CN110872203B - Method for preparing bromization reagent and further preparing bromine-containing compound through oxidation bromination reaction - Google Patents
Method for preparing bromization reagent and further preparing bromine-containing compound through oxidation bromination reaction Download PDFInfo
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- CN110872203B CN110872203B CN201811001380.5A CN201811001380A CN110872203B CN 110872203 B CN110872203 B CN 110872203B CN 201811001380 A CN201811001380 A CN 201811001380A CN 110872203 B CN110872203 B CN 110872203B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B39/00—Halogenation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
- C07C209/74—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton by halogenation, hydrohalogenation, dehalogenation, or dehydrohalogenation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/62—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by introduction of halogen; by substitution of halogen atoms by other halogen atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
- C07C41/22—Preparation of ethers by reactions not forming ether-oxygen bonds by introduction of halogens; by substitution of halogen atoms by other halogen atoms
Abstract
The invention relates to a synthesis method of a brominating reagent and a method for preparing a bromine-containing compound by reacting the brominating reagent, which comprises the following steps: reacting bromo reagent obtained by reacting the bromine anion compound with triphosgene or phosgene with aromatic or unsaturated bond-containing compound. Wherein, the aromatic compounds comprise: the electron-rich substituted benzene compound, the electron-rich substituted naphthalene compound, the electron-rich substituted thiophene compound, the electron-rich substituted furan compound, the electron-rich substituted indole compound and the electron-rich substituted pyrrole compound. The unsaturated bond-containing compound includes double bonds (olefins) and triple bonds (alkynes). The substituent is alkyl, hydroxyl, amino substituted by alkyl, alkoxy or ester group. More preferably, the aromatic compound is
Description
Technical Field
The invention relates to the field of chemical synthesis, in particular to a method for preparing a bromination reagent and further preparing a bromine-containing compound by oxidation bromination reaction.
Background
The bromine-containing compound has various types and wide application, and plays an important role in the production process of medicines, dyes, pesticides, spices, pigments, plasticizers and flame retardants. For example, in the pharmaceutical industry, bromine-containing compounds are used for manufacturing various sedatives and disinfectants and also as intermediates for manufacturing antibacterial drugs, decabromodiphenyl ether is a flame retardant with wide application, and methyl bromide is a fumigant insecticide widely adopted in the world.
The oxidative bromination reaction is a more commonly used method for preparing bromine-containing compounds. Currently, many studies are made on the oxidation bromination reaction. In recent years, the oxidation bromination reaction using aromatic compounds as raw materials is a synthesis method with more researches due to simple operation, mild reaction and higher yieldThe method is carried out. Commonly used oxidizing agents are: chlorine, hydrogen peroxide, sodium hypochlorite and V 2 O 5 ，NH 4 VO 3 And the like. These are all carried out by oxidizing the negative bromide ions with an oxidizing agent and, moreover, by the action of a catalyst. The use of oxidants has matured and the development of new oxidants has ceased. Through continuous research, the inventor of the invention accidentally finds that a reagent which is not called an oxidant exerts the oxidation property, so that the bromine-containing compound prepared by the oxidation bromination reaction has very high yield, low cost, environmental protection, economy and obvious effect.
Disclosure of Invention
The invention aims to provide a method for preparing a bromine-containing compound through oxidation bromination reaction under mild conditions. Moreover, the technical purpose of environmental protection and economy is achieved, and therefore the technical scheme provided by the invention is as follows:
firstly, the method for preparing the brominating reagent by oxidation reaction and preparing the bromine-containing compound by bromination reaction by using the reagent provided by the invention comprises the following steps: reacting bromine negative ion compound with triphosgene or phosgene to obtain bromization reagent, and reacting with aromatic or unsaturated bond-containing compound. Further, the method for preparing the bromine-containing compound comprises the step of preparing bromine by the triphosgene acting on the bromine-containing reagent.
Thus, in another aspect, the invention provides a method of producing bromine. Prepared by the action of triphosgene on a bromine-containing reagent. The bromine-containing reagent is a compound containing bromine anions.
The bromine negative ion compound can be one or more of tetraalkylamine bromide, hydrogen bromide, lithium bromide, sodium bromide, potassium bromide, magnesium bromide, calcium bromide and barium bromide. Wherein, the alkyl can be a straight chain or branched chain alkyl of C1-C8.
