CN107216242A - A kind of method of iron catalysis oxidation alkyl aromatic compound synthesis aromatic aldehyde, arone and aromatic ester - Google Patents

A kind of method of iron catalysis oxidation alkyl aromatic compound synthesis aromatic aldehyde, arone and aromatic ester Download PDF

Info

Publication number
CN107216242A
CN107216242A CN201710550257.8A CN201710550257A CN107216242A CN 107216242 A CN107216242 A CN 107216242A CN 201710550257 A CN201710550257 A CN 201710550257A CN 107216242 A CN107216242 A CN 107216242A
Authority
CN
China
Prior art keywords
iron
aromatic
silane
arone
epoxide
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201710550257.8A
Other languages
Chinese (zh)
Other versions
CN107216242B (en
Inventor
韩维
赵宏元
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nanjing Normal University
Original Assignee
Nanjing Normal University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nanjing Normal University filed Critical Nanjing Normal University
Priority to CN201710550257.8A priority Critical patent/CN107216242B/en
Publication of CN107216242A publication Critical patent/CN107216242A/en
Application granted granted Critical
Publication of CN107216242B publication Critical patent/CN107216242B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/28—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of CHx-moieties
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B41/00—Formation or introduction of functional groups containing oxygen
    • C07B41/06—Formation or introduction of functional groups containing oxygen of carbonyl groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B41/00—Formation or introduction of functional groups containing oxygen
    • C07B41/12—Formation or introduction of functional groups containing oxygen of carboxylic acid ester groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
    • C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
    • C07C319/20—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides by reactions not involving the formation of sulfide groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
    • C07C51/373—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by introduction of functional groups containing oxygen only in doubly bound form
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/39—Preparation of carboxylic acid esters by oxidation of groups which are precursors for the acid moiety of the ester
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
    • C07D209/04—Indoles; Hydrogenated indoles
    • C07D209/30—Indoles; Hydrogenated indoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to carbon atoms of the hetero ring
    • C07D209/42—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/44—Radicals substituted by doubly-bound oxygen, sulfur, or nitrogen atoms, or by two such atoms singly-bound to the same carbon atom
    • C07D213/46—Oxygen atoms
    • C07D213/50—Ketonic radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/12—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
    • C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D311/76—Benzo[c]pyrans
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
    • C07D333/22—Radicals substituted by doubly bound hetero atoms, or by two hetero atoms other than halogen singly bound to the same carbon atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic System
    • C07F5/02—Boron compounds
    • C07F5/025—Boronic and borinic acid compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
    • C07H1/00—Processes for the preparation of sugar derivatives
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
    • C07H15/00—Compounds containing hydrocarbon or substituted hydrocarbon radicals directly attached to hetero atoms of saccharide radicals
    • C07H15/20—Carbocyclic rings
    • C07H15/203—Monocyclic carbocyclic rings other than cyclohexane rings; Bicyclic carbocyclic ring systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07J—STEROIDS
    • C07J1/00—Normal steroids containing carbon, hydrogen, halogen or oxygen, not substituted in position 17 beta by a carbon atom, e.g. estrane, androstane
    • C07J1/0003—Androstane derivatives
    • C07J1/0011—Androstane derivatives substituted in position 17 by a keto group
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07J—STEROIDS
    • C07J9/00—Normal steroids containing carbon, hydrogen, halogen or oxygen substituted in position 17 beta by a chain of more than two carbon atoms, e.g. cholane, cholestane, coprostane
    • C07J9/005—Normal steroids containing carbon, hydrogen, halogen or oxygen substituted in position 17 beta by a chain of more than two carbon atoms, e.g. cholane, cholestane, coprostane containing a carboxylic function directly attached or attached by a chain containing only carbon atoms to the cyclopenta[a]hydrophenanthrene skeleton

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Biochemistry (AREA)
  • Biotechnology (AREA)
  • Genetics & Genomics (AREA)
  • Molecular Biology (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)

Abstract

The invention discloses the method for a kind of iron catalysis oxidation alkyl aromatic compound synthesis aromatic aldehyde, arone and aromatic ester, belong to catalytic synthetic techniques field.The present invention is at ambient pressure with the iron catalyst of cheap environmental protection, in the presence of hydrogen silica reagent is accelerator and oxidant, and aromatic side chain is oxidized into carbonyl and generates corresponding aromatic aldehyde, arone and aromatic ester.The method that catalytic oxidation of the present invention prepares aromatic aldehyde, arone and aromatic ester has many advantages：Catalyst, reaction raw materials, oxidant and silica reagent wide material sources, cheap, environmental protection and stability are good；Alkyl aromatic compound metering participates in reaction；Reaction condition is gentle, functional group's compatibility and applied widely；Good reaction selectivity, under the reaction condition of optimization, target product separation yield may be up to 95% or so.

