CN109796293A - A kind of method of iron catalysis oxidation allyl aromatic compound synthesis aromatic aldehyde - Google Patents
A kind of method of iron catalysis oxidation allyl aromatic compound synthesis aromatic aldehyde Download PDFInfo
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- CN109796293A CN109796293A CN201910090032.8A CN201910090032A CN109796293A CN 109796293 A CN109796293 A CN 109796293A CN 201910090032 A CN201910090032 A CN 201910090032A CN 109796293 A CN109796293 A CN 109796293A
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Abstract
The invention discloses a kind of methods of iron catalysis oxidation allyl aromatic compound synthesis aromatic aldehyde, specific method is under the facilitation of hydrogen silane, using air or oxygen as oxidant, iron catalysis oxidation allyl aromatic compound synthesizes fragrant aldehyde compound, the temperature of reaction is 20~150 DEG C, and the time is 0.25~60h.The advantage that the method for the present invention has catalyst source extensive, cheap and environmentally friendly；Oxidant source extensively, it is cheap and do not generate waste；Reaction condition is mild, selectivity is high and yield is high；Substrate source is extensively and stable；Substrate functional group compatibility is good and substrate it is applied widely；Complicated small molecule is compatible, can be converted to aldehyde well.Under the reaction condition of optimization, target product separation yield may be up to 96%.
Description
Technical field
The invention belongs to catalytic synthetic techniques and catalyst preparation field, are catalyzed oxygen more particularly, to a kind of iron
Change the method for allyl aromatic compound synthesis aromatic aldehyde.
Background technique
Aromatic aldehyde is a kind of important organic synthesis intermediate, is widely used in medicine, pesticide, natural prodcuts, organic material
Deng synthesis.Therefore, a kind of method for inventing general, efficient, safe and economic synthesis aromatic aldehyde has important research significance
And application value.Allyl aromatic compound is widely present in natural products, from a wealth of sources；It is studied as raw material to close
Have great importance at high value-added product.Aromatic aldehyde is usually synthesized with allyl aromatic compound, at least needs two
Step reaction: the isomerization that alkene occurs in the presence of alkali first forms fragrant alkene；And then the oxicracking that double bond occurs obtains virtue
Aldehyde (T.X.T.Luu, T.T.Lam, T.N.Le, F.Duus, Molcules 2009,14,3411-3424；M.D.Marquez-
Medina,P.Prinsen,H.Li,K.Shih,A.A.Romero,R.Luque,ChemSusChem 2018,11,389-396)。
Since reaction is typically used for highly basic and strong oxidizer, lead to functional group's poor compatibility, the problem of narrow application range；It is anti-to be related to multistep
Total recovery should be caused lower, while generating the deficiencies of waste discharge is more.These all seriously limit the large-scale application of this method.
Iron big, cheap and toxicity very little with natural abundance, is ideal catalyst metals.Developing the method that iron is catalyzed is always
The hot and difficult issue of research.However so far, directly effective iron catalysis oxidation allyl aromatic compound synthesizes aromatic aldehyde
Reaction be not yet seen in report.
Summary of the invention
In view of the deficiencies of the prior art, present invention aim to address existing allyl aromatic compounds to synthesize aromatic aldehyde
It needs reaction step more, needs to use highly basic and/or strong oxidizer, lead to that overall yield of reaction is lower, functional group's poor compatibility, fit
With narrow range, leads to the problem of more than waste discharge and not environmentally, provide a kind of iron catalysis oxidation allyl aromatic compound
The method for synthesizing aromatic aldehyde, this method only need single step reaction, do not need alkali and strong oxidizer participates in, while having catalyst source
Extensively, cheap and environmentally friendly feature；Oxidant is cheap, does not generate any waste；Substrate source is extensively and stable；Reaction condition temperature
With selective good and yield height；Substrate functional group compatibility is good；Complicated small molecule can efficiently synthesize corresponding aromatic aldehyde.
The present invention is achieved by the following technical solutions:
The method of a kind of iron catalysis oxidation allyl aromatic compound synthesis aromatic aldehyde, in organic solvent, water or organic molten
In the aqueous solution of agent, using hydrogen silane as additive, air or oxygen be oxidant, iron is catalyst, aoxidizes allyl aromatic series
Aromatic aldehyde is made in compound, and reaction temperature is 20~150 DEG C, and the time is 0.25~60h；
Reaction formula is expressed as follows:
In formula: Ar is aryl or heteroaryl；
R be hydrogen, the alkyl of C1~C20, C1~C20 halogen replace alkyl, the naphthenic base of C3~C20, fluorine, chlorine, bromine, iodine,
The alkyl-carbonyl of C1~C20, the alkoxy carbonyl of C1~C20, the alkylaminocarbonyl of C1~C20, aryl carbonyl, heteroaryl carbonyl
One of base, alkane sulfonyl of C1~C20；
Wherein, aryl is one of substituted or non-substituted phenyl, xenyl, naphthalene, anthryl, phenanthryl, pyrenyl；
Heteroaryl be containing N, O or S five to thirteen ring heteroaryl.
Further, the heteroaryl is furyl, benzofuranyl, thienyl, pyrrole radicals, indyl, carbazyl, pyrrole
One of piperidinyl, isoxazolyl, pyrazolyl, imidazole radicals, oxazolyl, thiazolyl.
