CN110922294A - Method for preparing organic bromide from organic chloride - Google Patents
Method for preparing organic bromide from organic chloride Download PDFInfo
- Publication number
- CN110922294A CN110922294A CN201911266669.4A CN201911266669A CN110922294A CN 110922294 A CN110922294 A CN 110922294A CN 201911266669 A CN201911266669 A CN 201911266669A CN 110922294 A CN110922294 A CN 110922294A
- Authority
- CN
- China
- Prior art keywords
- bromide
- organic
- salt
- metal
- preparing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/20—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms
- C07C17/202—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction
- C07C17/208—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction the other compound being MX
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a method for preparing organic bromide from organic chloride, which comprises the following steps: mixing and reacting organic chloride, brominated metal salt, a catalyst and water to obtain brominated compound synthetic liquid, and separating the brominated compound synthetic liquid to obtain brominated compounds. Through the mode, the method for preparing the organic bromide from the organic chloride generates metal chloride without environmental pollution, reduces the production cost, reduces the pollution to the environment, greatly improves the operation environment, reduces harmful substances, and is suitable for preparing and synthesizing the monobromide and also suitable for producing polybrominated hydrocarbons such as dibromide, tribromide and the like and brominated aromatic hydrocarbon compounds, and the purity of the prepared organic bromide is over 98 percent.
Description
Technical Field
The invention relates to the technical field of basic chemical engineering, in particular to a method for preparing organic bromide from organic chloride.
Background
The organic bromide is an important industrial solvent and chemical raw material, can be particularly used as an intermediate of medicines, pesticides, spices, dyes and surfactants, and is an important fine chemical product. The traditional method for synthesizing the alkyl bromide mainly comprises the following steps: (1) taking phosphorus tribromide and phosphorus pentabromide as brominating reagents, chloroform and dichloromethane as solvents, and taking corresponding alcohol as a raw material to synthesize bromide; (2) synthesizing bromide by using corresponding alcohol and hydrobromic acid as raw materials and concentrated sulfuric acid as a catalyst; (3) bromine, corresponding alkyl compound or alcohol is used as raw material to synthesize bromide.
As reported in patent CN 102010384: phosphorus bromide was used as the brominating agent and phosphorous acid was the byproduct. Production is comparatively dangerous on the one hand, and the phosphorous acid that on the other hand reaction generated corrodes the pipeline, and production and maintenance cost is big, and the pollution of phosphorous acid is big simultaneously, is unfavorable for green production, has improved environmental protection cost.
37-39 and patent CN103804121 respectively as reported in fine chemical intermediate 2008(01): hydrogen bromide and concentrated sulfuric acid are used for preparation or bromine and sulfur are used as raw materials for production. The environment is polluted, the strong acid can corrode pipelines and reaction kettles, and the equipment cost and the maintenance cost are increased.
The commonly used synthesis method has the disadvantages of large pollution and harm of used raw materials, no environmental friendliness, high requirements on production equipment, dangerous and environmentally-friendly production process, severe production environment and no accordance with the modern industrial green and environment-friendly concept.
Disclosure of Invention
The invention mainly solves the technical problem of providing a method for preparing organic bromide from organic chloride, which can effectively prepare the organic bromide, not only reduce the harm and pollution to the environment, but also reduce the production cost, greatly improve the operating environment, reduce the diffusion of harmful substances in the air and realize clean production.
In order to solve the technical problems, the invention adopts a technical scheme that: provides a preparation method of organic bromide. The method specifically comprises the following steps: mixing and reacting organic chloride, brominated metal salt, a catalyst and water to obtain organic bromide synthetic liquid, and separating the organic bromide synthetic liquid to obtain the organic bromide.
In a preferred embodiment of the invention, the organochlorine is R1R2CHCl、R1R2CHn-xClx、CCl4、ArClxWherein R is1、R2Is C containing a C-H bond1-C20The alkane is a straight-chain, branched-chain or cyclic alkane, or an alkane with one or more substituents, or an H atom, Ar is an aromatic hydrocarbon or an aromatic hydrocarbon compound with one or more substituents, n is 1-4, X is 1-4, and Cl atoms are positioned on the same carbon atom or different carbon atoms.
