao Qi seminar, in 2006, has developed take ionic liquid as solvent, the diselenide by CuI/L-Proline-Catalyzed ((PhSe) under Metal Zn promotes
2) with the coupling of thiazolinyl bromine (Ar-C=CBr), this reaction is all suitable for aliphatics and aromatic series diselenide, alkyl thiazolinyl bromine and aryl alkenyl bromine is had to good reaction simultaneously.
As mentioned above, in prior art, disclose the multiple method of preparing diaryliodonium, but all there is certain defect in these methods, for example: react with corresponding electrophilic reagent by the selenium species of nucleophilicity (1).Wherein virtue (alkane) base selenium anion is the nucleophilicity selenium species of commonly using the most.They are reacted preparation conventionally with reductive agent by diselenide, but the defect of this synthetic organoselenium compounds method is to use diselenide as reacting precursor, and the preparation of diselenide relates to polystep reaction, to pass through especially foul smelling and the large selenium phenol oxidising process of toxicity; (2) by electrophilic selenium species, react with corresponding nucleophilic reagent, diselenide can serve as Electron Affinities seleno reagent, but it is when use as electrophilic reagent, conventionally only has 50% selenium atom to participate in reaction and enters product, therefore, the atom utilization of this type of reaction is not ideal enough; Virtue selenium acyl chlorides or acylbromide are another kind of conventional Electron Affinities seleno reagents, but their preparation need be used diselenide as reacting precursor equally, but also need use poisonous and environmentally harmful halide reagent (as chlorine, SO
2cl
2, bromine etc.).In addition, by other oxygenant as ammonium persulphate, bromine/silver trifluoromethanesulfonate system, iodobenzene diacetate etc. react with diselenide also can in situ preparation Electron Affinities selenium species, but these processes all need to use the oxygenant of equivalent, and easily cause the problems such as the compatible variation of side reaction and functional group.
For these reasons, explore efficient, gentle, the easy and compatible good synthetic organoselenium compounds of functional group, especially the novel method of aryl list selenide compound still has great importance, still there is necessity of proceeding research and exploring, this basis and power place that also the present invention is accomplished just.
Summary of the invention
In order to overcome above-mentioned pointed many defects, seek the brand-new and simple method of synthesizing aryl list selenide compound, the inventor conducts in-depth research, and is paying after a large amount of creative works, thereby is completing the present invention.
Particularly, technical scheme of the present invention and content relate to the synthetic method of the aryl list selenide compound shown in following formula (I), described method is: using copper compound as catalyzer, under oxygenant and organic ligand existence, in reaction solvent, by formula (II) aryl boric acid compound and simple substance selenium (Se), reacted, and make described formula (I) compound
Wherein R is selected from H, C
1-C
6alkyl, C
2-C
6thiazolinyl, C
1-C
6alkoxyl group, halogen, halo C
1-C
6alkyl, halo C
1-C
6alkoxyl group, phenyl or nitro.
In described synthetic method of the present invention, as one is exemplary, enumerate, the position of R in formula (II) aryl boric acid for example can be arranged in boronate between position or contraposition (at product formula (I), R be positioned at Se between position or contraposition).
In described synthetic method of the present invention, unless otherwise prescribed, from start to finish, C
1-C
6the implication of alkyl refers to the straight or branched alkyl with 1-6 carbon atom, and it has comprised C
1alkyl, C
2alkyl, C
3alkyl, C
4alkyl, C
5alkyl or C
6alkyl, for example can be to indefiniteness methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl or n-hexyl etc.
In described synthetic method of the present invention, unless otherwise prescribed, from start to finish, C
2-C
6the implication of thiazolinyl refers to the straight or branched thiazolinyl with 2-6 carbon atom, such as vinyl, 1-propenyl, 2-propenyl, 1-butylene base, crotyl, 1-pentenyl, 1-hexenyl etc.
In described synthetic method of the present invention, unless otherwise prescribed, from start to finish, C
1-C
6alkoxyl group refers to " C defined above
1-C
6alkyl " group after being connected with O atom.
In described synthetic method of the present invention, unless otherwise prescribed, from start to finish, the implication of halogen refers to haloid element, non-exclusively for example can be F, Cl, Br or I.
