CN111423299B - Photochemical catalytic synthesis method of aryl olefin compound - Google Patents
Photochemical catalytic synthesis method of aryl olefin compound Download PDFInfo
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- CN111423299B CN111423299B CN201910024248.4A CN201910024248A CN111423299B CN 111423299 B CN111423299 B CN 111423299B CN 201910024248 A CN201910024248 A CN 201910024248A CN 111423299 B CN111423299 B CN 111423299B
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- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
- C07C5/08—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of carbon-to-carbon triple bonds
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- C07C15/42—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts substituted by unsaturated carbon radicals monocyclic
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- C07C15/50—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts substituted by unsaturated carbon radicals polycyclic non-condensed
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- C07C69/612—Esters of carboxylic acids having a carboxyl group bound to an acyclic carbon atom and having a six-membered aromatic ring in the acid moiety
- C07C69/618—Esters of carboxylic acids having a carboxyl group bound to an acyclic carbon atom and having a six-membered aromatic ring in the acid moiety having unsaturation outside the six-membered aromatic ring
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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 an aromatic olefin compound, which comprises the following steps: in the presence of light, a photocatalyst, a cocatalyst, a ligand, alkali and a hydrogen donor, the aromatic alkyne compound undergoes a C ≡ C reduction reaction to obtain the aromatic olefin compound. The yield of the reaction system product can reach 83 percent at most.
Description
Technical Field
The invention belongs to the technical field of photochemical organic synthesis, and particularly relates to a photochemical catalytic synthesis method of an aryl olefin compound.
Background
Aryl olefins are a common and important structural segment in organic synthesis, and are widely present in natural products, artificially synthesized drugs and pesticide chemical products. The arylalkenyl compound refers to an organic compound containing an arylalkenyl group (Ar-C = C) in a molecular structure.
The existing synthetic methods of aryl olefin compounds mainly comprise stoichiometric and catalytic synthetic methods such as dehydration reaction of aromatic alcohol, dehydrohalogenation reaction of aryl halogenated hydrocarbon, thermal cracking of quaternary ammonium salt, pyrolysis of xanthate, cope reaction, mcmmurry reaction, wittig reaction, julia-Lythgoe reaction, partial hydrogenation reduction synthesis of aryl alkyne, heck reaction, tsuji-Trost reaction and the like.
The existing method for preparing aromatic olefin compounds by catalytic reaction is mainly carried out by adopting a homogeneous Pd metal organic reagent as a catalyst. However, the method has the defects of mild reaction conditions, environmental pollution, high cost, difficult separation of the catalyst and the product, difficult regeneration and utilization of the catalyst 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 photocatalyst 2 Has the advantages of environmental protection, good light stability, stable acid-base, low price, abundant reserves and the like. Under UV irradiation, tiO 2 The 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 CO 2 And H 2 O, 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 phase 2 The semiconductor photocatalysis system can directly trigger the complete mineralization of organic matters. Even under inert atmosphere in organic solvent, because of the extremely high oxidation-reduction potential of titanium dioxide photo-generated holes (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 TiO 2 The photocatalysis is less applied to organic synthesis reaction with high synthesis value.
Disclosure of Invention
In order to improve the above problems, the present invention provides a method for photochemical catalytic synthesis of an aromatic olefin compound, comprising the steps of:
in the presence of light, a photocatalyst, a cocatalyst, a ligand, a hydrogen donor and alkali, the aromatic alkyne compound undergoes a C ≡ C reduction reaction to obtain an aromatic olefin compound.
According to an embodiment of the present invention, the aromatic olefinic compounds obtained by the process comprise a compound in trans configuration; preferably, the molar percentage of the trans-configured compound obtained by the reaction is 97.5% or more, preferably 98% or more, more preferably 99% or more, and most preferably 99.5% or more.
According to an embodiment of the present invention, the aromatic olefinic compounds obtained by the method comprise cis-configuration compounds; preferably, the molar percentage of the cis-configured compound obtained by the reaction is 2.5% or less, preferably 2% or less, more preferably 1% or less, and most preferably 0.5% or less.
