CN110423185A - A kind of method of isopropyl benzene-like compounds selective oxidation - Google Patents
A kind of method of isopropyl benzene-like compounds selective oxidation Download PDFInfo
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- CN110423185A CN110423185A CN201910801132.7A CN201910801132A CN110423185A CN 110423185 A CN110423185 A CN 110423185A CN 201910801132 A CN201910801132 A CN 201910801132A CN 110423185 A CN110423185 A CN 110423185A
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- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
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- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/48—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups
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- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
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Abstract
A kind of method of isopropyl benzene-like compounds selective oxidation, the method are as follows: isopropyl benzene-like compounds shown in formula (I), ferriporphyrin catalyst, oxidant, dispersing agent are placed in ball grinder, seal ball grinder, at room temperature, with the revolving speed ball milling 3 of 100~800rpm~for 24 hours, in mechanical milling process, it is primary to stop ball milling every 1~3h, release gas in ball grinder, end of reaction, reaction mixture is post-treated, obtains 2- phenyl -2- propanol compound shown in product formula (II)；The present invention realizes that the oxidation of isopropyl benzene and its derivative converts by solid-phase ball milling, and reactive mode is novel, and easy to operate, low energy consumption；Without organic solvent, the use of poisonous and harmful organic solvent is effectively prevented, it is environmentally protective；Peroxide content is low, and safety coefficient is high；2- phenyl -2- propyl alcohol and its derivatives selectively are high, meet current Green Chemical Engineering Process, environment compatibility chemical process, the social demand of bio-compatibility chemical process.
Description
Technical field
The present invention relates to the new sides that a kind of isopropyl benzene-like compounds selective oxidation prepares 2- phenyl -2- propanol compound
Method belongs to organic chemical industry and Minute Organic Synthesis field.
Background technique
2- phenyl -2- propyl alcohol and its derivative are a kind of important fine-chemical intermediates, are widely used in medicine, agriculture
Synthesis (the WO 2017068412 of the fine chemical products such as medicine, dyestuff, fragrance；WO 2015135094；Chemical
Engineering Science 2018,177: 391-398；ChemCatChem 2014,6:555-560).Currently, 2- benzene
The synthesis of base -2- propyl alcohol and its derivative, using oxygen as oxidant, passes through oxygen mainly using isopropyl benzene and its derivative as raw material
Change to react and (ACS Sustainable Chemistry&Engineering 2019,7:7708-7715 is made；
ChemCatChem 2018,10:198-205).In the oxidation process, due to intermediate product 2- phenyl -2- propyl hydrogen peroxide
And its derivative stability is good, is not easy to convert, and causes target product 2- phenyl -2- propyl alcohol and its derivatives selectively not high.Together
When due to the peroxide in reaction system there are higher concentration, also reduce the safety of the oxidation system.In addition, current portion
The oxidation process of point isopropyl benzene and its derivative also uses largely to the poisonous and hazardous organic solvent of environmental and biological materials and mistake
Metallic catalyst is crossed, the environment compatibility and bio-compatibility of reaction process is not only reduced, also results in a degree of product
Transition metal contamination (Inorganica Chimica Acta 2019,486:425-434；Applied Surface Science
2017,419:98-106；Advanced Synthesis&Catalysis 2011,353:147-154).Therefore, temperate condition
Under, with environment compatibility and bio-compatibility good reagent and catalyst, realize the highly selective oxygen of isopropyl benzene and its derivative
Change, no matter preparation 2- phenyl -2- propyl alcohol all has important meaning, also comply with mesh in industrial production or in theoretical research
Urgent need of the preceding whole society to green, safe and environment-friendly type chemical industry.
Solid-phase ball milling reaction be by relative motion two interfaces between shearing, friction, impact, squeeze the effects of,
Promote the interaction between the material of interface, and then realizes chemical reaction (Green Chemistry 2018,20:1435-
1443；Angewandte Chemie International Edition 2018,57:10718-10722).Solid-phase ball milling is anti-
Should be not necessarily to solvent, room temperature can be reacted, effectively prevent the use of poisonous and harmful organic solvent, and without to material into
Row heat treatment, less energy consumption, safety coefficient are high.Simultaneously as solid-phase ball milling process, mechanical force act directly on reaction mass,
It often can produce and be distributed different from liquid reactive product.In exploitation environment, society compels with human body compatibility chemical process
It cuts under social demand, solid-phase ball milling is used for the catalysis oxidation of isopropyl benzene and its derivative, can not only realize at room temperature different
The catalysis oxidation of third benzene and its derivative, but also the use of poisonous and harmful organic solvent can be reduced, it might even be possible to change oxygen
Change the distribution of product.
It is widely applied in the model compound metalloporphyrin of environment and bio-compatibility catalyst field, Cytochrome P450
In catalysis oxidation (the ChemSusChem 2019,12:684-691 of hydrocarbon；Applied Surface Science
2017,402:436-443), especially ferriporphyrin not only has good bio-compatibility, effectively prevent metallic catalyst dirty
Dye gained oxidation product and its downstream product, and catalysis of metalloporphyrin activity is high, reaction substrate 1/106~1/105(mol/
Mol catalyzed conversion can be completed in amount), also it is possible to prevente effectively from pollution of the metallic catalyst to oxygenated products.Therefore, of the invention
By the method for solid-phase ball milling, using metal ferriporphyrin as catalyst, with the preferable t- butylhydroperoxide of environment compatibility, peroxide
Changing hydrogen, sodium chlorite or sodium hypochlorite is oxidant, carries out the catalysis oxidation of isopropyl benzene and its derivative, not only realizes isopropyl
The oxidation conversion of benzene and its derivative in a mild condition, effectively prevents the use of poisonous and harmful organic solvent, and significant
The selectivity for improving 2- phenyl -2- propyl alcohol and its derivative meets current Green Chemical Engineering Process, environment compatibility chemical industry mistake
Journey, the social demand of bio-compatibility chemical process have important application value and theoretical significance.
Summary of the invention
The purpose of the present invention is to provide a kind of isopropyl benzene-like compounds selective oxidations to prepare 2- phenyl -2- propyl alcohol class
Close the new method of object.
Technical scheme is as follows:
A kind of method of isopropyl benzene-like compounds selective oxidation, the method are as follows:
Isopropyl benzene-like compounds shown in formula (I), ferriporphyrin catalyst, oxidant, dispersing agent are placed in ball grinder, sealed
Ball grinder, under room temperature (20~30 DEG C), with the revolving speed ball milling 3 of 100~800rpm (preferably 500~800rpm)~for 24 hours (preferably 8
~16h), primary every 1~3h (preferably 1h) stopping ball milling in mechanical milling process, gas in releasing ball grinder, end of reaction,
Reaction mixture is post-treated, obtains 2- phenyl -2- propanol compound shown in product formula (II)；
The material of the ball grinder is agate, the ball milling pearl of agate is similarly equipped with material, usual ball milling pearl diameter is
8.0mm, the gross mass and reaction mass of ball milling pearl add up to mass ratio to be about 3:1；
The ratio between amount of substance of isopropyl benzene-like compounds shown in the ferriporphyrin catalyst and formula (I) for 1:200000~
1000, preferably 1:20000~4000；
The ratio between amount of substance of isopropyl benzene-like compounds shown in the formula (I) and oxidant be 1:1~50, preferably 1:2~
5；
The mass ratio of isopropyl benzene-like compounds shown in the formula (I) and dispersing agent is 1:0.1~10, preferably 1:3~5；
The method of the post-processing are as follows: after reaction, reaction mixture is dissolved in dehydrated alcohol, is stirred at room temperature
30min, filtering, filter cake are washed with dehydrated alcohol, merging filtrate and cleaning solution, recycle dehydrated alcohol, decompression by air-distillation
Unreacted raw material is recycled in rectifying, separates desirable oxidation product 2- phenyl -2- propanol compound；
Oxidation reaction of the present invention can also in system in addition to obtaining 2- phenyl -2- propanol compound shown in product formula (II)
Oxidation generates acetophenone compounds shown in formula (III), cumene peroxide class compound shown in formula (IV)；The present invention couple
The analysis method of reaction result are as follows: after reaction, reaction mixture is dissolved in dehydrated alcohol, stirs 30min, mistake at room temperature
Filter, filter cake are washed with dehydrated alcohol, merging filtrate and cleaning solution, and sampling is analyzed, and using 2- naphthoic acid as internal standard, carry out liquid phase
Chromatography calculates the conversion ratio of isopropyl benzene-like compounds shown in raw material formula (I), 2- phenyl -2- propyl alcohol shown in product formula (II)
The selectivity of the selectivity of acetophenone compounds shown in class compound, formula (III), cumene peroxide shown in formula (IV) is logical
It crosses1H NMR analysis obtains；
In the present invention, the oxidant be t- butylhydroperoxide, hydrogen peroxide, sodium chlorite or sodium hypochlorite, preferably
T- butylhydroperoxide or hydrogen peroxide；
The dispersing agent is one or both of silica gel, neutral aluminum oxide, anhydrous sodium sulfate or anhydrous magnesium sulfate
The mixture of any of the above ratio, preferably anhydrous sodium sulfate or anhydrous magnesium sulfate；
The ferriporphyrin catalyst is at least one of compound shown in formula (V), preferably 5,10,15,20- tetra- (4- chlorine
Phenyl) PORPHYRIN IRON (II), 5,10,15,20- tetra- (2- chlorphenyl) PORPHYRIN IRON (II), (the 2,6- dichloro-benzenes of 5,10,15,20- tetra-
Base) PORPHYRIN IRON (II), 5,10,15,20- tetra- (2,4 dichloro benzene base) PORPHYRIN IRON (II) or 5,10,15,20- tetra- (2,3,4,5,
6- pentafluorophenyl group) PORPHYRIN IRON (II))；
In formula (V), Ra、Rb、Rc、Rd、ReIt is respectively independent are as follows: hydrogen, methyl, ethyl, propyl, butyl, isopropyl, tert-butyl,
Phenyl, methoxyl group, ethyoxyl, hydroxyl, sulfydryl, amino, methylamino, ethylamino, dimethylamino, 1- hydroxyethyl, nitro, cyanogen
Base, carboxyl, benzyl, fluorine, chlorine, bromine or iodine；
Shown in the structural formula such as formula (I) of the isopropyl benzene-like compounds, corresponding obtained product 2- phenyl -2- propyl alcohol class
Shown in the structural formula such as formula (II) for closing object, by-product acetophenone compounds, the cumene peroxide generated in oxidation reaction
Structural formula respectively as shown in formula (III), (IV):
In formula (I), (II), (III) or (IV), R1、R2、R3、R4、R5It is respectively independent are as follows: hydrogen, methyl, ethyl, propyl, fourth
Base, isopropyl, tert-butyl, phenyl, 1- naphthalene, 2- naphthalene, methoxyl group, ethyoxyl, hydroxyl, sulfydryl, amino, methylamino, second ammonia
Base, dimethylamino, 1- hydroxyethyl, nitro, cyano, carboxyl, benzyl, fluorine, chlorine, bromine or iodine.
