CN113548948A - Preparation method of methyl octabromoether - Google Patents
Preparation method of methyl octabromoether Download PDFInfo
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- CN113548948A CN113548948A CN202110943319.8A CN202110943319A CN113548948A CN 113548948 A CN113548948 A CN 113548948A CN 202110943319 A CN202110943319 A CN 202110943319A CN 113548948 A CN113548948 A CN 113548948A
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- octabromoether
- tetrabromobisphenol
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- 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
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Abstract
The invention belongs to the technical field of organic synthesis, and particularly relates to a preparation method of methyl octabromo ether, which takes tetrabromobisphenol A-bis (2-methyl) allyl ether as a raw material to prepare the methyl octabromo ether under the catalysis system of N-bromosuccinimide (NBS), an auxiliary agent and a catalyst, wherein the yield is more than or equal to 98.6%, and the purity is more than or equal to 99.0%; the method for synthesizing methyl octabromoether is simple and convenient to operate and high in selectivity, bromine is not required to be used as an initial raw material, and the process safety is better; high product yield and good product quality.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to a preparation method of methyl octabromoether.
Background
Methyl octabromoether is also called tetrabromobisphenol A-bis (2, 3-dibromo (methyl) propyl) ether, is an important variety in bromine flame retardants, and is a high-molecular organic flame retardant with aromatic bromine and aliphatic bromine. The product is white crystal powder, can be dissolved in organic solvent such as acetone and ester, and has good stability to heat and ultraviolet light. The product has a flame retardant effect higher than that of a brominated aromatic flame retardant, has excellent thermal stability, can ensure safer processing equipment and more excellent product performance, and is particularly suitable for plastic products processed at higher temperature.
In the prior art, a plurality of methods for synthesizing methyl octabromoether are reported, and patent CN202110141249.4 reports that tetrabromobisphenol A-bis (2-methyl) allyl ether is used as a raw material and bromine (Br)2) Is a brominating reagent, and titanium tetrachloride or stannic chloride is used as a synthesis route of the catalyst; patent CN201811398873.7 discloses a method for preparing methyl octabromoether by using tetrabromobisphenol A-bis (2-methyl) allyl ether as a raw material, HBr/NaBr as a catalyst, bromopyridine, tribromotetrabutylammonium bromide and the like as brominating reagents; patent CN201610178997.9 reports synthesis of methyl octabromo ether from tetrabromobisphenol A-bis (2-methyl) allyl ether as raw material and hydrobromic acid and hydrogen peroxide as bromination system; the patent US4302614 reports that tetrabromobisphenol a-bis (2-methyl) allyl ether is used as raw material and reacts with bromine to prepare methyl octabromo ether.
The method for preparing methyl octabromoether by the method has the problems that highly corrosive fuming liquid and air pollutant bromine are required to be used, the preparation method is complex and the like.
Disclosure of Invention
In order to solve the problems, the invention discloses a preparation method of methyl octabromoether, which does not need to use bromine as an initial raw material and has simple preparation method.
In order to achieve the purpose, the invention provides the following technical scheme:
the preparation method of methyl octabromoether is characterized by comprising the following steps: tetrabromobisphenol A-bis (2-methyl) allyl ether, N-bromosuccinimide (NBS), an auxiliary agent and a catalyst are added into a solvent, the catalyst and the NBS react under the promotion of the auxiliary agent to generate a high-valence iodine bromine compound in situ, and then the high-valence iodine bromine compound reacts with the tetrabromobisphenol A-bis (2-methyl) allyl ether to obtain methyl octabromo ether.
Further, the molar ratio of the auxiliary agent to the tetrabromobisphenol A-bis (2-methyl) allyl ether is 0.02-0.06: 1.
Further, the auxiliary agent is one or more of lithium bromide, ammonium bromide and ammonium chloride.
Further, the molar ratio of the catalyst to tetrabromobisphenol A-bis (2-methyl) allyl ether is 0.03-0.08: 1.
Further, the catalyst is one or more of N-methyl o-iodobenzamide, N-benzyl o-iodobenzamide, N-phenyl o-iodobenzamide and N-tert-butyl o-iodobenzamide.
Further, the molar ratio of NBS to tetrabromobisphenol A-bis (2-methyl) allyl ether is 3.95 to 4.3: 1.
Further, the mass ratio of the solvent to the tetrabromobisphenol A-bis (2-methyl) allyl ether is 1.05-1.60: 1.
Further, the solvent is one or more of 1, 2-dichloroethane, dichloromethane and chloroform.
Further, the temperature of the reaction is 10-30 ℃.
Further, the reaction time is 3-10 h.
Compared with the prior art, the invention has the following advantages and beneficial effects:
the preparation method of methyl octabromoether provided by the invention has the advantages that (1) bromine is not required to be used as an initial raw material, and the process safety is better; (2) high product yield and good product quality.
