CN117700309A - Preparation method of o-bromoanisole - Google Patents
Preparation method of o-bromoanisole Download PDFInfo
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- CN117700309A CN117700309A CN202311800454.2A CN202311800454A CN117700309A CN 117700309 A CN117700309 A CN 117700309A CN 202311800454 A CN202311800454 A CN 202311800454A CN 117700309 A CN117700309 A CN 117700309A
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- bromoanisole
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- anisole
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- HTDQSWDEWGSAMN-UHFFFAOYSA-N 1-bromo-2-methoxybenzene Chemical compound COC1=CC=CC=C1Br HTDQSWDEWGSAMN-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 52
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 50
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims abstract description 48
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 33
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000002994 raw material Substances 0.000 claims abstract description 23
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 18
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 17
- ZPEIYQRXTBCRFA-UHFFFAOYSA-N 3-bromo-4-methoxybenzenesulfonic acid Chemical compound COC1=CC=C(S(O)(=O)=O)C=C1Br ZPEIYQRXTBCRFA-UHFFFAOYSA-N 0.000 claims abstract description 8
- IWYVYUZADLIDEY-UHFFFAOYSA-N 4-methoxybenzenesulfonic acid Chemical compound COC1=CC=C(S(O)(=O)=O)C=C1 IWYVYUZADLIDEY-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims description 13
- 238000010992 reflux Methods 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 claims description 10
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 6
- -1 p-sulfoanisole Anisole Chemical compound 0.000 claims 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 abstract description 22
- 229910052794 bromium Inorganic materials 0.000 abstract description 22
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 abstract description 21
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 15
- 239000006227 byproduct Substances 0.000 abstract description 6
- 238000006266 etherification reaction Methods 0.000 abstract description 6
- 239000000047 product Substances 0.000 abstract description 4
- 239000002699 waste material Substances 0.000 abstract description 4
- 230000001590 oxidative effect Effects 0.000 abstract description 3
- 125000000542 sulfonic acid group Chemical group 0.000 abstract description 3
- VADKRMSMGWJZCF-UHFFFAOYSA-N 2-bromophenol Chemical compound OC1=CC=CC=C1Br VADKRMSMGWJZCF-UHFFFAOYSA-N 0.000 description 16
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 15
- 239000000243 solution Substances 0.000 description 14
- 239000000203 mixture Substances 0.000 description 10
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 8
- 238000005893 bromination reaction Methods 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000031709 bromination Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000001308 synthesis method Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- FNAKEOXYWBWIRT-UHFFFAOYSA-N 2,3-dibromophenol Chemical compound OC1=CC=CC(Br)=C1Br FNAKEOXYWBWIRT-UHFFFAOYSA-N 0.000 description 3
- GZFGOTFRPZRKDS-UHFFFAOYSA-N 4-bromophenol Chemical compound OC1=CC=C(Br)C=C1 GZFGOTFRPZRKDS-UHFFFAOYSA-N 0.000 description 3
- 239000012295 chemical reaction liquid Substances 0.000 description 3
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000006277 sulfonation reaction Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 238000006193 diazotization reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 238000003541 multi-stage reaction Methods 0.000 description 1
- 238000007040 multi-step synthesis reaction Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 235000011837 pasties Nutrition 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000001256 steam distillation Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
- C07C303/04—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof by substitution of hydrogen atoms by sulfo or halosulfonyl groups
- C07C303/08—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof by substitution of hydrogen atoms by sulfo or halosulfonyl groups by reaction with halogenosulfonic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
- C07C303/22—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof from sulfonic acids, by reactions not involving the formation of sulfo or halosulfonyl groups; from sulfonic halides by reactions not involving the formation of halosulfonyl groups
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method of o-bromoanisole, which is synthesized through three steps, anisole is taken as a raw material, p-sulfoanisole is synthesized firstly, 2-bromo-4-sulfoanisole is synthesized on the basis, and finally, a sulfonic acid group is removed to obtain o-bromoanisole, and the problems of more byproducts, low yield, low purity and the like in a phenol synthesis path are avoided due to the adoption of anisole as a raw material; meanwhile, the cost of all reaction raw materials is low, the process steps are simple, and etherification is not required; meanwhile, as anisole can be used as a raw material in an intermediate step, hydrobromic acid and hydrogen peroxide can be used for oxidizing hydrobromic acid to generate bromine, so that the reaction rate can be controlled, the reaction efficiency can be improved, the waste of bromine can be reduced, the purity of the prepared product can reach 99.4%, the yield can also reach 96.26%, and the method can be applied to industrial large scale.
