CN111423331A - Photochemical catalytic synthesis method of aryl alkyl ether - Google Patents

Photochemical catalytic synthesis method of aryl alkyl ether Download PDF

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CN111423331A
CN111423331A CN201910024258.8A CN201910024258A CN111423331A CN 111423331 A CN111423331 A CN 111423331A CN 201910024258 A CN201910024258 A CN 201910024258A CN 111423331 A CN111423331 A CN 111423331A
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nickel
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CN111423331B (en
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马东阁
翟姗
王谊
刘阿楠
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Beijing Technology and Business University
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
    • C07C213/06—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton from hydroxy amines by reactions involving the etherification or esterification of hydroxy groups
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract

The invention belongs to the field of photochemical organic synthesis, and particularly relates to a photochemical catalytic synthesis method of aryl alkyl ether compounds, which comprises the following steps: under the existence of light, a photocatalyst, a cocatalyst, a ligand and alkali, the halogenated aromatic hydrocarbon compound and the fatty alcohol compound are subjected to C-O bond coupling reaction to obtain the aryl alkyl ether compound. The reaction system of the invention can lead halogenated aromatic hydrocarbon and fatty alcohol to be coupled through selective C-O to obtain aromatic azo compounds under the action of inert organic solvent, photocatalyst, cocatalyst, ligand and alkali, and the GC yield of the product can reach 90 percent.

Description

Photochemical catalytic synthesis method of aryl alkyl ether
Technical Field
The invention belongs to the technical field of photochemical organic synthesis, and particularly relates to a photochemical catalytic synthesis method of aryl alkyl ether compounds.
Background
Arylalkyl ethers are a common and important class of structural fragments in organic synthesis, which are widely found in natural and synthetic drugs. The arylalkyl ether compound is an organic compound having an aryloxyalkoxy group (Ar-O-R) in its molecular structure.
There are three main classical methods for synthesizing aryl alkyl ether compounds, i.e., Williamson ether synthesis, Ullmann coupling, Chan-L am oxidative coupling, aryl nucleophilic substitution, and Mitsunobu reaction, but all of the above methods are stoichiometric synthesis methods.
At present, the existing method for preparing aryl alkyl ether by catalytic reaction mainly adopts homogeneous Pd metal organic reagent as a catalyst, and has the problems of mild reaction conditions, environmental pollution, high cost, difficult separation of the catalyst and products, difficult catalyst regeneration and utilization and the like. Because of the global environmental problems, the development of society and science and technology makes the chemical production which is the primary purpose of environmental protection indispensable, and the urgent needs of some chemical products make us to find a simpler, green, cheap, high-yield, high-efficiency and high-selectivity synthetic method.
In recent years, research on heterogeneous photocatalysis has been advanced. TiO, a widely studied heterogeneous photocatalyst2Has the advantages of environmental protection, good light stability, stable acid-base, low price, abundant reserves and the like. Under UV irradiation, TiO2The photocatalyst can perform charge separation to generate hole and electron pair, initiate respective surface oxidation and reduction reactions in a conduction band and a valence band, and generate a secondary radical oxidation species such as hydroxyl radical, superoxide anion radical, hydrogen peroxide radical and the like which can indiscriminately oxidize almost all organic matters into CO2And H2O, and thus is widely used as an advanced oxidation technology in the elimination of water and indoor pollutants. However, due to the strong oxidizing property of photo-generated holes and secondary free radicals of titanium dioxide, TiO in the general water phase2The semiconductor photocatalysis system can directly trigger the complete mineralization of organic matters. Even under the inert atmosphere in an organic solvent, because of the extremely high oxidation-reduction potential of titanium dioxide photoproduction cavity (2.9V vs standard hydrogen electrode), almost all non-selective bond breaking of organic compounds can be initiated, and further non-selective processes such as hydrogen extraction, halogen extraction, free radical addition and the like are initiated. Thus TiO2Less application of photocatalysis to synthesis with high valueAnd (4) carrying out organic synthesis reaction.
