CN115010584B - Method for synthesizing aromatic ketone by iron-catalyzed oxidation of tertiary carbon bond breaking of benzyl position - Google Patents

Method for synthesizing aromatic ketone by iron-catalyzed oxidation of tertiary carbon bond breaking of benzyl position Download PDF

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CN115010584B
CN115010584B CN202210658906.7A CN202210658906A CN115010584B CN 115010584 B CN115010584 B CN 115010584B CN 202210658906 A CN202210658906 A CN 202210658906A CN 115010584 B CN115010584 B CN 115010584B
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韩维
蔡恒睿
赵宏元
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Nanjing Normal University
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Abstract

The invention discloses a method for synthesizing aryl ketone by iron-catalyzed bond breaking oxidation of tertiary carbon in benzyl position, which takes an organic solvent and an aqueous solution as solvents, and synthesizes aryl ketone by catalytic oxidation of tertiary carbon in benzyl position under the action of an oxidant, wherein the reaction general formula is shown as follows. The method uses an inexpensive green iron catalyst, takes acetonitrile and water as solvents under the action of green oxidant hydrogen peroxide, and oxidizes benzyl tertiary carbon to carbonyl by breaking bondsThe radicals form the corresponding aromatic ketones. The method for preparing the aryl ketone by catalytic oxidation reaction uses an environment-friendly cheap metal catalyst and an oxidant, and has the advantages of cheap and easily obtained reaction substrate, stable property and better functional group compatibility. Under optimized reaction conditions, the separation yield of the target product is as high as 96%.

Description

Method for synthesizing aromatic ketone by iron-catalyzed oxidation of tertiary carbon bond breaking of benzyl position
Technical Field
The invention belongs to the technical field of catalytic synthesis, relates to a method for synthesizing aryl ketone by iron catalysis, and in particular relates to a method for synthesizing aryl ketone by iron catalysis of tertiary carbon bond breaking oxidation of benzyl.
Background
The C-C bond has higher thermodynamic stability, which is a great difficulty in the field of inert chemical bond activation; aromatic ketone is an organic synthesis intermediate with high added value, and is widely applied to the synthesis of medicines, pesticides, dyes, fragrances and the like. In the current method for synthesizing aryl ketone by oxidation reaction of tertiary carbon bond breaking of benzyl position, two reactions of aryl ketone synthesis by oxidation of tertiary alcohol of benzyl position through C-C bond breaking and aryl ketone synthesis by decarboxylation of phenylacetic acid derivatives are mainly adopted, for example, a copper-catalyzed reaction of alpha-substituted phenylacetic acid for synthesizing corresponding ketone by decarboxylation of tertiary carbon of benzyl position is reported in Song Qiuling subject group (J.org. chem.2014,79, 1867-1871), but the application of the copper-catalyzed reaction is limited by higher reaction temperature and limited substrate range. The substrate for the bond-breaking oxidation reaction of benzyl cumene is widely available and inexpensive, and although a small amount of the reaction has been reported, the use of NaNO has also been reported in the group of the subject Liu Zhongquan of 2021 (org. Lett.2021,23, 4057-4061) 2 The reaction condition of taking HCl as a key additive has the problems of generating a nitrosation byproduct and increasing the treatment difficulty after the reaction; in addition, the high requirement of the photoelectrocatalysis reaction condition on the reaction equipment is reported in the early stage, so that the application cost is increased. Therefore, from the viewpoints of economic factors, efficiency factors and environmental factors, the method for preparing the aromatic ketone by catalyzing and oxidizing the tertiary carbon bond of the benzyl tertiary in an environment-friendly way has considerable significance and value.
Disclosure of Invention
The invention aims to: aiming at the problems of complex application conditions, high equipment requirement, or excessive byproducts generated by using toxic and harmful raw materials and the like in the prior art, the invention provides a brand-new method for synthesizing the aryl ketone by catalyzing the bond breaking oxidation of tertiary carbon at a benzyl position by using a simple iron catalyst and a common oxidant, and the aryl ketone is synthesized by using a method which is mild in condition, high in efficiency and environment-friendly and only needs conventional kettle type equipment; effectively solves the problems of higher reaction temperature, large consumption of reaction substrates, high practical reaction cost and the like of the traditional aryl ketone synthesis method.
The technical scheme is as follows: in order to achieve the above purpose, the method for synthesizing the aryl ketone by iron-catalyzed benzyl tertiary carbon bond breaking oxidation uses an organic solvent and an aqueous solution as solvents, and the reaction general formula of the method is shown as follows:
wherein R is 1 And R is 2 Each independently selected from any one of alkyl, alkoxy, benzyl, aryl and halogen;
ar represents an aryl group or an aryl group having a substituent.
Wherein the aryl represented by Ar is substituted or unsubstituted phenyl, biphenyl, naphthyl, anthryl, phenanthryl or pyrenyl.
Wherein the substituent on Ar is hydrogen on a monosubstituted or polysubstituted 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, methyl ester group, ethyl ester group, propyl ester group, 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: 50-100 ℃.
Wherein the molar ratio of the tertiary benzyl carbon to the oxidant to the iron catalyst is 1 (1-10) (0.04-0.5).
