CN115724721A - Preparation method of 2-substituent-4-bromophenol - Google Patents
Preparation method of 2-substituent-4-bromophenol Download PDFInfo
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- CN115724721A CN115724721A CN202211632454.1A CN202211632454A CN115724721A CN 115724721 A CN115724721 A CN 115724721A CN 202211632454 A CN202211632454 A CN 202211632454A CN 115724721 A CN115724721 A CN 115724721A
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- 238000002360 preparation method Methods 0.000 title abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 60
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 claims abstract description 54
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000003960 organic solvent Substances 0.000 claims abstract description 19
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 45
- 239000002904 solvent Substances 0.000 claims description 22
- 238000002425 crystallisation Methods 0.000 claims description 17
- 230000008025 crystallization Effects 0.000 claims description 17
- 238000001704 evaporation Methods 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 14
- -1 2-substituted phenol Chemical class 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- 230000008020 evaporation Effects 0.000 claims description 9
- 239000012535 impurity Substances 0.000 claims description 9
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 8
- 239000012295 chemical reaction liquid Substances 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 6
- 238000004821 distillation Methods 0.000 claims description 6
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 claims description 6
- 239000012454 non-polar solvent Substances 0.000 claims description 5
- 239000003208 petroleum Substances 0.000 claims description 5
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 claims description 3
- 125000006552 (C3-C8) cycloalkyl group Chemical group 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 30
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 4
- 238000007086 side reaction Methods 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 73
- 239000000243 solution Substances 0.000 description 36
- 238000004817 gas chromatography Methods 0.000 description 26
- WJQOZHYUIDYNHM-UHFFFAOYSA-N 2-tert-Butylphenol Chemical compound CC(C)(C)C1=CC=CC=C1O WJQOZHYUIDYNHM-UHFFFAOYSA-N 0.000 description 24
- 238000004458 analytical method Methods 0.000 description 24
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 24
- 239000006227 byproduct Substances 0.000 description 23
- IKMJSWBFODAWTC-UHFFFAOYSA-N 4-bromo-2-tert-butylphenol Chemical compound CC(C)(C)C1=CC(Br)=CC=C1O IKMJSWBFODAWTC-UHFFFAOYSA-N 0.000 description 21
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 20
- IXQGCWUGDFDQMF-UHFFFAOYSA-N 2-Ethylphenol Chemical compound CCC1=CC=CC=C1O IXQGCWUGDFDQMF-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- 239000007795 chemical reaction product Substances 0.000 description 10
- 238000004587 chromatography analysis Methods 0.000 description 10
- 239000007789 gas Substances 0.000 description 10
- 229960002317 succinimide Drugs 0.000 description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- 239000001257 hydrogen Substances 0.000 description 9
- KSURDFVRHGKTAA-UHFFFAOYSA-N 2,4-dibromo-6-tert-butylphenol Chemical compound CC(C)(C)C1=CC(Br)=CC(Br)=C1O KSURDFVRHGKTAA-UHFFFAOYSA-N 0.000 description 8
- AXYXIQJROSLHJZ-UHFFFAOYSA-N 2-bromo-6-tert-butylphenol Chemical compound CC(C)(C)C1=CC=CC(Br)=C1O AXYXIQJROSLHJZ-UHFFFAOYSA-N 0.000 description 8
- 238000001228 spectrum Methods 0.000 description 8
- MAAADQMBQYSOOG-UHFFFAOYSA-N 4-bromo-2-ethylphenol Chemical compound CCC1=CC(Br)=CC=C1O MAAADQMBQYSOOG-UHFFFAOYSA-N 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 238000005893 bromination reaction Methods 0.000 description 4
- 229910052799 carbon Inorganic materials 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
- 230000031709 bromination Effects 0.000 description 3
- 239000012141 concentrate Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- XDBDWJLJICFFEE-UHFFFAOYSA-N 2,4-dibromo-6-ethylphenol Chemical compound CCC1=CC(Br)=CC(Br)=C1O XDBDWJLJICFFEE-UHFFFAOYSA-N 0.000 description 2
- KTIRRDOBTNZKNL-UHFFFAOYSA-N 2-bromo-6-ethylphenol Chemical compound CCC1=CC=CC(Br)=C1O KTIRRDOBTNZKNL-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 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
- 239000003054 catalyst Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention provides a preparation method of 2-substituent-4-bromophenol, which comprises the following steps: reacting 2-substituent phenol with N-bromosuccinimide in an organic solvent to obtain 2-substituent-4-bromophenol; the preparation method provided by the application has mild conditions, and can reduce the occurrence of side reactions by optimizing the preparation conditions, so that the raw materials have high conversion rate and the products have high target selectivity; therefore, the preparation method has the advantages of simple and convenient operation, low material consumption and energy consumption, environmental protection, high conversion rate of the raw material 2-substituent phenol and high selectivity of the target product 2-substituent-4-bromophenol, the conversion rate of the raw material 2-substituent phenol can reach 99%, and the selectivity of the product 2-substituent-4-bromophenol can reach more than 96%.
