CN115010584A - Method for synthesizing arone by oxidizing benzyl tertiary carbon broken bond under catalysis of iron - Google Patents

Method for synthesizing arone by oxidizing benzyl tertiary carbon broken bond under catalysis of iron Download PDF

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CN115010584A
CN115010584A CN202210658906.7A CN202210658906A CN115010584A CN 115010584 A CN115010584 A CN 115010584A CN 202210658906 A CN202210658906 A CN 202210658906A CN 115010584 A CN115010584 A CN 115010584A
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韩维
蔡恒睿
赵宏元
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Nanjing Normal University
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    • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
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Abstract

The invention discloses a method for synthesizing aryl ketone by oxidizing benzyl tertiary carbon through breaking bonds under the catalysis of iron, which takes an organic solvent and an aqueous solution as solvents and catalyzes and oxidizes the benzyl tertiary carbon to synthesize aryl ketone under the action of an oxidant, wherein the general reaction formula is shown as follows. The method uses a cheap green iron catalyst, and under the action of a green oxidant, namely hydrogen peroxide, acetonitrile and water are used as solvents to oxidize the bond breaking of a benzyl tertiary carbon into a carbonyl group to generate corresponding arone. The method for preparing the arone by catalytic oxidation reaction uses the cheap metal catalyst and the oxidant which are environment-friendly, and the reaction substrate is cheap and easy to obtain, has stable property and has better functional group compatibility. Under the optimized reaction conditions, the isolation yield of the target product is up to 96%.

Description

Method for synthesizing arone by oxidizing benzyl tertiary carbon broken bond under catalysis of iron
Technical Field
The invention belongs to the technical field of catalytic synthesis, relates to a method for synthesizing arone by iron catalysis, and particularly relates to a method for synthesizing arone by oxidizing benzyl tertiary carbon broken bonds under the catalysis of iron.
Background
The C-C bond has higher thermodynamic stability and is a great problem in the field of inert chemical bond activation; the arone is an organic synthesis intermediate with high added value, and is widely applied to the synthesis of medicines, pesticides, dyes, spices and the like. In the existing method for synthesizing arone through benzyl tertiary carbon bond breaking oxidation reaction, two reactions, namely arone synthesized through benzyl tertiary alcohol via C-C bond breaking oxidation and arone synthesized through phenylacetic acid derivatives via decarboxylation, are mainly used, for example, a copper-catalyzed reaction for synthesizing corresponding ketone through decarboxylation oxidation of benzyl tertiary carbon by alpha-substituted phenylacetic acid is reported in the song autumn theme group (J.org.chem.2014,79, 1867-one 1871), but the application of the copper-catalyzed reaction is limited by a higher reaction temperature and a limited substrate range. And benzyl isopropylAlthough the substrate for the reaction of the cleavage of the bond of benzene is widely available and inexpensive, this reaction has been reported in a small amount, for example, the use of NaNO reported by the Liuzhou Kagaku group (org. Lett.2021,23,4057-4061) in 2021 has been reported 2 The reaction condition of HCl as a key additive has the problems of generating nitration by-products and increasing the treatment difficulty after the reaction; in addition, the higher requirement of the reaction equipment by the previous reported photoelectrocatalysis reaction condition raises the problem of application cost. Therefore, from the aspects of economic factors, efficiency factors and environmental factors, the invention provides an efficient, economical, practical and environment-friendly method for preparing the arone by catalytically oxidizing the benzyl tertiary carbon to break bonds, which has considerable significance and value.
Disclosure of Invention
The purpose of the invention is as follows: aiming at the problems of complex application conditions, high equipment requirements, or the use of toxic and harmful raw materials, the generation of redundant byproducts and the like in the prior art, the invention provides a brand-new method for synthesizing arone by oxidizing benzyl tertiary carbon through bond scission under iron catalysis, wherein a simple iron catalyst and a common oxidant are used in the method, and the arone is synthesized by a method which is mild in conditions, high-efficiency and environment-friendly and only needs the requirements of conventional kettle type equipment; effectively solves the problems of higher reaction temperature, large reaction substrate dosage, high practical reaction cost and the like in the existing aromatic ketone synthesis method.
The technical scheme is as follows: in order to achieve the purpose, the method for synthesizing the aryl ketone by oxidizing the benzyl tertiary carbon through bond scission catalyzed by iron uses an organic solvent and an aqueous solution as solvents, and under the action of an oxidizing agent, the aryl ketone is synthesized by oxidizing the benzyl tertiary carbon through iron catalysis, and the reaction general formula is as follows:
Figure BDA0003689847890000011
in the formula R 1 And R 2 Each is independently selected from any one of alkyl, alkoxy, benzyl, aryl and halogen;
ar represents an aryl group or a substituted aryl group.
Wherein, the aryl group represented by Ar is substituted or unsubstituted phenyl, biphenyl, naphthyl, anthryl, phenanthryl or pyrenyl.
The substituent on Ar is hydrogen on a mono-substituted or multi-substituted aromatic ring, and the substituent is selected from hydrogen, C1-C12 straight-chain or branched-chain alkyl, C1-C12 straight-chain or branched-chain alkoxy, C3-C12 cycloalkyl, phenyl, fluorine, chlorine, bromine, hydroxyl, carboxyl, carbomethoxy, carbethoxy, propisocarbonyl, cyano, nitro, formyl or boric acid group.
Wherein the organic solvent is any one of acetonitrile, ethanol and DMSO.
Preferably, the organic solvent is acetonitrile.
Wherein the reaction temperature is 20-100 ℃, and the reaction time is 0.5-60 hours. The preferred temperatures are: 50 to 100 ℃.
Wherein the molar ratio of the benzyl tertiary carbon to the oxidant to the iron catalyst is 1 (1-10) to 0.04-0.5.
Wherein the weight ratio of the benzyl tertiary carbon to the acetonitrile to the water is 1 (5-1000) to (5-1000).
Wherein, the iron catalyst comprises any one of ferrous chloride, ferrous bromide, ferrous iodide, ferrous fluoride, ferrous oxide, ferrous acetate, ferrous oxalate, ferrous acetylacetonate, ferrous phthalocyanine, ferrous phosphate, ferrocene, ferric chloride, ferric bromide, ferric fluoride, ferric acetylacetonate, ferric trifluoromethanesulfonate, ferric tetrafluoroborate, ferric p-toluenesulfonate, ferric acrylate, ferric ethoxide, ferbamate, ferric isopropoxide, 2-ethyl acetate, ferroferric dodecacarbonyl, ferric oxide and ferric tris (trifluoro-2, 4-pentanedionate) or the combination thereof.