Wherein the weight ratio of the tertiary benzyl carbon to acetonitrile to water is 1 (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 triflate, ferric tetrafluoroborate, ferric p-toluenesulfonate, ferric acrylate, ferric ethoxide, ferme iron, iron isopropoxide, iron 2-ethylacetate, ferric laurcarbonyl, ferric oxide, tris (trifluoro-2, 4-pentanedione) iron, or a combination thereof.
Wherein the oxidant comprises any one or combination of hydrogen peroxide, tert-butyl hydroperoxide, di-tert-butyl peroxide, potassium persulfate, potassium peroxypyrophosphate, potassium persulfate, sodium persulfate, ammonium persulfate, benzoyl peroxide, potassium peroxymonosulphonate and 3-chloroperoxybenzoic acid.
Preferably, air and oxygen may be used as the atmosphere gas when the oxidizing agent is used.
Design principle: the invention utilizes the oxidation-reduction capability of transition metal iron to catalyze an oxidant to form an active intermediate, then the active intermediate deprives hydrogen on benzyl tertiary carbon and continuously reacts with the hydrogen to form a benzyl peroxide intermediate, then the benzyl peroxide intermediate is homolytic to form an alkoxy free radical, and then a branched alkyl free radical is removed through a beta-fracture process to form a final product. The current method for directly forming aryl ketone through breaking the carbon-carbon bond at the benzyl position is more than a photoelectrocatalysis method, and a strong oxidant or an organic solvent is needed, or additional side reaction products exist to influence the post-treatment efficiency. The invention uses cheap, environment-friendly and low-toxicity iron catalyst, can use easily-obtained nontoxic oxidant, has no addition or less addition of auxiliary agent, has simple kettle-type reaction condition, has no side reaction or less side reaction, has no similar reaction method at present, and in addition, the substrate does not need carbonyl source, the corresponding product is obtained by directly oxidizing aryl alkane, the alkyl aromatic compound is cheaper and more stable, and the separation yield of the target product is up to 96%.
The beneficial effects are that: compared with the prior art, the invention has the following advantages:
(1) The invention provides a new method for preparing aromatic ketone by iron-catalyzed benzyl tertiary carbon bond-breaking oxidation reaction in a mixed solvent of acetonitrile and water, which has the advantages of wide substrate source, low cost, low raw material dosage, 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, low cost of iron catalyst and simple stirring reaction condition, no additional byproduct, simple post-treatment, low equipment requirement and the like;
(2) In the method for synthesizing the aryl ketone, provided by the invention, 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 aryl ketone is directly obtained by a one-step method, the yield of the separated target product is up to 96%, the raw material source for preparing the aryl ketone is greatly expanded, and the method is a general, efficient, economic and environment-friendly method for synthesizing the aryl ketone.
(3) The method can be applied to complex active molecular substrates, active groups do not need to be protected, and the method has the remarkable advantage, and is expected to be applied to the synthesis of medicines.
Detailed Description
The invention will be better understood from the following examples. However, it will be readily appreciated by those skilled in the art that the description of the embodiments is provided for illustration only and should not limit the invention as described in detail in the claims.
Example 1
Compound 1: ferrous chloride (0.025 mmol), potassium persulfate (0.75 mmol), p-bromocumene (0.25 mmol), acetonitrile (1 mL), water (1 mL) were added sequentially to a 25mL reaction flask, and the reaction mixture was reacted at 80℃for 3h. After completion of the reaction, 10mL of saturated brine was added, the mixture was extracted with diethyl ether (10 mL. Times.3), the organic phases were combined, and the solvent was distilled off under reduced pressure, followed by column chromatography to give 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: ferrous chloride (0.015 mmol), hydrogen peroxide (0.75 mmol), potassium persulfate (0.25 mmol), cumene o-bromide (0.25 mmol), acetonitrile (1 mL), water (1 mL) were added sequentially to a 25mL reaction flask, and the reaction mixture was reacted at 80℃for 3h. After completion of the reaction, 10mL of saturated brine was added, the mixture was extracted with diethyl ether (10 mL. Times.3), the organic phases were combined, and the solvent was distilled off under reduced pressure, followed by column chromatography to give a yield of 65%.
Example 3
Compound 3: ferrous chloride (0.010 mmol), hydrogen peroxide (0.75 mmol), m-bromocumene (0.25 mmol), acetonitrile (1 mL), water (1 mL) were added sequentially to a 25mL reaction flask, and the reaction mixture was reacted at 80℃for 17h. After completion of the reaction, 10mL of saturated brine was added, the mixture was extracted with diethyl ether (10 mL. Times.3), and the organic phases were combined, and after evaporation of the solvent under reduced pressure, the mixture was separated by column chromatography to give 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 (0.020 mmol), hydrogen peroxide (0.75 mmol), potassium persulfate (0.25 mmol), 1-bromo-2, 4, 6-triisopropylbenzene (0.25 mmol), acetonitrile (1 mL), water (1 mL) were sequentially added to a 25mL reaction flask, and the reaction mixture was reacted at 80℃for 24h. After completion of the reaction, 10mL of saturated brine was added, the mixture was extracted with diethyl ether (10 mL. Times.3), the organic phases were combined, and the solvent was distilled off under reduced pressure, followed by column chromatography to give a yield of 65%.
