CN114181244A - Preparation method of alkyl siloxy halogenated benzene - Google Patents
Preparation method of alkyl siloxy halogenated benzene Download PDFInfo
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- CN114181244A CN114181244A CN202111630929.9A CN202111630929A CN114181244A CN 114181244 A CN114181244 A CN 114181244A CN 202111630929 A CN202111630929 A CN 202111630929A CN 114181244 A CN114181244 A CN 114181244A
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- -1 alkyl siloxy halogenated benzene Chemical class 0.000 title claims abstract description 115
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 57
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000005046 Chlorosilane Substances 0.000 claims abstract description 10
- 150000002989 phenols Chemical class 0.000 claims abstract description 5
- 239000002608 ionic liquid Substances 0.000 claims description 40
- 239000007864 aqueous solution Substances 0.000 claims description 28
- 229910001495 sodium tetrafluoroborate Inorganic materials 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 150000005171 halobenzenes Chemical class 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 6
- 230000032798 delamination Effects 0.000 claims description 2
- 239000002253 acid Substances 0.000 abstract description 7
- 239000011230 binding agent Substances 0.000 abstract description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 18
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 16
- 238000003756 stirring Methods 0.000 description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- HWKPTBHJWBSOOP-UHFFFAOYSA-N (4-bromophenoxy)-trimethylsilane Chemical compound C[Si](C)(C)OC1=CC=C(Br)C=C1 HWKPTBHJWBSOOP-UHFFFAOYSA-N 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- 238000001514 detection method Methods 0.000 description 9
- 239000011780 sodium chloride Substances 0.000 description 9
- STCBHSHARMAIOM-UHFFFAOYSA-N 1-methyl-1h-imidazol-1-ium;chloride Chemical group Cl.CN1C=CN=C1 STCBHSHARMAIOM-UHFFFAOYSA-N 0.000 description 8
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 8
- 229910052938 sodium sulfate Inorganic materials 0.000 description 8
- 235000011152 sodium sulphate Nutrition 0.000 description 8
- 239000005051 trimethylchlorosilane Substances 0.000 description 8
- 229910020808 NaBF Inorganic materials 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 239000003960 organic solvent Substances 0.000 description 7
- 239000012071 phase Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 6
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 5
- GZFGOTFRPZRKDS-UHFFFAOYSA-N 4-bromophenol Chemical compound OC1=CC=C(Br)C=C1 GZFGOTFRPZRKDS-UHFFFAOYSA-N 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- PKEYKFADHPXIRN-UHFFFAOYSA-N (4-bromo-2,3,5,6-tetrafluorophenoxy)-trimethylsilane Chemical compound C[Si](C)(C)OC1=C(F)C(F)=C(Br)C(F)=C1F PKEYKFADHPXIRN-UHFFFAOYSA-N 0.000 description 4
- LMPXUWTYLZMITI-UHFFFAOYSA-N (4-bromo-2-fluorophenoxy)-tert-butyl-dimethylsilane Chemical compound CC(C)(C)[Si](C)(C)OC1=CC=C(Br)C=C1F LMPXUWTYLZMITI-UHFFFAOYSA-N 0.000 description 4
- POVPOADUCDQYMB-UHFFFAOYSA-N 3-butyl-1h-imidazol-3-ium;chloride Chemical group [Cl-].CCCCN1C=C[NH+]=C1 POVPOADUCDQYMB-UHFFFAOYSA-N 0.000 description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- LOUTXSPUHCFDCO-UHFFFAOYSA-N tert-butyl-(2-chlorophenoxy)-dimethylsilane Chemical compound CC(C)(C)[Si](C)(C)OC1=CC=CC=C1Cl LOUTXSPUHCFDCO-UHFFFAOYSA-N 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- BCNZYOJHNLTNEZ-UHFFFAOYSA-N tert-butyldimethylsilyl chloride Chemical compound CC(C)(C)[Si](C)(C)Cl BCNZYOJHNLTNEZ-UHFFFAOYSA-N 0.000 description 3
- MCMFEZDRQOJKMN-UHFFFAOYSA-N 1-butylimidazole Chemical compound CCCCN1C=CN=C1 MCMFEZDRQOJKMN-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- ABDVJABGTGHCPI-UHFFFAOYSA-N 3-ethyl-1h-imidazol-3-ium;chloride Chemical group Cl.CCN1C=CN=C1 ABDVJABGTGHCPI-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- DCFKHNIGBAHNSS-UHFFFAOYSA-N chloro(triethyl)silane Chemical compound CC[Si](Cl)(CC)CC DCFKHNIGBAHNSS-UHFFFAOYSA-N 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 1
