CN103724246B - 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 elemental selenium, belong to organic chemical synthesis field.
Background technology
As a kind of trace element, selenium is that multiple metabolism in organism and physiological activity are 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 shows, many organoselenium compounds not only have effect that is antiviral, antitumor and treatment neural system aspect disease, but also have the biochemical and pharmacological actions such as anti-inflammatory, anti-ageing, prevention and cure of cardiovascular disease and prevention liver disease.Such as 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 the focus of current organic chemistry, pharmaceutical chemistry and Materials science research already.
At present, people have developed the method for a large amount of synthesis list selenide compounds.
The people (" Eco-friendly cross-coupling of diaryldiselenides with aryl and alkyl bromides catalyzed by CuO nanopowderin ionic liquid " such as Devender Singh, Green Chem., 2009,11,1521-1524) disclose aromatic bromide or alkyl bromide under the catalysis of nanometer CuO powder and different ionic liquid, with diphenyl disenenide ether ((PhSe)
2) there is linked reaction, and obtain Aryl elemental selenium.
The people (" Synthesis of diaryl selenides usingelectrophilic selenium species and nucleophilic boron regents in ionicliquids " such as Camilo S.Freitas, Green Chem., 2011,13,2931-2938) in disclose Electron Affinities compd A r-Se-Cl (Br) and nucleophilic compound aryl boric acid (Ar
1-B (OH)
2) or aromatic yl acid salt (Ar
1-BF
3k) under ionic liquid-catalyzed, and Aryl elemental selenium compound Ar-Se-Ar is obtained
1.
The people (" Microwave-assisted reaction of aryldiazonium fluoroborate and diaryl dichalcogenides in dimethylcarbonate:a general procedure for the synthesis of unsymmetrical diarylchalcogenides " such as Debasish Kundu, Green Chem., 2012,14, disclose under existing with Zn under microwave-assisted 2024-2030), diazotization fluoroborate (Ar
1-N
2bF
4) and diaryl chalcogenide (Ar
2 2x
2, X=S, Se, Te) react in methylcarbonate, thus obtain asymmetric diaryl chalcogenide Ar
1-X-Ar
2.
The people (" An efficient synthesis of alkynyl selenidesand tellurides from terminal acetylenes and diorganyl diselenides orditellurides catalyzed by recyclable copper oxide nanopowder " such as Marcelo Godoi, Tetrahedron, 2012,68,10426-10430) disclose the synthetic method of the selenide compound containing 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 obtained R
1c ≡ CSe-R
2.
People (" Solvent-Controlled Hlao-SelectiveSelenylation of Aryl Halides Catalyzed by Cu (II) the Supported on Al such as Tanmay Chatterjee
2o
3.AGeneral Protocol for the Synthesis of Unsymmetrical Organo Mono-andBis-selenides ") disclose under the effect of Cu-aluminum oxide, (R is aryl, vinyl, heteroaryl to R-X; X is halogen) and R '-Se-Se-R ' (R ' be aryl, alkyl, heteroaryl) react, can R-Se-R ' be obtained.
Yunyun Liu reports its seminar in 2006 in (Zhejiang University Ph.D. Dissertation, in April, 2010), and developing with ionic liquid is solvent, under Metal Zn promotes by the diselenide ((PhSe) of CuI/L-Proline-Catalyzed
2) with the coupling of thiazolinyl bromine (Ar-C=CBr), this reaction to aliphatics and aromatic series diselenide all applicable, have good reaction to alkylalkenyl bromine and aryl alkenyl bromine simultaneously.