Example 5
Compound 5: ferrous chloride (0.020 mmol), hydrogen peroxide (0.75 mmol), p-chlorocumene (0.25 mmol), acetonitrile (1 mL), water (1 mL) were added sequentially to a 25mL reaction flask, and the reaction mixture was reacted at 80℃for 9h. After completion of the reaction, 10mL of saturated brine was added, the mixture was extracted with diethyl ether (10 mL. Times.3), the organic phases were combined, and the solvent was distilled off under reduced pressure, followed by column chromatography to give a yield of 78%.
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: to a 25mL reaction flask was successively added ferrous chloride (0.010 mmol), hydrogen peroxide (0.75 mmol), potassium persulfate (0.25 mmol), 1, 3-diisopropylbenzene (0.25 mmol), acetonitrile (1 mL), water (1 mL), and the reaction mixture was reacted at 80℃for 6 hours. After completion of the reaction, 10mL of saturated brine was added, the mixture was extracted with diethyl ether (10 mL. Times.3), the organic phases were combined, and the solvent was distilled off under reduced pressure, followed by column chromatography to give 70% yield.
Example 7
Compound 7: to a 25mL reaction flask was successively added ferrous chloride (0.025 mmol), hydrogen peroxide (0.75 mmol), potassium persulfate (0.25 mmol), 1, 4-diisopropylbenzene (0.25 mmol), acetonitrile (1 mL), water (1 mL), and the reaction mixture was reacted at 80℃for 6h. After completion of the reaction, 10mL of saturated brine was added, the mixture was extracted with diethyl ether (10 mL. Times.3), the organic phases were combined, and the solvent was distilled off under reduced pressure, followed by column chromatography to give 70% yield.
Example 8
Compound 8: to a 25mL reaction flask was successively added ferrous chloride (0.030 mmol), hydrogen peroxide (0.75 mmol), potassium persulfate (0.25 mmol), 1, 2-diisopropylbenzene (0.25 mmol), acetonitrile (1 mL), water (1 mL), and the reaction mixture was reacted at 80℃for 3 hours. After completion of the reaction, 10mL of saturated brine was added, the mixture was extracted with diethyl ether (10 mL. Times.3), the organic phases were combined, and the solvent was distilled off under reduced pressure, followed by column chromatography to give 67% yield.
Example 9
Compound 9: ferrous chloride (0.035 mmol), hydrogen peroxide (0.75 mmol), cymene (0.25 mmol), acetonitrile (1 mL), water (1 mL) were added sequentially to a 25mL reaction flask, and the reaction mixture was reacted at 80℃for 3h. After completion of the reaction, 10mL of saturated brine was added, the mixture was extracted with diethyl ether (10 mL. Times.3), the organic phases were combined, and the solvent was distilled off under reduced pressure, followed by column chromatography to give a yield of 74%.
Example 10
Compound 10: ferrous chloride (0.040 mmol), hydrogen peroxide (0.75 mmol), potassium persulfate (0.25 mmol), 2-ethoxycumene (0.25 mmol), acetonitrile (1 mL), water (1 mL) were sequentially added to a 25mL reaction flask, and the reaction mixture was reacted at 80℃for 12h. After completion of the reaction, 10mL of saturated brine was added, the mixture was extracted with diethyl ether (10 mL. Times.3), the organic phases were combined, and the solvent was distilled off under reduced pressure, followed by column chromatography to give 80% yield.
Example 11
Compound 11: to a 25mL reaction flask were successively added ferrous bromide (0.035 mmol), oxygen (1 atm), hydrogen peroxide (0.75 mmol), potassium persulfate (0.25 mmol), 4-ethoxycumene (0.25 mmol), acetonitrile (1 mL), water (1 mL), and the reaction mixture was reacted at 80℃for 12 hours. After completion of the reaction, 10mL of saturated brine was added, the mixture was extracted with diethyl ether (10 mL. Times.3), the organic phases were combined, and the solvent was distilled off under reduced pressure, followed by column chromatography to give 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: ferrous iodide (0.025 mmol), di-t-butyl peroxide (0.75 mmol), 4-isopropoxycropylcumene (0.25 mmol), acetonitrile (1 mL), water (1 mL) were added sequentially to a 25mL reaction flask, and the reaction mixture was reacted at 100℃for 20h. After completion of the reaction, 10mL of saturated brine was added, the mixture was extracted with diethyl ether (10 mL. Times.3), the organic phases were combined, and the solvent was distilled off under reduced pressure, followed by column chromatography to give 85% yield.
Example 13
Compound 13: ferrous fluoride (0.040 mmol), tert-butyl hydroperoxide (0.75 mmol), air (1 atm), p-isopropyl phenol benzoate (0.25 mmol), acetonitrile (1 mL), water (1 mL) were added sequentially to the 25mL reaction flask, and the reaction mixture was reacted at 80℃for 12h. After completion of the reaction, 10mL of saturated brine was added, the mixture was extracted with diethyl ether (10 mL. Times.3), the organic phases were combined, and the solvent was distilled off under reduced pressure, followed by column chromatography to give 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: ferrous oxide (0.050 mmol), sodium persulfate (2.50 mmol), 2-methyl-4-ethoxycumene (0.25 mmol), acetonitrile (1 mL), water (1 mL) were added sequentially to the 25mL reaction flask, and the reaction mixture was reacted at 20℃for 17h. After completion of the reaction, 10mL of saturated brine was added, the mixture was extracted with diethyl ether (10 mL. Times.3), the organic phases were combined, and the solvent was distilled off under reduced pressure, followed by column chromatography to give a yield of 65%.