Description

A kind of iron catalysis oxidation alkyl aromatic compound synthesizes aromatic aldehyde, arone and aromatic ester Method
Technical field
The invention belongs to catalytic synthetic techniques field, aromatic aldehyde, arone and virtue are catalyzed and synthesized more specifically to a kind of iron The method of ester, is that the benzyl position of the alkyl aromatic compound of iron high selectivity catalysis oxidation stoichiometry prepares aromatic aldehyde, arone With the method for aromatic ester.
Background technology
Aromatic aldehyde, arone and aromatic ester are the organic synthesis intermediates with high additive value, be widely used in medicine, agricultural chemicals, The synthesis of dyestuff and spices etc..At present in synthesis aromatic aldehyde, arone and aromatic ester method, alkylaromatic hydrocarbon is that substrate uses iron catalyst Liquid phase catalytic oxidation benzyl carbon-hydrogen reaction has obtained extensive concern, because this method has catalyst cheap and environment-friendly； Substrate source is extensive, stable and cheap；High and low emission the advantage of Atom economy.But this method has some challenges Problem：Reaction needs complicated catalyst, and catalytic efficiency is not high, and substrate is big activeization of benzyl carbon-hydracid mostly Compound；The efficiency that inert substrate such as methyl benzene-like compounds participate in reaction is low, and poor selectivity and quantity of solvent participate in reaction, these All hinder extensive use (Jian-Bo Feng, Xiao- of the benzyl carbon-hydroxide of iron catalysis in actual organic synthesis Feng Wu,Appl.Organometal.Chem.2015,29,63–86)。
The content of the invention
Goal of the invention：Pass through iron catalysis oxidation alkylaromatic hydrocarbon benzyl position carbon-hydrogen link synthesis aromatic aldehyde, arone and virtue for existing Reaction cost is high, reaction efficiency is low, poor selectivity (particularly aoxidizes first in the presence of needing to use complicated part to cause for Lipase absobed method Base benzene-like compounds exist peroxidating and cross reduction the problem of, be not resolved always) quantity of solvent participate in reaction and/or functional group Poor compatibility, the challenge of narrow application range, use simple and cheap iron catalyst, inexpensively the invention provides a kind of With the oxidant of environmental protection, the catalysis oxidation alkylaromatic hydrocarbon benzyl position of efficient and high selectivity under safety and stable accelerator effect Carbon-hydrogen link synthesis aromatic aldehyde, arone and aromatic ester.This method has a preferable versatility, the compatibility of susceptible functionality and can be effective Realize the later stage oxidative carbonylation to complicated molecule.
Technical scheme：In order to solve the above problems, the technical solution adopted in the present invention is as follows：
A kind of method of iron catalysis oxidation alkyl aromatic compound synthesis aromatic aldehyde, arone and aromatic ester, this method using iron as Catalyst, in the case where hydrogen silane is the collective effect of accelerator and oxidant, aoxidizes the alkyl aromatic compound of metering, prepares virtue Aldehyde, arone and aromatic ester, reaction expression are expressed as follows：
The general structure of aromatic aldehyde, arone and aromatic ester product synthesized by the method for the present invention is：
In formula, the aryl that Ar is represented is substituted or non-substituted phenyl, xenyl, naphthyl, anthryl, phenanthryl or pyrenyl；Ar The heteroaryl of expression for containing N, O or S five to thirteen ring heteroaryl.R represents hydrogen, aryl, heteroaryl, alkyl, alkoxy Or aryloxy group.
Further, the heteroaryl that the Ar is represented be substituted or non-substituted furyl, benzofuranyl, thienyl, Pyrrole radicals, indyl, pyridine radicals, isoxazolyl, pyrazolyl, imidazole radicals, oxazolyl or thiazolyl.
Further, the aryl that R is represented is substituted or non-substituted phenyl, xenyl, naphthyl, anthryl, phenanthryl or pyrenyl； The heteroaryl that R is represented is substituted or non-substituted furyl, benzofuranyl, thienyl, pyrrole radicals, indyl, pyridine radicals, different Oxazolyl, pyrazolyl, imidazole radicals, oxazolyl or thiazolyl；The alkyl that R is represented is the alkyl of C1~C20 straight or brancheds；R tables The alkoxy shown is the alkoxy of C1~C20 straight or brancheds；The aryloxy group that R is represented is substituted or non-substituted phenoxy group, connection Phenoxy group, naphthoxy, anthracene epoxide, luxuriant and rich with fragrance epoxide, pyrene epoxide, furans epoxide, benzofuran epoxide, thiophene oxy, pyrroles's epoxide, Yin Diindyl epoxide, pyridine epoxide, isoxazole epoxide, pyrazoles epoxide, imidazoles epoxide, oxazole epoxide or thiazole epoxide.
Further, when the aryl that the Ar or R are represented is substituted aryl, substituent thereon is monosubstituted or polysubstituted virtue Ring hydrogen, described substituent is arbitrarily selected from hydrogen, the alkyl of C1~C20 straight or brancheds, the alkane of C1~C30 straight or brancheds Epoxide, the alkane sulfydryl of C1~C30 straight or brancheds, aryl, heteroaryl, hydroxyl, carboxyl ,-B (OH)2, fluorine, chlorine, bromine, iodine, alkane acyl Epoxide or aryl acyloxy.
Further, when the heteroaryl that the Ar or R are represented is pyrrole radicals, imidazole radicals, indyl and pyrazolyl, its nitrogen is former Substituent on son arbitrarily selected from hydrogen, the alkyl of C1~C12 straight or brancheds, C3~C12 cycloalkyl, aryl, to toluene sulphur Acyl group, acetyl group, benzoyl or tertiary fourth oxygen acyl group.
Further, the iron catalyst is selected from iron powder, trifluoromethanesulfonic acid ferrous iron, trifluoromethanesulfonic acid iron, frerrous chloride, second Acyl acetone ferrous iron, ferric acetyl acetonade, DPM dpm,dipivalomethane are ferrous, DPM dpm,dipivalomethane Iron, 1,3- diphenylprops diketone ferrous iron, 1,3- diphenylprop diketone iron, benzoyl acetone ferrous iron, benzoyl acetone iron, iron cyaniding Ferrous iron, ferric ferricyanide, ferrous acetate, ferrous sulfate, iron ammonium sulfate, ferric sulfate, ferrous phthalocyanine, ferrocene, ferrous fluoride, fluorine Change iron, ferrous bromide, ferric bromide, iron iodide, ferric iodide, ferric trichloride, iron oxide or ferroso-ferric oxide.
Further, described hydrogen silane is triethyl silicane, triethoxysilane, polymethyl hydrogen siloxane, three isopropyls Base silane, dimethylphenylsilaneand, a phenyl silane, diphenyl silane, tri-phenyl-silane or the silica of 1,1,3,3- tetramethyls two Alkane, dimethylethoxysilane, dimethyl ethyl silane, benzyl dimethyl silane, diethylsilane, dichlorophenyl silane, two The chlorosilane of methyl one, diisopropyl chlorosilane, chloromethyl (dimethyl) silane, di-t-butyl chlorosilane, diphenyl chlorosilane, Ethyl dichlorosilane, di-t-butyl silane, methyldiphenyl base silane, dimethyl dichlorosilane (DMCS), t-butyldimethyl silane, 1,4- are double (dimetylsilyl) benzene, isopropoxy benzene base silane, methyldiethoxysilane, dimethoxy (methyl) silane, diformazan Ylmethyl hydrogen (siloxanes and polysiloxanes), 1,1,3,3- tetra isopropyl disiloxanes, three (trimethylsilyl) silane, aminomethyl phenyl Double (3,3,3- the trifluoro propyls) -1,1,3,3- tetramethyls two of silicone oil, pentamethyl disiloxane, four (dimethyl-silicon) silane, 1,3- Silicon is for oxygen alkane, four (dimethylsilyl bis) silane, (dimethyl siloxane) silane of phenyl three or the silicon of 1,1,2,2- tetraphenyls two Alkane.
Further, described oxidant is oxygen, hydrogen peroxide, Peracetic acid, peroxosulphuric hydrogen potassium complex salt, peroxide sulphur Sour potassium, peroxosulphuric ammonium or peroxosulphuric sodium；When oxygen is oxidant, 0.5~2.0 atmospheric pressure of gas pressure is preferably 1 big Air pressure.
Further, the reaction medium used in methods described for the aqueous solution, the aqueous solution of cyanophenyl, acetone of acetonitrile water Solution, the aqueous solution of ethanol, the aqueous solution of the tert-butyl alcohol, the aqueous solution of 1,2- dichloroethanes, the aqueous solution of ethyl acetate, tetrahydrochysene furan The aqueous solution or the aqueous solution of dimethyl sulfoxide muttered, the wherein volume ratio of organic solvent and water are 1:(0.5~100), preferably 1：(1- 10)。