In a preferred embodiment of the present invention, the metal bromide salt is one or more of magnesium bromide, zinc bromide, calcium bromide, copper bromide, sodium bromide, ferric bromide, lithium bromide, potassium bromide, ferrous bromide, aluminum bromide, and tin bromide.
In a preferred embodiment of the present invention, the metal bromide salt is one or a mixture of magnesium bromide and sodium bromide.
In a preferred embodiment of the invention, the brominated metal salt is industrially recycled brominated metal salt with various contents or metal salt with the mass content of more than 98%; the metal bromide salt is present as a solid or as an aqueous solution of the metal bromide salt.
In a preferred embodiment of the invention, the catalyst is a phase transfer catalyst.
In a preferred embodiment of the invention, the catalyst is a quaternary ammonium salt R1R2R3R4NX, Quaternary phosphonium salt R1R2R3R4One or two of PX are mixed, wherein R is1、R2、R3、R4Is C containing a C-H bond1-C20Is a straight-chain, branched or cyclic alkane, a phenylarene or a hydrogen atom, X is F, Cl, Br, I, HSO4Crown ethers, polyethers.
In a preferred embodiment of the present invention, the mass ratio of the organic chloride to the metal bromide salt is 1: 1 to 10.
In a preferred embodiment of the present invention, the amount of the catalyst added is 0 to 30% of the amount of the organochlorine compound.
In a preferred embodiment of the present invention, the temperature during the reaction is 80-300 ℃ and the pressure is 0.1 MPa-10 MPa.
The invention has the beneficial effects that: the method for preparing the organic bromide from the organic chloride generates metal chloride without environmental pollution, reduces the production cost, reduces the environmental pollution, greatly improves the operating environment, reduces harmful substances, and ensures that the prepared organic bromide contains more than 98 percent of purity, thereby being suitable for the preparation and synthesis of the monobromide and the production of polybrominated hydrocarbon and brominated aromatic hydrocarbon compounds such as dibromide, tribromide and the like.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the description of the embodiments are briefly introduced below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without inventive efforts, wherein:
FIG. 1 is a flow chart of the process of the present invention for preparing organic bromides from organic chlorides.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The first embodiment is as follows:
255g (2.5 mol) of magnesium bromide are added to 500g of water, stirred until completely dissolved, 19.32g (0.06 mol) of tetrabutylammonium bromide and 169.86g (2mol) of dichloromethane are added, the temperature is raised to 190 ℃ and the pressure is about 2-3 MPa. Stirring rapidly, and reacting for 5 h. Separating liquid, rectifying an organic phase, keeping the temperature at the top of the tower at 67 ℃, taking the material at 97 ℃, recovering light components (unreacted dichloromethane and 1-chloro-1-bromomethane), and taking the light components as raw materials to continue reaction. The yield of dibromomethane is 78 percent, and the GC content is more than 98 percent.
Example two:
an excess of a mixed salt of magnesium bromide and sodium bromide was added to 300g of water, stirred to be completely dissolved, and 6.83g (0.03 mol) of benzyltriethylammonium chloride and 92.57g (1 mol) of 1-chlorobutane were added. Heating to 180 deg.C and pressure of 2-2.5 MPa. Stirring rapidly, and reacting for 5 h. Separating, rectifying the organic phase, recovering the unreacted 1-chlorobutane, and continuing the reaction, wherein the yield of the 1-bromobutane is 75 percent, and the GC content is more than 98 percent.
Example three:
excess magnesium bromide and potassium chloride were added to 300g of water, stirred to complete dissolution, and 6.83g (0.03 mol) of benzyltriethylammonium chloride and 112.57g (1 mol) of chlorobenzene were added. The temperature is raised to 180 ℃ and the pressure is about 2-3 MPa. Stirring rapidly, and reacting for 6 h. Separating, rectifying the organic phase, recovering unreacted chlorobenzene, and continuing to react, wherein the yield of bromobenzene is 55%, and the GC content is more than 98%.
