CN110590559A - Method for selectively preparing benzoic acid and derivatives thereof by oxidizing toluene and derivatives thereof through ball milling method - Google Patents
Method for selectively preparing benzoic acid and derivatives thereof by oxidizing toluene and derivatives thereof through ball milling method Download PDFInfo
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- 238000000498 ball milling Methods 0.000 title claims abstract description 131
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 title claims abstract description 120
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 238000000034 method Methods 0.000 title claims abstract description 29
- 239000005711 Benzoic acid Substances 0.000 title claims abstract description 28
- 235000010233 benzoic acid Nutrition 0.000 title claims abstract description 28
- 230000001590 oxidative effect Effects 0.000 title claims abstract description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 255
- 238000006243 chemical reaction Methods 0.000 claims abstract description 115
- 235000019441 ethanol Nutrition 0.000 claims abstract description 63
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 48
- 230000003647 oxidation Effects 0.000 claims abstract description 47
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000011541 reaction mixture Substances 0.000 claims abstract description 36
- UOBYKYZJUGYBDK-UHFFFAOYSA-N 2-naphthoic acid Chemical compound C1=CC=CC2=CC(C(=O)O)=CC=C21 UOBYKYZJUGYBDK-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000001914 filtration Methods 0.000 claims abstract description 33
- 238000004811 liquid chromatography Methods 0.000 claims abstract description 33
- 238000005406 washing Methods 0.000 claims abstract description 33
- 238000007599 discharging Methods 0.000 claims abstract description 26
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- 239000007800 oxidant agent Substances 0.000 claims abstract description 9
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical class [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910000001 cobalt(II) carbonate Inorganic materials 0.000 claims abstract description 8
- 239000002270 dispersing agent Substances 0.000 claims abstract description 7
- 238000004458 analytical method Methods 0.000 claims abstract description 3
- 238000004440 column chromatography Methods 0.000 claims abstract description 3
- 238000007789 sealing Methods 0.000 claims abstract description 3
- 238000000926 separation method Methods 0.000 claims abstract description 3
- 239000007787 solid Substances 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims abstract description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 32
- 239000007789 gas Substances 0.000 claims description 32
- 229940011182 cobalt acetate Drugs 0.000 claims description 28
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 28
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical group CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 28
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 20
- UKLNMMHNWFDKNT-UHFFFAOYSA-M sodium chlorite Chemical compound [Na+].[O-]Cl=O UKLNMMHNWFDKNT-UHFFFAOYSA-M 0.000 claims description 8
- 229960002218 sodium chlorite Drugs 0.000 claims description 8
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 5
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 4
- -1 methoxy, ethoxy, hydroxy, mercapto, amino, methylamino, ethylamino, dimethylamino, 1-hydroxyethyl Chemical group 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 4
- 239000000741 silica gel Substances 0.000 claims description 4
- 229910002027 silica gel Inorganic materials 0.000 claims description 4
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 4
- 229910021446 cobalt carbonate Inorganic materials 0.000 claims description 3
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 3
- 229940044175 cobalt sulfate Drugs 0.000 claims description 3
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 3
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 3
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 claims description 3
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 claims description 2
- 125000001622 2-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C(*)C([H])=C([H])C2=C1[H] 0.000 claims description 2
- 125000001246 bromo group Chemical group Br* 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- FJDJVBXSSLDNJB-LNTINUHCSA-N cobalt;(z)-4-hydroxypent-3-en-2-one Chemical compound [Co].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FJDJVBXSSLDNJB-LNTINUHCSA-N 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000001153 fluoro group Chemical group F* 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 2
- 125000002346 iodo group Chemical group I* 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 150000004677 hydrates Chemical class 0.000 claims 6
- FHYLEJSGUQBKRQ-UHFFFAOYSA-N 6-methyl-7-oxabicyclo[4.1.0]hepta-2,4-diene Chemical compound C1=CC=CC2(C)C1O2 FHYLEJSGUQBKRQ-UHFFFAOYSA-N 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 abstract description 3
- 239000002904 solvent Substances 0.000 abstract description 2
- 150000005172 methylbenzenes Chemical class 0.000 abstract 1
- 125000002081 peroxide group Chemical group 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 92
- ZPTVNYMJQHSSEA-UHFFFAOYSA-N 4-nitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1 ZPTVNYMJQHSSEA-UHFFFAOYSA-N 0.000 description 58
- 239000000047 product Substances 0.000 description 34
- OTLNPYWUJOZPPA-UHFFFAOYSA-N 4-nitrobenzoic acid Chemical compound OC(=O)C1=CC=C([N+]([O-])=O)C=C1 OTLNPYWUJOZPPA-UHFFFAOYSA-N 0.000 description 30
- 239000012065 filter cake Substances 0.000 description 30
- 239000007864 aqueous solution Substances 0.000 description 20
- 238000001311 chemical methods and process Methods 0.000 description 8
- SAXCKUIOAKKRAS-UHFFFAOYSA-N cobalt;hydrate Chemical compound O.[Co] SAXCKUIOAKKRAS-UHFFFAOYSA-N 0.000 description 6
- 239000007790 solid phase Substances 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 5
- 231100000331 toxic Toxicity 0.000 description 5
- 230000002588 toxic effect Effects 0.000 description 5
- 230000007613 environmental effect Effects 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- 239000012847 fine chemical Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 230000003116 impacting effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003613 toluenes Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A method for selectively preparing benzoic acid and derivatives thereof by oxidizing toluene and derivatives thereof by a ball milling method comprises the steps of placing toluene and derivatives thereof, a cobalt (II) salt catalyst, an oxidant and a dispersant in an agate ball milling tank, sealing the ball milling tank, carrying out ball milling at room temperature, stopping ball milling once every 1.0h, and discharging gas in the ball milling tank; after the reaction is finished, dissolving the obtained reaction mixture in absolute ethyl alcohol, stirring for 30min at room temperature, filtering, washing the obtained solid by the absolute ethyl alcohol, combining the obtained ethanol solution, and fixing the volume; and (3) performing liquid chromatography analysis or column chromatography separation on the obtained reaction mixture by taking 2-naphthoic acid as an internal standard, and calculating the conversion rate of the toluene and the derivatives thereof and the selectivity of the benzoic acid and the derivatives thereof. The method has the advantages of low catalyst consumption, no solvent, no need of heating, low reaction temperature, convenient operation, high benzoic acid selectivity, no obvious peroxide residue, high safety coefficient and capability of realizing the selective oxidation of various methylbenzenes and derivatives thereof.