- IWDFHWZHHOSSGR-UHFFFAOYSA-N 1-ethylimidazole Chemical compound CCN1C=CN=C1 IWDFHWZHHOSSGR-UHFFFAOYSA-N 0.000 description 1
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 1
- MNOJRWOWILAHAV-UHFFFAOYSA-N 3-bromophenol Chemical compound OC1=CC=CC(Br)=C1 MNOJRWOWILAHAV-UHFFFAOYSA-N 0.000 description 1
- FXTKWBZFNQHAAO-UHFFFAOYSA-N 3-iodophenol Chemical compound OC1=CC=CC(I)=C1 FXTKWBZFNQHAAO-UHFFFAOYSA-N 0.000 description 1
- ZBYSEVWUBQSGKC-UHFFFAOYSA-N 4-bromo-2,3,5,6-tetrafluorophenol Chemical compound OC1=C(F)C(F)=C(Br)C(F)=C1F ZBYSEVWUBQSGKC-UHFFFAOYSA-N 0.000 description 1
- RYVOZMPTISNBDB-UHFFFAOYSA-N 4-bromo-2-fluorophenol Chemical compound OC1=CC=C(Br)C=C1F RYVOZMPTISNBDB-UHFFFAOYSA-N 0.000 description 1
- HHGOLZGZHXELSW-UHFFFAOYSA-N 4-bromo-3,5-difluorophenol Chemical compound OC1=CC(F)=C(Br)C(F)=C1 HHGOLZGZHXELSW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- TZPZCTBZJKZFGY-UHFFFAOYSA-N chloro-tris(2-methylpropyl)silane Chemical compound CC(C)C[Si](Cl)(CC(C)C)CC(C)C TZPZCTBZJKZFGY-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000010888 waste organic solvent Substances 0.000 description 1
- 239000010887 waste solvent Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
- C07D233/58—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring nitrogen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
- C07F7/188—Preparation; Treatments not provided for in C07F7/20 by reactions involving the formation of Si-O linkages
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a preparation method of alkyl siloxy halogenated benzene, which comprises the following steps: adding alkyl chlorosilane into halogenated phenol and N-alkyl imidazole for reaction, and directly layering after the reaction is finished to obtain the alkyl siloxy halogenated benzene and N-alkyl imidazole hydrochloride. The invention provides the alkyl siloxy halogenated benzene, which adopts specific N-alkyl imidazole as an acid-binding agent, and can obtain the alkyl siloxy halogenated benzene and the N-alkyl imidazole hydrochloride by direct layering without post-treatment after the reaction is finished.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to a preparation method of alkyl siloxy halogenated benzene.
Background
The alkyl siloxy halogenated benzene is prepared by reacting halogenated phenol with alkyl chlorosilane, the hydroxyl is protected by alkyl silicon to stabilize the phenolic hydroxyl so as to eliminate or lighten side reactions caused by the phenolic hydroxyl in the subsequent reaction process, and various aromatic compounds containing hydroxyl functional groups can be efficiently prepared by protecting. Thus, the alkylsiloxy halobenzenes are important organic synthesis intermediates.
The existing preparation method of the alkyl siloxy halogenated benzene comprises the steps of firstly adding halogenated phenol and slightly excessive alkyl chlorosilane into a closed system communicated with an HCl collecting device, heating to 150 ℃, cooling after most of the alkyl chlorosilane reacts, then adding a large amount of alkyl chlorosilane, finishing the reaction when HCl is not generated, and then directly distilling to obtain the alkyl siloxy halogenated benzene. Although this method does not use an organic solvent, a large amount of alkylchlorosilane is required, and a large amount of acid gas HCl is generated during the reaction. In order to prevent HCl volatilization from polluting the environment and corroding equipment, the prior art improves the scheme, ammonium chloride is added into a system, after reflux reaction is carried out overnight, redundant alkyl chlorosilane is evaporated to dryness, then the temperature is raised to 40-50 ℃, reduced pressure and vacuum pumping is carried out for 40min, and the alkyl siloxy halogenated benzene is obtained.