Wherein, the oxidant comprises any one or the combination of hydrogen peroxide, tert-butyl hydroperoxide, di-tert-butyl peroxide, potassium peroxysulfate, potassium peroxypyrophosphate, potassium persulfate, sodium persulfate, ammonium persulfate, benzoyl peroxide, potassium peroxymonosulfonate and 3-chloroperoxybenzoic acid.
Preferably, air and oxygen may be used as the atmosphere gas when the oxidizing agent is used.
The design principle is as follows: the invention utilizes the redox ability of transition metal iron to catalyze an oxidant to form an active intermediate, then the active intermediate captures hydrogen on a benzyl tertiary carbon and continuously acts with the hydrogen to form a benzyl peroxide intermediate, and then the benzyl peroxide intermediate is homocracked to form an alkoxy radical, and a branched alkyl free radical is removed through a beta-cracking process to form a final product. At present, the method for directly forming aryl ketone by breaking carbon-carbon bond at benzyl position is mostly seen in a photoelectrocatalysis mode, and strong oxidant or organic solvent is necessary, or additional side reaction products exist to influence the post-treatment efficiency. The method uses a cheap, environment-friendly and low-toxicity iron catalyst, can use easily-obtained nontoxic oxidant, does not add or add few auxiliary agents, has simple kettle type reaction conditions, does not have side reaction or a small amount of side reaction, does not have a reaction method with similar conditions at present, in addition, a substrate does not need a carbonyl source, a corresponding product is obtained by directly oxidizing aryl alkane, and the alkyl aromatic compound is cheaper and more stable, so that the separation yield of a target product is up to 96%.
Has the beneficial effects that: compared with the prior art, the invention has the following advantages:
(1) the invention provides a new method for preparing arone by iron-catalyzed bond-breaking oxidation reaction of benzyl tertiary carbon in a mixed solvent of acetonitrile and water, which has the advantages of wide substrate source, low price, low raw material feeding amount, no need of pre-functionalization, simple and easily obtained catalyst and oxidant and high reaction yield; on the basis of the advantages, the method has the advantages of simple and practical reaction mode, no additional by-product, simple post-treatment, low equipment requirement and the like, and only needs a cheap iron catalyst and simple stirring reaction conditions;
(2) in the method for synthesizing the aromatic ketone, the compatibility of the substrate functional group is good, and the application range of the substrate is wide; under the optimized reaction condition, the method is simple and feasible, the aromatic ketone is directly obtained by one-step method, the yield of the target product after separation is up to 96%, the raw material source for preparing the aromatic ketone is greatly expanded, and the method is a universal, efficient, economic and environment-friendly method for synthesizing the aromatic ketone.
(3) The method can be suitable for complex active molecular substrates, and active groups do not need to be protected, so that the method has the remarkable advantage and is expected to have important application in drug synthesis.
Detailed Description
The invention will be better understood from the following examples. However, those skilled in the art will readily appreciate that the description of the embodiments is only for illustrating the present invention and should not be taken as limiting the invention as detailed in the claims.
Example 1
Compound 1: a25 mL reaction flask was charged with ferrous chloride (0.025mmol), potassium persulfate (0.75mmol), p-bromocumene (0.25mmol), acetonitrile (1mL), and water (1mL) in that order, and the reaction mixture was reacted at 80 ℃ for 3 h. After the reaction, 10mL of saturated brine was added, and the mixture was extracted with ether (10 mL. times.3), and the organic phases were combined, evaporated under reduced pressure to remove the solvent, and then subjected to column chromatography to obtain 93% yield.
1 H NMR(400MHz,CDCl 3 )δ:7.85-7.82(m,2H),7.64-7.60(m,2H),2.60ppm(s,3H)； 13 C NMR(100MHz,CDCl 3 )δ:196.9,135.8,131.8,129.8,128.2,26.5ppm
Example 2
Compound 2: a25 mL reaction flask was charged with ferrous chloride (0.015mmol), hydrogen peroxide (0.75mmol), potassium persulfate (0.25mmol), o-bromocumene (0.25mmol), acetonitrile (1mL), and water (1mL) in that order, and the reaction mixture was reacted at 80 ℃ for 3 h. After the reaction, 10mL of saturated brine was added, and the mixture was extracted with ether (10 mL. times.3), and the organic phases were combined, evaporated under reduced pressure to remove the solvent, and then subjected to column chromatography to obtain a yield of 65%.
Example 3
Compound 3: a25 mL reaction flask was charged with ferrous chloride (0.010mmol), hydrogen peroxide (0.75mmol), m-bromocumene (0.25mmol), acetonitrile (1mL), and water (1mL) in this order, and the reaction mixture was reacted at 80 ℃ for 17 h. After the reaction, 10mL of saturated brine was added, and the mixture was extracted with ether (10 mL. times.3), and the organic phases were combined, evaporated under reduced pressure to remove the solvent, and then subjected to column chromatography to obtain 82% yield.
1 H NMR(400MHz,CDCl 3 )δ:8.10-8.08(m,1H),7.90-7.87(m,1H),7.72-7.69(m,1H),7.39-7.33(m,1H),2.60ppm(s,3H)； 13 C NMR(100MHz,CDCl 3 )δ:196.6,138.6,135.9,131.3,130.1,126.8,122.8,26.5ppm.
Example 4
Compound 4: ferrous chloride (0.020mmol), hydrogen peroxide (0.75mmol), potassium persulfate (0.25mmol), 1-bromo-2, 4, 6-triisopropylbenzene (0.25mmol), acetonitrile (1mL), and water (1mL) were sequentially added to a 25mL reaction flask, and the reaction mixture was reacted at 80 ℃ for 24 h. After the reaction, 10mL of saturated brine was added, and the mixture was extracted with ether (10 mL. times.3), and the organic phases were combined, evaporated under reduced pressure to remove the solvent, and then subjected to column chromatography to obtain a yield of 65%.
Example 5
Compound 5: ferrous chloride (0.020mmol), hydrogen peroxide (0.75mmol), p-chlorocumene (0.25mmol), acetonitrile (1mL), and water (1mL) were sequentially added to a 25mL reaction flask, and the reaction mixture was reacted at 80 ℃ for 9 h. After the reaction, 10mL of saturated brine was added, and the mixture was extracted with ether (10 mL. times.3), the organic phases were combined, and the solvent was distilled off under reduced pressure, followed by column chromatography to obtain 78% yield.
