CN110156635A - A kind of EDA transient state electron donor-acceptor complex, preparation method and applications - Google Patents
A kind of EDA transient state electron donor-acceptor complex, preparation method and applications Download PDFInfo
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- CN110156635A CN110156635A CN201910385937.8A CN201910385937A CN110156635A CN 110156635 A CN110156635 A CN 110156635A CN 201910385937 A CN201910385937 A CN 201910385937A CN 110156635 A CN110156635 A CN 110156635A
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- C07—ORGANIC CHEMISTRY
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- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/64—Preparation of O-metal compounds with O-metal group bound to a carbon atom belonging to a six-membered aromatic ring
- C07C37/66—Preparation of O-metal compounds with O-metal group bound to a carbon atom belonging to a six-membered aromatic ring by conversion of hydroxy groups to O-metal groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/64—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by introduction of functional groups containing oxygen only in singly bound form
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Abstract
The present invention relates to a kind of EDA transient state electron donor-acceptor complex, preparation method and applications.The structural formula of the compound are as follows:Wherein, substituent R1For cyano, nitro, acetyl group, the electron-withdrawing groups such as trifluoromethyl, R2For hydrogen, methyl, the alkyl such as ethyl, chlorine, bromine, iodine, methoxyl group, any one in any substituent group such as nitro, the position of substituent group is any one of ortho position, meta position and contraposition.Synthetic method is not add any transition-metal catalyst and ligand or photoredox agent, phenol derivatives react under the action of alkali cesium carbonate with electron deficient aryl halide under visible light-inducing.A series of diaryl ether analog derivatives are additionally prepared for by the reaction mechanism.Mild condition, green, it is efficiently, at low cost, it is easy to operate.
Description
Technical field
And a kind of novel EDA (transient state electron donor-acceptor (EDA)) complex compound and its application, belong to technical field of organic synthesis.
Background technique
Eda complex is called EDA compound, is a kind of transient state push-and-pull electron donor receptor, and english name is
Transient Electron Donor Acceptor.Eda complex is in the especially photocatalysis field of free-radical chemistry field
A very important concept.The electron donor of eda complex is generally the anions such as stable phosphine sulfide at present, and phenoxy group is negative
Ion is not yet reported that as electron donor.Diaryl ether compound object has played in organic synthesis field important for many years
Effect, while being also medicine, the important synthetic intermediate of pesticide etc..Some organic compounds being made of diaryl ether unit
Object such as antibiotic vancomycin and HIV antibiotic have been demonstrated there is apparent bioactivity.However, diaryl ether intermediate
Traditional synthetic method there are at high cost, it is inefficient, the deficiencies of complex operation.Therefore seek a kind of novel, behaviour
It is imperative to make simple and highly efficient synthetic method.
Summary of the invention
The main purpose of the present invention is to provide a kind of novel EDA (transient state electron donor-acceptor (EDA)) complex compound and its application are real
Example.
Technical scheme is as follows:
A kind of novel EDA (transient state electron donor-acceptor (EDA)) complex compound, which is characterized in that the chemical structural formula of the compound
It indicates are as follows:
Wherein, substituent R1For cyano, nitro, the electron-withdrawing groups such as acetyl group or trifluoromethyl, R2For hydrogen, methyl, second
The alkyl such as base, chlorine, bromine, iodine, methoxyl group, any one in any substituent group such as nitro, the position of substituent group is ortho position, meta position
With contraposition any one.
The preparation method of described EDA (transient state electron donor-acceptor (EDA)) complex compound, which is characterized in that synthetic method is as follows:
It the described method comprises the following steps:
(1) compound 1 is sequentially added into reactor, solvent, cesium carbonate, compound 2 is stirred at room temperature 3 minutes；
(2) reactor is then placed in reaction temperature is that (preferred embodiment is that oil bath is anti-in the oil bath pan for be set as 70-90 DEG C
Answering temperature is 80 DEG C) it is irradiated with LED lamplight, reaction process is detected by UV detector, and EDA can be realized in 3-10 minutes in reaction
The preparation of (transient state electron donor-acceptor (EDA)) complex compound.In reaction process, the system of reaction can be with (the reaction of apparent color change
System can be gradually varied to sundown by colorless and transparent solution).
The compound 1, compound 2, the molar ratio of alkali are 1:0.5-6:0.5-6.
The solvent is dimethyl sulfoxide or N,N-dimethylformamide.
The application example of the novel eda complex, synthesis of diaryl ether derivant, process are as follows:
It the described method comprises the following steps:
(1) compound 1 is sequentially added into reactor, solvent, cesium carbonate, compound 2 is stirred at room temperature 3 minutes；
(2) reactor is then placed in reaction temperature is in the oil bath pan for be set as 70-90 DEG C, and is irradiated with LED lamplight,
Reaction process is detected by TLC, to which after the reaction was completed, reaction solution obtains target compound through filtering, extraction and column chromatography, completion
The preparation of diaryl ether compound object.
