CN117088761A - Method for preparing trichloromethoxybenzene by near infrared radiation - Google Patents
Method for preparing trichloromethoxybenzene by near infrared radiation Download PDFInfo
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- CN117088761A CN117088761A CN202311061092.XA CN202311061092A CN117088761A CN 117088761 A CN117088761 A CN 117088761A CN 202311061092 A CN202311061092 A CN 202311061092A CN 117088761 A CN117088761 A CN 117088761A
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- Prior art keywords
- trichloromethoxybenzene
- near infrared
- infrared light
- conversion agent
- reaction
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- CLYZNABPUKUSDX-UHFFFAOYSA-N trichloromethoxybenzene Chemical compound ClC(Cl)(Cl)OC1=CC=CC=C1 CLYZNABPUKUSDX-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title claims abstract description 10
- 230000005855 radiation Effects 0.000 title claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 47
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims abstract description 22
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000000460 chlorine Substances 0.000 claims abstract description 20
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 20
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 19
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 claims abstract description 13
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000003960 organic solvent Substances 0.000 claims abstract description 8
- 239000003999 initiator Substances 0.000 claims abstract description 7
- 239000003054 catalyst Substances 0.000 claims abstract description 6
- 239000012320 chlorinating reagent Substances 0.000 claims abstract description 3
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 5
- ZQBFAOFFOQMSGJ-UHFFFAOYSA-N hexafluorobenzene Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1F ZQBFAOFFOQMSGJ-UHFFFAOYSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- GETTZEONDQJALK-UHFFFAOYSA-N (trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1 GETTZEONDQJALK-UHFFFAOYSA-N 0.000 claims description 3
- USPWUOFNOTUBAD-UHFFFAOYSA-N 1,2,3,4,5-pentafluoro-6-(trifluoromethyl)benzene Chemical compound FC1=C(F)C(F)=C(C(F)(F)F)C(F)=C1F USPWUOFNOTUBAD-UHFFFAOYSA-N 0.000 claims description 3
- 239000002105 nanoparticle Substances 0.000 claims description 3
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 claims description 2
- 229940117389 dichlorobenzene Drugs 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 5
- DGRVQOKCSKDWIH-UHFFFAOYSA-N 1-chloro-2-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1Cl DGRVQOKCSKDWIH-UHFFFAOYSA-N 0.000 claims 1
- 238000005660 chlorination reaction Methods 0.000 abstract description 5
- 230000000149 penetrating effect Effects 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000003889 chemical engineering Methods 0.000 abstract description 2
- 239000012847 fine chemical Substances 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 238000004321 preservation Methods 0.000 description 3
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 2
- 208000027418 Wounds and injury Diseases 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 208000014674 injury Diseases 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- IGUMWDXKAUEIDE-UHFFFAOYSA-N 2-chloro-1,3,4-trifluoro-5-methylbenzene Chemical compound CC1=CC(F)=C(Cl)C(F)=C1F IGUMWDXKAUEIDE-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
- C07C41/22—Preparation of ethers by reactions not forming ether-oxygen bonds by introduction of halogens; by substitution of halogen atoms by other halogen atoms
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for preparing trichloromethoxybenzene by near infrared radiation, belonging to the technical field of fine chemical engineering. In an organic solvent, azodiisobutyronitrile is used as an initiator, phosphorus trichloride is used as a catalyst, and NaYF 4 Yb/Tm is an up-conversion agent, chlorine is a chlorinating agent, and under the radiation of near infrared light, the anisole photo-chlorination reaction is realized to prepare the trichloromethoxybenzene. The invention solves the problems caused by poor penetrating power of ultraviolet light irradiated by the ultraviolet lamp and uneven ultraviolet light distribution in the reaction system in the prior art, has the advantages of easily available raw materials, simpler and more convenient operation, milder reaction conditions, higher chlorine utilization rate and the like, and has potential industrialized prospect.
Description
Technical Field
The invention relates to a method for preparing trichloromethoxybenzene by near infrared radiation, belonging to the technical field of fine chemical engineering.
Background
The trichloromethoxybenzene is an important intermediate of pesticides/medicines, and is prepared by taking anisole as an initial reaction raw material, taking azodiisobutyronitrile as an initiator and phosphorus trichloride as a catalyst under the condition of illumination and introducing chlorine gas for chlorination in the traditional synthesis method.
Since the maximum absorption wavelength of the azobisisobutyronitrile in the solution is in the ultraviolet region of the spectrum (Guizhou chemical industry, 4 th 1993), the effect of initiating azobisisobutyronitrile to generate free radicals by ultraviolet irradiation and then performing photochlorination reaction is better than that of other wavelength light sources (organic fluorine industry, 3 rd 2005). For example, liu Ansheng et al reported the preparation of trichloromethoxybenzene by chlorination with chlorine gas using chlorobenzene as solvent, azobisisobutyronitrile as initiator, phosphorus trichloride as catalyst, with a high pressure mercury lamp (main emission wavelength 365.0 nm) as light source and at a temperature of 120-130 ℃ (patent CN 102120717B).