Further, the mol ratio of alkyl aromatic compound, hydrogen silane, oxidant and iron catalyst is 1:(1~10): (1~10):(0.005~0.5), preferably 1：(3-6)：(1-3)：(0.01-0.11), alkyl aromatic compound and reaction medium Weight ratio be 1:(5~1000).In methods described, reaction temperature is 20~180 DEG C, and preferably 25-80 DEG C, the reaction time is 0.5~60 hour, preferably 3-25h.
Beneficial effect
Compared to prior art, beneficial effects of the present invention are：
(1) the invention provides a kind of iron in the aqueous solution of organic solvent catalysis alkylaromatic hydrocarbon side chain benzyl position oxidation carbonyl Change reaction to prepare aromatic aldehyde, arone and the new method of aromatic ester, this method has without complicated part, simple and easy to get excellent of catalyst Gesture；Oxidant and accelerator that this method needs, wide material sources and environment-friendly；Good reaction selectivity and yield are high；Functional group Compatibility is good, applied widely；Suitable for the later stage oxidative carbonylation of complicated molecule, this has weight in medicine and biochemical field The application value wanted；
(2) in aromatic aldehyde, arone and the aromatic ester synthetic method that the present invention is provided, substrate source is extensive, stable and cheap, method Simple and easy to apply, one-step method directly obtains aromatic aldehyde, arone and aromatic ester, under the reaction condition of optimization, target product separation yield Up to 95%, it is a kind of method of general, efficient, economic and environment-friendly synthesis aromatic aldehyde, arone and aromatic ester；
(3) method of the invention can obtain desired catalytic effect it is critical that being found that organic catalyst system and catalyzing is " organic The aqueous solution-iron catalyst-oxidant-accelerator of solvent ".Organic catalysis combination, which ensure that, is formed in situ highly active catalytic thing Kind, it is ensured that the high efficiency of reaction；While reaction is efficiently carried out, it is suppressed that peroxidating and the problem for crossing reduction, it is ensured that The good and applied widely advantage of high selectivity, the functional group's compatibility of reaction.
Embodiment
The present invention is further described below with reference to specific embodiment.
Further to illustrate the present invention to reach the technological means and effect that predetermined goal of the invention is taken, to according to this Technical scheme embodiment, feature and its effect proposed is invented, is described in detail as after.
Embodiment 1
Compound 1：Acetylacetone,2,4-pentanedione is sequentially added in 25mL reaction bulbs ferrous (0.025mmol), polymethyl hydrogen siloxane (0.75mmol), potassium peroxydisulfate (0.25mmol), 1a (0.25mmol), acetonitrile (1mL), water (1mL), reactant mixture is at 80 DEG C Lower reaction 6h.Reaction terminates to add ammoniacal liquor (2mL) removing polymethyl hydrogen siloxane, adds saturated aqueous common salt 10mL, and use ether Extract (10mL × 3), merge organic phase, remove column chromatography for separation after solvent under reduced pressure and obtain yield 80%.
Embodiment 2
Compound 2：Ferric acetyl acetonade (0.025mmol), polymethyl hydrogen siloxane are sequentially added in 25mL reaction bulbs (0.75mmol), potassium peroxydisulfate (0.25mmol), 1b (0.25mmol), acetonitrile (1mL), water (1mL), reactant mixture is at 80 DEG C Lower reaction 3h.Reaction terminates to add ammoniacal liquor (2mL) removing polymethyl hydrogen siloxane, adds saturated aqueous common salt 10mL, and use ether Extract (10mL × 3), merge organic phase, remove column chromatography for separation after solvent under reduced pressure and obtain yield 80%.
Embodiment 3
Compound 3：Acetylacetone,2,4-pentanedione is sequentially added in 25mL reaction bulbs ferrous (0.025mmol), polymethyl hydrogen siloxane (0.75mmol), potassium peroxydisulfate (0.25mmol), 1c (0.25mmol), acetonitrile (1mL), water (1mL), reactant mixture is at 80 DEG C Lower reaction 3h.Reaction terminates to add ammoniacal liquor (2mL) removing polymethyl hydrogen siloxane, adds saturated aqueous common salt 10mL, and use ether Extract (10mL × 3), merge organic phase, remove column chromatography for separation after solvent under reduced pressure and obtain yield 80%.
Embodiment 4
Compound 4：Acetylacetone,2,4-pentanedione is sequentially added in 25mL reaction bulbs ferrous (0.025mmol), polymethyl hydrogen siloxane (0.75mmol), potassium peroxydisulfate (0.25mmol), 1d (0.25mmol), acetonitrile (1mL), water (1mL), reactant mixture is at 80 DEG C Lower reaction 6h.Reaction terminates to add ammoniacal liquor (2mL) removing polymethyl hydrogen siloxane, adds saturated aqueous common salt 10mL, and use ether Extract (10mL × 3), merge organic phase, remove column chromatography for separation after solvent under reduced pressure and obtain yield 87%.
Embodiment 5
Compound 5：Acetylacetone,2,4-pentanedione is sequentially added in 25mL reaction bulbs ferrous (0.025mmol), polymethyl hydrogen siloxane (0.75mmol), potassium peroxydisulfate (0.25mmol), 1e (0.25mmol), acetonitrile (1mL), water (1mL), reactant mixture is at 80 DEG C Lower reaction 3h.Reaction terminates to add ammoniacal liquor (2mL) removing polymethyl hydrogen siloxane, adds saturated aqueous common salt 10mL, and use ether Extract (10mL × 3), merge organic phase, remove column chromatography for separation after solvent under reduced pressure and obtain yield 85%.
Embodiment 6
Compound 6：Acetylacetone,2,4-pentanedione is sequentially added in 25mL reaction bulbs ferrous (0.025mmol), 1,1,3,3- tetramethyl two Siloxanes (0.75mmol), potassium peroxydisulfate (0.25mmol), 1f (0.25mmol), 1,2- dichloroethanes (1mL), water (1mL), instead Mixture is answered to react 3h at 80 DEG C.Reaction terminates to add ammoniacal liquor (2mL) removing polymethyl hydrogen siloxane, adds saturated aqueous common salt 10mL, and extracted (10mL × 3) with ether, merge organic phase, remove column chromatography for separation after solvent under reduced pressure and obtain yield 70%.
Embodiment 7
Compound 7：Ferrocene (0.025mmol) is sequentially added in 25mL reaction bulbs, ferrous phthalocyanine (0.0025mmol) gathers Methyl hydrogen siloxane (0.75mmol), potassium peroxydisulfate (0.75mmol), 1g (0.25mmol), acetonitrile (1mL), water (1mL), reaction Mixture reacts 3h at 80 DEG C.Reaction terminates to add ammoniacal liquor (2mL) removing polymethyl hydrogen siloxane, adds saturated aqueous common salt 10mL, and extracted (10mL × 3) with ether, merge organic phase, remove column chromatography for separation after solvent under reduced pressure and obtain yield 78%.
Embodiment 8
Compound 8：Acetylacetone,2,4-pentanedione is sequentially added in 25mL reaction bulbs ferrous (0.025mmol), triethyl silicane (0.75mmol), potassium peroxydisulfate (0.25mmol), 1h (0.25mmol), the tert-butyl alcohol (1mL), water (1mL), reactant mixture is 80 9h is reacted at DEG C.Reaction terminates to add ammoniacal liquor (2mL) removing polymethyl hydrogen siloxane, adds saturated aqueous common salt 10mL, and use second Ether extracts (10mL × 3), merges organic phase, removes column chromatography for separation after solvent under reduced pressure and obtain yield 72%.
Embodiment 9
Compound 9：Trifluoromethanesulfonic acid is sequentially added in 25mL reaction bulbs ferrous (0.025mmol), ferrous phthalocyanine (0.0025mmol) polymethyl hydrogen siloxane (0.75mmol), potassium peroxydisulfate (0.75mmol), 1i (0.25mmol), acetonitrile (1mL), water (1mL), reactant mixture reacts 16h at 80 DEG C.Reaction terminates to add the poly- methyl hydrogen silica of ammoniacal liquor (2mL) removing Alkane, adds saturated aqueous common salt 10mL, and is extracted (10mL × 3) with ether, merges organic phase, removes column chromatography point after solvent under reduced pressure From obtaining yield 70%.
Embodiment 10
Compound 10：Ferric iodide (0.025mmol), polymethyl hydrogen siloxane are sequentially added in 25mL reaction bulbs (0.75mmol), potassium peroxydisulfate (0.25mmol), 1j (0.25mmol), acetonitrile (1mL), water (1mL), reactant mixture is at 80 DEG C Lower reaction 3h.Reaction terminates to add ammoniacal liquor (2mL) removing polymethyl hydrogen siloxane, adds saturated aqueous common salt 10mL, and use ether Extract (10mL × 3), merge organic phase, remove column chromatography for separation after solvent under reduced pressure and obtain yield 60%.