The beneficial effects are mainly reflected as follows:
Isopropylbenzene and its derivatives selectively of the present invention aoxidize the method for preparing 2- phenyl -2- propyl alcohol and its derivative, lead to
The oxidation conversion that solid-phase ball milling realizes isopropyl benzene and its derivative is crossed, reactive mode is novel, easy to operate；Room temperature is reacted,
Low energy consumption；Without organic solvent, the use of poisonous and harmful organic solvent is effectively prevented, it is environmentally protective；Peroxide content is low,
Safety coefficient is high；The selectivity of 2- phenyl -2- propyl alcohol and its derivative is high, meets current Green Chemical Engineering Process, environment compatibility
Chemical process, the social demand of bio-compatibility chemical process.The present invention is a kind of isopropylbenzene efficiently, green, environmentally friendly, safe
And its derivative method for oxidation.
Specific embodiment
Invention is further explained combined with specific embodiments below, but protection scope of the present invention is not limited in
This.
Metalloporphyrin used in the present invention refers to Journal of the American Chemical Society
2017,139:18590-18597； Journal of the American Chemical Society 2018,140:6383-
6390 synthesis.
Agents useful for same is that commercially available analysis is pure.
It are furnished with 50 agate ball milling pearls in 100mL agate jar used, every ball milling pearl diameter is 0.80mm, quality
0.9g。
Embodiment 1
In 100mL agate jar, by 1.20g (10mmol) isopropylbenzene, 0.0004g (0.0005mmol) 5,10,15,
20- tetra- (4- chlorphenyl) PORPHYRIN IRON (II), 2.57g (20mmol) 70%t- butyl peroxy aqueous solution of hydrogen and the anhydrous sulphur of 3.60g
Sour sodium is uniformly mixed, and seals ball grinder.At room temperature, ball-milling reaction 12.0h under 600rpm revolving speed stops ball milling one every 1.0h
It is secondary, release gas in ball grinder.Gained reaction mixture is dissolved in 30mL dehydrated alcohol, stirred at room temperature by end of reaction
30.0min.Filtering, 2 × 10mL dehydrated alcohol washing gained filter cake, merges ethanol solution, and gained ethanol solution is settled to
100mL.10mL acquired solution is pipetted, internal standard 2- naphthoic acid is added, carries out liquid-phase chromatographic analysis.Isopropylbenzene conversion ratio 33%, 2-
Phenyl -2- propyl alcohol selectivity 89%, acetophenone selectivity 5%, 2- phenyl -2- propyl hydrogen peroxide selectivity 6% (1H NMR
Analysis obtains), apparent benzoic acid is not detected.
Embodiment 2
In 100mL agate jar, by 1.20g (10mmol) isopropylbenzene, 0.0020g (0.0025mmol) 5,10,15,
20- tetra- (4- chlorphenyl) PORPHYRIN IRON (II), 2.57g (20mmol) 70%t- butyl peroxy aqueous solution of hydrogen and the anhydrous sulphur of 3.60g
Sour sodium is uniformly mixed, and seals ball grinder.At room temperature, ball-milling reaction 12.0h under 600rpm revolving speed stops ball milling one every 1.0h
It is secondary, release gas in ball grinder.Gained reaction mixture is dissolved in 30mL dehydrated alcohol, stirred at room temperature by end of reaction
30.0min.Filtering, 2 × 10mL dehydrated alcohol washing gained filter cake, merges ethanol solution, and gained ethanol solution is settled to
100mL.10mL acquired solution is pipetted, internal standard 2- naphthoic acid is added, carries out liquid-phase chromatographic analysis.Isopropylbenzene conversion ratio 41%, 2-
Phenyl -2- propyl alcohol selectivity 90%, acetophenone selectivity 5%, 2- phenyl -2- propyl hydrogen peroxide selectivity 5% (1H NMR
Analysis obtains), apparent benzoic acid is not detected.
Embodiment 3
In 100mL agate jar, by 1.20g (10mmol) isopropylbenzene, 0.0008g (0.0010mmol) 5,10,15,
20- tetra- (4- chlorphenyl) PORPHYRIN IRON (II), 2.57g (20mmol) 70%t- butyl peroxy aqueous solution of hydrogen and the anhydrous sulphur of 3.60g
Sour sodium is uniformly mixed, and seals ball grinder.At room temperature, ball-milling reaction 12.0h under 600rpm revolving speed stops ball milling one every 1.0h
It is secondary, release gas in ball grinder.Gained reaction mixture is dissolved in 30mL dehydrated alcohol, stirred at room temperature by end of reaction
30.0min.Filtering, 2 × 10mL dehydrated alcohol washing gained filter cake, merges ethanol solution, and gained ethanol solution is settled to
100mL.10mL acquired solution is pipetted, internal standard 2- naphthoic acid is added, carries out liquid-phase chromatographic analysis.Isopropylbenzene conversion ratio 38%, 2-
Phenyl -2- propyl alcohol selectivity 91%, acetophenone selectivity 5%, 2- phenyl -2- propyl hydrogen peroxide selectivity 4% (1H NMR
Analysis obtains), apparent benzoic acid is not detected.
Embodiment 4
In 100mL agate jar, by 1.20g (10mmol) isopropylbenzene, 0.0008g (0.0010mmol) 5,10,15,
20- tetra- (4- chlorphenyl) PORPHYRIN IRON (II), 1.29g (10mmol) 70%t- butyl peroxy aqueous solution of hydrogen and the anhydrous sulphur of 3.60g
Sour sodium is uniformly mixed, and seals ball grinder.At room temperature, ball-milling reaction 12.0h under 600rpm revolving speed stops ball milling one every 1.0h
It is secondary, release gas in ball grinder.Gained reaction mixture is dissolved in 30mL dehydrated alcohol, stirred at room temperature by end of reaction
30.0min.Filtering, 2 × 10mL dehydrated alcohol washing gained filter cake, merges ethanol solution, and gained ethanol solution is settled to
100mL.10mL acquired solution is pipetted, internal standard 2- naphthoic acid is added, carries out liquid-phase chromatographic analysis.Isopropylbenzene conversion ratio 18%, 2-
Phenyl -2- propyl alcohol selectivity 88%, acetophenone selectivity 3%, 2- phenyl -2- propyl hydrogen peroxide selectivity 9% (1H NMR
Analysis obtains), apparent benzoic acid is not detected.
Embodiment 5
In 100mL agate jar, by 1.20g (10mmol) isopropylbenzene, 0.0008g (0.0010mmol) 5,10,15,
20- tetra- (4- chlorphenyl) PORPHYRIN IRON (II), 6.44g (50mmol) 70%t- butyl peroxy aqueous solution of hydrogen and the anhydrous sulphur of 6.00g
Sour sodium is uniformly mixed, and seals ball grinder.At room temperature, ball-milling reaction 12.0h under 600rpm revolving speed stops ball milling one every 1.0h
It is secondary, release gas in ball grinder.Gained reaction mixture is dissolved in 30mL dehydrated alcohol, stirred at room temperature by end of reaction
30.0min.Filtering, 2 × 10mL dehydrated alcohol washing gained filter cake, merges ethanol solution, and gained ethanol solution is settled to
100mL.10mL acquired solution is pipetted, internal standard 2- naphthoic acid is added, carries out liquid-phase chromatographic analysis.Isopropylbenzene conversion ratio 51%, 2-
Phenyl -2- propyl alcohol selectivity 92%, acetophenone selectivity 3%, 2- phenyl -2- propyl hydrogen peroxide selectivity 5% (1H NMR
Analysis obtains), apparent benzoic acid is not detected.
Embodiment 6
In 100mL agate jar, by 1.20g (10mmol) isopropylbenzene, 0.0008g (0.0010mmol) 5,10,15,
20- tetra- (4- chlorphenyl) PORPHYRIN IRON (II), 6.44g (50mmol) 70%t- butyl peroxy aqueous solution of hydrogen and the anhydrous sulphur of 4.80g
Sour sodium is uniformly mixed, and seals ball grinder.At room temperature, ball-milling reaction 12.0h under 600rpm revolving speed stops ball milling one every 1.0h
It is secondary, release gas in ball grinder.Gained reaction mixture is dissolved in 30mL dehydrated alcohol, stirred at room temperature by end of reaction
30.0min.Filtering, 2 × 10mL dehydrated alcohol washing gained filter cake, merges ethanol solution, and gained ethanol solution is settled to
100mL.10mL acquired solution is pipetted, internal standard 2- naphthoic acid is added, carries out liquid-phase chromatographic analysis.Isopropylbenzene conversion ratio 48%, 2-
Phenyl -2- propyl alcohol selectivity 90%, acetophenone selectivity 4%, 2- phenyl -2- propyl hydrogen peroxide selectivity 6% (1H NMR
Analysis obtains), apparent benzoic acid is not detected.
