CN112521254A - Preparation method of trifluoromethoxybenzene compound - Google Patents
Preparation method of trifluoromethoxybenzene compound Download PDFInfo
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- CN112521254A CN112521254A CN201910885268.0A CN201910885268A CN112521254A CN 112521254 A CN112521254 A CN 112521254A CN 201910885268 A CN201910885268 A CN 201910885268A CN 112521254 A CN112521254 A CN 112521254A
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- trichloromethoxybenzene
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- trifluoromethoxybenzene
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- -1 trifluoromethoxybenzene compound Chemical class 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims description 10
- 239000007788 liquid Substances 0.000 claims abstract description 31
- 239000002904 solvent Substances 0.000 claims abstract description 30
- 238000005660 chlorination reaction Methods 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 26
- CLYZNABPUKUSDX-UHFFFAOYSA-N trichloromethoxybenzene Chemical class ClC(Cl)(Cl)OC1=CC=CC=C1 CLYZNABPUKUSDX-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000003682 fluorination reaction Methods 0.000 claims abstract description 11
- GQHWSLKNULCZGI-UHFFFAOYSA-N trifluoromethoxybenzene Chemical class FC(F)(F)OC1=CC=CC=C1 GQHWSLKNULCZGI-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 238000004519 manufacturing process Methods 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 36
- 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 description 26
- 239000003999 initiator Substances 0.000 claims description 26
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims description 19
- 229910052801 chlorine Inorganic materials 0.000 claims description 19
- 239000000460 chlorine Substances 0.000 claims description 19
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 17
- 150000001875 compounds Chemical class 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000004821 distillation Methods 0.000 claims description 9
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 8
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 7
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 7
- 230000003472 neutralizing effect Effects 0.000 claims description 7
- 238000010926 purge Methods 0.000 claims description 7
- 238000001256 steam distillation Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 239000012074 organic phase Substances 0.000 claims description 4
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims description 4
- 239000000047 product Substances 0.000 claims description 4
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- UICXTANXZJJIBC-UHFFFAOYSA-N 1-(1-hydroperoxycyclohexyl)peroxycyclohexan-1-ol Chemical compound C1CCCCC1(O)OOC1(OO)CCCCC1 UICXTANXZJJIBC-UHFFFAOYSA-N 0.000 claims description 2
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- ZQMHJBXHRFJKOT-UHFFFAOYSA-N methyl 2-[(1-methoxy-2-methyl-1-oxopropan-2-yl)diazenyl]-2-methylpropanoate Chemical compound COC(=O)C(C)(C)N=NC(C)(C)C(=O)OC ZQMHJBXHRFJKOT-UHFFFAOYSA-N 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
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 claims 1
- 230000002194 synthesizing effect Effects 0.000 abstract description 9
- 239000002699 waste material Substances 0.000 abstract description 8
- 239000007810 chemical reaction solvent Substances 0.000 abstract description 3
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 27
- 239000000243 solution Substances 0.000 description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 13
- 239000012295 chemical reaction liquid Substances 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- SELFZOLQRDPBKC-UHFFFAOYSA-N 1-chloro-4-(trifluoromethoxy)benzene Chemical compound FC(F)(F)OC1=CC=C(Cl)C=C1 SELFZOLQRDPBKC-UHFFFAOYSA-N 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 4
- GETTZEONDQJALK-UHFFFAOYSA-N (trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1 GETTZEONDQJALK-UHFFFAOYSA-N 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 239000003365 glass fiber Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- QGRPVMLBTFGQDQ-UHFFFAOYSA-N 1-chloro-2-methoxybenzene Chemical compound COC1=CC=CC=C1Cl QGRPVMLBTFGQDQ-UHFFFAOYSA-N 0.000 description 2