Example 15
Compound 15: to a 25mL reaction flask was added ferrous acetylacetonate (0.020 mmol), ferrous phthalocyanine (0.020 mmol), potassium peroxypyrophosphate (0.75 mmol), 3-isopropoxy-4-cymene (0.25 mmol), acetonitrile (1 mL), water (1 mL), and the reaction mixture was reacted at 20℃for 48h. After completion of the reaction, 10mL of saturated brine was added, the mixture was extracted with diethyl ether (10 mL. Times.3), the organic phases were combined, and the solvent was distilled off under reduced pressure, followed by column chromatography to give 70% yield.
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: ferrous oxide (0.050 mmol), benzoyl peroxide (0.25 mmol), 2-methyl-4-ethoxycumene (0.25 mmol), acetonitrile (1 mL), water (1 mL) were added sequentially to a 25mL reaction flask, and the reaction mixture was reacted at 20℃for 17h. After completion of the reaction, 10mL of saturated brine was added, the mixture was extracted with diethyl ether (10 mL. Times.3), the organic phases were combined, and the solvent was distilled off under reduced pressure, followed by column chromatography to give a yield of 65%.
Example 17
Compound 17: to a 25mL reaction flask was added sequentially, tris (iron) dodecacarbonyl (0.020 mmol), potassium peroxymonosulfonate (0.75 mmol), 4-isopropyl phenol 2-fluoro-4-iodobenzoate (0.25 mmol), acetonitrile (1 mL), water (1 mL), and the reaction mixture was reacted at 80℃for 60h. After completion of the reaction, 10mL of saturated brine was added, the mixture was extracted with diethyl ether (10 mL. Times.3), the organic phases were combined, and the solvent was distilled off under reduced pressure, followed by column chromatography to give 60% yield.
Example 18
Compound 18: ferrous chloride (0.015 mmol), hydrogen peroxide (2.0 mmol), ethyl p-isopropyl benzoate (0.25 mmol), acetonitrile (1 mL), water (1 mL) were added sequentially to a 25mL reaction flask, and the reaction mixture was reacted at 80℃for 24h. After completion of the reaction, 10mL of saturated brine was added, the mixture was extracted with diethyl ether (10 mL. Times.3), the organic phases were combined, and the solvent was distilled off under reduced pressure, followed by column chromatography to give 57% yield.
Example 19
Compound 19: to a 25mL reaction flask was added ferric tetrafluoroborate (0.015 mmol), ammonium persulfate (1.75 mmol), p-isopropylphenylboronic acid (0.25 mmol), acetonitrile (1 mL), water (1 mL), and the reaction mixture was reacted at 80℃for 36h. After completion of the reaction, 10mL of saturated brine was added, the mixture was extracted with diethyl ether (10 mL. Times.3), the organic phases were combined, and the solvent was distilled off under reduced pressure, followed by column chromatography to give a yield of 65%.
Example 20
Compound 20: to a 25mL reaction flask was successively added ferric trifluoromethanesulfonate (0.015 mmol), m-chloroperoxybenzoic acid (1.25 mmol), m-isopropylbenzene boric acid (0.25 mmol), acetonitrile (1 mL), water (1 mL), and the reaction mixture was reacted at 80℃for 39h. After completion of the reaction, 10mL of saturated brine was added, the mixture was extracted with diethyl ether (10 mL. Times.3), the organic phases were combined, and the solvent was distilled off under reduced pressure, followed by column chromatography to give 62% yield.
Example 21
Compound 21: to a 25mL reaction flask was successively added tris (trifluoro-2, 4-pentanedione) iron (0.015 mmol), hydrogen peroxide (1.50 mmol), 2,4, 6-triisopropylphenylboronic acid (0.25 mmol), acetonitrile (1 mL), water (1 mL), and the reaction mixture was reacted at 80℃for 36h. After completion of the reaction, 10mL of saturated brine was added, the mixture was extracted with diethyl ether (10 mL. Times.3), the organic phases were combined, and the solvent was distilled off under reduced pressure, followed by column chromatography to give 40% yield.
Example 22
Compound 22: to a 25mL reaction flask was added successively ferox (0.015 mmol), hydrogen peroxide (1.0 mmol), 3-phenylpentane (0.25 mmol), acetonitrile (1 mL), water (1 mL), and the reaction mixture was reacted at 80℃for 1h. After completion of the reaction, 10mL of saturated brine was added, the mixture was extracted with diethyl ether (10 mL. Times.3), the organic phases were combined, and the solvent was distilled off under reduced pressure, followed by column chromatography to give 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: to a 25mL reaction flask was successively added ferric bromide (0.015 mmol), hydrogen peroxide (0.50 mmol), 2- (4-pentoxyphenyl) butane (0.25 mmol), acetonitrile (1 mL), water (1 mL), and the reaction mixture was reacted at 80℃for 48h. After completion of the reaction, 10mL of saturated brine was added, the mixture was extracted with diethyl ether (10 mL. Times.3), the organic phases were combined, and the solvent was distilled off under reduced pressure, followed by column chromatography to give 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: to a 25mL reaction flask was successively added ferric fluoride (0.05 mmol), hydrogen peroxide (0.50 mmol), 1, 2-diphenylbutane (0.25 mmol), acetonitrile (3 mL), water (2 mL), and the reaction mixture was reacted at 80℃for 9h. After completion of the reaction, 10mL of saturated brine was added, the mixture was extracted with diethyl ether (10 mL. Times.3), the organic phases were combined, and the solvent was distilled off under reduced pressure, followed by column chromatography to give a yield of 75%.
Example 25
Compound 25: to a 25mL reaction flask was successively added ferric acetylacetonate (0.015 mmol), hydrogen peroxide (0.75 mmol), potassium persulfate (0.25 mmol), 1-methoxy-4- (1-phenylethyl) benzene (0.25 mmol), acetonitrile (1 mL), water (1 mL), and the reaction mixture was reacted at 50℃for 0.5h. After completion of the reaction, 10mL of saturated brine was added, the mixture was extracted with diethyl ether (10 mL. Times.3), the organic phases were combined, and the solvent was distilled off under reduced pressure, followed by column chromatography to give 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: to a 25mL reaction flask was added iron isopropoxide (0.05 mmol), hydrogen peroxide (0.75 mmol), potassium persulfate (0.25 mmol), triphenylmethane (0.25 mmol), acetonitrile (5 mL), water (5 mL) in this order, and the reaction mixture was reacted at 50℃for 1.5h. After completion of the reaction, 10mL of saturated brine was added, the mixture was extracted with diethyl ether (10 mL. Times.3), the organic phases were combined, and the solvent was distilled off under reduced pressure, followed by column chromatography to give 87% yield.
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: to a 25mL reaction flask was successively added iron p-toluenesulfonate (0.015 mmol), hydrogen peroxide (0.75 mmol), potassium persulfate (0.25 mmol), tris (4-methoxyphenyl) methane (0.25 mmol), acetonitrile (1 mL), water (1 mL), and the reaction mixture was reacted at 50℃for 24 hours. After completion of the reaction, 10mL of saturated brine was added, the mixture was extracted with diethyl ether (10 mL. Times.3), the organic phases were combined, and the solvent was distilled off under reduced pressure, followed by column chromatography to give 85% yield.
Example 28
Compound 28: to a 100mL reaction flask was added ferrous oxalate (0.05 mmol), hydrogen peroxide (0.75 mmol), potassium persulfate (0.25 mmol), 2-biphenyl-3-ethoxypropane (0.25 mmol), acetonitrile (15 mL), water (10 mL), and the reaction mixture was reacted at 100℃for 48h. After completion of the reaction, 10mL of saturated brine was added, the mixture was extracted with diethyl ether (10 mL. Times.3), the organic phases were combined, and the solvent was distilled off under reduced pressure, followed by column chromatography to give 50% yield.
Example 29
Compound 29: ferrous phosphate (0.05 mmol), hydrogen peroxide (0.75 mmol), potassium persulfate (0.25 mmol), 2- (1-chloroethyl) naphthalene (0.25 mmol), acetonitrile (15 mL), water (5 mL) were sequentially added to a 100mL reaction flask, and the reaction mixture was reacted at 100℃for 48h. After completion of the reaction, 10mL of saturated brine was added, the mixture was extracted with diethyl ether (10 mL. Times.3), the organic phases were combined, and the solvent was distilled off under reduced pressure, followed by column chromatography to give 55% yield.
Example 30
Compound 30: to a 100mL reaction flask was successively added ferric chloride (0.05 mmol), hydrogen peroxide (0.75 mmol), potassium persulfate (0.75 mmol), 2-isopropylanthracene (0.25 mmol), acetonitrile (15 mL), water (2 mL), and the reaction mixture was reacted at 100℃for 48h. After completion of the reaction, 10mL of saturated brine was added, the mixture was extracted with diethyl ether (10 mL. Times.3), the organic phases were combined, and the solvent was distilled off under reduced pressure, followed by column chromatography to give 45% yield.
Example 31
Compound 31: to a 100mL reaction flask was added ferric ethoxide (0.05 mmol), hydrogen peroxide (0.25 mmol), potassium persulfate (0.75 mmol), 3-isopropylphenanthrene (0.25 mmol), acetonitrile (15 mL), water (10 mL), and the reaction mixture was reacted at 80℃for 48h. After completion of the reaction, 10mL of saturated brine was added, the mixture was extracted with diethyl ether (10 mL. Times.3), the organic phases were combined, and the solvent was distilled off under reduced pressure, followed by column chromatography to give 50% yield.
Example 32
Compound 32: to a 50mL reaction flask was successively added 2-ethyl iron acetate (0.05 mmol), hydrogen peroxide (0.75 mmol), potassium persulfate (0.75 mmol), 2-isopropyl pyrene (0.25 mmol), acetonitrile (15 mL), water (1.5 mL), and the reaction mixture was reacted at 120℃for 48 hours. After completion of the reaction, 10mL of saturated brine was added, the mixture was extracted with diethyl ether (10 mL. Times.3), the organic phases were combined, and the solvent was distilled off under reduced pressure, followed by column chromatography to give 45% yield.