Description
Technical Field
The invention relates to the technical field of chemical synthesis, in particular to a preparation method of 2-substituent-4-bromophenol.
Background
The 2-substituent-4-bromophenol is an important fine chemical product and intermediate, and has important application in the aspects of complex, special polymer, catalyst synthesis and the like, but the preparation method of the 2-substituent-4-bromophenol is rarely reported in the literature at present. How to obtain the 2-substituent-4-bromophenol with high conversion rate and high selectivity has important significance.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a preparation method of 2-substituent-4-bromophenol with high conversion rate and selectivity.
In view of the above, the present application provides a method for preparing 2-substituent-4-bromophenol represented by formula (I), comprising:
reacting 2-substituent phenol shown as a formula (II) with N-bromosuccinimide in an organic solvent to obtain 2-substituent-4-bromophenol shown as a formula (I);
wherein R is 1 Selected from C1-C8 alkyl, C3-C8 cycloalkyl or C1-C8 alkoxy.
Preferably, the method further comprises the following steps:
evaporating and concentrating the obtained reaction liquid until solid is separated out, adding a crystallization solvent for crystallization and impurity removal, and separating to obtain a solution containing 2-substituent-4-bromophenol;
distilling the solution containing the 2-substituent-4-bromophenol.
Preferably, the organic solvent is an organic solvent with polarity greater than 5.0.
Preferably, the organic solvent is selected from one or more of acetonitrile, acetone and methanol.
Preferably, the molar ratio of the 2-substituted phenol to the N-bromosuccinimide is (0.8 to 1.2): (0.8-1.2).
Preferably, the reaction temperature is-30-60 ℃, and the pressure is 0-2 MPa; the reaction is carried out with stirring.
Preferably, the temperature of the evaporation is 20-200 ℃; the crystallization solvent is a nonpolar solvent, the nonpolar solvent is selected from one or more of petroleum ether, pentane, heptane, octane and nonane, and the crystallization temperature is-30-50 ℃.
Preferably, the distillation temperature is 20 to 200 ℃.
The application provides a preparation method of 2-substituent-4-bromophenol, which takes 2-substituent phenol and N-bromosuccinimide as raw materials to react in an organic solvent, so as to obtain the 2-substituent-4-bromophenol. The preparation method provided by the application has mild conditions, and can reduce the occurrence of side reactions by optimizing the preparation conditions, so that the raw materials have high conversion rate and the products have high target selectivity. Therefore, the preparation method has the advantages of simple and convenient operation, low material consumption and energy consumption, environmental protection, high conversion rate of the raw material 2-substituent phenol and high selectivity of the target product 2-substituent-4-bromophenol, the conversion rate of the raw material 2-substituent phenol can reach 99%, and the selectivity of the product 2-substituent-4-bromophenol can reach more than 96%.