In order to reduce the dosage of alkyl chlorosilane and save cost and energy consumption, most of the existing common preparation methods adopt organic alkali (such as pyridine, triethylamine and imidazole) as an acid-binding agent, organic solvents such as toluene and dichloromethane are added, the dosage of the alkyl chlorosilane is reduced, and the target product is obtained after the reaction is finished and water is used for removing salt. Although the method saves cost and energy consumption, a large amount of waste organic solvent is generated after the reaction is finished, the cost of subsequent treatment of the waste solvent is increased, and the method is not environment-friendly.
Disclosure of Invention
In view of the above, the invention provides a method for preparing the alkyl siloxy halogenated benzene, which does not need an organic solvent, is environment-friendly, has low cost, mild reaction conditions and high product yield, and can reuse the generated by-products without generating three wastes.
In order to achieve the purpose of the invention, the embodiment of the invention adopts the following technical scheme:
a method for preparing an alkylsiloxy halobenzene, comprising the steps of:
adding alkyl chlorosilane into halogenated phenol and N-alkyl imidazole for reaction, and directly layering after the reaction is finished to obtain the alkyl siloxy halogenated benzene and N-alkyl imidazole hydrochloride.
The inventor unexpectedly finds that the specific N-alkyl imidazole is adopted as an acid-binding agent in the process of improving the existing method for synthesizing the alkyl siloxy halogenated benzene, the yield of the prepared alkyl siloxy halogenated benzene is over 90 percent, after the reaction is finished, the alkyl siloxy halogenated benzene and the N-alkyl imidazole hydrochloride can be obtained by directly layering without post-treatment, and the whole reaction and post-treatment process does not use an organic solvent, so that the method is environment-friendly, simple to operate, low in cost and easy for industrial production. If the acid-binding agent N-alkyl imidazole is replaced by imidazole or other acid-binding agents, the yield of the alkyl siloxy halogenated benzene is obviously reduced, for example, when the acid-binding agent N-alkyl imidazole is replaced by imidazole, the yield of the alkyl siloxy halogenated benzene is only about 20 percent, the product state is poor, and the purity is only about 80 percent.
Alternatively, the reaction equation for the alkylsiloxy halobenzene is as follows:
wherein R is1Is C1-C4 alkyl; such as methyl, ethyl, propyl, isopropyl, butylIsobutyl or tert-butyl;
R2、R3、R4may each be independently selected from methyl, ethyl, isobutyl or tert-butyl; x1、X2、X3、X4、X5Can be independently selected from hydrogen, fluorine, chlorine, bromine or iodine, wherein X1、X2、X3、X4And X5Not both hydrogen.
Optionally, the molar ratio of the halophenol, the N-alkylimidazole and the alkylchlorosilane is 1:1: 1.
By limiting the dosage of each reaction raw material, the yield and the purity of the alkyl siloxy halogenated benzene are ensured, and simultaneously, the generation of residue due to excessive dosage of the raw materials can be prevented, and a purification step of removing the residual raw materials by post-treatment is added.
Optionally, the reaction time is 0.5-2 h.
Optionally, the reaction temperature is 10-50 ℃.
The preparation method of the alkyl siloxy halogenated benzene provided by the invention has the advantages of mild reaction conditions, short reaction time and easiness in industrial large-scale popularization.
Optionally, the method further comprises the step of washing the alkylsiloxy halogenated benzene obtained after the delamination.
Optionally, the method further comprises the step of co-producing the alkyl imidazole tetrafluoroborate ionic liquid: and adding the N-alkyl imidazole hydrochloride into a sodium tetrafluoroborate aqueous solution for reaction, and after the reaction is finished, performing post-treatment to obtain the alkyl imidazole tetrafluoroborate ionic liquid.
The N-alkyl imidazole hydrochloride obtained by the preparation method of the alkyl siloxy halogenated benzene provided by the invention can further react with sodium tetrafluoroborate to prepare the alkyl imidazole tetrafluoroborate ionic liquid (the yield is more than 90%), an organic solvent is not needed in the process of coproducing the alkyl imidazole tetrafluoroborate ionic liquid, the preparation method is green and environment-friendly, and the alkyl imidazole tetrafluoroborate ionic liquid and the sodium chloride aqueous solution can be obtained by directly layering after the reaction is finished. The prepared alkyl imidazole tetrafluoroborate ionic liquid can be used for catalyzing various organic reactions, can be repeatedly used, and has the advantages of high reaction rate, high yield and the like.