Embodiment 7
In 100mL agate jar, by 1.20g (10mmol) isopropylbenzene, 0.0008g (0.0010mmol) 5,10,15,
20- tetra- (4- chlorphenyl) PORPHYRIN IRON (II), 6.44g (50mmol) 70%t- butyl peroxy aqueous solution of hydrogen and the anhydrous sulphur of 7.20g
Sour sodium is uniformly mixed, and seals ball grinder.At room temperature, ball-milling reaction 12.0h under 600rpm revolving speed stops ball milling one every 1.0h
It is secondary, release gas in ball grinder.Gained reaction mixture is dissolved in 30mL dehydrated alcohol, stirred at room temperature by end of reaction
30.0min.Filtering, 2 × 10mL dehydrated alcohol washing gained filter cake, merges ethanol solution, and gained ethanol solution is settled to
100mL.10mL acquired solution is pipetted, internal standard 2- naphthoic acid is added, carries out liquid-phase chromatographic analysis.Isopropylbenzene conversion ratio 50%, 2-
Phenyl -2- propyl alcohol selectivity 92%, acetophenone selectivity 5%, 2- phenyl -2- propyl hydrogen peroxide selectivity 3% (1H NMR
Analysis obtains), apparent benzoic acid is not detected.
Embodiment 8
In 100mL agate jar, by 1.20g (10mmol) isopropylbenzene, 0.0008g (0.0010mmol) 5,10,15,
20- tetra- (4- chlorphenyl) PORPHYRIN IRON (II), 6.44g (50mmol) 70%t- butyl peroxy aqueous solution of hydrogen and 12.00g are anhydrous
Sodium sulphate is uniformly mixed, and seals ball grinder.At room temperature, ball-milling reaction 12.0h under 600rpm revolving speed stops ball milling one every 1.0h
It is secondary, release gas in ball grinder.Gained reaction mixture is dissolved in 30mL dehydrated alcohol, stirred at room temperature by end of reaction
30.0min.Filtering, 2 × 10mL dehydrated alcohol washing gained filter cake, merges ethanol solution, and gained ethanol solution is settled to
100mL.10mL acquired solution is pipetted, internal standard 2- naphthoic acid is added, carries out liquid-phase chromatographic analysis.Isopropylbenzene conversion ratio 29%, 2-
Phenyl -2- propyl alcohol selectivity 86%, acetophenone selectivity 6%, 2- phenyl -2- propyl hydrogen peroxide selectivity 8% (1H NMR
Analysis obtains), apparent benzoic acid is not detected.
Embodiment 9
In 100mL agate jar, by 1.20g (10mmol) isopropylbenzene, 0.0008g (0.0010mmol) 5,10,15,
20- tetra- (4- chlorphenyl) PORPHYRIN IRON (II), 6.44g (50mmol) 70%t- butyl peroxy aqueous solution of hydrogen and the anhydrous sulphur of 6.00g
Sour sodium is uniformly mixed, and seals ball grinder.At room temperature, ball-milling reaction 12.0h under 500rpm revolving speed stops ball milling one every 1.0h
It is secondary, release gas in ball grinder.Gained reaction mixture is dissolved in 30mL dehydrated alcohol, stirred at room temperature by end of reaction
30.0min.Filtering, 2 × 10mL dehydrated alcohol washing gained filter cake, merges ethanol solution, and gained ethanol solution is settled to
100mL.10mL acquired solution is pipetted, internal standard 2- naphthoic acid is added, carries out liquid-phase chromatographic analysis.Isopropylbenzene conversion ratio 26%, 2-
Phenyl -2- propyl alcohol selectivity 81%, acetophenone selectivity 5%, 2- phenyl -2- propyl hydrogen peroxide selectivity 14% (1H NMR
Analysis obtains), apparent benzoic acid is not detected.
Embodiment 10
In 100mL agate jar, by 1.20g (10mmol) isopropylbenzene, 0.0008g (0.0010mmol) 5,10,15,
20- tetra- (4- chlorphenyl) PORPHYRIN IRON (II), 6.44g (50mmol) 70%t- butyl peroxy aqueous solution of hydrogen and the anhydrous sulphur of 6.00g
Sour sodium is uniformly mixed, and seals ball grinder.At room temperature, ball-milling reaction 12.0h under 100rpm revolving speed stops ball milling one every 1.0h
It is secondary, release gas in ball grinder.Gained reaction mixture is dissolved in 30mL dehydrated alcohol, stirred at room temperature by end of reaction
30.0min.Filtering, 2 × 10mL dehydrated alcohol washing gained filter cake, merges ethanol solution, and gained ethanol solution is settled to
100mL.10mL acquired solution is pipetted, internal standard 2- naphthoic acid is added, carries out liquid-phase chromatographic analysis.Isopropylbenzene conversion ratio 12%, 2-
Phenyl -2- propyl alcohol selectivity 16%, acetophenone selectivity 1%, 2- phenyl -2- propyl hydrogen peroxide selectivity 83% (1H NMR
Analysis obtains), apparent benzoic acid is not detected.
Embodiment 11
In 100mL agate jar, by 1.20g (10mmol) isopropylbenzene, 0.0008g (0.0010mmol) 5,10,15,
20- tetra- (4- chlorphenyl) PORPHYRIN IRON (II), 6.44g (50mmol) 70%t- butyl peroxy aqueous solution of hydrogen and the anhydrous sulphur of 6.00g
Sour sodium is uniformly mixed, and seals ball grinder.At room temperature, ball-milling reaction 12.0h under 800rpm revolving speed stops ball milling one every 1.0h
It is secondary, release gas in ball grinder.Gained reaction mixture is dissolved in 30mL dehydrated alcohol, stirred at room temperature by end of reaction
30.0min.Filtering, 2 × 10mL dehydrated alcohol washing gained filter cake, merges ethanol solution, and gained ethanol solution is settled to
100mL.10mL acquired solution is pipetted, internal standard 2- naphthoic acid is added, carries out liquid-phase chromatographic analysis.Isopropylbenzene conversion ratio 54%, 2-
Phenyl -2- propyl alcohol selectivity 90%, acetophenone selectivity 4%, 2- phenyl -2- propyl hydrogen peroxide selectivity 6% (1H NMR
Analysis obtains), apparent benzoic acid is not detected.
Embodiment 12
In 100mL agate jar, by 1.20g (10mmol) isopropylbenzene, 0.0008g (0.0010mmol) 5,10,15,
20- tetra- (4- chlorphenyl) PORPHYRIN IRON (II), 6.44g (50mmol) 70%t- butyl peroxy aqueous solution of hydrogen and the anhydrous sulphur of 6.00g
Sour sodium is uniformly mixed, and seals ball grinder.At room temperature, ball-milling reaction 8.0h under 800rpm revolving speed, it is primary every 1.0h stopping ball milling,
Release gas in ball grinder.Gained reaction mixture is dissolved in 30mL dehydrated alcohol, stirs 30.0min at room temperature by end of reaction.
Filtering, 2 × 10mL dehydrated alcohol washing gained filter cake, merges ethanol solution, and gained ethanol solution is settled to 100mL.It moves
10mL acquired solution is taken, internal standard 2- naphthoic acid is added, carries out liquid-phase chromatographic analysis.Isopropylbenzene conversion ratio 42%, 2- phenyl -2- third
Alcohol selectivity 88%, acetophenone selectivity 7%, 2- phenyl -2- propyl hydrogen peroxide selectivity 5% (1H NMR analysis obtains),
Apparent benzoic acid is not detected.
Embodiment 13
In 100mL agate jar, by 1.20g (10mmol) isopropylbenzene, 0.0008g (0.0010mmol) 5,10,15,
20- tetra- (4- chlorphenyl) PORPHYRIN IRON (II), 6.44g (50mmol) 70%t- butyl peroxy aqueous solution of hydrogen and the anhydrous sulphur of 6.00g
Sour sodium is uniformly mixed, and seals ball grinder.At room temperature, ball-milling reaction 16.0h under 800rpm revolving speed stops ball milling one every 1.0h
It is secondary, release gas in ball grinder.Gained reaction mixture is dissolved in 30mL dehydrated alcohol, stirred at room temperature by end of reaction
30.0min.Filtering, 2 × 10mL dehydrated alcohol washing gained filter cake, merges ethanol solution, and gained ethanol solution is settled to
100mL.10mL acquired solution is pipetted, internal standard 2- naphthoic acid is added, carries out liquid-phase chromatographic analysis.Isopropylbenzene conversion ratio 56%, 2-
Phenyl -2- propyl alcohol selectivity 92%, acetophenone selectivity 4%, 2- phenyl -2- propyl hydrogen peroxide selectivity 4% (1H NMR
Analysis obtains), apparent benzoic acid is not detected.
Embodiment 14
In 100mL agate jar, by 1.20g (10mmol) isopropylbenzene, 0.0008g (0.0010mmol) 5,10,15,
20- tetra- (4- chlorphenyl) PORPHYRIN IRON (II), 6.44g (50mmol) 70%t- butyl peroxy aqueous solution of hydrogen and the anhydrous sulphur of 6.00g
Sour sodium is uniformly mixed, and seals ball grinder.At room temperature, ball-milling reaction 3.0h under 800rpm revolving speed, it is primary every 1.0h stopping ball milling,
Release gas in ball grinder.Gained reaction mixture is dissolved in 30mL dehydrated alcohol, stirs 30.0min at room temperature by end of reaction.
Filtering, 2 × 10mL dehydrated alcohol washing gained filter cake, merges ethanol solution, and gained ethanol solution is settled to 100mL.It moves
10mL acquired solution is taken, internal standard 2- naphthoic acid is added, carries out liquid-phase chromatographic analysis.Isopropylbenzene conversion ratio 11%, 2- phenyl -2- third
Alcohol selectivity 64%, acetophenone selectivity 2%, 2- phenyl -2- propyl hydrogen peroxide selectivity 34% (1H NMR analysis obtains
), apparent benzoic acid is not detected.