- SFTPDMXEKLOAAX-UHFFFAOYSA-N 1-chloro-3-(trichloromethoxy)benzene Chemical compound ClC1=CC=CC(OC(Cl)(Cl)Cl)=C1 SFTPDMXEKLOAAX-UHFFFAOYSA-N 0.000 description 2
- ATKSGXRJMHLMIE-UHFFFAOYSA-N 1-chloro-4-(chloromethoxy)-2,3-difluorobenzene Chemical compound Fc1c(F)c(OCCl)ccc1Cl ATKSGXRJMHLMIE-UHFFFAOYSA-N 0.000 description 2
- YRGAYAGBVIXNAQ-UHFFFAOYSA-N 1-chloro-4-methoxybenzene Chemical compound COC1=CC=C(Cl)C=C1 YRGAYAGBVIXNAQ-UHFFFAOYSA-N 0.000 description 2
- IDTKMRKZNUPFHJ-UHFFFAOYSA-N ClC1(CC=CC=C1)OC(Cl)(Cl)Cl Chemical compound ClC1(CC=CC=C1)OC(Cl)(Cl)Cl IDTKMRKZNUPFHJ-UHFFFAOYSA-N 0.000 description 2
- JMWZWGXLVQENRP-UHFFFAOYSA-N ClC1(CC=CC=C1)OC(F)(F)F Chemical compound ClC1(CC=CC=C1)OC(F)(F)F JMWZWGXLVQENRP-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- JFCMAIACBGBZRX-UHFFFAOYSA-N dichloromethoxybenzene Chemical compound ClC(Cl)OC1=CC=CC=C1 JFCMAIACBGBZRX-UHFFFAOYSA-N 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 150000002222 fluorine compounds Chemical class 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 239000002516 radical scavenger Substances 0.000 description 2
- CQCISJXNGWFMSX-UHFFFAOYSA-N 1-(chloromethoxy)-2,3-difluorobenzene Chemical compound FC1=CC=CC(OCCl)=C1F CQCISJXNGWFMSX-UHFFFAOYSA-N 0.000 description 1
- YHLWGETVNYCUNS-UHFFFAOYSA-N 1-chloro-3-(dichloromethoxy)benzene Chemical compound ClC(Cl)OC1=CC=CC(Cl)=C1 YHLWGETVNYCUNS-UHFFFAOYSA-N 0.000 description 1
- JYMJYRCUFIYTEZ-UHFFFAOYSA-N COC1=CC=CC=C1.[F] Chemical compound COC1=CC=CC=C1.[F] JYMJYRCUFIYTEZ-UHFFFAOYSA-N 0.000 description 1
- YLBXKVNIOGZLFN-UHFFFAOYSA-N FC1=CC=CC(OCl)=C1F Chemical compound FC1=CC=CC(OCl)=C1F YLBXKVNIOGZLFN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction 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
- 239000000975 dye Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- QULYNCCPRWKEMF-UHFFFAOYSA-N parachlorobenzotrifluoride Chemical compound FC(F)(F)C1=CC=C(Cl)C=C1 QULYNCCPRWKEMF-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical group 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 150000003254 radicals Chemical class 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
-
- 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
- C07C41/34—Separation; Purification; Stabilisation; Use of additives
- C07C41/40—Separation; Purification; Stabilisation; Use of additives by change of physical state, e.g. by crystallisation
- C07C41/42—Separation; Purification; Stabilisation; Use of additives by change of physical state, e.g. by crystallisation by distillation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for preparing trichloromethoxybenzene compounds and trifluoromethoxybenzene compounds. In the method, the trichloromethoxybenzene compound is synthesized by taking the rectification residual liquid obtained when the trichloromethoxybenzene compound is used for synthesizing a trifluoromethoxybenzene compound product as a solvent, and the content of the trichloromethoxybenzene compound in the obtained chlorination liquid can reach more than 95%. After desolventizing, the obtained crude trichloromethoxybenzene compound can be directly used for fluorination reaction to produce the corresponding trifluoromethoxybenzene compound. By utilizing the method, the waste fluorinated rectification residual liquid in the original process can be fully utilized, the waste discharge and treatment cost in the production process are greatly reduced, the rectification residual liquid treated as waste is changed into an excellent chlorination reaction solvent, the raw material consumption and the production cost are greatly reduced, the purpose of waste utilization is achieved, and the process is more green and environment-friendly.
Description
Technical Field
The invention relates to the technical field of organic chemical synthesis, and particularly relates to a preparation method of a trichloromethoxybenzene compound and a preparation method of a trifluoromethoxybenzene compound based on the trichloromethoxybenzene compound.