Description
Technical Field
The invention relates to a novel method for preparing benzoic acid and derivatives thereof by selective oxidation of toluene and derivatives thereof, belonging to the field of organic chemical industry and fine organic synthesis.
Background
Benzoic acid and derivatives thereof are important fine chemical intermediates and widely applied to synthesis of fine chemical products such as medicines, pesticides, dyes, spices and the like (WO 2019028362; CN 108774228; CN 108774218; Bioorganic and Medicinal Chemistry Letters 2019, 29: 115-12910; Journal of Agricultural and food Chemistry 2018, 66: 12898-12910). At present, the synthesis of benzoic acid and derivatives thereof is mainly realized by taking toluene, benzyl alcohol, benzaldehyde and derivatives thereof as raw materials through oxidation reaction (CN 107805194; CN 108467342; ACSCatalysis 2017, 7: 2786-. Wherein, the method takes toluene and derivatives thereof as raw materials and oxygen as an oxidant, and is a reaction route commonly adopted in industry. However, because aromatic hydrocarbon benzyl primary C-H bond has higher bond energy, the oxidation of toluene and its derivatives usually needs higher reaction temperature, the energy consumption is large, and the reaction is not easy to control; meanwhile, toxic and harmful organic solvents such as acetonitrile or corrosive auxiliaries such as acetic acid or nitric acid are used in the reaction process, so that the environmental compatibility of the existing industrial synthetic route of the benzoic acid and the derivatives thereof is poor, and the actual requirement of the existing 'green chemical process' is not met. Therefore, the development of a new method for oxidizing toluene and its derivatives to realize the selective synthesis of benzoic acid and its derivatives in a simple reaction manner under mild conditions is an urgent need for the oxidation conversion of toluene and its derivatives in the industry at present.
The solid phase ball milling reaction is characterized in that the interaction between interface materials is promoted by the actions of shearing, rubbing, impacting, extruding and the like between two interfaces which move relatively, so as to realize chemical reaction (Green Chemistry 2018, 20: 1435-. The solid-phase ball-milling reaction does not need a solvent, the reaction can be carried out at room temperature, the use of toxic and harmful organic solvents is effectively avoided, the materials do not need to be subjected to heat treatment, the energy consumption is low, and the safety coefficient is high. Meanwhile, due to the solid phase ball milling process, mechanical force is directly applied to the reaction mass, often resulting in a product distribution different from that of the liquid phase reaction. Under the urgent social requirements of development environment, society and human body compatibility chemical process, the solid phase ball milling is used for the catalytic oxidation of toluene and the derivatives thereof, so that the catalytic oxidation of toluene and the derivatives thereof can be realized at room temperature, the use of toxic and harmful organic solvents can be reduced, the distribution of oxidation products can be even changed, and the practical requirements of society and production are met.
According to the invention, catalytic oxidation of toluene and the derivatives thereof is carried out by using cobalt (II) salt as a catalyst and t-butyl hydroperoxide, hydrogen peroxide, sodium chlorite or sodium hypochlorite with good environmental compatibility as an oxidant through a solid-phase ball milling method, so that the toluene and the derivatives thereof are simply oxidized and converted under mild conditions, the use of toxic and harmful organic solvents is effectively avoided, the selectivity of benzoic acid and the derivatives thereof is remarkably improved, the social requirements of the current green chemical process, environmental compatibility chemical process and biological compatibility chemical process are met, and the method has important application value and theoretical research significance.
Disclosure of Invention
The invention aims to provide a novel method for preparing benzoic acid and derivatives thereof by selective oxidation of toluene and derivatives thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for selectively preparing benzoic acid and derivatives thereof by oxidizing toluene and derivatives thereof by a ball milling method comprises the following steps:
placing toluene and derivatives thereof, a cobalt (II) salt catalyst, an oxidant (t-butyl hydroperoxide, hydrogen peroxide, sodium chlorite or sodium hypochlorite) (preferably t-butyl hydroperoxide and hydrogen peroxide) and a dispersant (silica gel, neutral aluminum oxide, anhydrous sodium sulfate or anhydrous magnesium sulfate) (preferably anhydrous sodium sulfate and anhydrous magnesium sulfate) in an agate ball milling tank, sealing the ball milling tank, ball milling for 3.0-24.0 h (preferably 8.0-16.0 h) at the rotating speed of 100-800 rpm (preferably 500-800 rpm) at room temperature, stopping ball milling once every 1.0h, and discharging gas in the ball milling tank; after the reaction is finished, dissolving the obtained reaction mixture in absolute ethyl alcohol, stirring for 30min at room temperature, filtering, washing the obtained solid by the absolute ethyl alcohol, combining the obtained ethanol solution, and fixing the volume; and (3) performing liquid chromatography analysis or column chromatography separation on the obtained reaction mixture by taking 2-naphthoic acid as an internal standard, and calculating the conversion rate of the toluene and the derivatives thereof and the selectivity of the benzoic acid and the derivatives thereof.
Further, the reaction mode is ball milling.
And further, the structural formulas of the toluene and the derivatives thereof are shown as a formula (I), and the structural formulas of the obtained benzoic acid products and the derivatives thereof are shown as a formula (II) respectively.
In the formulae (I) and (II), R1、R2、R3、R4And R5Each independently hydrogen, methyl, ethyl, propyl, butyl, isopropyl, tert-butyl, phenyl, 1-naphthyl, 2-naphthyl, methoxy, ethoxy, hydroxy, mercapto, amino, methylamino, ethylamino, dimethylamino, 1-hydroxyethyl, nitro, cyano, carboxy, benzyl, fluoro, chloro, bromo, or iodo.
The catalyst cobalt (II) salt is anhydrous cobalt acetate and hydrate thereof, anhydrous cobalt sulfate and hydrate thereof, anhydrous cobalt chloride and hydrate thereof, anhydrous cobalt nitrate and hydrate thereof, anhydrous cobalt carbonate and hydrate thereof, anhydrous cobalt acetylacetonate and hydrate thereof or any combination thereof, and the molar ratio of the cobalt (II) salt catalyst to toluene and derivatives thereof is 1: 2000-1: 400, preferably 1: 1000-1: 500.