Drawings
FIG. 1 is a nuclear magnetic spectrum of 2-tert-butyl-4-bromophenol prepared in example 1 according to the present invention;
FIG. 2 is a nuclear magnetic carbon spectrum of 2-tert-butyl-4-bromophenol prepared in example 1 of the present invention;
FIG. 3 is a nuclear magnetic hydrogen spectrum of 2-ethyl-4-bromophenol prepared in example 2 of the present invention;
FIG. 4 is a nuclear magnetic carbon spectrum of 2-ethyl-4-bromophenol prepared in example 2 of the present invention;
FIG. 5 is a gas chromatography analysis chart of the product of step 1) in example 1 of the present invention;
FIG. 6 is a gas chromatography analysis chart of the product of step 1) in example 2 of the present invention;
FIG. 7 is a gas chromatographic analysis of the product of step 1) in example 3 of the present invention;
FIG. 8 is a gas chromatography analysis chart of the product of step 1) in example 4 of the present invention;
FIG. 9 is a gas chromatographic analysis of the product of step 1) in comparative example 1 of the present invention;
FIG. 10 is a gas chromatographic analysis of the product of step 1) in comparative example 2 of the present invention;
FIG. 11 is a gas chromatographic analysis of the product of step 1) in comparative example 3 of the present invention;
FIG. 12 is a gas chromatographic analysis of the product of step 1) in comparative example 4 of the present invention;
FIG. 13 is a gas chromatographic analysis of the product of step 1) in comparative example 5 of the present invention;
FIG. 14 is a gas chromatography analysis chart of the product of step 1) in comparative example 6 of the present invention.
Detailed Description
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.
The application provides a preparation method of 2-substituent-4-bromophenol, the method is simple and convenient to operate, low in material consumption and energy consumption, green and environment-friendly, and the conversion rate of raw material 2-substituent phenol and the selectivity of a target product are high. Specifically, the embodiment of the invention discloses a preparation method of 2-substituent-4-bromophenol shown as a formula (I), which comprises the following steps:
reacting 2-substituent phenol shown as a formula (II) with N-bromosuccinimide in an organic solvent to obtain 2-substituent-4-bromophenol shown as a formula (I);
wherein R is 1 Selected from C1-C8 alkyl, C3-C8 cycloalkyl or C1-C8 alkoxy.
The 2-substituent-4-bromophenol described herein is a compound well known to those skilled in the art, where substituents may be selected from substituents well known to those skilled in the art, exemplified by the R 1 In particular from ethyl, methoxy, ethoxy or tert-butyl.
The applicant has found through research that: for the reaction of 2-substituent phenol and N-bromosuccinimide, products comprise 2-substituent-4-bromophenol, 2-substituent-6-bromophenol and 2-substituent-4, 6-dibromophenol, only 2-substituent-4-bromophenol is prepared in the application, and on the basis, the application greatly reduces the generation of by-products of 2-substituent-6-bromophenol and 2-substituent-4, 6-dibromophenol by adjusting reaction conditions and solvents in the reaction process, so that the selectivity of the target product 2-substituent-4-bromophenol is greatly improved.
Specifically, the 2-substituted phenol and the N-bromosuccinimide are firstly added into the organic solvent, and more specifically, the N-bromosuccinimide is dissolved in the organic solvent and then slowly added into the 2-substituted phenol, and in this application, the organic solvent is an organic solvent with a polarity greater than 5.0, which is specifically selected from one or two of acetonitrile and methanol. The phenolic hydroxyl in the 2-substituent phenol can influence the activity of ortho-position hydrogen and para-position hydrogen on a benzene ring of the 2-substituent phenol, so that the 2-substituent phenol can generate bromination reaction when being contacted with a bromination reagent, namely N-bromosuccinimide, but the ortho-position hydrogen and the para-position hydrogen on the benzene ring in the 2-substituent phenol in different solvents have different activities, and therefore, the organic solvent can ensure the conversion rate and the selectivity of bromination of the 2-substituent phenol. The amount of the organic solvent added is 5 to 200ml of solvent per 1g of 2-substituted phenol, preferably 10 to 100ml of solvent per 1g of 2-substituted phenol, and more preferably 18 to 50ml of solvent per 1g of 2-substituted phenol.
