CN109761762B - Preparation method of diaryl ether compound - Google Patents
Preparation method of diaryl ether compound Download PDFInfo
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- CN109761762B CN109761762B CN201910071920.5A CN201910071920A CN109761762B CN 109761762 B CN109761762 B CN 109761762B CN 201910071920 A CN201910071920 A CN 201910071920A CN 109761762 B CN109761762 B CN 109761762B
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Abstract
The invention relates to a preparation method of diaryl ether compounds, in particular to a preparation method for arylation of phenols under catalysis of chitosan supported cuprous oxide to obtain corresponding diaryl ether compounds, which has the advantages of simple process conditions, good yield, strong operability and wide functional group tolerance.
Description
Technical Field
The invention belongs to the field of chemical medicines, and relates to a preparation method of diaryl ether compounds.
Background
Aryl ethers are valuable compounds in the fields of organic synthesis, medicine or biology. One of the most common preparation methods is the Ullmann-type coupling reaction. In order to solve the problems of long reaction time, high temperature (> 200 ℃) and stoichiometric amount of copper required by a catalyst, organic chemists screen different ligands and realize the coupling of aryl bromide and aryl iodide with phenol and imidazole under mild conditions. Such reaction conditions still have limitations in their applications such as corrosion, toxicity, difficulty in handling the catalyst, difficulty in separation from the reaction system, generation of solid waste, and the like.
The immobilization of the catalyst on a heterogeneous support is one of the main strategies to solve the above problems. Thus, various heterogeneous supports were applied on fixed type copper catalysts to improve these coupling reactions, such as polysaccharides, graphene, silica gel, magnetic materials, hematite and functionalized MWCNTs 25. Among these supports, the green and essential role of Chitosan (CS) in transition metal-catalyzed reactions has attracted considerable interest. The chitosan-supported metal complex is used as a catalyst for a C-C bond formation reaction, such as Suzuki cross-coupling reaction (CS-supported Pd catalyst), henry reaction (CS-supported Ti catalyst), carbonylation reaction (CS-supported Rh catalyst), C-N bond and C-S bond formation reaction (CS-supported Cu catalyst).
The invention provides an arylation reaction of a phenol compound by applying a Cu catalyst loaded by CS, the method has good environmental friendliness, strong process operability and high yield, and the catalyst is repeatedly utilized for many times without obvious attenuation of catalytic activity, thereby being convenient for industrial production.
Disclosure of Invention
The invention provides a preparation method of a compound shown as a diaryl ether compound formula I on one hand,
comprises the step of reacting a compound shown as a formula II with a compound shown as a formula III in the presence of a chitosan supported copper catalyst,
wherein Ar is 1 Or Ar 2 Each independently selected from aryl or heteroaryl, wherein said aryl or heteroaryl is optionally substituted with one or more substituents selected from alkyl, halogen, hydroxy, amino, oxy, carboxy, nitro, cyano, alkoxy, acyl, cycloalkyl, heterocyclyl, aryl and heteroaryl;
x is selected from fluorine, chlorine, bromine, iodine, preferably chlorine or bromine.
In certain embodiments, the compound of formula II is selected from
Wherein R is 1 Is selected from C 1-6 Alkyl radical, C 1-6 Acyl radical, C 1-6 Alkoxy, halogen, C 3-12 Cycloalkyl radical, C 3-12 Heterocyclic group, C 6-12 Aryl and C 6-12 Heteroaryl, preferably from methyl, ethyl, propyl, acetyl, formyl, methoxy, ethoxy, propoxy, cyclopropyl, phenyl or tolyl.
In other embodiments, the Ar is 2 Selected from phenyl or naphthyl, said phenyl or naphthyl being optionally selected from C 1-6 Alkyl (including but not limited to methyl, ethyl or propyl), nitro, cyano, C 1-6 Alkoxy (including but not limited to ethoxy or propoxy), C 1-6 Acyl (including but not limited to acetyl or formyl) is substituted with one or more substituents.
In another aspect, in some embodiments, the chitosan-loaded copper is selected from the group consisting of monovalent copper, preferably the chitosan-loaded copper is chitosan-loaded cuprous oxide (C)S@Cu 2 O). Further, CS @ Cu 2 O can be recovered for reuse, in embodiments CS @ Cu 2 O is recycled at least 3 times, 5 times or even more, and still maintains high catalytic activity.