Disclosure of Invention
In order to improve the above problems, the present invention provides a method for photochemical catalytic synthesis of aryl alkyl ether compounds, comprising the following steps:
in the presence of light, a photocatalyst, a cocatalyst, a ligand and alkali, halogenated aromatic hydrocarbon and fatty alcohol are subjected to C-O bond coupling reaction to obtain the aryl alkyl ether compound.
In accordance with an embodiment of the present invention,
the photocatalyst can be titanium dioxide, and the titanium dioxide is one, two or more selected from mixed crystal type P25 titanium dioxide, anatase type titanium dioxide, rutile type titanium dioxide and the like;
the light may be one, two or more of ultraviolet light, visible light or sunlight;
the light source of the light can be a xenon lamp or 395nm L ED, the power of the xenon lamp can be 200-400W, such as 300W, the power of the L ED light source can be 50-150W, such as 100W;
the halogenated aromatic hydrocarbon or halogenated hetero aromatic hydrocarbon is an aromatic molecule of which at least one H on the aromatic ring or the hetero aromatic ring is substituted by halogen, wherein the halogen can be fluorine, chlorine, bromine and iodine, for example, the aromatic ring or the hetero aromatic ring substituted by the halogen; the halogen-substituted aromatic or heteroaromatic ring may be further substituted by one, two or more (e.g. 1,2, 3,4, 5) substituents RaSubstitution;
the substituent RaSelected from hydroxy, cyano, amino, halogen, unsubstituted or substituted by one, two or more RbSubstituted of the following groups: alkyl, cycloalkyl, heterocyclyl, aryl, heteroaryl, arylalkyl, heteroarylalkyl, cycloalkylalkyl, heterocyclylalkyl, alkyloxy, cycloalkyloxy, heterocyclyloxy, aryloxy, heteroaryloxy, -C (O) -alkyl;
the R isbSelected from alkyl, cyano, hydroxy, amino, halogen;
preferably, the halogenated aromatic hydrocarbon is selected from halogenated aryl groups, which may be further substituted by cyano, haloalkyl,C1-3Acyl group substitution.
The halogenated aromatic hydrocarbon can be at least one of bromoacetophenone, bromobenzonitrile, o-chlorotrifluoromethylbenzene, bromobenzene-p-trifluoromethyl bromobenzene;
the fatty alcohol compound may be C1-40A compound in which at least one H in the alkane is substituted by OH, said C1-40The alkane may be further substituted with one, two or more (e.g., 1,2, 3,4, 5) of the following substituents: alkyl, cycloalkyl, heterocyclyl, aryl, heteroaryl, arylalkyl, heteroarylalkyl, cycloalkylalkyl, heterocyclylalkyl, hydroxy, alkyloxy, cycloalkyloxy, heterocyclyloxy, aryloxy, heteroaryloxy.
Preferably, the fatty alcohol compound is selected from C1-8Of an alkane in which at least one H is substituted by OH, said C1-8May be further substituted by C1-8Is substituted with an alkyloxy group; the aliphatic alcohol compound may be at least one of methanol, ethanol, isopropanol, tert-butanol, methoxymethyl alcohol, and 3-methylamino-1-phenyl-1-propanol, for example.
The cocatalyst may be a divalent nickel and/or a zero-valent nickel compound, and may be, for example, at least one of nickel chloride, nickel bromide, nickel iodide, nickel chloride dimethoxyethane, bis (triphenylphosphine) nickel dichloride, nickel trifluoromethanesulfonate, nickel acetylacetonate, tetrakis (triphenylphosphine) nickel, bis (1, 5-cyclooctadiene) nickel.
The ligand may be a ligand containing a nitrogen atom and a phosphorus atom, and may be at least one of 2,2 '-bipyridine, 4' -dimethoxy-2, 2 '-bipyridine, 4' -di-tert-butyl-2, 2 '-bipyridine, 4' -dimethyl-2, 2 '-bipyridine, 2': 6 ', 2 ″ -terpyridine, 4', 4 ″ -tri-tert-butyl-2, 2 ': 6', 2 ″ -terpyridine, triphenylphosphine, and 1, 10-phenanthroline, for example.
The base may be an organic base or an inorganic base, preferably an inorganic base, for example at least one selected from potassium carbonate, cesium carbonate, sodium carbonate, potassium phosphate, sodium phosphate, cesium phosphate, potassium hydroxide, sodium hydroxide.