Optionally, the reaction equation of the co-production of the alkyl imidazole tetrafluoroborate ionic liquid is as follows:
wherein R is1The definition of (A) is as above.
Optionally, the molar ratio of sodium tetrafluoroborate to the N-alkyl imidazole hydrochloride in the aqueous sodium tetrafluoroborate solution is 1: 1.
Optionally, the content of sodium tetrafluoroborate in the sodium tetrafluoroborate aqueous solution is 10 wt% to 30 wt%.
Optionally, the reaction time for co-producing the alkyl imidazole tetrafluoroborate ionic liquid is 0.5-2 h.
Optionally, the reaction temperature for co-producing the alkyl imidazole tetrafluoroborate ionic liquid is 10-50 ℃.
The purity and yield of the alkyl imidazole tetrafluoroborate ionic liquid can be further improved by limiting parameters such as the material ratio, the reaction time, the temperature and the like of all raw materials.
The preparation method of the alkyl siloxy halogenated benzene provided by the invention has the advantages of high yield, mild reaction conditions, no need of organic solvents and environmental protection. In addition, the byproduct N-alkyl imidazole hydrochloride produced by the reaction can be subjected to subsequent reaction to prepare alkyl imidazole tetrafluoroborate ionic liquid or other types of ionic liquid, new economic benefits are generated, a byproduct sodium chloride aqueous solution generated in the process of coproducing the alkyl imidazole tetrafluoroborate ionic liquid can be used for preparing various chemical raw materials in the chlor-alkali industry, and the waste water after washing the alkyl siloxy halogenated benzene can be used for preparing a sodium tetrafluoroborate aqueous solution. The method for preparing the alkyl siloxy halogenated benzene and co-producing the alkyl imidazole ionic liquid has the advantages of high yield of the alkyl siloxy halogenated benzene and the alkyl imidazole ionic liquid, simple post-treatment (direct layering), high utilization rate of raw materials, stable process, simple operation, no use of organic solvents in the whole process, no generation of three wastes, environmental friendliness and contribution to industrial production.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The examples do not show the specific experimental steps or conditions, and can be performed according to the conventional experimental steps described in the literature in the field. The reagents or instruments used are not indicated by manufacturers, and are all conventional reagent products which can be obtained commercially.
Example 1
The embodiment provides a preparation method of 4- (trimethylsiloxy) bromobenzene and N-methylimidazole tetrafluoroborate ionic liquid, which comprises the following steps:
41.0g (0.5mol) of N-methylimidazole and 86.5g (0.5mol) of p-bromophenol are added into a 500mL three-neck flask, after air is exhausted by introducing nitrogen under stirring, the temperature of an ice-water bath is controlled to be 10-15 ℃, 54.3g (0.5mol) of trimethylchlorosilane is dropwise added (the dropwise adding rate is controlled to control the system temperature to be 10-15 ℃), after about 1h of dropwise adding is finished, the reaction is continued for 0.5h at the temperature until the reaction is finished, then the mixture in the three-neck flask is placed into a 1L separating funnel for standing and separating, the upper layer is 4- (trimethylsiloxy) bromobenzene, and the lower layer is N-methylimidazole hydrochloride. Washing 4- (trimethylsiloxy) bromobenzene (50mL multiplied by 1, the water phase after washing is used for preparing the subsequent sodium tetrafluoroborate water solution), drying sodium sulfate to obtain 110.6g of 4- (trimethylsiloxy) bromobenzene, the yield is 90.3%, and the purity is more than 99.2% by GC detection.
The N-methylimidazole hydrochloride obtained as the lower layer was dropped into a sodium tetrafluoroborate aqueous solution (55g NaBF)4Dissolving in 130g of water), controlling the temperature of the system to be 10-15 ℃ according to the dropping speed, continuing stirring for 0.5h at the temperature after the dropping is finished until the reaction is finished, then standing and separating the system, wherein the lower layer is 77.5g of N-methylimidazole tetrafluoroborate ionic liquid (the yield is 91.2 percent), and the upper layer is sodium chloride aqueous solution.