Background
The trifluoromethoxybenzene compounds are important organic synthesis intermediates, wherein the trifluoromethoxybenzene is widely applied, and is widely applied to synthesis of products such as medicines, pesticides and dyes. Trichloromethoxybenzene is an important raw material for producing trifluoromethoxybenzene. In the prior art, the synthesis method of trifluoromethoxybenzene mainly comprises the steps of chlorinating anisole with chlorine in a solvent in the presence of an initiator and illumination to obtain corresponding trichloromethoxybenzene, and then fluorinating the trichloromethoxybenzene with HF to obtain the trifluoromethoxybenzene. The solvents used for the chlorination of anisole include carbon tetrachloride, chlorobenzene, benzotrifluoride, p-chlorotrifluoroethylene and the like. Among the above solvents, carbon tetrachloride is restricted by the protocol of Montreal protocol and cannot be used. Patent CA2222104 provides a method for synthesizing trichloromethoxybenzene by chlorination of anisole in solvents such as trifluorotoluene, p-chlorotrifluoromethylbenzene and the like, and the trichloromethoxybenzene content in the reaction liquid at the end of the reaction can reach more than 87%; patent US5840998 describes a method of anisole chlorination using fluorocarbons as solvent, the trichloromethoxybenzene content after the reaction being up to 90% or more; patent CN102120717A provides a method for synthesizing trichloromethoxybenzene by chlorination of anisole in chlorobenzene solvent, and the trichloromethoxybenzene content after reaction can reach more than 90%. The common feature of the above techniques is that a pure organic compound solvent is used for the chlorination of anisole, so there are inevitable solvent consumption and thus solvent cost problems.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a preparation method of a trichloromethoxybenzene compound with a structure shown in a formula I.
The preparation method of the trichloromethoxybenzene compound comprises the step of reacting a compound with a structure shown in a formula II with chlorine in a solvent, wherein the solvent is a rectification residue obtained by rectifying a fluorination reaction product of the trichloromethoxybenzene compound with the structure shown in the formula I and collecting a trifluoromethoxybenzene compound;
the formulas I and II are respectively as follows:
wherein R is1Represents one or more (e.g. 2, 3, 4, 5) optional, independent substituents on the phenyl group and is selected from: H. cl, Br, I, CN and NCO;
in one embodiment of the invention, R1Is H or Cl.
In one embodiment of the present invention, the compound of the structure of formula II above is selected from:
in one embodiment of the invention, R2And R1The same; in one embodiment of the invention, R2And R1Are all hydrogen.
In one embodiment of the present invention, the above-mentioned rectification residue is obtained by the following steps:
(1-1) reacting a trichloromethoxybenzene compound with a structure shown in a formula I with HF to obtain a fluorinated solution;
(1-2) neutralizing the fluorinated liquid obtained in the step (1-1), and performing steam distillation;
and (1-3) rectifying the organic phase obtained in the step (1-2), and collecting trifluoromethoxybenzene compounds to obtain a rectification residual liquid which can be used as a chlorinated solvent.
Specifically, in step (1-1), in order to fully perform the fluorination reaction, HF is excessive, for example, the molar ratio of the trichloromethoxybenzene compound with the structure of formula I to HF can be 1:3-10, and the excessive HF can be recycled.
Specifically, in the step (1-1), the reaction temperature is 60-200 ℃; more specifically, the reaction temperature is 80-140 ℃; in one embodiment of the present invention, the reaction temperature is 100-110 ℃.
Specifically, in the step (1-1), the reaction time is 0.5-10 hours; more specifically, the reaction time is 1 to 5 hours; in one embodiment of the invention, the reaction time is 2 hours.
In one embodiment of the present invention, the step (1-1) comprises: adding the trichloromethoxybenzene compound with the structure shown in the formula I and HF into an autoclave, heating under a closed condition, and reacting to obtain a fluorinated liquid.
In one embodiment of the present invention, the step (1-2) comprises: cooling the fluorinated liquid obtained in the step (1) (such as to below 30 ℃), evacuating the autoclave to normal pressure, and discharging N2Excess HF was purged, neutralized, and steam distilled.