However, due to the defects of shorter ultraviolet wavelength, stronger human body injury, larger Rayleigh scattering, poorer system penetrating power and the like, the traditional ultraviolet lamp irradiates the photochlorination reaction, particularly in the later period, high temperature is needed, an initiator and a solvent are added, the reaction condition is more severe, the reaction time is longer, the chlorine consumption is larger, the three wastes are more, the industrialized scale is limited and the like, and the application prospect is greatly limited.
Disclosure of Invention
In order to solve the above-mentioned ending problem, the present invention provides a method for preparing trichloromethoxybenzene by near infrared light irradiation. The method comprises the steps of using azodiisobutyronitrile as an initiator, phosphorus trichloride as a catalyst, UCPs and NaYF in an organic solvent 4 Yb and Tm are up-conversion agents, chlorine is a chlorinating agent, and under the radiation of near infrared light, anisole photochlorination reaction is realized to prepare trichloromethoxybenzene. The invention provides a feasible method for preparing the trichloromethoxybenzene, and has potential industrialized prospect.
The invention discloses a preparation method of trichloromethoxybenzene by near infrared light radiation, which comprises the following steps: in an organic solvent, azodiisobutyronitrile is used as an initiator, phosphorus trichloride is used as a catalyst, and NaYF 4 Yb/Tm is an up-conversion agent, chlorine is a chlorination agent, and the anisole photo-chlorination reaction is realized under the radiation of Near Infrared (NIR) light to prepare the trichloromethoxybenzene. The reaction equation is expressed as follows:
further, in the above technical scheme, the organic solvent is one or more of chlorobenzene, dichlorobenzene, hexafluorobenzene, trifluoromethyl benzene, perfluorotoluene, p-chlorotrifluorotoluene, and the like.
Further, in the above technical solution, the up-conversion nano-ion agent is commercial UCPs (up-conversion nano-particle agent for short, english) and the main components of the nano-particle are: naYF 4 :Yb/Tm。
Further, in the technical scheme, the mass ratio of the up-conversion agent to anisole is 0.05-30% to 1, preferably 0.1-8% to 1; the mass ratio of the up-conversion agent to the azodiisobutyronitrile is 5-15% to 1, preferably 8-10% to 1; the mass ratio of the up-conversion agent to the phosphorus trichloride is 5-15% to 1, preferably 8-10% to 1; the mass ratio of the up-conversion agent to the chlorine is 0.02-10% to 1, preferably 0.03-2.7% to 1; the mass ratio of the up-conversion agent to the organic solvent is 0.01-6% to 1, preferably 0.02-1.6% to 1.
Further, in the above technical scheme, the reaction temperature is 60-130 ℃, preferably 65-85 ℃; the reaction time is 2 to 12 hours, preferably 2.5 to 4 hours.
Further, in the above technical scheme, the near infrared light source is a 950-980nm near infrared laser.
Further, in the above technical scheme, typical reaction operations are as follows:
1) Sequentially adding an organic solvent, anisole, phosphorus trichloride, azodiisobutyronitrile and an up-conversion agent into a four-port reaction bottle with a stirring and thermometer sleeve, stirring at room temperature after adding, and starting an infrared laser irradiation reaction device of 950-980 nm;
2) Then slowly heating the reaction liquid to the reaction temperature, slowly introducing chlorine, and keeping the temperature and stirring until the reaction is finished;
3) The reaction liquid is decompressed and desolventized to recycle the solvent, and then the product is decompressed and distilled out to obtain the trichloromethoxybenzene.
Advantageous effects of the invention
1. The invention solves the problems of poor penetrating power of ultraviolet lamp irradiation, uneven ultraviolet distribution in the reaction system, long reaction time, high reaction temperature, large chlorine consumption, more three wastes, limited industrialized scale and the like in the prior art.
2. The method provided by the invention has the advantages of easily available raw materials, simple and convenient operation, mild reaction conditions, short time, high chlorine utilization rate, safer infrared light, less human body injury and light environmental pollution compared with ultraviolet light, provides a feasible method for preparing trichloromethoxybenzene, and has potential industrialized prospect.
Detailed Description
The following examples will provide those of ordinary skill with a more complete understanding of the present invention and are not intended to limit the invention in any way.
Comparative example 1
Sequentially adding 275g of chlorobenzene and 3.94g of phosphorus trichloride into a 1000mL photochlorination reaction kettle, starting an ultraviolet lamp and water-cooling the ultraviolet lamp, heating to 105-115 ℃ in the kettle, introducing chlorine, dropwise adding 100g of anisole and 5g of azobisisobutyronitrile to prepare a mixed solution, dropwise adding 6-7h at 120-130 ℃, continuously dropwise adding 25g of chlorobenzene and 1.25g of azobisisobutyronitrile to prepare the mixed solution after dropwise adding is completed for 1h, continuously preserving heat and introducing chlorine for 2h after dropwise adding is completed, stopping introducing chlorine, and continuously heating and decompressing to evaporate 175.16g of trichloromethoxybenzene product after decompressing and decompressing, wherein the gas phase normalized content is 93.8%, and the yield is 89.57%.
Example 1
300g of chlorobenzene, 100g of anisole, 1.12g of phosphorus trichloride and 1.50g of azodiisobutyronitrile are sequentially added into a 1000mL photochlorination reaction kettle, and NaYF is added under stirring 4 0.99g of Yb/Tm up-converter, starting a 980nm infrared laser to irradiate a reaction device, heating the reaction kettle to 70-80 ℃, slowly introducing 300g of chlorine, and stirring for 3.5-4 hours under heat preservation; stopping chlorine introduction, decompressing and desolventizing, and continuously heating and decompressing to evaporate 183.21g of trichloromethoxybenzene product, wherein the gas phase normalized content is 98.5%, and the yield is 93.69%.
Example 2
300g of perfluorotoluene, 100g of anisole, 1.50g of phosphorus trichloride and 1.50g of azobisisobutyronitrile are sequentially added into a 1000mL photochlorination reaction kettle, and NaYF is added under stirring 4 0.5g of Yb/Tm up-converter, starting a 980nm infrared laser to irradiate a reaction device, heating the reaction kettle to 70-80 ℃, slowly introducing 300g of chlorine, and stirring for 3.5-4 hours under heat preservation; stopping chlorine supply, removing solvent under reduced pressure, and continuously heating and steaming under reduced pressure178.60g of trichloromethoxybenzene is obtained, the gas phase normalized content is 99.5%, and the yield is 91.33%.
Example 3
300g of trifluoromethyl benzene, 100g of anisole, 2.99g of phosphorus trichloride and 2.0g of azodiisobutyronitrile are sequentially added into a 1000mL photochlorination reaction kettle, and NaYF is added under stirring 4 2.0g of Yb/Tm up-converter, starting a 980nm infrared laser to irradiate a reaction device, heating the reaction kettle to 70-80 ℃, slowly introducing 300g of chlorine, and stirring for 3.5-4 hours under heat preservation; stopping chlorine introduction, decompressing and desolventizing, and continuously heating and decompressing to evaporate 185.34g of trichloromethoxybenzene product, wherein the gas phase normalized content is 98.9%, and the yield is 94.78%.
The foregoing is merely a preferred embodiment of the present invention, and it should be noted that the above-mentioned preferred embodiment should not be construed as limiting the invention, and the scope of the invention should be defined by the appended claims. It will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the spirit and scope of the invention, and such modifications and adaptations are intended to be comprehended within the scope of the invention.
Claims (6)
1. A method for preparing trichloromethoxybenzene by near infrared radiation, comprising the steps of:
in a solvent, azodiisobutyronitrile is used as an initiator, phosphorus trichloride is used as a catalyst, and NaYF 4 Yb/Tm is an up-conversion agent, chlorine is a chlorinating agent, and the photochlorination reaction of anisole is realized under the radiation of near infrared light to prepare trichloromethoxybenzene.
2. The method for producing trichloromethoxybenzene by near infrared light irradiation according to claim 1, wherein: the organic solvent is one or more of chlorobenzene, dichlorobenzene, hexafluorobenzene, benzotrifluoride, perfluorotoluene, chlorotrifluorotoluene and the like.
3. The method for producing trichloromethoxybenzene by near infrared light irradiation according to claim 1, wherein: the up-conversion agent is commercial UCPs, and the main components of the nano particles are as follows: naYF 4 :Yb/Tm。
4. The method for producing trichloromethoxybenzene by near infrared light irradiation according to claim 1, wherein: the mass ratio of the up-conversion agent to anisole is 0.05-30 percent to 1; the mass ratio of the up-conversion agent to the azodiisobutyronitrile is 5-15 percent to 1; the mass ratio of the up-conversion agent to the phosphorus trichloride is 5-15 percent to 1; the mass ratio of the up-conversion agent to the chlorine is 0.02-10 percent to 1; the mass ratio of the up-conversion agent to the organic solvent is 0.01-6 percent to 1.
5. The method for producing trichloromethoxybenzene by near infrared light irradiation according to claim 1, wherein: the reaction temperature is 60-130 ℃, and the reaction time is 2-12h.
6. The method for producing trichloromethoxybenzene by near infrared light irradiation according to claim 1, wherein: the near infrared light source is 950-980nm near infrared laser.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311061092.XA CN117088761A (en) | 2023-08-23 | 2023-08-23 | Method for preparing trichloromethoxybenzene by near infrared radiation |
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| CN202311061092.XA CN117088761A (en) | 2023-08-23 | 2023-08-23 | Method for preparing trichloromethoxybenzene by near infrared radiation |
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| CN117088761A true CN117088761A (en) | 2023-11-21 |
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| CN202311061092.XA Pending CN117088761A (en) | 2023-08-23 | 2023-08-23 | Method for preparing trichloromethoxybenzene by near infrared radiation |
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- 2023-08-23 CN CN202311061092.XA patent/CN117088761A/en active Pending
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