1 H NMR(400MHz,CDCl 3 )δ:7.91(d,J＝8.57Hz,2H),7.45(d,J＝8.57Hz,2H),2.61ppm(s,3H)； 13 C NMR(100MHz,CDCl 3 )δ:196.9,139.5,135.3,129.7,128.8,26.6ppm.
Example 6
Compound 6: a25 mL reaction flask was charged with ferrous chloride (0.010mmol), hydrogen peroxide (0.75mmol), potassium persulfate (0.25mmol), 1, 3-diisopropylbenzene (0.25mmol), acetonitrile (1mL), and water (1mL) in that order, and the reaction mixture was reacted at 80 ℃ for 6 h. After the reaction, 10mL of saturated brine was added, and the mixture was extracted with ether (10 mL. times.3), and the organic phases were combined, evaporated under reduced pressure to remove the solvent, and then subjected to column chromatography to obtain a yield of 70%.
Example 7
Compound 7: a25 mL reaction flask was charged with ferrous chloride (0.025mmol), hydrogen peroxide (0.75mmol), potassium persulfate (0.25mmol), 1, 4-diisopropylbenzene (0.25mmol), acetonitrile (1mL), and water (1mL) in that order, and the reaction mixture was reacted at 80 ℃ for 6 h. After the reaction, 10mL of saturated brine was added, and the mixture was extracted with ether (10 mL. times.3), and the organic phases were combined, evaporated under reduced pressure to remove the solvent, and then subjected to column chromatography to obtain a yield of 70%.
Example 8
Compound 8: a25 mL reaction flask was charged with ferrous chloride (0.030mmol), hydrogen peroxide (0.75mmol), potassium persulfate (0.25mmol), 1, 2-diisopropylbenzene (0.25mmol), acetonitrile (1mL), and water (1mL) in that order, and the reaction mixture was reacted at 80 ℃ for 3 h. After the reaction, 10mL of saturated brine was added, and the mixture was extracted with ether (10 mL. times.3), and the organic phases were combined, evaporated under reduced pressure to remove the solvent, and then subjected to column chromatography to obtain 67% yield.
Example 9
Compound 9: a25 mL reaction flask was charged with ferrous chloride (0.035mmol), hydrogen peroxide (0.75mmol), s-triisopropylbenzene (0.25mmol), acetonitrile (1mL), and water (1mL) in that order, and the reaction mixture was reacted at 80 ℃ for 3 h. After the reaction, 10mL of saturated brine was added, and the mixture was extracted with ether (10 mL. times.3), and the organic phases were combined, evaporated under reduced pressure to remove the solvent, and then subjected to column chromatography to obtain 74% yield.
Example 10
Compound 10: a25 mL reaction flask was charged with ferrous chloride (0.040mmol), hydrogen peroxide (0.75mmol), potassium persulfate (0.25mmol), 2-ethoxycumene (0.25mmol), acetonitrile (1mL), and water (1mL) in that order, and the reaction mixture was reacted at 80 ℃ for 12 h. After the reaction, 10mL of saturated brine was added, and the mixture was extracted with ether (10 mL. times.3), and the organic phases were combined, evaporated under reduced pressure to remove the solvent, and then subjected to column chromatography to obtain 80% yield.
Example 11
Compound 11: a25 mL reaction flask was charged with ferrous bromide (0.035mmol), oxygen (1atm), hydrogen peroxide (0.75mmol), potassium persulfate (0.25mmol), 4-ethoxycumene (0.25mmol), acetonitrile (1mL), and water (1mL) in this order, and the reaction mixture was reacted at 80 ℃ for 12 h. After the reaction, 10mL of saturated saline was added, extraction was performed with diethyl ether (10 mL. times.3), the organic phases were combined, the solvent was distilled off under reduced pressure, and column chromatography was performed to obtain 80% yield
1 H NMR(400MHz,CDCl 3 )δ:7.95(d,J＝8.44Hz,2H),6.94(d,J＝8.44Hz,2H),4.13(q,J＝6.73Hz,2H),2.56(s,3H),1.47ppm(t,J＝6.82Hz,3H)； 13 C NMR(100MHz,CDCl 3 )δ:196.8,162.7,130.5,130.1,114.0,63.7,26.3,14.6ppm
Example 12
Compound 12: a25 mL reaction flask was charged with ferrous iodide (0.025mmol), di-tert-butyl peroxide (0.75mmol), 4-isopropylcumyl peroxide (0.25mmol), acetonitrile (1mL), and water (1mL) in that order, and the reaction mixture was reacted at 100 ℃ for 20 h. After the reaction, 10mL of saturated brine was added, and the mixture was extracted with ether (10 mL. times.3), and the organic phases were combined, evaporated under reduced pressure to remove the solvent, and then subjected to column chromatography to obtain 85% yield.
Example 13
Compound 13: a25 mL reaction flask was charged with ferrous fluoride (0.040mmol), t-butyl hydroperoxide (0.75mmol), air (1atm), p-isopropylphenol benzoate (0.25mmol), acetonitrile (1mL), and water (1mL) in that order, and the reaction mixture was reacted at 80 ℃ for 12 h. After the reaction, 10mL of saturated brine was added, and the mixture was extracted with ether (10 mL. times.3), and the organic phases were combined, evaporated under reduced pressure to remove the solvent, and then subjected to column chromatography to obtain 80% yield.
1 H NMR(400MHz,CDCl 3 )δ:8.23(d,J＝7.98Hz,2H),8.05(d,J＝8.53Hz,2H),7.69(t,J＝7.44Hz,1H),7.56(t,J＝7.84Hz,2H),7.37(dt,J 1 ＝8.68Hz,J 2 ＝2.23Hz,2H),2.64ppm(s,3H)； 13 C NMR(100MHz,CDCl 3 )δ:196.8,164.5,154.5,134.6,133.8,130.1,129.9,128.9,128.6,121.8,26.1ppm
Example 14
Compound 14: a25 mL reaction flask was charged with ferrous oxide (0.050mmol), sodium persulfate (2.50mmol), 2-methyl-4-ethoxycumene (0.25mmol), acetonitrile (1mL), and water (1mL) in that order, and the reaction mixture was reacted at 20 ℃ for 17 h. After the reaction, 10mL of saturated brine was added, and the mixture was extracted with ether (10 mL. times.3), the organic phases were combined, and the solvent was distilled off under reduced pressure, followed by column chromatography to obtain a yield of 65%.