Specifically, the distillation in the step (1-3) is atmospheric distillation, for example, atmospheric distillation is performed by using a glass fiber packed tower.
Specifically, the solvent comprises a solvent selected from:
one or more ingredients of (a).
In one embodiment of the present invention, the preparation method of the trichloromethoxybenzene compound comprises the following steps:
(2-1) dropwise adding a compound with a structure shown in a formula II and an initiator into a solvent, and introducing chlorine gas to perform chlorination reaction to obtain a reaction solution;
(2-2) after the compound with the formula II structure in the step (2-1) and the initiator are dripped, continuing to introduce chlorine, dripping the initiator solution into the reaction solution, and carrying out deep chlorination reaction to obtain a product.
Specifically, in the step (2-1), the initiator is a peroxide capable of providing a free radical (including lauroyl peroxide, cyclohexanone peroxide, dibenzoyl peroxide, tert-butyl hydroperoxide, Benzoyl Peroxide (BPO)) or an azo compound (including Azobisisobutyronitrile (AIBN), azobisisoheptonitrile, and dimethyl azobisisobutyrate), and preferably, the initiator is benzoyl peroxide or azobisisobutyronitrile.
Specifically, in the step (2-1), the mass ratio of the initiator to the compound with the structure of formula II is 1: 10-100; more specifically, the ratio is 1: 40-100; in one embodiment of the invention, the ratio is 1:60 or 1: 80.
In one embodiment of the present invention, in the step (2-1), the compound having the structure of formula II is mixed with an initiator to prepare a raw material solution, and then the raw material solution is added dropwise to a solvent.
In an embodiment of the invention, the reaction system in the step (2-1) further comprises a water removing agent, and the water removing agent can be polychloride (including phosphorus trichloride, phosphorus oxychloride and phosphorus pentachloride); in one embodiment of the present invention, the water scavenger is phosphorus trichloride.
Specifically, the mass ratio of the water scavenger to the compound with the structure of formula II is 1: 10-100; more specifically, the ratio is 1: 40-100; in one embodiment of the invention, the ratio is 1:60 or 1: 80.
Specifically, in the step (2-1), the mass ratio of the solvent to the compound with the structure of the formula II is 0.1-100: 1; more specifically, the ratio is 1-10: 1; in one embodiment of the invention, the ratio is 3: 1.
Specifically, in the step (2-1), the ratio of the dropping rate of the raw material liquid to the rate of chlorine gas introduction is 1:1 to 10, more specifically, 1:1 to 5.
Specifically, in the step (2-1), the chlorine gas is introduced at a rate of 30-50 g/h.
Specifically, in the step (2-1), the reaction temperature is 60-200 ℃; more specifically, the reaction temperature is 100-160 ℃; in one embodiment of the present invention, the reaction temperature is 120-130 ℃.
Specifically, the step (2-1) further comprises the following steps after the reaction is finished: absorbing HCl in the reaction tail gas by water, and then absorbing unreacted chlorine by NaOH solution.
Specifically, in the step (2-1), the chlorination reaction can also be carried out under the condition of photocatalysis, so that one or two modes of photocatalysis and initiator catalysis can be selected for carrying out the chlorination reaction.
Specifically, in the step (2-2), the initiator solution may be prepared by dissolving the initiator in the reaction solution obtained in the step (2-1), or may be prepared by dissolving the initiator in the deep reaction chlorination solution obtained in the step (2-2), and particularly, may be prepared by dissolving the initiator in the solvent obtained in the step (2-1).
Specifically, in the step (2-2), the mass ratio of the initiator to the compound with the structure of the formula II is 1: 50-200; more specifically, the ratio is 1: 50-120; in one embodiment of the invention, the ratio is 1:75 or 1: 100.
Specifically, in the step (2-2), the concentration of the initiator solution is 0.1-10 wt%; more specifically, the concentration of the initiator solution is 1-5%; in one embodiment of the invention, the concentration of the initiator solution is 2%.
Specifically, the ratio of the dropping speed of the initiator solution to the chlorine introducing speed in the step (2-2) is 1: 1-10; more specifically, the ratio is 1: 1-5.