The molar ratio of the 2-substituent phenol to the N-bromosuccinimide is (0.8-1.2): (0.8-1.2); specifically, the molar ratio of the 2-substituent phenol to the N-bromosuccinimide is (0.8-1.2): (0.85-1.1); more specifically, the molar ratio of the 2-substituted phenol to the N-bromosuccinimide is (0.95 to 1.05): (0.95-1.05); more specifically, the molar ratio of the 2-substituted phenol to the N-bromosuccinimide is (0.99 to 1.01): (0.99-1.01).
In the application, the temperature of the reaction is-30 to 60 ℃, and the pressure is 0 to 2MPa; the reaction is carried out under stirring; specifically, the temperature of the reaction is-5 to 45 ℃, and the pressure is 0 to 0.5MPa; more specifically, the reaction is carried out under normal temperature, normal pressure and stirring conditions. The reaction temperature can affect the activity of ortho-position hydrogen and para-position hydrogen on a benzene ring in 2-substituent phenol and can also affect the speed of decomposing N-bromosuccinimide to form bromine, so that the temperature is adopted to ensure the conversion rate and the selectivity of the 2-substituent-4-bromophenol.
After the reaction, in order to obtain the 2-substituent-4-bromophenol with higher purity, the method further comprises the following steps:
evaporating and concentrating the obtained reaction liquid until solid is separated out, adding a crystallization solvent for crystallization and impurity removal, and separating to obtain a solution containing 2-substituent-4-bromophenol;
distilling the solution containing the 2-substituent-4-bromophenol.
In the above process, the obtained reaction solution is evaporated and concentrated until a solid is precipitated, and the evaporation and concentration is any evaporation and concentration method, preferably evaporation under reduced pressure. The temperature of the evaporation is 20-200 ℃, specifically, the temperature of the evaporation is 50-100 ℃, more specifically, the temperature of the evaporation is 60-80 ℃.
And adding a crystallization solvent into the concentrated solution after evaporation and concentration for crystallization and impurity removal, wherein the crystallization solvent is a non-polar solvent, specifically a C5-C16 hydrocarbon solvent, more specifically one or more of petroleum ether, pentane, hexane, heptane, octane and nonane, and more specifically one or more of petroleum ether, hexane and heptane. The amount of the crystallization solvent is 2 to 100ml of solvent per 1g of the concentrate, preferably 5 to 60ml of solvent per 1g of the concentrate, and more preferably 10 to 30ml of solvent per 1g of the concentrate. The crystallization temperature is-30 to 50 deg.C, preferably-10 to 35 deg.C, more preferably 0 to 30 deg.C, and more preferably 5 to 25 deg.C. The number of crystallization may be single or multiple. The impurities separated out by crystallization need to be separated to obtain a solution containing a target product, and the separation method is any solid-liquid separation method.
The solution containing the target product obtained at the end of the present application is distilled to remove the solvent to obtain the target product, wherein the distillation is any one of distillation methods, preferably distillation under reduced pressure. The distillation temperature is 20-200 ℃, preferably 50-100 ℃, and preferably 60-80 ℃. The reaction involved in the preparation of 2-substituent-4-bromophenol herein is specifically shown below:
in the synthesis method provided by the application, formula 1 is a main reaction, and formula 2 and formula 3 are side reactions; wherein, formula 1 and formula 2 are two competing reactions occurring simultaneously, and in the side reaction occurring in formula 3, 2N-bromosuccinimide and one 2-substituted phenol are consumed to generate one by-product. Therefore, the application further ensures the conversion rate and selectivity of the 2-substituent-4-bromophenol through the limitation of reaction conditions.
The invention provides a preparation method of 2-substituent-4-bromophenol, wherein a bromination reagent N-bromosuccinimide is common and easy to obtain as a raw material; the conversion rate of the raw material 2-substituent phenol is high and can reach more than 99 percent, the selectivity of a target product is good and can reach more than 96 percent, and the product yield is high; the synthesis method has the advantages of simple operation, mild synthesis conditions, low material consumption and energy consumption, less three wastes, environmental protection and suitability for large-scale industrial production.
For further understanding of the present invention, the following examples are provided to illustrate the preparation of 2-substituted-4-bromophenol according to the present invention, and the scope of the present invention is not limited by the following examples.
The analytical conditions for the gas chromatography used in the following examples were: agilent 7890 gas chromatography model B; the chromatographic column is an Agilent HP-5 capillary column; the sample introduction amount is 0.2 mu L, the temperature raising procedure of the column box is that the temperature is raised to 240 ℃ from 37 ℃ and is kept for 2min at 240 ℃, and the temperature raising rate is 10 ℃/min; the injection port temperature is 280 ℃, the split ratio is 50:1; the chromatographic detector was a FID detector and the detector temperature was 290 ℃.
Example 1
1) Adding 10g of 2-tert-butylphenol and 12g of N-bromosuccinimide into 190ml of acetonitrile, and carrying out synthetic reaction for 6h under the conditions of normal pressure, normal temperature and stirring to obtain a reaction solution;
2) Evaporating and concentrating the reaction solution obtained in the step 1) at the vacuum degree of 0.09MPa and the temperature of 65 ℃ until solid is separated out, then adding 200ml of hexane, crystallizing and removing impurities overnight at normal temperature, and finally separating out the separated solid to obtain a solution containing a target product;
3) Distilling the solution containing the target product obtained in step 2) at a vacuum degree of 0.09MPa and a temperature of 75 ℃ to remove the solvent to obtain the target product, wherein a hydrogen spectrum and a carbon spectrum of the target product are shown in FIG. 1 and FIG. 2.
The reaction product solution of step 1) was subjected to gas chromatography analysis, and the results showed: the conversion rate of the raw material 2-tert-butylphenol is 99.41 percent, and the selectivity of the target product 2-tert-butyl-4-bromophenol is 96.31 percent; as shown in FIG. 5, FIG. 5 is a gas chromatography analysis chart of the product of step 1), wherein the peak at 3.730min is acetonitrile, the peak at 10.961min is succinimide, the peak at 12.749min is raw material 2-tert-butylphenol, the peak at 14.212min is byproduct 2-tert-butyl-6-bromophenol, the peak at 16.541min is main product 2-tert-butyl-4-bromophenol, and the peak at 17.384min is byproduct 2-tert-butyl-4, 6-dibromophenol.
The target product obtained in the step 3) is subjected to gas chromatographic analysis, and the result shows that: the purity of the target product 2-tert-butyl-4-bromophenol is 95.31%.
Example 2
1) Adding 10g of 2-ethylphenol and 14.72g of N-bromosuccinimide into 190ml of acetonitrile, and carrying out synthetic reaction for 6 hours under the conditions of normal pressure, normal temperature and stirring to obtain a reaction solution;
2) Evaporating and concentrating the reaction solution obtained in the step 1) at the vacuum degree of 0.09MPa and the temperature of 65 ℃ until solid is separated out, then adding 200ml of hexane, crystallizing and removing impurities overnight at normal temperature, and finally separating out the separated solid to obtain a solution containing a target product;
3) Distilling the solution containing the target product obtained in step 2) at a vacuum degree of 0.09MPa and a temperature of 75 ℃ to remove the solvent to obtain the target product, wherein a hydrogen spectrum and a carbon spectrum of the target product are shown in FIG. 3 and FIG. 4.
The reaction product solution of step 1) was subjected to gas chromatography analysis, and the results showed: the conversion rate of the raw material 2-ethylphenol is 100 percent, and the selectivity of the target product 2-ethyl-4-bromophenol is 96.55 percent; as shown in FIG. 6, FIG. 6 is a gas chromatography analysis chart of the product of step 1), wherein the peak at 3.764min is acetonitrile, the peak at 10.854min is succinimide, the peak at 12.530min is by-product 2-ethyl-6-bromophenol, the peak at 14.991min is by-product 2-ethyl-4-bromophenol, the peak at 16.040min is by-product 2-ethyl-4, 6-dibromophenol, and the raw material 2-ethylphenol is not detected.
The target product obtained in step 3) is subjected to gas chromatographic analysis, and the result shows that: the purity of the target product 2-ethyl-4-bromophenol is 95.31%.
Example 3
1) 30g 2-tert-butylphenol and 36g N-bromosuccinimide are added into 620ml acetonitrile, and the mixture is subjected to synthetic reaction for 6 hours under the conditions of normal pressure, 15 ℃ and stirring to obtain reaction liquid;
2) Evaporating and concentrating the reaction solution obtained in the step 1) at the vacuum degree of 0.09MPa and the temperature of 65 ℃ until solid is separated out, then adding 360ml of petroleum ether, crystallizing overnight at normal temperature to remove impurities, and finally separating out the separated solid to obtain a solution containing a target product;
3) Distilling the solution containing the target product obtained in the step 2) at the vacuum degree of 0.09MPa and the temperature of 75 ℃ to remove the solvent to obtain the target product.
The reaction product solution of step 1) was subjected to gas chromatography analysis, and the results showed: the conversion rate of the raw material 2-tert-butylphenol is 99.88 percent, and the selectivity of the target product 2-tert-butyl-4-bromophenol is 96.06 percent; as shown in FIG. 7, FIG. 7 is a gas chromatography analysis chart of the product of step 1), wherein the peak at 3.747min is acetonitrile, the peak at 10.988min is succinimide, the peak at 12.765min is raw material 2-tert-butylphenol, the peak at 14.228min is byproduct 2-tert-butyl-6-bromophenol, the peak at 16.556min is main product 2-tert-butyl-4-bromophenol, and the peak at 17.400min is byproduct 2-tert-butyl-4, 6-dibromophenol.
The target product obtained in the step 3) is subjected to gas chromatographic analysis, and the result shows that: the purity of the target product 2-tert-butyl-4-bromophenol is 95.14%.
Example 4
1) Adding 15g of 2-tert-butylphenol and 18g of N-bromosuccinimide into 280ml of methanol, and carrying out synthetic reaction for 24 hours under the conditions of normal pressure, room temperature and stirring to obtain a reaction liquid;
2) Evaporating and concentrating the reaction solution obtained in the step 1) at the vacuum degree of 0.09MPa and the temperature of 75 ℃ until solid is separated out, then adding 390ml of hexane, crystallizing at normal temperature overnight to remove impurities, and finally separating out the separated solid to obtain a solution containing a target product;
3) Distilling the solution containing the target product obtained in the step 2) at the vacuum degree of 0.09MPa and the temperature of 67 ℃ to remove the solvent to obtain the target product.
The reaction product solution of step 1) was subjected to gas chromatography analysis, and the results showed: the conversion rate of the raw material 2-tert-butylphenol is 99.52 percent, and the selectivity of the target product 2-tert-butyl-4-bromophenol is 96.17 percent; as shown in FIG. 8, FIG. 8 is a gas chromatography analysis chart of the product of step 1), wherein the peak at 3.546min is methanol, the peak at 10.817min is succinimide, the peak at 12.736min is raw material 2-tert-butylphenol, the peak at 14.187min is by-product 2-tert-butyl-6-bromophenol, the peak at 16.507min is main product 2-tert-butyl-4-bromophenol, and the peak at 17.351min is by-product 2-tert-butyl-4, 6-dibromophenol.
The target product obtained in the step 3) is subjected to gas chromatographic analysis, and the result shows that: the purity of the target product 2-tert-butyl-4-bromophenol is 95.25%.
Comparative example 1
The same preparation method as that of example 1 is only distinguished by adjusting the organic solvent, specifically: 1) Adding 10g of 2-tert-butylphenol and 12g of N-bromosuccinimide into 190ml of hexane, and carrying out synthetic reaction for 6 hours under the conditions of normal pressure, normal temperature and stirring to obtain a reaction liquid.
The reaction product solution of step 1) was subjected to gas chromatography analysis, and the results showed: the conversion rate of the raw material 2-tert-butyl phenol is 37.81%, and the selectivity of the target product 2-tert-butyl-4-bromophenol is 10.68%. As shown in FIG. 9, FIG. 9 is a gas chromatography analysis chart of the product of step 1), wherein the peak in the interval from 3.996min to 4.613min is the peak of hexane (mixed hexane), succinimide is not detected, the peak at 12.746min is the raw material 2-tert-butylphenol, the peak at 14.194min is the by-product 2-tert-butyl-6-bromophenol, the peak at 16.480min is the main product 2-tert-butyl-4-bromophenol, and the peak at 17.350min is the by-product 2-tert-butyl-4, 6-dibromophenol.
Comparative example 2
The same preparation method as that of example 1 is only distinguished by adjusting the organic solvent, specifically: 1) Adding 5g of 2-tert-butylphenol and 6g of N-bromosuccinimide into 95ml of carbon tetrachloride, and carrying out synthetic reaction for 6 hours under the conditions of normal pressure, normal temperature and stirring to obtain a reaction solution.
The reaction product solution of step 1) was subjected to gas chromatography analysis, and the results showed: the conversion rate of the raw material 2-tert-butylphenol is 95.17%, and the selectivity of the target product 2-tert-butyl-4-bromophenol is 11.85%. As shown in FIG. 10, FIG. 10 is a gas chromatography analysis chart of the product of step 1), in which the peak at 4.638min is a peak of carbon tetrachloride, succinimide is not detected, the peak at 12.734min is raw material 2-tert-butylphenol, the peak at 14.217min is by-product 2-tert-butyl-6-bromophenol, the peak at 16.479min is main product 2-tert-butyl-4-bromophenol, and the peak at 17.348min is by-product 2-tert-butyl-4, 6-dibromophenol.
Comparative example 3
1) Adding 10g of 2-tert-butylphenol and 12g of N-bromosuccinimide into 190ml of dichloromethane, and carrying out synthetic reaction for 6 hours under the conditions of normal pressure, normal temperature and stirring to obtain a reaction liquid.
The reaction product solution of step 1) was subjected to gas chromatography analysis, and the results showed: the conversion rate of the raw material 2-tert-butyl phenol is 88.05 percent, and the selectivity of the target product 2-tert-butyl-4-bromophenol is 20.39 percent. As shown in FIG. 11, FIG. 11 is a gas chromatography analysis chart of the product of step 1), in which the peak at 3.856min is a peak of methylene chloride, the peak at 10.884min is succinimide, the peak at 12.745min is raw material 2-tert-butylphenol, the peak at 14.226min is by-product 2-tert-butyl-6-bromophenol, the peak at 16.490min is main product 2-tert-butyl-4-bromophenol, and the peak at 17.358min is by-product 2-tert-butyl-4, 6-dibromophenol.
Comparative example 4
1) 10g of 2-ethylphenol and 18.5g of N-bromosuccinimide are added into 175ml of acetonitrile, and the mixture is subjected to synthesis reaction for 12 hours under the conditions of normal pressure, normal temperature and stirring to obtain a reaction solution.
The reaction product solution of step 1) was subjected to gas chromatography analysis, and the results showed: the conversion rate of the raw material 2-ethylphenol is 100 percent, and the selectivity of the target product 2-ethyl-4-bromophenol is 70.13 percent. As shown in fig. 12, fig. 12 is a gas chromatography analysis chart of the product of step 1), wherein the peak at 3.767min is acetonitrile, the peak at 11.011min is succinimide, the peak at 12.533min is by-product 2-ethyl-6-bromophenol, the peak at 15.006min is main product 2-ethyl-4-bromophenol, the peak at 16.059min is by-product 2-ethyl-4, 6-dibromophenol, and the raw material 2-ethylphenol is not detected.