Example 15
Compound 15: a25 mL reaction flask was charged with ferrous acetylacetonate (0.020mmol), ferrous phthalocyanine (0.020mmol), potassium peroxypyrophosphate (0.75mmol), 3-isopropoxy-4-cymene (0.25mmol), acetonitrile (1mL), and water (1mL) in this order, and the reaction mixture was reacted at 20 ℃ for 48 hours. After the reaction, 10mL of saturated brine was added, and the mixture was extracted with ether (10 mL. times.3), and the organic phases were combined, evaporated under reduced pressure to remove the solvent, and then subjected to column chromatography to obtain a yield of 70%.
1 H NMR(400MHz,CDCl 3 )δ:7.76(q,J＝3.12Hz,1H),6.78-6.75(m,2H),3.86(d,J＝6.97Hz,2H),2.57(s,3H),2.56(s,3H),1.32-1.26(m,1H),0.70-0.66(m,2H),0.40-0.36ppm(m,2H)； 13 C NMR(100MHz,CDCl 3 )δ:199.5,161.4,142.2,132.6,129.7,117.9,111.1,72.8,29.1,22.7,10.1,3.2ppm
Example 16
Compound 16: a25 mL reaction flask was charged with ferrous oxide (0.050mmol), benzoyl peroxide (0.25mmol), 2-methyl-4-ethoxycumene (0.25mmol), acetonitrile (1mL), and water (1mL) in that order, and the reaction mixture was reacted at 20 ℃ for 17 h. After the reaction, 10mL of saturated brine was added, and the mixture was extracted with ether (10 mL. times.3), and the organic phases were combined, evaporated under reduced pressure to remove the solvent, and then subjected to column chromatography to obtain a yield of 65%.
Example 17
Compound 17: in a 25mL reaction flask, dodecacarbonyl ferroferric oxide (0.020mmol), potassium peroxymonosulfonate (0.75mmol), 4-isopropylphenol 2-fluoro-4-iodobenzoate (0.25mmol), acetonitrile (1mL) and water (1mL) are sequentially added, and the reaction mixture reacts for 60 hours at 80 ℃. After the reaction, 10mL of saturated brine was added, and the mixture was extracted with ether (10 mL. times.3), and the organic phases were combined, evaporated under reduced pressure to remove the solvent, and then subjected to column chromatography to obtain a yield of 60%.
Example 18
Compound 18: a25 mL reaction flask was charged with ferrous chloride (0.015mmol), hydrogen peroxide (2.0mmol), ethyl p-isopropylbenzoate (0.25mmol), acetonitrile (1mL), and water (1mL) in that order, and the reaction mixture was reacted at 80 ℃ for 24 h. After the reaction, 10mL of saturated brine was added, and the mixture was extracted with ether (10 mL. times.3), and the organic phases were combined, evaporated under reduced pressure to remove the solvent, and then subjected to column chromatography to obtain a yield of 57%.
Example 19
Compound 19: a25 mL reaction flask was charged with ferric tetrafluoroborate (0.015mmol), ammonium persulfate (1.75mmol), p-isopropylphenylboronic acid (0.25mmol), acetonitrile (1mL), and water (1mL) in this order, and the reaction mixture was reacted at 80 ℃ for 36 h. After the reaction, 10mL of saturated brine was added, and the mixture was extracted with ether (10 mL. times.3), and the organic phases were combined, evaporated under reduced pressure to remove the solvent, and then subjected to column chromatography to obtain a yield of 65%.
Example 20
Compound 20: ferric triflate (0.015mmol), m-chloroperoxybenzoic acid (1.25mmol), m-isopropylphenylboronic acid (0.25mmol), acetonitrile (1mL), and water (1mL) were added sequentially to a 25mL reaction flask, and the reaction mixture was reacted at 80 ℃ for 39 h. After the reaction, 10mL of saturated brine was added, and the mixture was extracted with ether (10 mL. times.3), and the organic phases were combined, evaporated under reduced pressure to remove the solvent, and then subjected to column chromatography to obtain 62% yield.
Example 21
Compound 21: a25 mL reaction flask was charged with tris (trifluoro-2, 4-pentanedionato) iron (0.015mmol), hydrogen peroxide (1.50mmol), 2,4, 6-triisopropylphenylboronic acid (0.25mmol), acetonitrile (1mL), and water (1mL) in that order, and the reaction mixture was reacted at 80 ℃ for 36 hours. After the reaction, 10mL of saturated brine was added, and the mixture was extracted with ether (10 mL. times.3), and the organic phases were combined, evaporated under reduced pressure to remove the solvent, and then subjected to column chromatography to obtain a 40% yield.
Example 22
Compound 22: a25 mL reaction flask was charged with ferbam (0.015mmol), hydrogen peroxide (1.0mmol), 3-phenylpentane (0.25mmol), acetonitrile (1mL), water (1mL) in that order, and the reaction mixture was reacted at 80 ℃ for 1 h. After the reaction, 10mL of saturated brine was added, and the mixture was extracted with ether (10 mL. times.3), and the organic phases were combined, evaporated under reduced pressure to remove the solvent, and then subjected to column chromatography to obtain 92% yield.
1 H NMR(400MHz,CDCl 3 )δ:7.97(d,J＝7.95Hz,2H),7.55(t,J＝7.34Hz,1H),7.46(t,J＝7.64Hz,2H),3.00(q,J＝7.24Hz,2H),1.23ppm(t,J＝7.24Hz,3H)； 13 C NMR(100MHz,CDCl 3 )δ:200.7,136.8,132.8,128.4,127.9,31.7,8.1ppm
Example 23
Compound 23: a25 mL reaction flask was charged with ferric bromide (0.015mmol), hydrogen peroxide (0.50mmol), 2- (4-pentyloxyphenyl) butane (0.25mmol), acetonitrile (1mL), and water (1mL) in that order, and the reaction mixture was reacted at 80 ℃ for 48 h. After the reaction, 10mL of saturated brine was added, and the mixture was extracted with ether (10 mL. times.3), and the organic phases were combined, evaporated under reduced pressure to remove the solvent, and then subjected to column chromatography to obtain a yield of 65%.
1 H NMR(400MHz,CDCl 3 )δ:7.94(d,J＝8.81Hz,2H),6.93(d,J＝8.81Hz,2H),4.03(t,J＝6.57Hz,2H),2.56(s,3H),1.85(quint,J＝6.99Hz,2H),1.49-1.35(m,4H),0.96ppm(t,J＝7.12Hz,3H)； 13 C NMR(100MHz,CDCl 3 )δ:196.7,163.0,130.4,129.9,114.0,68.1,28.7,28.0,26.2,22.3,13.9ppm
Example 24
Compound 24: a25 mL reaction flask was charged with ferric fluoride (0.05mmol), hydrogen peroxide (0.50mmol), 1, 2-diphenylbutane (0.25mmol), acetonitrile (3mL), and water (2mL) in that order, and the reaction mixture was reacted at 80 ℃ for 9 h. After the reaction, 10mL of saturated brine was added, and the mixture was extracted with ether (10 mL. times.3), and the organic phases were combined, evaporated under reduced pressure to remove the solvent, and then subjected to column chromatography to obtain 75% yield.