As mentioned above, disclose the multiple method preparing diaryliodonium in prior art, but all there is certain defect in these methods, such as: (1) is reacted by the selenium species of nucleophilicity and corresponding electrophilic reagent.Wherein virtue (alkane) base selenium anion is the nucleophilicity selenium species commonly used the most.They are usually reacted by diselenide and reductive agent and prepare, but the defect of this synthesis organoselenium compounds method to use diselenide as reacting precursor, and the preparation of diselenide relates to polystep reaction, especially will through foul smelling and the large selenium phenol oxidising process of toxicity; (2) reacted by electrophilic selenium species and corresponding nucleophilic reagent, diselenide can serve as Electron Affinities seleno reagent, but when it uses as electrophilic reagent, usually only has the selenium atom of 50% to participate in reaction and enter 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 use 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. and diselenide react also can in situ preparation Electron Affinities selenium species, but these processes all need the oxygenant using equivalent, and easily cause the problem such as side reaction and functional group compatibility variation.
For these reasons, explore efficient, gentle, easy and that functional group compatibility is good synthesis organoselenium compounds, especially the novel method of Aryl elemental selenium compound still has great importance, still there is the necessity proceeding to study and explore, this is the basis that is accomplished of the present invention and power place just also.
Summary of the invention
In order to overcome above-mentioned pointed many defects, seeking the brand-new of synthesizing aryl list selenide compound and simple method, present inventor has performed deep research, after having paid a large amount of creative works, thus complete the present invention.
Specifically, technical scheme of the present invention and content relate to the synthetic method of the Aryl elemental selenium compound shown in following formula (I), described method is: using copper compound as catalyzer, under oxygenant and organic ligand exist, reacted by formula (II) arylboronic acid compound and elemental selenium (Se) in reaction solvent, and obtained 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, enumerate as one is exemplary, the position of R in formula (II) aryl boric acid such as can be arranged in position or contraposition (namely at product formula (I), R is positioned at position or contraposition between Se) between boronate.
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, that includes C
1alkyl, C
2alkyl, C
3alkyl, C
4alkyl, C
5alkyl or C
6alkyl, such as can be methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl or n-hexyl etc. in non-limiting manner.
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 " be connected with O atom after group.
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 such as 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 be optionally substituted by halogen
1-C
6alkyl ", be such as trifluoromethyl, pentafluoroethyl group, difluoromethyl, chloromethyl etc. in non-limiting manner.
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 be optionally substituted by halogen
1-C
6alkoxyl group ", be such as trifluoromethoxy, five fluorine oxyethyl groups, difluoro-methoxy, chlorine methoxyl group etc. in non-limiting manner.
In described synthetic method of the present invention, the described copper compound as catalyzer is monovalence copper compound, cupric compound or both mixtures.
Described monovalence copper compound is selected from inorganic monovalent copper compound or monovalence organocopper compound, such as can be CuCl, CuBr, CuCN, Cu in non-limiting manner
2in S etc. any one or multiple.
Described cupric compound is selected from divalent inorganic copper compound or divalence organocopper compound, such as can be CuO, CuCl in non-limiting manner
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, is more preferably inorganic monovalent copper compound, most preferably is CuCl.
In described synthetic method of the present invention, oxygenant can be ditertiary butyl peroxide (also known as 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 is any one in following formula L1-L6:
Wherein, L1 part most preferably is.
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 elemental selenium and formula (II) compound is 1:1-3, such as can be 1:1,1:1.5,1:2,1:2.5 or 1:3 in non-limiting manner.
In described synthetic method of the present invention, the mol ratio of elemental selenium and oxygenant is 1:1-3, such as can be 1:1,1:1.5,1:2,1:2.5 or 1:3 in non-limiting manner.
In described synthetic method of the present invention, the mol ratio of elemental selenium and organic ligand is 1:0.05-0.2, such as can be 1:0.05,1:0.1,1:0.15 or 1:0.2 in non-limiting manner.
In described synthetic method of the present invention, the mol ratio of elemental selenium and copper compound is 1:0.05-0.15, such as can be 1:0.05,1:0.07,1:0.09,1:0.11,1:0.13 or 1:0.15 in non-limiting manner.
In described synthetic method of the present invention, temperature of reaction is 50-90 DEG C, such as can be 50 DEG C, 60 DEG C, 70 DEG C, 80 DEG C or 90 DEG C in non-limiting manner.
In described synthetic method of the present invention, reaction times, there is no particular limitation, such as detect the residual quantity of raw material by liquid chromatography or TLC how many and determine the suitable reaction times, it typically is 12-30 hour, is such as 12 hours, 14 hours, 16 hours, 18 hours, 20 hours, 22 hours, 24 hours, 26 hours, 28 hours or 30 hours in non-limiting manner.
In described synthetic method of the present invention, there is no particular limitation for the atmosphere of described reaction, such as, can react in air atmosphere or in oxygen atmosphere.When enclosing environment for oxygen atmosphere, such as, oxygen can be continued to be passed into and carry out bubbling in reaction system and be achieved.
In described synthetic method of the present invention, select the citing of preferred implementation as some key element a kind of, 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, the selection mode as R group is enumerated, and exemplify as one is exemplary, R can be H, F, Cl, methyl, vinyl, phenyl or nitro.
In described synthetic method of the present invention, aftertreatment after reaction terminates can adopt any known conventional processing means, such as, any one process means in crystallization, recrystallization, chromatography over CC, extraction etc. or the combination of multiple process means in organic synthesis field.As a kind of exemplary aftertreatment means, such as can be: after reaction terminates, reaction system is cooled to room temperature, then with Rotary Evaporators from the mixture that obtains after reaction terminates except desolventizing, residue is crossed 300-400 order silica gel column chromatography and is carried out purifying and obtaining target product, and column chromatography procedure can use 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) arylboronic acid compound and elemental selenium (Se) can react and a step obtains Aryl elemental selenium.Described method is owing to employing specific catalysis/oxidation/ligand system and elemental 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 elemental selenium compound, preparation for this compounds provides new synthetic route, has 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 any type of any restriction is formed to real protection scope of the present invention, more non-protection scope of the present invention is confined to this.
Embodiment 1: the synthesis of phenylbenzene selenide
In the reactor of dried and clean, add 50ml solvent THF, then 10mmol elemental selenium, 10mmol (II) compound, 0.5mmol CuCl, 0.5mmol organic ligand L1 is added successively, and then add 10mmol ditertiary butyl peroxide, by reaction system under air atmosphere at 50 DEG C stirring reaction 30 hours.
After reaction terminates, reaction system is cooled to room temperature, then with Rotary Evaporators revolve steam with in the mixture that obtains after terminating from reaction except desolventizing, residue is crossed 300-400 order silica gel column chromatography and is carried out purifying and obtaining 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)。
The synthesis of embodiment 2: two (3-tolyl) selenide
In the reactor of dried and clean, add 50ml solvent 2-methyltetrahydrofuran, then 10mmol elemental selenium, 20mmol (II) compound, 1mmol CuCl, 1mmol organic ligand L1 is added successively, and then add 20mmol ditertiary butyl peroxide, by reaction system under air atmosphere at 60 DEG C stirring reaction 25 hours.
After reaction terminates, reaction system is cooled to room temperature, then with Rotary Evaporators revolve steam with in the mixture that obtains after terminating from reaction except desolventizing, residue is crossed 300-400 order silica gel column chromatography and is carried out purifying and obtaining 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)。
The synthesis of embodiment 3: two (3-nitrophenyl) selenide
In the reactor of dried and clean, add 50ml solvent DMF, then 10mmol elemental selenium, 30mmol (II) compound, 1.5mmol CuCl, 1.5mmol organic ligand L1 is added successively, and then add 30mmol ditertiary butyl peroxide, by reaction system under air atmosphere at 70 DEG C stirring reaction 20 hours.
After reaction terminates, reaction system is cooled to room temperature, then with Rotary Evaporators revolve steam with in the mixture that obtains after terminating from reaction except desolventizing, residue is crossed 300-400 order silica gel column chromatography and is carried out purifying and obtaining 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)。
The synthesis of embodiment 4: two (4-xenyl) selenide
In the reactor of dried and clean, add 50ml methylene chloride, then 10mmol elemental selenium, 15mmol (II) compound, 0.7mmol CuCl, 2mmol organic ligand L1 is added successively, and then add 25mmol ditertiary butyl peroxide, by reaction system under air atmosphere at 80 DEG C stirring reaction 15 hours.
After reaction terminates, reaction system is cooled to room temperature, then with Rotary Evaporators revolve steam with in the mixture that obtains after terminating from reaction except desolventizing, residue is crossed 300-400 order silica gel column chromatography and is carried out purifying and obtaining 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)。
The synthesis of embodiment 5: two (3-chloro-phenyl-) selenide
In the reactor of dried and clean, add 50ml solvent methanol, then 10mmol elemental selenium, 25mmol (II) compound, 1.5mmol CuCl, 0.7mmol organic ligand L1 is added successively, and then add 10mmol ditertiary butyl peroxide, by reaction system under air atmosphere at 90 DEG C stirring reaction 12 hours.
After reaction terminates, reaction system is cooled to room temperature, then with Rotary Evaporators revolve steam with in the mixture that obtains after terminating from reaction except desolventizing, residue is crossed 300-400 order silica gel column chromatography and is carried out purifying and obtaining 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)。
The synthesis of embodiment 6: two (4-fluoroform phenyl) selenide
In the reactor of dried and clean, add 50ml solvent acetone, then 10mmol elemental selenium, 30mmol (II) compound, 1.2mmol CuCl, 1.8mmol organic ligand L1 is added successively, and then add 22mmol ditertiary butyl peroxide, by reaction system under air atmosphere at 55 DEG C stirring reaction 26 hours.
After reaction terminates, reaction system is cooled to room temperature, then with Rotary Evaporators revolve steam with in the mixture that obtains after terminating from reaction except desolventizing, residue is crossed 300-400 order silica gel column chromatography and is carried out purifying and obtaining 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)。
The synthesis of embodiment 7: two (4-ethenylphenyl) selenide
In the reactor of dried and clean, add 50ml solvent hexane, then 10mmol elemental selenium, 10mmol (II) compound, 1.5mmol CuCl, 1mmol organic ligand L1 is added successively, and then add 30mmol ditertiary butyl peroxide, by reaction system under air atmosphere at 65 DEG C stirring reaction 20 hours.
After reaction terminates, reaction system is cooled to room temperature, then with Rotary Evaporators revolve steam with in the mixture that obtains after terminating from reaction except desolventizing, residue is crossed 300-400 order silica gel column chromatography and is carried out purifying and obtaining 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)。
Can be found out by above-described embodiment 1-7, when adopting described method of the present invention, can so that by elemental selenium and aryl boric acid, one step obtains the Aryl elemental selenium compound of general formula (I).
Embodiment 8-16
Replace with except following copper compound except by CuCl wherein, implement embodiment 8-16 respectively in the mode identical with embodiment 1-7, use the yield of copper compound, embodiment corresponding relation and corresponding product as shown in the table.
As seen from the above table, when using other copper compound, corresponding product can be obtained equally, but productive rate is wanted significantly lower than productive rate during CuCl, even if when employing and Cl negatively charged ion belong to the Br of gang together, when namely adopting CuBr, its productive rate is also remarkable in productive rate during CuCl.
Embodiment 17-23
Replace with except following organic ligand except by L1 part wherein, implement embodiment 17-23 respectively in the mode identical with embodiment 1-7, use the yield of organic ligand, embodiment corresponding relation and corresponding product as shown in the table.
As seen from the above table, when using other organic ligand, even if when using L2 (phenanthroline), phenanthroline monohydrate (i.e. the embodiment 23) with L1 with identical precursor structure, its productive rate also significantly declines.This demonstrate that organic ligand L1 and the CuCl of the method for the invention has good concerted catalysis performance together.
