CN104761510B - Synthesis method of 2,4,6-tris(2,4,6-tribromophenoxy)-1,3,5-triazine - Google Patents
Synthesis method of 2,4,6-tris(2,4,6-tribromophenoxy)-1,3,5-triazine Download PDFInfo
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- CN104761510B CN104761510B CN201510217627.7A CN201510217627A CN104761510B CN 104761510 B CN104761510 B CN 104761510B CN 201510217627 A CN201510217627 A CN 201510217627A CN 104761510 B CN104761510 B CN 104761510B
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- tribromophenoxy
- triazines
- methylimidazole
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- BDFBPPCACYFGFA-UHFFFAOYSA-N 2,4,6-tris(2,4,6-tribromophenoxy)-1,3,5-triazine Chemical compound BrC1=CC(Br)=CC(Br)=C1OC1=NC(OC=2C(=CC(Br)=CC=2Br)Br)=NC(OC=2C(=CC(Br)=CC=2Br)Br)=N1 BDFBPPCACYFGFA-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 238000001308 synthesis method Methods 0.000 title abstract 3
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 claims abstract description 17
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000002904 solvent Substances 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 12
- BSWWXRFVMJHFBN-UHFFFAOYSA-N 2,4,6-tribromophenol Chemical group OC1=C(Br)C=C(Br)C=C1Br BSWWXRFVMJHFBN-UHFFFAOYSA-N 0.000 claims abstract description 11
- 150000007529 inorganic bases Chemical class 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 30
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Substances ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 16
- 238000005660 chlorination reaction Methods 0.000 claims description 11
- 238000010189 synthetic method Methods 0.000 claims description 11
- 239000002608 ionic liquid Substances 0.000 claims description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 3
- MVPPADPHJFYWMZ-IDEBNGHGSA-N chlorobenzene Chemical group Cl[13C]1=[13CH][13CH]=[13CH][13CH]=[13CH]1 MVPPADPHJFYWMZ-IDEBNGHGSA-N 0.000 claims description 2
- NCSHGROOCJHAFK-UHFFFAOYSA-N [Cl].N#CC#N Chemical compound [Cl].N#CC#N NCSHGROOCJHAFK-UHFFFAOYSA-N 0.000 claims 1
- 238000005829 trimerization reaction Methods 0.000 claims 1
- 239000002351 wastewater Substances 0.000 abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000000047 product Substances 0.000 description 11
- 239000007788 liquid Substances 0.000 description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 230000002378 acidificating effect Effects 0.000 description 8
- 239000012065 filter cake Substances 0.000 description 8
- 150000002500 ions Chemical class 0.000 description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 7
- 239000003513 alkali Substances 0.000 description 6
- 150000008422 chlorobenzenes Chemical class 0.000 description 6
- -1 inorganic base Salt Chemical class 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 238000009413 insulation Methods 0.000 description 4
- 238000012544 monitoring process Methods 0.000 description 4
- 235000002639 sodium chloride Nutrition 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 150000001805 chlorine compounds Chemical class 0.000 description 3
- 239000003063 flame retardant Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- YWDUZLFWHVQCHY-UHFFFAOYSA-N 1,3,5-tribromobenzene Chemical class BrC1=CC(Br)=CC(Br)=C1 YWDUZLFWHVQCHY-UHFFFAOYSA-N 0.000 description 2
- OUCSIUCEQVCDEL-UHFFFAOYSA-N 2,3,4-tribromophenol Chemical compound OC1=CC=C(Br)C(Br)=C1Br OUCSIUCEQVCDEL-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 2
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229910017053 inorganic salt Inorganic materials 0.000 description 2
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N methylimidazole Natural products CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 description 2
- 150000007530 organic bases Chemical class 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- GNXVDBYKPKQXFU-UHFFFAOYSA-N 1-methylimidazole;phenol Chemical compound CN1C=CN=C1.OC1=CC=CC=C1 GNXVDBYKPKQXFU-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- YFQFTOCCYRNGIY-UHFFFAOYSA-N Br[N] Chemical compound Br[N] YFQFTOCCYRNGIY-UHFFFAOYSA-N 0.000 description 1
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- GNHQSAUHXKRQMC-UHFFFAOYSA-N benzene;chlorine Chemical compound [Cl].C1=CC=CC=C1 GNHQSAUHXKRQMC-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229920005669 high impact polystyrene Polymers 0.000 description 1
- 239000004797 high-impact polystyrene Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003444 phase transfer catalyst Substances 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 150000004714 phosphonium salts Chemical class 0.000 description 1
- 125000004193 piperazinyl group Chemical group 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
- C07D251/30—Only oxygen atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
The invention discloses a synthesis method of 2,4,6-tris(2,4,6-tribromophenoxy)-1,3,5-triazine. The method includes the steps that N-methylimidazole and 2,4,6-tribromophenol form salt when a solvent exists or no solvent exists, then, N-methylimidazole and 2,4,6-tribromophenol react with tricyanogen chloride, and the 2,4,6-tris(2,4,6-tribromophenoxy)-1,3,5-triazine is obtained. According to the synthesis method, inorganic base is not needed, no waste water with inorganic base is generated, and the method is an atom-economical and pollution-free method for preparing the 2,4,6-tris(2,4,6-tribromophenoxy)-1,3,5-triazine.