Embodiment 11
Compound 11：Acetylacetone,2,4-pentanedione is sequentially added in 25mL reaction bulbs ferrous (0.025mmol), polymethyl hydrogen siloxane (0.75mmol), potassium peroxydisulfate (0.25mmol), 1k (0.25mmol), acetonitrile (1mL), water (1mL), reactant mixture is at 80 DEG C Lower reaction 3h.Reaction terminates to add ammoniacal liquor (2mL) removing polymethyl hydrogen siloxane, adds saturated aqueous common salt 10mL, and use ether Extract (10mL × 3), merge organic phase, remove column chromatography for separation after solvent under reduced pressure and obtain yield 95%.
Embodiment 12
Compound 12：Ferrocene (0.025mmol) is sequentially added in 25mL reaction bulbs, ferrous phthalocyanine (0.0025mmol) gathers Methyl hydrogen siloxane (0.75mmol), potassium peroxydisulfate (0.75mmol), 1l (0.25mmol), acetonitrile (1mL), water (1mL), reaction Mixture reacts 6h at 80 DEG C.Reaction terminates to add ammoniacal liquor (2mL) removing polymethyl hydrogen siloxane, adds saturated aqueous common salt 10mL, and extracted (10mL × 3) with ether, merge organic phase, remove column chromatography for separation after solvent under reduced pressure and obtain yield 92%.
Embodiment 13
Compound 13：Ferrocene (0.025mmol) is sequentially added in 25mL reaction bulbs, ferrous phthalocyanine (0.0025mmol) gathers Methyl hydrogen siloxane (0.75mmol), potassium peroxydisulfate (0.75mmol), 1m (0.25mmol), acetonitrile (1mL), water (1mL), reaction Mixture reacts 9h at 80 DEG C.Reaction terminates to add ammoniacal liquor (2mL) removing polymethyl hydrogen siloxane, adds saturated aqueous common salt 10mL, and extracted (10mL × 3) with ether, merge organic phase, remove column chromatography for separation after solvent under reduced pressure and obtain yield 80%.
Embodiment 14
Compound 14：1,3- diphenylprop diketone iron (0.025mmol), ferrous phthalocyanine are sequentially added in 25mL reaction bulbs (0.0025mmol), triethoxysilane (1.5mmol), sodium peroxydisulfate (0.75mmol), 1n (0.25mmol), acetonitrile (1mL), Water (1mL), reactant mixture reacts 17h at 80 DEG C.Reaction terminates to add ammoniacal liquor (2mL) removing polymethyl hydrogen siloxane, plus Enter saturated aqueous common salt 10mL, and extracted (10mL × 3) with ether, merge organic phase, remove column chromatography for separation after solvent under reduced pressure and obtain To yield 60%.
Embodiment 15
Compound 15：Ferrocene (0.025mmol) is sequentially added in 25mL reaction bulbs, ferrous phthalocyanine (0.0025mmol) gathers Methyl hydrogen siloxane (0.75mmol), potassium peroxydisulfate (0.75mmol), 1o (0.25mmol), acetonitrile (1mL), water (1mL), reaction Mixture reacts 3h at 80 DEG C.Reaction terminates to add ammoniacal liquor (2mL) removing polymethyl hydrogen siloxane, adds saturated aqueous common salt 10mL, and extracted (10mL × 3) with ether, merge organic phase, remove column chromatography for separation after solvent under reduced pressure and obtain yield 95%.
Embodiment 16
Compound 16：Ferrous sulfate (0.025mmol), ferrous phthalocyanine (0.0025mmol) are sequentially added in 25mL reaction bulbs One phenyl silane (0.75mmol), peroxosulphuric hydrogen potassium complex salt (0.75mmol), 1p (0.25mmol), acetonitrile (1mL), water (1mL), reactant mixture reacts 9h at 80 DEG C.Reaction terminates to add ammoniacal liquor (2mL) removing polymethyl hydrogen siloxane, adds full With saline solution 10mL, and extracted (10mL × 3) with ether, merge organic phase, remove column chromatography for separation after solvent under reduced pressure and produced Rate 60%.
Embodiment 17
Compound 17：Ferrocene (0.025mmol), ferrous phthalocyanine (0.0025mmol) two are sequentially added in 25mL reaction bulbs Phenyl chlorosilane (1.5mmol), potassium peroxydisulfate (0.75mmol), 1q (0.25mmol), acetonitrile (1mL), water (1mL), reaction is mixed Compound reacts 6h at 80 DEG C.Reaction terminates to add ammoniacal liquor (2mL) removing polymethyl hydrogen siloxane, adds saturated aqueous common salt 10mL, and extracted (10mL × 3) with ether, merge organic phase, remove column chromatography for separation after solvent under reduced pressure and obtain yield 72%.
Embodiment 18
Compound 18：Ferroso-ferric oxide (0.025mmol), ferrous phthalocyanine are sequentially added in 25mL reaction bulbs (0.0025mmol) polymethyl hydrogen siloxane (0.75mmol), oxygen (1atm), 1r (0.25mmol), acetonitrile (1mL), water (1mL), reactant mixture reacts 12h at 80 DEG C.Reaction terminates to add ammoniacal liquor (2mL) removing polymethyl hydrogen siloxane, adds Saturated aqueous common salt 10mL, and extracted (10mL × 3) with ether, merge organic phase, remove column chromatography for separation after solvent under reduced pressure and obtain Yield 50%.
Embodiment 19
Compound 19：Ferrocene (0.025mmol) is sequentially added in 25mL reaction bulbs, ferrous phthalocyanine (0.0025mmol) gathers Methyl hydrogen siloxane (0.75mmol), potassium peroxydisulfate (0.75mmol), 1s (0.25mmol), acetonitrile (1mL), water (1mL), reaction Mixture reacts 6h at 80 DEG C.Reaction terminates to add ammoniacal liquor (2mL) removing polymethyl hydrogen siloxane, adds saturated aqueous common salt 10mL, and extracted (10mL × 3) with ether, merge organic phase, remove column chromatography for separation after solvent under reduced pressure and obtain yield 92%.
Embodiment 20
Compound 20：Acetylacetone,2,4-pentanedione is sequentially added in 25mL reaction bulbs ferrous (0.025mmol), polymethyl hydrogen siloxane (0.75mmol), potassium peroxydisulfate (0.25mmol), 1t (0.25mmol), acetonitrile (1mL), water (1mL), reactant mixture is at 80 DEG C Lower reaction 8h.Reaction terminates to add ammoniacal liquor (2mL) removing polymethyl hydrogen siloxane, adds saturated aqueous common salt 10mL, and use ether Extract (10mL × 3), merge organic phase, remove column chromatography for separation after solvent under reduced pressure and obtain yield 95%.
Embodiment 21
Compound 21：Ferric acetyl acetonade (0.025mmol), ferrous phthalocyanine are sequentially added in 25mL reaction bulbs (0.0025mmol) isopropoxy benzene base silane (0.75mmol), hydrogen peroxide (0.75mmol), 1u (0.25mmol), acetonitrile (1mL), water (1mL), reactant mixture reacts 3h at 80 DEG C.Reaction terminates to add the poly- methyl hydrogen silica of ammoniacal liquor (2mL) removing Alkane, adds saturated aqueous common salt 10mL, and is extracted (10mL × 3) with ether, merges organic phase, removes column chromatography point after solvent under reduced pressure From obtaining yield 65%.
Embodiment 22
Compound 22：Ferrocene (0.025mmol), polymethyl hydrogen siloxane are sequentially added in 25mL reaction bulbs (0.75mmol), potassium peroxydisulfate (0.25mmol), 1v (0.25mmol), acetonitrile (1mL), water (1mL), reactant mixture is at 50 DEG C Lower reaction 3h.Reaction terminates to add ammoniacal liquor (2mL) removing polymethyl hydrogen siloxane, adds saturated aqueous common salt 10mL, and use ether Extract (10mL × 3), merge organic phase, remove column chromatography for separation after solvent under reduced pressure and obtain yield 67%.
Embodiment 23
Compound 23：Benzoyl acetone is sequentially added in 25mL reaction bulbs ferrous (0.025mmol), ferrous phthalocyanine (0.0025mmol) polymethyl hydrogen siloxane (0.75mmol), Peracetic acid (0.75mmol), 1w (0.25mmol), cyanophenyl (1mL), water (1mL), reactant mixture reacts 12h at 80 DEG C.Reaction terminates to add the poly- methyl hydrogen silica of ammoniacal liquor (2mL) removing Alkane, adds saturated aqueous common salt 10mL, and is extracted (10mL × 3) with ether, merges organic phase, removes column chromatography point after solvent under reduced pressure From obtaining yield 65%.
Embodiment 24
Compound 24：Frerrous chloride (0.025mmol), polymethyl hydrogen siloxane are sequentially added in 25mL reaction bulbs (0.75mmol), potassium peroxydisulfate (0.25mmol), 1x (0.25mmol), acetonitrile (1mL), water (1mL), reactant mixture is at 80 DEG C Lower reaction 18h.Reaction terminates to add ammoniacal liquor (2mL) removing polymethyl hydrogen siloxane, adds saturated aqueous common salt 10mL, and use ether Extract (10mL × 3), merge organic phase, remove column chromatography for separation after solvent under reduced pressure and obtain yield 68%.