According to an embodiment of the invention, the reaction may optionally be with or without the addition of a solvent; when no solvent is added, the fatty alcohol may act as a reaction solvent; when a solvent is used, it may be an inert organic solvent, which may be selected from any organic solvent which is inert under the reaction conditions described above, in particular does not react chemically with the starting materials and products, including for example one, a mixture of two or more selected from: ester solvents such as ethyl acetate or butyl acetate; hydrocarbon solvents such as benzene, toluene, xylene, hexane and cyclohexane; halogenated hydrocarbon solvents such as dichloromethane, trichloromethane, 1, 2-dichloroethane and chlorobenzene; alcohol solvents such as methanol, ethanol, isopropanol, n-propanol, n-butanol; or other solvents such as N, N-Dimethylformamide (DMF), dimethyl sulfoxide (DMSO), N-methylpyrrolidone (NMP), acetonitrile, or pyridine;
according to an embodiment of the invention, the solvent is preferably methanol, acetonitrile, N-Dimethylformamide (DMF), dimethyl sulfoxide (DMSO);
according to an embodiment of the present invention, the molar ratio of the photocatalyst, the halogenated aromatic hydrocarbon, the aliphatic alcohol, the cocatalyst, the ligand and the base may be 1 (1-200) to (1-200): (1-10): (1-10): 1-200), preferably 1 (1-100): 1-150): 1-3): 1-100, e.g. 1:10:10:1:1:10, 1:20:20:1: 20;
the concentration of the photocatalyst in the reaction system can be 0.1-50 g/L, preferably 1-50 g/L, and further preferably 5-45 g/L, such as 8 g/L, 16 g/L and 40 g/L;
according to an embodiment of the present invention, the concentration of the halogenated aromatic hydrocarbon compound in the reaction system is 0.01 to 10 mol/L, preferably 0.1 to 8 mol/L, and further preferably 1 to 5 mol/L, for example 0.5 mol/L, 2 mol/L, 5 mol/L;
according to an embodiment of the present invention, the concentration of the fatty alcohol compound in the reaction system is 1 to 100 mol/L, preferably 1 to 50 mol/L, and further preferably 1 to 10 mol/L, such as 1 mol/L, 2 mol/L, 2.5 mol/L;
according to an embodiment of the present invention, the concentration of the cocatalyst in the reaction system is 0.01 to 1 mol/L, for example 0.1 mol/L, 0.2 mol/L, 0.5 mol/L;
according to an embodiment of the present invention, the concentration of the ligand in the reaction system is 0.01 to 1 mol/L, such as 0.1 mol/L, 0.2 mol/L, 0.5 mol/L;
according to an embodiment of the present invention, the concentration of the base in the reaction system is 0.01 to 10 mol/L, for example, 1 mol/L, 2 mol/L, 5 mol/L;
according to an embodiment of the invention, the reaction may be carried out in a transparent reactor, for example a closed transparent reactor;
according to an embodiment of the invention, the reaction is preferably carried out in an inert atmosphere; the inert atmosphere can be nitrogen, helium, argon and other atmospheres;
the pressure of the inert atmosphere may be 0.01-2 MPa;
the reaction time of the reaction may be from 10 minutes to 24 hours, preferably from 8 minutes to 24 hours, for example from 8 to 20 hours, such as 8, 10, 12, 18, 20 hours;
the reaction temperature may be 10-50 deg.C, for example 25 deg.C.
According to the embodiment of the invention, the reaction can be carried out by adding the photocatalyst, the halogenated aromatic hydrocarbon compound, the aliphatic alcohol, the cocatalyst, the ligand, the alkali and optionally the solvent, stirring, then illuminating, or illuminating when stirring is started, and continuously stirring to obtain the aromatic azo compound;
according to an embodiment of the present invention, if stirring is performed before light irradiation, the stirring time before light irradiation is 10 minutes to 1 hour, preferably 20 to 50 minutes.