Embodiment 15
In 100mL agate jar, by 1.20g (10mmol) isopropylbenzene, 0.0008g (0.0010mmol) 5,10,15,
20- tetra- (4- chlorphenyl) PORPHYRIN IRON (II), 6.44g (50mmol) 70%t- butyl peroxy aqueous solution of hydrogen and the anhydrous sulphur of 6.00g
Sour sodium is uniformly mixed, and seals ball grinder.At room temperature, ball-milling reaction 24.0h under 800rpm revolving speed stops ball milling one every 1.0h
It is secondary, release gas in ball grinder.Gained reaction mixture is dissolved in 30mL dehydrated alcohol, stirred at room temperature by end of reaction
30.0min.Filtering, 2 × 10mL dehydrated alcohol washing gained filter cake, merges ethanol solution, and gained ethanol solution is settled to
100mL.10mL acquired solution is pipetted, internal standard 2- naphthoic acid is added, carries out liquid-phase chromatographic analysis.Isopropylbenzene conversion ratio 53%, 2-
Phenyl -2- propyl alcohol selectivity 87%, acetophenone selectivity 7%, 2- phenyl -2- propyl hydrogen peroxide selectivity 6% (1H NMR
Analysis obtains), apparent benzoic acid is not detected.
Embodiment 16
In 100mL agate jar, by 1.20g (10mmol) isopropylbenzene, 0.0008g (0.0010mmol) 5,10,15,
20- tetra- (4- chlorphenyl) PORPHYRIN IRON (II), 30% aqueous hydrogen peroxide solution of 5.67g (50mmol) and 7.20g anhydrous sodium sulfate are mixed
It closes uniformly, seals ball grinder.At room temperature, ball-milling reaction 16.0h under 800rpm revolving speed, it is primary every 1.0h stopping ball milling, it releases
Gas in ball grinder.Gained reaction mixture is dissolved in 30mL dehydrated alcohol, stirs 30.0min at room temperature by end of reaction.It crosses
Filter, 2 × 10mL dehydrated alcohol washing gained filter cake, merges ethanol solution, and gained ethanol solution is settled to 100mL.It pipettes
Internal standard 2- naphthoic acid is added in 10mL acquired solution, carries out liquid-phase chromatographic analysis.Isopropylbenzene conversion ratio 46%, 2- phenyl -2- third
Alcohol selectivity 89%, acetophenone selectivity 3%, 2- phenyl -2- propyl hydrogen peroxide selectivity 8% (1H NMR analysis obtains),
Apparent benzoic acid is not detected.
Embodiment 17
In 100mL agate jar, by 1.20g (10mmol) isopropylbenzene, 0.0008g (0.0010mmol) 5,10,15,
20- tetra- (4- chlorphenyl) PORPHYRIN IRON (II), 30% aqueous hydrogen peroxide solution of 5.67g (50mmol) and 6.00g anhydrous sodium sulfate are mixed
It closes uniformly, seals ball grinder.At room temperature, ball-milling reaction 16.0h under 800rpm revolving speed, it is primary every 1.0h stopping ball milling, it releases
Gas in ball grinder.Gained reaction mixture is dissolved in 30mL dehydrated alcohol, stirs 30.0min at room temperature by end of reaction.It crosses
Filter, 2 × 10mL dehydrated alcohol washing gained filter cake, merges ethanol solution, and gained ethanol solution is settled to 100mL.It pipettes
Internal standard 2- naphthoic acid is added in 10mL acquired solution, carries out liquid-phase chromatographic analysis.Isopropylbenzene conversion ratio 51%, 2- phenyl -2- third
Alcohol selectivity 89%, acetophenone selectivity 3%, 2- phenyl -2- propyl hydrogen peroxide selectivity 8% (1H NMR analysis obtains),
Apparent benzoic acid is not detected.
Embodiment 18
In 100mL agate jar, by 1.20g (10mmol) isopropylbenzene, 0.0008g (0.0010mmol) 5,10,15,
20- tetra- (4- chlorphenyl) PORPHYRIN IRON (II), 30% aqueous hydrogen peroxide solution of 5.67g (50mmol) and 12.00g anhydrous sodium sulfate
It is uniformly mixed, seals ball grinder.At room temperature, ball-milling reaction 16.0h under 800rpm revolving speed, it is primary every 1.0h stopping ball milling, it puts
Gas in ball grinder out.Gained reaction mixture is dissolved in 30mL dehydrated alcohol, stirs 30.0min at room temperature by end of reaction.It crosses
Filter, 2 × 10mL dehydrated alcohol washing gained filter cake, merges ethanol solution, and gained ethanol solution is settled to 100mL.It pipettes
Internal standard 2- naphthoic acid is added in 10mL acquired solution, carries out liquid-phase chromatographic analysis.Isopropylbenzene conversion ratio 23%, 2- phenyl -2- third
Alcohol selectivity 72%, acetophenone selectivity 4%, 2- phenyl -2- propyl hydrogen peroxide selectivity 24% (1H NMR analysis obtains
), apparent benzoic acid is not detected.
Embodiment 19
In 100mL agate jar, by 1.20g (10mmol) isopropylbenzene, 0.0008g (0.0010mmol) 5,10,15,
20- tetra- (4- chlorphenyl) PORPHYRIN IRON (II), 30% aqueous hydrogen peroxide solution of 5.67g (50mmol) and 7.20g anhydrous sodium sulfate are mixed
It closes uniformly, seals ball grinder.At room temperature, ball-milling reaction 8.0h under 800rpm revolving speed, it is primary every 1.0h stopping ball milling, release ball
Gas in grinding jar.Gained reaction mixture is dissolved in 30mL dehydrated alcohol, stirs 30.0min at room temperature by end of reaction.Filtering, 2
× 10mL dehydrated alcohol washing gained filter cake, merges ethanol solution, and gained ethanol solution is settled to 100mL.Pipette 10mL
Internal standard 2- naphthoic acid is added in acquired solution, carries out liquid-phase chromatographic analysis.Isopropylbenzene conversion ratio 33%, the choosing of 2- phenyl -2- propyl alcohol
Selecting property 68%, acetophenone selectivity 6%, 2- phenyl -2- propyl hydrogen peroxide selectivity 26% (1H NMR analysis obtains), not
Detect apparent benzoic acid.
Embodiment 20
In 100mL agate jar, by 1.20g (10mmol) isopropylbenzene, 0.0008g (0.0010mmol) 5,10,15,
20- tetra- (4- chlorphenyl) PORPHYRIN IRON (II), 0.90g (10mmol) sodium chlorite and 2.40g anhydrous sodium sulfate are uniformly mixed, close
Blocking grinding jar.At room temperature, ball-milling reaction 12.0h under 800rpm revolving speed, it is primary every 1.0h stopping ball milling, it releases in ball grinder
Gas.Gained reaction mixture is dissolved in 30mL dehydrated alcohol, stirs 30.0min at room temperature by end of reaction.Filtering, 2 × 10mL
Dehydrated alcohol washing gained filter cake, merges ethanol solution, and gained ethanol solution is settled to 100mL.It pipettes molten obtained by 10mL
Internal standard 2- naphthoic acid is added in liquid, carries out liquid-phase chromatographic analysis.Isopropylbenzene conversion ratio 14%, 2- phenyl -2- propyl alcohol selectivity
91%, acetophenone selectivity 3%, 2- phenyl -2- propyl hydrogen peroxide selectivity 6% (1H NMR analysis obtains), it is not detected
Apparent benzoic acid.
Embodiment 21
In 100mL agate jar, by 1.20g (10mmol) isopropylbenzene, 0.0008g (0.0010mmol) 5,10,15,
20- tetra- (4- chlorphenyl) PORPHYRIN IRON (II), 4.51g (50mmol) sodium chlorite and 6.00g anhydrous sodium sulfate are uniformly mixed, close
Blocking grinding jar.At room temperature, ball-milling reaction 12.0h under 800rpm revolving speed, it is primary every 1.0h stopping ball milling, it releases in ball grinder
Gas.Gained reaction mixture is dissolved in 30mL dehydrated alcohol, stirs 30.0min at room temperature by end of reaction.Filtering, 2 × 10mL
Dehydrated alcohol washing gained filter cake, merges ethanol solution, and gained ethanol solution is settled to 100mL.It pipettes molten obtained by 10mL
Internal standard 2- naphthoic acid is added in liquid, carries out liquid-phase chromatographic analysis.Isopropylbenzene conversion ratio 49%, 2- phenyl -2- propyl alcohol selectivity
86%, acetophenone selectivity 9%, 2- phenyl -2- propyl hydrogen peroxide selectivity 5% (1H NMR analysis obtains), it is not detected
Apparent benzoic acid.
Embodiment 22
In 100mL agate jar, by 1.20g (10mmol) isopropylbenzene, 0.0008g (0.0010mmol) 5,10,15,
20- tetra- (4- chlorphenyl) PORPHYRIN IRON (II), 4.51g (50mmol) sodium chlorite and 6.00g anhydrous sodium sulfate are uniformly mixed, close
Blocking grinding jar.At room temperature, ball-milling reaction 8.0h under 800rpm revolving speed, it is primary every 1.0h stopping ball milling, release gas in ball grinder
Body.Gained reaction mixture is dissolved in 30mL dehydrated alcohol, stirs 30.0min at room temperature by end of reaction.Filtering, 2 × 10mL without
Water-ethanol washing gained filter cake, merges ethanol solution, and gained ethanol solution is settled to 100mL.10mL acquired solution is pipetted,
Internal standard 2- naphthoic acid is added, carries out liquid-phase chromatographic analysis.Isopropylbenzene conversion ratio 39%, 2- phenyl -2- propyl alcohol selectivity 90%, benzene
Ethyl ketone selectivity 6%, 2- phenyl -2- propyl hydrogen peroxide selectivity 4% (1H NMR analysis obtains), apparent benzene is not detected
Formic acid.
