CN114057550A - Safe and efficient C-H bond halogenation catalytic reaction method - Google Patents

Safe and efficient C-H bond halogenation catalytic reaction method Download PDF

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CN114057550A
CN114057550A CN202111466683.6A CN202111466683A CN114057550A CN 114057550 A CN114057550 A CN 114057550A CN 202111466683 A CN202111466683 A CN 202111466683A CN 114057550 A CN114057550 A CN 114057550A
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halogenation
mixture
bond
reaction
stirring
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李骁勇
孙杨
张亚男
王向东
王新
潘琴
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Xixian New Area Xingyi Advanced Material Technology Co ltd
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Xixian New Area Xingyi Advanced Material Technology Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C07C37/62—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by introduction of halogen; by substitution of halogen atoms by other halogen atoms
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/063—Titanium; Oxides or hydroxides thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B39/00—Halogenation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/63—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by introduction of halogen; by substitution of halogen atoms by other halogen atoms

Abstract

The invention discloses a safe and efficient C-H bond halogenation catalytic reaction method, which comprises the following steps: 1) preparing a titanium-aluminum binary oxide catalyst; 2) the effect of the catalyst on the halogenation catalysis; 4) the effect of the substrate on the halogenation catalysis; 5) the effect of the solvent on the halogenation catalysis; 6) identification and quantification of products of the halogenation catalysis reaction. Halogenating agents used in the halogenation of C-H bonds have long been limited by their dangerousness and undesirable by-product formation. The invention provides a method for C-H bond halogenation catalytic reaction, which improves the safety of the reaction process, effectively reduces the influence of the reaction process on the environment, improves the reaction efficiency and effectively reduces the generation of byproducts.

Description

Safe and efficient C-H bond halogenation catalytic reaction method
Technical Field
The invention belongs to the field of organic matter halogenation processes, and relates to a novel C-H bond halogenation catalytic reaction system.
Background
Activation of various C-H bonds has been a powerful approach to the construction of C-C or C-heteroatom bonds, using available starting materials, with great potential for sustainable development. In particular, direct C-H activation avoids lengthy synthesis processes and undesirable by-products, which are of great importance to the pharmaceutical industry.
In the known C-H activation, the formation of C-X (halogen) bonds plays an irreplaceable important role in molecular conversion. Here, the organic halide appears to be the primary product of the halogenation reaction, and its substitution with nucleophiles such as amines and azides will yield useful chemicals. Their reaction with metals gives rise to synthetic tools like grignard reagents, their coupling with boronic acids, olefins or organotins gives rise to various C — C bonds, which have shown great value in the manufacture of fine chemicals, pharmaceuticals or polymers.
Early, molecular halogen (Cl)2Or Br2) Is used for halogenation of organic compounds, but its toxicity and inconvenient operation bring environmental burden. Later, acidic compounds such as hydrogen Halide (HX), phosphorus halide (PX) have appeared3、PX5Or POX3) However, their acidity, corrosiveness and water sensitivity not only make their use dangerous, but also do not result inGood by-products. To overcome these disadvantages, various alternatives have emerged over the past few years. The series of compounds represented by N-halogenated succinimide (NBS, NCS or NIS) have the advantages of simple operation, convenient removal of by-products (succinimide), low total reaction cost and the like, but also have the defects of low chlorination and iodination efficiency, limited solvent range and the like. Thus, the catalyst can be optimized to enhance the halogenation of the C-H bond, resulting in more efficient and benign conversion and more effective and milder halogenating agent. Recent research has provided some new strategies for catalyzing halogenation reactions.
Most C-H halogenation reactions suffer from poor tolerance to functional groups on the substrate, which remains a difficult point for future research, mainly due to the known high reactivity of halogen sources, including molecular halogens, tetrahalomethanes, and sodium-containing compounds. Taking into account the inertness of the C-H bond, the use of titanium-aluminum mixed oxides as catalysts may bring about new halogenation reactivity.