Warp beam1H-NMR test shows that the purity of the N-methylimidazole tetrafluoroborate ionic liquid is 99.1 percent,1H-NMR(D2O，400MHz)δ：3.82(s,3H),7.33(s,2H),8.53(s,1H)。
example 2
The embodiment provides a preparation method of 2- (tert-butyldimethylsilyloxy) chlorobenzene and N-ethylimidazole tetrafluoroborate ionic liquid, which comprises the following specific steps:
48.0g (0.5mol) of N-ethylimidazole and 64.3g (0.5mol) of 2-chlorophenol are added into a 500mL three-neck flask at room temperature (25-30 ℃), nitrogen is introduced while stirring to evacuate air, 75.4g (0.5mol) of tert-butyldimethylchlorosilane is added dropwise (the dropping rate is controlled to control the system temperature to be 25-30 ℃), after about 1h of dropwise addition, the reaction is continued for 1h at the temperature until the reaction is finished, then the mixture in the three-neck flask is placed into a 1L separating funnel for standing and separating, the upper layer is 2- (tert-butyldimethylsiloxy) chlorobenzene, and the lower layer is N-ethylimidazole hydrochloride. Washing 2- (tert-butyldimethylsilyloxy) chlorobenzene (50mL multiplied by 1, using the washed water phase for preparing the subsequent sodium tetrafluoroborate aqueous solution), and drying sodium sulfate to obtain 110.5g of 2- (tert-butyldimethylsilyloxy) chlorobenzene, wherein the yield is 91.1%, and the purity is more than 99.2% by GC detection.
The N-ethylimidazole hydrochloride obtained in the lower layer was dropped into a sodium tetrafluoroborate aqueous solution (55g NaBF)4Dissolved in 495g of water), the dropping rate is controlled according to the temperature of the system to be 25-30 ℃, the stirring is continued for 1h at the temperature after the dropping is finished until the reaction is finished, then the system is kept stand for liquid separation, the lower layer is 83.3g of N-ethylimidazole tetrafluoroborate ionic liquid (the yield is 90.5 percent), and the upper layer is sodium chloride aqueous solution.
Warp beam1The purity of the N-ethylimidazole tetrafluoroborate ionic liquid is 99.0 percent by H-NMR test.
Example 3
The embodiment provides a preparation method of 3- (triisobutylsiloxy) bromobenzene and N-butylimidazolium tetrafluoroborate ionic liquid, which comprises the following specific steps:
at room temperature (25-30 ℃), 62.1g (0.5mol) of N-butylimidazole and 86.5g (0.5mol) of m-bromophenol are added into a 500mL three-necked flask, nitrogen is introduced while stirring to evacuate air, 117.5g (0.5mol) of triisobutylchlorosilane is added dropwise (the dropping rate is controlled to 25-30 ℃ C.) approximately 1h later, the reaction is continued for 1h at the temperature until the reaction is finished, and then the mixture in the three-necked flask is placed into a 1L separating funnel for standing and separating, wherein the upper layer is 3- (triisobutylsiloxy) bromobenzene, and the lower layer is N-butylimidazole hydrochloride. 3- (triisobutylsilyloxy) bromobenzene (50mL multiplied by 1, the washed water phase is used for preparing the subsequent sodium tetrafluoroborate aqueous solution), and sodium sulfate is dried to obtain 168.7g of 3- (triisobutylsilyloxy) bromobenzene, the yield is 90.9%, and the purity is more than 99% by GC detection.
The N-butylimidazole hydrochloride obtained in the lower layer was dropped into a sodium tetrafluoroborate aqueous solution (55g NaBF)4Dissolving in 220g of water), controlling the temperature of the system to be 25-30 ℃ according to the dropping rate, continuing stirring for 1h at the temperature after the dropping is finished until the reaction is finished, then standing and separating the system, wherein the lower layer is 98.6g (yield is 93%) of N-butylimidazolium tetrafluoroborate ionic liquid, and the upper layer is sodium chloride aqueous solution.
Warp beam1The purity of the N-butylimidazolium tetrafluoroborate ionic liquid was 99.1% by H-NMR test.
Example 4
The embodiment provides a preparation method of 3- (triethylsiloxy) iodobenzene and N-butylimidazolium tetrafluoroborate ionic liquid, which comprises the following specific steps:
62.1g (0.5mol) of N-butylimidazole and 110g (0.5mol) of 3-iodophenol are added into a 500mL three-neck flask, after nitrogen is introduced to the flask under stirring to evacuate air, the flask is heated to 45-50 ℃ in a water bath, 75.4g (0.5mol) of triethylchlorosilane is dropwise added (the dropwise adding rate is controlled to control the system temperature to be 45-50 ℃), after about 1h of dropwise adding is finished, the reaction is continued for 2h at the temperature until the reaction is finished, then the mixture in the three-neck flask is placed into a 1L separating funnel for standing and separating, the upper layer is 3- (triethylsiloxy) iodobenzene, and the lower layer is N-butylimidazole hydrochloride. Washing 3- (triethylsiloxy) iodobenzene (50mL multiplied by 1, the water phase after washing is used for preparing the subsequent sodium tetrafluoroborate aqueous solution), and drying sodium sulfate to obtain 151.8g of 3- (triethylsiloxy) iodobenzene, wherein the yield is 90.6%, and the purity is more than 99.1% by GC detection.
The N-butylimidazole hydrochloride obtained in the lower layer was dropped into a sodium tetrafluoroborate aqueous solution (55g NaBF)4Dissolving in 200g of water), controlling the temperature of the system to be 45-50 ℃ according to the dropping rate, continuing stirring for 0.5h at the temperature after the dropping is finished until the reaction is finished, then standing and separating the system, wherein the lower layer is 97.7g of N-butylimidazolium tetrafluoroborate ionic liquid (the yield is 92.2 percent), and the upper layer is sodium chloride aqueous solution.
Warp beam1The purity of the N-butylimidazolium tetrafluoroborate ionic liquid was 99.2% by H-NMR test.
Example 5
The embodiment provides a preparation method for co-producing N-methylimidazole tetrafluoroborate ionic liquid from 3-fluoro-4- (tert-butyldimethylsilyloxy) bromobenzene, which comprises the following specific steps:
at room temperature (25-30 ℃), 41.0g (0.5mol) of N-methylimidazole and 95.5g (0.5mol) of 2-fluoro-4-bromophenol are added into a 500mL three-neck flask, after air is exhausted by introducing nitrogen under stirring, 75.4g (0.5mol) of tert-butyldimethylchlorosilane is added dropwise (the dropping rate is controlled to control the system temperature to be 25-30 ℃), after about 1h of dropping, the reaction is continued for 1h at the temperature until the reaction is finished, then the mixture in the three-neck flask is placed into a 1L separating funnel for standing and separating, the upper layer is 3-fluoro-4- (tert-butyldimethylsiloxy) bromobenzene, and the lower layer is N-methylimidazole hydrochloride. 3-fluoro-4- (tert-butyldimethylsilyloxy) bromobenzene (50mL multiplied by 1, the washed water phase is used for preparing the subsequent sodium tetrafluoroborate aqueous solution), and sodium sulfate is dried to obtain 140.8g of 3-fluoro-4- (tert-butyldimethylsilyloxy) bromobenzene, the yield is 92.3%, and the purity is more than 99.2% by GC detection.
The N-methylimidazole hydrochloride obtained as the lower layer was dropped into a sodium tetrafluoroborate aqueous solution (55g NaBF)4Dissolved in 350g of water), the dropping rate is controlled according to the temperature of the system controlled between 20 ℃ and 25 ℃, the stirring is continued for 1h at the temperature after the dropping is finished until the reaction is finished, then the system is kept stand for liquid separation, the lower layer is 78.3g of N-methylimidazole tetrafluoroborate ionic liquid (the yield is 92.1 percent), and the upper layer is sodium chloride aqueous solution.
Warp beam1And (3) performing H-NMR (hydrogen-nuclear magnetic resonance) testing,the purity of the N-methylimidazole tetrafluoroborate ionic liquid is 99.0 percent.
Example 6
The embodiment provides a preparation method for co-producing 2, 6-difluoro-4- (tert-butyldimethylsilyloxy) bromobenzene and N-methylimidazolium tetrafluoroborate ionic liquid, which comprises the following specific steps:
at room temperature (25-30 ℃), 41.0g (0.5mol) of N-methylimidazole and 104.5g (0.5mol) of 3, 5-difluoro-4-bromophenol are added into a 500mL three-neck flask, nitrogen is introduced to evacuate air under stirring, 75.4g (0.5mol) of tert-butyldimethylchlorosilane is added dropwise (the dropping rate is controlled according to the system temperature of 25-30 ℃), after about 1h of dropping, the reaction is continued for 1h at the temperature until the reaction is finished, then the mixture in the three-neck flask is placed into a 1L separating funnel for standing and separating, the upper layer is 2, 6-difluoro-4- (tert-butyldimethylsilyloxy) bromobenzene, and the lower layer is N-methylimidazole hydrochloride. Washing 2, 6-difluoro-4- (tert-butyldimethylsilyloxy) bromobenzene (50mL multiplied by 1, the washed water phase is used for preparing the subsequent sodium tetrafluoroborate aqueous solution), drying sodium sulfate to obtain 147.5g of 2, 6-difluoro-4- (tert-butyldimethylsilyloxy) bromobenzene, wherein the yield is 91.3%, and the purity is more than 99.1% by GC detection.