In described synthetic method of the present invention, unless otherwise prescribed, from start to finish, halo C
1-C
6the implication of alkyl refers to the " C defined above being replaced by halogen
1-C
6alkyl ", be indefiniteness for example trifluoromethyl, pentafluoroethyl group, difluoromethyl, chloromethyl etc.
In described synthetic method of the present invention, unless otherwise prescribed, from start to finish, halo C
1-C
6the implication of alkoxyl group refers to the " C defined above being replaced by halogen
1-C
6alkoxyl group ", be for example indefiniteness trifluoromethoxy, five fluorine oxyethyl groups, difluoro-methoxy, chlorine methoxyl group etc.
In described synthetic method of the present invention, as the described copper compound of catalyzer, be monovalence copper compound, cupric compound or both mixtures.
Described monovalence copper compound is selected from monovalence Inorganic Copper compound or monovalence organocopper compound, for example can be to indefiniteness CuCl, CuBr, CuCN, Cu
2any one in S etc. or multiple.
Described cupric compound is selected from divalence Inorganic Copper compound or divalence organocopper compound, for example can be to indefiniteness CuO, CuCl
2, CuBr
2, CuSO
4, acetylacetone copper [Cu (acac)
2], Cu (OTf)
2deng in any one or multiple.
Described copper compound is preferably monovalence copper compound, and more preferably monovalence Inorganic Copper compound, most preferably is CuCl.
In described synthetic method of the present invention, oxygenant can be ditertiary butyl peroxide (claim again di-t-butyl peroxide, below or with " (
tbuO)
2" represent), tertbutyl peroxide (TBHP), DDQ (DDQ), hydrogen peroxide, iodobenzene diacetate (PhI (OAc)
2), oxygen, ozone, Ag
2any one in O, most preferably is ditertiary butyl peroxide.
In described synthetic method of the present invention, described organic ligand be in following formula L1-L6 any:
Wherein, most preferably be L1 part.
In described synthetic method of the present invention, described reaction solvent can be in tetrahydrofuran (THF) (THF), 2-methyltetrahydrofuran (2-MeTHF), acetonitrile, DMF (DMF), ethanol, methylene dichloride, dimethyl sulfoxide (DMSO) (DMSO), trichloromethane, tetracol phenixin, ethylene dichloride, normal hexane, ether, methyl alcohol, ethanol, n-propyl alcohol, Virahol, butanols, amylalcohol, hexanol, acetone etc. any one or multiple.
In described synthetic method of the present invention, the mol ratio of simple substance selenium and formula (II) compound is 1:1-3, for example can be to indefiniteness 1:1,1:1.5,1:2,1:2.5 or 1:3.
In described synthetic method of the present invention, the mol ratio of simple substance selenium and oxygenant is 1:1-3, for example can be to indefiniteness 1:1,1:1.5,1:2,1:2.5 or 1:3.
In described synthetic method of the present invention, the mol ratio of simple substance selenium and organic ligand is 1:0.05-0.2, for example can be to indefiniteness 1:0.05,1:0.1,1:0.15 or 1:0.2.
In described synthetic method of the present invention, the mol ratio of simple substance selenium and copper compound is 1:0.05-0.15, for example can be to indefiniteness 1:0.05,1:0.07,1:0.09,1:0.11,1:0.13 or 1:0.15.
In described synthetic method of the present invention, temperature of reaction is 50-90 ℃, for example can be to indefiniteness 50 ℃, 60 ℃, 70 ℃, 80 ℃ or 90 ℃.
In described synthetic method of the present invention, reaction times there is no special restriction, for example can how much determine the suitable reaction times by the residual quantity of liquid chromatography or TLC detection raw material, it typically is 12-30 hour, is indefiniteness for example 12 hours, 14 hours, 16 hours, 18 hours, 20 hours, 22 hours, 24 hours, 26 hours, 28 hours or 30 hours.
In described synthetic method of the present invention, the atmosphere of described reaction there is no special restriction, for example, can in air atmosphere or in oxygen atmosphere, react.When enclosing environment for oxygen atmosphere, for example, oxygen can be continued to be passed into and in reaction system, carry out bubbling and be achieved.
In described synthetic method of the present invention, as a kind of some key element, select giving an example of preferred implementation, can be as follows:
Described copper compound is CuCl, and/or
Described organic ligand is L1, and/or
Described oxygenant is ditertiary butyl peroxide.
In described synthetic method of the present invention, as the selection mode of R group, enumerate, as one is exemplary, exemplify, R can be H, F, Cl, methyl, vinyl, phenyl or nitro.
In described synthetic method of the present invention, aftertreatment after reaction finishes can adopt any known conventional processing means in organic synthesis field, such as, any processing means in crystallization, recrystallization, column chromatography purification, extraction etc. or the combination of multiple processing means.As a kind of exemplary aftertreatment means, for example can be: after reaction finishes, reaction system is cooled to room temperature, then in the mixture obtaining from reaction finishes with Rotary Evaporators, remove desolventizing, residue is crossed 300-400 order silica gel column chromatography and is purified and obtain target product, and column chromatography process can be used TLC tracing and monitoring and determine suitable wash-out terminal.
In sum, the present invention uses copper compound as catalyzer, and under oxygenant and organic ligand exist, formula (II) aryl boric acid compound and simple substance selenium (Se) can react and a step makes aryl list selenide.Described method is owing to having used specific catalysis/oxidation/ligand system and simple substance selenium, and have that reaction is simple, product yield and the more high plurality of advantages of purity, it is the brand-new synthetic method of aryl list selenide compound, for the preparation of this compounds provides new synthetic route, there is good researching value and prospects for commercial application.
Embodiment
Below by specific embodiment, the present invention is described in detail; but the purposes of these exemplary embodiments and object are only used for exemplifying the present invention; not real protection scope of the present invention is formed to any type of any restriction, more non-protection scope of the present invention is confined to this.
Embodiment 1: phenylbenzene selenide synthetic
In the reactor of dried and clean, add 50ml solvent THF, then add successively 10mmol simple substance selenium, 10mmol (II) compound, 0.5mmol CuCl, 0.5mmol organic ligand L1, and then add 10mmol ditertiary butyl peroxide, by reaction system under air atmosphere at 50 ℃ stirring reaction 30 hours.
After reaction finishes, reaction system is cooled to room temperature, then with Rotary Evaporators, revolves in the mixture steaming to obtain from reaction finishes and remove desolventizing, residue is crossed 300-400 order silica gel column chromatography and is purified and obtain target product, productive rate is 92.5%, and purity is 98.9% (HPLC).
Nucleus magnetic resonance:
1h NMR (CDCl
3, 500MHz): δ 7.49 (d, J=5Hz, 4H), 7.27-7.29 (m, 6H);
13C?NMR(CDCl
3,125MHz)：δ133.0(4C),131.1(2C),129.3(4C),127.3(2C)。
Synthesizing of 2: two (3-tolyl) selenides of embodiment
In the reactor of dried and clean, add 50ml solvent 2-methyltetrahydrofuran, then add successively 10mmol simple substance selenium, 20mmol (II) compound, 1mmol CuCl, 1mmol organic ligand L1, and then add 20mmol ditertiary butyl peroxide, by reaction system under air atmosphere at 60 ℃ stirring reaction 25 hours.
After reaction finishes, reaction system is cooled to room temperature, then with Rotary Evaporators, revolves in the mixture steaming to obtain from reaction finishes and remove desolventizing, residue is crossed 300-400 order silica gel column chromatography and is purified and obtain target product, productive rate is 73.8%, and purity is 99.1% (HPLC).
Nucleus magnetic resonance:
1h NMR (DMSO-d
6, 500MHz): δ 7.42 (s, 2H), 7.35 (d, J=5Hz, 4H), 7.23-7.27 (m, 2H), 2.39 (s, 6H);
13C?NMR(CDCl
3,125MHz):δ138.8(2C),132.7(2C),130.9(2C),130.0(2C),128.0(2C),126.8(2C),22.2(2C)。
Synthesizing of 3: two (3-nitrophenyl) selenides of embodiment
In the reactor of dried and clean, add 50ml solvent DMF, then add successively 10mmol simple substance selenium, 30mmol (II) compound, 1.5mmol CuCl, 1.5mmol organic ligand L1, and then add 30mmol ditertiary butyl peroxide, by reaction system under air atmosphere at 70 ℃ stirring reaction 20 hours.