Disclosure of Invention
The invention aims to overcome the existing defects and provides a method for C-H bond halogenation catalytic reaction, which comprises the following steps:
1) preparing a titanium-aluminum binary oxide catalyst; 2) the effect of the catalyst on the halogenation catalysis; 4) the effect of the substrate on the halogenation catalysis; 5) the effect of the solvent on the halogenation catalysis; 6) identification and quantification of products of the halogenation catalysis reaction. Halogenating agents used in the halogenation of C-H bonds have long been limited by their dangerousness and undesirable by-product formation. The invention provides a method for C-H bond halogenation catalytic reaction, which improves the safety of the reaction process, effectively reduces the influence of the reaction process on the environment, improves the reaction efficiency and effectively reduces the generation of byproducts.
The invention aims to provide a novel C-H bond halogenation catalytic reaction method, which solves the problems of low halogenation reaction yield, high danger and more byproducts in the prior art.
The invention adopts the technical scheme that a C-H bond halogenation catalytic reaction method comprises the following specific steps,
1) preparing a titanium-aluminum binary oxide catalyst;
2) the substrate, halogenating agent, catalyst and solvent were placed in a round bottom flask.
3) Stirring the mixture at a certain temperature, filtering and extracting the mixture.
The invention further improves the following steps:
in the step 1), equimolar Ti (OBu)4And Al (NO)3)3·9H2Adding O into PVP aqueous solution, stirring for 5-10 min, and then adding 1-4 mmol of NH3·H2O, stirring for 1-2 h at normal temperature;
transferring the mixture into a high-pressure kettle, wherein the reaction temperature is 100-200 ℃, and the reaction time is 8-24 hours, so as to obtain a titanium-aluminum binary oxide catalyst;
the substrate in the step 2) is phenol, 4-tert-butylphenol, 2, 4-di-tert-butylphenol and acetophenone
The addition amount of the substrate in the step 2) is 1-4 mmol;
the halogenating agent in the step 2) is CuCl2、CuBr2Or CuI;
adding a halogenating agent CuCl in the step 2)2、CuBr21-4 mmol of CuI, and the addition amount is 1-4 mmol;
the solvent in the step 2) is CH3CN,HCOOH,CH3COH or CF3COOH；
The amount of the solvent in the step 2) is 5-10 mL;
the reaction temperature in the step 3) is 20 ℃ or 80 ℃;
after the reaction in the step 3) was completed, the solid catalyst was filtered, and the filtrate was diluted with distilled water (20mL) and transferred to a separatory funnel (250 mL). The obtained mixture is substituted by CH2Cl2(3X 15mL), and the organic layer was extracted with Na2CO3Solution (1.0 mol. L)-1) Washing was continued until no bubbles were generated. CH (CH)2Cl2Layer channel anhydrous Na2SO4Drying, filtering, concentrating, and further identifying and quantitatively testing.
Compared with the prior art, the invention has the following beneficial effects:
(1) the reaction system is safe, and the catalytic efficiency is high: the halogenation catalytic reaction method provided by the invention has higher conversion rate, and simultaneously, the reaction system is safer compared with the traditional process;
(2) the production cost is low: the method provided by the invention can realize the synthesis of the target product through the cheap and easily obtained halogenating agent and catalyst, does not need to additionally add any auxiliary reagent, does not need any other gradient temperature raising and lowering device, and does not need to additionally stir after the raw materials are uniformly mixed;
(3) the harmfulness is small, and the safety and environmental protection: the method provided by the invention is utilized to carry out halogenation catalytic reaction, and the reaction system is closed, so that the reaction temperature is moderate, and no three wastes are discharged in the preparation process.