The amount of copper supported by chitosan catalyst in the method of the present invention is 0.5 to 5% of the molar amount of the compound of formula II, and may be 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.5, 2, 3, 4, 5%, preferably 0.5 to 2%, more preferably 0.5 to 1%.
In certain embodiments, the reaction further comprises a base, known to those skilled in the art, selected from organic or inorganic bases, preferably a base suitable for the pKa value, which is one of the necessary conditions for the catalytic reaction to be efficient, and potassium phosphate.
Further, in some embodiments, the molar ratio of the compound of formula II to base is 1:1 to 1:5 (including 1:1, 1:2, 1:3, 1:4, 1:5 or any value in between), preferably 1:2 to 1:3.
In a preferred embodiment, the molar ratio of the compound represented by formula II to the compound represented by formula III is 1:1 to 1:5 (including 1:1, 1:2, 1:3, 1:4, 1:5 or any value therebetween), preferably 1.5 to 1:3.
Preferably, the reaction according to the present invention is carried out in a solvent selected from one or more of dimethylformamide, dimethylacetamide, 1-methyl-2-pyrrolidone, tetrahydrofuran, methyltetrahydrofuran, dioxane, acetonitrile, toluene, xylene, dimethylsulfoxide, preferably dimethylformamide or dimethylsulfoxide, more preferably dimethylformamide.
The reaction temperature may be 80 to 120 ℃ (may be 80 ℃, 85 ℃, 90 ℃, 95 ℃, 100 ℃, 110 ℃, 115 ℃ or 120 ℃), preferably 110 ℃.
In a preferred embodiment, the process for preparing a compound of formula I comprises: comprises the step of reacting a compound shown as a formula II with a compound shown as a formula III in the presence of a chitosan supported cuprous oxide catalyst, potassium phosphate and an N, N-dimethyl formyl solvent,
the invention also provides application of the preparation method of the diaryl ether compound shown in the formula I in preparation of medicines, spices or pesticides.
Unless stated to the contrary, the terms used in the specification and claims have the following meanings.
The term "alkyl" refers to a saturated aliphatic hydrocarbon group which is a straight or branched chain group containing 1 to 20 carbon atoms, preferably an alkyl group containing 1 to 12 carbon atoms. Non-limiting examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, sec-butyl, n-pentyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, 1-ethylpropyl, 2-methylbutyl, 3-methylbutyl, n-hexyl, 1-ethyl-2-methylpropyl, 1,1,2-trimethylpropyl, 1,1-dimethylbutyl, and the various branched chain isomers thereof, and the like. More preferred are lower alkyl groups containing 1 to 6 carbon atoms, non-limiting examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, sec-butyl, n-pentyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, 1-ethylpropyl, 2-methylbutyl, 3-methylbutyl, n-hexyl, 1-ethyl-2-methylpropyl, 1,1,2-trimethylpropyl, 1,1-dimethylbutyl, and the like. The alkyl group may be substituted or unsubstituted, and when substituted, the substituent may be substituted at any available point of attachment, preferably one or more groups independently selected from alkyl, alkenyl, alkynyl, alkoxy, alkylthio, alkylamino, halo, mercapto, hydroxy, nitro, cyano, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, cycloalkoxy, heterocycloalkoxy, cycloalkylthio, heterocycloalkylthio, oxo, carboxy or carboxylate.
The term "cycloalkyl" refers to a saturated or partially unsaturated monocyclic or polycyclic cyclic hydrocarbon substituent, the cycloalkyl ring containing from 3 to 20 carbon atoms, preferably from 3 to 12 carbon atoms, more preferably from 3 to 6 carbon atoms. Non-limiting examples of monocyclic cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclopentenyl, cyclohexyl, cyclohexenyl, cyclohexadienyl, and the like; polycyclic cycloalkyl groups include spiro, fused and bridged cycloalkyl groups.
The term "heterocyclyl" refers to a saturated or partially unsaturated mono-or polycyclic cyclic hydrocarbon substituent containing from 3 to 20 ring atoms wherein one or more of the ring atoms is selected from nitrogen, oxygen, or S (O) m (wherein m is an integer of 0 to 2). Preferably 3 to 12 ring atoms, of which 1 to 4 are heteroatoms; more preferably from 3 to 6 ring atoms. Non-limiting examples of monocyclic heterocyclyl groups include pyrrolidinyl, imidazolidinyl, tetrahydrofuranyl, tetrahydrothienyl, dihydroimidazolyl, dihydrofuranyl, dihydropyrazolyl, dihydropyrrolyl, piperidinyl, piperazinyl, morpholinyl.