In the oxidation bromination reaction, the aromatic compounds are: electron-rich substituted benzene compounds, electron-rich substituted naphthalene compounds, electron-rich substituted thiophene compounds, electron-rich substituted furan compounds, electron-rich substituted indole compounds, electron-rich substitutionThe pyrrole compound or the compound containing unsaturated bonds comprises double-bond olefin compounds and triple-bond alkyne compounds. The substituent is alkyl, hydroxyl, amino substituted by alkyl, alkoxy or ester group. More preferably, the aromatic compound is
The bromine-containing reagent disclosed by the invention is a compound containing bromine anions commonly used in the field, such as one or more of tetraalkylamine bromide, hydrogen bromide, lithium bromide, sodium bromide, potassium bromide, magnesium bromide, calcium bromide and barium bromide. More preferably selected from one or two of TBAB and KBr.
The alkyl of the tetraalkylamine bromide can be a linear or branched alkyl of C1-C8 or benzyl.
The oxidative bromination reaction is carried out under the action of a solvent, and preferably, the solvent can be a protic solvent or an aprotic solvent. More preferably, the solvent is selected from water, 1, 2-dichloroethane, chloroform, petroleum ether or ethyl acetate.
The reaction temperature of the oxidation bromination reaction is as follows: 0 ℃ to 60 ℃, preferably 10 ℃ to 25 ℃.
The molar equivalent ratio of the triphosgene to the aromatic compound is 1-2: 1, preferably 1 to 1.5: 1.
the product of the oxidation bromination reaction can be a monobromine substitution product and can also be a dibromo substitution product. More preferably, it is a monobromo substitution product.
The oxybromination reaction of the present invention can be represented by the following reaction equation:
a more preferred embodiment of the present invention is: under the action of triphosgene, anisole reacts with bromine-containing reagents TBAB and KBr at 40 ℃ to prepare p-bromoanisole.
Compared with the prior art, the invention has the beneficial effects that:
in the oxidation bromination reaction in the prior art, except for the use of an oxidant, a catalyst is added during the reaction, and triphosgene is added, so that the reagent is not an oxidant, but exerts the effect of the oxidant. Compared with the prior art, the method has the advantages of high yield, high purity and less by-products in the preparation of monobromo substitution products.
In addition, compared with the oxidation bromination reaction in the prior art, the method uses highly toxic liquid bromine or other explosive oxidants, and the invention uses the safe, green and environment-friendly triphosgene or phosgene (phosgene has the same function) to react with the same safe and easily-operated bromine anion compound to obtain the novel bromination reagent, thereby solving the technical problem that the bromination reagent in the prior art is difficult to obtain and use, and having obvious effect.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Example 1:
anisole (5.00g,0.046mmol), TBAB (7.45g,0.023mmol), KBr (8.26g,0.069mmol), 1, 2-dichloroethane (20mL) and water (0.50mL) were added to a three-necked flask, stirred at 40 ℃, triphosgene (17.80g,0.060mmol) in 1, 2-dichloroethane (40mL) was added to the reaction mixture, and after the reaction was completed, the reaction mixture was washed with water and evaporated to obtain 8.57g of p-bromoanisole, the yield was 99% and the HPLC purity was 99%. Nuclear magnetic numberAccording to the following 1 H NMR(400MHz,CDCl 3 ,ppm):δ7.38(d,J＝8.8Hz,2H),6.78(d,J＝9.2Hz,2H),3.76(d,J＝20Hz,3H).
Example 2:
naphthylmethyl ether (7.27g,0.046mmol), TBAB (7.45g,0.023mmol), KBr (8.26g,0.069mmol) and 1, 2-dichloroethane (20mL) were added to a three-necked flask, stirred at 40 ℃, triphosgene (17.80g,0.060mmol) in 1, 2-dichloroethane (40mL) was added to the reaction mixture, and after the reaction was completed, the reaction mixture was washed with water and evaporated to give 11.03g of product with a yield of 96% and an HPLC purity of 99%.
Example 3:
phenol (4.33g,0.046mmol), TBAB (7.45g,0.023mmol), KBr (8.26g,0.069mmol) and 1, 2-dichloroethane (20mL) were added to a three-necked flask, stirred at 40 ℃, triphosgene (17.80g,0.060mmol) in 1, 2-dichloroethane (40mL) was added to the reaction mixture, and after completion of the reaction, the reaction mixture was washed with water and evaporated to give 7.40g of product in 93% yield and 99% HPLC purity.