Embodiment 25
Compound 25：DPM dpm,dipivalomethane is sequentially added in 25mL reaction bulbs ferrous (0.0025mmol), polymethyl hydrogen siloxane (0.75mmol), potassium peroxydisulfate (0.25mmol), 1y (0.25mmol), acetonitrile (1mL), water (1mL), reactant mixture reacts 3h at 25 DEG C.Reaction terminates to add the poly- methyl hydrogen silica of ammoniacal liquor (2mL) removing Alkane, adds saturated aqueous common salt 10mL, and is extracted (10mL × 3) with ether, merges organic phase, removes column chromatography point after solvent under reduced pressure From obtaining yield 74%.
Embodiment 26
Compound 26：Ferric ferricyanide (0.05mmol), ferrous phthalocyanine (0.0025mmol) are sequentially added in 25mL reaction bulbs Polymethyl hydrogen siloxane (0.75mmol), potassium peroxydisulfate (0.75mmol), 1z (0.25mmol), dimethyl sulfoxide (0.2mL), water (2mL), reactant mixture reacts 6h at 80 DEG C.Reaction terminates to add ammoniacal liquor (2mL) removing polymethyl hydrogen siloxane, adds full With saline solution 10mL, and extracted (10mL × 3) with ether, merge organic phase, remove column chromatography for separation after solvent under reduced pressure and produced Rate 68%.
Embodiment 27
Compound 27：Acetylacetone,2,4-pentanedione is sequentially added in 25mL reaction bulbs ferrous (0.025mmol), polymethyl hydrogen siloxane (0.75mmol), potassium peroxydisulfate (0.25mmol), 1aa (0.25mmol), acetonitrile (1mL), water (1mL), reactant mixture is 80 6h is reacted at DEG C.Reaction terminates to add ammoniacal liquor (2mL) removing polymethyl hydrogen siloxane, adds saturated aqueous common salt 10mL, and use second Ether extracts (10mL × 3), merges organic phase, removes column chromatography for separation after solvent under reduced pressure and obtain yield 87%.
Embodiment 28
Compound 28：Acetylacetone,2,4-pentanedione is sequentially added in 25mL reaction bulbs ferrous (0.025mmol), three (trimethylsilyl) silane (0.75mmol), potassium peroxydisulfate (0.25mmol), 1ab (0.25mmol), tetrahydrofuran (1mL), water (1mL), reactant mixture 8h is reacted at 80 DEG C.Reaction terminates to add ammoniacal liquor (2mL) removing polymethyl hydrogen siloxane, adds saturated aqueous common salt 10mL, and Extracted with ether (10mL × 3), merge organic phase, remove column chromatography for separation after solvent under reduced pressure and obtain yield 91%.
Embodiment 29
Compound 29：Sequentially add ferric bromide (0.025mmol) in 25mL reaction bulbs, dimethyl methyl hydrogen (siloxanes with Polysiloxanes) (0.75mmol), potassium peroxydisulfate (0.25mmol), 1ac (0.25mmol), ethyl acetate (1mL), water (1mL), instead Mixture is answered to react 12h at 80 DEG C.Reaction terminates to add ammoniacal liquor (2mL) removing polymethyl hydrogen siloxane, adds saturated common salt Water 10mL, and extracted (10mL × 3) with ether, merge organic phase, remove column chromatography for separation after solvent under reduced pressure and obtain yield 70%.
Embodiment 30
Compound 30：Acetylacetone,2,4-pentanedione is sequentially added in 25mL reaction bulbs ferrous (0.025mmol), dimethyl ethyl silane (1.5mmol), potassium peroxydisulfate (0.25mmol), 1ad (0.25mmol), acetonitrile (1mL), water (1mL), reactant mixture is at 80 DEG C Lower reaction 5h.Reaction terminates to add ammoniacal liquor (2mL) removing polymethyl hydrogen siloxane, adds saturated aqueous common salt 10mL, and use ether Extract (10mL × 3), merge organic phase, remove column chromatography for separation after solvent under reduced pressure and obtain yield 50%.
Embodiment 31
Compound 31：Ferrous bromide (0.025mmol), four (dimethylsilyl bis) silane are sequentially added in 25mL reaction bulbs (0.75mmol), potassium peroxydisulfate (0.25mmol), 1ae (0.25mmol), the tert-butyl alcohol (1mL), water (1mL), reactant mixture exists 20h is reacted at 80 DEG C.Reaction terminates to add ammoniacal liquor (2mL) removing polymethyl hydrogen siloxane, adds saturated aqueous common salt 10mL, is used in combination Ether extracts (10mL × 3), merges organic phase, removes column chromatography for separation after solvent under reduced pressure and obtain yield 40%.
Embodiment 32
Compound 32：Acetylacetone,2,4-pentanedione is sequentially added in 25mL reaction bulbs ferrous (0.025mmol), polymethyl hydrogen siloxane (0.75mmol), potassium peroxydisulfate (0.25mmol), 1af (0.25mmol), acetonitrile (1mL), water (1mL), reactant mixture is 80 5h is reacted at DEG C.Reaction terminates to add ammoniacal liquor (2mL) removing polymethyl hydrogen siloxane, adds saturated aqueous common salt 10mL, and use second Ether extracts (10mL × 3), merges organic phase, removes column chromatography for separation after solvent under reduced pressure and obtain yield 60%.
Embodiment 33
Compound 31：Acetylacetone,2,4-pentanedione is sequentially added in 25mL reaction bulbs ferrous (0.025mmol), 1,1,2,2- tetraphenyl two Silane (0.75mmol), potassium peroxydisulfate (0.25mmol), 1ag (0.25mmol), acetonitrile (1mL), water (1mL), reactant mixture 25h is reacted at 80 DEG C.Reaction terminates to add ammoniacal liquor (2mL) removing polymethyl hydrogen siloxane, adds saturated aqueous common salt 10mL, and Extracted with ether (10mL × 3), merge organic phase, remove column chromatography for separation after solvent under reduced pressure and obtain yield 50%.
Embodiment 34
Compound 31：Acetylacetone,2,4-pentanedione is sequentially added in 25mL reaction bulbs ferrous (0.025mmol), polymethyl hydrogen siloxane (0.75mmol), potassium peroxydisulfate (0.25mmol), 1ah (0.25mmol), acetonitrile (1mL), water (1mL), reactant mixture is 80 12h is reacted at DEG C.Reaction terminates to add ammoniacal liquor (2mL) removing polymethyl hydrogen siloxane, adds saturated aqueous common salt 10mL, and use second Ether extracts (10mL × 3), merges organic phase, removes column chromatography for separation after solvent under reduced pressure and obtain yield 73%.
The corresponding experimental result of synthetic method that embodiment 1~34 is related to specific aromatic aldehyde, arone and aromatic ester is listed in table 1：
The synthesis of the aromatic aldehyde of the iron catalysis oxidation alkylaromatic hydrocarbon side chain of table 1, arone and aromatic ester[a]
[a] reaction condition is shown in embodiment；[b] post separation yield.
The above described is only a preferred embodiment of the present invention, any formal limitation not is made to the present invention, though So the present invention is disclosed above with preferred embodiment, but is not limited to the present invention, the various iron catalysts in the present invention The catalytic activity thing to form high activity can be acted on hydrogen silica reagent, so as to ensure that effective progress of reaction；Hydrogen silica reagent Reaction is set effectively to carry out necessary accelerator, what is utilized is the reproducibility of silicon hydrogen, the various hydrogen silanes provided in theory all have There is certain reproducibility, should be able to all obtain similar effect；Oxidant is the key substance for playing oxidation during the course of the reaction, The various oxidants with oxygen supply function can promote the generation of reaction in theory；The change that alkyl-aromatic compounds react Learn the change influence of change and alkyl that key is the substituent on carbon-hydrogen link on its benzyl carbon, aromatic ring in itself is aromatic ring The modification of the steric hindrance of cloud density and reaction site, i.e. substituent simply influence reaction to a certain extent, can't be right Reaction plays a decisive role in itself.Any those skilled in the art are not it can be appreciated that departing from technical solution of the present invention In the range of, corresponding embodiment is obtained when that can be changed or modified, for example can be in the scope of the invention for described substituent Inside it is replaced, changes or modifies, can realizes the inventive method.In every case it is the objective without departing from technical solution of the present invention, According to any modification made to above example of the present invention, modification or equivalent and equivalent change, the present invention is still fallen within In the range of technical scheme.