The term "aryl" refers to a 6 to 14 membered all carbon monocyclic or fused polycyclic (i.e., rings which share adjacent pairs of carbon atoms) group having a conjugated pi-electron system, preferably 6 to 10 membered, such as phenyl and naphthyl.
Aryl groups may be substituted or unsubstituted, and when substituted, the substituents are preferably one or more groups independently selected from alkyl, alkenyl, alkynyl, alkoxy, alkylthio, alkylamino, halogen, mercapto, hydroxy, nitro, cyano, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, cycloalkoxy, preferably phenyl.
The term "heteroaryl" refers to a heteroaromatic system comprising 1 to 4 heteroatoms, 5 to 14 ring atoms, wherein the heteroatoms are selected from oxygen, sulfur and nitrogen. Heteroaryl is preferably 5 to 12 membered, such as imidazolyl, furyl, thienyl, thiazolyl, pyrazolyl, oxazolyl, pyrrolyl, tetrazolyl, pyridyl and the like, preferably imidazolyl, pyrazolyl, pyrimidinyl or thiazolyl; more preferably pyrazolyl or thiazolyl.
Heteroaryl groups may be optionally substituted or unsubstituted, and when substituted, the substituents are preferably one or more groups independently selected from alkyl, alkenyl, alkynyl, alkoxy, alkylthio, alkylamino, halogen, mercapto, hydroxy, nitro, cyano, cycloalkyl, heterocycloalkyl, aryl, heteroaryl.
The term "fused ring group" means a group formed by fusing a group selected from the group consisting of cycloalkyl, heterocyclyl, aryl and heteroaryl with 1 to 2 groups independently selected from the group consisting of cycloalkyl, heterocyclyl, aryl and heteroaryl, and non-limiting examples thereof include:
the term "alkoxy" refers to-O- (alkyl) and-O- (unsubstituted cycloalkyl), wherein alkyl is as defined above. Non-limiting examples of alkoxy groups include: methoxy, ethoxy, propoxy, butoxy, cyclopropoxy, cyclobutoxy, cyclopentyloxy, cyclohexyloxy. Alkoxy groups may be optionally substituted or unsubstituted, and when substituted, the substituents are preferably one or more groups independently selected from alkyl, alkenyl, alkynyl, alkoxy, alkylthio, alkylamino, halogen, mercapto, hydroxy, nitro, cyano, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, cycloalkoxy.
The term "hydroxy" refers to an-OH group.
The term "amino" refers to-NH 2 。
The term "cyano" refers to — CN.
The term "nitro" means-NO 2 。
"optional" or "optionally" means that the subsequently described event or circumstance may, but need not, occur, and that the description includes instances where the event or circumstance occurs or does not. For example, "a heterocyclic group optionally substituted with an alkyl" means that an alkyl may, but need not, be present, and the description includes the case where the heterocyclic group is substituted with an alkyl and the heterocyclic group is not substituted with an alkyl.
"substituted" means that one or more, preferably up to 5, more preferably 1 to 3, hydrogen atoms in a group are independently substituted with a corresponding number of substituents. It goes without saying that the substituents are only in their possible chemical positions, and that the person skilled in the art is able to determine (experimentally or theoretically) possible or impossible substitutions without undue effort. For example, amino or hydroxyl groups having free hydrogen may be unstable in combination with carbon atoms having unsaturated (e.g., olefinic) bonds.
The reagents used in the present invention are commercially available.
The present invention has the following technical advantages, but is not limited to:
1) The chitosan loaded copper catalyst can be recycled for multiple times, and the catalytic activity is unchanged;
2) The method has the advantages of saving production cost, realizing zero discharge of three wastes, being green and environment-friendly, and being suitable for the requirements of industrialized mass production by repeatedly utilizing the chitosan loaded copper catalyst. In addition, the method has mild reaction conditions and high efficiency.
Drawings
FIG. 1: the catalyst activity changes after the catalyst CS @ Cu2O is recycled, wherein the ordinate is the reaction yield (yield) and the abscissa is the Number of times of catalyst recovery (Number of run).
Detailed Description
The present invention will be explained in detail with reference to specific examples below, so that those skilled in the art can more fully understand the specific examples of the present invention to illustrate the technical solutions of the present invention, and not to limit the present invention in any way.