The N-methylimidazole hydrochloride obtained as the lower layer was dropped into a sodium tetrafluoroborate aqueous solution (55g NaBF)4Dissolved in 495g of water), the dropping speed is controlled according to the temperature of the system to be 35-40 ℃, the stirring is continued for 0.5h at the temperature after the dropping is finished until the reaction is finished, then the system is kept stand for liquid separation, the lower layer is 78.9g of N-methylimidazole tetrafluoroborate ionic liquid (the yield is 92.8 percent), and the upper layer is sodium chloride aqueous solution.
Warp beam1The purity of the N-methylimidazole tetrafluoroborate ionic liquid is 99.0 percent by H-NMR test.
Example 7
The embodiment provides a preparation method of 2, 3, 5, 6-tetrafluoro-4- (trimethylsiloxy) bromobenzene and N-methylimidazolium tetrafluoroborate ionic liquid, which comprises the following specific steps:
at room temperature (25-30 ℃), 41.0g (0.5mol) of N-methylimidazole and 122.5g (0.5mol) of 2, 3, 5, 6-tetrafluoro-4-bromophenol are added into a 500mL three-neck flask, after air is exhausted by introducing nitrogen under stirring, 54.3g (0.5mol) of trimethylchlorosilane is dropwise added (the dropwise adding rate is controlled to control the system temperature to be 25-30 ℃), after about 1h of dropwise adding is finished, the reaction is continued for 2h at the temperature until the reaction is finished, then the mixture in the three-neck flask is placed into a 1L separating funnel for standing and separating, the upper layer is 2, 3, 5, 6-tetrafluoro-4- (trimethylsiloxy) bromobenzene, and the lower layer is N-methylimidazole hydrochloride. Washing 2, 3, 5, 6-tetrafluoro-4- (trimethylsiloxy) bromobenzene (50mL multiplied by 1, the washed water phase is used for preparing the subsequent sodium tetrafluoroborate aqueous solution), drying sodium sulfate to obtain 145.2g of 2, 3, 5, 6-tetrafluoro-4- (trimethylsiloxy) bromobenzene, wherein the yield is 91.6%, and the purity is more than 99.1% by GC detection.
The N-methylimidazole hydrochloride obtained as the lower layer was dropped into a sodium tetrafluoroborate aqueous solution (55g NaBF)4Dissolved in 495g of water), the dropping rate is controlled according to the temperature of the system to be 25-30 ℃, the stirring is continued for 2h at the temperature after the dropping is finished until the reaction is finished, then the system is kept stand for liquid separation, the lower layer is 78.9g of N-methylimidazole tetrafluoroborate ionic liquid (the yield is 92.8 percent), and the upper layer is sodium chloride aqueous solution.
Warp beam1The purity of the N-methylimidazole tetrafluoroborate ionic liquid is 99.0 percent by H-NMR test.
Comparative example 1
The comparative example provides a preparation method of 4- (trimethylsiloxy) bromobenzene, which comprises the following steps:
86.5g (0.5mol) of p-bromophenol and 59.5g (0.55mol) of trimethylchlorosilane are added into a 1000mL three-neck flask, the temperature is raised to 150 ℃ under stirring, slight reflux is carried out to generate hydrogen chloride gas, the temperature is reduced to room temperature after about 30min, 30g of trimethylchlorosilane is added, and then the temperature is raised to carry out reflux reaction for 8h until no hydrogen chloride is generated. Distilling to remove excessive trimethylchlorosilane to obtain crude 4- (trimethylsiloxy) bromobenzene, carrying out reduced pressure rectification, and collecting 10mmHg95 deg.C fraction to obtain 82.0g of 4- (trimethylsiloxy) bromobenzene with yield of 67.1% and purity of 96% by GC detection.