Embodiment 23
In 100mL agate jar, by 1.20g (10mmol) isopropylbenzene, 0.0008g (0.0010mmol) 5,10,15,
20- tetra- (4- chlorphenyl) PORPHYRIN IRON (II), 4.51g (50mmol) sodium chlorite and 6.00g anhydrous sodium sulfate are uniformly mixed, close
Blocking grinding jar.At room temperature, ball-milling reaction 16.0h under 800rpm revolving speed, it is primary every 1.0h stopping ball milling, it releases in ball grinder
Gas.Gained reaction mixture is dissolved in 30mL dehydrated alcohol, stirs 30.0min at room temperature by end of reaction.Filtering, 2 × 10mL
Dehydrated alcohol washing gained filter cake, merges ethanol solution, and gained ethanol solution is settled to 100mL.It pipettes molten obtained by 10mL
Internal standard 2- naphthoic acid is added in liquid, carries out liquid-phase chromatographic analysis.Isopropylbenzene conversion ratio 51%, 2- phenyl -2- propyl alcohol selectivity
90%, acetophenone selectivity 5%, 2- phenyl -2- propyl hydrogen peroxide selectivity 5% (1H NMR analysis obtains), it is not detected
Apparent benzoic acid.
Embodiment 24
In 100mL agate jar, by 1.20g (10mmol) isopropylbenzene, 0.0008g (0.0010mmol) 5,10,15,
20- tetra- (4- chlorphenyl) PORPHYRIN IRON (II), 6.44g (50mmol) 70%t- butyl peroxy aqueous solution of hydrogen and 6.00g neutrality three
Al 2 O is uniformly mixed, and seals ball grinder.At room temperature, ball-milling reaction 16.0h under 800rpm revolving speed stops ball milling every 1.0h
Once, gas in ball grinder is released.Gained reaction mixture is dissolved in 30mL dehydrated alcohol, stirred at room temperature by end of reaction
30.0min.Filtering, 2 × 10mL dehydrated alcohol washing gained filter cake, merges ethanol solution, and gained ethanol solution is settled to
100mL.10mL acquired solution is pipetted, internal standard 2- naphthoic acid is added, carries out liquid-phase chromatographic analysis.Isopropylbenzene conversion ratio 42%, 2-
Phenyl -2- propyl alcohol selectivity 91%, acetophenone selectivity 5%, 2- phenyl -2- propyl hydrogen peroxide selectivity 4% (1H NMR points
Analysis obtains), apparent benzoic acid is not detected.
Embodiment 25
In 100mL agate jar, by 1.20g (10mmol) isopropylbenzene, 0.0008g (0.0010mmol) 5,10,15,
20- tetra- (4- chlorphenyl) PORPHYRIN IRON (II), 6.44g (50mmol) 70%t- butyl peroxy aqueous solution of hydrogen and the anhydrous sulphur of 6.00g
Sour magnesium is uniformly mixed, and seals ball grinder.At room temperature, ball-milling reaction 16.0h under 800rpm revolving speed stops ball milling one every 1.0h
It is secondary, release gas in ball grinder.Gained reaction mixture is dissolved in 30mL dehydrated alcohol, stirred at room temperature by end of reaction
30.0min.Filtering, 2 × 10mL dehydrated alcohol washing gained filter cake, merges ethanol solution, and gained ethanol solution is settled to
100mL.10mL acquired solution is pipetted, internal standard 2- naphthoic acid is added, carries out liquid-phase chromatographic analysis.Isopropylbenzene conversion ratio 51%, 2-
Phenyl -2- propyl alcohol selectivity 89%, acetophenone selectivity 5%, 2- phenyl -2- propyl hydrogen peroxide selectivity 6% (1H NMR
Analysis obtains), apparent benzoic acid is not detected.
Embodiment 26
In 100mL agate jar, by 1.20g (10mmol) isopropylbenzene, 0.0008g (0.0010mmol) 5,10,15,
20- tetra- (4- chlorphenyl) PORPHYRIN IRON (II), 6.44g (50mmol) 70%t- butyl peroxy aqueous solution of hydrogen and 6.00g silica gel are mixed
It closes uniformly, seals ball grinder.At room temperature, ball-milling reaction 16.0h under 800rpm revolving speed, it is primary every 1.0h stopping ball milling, it releases
Gas in ball grinder.Gained reaction mixture is dissolved in 30mL dehydrated alcohol, stirs 30.0min at room temperature by end of reaction.It crosses
Filter, 2 × 10mL dehydrated alcohol washing gained filter cake, merges ethanol solution, and gained ethanol solution is settled to 100mL.It pipettes
Internal standard 2- naphthoic acid is added in 10mL acquired solution, carries out liquid-phase chromatographic analysis.Isopropylbenzene conversion ratio 51%, 2- phenyl -2- third
Alcohol selectivity 92%, acetophenone selectivity 2%, 2- phenyl -2- propyl hydrogen peroxide selectivity 6% (1H NMR analysis obtains),
Apparent benzoic acid is not detected.
Embodiment 27
In 100mL agate jar, by 1.20g (10mmol) isopropylbenzene, 0.0008g (0.0010mmol) 5,10,15,
20- tetra- (2- chlorphenyl) PORPHYRIN IRON (II), 6.44g (50mmol) 70%t- butyl peroxy aqueous solution of hydrogen and the anhydrous sulphur of 6.00g
Sour sodium is uniformly mixed, and seals ball grinder.At room temperature, ball-milling reaction 16.0h under 800rpm revolving speed stops ball milling one every 1.0h
It is secondary, release gas in ball grinder.Gained reaction mixture is dissolved in 30mL dehydrated alcohol, stirred at room temperature by end of reaction
30.0min.Filtering, 2 × 10mL dehydrated alcohol washing gained filter cake, merges ethanol solution, and gained ethanol solution is settled to
100mL.10mL acquired solution is pipetted, internal standard 2- naphthoic acid is added, carries out liquid-phase chromatographic analysis.Isopropylbenzene conversion ratio 58%, 2-
Phenyl -2- propyl alcohol selectivity 94%, acetophenone selectivity 2%, 2- phenyl -2- propyl hydrogen peroxide selectivity 4% (1H NMR
Analysis obtains), apparent benzoic acid is not detected.
Embodiment 28
In 100mL agate jar, by 1.20g (10mmol) isopropylbenzene, 0.0009g (0.0010mmol) 5,10,15,
20- tetra- (2,6- dichlorophenyl) PORPHYRIN IRON (II), 6.44g (50mmol) 70%t- butyl peroxy aqueous solution of hydrogen and 6.00g without
Aqueous sodium persulfate is uniformly mixed, and seals ball grinder.At room temperature, ball-milling reaction 16.0h under 800rpm revolving speed stops ball milling every 1.0h
Once, gas in ball grinder is released.Gained reaction mixture is dissolved in 30mL dehydrated alcohol, stirred at room temperature by end of reaction
30.0min.Filtering, 2 × 10mL dehydrated alcohol washing gained filter cake, merges ethanol solution, and gained ethanol solution is settled to
100mL.10mL acquired solution is pipetted, internal standard 2- naphthoic acid is added, carries out liquid-phase chromatographic analysis.Isopropylbenzene conversion ratio 61%, 2-
Phenyl -2- propyl alcohol selectivity 90%, acetophenone selectivity 5%, 2- phenyl -2- propyl hydrogen peroxide selectivity 5% (1H NMR points
Analysis obtains), apparent benzoic acid is not detected.
Embodiment 29
In 100mL agate jar, by 1.20g (10mmol) isopropylbenzene, 0.0010g (0.0010mmol) 5,10,15,
20- tetra- (2,3,4,5,6- pentafluorophenyl group) PORPHYRIN IRON (II), 6.44g (50mmol) 70%t- butyl peroxy aqueous solution of hydrogen and
6.00g anhydrous sodium sulfate is uniformly mixed, and seals ball grinder.At room temperature, ball-milling reaction 16.0h under 800rpm revolving speed, every 1.0h
It is primary to stop ball milling, releases gas in ball grinder.Gained reaction mixture is dissolved in 30mL dehydrated alcohol, room temperature by end of reaction
Lower stirring 30.0min.Filtering, 2 × 10mL dehydrated alcohol washing gained filter cake, merges ethanol solution, and by gained ethanol solution
It is settled to 100mL.10mL acquired solution is pipetted, internal standard 2- naphthoic acid is added, carries out liquid-phase chromatographic analysis.Isopropylbenzene conversion ratio
66%, 2- phenyl -2- propyl alcohol selectivity 95%, acetophenone selectivity 3%, 2- phenyl -2- propyl hydrogen peroxide selectivity 2%
(1H NMR analysis obtains), apparent benzoic acid is not detected.
Embodiment 30
In 100mL agate jar, by 1.20g (10mmol) isopropylbenzene, 0.0007g (0.0010mmol) 5,10,15,
20- tetra- (4- aminomethyl phenyl) PORPHYRIN IRON (II), 6.44g (50mmol) 70%t- butyl peroxy aqueous solution of hydrogen and 6.00g are anhydrous
Sodium sulphate is uniformly mixed, and seals ball grinder.At room temperature, ball-milling reaction 16.0h under 800rpm revolving speed stops ball milling one every 1.0h
It is secondary, release gas in ball grinder.Gained reaction mixture is dissolved in 30mL dehydrated alcohol, stirred at room temperature by end of reaction
30.0min.Filtering, 2 × 10mL dehydrated alcohol washing gained filter cake, merges ethanol solution, and gained ethanol solution is settled to
100mL.10mL acquired solution is pipetted, internal standard 2- naphthoic acid is added, carries out liquid-phase chromatographic analysis.Isopropylbenzene conversion ratio 18%, 2-
Phenyl -2- propyl alcohol selectivity 69%, acetophenone selectivity 5%, 2- phenyl -2- propyl hydrogen peroxide selectivity 26% (1H NMR
Analysis obtains), apparent benzoic acid is not detected.