According to an embodiment of the present invention, the preparation method may further include the steps of: firstly, dissolving a halogenated aromatic hydrocarbon compound, aliphatic alcohol, a cocatalyst, a ligand and alkali in an inert organic solvent or aliphatic alcohol, then adding a photocatalyst into a transparent container to form a reaction system, introducing inert gas into the transparent container, stirring for a period of time under the stirring state, then irradiating the reaction system in the transparent container with a light source for reaction, and obtaining the aryl alkyl ether compound after the reaction is finished.
According to an embodiment of the present invention, the preparation method can prepare Prozac (Prozac) by the steps of:
Figure BDA0001941888950000051
under the existence of light, a photocatalyst, a cocatalyst, a ligand and alkali, the trifluoromethyl bromobenzene and 3-methylamino-1-phenyl-1-propanol hydrochloride undergo a C-O bond coupling reaction to obtain Prozac.
The invention also provides the aryl alkyl ether compound prepared by the method.
Term interpretation and definition
Unless otherwise indicated, the description and claims reciting numerical ranges, when defined as "numbers," are to be understood as reciting both endpoints of the range, each integer within the range, and each decimal within the range. For example, "a number of 0 to 10" should be understood to not only recite each integer of 0, 1,2, 3,4, 5,6, 7, 8, 9, and 10, but also to recite at least the sum of each integer and 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, respectively. "more" means more than three.
The term "halogen" refers to F, Cl, Br and I. In other words, F, Cl, Br, and I may be described as "halogen" in the present specification.
The term "alkyl" is understood to mean preferably a straight-chain or branched, saturated monovalent hydrocarbon radical having from 1 to 40 carbon atoms, preferably C1-10An alkyl group. "C1-10Alkyl "is understood to preferably mean a straight-chain or branched, saturated monovalent hydrocarbon radical having 1,2, 3,4, 5,6, 7, 8, 9 or 10 carbon atoms. The alkyl group is, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, 2-methylbutyl, 1-ethylpropyl, 1, 2-dimethylpropyl, neopentyl, 1-dimethylpropyl, 4-methylpentyl, 3-methylpentyl, 2-methylpentyl, 1-methylpentyl, 2-ethylbutyl, 1-ethylbutyl, 3-dimethylbutyl, 2-dimethylbutyl, 1-dimethylbutyl, 2,3-Dimethylbutyl, 1, 3-dimethylbutyl, 1, 2-dimethylbutyl, and the like, or isomers thereof. In particular, the radicals have 1,2, 3,4, 5,6 carbon atoms ("C)1-6Alkyl groups) such as methyl, ethyl, propyl, butyl, isopropyl, isobutyl, sec-butyl, tert-butyl, more particularly groups having 1,2 or 3 carbon atoms ("C)1-3Alkyl groups) such as methyl, ethyl, n-propyl or isopropyl.
The term "C1-40Alkane "is formed by removing one H to form C1-40Alkyl compounds.
The term "cycloalkyl" is understood to mean an unsaturated monovalent monocyclic or bicyclic hydrocarbon ring having 3 to 20 carbon atoms, preferably "C3-10Cycloalkyl groups ". The term "C3-10Cycloalkyl "is understood to mean a saturated monovalent monocyclic or bicyclic hydrocarbon ring having 3,4, 5,6, 7, 8, 9 or 10 carbon atoms. Said C is3-10Cycloalkyl groups may be monocyclic hydrocarbon groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl or cyclodecyl, or bicyclic hydrocarbon groups such as decalin rings.