Comparative example 5
1) 30g of 2-tert-butylphenol and 27g of N-bromosuccinimide are added into 620ml of acetonitrile, and the mixture is subjected to synthetic reaction for 6 hours under the conditions of normal pressure, normal temperature and stirring to obtain a reaction solution.
The reaction product solution of step 1) was subjected to gas chromatography analysis, and the results showed: the conversion rate of the raw material 2-tert-butyl phenol is 75.92%, and the selectivity of the target product 2-tert-butyl-4-bromophenol is 96.03%. As shown in FIG. 13, FIG. 13 is a gas chromatography analysis chart of the product of step 1), wherein the peak at 3.764min is acetonitrile, the peak at 11.136min is succinimide, the peak at 12.748min is raw material 2-tert-butylphenol, the peak at 14.188min is by-product 2-tert-butyl-6-bromophenol, the peak at 16.537min is main product 2-tert-butyl-4-bromophenol, and the peak at 17.356min is by-product 2-tert-butyl-4, 6-dibromophenol.
Comparative example 6
1) Adding 10g of 2-tert-butylphenol and 12g of N-bromosuccinimide into 260ml of acetonitrile, and carrying out synthetic reaction for 11h under the conditions of normal pressure, 80 ℃ and stirring to obtain a reaction solution.
The reaction product solution of step 1) was subjected to gas chromatography analysis, and the results showed: the conversion rate of the raw material 2-tert-butyl phenol is 95.18%, and the selectivity of the target product 2-tert-butyl-4-bromophenol is 87.33%. As shown in FIG. 14, FIG. 14 is a gas chromatography analysis chart of the product of step 1), wherein the peak at 3.770min is acetonitrile, the peak at 10.953min is succinimide, the peak at 12.739min is raw material 2-tert-butylphenol, the peak at 14.193min is by-product 2-tert-butyl-6-bromophenol, the peak at 16.514min is main product 2-tert-butyl-4-bromophenol, and the peak at 17.353min is by-product 2-tert-butyl-4, 6-dibromophenol.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (8)
1. A method for preparing 2-substituent-4-bromophenol represented by formula (I) comprises the following steps:
reacting 2-substituent phenol shown as a formula (II) with N-bromosuccinimide in an organic solvent to obtain 2-substituent-4-bromophenol shown as a formula (I);
wherein R is 1 Selected from C1-C8 alkyl, C3-C8 cycloalkyl or C1-C8 alkoxy.
2. The method of claim 1, further comprising, after the reacting:
evaporating and concentrating the obtained reaction liquid until solid is separated out, adding a crystallization solvent for crystallization and impurity removal, and separating to obtain a solution containing 2-substituent-4-bromophenol;
distilling the solution containing the 2-substituent-4-bromophenol.
3. The method according to claim 1 or 2, wherein the organic solvent is an organic solvent having a polarity of more than 5.0.
4. The method according to claim 3, wherein the organic solvent is one or more selected from acetonitrile, acetone, and methanol.
5. The process according to claim 1 or 2, wherein the molar ratio of the 2-substituted phenol to the N-bromosuccinimide is (0.8 to 1.2): (0.8-1.2).
6. The production method according to claim 1 or 2, wherein the reaction temperature is-30 to 60 ℃ and the pressure is 0 to 2MPa; the reaction is carried out with stirring.
7. The method according to claim 2, wherein the temperature of the evaporation is 20 to 200 ℃; the crystallization solvent is a nonpolar solvent, the nonpolar solvent is selected from one or more of petroleum ether, pentane, heptane, octane and nonane, and the crystallization temperature is-30-50 ℃.
8. The method according to claim 2, wherein the distillation temperature is 20 to 200 ℃.
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| CN116283507A (en) * | 2022-12-19 | 2023-06-23 | 山东京博石油化工有限公司 | Preparation method of 2-substituted-4, 6-dibromophenol |
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