Example 33
Compound 33: to a 25mL reaction flask was successively added ferric oxide (0.05 mmol), hydrogen peroxide (0.75 mmol), potassium persulfate (0.75 mmol), 2- (4-dodecylphenyl) butane (0.25 mmol), acetonitrile (1 mL), water (1 mL), and the reaction mixture was reacted at 50℃for 1h. After completion of the reaction, 10mL of saturated brine was added, the mixture was extracted with diethyl ether (10 mL. Times.3), the organic phases were combined, and the solvent was distilled off under reduced pressure, followed by column chromatography to give 90% yield.
Example 34
Compound 34: ferrous chloride (0.05 mmol), hydrogen peroxide (1.75 mmol), potassium persulfate (0.75 mmol), 3,4, 5-trimethoxycumene (0.25 mmol), acetonitrile (0.5 mL), water (0.5 mL) were sequentially added to a 10mL reaction tube, and the reaction mixture was reacted at 50℃for 60 hours. After completion of the reaction, 10mL of saturated brine was added, the mixture was extracted with diethyl ether (10 mL. Times.3), the organic phases were combined, and the solvent was distilled off under reduced pressure, followed by column chromatography to give 55% yield.
Example 35
Compound 35: ferrous chloride (0.05 mmol), hydrogen peroxide (1.75 mmol), 1-bromo-1- (4-dodecyloxyphenyl) ethane (0.25 mmol), acetonitrile (1.5 mL), water (0.5 mL) were added sequentially to the 25mL reaction flask, and the reaction mixture was reacted at 50 ℃ for 1.5h. After completion of the reaction, 10mL of saturated brine was added, the mixture was extracted with diethyl ether (10 mL. Times.3), the organic phases were combined, and the solvent was distilled off under reduced pressure, followed by column chromatography to give 89% yield.
Example 36
Compound 36: to a 100mL reaction flask was added ferrous chloride (0.05 mmol), hydrogen peroxide (0.75 mmol), potassium persulfate (0.75 mmol), 4-isopropylphenyl cyclohexyl ether (0.25 mmol), acetonitrile (15 mL), water (15 mL) in this order, and the reaction mixture was reacted at 200℃for 9h. After completion of the reaction, 10mL of saturated brine was added, the mixture was extracted with diethyl ether (10 mL. Times.3), the organic phases were combined, and the solvent was distilled off under reduced pressure, followed by column chromatography to give 80% yield.
Example 37
Compound 37: ferrous bromide (0.05 mmol), hydrogen peroxide (0.75 mmol), potassium persulfate (0.75 mmol), 4-isopropylphenyl cyclooctylether (0.25 mmol), acetonitrile (1.5 mL), water (1 mL) were added sequentially to the 25mL reaction flask, and the reaction mixture was reacted at 100℃for 12h. After completion of the reaction, 10mL of saturated brine was added, the mixture was extracted with diethyl ether (10 mL. Times.3), the organic phases were combined, and the solvent was distilled off under reduced pressure, followed by column chromatography to give 85% yield.
Example 38
Compound 38: to a 25mL reaction flask was added ferrous phthalocyanine (0.05 mmol), hydrogen peroxide (0.75 mmol), potassium persulfate (1.75 mmol), 3- (2-fluoro-4-iodophenyl) pentane (0.25 mmol), acetonitrile (2.5 mL), water (5.0 mL) in this order, and the reaction mixture was reacted at 80℃for 24h. After completion of the reaction, 10mL of saturated brine was added, the mixture was extracted with diethyl ether (10 mL. Times.3), the organic phases were combined, and the solvent was distilled off under reduced pressure, followed by column chromatography to give a yield of 78%.
Example 39
Compound 39: ferrous acetylacetonate (0.05 mmol), hydrogen peroxide (0.75 mmol), potassium persulfate (0.75 mmol), 2-isopropoxy-2- (4-hydroxyphenyl) ethane (0.25 mmol), acetonitrile (1.5 mL), water (2.5 mL) were added sequentially to the reaction flask, and the reaction mixture was reacted at 50℃for 3h. After completion of the reaction, 10mL of saturated brine was added, the mixture was extracted with diethyl ether (10 mL. Times.3), the organic phases were combined, and the solvent was distilled off under reduced pressure, followed by column chromatography to give a yield of 65%.
Example 40
Compound 40: to a 25mL reaction flask was added ferrous phthalocyanine (0.05 mmol), hydrogen peroxide (0.75 mmol), potassium persulfate (1.25 mmol), 2- (4-carboxyphenyl) pentane (0.25 mmol), acetonitrile (1.5 mL), water (2.5 mL) in this order, and the reaction mixture was reacted at 80℃for 24h. After completion of the reaction, 10mL of saturated brine was added, the mixture was extracted with diethyl ether (10 mL. Times.3), the organic phases were combined, and the solvent was distilled off under reduced pressure, followed by column chromatography to give 70% yield.
Example 41
Compound 41: to a 25mL reaction flask was added ferric acetylacetonate (0.025 mmol), ferrocene (0.025 mmol), hydrogen peroxide (0.75 mmol), potassium persulfate (0.75 mmol), propyl 4-isopropylbenzoate (0.25 mmol), acetonitrile (1.5 mL), water (0.5 mL), and the reaction mixture was reacted at 50℃for 24h. After completion of the reaction, 10mL of saturated brine was added, the mixture was extracted with diethyl ether (10 mL. Times.3), the organic phases were combined, and the solvent was distilled off under reduced pressure, followed by column chromatography to give a yield of 75%.