Specifically, the chlorination reaction in the step (2-1) and the deep chlorination reaction in the step (2-2) are carried out in a batch mode or a continuous mode.
Specifically, the chlorination reaction in the step (2-1) and the deep chlorination reaction in the step (2-2) are carried out in one or two modes of a single kettle and a multi-kettle series connection.
Specifically, the step (2-2) may be followed by a step (2-3): and (3) desolventizing the reaction system in the step (2-2) for subsequent fluorination reaction.
The compound with the structure of formula I prepared by the invention can be further reacted with HF to synthesize a trifluoromethoxybenzene compound with the structure of formula III (the fluorination reaction part is general knowledge and is not included in the invention), which comprises the step of carrying out fluorination reaction on the trichloromethoxybenzene compound with the structure of formula I prepared by the method;
wherein R is1Having the above definitions of the invention.
In one embodiment of the present invention, the preparation method of the trifluoromethoxybenzene compound comprises the following steps:
(3-1) preparing trichloromethoxybenzene compounds according to the method;
(3-2) reacting the trichloromethoxybenzene compound obtained in the step (3-1) with HF to obtain a fluorinated liquid;
(3-3) neutralizing the fluorinated liquid obtained in the step (3-2), and performing steam distillation;
and (3-4) rectifying the organic phase obtained in the step (3-3) and collecting the trifluoromethoxybenzene compounds.
Specifically, in step (3-1), in order to fully perform the fluorination reaction, HF is excessive, for example, the molar ratio of the trichloromethoxybenzene compound with the structure of formula I to HF can be 1:3-10, and the excessive HF can be recycled.
Specifically, in the step (3-1), the reaction temperature is 60-200 ℃; more specifically, the reaction temperature is 80-140 ℃; in one embodiment of the present invention, the reaction temperature is 100-110 ℃.
Specifically, in the step (3-1), the reaction time is 0.5 to 10 hours; more specifically, the reaction time is 1 to 5 hours; in one embodiment of the invention, the reaction time is 2 hours.
In one embodiment of the present invention, the step (3-2) comprises: adding the trichloromethoxybenzene compound with the structure shown in the formula I and HF into an autoclave, heating under a closed condition, and reacting to obtain a fluorinated liquid.
In one embodiment of the present invention, the step (3-3) comprises: cooling the fluorinated liquid obtained in the step (1) (such as to below 30 ℃), evacuating the autoclave to normal pressure, and discharging N2Excess HF was purged, neutralized, and steam distilled.
Specifically, the distillation in the step (3-4) is atmospheric distillation, for example, atmospheric distillation is performed by using a glass fiber packed tower.
Specifically, in the step (3-4), the rectification residual liquid obtained after collecting the trifluoromethoxybenzene compound can be used as a solvent for chlorination reaction in the preparation method of the trichloromethoxybenzene compound.
Compared with the prior art for synthesizing trichloromethoxybenzene by chlorination of anisole side chain, the invention adopts the rectification residual liquid of the trichloromethoxybenzene compound for synthesizing the trifluoromethoxybenzene compound product as the solvent to synthesize the trichloromethoxybenzene compound, and the trichloromethoxybenzene compound content in the obtained chlorination liquid can reach more than 95%. After desolventizing, the obtained crude trichloromethoxybenzene compound can be directly used for fluorination reaction to produce the trifluoromethoxybenzene compound. The waste fluorinated rectification residual liquid in the original process can be fully utilized (the amount of the fluorinated rectification residual liquid generated in the synthesis process of the trifluoromethoxybenzene compound can meet the consumption of the fluorinated rectification residual liquid used as a chlorination reaction solvent for synthesizing the trichloromethoxybenzene compound), the waste discharge and the treatment cost in the production process are greatly reduced, the rectification residual liquid treated as the waste is changed into an excellent chlorination reaction solvent, the consumption of raw materials and the production cost are greatly reduced, the purpose of waste utilization is achieved, and the process is more green and environment-friendly.
Detailed Description
Unless defined otherwise, all scientific and technical terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains.