Embodiment 31
In 100mL agate jar, by 1.20g (10mmol) isopropylbenzene, 0.0008g (0.0010mmol) 5,10,15,
20- tetra- (4- carboxyl phenyl) PORPHYRIN IRON (II), 6.44g (50mmol) 70%t- butyl peroxy aqueous solution of hydrogen and 6.00g are anhydrous
Sodium sulphate is uniformly mixed, and seals ball grinder.At room temperature, ball-milling reaction 16.0h under 800rpm revolving speed stops ball milling one every 1.0h
It is secondary, release gas in ball grinder.Gained reaction mixture is dissolved in 30mL dehydrated alcohol, stirred at room temperature by end of reaction
30.0min.Filtering, 2 × 10mL dehydrated alcohol washing gained filter cake, merges ethanol solution, and gained ethanol solution is settled to
100mL.10mL acquired solution is pipetted, internal standard 2- naphthoic acid is added, carries out liquid-phase chromatographic analysis.Isopropylbenzene conversion ratio 56%, 2-
Phenyl -2- propyl alcohol selectivity 89%, acetophenone selectivity 7%, 2- phenyl -2- propyl hydrogen peroxide selectivity 4% (1H NMR points
Analysis obtains), apparent benzoic acid is not detected.
Embodiment 32
In 100mL agate jar, by 1.20g (10mmol) isopropylbenzene, 0.0008g (0.0010mmol) 5,10,15,
20- tetra- (4- fluorophenyl) PORPHYRIN IRON (II), 6.44g (50mmol) 70%t- butyl peroxy aqueous solution of hydrogen and the anhydrous sulphur of 6.00g
Sour sodium is uniformly mixed, and seals ball grinder.At room temperature, ball-milling reaction 16.0h under 800rpm revolving speed stops ball milling one every 1.0h
It is secondary, release gas in ball grinder.Gained reaction mixture is dissolved in 30mL dehydrated alcohol, stirred at room temperature by end of reaction
30.0min.Filtering, 2 × 10mL dehydrated alcohol washing gained filter cake, merges ethanol solution, and gained ethanol solution is settled to
100mL.10mL acquired solution is pipetted, internal standard 2- naphthoic acid is added, carries out liquid-phase chromatographic analysis.Isopropylbenzene conversion ratio 55%, 2-
Phenyl -2- propyl alcohol selectivity 92%, acetophenone selectivity 3%, 2- phenyl -2- propyl hydrogen peroxide selectivity 5% (1H NMR
Analysis obtains), apparent benzoic acid is not detected.
Embodiment 33
In 100mL agate jar, by 1.20g (10mmol) isopropylbenzene, 0.0008g (0.0010mmol) 5,10,15,
20- tetra- (4- cyano-phenyl) PORPHYRIN IRON (II), 6.44g (50mmol) 70%t- butyl peroxy aqueous solution of hydrogen and 6.00g are anhydrous
Sodium sulphate is uniformly mixed, and seals ball grinder.At room temperature, ball-milling reaction 16.0h under 800rpm revolving speed stops ball milling one every 1.0h
It is secondary, release gas in ball grinder.Gained reaction mixture is dissolved in 30mL dehydrated alcohol, stirred at room temperature by end of reaction
30.0min.Filtering, 2 × 10mL dehydrated alcohol washing gained filter cake, merges ethanol solution, and gained ethanol solution is settled to
100mL.10mL acquired solution is pipetted, internal standard 2- naphthoic acid is added, carries out liquid-phase chromatographic analysis.Isopropylbenzene conversion ratio 12%, 2-
Phenyl -2- propyl alcohol selectivity 64%, acetophenone selectivity 2%, 2- phenyl -2- propyl hydrogen peroxide selectivity 34% (1H NMR
Analysis obtains), apparent benzoic acid is not detected.
Embodiment 34
In 100mL agate jar, by 1.34g (10mmol) 4- cymene, 0.0010g (0.0010mmol) 5,
10,15,20- tetra- (2,3,4,5,6- pentafluorophenyl group) PORPHYRIN IRON (II), 6.44g (50mmol) 70%t- butylhydroperoxide water
Solution and 8.00g anhydrous sodium sulfate are uniformly mixed, and seal ball grinder.At room temperature, ball-milling reaction 16.0h under 800rpm revolving speed, often
It is primary every 1.0h stopping ball milling, release gas in ball grinder.Gained reaction mixture is dissolved in the anhydrous second of 30mL by end of reaction
Alcohol stirs 30.0min at room temperature.Filtering, 2 × 10mL dehydrated alcohol washing gained filter cake, merges ethanol solution, and by gained
Ethanol solution is settled to 100mL.20mL acquired solution is pipetted, precipitation is depressurized, reaction mixture (V obtained by column chromatography for separationHexamethylene︰
VEthyl acetate1~1 ︰ 4 of=4 ︰).4- cymene conversion ratio 57%, 2- (4- aminomethyl phenyl) -2- propyl alcohol selectivity 87%, 4- first
Benzoylformaldoxime selectivity 8%, 2- (4- aminomethyl phenyl) -2- propyl hydrogen peroxide selectivity 5%, is not detected apparent 4- methyl
Benzoic acid.
Embodiment 35
In 100mL agate jar, by 1.50g (10mmol) 4- methoxyl group isopropylbenzene, 0.0010g (0.0010mmol)
5,10,15,20- tetra- (2,3,4,5,6- pentafluorophenyl group) PORPHYRIN IRON (II), 6.44g (50mmol) 70%t- butylhydroperoxide
Aqueous solution and 8.00g anhydrous sodium sulfate are uniformly mixed, and seal ball grinder.At room temperature, ball-milling reaction 16.0h under 800rpm revolving speed,
It is primary every 1.0h stopping ball milling, release gas in ball grinder.Gained reaction mixture is dissolved in the anhydrous second of 30mL by end of reaction
Alcohol stirs 30.0min at room temperature.Filtering, 2 × 10mL dehydrated alcohol washing gained filter cake, merges ethanol solution, and by gained second
Alcoholic solution is settled to 100mL.20 mL acquired solutions are pipetted, precipitation is depressurized, reaction mixture (V obtained by column chromatography for separationHexamethylene︰
VEthyl acetate1~1 ︰ 4 of=4 ︰).4- methoxyl group isopropylbenzene conversion ratio 49%, 2- (4- methoxyphenyl) -2- propyl alcohol selectivity 85%,
4- methoxyacetophenone selectivity 6%, 2- (4- methoxyphenyl) -2- propyl hydrogen peroxide selectivity 9%, is not detected obvious
4- methoxy benzoic acid.
Embodiment 36
In 100mL agate jar, by 1.50g (10mmol) 2- methoxyl group isopropylbenzene, 0.0010g (0.0010mmol)
5,10,15,20- tetra- (2,3,4,5,6- pentafluorophenyl group) PORPHYRIN IRON (II), 6.44g (50mmol) 70%t- butylhydroperoxide
Aqueous solution and 8.00g anhydrous sodium sulfate are uniformly mixed, and seal ball grinder.At room temperature, ball-milling reaction 16.0h under 800rpm revolving speed,
It is primary every 1.0h stopping ball milling, release gas in ball grinder.Gained reaction mixture is dissolved in the anhydrous second of 30mL by end of reaction
Alcohol stirs 30.0min at room temperature.Filtering, 2 × 10mL dehydrated alcohol washing gained filter cake, merges ethanol solution, and by gained second
Alcoholic solution is settled to 100mL.20 mL acquired solutions are pipetted, precipitation is depressurized, reaction mixture (V obtained by column chromatography for separationHexamethylene︰
VEthyl acetate1~1 ︰ 4 of=4 ︰).2- methoxyl group isopropylbenzene conversion ratio 38%, 2- (2- methoxyphenyl) -2- propyl alcohol selectivity 89%,
2- methoxyacetophenone selectivity 6%, 2- (2- methoxyphenyl) -2- propyl hydrogen peroxide selectivity 5%, is not detected obvious
O-Anisic Acid.
Embodiment 37
In 100mL agate jar, by 1.65g (10mmol) 4- nitrocumene, 0.0010g (0.0010mmol) 5,
10,15,20- tetra- (2,3,4,5,6- pentafluorophenyl group) PORPHYRIN IRON (II), 6.44g (50mmol) 70%t- butylhydroperoxide water
Solution and 8.00g anhydrous sodium sulfate are uniformly mixed, and seal ball grinder.At room temperature, ball-milling reaction 16.0h under 800rpm revolving speed, often
It is primary every 1.0h stopping ball milling, release gas in ball grinder.Gained reaction mixture is dissolved in the anhydrous second of 30mL by end of reaction
Alcohol stirs 30.0min at room temperature.Filtering, 2 × 10mL dehydrated alcohol washing gained filter cake, merges ethanol solution, and by gained
Ethanol solution is settled to 100mL.20mL acquired solution is pipetted, precipitation is depressurized, reaction mixture (V obtained by column chromatography for separationHexamethylene︰
VEthyl acetate1~1 ︰ 4 of=4 ︰).4- nitrocumene conversion ratio 66%, 2- (4- nitrobenzophenone) -2- propyl alcohol selectivity 86%, 4- nitre
Benzoylformaldoxime selectivity 4%, 2- (4- nitrobenzophenone) -2- propyl hydrogen peroxide selectivity 10%, is not detected apparent 4- nitre
Yl benzoic acid.
Embodiment 38
In 100mL agate jar, by 1.64g (10mmol) 4- carboxyl isopropylbenzene, 0.0010g (0.0010mmol) 5,
10,15,20- tetra- (2,3,4,5,6- pentafluorophenyl group) PORPHYRIN IRON (II), 6.44g (50mmol) 70%t- butylhydroperoxide water
Solution and 8.00g anhydrous sodium sulfate are uniformly mixed, and seal ball grinder.At room temperature, ball-milling reaction 16.0h under 800rpm revolving speed, often
It is primary every 1.0h stopping ball milling, release gas in ball grinder.Gained reaction mixture is dissolved in the anhydrous second of 30mL by end of reaction
Alcohol stirs 30.0min at room temperature.Filtering, 2 × 10mL dehydrated alcohol washing gained filter cake, merges ethanol solution, and by gained
Ethanol solution is settled to 100mL.20mL acquired solution is pipetted, precipitation is depressurized, reaction mixture (V obtained by column chromatography for separationHexamethylene︰
VEthyl acetate1~1 ︰ 4 of=4 ︰).4- carboxyl isopropylbenzene conversion ratio 57%, 2- (4- carboxyl phenyl) -2- propyl alcohol selectivity 92%, 4- carboxylic
Benzoylformaldoxime selectivity 5%, 2- (4- carboxyl phenyl) -2- propyl hydrogen peroxide selectivity 3%, is not detected apparent 4- carboxyl
Benzoic acid.
Embodiment 39
In 100mL agate jar, by 1.96g (10mmol) 4- propyloxy phenyl benzene, 0.0010g (0.0010mmol) 5,
10,15,20- tetra- (2,3,4,5,6- pentafluorophenyl group) PORPHYRIN IRON (II), 6.44g (50mmol) 70%t- butylhydroperoxide water
Solution and 8.00g anhydrous sodium sulfate are uniformly mixed, and seal ball grinder.At room temperature, ball-milling reaction 16.0h under 800rpm revolving speed, often
It is primary every 1.0h stopping ball milling, release gas in ball grinder.Gained reaction mixture is dissolved in the anhydrous second of 30mL by end of reaction
Alcohol stirs 30.0min at room temperature.Filtering, 2 × 10mL dehydrated alcohol washing gained filter cake, merges ethanol solution, and by gained
Ethanol solution is settled to 100mL.20mL acquired solution is pipetted, precipitation is depressurized, reaction mixture (V obtained by column chromatography for separationHexamethylene︰
VEthyl acetate1~1 ︰ 4 of=4 ︰).4- propyloxy phenyl benzene conversion ratio 21%, 2- (4- phenyl) -2- propyl alcohol selectivity 92%, 4- benzene
Benzoylformaldoxime selectivity 3%, 2- (4- phenyl) -2- propyl hydrogen peroxide selectivity 5%, is not detected apparent 4- phenyl
Benzoic acid.
Embodiment 40
In 100mL agate jar, by 1.49g (10mmol) 4- methylamino isopropylbenzene, 0.0010g (0.0010mmol)
5,10,15,20- tetra- (2,3,4,5,6- pentafluorophenyl group) PORPHYRIN IRON (II), 6.44g (50mmol) 70%t- butylhydroperoxide
Aqueous solution and 8.00g anhydrous sodium sulfate are uniformly mixed, and seal ball grinder.At room temperature, ball-milling reaction 16.0h under 800rpm revolving speed,
It is primary every 1.0h stopping ball milling, release gas in ball grinder.Gained reaction mixture is dissolved in the anhydrous second of 30mL by end of reaction
Alcohol stirs 30.0min at room temperature.Filtering, 2 × 10mL dehydrated alcohol washing gained filter cake, merges ethanol solution, and by gained second
Alcoholic solution is settled to 100mL.20 mL acquired solutions are pipetted, precipitation is depressurized, reaction mixture (V obtained by column chromatography for separationHexamethylene︰
VEthyl acetate1~1 ︰ 4 of=4 ︰).4- methylamino isopropylbenzene conversion ratio 71%, 2- (4- methylaminophenyl) -2- propyl alcohol selectivity 32%,
4- methylamine benzoylformaldoxime selectivity 5%, 2- (4- methylaminophenyl) -2- propyl hydrogen peroxide selectivity 12%, is not detected bright
Aobvious 4- methylamine yl benzoic acid.
Embodiment 41
In 100mL agate jar, by 1.99g (10mmol) 4- bromine isopropylbenzene, 0.0010g (0.0010mmol) 5,
10,15,20- tetra- (2,3,4,5,6- pentafluorophenyl group) PORPHYRIN IRON (II), 6.44g (50mmol) 70%t- butylhydroperoxide water
Solution and 10.00g anhydrous sodium sulfate are uniformly mixed, and seal ball grinder.At room temperature, ball-milling reaction 16.0h under 800rpm revolving speed, often
It is primary every 1.0h stopping ball milling, release gas in ball grinder.Gained reaction mixture is dissolved in the anhydrous second of 30mL by end of reaction
Alcohol stirs 30.0min at room temperature.Filtering, 2 × 10mL dehydrated alcohol washing gained filter cake, merges ethanol solution, and by gained
Ethanol solution is settled to 100mL.20mL acquired solution is pipetted, precipitation is depressurized, reaction mixture (V obtained by column chromatography for separationHexamethylene︰
VEthyl acetate1~1 ︰ 4 of=4 ︰).4- bromine isopropylbenzene conversion ratio 58%, 2- (4- bromophenyl) -2- propyl alcohol selectivity 90%, 4- bromobenzene second
Ketone selectivity 5%, 2- (4- bromophenyl) -2- propyl hydrogen peroxide selectivity 5%, is not detected apparent 4- bromobenzoic acid.
Embodiment 42
In 100mL agate jar, by 1.36g (10mmol) 4- hydroxyl isopropylbenzene, 0.0010g (0.0010mmol) 5,
10,15,20- tetra- (2,3,4,5,6- pentafluorophenyl group) PORPHYRIN IRON (II), 6.44g (50mmol) 70%t- butylhydroperoxide water
Solution and 10.00g anhydrous sodium sulfate are uniformly mixed, and seal ball grinder.At room temperature, ball-milling reaction 16.0h under 800rpm revolving speed, often
It is primary every 1.0h stopping ball milling, release gas in ball grinder.Gained reaction mixture is dissolved in the anhydrous second of 30mL by end of reaction
Alcohol stirs 30.0min at room temperature.Filtering, 2 × 10mL dehydrated alcohol washing gained filter cake, merges ethanol solution, and by gained
Ethanol solution is settled to 100mL.20mL acquired solution is pipetted, precipitation is depressurized, reaction mixture (V obtained by column chromatography for separationHexamethylene︰
VEthyl acetate1~1 ︰ 4 of=4 ︰).4- hydroxyl isopropylbenzene conversion ratio 95%, 2- (4- hydroxy phenyl) -2- propyl alcohol selectivity 16%, 4- hydroxyl
Benzoylformaldoxime selectivity 0%, 2- (4- hydroxy phenyl) -2- propyl hydrogen peroxide selectivity 0%, is not detected apparent 4- hydroxyl
Benzoic acid.
Embodiment 43
In 100mL agate jar, by 1.36g (10mmol) 3- hydroxyl isopropylbenzene, 0.0010g (0.0010mmol) 5,
10,15,20- tetra- (2,3,4,5,6- pentafluorophenyl group) PORPHYRIN IRON (II), 6.44g (50mmol) 70%t- butylhydroperoxide water
Solution and 10.00g anhydrous sodium sulfate are uniformly mixed, and seal ball grinder.At room temperature, ball-milling reaction 16.0h under 800rpm revolving speed, often
It is primary every 1.0h stopping ball milling, release gas in ball grinder.Gained reaction mixture is dissolved in the anhydrous second of 30mL by end of reaction
Alcohol stirs 30.0min at room temperature.Filtering, 2 × 10mL dehydrated alcohol washing gained filter cake, merges ethanol solution, and by gained
Ethanol solution is settled to 100mL.20mL acquired solution is pipetted, precipitation is depressurized, reaction mixture (V obtained by column chromatography for separationHexamethylene︰
VEthyl acetate1~1 ︰ 4 of=4 ︰).3- hydroxyl isopropylbenzene conversion ratio 93%, 2- (3- hydroxy phenyl) -2- propyl alcohol selectivity 11%, 3- hydroxyl
Benzoylformaldoxime selectivity 0%, 2- (3- hydroxy phenyl) -2- propyl hydrogen peroxide selectivity 0%, is not detected apparent 3- hydroxyl
Benzoic acid.
Embodiment 44
In 100mL agate jar, by 1.35g (10mmol) 4- amino-cumene, 0.0010g (0.0010mmol) 5,
10,15,20- tetra- (2,3,4,5,6- pentafluorophenyl group) PORPHYRIN IRON (II), 6.44g (50mmol) 70%t- butylhydroperoxide water
Solution and 8.00g anhydrous sodium sulfate are uniformly mixed, and seal ball grinder.At room temperature, ball-milling reaction 16.0h under 800rpm revolving speed, often
It is primary every 1.0h stopping ball milling, release gas in ball grinder.Gained reaction mixture is dissolved in the anhydrous second of 30mL by end of reaction
Alcohol stirs 30.0min at room temperature.Filtering, 2 × 10mL dehydrated alcohol washing gained filter cake, merges ethanol solution, and by gained
Ethanol solution is settled to 100mL.20mL acquired solution is pipetted, precipitation is depressurized, reaction mixture (V obtained by column chromatography for separationHexamethylene︰
VEthyl acetate1~1 ︰ 4 of=4 ︰).4- amino-cumene conversion ratio 90%, 2- (4- aminophenyl) -2- propyl alcohol selectivity 25%, 4- ammonia
Benzoylformaldoxime selectivity 2%, 2- (4- aminophenyl) -2- propyl hydrogen peroxide selectivity 0%, is not detected apparent 4- amino
Benzoic acid.
Embodiment 45
In 100mL agate jar, by 1.35g (10mmol) 3- amino-cumene, 0.0010g (0.0010mmol) 5,
10,15,20- tetra- (2,3,4,5,6- pentafluorophenyl group) PORPHYRIN IRON (II), 6.44g (50mmol) 70%t- butylhydroperoxide water
Solution and 8.00g anhydrous sodium sulfate are uniformly mixed, and seal ball grinder.At room temperature, ball-milling reaction 16.0h under 800rpm revolving speed, often
It is primary every 1.0h stopping ball milling, release gas in ball grinder.Gained reaction mixture is dissolved in the anhydrous second of 30mL by end of reaction
Alcohol stirs 30.0min at room temperature.Filtering, 2 × 10mL dehydrated alcohol washing gained filter cake, merges ethanol solution, and by gained
Ethanol solution is settled to 100mL.20mL acquired solution is pipetted, precipitation is depressurized, reaction mixture (V obtained by column chromatography for separationHexamethylene︰
VEthyl acetate1~1 ︰ 4 of=4 ︰).3- amino-cumene conversion ratio 92%, 2- (3- aminophenyl) -2- propyl alcohol selectivity 28%, 3- ammonia
Benzoylformaldoxime selectivity 6%, 2- (3- aminophenyl) -2- propyl hydrogen peroxide selectivity 0%, is not detected apparent 3- amino
Benzoic acid.
Embodiment 46
In 100mL agate jar, by 1.62g (10mmol) 4- isopropyl propyl benzene, 0.0010g (0.0010mmol)
5,10,15,20- tetra- (2,3,4,5,6- pentafluorophenyl group) PORPHYRIN IRON (II), 6.44g (50mmol) 70%t- butylhydroperoxide
Aqueous solution and 8.00g anhydrous sodium sulfate are uniformly mixed, and seal ball grinder.At room temperature, ball-milling reaction 16.0h under 800rpm revolving speed,
It is primary every 1.0h stopping ball milling, release gas in ball grinder.Gained reaction mixture is dissolved in the anhydrous second of 30mL by end of reaction
Alcohol stirs 30.0min at room temperature.Filtering, 2 × 10mL dehydrated alcohol washing gained filter cake, merges ethanol solution, and by gained second
Alcoholic solution is settled to 100mL.20 mL acquired solutions are pipetted, precipitation is depressurized, reaction mixture (V obtained by column chromatography for separationHexamethylene︰
VEthyl acetate1~1 ︰ 4 of=4 ︰).4- isopropyl propyl benzene conversion ratio 62%, 2- (4- isopropyl phenyl) -2- propyl alcohol selectivity 61%,
4- cumene ethyl ketone selectivity 3%, 2- (4- isopropyl phenyl) -2- propyl hydrogen peroxide selectivity 0%, is not detected obvious
4- isopropyl acid.
Embodiment 47 (amplification test)
In 500mL agate jar, by 6.01g (50mmol) isopropylbenzene, 0.0040g (0.0050mmol) 5,10,15,
20- tetra- (2- chlorphenyl) PORPHYRIN IRON (II), 32.19g (250mmol) 70%t- butyl peroxy aqueous solution of hydrogen and 30.05g without
Aqueous sodium persulfate is uniformly mixed, and seals ball grinder.At room temperature, ball-milling reaction 16.0h under 800rpm revolving speed stops ball milling every 1.0h
Once, gas in ball grinder is released.Gained reaction mixture is dissolved in 150mL dehydrated alcohol, stirred at room temperature by end of reaction
30.0min.Filtering, 2 × 50mL dehydrated alcohol washing gained filter cake, merges ethanol solution.Dehydrated alcohol is recycled in air-distillation,
Isopropylbenzene 2.26g, conversion ratio 62%, the isolated 2- phenyl -2- propyl alcohol 3.88g of rectification under vacuum, selectivity are recycled in rectification under vacuum
92%.
Embodiment 48 (amplification test)
In 500mL agate jar, by 6.01g (50mmol) isopropylbenzene, 0.0040g (0.0050mmol) 5,10,15,
20- tetra- (4- chlorphenyl) PORPHYRIN IRON (II), 32.19g (250mmol) 70%t- butyl peroxy aqueous solution of hydrogen and 30.05g without
Aqueous sodium persulfate is uniformly mixed, and seals ball grinder.At room temperature, ball-milling reaction 16.0h under 800rpm revolving speed stops ball milling every 1.0h
Once, gas in ball grinder is released.Gained reaction mixture is dissolved in 150mL dehydrated alcohol, stirred at room temperature by end of reaction
30.0min.Filtering, 2 × 50mL dehydrated alcohol washing gained filter cake, merges ethanol solution.Dehydrated alcohol is recycled in air-distillation,
Isopropylbenzene 2.85g, conversion ratio 53%, the isolated 2- phenyl -2- propyl alcohol 3.18g of rectification under vacuum, selectivity are recycled in rectification under vacuum
88%.
Claims (7)
1. a kind of method of isopropyl benzene-like compounds selective oxidation, which is characterized in that the method are as follows:
Isopropyl benzene-like compounds shown in formula (I), ferriporphyrin catalyst, oxidant, dispersing agent are placed in ball grinder, ball milling is sealed
Tank with the revolving speed ball milling 3 of 100~800rpm~for 24 hours, in mechanical milling process, it is primary to stop ball milling every 1~3h, puts at room temperature
Gas in ball grinder out, end of reaction, reaction mixture is post-treated, obtains 2- phenyl -2- propyl alcohol class shown in product formula (II)
Compound；
The ratio between the ferriporphyrin catalyst and the amount of substance of isopropyl benzene-like compounds shown in formula (I) are 1:200000~1000；
The ratio between amount of substance of isopropyl benzene-like compounds shown in the formula (I) and oxidant is 1:1~50；
The mass ratio of isopropyl benzene-like compounds shown in the formula (I) and dispersing agent is 1:0.1~10；
The oxidant is t- butylhydroperoxide, hydrogen peroxide, sodium chlorite or sodium hypochlorite；
The dispersing agent is one or more of silica gel, neutral aluminum oxide, anhydrous sodium sulfate or anhydrous magnesium sulfate
The mixture of arbitrary proportion；
The ferriporphyrin catalyst is at least one of compound shown in formula (V):
In formula (V), Ra、Rb、Rc、Rd、ReIt is respectively independent are as follows: hydrogen, methyl, ethyl, propyl, butyl, isopropyl, tert-butyl, phenyl,
Methoxyl group, ethyoxyl, hydroxyl, sulfydryl, amino, methylamino, ethylamino, dimethylamino, 1- hydroxyethyl, nitro, cyano, carboxylic
Base, benzyl, fluorine, chlorine, bromine or iodine；
Shown in the structural formula such as formula (I) of the isopropyl benzene-like compounds, corresponding obtained product 2- phenyl -2- propanol compound
Structural formula such as formula (II) shown in:
In formula (I) or (II), R1、R2、R3、R4、R5It is respectively independent are as follows: hydrogen, methyl, ethyl, propyl, butyl, isopropyl, tertiary fourth
Base, phenyl, 1- naphthalene, 2- naphthalene, methoxyl group, ethyoxyl, hydroxyl, sulfydryl, amino, methylamino, ethylamino, dimethylamino, 1-
Hydroxyethyl, nitro, cyano, carboxyl, benzyl, fluorine, chlorine, bromine or iodine.
2. the method for isopropyl benzene-like compounds selective oxidation as described in claim 1, which is characterized in that the ferriporphyrin catalysis
The ratio between agent and the amount of substance of isopropyl benzene-like compounds shown in formula (I) are 1:20000~4000.
3. the method for isopropyl benzene-like compounds selective oxidation as described in claim 1, which is characterized in that shown in the formula (I)
The ratio between amount of substance of isopropyl benzene-like compounds and oxidant is 1:2~5.
4. the method for isopropyl benzene-like compounds selective oxidation as described in claim 1, which is characterized in that shown in the formula (I)
The mass ratio of isopropyl benzene-like compounds and dispersing agent is 1:3~5.
5. the method for isopropyl benzene-like compounds selective oxidation as described in claim 1, which is characterized in that the oxidant is t-
Butylhydroperoxide or hydrogen peroxide.
6. the method for isopropyl benzene-like compounds selective oxidation as described in claim 1, which is characterized in that the dispersing agent is nothing
Aqueous sodium persulfate or anhydrous magnesium sulfate.
7. the method for isopropyl benzene-like compounds selective oxidation as described in claim 1, which is characterized in that the ferriporphyrin catalysis
Agent be 5,10,15,20- tetra- (4- chlorphenyl) PORPHYRIN IRON (II), 5,10,15,20- tetra- (2- chlorphenyl) PORPHYRIN IRON (II), 5,10,
15,20- tetra- (2,6- dichlorophenyl) PORPHYRIN IRON (II), 5,10,15,20- tetra- (2,4 dichloro benzene base) PORPHYRIN IRON (II) or 5,10,
15,20- tetra- (2,3,4,5,6- pentafluorophenyl group) PORPHYRIN IRON (II)).
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| 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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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103058821A (en) * | 2012-12-20 | 2013-04-24 | 华南理工大学 | Synthesis method of 2-phenyl-2-propanol and acetophenone through catalytic oxidation of cumene |
| CN107879907A (en) * | 2017-09-26 | 2018-04-06 | 湖南大学 | A kind of high selectivity Oxidation Ethylbenzene acetophenone technique |
| CN109503328A (en) * | 2018-12-21 | 2019-03-22 | 大连理工大学 | The method of 2- phenyl -2- propyl alcohol is prepared at normal temperature |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103058821A (en) * | 2012-12-20 | 2013-04-24 | 华南理工大学 | Synthesis method of 2-phenyl-2-propanol and acetophenone through catalytic oxidation of cumene |
| CN107879907A (en) * | 2017-09-26 | 2018-04-06 | 湖南大学 | A kind of high selectivity Oxidation Ethylbenzene acetophenone technique |
| CN109503328A (en) * | 2018-12-21 | 2019-03-22 | 大连理工大学 | The method of 2- phenyl -2- propyl alcohol is prepared at normal temperature |
Non-Patent Citations (2)
| Title |
|---|
| JUN JIANG等: "Metalloporphyrin-mediated aerobic oxidation of hydrocarbons in cumene: Co-substrate specificity and mechanistic consideration", 《MOLECULAR CATALYSIS》 * |
| YUNING YANG等: "Selective Aerobic Oxidation of 4‑Ethylnitrobenzene to 4‑Nitroacetophenone Promoted by Metalloporphyrins", 《ORG. PROCESS RES. DEV.》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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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