Example 42
Compound 42: to a 10mL reaction tube were added ferric acetylacetonate (0.025 mmol), ferrocene (0.025 mmol), hydrogen peroxide (0.75 mmol), potassium persulfate (0.75 mmol), methyl 4-isopropylbenzoate (0.25 mmol), acetonitrile (1 mL), water (0.25 mL), and the reaction mixture was reacted at 50℃for 24h. After completion of the reaction, 10mL of saturated brine was added, the mixture was extracted with diethyl ether (10 mL. Times.3), and the organic phases were combined, and after evaporation of the solvent under reduced pressure, the mixture was separated by column chromatography to give 77% yield.
Example 43
Compound 41: to a 25mL reaction flask was successively added ferric acetylacetonate (0.025 mmol), hydrogen peroxide (0.25 mmol), potassium persulfate (2.25 mmol), 4-formylisopropylbenzene (0.25 mmol), acetonitrile (5.0 mL), water (5.0 mL), and the reaction mixture was reacted at 150℃for 9 hours. After completion of the reaction, 10mL of saturated brine was added, the mixture was extracted with diethyl ether (10 mL. Times.3), the organic phases were combined, and the solvent was distilled off under reduced pressure, followed by column chromatography to give a yield of 79%.
Example 44
Compound 44: ferrocene (0.05 mmol), hydrogen peroxide (2.5 mmol), 4-cyanocumene (0.25 mmol), acetonitrile (2.5 mL), water (2.5 mL) were added sequentially to a 25mL reaction flask, and the reaction mixture was reacted at 150℃for 48h. After completion of the reaction, 10mL of saturated brine was added, the mixture was extracted with diethyl ether (10 mL. Times.3), the organic phases were combined, and the solvent was distilled off under reduced pressure, followed by column chromatography to give 50% yield.
Example 45
Compound 45: ferrocene (0.05 mmol), hydrogen peroxide (2.5 mmol), 4-nitrocumene (0.25 mmol), acetonitrile (15.0 mL), water (15.0 mL) were added sequentially to a 100mL reaction flask, and the reaction mixture was reacted at 150℃for 48h. After completion of the reaction, 10mL of saturated brine was added, the mixture was extracted with diethyl ether (10 mL. Times.3), the organic phases were combined, and the solvent was distilled off under reduced pressure, followed by column chromatography to give a yield of 65%.
Example 46
Compound 46: ferrous chloride (0.025 mmol), hydrogen peroxide (0.75 mmol), 3-phenylhexadecane (0.25 mmol), acetonitrile (1.5 mL), water (1.5 mL) were added sequentially to a 25mL reaction flask, and the reaction mixture was reacted at 50℃for 3h. After completion of the reaction, 10mL of saturated brine was added, the mixture was extracted with diethyl ether (10 mL. Times.3), the organic phases were combined, and the solvent was distilled off under reduced pressure, followed by column chromatography to give 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: ferrous chloride (0.025 mmol), hydrogen peroxide (0.75 mmol), potassium persulfate (0.25 mmol), cholic acid p-bromoisopropyl phenol ester (0.25 mmol), acetonitrile (2.0 mL), water (1.0 mL) were sequentially added to a 25mL reaction flask, and the reaction mixture was reacted at 80℃for 15h. After completion of the reaction, 10mL of saturated brine was added, the mixture was extracted with diethyl ether (10 mL. Times.3), the organic phases were combined, and the solvent was distilled off under reduced pressure, followed by column chromatography to give 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 (0.025 mmol), hydrogen peroxide (0.75 mmol), potassium persulfate (0.25 mmol), p-bromoisopropyl phenol glycyrrhetinate (0.25 mmol), acetonitrile (2.0 mL), water (1.0 mL) were added sequentially to a 25mL reaction flask, and the reaction mixture was reacted at 80 ℃ for 20h. After completion of the reaction, 10mL of saturated brine was added, the mixture was extracted with diethyl ether (10 mL. Times.3), the organic phases were combined, and the solvent was distilled off under reduced pressure, followed by column chromatography to give 45% yield.
The experimental results corresponding to the synthetic methods of examples 1 to 48 involving specific aromatic aldehydes are shown in table 1:
TABLE 1 iron catalyzed Synthesis of benzyl tertiary carbon bond-breaking oxidized aryl ketone [a]
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[a] The reaction conditions are described in the examples; [b] and (5) separating the yield by a column.
Example 49
Compound 1: ferrous chloride (0.02 mmol), potassium persulfate (0.5 mmol), p-bromocumene (0.5 mmol), acetonitrile (0.64 mL), water (0.5 mL) were sequentially added to a 10mL reaction tube, and the reaction mixture was reacted at 100℃for 1h. After completion of the reaction, 10mL of saturated brine was added, the mixture was extracted with diethyl ether (10 mL. Times.3), the organic phases were combined, and the solvent was distilled off under reduced pressure, followed by column chromatography to give a yield of 64%.