Further, when Ar or R is heteroaryl pyrrole radicals, indyl, carbazyl, pyrazolyl or imidazole radicals, nitrogen is former
Substituent group on son be arbitrarily selected from hydrogen, the alkyl of C1~C20, C1~C20 halogen replace alkyl, the naphthenic base of C3~C20, aryl,
Heteroaryl, the alkane sulfonyl of C1~C20, p-toluenesulfonyl, benzyl, the alkyl-carbonyl of C1~C20, tertiary fourth oxygen acyl group, fragrant acyl
One of base.
Further, with R1Indicate the substituent group in Ar on aryl, R1Hydrogen on monosubstituted or polysubstituted aromatic ring, R1It is selected from
Hydrogen, the alkyl of C1~C20, alkynyl, the alkoxy of C1~C20, C1~C20 halogen replace alkyl, the naphthenic base of C3~C20, virtue
Base, aryloxy group, heteroaryl, heteroaryloxy, heteroaryl amido, aryl carbonyl, Heteroarylcarbonyl, aryloxy carbonyl, Heteroaryloxycarbonyl,
The sulfydryl of C1~C20, fluorine, chlorine, bromine, hydroxyl, the alkyl-carbonyl of C1~C20, carboxyl, the alkoxy carbonyl of C1~C20, C1~
Alkylaminocarbonyl, aryl carbonyl, C1~C20 alkane sulfonyl, the sulfonic group ,-B (OH) of C202, cyano, one of nitro；
With R2Indicate the substituent group on R, R2Hydrogen on monosubstituted or polysubstituted aromatic ring, R2Selected from hydrogen, C1~C20 alkyl,
Alkynyl, the alkoxy of C1~C20, C1~C20 halogen replace alkyl, the naphthenic base of C3~C20, aryl, aryloxy group, heteroaryl,
Heteroaryloxy, heteroaryl amido, aryl carbonyl, Heteroarylcarbonyl, aryloxy carbonyl, Heteroaryloxycarbonyl, the sulfydryl of C1~C20, fluorine,
Chlorine, bromine, hydroxyl, the alkyl-carbonyl of C1~C20, carboxyl, the alkoxy carbonyl of C1~C20, the alkylaminocarbonyl of C1~C20, virtue
One of base carbonyl, the alkane sulfonyl of C1~C20, sulfonic group, cyano, nitro.
Further, the iron be selected from trifluoromethanesulfonic acid ferrous iron, trifluoromethanesulfonic acid iron, frerrous chloride, acetylacetone,2,4-pentanedione ferrous iron,
Ferric acetyl acetonade, DPM dpm,dipivalomethane ferrous iron, DPM dpm,dipivalomethane iron, 1,3- hexichol
Base propanedione ferrous iron, 1,3- diphenylprop diketone iron, benzoyl acetone ferrous iron, benzoyl acetone iron, ferroferricyanide, iron cyaniding
Iron, ferrous acetate, ferrous sulfate, iron ammonium sulfate, ferric sulfate, ferrous oxalate, ferric oxalate, ferrous fluoride, ferric flouride, protobromide
One of iron, ferric bromide, iron iodide, ferric iodide, ferric trichloride, iron oxide, ferroso-ferric oxide.
Further, the hydrogen silane is selected from trimethoxy silane, dimethylethoxysilane, triethylsilane, diformazan
Base ethylsilane, benzyl dimethyl silane, tri isopropyl silane, diethylsilane, dichlorophenyl silane, one chlorine silicon of dimethyl
Alkane, diisopropyl chlorosilane, chloromethyl (dimethyl) silane, di-t-butyl chlorosilane, diphenyl chlorosilane, ethyl dichloro silicon
Alkane, di-t-butyl silane, methyldiphenyl base silane, dimethyl dichlorosilane (DMCS), phenylsilane, diphenyl silane, triethoxysilane, tertiary fourth
Bis- (dimetylsilyl) benzene of base dimethylsilane, dimethylphenylsilaneand, 1,4-, isopropoxy benzene base silane, methyl diethyl
Oxysilane, dimethoxy (methyl) silane, dimethyl methyl hydrogen (siloxanes and polysiloxanes), two silicon of 1,1,3,3- tetra isopropyl
Oxygen alkane, three (trimethylsilyl) silane, polymethyl hydrogen siloxane, methyl phenyl silicone oil, 1,1,3,3- tetramethyl disiloxane, five first
Bis- two silicon of (3,3,3- trifluoro propyl) -1,1,3,3- tetramethyl of base disiloxane, four (dimethyl-silicon) silane, 1,3- for oxygen alkane,
One of four (dimethylsilyl bis) silane, phenyl three (dimethyl siloxane) silane, 1,1,2,2- tetraphenyl disilane.
Further, the organic solvent is selected from methanol, ethyl alcohol, ethylene glycol, normal propyl alcohol, isopropanol, 1,3-PD, sweet
Oil, n-butanol, isobutanol, the tert-butyl alcohol, trifluoroethanol, 2- methyl -2- butanol, 3- methoxybutanol, sec-butyl alcohol, tert-pentyl alcohol, 4-
Methyl-2- amylalcohol, isoamyl alcohol, 2- amylalcohol, 3- amylalcohol, cyclopentanol, n-amyl alcohol, polyethylene glycol 200-10000, acetonitrile, cyanophenyl, first
Benzene, methylene chloride, 1,2- dichloroethanes, dimethyl sulfoxide, N, N- diformamide, N, N- diacetayl amide, ethyl acetate, 1,4- dioxy
One of six rings, tetrahydrofuran.