Drawings
FIG. 1 is a chromatogram of halogenation catalysis according to the present invention;
FIG. 2 is an MS image of a halogenated catalytic product C6H5OCl (product A) of the present invention (note: the upper MS image is the experimental result and the lower is a reference image from a GC-MS library);
FIG. 3 is an MS image of the halogenated catalytic product of the invention, C6H4OCl2 (product C) (note: the upper MS image is the experimental result and the lower reference image from the GC-MS library);
FIG. 4 is an MS image of a halogenated catalytic product of the invention, C6H5OCl (product B) (note: the upper MS image is the experimental result and the lower reference image from the GC-MS library);
FIG. 5 is an MS image of the halogenated catalytic product of the invention, C6H3OCl3 (product D) (note: the upper MS image is the experimental result and the lower reference image from the GC-MS library);
FIG. 6 is a chromatogram of sample 2 halogenation catalysis;
FIG. 7 is an MS image of sample halogenation catalyst product No. 2, C8H5O2F3 (product E) (note: the upper MS image is the experimental result and the lower reference image from the GC-MS library);
FIG. 8 is a chromatogram of sample 3 halogenation catalysis;
FIG. 9 is a chromatogram of sample No. 4 halogenation catalysis;
FIG. 10 is an MS image of sample No. 4 halogenated catalytic product C6H5OI (product A) (note: the upper MS image is the experimental result and the lower reference image from the GC-MS library);
FIG. 11 is a chromatogram of sample 5 halogenation catalysis;
FIG. 12 is an MS image of an unreacted substrate in sample No. 5 reaction system (note: upper MS image is experimental result, lower is reference image from GC-MS library);
FIG. 13 is an MS image of sample No. 5 halogenated catalytic product C10H13Ocl (product A) (note: the upper MS image is the experimental result and the lower reference image from GC-MS library);
FIG. 14 is an MS image of sample No. 5 halogenated catalytic product C10H12OCl2 (product C) (note: the upper MS image is the experimental result and the lower reference image from the GC-MS library);
FIG. 15 is a chromatogram of sample No. 6 halogenation catalysis;
FIG. 16 is a chromatogram of sample No. 7 halogenation catalysis;
FIG. 17 is an MS image of the catalytic product C12H13O2F3 (product B) of sample halogenation No. 7;
FIG. 18 is a chromatogram of sample No. 8 halogenation catalysis;
FIG. 19 is a chromatogram of sample No. 10 halogenation catalysis;
FIG. 20 is a chromatogram of sample No. 12 halogenation catalysis;
FIG. 21 is a chromatogram of sample No. 13 halogenation catalysis;
FIG. 22 is a chromatogram of sample No. 14 halogenation catalysis;
FIG. 23 is an MS image of an unreacted substrate in the reaction system No. 14 (note: upper MS image is an experimental result, and lower MS image is a reference image from a GC-MS library);
FIG. 24 is an MS image of sample No. 14 halogenated catalytic product C8H7OCl (product A) (note: the upper MS image is the experimental result and the lower reference image from the GC-MS library);
FIG. 25 is an MS image of sample No. 14 halogenated catalytic product C8H6OCl2 (product B) (note: the upper MS image is the experimental result and the lower reference image from the GC-MS library);
FIG. 26 is a chromatogram of sample 15 halogenation catalysis;
FIG. 27 is an MS image of sample No. 15 halogenated catalytic product C8H7OBr (product A) (note: the upper MS image is the experimental result and the lower reference image from the GC-MS library);
FIG. 28 is an MS image of sample No. 15 halogenated catalytic product C8H6OBr2 (product B) (note: the upper MS image is the experimental result and the lower reference image from the GC-MS library).
Detailed Description
The invention comprises the following steps:
1) preparing a titanium-aluminum binary oxide catalyst;
2) the substrate, halogenating agent, catalyst and solvent were placed in a round bottom flask.
3) Stirring the mixture at a certain temperature for 6h, filtering and extracting the mixture.
Example 1
1) A mixture of Ti (OBu)4And Al (NO)3)3·9H2Adding O into PVP water solution at a molar ratio of 1:1, stirring for 5min, and adding 2.6mmol NH3·H2O, stirring for 2 hours at normal temperature; then transferring the mixture into a high-pressure kettle, and reacting for 24 hours at the temperature of 100 ℃ to obtain a titanium-aluminum binary oxide catalyst;
2) 2.0mmol of phenol and 2.0mmol of CuCl22.0 mol% titanium-aluminum binary oxide catalyst dissolved in 10mL CH3In CN, stirring at 80 ℃ for 6h
3) And filtering and extracting the mixture after the reaction. The filtrate was diluted with distilled water and transferred to a separatory funnel. The obtained mixture is substituted by CH2Cl2(3X 15m L) and the organic layer was extracted with Na2CO3Solution (1.0mol L)-1) Washing was continued until no bubbles were generated. CH (CH)2Cl2Layer channel anhydrous Na2SO4After drying, filtration, concentration, for further identification and quantitative testing.