After reaction finishes, reaction system is cooled to room temperature, then with Rotary Evaporators, revolves in the mixture steaming to obtain from reaction finishes and remove desolventizing, residue is crossed 300-400 order silica gel column chromatography and is purified and obtain target product, productive rate is 81.8%, and purity is 98.6% (HPLC).
Nucleus magnetic resonance:
1h NMR (CDCl
3, 500MHz): δ 8.32 (s, 2H), 8.16 (d, J=10Hz, 2H), 7.78 (d, J=10Hz, 2H), 7.45-7.51 (m, 2H);
13C?NMR(CDCl
3,125MHz):δ148.7(2C),138.9(2C),131.7(2C),130.4(2C),127.7(2C),123.1(2C)。
Synthesizing of 4: two (4-xenyl) selenides of embodiment
In the reactor of dried and clean, add 50ml methylene chloride, then add successively 10mmol simple substance selenium, 15mmol (II) compound, 0.7mmol CuCl, 2mmol organic ligand L1, and then add 25mmol ditertiary butyl peroxide, by reaction system under air atmosphere at 80 ℃ stirring reaction 15 hours.
After reaction finishes, reaction system is cooled to room temperature, then with Rotary Evaporators, revolves in the mixture steaming to obtain from reaction finishes and remove desolventizing, residue is crossed 300-400 order silica gel column chromatography and is purified and obtain target product, productive rate is 88.7%, and purity is 99.4% (HPLC).
Nucleus magnetic resonance:
1h NMR (CDCl
3, 500MHz): δ 7.61 (d, J=5Hz, 8H), 7.55 (d, J=5Hz, 4H), 7.43-7.47 (m, 4H), 7.36-7.40 (m, 2H);
13C?NMR(CDCl
3,125MHz):δ140.4(2C),140.3(2C),133.4(4C),130.1(2C),128.8(4C),128.0(4C),127.5(2C),127.0(4C)。
Synthesizing of 5: two (3-chloro-phenyl-) selenides of embodiment
In the reactor of dried and clean, add 50ml solvent methanol, then add successively 10mmol simple substance selenium, 25mmol (II) compound, 1.5mmol CuCl, 0.7mmol organic ligand L1, and then add 10mmol ditertiary butyl peroxide, by reaction system under air atmosphere at 90 ℃ stirring reaction 12 hours.
After reaction finishes, reaction system is cooled to room temperature, then with Rotary Evaporators, revolves in the mixture steaming to obtain from reaction finishes and remove desolventizing, residue is crossed 300-400 order silica gel column chromatography and is purified and obtain target product, productive rate is 92.7%, and purity is 98.1% (HPLC).
Nucleus magnetic resonance:
1h NMR (CDCl
3, 500MHz): δ 7.37 (d, J=5Hz, 2H), 7.34 (d, J=5Hz, 2H), 7.20 (s, 2H), 7.20-7.18 (m, 2H);
13C?NMR(CDCl
3,125MHz):δ141.6(2C),135.1(2C),132.7(2C),130.4(2C),127.9(2C),127.2(2C)。
Synthesizing of 6: two (4-fluoroform phenyl) selenides of embodiment
In the reactor of dried and clean, add 50ml solvent acetone, then add successively 10mmol simple substance selenium, 30mmol (II) compound, 1.2mmol CuCl, 1.8mmol organic ligand L1, and then add 22mmol ditertiary butyl peroxide, by reaction system under air atmosphere at 55 ℃ stirring reaction 26 hours.
After reaction finishes, reaction system is cooled to room temperature, then with Rotary Evaporators, revolves in the mixture steaming to obtain from reaction finishes and remove desolventizing, residue is crossed 300-400 order silica gel column chromatography and is purified and obtain target product, productive rate is 90.4%, and purity is 98.3% (HPLC).