Further, the organic solvent and water are configured to solution, wherein the volume ratio of organic solvent and water is 1:(1~100).
Further, the gas pressure of the air or oxygen is 0.1~10 atmospheric pressure.
Further, the allyl aromatic compound, hydrogen silane, iron molar ratio be 1:(0.5~50): (0.001
~10)；The mass ratio of the allyl aromatic compound and organic solvent is 1:(5~1000).
Beneficial effects of the present invention are as follows:
(1) the present invention provides iron catalytic airs or dioxygen oxidation allyl aromatic compound that a kind of hydrogen silane promotes
The new method of aromatic aldehyde is prepared, this method only needs single step reaction, without the participation of alkali and strong oxidizer, and has catalyst, promotes
Agent and cheap, the from a wealth of sources and environmentally friendly unique advantage of oxidant；Reaction condition is mild, and selectivity is high and yield is high；Substrate
It is from a wealth of sources, stablize and be easily handled；Substrate functional group compatibility is good and substrate it is applied widely；Reaction is suitable for complicated small
The advantage of molecular oxidation.
(2) aromatic aldehyde synthetic method provided by the invention is simple and easy and safe, and one-step method directly obtains aromatic aldehyde, in optimization
Under reaction condition, yield is up to 96% after target product separation, is a kind of general, efficient, economic and environmental-friendly synthesis
The method of aromatic aldehyde.
(3) it is that catalyst is reacted why method of the invention, which is able to use ideal iron, and key is to have used hydrogen silane
For promotor, activated iron catalyst, highly active catalytic species be formed in situ, make reaction can in very mild conditions into
Row air or oxygen aoxidizes allyl aromatic compound, especially can also obtain ideal catalytic effect to complicated substrate.
(4) aromatic aldehyde of method of the invention synthesis can be used as drug or bioactive molecule, while be important organic
Intermediate is widely used in the synthesis of medicine intermediate, heterocycle and high added value fine chemicals.
Specific embodiment
The present invention is further described below combined with specific embodiments below.
The method of a kind of iron catalysis oxidation allyl aromatic compound synthesis aromatic aldehyde: in organic solvent, water or organic molten
In the aqueous solution of agent, using hydrogen silane as additive, air or oxygen (0.1~10 atmospheric pressure) be oxidant, iron is catalyst, oxygen
Change allyl aromatic compound and aromatic aldehyde is made, the temperature of reaction is 20~150 DEG C, the time is 0.25~60h；
Reaction formula is expressed as follows:
In formula: Ar is aryl or heteroaryl；
R be hydrogen, the alkyl of C1~C20, C1~C20 halogen replace alkyl, the naphthenic base of C3~C20, fluorine, chlorine, bromine, iodine,
The alkyl-carbonyl of C1~C20, the alkoxy carbonyl of C1~C20, the alkylaminocarbonyl of C1~C20, aryl carbonyl, heteroaryl carbonyl
One of base, alkane sulfonyl of C1~C20；
Wherein, aryl is one of substituted or non-substituted phenyl, xenyl, naphthalene, anthryl, phenanthryl, pyrenyl；
Heteroaryl be containing N, O or S five to thirteen ring heteroaryl.
Further to illustrate the present invention to reach the technical means and efficacy that predetermined goal of the invention is taken, to according to this
Technical solution specific embodiment, feature and its effect proposed is invented, detailed description are as follows.
Embodiment 1
The synthesis of compound 1:
It in air, is sequentially added in 25mL reaction flask iron chloride (0.05mmol), alkene 1a (0.5mmol), 1,1,3,3- tetra-
Tetramethyldisiloxane (1.5mmol) and ethyl alcohol (2.0mL).At room temperature after mixing, reaction mixture reacts 3h at room temperature.
Reaction terminates, and direct chromatography obtains yield 96%.
Embodiment 2
The synthesis of compound 2:
It in air, is sequentially added in 25mL reaction flask ferric trichloride (0.05mmol), alkene 1b (0.5mmol), triethoxy
Silane (1.5mmol) and methanol (2.0mL).At room temperature after mixing, reaction mixture reacts 12h under reflux conditions.Instead
It should terminate, direct chromatography obtains yield 88%.
Embodiment 3
The synthesis of compound 3:
In air, it is ferrous (0.05mmol) to sequentially add trifluoromethanesulfonic acid in 25mL reaction flask, alkene 1c (0.5mmol), and two
Methylethoxy base silane (1.5mmol) and the tert-butyl alcohol (2.0mL).At room temperature after mixing, reaction mixture is in counterflow condition
Lower reaction 9h.Reaction terminates, and direct chromatography obtains yield 80%.