Description
Technical Field
The invention relates to the field of organic synthesis, in particular to a preparation method of o-bromoanisole.
Background
O-bromoanisole is an intermediate material in the synthesis field, and plays an important role in the fields of perfume and medicine. In the prior art, the preparation and synthesis of the o-bromoanisole have more synthesis processes, and the synthesis of the o-bromoanisole mainly comprises two steps of the synthesis of the o-bromophenol and the etherification of the o-bromophenol.
The synthesis method of the o-bromophenol mainly comprises a phenol direct bromination method, an o-aminophenol diazotization method and a sulfonation bromination method. The direct bromination method of phenol is to directly substitute phenol with bromine to produce o-bromophenol, p-bromophenol and dibromophenol. Then, o-bromophenol, p-bromophenol and dibromophenol are obtained through separation, but after phenol is subjected to bromination substitution, o-bromophenol is generated, byproducts such as p-bromophenol and dibromophenol are generated, the products are similar in property, and separation is difficult; the synthesis of the o-bromoanisole by the o-aminophenol diazotization method is to synthesize the o-aminophenol first and then to diazotize the o-aminophenol to obtain the o-bromophenol, but the method has complex process, low yield (less than 30 percent) and high cost; the sulfonation bromination method is the most commonly used synthesis method in industry, wherein a sulfonic acid group is firstly introduced into the para position of phenol, so that the substitution of a bromine position can only be carried out in the ortho position, and the method has the advantages of low cost and less pollution, but the yield of the obtained o-bromophenol is only about 40%. In the prior art, li Yingchun is prepared by using phenol, bromine and dimethyl sulfate as raw materials to synthesize o-bromoanisole (Li Yingchun, teng Junjiang. Synthesis of o-bromoanisole [ J ]. Application chemical industry, 2004, (04)), although the higher yield is obtained by adjusting the proportion and the reaction condition, on one hand, o-bromobenzene is synthesized first and then the o-bromoanisole is obtained by etherification, and on the other hand, the yield of the o-bromoanisole cannot be improved to the maximum extent due to the limitation of the yield of the multi-step reaction.
In summary, the existing synthesis technology of o-bromoanisole has the disadvantages of high yield, high technical cost, simple process, low yield, serious raw material waste, and complex reaction separation due to the adoption of a large amount of inorganic strong alkali and the generation of a large amount of inorganic salt in the etherification process by dimethyl sulfate reaction. Aiming at the problems, the synthesis thought is improved, and the synthesis method starts from other raw materials of anisole to synthesize the o-bromoanisole, so that byproducts are avoided, and the o-bromoanisole with high purity and high yield is obtained.
Technical content
The application provides a preparation method of o-bromoanisole, which has the following technical scheme.
The preparation method of the o-bromoanisole comprises the following steps of
Step 1: synthesis of p-sulfoanisole
Anisole is taken as a raw material, chlorosulfonic acid is added to react with anisole to synthesize p-sulfoanisole;
step 2: synthesis of 2-bromo-4-sulfoanisole
After the reaction of the step 1 is completed, hydrobromic acid and hydrogen peroxide are added into the solution after the reaction is completed, and the reaction is carried out at a constant temperature after the addition is completed, so as to obtain 2-bromo-4-sulfoanisole;
step 3: synthesis of O-bromoanisole
And (2) adding concentrated sulfuric acid into the reaction solution in the step (2), heating for refluxing, standing for liquid separation, and rectifying an oil phase to obtain the high-purity o-bromoanisole.
In the step 1, the ratio of anisole to chlorosulfonic acid is 1:1 to 1.3;
in the step 2, the mass ratio of hydrobromic acid to hydrogen peroxide is 1:1 to 1.2;
the ratio of anisole to hydrobromic acid mass is 1:1 to 1.2;
in the step 3, the mass ratio of anisole to concentrated sulfuric acid is 1:0.4 to 0.6;
in the step 1, the reaction temperature is 10-20 ℃; the chlorosulfonic acid is added dropwise; the dripping time is 3-5h; preserving heat for 3-6 hours after the dripping is completed;
in the step 2, the reaction temperature is-5 ℃, the feeding speed of hydrogen peroxide is slightly faster than hydrobromic acid, and the dripping time is 3-4h; preserving heat for 3-5 hours after the dripping is completed;
in the step 3, the feeding time of the concentrated sulfuric acid is 1-3 hours; the feeding mode is dripping; stirring and heating to 190-200 ℃; the reflux time is 6-9 hours.