Embodiment 23-29
Replace with except following oxygenant except by ditertiary butyl peroxide wherein, implement embodiment 23-29 respectively in the mode identical with embodiment 1-7, use the yield of oxygenant, embodiment corresponding relation and corresponding product as shown in the table.
As seen from the above table, when using other oxygenant, also object product can be obtained with high yield.
In sum, can clearly be found out by above-mentioned all embodiments, when applying the method according to the invention, object product Aryl elemental selenium derivative can be obtained with high yield and high purity smoothly by elemental selenium and arylboronic acid compound, a kind of brand-new synthetic method having very much prospects for commercial application, for the efficient quick synthesis of Aryl elemental selenium derivative provides brand-new synthetic route.
Should be appreciated that the purposes of these embodiments is only not intended to for illustration of the present invention limit the scope of the invention.In addition; also should understand; after having read technology contents of the present invention, those skilled in the art can make various change, amendment and/or modification to the present invention, and these all equivalent form of values fall within the protection domain that the application's appended claims limits equally.
Claims (6)
1. the synthetic method of an Aryl elemental selenium compound, described method comprises: using copper compound as catalyzer, under oxygenant and organic ligand exist, reacted by formula (II) arylboronic acid compound and elemental selenium (Se) in reaction solvent, and obtained 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;
Wherein, described copper compound is CuCl, CuBr, CuCN, Cu
2in S any one or multiple, or be CuO, CuCl
2, CuBr
2, CuSO
4, Cu (OTf)
2in any one or multiple;
Described organic ligand is any one in following formula L1-L6:
Described oxygenant is ditertiary butyl peroxide, tertbutyl peroxide, DDQ, hydrogen peroxide, iodobenzene diacetate, oxygen, ozone, Ag
2any one in O.
2. synthetic method as claimed in claim 1, is characterized in that:
The mol ratio of elemental selenium and formula (II) compound is 1:1-3.
3. synthetic method as claimed in claim 1 or 2, is characterized in that:
The mol ratio of elemental selenium and oxygenant is 1:1-3.
4. synthetic method as claimed in claim 1 or 2, is characterized in that:
The mol ratio of elemental selenium and organic ligand is 1:0.05-0.2.
5. synthetic method as claimed in claim 1 or 2, is characterized in that:
The mol ratio of elemental selenium and copper compound is 1:0.05-0.15.
6. synthetic method as claimed in claim 1 or 2, is characterized in that:
The temperature of reaction of described synthetic method is 50-90 DEG C; Reaction times is 12-30 hour.
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| CN107382803B (en) * | 2017-08-18 | 2019-03-29 | 温州大学 | A kind of preparation method of beta-hydroxy phenyl selenide compound |
| CN110643822B (en) * | 2019-10-31 | 2020-07-28 | 清华大学 | Method for extracting and enriching gold element by utilizing selenoether |
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| US4597914A (en) * | 1983-06-23 | 1986-07-01 | Gte Laboratories Incorporated | Method for the preparation of aromatic selenium compounds |
| US4613468A (en) * | 1984-01-12 | 1986-09-23 | Gte Laboratories Incorporated | Method for preparing aromatic and olefinic organoselenium and organotellurium compounds |
| US7112697B1 (en) * | 2003-07-11 | 2006-09-26 | University Of Massachusetts | Methods for formation of aryl-sulfur and aryl-selenium compounds using copper(I) catalysts |
| CN102010282B (en) * | 2010-10-18 | 2014-04-16 | 四川大学 | Method for preparing diaryl disulfide and diaryl diselenide under catalysis of aqueous phase |
| CN103086935B (en) * | 2011-10-28 | 2015-05-20 | 沈阳药科大学 | Diphenyl selenide, diphenyl selenoxide, diphenyl selenone compounds and uses thereof |
| CN103193803B (en) * | 2013-04-25 | 2015-03-04 | 福州大学 | Copper trifluoromethseleno (I) reagent for aryl halides/alkanes |
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