The term "heterocyclyl" means a saturated or unsaturated monovalent monocyclic or bicyclic hydrocarbon ring comprising 1-5 heteroatoms independently selected from N, O and S, preferably "3-10 membered heterocyclyl". The term "3-10 membered heterocyclyl" means a saturated monovalent monocyclic or bicyclic hydrocarbon ring comprising 1-5, preferably 1-3 heteroatoms selected from N, O and S. The heterocyclic group may be attached to the rest of the molecule through any of the carbon atoms or nitrogen atom (if present). In particular, the heterocyclic group may include, but is not limited to: 4-membered rings such as azetidinyl, oxetanyl; 5-membered rings such as tetrahydrofuranyl, dioxolyl, pyrrolidinyl, imidazolidinyl, pyrazolidinyl, pyrrolinyl; or a 6-membered ring such as tetrahydropyranyl, piperidinyl, morpholinyl, dithianyl, thiomorpholinyl, piperazinyl, or trithianyl; or a 7-membered ring such as diazepanyl. Optionally, the heterocyclic group may be benzo-fused. The heterocyclyl group may be bicyclic, for example but not limited to a 5,5 membered ring, such as a hexahydrocyclopenta [ c ] pyrrol-2 (1H) -yl ring, or a 5,6 membered bicyclic ring, such as a hexahydropyrrolo [1,2-a ] pyrazin-2 (1H) -yl ring. The nitrogen atom containing ring may be partially unsaturated, i.e., it may contain one or more double bonds, such as, but not limited to, 2, 5-dihydro-1H-pyrrolyl, 4H- [1,3,4] thiadiazinyl, 4, 5-dihydrooxazolyl, or 4H- [1,4] thiazinyl, or it may be benzo-fused, such as, but not limited to, dihydroisoquinolinyl. According to the invention, the heterocyclic radical is non-aromatic.
The term "aryl" is understood to mean preferably a mono-, bi-or tricyclic hydrocarbon ring having a monovalent aromatic or partially aromatic character of 6 to 20 carbon atoms, preferably "C6-14Aryl ". The term "C6-14Aryl "is to be understood as preferably meaning a mono-, bi-or tricyclic hydrocarbon ring having a monovalent or partially aromatic character with 6, 7, 8, 9, 10, 11, 12, 13 or 14 carbon atoms (" C6-14Aryl group "), in particular a ring having 6 carbon atoms (" C6Aryl "), such as phenyl; or biphenyl, or is a ring having 9 carbon atoms ("C9Aryl), such as indanyl or indenyl, or a ring having 10 carbon atoms ("C10Aryl radicals), such as tetralinyl, dihydronaphthyl or naphthyl, or rings having 13 carbon atoms ("C13Aryl radicals), such as the fluorenyl radical, or a ring having 14 carbon atoms ("C)14Aryl), such as anthracenyl.
The term "heteroaryl" is understood to include such monovalent monocyclic, bicyclic or tricyclic aromatic ring systems: having 5 to 20 ring atoms and comprising 1 to 5 heteroatoms independently selected from N, O and S, such as "5-14 membered heteroaryl". The term "5-14 membered heteroaryl" is understood to include such monovalent monocyclic, bicyclic or tricyclic aromatic ring systems: which has 5,6, 7, 8, 9, 10, 11, 12, 13 or 14 ring atoms, in particular 5 or 6 or 9 or 10 carbon atoms, and which comprises 1 to 5, preferably 1 to 3, heteroatoms each independently selected from N, O and S and, in addition, can be benzo-fused in each case. In particular, heteroaryl is selected from thienyl, furyl, pyrrolyl, oxazolyl, thiazolyl, imidazolyl, pyrazolyl, isoxazolyl, isothiazolyl, oxadiazolyl, triazolyl, thiadiazolyl, thia-4H-pyrazolyl and the like and their benzo derivatives, such as benzofuryl, benzothienyl, benzoxazolyl, benzisoxazolyl, benzimidazolyl, benzotriazolyl, indazolyl, indolyl, isoindolyl and the like; or pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, and the like, and benzo derivatives thereof, such as quinolyl, quinazolinyl, isoquinolyl, and the like; or azocinyl, indolizinyl, purinyl and the like and benzo derivatives thereof; or cinnolinyl, phthalazinyl, quinazolinyl, quinoxalinyl, naphthyridinyl, pteridinyl, carbazolyl, acridinyl, phenazinyl, phenothiazinyl, phenoxazinyl, and the like.
Unless otherwise indicated, heterocyclyl, heteroaryl or heteroarylene include all possible isomeric forms thereof, e.g., positional isomers thereof. Thus, for some illustrative, non-limiting examples, pyridyl or pyridinylene includes pyridin-2-yl, pyridinylene-2-yl, pyridin-3-yl, pyridinylene-3-yl, pyridin-4-yl, and pyridinylene-4-yl; thienyl or thienylene includes thien-2-yl, thien-3-yl and thien-3-yl.
