CN106957218A - A kind of solid phase synthesis process of PBBs ether monomer and application - Google Patents
A kind of solid phase synthesis process of PBBs ether monomer and application Download PDFInfo
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- CN106957218A CN106957218A CN201710169529.XA CN201710169529A CN106957218A CN 106957218 A CN106957218 A CN 106957218A CN 201710169529 A CN201710169529 A CN 201710169529A CN 106957218 A CN106957218 A CN 106957218A
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- solid phase
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- bromophenol
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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
- C07C41/09—Preparation of ethers by dehydration of compounds containing hydroxy groups
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Abstract
The invention discloses a kind of solid phase synthesis process of PBBs ether monomer and application, which solve the problem of synthetic method reaction time length in the prior art for PBDE, reagent corrosivity are big, it is cumbersome to post-process and need special equipment, with using the method that solid superacid as catalyst synthesizes PBDE under grinding condition, avoid using highly basic strong acidic liquid reagent, safe and clean environment firendly；Generated time is 10 30 minutes, compared with the effect that greatly shortens of reaction time of " salt compounded of iodine coupling two-step reaction method ".Its technical scheme is：Comprise the following steps：Bromophenol occurs to be dehydrated coupling reaction under the catalysis of solid super-strong acid, produces PBBs ether monomer.
Description
Technical field
The invention belongs to organic synthesis field, it is related to solid phase synthesis process and the application of a kind of PBBs ether monomer.
Background technology
PBDE is different with the position at place according to bromine atoms quantity, has 209 kinds of isomers, carries out as early as possible
The Environmental Studies of such compound, are beneficial to more comprehensively understand environmental behaviour and the home to return to of PBDEs, so as to do
Go out objective, reliably environmental risk assessment.
It is main at present that PBDE is synthesized using " salt compounded of iodine-coupling two-step reaction method ", such as SwedenMarsh
(Chemosphere,2008,74,421-427；Environ.Sci.Technol., 1999,33,3033-3037), Norway
Anne Fiksdahl (Tetrahedron, the 2006,62,3564-3572) and Zheng Kewen (CN101880220A of China；
CN101423463), " salt compounded of iodine-coupling two-step reaction method " synthetic method is that occur coupling instead by salt compounded of iodine and bromophenol
It should be made.The preparation of wherein salt compounded of iodine needs to use 65% oleum and 100% fuming nitric aicd, and the reaction time is small no less than 24
When, two kinds of sour concentration are to having reacted key effect (A of US 4440943).The oleum and fuming nitric aicd of high concentration are not
Easily prepare and preserve, there is also sizable danger for experimental implementation.In addition, being provided in Chinese patent ZL201510218577.4
A kind of microwave synthesis method of PBBs ether monomer, although avoid using highly acid solvent, but need specific micro-
Wave device, is unfavorable for the popularization production of PBDE.
In summary, in the prior art for PBDE synthetic method reaction time length, reagent corrosivity is big, after
The problem of processing is cumbersome and needs special equipment, still lacks effective solution.
The content of the invention
For technical problem present in above-mentioned prior art, the invention provides a kind of solid phase of PBBs ether monomer
Synthetic method, this method synthesis device is simple, the reaction time greatly shortens, while using solid super-strong acid, it is to avoid highly basic is strong
The use of acidic liquid reagent, safe, chemically react thorough and safety non-pollution.
In order to solve the above technical problems, the technical scheme is that：
A kind of solid phase synthesis process of PBBs ether monomer, comprises the following steps：Bromophenol is in solid super-strong acid
Catalysis is lower to occur dehydration coupling reaction, produces PBBs ether monomer.
Further, the dehydration coupling reaction is reacted under conditions of grinding.
Grinding can improve the contact area of solid super-strong acid and bromophenol, improve the reaction of bromophenol dehydration coupling
Speed and the extent of reaction.
Further, the time of griding reaction is 10-30min.
Further, the solid super-strong acid is SiO2-TiO2、SiO2-Zr2、SiO2-A12O3Or TiO2-ZrO3。
Further, the step of solid phase synthesis process also includes isolating and purifying product.
Further, it is described the step of isolate and purify for directly using silica gel column chromatography separation, the mobile phase used is
Linear paraffin CH3(CH2)nCH3, n=3,4,5,6.
Further, shown in the bromophenol structure such as formula (I)：
Wherein, m=1-5, and m is integer.
Further, the bromophenol be p bromophenol, 2,4- dibromophenols, 2,4,5- tribromphenols or 2,3,4,
5- tetrabromophenols.
Further, the mass ratio of the bromophenol and solid super-strong acid is 1:0.02-0.05.
Application of the above-mentioned solid phase synthetic method in PBBs ether monomer is prepared.
The preparation method synthetic route of PBDE of the present invention is as follows：
Beneficial effects of the present invention are：
1st, the present invention is using the method that solid superacid as catalyst synthesizes PBDE under grinding condition, it is to avoid using strong
Alkali strong acidic liquid reagent, safe and clean environment firendly；
2nd, the present invention is single step reaction, and generated time is 10-30 minutes, anti-compared with " salt compounded of iodine-coupling two-step reaction method "
Greatly shortened between seasonable；
3rd, the present invention is compared with microwave process for synthesizing Non-energy-consumption, it is not necessary to special equipment.
Brief description of the drawings
The Figure of description for constituting the part of the application is used for providing further understanding of the present application, and the application's shows
Meaning property embodiment and its illustrate be used for explain the application, do not constitute the improper restriction to the application.
Fig. 1 is 4 kinds of common PBDE structural formulas；
The proton nmr spectra of PBDE -47 that Fig. 2 synthesizes for the present invention；
The proton nmr spectra of PBDE -153 that Fig. 3 synthesizes for the present invention.
Specific embodiment
It is noted that described further below is all exemplary, it is intended to provide further instruction to the application.Unless another
Indicate, all technologies used herein and scientific terminology are with usual with the application person of an ordinary skill in the technical field
The identical meanings of understanding.
It should be noted that term used herein above is merely to describe embodiment, and be not intended to restricted root
According to the illustrative embodiments of the application.As used herein, unless the context clearly indicates otherwise, otherwise singulative
It is also intended to include plural form, additionally, it should be understood that, when in this manual using term "comprising" and/or " bag
Include " when, it indicates existing characteristics, step, operation, device, component and/or combinations thereof.
Term explains part：
Solid acid：Solid acid is the safe acids of solid of powder formulation, and the various safety of function are used by alternative part
Powder formulation organic complex is formed, and can substitute the acid such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, hydrofluoric acid.The acid strength of 100% sulfuric acid
During with Hammett acid strength function representations, its acid strength is H.=-11.9, by acid strength H.＜ -11.9 solid acid is referred to as solid
Body super acids.
Grinding：It is that a kind of unit that solid matter is turned into smaller particle is operated.
The separation principle of silica gel chromatography is different and separated, ordinary circumstance according to absorption affinity of the material on silica gel
Under, the larger material of polarity is easily by silica gel absorption, and the weaker material of polarity is difficult by silica gel absorption, and whole chromatography process is suction
Attached, desorption, the process adsorbed, desorbed again again.
The source of various materials herein：
Solid super-strong acid (SiO2-Zr2, p-methyl benzenesulfonic acid, SiO2-TiO2、SiO2-A12O3、TiO2-ZrO3), it is purchased from：Shanghai
With rich material Science and Technology Ltd.；
2,4- dibromophenols, p bromophenol, 2,4,5- tribromphenols, 2,3,4,5- tetrabromophenols are purchased from：Shanghai Aladdin
Reagent；
Linear paraffin CH3(CH2)nCH3(n=3,4,5,6), is purchased from：Shanghai Aladdin reagent；
Silica gel, is purchased from：Qingdao Haiyang silica gel factory.
Preparation by taking the preparation method of four kinds of common PBDEs (its structural formula is as shown in Figure 1) as an example to this paper below
Method is described further.
Embodiment 1
The preparation of tetrabromo Biphenyl Ether -47
By SiO2-Zr2(0.05g) and 2,4- dibromophenol (2.50g) are mixed in mortar, are ground 12 minutes, product silicon
Plastic column chromatography is separated, and pentane makees eluant, eluent, obtains white solid 2.16g, yield 89%.
Comparative example 1
SiO is distinguished as with embodiment 12-Zr2P-methyl benzenesulfonic acid is replaced with, is mixed in mortar, is ground 12 minutes, product
Separated with silica gel column chromatography, pentane does eluant, eluent, yield 39%.
Embodiment 2
The preparation of '-dibromobiphenyl ether -18
By SiO2-TiO2(0.05g) and p bromophenol (1.73g) are mixed in mortar, are ground 20 minutes, product silica gel
Column chromatography for separation, n-hexane makees eluant, eluent, obtains white solid 1.34g, yield 82%.
Embodiment 3
The preparation of hexabromobiphenyl ether -153
SiO2-A12O3(0.10g) and 2,4,5- tribromphenols (3.30g) are mixed in mortar, are ground 30 minutes, and product is used
Silica gel column chromatography is separated, and normal heptane is cooked eluant, eluent, obtains white solid 2.54g, yield 79%.
Embodiment 4
The preparation of octa-BDE -185
TiO2-ZrO3(0.075g) and 2,3,4,5- tetrabromophenols (4.10g) are mixed in mortar, are ground 30 minutes, product
Separated with silica gel column chromatography, pentane makees eluant, eluent, obtain white solid 3.00g, yield 75%.
The preferred embodiment of the application is the foregoing is only, the application is not limited to, for the skill of this area
For art personnel, the application can have various modifications and variations.It is all within spirit herein and principle, made any repair
Change, equivalent, improvement etc., should be included within the protection domain of the application.
Claims (10)
1. a kind of solid phase synthesis process of PBBs ether monomer, it is characterised in that：Comprise the following steps：Bromophenol is in solid
Dehydration coupling reaction occurs under the catalysis of super acids, PBBs ether monomer is produced.
2. solid phase synthesis process according to claim 1, it is characterised in that：The dehydration coupling reaction is the bar in grinding
Reacted under part.
3. solid phase synthesis process according to claim 2, it is characterised in that：The time of griding reaction is 10-30min.
4. solid phase synthesis process according to claim 1, it is characterised in that：The solid super-strong acid is SiO2-TiO2、
SiO2-Zr2、SiO2-A12O3Or TiO2-ZrO3。
5. solid phase synthesis process according to claim 1, it is characterised in that：The solid phase synthesis process also includes to product
The step of being isolated and purified.
6. solid phase synthesis process according to claim 6, it is characterised in that：Described is directly utilization the step of isolate and purify
Silica gel column chromatography is separated, and the mobile phase used is linear paraffin CH3(CH2)nCH3, n=3,4,5,6.
7. solid phase synthesis process according to claim 1, it is characterised in that：The bromophenol structure such as formula (I) institute
Show：
Wherein, m=1-5, and m is integer.
8. solid phase synthesis process according to claim 7, it is characterised in that：The bromophenol is p bromophenol, 2,4-
Dibromophenol, 2,4,5- tribromphenols or 2,3,4,5- tetrabromophenols.
9. solid phase synthesis process according to claim 1, it is characterised in that：The matter of the bromophenol and solid super-strong acid
Amount is than being 1:0.02-0.05.
10. application of any solid phase synthesis process of claim 1-9 in PBBs ether monomer is prepared.
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| CN201710169529.XA CN106957218B (en) | 2017-03-21 | 2017-03-21 | Solid-phase synthesis method and application of polybrominated diphenyl ether monomer |
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| CN201710169529.XA CN106957218B (en) | 2017-03-21 | 2017-03-21 | Solid-phase synthesis method and application of polybrominated diphenyl ether monomer |
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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 |
-
2017
- 2017-03-21 CN CN201710169529.XA patent/CN106957218B/en active Active
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 (2)
| Title |
|---|
| 张应鹏等: "研磨法运用于固相有机合成中的新进展", 《江西化工》 * |
| 服部英等: "《固体酸催化》", 31 May 2016, 复旦大学出版社 * |
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