Nucleus magnetic resonance:
1h NMR (CDCl
3, 500MHz): δ 7.70 (d, J=5Hz, 4H), 7.52 (d, J=5Hz, 4H);
13C?NMR(CDCl
3,125MHz):δ134.8(2C),132.7(2C),130.8(4C),126.1(2C),122.8(4C)。
Synthesizing of 7: two (4-ethenylphenyl) selenides of embodiment
In the reactor of dried and clean, add 50ml solvent normal hexane, then add successively 10mmol simple substance selenium, 10mmol (II) compound, 1.5mmol CuCl, 1mmol organic ligand L1, and then add 30mmol ditertiary butyl peroxide, by reaction system under air atmosphere at 65 ℃ stirring reaction 20 hours.
After reaction finishes, reaction system is cooled to room temperature, then with Rotary Evaporators, revolves in the mixture steaming to obtain from reaction finishes and remove desolventizing, residue is crossed 300-400 order silica gel column chromatography and is purified and obtain target product, productive rate is 73.9%, and purity is 98.7% (HPLC).
Nucleus magnetic resonance:
1h NMR (CDCl
3, 500MHz): δ 7.69 (d, J=10Hz, 2H), 7.50 (d, J=10Hz, 2H), 7.44 (d, J=10Hz, 2H), 7.33 (d, J=10Hz, 2H), 6.80-6.66 (m, 2H), 5.79 (dd, J=25Hz, 15Hz, 2H), 5.29 (dd, J=25Hz, 15Hz, 2H);
13C?NMR(CDCl
3,125MHz):δ136.8(2C),136.1(2C),133.1(4C),127.1(4C),122.8(2C),113.9(2C)。
By above-described embodiment 1-7, can be found out, when adopting during described method of the present invention, can be with by simple substance selenium and aryl boric acid and a step obtains the aryl list selenide compound of general formula (I).
Embodiment 8-16
Except CuCl is wherein replaced with following copper compound, in the mode identical with embodiment 1-7, implemented respectively embodiment 8-16, the yield of the copper compound that uses, embodiment corresponding relation and corresponding product is as shown in the table.
As seen from the above table, when using other copper compound, can obtain equally corresponding product, but productive rate when productive rate is wanted significantly lower than CuCl, even if adopt with Cl negatively charged ion while belonging to the Br of gang together, while adopting CuBr, the productive rate of its productive rate during also significantly lower than CuCl.
Embodiment 17-23
Except L1 part is wherein replaced with following organic ligand, in the mode identical with embodiment 1-7, implemented respectively embodiment 17-23, the yield of the organic ligand that uses, embodiment corresponding relation and corresponding product is as shown in the table.
As seen from the above table, when using during other organic ligand, even if use while having L2 (phenanthroline), the phenanthroline monohydrate (being embodiment 23) of identical precursor structure with L1, its productive rate is significantly decline also.This has proved that the organic ligand L1 of the method for the invention has good concerted catalysis performance together with CuCl.
Embodiment 23-29
Except ditertiary butyl peroxide is wherein replaced with following oxygenant, in the mode identical with embodiment 1-7, implemented respectively embodiment 23-29, the yield of the oxygenant that uses, embodiment corresponding relation and corresponding product is as shown in the table.
As seen from the above table, when using other oxygenant, also can obtain object product with high yield.
In sum, by above-mentioned all embodiment, can clearly be found out, when adopting method of the present invention, can be smoothly by simple substance selenium and aryl boric acid compound with high yield and high purity and obtain object product aryl list selenide derivative, be a kind of brand-new synthetic method that has very much prospects for commercial application, for the efficient quick of aryl list selenide derivative synthesizes, provide brand-new synthetic route.
The purposes that should be appreciated that these embodiment only limits the scope of the invention for the present invention being described but not being intended to.In addition; also should understand; after having read technology contents of the present invention, those skilled in the art can make various changes, modification and/or modification to the present invention, within these all equivalent form of values fall within the protection domain that the application's appended claims limits equally.