Reaction process of the invention only needs to carry out under visible light illumination, does not need any transition-metal catalyst, matches
Body or photoredox agent.
The present invention has the beneficial effect that:
1, present invention firstly discloses a kind of novel eda complexs.
2, present invention firstly discloses a kind of preparation methods of novel eda complex.This method is only needed in visible light
Irradiation, does not need any transition-metal catalyst, ligand or photoredox agent.
3, present invention firstly discloses a kind of application examples of novel eda complex.The diaryl synthesized with this method
Ether compound yield and purity are preferable.This method is at low cost, easy to operate.
Detailed description of the invention
Fig. 1 is that concentration is 5 × 10 in embodiment 1-3Mole every liter of compound 1a；Concentration is 5 × 10-3Mole every liter
Compound；Concentration is 5 × 10-3Mole every liter of compound 1a and concentration is 5 × 10-3Mole every liter of cesium carbonate；Concentration is 5
×10-3Mole every liter of compound 2a and concentration is 5 × 10-3Mole every liter of cesium carbonate；Concentration is 5 × 10-3Mole every liter
Compound 1a and concentration are 5 × 10-3Mole every liter of compound 2a；Concentration is 5 × 10-3Mole every liter of compound 1a, concentration
It is 5 × 10-3Mole every liter of compound 2a and concentration is 5 × 10-3The purple of the dimethyl sulphoxide solution of mole every liter of cesium carbonate
Outer visible absorption spectra figure.
Fig. 2 is the dimethyl sulphoxide solution of concentration is 0.1 mole every liter in embodiment 1 compound 1a, 2a and cesium carbonate
Photo, a be 0.1M phenol dimethyl sulphoxide solution, b be 0.1M phenol and 0.1M cesium carbonate dimethyl sulphoxide solution, c
For the dimethyl sulphoxide solution of 0.1M 4- cyano iodobenzene, d is the dimethyl sulfoxide of 0.1M 4- cyano iodobenzene and 0.1M cesium carbonate
Solution, e are the dimethyl sulphoxide solution of 0.1M phenol and 0.1M 4- cyano iodobenzene, and f is 0.1M phenol, 0.1M 4- cyano iodobenzene
With the dimethyl sulphoxide solution of 0.1M cesium carbonate.
Specific embodiment
The present invention is further illustrated below with reference to embodiment, but the scope of protection of present invention is not limited to implement
The range of example statement.
Instrument and reagent:
1H NMR and13C NMR 400 type 400MHz Nuclear Magnetic Resonance of Varian Mercury or Varian
600 type 600MHz nmr determination of Mercury, deuterated chloroform (CDCl3) or deuterated dimethyl sulfoxide (DMSO-d6) it is molten
Agent, TMS are internal standard；Solvent methanol is dried.
Embodiment 1
A kind of synthesisMethod, including following experimental procedure:
(1) compound 1 is sequentially added into reactor, solvent, alkali, compound 2 is stirred at room temperature 3 minutes；
(2) reactor is then placed in reaction temperature is in the oil bath pan for be set as 80 DEG C, and is irradiated with LED lamplight, instead
Process is answered to detect by UV detector, the preparation of EDA (transient state electron donor-acceptor (EDA)) complex compound can be realized for 5 minutes in reaction.Instead
During answering, the system of reaction can be accompanied by apparent color change, and (reaction system can be gradually changed by colorless and transparent solution
For sundown).
It weighs to cyano bromobenzene 1a (1mmol), phenol 2a (1.2mmol) and cesium carbonate (2mmol) are added to equipped with 5ml bis-
In the flask of methyl sulfoxide solvent, it is stirred at room temperature 3 minutes, it is to be set as 80 DEG C that reactor, which is then placed in reaction temperature,
It in oil bath pan, and is irradiated with LED lamplight, reaction process is detected by UV detector, and EDA can be realized in reaction ten minutes later
The preparation of (transient state electron donor-acceptor (EDA)) complex compound.In reaction process, reaction system can be gradually varied to from colorless and transparent solution
Sundown.
By compound 1a, the ultraviolet-visible absorption spectroscopy of the dimethyl sulphoxide solution of 2a and cesium carbonate can be seen that a and be
The dimethyl sulphoxide solution of 0.1M phenol is colourless transparent solution；B is that 0.1M phenol and the dimethyl sulfoxide of 0.1M cesium carbonate are molten
It is lightpink that liquid, which passes through the reaction solution that the step of embodiment 1 carries out,；C is that the dimethyl sulphoxide solution of 0.1M 4- cyano iodobenzene is
Colourless transparent solution；The step of d passes through embodiment 1 for the dimethyl sulphoxide solution of 0.1M 4- cyano iodobenzene and 0.1M cesium carbonate
The reaction solution of progress is colourless transparent solution；E is that 0.1M phenol and the dimethyl sulphoxide solution of 0.1M 4- cyano iodobenzene pass through in fact
The reaction solution that the step of applying example 1 carries out is colourless transparent solution；F is 0.1M phenol, 0.1M 4- cyano iodobenzene and 0.1M cesium carbonate
Dimethyl sulfoxide by the step of embodiment 1 carry out reaction six minutes after ultraviolet-visible absorption spectroscopy have apparent change
Change.The color of its system transparent becomes sundown by anhydrous.
