CN106957218B - Solid-phase synthesis method and application of polybrominated diphenyl ether monomer - Google Patents
Solid-phase synthesis method and application of polybrominated diphenyl ether monomer Download PDFInfo
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Abstract
The invention discloses a solid-phase synthesis method and application of a polybrominated diphenyl ether monomer, which solve the problems of long reaction time, high reagent corrosivity, complex post-treatment and special equipment requirement of the synthesis method of the polybrominated diphenyl ether in the prior art, and have the advantages that the method for synthesizing the polybrominated diphenyl ether under the catalysis of solid super acid under the grinding condition is adopted, the use of strong base and strong acid liquid reagents is avoided, the safety is high, and the method is clean and environment-friendly; the synthesis time is 10-30 minutes, and the reaction time is greatly shortened compared with the reaction time of an iodonium salt-coupling two-step reaction method. The technical scheme is as follows: the method comprises the following steps: the bromophenol is subjected to dehydration coupling reaction under the catalysis of solid super acid, and the polybrominated diphenyl ether monomer is obtained.
Description
Technical Field
The invention belongs to the field of organic synthesis, and relates to a solid-phase synthesis method and application of a polybrominated diphenyl ether monomer.
Background
The polybrominated diphenyl ether has 209 isomers according to the number and the position of bromine atoms, so that the environmental research of the compound is developed as soon as possible, the environmental behavior and the homing of the polybrominated diphenyl ether can be more comprehensively known, and the objective and reliable environmental risk evaluation can be made.
At present, the synthesis of polybrominated diphenyl ethers, such as Swedish, is mainly carried out by an iodonium salt-coupling two-step reaction method
Marsh (Chemosphere,2008,74, 421-. Wherein the preparation of iodonium salts requires 65% fuming sulfuric acid and 100% fuming nitric acid, the reaction time is not less than 24 hours, and the concentrations of the two acids play a critical role in the reaction (US 4440943A). High-concentration fuming sulfuric acid and fuming nitric acid are not easy to prepareIn addition, Chinese patent Z L201510218577.4 provides a microwave synthesis method of polybrominated diphenyl ether monomer, which avoids using strong acid solvent, but needs specific microwave equipment, thus being not beneficial to the popularization and production of polybrominated diphenyl ether.
In summary, in the prior art, an effective solution is still lacking for the problems of long reaction time, high reagent corrosivity, complicated post-treatment and the need for special equipment in the synthesis method of polybrominated diphenyl ethers.
Disclosure of Invention
Aiming at the technical problems in the prior art, the invention provides a solid-phase synthesis method of a polybrominated diphenyl ether monomer, which has the advantages of simple synthesis equipment, greatly shortened reaction time, use of solid super acid, avoidance of use of strong base and strong acid liquid reagents, high safety, thorough chemical reaction, safety and no pollution.
In order to solve the technical problems, the technical scheme of the invention is as follows:
a solid phase synthesis method of polybrominated diphenyl ether monomers comprises the following steps: the bromophenol is subjected to dehydration coupling reaction under the catalysis of solid super acid, and the polybrominated diphenyl ether monomer is obtained.
Further, the dehydration coupling reaction is carried out under grinding conditions.
The grinding can improve the contact area of the solid super acid and the bromophenol and improve the reaction rate and the reaction degree of the dehydration coupling of the bromophenol.
Furthermore, the time of the grinding reaction is 10-30 min.
Further, the solid super acid is SiO2-TiO2、SiO2-Zr2、SiO2-A12O3Or TiO2-ZrO3。
Further, the solid phase synthesis method also comprises the step of separating and purifying the product.
Further, the separation and purification steps are directly separating by silica gel column chromatography and using flowThe phase is straight-chain alkane CH3(CH2)nCH3，n＝3,4,5,6。
Further, the structure of the bromophenol is shown as the general formula (I):
wherein m is 1-5, and m is an integer.
Further, the bromophenol is p-bromophenol, 2, 4-dibromophenol, 2,4, 5-tribromophenol, or 2,3,4, 5-tetrabromophenol.
Further, the mass ratio of the bromophenol to the solid superacid is 1: 0.02-0.05.
The solid phase synthesis method is applied to the preparation of the polybrominated diphenyl ether monomer.
The synthetic route of the preparation method of the polybrominated diphenyl ether is as follows:
the invention has the beneficial effects that:
1. the method for synthesizing polybrominated diphenyl ethers under the catalysis of the solid super acid under the grinding condition is adopted, the use of strong base and strong acid liquid reagents is avoided, and the method is high in safety, clean and environment-friendly;
2. the invention is a one-step reaction, the synthesis time is 10-30 minutes, and the reaction time is greatly shortened compared with the reaction time of an iodonium salt-coupling two-step reaction method;
3. compared with microwave synthesis, the method has no energy consumption and does not need special equipment.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the application and, together with the description, serve to explain the application and are not intended to limit the application.
FIG. 1 shows the structural formula of 4 common polybrominated diphenyl ethers;
FIG. 2 is a hydrogen nuclear magnetic resonance spectrum of polybrominated diphenyl ether-47 synthesized by the present invention;
FIG. 3 shows the hydrogen nuclear magnetic resonance spectrum of polybrominated diphenyl ether-153 synthesized by the present invention.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the disclosure. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments according to the present application. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
Term interpretation section:
solid acid: the solid acid is a solid safe acid of a powder preparation, is organically compounded by various safe powder preparations which can replace part of using functions, and can replace acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, hydrofluoric acid and the like. The acid strength of 100% sulfuric acid is H when it is expressed as a Hammett acid strength function. Acid strength H ═ 11.9. Solid acids < -11.9 are referred to as solid superacids.
Grinding: is a unit operation that converts solid matter into smaller particles.
The separation principle of silica gel chromatography is to separate substances according to different adsorption forces of the substances on silica gel, generally, substances with larger polarity are easy to be adsorbed by silica gel, substances with weaker polarity are not easy to be adsorbed by silica gel, and the whole chromatography process is a process of adsorption, desorption, re-adsorption and re-desorption.
Sources of various materials herein:
solid super acid (SiO)2-Zr2P-toluenesulfonic acid, SiO2-TiO2、SiO2-A12O3、TiO2-ZrO3) Purchased from: shanghai Tongbo materials science and technology, Inc.;
2, 4-dibromophenol, p-bromophenol, 2,4, 5-tribromophenol, 2,3,4, 5-tetrabromophenol, available from: shanghai avastin reagent;
straight chain alkane CH3(CH2)nCH3(n-3, 4,5,6) from: shanghai avastin reagent;
silica gel, available from: qingdao ocean silica gel factory.
The preparation method of four common polybrominated diphenyl ethers (the structural formula of which is shown in figure 1) is further described as an example.
Example 1
Preparation of tetrabromobisphenol-47
Mixing SiO2-Zr2(0.05g) and 2, 4-dibromophenol (2.50g) were mixed well in a mortar, triturated for 12 minutes, and the product was chromatographed on a silica gel column using n-pentane as the eluent to give 2.16g of a white solid in 89% yield.
Comparative example 1
The difference from example 1 is SiO2-Zr2The replacement was replaced with p-toluenesulfonic acid, mixed well in a mortar, ground for 12 minutes, and the product was chromatographed on a silica gel column with n-pentane as the eluent in 39% yield.
Example 2
Preparation of dibromodiphenyl ether-18
Mixing SiO2-TiO2(0.05g) and p-bromophenol (1.73g) were mixed in a mortar and ground for 20 minutes, and the product was separated by silica gel column chromatography using n-hexane as an eluent to give 1.34g of a white solid in 82% yield.
Example 3
Preparation of hexabromodiphenyl ether-153
SiO2-A12O3(0.10g) and 2,4, 5-tribromophenol (3.30g) were mixed well in a mortar and triturated for 30 minutes, the product was separated by column chromatography over silica gel with n-heptane as eluent to give 2.54g of a white solid in 79% yield.
Example 4
Preparation of octabromodiphenyl ether-185
TiO2-ZrO3(0.075g) and 2,3,4, 5-tetrabromophenol (4.10g) were mixed well in a mortar and triturated for 30 minutes, and the product was chromatographed on a silica gel column using n-pentane as the eluent to give 3.00g of a white solid in 75% yield.
The above description is only a preferred embodiment of the present application and is not intended to limit the present application, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present application shall be included in the protection scope of the present application.
Claims (6)
1. A solid phase synthesis method of polybrominated diphenyl ether monomer is characterized in that: the method comprises the following steps: the bromophenol is subjected to dehydration coupling reaction under the catalysis of solid super acid to obtain a polybrominated diphenyl ether monomer;
the dehydration coupling reaction is carried out under the grinding condition, and the grinding reaction time is 10-30 min;
the solid super acid is SiO2-TiO2、SiO2-A12O3Or TiO2-ZrO3；
The mass ratio of the bromophenol to the solid superacid is 1: 0.02-0.05.
2. The solid phase synthesis method of claim 1, wherein: the solid phase synthesis method also comprises the step of separating and purifying the product.
3. The solid phase synthesis method of claim 2, wherein: the separation and purification steps are that silica gel column chromatography is directly utilized for separation, and the used mobile phase is straight-chain alkane CH3(CH2)nCH3，n = 3, 4, 5, 6。
4. The solid phase synthesis method of claim 1, wherein: the structure of the bromophenol is shown as a general formula (I):
（Ⅰ）
wherein m =1-5, and m is an integer.
5. The solid phase synthesis method of claim 4, wherein: the bromophenol is p-bromophenol, 2, 4-dibromophenol, 2,4, 5-tribromophenol or 2,3,4, 5-tetrabromophenol.
6. Use of the solid phase synthesis method according to any one of claims 1 to 5 for the preparation of polybrominated diphenyl ether monomers.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4453017A (en) * | 1982-04-01 | 1984-06-05 | International Telephone And Telegraph Corporation | Process for the methylation of phenolic compounds with trimethyl phosphate |
| CN104292082A (en) * | 2014-09-05 | 2015-01-21 | 中国科学院青岛生物能源与过程研究所 | Preparation method for hydroquinone monoether compound |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4453017A (en) * | 1982-04-01 | 1984-06-05 | International Telephone And Telegraph Corporation | Process for the methylation of phenolic compounds with trimethyl phosphate |
| CN104292082A (en) * | 2014-09-05 | 2015-01-21 | 中国科学院青岛生物能源与过程研究所 | Preparation method for hydroquinone monoether compound |
Non-Patent Citations (1)
| Title |
|---|
| 研磨法运用于固相有机合成中的新进展;张应鹏等;《江西化工》;20080630(第2期);13-14页 * |
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