The reaction mode is ball milling; the oxidant is t-butyl hydroperoxide, hydrogen peroxide, sodium chlorite or sodium hypochlorite, and the t-butyl hydroperoxide and the hydrogen peroxide are preferred; the molar ratio of the toluene and the toluene derivatives to the oxidant is 1: 1-1: 30, preferably 1: 2-1: 5; the dispersing agent is silica gel, neutral aluminum oxide, anhydrous sodium sulfate or anhydrous magnesium sulfate or any combination thereof, and preferably, the anhydrous sodium sulfate; the mass ratio of the toluene and the derivatives thereof to the dispersant is 1: 0.01-1: 10, preferably 1: 3-1: 5; the ball milling time is 3.0-24.0 h, preferably 8.0-16.0 h; the ball milling rotating speed is 100-800 rpm, preferably 500-800 rpm; the air bleeding time interval is 1.0-3.0 h, and preferably 1.0 h.
The invention has the following beneficial effects: according to the method for preparing the benzoic acid and the derivatives thereof through selective oxidation of the toluene and the derivatives thereof, the oxidation conversion of the toluene and the derivatives thereof is realized through solid-phase ball milling, the reaction mode is novel, and the operation is convenient; the reaction is carried out at room temperature, heating is not needed, and the energy consumption is low; organic solvent and other auxiliary agents are not needed, so that the use of toxic and harmful organic reagents is effectively avoided, and the environment is protected; the peroxide content is low, and the safety coefficient is high; the benzoic acid and the derivatives thereof have high selectivity, and meet the social requirements of the current green chemical process, the environmental compatibility chemical process and the biological compatibility chemical process. The invention is a high-efficiency, green, environment-friendly, safe and feasible method for oxidizing the toluene and the derivatives thereof.
Detailed Description
The invention will be further illustrated with reference to specific examples, without limiting the scope of the invention thereto. All reagents used were commercially available analytical grade.
Example 1
In a 100mL agate jar, 1.37g (10mmol) of 4-nitrotoluene, 0.0009g (0.0050mmol) of cobalt acetate, 2.57g (20mmol) of 70% t-butylhydroperoxide aqueous solution, and 4.11g of anhydrous sodium sulfate were mixed well, and the jar was sealed. And performing ball milling reaction at the rotation speed of 600rpm for 12.0h at room temperature, stopping ball milling once every 1.0h, and discharging gas in the ball milling tank. After completion of the reaction, the resulting reaction mixture was dissolved in 30mL of anhydrous ethanol and stirred at room temperature for 30.0 min. Filtering, washing the obtained filter cake by 2X 10mL of absolute ethyl alcohol, combining the ethanol solutions, and fixing the volume of the obtained ethanol solution to 100 mL. 10mL of the resulting solution was removed, and an internal standard 2-naphthoic acid was added to conduct liquid chromatography. The conversion rate of 4-nitrotoluene is 11%, the selectivity of 4-nitrobenzoic acid is 99%, and no other obvious oxidation products are detected.
Example 2
In a 100mL agate jar, 1.37g (10mmol) of 4-nitrotoluene, 0.0044g (0.0250mmol) of cobalt acetate, 2.57g (20mmol) of 70% aqueous t-butylhydroperoxide solution and 4.11g of anhydrous sodium sulfate were mixed well, and the jar was sealed. And performing ball milling reaction at the rotation speed of 600rpm for 12.0h at room temperature, stopping ball milling once every 1.0h, and discharging gas in the ball milling tank. After completion of the reaction, the resulting reaction mixture was dissolved in 30mL of anhydrous ethanol and stirred at room temperature for 30.0 min. Filtering, washing the obtained filter cake by 2X 10mL of absolute ethyl alcohol, combining the ethanol solutions, and fixing the volume of the obtained ethanol solution to 100 mL. 10mL of the resulting solution was removed, and an internal standard 2-naphthoic acid was added to conduct liquid chromatography. 4-nitrotoluene conversion 14%, 4-nitrobenzoic acid selectivity 99%, no other significant oxidation products were detected.
Example 3
In a 100mL agate jar, 1.37g (10mmol) of 4-nitrotoluene, 0.0018g (0.0100mmol) of cobalt acetate, 2.57g (20mmol) of 70% t-butylhydroperoxide aqueous solution and 4.11g of anhydrous sodium sulfate were mixed well and the jar was sealed. And performing ball milling reaction at the rotation speed of 600rpm for 12.0h at room temperature, stopping ball milling once every 1.0h, and discharging gas in the ball milling tank. After completion of the reaction, the resulting reaction mixture was dissolved in 30mL of anhydrous ethanol and stirred at room temperature for 30.0 min. Filtering, washing the obtained filter cake by 2X 10mL of absolute ethyl alcohol, combining the ethanol solutions, and fixing the volume of the obtained ethanol solution to 100 mL. 10mL of the resulting solution was removed, and an internal standard 2-naphthoic acid was added to conduct liquid chromatography. 4-nitrotoluene conversion was 12%, 4-nitrobenzoic acid selectivity was 99%, and no other significant oxidation products were detected.
Example 4
In a 100mL agate jar, 1.37g (10mmol) of 4-nitrotoluene, 0.0018g (0.0100mmol) of cobalt acetate, 1.29g (10mmol) of 70% t-butylhydroperoxide aqueous solution and 4.11g of anhydrous sodium sulfate were mixed well and the jar was sealed. And performing ball milling reaction at the rotation speed of 600rpm for 12.0h at room temperature, stopping ball milling once every 1.0h, and discharging gas in the ball milling tank. After completion of the reaction, the resulting reaction mixture was dissolved in 30mL of anhydrous ethanol and stirred at room temperature for 30.0 min. Filtering, washing the obtained filter cake by 2X 10mL of absolute ethyl alcohol, combining the ethanol solutions, and fixing the volume of the obtained ethanol solution to 100 mL. 10mL of the resulting solution was removed, and an internal standard 2-naphthoic acid was added to conduct liquid chromatography. 4-nitrotoluene conversion was 6%, 4-nitrobenzoic acid selectivity was 99%, and no other significant oxidation products were detected.
Example 5
In a 100mL agate jar, 1.37g (10mmol) of 4-nitrotoluene, 0.0018g (0.0100mmol) of cobalt acetate, 6.44g (50mmol) of 70% t-butylhydroperoxide aqueous solution and 6.85g of anhydrous sodium sulfate were mixed well, and the jar was sealed. And performing ball milling reaction at the rotation speed of 600rpm for 12.0h at room temperature, stopping ball milling once every 1.0h, and discharging gas in the ball milling tank. After completion of the reaction, the resulting reaction mixture was dissolved in 30mL of anhydrous ethanol and stirred at room temperature for 30.0 min. Filtering, washing the obtained filter cake by 2X 10mL of absolute ethyl alcohol, combining the ethanol solutions, and fixing the volume of the obtained ethanol solution to 100 mL. 10mL of the resulting solution was removed, and an internal standard 2-naphthoic acid was added to conduct liquid chromatography. The conversion rate of 4-nitrotoluene is 21 percent, the selectivity of 4-nitrobenzoic acid is 99 percent, and other obvious oxidation products are not detected.
Example 6
In a 100mL agate jar, 1.37g (10mmol) of 4-nitrotoluene, 0.0018g (0.0100mmol) of cobalt acetate, 6.44g (50mmol) of 70% t-butylhydroperoxide aqueous solution and 5.48g of anhydrous sodium sulfate were mixed well and the jar was sealed. And performing ball milling reaction at the rotation speed of 600rpm for 12.0h at room temperature, stopping ball milling once every 1.0h, and discharging gas in the ball milling tank. After completion of the reaction, the resulting reaction mixture was dissolved in 30mL of anhydrous ethanol and stirred at room temperature for 30.0 min. Filtering, washing the obtained filter cake by 2X 10mL of absolute ethyl alcohol, combining the ethanol solutions, and fixing the volume of the obtained ethanol solution to 100 mL. 10mL of the resulting solution was removed, and an internal standard 2-naphthoic acid was added to conduct liquid chromatography. 4-nitrotoluene conversion was 12%, 4-nitrobenzoic acid selectivity was 99%, and no other significant oxidation products were detected.
Example 7
In a 100mL agate jar, 1.37g (10mmol) of 4-nitrotoluene, 0.0018g (0.0100mmol) of cobalt acetate, 6.44g (50mmol) of 70% t-butylhydroperoxide aqueous solution and 8.22g of anhydrous sodium sulfate were mixed uniformly, and the jar was sealed. And performing ball milling reaction at the rotation speed of 600rpm for 12.0h at room temperature, stopping ball milling once every 1.0h, and discharging gas in the ball milling tank. After completion of the reaction, the resulting reaction mixture was dissolved in 30mL of anhydrous ethanol and stirred at room temperature for 30.0 min. Filtering, washing the obtained filter cake by 2X 10mL of absolute ethyl alcohol, combining the ethanol solutions, and fixing the volume of the obtained ethanol solution to 100 mL. 10mL of the resulting solution was removed, and an internal standard 2-naphthoic acid was added to conduct liquid chromatography. 4-nitrotoluene conversion was 22%, 4-nitrobenzoic acid selectivity was 99%, and no other significant oxidation products were detected.
Example 8
In a 100mL agate jar, 1.37g (10mmol) of 4-nitrotoluene, 0.0018g (0.0100mmol) of cobalt acetate, 6.44g (50mmol) of 70% t-butylhydroperoxide aqueous solution and 13.71g of anhydrous sodium sulfate were mixed uniformly, and the jar was sealed. And performing ball milling reaction at the rotation speed of 600rpm for 12.0h at room temperature, stopping ball milling once every 1.0h, and discharging gas in the ball milling tank. After completion of the reaction, the resulting reaction mixture was dissolved in 30mL of anhydrous ethanol and stirred at room temperature for 30.0 min. Filtering, washing the obtained filter cake by 2X 10mL of absolute ethyl alcohol, combining the ethanol solutions, and fixing the volume of the obtained ethanol solution to 100 mL. 10mL of the resulting solution was removed, and an internal standard 2-naphthoic acid was added to conduct liquid chromatography. The conversion rate of 4-nitrotoluene is 16 percent, the selectivity of 4-nitrobenzoic acid is 99 percent, and other obvious oxidation products are not detected.
Example 9
In a 100mL agate jar, 1.37g (10mmol) of 4-nitrotoluene, 0.0018g (0.0100mmol) of cobalt acetate, 6.44g (50mmol) of 70% t-butylhydroperoxide aqueous solution and 6.85g of anhydrous sodium sulfate were mixed well, and the jar was sealed. And performing ball milling reaction at the rotation speed of 500rpm for 12.0h at room temperature, stopping ball milling once every 1.0h, and discharging gas in the ball milling tank. After completion of the reaction, the resulting reaction mixture was dissolved in 30mL of anhydrous ethanol and stirred at room temperature for 30.0 min. Filtering, washing the obtained filter cake by 2X 10mL of absolute ethyl alcohol, combining the ethanol solutions, and fixing the volume of the obtained ethanol solution to 100 mL. 10mL of the resulting solution was removed, and an internal standard 2-naphthoic acid was added to conduct liquid chromatography. 4-nitrotoluene conversion was 17%, 4-nitrobenzoic acid selectivity was 99%, and no other significant oxidation products were detected.
Example 10
In a 100mL agate jar, 1.37g (10mmol) of 4-nitrotoluene, 0.0018g (0.0100mmol) of cobalt acetate, 6.44g (50mmol) of 70% t-butylhydroperoxide aqueous solution and 6.85g of anhydrous sodium sulfate were mixed well, and the jar was sealed. And (3) performing ball milling reaction for 12.0h at the rotating speed of 100rpm at room temperature, stopping ball milling once every 1.0h, and discharging gas in the ball milling tank. After completion of the reaction, the resulting reaction mixture was dissolved in 30mL of anhydrous ethanol and stirred at room temperature for 30.0 min. Filtering, washing the obtained filter cake by 2X 10mL of absolute ethyl alcohol, combining the ethanol solutions, and fixing the volume of the obtained ethanol solution to 100 mL. 10mL of the resulting solution was removed, and an internal standard 2-naphthoic acid was added to conduct liquid chromatography. The conversion rate of 4-nitrotoluene was 2%, the selectivity of 4-nitrobenzoic acid was 99%, and no other significant oxidation products were detected.
Example 11
In a 100mL agate jar, 1.37g (10mmol) of 4-nitrotoluene, 0.0018g (0.0100mmol) of cobalt acetate, 6.44g (50mmol) of 70% t-butylhydroperoxide aqueous solution and 6.85g of anhydrous sodium sulfate were mixed well, and the jar was sealed. And (3) performing ball milling reaction at the rotation speed of 800rpm for 12.0h at room temperature, stopping ball milling once every 1.0h, and discharging gas in the ball milling tank. After completion of the reaction, the resulting reaction mixture was dissolved in 30mL of anhydrous ethanol and stirred at room temperature for 30.0 min. Filtering, washing the obtained filter cake by 2X 10mL of absolute ethyl alcohol, combining the ethanol solutions, and fixing the volume of the obtained ethanol solution to 100 mL. 10mL of the resulting solution was removed, and an internal standard 2-naphthoic acid was added to conduct liquid chromatography. The conversion rate of 4-nitrotoluene was 26%, the selectivity of 4-nitrobenzoic acid was 99%, and no other significant oxidation products were detected.
Example 12
In a 100mL agate jar, 1.37g (10mmol) of 4-nitrotoluene, 0.0018g (0.0100mmol) of cobalt acetate, 6.44g (50mmol) of 70% t-butylhydroperoxide aqueous solution and 6.85g of anhydrous sodium sulfate were mixed well, and the jar was sealed. And (3) performing ball milling reaction for 8.0h at the rotating speed of 800rpm at room temperature, stopping ball milling once every 1.0h, and discharging gas in the ball milling tank. After completion of the reaction, the resulting reaction mixture was dissolved in 30mL of anhydrous ethanol and stirred at room temperature for 30.0 min. Filtering, washing the obtained filter cake by 2X 10mL of absolute ethyl alcohol, combining the ethanol solutions, and fixing the volume of the obtained ethanol solution to 100 mL. 10mL of the resulting solution was removed, and an internal standard 2-naphthoic acid was added to conduct liquid chromatography. 4-nitrotoluene conversion was 18%, 4-nitrobenzoic acid selectivity was 99%, and no other significant oxidation products were detected.
Example 13
In a 100mL agate jar, 1.37g (10mmol) of 4-nitrotoluene, 0.0018g (0.0100mmol) of cobalt acetate, 6.44g (50mmol) of 70% t-butylhydroperoxide aqueous solution and 6.85g of anhydrous sodium sulfate were mixed well, and the jar was sealed. Ball milling reaction is carried out for 16.0h at the rotating speed of 800rpm at room temperature, ball milling is stopped once every 1.0h, and gas in a ball milling tank is discharged. After completion of the reaction, the resulting reaction mixture was dissolved in 30mL of anhydrous ethanol and stirred at room temperature for 30.0 min. Filtering, washing the obtained filter cake by 2X 10mL of absolute ethyl alcohol, combining the ethanol solutions, and fixing the volume of the obtained ethanol solution to 100 mL. 10mL of the resulting solution was removed, and an internal standard 2-naphthoic acid was added to conduct liquid chromatography. The conversion of 4-nitromethane was 31% and the selectivity of 4-nitrobenzoic acid was 99%, and no other significant oxidation products were detected.
Example 14
In a 100mL agate jar, 1.37g (10mmol) of 4-nitrotoluene, 0.0018g (0.0100mmol) of cobalt acetate, 6.44g (50mmol) of 70% t-butylhydroperoxide aqueous solution and 6.85g of anhydrous sodium sulfate were mixed well, and the jar was sealed. And (3) performing ball milling reaction at the rotation speed of 800rpm for 3.0h at room temperature, stopping ball milling once every 1.0h, and discharging gas in the ball milling tank. After completion of the reaction, the resulting reaction mixture was dissolved in 30mL of anhydrous ethanol and stirred at room temperature for 30.0 min. Filtering, washing the obtained filter cake by 2X 10mL of absolute ethyl alcohol, combining the ethanol solutions, and fixing the volume of the obtained ethanol solution to 100 mL. 10mL of the resulting solution was removed, and an internal standard 2-naphthoic acid was added to conduct liquid chromatography. The conversion rate of 4-nitrotoluene was 3%, the selectivity of 4-nitrobenzoic acid was 99%, and no other significant oxidation products were detected.
Example 15
In a 100mL agate jar, 1.37g (10mmol) of 4-nitrotoluene, 0.0018g (0.0100mmol) of cobalt acetate, 6.44g (50mmol) of 70% t-butylhydroperoxide aqueous solution and 6.85g of anhydrous sodium sulfate were mixed well, and the jar was sealed. And (3) performing ball milling reaction at the rotation speed of 800rpm for 24.0h at room temperature, stopping ball milling once every 1.0h, and discharging gas in the ball milling tank. After completion of the reaction, the resulting reaction mixture was dissolved in 30mL of anhydrous ethanol and stirred at room temperature for 30.0 min. Filtering, washing the obtained filter cake by 2X 10mL of absolute ethyl alcohol, combining the ethanol solutions, and fixing the volume of the obtained ethanol solution to 100 mL. 10mL of the resulting solution was removed, and an internal standard 2-naphthoic acid was added to conduct liquid chromatography. The conversion of 4-nitrotoluene was 33%, the selectivity of 4-nitrobenzoic acid was 96%, and no other significant oxidation products were detected.
Example 16
In a 100mL agate jar, 1.37g (10mmol) of 4-nitrotoluene, 0.0018g (0.0100mmol) of cobalt acetate, 5.67g (50mmol) of 30% aqueous hydrogen peroxide and 8.22g of anhydrous sodium sulfate were mixed well and the jar was sealed. Ball milling reaction is carried out for 16.0h at the rotating speed of 800rpm at room temperature, ball milling is stopped once every 1.0h, and gas in a ball milling tank is discharged. After completion of the reaction, the resulting reaction mixture was dissolved in 30mL of anhydrous ethanol and stirred at room temperature for 30.0 min. Filtering, washing the obtained filter cake by 2X 10mL of absolute ethyl alcohol, combining the ethanol solutions, and fixing the volume of the obtained ethanol solution to 100 mL. 10mL of the resulting solution was removed, and an internal standard 2-naphthoic acid was added to conduct liquid chromatography. 4-nitrotoluene conversion was 24%, 4-nitrobenzoic acid selectivity was 89%, and no other significant oxidation products were detected.
Example 17
In a 100mL agate jar, 1.37g (10mmol) of 4-nitrotoluene, 0.0018g (0.0100mmol) of cobalt acetate, 5.67g (50mmol) of 30% aqueous hydrogen peroxide and 6.85g of anhydrous sodium sulfate were mixed well and the jar was sealed. Ball milling reaction is carried out for 16.0h at the rotating speed of 800rpm at room temperature, ball milling is stopped once every 1.0h, and gas in a ball milling tank is discharged. After completion of the reaction, the resulting reaction mixture was dissolved in 30mL of anhydrous ethanol and stirred at room temperature for 30.0 min. Filtering, washing the obtained filter cake by 2X 10mL of absolute ethyl alcohol, combining the ethanol solutions, and fixing the volume of the obtained ethanol solution to 100 mL. 10mL of the resulting solution was removed, and an internal standard 2-naphthoic acid was added to conduct liquid chromatography. The conversion of 4-nitrotoluene was 26% and the selectivity of 4-nitrobenzoic acid was 90%, and no other significant oxidation products were detected.
Example 18
In a 100mL agate jar, 1.37g (10mmol) of 4-nitrotoluene, 0.0018g (0.0100mmol) of cobalt acetate, 5.67g (50mmol) of 30% aqueous hydrogen peroxide, and 13.71g of anhydrous sodium sulfate were mixed well and the jar was sealed. Ball milling reaction is carried out for 16.0h at the rotating speed of 800rpm at room temperature, ball milling is stopped once every 1.0h, and gas in a ball milling tank is discharged. After completion of the reaction, the resulting reaction mixture was dissolved in 30mL of anhydrous ethanol and stirred at room temperature for 30.0 min. Filtering, washing the obtained filter cake by 2X 10mL of absolute ethyl alcohol, combining the ethanol solutions, and fixing the volume of the obtained ethanol solution to 100 mL. 10mL of the resulting solution was removed, and an internal standard 2-naphthoic acid was added to conduct liquid chromatography. The conversion of 4-nitrotoluene was 16% and the selectivity of 4-nitrobenzoic acid was 94%, and no other significant oxidation products were detected.
Example 19
In a 100mL agate jar, 1.37g (10mmol) of 4-nitrotoluene, 0.0018g (0.0100mmol) of cobalt acetate, 5.67g (50mmol) of 30% aqueous hydrogen peroxide and 8.22g of anhydrous sodium sulfate were mixed well and the jar was sealed. And (3) performing ball milling reaction for 8.0h at the rotating speed of 800rpm at room temperature, stopping ball milling once every 1.0h, and discharging gas in the ball milling tank. After completion of the reaction, the resulting reaction mixture was dissolved in 30mL of anhydrous ethanol and stirred at room temperature for 30.0 min. Filtering, washing the obtained filter cake by 2X 10mL of absolute ethyl alcohol, combining the ethanol solutions, and fixing the volume of the obtained ethanol solution to 100 mL. 10mL of the resulting solution was removed, and an internal standard 2-naphthoic acid was added to conduct liquid chromatography. The conversion of 4-nitrotoluene was 11% and the selectivity of 4-nitrobenzoic acid was 92%, and no other significant oxidation products were detected.
Example 20
In a 100mL agate jar, 1.37g (10mmol) of 4-nitrotoluene, 0.0018g (0.0100mmol) of cobalt acetate, 0.90g (10mmol) of sodium chlorite and 2.74g of anhydrous sodium sulfate were mixed well and the jar was sealed. And (3) performing ball milling reaction at the rotation speed of 800rpm for 12.0h at room temperature, stopping ball milling once every 1.0h, and discharging gas in the ball milling tank. After completion of the reaction, the resulting reaction mixture was dissolved in 30mL of anhydrous ethanol and stirred at room temperature for 30.0 min. Filtering, washing the obtained filter cake by 2X 10mL of absolute ethyl alcohol, combining the ethanol solutions, and fixing the volume of the obtained ethanol solution to 100 mL. 10mL of the resulting solution was removed, and an internal standard 2-naphthoic acid was added to conduct liquid chromatography. 4-nitrotoluene conversion 9%, 4-nitrobenzoic acid selectivity 96%, no other significant oxidation products were detected.
Example 21
In a 100mL agate jar, 1.37g (10mmol) of cumene, 0.0018g (0.0100mmol) of cobalt acetate, 4.51g (50mmol) of sodium chlorite, and 6.85g of anhydrous sodium sulfate were mixed uniformly, and the jar was sealed. And (3) performing ball milling reaction at the rotation speed of 800rpm for 12.0h at room temperature, stopping ball milling once every 1.0h, and discharging gas in the ball milling tank. After completion of the reaction, the resulting reaction mixture was dissolved in 30mL of anhydrous ethanol and stirred at room temperature for 30.0 min. Filtering, washing the obtained filter cake by 2X 10mL of absolute ethyl alcohol, combining the ethanol solutions, and fixing the volume of the obtained ethanol solution to 100 mL. 10mL of the resulting solution was removed, and an internal standard 2-naphthoic acid was added to conduct liquid chromatography. 4-nitrotoluene conversion was 13%, 4-nitrobenzoic acid selectivity was 94%, and no other significant oxidation products were detected.
Example 22
In a 100mL agate jar, 1.37g (10mmol) of 4-nitrotoluene, 0.0018g (0.0100mmol) of cobalt acetate, 4.51g (50mmol) of sodium chlorite and 6.85g of anhydrous sodium sulfate were mixed well and the jar was sealed. And (3) performing ball milling reaction at the rotation speed of 800rpm for 8 hours at room temperature, stopping ball milling once every 1.0 hour, and discharging gas in the ball milling tank. After completion of the reaction, the resulting reaction mixture was dissolved in 30mL of anhydrous ethanol and stirred at room temperature for 30.0 min. Filtering, washing the obtained filter cake by 2X 10mL of absolute ethyl alcohol, combining the ethanol solutions, and fixing the volume of the obtained ethanol solution to 100 mL. 10mL of the resulting solution was removed, and an internal standard 2-naphthoic acid was added to conduct liquid chromatography. 4-nitrotoluene conversion was 8%, 4-nitrobenzoic acid selectivity was 97%, and no other significant oxidation products were detected.
Example 23
In a 100mL agate jar, 1.37g (10mmol) of 4-nitrotoluene, 0.0018g (0.0100mmol) of cobalt acetate, 4.51g (50mmol) of sodium chlorite and 6.85g of anhydrous sodium sulfate were mixed well and the jar was sealed. And (3) carrying out ball milling reaction for 16h at the rotating speed of 800rpm at room temperature, stopping ball milling once every 1.0h, and discharging gas in the ball milling tank. After completion of the reaction, the resulting reaction mixture was dissolved in 30mL of anhydrous ethanol and stirred at room temperature for 30.0 min. Filtering, washing the obtained filter cake by 2X 10mL of absolute ethyl alcohol, combining the ethanol solutions, and fixing the volume of the obtained ethanol solution to 100 mL. 10mL of the resulting solution was removed, and an internal standard 2-naphthoic acid was added to conduct liquid chromatography. The conversion of 4-nitrotoluene was 19% and the selectivity of 4-nitrobenzoic acid was 98%, no other significant oxidation products were detected.
Example 24
In a 100mL agate jar, 1.37g (10mmol) of 4-nitrotoluene, 0.0018g (0.0100mmol) of cobalt acetate, 6.44g (50mmol) of 70% t-butylhydroperoxide aqueous solution and 6.85g of neutral aluminum oxide were mixed uniformly, and the jar was sealed. Ball milling reaction is carried out for 16.0h at the rotating speed of 800rpm at room temperature, ball milling is stopped once every 1.0h, and gas in a ball milling tank is discharged. After completion of the reaction, the resulting reaction mixture was dissolved in 30mL of anhydrous ethanol and stirred at room temperature for 30.0 min. Filtering, washing the obtained filter cake by 2X 10mL of absolute ethyl alcohol, combining the ethanol solutions, and fixing the volume of the obtained ethanol solution to 100 mL. 10mL of the resulting solution was removed, and an internal standard 2-naphthoic acid was added to conduct liquid chromatography. 4-nitrotoluene conversion was 22%, 4-nitrobenzoic acid selectivity was 99%, and no other significant oxidation products were detected.
Example 25
In a 100mL agate jar, 1.37g (10mmol) of 4-nitrotoluene, 0.0018g (0.0100mmol) of cobalt acetate, 6.44g (50mmol) of 70% t-butylhydroperoxide aqueous solution and 6.85g of anhydrous magnesium sulfate were mixed uniformly, and the jar was sealed. Ball milling reaction is carried out for 16.0h at the rotating speed of 800rpm at room temperature, ball milling is stopped once every 1.0h, and gas in a ball milling tank is discharged. After completion of the reaction, the resulting reaction mixture was dissolved in 30mL of anhydrous ethanol and stirred at room temperature for 30.0 min. Filtering, washing the obtained filter cake by 2X 10mL of absolute ethyl alcohol, combining the ethanol solutions, and fixing the volume of the obtained ethanol solution to 100 mL. 10mL of the resulting solution was removed, and an internal standard 2-naphthoic acid was added to conduct liquid chromatography. The conversion rate of 4-nitrotoluene is 25 percent, the selectivity of 4-nitrobenzoic acid is 99 percent, and other obvious oxidation products are not detected.
Example 26
In a 100mL agate jar, 1.37g (10mmol) of 4-nitrotoluene, 0.0018g (0.0100mmol) of cobalt acetate, 6.44g (50mmol) of 70% aqueous t-butylhydroperoxide, and 6.85g of silica gel were mixed well and the jar was sealed. Ball milling reaction is carried out for 16.0h at the rotating speed of 800rpm at room temperature, ball milling is stopped once every 1.0h, and gas in a ball milling tank is discharged. After completion of the reaction, the resulting reaction mixture was dissolved in 30mL of anhydrous ethanol and stirred at room temperature for 30.0 min. Filtering, washing the obtained filter cake by 2X 10mL of absolute ethyl alcohol, combining the ethanol solutions, and fixing the volume of the obtained ethanol solution to 100 mL. 10mL of the resulting solution was removed, and an internal standard 2-naphthoic acid was added to conduct liquid chromatography. The conversion of 4-nitrotoluene was 20%, the selectivity of 4-nitrobenzoic acid was 96%, and no other significant oxidation products were detected.
Example 27
In a 100mL agate jar, 1.37g (10mmol) of 4-nitrotoluene, 0.0016g (0.0100mmol) of cobalt sulfate, 2.57g (20mmol) of 70% t-butylhydroperoxide aqueous solution and 4.11g of anhydrous sodium sulfate were mixed well, and the jar was sealed. And performing ball milling reaction at the rotation speed of 600rpm for 12.0h at room temperature, stopping ball milling once every 1.0h, and discharging gas in the ball milling tank. After completion of the reaction, the resulting reaction mixture was dissolved in 30mL of anhydrous ethanol and stirred at room temperature for 30.0 min. Filtering, washing the obtained filter cake by 2X 10mL of absolute ethyl alcohol, combining the ethanol solutions, and fixing the volume of the obtained ethanol solution to 100 mL. 10mL of the resulting solution was removed, and an internal standard 2-naphthoic acid was added to conduct liquid chromatography. The conversion rate of 4-nitrotoluene is 10 percent, the selectivity of 4-nitrobenzoic acid is 99 percent, and other obvious oxidation products are not detected.
Example 28
In a 100mL agate jar, 1.37g (10mmol) of 4-nitrotoluene, 0.0013g (0.0100mmol) of cobalt chloride, 2.57g (20mmol) of 70% t-butylhydroperoxide aqueous solution and 4.11g of anhydrous sodium sulfate were mixed uniformly, and the jar was sealed. And performing ball milling reaction at the rotation speed of 600rpm for 12.0h at room temperature, stopping ball milling once every 1.0h, and discharging gas in the ball milling tank. After completion of the reaction, the resulting reaction mixture was dissolved in 30mL of anhydrous ethanol and stirred at room temperature for 30.0 min. Filtering, washing the obtained filter cake by 2X 10mL of absolute ethyl alcohol, combining the ethanol solutions, and fixing the volume of the obtained ethanol solution to 100 mL. 10mL of the resulting solution was removed, and an internal standard 2-naphthoic acid was added to conduct liquid chromatography. 4-nitrotoluene conversion was 12%, 4-nitrobenzoic acid selectivity was 99%, and no other significant oxidation products were detected.
Example 29
In a 100mL agate jar, 1.37g (10mmol) of 4-nitrotoluene, 0.0012g (0.0100mmol) of cobalt carbonate, 2.57g (20mmol) of 70% t-butylhydroperoxide aqueous solution and 4.11g of anhydrous sodium sulfate were mixed well, and the jar was sealed. And performing ball milling reaction at the rotation speed of 600rpm for 12.0h at room temperature, stopping ball milling once every 1.0h, and discharging gas in the ball milling tank. After completion of the reaction, the resulting reaction mixture was dissolved in 30mL of anhydrous ethanol and stirred at room temperature for 30.0 min. Filtering, washing the obtained filter cake by 2X 10mL of absolute ethyl alcohol, combining the ethanol solutions, and fixing the volume of the obtained ethanol solution to 100 mL. 10mL of the resulting solution was removed, and an internal standard 2-naphthoic acid was added to conduct liquid chromatography. The conversion rate of 4-nitrotoluene is 13 percent, the selectivity of 4-nitrobenzoic acid is 99 percent, and other obvious oxidation products are not detected.
Example 30
In a 100mL agate jar, 1.37g (10mmol) of 4-nitrotoluene, 0.0018g (0.0100mmol) of cobalt nitrate, 2.57g (20mmol) of 70% t-butylhydroperoxide aqueous solution and 4.11g of anhydrous sodium sulfate were mixed uniformly, and the jar was sealed. And performing ball milling reaction at the rotation speed of 600rpm for 12.0h at room temperature, stopping ball milling once every 1.0h, and discharging gas in the ball milling tank. After completion of the reaction, the resulting reaction mixture was dissolved in 30mL of anhydrous ethanol and stirred at room temperature for 30.0 min. Filtering, washing the obtained filter cake by 2X 10mL of absolute ethyl alcohol, combining the ethanol solutions, and fixing the volume of the obtained ethanol solution to 100 mL. 10mL of the resulting solution was removed, and an internal standard 2-naphthoic acid was added to conduct liquid chromatography. The conversion rate of 4-nitrotoluene is 11%, the selectivity of 4-nitrobenzoic acid is 99%, and no other obvious oxidation products are detected.
Claims (9)
1. A method for selectively preparing benzoic acid and derivatives thereof by oxidizing toluene and derivatives thereof by a ball milling method is characterized by comprising the following steps: placing toluene and derivatives thereof, a cobalt (II) salt catalyst, an oxidant and a dispersant in an agate ball milling tank, sealing the ball milling tank, ball milling for 3.0-24.0 hours at the room temperature at the rotating speed of 100-800 rpm, stopping ball milling once every 1.0 hour, and discharging gas in the ball milling tank; after the reaction is finished, dissolving the obtained reaction mixture in absolute ethyl alcohol, stirring for 30min at room temperature, filtering, washing the obtained solid by the absolute ethyl alcohol, combining the obtained ethanol solution, and fixing the volume; and (3) performing liquid chromatography analysis or column chromatography separation on the obtained reaction mixture by taking 2-naphthoic acid as an internal standard, and calculating the conversion rate of the toluene and the derivatives thereof and the selectivity of the benzoic acid and the derivatives thereof.
2. The method for selectively preparing benzoic acid and derivatives thereof by ball milling toluene and derivatives thereof oxidation according to claim 1, wherein the reaction mode is ball milling.
3. The method for selectively preparing benzoic acid and derivatives thereof by ball milling oxidation of toluene and derivatives thereof as claimed in claim 1 or 2, wherein the structural formula of toluene and derivatives thereof is shown as formula (I), and the structural formula of the obtained benzoic acid and derivatives thereof is shown as formula (II).
In the formulae (I) and (II), R1、R2、R3、R4And R5Each independently hydrogen, methyl, ethyl, propyl, butyl, isopropyl, tert-butyl, phenyl, 1-naphthyl, 2-naphthyl, methoxy, ethoxy, hydroxy, mercapto, amino, methylamino, ethylamino, dimethylamino, 1-hydroxyethyl, nitro, cyano, carboxy, benzyl, fluoro, chloro, bromo, or iodo.
4. The method for selectively preparing benzoic acid and derivatives thereof through ball milling toluene oxidation and derivatives thereof according to claim 1 or 2, wherein the catalyst cobalt (II) salt is anhydrous cobalt acetate and hydrates thereof, anhydrous cobalt sulfate and hydrates thereof, anhydrous cobalt chloride and hydrates thereof, anhydrous cobalt nitrate and hydrates thereof, anhydrous cobalt carbonate and hydrates thereof, anhydrous cobalt acetylacetonate and hydrates thereof, or any combination thereof, and the molar ratio of the cobalt (II) salt catalyst to toluene and derivatives thereof is 1: 2000-1: 400.
5. The method for selectively preparing benzoic acid and derivatives thereof through ball milling oxidation of toluene and derivatives thereof as claimed in claim 1 or 2, wherein the oxidant is t-butyl hydroperoxide, hydrogen peroxide, sodium chlorite or sodium hypochlorite, and the molar ratio of toluene and derivatives thereof to the oxidant is 1: 1-1: 30.
6. The method for selectively preparing benzoic acid and derivatives thereof through ball milling toluene oxide and derivatives thereof according to claim 1 or 2, wherein the dispersant is silica gel, neutral aluminum oxide, anhydrous sodium sulfate or anhydrous magnesium sulfate or any combination thereof, and the mass ratio of toluene and derivatives thereof to the dispersant is 1: 0.01-1: 10.
7. The method for selectively preparing the benzoic acid and the derivatives thereof through oxidizing the toluene and the derivatives thereof through the ball milling method according to claim 1 or 2, wherein the ball milling time is 3.0-24.0 h.
8. The method for selectively preparing benzoic acid and derivatives thereof through ball milling oxidation of toluene and derivatives thereof as claimed in claim 1 or 2, wherein the ball milling rotation speed is 100-800 rpm.
9. The method for selectively preparing benzoic acid and derivatives thereof through ball milling toluene oxidation and derivatives thereof as claimed in claim 1 or 2, wherein the air-bleeding time interval is 1.0-3.0 h.
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| 樊能廷: "《有机合成事典》", 31 January 1992, 北京理工大学出版社 * |
| 海关总署关税征管司: "《危险化学品归类指南 上》", 31 August 2017, 中国海关出版社 * |
| 金少瑾等: "乙酰丙酮钴(Ⅱ)对甲苯液相空气氧化反应的催化性能", 《化工学报》 * |
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