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
450g of a fluorine material rectification residue (main components: 35.1% of 4-chloro-trifluoromethoxybenzene, 20.4% of difluorochloromethoxybenzene, 15.7% of 4-chloro-difluorochloromethoxybenzene), 2.5g of phosphorus trichloride were added to 1000mL of a solution equipped with a stirrer, a reflux condenser, and a chlorine introduction deviceAnd (4) heating to 120-130 ℃ in a reaction bottle of the tube. Adding 150g of anisole and 2.5g of AIBN, and introducing chlorine gas, wherein the chlorine gas flow is controlled to be 40-50L/h. The HCl in the reaction tail gas is absorbed by water, and then unreacted chlorine gas is absorbed by 30 percent NaOH. After the anisole is added, the chlorine is continuously introduced, and 100g of the mixed solution of the fluorine material rectification residual liquid and 2g of AIBN is added. Until the content of dichloromethoxybenzene in the reaction liquid is less than 1%, closing chlorine gas, and N2Purging and desolventizing until the kettle temperature reaches 150 +/-0.096 Mpa, and continuously using the extracted solvent for the chlorination reaction of anisole.
And adding the chlorination solution obtained after desolventizing and 300g of anhydrous HF into a 2000mL high-pressure kettle, heating to 100-110 ℃, and carrying out heat preservation reaction for 2 hours. After the reaction is finished, the temperature of the reaction liquid is reduced to below 30 ℃. The autoclave was evacuated to atmospheric pressure, N2And (5) purging. And neutralizing the obtained fluorinated solution to the pH of 7-8 by using a 10% NaOH solution. And (5) steam distillation. Will separate out the oil phase
Rectifying the mixture at normal pressure in a glass fiber packed tower, and collecting fractions at 100-105 ℃ to obtain 166g of trifluoromethoxybenzene with the content of 99.5% and the yield of 73.4%. Collecting 60-100 ℃/-0.096Mpa fraction to obtain 15g of raffinate which can be used as solvent in anisole chlorination reaction process (as described above).
Example 2
450g of fluoride rectification raffinate (the main components are 20.2 percent of 4-chloro-trifluoromethoxybenzene, 35.8 percent of difluoro monochloro oxybenzene, 16.7 percent of 4-chloro-difluoro monochloro oxybenzene) and 2.5g of phosphorus trichloride are added into a 1000mL reaction bottle with a stirring, reflux condenser and chlorine inlet pipe, and the temperature is raised to 120-130 ℃. Adding 150g of anisole and 2.5g of AIBN, and introducing chlorine gas, wherein the chlorine gas flow is controlled to be 40-50L/h. The HCl in the reaction tail gas is absorbed by water, and then unreacted chlorine gas is absorbed by 30 percent NaOH. After the anisole is added, the chlorine is continuously introduced, and 100g of the mixed solution of the fluorine material rectification residual liquid and 2g of AIBN is added. Until the content of dichloromethoxybenzene in the reaction liquid is less than 1%, closing chlorine gas, and N2Purging and desolventizing until the kettle temperature reaches 150 +/-0.096 Mpa, and continuously using the extracted solvent for the chlorination reaction of anisole. The content of the trichloromethoxybenzene is 98.7 percent, and the trichloromethoxybenzene is used for synthesizing the trichloromethoxybenzene through fluorinationAnd (3) fluorine methoxy benzene.
Example 3
600g of fluoride rectification raffinate (main components: 41% of 4-chloro-trifluoromethoxybenzene and 35% of 4-chloro-difluorochloromethoxybenzene) and 2.5g of phosphorus trichloride are added into a 1000mL reaction bottle with a stirring, reflux condenser and chlorine introducing tube, and the temperature is raised to 120-130 ℃. Adding 200g of 4-chloro anisole and 2.5g of AIBN, and introducing chlorine gas, wherein the chlorine gas flow is controlled to be 40-50L/h. The HCl in the reaction tail gas is absorbed by water, and then unreacted chlorine gas is absorbed by 30 percent NaOH. After the addition of 4-chloromethylated ether, chlorine was continuously introduced, and a mixture of 100g of the fluorine compound distillation residue and 2g of AIBN was added. Until the content of 4-chloro-dichloromethoxybenzene in the reaction liquid is less than 1%, closing chlorine, and N2Purging and desolventizing until the kettle temperature reaches 150 +/-0.096 Mpa, and continuously using the extracted solvent for chlorination reaction of 4-chloro anisole. The content of the obtained 4-chloro-trichloromethoxybenzene is 97.1 percent, and the 4-chloro-trichloromethoxybenzene is used for synthesizing 4-chloro-trifluoromethoxybenzene through fluorination.