Example four:
125g (1.25 mol) of magnesium bromide were added to 300g of water, stirred until completely dissolved, and 9.66g (0.03 mol) of tetrabutylammonium bromide (TBAB) and 126.59g (1 mol) of benzyl chloride were added. Heating to 190 deg.C, and pressurizing to 2-3 MPa. Stirring rapidly, and reacting for 5 h. Separating, rectifying the organic phase, recovering unreacted benzyl chloride, and continuing the reaction, wherein the yield of benzyl bromide is 68%, and the GC content is more than 98%.
Example five:
255g (2.5 mol) of magnesium bromide were added to 300g of water, stirred until completely dissolved, and 9.66g (0.03 mol) of tetrabutylammonium bromide (TBAB) and 98.96g (1 mol) of 1, 2-dichloroethane were added. Heating to 180 deg.C and pressure of 2-3 MPa. Stirring rapidly, and reacting for 4 h. Separating, rectifying the organic phase, recovering the unreacted 1, 2-dichloroethane, and continuing the reaction, wherein the yield of the 1, 2-dibromoethane is 77 percent, and the GC content is more than 98 percent.
Example six:
255g (2.5 mol) of sodium bromide were added to 300g of water, stirred until completely dissolved, and 9.66g (0.03 mol) of tetrabutylammonium bromide (TBAB) and 141.04g (1 mol) of 1, 5-dichloropentane were added. Heating to 200 deg.C and pressure of 2-3 MPa. Stirring rapidly, and reacting for 4 h. Separating, rectifying the organic phase, recovering the unreacted 1, 5-dichloropentane, and continuing the reaction, wherein the yield of the 1, 5-dibromopentane is 81 percent, and the GC content is more than 98 percent.
Example seven:
357g (3.5 mol) of sodium bromide was added to 300g of water, stirred until completely dissolved, and 9.66g (0.03 mol) of tetrabutylammonium bromide (TBAB) and 119.38g (1 mol) of chloroform were added. The temperature is raised to 190 ℃ and the pressure is about 0.45 MPa. Stirring rapidly, and reacting for 4 h. Separating, rectifying the organic phase, recovering unreacted trichloromethane, and continuing to react, wherein the yield of the tribromomethane is 82%, and the GC content is more than 98%.
In modern industrial production, a large amount of brominated metal salt byproducts such as magnesium bromide and the like or waste brominated metal mixed salt can be generated. The method has the advantages of cheap and easily obtained raw materials, green and environment-friendly reaction, high yield and wide application range.
The method takes chloride and bromide metal salt as raw materials to synthesize bromide synthetic solution under the condition of high temperature and high pressure, then rectifies the synthetic solution to prepare bromide, and the rest of the rectified component is the raw material chloride or the mixture of the chloride and other bromide, and the rest of the component can be returned to the original component to continue the reaction. The method synthesizes the organic bromide, and meanwhile, the byproduct is the metal chloride salt, so that the raw materials are simple and easy to obtain, and the pollution is small. Bromine or acid is not used in the reaction, so that the diffusion of harmful substances in the air is reduced, the production environment is better, the pollution is less, the method can accord with the idea of modern green and environment-friendly production, simultaneously reduces the environment-friendly pollution discharge cost, improves the profit, and is more economic.
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications of equivalent structures and equivalent processes, which are made by the present specification, or directly or indirectly applied to other related technical fields, are included in the scope of the present invention.
Claims (10)
1. A method for preparing organic bromide from organic chloride is characterized by comprising the following steps: mixing and reacting organic chloride, brominated metal salt, a catalyst and water to obtain organic bromide synthetic liquid, and separating the organic bromide synthetic liquid to obtain the organic bromide.