Example 25
Compound 25: a25 mL reaction flask was charged with ferric acetylacetonate (0.015mmol), hydrogen peroxide (0.75mmol), potassium persulfate (0.25mmol), 1-methoxy-4- (1-phenylethyl) benzene (0.25mmol), acetonitrile (1mL), and water (1mL) in that order, and the reaction mixture was reacted at 50 ℃ for 0.5 h. After the reaction, 10mL of saturated brine was added, and the mixture was extracted with ether (10 mL. times.3), and the organic phases were combined, evaporated under reduced pressure to remove the solvent, and then subjected to column chromatography to obtain a yield of 35%.
1 H NMR(400MHz,CDCl 3 )δ:7.87(d,J＝9.0Hz,2H),7.73(d,J＝7.5Hz,2H),7.69-7.53(m,1H),7.54-7.41(m,2H),6.99(d,J＝8.9Hz,2H),3.91ppm(s,3H)； 13 C NMR(100MHz,CDCl 3 )δ:195.5,163.1,138.2,132.5,131.8,130.0,129.7,128.1,113.5,55.4ppm
Example 26
Compound 26: a25 mL reaction flask was charged with iron isopropoxide (0.05mmol), hydrogen peroxide (0.75mmol), potassium persulfate (0.25mmol), triphenylmethane (0.25mmol), acetonitrile (5mL), water (5mL) in that order, and the reaction mixture was reacted at 50 ℃ for 1.5 h. After the reaction, 10mL of saturated brine was added, and the mixture was extracted with ether (10 mL. times.3), the organic phases were combined, and the solvent was distilled off under reduced pressure, followed by column chromatography to obtain a yield of 87%.
1 H NMR(400MHz,CDCl 3 )δ:7.80-7.78(m,4H),7.60-7.55(m,2H),7.49-7.45ppm(m,4H)； 13 C NMR(400MHz,CDCl 3 )δ:196.76,137.59,132.40,130.05,128.26ppm
Example 27
Compound 27: a25 mL reaction flask was charged with ferric p-toluenesulfonate (0.015mmol), hydrogen peroxide (0.75mmol), potassium persulfate (0.25mmol), tris (4-methoxyphenyl) methane (0.25mmol), acetonitrile (1mL), and water (1mL) in this order, and the reaction mixture was reacted at 50 ℃ for 24 hours. After the reaction, 10mL of saturated brine was added, and the mixture was extracted with ether (10 mL. times.3), and the organic phases were combined, evaporated under reduced pressure to remove the solvent, and then subjected to column chromatography to obtain 85% yield.
Example 28
Compound 28: a100 mL reaction flask was charged with iron oxalate (0.05mmol), hydrogen peroxide (0.75mmol), potassium persulfate (0.25mmol), 2-biphenyl-3-ethoxypropane (0.25mmol), acetonitrile (15mL), and water (10mL) in this order, and the reaction mixture was reacted at 100 ℃ for 48 hours. After the reaction, 10mL of saturated brine was added, and the mixture was extracted with ether (10 mL. times.3), and the organic phases were combined, evaporated under reduced pressure to remove the solvent, and then subjected to column chromatography to obtain 50% yield.
Example 29
Compound 29: a100 mL reaction flask was charged with ferrous phosphate (0.05mmol), hydrogen peroxide (0.75mmol), potassium persulfate (0.25mmol), 2- (1-chloroethyl) naphthalene (0.25mmol), acetonitrile (15mL), and water (5mL) in this order, and the reaction mixture was reacted at 100 ℃ for 48 h. After the reaction, 10mL of saturated brine was added, and the mixture was extracted with ether (10 mL. times.3), and the organic phases were combined, evaporated under reduced pressure to remove the solvent, and then subjected to column chromatography to obtain 55% yield.
Example 30
Compound 30: a100 mL reaction flask was charged with ferric chloride (0.05mmol), hydrogen peroxide (0.75mmol), potassium persulfate (0.75mmol), 2-isopropylanthracene (0.25mmol), acetonitrile (15mL), and water (2mL) in that order, and the reaction mixture was reacted at 100 ℃ for 48 h. After the reaction, 10mL of saturated brine was added, and the mixture was extracted with ether (10 mL. times.3), and the organic phases were combined, evaporated under reduced pressure to remove the solvent, and then subjected to column chromatography to obtain a yield of 45%.
Example 31
Compound 31: to a 100mL reaction flask were added successively ferric ethoxide (0.05mmol), hydrogen peroxide (0.25mmol), potassium persulfate (0.75mmol), 3-isopropylphenanthrene (0.25mmol), acetonitrile (15mL), and water (10mL), and the reaction mixture was reacted at 80 ℃ for 48 h. After the reaction, 10mL of saturated brine was added, and the mixture was extracted with ether (10 mL. times.3), and the organic phases were combined, evaporated under reduced pressure to remove the solvent, and then subjected to column chromatography to obtain 50% yield.
Example 32
Compound 32: 2-Ethyl iron acetate (0.05mmol), hydrogen peroxide (0.75mmol), potassium persulfate (0.75mmol), 2-isopropylpyrene (0.25mmol), acetonitrile (15mL), water (1.5mL) were added sequentially to a 50mL reaction flask and the reaction mixture was reacted at 120 ℃ for 48 h. After the reaction, 10mL of saturated brine was added, and the mixture was extracted with ether (10 mL. times.3), and the organic phases were combined, evaporated under reduced pressure to remove the solvent, and then subjected to column chromatography to obtain a yield of 45%.
Example 33
Compound 33: a25 mL reaction flask was charged with iron oxide (0.05mmol), hydrogen peroxide (0.75mmol), potassium persulfate (0.75mmol), 2- (4-dodecylphenyl) butane (0.25mmol), acetonitrile (1mL), and water (1mL) in that order, and the reaction mixture was reacted at 50 ℃ for 1 h. After the reaction, 10mL of saturated brine was added, and the mixture was extracted with ether (10 mL. times.3), and the organic phases were combined, evaporated under reduced pressure to remove the solvent, and then subjected to column chromatography to obtain 90% yield.