Embodiment 4
The synthesis of compound 4
In air, trifluoromethanesulfonic acid ferrous iron (0.05mmol) is sequentially added in 25mL reaction flask, alkene 1d (0.5mmol) gathers
Methyl hydrogen siloxane (1.5mmol), isopropanol (1.5mL) and water (0.5mL).At room temperature after mixing, reaction mixture exists
It is reacted for 24 hours at 80 DEG C.Reaction terminates, and is added ammonium hydroxide (0.5mL), and stir 1h.And then, water (5mL) is added, and is extracted with ether
It takes (5mL × 3), merges organic phase, column chromatography for separation obtains yield 81% after evaporating solvent under reduced pressure.
Embodiment 5
The synthesis of compound 5:
In air, acetylacetone,2,4-pentanedione ferrous iron (0.02mmol), alkene 1e (0.5mmol), diformazan are sequentially added in 25mL reaction flask
Base oxethyl silane (2.0mmol), glycerol (1.5mL) and water (0.5mL).At room temperature after mixing, reaction mixture is 80
It is reacted for 24 hours at DEG C.Reaction terminates, and is added ammonium hydroxide (0.5mL), and stir 1h.And then, water (5mL) is added, and is extracted with ether
(5mL × 3) merge organic phase, and column chromatography for separation obtains yield 90% after evaporating solvent under reduced pressure.
Embodiment 6
The synthesis of compound 6:
It in air, is sequentially added in 25mL reaction flask ferric acetyl acetonade (0.02mmol), alkene 1f (0.5mmol), three isopropyls
Base silane (2.0mmol), n-butanol (2.0mL).At room temperature after mixing, reaction mixture reacts for 24 hours at 100 DEG C.Instead
It should terminate, direct chromatography obtains yield 81%.
Embodiment 7
The synthesis of compound 7:
It in air, is sequentially added in 25mL reaction flask frerrous chloride (0.02mmol), alkene 1g (0.5mmol), diethyl silicon
Alkane (2.0mmol), acetonitrile (2.0mL).At room temperature after mixing, reaction mixture reacts for 24 hours at 50 DEG C.Reaction terminates,
Direct chromatography obtains yield 87%.
Embodiment 8
The synthesis of compound 8:
It in air, is sequentially added in 25mL reaction flask trifluoromethanesulfonic acid iron (0.02mmol), alkene 1h (0.5mmol), dichloro
Phenyl silane (2.0mmol), acetonitrile (2.0mL).At room temperature after mixing, reaction mixture reacts for 24 hours at 50 DEG C.Reaction
Terminate, is added ammonium hydroxide (0.5mL), and stir 1h.And then, water (5mL) is added, and extracts (5mL × 3) with ether, be associated with
Machine phase, column chromatography for separation obtains yield 50% after evaporating solvent under reduced pressure.
Embodiment 9
The synthesis of compound 9:
It in air, is sequentially added in 25mL reaction flask trifluoromethanesulfonic acid iron (0.02mmol), alkene 1i (0.5mmol), two is different
Propyl chlorosilane (2.0mmol), trifluoroethanol (2.0mL).At room temperature after mixing, reaction mixture reacts at 50 DEG C
12h.Reaction terminates, and direct chromatography obtains yield 65%.
Embodiment 10
The synthesis of compound 10:
It in air, is sequentially added in 25mL reaction flask benzoyl acetone iron (0.02mmol), alkene 1j (0.5mmol), two uncles
Butylsilane (2.0mmol), polyethylene glycol -600 (2.0mL).At room temperature after mixing, reaction mixture reacts at 80 DEG C
12h.Reaction terminates, and direct chromatography obtains yield 62%.
Embodiment 11
The synthesis of compound 11:
In air, 2,2,6,6- tetramethyl -3,5- heptadione ferrous irons (0.02mmol), alkene are sequentially added in 25mL reaction flask
1k (0.5mmol), diphenyl chlorosilane (2.0mmol), cyanophenyl (2.0mL).At room temperature after mixing, reaction mixture is 80
It is reacted for 24 hours at DEG C.Reaction terminates, and direct chromatography obtains yield 78%.
Embodiment 12
The synthesis of compound 12:
It in air, is sequentially added in 25mL reaction flask ferrous fluoride (0.02mmol), alkene 1l (0.5mmol), phenylsilane
(2.0mmol), methylene chloride (2.0mL).At room temperature after mixing, reaction mixture reacts for 24 hours under reflux.Reaction knot
Beam, direct chromatography obtain yield 76%.
Embodiment 13
The synthesis of compound 13:
It in air, is sequentially added in 25mL reaction flask ferroferricyanide (0.001mmol), alkene 1m (0.5mmol), diphenyl
Silane (2.0mmol), 1,2- dichloroethanes (2.0mL).At room temperature after mixing, reaction mixture reacts for 24 hours at 80 DEG C.
Reaction terminates, and direct chromatography obtains yield 92%.
Embodiment 14
The synthesis of compound 14:
It in air, is sequentially added in 25mL reaction flask ferrous acetate (0.05mmol), alkene 1n (0.5mmol), tert-butyl two
Methyl-monosilane (2.0mmol), dimethyl sulfoxide (2.0mL).At room temperature after mixing, reaction mixture reacts at 100 DEG C
24h.Reaction terminates, and direct chromatography obtains yield 80%.