Example 2
1) A mixture of Ti (OBu)4And Al (NO)3)3·9H2Adding O into PVP water solution at a molar ratio of 1:1, stirring for 5min, and adding 2.6mmol NH3·H2O, stirring for 2 hours at normal temperature;then transferring the mixture into a high-pressure kettle, and reacting for 24 hours at the temperature of 100 ℃ to obtain a titanium-aluminum binary oxide catalyst;
2) 2.0mmol of phenol and 2.0mmol of CuCl22.0 mol% titanium-aluminum binary oxide catalyst in 10mL CF3In COOH, stirred at 80 ℃ for 6h
3) And filtering and extracting the mixture after the reaction. The filtrate was diluted with distilled water and transferred to a separatory funnel. The obtained mixture is substituted by CH2Cl2(3X 15m L) and the organic layer was extracted with Na2CO3Solution (1.0mol L)-1) Washing was continued until no bubbles were generated. CH (CH)2Cl2Layer channel anhydrous Na2SO4After drying, filtration, concentration, for further identification and quantitative testing.
Example 3
1) A mixture of Ti (OBu)4And Al (NO)3)3·9H2Adding O into PVP water solution at a molar ratio of 1:1, stirring for 5min, and adding 2.6mmol NH3·H2O, stirring for 2 hours at normal temperature; then transferring the mixture into a high-pressure kettle, and reacting for 24 hours at the temperature of 100 ℃ to obtain a titanium-aluminum binary oxide catalyst;
2) 2.0mmol of phenol and 2.0mmol of CuBr22.0 mol% titanium-aluminum binary oxide catalyst in 10mL CF3In COOH, stirred at 20 ℃ for 6h
3) And filtering and extracting the mixture after the reaction. The filtrate was diluted with distilled water and transferred to a separatory funnel. The obtained mixture is substituted by CH2Cl2(3X 15m L) and the organic layer was extracted with Na2CO3Solution (1.0mol L)-1) Washing was continued until no bubbles were generated. CH (CH)2Cl2Layer channel anhydrous Na2SO4After drying, filtration, concentration, for further identification and quantitative testing.
Example 4
1) A mixture of Ti (OBu)4And Al (NO)3)3·9H2Adding O into PVP water solution at a molar ratio of 1:1, stirring for 5min, and adding 2.6mmol NH3·H2O, at ambient temperatureStirring for 2 hours; then transferring the mixture into a high-pressure kettle, and reacting for 24 hours at the temperature of 100 ℃ to obtain a titanium-aluminum binary oxide catalyst;
2) 2.0mmol of phenol, 2.0mmol of CuI and 2.0 mol% of titanium-aluminum binary oxide catalyst are dissolved in 10mL of HCOOH and stirred for 6h at 80 DEG C
3) And filtering and extracting the mixture after the reaction. The filtrate was diluted with distilled water and transferred to a separatory funnel. The obtained mixture is substituted by CH2Cl2(3X 15m L) and the organic layer was extracted with Na2CO3Solution (1.0mol L)-1) Washing was continued until no bubbles were generated. CH (CH)2Cl2Layer channel anhydrous Na2SO4After drying, filtration, concentration, for further identification and quantitative testing.
Example 5
1) A mixture of Ti (OBu)4And Al (NO)3)3·9H2Adding O into PVP water solution at a molar ratio of 1:1, stirring for 5min, and adding 2.6mmol NH3·H2O, stirring for 2 hours at normal temperature; then transferring the mixture into a high-pressure kettle, and reacting for 24 hours at the temperature of 100 ℃ to obtain a titanium-aluminum binary oxide catalyst;
2) 2.0mmol of 4-tert-butylphenol and 2.0mmol of CuCl22.0 mol% titanium-aluminum binary oxide catalyst dissolved in 10mL CH3In CN, stirring at 80 ℃ for 6h
3) And filtering and extracting the mixture after the reaction. The filtrate was diluted with distilled water and transferred to a separatory funnel. The obtained mixture is substituted by CH2Cl2(3X 15m L) and the organic layer was extracted with Na2CO3Solution (1.0mol L)-1) Washing was continued until no bubbles were generated. CH (CH)2Cl2Layer channel anhydrous Na2SO4After drying, filtration, concentration, for further identification and quantitative testing.