Description
Technical field
The present invention relates to chemosynthesis technical field, and in particular to a kind of (2,4, the 6- tribromo-benzene oxygen of fire retardant 2,4,6- tri-
Base) -1,3,5- triazines synthetic method.
Background technology
2,4,6- tri- (2,4,6- tribromophenoxy) -1,3,5-triazines (CAS No 25713-60-4), also known as three (tribromos
Phenoxy group) cyanurate, it is a kind of fire retardant (abbreviation FR245) of bromo- nitrogen collaboration, flame retarding efficiency is high, and heat stability is good, is difficult
Volatilization is separated out, white appearance, and anti-ultraviolet radiation and light resistance are superior, and shock resistance and processing characteristics are good, is particularly well-suited to have
The plastics such as ABS, PBT, HIPS of higher processing temperature, are widely used in electronic device, audition device housings, instrument instrument
Table, insulation equipment, white domestic appliances, office electronic apparatus shell etc..After French Patent (FRP) FR1566675 in 1969, FR
245 research is seen in many reports, such as US3843652, JP47-25232, with 2,4,6- tribromphenols with Cyanuric Chloride in alkali,
Such as carry out condensation reaction in the presence of sodium hydroxide, potassium hydroxide, sodium carbonate to obtain.JP 53-116390 disclose a kind of phase and turn
In the presence of shifting catalyst in heterogeneous system 2,4,6- tribromphenols and Cyanuric Chloride condensation reaction.EP0633253、
EP0634407 etc. first forms phenates using sodium hydroxide or potassium hydroxide with 2,4,6- tribromphenols, then with Cyanuric Chloride in season
In the presence of phosphonium salt phase transfer catalyst, reacted in non-protonic solvent, they think so prevent tribromphenol
Oxidation polymerization.Patent WO2008071214 makees alkali with sodium carbonate, using FR245 in acetone solubility property difference the characteristics of third
Synthesized in ketone solvent.Domestic CN103275025 reports in chlorine benzene/methylbenzene in the presence of cetyl trimethylammonium bromide,
Natrium carbonicum calcinatum is preparation method in the system of alkali；CN102838554 carries out FR245 synthesis using anhydrous system, and they think
Anhydrous system can prevent Cyanuric Chloride from hydrolyzing；CN1844109 is then dropped by the excessive method of the Cyanuric Chloride by cheaper
Low cost；CN101070475 reports " one kettle way " and prepares FR245 methods, and it is water-soluble that reaction system still employs sodium hydroxide
Liquid.
In prior art, in large-scale production process, due to inorganic using sodium hydroxide, potassium hydroxide, sodium carbonate etc.
Alkali, can produce a large amount of inorganic salts such as Sodium Chloride, potassium chloride, sodium bicarbonate etc..It is a large amount of inorganic because what is produced using inorganic base
Salt, either as solid waste or as brine waste discharge, causes Heavy environmental pollution, and does not recycle valency
Value.