Embodiment 15
The synthesis of compound 15:
In air, 2,2,6,6- tetramethyl -3,5- heptadione iron (0.05mmol), alkene 1o are sequentially added in 25mL reaction flask
(0.5mmol), dimethylphenylsilaneand (2.0mmol), N, N- diformamide (2.0mL).At room temperature after mixing, reaction is mixed
Object is closed to react for 24 hours at 100 DEG C.Reaction terminates, and direct chromatography obtains yield 87%.
Embodiment 16
The synthesis of compound 16:
In air, 1,3- diphenylprop diketone iron (0.05mmol), alkene 1p are sequentially added in 25mL reaction flask
(0.5mmol), bis- (dimetylsilyl) benzene (2.0mmol) of Isosorbide-5-Nitrae-, ethyl acetate (2.0mL).At room temperature after mixing,
Reaction mixture reacts 12h under reflux conditions.Reaction terminates, and direct chromatography obtains yield 86%.
Embodiment 17
The synthesis of compound 17:
In air, 1,3- diphenylprop diketone ferrous iron (0.05mmol), alkene 1q are sequentially added in 25mL reaction flask
(0.5mmol), isopropoxy benzene base silane (2.0mmol), Isosorbide-5-Nitrae-dioxane (2.0mL).At room temperature after mixing, it reacts
Mixture reacts for 24 hours under reflux conditions.Reaction terminates, and direct chromatography obtains yield 70%.
Embodiment 18
The synthesis of compound 18:
In air, benzoyl acetone ferrous iron (0.05mmol), alkene 1r (0.5mmol), first are sequentially added in 25mL reaction flask
Base diethoxy silane (2.0mmol), 2- amylalcohol (2.0mL).At room temperature after mixing, reaction mixture is anti-at 100 DEG C
It should for 24 hours.Reaction terminates, and direct chromatography obtains yield 85%.
Embodiment 19
The synthesis of compound 19:
In air, benzoyl acetone ferrous iron (0.05mmol), alkene 1s (0.5mmol), first are sequentially added in 25mL reaction flask
Base diethoxy silane (2.0mmol), sec-butyl alcohol (2.0mL).At room temperature after mixing, reaction mixture reacts at 80 DEG C
24h.Reaction terminates, and reaction terminates, and direct chromatography obtains yield 84%.
Embodiment 20
The synthesis of compound 20:
It in air, is sequentially added in 25mL reaction flask ferric ferricyanide (0.05mmol), alkene 1t (0.5mmol), dimethyl methyl
Base hydrogen (siloxanes and polysiloxanes) (2.0mmol), Polyethylene glycol-2000 (0.5g) and water (1.5mL).It is uniformly mixed at room temperature
Afterwards, reaction mixture reacts 6h at 120 DEG C.Reaction terminates, and is added ammonium hydroxide (0.5mL), and stir 1h.And then, water is added
(5mL), and (5mL × 3) are extracted with ether, merge organic phase, column chromatography for separation obtains yield 90% after evaporating solvent under reduced pressure.
Embodiment 21
The synthesis of compound 21:
It in air, is sequentially added in 25mL reaction flask ferric bromide (0.05mmol), alkene 1u (0.5mmol), aminomethyl phenyl silicon
Oily (2.0mmol), 4- methyl -2- amylalcohol (2.0mL).At room temperature after mixing, reaction mixture reacts 12h at 80 DEG C.
Reaction terminates, and direct chromatography obtains yield 88%.
Embodiment 22
The synthesis of compound 22:
It in air, is sequentially added in 25mL reaction flask iron iodide (0.05mmol), alkene 1v (0.5mmol), three (front three silicon
Base) silane (2.0mmol), cyclopentanol (2.0mL).At room temperature after mixing, reaction mixture reacts for 24 hours at 80 DEG C.Instead
It should terminate, direct chromatography obtains yield 82%.
Embodiment 23
The synthesis of compound 23:
It in air, is sequentially added in 25mL reaction flask iron iodide (0.05mmol), alkene 1w (0.5mmol), three (front three silicon
Base) silane (2.0mmol), cyclopentanol (2.0mL).At room temperature after mixing, reaction mixture reacts for 24 hours at 80 DEG C.Instead
It should terminate, direct chromatography obtains yield 86%.
Embodiment 24
The synthesis of compound 24:
It in air, is sequentially added in 25mL reaction flask ferric iodide (0.05mmol), alkene 1x (0.5mmol), 1,1,3,3- tetra-
Tetramethyldisiloxane (2.0mmol), 3- methoxybutanol (2.0mL).At room temperature after mixing, reaction mixture is at 80 DEG C
Reaction is for 24 hours.Reaction terminates, and direct chromatography obtains yield 91%.
Embodiment 25
The synthesis of compound 25:
It in air, is sequentially added in 25mL reaction flask ferric trichloride (0.05mmol), alkene 1y (0.5mmol), 1,1,3,3-
Tetra isopropyl disiloxane (2.0mmol), normal propyl alcohol (2.0mL).At room temperature after mixing, reaction mixture is anti-at 80 DEG C
It should for 24 hours.Reaction terminates, and direct chromatography obtains yield 80%.
Embodiment 26
The synthesis of compound 26:
It in air, is sequentially added in 25mL reaction flask ferroso-ferric oxide (0.05mmol), alkene 1z (0.5mmol), pentamethyl
Disiloxane (2.0mmol), isopropanol (2.0mL).At room temperature after mixing, reaction mixture reacts for 24 hours at 80 DEG C.Instead
It should terminate, direct chromatography obtains yield 78%.
Embodiment 27
The synthesis of compound 27:
It in air, is sequentially added in 25mL reaction flask iron ammonium sulfate (0.05mmol), alkene 1aa (0.5mmol), four (two
Methyl silicon) silane (2.0mmol), 1,3-PD (2.0mL).At room temperature after mixing, reaction mixture is anti-at 80 DEG C
Answer 9h.Reaction terminates, and direct chromatography obtains yield 85%.
Embodiment 28
The synthesis of compound 28:
It in air, is sequentially added in 25mL reaction flask ferric flouride (0.05mmol), alkene 1ab (0.5mmol), 1,3- bis- (3,
3,3- trifluoro propyls) -1,1,3,3- tetramethyl, two silicon is for oxygen alkane (2.0mmol), ethyl alcohol (2.0mL).At room temperature after mixing,
Reaction mixture reacts for 24 hours at 80 DEG C.Reaction terminates, and direct chromatography obtains yield 80%.
Embodiment 29
The synthesis of compound 29:
It in air, is sequentially added in 25mL reaction flask ferrous sulfate (0.05mmol), alkene 1ac (0.5mmol), 1,1,2,2-
Tetraphenyl disilane (2.0mmol), ethyl alcohol (2.0mL).At room temperature after mixing, reaction mixture reacts for 24 hours at 80 DEG C.
Reaction terminates, and direct chromatography obtains yield 79%.
Embodiment 30
The synthesis of compound 30:
It in air, is sequentially added in 25mL reaction flask ferrous sulfate (0.05mmol), alkene 1ad (0.5mmol), four (diformazans
Base siloxy) silane (2.0mmol), ethyl alcohol (2.0mL).At room temperature after mixing, reaction mixture reacts at 80 DEG C
24h.Reaction terminates, and direct chromatography obtains yield 87%.
Embodiment 31
The synthesis of compound 31:
It in air, is sequentially added in 25mL reaction flask ferric oxalate (0.05mmol), alkene 1ae (0.5mmol), four (dimethyl
Silicon) silane (2.0mmol), ethyl alcohol (2.0mL).At room temperature after mixing, reaction mixture reacts for 24 hours at 80 DEG C.Reaction
Terminate, direct chromatography obtains yield 74%.
Embodiment 32
The synthesis of compound 32:
It in air, is sequentially added in 25mL reaction flask frerrous chloride (0.05mmol), alkene 1af (0.5mmol), phenyl three
(dimethyl siloxane) silane (2.0mmol), ethyl alcohol (2.0mL).At room temperature after mixing, reaction mixture is at 80 DEG C
Reaction is for 24 hours.Reaction terminates, and direct chromatography obtains yield 90%.
Embodiment 33
The synthesis of compound 33:
It in air, is sequentially added in 25mL reaction flask iron chloride (0.05mmol), alkene 1ag (0.5mmol), 1,1,2,2- tetra-
Phenyl disilane (2.0mmol), ethyl alcohol (2.0mL).At room temperature after mixing, reaction mixture reacts for 24 hours at 80 DEG C.Instead
It should terminate, direct chromatography obtains yield 86%.
Embodiment 34
The synthesis of compound 34:
It in air, is sequentially added in 25mL reaction flask iron chloride (0.05mmol), alkene 1ah (0.5mmol), 1,1,3,3- tetra-
Tetramethyldisiloxane (2.0mmol), ethyl alcohol (2.0mL).At room temperature after mixing, reaction mixture reacts for 24 hours at 80 DEG C.
Reaction terminates, and direct chromatography obtains yield 62%.
Embodiment 35
The synthesis of compound 35:
In atmospheric oxygen, it is ferrous (0.05mmol) to sequentially add acetylacetone,2,4-pentanedione in 25mL reaction flask, alkene 1ai (0.5mmol),
Triethoxysilane (2.0mmol), ethyl alcohol (2.0mL).At room temperature after mixing, reaction mixture reacts 6h at 80 DEG C.
Reaction terminates, and direct chromatography obtains yield 82%.
Embodiment 36
The synthesis of compound 36:
It in atmospheric oxygen, is sequentially added in 25mL reaction flask ferric acetyl acetonade (0.05mmol), alkene 1aj (0.5mmol), 1,
1,3,3- tetramethyl disiloxane (2.0mmol), N, N- diacetayl amide (1.5mL) and water (0.1mL).It is uniformly mixed at room temperature
Afterwards, reaction mixture reacts for 24 hours at 80 DEG C.Reaction terminates, and is added ammonium hydroxide (0.5mL), and stir 1h.And then, water is added
(5mL), and (5mL × 3) are extracted with ether, merge organic phase, column chromatography for separation obtains yield 70% after evaporating solvent under reduced pressure.
Embodiment 37
The synthesis of compound 37:
It in atmospheric oxygen, is sequentially added in 25mL reaction flask iron chloride (0.05mmol), alkene 1ak (0.5mmol), 1,1,3,
3- tetramethyl disiloxane (2.0mmol), ethyl alcohol (2.0mL).At room temperature after mixing, reaction mixture reacts at 80 DEG C
24h.Reaction terminates, and direct chromatography obtains yield 82%.
The raw material and product structure formula of Examples 1 to 37 and corresponding experimental result are as shown in table 1 below:
1 raw material of table, product, reaction time and experimental result
The above is only used as presently preferred embodiments of the present invention, is not intended to limit the present invention in any form, although
The present invention has been disclosed as a preferred embodiment, and however, it is not intended to limit the invention, the various iron catalysts reason in the present invention
By above the iron catalyst species of high activity can be formed with hydrogen silane, to be conducive to going on smoothly for reaction；Hydrogen silane is hair
Promotor necessary to raw allyl oxidation reacts, what is utilized is the reproducibility of its silicon hydrogen, the various hydrogen silanes theoretically provided
All there is certain reproducibility, should be able to all obtain similar effect；Air or oxygen is the oxygenate of reaction, is oxidant,
It is reactant；The chemical bond that alkene substrate reacts is carbon-to-carbon double bond, and the structure influence at its double bond both ends is double bond
Steric hindrance size when cloud density size and reaction, the i.e. modification of substituent group only influence reaction to a certain extent,
It does not play a decisive role to reaction.Any person skilled in the art is not it can be appreciated that departing from the technology of the present invention
In aspects, when can be changed or modify to obtain corresponding embodiment, such as can be in the present invention for the substituent group
It is replaced, changes or modifies in range, the method for the present invention may be implemented.But all ancestors without departing from technical solution of the present invention
Purport, any modification, modification or equivalent and equivalent variation to the above embodiments according to the present invention, still falls within this hair
In the range of bright technical solution.
Claims (10)
1. a kind of method of iron catalysis oxidation allyl aromatic compound synthesis aromatic aldehyde, which is characterized in that in organic solvent, water
Or in the aqueous solution of organic solvent, using hydrogen silane as additive, air or oxygen be oxidant, iron is catalyst, oxyalkylene third
Aromatic aldehyde is made in base aromatic compound, and reaction temperature is 20~150 DEG C, and the time is 0.25~60h；
Reaction formula is expressed as follows:
In formula: Ar is aryl or heteroaryl；
R be hydrogen, the alkyl of C1~C20, C1~C20 halogen replace alkyl, the naphthenic base of C3~C20, fluorine, chlorine, bromine, iodine, C1~
The alkyl-carbonyl of C20, the alkoxy carbonyl of C1~C20, C1~C20 alkylaminocarbonyl, aryl carbonyl, Heteroarylcarbonyl, C1
One of alkane sulfonyl of~C20；
Wherein, aryl is one of substituted or non-substituted phenyl, xenyl, naphthalene, anthryl, phenanthryl, pyrenyl；Heteroaryl is
Containing N, O or S five to thirteen ring heteroaryl.
2. a kind of method of iron catalysis oxidation allyl aromatic compound synthesis aromatic aldehyde according to claim 1, special
Sign is that the heteroaryl is furyl, benzofuranyl, thienyl, pyrrole radicals, indyl, carbazyl, pyridyl group, different evil
One of oxazolyl, pyrazolyl, imidazole radicals, oxazolyl, thiazolyl.
3. a kind of method of iron catalysis oxidation allyl aromatic compound synthesis aromatic aldehyde according to claim 1, special
Sign is, the substitution when Ar or R is heteroaryl pyrrole radicals, indyl, carbazyl, pyrazolyl or imidazole radicals, on nitrogen-atoms
Base be arbitrarily selected from hydrogen, the alkyl of C1~C20, C1~C20 halogen replace alkyl, the naphthenic base of C3~C20, aryl, heteroaryl, C1~
One of the alkane sulfonyl of C20, p-toluenesulfonyl, benzyl, the alkyl-carbonyl of C1~C20, tertiary fourth oxygen acyl group, aroyl.
4. a kind of method of iron catalysis oxidation allyl aromatic compound synthesis aromatic aldehyde according to claim 1, special
Sign is, with R1Indicate the substituent group in Ar on aryl, R1Hydrogen on monosubstituted or polysubstituted aromatic ring, R1Selected from hydrogen, C1~C20
Alkyl, alkynyl, the alkoxy of C1~C20, C1~C20 halogen replace alkyl, the naphthenic base of C3~C20, aryl, aryloxy group,
Heteroaryl, heteroaryloxy, heteroaryl amido, aryl carbonyl, Heteroarylcarbonyl, aryloxy carbonyl, Heteroaryloxycarbonyl, C1~C20
Sulfydryl, fluorine, chlorine, bromine, hydroxyl, the alkyl-carbonyl of C1~C20, carboxyl, the alkoxy carbonyl of C1~C20, C1~C20 alkylamino radical
Carbonyl, aryl carbonyl, C1~C20 alkane sulfonyl, sulfonic group ,-B (OH)2, cyano, one of nitro；
With R2Indicate the substituent group on R, R2Hydrogen on monosubstituted or polysubstituted aromatic ring, R2Selected from hydrogen, the alkyl of C1~C20, alkynes
Base, the alkoxy of C1~C20, C1~C20 halogen replace the alkyl, naphthenic base of C3~C20, aryl, aryloxy group, heteroaryl, miscellaneous
Aryloxy group, heteroaryl amido, aryl carbonyl, Heteroarylcarbonyl, aryloxy carbonyl, Heteroaryloxycarbonyl, the sulfydryl of C1~C20, fluorine,
Chlorine, bromine, hydroxyl, the alkyl-carbonyl of C1~C20, carboxyl, the alkoxy carbonyl of C1~C20, the alkylaminocarbonyl of C1~C20, virtue
One of base carbonyl, the alkane sulfonyl of C1~C20, sulfonic group, cyano, nitro.