Claims (10)
1. the synthetic method of an aryl list selenide compound, described method comprises: using copper compound as catalyzer, under oxygenant and organic ligand existence, in reaction solvent, by formula (II) aryl boric acid compound and simple substance selenium (Se), reacted, and make described formula (I) compound;
Wherein R is selected from H, C
1-C
6alkyl, C
2-C
6thiazolinyl, C
1-C
6alkoxyl group, halogen, halo C
1-C
6alkyl, halo C
1-C
6alkoxyl group, phenyl or nitro.
2. synthetic method as claimed in claim 1, is characterized in that:
Described copper compound is monovalence copper compound, cupric compound or both mixtures.
3. synthetic method as claimed in claim 2, is characterized in that:
Described copper compound is for being CuCl, CuBr, CuCN, Cu
2any one in S or multiple, or be CuO, CuCl
2, CuBr
2, CuSO
4, acetylacetone copper [Cu (acac)
2], Cu (OTf)
2in any one or multiple.
4. the synthetic method as described in claim 1-3 any one, is characterized in that:
Described organic ligand be in following formula L1-L6 any:
5. the synthetic method as described in claim 1-4 any one, is characterized in that:.
Described oxygenant is ditertiary butyl peroxide, tertbutyl peroxide, DDQ, hydrogen peroxide, iodobenzene diacetate, oxygen, ozone, Ag
2any one in O.
6. the synthetic method as described in claim 1-5 any one, is characterized in that:
The mol ratio of simple substance selenium and formula (II) compound is 1:1-3.
7. the synthetic method as described in claim 1-6 any one, is characterized in that:
The mol ratio of simple substance selenium and oxygenant is 1:1-3.
8. the synthetic method as described in claim 1-7 any one, is characterized in that:
The mol ratio of simple substance selenium and organic ligand is 1:0.05-0.2.
9. the synthetic method as described in claim 1-8 any one, is characterized in that:
The mol ratio of simple substance selenium and copper compound is 1:0.05-0.15.
10. the synthetic method as described in claim 1-9 any one, is characterized in that:
The temperature of reaction of described synthetic method is 50-90 ℃; Reaction times is 12-30 hour.
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| CN106496087A (en) * | 2016-09-12 | 2017-03-15 | 广西师范大学 | A kind of method by the decarboxylation coupling reaction one pot process compound of class containing selenium |
| CN107382803A (en) * | 2017-08-18 | 2017-11-24 | 温州大学 | A kind of preparation method of β hydroxy phenyls selenide compound |
| CN110643822A (en) * | 2019-10-31 | 2020-01-03 | 清华大学 | Method for extracting and enriching gold element by utilizing selenoether |
| CN112062748A (en) * | 2020-09-16 | 2020-12-11 | 温州大学 | Synthesis method of phenoxaseleno/phenothiazine selenium compound |
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| CN102010282A (en) * | 2010-10-18 | 2011-04-13 | 四川大学 | Method for preparing diaryl disulfide and diaryl diselenide under catalysis of aqueous phase |
| CN103086935A (en) * | 2011-10-28 | 2013-05-08 | 沈阳药科大学 | Diphenyl selenide, diphenyl selenoxide, diphenyl selenone compounds and uses thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106496087A (en) * | 2016-09-12 | 2017-03-15 | 广西师范大学 | A kind of method by the decarboxylation coupling reaction one pot process compound of class containing selenium |
| CN106496087B (en) * | 2016-09-12 | 2018-01-23 | 广西师范大学 | A kind of method by the decarboxylation coupling reaction one pot process compound of class containing selenium |
| CN107382803A (en) * | 2017-08-18 | 2017-11-24 | 温州大学 | A kind of preparation method of β hydroxy phenyls selenide compound |
| CN107382803B (en) * | 2017-08-18 | 2019-03-29 | 温州大学 | A kind of preparation method of beta-hydroxy phenyl selenide compound |
| CN110643822A (en) * | 2019-10-31 | 2020-01-03 | 清华大学 | Method for extracting and enriching gold element by utilizing selenoether |
| CN112062748A (en) * | 2020-09-16 | 2020-12-11 | 温州大学 | Synthesis method of phenoxaseleno/phenothiazine selenium compound |
| CN112062748B (en) * | 2020-09-16 | 2021-07-27 | 温州大学 | Synthesis method of phenoxaseleno/phenothiazine selenium compound |
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