Example 50
Compound 1: ferrous chloride (0.125 mmol), potassium persulfate (2.5 mmol), p-bromocumene (0.25 mmol), acetonitrile (64 mL), water (50 mL) were added sequentially to a 250mL reaction flask, and the reaction mixture was reacted at 20℃for 60h. After the reaction, the mixture was concentrated in vacuo, 10mL of saturated brine was added to the concentrated solution, the mixture was extracted with diethyl ether (10 mL. Times.3), the organic phases were combined, and the solvent was distilled off under reduced pressure, followed by column chromatography separation to give a yield of 31%.
Comparative example
Sequence 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
Wherein, the number 1 is the embodiment 1 of the present invention.
Serial No. 2 was prepared as in example 1, with the following conditions: replacement of iron catalyst to Fe (acac) 2 The result is: the reaction took place, verifying compatibility with other iron catalysts.
Sequence number 3 was prepared as in example 1, with the following variations: the addition of the iron catalyst was removed and the result was: the reaction rate was very low and no corresponding product was detected, proving the necessity of an iron catalyst.
Serial No. 4 was prepared as in example 1, with the following conditions: the addition of the oxidizing agent was removed, resulting in: the reaction rate was very low, no corresponding product was detected, proving the necessity of an oxidizing agent.
Both serial numbers 5 and 6 were prepared according to the method of example 1, with the following conditions: replacement of oxidant with H 2 O 2 Or potassium peroxomonosulphonate (oxone), with the result that: the reactions all occurred, only the yields varied, verifying compatibility with other oxidants.
Serial No. 7 was prepared as in example 1, with the following conditions: no aqueous solvent was used, only acetonitrile was used as the sole solvent, resulting in: the reaction rate was very low, the corresponding product was not monitored, and the necessity of an aqueous solvent was demonstrated.
Serial No. 8 was prepared as in example 1, with the following conditions: ethanol is used for replacing acetonitrile to be used as an organic solvent, and a mixed solvent is formed by the ethanol and water, and the result is that: the reaction took place in moderate yields, demonstrating the compatibility of other organic solvents.
The various iron catalysts in the invention can catalyze the reaction; the oxidant is a key substance playing an oxidation role in the reaction process, and theoretically, various oxidants can promote the reaction; the chemical bond of the reaction of the substrate of the tertiary carbon at the benzyl position is a hydrocarbon bond on the tertiary carbon at the benzyl position, the change of the substituent group on the aromatic ring and the change of the alkyl group influence the electron cloud density of the aromatic ring and the steric hindrance of the reaction site, and the reaction does not play a decisive role.

Claims (7)

1. A method for synthesizing aryl ketone by iron-catalyzed oxidation of tertiary benzyl carbon is characterized in that an organic solvent and an aqueous solution are used as solvents, and under the action of an oxidant, the tertiary benzyl carbon is catalyzed and oxidized by iron to synthesize aryl ketone, and the reaction general formula is shown as follows:
；
wherein R is 1 And R is 2 Each independently selected from any one of alkyl, alkoxy, aryl and halogen;
ar represents an aryl group or an aryl group having a substituent;
the organic solvent is any one of acetonitrile, ethanol and DMSO; the iron-catalyzed catalyst comprises any one of or a 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 triflate, ferric tetrafluoroborate, ferric p-toluenesulfonate, ferric acrylate, ferric ethoxide, thiram iron, ferric isopropoxide, ferric 2-ethylacetate, ferric dodecacarbonyl, ferric oxide, tris (trifluoro-2, 4-pentanedione) iron; the oxidant comprises any one or combination of hydrogen peroxide, tert-butyl hydroperoxide, di-tert-butyl peroxide, potassium persulfate, potassium peroxypyrophosphate, potassium persulfate, sodium persulfate, ammonium persulfate, benzoyl peroxide, potassium peroxymonosulphonate and 3-chloroperoxybenzoic acid.
2. The method for synthesizing aryl ketone by iron-catalyzed benzyl tertiary carbon bond-breaking oxidation according to claim 1, wherein the aryl group represented by Ar is a substituted or unsubstituted phenyl, biphenyl, naphthyl, anthryl, phenanthryl or pyrenyl group.
3. The method for synthesizing aryl ketone by iron-catalyzed benzyl tertiary carbon bond-breaking oxidation according to claim 2, wherein the substituent on Ar is hydrogen on a single or multiple substituted aryl 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, methyl ester group, ethyl ester group, propyl ester group, cyano group, nitro group, formyl group or boric acid group.
4. The method for synthesizing aryl ketone by iron-catalyzed benzyl tertiary carbon bond-breaking oxidation according to claim 1, wherein the reaction temperature is 20-100 ℃ and the reaction time is 0.5-60 hours.
5. The method for synthesizing aromatic ketone by iron-catalyzed bond-breaking oxidation of benzyl tertiary carbon, which is characterized in that the molar ratio of the benzyl tertiary carbon to the oxidant to the iron catalyst is 1 (1-10): 0.04-0.5.
6. The method for synthesizing aromatic ketone by iron-catalyzed bond-breaking oxidation of benzyl tertiary carbon, which is characterized in that the weight ratio of the benzyl tertiary carbon to acetonitrile to water is 1 (5-1000).
7. The method for synthesizing aromatic ketone by iron-catalyzed benzyl tertiary carbon bond-breaking oxidation according to claim 1, wherein air or oxygen can be added as atmosphere gas when the oxidant is used.
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Citations (3)

* 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

Patent Citations (3)

* 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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