2. The method of claim 1, wherein the organochlorine compound is R1R2CHCl、R1R2CHn-xClx、CCl4、ArClxWherein R is1、R2Is C containing a C-H bond1-C20The alkane is a straight-chain, branched-chain or cyclic alkane, or an alkane with one or more substituents, or an H atom, Ar is an aromatic hydrocarbon or an aromatic hydrocarbon compound with one or more substituents, n is 1-4, X is 1-4, and Cl atoms are positioned on the same carbon atom or different carbon atoms.
3. The method for preparing organic bromide from organic chloride according to claim 1, wherein the metal bromide salt is one or more of magnesium bromide, zinc bromide, calcium bromide, copper bromide, sodium bromide, ferric bromide, lithium bromide, potassium bromide, ferrous bromide, aluminum bromide and tin bromide.
4. The method for preparing organic bromide from organic chloride as claimed in claim 3, wherein the metal bromide salt is one or a mixture of magnesium bromide and sodium bromide.
5. The method for preparing organic bromide from organic chloride according to claim 1, wherein the metal bromide salt is industrially recycled metal bromide salt or metal salt with mass content of more than 98%; the metal bromide salt is present as a solid or as an aqueous solution of the metal bromide salt.
6. The method of claim 1, wherein the catalyst is a phase transfer catalyst.
7. The method for preparing organic bromide from chloride according to claim 6, wherein the catalyst is quaternary ammonium salt R1R2R3R4NX, Quaternary phosphonium salt R1R2R3R4One or two of PX are mixed, wherein R is1、R2、R3、R4Is C containing a C-H bond1-C20Is a straight-chain, branched or cyclic alkane, a phenylarene or a hydrogen atom, X is F, Cl, Br, I, HSO4Crown ethers, polyethers.
8. The method for preparing organic bromide from organic chloride according to claim 1, wherein the mass ratio of the organic chloride to the metal bromide salt is 1: 1 to 10.
9. The method for preparing organic bromide from organic chloride according to claim 1, wherein the amount of the catalyst added is 0-30% of the amount of the organic chloride.
10. The method for preparing organic bromide from organic chloride according to claim 1, wherein the temperature during the reaction is 80-300 ℃ and the pressure is 0.1 MPa-10 MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911266669.4A CN110922294A (en) | 2019-12-11 | 2019-12-11 | Method for preparing organic bromide from organic chloride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911266669.4A CN110922294A (en) | 2019-12-11 | 2019-12-11 | Method for preparing organic bromide from organic chloride |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110922294A true CN110922294A (en) | 2020-03-27 |
Family
ID=69858962
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911266669.4A Pending CN110922294A (en) | 2019-12-11 | 2019-12-11 | Method for preparing organic bromide from organic chloride |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110922294A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114605223A (en) * | 2022-04-08 | 2022-06-10 | 浙江永太科技股份有限公司 | Method for preparing 2,4, 5-trifluorobenzyl bromide by using 2,4, 5-trifluorobenzyl chloride |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07126198A (en) * | 1993-10-28 | 1995-05-16 | Mitsui Toatsu Chem Inc | Production of allyl bromides |
| JPH07138195A (en) * | 1993-11-16 | 1995-05-30 | Mitsui Toatsu Chem Inc | Production of allyl bromides |
| WO2008126106A2 (en) * | 2007-04-16 | 2008-10-23 | Manne Satyanarayana Reddy | Novel and improved processes for the preparation of intermediates of darifenacin, darifenacin and its pharmaceutically acceptable salts |
| CN105622382A (en) * | 2016-02-23 | 2016-06-01 | 苏州天马精细化学品股份有限公司 | Synthesis method of 5-bromo-2-chloro benzoic acid |