Embodiment 2
The application example of above-mentioned novel eda complex, i.e., in the preparation of diaryl aether derivant.
The method for being used to prepare 4- cyano-diaryl ether (4-phenoxybenzonitrile) 4a, including following experiment step
It is rapid:
Compound 4- cyano iodobenzene 1a (1.0mmol), DMSO (5ml), Cs are sequentially added into reactor2CO3
(2.0mmol) is stirred 6 minutes under phenol 2a (1.2mmol) room temperature.It is subsequently placed in 80 DEG C of oil bath pans, reacts under light illumination
10h, TLC are detected after the reaction was completed, and reaction solution is chromatographed through filtering, extraction and column, obtain target product 4a, yield 79%.
1H NMR(CDCl3, 400MHz) δ (ppm) 7.60 (d, J=8.0Hz, 2H, Ar-H), 7.44-7.40 (m, 2H, Ar-
H),7.26-7.23(m,1H,Ar-H),7.08(m,2H,Ar-H),7.00(m,2H,Ar-H)；
13C NMR(101MHz,CDCl3)δ161.71,154.81,139.29,134.29,134.18,130.29,
125.21,122.46,120.47,118.92,118.19,117.93,105.80.
Embodiment 3
It is used to prepare 4- nitro -3 '-methyl diaryl ether (1-methyl-3- (4-nitrophenoxy) benzene) 4b
Method, including following experimental procedure:
Compound 4- nitro iodobenzene 1b (1.0mmol, 1.0eqv.), DMSO (3ml), Cs are sequentially added into reactor2CO3
(2.0mmol, 2.0eqv.), 3- methylphenol 2b (1.2mmol, 1.2eqv.) are stirred 3 minutes under room temperature.It is subsequently placed in 80 DEG C
In oil bath pan, 10h is reacted under light illumination, and TLC is detected after the reaction was completed, and reaction solution is chromatographed through filtering, extraction and column, obtains target
Product 4b, yield 85%.
Embodiment 4
It is used to prepare 4- acetyl group -4 '-methoxyl group diaryl ether (1- (4- (4-methoxyphenoxy) phenyl)
Ethanone) the method for 3d, including following experimental procedure:
Compound 4- acetyl group bromobenzene 1c (1.0mmol, 1.0eqv.), DMSO (3ml) are sequentially added into reactor,
Cs2CO3(2.0mmol, 2.0eqv.), 4- metoxyphenol 2c (1.2mmol, 1.2eqv.) are stirred 3 minutes under room temperature.Then it sets
In 80 DEG C of oil bath pans, 10h is reacted under light illumination, and TLC is detected after the reaction was completed, and reaction solution is chromatographed through filtering, extraction and column, is obtained
To target product 4c, yield 86%.
Claims (7)
1. a kind of EDA transient state electron donor-acceptor complex, which is characterized in that the chemical structural formula of the compound are as follows:
Wherein, substituent R1For cyano, nitro, acetyl group, trifluoromethyl any one electron-withdrawing group；R2For hydrogen, methyl, second
The alkyl such as base, chlorine, bromine, iodine, methoxyl group, any one in nitro；R1、R2The position of substituent group is ortho position, meta position and contraposition
Any one.
2. EDA transient state electron donor-acceptor complex according to claim 1, which is characterized in that the structural formula of the compound
Are as follows:
3. the preparation method of EDA transient state electron donor-acceptor complex according to claim 1 or 2, which is characterized in that synthesis
Method is as follows:
It the described method comprises the following steps:
Compound 1, solvent, cesium carbonate, compound 2, after being stirred at room temperature uniformly, reactor are sequentially added into reactor
It is placed in oil bath pan, is reacted under 70-90 DEG C and LED lamplight irradiation, by the process of UV detector detection reaction, instead
It answers and EDA transient state electron donor-acceptor complex can be obtained within 3-10 minutes.
4. the preparation method of EDA transient state electron donor-acceptor complex according to claim 3, which is characterized in that described
Compound 1, compound 2, the molar ratio of alkali are 1:0.5-6:0.5-6.
5. the preparation method of EDA transient state electron donor-acceptor complex according to claim 3, which is characterized in that oil bath is anti-
Answering temperature is 80 DEG C.
6. the preparation method of EDA transient state electron donor-acceptor complex according to claim 3, which is characterized in that described
Solvent is dimethyl sulfoxide or N,N-dimethylformamide.
7. according to the preparation-obtained EDA transient state electron donor-acceptor complex of mono- method of claim 3-6 in synthesis of diaryl
Application on ether derivant.
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Application publication date: 20190823 |