The above definitions of the term "alkyl", such as "alkyl", apply equally to other terms containing "alkyl", such as the terms "alkyloxy", "alkyloxyalkyl", and the like. Likewise, the above pair of terms "C3-20Cycloalkyl group "," C5-20Cycloalkenyl group "," 3-20 membered heterocyclic group "," C6-20The definitions of aryl "and" 5-to 20-membered heteroaryl "apply correspondingly equally to the other terms containing it, such as the term" C3-20Cycloalkyloxy "," 3-20 membered heterocyclyl "," 3-20 membered heterocyclyloxy "," C6-20Aryloxy group and C6-20Arylalkyl "and" 5-20 membered heteroarylalkyl "and the like.
The term "alkylamino" denotes NH2The structure obtained by substituting one H or both H with alkyl. Wherein the alkyl group is as defined above.
The term "aromatic ring" denotes an aromatic or partially aromatic monocyclic, bicyclic or tricyclic hydrocarbon ring having 6 to 20 carbon atoms, preferably "C6-14Aromatic ring ". The term "C6-14Aromatic ring "is understood to preferably mean an aromatic or partially aromatic monocyclic, bicyclic or tricyclic hydrocarbon ring having 6, 7, 8, 9, 10, 11, 12, 13 or 14 carbon atoms, in particular a ring having 6 carbon atoms, for example benzene. The aromatic ring may be selected from biphenyl, or a ring having 9 carbon atoms, such as indane or indene, or a ring having 10 carbon atoms, such as tetralin, dihydronaphthalene or naphthalene, or a ring having 13 carbon atoms, such as fluorene, or a ring having 14 carbon atoms, such as anthracene.
The term "heteroaryl ring" is understood to include monocyclic, bicyclic or tricyclic aromatic ring systems having preferably 5 to 20 ring atoms and preferably containing 1 to 5 heteroatoms independently selected from N, O and S, for example a "5-14 membered heteroaryl ring". The term "5-to 14-membered heteroaromatic ring" is to be understood as including monocyclic, bicyclic or tricyclic aromatic ring systems having 5,6, 7, 8, 9, 10, 11, 12, 13 or 14 ring atoms, in particular 5 or 6 or 9 or 10 carbon atoms, and which contain 1 to 5, preferably 1 to 3 heteroatoms each independently selected from N, O and S, and which, in addition, in each case may be benzo-fused. In particular, the heteroaromatic ring is selected from thiophene, furan, pyrrole, oxazole, thiazole, imidazole, pyrazole, isoxazole, isothiazole, oxadiazole, triazole, thiadiazole, thia-4H-pyrazole and the like and their benzo derivatives, such as benzofuran, benzothiophene, benzoxazole, benzisoxazole, benzimidazole, benzotriazole, indazole, indole, isoindole and the like; or pyridine, pyridazine, pyrimidine, pyrazine, triazine, and the like, and their benzo derivatives, such as quinoline, quinazoline, isoquinoline, and the like; or azocine, indolizine, purine, etc. and benzo derivatives thereof; or cinnoline, phthalazine, quinazoline, quinoxaline, naphthyridine, pteridine, carbazole, acridine, phenazine, phenothiazine, phenoxazine, and the like.
Advantageous effects
The invention discloses a method for synthesizing aryl alkyl ether compounds by selectively carrying out a C-O bond coupling reaction on a photocatalytic halogenated aromatic hydrocarbon and fatty alcohol. The reaction system of the invention can lead halogenated aromatic hydrocarbon and fatty alcohol to be coupled through selective C-O to obtain aromatic azo compounds under the action of inert organic solvent, photocatalyst, cocatalyst, ligand and alkali, and the GC yield of the product can reach 90 percent.
Compared with the method for preparing the aryl alkyl ether compound by adopting the Williamson ether forming method in the prior art, the method has the advantages of greener and milder conditions. The preparation process is simple, the product can be obtained through one-step reaction, and the method is economical, environment-friendly and convenient to operate. And, TiO in the catalytic system of the present invention2Low biological toxicity, low cost, easy separation of catalyst and product, and easy regeneration.
Furthermore, the method of the invention can be used for synthesizing antidepressant drugs with great anxiety and high practicability.