Drawings
FIG. 1 shows the chemical reaction formula of the synthesis of methyl octabromoether.
FIG. 2 is a liquid chromatography detection chromatogram of methyl octabromoether prepared in example 1 of the present invention.
FIG. 3 is a liquid chromatography detection chromatogram of methyl octabromoether prepared in comparative example 1 of the present invention.
Detailed Description
The technical solutions provided by the present invention will be described in detail below with reference to specific examples, and it should be understood that the following specific embodiments are only illustrative of the present invention and are not intended to limit the scope of the present invention.
Example 1:
652.06g of tetrabromobisphenol A-bis (2-methyl) allyl ether, 747.52g of NBS, 15.66g N-methyl o-iodobenzamide, 3.05g of NH4Cl and 1000g of 1, 2-dichloroethane react in a reaction kettle at 25 ℃ for 5 hours, and after the reaction is finished, methyl octabromoether is obtained by separation, the yield of the product is 98.6 percent, and the purity is 99.7 percent.
Example 2:
652.06g of tetrabromobisphenol A-bis (2-methyl) allyl ether, 731.92g of NBS, 13.66g N-methyl o-iodobenzamide, 3.55g of NH4Br and 1000g of dichloromethane are put into a reaction kettle to react for 6 hours at 15 ℃, and after the reaction is finished, methyl octabromoether is obtained by separation, the yield of the product is 98.7 percent, and the purity is 99.6 percent.
Example 3:
652.06g of tetrabromobisphenol A-bis (2-methyl) allyl ether, 705.96g of NBS, 20.23g N-benzyl o-iodobenzamide, 2.67g of NH4Cl, 300g of 1, 2-dichloroethane and 600g of chloroform are put in a reaction kettle to react for 9 hours at 20 ℃, and after the reaction is finished, methyl octabromoether is obtained by separation, the yield of the product is 98.8 percent, and the purity is 99.1 percent.
Example 4:
652.06g of tetrabromobisphenol A-bis (2-methyl) allyl ether, 705.88g of NBS, 16.86g N-benzyl o-iodobenzamide, 4.90g of NH4Br, 700g of 1, 2-dichloroethane and 200g of dichloromethane are put in a reaction kettle to react for 5 hours at 25 ℃, and after the reaction is finished, methyl octabromoether is obtained by separation, the yield of the product is 98.7 percent, and the purity is 99.2 percent.
Example 5:
652.06g of tetrabromobisphenol A-bis (2-methyl) allyl ether, 711.12g of NBS, 12.93g N-phenylo-iodobenzamide, 2.94g of NH4Br and 700g of 1, 2-dichloroethane are put in a reaction kettle to react for 5 hours at 20 ℃, and after the reaction is finished, methyl octabromoether is obtained by separation, the yield of the product is 99.0 percent, and the purity is 99.2 percent.
Example 6:
652.06g of tetrabromobisphenol A-bis (2-methyl) allyl ether, 708.58g of NBS, 15.16g N-tert-butyl o-iodobenzamide, 3.92g of NH4Br and 750g of chloroform are put into a reaction kettle to react for 4.5 hours at the temperature of 22 ℃, and after the reaction is finished, methyl octabromoether is obtained by separation, the yield of the product is 99.0 percent, and the purity is 99.7 percent.
Example 7:
652.06g of tetrabromobisphenol A-bis (2-methyl) allyl ether, 707.98g of NBS, 7.20g N-tert-butyl o-iodobenzamide, 6.50g N-phenyl o-iodobenzamide, 2.99g of NH4Br and 860g of 1, 2-dichloroethane are put in a reaction kettle to react for 4.5 hours at 22 ℃, and after the reaction is finished, methyl octabromoether is obtained by separation, the yield of the product is 99.0 percent, and the purity is 99.2 percent.
Example 8:
652.06g of tetrabromobisphenol A-bis (2-methyl) allyl ether, 726.58g of NBS, 5.20g N-tert-butyl o-iodobenzamide, 3.50g N-phenyl o-iodobenzamide, 2.60g N-benzyl o-iodobenzamide, 2.99g of NH4Br and 860g of chloroform are put into a reaction kettle to react for 6 hours at 25 ℃, and after the reaction is finished, methyl octabromoether is obtained by separation, the yield of the product is 99.1 percent, and the purity is 99.5 percent.
Example 9:
652.06g of tetrabromobisphenol A-bis (2-methyl) allyl ether, 712.58g of NBS, 7.05g N-methyl o-iodobenzamide, 6.80g N-benzyl o-iodobenzamide, and 1.08g of NH4Br、1.20g NH4Cl and 1000g of 1, 2-dichloroethane react in a reaction kettle at 28 ℃ for 4.0 hours, and after the reaction is finished, methyl octabromoether is obtained by separation, the yield of the product is 99.1 percent, and the purity is 99.3 percent.