According to an embodiment of the present invention, the photocatalyst may be titanium dioxide selected from one, two or more of mixed crystal type P25 titanium dioxide, anatase type titanium dioxide, rutile type titanium dioxide, and the like;
according to embodiments of the present invention, the light may be one, two or more of ultraviolet light, visible light, or sunlight;
according to an embodiment of the present invention, the light source of the light may be a xenon lamp or a 395nm LED; the xenon lamp may have a power of 200-400 watts, for example 300 watts; the LED light source power may be 50-150 watts, for example 100 watts;
according to an embodiment of the invention, said aromatic alkynes are aromatic molecules having in their molecular structure an Ar-C.ident.C-R group, said Ar representing an aryl or heteroaryl group, which may be further substituted by one, two or more (e.g. 1,2, 3,4, 5) substituents R a Substitution;
the substituent R a May be selected from hydroxy, cyano, amino, halogen, unsubstituted or substituted by one, two or more R b Substituted of the following groups: alkyl, cycloalkyl, heterocyclyl, aryl, heteroaryl, arylalkyl, heteroarylalkyl, cycloalkylalkyl, heterocyclylalkyl, alkyloxy, cycloalkyloxy, heteroCyclyloxy, aryloxy, heteroaryloxy, -C (O) -alkyl;
the R is b May be selected from alkyl, cyano, hydroxy, amino, halogen;
r represents H, hydroxy, cyano, amino, halogen, unsubstituted or substituted by one, two or more (e.g. 1,2, 3,4, 5) substituents R c Substituted of the following groups: alkyl, cycloalkyl, heterocyclyl, aryl, heteroaryl, arylalkyl, heteroarylalkyl, cycloalkylalkyl, heterocyclylalkyl, alkyloxy, cycloalkyloxy, heterocyclyloxy, aryloxy, heteroaryloxy, -C (O) -alkyl, -COO-alkyl, alkylaminoaryl, alkenyl;
the substituent R c Can be selected from alkyl, cyano, hydroxyl, amino, halogen.
According to a preferred embodiment of the invention, in said aromatic alkynes Ar-C ≡ C-R, ar is chosen either unsubstituted or substituted by C 1-6 Alkyl radical, C 1-6 Alkyloxy-substituted C 5-12 Aryl, the R group is selected from H and C 1-6 Alkyl, -COO-C 1-6 Alkyl or C 5-12 An aryl group;
for example, the aromatic alkyne compound Ar-C ≡ C-R may be at least one of tolane, 1-phenylpropyne, ethyl 1-phenylpropionate, and 1- (4-methoxyphenyl) -propyne;
according to an embodiment of the present invention, the co-catalyst 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 dimethoxyethane chloride, bis (triphenylphosphine) nickel dichloride, nickel trifluoromethanesulfonate, nickel acetylacetonate, tetrakis (triphenylphosphine) nickel, bis (1, 5-cyclooctadiene) nickel.
According to an embodiment of the present invention, the ligand may be a ligand containing a nitrogen atom and a phosphorus atom, and may be, for example, 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.
According to an embodiment of the present invention, the hydrogen donor may be an alcohol compound and/or an organic amine (such as a primary amine, a secondary amine, and a tertiary amine), and may be at least one of methanol, ethanol, isopropanol, ethylamine, propylamine, butylamine, isopropylamine, diethylmethylamine, dimethylethylamine, diisopropylethylamine, triethylamine, and tributylamine, for example.
According to an embodiment of the present invention, the base may be an organic base and/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 present application, the resulting product aromatic olefin-based compound may be an aromatic olefin-based molecule having a molecular structure of Ar-C = C-R (aryloxyalkoxy) wherein Ar and R have the definitions described above.
The products may be, for example, 1, 2-stilbene, ethyl 1-phenylacrylate, 1-phenylpropylene, 1- (4-methoxyphenyl) -propene.
According to an embodiment of the invention, the reaction may optionally be with or without the addition of a solvent;
when a solvent is added, the solvent may be selected from an inert solvent or a reactive solvent.
According to an embodiment of the present invention, the inert solvent refers to a solvent that does not participate in the reaction under the reaction conditions. The reactive solvent is a solvent which participates in the reaction under the reaction conditions, and is selected from, for example, solvents which can participate in the reaction as a solvent, and also as one or more reactants (for example, one or more of the above-mentioned hydrogen donor and base).