Example 4:
1-naphthol (6.63g,0.046mmol), TBAB (7.45g,0.023mmol), KBr (8.26g,0.069mmol) and 1, 2-dichloroethane (20mL) were added to a three-necked flask, stirred at 40 ℃, triphosgene (17.80g,0.060mmol) in 1, 2-dichloroethane (40mL) was added to the reaction mixture, and after the reaction was completed, the reaction mixture was washed with water and evaporated to give 10.16g of product in 99% yield and 99% purity by HPLC.
Example 5:
2-naphthol (6.63g,0.046mmol), TBAB (7.45g,0.023mmol), KBr (8.26g,0.069mmol) and 1, 2-dichloroethane (20mL) were added to a three-necked flask, stirred at 40 ℃, triphosgene (17.80g,0.060mmol) in 1, 2-dichloroethane (40mL) was added to the reaction mixture, and after completion of the reaction, the reaction mixture was washed with water and evaporated to give 10.16g of product in 99% yield and 99% purity by HPLC.
Example 6:
n, N-dimethylaniline (5.57g,0.046mmol), TBAB (7.45g,0.023mmol), KBr (8.26g,0.069mmol) and 1, 2-dichloroethane (20mL) were added to a three-necked flask, and stirred at 40 ℃, triphosgene (17.80g,0.060mmol) in 1, 2-dichloroethane (40mL) was added to the reaction mixture, and after the reaction was completed, the reaction mixture was washed with water and evaporated to give 9.02g of a product, yield 98%, and HPLC purity was 99%.
Example 7:
n, N-dimethylnaphthylamine (7.88g,0.046mmol), TBAB (7.45g,0.023mmol), KBr (8.26g,0.069mmol) and 1, 2-dichloroethane (20mL) were added into a three-necked flask, stirred at 40 ℃, triphosgene (17.80g,0.060mmol) in 1, 2-dichloroethane (40mL) was added to the reaction mixture, and after the reaction was completed, the reaction mixture was washed with water and evaporated to obtain 10.70g of a product with a yield of 93% and an HPLC purity of 99%.
Example 8:
naphthalene-2, 6-diol (7.37g,0.046mmol), TBAB (7.45g,0.023mmol), KBr (8.26g,0.069mmol) and 1, 2-dichloroethane (20mL) were added to a three-necked flask, and stirred at 40 ℃, triphosgene (17.80g,0.060mmol) in 1, 2-dichloroethane (40mL) was added to the reaction mixture, after the reaction was completed, the reaction mixture was washed with water and evaporated to give 9.90g of product, yield 90%, HPLC purity 99%.
Claims (4)
1. A preparation method for preparing a bromine-containing compound by oxidation bromination reaction is characterized by comprising the step of preparing a brominated product under the action of TBAB, KBr and triphosgene;
the oxidative bromination reaction is carried out under the action of a solvent, and the solvent is selected from a protic solvent or an aprotic solvent;
the product of the oxidative bromination reaction is a monobromine substitution product or a dibromo substitution product, and is represented by the following equation:
2. the method according to claim 1, wherein the solvent is selected from water, 1, 2-dichloroethane, chloroform, petroleum ether and ethyl acetate, and may be a single solvent or a mixed solvent.
3. The preparation method according to claim 1, wherein the reaction temperature of the oxidative bromination reaction is 0 ℃ to 60 ℃.
4. The preparation method of claim 1, wherein anisole is reacted with bromine-containing reagents TBAB and KBr at 40 ℃ under the action of triphosgene to prepare p-bromoanisole.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102260127A (en) * | 2011-06-16 | 2011-11-30 | 华东师范大学 | Method for preparing halogenated aryl compounds through oxidation and halogenation |
| CN107098791A (en) * | 2017-04-18 | 2017-08-29 | 浙江师范大学 | A kind of preparation method of benzyl bromide a-bromotoluene |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102260127A (en) * | 2011-06-16 | 2011-11-30 | 华东师范大学 | Method for preparing halogenated aryl compounds through oxidation and halogenation |
| CN107098791A (en) * | 2017-04-18 | 2017-08-29 | 浙江师范大学 | A kind of preparation method of benzyl bromide a-bromotoluene |
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