The content of the invention
The present invention provides 2,4,6- tri- (2,4,6- the tribromophenoxies) -1,3,5- three that a kind of alkali metal-free compound is participated in
The synthetic method of piperazine Atom economy.The conjunction of 2,4,6- tri- (2,4,6- the tribromophenoxies) -1,3,5- triazines that the present invention is provided
Into method, by N- Methylimidazole .s and 2,4,6- tribromphenols in the case where having solvent or condition of no solvent into salt, then with Cyanuric Chloride
Reacted, product 2,4,6- tri- (2,4,6- tribromophenoxy) -1,3,5-triazines is obtained in high yield；The reaction is without the need for inorganic
Alkali is participated in；Its reaction scheme is as follows：
Synthetic method of the present invention, when product 2,4,6- tri- (2,4,6- tribromophenoxy) -1,3,5-triazines is prepared,
Can simultaneously prepare a kind of useful and can be conveniently separated the acidic ion liquid for obtaining --- chlorination N- methylimidazole salt.
In synthetic reaction of the present invention, participate in without the need for inorganic base, produce because inorganic base participates in reaction in a large number so as to avoid
Environmental pollution caused by waste water containing inorganic salt.In the inventive method, 2,4,6- tribromo-benzenes are generated with organic base and tribromphenol
Phenol N- methylimidazole salt, reacts with Cyanuric Chloride then, is generating (2,4, the 6- tribromophenoxy) -1,3,5- of product 2,4,6- tri-
During triazine, the chlorine in Cyanuric Chloride molecule is combined a kind of useful ionic liquid chlorination of generation with N- methyl imidazolium cations
N- methylimidazole salt, and product easily separates with ionic liquid.Whole reaction is all in raw material almost without waste discharge
Atom is converted to 2,4,6- tri- (2,4,6- tribromophenoxy) -1,3,5-triazines and ionic liquid, belongs to a kind of atom economy
Property cleaning reaction.
In synthetic reaction of the present invention, raw material N- Methylimidazole .s and 2, the mol ratio of 4,6- tribromphenols is 1:1, the two mole
Number is 3 with the ratio of the molal quantity of Cyanuric Chloride:1, i.e. N- Methylimidazole .s：2,4,6- tribromphenols：The mol ratio of Cyanuric Chloride is
3:3:1。
In synthetic reaction of the present invention, the solvent is chlorobenzene, dichloromethane or chloroform etc..Preferably, using chlorobenzene as molten
Agent.The solvent is 2~4 with the mol ratio of 2,4,6- tribromphenols：1.
In synthetic reaction of the present invention, the yield of product 2,4,6- tri- (2,4,6- tribromophenoxy) -1,3,5-triazines is obtained
Up to more than 95%.Obtain the yield more than 93% of acidic ion liquid chlorination N- methylimidazole salt.
In a particular embodiment, the preparation side of 2,4,6- tri- (2,4,6- tribromophenoxy) -1,3,5-triazines of the invention
Method, concrete operations are as follows：2,4,6- tribromphenols and N- Methylimidazole .s are added in reaction bulb, in chlorobenzene as solvent or without molten
It is warming up to clarification under the conditions of agent, adds Cyanuric Chloride, 20 DEG C~70 DEG C insulation reaction 4~6 hours, TLC monitoring reactions are complete.Take out
Filter, filter cake is washed with chlorobenzene, and the filtrate decompression of merging reclaims chlorobenzene, dries to obtain white solid product 2,4,6- tri- (2,4,6- tri-
Bromobenzene epoxide) -1,3,5- triazines.Filter cake is reclaimed, acidic ion liquid chlorination N- methylimidazole salt is obtained.
The invention allows for a kind of (2,4,6- tribromo-benzenes of fire retardant 2,4,6- tri- prepared by above-mentioned synthetic method
Epoxide) -1,3,5- triazines.