Principle of the technology
The o-bromoanisole is synthesized through three steps, anisole is taken as a raw material, p-sulfoanisole is synthesized firstly, 2-bromo-4-sulfoanisole is synthesized, and finally a sulfonic acid group is removed to obtain the o-bromoanisole. In the second step, hydrobromic acid and hydrogen peroxide are added for reaction, and the reaction of oxidizing hydrobromic acid by hydrogen peroxide is also carried out, so that the hydrobromic acid is oxidized into bromine, and then the bromine reacts with p-sulfoanisole to generate 2-bromo-4-sulfoanisole. The method has the advantages that hydrobromic acid with low reaction efficiency can be oxidized into bromine simple substance due to the existence of hydrogen peroxide, the activity is stronger, the p-sulfoanisole is fully reacted to generate 2-bromo-4-sulfoanisole, the bromine use efficiency is improved, and the waste of resources caused by insufficient reaction due to direct use of bromine can be avoided.
Technical effects
According to the preparation method of the o-bromoanisole, anisole is adopted from synthetic raw materials, so that the problems of more byproducts, low yield, low purity and the like in a phenol synthetic path are avoided. Meanwhile, the cost of all reaction raw materials is lower, the process steps are simple, and the raw materials are anisole, so that the cost is low, and etherification is not required unlike a sulfonation process which takes phenol as a raw material in a conventional process; the hydrobromic acid is used as a reaction raw material, and is oxidized by hydrogen peroxide to generate bromine, so that the reaction rate can be controlled, the reaction efficiency can be improved, the waste of bromine can be reduced, and the storage and transportation of bromine are avoided; meanwhile, other byproducts can be avoided by taking anisole as a raw material, so that the purity and the yield of the o-bromoanisole are greatly improved, the purity of the o-bromoanisole product prepared by the method can reach 99.4%, and the yield also reaches 96.26%. Meanwhile, the synthesis process is simple, a plurality of reaction sections are not required to be arranged, all reactions can be carried out in the same reaction vessel, the production cost of products can be reduced due to multi-step synthesis, and the method can be applied to industrial large scale.
Detailed Description
The technical solutions provided by the present invention will be described in detail below with reference to the embodiments, and the technical solutions in the embodiments of the present invention will be clearly and completely described, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
108g of anisole is put into a reaction kettle, stirred, the temperature is kept at 20 ℃, 140g of chlorosulfonic acid is dripped, the dripping temperature is controlled, the dripping is carried out for 4 hours, and after the dripping, the reaction is carried out for 4 hours at 20 ℃, and the reaction is finished; the temperature of the reaction kettle is reduced to 0 ℃, hydrobromic acid and hydrogen peroxide are dripped at the same time, wherein the hydrobromic acid is a hydrobromic acid solution with the mass fraction of 40% of 212.6g, the hydrogen peroxide is hydrogen peroxide with the mass fraction of 27.5%, the feeding amount is 130.3g, the dripping speed of the hydrogen peroxide is controlled to be slightly faster than that of the hydrobromic acid, the material is dripped in 3 hours, and the temperature is kept at 0 ℃ for 5 hours after the dripping; then, 98% of concentrated sulfuric acid is added dropwise into the reaction liquid, after the dripping is completed within 3 hours, stirring and heating to 190 ℃ and refluxing are carried out, refluxing is carried out for 7-8 hours, standing and separating liquid is carried out, the lower layer is light yellow oily liquid, oil phase is separated, 180g of o-bromoanisole is obtained by rectification, the content is 99.4%, and the yield is 96.26%.
Example 2
108g of anisole is put into a reaction kettle, the temperature is kept at 20 ℃, 120g of chlorosulfonic acid is dripped, the dripping temperature is controlled, the dripping is carried out for 4 hours, and after dripping, the reaction is carried out for 3 hours at 20 ℃, and the reaction is finished; the temperature of the reaction kettle is reduced to 0 ℃, hydrobromic acid and hydrogen peroxide are dripped at the same time, wherein the hydrobromic acid is a hydrobromic acid solution with the mass fraction of 40% of 212.6g, the hydrogen peroxide is hydrogen peroxide with the mass fraction of 27.5%, the feeding amount is 130.3g, the dripping speed of the hydrogen peroxide is controlled to be slightly faster than that of the hydrobromic acid, the material is dripped in 3 hours, and the material is preserved for 5 hours at 0 ℃ after the dripping is finished; then, 98% of concentrated sulfuric acid is added dropwise into the reaction liquid in mass percent, after the dripping is completed in 3 hours, stirring and heating to 190 ℃ and refluxing are carried out, refluxing is carried out for 7-8 hours, standing and separating liquid is carried out, the lower layer is light yellow oily liquid, oil phase is separated, 175g of o-bromoanisole is obtained by rectification, the content is 99.1%, and the yield is 93.86%.