Figure BDA0001941888950000101
Detailed Description
The technical solution of the present invention is explained in detail by the exemplary embodiments below. These examples should not be construed as limiting the scope of the invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
Unless otherwise indicated, the starting materials and reagents described are either commercially available or prepared by known methods.
Example 1
Adding mixed crystal type P25 titanium dioxide, bromoacetophenone, bis (triphenylphosphine) nickel dichloride, 4 '-di-tert-butyl-2, 2' -bipyridine and cesium carbonate into a temperature-controlled transparent reaction bottle containing methanol according to a molar ratio (0.5mmol:5mmol:0.5mmol:0.5mmol:5mmol) of 1:10:1:1:10, controlling the temperature to be 25 ℃ so that the concentration of the mixed crystal type P25 titanium dioxide in the reaction system is 40 g/L, sealing the temperature-controlled transparent reaction bottle, introducing inert gas into the temperature-controlled transparent reaction bottle, controlling the pressure of the inert gas to be 0.01MPa, controlling the temperature to be 25 ℃ and stirring for half an hour so that the bromoacetophenone is adsorbed to reach equilibrium, then stirring for half an hour so that the bromoacetophenone is adsorbed to reach equilibrium, keeping the temperature of the temperature-controlled transparent reaction bottle for 300 watts, keeping the irradiation of the temperature-controlled transparent reaction bottle for a reaction time, and separating acetyl methyl ether, wherein the reaction product is 18 ℃ after the reaction is finished.
And (3) recycling the catalyst mixed crystal type P25 titanium dioxide by adopting a high-speed centrifugation method. The recovered titanium dioxide is catalyzed again to prepare the p-acetyl anisole according to the method, and the product yield is basically unchanged after 5 times of cyclic utilization according to the catalysis result.
Example 2
Adding anatase type titanium dioxide, p-bromobenzonitrile, nickel chloride, 4 '-dimethoxy-2, 2' -bipyridine, ethanol and potassium carbonate into a temperature-controlled transparent reaction bottle containing acetonitrile according to the molar ratio of 1:20:1:1:20:20(0.25mmol:5mmol:0.25mmol:0.25mmol: 5mmol) and controlling the temperature at 25 ℃ so that the concentration of the anatase type titanium dioxide in the reaction system is 8 g/L, and the concentrations of the p-bromobenzonitrile, nickel chloride, 4 '-dimethoxy-2, 2' -bipyridine, ethanol and potassium carbonate in the reaction system are 2 mol/L, 0.1 mol/L, 0.1 mol/L, 2 mol/L and 2 mol/L respectively, sealing, introducing inert gas, keeping the inert gas pressure in the temperature-controlled transparent reaction bottle at 0.01MPa, controlling the temperature at 25 ℃ and stirring to enable the adsorption of the p-bromobenzonitrile to be balanced, then irradiating a temperature-controlled lamp at 300 watts and keeping the reaction temperature of the transparent reaction bottle at 25 hours and separating the cyano benzene product at 80 ℃.
Example 3
Adding rutile type titanium dioxide and o-trifluoromethylchlorobenzene, tetrakis (triphenylphosphine) nickel, 2' -bipyridine, isopropanol and potassium phosphate into a temperature-controlled transparent reaction bottle containing dimethyl sulfoxide according to a molar ratio of 1:10:10:1: 10:10 (0.5mmol:5mmol:0.5mmol:0.5mmol:5mmol) and controlling the temperature to be 25 ℃ so that the concentration of rutile type titanium dioxide in the reaction system is 16 g/L, and the concentration of o-trifluoromethylchlorobenzene, tetrakis (triphenylphosphine) nickel, bipyridine, isopropanol and potassium phosphate in the reaction system is respectively 2 mol/L, 0.2 mol/L, 0.2 mol/L, 2 mol/L and 2 mol/L, sealing, introducing inert gas, keeping the pressure of the inert gas in the temperature-controlled transparent reaction bottle to be 0.01MPa, controlling the temperature to be 25 ℃ and stirring to enable the o-trifluoromethylchlorobenzene to reach sunlight adsorption equilibrium, then irradiating the temperature-controlled transparent reaction bottle with illumination for 25 hours, stopping irradiation of an irradiation column, and separating a phenyl isopropyl ether reaction product, wherein the GC is 72%.
Example 4
This example prepares a antidepressant drug according to the procedure described above in example 1.
Figure BDA0001941888950000121
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. A photochemical catalysis synthesis method of aryl alkyl ether is characterized by comprising the following steps: in the presence of light, a photocatalyst, a cocatalyst, a ligand and alkali, halogenated aromatic hydrocarbon and fatty alcohol are subjected to C-O bond coupling reaction to obtain the aryl alkyl ether compound.
2. The method according to claim 1, wherein the photocatalyst is titanium dioxide selected from one, two or more of mixed crystal type P25 titanium dioxide, anatase titanium dioxide, rutile titanium dioxide, and the like;
3. the method according to claim 1 or 2, wherein the halogenated arene or halogenated heteroarene is an aromatic molecule in which at least one H on the aromatic or heteroaromatic ring is substituted by halogen; the halogen-substituted aromatic or heteroaromatic ring may be further substituted with one, two or more substituents RaSubstitution;
the substituent RaSelected from hydroxy, cyano, amino, halogen, unsubstituted or substituted by one, two or more RbSubstituted of the following groups: alkyl, cycloalkyl, heterocyclyl, aryl, heteroaryl, arylalkyl, heteroarylalkyl, cycloalkylalkyl, heterocyclylalkyl, alkyloxy, cycloalkyloxy, heterocyclyloxy, aryloxy, heteroaryloxy, -C (O) -alkyl;
the R isbSelected from alkyl, cyano, hydroxyl, amino, halogen.
4. The method according to any one of claims 1 to 3, wherein the fatty alcohol compound is C1-40A compound in which at least one H in the alkane is substituted by OH, said C1-40The alkane may be further substituted with one, two or more of the following substituents: alkyl, cycloalkyl, heterocyclyl, aryl, heteroaryl, arylalkyl, heteroarylalkyl, cycloalkylalkyl, heterocyclylalkyl, hydroxy, alkyloxy, cycloalkyloxy, heterocyclyloxy, aryloxy, heteroaryloxy.
5. A process according to any one of claims 1 to 4, wherein the promoter is a divalent and/or zero-valent nickel compound, such as at least one of nickel chloride, nickel bromide, nickel iodide, nickel dimethoxyethane chloride, bis (triphenylphosphine) nickel dichloride, nickel trifluoromethanesulfonate, nickel acetylacetonate, tetrakis (triphenylphosphine) nickel, bis (1, 5-cyclooctadiene) nickel.
6. The method according to any one of claims 1 to 5, wherein the ligand is a ligand containing a nitrogen atom and a phosphorus atom, such as at least one of 2,2 '-bipyridine, 4' -dimethoxy-2, 2 '-bipyridine, 4' -di-tert-butyl-2, 2 '-bipyridine, 4' -dimethyl-2, 2 '-bipyridine, 2': 6 ', 2 "-terpyridine, 4', 4" -tri-tert-butyl-2, 2 ': 6', 2 "-terpyridine, triphenylphosphine, 1, 10-phenanthroline.
7. The process according to any one of claims 1 to 6, wherein the base is an organic or inorganic base, preferably an inorganic base, such as at least one selected from the group consisting of potassium carbonate, cesium carbonate, sodium carbonate, potassium phosphate, sodium phosphate, cesium phosphate, potassium hydroxide, sodium hydroxide.
8. The method of any one of claims 1-7, wherein the molar ratio of the photocatalyst, the halogenated aromatic hydrocarbon, the aliphatic alcohol, the co-catalyst, the ligand, and the base is 1 (1-200) to (1-200): (1-10):(1-10):(1-200).
9. The method according to any one of claims 1 to 8, wherein the preparation method is used for preparing Prozac (Prozac), and the preparation steps comprise:
Figure FDA0001941888940000021
under the existence of light, a photocatalyst, a cocatalyst, a ligand and alkali, the trifluoromethyl bromobenzene and 3-methylamino-1-phenyl-1-propanol hydrochloride undergo a C-O bond coupling reaction to obtain Prozac.
10. An arylalkyl ether prepared according to the process of any one of claims 1 to 9.
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