Example 34
Compound 34: ferrous chloride (0.05mmol), hydrogen peroxide (1.75mmol), potassium persulfate (0.75mmol), 3,4, 5-trimethoxycumene (0.25mmol), acetonitrile (0.5mL), water (0.5mL) were added to a 10mL reaction tube in this order, and the reaction mixture was reacted at 50 ℃ for 60 hours. After the reaction, 10mL of saturated brine was added, and the mixture was extracted with ether (10 mL. times.3), and the organic phases were combined, evaporated under reduced pressure to remove the solvent, and then subjected to column chromatography to obtain 55% yield.
Example 35
Compound 35: a25 mL reaction flask was charged with ferrous chloride (0.05mmol), hydrogen peroxide (1.75mmol), 1-bromo-1- (4-dodecyloxyphenyl) ethane (0.25mmol), acetonitrile (1.5mL), water (0.5mL) in that order, and the reaction mixture was reacted at 50 ℃ for 1.5 h. After the reaction, 10mL of saturated brine was added, and the mixture was extracted with ether (10 mL. times.3), and the organic phases were combined, evaporated under reduced pressure to remove the solvent, and then subjected to column chromatography to obtain 89% yield.
Example 36
Compound 36: ferrous chloride (0.05mmol), hydrogen peroxide (0.75mmol), potassium persulfate (0.75mmol), 4-isopropylcyclohexyl ether (0.25mmol), acetonitrile (15mL), water (15mL) were added sequentially to a 100mL reaction flask and the reaction mixture was reacted at 200 ℃ for 9 h. After the reaction, 10mL of saturated brine was added, and the mixture was extracted with ether (10 mL. times.3), the organic phases were combined, and the solvent was distilled off under reduced pressure, followed by column chromatography to obtain 80% yield.
Example 37
Compound 37: a25 mL reaction flask was charged with ferrous bromide (0.05mmol), hydrogen peroxide (0.75mmol), potassium persulfate (0.75mmol), 4-isopropylcyclooctylether (0.25mmol), acetonitrile (1.5mL), and water (1mL) in that order, and the reaction mixture was reacted at 100 ℃ for 12 h. After the reaction, 10mL of saturated brine was added, and the mixture was extracted with ether (10 mL. times.3), and the organic phases were combined, evaporated under reduced pressure to remove the solvent, and then subjected to column chromatography to obtain 85% yield.
Example 38
Compound 38: a25 mL reaction flask was charged with ferrous phthalocyanine (0.05mmol), hydrogen peroxide (0.75mmol), potassium persulfate (1.75mmol), 3- (2-fluoro-4-iodophenyl) pentane (0.25mmol), acetonitrile (2.5mL), and water (5.0mL) in that order, and the reaction mixture was reacted at 80 ℃ for 24 h. After the reaction, 10mL of saturated brine was added, and the mixture was extracted with ether (10 mL. times.3), and the organic phases were combined, evaporated under reduced pressure to remove the solvent, and then subjected to column chromatography to obtain a yield of 78%.
Example 39
Compound 39: a25 mL reaction flask was charged with ferrous acetylacetonate (0.05mmol), hydrogen peroxide (0.75mmol), potassium persulfate (0.75mmol), 2-isopropoxy-2- (4-hydroxyphenyl) ethane (0.25mmol), acetonitrile (1.5mL), and water (2.5mL) in that order, and the reaction mixture was reacted at 50 ℃ for 3 h. After the reaction, 10mL of saturated brine was added, and the mixture was extracted with ether (10 mL. times.3), and the organic phases were combined, evaporated under reduced pressure to remove the solvent, and then subjected to column chromatography to obtain a yield of 65%.
Example 40
Compound 40: a25 mL reaction flask was charged with ferrous phthalocyanine (0.05mmol), hydrogen peroxide (0.75mmol), potassium persulfate (1.25mmol), 2- (4-carboxyphenyl) pentane (0.25mmol), acetonitrile (1.5mL), and water (2.5mL) in that order, and the reaction mixture was reacted at 80 ℃ for 24 h. After the reaction, 10mL of saturated brine was added, and the mixture was extracted with ether (10 mL. times.3), and the organic phases were combined, evaporated under reduced pressure to remove the solvent, and then subjected to column chromatography to obtain a yield of 70%.
EXAMPLE 41
Compound 41: a25 mL reaction flask was charged with iron acetylacetonate (0.025mmol), ferrocene (0.025mmol), hydrogen peroxide (0.75mmol), potassium persulfate (0.75mmol), propyl 4-isopropylbenzoate (0.25mmol), acetonitrile (1.5mL), and water (0.5mL) in that order, and the reaction mixture was reacted at 50 ℃ for 24 h. After the reaction, 10mL of saturated brine was added, and the mixture was extracted with ether (10 mL. times.3), and the organic phases were combined, evaporated under reduced pressure to remove the solvent, and then subjected to column chromatography to obtain 75% yield.
Example 42
Compound 42: iron acetylacetonate (0.025mmol), ferrocene (0.025mmol), hydrogen peroxide (0.75mmol), potassium persulfate (0.75mmol), methyl 4-isopropylbenzoate (0.25mmol), acetonitrile (1mL), and water (0.25mL) were sequentially added to a 10mL reaction tube, and the reaction mixture was reacted at 50 ℃ for 24 h. After the reaction, 10mL of saturated brine was added, and the mixture was extracted with ether (10 mL. times.3), and the organic phases were combined, evaporated under reduced pressure to remove the solvent, and then subjected to column chromatography to obtain a yield of 77%.
Example 43
Compound 41: a25 mL reaction flask was charged with ferric acetylacetonate (0.025mmol), hydrogen peroxide (0.25mmol), potassium peroxysulfate (2.25mmol), 4-formylcumene (0.25mmol), acetonitrile (5.0mL), and water (5.0mL) in that order, and the reaction mixture was reacted at 150 ℃ for 9 h. After the reaction, 10mL of saturated brine was added, and the mixture was extracted with ether (10 mL. times.3), and the organic phases were combined, evaporated under reduced pressure to remove the solvent, and then subjected to column chromatography to obtain a yield of 79%.
Example 44
Compound 44: a25 mL reaction flask was charged with ferrocene (0.05mmol), hydrogen peroxide (2.5mmol), 4-cyanocumene (0.25mmol), acetonitrile (2.5mL), and water (2.5mL) in that order, and the reaction mixture was reacted at 150 ℃ for 48 h. After the reaction, 10mL of saturated brine was added, and the mixture was extracted with ether (10 mL. times.3), and the organic phases were combined, evaporated under reduced pressure to remove the solvent, and then subjected to column chromatography to obtain 50% yield.
Example 45
Compound 45: ferrocene (0.05mmol), hydrogen peroxide (2.5mmol), 4-nitrocumene (0.25mmol), acetonitrile (15.0mL), and water (15.0mL) are sequentially added to a 100mL reaction flask and the reaction mixture is reacted at 150 ℃ for 48 h. After the reaction, 10mL of saturated brine was added, and the mixture was extracted with ether (10 mL. times.3), and the organic phases were combined, evaporated under reduced pressure to remove the solvent, and then subjected to column chromatography to obtain a yield of 65%.
Example 46
Compound 46: a25 mL reaction flask was charged with ferrous chloride (0.025mmol), hydrogen peroxide (0.75mmol), 3-phenylhexadecane (0.25mmol), acetonitrile (1.5mL), and water (1.5mL) in that order, and the reaction mixture was reacted at 50 ℃ for 3 h. After the reaction, 10mL of saturated brine was added, and the mixture was extracted with ether (10 mL. times.3), and the organic phases were combined, evaporated under reduced pressure to remove the solvent, and then subjected to column chromatography to obtain 96% yield.
1 H NMR(400MHz,CDCl 3 )δ:7.97(d,J＝7.95Hz,2H),7.55(t,J＝7.34Hz,1H),7.46(t,J＝7.64Hz,2H),3.00(q,J＝7.24Hz,2H),1.23ppm(t,J＝7.24Hz,3H)； 13 C NMR(100MHz,CDCl 3 )δ:200.7,136.8,132.8,128.4,127.9,31.7,8.1ppm
Example 47
Compound 47: a25 mL reaction flask was charged with ferrous chloride (0.025mmol), hydrogen peroxide (0.75mmol), potassium persulfate (0.25mmol), cholic acid p-bromoisopropylphenol ester (0.25mmol), acetonitrile (2.0mL), water (1.0mL) in that order, and the reaction mixture was reacted at 80 ℃ for 15 h. After the reaction, 10mL of saturated brine was added, and the mixture was extracted with ether (10 mL. times.3), and the organic phases were combined, evaporated under reduced pressure to remove the solvent, and then subjected to column chromatography to obtain a yield of 30%.
1 H NMR(400MHz,CDCl 3 )δ:8.0(d,J＝8.50Hz,2H),7.19(d,J＝8.56Hz,2H),3.99(d,J＝52.83Hz,2H),3.46(s,1H),3.34(brs,3H),2.60(s,3H),2.25-2.19(m,2H),1.94-1.26(m,20H),1.10-0.97(m,5H),0.92(d,J＝14.22Hz,3H),0.72ppm(d,J＝10.44Hz,3H)； 13 C NMR(100MHz,CDCl 3 )δ:196.9,172.1,154.4,134.3,129.8,121.7,73.0,71.8,68.4,46.8,46.4,46.3,41.5,41.3,39.3,35.2,34.7,31.3,30.9,30.6,30.2,29.6,28.1,27.4,26.5,26.2,23.1,22.3,17.3,12.4ppm
Example 48
Compound 48: ferrous chloride (0.025mmol), hydrogen peroxide (0.75mmol), potassium persulfate (0.25mmol), p-bromoisopropylphenol glycyrrhetinate (0.25mmol), acetonitrile (2.0mL), and water (1.0mL) were sequentially added to a 25mL reaction flask, and the reaction mixture was reacted at 80 ℃ for 20 h. After the reaction, 10mL of saturated brine was added, and the mixture was extracted with ether (10 mL. times.3), and the organic phases were combined, evaporated under reduced pressure to remove the solvent, and then subjected to column chromatography to obtain a yield of 45%.
Examples 1-48 Experimental results corresponding to specific methods for synthesizing aromatic aldehydes are listed in Table 1:
TABLE 1 iron catalysis Synthesis of aryl ketones by bond cleavage of the tertiary carbon at the benzylic position [a]
Figure BDA0003689847890000121
Figure BDA0003689847890000131
Figure BDA0003689847890000141
Figure BDA0003689847890000151
Figure BDA0003689847890000161
Figure BDA0003689847890000171
[a] The reaction conditions are shown in the examples; [b] column isolation yield.
Example 49
Compound 1: ferrous chloride (0.02mmol), potassium persulfate (0.5mmol), p-bromocumene (0.5mmol), acetonitrile (0.64mL), and water (0.5mL) were sequentially added to a 10mL reaction tube, and the reaction mixture was reacted at 100 ℃ for 1 h. After the reaction, 10mL of saturated brine was added, and the mixture was extracted with ether (10 mL. times.3), and the organic phases were combined, evaporated under reduced pressure to remove the solvent, and then subjected to column chromatography to obtain a yield of 64%.
Example 50
Compound 1: a250 mL reaction flask was charged with ferrous chloride (0.125mmol), potassium persulfate (2.5mmol), p-bromocumene (0.25mmol), acetonitrile (64mL), and water (50mL) in that order, and the reaction mixture was reacted at 20 ℃ for 60 h. After the reaction, vacuum concentration is carried out, 10mL of saturated saline is added into a concentrated liquid phase, ether extraction (10mL multiplied by 3) is carried out, organic phases are combined, the solvent is removed by reduced pressure evaporation, and column chromatography separation is carried out to obtain the yield of 31%.
Comparative example
Serial number [Fe] [O] Solvent(s) Yield (%)
1 FeCl 2 K 2 S 2 O 8 CH 3 CN/H 2 O 93
2 Fe(acac) 2 K 2 S 2 O 8 CH 3 CN/H 2 O 83
3 - K 2 S 2 O 8 CH 3 CN/H 2 O -
4 FeCl 2 - CH 3 CN/H 2 O -
5 FeCl 2 H 2 O 2 CH 3 CN/H 2 O 92
6 FeCl 2 Oxone CH 3 CN/H 2 O 37
7 FeCl 2 K 2 S 2 O 8 CH 3 CN/- -
8 FeCl 2 K 2 S 2 O 8 EtOH/H 2 O 43
In this case, numeral 1 is example 1 of the present invention.
Number 2 the preparation of example 1 was carried out with the following conditions: replacing the iron catalyst as Fe (acac) 2 The result is: the reaction takes place, verifying compatibility with other iron catalysts.
Number 3 the preparation of example 1 was carried out with the following conditions: the iron catalyst addition was removed and the results were: the reaction rate was very low and no corresponding product was detected, demonstrating the necessity of an iron catalyst.