Comparative example 2
The comparative example provides a preparation method of 4- (trimethylsiloxy) bromobenzene, which comprises the following steps:
17.3g of p-bromophenol, 0.3g of ammonium chloride and 110mL of trimethylchlorosilane were added to a 250mL reaction flask, the mixture was heated to reflux with stirring and reacted overnight, the target product, 4- (trimethylsiloxy) bromobenzene, was not detected by GC, and a large amount of p-bromophenol was detected by TLC, indicating that there was substantially no reaction.
Comparative example 3
The comparative example provides a preparation method of 4- (trimethylsiloxy) bromobenzene, which comprises the following steps:
346g of p-bromophenol and 196.8g of N-methylimidazole are placed in a 3000mL three-necked bottle, 1000mL of dichloromethane is added, the mixture is fully stirred, the temperature of the system is controlled to be 0 ℃ by using an ice salt bath, dichloromethane solution of trimethylchlorosilane (250g of trimethylchlorosilane is dissolved in 700mL of dichloromethane) is dropwise added, the temperature of the system is controlled not to exceed 30 ℃, after 60min of dropwise addition is finished, the temperature is increased to 30 ℃, the mixture is stirred for 3h, 600mL of water is added into the system, the mixture is stirred, kept stand and layered, an organic phase is dried by sodium sulfate, and then the solvent is removed, so 357.6g of 4- (trimethylsiloxy) bromobenzene is obtained, the yield is 73.0%, and the purity is 97% by GC detection.
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 or improvements made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. A method for preparing alkyl siloxy halogenated benzene is characterized by comprising the following steps:
adding alkyl chlorosilane into halogenated phenol and N-alkyl imidazole for reaction, and directly layering after the reaction is finished to obtain the alkyl siloxy halogenated benzene and N-alkyl imidazole hydrochloride.
2. The process for preparing an alkylsiloxy halobenzene as claimed in claim 1, wherein said halophenol, N-alkylimidazole and alkylchlorosilane are present in a molar ratio of 1:1: 1.
3. The process for preparing an alkylsiloxy halobenzene according to claim 1, wherein the reaction time is from 0.5 to 2 hours.
4. The process for preparing an alkylsiloxy halobenzene according to claim 1, wherein said reaction temperature is 10 to 50 ℃.
5. The process for preparing an alkylsiloxy halobenzene according to claim 1, further comprising the step of washing the alkylsiloxy halobenzene obtained after the delamination with water.
6. The process for the preparation of an alkylsiloxy halobenzene as claimed in any one of claims 1 to 5 further comprising the step of co-producing an alkylimidazolium tetrafluoroborate ionic liquid: and adding the N-alkyl imidazole hydrochloride into a sodium tetrafluoroborate aqueous solution for reaction, and after the reaction is finished, performing post-treatment to obtain the alkyl imidazole tetrafluoroborate ionic liquid.
7. The process for preparing an alkylsiloxy halobenzene as claimed in claim 6, wherein the molar ratio of sodium tetrafluoroborate to said N-alkylimidazole hydrochloride in the aqueous solution of sodium tetrafluoroborate is 1: 1.
8. The process for preparing an alkylsiloxy halobenzene as claimed in claim 6, wherein said sodium tetrafluoroborate aqueous solution has a sodium tetrafluoroborate content ranging from 10% to 30% by weight.
9. The method of claim 6, wherein the reaction time for co-producing the alkylimidazolium tetrafluoroborate ionic liquid is from 0.5 to 2 hours.
10. The method of claim 6, wherein the reaction temperature for co-production of the alkylimidazolium tetrafluoroborate ionic liquid is between 10 ℃ and 50 ℃.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1807432A (en) * | 2005-10-26 | 2006-07-26 | 杭州师范学院 | Methylphenyldichlor disilane synthesis method |
| CN102060775A (en) * | 2010-12-24 | 2011-05-18 | 浙江师范大学 | Preparation method of imidazole ion liquid |
| CN112142573A (en) * | 2019-06-28 | 2020-12-29 | 天津药业研究院股份有限公司 | Method for synthesizing triclosan |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1807432A (en) * | 2005-10-26 | 2006-07-26 | 杭州师范学院 | Methylphenyldichlor disilane synthesis method |
| CN102060775A (en) * | 2010-12-24 | 2011-05-18 | 浙江师范大学 | Preparation method of imidazole ion liquid |
| CN112142573A (en) * | 2019-06-28 | 2020-12-29 | 天津药业研究院股份有限公司 | Method for synthesizing triclosan |
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