-
2019
- 2019-12-11 CN CN201911266669.4A patent/CN110922294A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07126198A (en) * | 1993-10-28 | 1995-05-16 | Mitsui Toatsu Chem Inc | Production of allyl bromides |
| JPH07138195A (en) * | 1993-11-16 | 1995-05-30 | Mitsui Toatsu Chem Inc | Production of allyl bromides |
| WO2008126106A2 (en) * | 2007-04-16 | 2008-10-23 | Manne Satyanarayana Reddy | Novel and improved processes for the preparation of intermediates of darifenacin, darifenacin and its pharmaceutically acceptable salts |
| CN105622382A (en) * | 2016-02-23 | 2016-06-01 | 苏州天马精细化学品股份有限公司 | Synthesis method of 5-bromo-2-chloro benzoic acid |
Non-Patent Citations (3)
| Title |
|---|
| RICHARD S. GIVENS ET AL.: "p-Hydroxyphenacyl photoremovable protecting groups — Robust photochemistry despite substituent diversity", 《CAN. J. CHEM.》 * |
| SCOTT C. BERK ET AL.: "Preparation and Reactions of Functionalized Benzylic Organometallics of Zinc and Copped", 《ORGANOMETALLICS》 * |
| SHEKAR MEKALA ET AL.: "A Scalable, Nonenzymatic Synthesis of Highly Stereopure Difunctional C4 Secondary Methyl Linchpin Synthons", 《J. ORG. CHEM.》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114605223A (en) * | 2022-04-08 | 2022-06-10 | 浙江永太科技股份有限公司 | Method for preparing 2,4, 5-trifluorobenzyl bromide by using 2,4, 5-trifluorobenzyl chloride |
| CN114605223B (en) * | 2022-04-08 | 2024-03-15 | 浙江永太科技股份有限公司 | Method for preparing 2,4, 5-trifluoro-benzyl bromide by using 2,4, 5-trifluoro-benzyl chloride |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Adimurthy et al. | An alternative method for the regio-and stereoselective bromination of alkenes, alkynes, toluene derivatives and ketones using a bromide/bromate couple | |
| US20040077901A1 (en) | Process for the synthesis of trifluorophenylacetic acids | |
| JP5724250B2 (en) | Process for producing 1,1,3-trichloro-1-propene | |
| CN1301210C (en) | Preparation of safety brominized reagent | |
| CN104016901B (en) | Aryl halide derivatives and synthesis method thereof | |
| CN112457153B (en) | Industrial preparation method of 2,4, 5-trifluoro-phenylacetic acid | |
| CN103980113A (en) | Preparation method of 4-bromophthalic acid | |
| CN110922294A (en) | Method for preparing organic bromide from organic chloride | |
| CN105669364A (en) | Method for synthesizing bromotoluene | |
| CN108002976B (en) | Preparation method of 1-fluoro-2-bromo-3-iodobenzene | |
| CN102964207A (en) | Preparation method of 2-bromo-3,3,3-trifluoropropene | |
| DE60219746T2 (en) | Process for the preparation of biaryl compounds | |
| CN110950778A (en) | Process and catalyst system for preparing aromatic malononitrile | |
| CN110845414A (en) | Preparation method and application of N-bis (dimethylamino) -1, 3-dimethylimidazoline | |
| WO2007052516A1 (en) | Process for production of biphenyl derivatives | |
| CN107641067B (en) | Alpha-bromination method of o-diketone | |
| Kim et al. | Direct preparation of arylmanganese bromides using active manganese | |
| CN110041176B (en) | Preparation method of thermosensitive paper sensitizer ethylene glycol diphenyl ether | |
| JP5219086B2 (en) | Process for producing trifluoromethylarenes | |
| JP6861060B2 (en) | Method for Producing 4,4'-Diiodot-3,3'-Dimethylbiphenyl | |
| CN110683949B (en) | Method for preparing 9, 10-phenanthrene dicarboxylic ester compound | |
| Das et al. | Bromination of alkenes and alkynes with (bromodimethyl) sulfonium bromide | |
| CN111362775B (en) | Synthesis method of 2-bromo-5-fluorobenzotrifluoride | |
| CN114920622B (en) | Technological method for preparing pentafluorobromide benzene | |
| US4239707A (en) | Novel 8-substituted bicyclo(3,2,)-octanes |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |