CN109796293B - Method for synthesizing aromatic aldehyde by catalyzing and oxidizing allyl aromatic compound with iron - Google Patents
Method for synthesizing aromatic aldehyde by catalyzing and oxidizing allyl aromatic compound with iron Download PDFInfo
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Abstract
The invention discloses a method for synthesizing aromatic aldehyde by oxidizing allyl aromatic compounds under the catalysis of iron, which is characterized in that under the promotion action of hydrosilane, air or oxygen is used as an oxidant, and the allyl aromatic compounds are oxidized under the catalysis of iron to synthesize the aromatic aldehyde compounds, wherein the reaction temperature is 20-150 ℃, and the reaction time is 0.25-60 hours. The method has the advantages of wide catalyst source, low cost and environmental protection; the oxidant is wide in source, cheap and does not generate waste; the reaction condition is mild, the selectivity is high and the yield is high; the substrate is wide and stable in source; the compatibility of the substrate functional group is good and the application range of the substrate is wide; the complex small molecules are compatible and can be well converted into aldehyde. Under the optimized reaction conditions, the isolation yield of the target product can reach 96%.
Description
Technical Field
The invention belongs to the field of catalytic synthesis technology and fine chemical synthesis, and particularly relates to a method for synthesizing aromatic aldehyde by oxidizing allyl aromatic compounds under the catalysis of iron.
Background
Aromatic aldehyde is an important organic synthesis intermediate and is widely applied to synthesis of medicines, pesticides, natural products, organic materials and the like. Therefore, the universal, efficient, safe and economic method for synthesizing the aromatic aldehyde has important research significance and application value. The allyl aromatic compound is widely existed in natural products and has wide sources; the research on the synthesis of high value-added products by using the compound as a raw material has important significance. The synthesis of aromatic aldehydes usually employs allylic aromatics, which requires at least two reactions: firstly, alkene isomerization is carried out under the action of alkali to form aromatic alkene; subsequent oxidative cleavage of the double bond occurs to give the aromatic aldehyde (T.X.T.Luu, T.T.Lam, T.N.Le, F.Duus, Molcules 2009,14, 3411-. Because the reaction usually uses strong base and strong oxidizer, the compatibility of functional groups is poor, and the application range is narrow; the multi-step reaction is involved, so that the total yield is low, and the defects of high waste discharge and the like are generated. These severely limit the large scale application of the process. Iron has high natural abundance, low price and low toxicity, and is an ideal catalyst metal. The development of iron-catalyzed processes has been a hotspot and difficulty of research. However, so far, the direct and effective iron-catalyzed reaction for oxidizing allyl aromatic compounds to synthesize aromatic aldehydes has not been reported.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to solve the problems that the reaction steps are more, strong base and/or strong oxidant are needed to be used, the total reaction yield is lower, the compatibility of functional groups is poor, the application range is narrow, the generated waste is discharged more and the environment is not protected in the synthesis of aromatic aldehyde by using the existing allyl aromatic compound, and provides the method for synthesizing aromatic aldehyde by using the iron to catalyze and oxidize the allyl aromatic compound, wherein the method only needs one-step reaction, does not need the participation of the base and the strong oxidant, and has the characteristics of wide catalyst source, low cost and environmental protection; the oxidant is cheap and does not generate any waste; the substrate is wide and stable in source; the reaction condition is mild, the selectivity is good and the yield is high; the compatibility of substrate functional groups is good; the complex small molecules can efficiently synthesize corresponding aromatic aldehyde.
The invention is realized by the following technical scheme:
a method for synthesizing aromatic aldehyde by oxidizing allyl aromatic compound with iron catalysis comprises the steps of oxidizing allyl aromatic compound to prepare aromatic aldehyde in an organic solvent, water or an aqueous solution of the organic solvent by taking hydrosilane as an additive, air or oxygen as an oxidant and iron as a catalyst, wherein the reaction temperature is 20-150 ℃, and the reaction time is 0.25-60 hours;
the general reaction formula is shown as follows:
in the formula: ar is aryl or heteroaryl;
r is one of hydrogen, C1-C20 alkyl, C1-C20 halogen substituted alkyl, C3-C20 cycloalkyl, fluorine, chlorine, bromine, iodine, C1-C20 alkyl carbonyl, C1-C20 alkoxy carbonyl, C1-C20 alkylamino carbonyl, aryl carbonyl, heteroaryl carbonyl and C1-C20 alkylsulfonyl;
wherein, the aryl is one of substituted or unsubstituted phenyl, biphenyl, naphthyl, anthryl, phenanthryl and pyrenyl;
heteroaryl is a heteroaryl group containing a five to thirteen membered ring of N, O or S.
Further, the heteroaryl is one of furyl, benzofuryl, thienyl, pyrrolyl, indolyl, carbazolyl, pyridyl, isoxazolyl, pyrazolyl, imidazolyl, oxazolyl and thiazolyl.
When Ar or R is heteroaryl pyrrolyl, indolyl, carbazolyl, pyrazolyl or imidazolyl, the substituent on nitrogen atom is selected from hydrogen, C1-C20 alkyl, C1-C20 halogen substituted alkyl, C3-C20 cycloalkyl, aryl, heteroaryl, C1-C20 alkylsulfonyl, p-toluenesulfonyl, benzyl, C1-C20 alkylcarbonyl, tert-butoxy acyl and aroyl.
Further, with R1Represents a substituent on the aryl group in Ar, R1Mono-or polysubstituted hydrogen on aromatic rings, R1Selected from hydrogen, C1-C20Alkyl, alkynyl, alkoxy of C1-C20, halogen substituted alkyl of C1-C20, cycloalkyl of C3-C20, aryl, aryloxy, heteroaryl, heteroaryloxy, heteroarylamino, arylcarbonyl, heteroarylcarbonyl, aryloxycarbonyl, heteroaryloxycarbonyl, mercapto of C1-C20, fluorine, chlorine, bromine, hydroxyl, alkylcarbonyl of C1-C20, carboxyl, alkoxycarbonyl of C1-C20, alkylaminocarbonyl of C1-C20, arylcarbonyl, alkylsulfonyl of C1-C20, sulfonic acid group, -B (OH)2One of cyano and nitro;
with R2Represents a substituent on R, R2Mono-or polysubstituted hydrogen on aromatic rings, R2One selected from hydrogen, C1-C20 alkyl, alkynyl, C1-C20 alkoxy, C1-C20 halogen substituted alkyl, C3-C20 cycloalkyl, aryl, aryloxy, heteroaryl, heteroaryloxy, heteroarylamino, arylcarbonyl, heteroarylcarbonyl, aryloxycarbonyl, heteroaryloxycarbonyl, C1-C20 sulfhydryl, fluorine, chlorine, bromine, hydroxyl, C1-C20 alkylcarbonyl, carboxyl, C1-C20 alkoxycarbonyl, C1-C20 alkylaminocarbonyl, arylcarbonyl, C1-C20 alkylsulfonyl, sulfonic acid group, cyano and nitro.
Further, the iron is selected from one of ferrous trifluoromethanesulfonate, ferric trifluoromethanesulfonate, ferrous chloride, ferrous acetylacetonate, ferric acetylacetonate, ferrous 2,2,6, 6-tetramethyl-3, 5-heptanedionate, ferrous 1, 3-diphenylpropanedionate, ferric 1, 3-diphenylpropanedionate, ferrous benzoylacetonate, ferric benzoylacetonate, ferrous ferricyanide, ferric ferricyanide, ferrous acetate, ferrous sulfate, ferrous ammonium sulfate, ferric sulfate, ferrous oxalate, ferric oxalate, ferrous fluoride, ferric fluoride, ferrous bromide, ferric iodide, ferric trichloride, ferric oxide, and ferroferric oxide.
Further, the hydrosilane is selected from the group consisting of trimethoxysilane, dimethylethoxysilane, triethylsilane, dimethylethylsilane, benzyldimethylsilane, triisopropylsilane, diethylsilane, dichlorosilanesdimethylmonochlorosilane, diisopropylchlorosilane, chloromethyl (dimethyl) silane, di-t-butylchlorosilane, diphenylchlorosilane, ethyldichlorosilane, di-t-butylsilane, methyldiphenylsilane, methyldichlorosilane, phenylsilane, diphenylsilane, triethoxysilane, t-butyldimethylsilane, dimethylphenylsilane, 1, 4-bis (dimethylsilyl) benzene, isopropoxyphenylsilane, methyldiethoxysilane, dimethoxy (methyl) silane, dimethylmethylhydrogen (siloxanes and polysiloxanes), 1,3, 3-tetraisopropyldisiloxane, dimethyldichlorosilane, 1,3, 3-dimethyldichlorosilane, and dimethyldichlorosilane, One of tris (trimethylsilyl) silane, polymethylhydrosiloxane, methylphenyl silicone oil, 1,3, 3-tetramethyldisiloxane, pentamethyldisiloxane, tetra (dimethylsilyl) silane, 1, 3-bis (3,3, 3-trifluoropropyl) -1,1,3, 3-tetramethyldisiloxane, tetra (dimethylsiloxy) silane, phenyltri (dimethylsiloxy) silane, and 1,1,2, 2-tetraphenyldisilane.
Further, the organic solvent is selected from one of methanol, ethanol, ethylene glycol, N-propanol, isopropanol, 1, 3-propanediol, glycerol, N-butanol, isobutanol, t-butanol, trifluoroethanol, 2-methyl-2-butanol, 3-methoxybutanol, sec-butanol, t-amyl alcohol, 4-methyl-2-pentanol, isoamyl alcohol, 2-pentanol, 3-pentanol, cyclopentanol, N-pentanol, polyethylene glycol 200-10000, acetonitrile, benzonitrile, toluene, dichloromethane, 1, 2-dichloroethane, dimethyl sulfoxide, N-dimethylformamide, N-diethylamide, ethyl acetate, 1, 4-dioxane, and tetrahydrofuran.
Furthermore, the organic solvent and water are prepared into a solution, wherein the volume ratio of the organic solvent to the water is 1 (1-100).
Further, the gas pressure of the air or the oxygen is 0.1 to 10 atmospheres.
Furthermore, the mol ratio of the allyl aromatic compound, the hydrosilane and the iron is 1 (0.5-50) to 0.001-10; the mass ratio of the allyl aromatic compound to the organic solvent is 1 (5-1000).
The invention has the following beneficial effects:
(1) the invention provides a novel method for preparing aromatic aldehyde by oxidizing allyl aromatic compound with air or oxygen under the catalysis of iron promoted by hydrosilane, which only needs one-step reaction without the participation of alkali and strong oxidant and has the unique advantages of cheap catalyst, promoter and oxidant, wide sources and environmental protection; the reaction condition is mild, the selectivity is high and the yield is high; the substrate has wide source, stability and easy processing; the compatibility of the substrate functional group is good and the application range of the substrate is wide; the reaction is suitable for the oxidation of complex micromolecules.
(2) The method for synthesizing the aromatic aldehyde is simple, feasible and safe, the aromatic aldehyde is directly obtained by a one-step method, under the optimized reaction condition, the yield of the target product after separation is up to 96%, and the method is universal, efficient, economical and environment-friendly.
(3) The method of the invention can use ideal iron as a catalyst for reaction, and the key point is that hydrosilane is used as an accelerant, the iron catalyst is activated, and high-activity catalytic species are formed in situ, so that the reaction can be carried out under very mild conditions for oxidizing allyl aromatic compounds by air or oxygen, and especially, the ideal catalytic effect can be obtained on complex substrates.
(4) The aromatic aldehyde synthesized by the method can be used as a medicine or a bioactive molecule, is an important organic intermediate, and is widely applied to synthesis of medical intermediates, heterocycles and fine chemicals with high added values.
Detailed Description
The invention is further described with reference to specific examples.
A method for synthesizing aromatic aldehyde by oxidizing allyl aromatic compound under the catalysis of iron comprises the following steps: oxidizing an allyl aromatic compound to prepare aromatic aldehyde in an organic solvent, water or an aqueous solution of the organic solvent by taking hydrosilane as an additive, air or oxygen (0.1-10 atm) as an oxidant and iron as a catalyst, wherein the reaction temperature is 20-150 ℃ and the reaction time is 0.25-60 hours;
the general reaction formula is shown as follows:
in the formula: ar is aryl or heteroaryl;
r is one of hydrogen, C1-C20 alkyl, C1-C20 halogen substituted alkyl, C3-C20 cycloalkyl, fluorine, chlorine, bromine, iodine, C1-C20 alkyl carbonyl, C1-C20 alkoxy carbonyl, C1-C20 alkylamino carbonyl, aryl carbonyl, heteroaryl carbonyl and C1-C20 alkylsulfonyl;
wherein, the aryl is one of substituted or unsubstituted phenyl, biphenyl, naphthyl, anthryl, phenanthryl and pyrenyl;
heteroaryl is a heteroaryl group containing a five to thirteen membered ring of N, O or S.
To further illustrate the technical means and effects of the present invention adopted to achieve the predetermined objects, the detailed description of the embodiments, features and effects of the technical solutions proposed by the present invention is as follows.
Example 1
Synthesis of Compound 1:
to a 25mL reaction flask, ferric chloride (0.05mmol), alkene 1a (0.5mmol), 1,1,3, 3-tetramethyldisiloxane (1.5mmol) and ethanol (2.0mL) were added in that order in air. After mixing well at room temperature, the reaction mixture was reacted at room temperature for 3 hours. After the reaction, the product was directly chromatographed to give a yield of 96%.
Example 2
Synthesis of Compound 2:
to a 25mL reaction flask, ferric trichloride (0.05mmol), alkene 1b (0.5mmol), triethoxysilane (1.5mmol) and methanol (2.0mL) were added in that order in air. After mixing well at room temperature, the reaction mixture was reacted under reflux for 12 h. At the end of the reaction, direct chromatographic separation gave a yield of 88%.
Example 3
Synthesis of Compound 3:
to a 25mL reaction flask, iron triflate (0.05mmol), alkene 1c (0.5mmol), dimethylethoxysilane (1.5mmol) and tert-butanol (2.0mL) were added sequentially. After mixing well at room temperature, the reaction mixture was reacted under reflux for 9 h. After the reaction, the product was directly chromatographed to give a yield of 80%.
Example 4
Synthesis of Compound 4
In air, a 25mL reaction flask was charged with ferrous triflate (0.05mmol), alkene 1d (0.5mmol), polymethylhydrosiloxane (1.5mmol), isopropanol (1.5mL) and water (0.5mL) in that order. After mixing well at room temperature, the reaction mixture was reacted at 80 ℃ for 24 h. After the reaction was complete, aqueous ammonia (0.5mL) was added and stirred for 1 h. Subsequently, water (5mL) was added and extracted with ether (5 mL. times.3), the organic phases were combined, the solvent was distilled off under reduced pressure and column chromatography was performed to obtain a yield of 81%.
Example 5
Synthesis of Compound 5:
to a 25mL reaction flask, ferrous acetylacetonate (0.02mmol), ene 1e (0.5mmol), dimethylethoxysilane (2.0mmol), glycerol (1.5mL) and water (0.5mL) were added in this order in air. After mixing well at room temperature, the reaction mixture was reacted at 80 ℃ for 24 h. After the reaction was complete, aqueous ammonia (0.5mL) was added and stirred for 1 h. Subsequently, water (5mL) was added and extracted with ether (5 mL. times.3), the organic phases were combined, the solvent was distilled off under reduced pressure and column chromatography was performed to obtain a yield of 90%.
Example 6
Synthesis of Compound 6:
to a 25mL reaction flask, iron acetylacetonate (0.02mmol), alkene 1f (0.5mmol), triisopropylsilane (2.0mmol) and n-butanol (2.0mL) were sequentially added in the air. After mixing well at room temperature, the reaction mixture was reacted at 100 ℃ for 24 h. At the end of the reaction, direct chromatographic separation gave a yield of 81%.
Example 7
Synthesis of compound 7:
in an air atmosphere, ferrous chloride (0.02mmol), alkene (1 g) (0.5mmol), diethylsilane (2.0mmol), and acetonitrile (2.0mL) were sequentially added to a 25mL reaction flask. After mixing well at room temperature, the reaction mixture was reacted at 50 ℃ for 24 h. At the end of the reaction, direct chromatographic separation gave a yield of 87%.
Example 8
Synthesis of compound 8:
in air, 25mL reaction flask was charged with ferric triflate (0.02mmol), alkene 1h (0.5mmol), dichlorosilance (2.0mmol), and acetonitrile (2.0mL) in order. After mixing well at room temperature, the reaction mixture was reacted at 50 ℃ for 24 h. After the reaction was complete, aqueous ammonia (0.5mL) was added and stirred for 1 h. Subsequently, water (5mL) was added and extracted with ether (5 mL. times.3), the organic phases were combined, the solvent was distilled off under reduced pressure and column chromatography was performed to obtain a yield of 50%.
Example 9
Synthesis of compound 9:
in air, 25mL of a reaction flask was charged with ferric triflate (0.02mmol), alkene 1i (0.5mmol), diisopropylchlorosilane (2.0mmol), and trifluoroethanol (2.0mL) in this order. After mixing well at room temperature, the reaction mixture was reacted at 50 ℃ for 12 h. After the reaction was complete, direct chromatographic separation gave a yield of 65%.
Example 10
Synthesis of compound 10:
in air, a 25mL reaction flask was charged with iron benzoylacetonate (0.02mmol), alkene 1j (0.5mmol), di-tert-butylsilane (2.0mmol), and polyethylene glycol-600 (2.0mL) in that order. After mixing well at room temperature, the reaction mixture was reacted at 80 ℃ for 12 h. At the end of the reaction, direct chromatographic separation gave a yield of 62%.
Example 11
Synthesis of compound 11:
in the air, 2,6, 6-tetramethyl-3, 5-heptanedionato ferrous (0.02mmol), alkene 1k (0.5mmol), diphenylchlorosilane (2.0mmol) and benzonitrile (2.0mL) were added in this order to a 25mL reaction flask. After mixing well at room temperature, the reaction mixture was reacted at 80 ℃ for 24 h. At the end of the reaction, direct chromatographic separation gave a yield of 78%.
Example 12
Synthesis of compound 12:
to a 25mL reaction flask, ferrous fluoride (0.02mmol), alkene 1l (0.5mmol), phenylsilane (2.0mmol), and dichloromethane (2.0mL) were added in this order under air. After mixing well at room temperature, the reaction mixture was reacted under reflux for 24 h. At the end of the reaction, direct chromatographic separation gave a yield of 76%.
Example 13
Synthesis of compound 13:
in an air 25mL reaction flask were added ferrous ferricyanide (0.001mmol), limonene 1m (0.5mmol), diphenylsilane (2.0mmol), 1, 2-dichloroethane (2.0mL) in that order. After mixing well at room temperature, the reaction mixture was reacted at 80 ℃ for 24 h. At the end of the reaction, direct chromatographic separation gave a yield of 92%.
Example 14
Synthesis of compound 14:
in air, a 25mL reaction flask was charged with ferrous acetate (0.05mmol), alkene 1n (0.5mmol), tert-butyldimethylsilane (2.0mmol), and dimethyl sulfoxide (2.0mL) in that order. After mixing well at room temperature, the reaction mixture was reacted at 100 ℃ for 24 h. After the reaction, the product was directly chromatographed to give a yield of 80%.
Example 15
Synthesis of compound 15:
to a 25mL reaction flask in air was added 2,2,6, 6-tetramethyl-3, 5-heptanedionato-iron (0.05mmol), ene 1o (0.5mmol), dimethylphenylsilane (2.0mmol), and N, N-dimethylamide (2.0mL) in this order. After mixing well at room temperature, the reaction mixture was reacted at 100 ℃ for 24 h. At the end of the reaction, direct chromatographic separation gave a yield of 87%.
Example 16
Synthesis of compound 16:
to a 25mL reaction flask, 1, 3-diphenylpropanedione iron (0.05mmol), ene 1p (0.5mmol), 1, 4-bis (dimethylsilyl) benzene (2.0mmol), and ethyl acetate (2.0mL) were added in this order under air. After mixing well at room temperature, the reaction mixture was reacted under reflux for 12 h. After the reaction was completed, the yield was 86% by direct chromatographic separation.
Example 17
Synthesis of compound 17:
to a 25mL reaction flask, 1, 3-diphenylpropanedione ferrous (0.05mmol), alkene 1q (0.5mmol), isopropoxyphenylsilane (2.0mmol), and 1, 4-dioxane (2.0mL) were sequentially added in the air. After mixing well at room temperature, the reaction mixture was reacted under reflux for 24 h. After the reaction, the product was directly chromatographed to give a yield of 70%.
Example 18
Synthesis of compound 18:
to a 25mL reaction flask, in order, was added ferrous benzoylacetonate (0.05mmol), alkene 1r (0.5mmol), methyldiethoxysilane (2.0mmol), and 2-pentanol (2.0 mL). After mixing well at room temperature, the reaction mixture was reacted at 100 ℃ for 24 h. After the reaction, the yield was 85% by direct chromatographic separation.
Example 19
Synthesis of compound 19:
in an air 25mL reaction flask were added ferrous benzoylacetonate (0.05mmol), limonene 1s (0.5mmol), methyldiethoxysilane (2.0mmol), sec-butanol (2.0mL) in that order. After mixing well at room temperature, the reaction mixture was reacted at 80 ℃ for 24 h. The reaction was complete and the yield was 84% by direct chromatographic separation.
Example 20
Synthesis of compound 20:
in air, a 25mL reaction flask was charged with ferric ferricyanide (0.05mmol), alkene 1t (0.5mmol), dimethylmethylhydrogen (siloxane and polysiloxane) (2.0mmol), polyethylene glycol-2000 (0.5g) and water (1.5mL) in that order. After mixing well at room temperature, the reaction mixture was reacted at 120 ℃ for 6 h. After the reaction was complete, aqueous ammonia (0.5mL) was added and stirred for 1 h. Subsequently, water (5mL) was added and extracted with ether (5 mL. times.3), the organic phases were combined, the solvent was distilled off under reduced pressure and column chromatography was performed to obtain a yield of 90%.
Example 21
Synthesis of compound 21:
to a 25mL reaction flask, ferric bromide (0.05mmol), alkene 1u (0.5mmol), methylphenyl silicone oil (2.0mmol), and 4-methyl-2-pentanol (2.0mL) were added in this order under air. After mixing well at room temperature, the reaction mixture was reacted at 80 ℃ for 12 h. At the end of the reaction, direct chromatographic separation gave a yield of 88%.
Example 22
Synthesis of compound 22:
in air, a 25mL reaction flask was charged with ferrous iodide (0.05mmol), alkene 1v (0.5mmol), tris (trimethylsilyl) silane (2.0mmol), and cyclopentanol (2.0mL) in that order. After mixing well at room temperature, the reaction mixture was reacted at 80 ℃ for 24 h. At the end of the reaction, direct chromatographic separation gave a yield of 82%.
Example 23
Synthesis of compound 23:
in air, a 25mL reaction flask was charged with ferrous iodide (0.05mmol), alkene 1w (0.5mmol), tris (trimethylsilyl) silane (2.0mmol), and cyclopentanol (2.0mL) in that order. After mixing well at room temperature, the reaction mixture was reacted at 80 ℃ for 24 h. After the reaction was completed, the yield was 86% by direct chromatographic separation.
Example 24
Synthesis of compound 24:
to a 25mL reaction flask, iron iodide (0.05mmol), alkene 1X (0.5mmol), 1,1,3, 3-tetramethyldisiloxane (2.0mmol), and 3-methoxybutanol (2.0mL) were added in this order in air. After mixing well at room temperature, the reaction mixture was reacted at 80 ℃ for 24 h. After the reaction was completed, the product was directly chromatographed to give a yield of 91%.
Example 25
Synthesis of compound 25:
in air, ferric trichloride (0.05mmol), alkene 1y (0.5mmol), 1,1,3, 3-tetraisopropyl disiloxane (2.0mmol), and n-propanol (2.0mL) were added sequentially to a 25mL reaction flask. After mixing well at room temperature, the reaction mixture was reacted at 80 ℃ for 24 h. After the reaction, the product was directly chromatographed to give a yield of 80%.
Example 26
Synthesis of compound 26:
to a 25mL reaction flask, ferroferric oxide (0.05mmol), alkene 1z (0.5mmol), pentamethyldisiloxane (2.0mmol), and isopropanol (2.0mL) were sequentially added in the air. After mixing well at room temperature, the reaction mixture was reacted at 80 ℃ for 24 h. At the end of the reaction, direct chromatographic separation gave a yield of 78%.
Example 27
Synthesis of compound 27:
in air, ferrous ammonium sulfate (0.05mmol), alkene 1aa (0.5mmol), tetra (dimethylsilyl) silane (2.0mmol) and 1, 3-propanediol (2.0mL) are sequentially added into a 25mL reaction bottle. After mixing well at room temperature, the reaction mixture was reacted at 80 ℃ for 9 h. After the reaction, the yield was 85% by direct chromatographic separation.
Example 28
Synthesis of compound 28:
in air, iron fluoride (0.05mmol), alkene 1ab (0.5mmol), 1, 3-bis (3,3, 3-trifluoropropyl) -1,1,3, 3-tetramethyldisiloxane (2.0mmol), and ethanol (2.0mL) were sequentially added to a 25mL reaction flask. After mixing well at room temperature, the reaction mixture was reacted at 80 ℃ for 24 h. After the reaction, the product was directly chromatographed to give a yield of 80%.
Example 29
Synthesis of compound 29:
in air, ferrous sulfate (0.05mmol), alkene 1ac (0.5mmol), 1,1,2, 2-tetraphenyldisilane (2.0mmol), and ethanol (2.0mL) were added sequentially to a 25mL reaction flask. After mixing well at room temperature, the reaction mixture was reacted at 80 ℃ for 24 h. At the end of the reaction, direct chromatographic separation gave a yield of 79%.
Example 30
Synthesis of compound 30:
in air, ferrous sulfate (0.05mmol), alkene 1ad (0.5mmol), tetrakis (dimethylsiloxy) silane (2.0mmol), and ethanol (2.0mL) were added sequentially to a 25mL reaction flask. After mixing well at room temperature, the reaction mixture was reacted at 80 ℃ for 24 h. At the end of the reaction, direct chromatographic separation gave a yield of 87%.
Example 31
Synthesis of compound 31:
to a 25mL reaction flask, iron oxalate (0.05mmol), ene 1ae (0.5mmol), tetrakis (dimethylsilyl) silane (2.0mmol), and ethanol (2.0mL) were added in this order in air. After mixing well at room temperature, the reaction mixture was reacted at 80 ℃ for 24 h. At the end of the reaction, direct chromatographic separation gave a yield of 74%.
Example 32
Synthesis of compound 32:
in air, a 25mL reaction flask was charged with ferrous chloride (0.05mmol), alkene 1af (0.5mmol), phenyltri (dimethylsiloxy) silane (2.0mmol), and ethanol (2.0mL) in that order. After mixing well at room temperature, the reaction mixture was reacted at 80 ℃ for 24 h. After the reaction is finished, the yield is 90 percent by direct chromatographic separation.
Example 33
Synthesis of compound 33:
to a 25mL reaction flask, ferric chloride (0.05mmol), ene 1ag (0.5mmol), 1,1,2, 2-tetraphenyldisilane (2.0mmol), and ethanol (2.0mL) were added in this order under air. After mixing well at room temperature, the reaction mixture was reacted at 80 ℃ for 24 h. After the reaction was completed, the yield was 86% by direct chromatographic separation.
Example 34
Synthesis of compound 34:
to a 25mL reaction flask, ferric chloride (0.05mmol), alkene 1ah (0.5mmol), 1,1,3, 3-tetramethyldisiloxane (2.0mmol), and ethanol (2.0mL) were added in this order in air. After mixing well at room temperature, the reaction mixture was reacted at 80 ℃ for 24 h. At the end of the reaction, direct chromatographic separation gave a yield of 62%.
Example 35
Synthesis of compound 35:
to a 25mL reaction flask under atmospheric pressure in oxygen was added ferrous acetylacetonate (0.05mmol), ene 1ai (0.5mmol), triethoxysilane (2.0mmol), and ethanol (2.0mL) in that order. After mixing well at room temperature, the reaction mixture was reacted at 80 ℃ for 6 h. At the end of the reaction, direct chromatographic separation gave a yield of 82%.
Example 36
Synthesis of compound 36:
ferric acetylacetonate (0.05mmol), ene 1aj (0.5mmol), 1,1,3, 3-tetramethyldisiloxane (2.0mmol), N, N-diethylamide (1.5mL) and water (0.1mL) were added sequentially to a 25mL reaction flask under atmospheric pressure in oxygen. After mixing well at room temperature, the reaction mixture was reacted at 80 ℃ for 24 h. After the reaction was complete, aqueous ammonia (0.5mL) was added and stirred for 1 h. Subsequently, water (5mL) was added and extracted with ether (5 mL. times.3), the organic phases were combined, the solvent was distilled off under reduced pressure and column chromatography was performed to obtain a yield of 70%.
Example 37
Synthesis of compound 37:
ferric chloride (0.05mmol), alkene 1ak (0.5mmol), 1,1,3, 3-tetramethyldisiloxane (2.0mmol), and ethanol (2.0mL) were added sequentially to a 25mL reaction flask under atmospheric pressure in oxygen. After mixing well at room temperature, the reaction mixture was reacted at 80 ℃ for 24 h. At the end of the reaction, direct chromatographic separation gave a yield of 82%.
The structural formulas of the raw materials and the products of the examples 1-37 and the corresponding experimental results are shown in the following table 1:
table 1 raw materials, products, reaction times and experimental results
Although the present invention has been described in terms of the preferred embodiment, it is not intended to be limited thereto, and various iron catalysts can theoretically form highly active iron catalyst species with hydrosilane, thereby facilitating the reaction; hydrosilane is an accelerator necessary for generating allyl oxidation reaction, and utilizes the reducibility of silicon hydrogen, and theoretically, various hydrosilanes have certain reducibility and can achieve similar effects; air or oxygen is an oxygen donor of the reaction, is an oxidant and is a reactant; the chemical bond of the alkene substrate is a carbon-carbon double bond, and substituents at two ends of the double bond influence the electron cloud density of the double bond and the steric hindrance during the reaction, namely, the modification of the substituents only influences the reaction to a certain extent and does not determine the reaction. It will be understood by those skilled in the art that the process of the present invention can be carried out while variations or modifications can be made to the corresponding embodiments without departing from the scope of the present invention, for example, substitutions, changes or modifications can be made to the substituents described within the scope of the present invention. However, any modification, equivalence and equivalent changes made to the above embodiments according to the present invention are still within the scope of the technical solution of the present invention, without departing from the spirit of the technical solution of the present invention.
Claims (9)
1. A method for synthesizing aromatic aldehyde by catalyzing and oxidizing allyl aromatic compound with iron is characterized in that hydrosilane is used as an additive and air or oxygen is used as an oxidant in an organic solvent or an aqueous solution of the organic solvent, the catalyst is selected from ferrous trifluoromethanesulfonate, ferric trifluoromethanesulfonate, ferrous chloride, ferrous acetylacetonate, ferric acetylacetonate, 2,6, 6-tetramethyl-3, 5-heptanedionate ferrous, 2,6, 6-tetramethyl-3, 5-heptanedionate ferric, 1, 3-diphenylpropanedionate ferrous, 1, 3-diphenylpropanedionate ferric, benzoylacetonate ferrous, benzoylacetonate ferric, ferricyanide, ferric cyanide, acetic acid, ferrous sulfate, ammonium sulfate, ferric sulfate, ferrous oxalate, ferric fluoride, ferrous bromide, Oxidizing an allyl aromatic compound to prepare aromatic aldehyde by one of ferric bromide, ferrous iodide, ferric trichloride, ferric oxide and ferroferric oxide at the reaction temperature of 20-150 ℃ for 0.25-60 h;
the general reaction formula is shown as follows:
in the formula: ar is aryl or heteroaryl;
r is one of hydrogen, C1-C20 alkyl, C1-C20 halogen substituted alkyl, C3-C20 cycloalkyl, fluorine, chlorine, bromine, iodine, C1-C20 alkyl carbonyl, C1-C20 alkoxy carbonyl, C1-C20 alkylamino carbonyl, aryl carbonyl, heteroaryl carbonyl and C1-C20 alkylsulfonyl;
wherein, the aryl is one of substituted or unsubstituted phenyl, biphenyl, naphthyl, anthryl, phenanthryl and pyrenyl; heteroaryl is a heteroaryl group containing a five to thirteen membered ring of N, O or S.
2. The method of claim 1, wherein the heteroaryl group is one of furyl, benzofuryl, thienyl, pyrrolyl, indolyl, carbazolyl, pyridyl, isoxazolyl, pyrazolyl, imidazolyl, oxazolyl, and thiazolyl.
3. The method for synthesizing aromatic aldehyde by iron-catalyzed oxidation of allyl aromatic compound according to claim 1, wherein when Ar or R is heteroaryl pyrrolyl, indolyl, carbazolyl, pyrazolyl or imidazolyl, the substituent on nitrogen atom is selected from hydrogen, C1-C20 alkyl, C1-C20 halogen substituted alkyl, C3-C20 cycloalkyl, aryl, heteroaryl, C1-C20 alkylsulfonyl, p-toluenesulfonyl, benzyl, C1-C20 alkylcarbonyl, tert-butoxy acyl and aroyl.
4. The method for synthesizing aromatic aldehyde by oxidizing allyl aromatic compound under the catalysis of iron according to claim 1, wherein R is1Represents a substituent on the aryl group in Ar, R1Mono-or polysubstituted hydrogen on aromatic rings, R1Selected from hydrogen, C1-C20 alkyl, alkynyl, C1-C20 alkoxy, C1-C20 halogen substituted alkyl, C3-C20 cycloalkyl, aryl, aryloxy, heteroaryl, heteroaryloxy, heteroarylamino, arylcarbonyl, heteroarylcarbonyl, aryloxycarbonyl, heteroaryloxycarbonyl, C1-C20 sulfhydryl, fluorine, chlorine, bromine, hydroxyl, C1-C20 alkylcarbonyl, carboxyl, C1-C20 alkoxycarbonyl, C1-C20 alkylaminocarbonyl, arylcarbonyl, C1-C20 alkylsulfonyl, sulfonic group, -B (OH)2One of cyano and nitro;
with R2Represents a substituent on R, R2Mono-or polysubstituted hydrogen on aromatic rings, R2Selected from hydrogen, C1-C20 alkyl, alkynyl, C1-C20 alkoxy, C1-C20 halogen substituted alkyl, C3-C20 cycloalkyl, aryl, aryloxy, heteroarylOne of oxy, heteroaryl amine, aryl carbonyl, heteroaryl carbonyl, aryloxycarbonyl, heteroaryloxycarbonyl, sulfydryl of C1-C20, fluorine, chlorine, bromine, hydroxyl, alkyl carbonyl of C1-C20, carboxyl, alkoxy carbonyl of C1-C20, alkyl amino carbonyl of C1-C20, aryl carbonyl, alkyl sulfonyl of C1-C20, sulfonic group, cyano and nitro.
5. The method for synthesizing aromatic aldehyde by iron-catalyzed oxidation of allyl aromatic compound according to any one of claims 1 to 4, wherein the hydrosilane is selected from trimethoxysilane, dimethylethoxysilane, triethylsilane, dimethylethylsilane, benzyldimethylsilane, triisopropylsilane, diethylsilane, dichlorosilance, dimethylmonochlorosilane, diisopropylchlorosilane, chloromethyl (dimethyl) silane, di-t-butylchlorosilane, diphenylchlorosilane, ethyldichlorosilane, di-t-butylsilane, methyldiphenylsilane, methyldichlorosilane, phenylsilane, diphenylsilane, triethoxysilane, t-butyldimethylsilane, dimethylphenylsilane, 1, 4-bis (dimethylsilyl) benzene, isopropoxyphenylsilane, methyldiethoxysilane, dimethoxy (methyl) silane, dimethoxysilane, dimethyldichlorosilane, dimethylchlorosilane, dimethyldichlorosilane, dimethylchlorosilane, dimethyldichlorosilane, dimethylchlorosilane, dimethyldichlorosilane, dimethylchlorosilane, dimethylsilane, dimethylchlorosilane, dimethyldichlorosilane, dimethylchlorosilane, dimethyldichlorosilane, dimethylsilane, one of dimethylmethylhydrogen (siloxane and polysiloxane), 1,3, 3-tetraisopropyl disiloxane, tris (trimethylsilyl) silane, polymethylhydrosiloxane, methylphenylsilicone oil, 1,3, 3-tetramethyldisiloxane, pentamethyldisiloxane, tetrakis (dimethylsilyl) silane, 1, 3-bis (3,3, 3-trifluoropropyl) -1,1,3, 3-tetramethyldisiloxane, tetrakis (dimethylsiloxy) silane, phenyltris (dimethylsiloxy) silane, and 1,1,2, 2-tetraphenyldisilane.
6. The method as claimed in any one of claims 1 to 4, wherein the organic solvent is selected from methanol, ethanol, ethylene glycol, N-propanol, isopropanol, 1, 3-propanediol, glycerol, N-butanol, isobutanol, t-butanol, trifluoroethanol, 2-methyl-2-butanol, 3-methoxybutanol, sec-butanol, t-pentanol, 4-methyl-2-pentanol, isopentanol, 2-pentanol, 3-pentanol, cyclopentanol, N-pentanol, polyethylene glycol 200-10000, acetonitrile, benzonitrile, toluene, dichloromethane, 1, 2-dichloroethane, dimethyl sulfoxide, N-dimethylformamide, N-diethylamide, ethyl acetate, 1, 4-dioxane, methanol, ethanol, 2-propanol, 2-butanol, 2-methyl-2-butanol, 3-methoxybutanol, sec-butanol, t-pentanol, 4-methyl-2-pentanol, N-pentanol, polyethylene glycol 200-10000, acetonitrile, benzonitrile, toluene, dichloromethane, 1, 2-dichloroethane, dimethyl sulfoxide, N-dimethylformamide, N-diethylamide, ethyl acetate, 1, dioxane, 1, 4-dioxane, and mixtures thereof, One of tetrahydrofuran.
7. The method for synthesizing aromatic aldehyde by iron-catalyzed oxidation of allyl aromatic compound according to claim 6, wherein the organic solvent and water are prepared into a solution, wherein the volume ratio of the organic solvent to the water is 1 (1-100).
8. The method for synthesizing aromatic aldehyde by iron-catalyzed oxidation of allyl aromatic compound according to any one of claims 1 to 4, wherein the gas pressure of the air or oxygen is 0.1 to 10 atm.
9. The method for synthesizing aromatic aldehyde by iron-catalyzed oxidation of allyl aromatic compound according to any one of claims 1 to 4, wherein the molar ratio of the allyl aromatic compound, the hydrosilane, and the catalyst is 1 (0.5-50) to (0.001-10); the mass ratio of the allyl aromatic compound to the organic solvent is 1 (5-1000).
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| CN106748690A (en) * | 2016-12-13 | 2017-05-31 | 南京师范大学 | A kind of iron catalysis oxidation alkene synthesizes the method for ketone |
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| CN106748690A (en) * | 2016-12-13 | 2017-05-31 | 南京师范大学 | A kind of iron catalysis oxidation alkene synthesizes the method for ketone |
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