Present invention firstly provides above-mentioned synthetic method, i.e. generate 2,4,6- tribromphenol N- with organic base and tribromphenol
Methylimidazole salt, reacts with Cyanuric Chloride then, is generating product 2,4,6- tri- (2,4,6- tribromophenoxy) -1,3,5-triazines
During, the chlorine in Cyanuric Chloride molecule is combined a kind of useful ionic liquid chlorination N- first of generation with N- methyl imidazolium cations
Base imidazole salts, and product easily separates with ionic liquid.Whole reaction is almost without waste discharge, all atoms in raw material
2,4,6- tri- (2,4,6- tribromophenoxy) -1,3,5-triazines and ionic liquid are converted to, belong to a kind of Atom economy clear
Clean reaction.
Beneficial effect of the present invention includes：In synthetic reaction process of the present invention, it is entirely avoided the use of inorganic base, reaction
Process does not produce waste water containing inorganic salt, so as to for 2, the clean manufacturing of 4,6- tri- (2,4,6- tribromophenoxy) -1,3,5-triazines
There is provided solution, existing synthetic method has been overturned.
Synthetic reaction of the present invention is except generating (2,4,6- tribromophenoxies) -1,3,5- triazines of 2,4,6- tri- and a kind of usefulOutside acidic ion liquid chlorination N- methylimidazole salt, generate without other by-products, therefore, it is a kind of atom economy
Property reaction.And, product 2,4, (2,4,6- the tribromophenoxy) -1,3,5-triazines of 6- tri- and acidic ion liquid chlorination N- methyl miaows
The separation of azoles salt is very convenient, need to only filter and be capable of achieving.
Description of the drawings
Fig. 1 is 2,4,6- tri- (2,4,6- tribromophenoxies) -1,3,5- triazines1H NMR scheme.
Fig. 2 is 2,4,6- tri- (2,4,6- tribromophenoxies) -1,3,5- triazines13C NMR spectras.
Fig. 3 is HRMS (ESI) spectrogram of 2,4,6- tri- (2,4,6- tribromophenoxies) -1,3,5- triazines.
Fig. 4 is the differential thermal figure of 2,4,6- tri- (2,4,6- tribromophenoxies) -1,3,5- triazines.
Specific embodiment
With reference to specific examples below and accompanying drawing, the present invention is described in further detail, the protection content of the present invention
It is not limited to following examples.Under the spirit and scope without departing substantially from inventive concept, those skilled in the art it is conceivable that change
Change and advantage is all included in the present invention, and with appending claims as protection domain.The process of the enforcement present invention,
Condition, reagent, experimental technique etc., in addition to the following content for specially referring to, are the universal knowledege and common knowledge of this area,
The present invention is not particularly limited content.
Embodiment 1
The tribromphenols of 99.3g 2,4,6- and 120ml chlorobenzenes are added in there-necked flask, the lower rising temperature for dissolving of stirring is molten clear, adds
24.6gN- Methylimidazole .s, 40 DEG C of stirring reactions 2 hours.
18.4g Cyanuric Chlorides are added, 20 DEG C~25 DEG C insulation reaction 4 hours, TLC monitoring reactions are complete.
Sucking filtration, filter cake is washed twice with 10ml chlorobenzenes, merging filtrate, recovered under reduced pressure chlorobenzene, dry 104.5g whites are solid
Body.Yield 98%.m.p.225-229℃；1H NMR(CDCl3):δ 7.67 (s, 6H ,=CH)；13C NMR(CDCl3):δ172.51
(3C),146.14(3C),134.78(6CH),120.33(3C),118.21(6C)；HRMS(ESI):Calcd1089.2875for
C21H6Br9N3NaO3[M+8+Na]+, found 1089.2798.The product 2,4,6- tri- (2,4,6- tribromophenoxies) -1 for obtaining,
3,5- triazines, its1H NMR scheme as shown in figure 1, its13C NMR spectras as shown in Fig. 2 its HRMS (ESI) spectrogram as shown in figure 3,
Its differential thermal figure is as shown in Figure 4.
Filter cake is reclaimed, acidic ion liquid chlorination N- methylimidazole salt 33.6g, yield 95% is obtained.
Embodiment 2
The tribromphenols of 99.3g 2,4,6- and 24.6g N- Methylimidazole .s, stirring is added to be warming up to 70 DEG C of shapes in there-necked flask
Into supernatant liquid.Add 18.4g Cyanuric Chlorides and 60ml chlorobenzenes, 70 DEG C of stirring reactions 5 hours, TLC monitoring reactions are complete.Take out
Filter, filter cake is washed twice with 20ml chlorobenzenes, and merging filtrate, recovered under reduced pressure chlorobenzene dries to obtain 101.4g white solids.Yield
95%.Product 2,4,6- tri- (2,4,6- the tribromophenoxies) -1,3,5- triazines for obtaining.Structural characterization and performance characterization and enforcement
Example 1 is basically identical.
Filter cake is reclaimed, acidic ion liquid chlorination N- methylimidazole salt 32.9g, yield 93% is obtained.
Embodiment 3
The tribromphenols of 331g 2,4,6- and 320ml chlorobenzenes are added in there-necked flask, the lower rising temperature for dissolving of stirring is molten clear, adds
82.1gN- Methylimidazole .s, 40 DEG C of stirring reactions 3 hours.
61.5g Cyanuric Chlorides are added, 20 DEG C~25 DEG C insulation reaction 6 hours, TLC monitoring reactions are complete.
Sucking filtration, filter cake is washed twice with 30ml chlorobenzenes, merging filtrate, recovered under reduced pressure chlorobenzene, dry 348.7g whites are solid
Body.Yield 98%.Product 2,4,6- tri- (2,4,6- the tribromophenoxies) -1,3,5- triazines for obtaining.Structural characterization and performance table
Levy basically identical with embodiment 1.
Filter cake is reclaimed, acidic ion liquid chlorination N- methylimidazole salt 114.9g, yield 97% is obtained.
Claims (4)
1. one kind 2, the synthetic method of 4,6- tri- (2,4,6- tribromophenoxy) -1,3,5-triazines, it is characterised in that methods described
For：By N- Methylimidazole .s and 2,4,6- tribromphenols, into salt, are then carried out in the case where having solvent or condition of no solvent with Cyanuric Chloride
Reaction, obtains described 2,4,6- tri- (2,4,6- tribromophenoxy) -1,3,5-triazines；The reaction is participated in without the need for inorganic base；Institute
State method and prepare 2,4,6- tri- (2,4,6- tribromophenoxies) -1,3,5- triazines while obtaining ionic liquid chlorination N-
Methylimidazole salt；Its reaction scheme is as follows：
2. synthetic method as claimed in claim 1, it is characterised in that the N- Methylimidazole .s:2,4,6- tribromphenols:Trimerization
The mol ratio of chlorine cyanogen is：3:3:1.
3. synthetic method as claimed in claim 1, it is characterised in that the solvent is chlorobenzene, dichloromethane or chloroform.
4. synthetic method as claimed in claim 1, it is characterised in that the solvent and described 2,4,6- tribromphenols mole
Than for 2~4:1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510217627.7A CN104761510B (en) | 2015-04-30 | 2015-04-30 | Synthesis method of 2,4,6-tris(2,4,6-tribromophenoxy)-1,3,5-triazine |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510217627.7A CN104761510B (en) | 2015-04-30 | 2015-04-30 | Synthesis method of 2,4,6-tris(2,4,6-tribromophenoxy)-1,3,5-triazine |
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| Publication Number | Publication Date |
|---|---|
| CN104761510A CN104761510A (en) | 2015-07-08 |
| CN104761510B true CN104761510B (en) | 2017-05-17 |
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| KR101369074B1 (en) * | 2009-05-01 | 2014-02-28 | 브로민 콤파운드 리미티드 | Flame retardant composition for flammable plastic materials comprising 2,4,6-tris（2,4,6-tribromophenoxy）-1,3,5-triazine and process for producing the same |
| CN102838554A (en) * | 2012-10-10 | 2012-12-26 | 孔庆池 | Novel method for synthesizing bromo-triazine |
| CN103275025B (en) * | 2013-06-17 | 2015-02-11 | 山东寿光神润发海洋化工有限公司 | Optimized production method of Tri (tribromophenyl) cyanurate |
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