Example 4
600g of fluoride rectification raffinate (the main components are 45% of 2-chloro-trifluoromethoxybenzene and 27% of 2-chloro-difluoro-monochloromethoxybenzene), 2.5g of phosphorus trichloride are added into 1000mL of a reaction bottle with a stirring device, a reflux condenser and a chlorine introducing pipe, and the temperature is raised to 120-130 ℃. Adding 200g of 2-chloro anisole and 2.5g of AIBN, and introducing chlorine gas, wherein the chlorine gas flow is controlled to be 40-50L/h. The HCl in the reaction tail gas is absorbed by water, and then unreacted chlorine gas is absorbed by 30 percent NaOH. After the addition of 4-chloromethylated ether, chlorine was continuously introduced, and a mixture of 100g of the fluorine compound distillation residue and 2g of AIBN was added. Until the content of 2-chloro-dichloromethoxybenzene in the reaction liquid is less than 1%, closing chlorine, and N2Purging and desolventizing until the kettle temperature reaches 150 +/-0.096 Mpa, and continuously using the extracted solvent for the chlorination reaction of the 2-chloro-anisole. The content of the obtained 2-chloro-trichloromethoxybenzene is 95.6 percent, and the 2-chloro-trichloromethoxybenzene is used for synthesizing 2-chloro-trifluoromethoxybenzene through fluorination.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and the like that are within the spirit and principle of the present invention are included in the present invention.
Claims (10)
1. A preparation method of trichloromethoxybenzene compounds comprises the step of reacting compounds with a structure shown in a formula II with chlorine in a solvent,
the trichloromethoxybenzene compound has a structure shown in a formula I, and the solvent is a rectification residue obtained by rectifying a fluorination reaction product of the trichloromethoxybenzene compound with the structure shown in the formula I and collecting a trifluoromethoxybenzene compound;
the formulas I and II are respectively as follows:
wherein R is1Represents one or more arbitrary, independent substituents on the phenyl group and is selected from: H. cl, Br, I, CN and NCO.
2. The method of claim 1, wherein the distillation residue is obtained by:
(1-1) reacting a trichloromethoxybenzene compound with a structure shown in a formula I with HF to obtain a fluorinated solution;
(1-2) neutralizing the fluorinated liquid obtained in the step (1-1), and performing steam distillation;
and (1-3) rectifying the organic phase obtained in the step (1-2), and collecting trifluoromethoxybenzene compounds to obtain a rectification residual liquid.
3. The method of claim 2, wherein the step (1-1) comprises: adding a trichloromethoxybenzene compound with a structure shown in a formula I and HF into an autoclave, heating under a closed condition, and reacting to obtain a fluorinated liquid;
the reaction temperature in the step (1-1) is 60-200 ℃, and the reaction time is 0.5-10 hours;
the step (1-2) comprises: cooling the fluorinated liquid obtained in the step (1), and evacuating the autoclave to normal pressure, wherein N is2Purging to remove excessive HF, neutralizing, and performing steam distillation;
and (3) the rectification in the step (1-3) is normal-pressure rectification.
4. The method of claim 1, wherein R is1Is H or Cl; preferably, the compound of formula II is selected from:
5. the process according to any one of claims 1 to 4, wherein the trichloromethoxybenzene compound is prepared by a process comprising the steps of:
(2-1) dropwise adding a compound with a structure shown in a formula II and an initiator into a solvent, and introducing chlorine gas to perform chlorination reaction to obtain a reaction solution;
(2-2) after the compound with the formula II structure in the step (2-1) and the initiator are dripped, continuing to introduce chlorine, dripping the initiator solution into the reaction solution, and carrying out deep chlorination reaction to obtain a product.