Example 3
108g of anisole is put into a reaction kettle, the temperature is kept at 20 ℃, 120g of chlorosulfonic acid is dripped, the dripping temperature is controlled, the dripping is carried out for 4 hours, and after dripping, the reaction is carried out for 4 hours at 20 ℃, and the reaction is finished; the temperature of the reaction kettle is reduced to 0 ℃, hydrobromic acid and hydrogen peroxide are dripped at the same time, wherein the hydrobromic acid is 177.2g of hydrobromic acid solution with the mass fraction of 48%, the hydrogen peroxide is 27.5% of hydrogen peroxide with the mass fraction, the feeding amount is 130.3g, the dripping speed of the hydrogen peroxide is controlled to be slightly faster than that of the hydrobromic acid, the material is dripped in 3 hours, and the temperature is kept at 0 ℃ for 5 hours after the dripping is finished; then, adding 98% concentrated sulfuric acid dropwise into the reaction solution within 3 hours, stirring and heating to 190 ℃ and refluxing after the dripping is completed, refluxing for 7-8 hours, standing and separating the solution, separating the oil phase from the lower layer to obtain 173g of o-bromoanisole with the content of 99.5% and the yield of 92.42%.
Example 4
108g of anisole is put into a reaction kettle, the temperature is kept at 20 ℃, 120g of chlorosulfonic acid is dripped, the dripping temperature is controlled, the dripping is carried out for 4 hours, and after dripping, the reaction is carried out for 4 hours at 20 ℃, and the reaction is finished; the temperature of the reaction kettle is reduced to 0 ℃, hydrobromic acid is dripped at the same time, wherein the hydrobromic acid is 177.2g of hydrobromic acid solution with the mass fraction of 48 percent, the material is dripped in 3 hours, and the temperature is kept for 5 hours at 0 ℃ after the dripping is finished; then, 98% of concentrated sulfuric acid is added dropwise into the reaction liquid, after the dripping is completed within 3 hours, stirring and heating to 190 ℃ and refluxing are carried out, refluxing is carried out for 7-8 hours, standing and separating liquid is carried out, the lower layer is light yellow oily liquid, oil phase is separated, 124g of o-bromoanisole is obtained through rectification, the content is 95.1%, and the yield is 63.1%.
Comparative example
The preparation is carried out by referring to the synthesis method of Li Yingchun in the background art:
a mixture of 47g (0.5 mol) of phenol and 175g (95 mL, 1.75 mol) of concentrated sulfuric acid was added to a three-necked flask, heated on a boiling water bath for 3 hours, stirred, and then cooled to room temperature with an ice-water bath. A solution of 140g (3.5 mol) NaOH and 350mL water was carefully added to turn the mixture dark brown, stirred for 2min, after which a white solid had formed and stirred for a further 10min, after which the solution turned dark brown and the alkaline solution was cooled to room temperature. 80g (0.5 mol) of bromine was added dropwise under stirring for 30min at a reaction temperature of 50℃and stirring was continued for 30min after the completion of bromine addition. The solution was still alkaline and contained a small amount of white suspension, and then the mixture was evaporated by stopping stirring on an oil bath at 150 ℃ until the residue left was a thick, pasty grey mass with an evaporation time of 40min. The slurry was cooled to room temperature to give a yellow solid, 400mL of concentrated sulfuric acid was added thereto at which the solid was dissolved to be dark green, the mixture was heated to 200℃in an oil bath, steam distillation was carried out, the distillate was a yellow green oil, the distillate was extracted with diethyl ether, the diethyl ether was distilled off, the residue was distilled off under normal pressure, and a fraction at 190 to 200℃was collected to give 79.1g of a pale yellow oily liquid in a yield of 91.52%.