Example 1
Adding 0.1g of copper oxide nanoparticles, 1g of chitosan and 20ml of toluene into a 50ml reaction bottle, performing ultrasonic wave to obtain a uniform suspension, stirring at room temperature to ensure that enough Cu2O nanoparticles are adsorbed on the surface of the chitosan, filtering, washing with ethanol, and performing vacuum drying at 50 ℃ to obtain Cu loaded with CS 2 O(CS@Cu 2 O). Preparation of CS @ CuSO with reference to the method 4 CS @ CuI and CS @ Cu (OAc) 2 For use.
Example 2
Adding bromobenzene, phenol, catalyst, alkali and solution into the reaction in sequence, heating and stirring the mixture to react for 18 hours, adding water to quench the reaction, filtering the reaction solution, extracting the reaction solution by using ethyl acetate, washing the reaction solution by using saturated saline solution, drying the reaction solution, concentrating the reaction solution, and performing silica gel column chromatography to obtain the diphenyl ether. To examine the catalyst effectiveness for different reaction conditions, the specific data are shown in table 1:
TABLE 1
a general reaction conditions 1.5mmol phenol, 1.0mmol bromobenzene, 2.0mmol potassium phosphate, 1mL of anhydrous solvent; b 3.0mmol potassium phosphate; c 2mmol of phenol.
And (4) conclusion: the catalytic effect of different catalysts (A, B, C, D) was preliminarily evaluated by using the coupling reaction of bromobenzene and phenol as a template. When 0.01 equivalent of [ Cu ] is present in DMF]And 2 equivalents of K 3 PO 4 The coupling reaction of bromobenzene and phenol shows good efficiency. A series of solvents were screened, indicating that DMF is much more effective than other solvents (e.g. toluene). In summary, the optimal conditions for the coupling reaction of phenol (2.0 Mmol) with bromobenzene (1 Mmol) were CS @ Cu 2 O concentration of 0.005 equivalent, K 3 PO 4 The yield was highest at a concentration of 3 equivalents.
Example 3:
to the reaction were added 1mmol of the compound of formula II, 2mmol of the compound of formula III, 0.5mmol% of the catalyst CS @ Cu in that order 2 O, 3mmol potassium phosphate and 0.5ml N, N-dimethylformamide solution, heating to 110 ℃, and stirring for reactionAfter TLC detection reaction, adding water to quench reaction, filtering, extracting with ethyl acetate, washing with saturated saline solution, drying, concentrating, and performing silica gel column chromatography to obtain diphenyl ether.
Example 4:
adding 1mmol bromobenzene, 2mmol phenol, 0.5% mmol CS @ Cu2O catalyst, 3mmol potassium phosphate and N, N-dimethylformamide into the reaction in sequence, adding to 110 deg.C, stirring, detecting by TLC, adding water to quench the reaction, washing the recovered catalyst with ethyl acetate, and drying. Extracting the filtrate with ethyl acetate, washing with saturated saline solution, drying, concentrating, and performing silica gel column chromatography to obtain the product.
The recovered catalyst is reused, the recovery times and the reaction yield data are shown in table 2, after 5 times of recovery, the copper content in the catalyst is 1.82mmol/g, which is equivalent to that of a newly prepared catalyst, and the catalytic efficiency is basically unchanged.
TABLE 2
| Number of recovery times | |
| 1 | 93 |
| 2 | 91 |
| 3 | 90 |
| 4 | 89 |
| 5 | 87 |
Claims (4)
1. A process for preparing a compound of formula I,
comprises the step of reacting a compound shown as a formula II with a compound shown as a formula III in the presence of chitosan-loaded cuprous oxide, potassium phosphate and dimethylformamide, wherein the molar ratio of the compound shown as the formula II to alkali is 1:2-1:3, the using amount of the chitosan-loaded cuprous oxide is 0.5 percent of the molar amount of the compound shown as the formula II, the reaction temperature is 80-120 ℃,
wherein the compound shown in the formula II is selected from:
the compound of formula III is selected from:
the compound of formula I is selected from:
2. the method of claim 1, wherein the molar ratio of the compound of formula II to the compound of formula III is 1:1 to 1:5.
3. The method of claim 2, wherein the molar ratio of the compound of formula II to the compound of formula III is 1.5 to 1:3.
4. The process of claim 1, wherein the reaction temperature is 110 ℃.
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| CN102344345A (en) * | 2011-07-28 | 2012-02-08 | 南京师范大学 | Preparation method of arylene ether compound |
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| CN101830766A (en) * | 2010-04-29 | 2010-09-15 | 金华双宏化工有限公司 | Synthesis method of amino aromatic ether compound |
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