Example 6
1) A mixture of Ti (OBu)4And Al (NO)3)3·9H2Adding O into PVP water solution at a molar ratio of 1:1, stirring for 5min, and adding 2.6mmol NH3·H2O, stirring at room temperature 2h; then transferring the mixture into a high-pressure kettle, and reacting for 24 hours at the temperature of 100 ℃ to obtain a titanium-aluminum binary oxide catalyst;
2) 2.0mmol of 4-tert-butylphenol and 2.0mmol of CuCl22.0 mol% titanium-aluminum binary oxide catalyst was dissolved in 10mL HCOOH and stirred at 80 ℃ for 6h
3) And filtering and extracting the mixture after the reaction. The filtrate was diluted with distilled water and transferred to a separatory funnel. The obtained mixture is substituted by CH2Cl2(3X 15m L) and the organic layer was extracted with Na2CO3Solution (1.0mol L)-1) Washing was continued until no bubbles were generated. CH (CH)2Cl2Layer channel anhydrous Na2SO4After drying, filtration, concentration, for further identification and quantitative testing.
Example 7
1) A mixture of Ti (OBu)4And Al (NO)3)3·9H2Adding O into PVP water solution at a molar ratio of 1:1, stirring for 5min, and adding 2.6mmol NH3·H2O, stirring for 2 hours at normal temperature; then transferring the mixture into a high-pressure kettle, and reacting for 24 hours at the temperature of 100 ℃ to obtain a titanium-aluminum binary oxide catalyst;
2) 2.0mmol of 4-tert-butylphenol and 2.0mmol of CuCl22.0 mol% titanium-aluminum binary oxide catalyst in 10mL CF3In COOH, stirred at 80 ℃ for 6h
3) And filtering and extracting the mixture after the reaction. The filtrate was diluted with distilled water and transferred to a separatory funnel. The obtained mixture is substituted by CH2Cl2(3X 15m L) and the organic layer was extracted with Na2CO3Solution (1.0mol L)-1) Washing was continued until no bubbles were generated. CH (CH)2Cl2Layer channel anhydrous Na2SO4After drying, filtration, concentration, for further identification and quantitative testing.
Example 8
1) A mixture of Ti (OBu)4And Al (NO)3)3·9H2Adding O into PVP water solution at a molar ratio of 1:1, stirring for 5min, and adding 2.6mmol NH3·H2O is atStirring for 2 hours at normal temperature; then transferring the mixture into a high-pressure kettle, and reacting for 24 hours at the temperature of 100 ℃ to obtain a titanium-aluminum binary oxide catalyst;
2) 2.0mmol of 4-tert-butylphenol and 2.0mmol of CuBr22.0 mol% titanium-aluminum binary oxide catalyst dissolved in 10mL CH3Stirring in COOH at 80 ℃ for 6 h;
3) and filtering and extracting the mixture after the reaction. The filtrate was diluted with distilled water and transferred to a separatory funnel. The obtained mixture is substituted by CH2Cl2(3X 15m L) and the organic layer was extracted with Na2CO3Solution (1.0mol L)-1) Washing was continued until no bubbles were generated. CH (CH)2Cl2Layer channel anhydrous Na2SO4After drying, filtration, concentration, for further identification and quantitative testing.
Example 9
1) A mixture of Ti (OBu)4And Al (NO)3)3·9H2Adding O into PVP water solution at a molar ratio of 1:1, stirring for 5min, and adding 2.6mmol NH3·H2O, stirring for 2 hours at normal temperature; then transferring the mixture into a high-pressure kettle, and reacting for 24 hours at the temperature of 100 ℃ to obtain a titanium-aluminum binary oxide catalyst;
2) 2.0mmol of 4-tert-butylphenol, 2.0mmol of CuI and 2.0 mol% of titanium-aluminum binary oxide catalyst are dissolved in 10mL of CH3Stirring in COOH at 80 ℃ for 6 h;
3) and filtering and extracting the mixture after the reaction. The filtrate was diluted with distilled water and transferred to a separatory funnel. The obtained mixture is substituted by CH2Cl2(3X 15m L) and the organic layer was extracted with Na2CO3Solution (1.0mol L)-1) Washing was continued until no bubbles were generated. CH (CH)2Cl2Layer channel anhydrous Na2SO4After drying, filtration, concentration, for further identification and quantitative testing.
Example 10
1) A mixture of Ti (OBu)4And Al (NO)3)3·9H2Adding O into PVP water solution at a molar ratio of 1:1, stirring for 5min, and adding 2.6mmol NH3·H2O, stirring for 2 hours at normal temperature; then transferring the mixture into a high-pressure kettle, and reacting for 24 hours at the temperature of 100 ℃ to obtain a titanium-aluminum binary oxide catalyst;
2) 2.0mmol of 4-tert-butylphenol and 2.0mmol of CuCl22.0 mol% titanium-aluminum binary oxide catalyst in 10mL CF3Stirring in COOH at 20 ℃ for 6 h;
3) and filtering and extracting the mixture after the reaction. The filtrate was diluted with distilled water and transferred to a separatory funnel. The obtained mixture is substituted by CH2Cl2(3X 15m L) and the organic layer was extracted with Na2CO3Solution (1.0mol L)-1) Washing was continued until no bubbles were generated. CH (CH)2Cl2Layer channel anhydrous Na2SO4After drying, filtration, concentration, for further identification and quantitative testing.
Example 11
1) A mixture of Ti (OBu)4And Al (NO)3)3·9H2Adding O into PVP water solution at a molar ratio of 1:1, stirring for 5min, and adding 2.6mmol NH3·H2O, stirring for 2 hours at normal temperature; then transferring the mixture into a high-pressure kettle, and reacting for 24 hours at the temperature of 100 ℃ to obtain a titanium-aluminum binary oxide catalyst;
2) 2.0mmol of 2, 4-di-tert-butylphenol and 2.0mmol of CuCl22.0 mol% titanium-aluminum binary oxide catalyst dissolved in 10mL CH3CN, stirring for 6h at 80 ℃;
3) and filtering and extracting the mixture after the reaction. The filtrate was diluted with distilled water and transferred to a separatory funnel. The obtained mixture is substituted by CH2Cl2(3X 15m L) and the organic layer was extracted with Na2CO3Solution (1.0mol L)-1) Washing was continued until no bubbles were generated. CH (CH)2Cl2Layer channel anhydrous Na2SO4After drying, filtration, concentration, for further identification and quantitative testing.
Example 12
1) A mixture of Ti (OBu)4And Al (NO)3)3·9H2Adding PVP water into O in a molar ratio of 1:1Stirring the solution for 5min, and then adding 2.6mmol of NH3·H2O, stirring for 2 hours at normal temperature; then transferring the mixture into a high-pressure kettle, and reacting for 24 hours at the temperature of 100 ℃ to obtain a titanium-aluminum binary oxide catalyst;
2) 2.0mmol of 2, 4-di-tert-butylphenol and 2.0mmol of CuCl22.0 mol% titanium-aluminum binary oxide catalyst was dissolved in 10mL HCOOH and stirred at 80 ℃ for 6h
3) And filtering and extracting the mixture after the reaction. The filtrate was diluted with distilled water and transferred to a separatory funnel. The obtained mixture is substituted by CH2Cl2(3X 15mL), and the organic layer was extracted with Na2CO3Solution (1.0mol L)-1) Washing was continued until no bubbles were generated. CH (CH)2Cl2Layer channel anhydrous Na2SO4After drying, filtration, concentration, for further identification and quantitative testing.
Example 13
1) A mixture of Ti (OBu)4And Al (NO)3)3·9H2Adding O into PVP water solution at a molar ratio of 1:1, stirring for 5min, and adding 2.6mmol NH3·H2O, stirring for 2 hours at normal temperature; then transferring the mixture into a high-pressure kettle, and reacting for 24 hours at the temperature of 100 ℃ to obtain a titanium-aluminum binary oxide catalyst;
2) 2.0mmol of 2, 4-di-tert-butylphenol and 2.0mmol of CuBr22.0 mol% titanium-aluminum binary oxide catalyst dissolved in 10mL CH3Stirring in COOH at 80 ℃ for 6 h;
3) and filtering and extracting the mixture after the reaction. The filtrate was diluted with distilled water and transferred to a separatory funnel. The obtained mixture is substituted by CH2Cl2(3X 15m L) and the organic layer was extracted with Na2CO3Solution (1.0mol L)-1) Washing was continued until no bubbles were generated. CH (CH)2Cl2Layer channel anhydrous Na2SO4After drying, filtration, concentration, for further identification and quantitative testing.
Example 14
1) A mixture of Ti (OBu)4And Al (NO)3)3·9H2Adding O into PVP water solution at a molar ratio of 1:1, stirring for 5min, and adding 2.6mmol NH3·H2O, stirring for 2 hours at normal temperature; then transferring the mixture into a high-pressure kettle, and reacting for 24 hours at the temperature of 100 ℃ to obtain a titanium-aluminum binary oxide catalyst;
2) 2.0mmol of acetophenone and 2.0mmol of CuCl22.0 mol% titanium-aluminum binary oxide catalyst dissolved in 10mL CH3CN, stirring for 6h at 80 ℃;
3) and filtering and extracting the mixture after the reaction. The filtrate was diluted with distilled water and transferred to a separatory funnel. The obtained mixture is substituted by CH2Cl2(3X 15m L) and the organic layer was extracted with Na2CO3Solution (1.0mol L)-1) Washing was continued until no bubbles were generated. CH (CH)2Cl2Layer channel anhydrous Na2SO4After drying, filtration, concentration, for further identification and quantitative testing.
Example 15
1) A mixture of Ti (OBu)4And Al (NO)3)3·9H2Adding O into PVP water solution at a molar ratio of 1:1, stirring for 5min, and adding 2.6mmol NH3·H2O, stirring for 2 hours at normal temperature; then transferring the mixture into a high-pressure kettle, and reacting for 24 hours at the temperature of 100 ℃ to obtain a titanium-aluminum binary oxide catalyst;
2) 2.0mmol of acetophenone and 2.0mmol of CuBr22.0 mol% of titanium-aluminum binary oxide catalyst is dissolved in 10mL of HCOOH, and stirred for 6h at 80 ℃;
3) and filtering and extracting the mixture after the reaction. The filtrate was diluted with distilled water (20mL) and transferred to a separatory funnel (250 mL). The obtained mixture is substituted by CH2Cl2(3X 15m L) and the organic layer was extracted with Na2CO3Solution (1.0mol L)-1) Washing was continued until no bubbles were generated. CH (CH)2Cl2Layer channel anhydrous Na2SO4After drying, filtration, concentration, for further identification and quantitative testing.
Example 16
1) A mixture of Ti (OBu)4And Al (NO)3)3·9H2Adding O into PVP water solution at a molar ratio of 1:1, stirring for 5min, and adding 2.6mmol NH3·H2O, stirring for 2 hours at normal temperature; then transferring the mixture into a high-pressure kettle, and reacting for 24 hours at the temperature of 100 ℃ to obtain a titanium-aluminum binary oxide catalyst;
2) 2.0mmol of acetophenone and 2.0mmol of CuBr22.0 mol% titanium-aluminum binary oxide catalyst dissolved in 10mL CH3Stirring in COOH at 80 ℃ for 6 h;
3) and filtering and extracting the mixture after the reaction. The filtrate was diluted with distilled water (20mL) and transferred to a separatory funnel (250 mL). The obtained mixture is substituted by CH2Cl2(3X 15m L) and the organic layer was extracted with Na2CO3Solution (1.0mol L)-1) Washing was continued until no bubbles were generated. CH (CH)2Cl2Layer channel anhydrous Na2SO4After drying, filtration, concentration, for further identification and quantitative testing.
The reaction products of examples 1 to 16 were further identified and quantified by GC-MS, and the test results are shown in Table 1, Table 2, Table 3 and Table 4.
The invention provides the catalytic efficiency of different substrates under different halogenating agents, different solvents and different temperatures. The reaction products of examples 1 to 16 were further identified and quantified by GC-MS, and the test results are shown in Table 1, Table 2, Table 3 and Table 4. The data in Table 1 are shown in FIGS. 1 to 10, the data in Table 2 are shown in FIGS. 11 to 19, part of the data in Table 3 are shown in FIGS. 20 and 21, and part of the data in Table 4 are shown in FIGS. 22 to 28. As can be seen from the figure and the table, under the reaction system of the invention, the conversion rate of halogenation catalytic reaction is higher, the obtained products are different, and no by-product is generated.
TABLE 1C-H halogenation catalysis of phenols
Figure BDA0003384173400000101
TABLE 24C-H halogenation catalysis of tert-butylphenol
Figure BDA0003384173400000102
Figure BDA0003384173400000111
TABLE 32C-H halogenation catalysis of 4, 4-di-tert-butylphenol
Figure BDA0003384173400000112
Note: in the table, 12-1, 12-2, 12-3, 12-4 and 12-5 respectively represent the experimental results of 1, 2, 3, 4 and 5 times of catalyst circulation after the halogenation catalysis of sample No. 12 is finished
TABLE 4C-H halogenation catalysis of acetophenone
Figure BDA0003384173400000113
The invention provides the catalytic efficiency of different substrates under different halogenating agents, different solvents and different temperatures. According to experimental results, the conversion rate of the halogenation catalytic reaction under the condition of the invention is higher, and the obtained products are different.

Claims (9)

1. A safe and efficient C-H bond halogenation catalytic reaction method is characterized by comprising the following steps:
1) preparing a titanium-aluminum binary oxide catalyst;
2) disposing a substrate, a halogenating agent, a catalyst and a solvent in a round-bottom flask, and adding an equimolar amount of Ti (OBu)4And Al (NO)3)3·9H2Adding O into PVP aqueous solution, stirring for 5-10 min, and then adding 1-4 mmol of NH3·H2O, stirring for 1-2 h at normal temperature; transferring the mixture into a high-pressure kettle, wherein the reaction temperature is 100-200 ℃, and the reaction time is 8-24 hours, so as to obtain a titanium-aluminum binary oxide catalyst;
3) stirring the mixture at a certain temperature, filtering and extracting the mixture.
2. The method for catalyzing C-H bond halogenation according to claim 1, wherein in the step 1), the substrate in the step 2) is phenol, 4-tert-butylphenol, 2, 4-di-tert-butylphenol or acetophenone.
3. The method for catalyzing C-H bond halogenation according to claim 1, wherein the addition amount of the substrate in the step 2) is 1-4 mmol.
4. The method as claimed in claim 1, wherein the halogenating agent in step 2) is CuCl2、CuBr2Or CuI.
5. The method for C-H bond halogenation catalysis according to claim 1, wherein a halogenating agent CuCl is added in the step 2)2、CuBr21-4 mmol of CuI, and the addition amount is 1-4 mmol.
6. The method for C-H bond halogenation catalysis according to claim 1, wherein the solvent in the step 2) is CH3CN,HCOOH,CH3COH or CF3COOH。
7. The method for catalyzing C-H bond halogenation according to claim 1, wherein the amount of the solvent in the step 2) is 5-10 mL.
8. The method for catalyzing C-H bond halogenation according to claim 1, wherein the reaction temperature in the step 3) is 20 ℃ or 80 ℃.
9. The method of claim 1, wherein the C-H bond is halogenated and catalyzedFiltering the solid catalyst after the reaction in the step 3), diluting the filtrate with distilled water and 20mL, transferring the diluted filtrate to a separating funnel with 250mL, and using CH to obtain a mixture2Cl2(3X 15mL), and the organic layer was extracted with Na2CO3Solution 1.0 mol. L-1Washing is continued until no bubbles are produced, CH2Cl2Layer channel anhydrous Na2SO4Drying, filtering, concentrating, and further identifying and quantitatively testing.
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