52g of o-bromophenol and 40g of 10% dilute sodium hydroxide solution are mixed and stirred, cooled to below 5 ℃ by using an ice water bath, 42g of dimethyl sulfate is slowly added under stirring, at the moment, the mixture turns into a milky paste, cooling is stopped after the mixture is added, and the mixture is heated to 45 ℃, turns into yellow oily liquid, the mixture is stirred and kept warm for 2 hours and discharged, the mixture is poured into a separating funnel, kept stand for 4 hours, layered, the upper layer is colorless liquid, the lower layer is pale yellow oily liquid, an oil layer is separated, the upper layer is extracted by using diethyl ether, the extract is distilled to remove diethyl ether and the oil layer, the diethyl ether is combined with the oil layer, water is washed to be neutral, and the mixture is dried by using anhydrous calcium chloride, so that 47.8g of light yellow transparent oily liquid o-bromoanisole is obtained, and the yield is 85.1%.
According to the embodiment, when the reaction substance is hydrobromic acid, although the bromination reaction can be carried out, the reaction efficiency is low, more bromine does not participate in the reaction, the yield of o-bromoanisole is about 60%, if the industrial phenol bromination method is used for synthesizing o-bromophenol from phenol, the yield of o-bromophenol is below 50% and is much lower than that of anisole serving as a raw material, even if the reaction substance is prepared by adopting the synthesis method of a comparison example, the yield of o-bromophenol can reach more than 90%, but the yield of o-bromophenol etherification can reach more than 80%, the comprehensive yield is below 80%, the yield is lower than the yield of more than 90%, the complex process can lead to high production cost, bromine must be used in the process of preparing the o-bromophenol by taking phenol as a raw material, the hydrobromic acid and the o-bromophenol cannot be obtained by oxidizing phenols, mainly because the reaction efficiency of hydrobromic acid is low, the oxidation of the o-bromophenol cannot be obtained, and the use of the more stable anisole as the raw material, and the hydrogen peroxide can be controlled to be directly used as the bromine, and the bromine is not oxidized by the hydrogen peroxide, compared with the bromine is directly generated in the process of the application, and the bromine is controlled to be compared with the bromine-2, and the bromine is directly used as the raw material.
Therefore, the yield of anisole serving as a raw material is far higher than that of phenol serving as a raw material, the o-bromoanisole can be reacted in one reactor without multiple separation in the production process, and the process is simple. The process can effectively reduce byproducts, has the characteristics of less pollution and low cost, and has the advantages of high yield and high purity, which is incomparable with the production of o-bromoanisole by taking phenol as a raw material.
Claims (7)
1. A preparation method of o-bromoanisole is characterized in that,
the preparation method comprises the following steps:
step 1: synthesis of p-sulfoanisole
Anisole is taken as a raw material, chlorosulfonic acid is added to react with anisole to synthesize p-sulfoanisole;
step 2: synthesis of 2-bromo-4-sulfoanisole
After the reaction of the step 1 is completed, hydrobromic acid and hydrogen peroxide are added into the solution after the reaction is completed, and the reaction is carried out at a constant temperature after the addition is completed, so as to obtain 2-bromo-4-sulfoanisole;
step 3: synthesis of O-bromoanisole
And (2) adding concentrated sulfuric acid into the reaction solution in the step (2), heating for refluxing, standing for liquid separation, and rectifying an oil phase to obtain the high-purity o-bromoanisole.
2. A process for the preparation of o-bromoanisole as defined in claim 1, wherein,
in the step 1, the ratio of anisole to chlorosulfonic acid is 1:1 to 1.3.
3. A process for the preparation of o-bromoanisole as defined in claim 1, wherein,
in the step 2, the mass ratio of hydrobromic acid to hydrogen peroxide is 1:1 to 1.2;
the ratio of anisole to hydrobromic acid mass is 1:1 to 1.2.
4. A process for the preparation of o-bromoanisole as defined in claim 1, wherein,
in the step 3, the mass ratio of anisole to concentrated sulfuric acid is 1:0.4 to 0.6.
5. A process for the preparation of o-bromoanisole as defined in claim 1, wherein,
in the step 1, the reaction temperature is 10-20 ℃; the chlorosulfonic acid is added dropwise; the dripping time is 3-5h; preserving the heat for 3-6 hours after the dripping is completed.
6. A process for the preparation of o-bromoanisole as defined in claim 1, wherein,
in the step 2, the reaction temperature is-5 ℃, the feeding speed of hydrogen peroxide is slightly faster than hydrobromic acid, and the dripping time is 3-4h; preserving heat for 3-5 hours after the dripping is completed.
7. A process for the preparation of o-bromoanisole as defined in claim 1, wherein,
in the step 3, the feeding time of the concentrated sulfuric acid is 1-3 hours; the feeding mode is dripping; stirring and heating to 190-200 ℃; the reflux time is 6-9 hours.
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