Number 4 the preparation of example 1 was carried out with the following conditions: the addition of the oxidizing agent was removed, and the results were: the reaction rate was low and the corresponding product was not detected, demonstrating the necessity of an oxidizing agent.
Numbers 5 and 6 were prepared according to the method of example 1, with the following conditions: oxidant for H 2 O 2 Or potassium peroxymonosulfonate (oxone) with the results: the reactions all occurred, only the yield was changed, and the compatibility with other oxidants was verified.
Number 7 the preparation of example 1 was carried out with the following conditions: without water solvent, acetonitrile was used as the only solvent, with the results: the reaction rate was very low and the corresponding product was not monitored, demonstrating the necessity of a water solvent.
Number 8 the preparation of example 1 was carried out with the following conditions: ethanol is used as an organic solvent instead of acetonitrile, and forms a mixed solvent with water, and the result is that: the reaction occurred with moderate yield, demonstrating the compatibility of other organic solvents.
Various iron catalysts in the invention can catalyze the reaction; the oxidant is a key substance playing a role in oxidation in the reaction process, and theoretically, various oxidants can promote the reaction; the chemical bond of the benzyl tertiary carbon substrate is a carbon-hydrogen bond on the benzyl tertiary carbon, and the change of the substituent on the aromatic ring and the change of the alkyl per se influence the electron cloud density of the aromatic ring and the steric hindrance of a reaction site, and cannot play a decisive role in the reaction per se.

Claims (10)

1. A method for synthesizing aryl ketone by oxidizing benzyl tertiary carbon through bond breaking under the catalysis of iron is characterized in that organic solvent and aqueous solution are used as solvents, and the benzyl tertiary carbon is oxidized under the catalysis of iron to synthesize aryl ketone, wherein the reaction general formula is shown as follows:
Figure FDA0003689847880000011
in the formula R 1 And R 2 Each is independently selected from any one of alkyl, alkoxy, benzyl, aryl and halogen;
ar represents an aryl group or a substituted aryl group.
2. The method for synthesizing arone through iron-catalyzed bond-breaking oxidation of the benzylic tertiary carbon according to claim 1, wherein the aryl group represented by Ar is a substituted or unsubstituted phenyl group, biphenyl group, naphthyl group, anthryl group, phenanthryl group or pyrenyl group.
3. The method for synthesizing aryl ketone through oxidation of benzyl tertiary carbon by iron catalysis according to claim 2, wherein the substituent on Ar is hydrogen on a mono-substituted or multi-substituted aryl ring, and the substituent is optionally selected from hydrogen, C1-C12 linear or branched alkyl, C1-C12 linear or branched alkoxy, C3-C12 cycloalkyl, phenyl, fluorine, chlorine, bromine, hydroxyl, carboxyl, carbomethoxy, carbethoxy, propisocarbonyl, cyano, nitro, formyl or boronic acid.
4. The method for synthesizing arone through iron-catalyzed bond-breaking oxidation of the benzyl tertiary carbon according to claim 1, wherein the organic solvent is preferably any one of acetonitrile, ethanol and DMSO.
5. The method for synthesizing arone through iron-catalyzed bond-breaking oxidation of benzyl tertiary carbon according to claim 1, wherein the reaction temperature is 20-100 ℃, and the reaction time is 0.5-60 hours.
6. The method for synthesizing arone through iron-catalyzed bond-breaking oxidation of benzyl tertiary carbon according to claim 1, wherein the molar ratio of the benzyl tertiary carbon to the oxidant to the iron catalyst is 1 (1-10) to (0.04-0.5).
7. The method for synthesizing aryl ketone by iron-catalyzed bond-breaking oxidation of benzyl tertiary carbon, as claimed in claim 1, wherein the weight ratio of benzyl tertiary carbon to acetonitrile and water is 1 (5-1000) to (5-1000).
8. The method for synthesizing arone through oxidation of benzyl tertiary carbon bond breaking catalyzed by iron according to claim 1, wherein the iron catalyst comprises any one or combination of ferrous chloride, ferrous bromide, ferrous iodide, ferrous fluoride, ferrous oxide, ferrous acetate, ferrous oxalate, ferrous acetylacetonate, ferrous phthalocyanine, ferrous phosphate, ferrocene, ferric chloride, ferric bromide, ferric fluoride, ferric acetylacetonate, ferric trifluoromethanesulfonate, ferric tetrafluoroborate, ferric p-toluenesulfonate, ferric acrylate, ferric ethoxide, ferbamate, ferric isopropoxide, 2-ethylacetate, ferroferric dodecacarbonyl, ferric oxide, and ferric tris (trifluoro-2, 4-pentanedionate).
9. The method for synthesizing arone through iron-catalyzed bond-breaking oxidation of the benzylic tertiary carbon according to claim 1, wherein the oxidant comprises any one or combination of hydrogen peroxide, tert-butyl hydroperoxide, di-tert-butyl peroxide, potassium peroxysulfate, potassium peroxypyrophosphate, potassium persulfate, sodium persulfate, ammonium persulfate, benzoyl peroxide, potassium peroxymonosulfonate, and 3-chloroperoxybenzoic acid.
10. The method for synthesizing arone through iron-catalyzed bond-breaking oxidation of the benzylic tertiary carbon according to claim 1, wherein air or oxygen can be added as an atmosphere gas when the oxidant is used.
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Publication number Priority date Publication date Assignee Title
CN107216242A (en) * 2017-07-07 2017-09-29 南京师范大学 A kind of method of iron catalysis oxidation alkyl aromatic compound synthesis aromatic aldehyde, arone and aromatic ester
CN109956863A (en) * 2017-12-22 2019-07-02 山东凯盛新材料股份有限公司 The synthesis technology of chlorobenzoyl chloride
CN111675599A (en) * 2020-04-27 2020-09-18 浙江工业大学 Method for catalyzing and oxidizing aromatic benzyl tertiary C-H bond into tertiary alcohol by metalloporphyrin

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107216242A (en) * 2017-07-07 2017-09-29 南京师范大学 A kind of method of iron catalysis oxidation alkyl aromatic compound synthesis aromatic aldehyde, arone and aromatic ester
CN109956863A (en) * 2017-12-22 2019-07-02 山东凯盛新材料股份有限公司 The synthesis technology of chlorobenzoyl chloride
CN111675599A (en) * 2020-04-27 2020-09-18 浙江工业大学 Method for catalyzing and oxidizing aromatic benzyl tertiary C-H bond into tertiary alcohol by metalloporphyrin

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