5. a kind of iron catalysis oxidation allyl aromatic compound synthesis aromatic aldehyde according to any one of claims 1 to 4
Method, which is characterized in that the iron be selected from trifluoromethanesulfonic acid ferrous iron, trifluoromethanesulfonic acid iron, frerrous chloride, acetylacetone,2,4-pentanedione ferrous iron,
Ferric acetyl acetonade, DPM dpm,dipivalomethane ferrous iron, DPM dpm,dipivalomethane iron, 1,3- hexichol
Base propanedione ferrous iron, 1,3- diphenylprop diketone iron, benzoyl acetone ferrous iron, benzoyl acetone iron, ferroferricyanide, iron cyaniding
Iron, ferrous acetate, ferrous sulfate, iron ammonium sulfate, ferric sulfate, ferrous oxalate, ferric oxalate, ferrous fluoride, ferric flouride, protobromide
One of iron, ferric bromide, iron iodide, ferric iodide, ferric trichloride, iron oxide, ferroso-ferric oxide.
6. a kind of iron catalysis oxidation allyl aromatic compound synthesis aromatic aldehyde according to any one of claims 1 to 4
Method, which is characterized in that the hydrogen silane is selected from trimethoxy silane, dimethylethoxysilane, triethylsilane, dimethyl
Ethylsilane, benzyl dimethyl silane, tri isopropyl silane, diethylsilane, dichlorophenyl silane, chlorodimethyl silane,
Diisopropyl chlorosilane, chloromethyl (dimethyl) silane, di-t-butyl chlorosilane, diphenyl chlorosilane, ethyl dichlorosilane,
Di-t-butyl silane, methyldiphenyl base silane, dimethyl dichlorosilane (DMCS), phenylsilane, diphenyl silane, triethoxysilane, tertiary fourth
Bis- (dimetylsilyl) benzene of base dimethylsilane, dimethylphenylsilaneand, 1,4-, isopropoxy benzene base silane, methyl two
Ethoxysilane, dimethoxy (methyl) silane, dimethyl methyl hydrogen (siloxanes and polysiloxanes), 1,1,3,3- tetra isopropyl
Disiloxane, three (trimethylsilyl) silane, polymethyl hydrogen siloxane, methyl phenyl silicone oil, 1,1,3,3- tetramethyl disiloxane,
Bis- two silicon of (3,3,3- trifluoro propyl) -1,1,3,3- tetramethyl of pentamethyl disiloxane, four (dimethyl-silicon) silane, 1,3- are for oxygen
Alkane, four (dimethylsilyl bis) silane, phenyl three (dimethyl siloxane) silane, one in 1,1,2,2- tetraphenyl disilane
Kind.
7. a kind of iron catalysis oxidation allyl aromatic compound synthesis aromatic aldehyde according to any one of claims 1 to 4
Method, which is characterized in that the organic solvent is selected from methanol, ethyl alcohol, ethylene glycol, normal propyl alcohol, isopropanol, 1,3-PD, sweet
Oil, n-butanol, isobutanol, the tert-butyl alcohol, trifluoroethanol, 2- methyl -2- butanol, 3- methoxybutanol, sec-butyl alcohol, tert-pentyl alcohol, 4-
Methyl-2- amylalcohol, isoamyl alcohol, 2- amylalcohol, 3- amylalcohol, cyclopentanol, n-amyl alcohol, polyethylene glycol 200-10000, acetonitrile, cyanophenyl, first
Benzene, methylene chloride, 1,2- dichloroethanes, dimethyl sulfoxide, N, N- diformamide, N, N- diacetayl amide, ethyl acetate, 1,4- dioxy
One of six rings, tetrahydrofuran.
8. a kind of method of iron catalysis oxidation allyl aromatic compound synthesis aromatic aldehyde according to claim 7, special
Sign is that the organic solvent and water are configured to solution, wherein the volume ratio of organic solvent and water is 1:(1~100).
9. a kind of iron catalysis oxidation allyl aromatic compound synthesis aromatic aldehyde according to any one of claims 1 to 4
Method, which is characterized in that the gas pressure of the air or oxygen is 0.1~10 atmospheric pressure.
10. a kind of iron catalysis oxidation allyl aromatic compound synthesis aromatic aldehyde according to any one of claims 1 to 4
Method, which is characterized in that the allyl aromatic compound, hydrogen silane, iron molar ratio be 1:(0.5~50): (0.001
~10)；The mass ratio of the allyl aromatic compound and organic solvent is 1:(5~1000).
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| CN114181066A (en) * | 2021-11-12 | 2022-03-15 | 安徽理工大学 | Gallic acid analogue, and preparation method and application thereof |
| CN115417756A (en) * | 2022-08-30 | 2022-12-02 | 安徽华业香料合肥有限公司 | Process for preparing vanillin from eugenol by one-pot method |
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