Comparative example 1
652.06g of tetrabromobisphenol A-bis (2-methyl) allyl ether and 1000g of 1, 2-dichloroethane are put into a reaction kettle, 747.52g of bromine is added (slowly dropwise added), reaction is carried out for 5 hours at 25 ℃, and after the reaction is finished, methyl octabromo ether is obtained by separation, wherein the yield of the product is 94.8%, and the purity is 95.6%.
Performing liquid chromatography detection on the products of example 1 and comparative example 1, wherein the liquid chromatography spectrogram of the product of example 1 is shown in figure 2, and the corresponding components, retention time and peak area are shown in table 1; the liquid chromatography spectrum of the product of comparative example 1 is shown in fig. 3, and the corresponding components, retention times and peak areas are shown in table 2.
TABLE 1 detection of liquid chromatogram of methyl octabromoether prepared in example 1 (area normalization method)
TABLE 2 detection of liquid chromatogram of methyl octabromoether prepared in comparative example 1 (area normalization method)
Comparison of the results of liquid chromatography measurements of the corresponding products prepared in example 1 and comparative example 1 shows that: the product prepared in the embodiment 1 has high purity, few impurity types and high product quality; the product prepared by the comparative example 1 has lower purity and more impurity types.
The technical means disclosed in the invention scheme are not limited to the technical means disclosed in the above embodiments, but also include the technical scheme formed by any combination of the above technical features. It should be noted that those skilled in the art can make various improvements and modifications without departing from the principle of the present invention, and such improvements and modifications are also considered to be within the scope of the present invention.
Claims (10)
1. The preparation method of methyl octabromoether is characterized by comprising the following steps: tetrabromobisphenol A-bis (2-methyl) allyl ether, N-bromosuccinimide (NBS), an auxiliary agent and a catalyst are added into a solvent to react to obtain the methyl octabromo ether.
2. The method for preparing methyl octabromo ether according to claim 1, wherein the molar ratio of said adjuvant to tetrabromobisphenol a-bis (2-methyl) allyl ether is 0.02-0.06: 1.
3. The method for preparing methyl octabromoether according to claim 2, wherein the auxiliary agent is one or more of lithium bromide, ammonium bromide and ammonium chloride.
4. The method for preparing methyl octabromo ether according to claim 1, wherein the molar ratio of said catalyst to tetrabromobisphenol a-bis (2-methyl) allyl ether is 0.03-0.08: 1.
5. The method for preparing methyl octabromoether according to claim 4, wherein the catalyst is one or more of N-methyl o-iodobenzamide, N-benzyl o-iodobenzamide, N-phenyl o-iodobenzamide and N-tert-butyl o-iodobenzamide.
6. The method of claim 1, wherein the molar ratio of NBS to tetrabromobisphenol A bis (2-methyl) allyl ether is 3.95-4.3: 1.
7. The method for preparing methyl octabromo ether according to claim 1, wherein the mass ratio of said solvent to tetrabromobisphenol a-bis (2-methyl) allyl ether is 1.05-1.60: 1.
8. The method for preparing methyl octabromoether according to claim 7, wherein the solvent is one or more of 1, 2-dichloroethane, dichloromethane and chloroform.
9. The method for preparing methyl octabromoether according to claim 1, wherein the reaction temperature is 10-30 ℃.
10. The method for preparing methyl octabromoether according to claim 1, wherein the reaction time is 3-10 h.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1210100A (en) * | 1997-08-22 | 1999-03-10 | 帝人化成株式会社 | Bromine compound production method |
| CN109796315A (en) * | 2019-02-22 | 2019-05-24 | 山东兄弟科技股份有限公司 | A kind of preparation method of high heat stability sex flame retardant methyl eight bromo ether |
| CN111187470A (en) * | 2020-02-17 | 2020-05-22 | 南京师范大学 | Efficient flame-retardant polypropylene flame-retardant master batch and preparation method and application thereof |
| CN112830868A (en) * | 2021-02-02 | 2021-05-25 | 山东迈特新材料科技有限公司 | Preparation method of high-purity methyl octabromoether |
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- 2021-08-17 CN CN202110943319.8A patent/CN113548948B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1210100A (en) * | 1997-08-22 | 1999-03-10 | 帝人化成株式会社 | Bromine compound production method |
| CN109796315A (en) * | 2019-02-22 | 2019-05-24 | 山东兄弟科技股份有限公司 | A kind of preparation method of high heat stability sex flame retardant methyl eight bromo ether |
| CN111187470A (en) * | 2020-02-17 | 2020-05-22 | 南京师范大学 | Efficient flame-retardant polypropylene flame-retardant master batch and preparation method and application thereof |
| CN112830868A (en) * | 2021-02-02 | 2021-05-25 | 山东迈特新材料科技有限公司 | Preparation method of high-purity methyl octabromoether |
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