As an example, the solvent includes, for example, a mixture of one, two or more selected from the group consisting of: ester solvents such as ethyl acetate or butyl acetate; hydrocarbon solvents such as benzene, toluene, xylene, hexane and cyclohexane; halogenated hydrocarbon solvents such as methylene chloride, chloroform, 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 present invention, the solvent is preferably at least one of methanol, acetonitrile, N-Dimethylformamide (DMF), dimethylsulfoxide (DMSO);
according to an embodiment of the present invention, the molar ratio of the photocatalyst to the aromatic alkyne compound may be 1 (1-200), preferably 1 (1-100), such as 1;
according to an embodiment of the present invention, the molar ratio of the photocatalyst to the cocatalyst can be 1 (1-10), preferably 1 (1-3), such as 1;
according to an embodiment of the present invention, the photocatalyst, ligand molar ratio may be 1 (1-10), preferably 1 (1-3), such as 1;
according to an embodiment of the present invention, the molar ratio of the photocatalyst to the hydrogen donor may be 1 (1-200), preferably 1 (1-150), such as 1;
according to an embodiment of the present invention, the molar ratio of the photocatalyst to the base may be 1 (1-100), preferably 1 (1-100), such as 1;
according to an embodiment of the present invention, the concentration of the photocatalyst in the reaction system may be 0.1 to 50g/L, for example, 0.5g/L, 8g/L, 10g/L, 16g/L, 40g/L;
according to an embodiment of the present invention, the concentration of the aromatic alkyne-based compound in the reaction system is 0.01 to 10mol/L, for example, 0.5mol/L, 2mol/L, 5mol/L;
according to an embodiment of the present invention, the concentration of the hydrogen donor in the reaction system is 1 to 100mol/L, for example, 1mol/L, 2mol/L, 2.5mol/L;
according to an embodiment of the present invention, the concentration of the cocatalyst in the reaction system is 0.01 to 1mol/L, such as 0.1mol/L, 0.2mol/L, 0.5mol/L;
according to an embodiment of the present invention, the concentration of the ligand in the reaction system is 0.01 to 1mol/L, such as 0.1mol/L, 0.2mol/L, 0.5mol/L;
according to an embodiment of the present invention, the concentration of the base in the reaction system is 0.01 to 10mol/L, such as 1mol/L, 2mol/L, 5mol/L;
according to embodiments of the present invention, the reaction may be carried out in a transparent reactor, such as 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 at least one of nitrogen, helium, argon and the like;
according to an embodiment of the invention, the pressure of the inert atmosphere may be between 0.01MPa and 3MPa;
according to an embodiment of the invention, the reaction time of the reaction may be 10 minutes to 24 hours, preferably 8 minutes to 24 hours, e.g. 8 to 20 hours, such as 8, 10, 12, 18, 20 hours;
according to an embodiment of the invention, the reaction temperature may be 0 to 100 ℃, preferably 10 to 50 ℃, e.g. 25 ℃.
According to the embodiment of the invention, the reaction can be carried out by adding the photocatalyst, the aromatic alkyne compound, the hydrogen donor, the cocatalyst, the ligand, the alkali and the solvent, stirring, then illuminating, or illuminating when stirring is started, and continuously stirring to obtain the aromatic alkene 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 an aromatic alkyne compound, a hydrogen donor, a cocatalyst, a ligand and alkali in an inert organic solvent, 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 product aromatic alkene compound after the reaction is finished.
The invention also provides the aromatic olefin compounds prepared by the method.
Terms 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 with 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 denote preferably a straight-chain or branched saturated monovalent hydrocarbon radical having from 1 to 40 carbon atoms, preferably C 1-10 An alkyl group. ' C 1-10 Alkyl "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, or 1, 2-dimethylbutyl, etc., or isomers thereof. In particular, the radicals have 1,2, 3,4, 5,6 carbon atoms ("C) 1-6 Alkyl groups) such as methyl, ethyl, propyl, butyl, isopropyl, isobutyl, sec-butyl, tert-butyl, more particularly groups having 1,2 or 3 carbon atoms ("C) 1-3 Alkyl), such as methyl, ethyl, n-propyl or isopropyl.
The term "cycloalkyl" is understood to mean a saturated monovalent monocyclic or bicyclic hydrocarbon ring having 3 to 20 carbon atoms, preferably "C 3-10 Cycloalkyl radicals". The term "C 3-10 Cycloalkyl "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 is 3-10 Cycloalkyl 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 containing 1 to 5 heteroatoms independently selected from N, O and S, preferably "3 to 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 "C 6-14 Aryl ". The term "C 6-14 Aryl "is to be understood as preferably meaning having 6, 7, 8, 9, 10, 11,12. Monocyclic, bicyclic or tricyclic hydrocarbon rings of monovalent or partially aromatic character of 13 or 14 carbon atoms ('C') 6-14 Aryl group "), in particular a ring having 6 carbon atoms (" C 6 Aryl "), such as phenyl; or biphenyl, or is a ring having 9 carbon atoms ("C 9 Aryl), such as indanyl or indenyl, or a ring having 10 carbon atoms ("C 10 Aryl radicals), such as tetralinyl, dihydronaphthyl or naphthyl, or rings having 13 carbon atoms ("C 13 Aryl radicals), such as the fluorenyl radical, or a ring having 14 carbon atoms ("C) 14 Aryl), 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 containing 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 in each case be benzo-fused. 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 benzofuranyl, benzothienyl, benzoxazolyl, benzoisoxazolyl, 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 pyridylene 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 "C 3-20 Cycloalkyl group "," C 5-20 Cycloalkenyl group "," 3-20 membered heterocyclic group "," C 6-20 The definitions of aryl "and" 5-20 membered heteroaryl "correspondingly apply equally to the other terms in which they are contained, such as the term" C 3-20 Cycloalkyloxy "," 3-20 membered heterocyclyl "," 3-20 membered heterocyclyloxy "," C 6-20 Aryloxy group and C 6-20 Arylalkyl "and" 5-20 membered heteroarylalkyl "and the like.
The term "alkylamino" denotes NH 2 The structure obtained by substituting one H or both H with alkyl. Wherein the alkyl group is as defined above.
Advantageous effects
The invention discloses a method for synthesizing an aromatic olefin compound by selectively carrying out C [ identical to ] C reduction reaction on an aromatic alkyne compound through photocatalysis. The inventor surprisingly finds that under the reaction system of the invention, nonselective hydroxyl free radical, superoxide anion free radical, hydrogen peroxide free radical and the like with strong oxidizing property are not generated, non-selective degradation reaction is remarkably avoided, the aromatic alkyne compound can be subjected to highly selective C [ identical to ] C reduction reaction to obtain trans-aromatic alkene compound, and the GC yield of the product can reach 83%.
Compared with the prior art, the method for preparing the aromatic olefin compound by adopting the aromatic alcohol dehydration reaction has more green and mild reaction conditions. In addition, the catalyst system of the invention has low cost, simple and convenient separation and easy reutilization.
Finally, 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.
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 are prepared by known methods.
The high performance Gas Chromatography (GC) is selected from Agilent 7890B, carrier gas is He gas, the flow rate is 104mL/min, an HP-5 column is adopted, the flow rate of the column is 1mL/min, the temperature of a sample inlet is 280 ℃, the temperature of the column is 80-300 ℃, the temperature of a detector FID is 280 ℃, and the detection limit is 20pg.
Example 1
Adding mixed crystal form P25 titanium dioxide, tolane, 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 of 1. The reaction product was trans-1, 2-stilbene with a GC yield of 83%, whereas the cis product had a GC yield of 2%.
Example 2
Adding anatase type titanium dioxide and ethyl 1-phenyl propiolate, nickel chloride, 4 '-dimethoxy-2, 2' -bipyridine, diisopropylethylamine and potassium carbonate into a temperature-controlled transparent reaction bottle containing acetonitrile according to the molar ratio of 1. The reaction product was trans-ethyl 1-phenylacrylate with a GC yield of 82% and no cis-product was detected.
Example 3
Adding rutile type titanium dioxide and 1-phenylpropyne, tetrakis (triphenylphosphine) nickel, 2' -bipyridine, tributylamine and potassium phosphate into a temperature-controlled transparent reaction bottle containing dimethyl sulfoxide according to the molar ratio of 1. The reaction product was trans-1-phenylpropylene, the GC yield was 72%, and no cis-product was detected.
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 (13)
1. A method for photochemical catalytic synthesis of an aromatic olefin compound, comprising the steps of:
in the presence of light, a photocatalyst, a cocatalyst, a ligand, a hydrogen donor and alkali, carrying out C ≡ C reduction reaction on an aromatic alkyne compound to obtain an aromatic olefin compound;
the aromatic alkyne compound is an aromatic molecule with Ar-C [ identical to ] C-R groups in the molecular structure, wherein Ar represents C 6-14 Aryl or 5-14 membered heteroaryl, said C 6-14 The aryl or 5-14 membered heteroaryl group may be further substituted by one, two or more substituents R a Substitution;
the substituent R a Selected from hydroxy, cyano, amino, halogen, unsubstituted or substituted by one, two or more R b Substituted of the following groups: c 1-10 Alkyl radical, C 3-10 Cycloalkyl, 3-10 membered heterocyclyl, C 6-14 Aryl, 5-14 membered heteroaryl, C 6-14 Aryl radical C 1-10 Alkyl, 5-14 membered heteroaryl C 1-10 Alkyl radical, C 3-10 Cycloalkyl radical C 1-10 Alkyl, 3-10 membered heterocyclyl C 1-10 Alkyl, -C (O) -C 1-10 An alkyl group;
the R is b Is selected from C 1-10 Alkyl, cyano, hydroxy, amino, halogen;
r represents H, hydroxy, cyano, amino, halogen, unsubstituted or substituted by one, two or more substituents R c Substituted of the following groups: c 1-10 Alkyl radical, C 3-10 Cycloalkyl, 3-10 membered heterocyclyl, C 6-14 Aryl, 5-14 membered heteroaryl, C 6-14 Aryl radical C 1-10 Alkyl, 5-14 membered heteroaryl C 1-10 Alkyl radical, C 3-10 Cycloalkyl radical C 1-10 Alkyl, 3-10 membered heterocyclyl C 1-10 Alkyl, -C (O) -C 1-10 Alkyl, -COO-C 1-10 Alkyl radical, C 1-10 Alkylamino radical C 6-14 An aryl group;
the substituent R c Is selected from C 1-10 Alkyl, cyano, hydroxy, amino, halogen;
the light is one, two or more of ultraviolet light, visible light or sunlight;
the photocatalyst is titanium dioxide;
the cocatalyst is a divalent nickel and/or a zero-valent nickel compound;
the ligand is 2,2' -bipyridine, 4' -dimethoxy-2, 2' -bipyridine, 4' -di-tert-butyl-2, 2' -bipyridine, 4' -dimethyl-2, 2' -bipyridine, 2': at least one of 6',2' ' -terpyridine, 4' ' -tri-tert-butyl-2, 2':6',2' ' -terpyridine, triphenylphosphine, 1, 10-phenanthroline;
the hydrogen donor is an alcohol compound and/or an organic amine;
the base is an organic base and/or an inorganic base.
2. The process of claim 1, wherein said aromatic olefinic compound comprises a compound having a trans configuration.
3. The method according to claim 1, wherein the titanium dioxide is selected from one, two or more of mixed crystal type P25 titanium dioxide, anatase titanium dioxide and rutile titanium dioxide.
4. The method according to claim 1, wherein the molar ratio of the photocatalyst to the aromatic alkyne compound is 1 (1-200).
5. The method of claim 1, wherein the molar ratio of the photocatalyst to the cocatalyst is 1 (1-10).
6. The method of claim 1, wherein the photocatalyst and the ligand are present in a molar ratio of 1 (1-10).
7. The method of claim 1, wherein the molar ratio of the photocatalyst to the hydrogen donor is 1 (1-200).
8. The method of claim 1, wherein the molar ratio of the photocatalyst to the base is 1 (1-100).
9. The method as claimed in claim 1, wherein in the aromatic alkyne compound Ar-C ≡ C-R, ar is selected from unsubstituted or substituted with C 1-6 Alkyl radical, C 1-6 Alkyloxy-substituted C 5-12 Aryl, R is selected from H and C 1-6 Alkyl, -COO-C 1-6 Alkyl or C 5-12 And (4) an aryl group.
10. The method as claimed in claim 9, wherein the aromatic alkyne-based compound Ar-C ≡ C-R is at least one of tolane, 1-phenylpropyne, ethyl 1-phenylpropionate, and 1- (4-methoxyphenyl) -propyne.
11. The method of claim 1, wherein the co-catalyst is 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.
12. The method of claim 1, wherein the hydrogen donor is at least one of methanol, ethanol, isopropanol, ethylamine, propylamine, butylamine, isopropylamine, diethylmethylamine, dimethylethylamine, diisopropylethylamine, triethylamine, and tributylamine.
13. The method of claim 1, wherein the base is selected from at least one of potassium carbonate, cesium carbonate, sodium carbonate, potassium phosphate, sodium phosphate, cesium phosphate, potassium hydroxide, and sodium hydroxide.
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