6. The method of claim 5, wherein the initiator is selected from the group consisting of: lauroyl peroxide, cyclohexanone peroxide, dibenzoyl peroxide, tert-butyl hydroperoxide, benzoyl peroxide, azobisisobutyronitrile, azobisisoheptonitrile, dimethyl azobisisobutyrate; preferably, the initiator is benzoyl peroxide or azobisisobutyronitrile;
the reaction system in the step (2-1) further comprises a water removal agent, wherein the water removal agent is selected from the following components: phosphorus trichloride, phosphorus oxychloride, phosphorus pentachloride; preferably, the water removing agent is phosphorus trichloride.
7. The method of claim 5, wherein in the step (2-1):
the mass ratio of the initiator to the compound with the structure of the formula II is 1: 10-100;
the mass ratio of the solvent to the compound with the structure of the formula II is 0.1-100: 1;
the ratio of the dropping speed of the raw material liquid to the chlorine gas introducing speed is 1: 1-10;
the reaction temperature is 60-200 ℃;
in the step (2-2):
the mass ratio of the initiator to the compound with the structure of the formula II is 1: 50-200;
the concentration of the initiator solution is 0.1-10%.
8. A method for producing a trifluoromethoxybenzene compound, which comprises the steps of the method for producing a trichloromethoxybenzene compound according to any one of claims 1 to 7.
9. The method of claim 8, wherein the trifluoromethoxybenzene compound is prepared by a process comprising the steps of:
(3-1) preparing a trichloromethoxybenzene compound according to the process of any one of claims 1 to 8;
(3-2) reacting the trichloromethoxybenzene compound obtained in the step (3-1) with HF to obtain a fluorinated liquid;
(3-3) neutralizing the fluorinated liquid obtained in the step (3-2), and performing steam distillation;
and (3-4) rectifying the organic phase obtained in the step (3-3) and collecting the trifluoromethoxybenzene compounds.
10. The method of claim 9, wherein the step (3-1) comprises: adding a trichloromethoxybenzene compound with a structure shown in a formula I and HF into an autoclave, heating under a closed condition, and reacting to obtain a fluorinated liquid;
the reaction temperature in the step (3-1) is 60-200 ℃, and the reaction time is 0.5-10 hours;
the step (3-2) comprises: cooling the fluorinated liquid obtained in the step (1), and evacuating the autoclave to normal pressure, wherein N is2Purging to remove excessive HF, neutralizing, and performing steam distillation;
and (4) in the step (3-3), the rectification is normal-pressure rectification.
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| US5440051A (en) * | 1992-04-27 | 1995-08-08 | Bayer Aktiengesellschaft | Process for the α-chlorination of aryl ethers |
| US5773668A (en) * | 1997-02-24 | 1998-06-30 | Occidental Chemical Corporation | Method of making trichloromethoxybenzene |
| CN103553884A (en) * | 2013-11-15 | 2014-02-05 | 金凯(辽宁)化工有限公司 | Method for preparing trifluoromethoxybenzene |
| CN106008175A (en) * | 2016-05-19 | 2016-10-12 | 山东道可化学有限公司 | Production method of trifluoromethoxybenzene |
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| US5440051A (en) * | 1992-04-27 | 1995-08-08 | Bayer Aktiengesellschaft | Process for the α-chlorination of aryl ethers |
| US5773668A (en) * | 1997-02-24 | 1998-06-30 | Occidental Chemical Corporation | Method of making trichloromethoxybenzene |
| CN103553884A (en) * | 2013-11-15 | 2014-02-05 | 金凯(辽宁)化工有限公司 | Method for preparing trifluoromethoxybenzene |
| CN106008175A (en) * | 2016-05-19 | 2016-10-12 | 山东道可化学有限公司 | Production method of trifluoromethoxybenzene |
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| CN114539036A (en) * | 2022-01-26 | 2022-05-27 | 金凯(辽宁)生命科技股份有限公司 | Method for efficiently synthesizing trichloromethoxybenzene by controlling chlorination depth |
| CN114539036B (en) * | 2022-01-26 | 2023-12-08 | 金凯(辽宁)生命科技股份有限公司 | Method for efficiently synthesizing trichloromethoxybenzene by controlling chlorination depth |
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