Claims (10)

1. a kind of method of iron catalysis oxidation alkyl aromatic compound synthesis aromatic aldehyde, arone and aromatic ester, it is characterised in that：The party Using iron as catalyst in method, in the case where hydrogen silane is the collective effect of accelerator and oxidant, the alkyl aromatic of metering is aoxidized Compound, prepares aromatic aldehyde, arone and aromatic ester.
Reaction expression is expressed as follows：
In formula：
The aryl that Ar is represented is substituted or non-substituted phenyl, xenyl, naphthyl, anthryl, phenanthryl or pyrenyl；The heteroaryl that Ar is represented Base for containing N, O or S five to thirteen ring heteroaryl；R represents hydrogen, aryl, heteroaryl, alkyl, alkoxy or aryloxy group.
2. a kind of iron catalysis oxidation alkyl aromatic compound according to claim 1 synthesizes aromatic aldehyde, arone and aromatic ester Method, it is characterised in that：The heteroaryl that the Ar is represented is substituted or non-substituted furyl, benzofuranyl, thienyl, pyrrole Cough up base, indyl, pyridine radicals, isoxazolyl, pyrazolyl, imidazole radicals, oxazolyl or thiazolyl.
3. a kind of iron catalysis oxidation alkyl aromatic compound according to claim 1 synthesizes aromatic aldehyde, arone and aromatic ester Method, it is characterised in that：The aryl that R is represented is substituted or non-substituted phenyl, xenyl, naphthyl, anthryl, phenanthryl or pyrenyl；R The heteroaryl of expression is substituted or non-substituted furyl, benzofuranyl, thienyl, pyrrole radicals, indyl, pyridine radicals, different Oxazolyl, pyrazolyl, imidazole radicals, oxazolyl or thiazolyl；The alkyl that R is represented is the alkyl of C1~C20 straight or brancheds；R tables The alkoxy shown is the alkoxy of C1~C20 straight or brancheds；The aryloxy group that R is represented is substituted or non-substituted phenoxy group, connection Phenoxy group, naphthoxy, anthracene epoxide, luxuriant and rich with fragrance epoxide, pyrene epoxide, furans epoxide, benzofuran epoxide, thiophene oxy, pyrroles's epoxide, Yin Diindyl epoxide, pyridine epoxide, isoxazole epoxide, pyrazoles epoxide, imidazoles epoxide, oxazole epoxide or thiazole epoxide.
4. a kind of iron catalysis oxidation alkyl aromatic compound according to claim 1 synthesizes aromatic aldehyde, arone and aromatic ester Method, it is characterised in that：When the aryl that the Ar or R are represented is substituted aryl, substituent thereon is monosubstituted or polysubstituted virtue Ring hydrogen, described substituent is arbitrarily selected from hydrogen, the alkyl of C1~C20 straight or brancheds, the alkane of C1~C30 straight or brancheds Epoxide, the alkane sulfydryl of C1~C30 straight or brancheds, aryl, heteroaryl, hydroxyl, carboxyl ,-B (OH)2, fluorine, chlorine, bromine, iodine, alkane acyl Epoxide or aryl acyloxy.
5. a kind of iron catalysis oxidation alkyl aromatic compound according to claim 1 synthesizes aromatic aldehyde, arone and aromatic ester Method, it is characterised in that：When the heteroaryl that the Ar or R are represented is pyrrole radicals, imidazole radicals, indyl and pyrazolyl, its nitrogen is former Substituent on son arbitrarily selected from hydrogen, the alkyl of C1~C12 straight or brancheds, C3~C12 cycloalkyl, aryl, to toluene sulphur Acyl group, acetyl group, benzoyl or tertiary fourth oxygen acyl group.
6. a kind of iron catalysis oxidation alkyl aromatic compound synthesis aromatic aldehyde, arone according to claim any one of 1-5 With the method for aromatic ester, it is characterised in that：The iron catalyst is selected from iron powder, trifluoromethanesulfonic acid ferrous iron, trifluoromethanesulfonic acid iron, chlorination Ferrous iron, acetylacetone,2,4-pentanedione ferrous iron, ferric acetyl acetonade, DPM dpm,dipivalomethane ferrous iron, 2,2,6,6- tetramethyl -3, 5- heptadione iron, 1,3- diphenylprops diketone ferrous iron, 1,3- diphenylprop diketone iron, benzoyl acetone ferrous iron, benzoyl acetone Iron, ferroferricyanide, ferric ferricyanide, ferrous acetate, ferrous sulfate, iron ammonium sulfate, ferric sulfate, ferrous phthalocyanine, ferrocene, fluorine Change ferrous iron, ferric flouride, ferrous bromide, ferric bromide, iron iodide, ferric iodide, ferric trichloride, iron oxide or ferroso-ferric oxide.
7. a kind of iron catalysis oxidation alkyl aromatic compound synthesis aromatic aldehyde, arone according to claim any one of 1-5 With the method for aromatic ester, it is characterised in that：Described hydrogen silane be triethyl silicane, triethoxysilane, polymethyl hydrogen siloxane, Tri isopropyl silane, dimethylphenylsilaneand, a phenyl silane, diphenyl silane, tri-phenyl-silane or 1,1,3,3- tetramethyls Disiloxane, dimethylethoxysilane, dimethyl ethyl silane, benzyl dimethyl silane, diethylsilane, dichlorophenyl silicon Alkane, chlorodimethyl silane, diisopropyl chlorosilane, chloromethyl (dimethyl) silane, di-t-butyl chlorosilane, diphenyl chlorine Silane, ethyl dichlorosilane, di-t-butyl silane, methyldiphenyl base silane, dimethyl dichlorosilane (DMCS), t-butyldimethyl silane, 1,4- double (dimetylsilyl) benzene, isopropoxy benzene base silane, methyldiethoxysilane, dimethoxy (methyl) silicon Alkane, dimethyl methyl hydrogen (siloxanes and polysiloxanes), 1,1,3,3- tetra isopropyl disiloxanes, three (trimethylsilyl) silane, Double (3,3,3- the trifluoro propyls) -1,1,3,3- of methyl phenyl silicone oil, pentamethyl disiloxane, four (dimethyl-silicon) silane, 1,3- The silicon of tetramethyl two is for oxygen alkane, four (dimethylsilyl bis) silane, (dimethyl siloxane) silane of phenyl three or 1,1,2,2- tetra- Phenyl disilane.
8. a kind of iron catalysis oxidation alkyl aromatic compound synthesis aromatic aldehyde, arone according to claim any one of 1-5 With the method for aromatic ester, it is characterised in that：Described oxidant is oxygen, hydrogen peroxide, Peracetic acid, peroxosulphuric hydrogen potassium are combined Salt, potassium peroxide, peroxosulphuric ammonium or peroxosulphuric sodium；When oxygen is oxidant, 0.5~2.0 atmospheric pressure of gas pressure.
9. a kind of iron catalysis oxidation alkyl aromatic compound synthesis aromatic aldehyde, arone according to claim any one of 1-5 With the method for aromatic ester, it is characterised in that：The reaction medium used in methods described for the aqueous solution of acetonitrile, the aqueous solution of cyanophenyl, The aqueous solution of acetone, the aqueous solution of ethanol, the aqueous solution of the tert-butyl alcohol, the aqueous solution of 1,2- dichloroethanes, ethyl acetate it is water-soluble The volume ratio of the aqueous solution of liquid, the aqueous solution of tetrahydrofuran or dimethyl sulfoxide, wherein organic solvent and water is 1:(0.5~100).
10. a kind of iron catalysis oxidation alkyl aromatic compound synthesis aromatic aldehyde, arone according to claim any one of 1-5 With the method for aromatic ester, it is characterised in that：The alkyl aromatic compound, hydrogen silane, the mol ratio of oxidant and iron catalyst For 1:(1~10):(1~10):The weight ratio of (0.005~0.5), alkyl aromatic compound and reaction medium is 1:(5~ 1000)；In methods described, reaction temperature is 20~180 DEG C, and the reaction time is 0.5~60 hour.
CN201710550257.8A 2017-07-07 2017-07-07 Method for synthesizing aromatic aldehyde, aromatic ketone and aromatic ester by oxidizing alkyl aromatic compound under catalysis of iron Active CN107216242B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710550257.8A CN107216242B (en) 2017-07-07 2017-07-07 Method for synthesizing aromatic aldehyde, aromatic ketone and aromatic ester by oxidizing alkyl aromatic compound under catalysis of iron

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710550257.8A CN107216242B (en) 2017-07-07 2017-07-07 Method for synthesizing aromatic aldehyde, aromatic ketone and aromatic ester by oxidizing alkyl aromatic compound under catalysis of iron

Publications (2)

Publication Number Publication Date
CN107216242A true CN107216242A (en) 2017-09-29
CN107216242B CN107216242B (en) 2020-04-03

Family

ID=59951906

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710550257.8A Active CN107216242B (en) 2017-07-07 2017-07-07 Method for synthesizing aromatic aldehyde, aromatic ketone and aromatic ester by oxidizing alkyl aromatic compound under catalysis of iron

Country Status (1)

Country Link
CN (1) CN107216242B (en)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107805271A (en) * 2017-10-19 2018-03-16 福州大学 A kind of method for preparing metapristone
CN111196754A (en) * 2020-01-17 2020-05-26 上海应用技术大学 Method for preparing aromatic aldehyde ketone by catalytic oxidation of aromatic hydrocarbon side chain by nickel compound
CN111909112A (en) * 2020-08-24 2020-11-10 浙江工业大学 Preparation method of C2 substituted 2H-benzothiazole acylated derivative
CN111978163A (en) * 2020-07-24 2020-11-24 华东理工大学 Method for synthesizing aromatic aldehyde ketone by catalyzing alkyl aromatic hydrocarbon with water as oxygen source
CN112812084A (en) * 2020-12-30 2021-05-18 温州大学新材料与产业技术研究院 Synthetic method of benzofuran compound
CN113402351A (en) * 2021-05-19 2021-09-17 南京师范大学 Method for synthesizing phenol by promoting iron catalytic oxidation of aromatic compound carbon-hydrogen bond through ligand
CN115010584A (en) * 2022-06-13 2022-09-06 南京师范大学 Method for synthesizing arone by oxidizing benzyl tertiary carbon broken bond under catalysis of iron

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4390728A (en) * 1981-12-07 1983-06-28 Ashland Oil, Inc. Process for conversion of toluene to benzaldehyde
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

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4390728A (en) * 1981-12-07 1983-06-28 Ashland Oil, Inc. Process for conversion of toluene to benzaldehyde
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

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
BINBIN LIU ET AL: "Wacker-Type Oxidation Using an Iron Catalyst and Ambient Air:Application to Late-Stage Oxidation of Complex Molecules", 《ANGEW. CHEM. INT. ED.》 *
PENGHUI HU ET AL: "Bio-inspired iron-catalyzed oxidation of alkylarenes enables latlate-stage oxidation of complex methylarenes to arylaldehydes", 《NATURE》 *
QI XING ET AL: "Iron-catalyzed aerobic oxidative cleavage of the C–C r-bond using air as the oxidant: chemoselective synthesis of carbon chain-shortened aldehydes, ketones and 1,2-dicarbonyl compounds", 《CHEM. COMMUN.》 *

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107805271B (en) * 2017-10-19 2019-10-15 福州大学 A method of preparing metapristone
CN107805271A (en) * 2017-10-19 2018-03-16 福州大学 A kind of method for preparing metapristone
CN111196754A (en) * 2020-01-17 2020-05-26 上海应用技术大学 Method for preparing aromatic aldehyde ketone by catalytic oxidation of aromatic hydrocarbon side chain by nickel compound
CN111196754B (en) * 2020-01-17 2022-08-23 上海应用技术大学 Method for preparing aromatic aldehyde ketone by catalytic oxidation of aromatic hydrocarbon side chain by nickel compound
CN111978163A (en) * 2020-07-24 2020-11-24 华东理工大学 Method for synthesizing aromatic aldehyde ketone by catalyzing alkyl aromatic hydrocarbon with water as oxygen source
CN111978163B (en) * 2020-07-24 2022-09-27 华东理工大学 Method for synthesizing aromatic aldehyde ketone by catalyzing alkyl aromatic hydrocarbon with water as oxygen source
CN111909112B (en) * 2020-08-24 2022-07-08 浙江工业大学 Preparation method of C2 substituted 2H-benzothiazole acylated derivative
CN111909112A (en) * 2020-08-24 2020-11-10 浙江工业大学 Preparation method of C2 substituted 2H-benzothiazole acylated derivative
CN112812084B (en) * 2020-12-30 2022-08-09 温州大学新材料与产业技术研究院 Synthetic method of benzofuran compound
CN112812084A (en) * 2020-12-30 2021-05-18 温州大学新材料与产业技术研究院 Synthetic method of benzofuran compound
CN113402351B (en) * 2021-05-19 2022-06-03 南京师范大学 Method for synthesizing phenol by promoting iron catalytic oxidation of aromatic compound carbon-hydrogen bond through ligand
CN113402351A (en) * 2021-05-19 2021-09-17 南京师范大学 Method for synthesizing phenol by promoting iron catalytic oxidation of aromatic compound carbon-hydrogen bond through ligand
CN115010584A (en) * 2022-06-13 2022-09-06 南京师范大学 Method for synthesizing arone by oxidizing benzyl tertiary carbon broken bond under catalysis of iron
CN115010584B (en) * 2022-06-13 2023-12-12 南京师范大学 Method for synthesizing aromatic ketone by iron-catalyzed oxidation of tertiary carbon bond breaking of benzyl position

Also Published As

Publication number Publication date
CN107216242B (en) 2020-04-03

Similar Documents

Publication Publication Date Title
CN107216242A (en) A kind of method of iron catalysis oxidation alkyl aromatic compound synthesis aromatic aldehyde, arone and aromatic ester
Addis et al. Selective reduction of carboxylic acid derivatives by catalytic hydrosilylation
Sindhu et al. Recent developments and applications of the Cadiot–Chodkiewicz reaction
Bai et al. Hydrosilane and bismuth-accelerated palladium catalyzed aerobic oxidative esterification of benzylic alcohols with air
Xiao et al. Recent Progress in the Transition‐Metal‐Catalyzed Activation of Si− Si Bonds To Form C− Si Bonds
Seliger et al. Making the silylation of alcohols chiral: Asymmetric protection of hydroxy groups
Wakabayashi et al. Practical conversion of chlorosilanes into alkoxysilanes without generating HCl
Yang et al. Chemoselective deoxygenation of ether-substituted alcohols and carbonyl compounds by B (C 6 F 5) 3-catalyzed reduction with (HMe 2 SiCH 2) 2
Miyamoto et al. Selective Reduction of Carboxylic Acids to Aldehydes by a Ruthenium-catalyzed Reaction with 1, 2-Bis (dimethylsilyl) benzene
CN106748690A (en) A kind of iron catalysis oxidation alkene synthesizes the method for ketone
Azuma et al. Synthesis of acylsilanes by palladium-catalyzed cross-coupling reaction of thiol esters and silylzinc chlorides
Minko et al. Oxenoids in organic synthesis
CN103923114B (en) Method for catalytically synthesizing silanol
Li et al. Practical and selective bio-inspired iron-catalyzed oxidation of Si–H bonds to diversely functionalized organosilanols
CN104250236A (en) Synthetic method of gamma-alkyl oxyacyl methyl-gamma-butyrolactone and delta- alkyl oxyacyl methyl-delta-valerolactone
Gao et al. Chiral silanols: strategies and tactics for their synthesis
Kong et al. Recent Progress in Transition Metal‐Catalyzed Hydrosilane‐Mediated C− H Silylation
Zhou et al. Catalytic C (sp)–Si cross-coupling silylation of alkynyl bromides with hydrosilanes by palladium catalysis
Xu et al. Lanthanum Ate Amide-Catalyzed Regio-and Stereoselective Hydrosilylation of Internal Alkynes
CN109796293A (en) A kind of method of iron catalysis oxidation allyl aromatic compound synthesis aromatic aldehyde
Indukuri et al. Recent developments in the chemistry of vinylsiloxanes
Velasquez-Hernandez et al. Novel route to silanetriols and silanediols based on acetoxysilylalkoxides
Ogasawara et al. Effects of Silyl Substituents on the Palladium‐Catalyzed Asymmetric Synthesis of Axially Chiral (Allenylmethyl) silanes and Their SE2′ Chirality Transfer Reactions
CN110256327A (en) A kind of method of iron catalysis oxidation Benzazole compounds synthesis 2- indole ketone compound
Mateos et al. Cyclopentadienyl-silsesquioxane titanium compounds as suitable candidates for immobilization on silica-based supports

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant