CN102382069B - Monomer preparation method of dihalide and binitro triaryl methyl-1, 3, 5-triazine - Google Patents
Monomer preparation method of dihalide and binitro triaryl methyl-1, 3, 5-triazine Download PDFInfo
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Abstract
The invention relates to a monomer preparation method of dihalide and binitro triaryl methyl-1, 3, 5-triazine, which is used for synthesizing a polyarylether polymer which contains a triaryl methyl s-triazine structure. The preparation process comprises two steps of: taking halide or nitrobenzonitrile as a starting material, generating imido ester in alcoholic solution under the catalysis of sodium alkoxide after addition reaction, producing halide or nitro amidine hydrochloride after ammonia which is released by heating ammonium chloride replaces alkoxy, and obtaining dihalide or binitro triphenyl s-triazine monomer after the high temperature cyclization reaction of purified amidine salt and benzoyl chloride. The halide or binitro triphenyl s-triazine monomer derivative which is prepared through the two steps is mainly disubstituted and trisubstituted, the mono-substituted byproduct is restrained, so during the purification process of the product, the solubility differences of the disubstituted and trisubstituted derivatives in the benzene derivative are mainly used, so the polymerized disubstituted halide or nitro triphenyl s-triazine monomer is produced at high yield. The reaction characteristics are high yield, reduced pollution and saved cost.
Description
Technical field
The present invention relates to the synthetic method of a kind of dihalo and dinitrobenzene triaryl-1,3,5-triazines monomer, specifically refer to a kind of for the synthesis of containing the dihalo of triaryl s-triazine structure polyarylether polymer and the method for preparing monomer of dinitrobenzene triaryl-1,3,5-triazines.
Background technology
Poly-(triaryl-1,3-5-s-triazine) because its special aromatic ring and s-triazine plane of a loop conjugated structure have excellent over-all properties, as there is excellent heat resistance, high strength, high-modulus, fire-retardant, resistance to chemical attack etc., therefore at aerospace, defence and military, electronics and other industrial circle, there is important application, simultaneously, triphenyl s-triazine and derivative thereof are important organic intermediates, due to its unique photoelectric property and crystalline nature, can be applicable to the fields such as photoelectric device and plane demonstration.Wherein, linear poly-(triaryl-1, 3, 5-s-triazine) or main chain containing triaryl s-triazine ring structure polymkeric substance, especially the synthetic of polyarylether is generally to obtain by two halogen monomers and active biphenol monomer polyreaction containing triaryl s-triazine structure, for example, 2, 4-bis-(4-fluorophenyl)-6-phenyl-1, 3, 5-triazine can be used as polymerization initial monomers, prepare polyarylether etc. (MATSUO S.Polycarbonates and triazine ring-containing divalent phenols for preparation of polycarbonates[P] .JP, 07003000, 1995-01-06, MATSUO S.synthesis and properties of poly (arylene ether phenyl-s-triazines) [J] .Journal of Polymer Science Part Polymer Chemistry, 1994,32:2093-2098.).
Synthetic and active about the two halogen monomers of triaryl s-triazine structure, both at home and abroad rarer reports all.The halogenated benzonitrile of take is the two halogen monomers of the synthetic this triaryl s-triazine of starting raw material, and what be seen in bibliographical information has three-step approach, four step rule and a single stage method.Four step rule: first by phenyl aldehyde and the synthetic Schiff's base of aniline reaction, afterwards by the hydrochloride that must narrow fluorobenzene fluorobenzonitrile and ethanol synthesis, the hydrochloride of finally fluorobenzene being narrowed makes to obtain target product with Schiff's base at DMF solution again, overall yield approximately 18% (FINK R, FRENZ C, et al.Synthesis and characterization of aromatic poly (1,3,5-triazine-ether) s for electroluminescent devices[J] .Macromolecules, 1997,30 (26): 8177-8181.).Three-step approach: through the synthetic NSC 2020 of cyanophenyl, to fluorobenzonitrile under sulphur trioxide katalysis, at 20～50 ℃ of synthesis of cyclic intermediates 4,6-bis-(4-fluorophenyl)-2-oxo 1,2,3,5-oxa-thiodiazine, cyclic intermediate reacts and can make target product with the hydrochloride that fluorobenzene is narrowed, overall yield be about 14% (MATSUO S.synthesis and properties of poly (arylene ether phenyl-s-triazine) s[J] .J Polym Sci Part A, Polym Chem, 1994,32:2093-2098.).Single stage method: Using Aluminium Trichloride as Catalyst p-nitrophenyl nitrile and Benzoyl chloride synthetic 2,4-bis-(4-nitrophenyl)-6-phenyl-1,3,5-triazine, overall yield is about 40% (COOKA H, JONES D G.Experiments in the triazine and the glyoxaline series[J] .J Chem Soc, 1941,278-282.).The reaction scheme of three-step approach and four step rule is long, and the cycle is long, and experimental procedure is loaded down with trivial details, and ultimate yield and purity are not high.In three-step approach, adopt highly acid catalyzer as SO
3, produced a large amount of spent acid, thus complicated operation and aftertreatment difficulty.Although single stage method is for simplifying synthesis step, yield is still not high, and reaction preference is poor, when generating dihalo product, with a halo and trihalogenated derivative, is difficult to separated.
The two-step approach that the present invention describes is that to take halo or p-nitrile be starting raw material, after alkaline process synthesizing halogen or nitro amidine salt, react with Benzoyl chloride and make dihalo or dinitrobenzene triphenyl s-triazine monomer, reaction characteristics is that yield is high, reduces and pollutes, cost-saving.The inventor does not find to disclose in existing technology the method that two-step approach of the present invention is prepared dihalo or dinitrobenzene triphenyl s-triazine monomer.
Summary of the invention
The invention provides a kind of yield high, reduce to pollute, cost-saving dihalo or the synthetic method of dinitrobenzene triphenyl s-triazine monomer.
It is starting raw material that technical scheme of the present invention be take halo or p-nitrile, with Benzoyl chloride through two step synthesis dihalo or dinitrobenzene triphenyl s-triazine.The general formula of the dihalo the present invention relates to or dinitrobenzene triphenyl s-triazine is as follows:
Wherein, X is selected from respectively halogen and nitro.
The feature of two-step approach is to comprise the following steps: successively
(1) halo or p-nitrile be in alcoholic solution, under sodium alkoxide catalysis, through addition reaction, generates imines ester, and then ammonium chloride is heated after the ammonia substituted alkoxy discharging and generates halo or nitro amidine hydrochloride.Reaction formula is as follows:
(2) halo or nitro amidine hydrochloride and Benzoyl chloride are not having under catalyzer or Louis acid catalysis, Cyclization dihalo or dinitrobenzene triphenyl-1,3,5-triazines monomer.Reaction formula is as follows:
(3) refining: dihalo or dinitrobenzene triphenyl-1,3,5-triazines monomer repeatedly obtain the fine work of polymerization purity after recrystallization, filtration, oven dry through the derivative of benzene.
In step (1), first halogenated benzonitrile, in alcoholic solvent, under sodium alkoxide catalysis, generates imines ester through addition reaction, and this is a balance thermopositive reaction, and temperature is lower, is more conducive to the carrying out of reaction; But temperature is too low, speed of reaction is slow, long reaction time.Therefore, temperature of reaction is at 15～30 ℃.The concentration of catalyzer sodium alkoxide is higher, and speed of reaction is larger, and general control is 0.05～0.15mol/L; More than reaction times 10h.Then add the ammonium chloride with nitrile equivalent, more than continuing reaction 3h, reaction solution is cooled to room temperature under reflux temperature, modulation solution is strongly-acid, and filtration, goes out desolventizing and obtain thick product amidine salt.Thick product, after acid deionized water recrystallization, recycles after unreacted raw material halogenated benzonitrile is reclaimed.
In step (2), the amidine salt that the first step obtains and Benzoyl chloride be solvent-free, or the derivative of benzene is under the environment of solvent and nitrogen protection, under catalyst-free or Louis acid catalysis, under heating condition, reacts certain hour.If without solvent, the Benzoyl chloride of take is reactant again in the situation of reaction medium, 8～20 times (mass ratioes) of the general relative nitrile consumption of its consumption; If employing solvent, preferentially selects Multi substituted benzenes, as dichlorobenzene, now the consumption of Benzoyl chloride is generally 5～10 times (mass ratioes) of nitrile consumption.Lewis acidic katalysis can improve the activity of acyl chlorides, and can further improve the selectivity of reaction, preferential selective chlorination zinc, aluminum chloride, iron trichloride etc.Temperature of reaction is higher, and speed of response is faster, and generally setting temperature of reaction is 100～190 ℃, and the reaction times is 5～15h.
If adopt halo or the nitrotrimethylolmethane phenyl s-triazine monomer derived owner two that two-step approach of the present invention makes to replace and three replacements, one replacement by product is zero substantially, so be mainly separated two substitution products and trisubstituted by product in product purification process, utilize the two in the difference of the solubleness of the derivative of benzene, the polymerization-grade two that makes of high yield replaces halo or nitrotrimethylolmethane phenyl s-triazine monomer.Wherein, the derivative of recrystallization solvent benzene is preferentially selected toluene, chlorobenzene and dimethylbenzene.
The order of the reactive behavior of the halo the present invention relates to or nitrotrimethylolmethane phenyl s-triazine monomer is-NO
2>-F >-Cl >-Br >-I.
Feature of the present invention is that yield is high, and monohalogenated derivative by product is suppressed, and product is easy to refine.
Below in conjunction with examples of implementation, the present invention will be further described.
Accompanying drawing explanation
The hydrogen nuclear magnetic spectrogram of Fig. 1 BCPT.Figure?1?
1H-NMR?spectrum?of?BCPT?in?CDCl
3
The hydrogen nuclear magnetic spectrogram of Fig. 2 BFPT.Figure?2?
1H-NMR?spectrum?of?BFPT?in?CDCl
3
Embodiment
Example 1:2,4-(4-dichlorophenyl)-6-phenyl-1,3,5-s-triazine (BCPT) synthetic
Under room temperature, sodium methylate (0.54g, 0.01mol) is dissolved in 100mL anhydrous methanol, adds 6-chlorophenyl nitrile (13.76g, 0.1mol), stir 10h, add ammonium chloride (5.4g, 0.1mol), rising temperature to reflux temperature reacts 3h, and reaction stops, acidification reaction liquid, decompression evaporates solvent methanol, with ether, reclaims unreacted raw material to 6-chlorophenyl nitrile, to spanon hydrochloride crude product after acid deionized water recrystallization, filter, dry, yield is 92%.IR (KBr): 3459cm
-1-3054cm
-1(N-H), 1679cm
-1(C=N stretching vibration peak), 1595cm
-1, 1529cm
-1, 1480cm
-1(stretching vibration that phenyl ring skeleton produces), 1089 cm
-1(δ (C-H)), 846cm
-1(γ (=C-H)).
1H?NMR(d
6-DMSO，δ)：9.53(2H，s)，9.35(2H，s)，7.87(2H，m)，7.72(2H，m).
In the there-necked flask of being furnished with mechanical stirring, spherical condensation tube and nitrogen conduit 100mL, add spanon hydrochloride 1.9106g (0.01mol); Benzoyl chloride 40mL; the lower 150 ℃ of reaction 12h of nitrogen protection finish; obtain filbert clear solution; reaction system is cooled to room temperature; adularescent solid is separated out, suction filtration.With methyl alcohol drip washing, fall remaining Benzoyl chloride, obtain white essentially continuous fine thread shape crystal, product is dried to Yield:93%.Use toluene recrystallization, obtain polymerization-grade monomer.249.7～251.8 ℃ of fusing points (DSC test).GC/MS(M+calcd?as?C
21H
13N
2Cl
2?363.0456)m/z：363.0983(M+)。
Embodiment 2:2,4-(4-difluorophenyl)-6-phenyl-1,3,5-s-triazine (BFPT) synthetic
Method, as embodiment 1, changes raw material to fluorobenzonitrile into.Other step is basic identical with example 1.260.2～260.8 ℃ of fusing points (DSC test).GC/MS(M+calcd?as?C
21H
13N
2F
2?345.1078)m/z：345.1067(M+)。
Embodiment 3: adopt synthetic 2,4-(4-difluorophenyl)-6-phenyl-1 of Louis acid catalysis, 3,5-s-triazine (BCPT)
To the synthetic method of spanon hydrochloride as embodiment 1.To spanon hydrochloride 0.01mol, Benzoyl chloride 10mL, 150 ℃ of temperature of reaction, zinc chloride consumption is 2.5mmol, reaction times 4h, the yield of crude product is 85%.Wherein the content of trisubstituted derivative is 2%, and dibasic principal product is 98%.
Claims (5)
1. a method for preparing monomer for dihalo and dinitrobenzene triaryl-1,3,5-triazines, is characterized in that, take halo or p-nitrile as starting raw material, with Benzoyl chloride through two step synthesis dihalo or dinitrobenzene triphenyl s-triazine; The general formula of the dihalo relating to or dinitrobenzene triphenyl s-triazine is as follows:
Wherein, X is selected from respectively halogen and nitro;
Specifically comprise two steps:
(1) halo or p-nitrile are in alcoholic solution, under sodium alkoxide catalysis, through addition reaction, generate imines ester, then ammonium chloride is heated after the ammonia substituted alkoxy discharging and generates halo or nitro amidine hydrochloride: the concentration of catalyzer sodium alkoxide is 0.05～0.15mol/L, temperature of reaction is at 15～30 ℃, more than reaction times 10h, then add ammonium chloride, its consumption is identical with the consumption of halo or p-nitrile, continue reaction 3h under reflux temperature more than, reaction solution is cooled to room temperature, and modulation solution is strongly-acid, revolves to boil off to obtain thick product amidine salt except alcoholic solvent; Refining of the thick product amidine salt making, thick product amidine salt, through acid deionized water recrystallization, recycles unreacted raw material halogenated benzonitrile after extracted with diethyl ether reclaims;
(2) halo or nitro amidine hydrochloride and Benzoyl chloride Cyclization dihalo or dinitrobenzene triphenyl-1; 3; 5-triazine monomers: refining amidine salt and Benzoyl chloride are under the environment of nitrogen protection; under lewis acid catalyst effect; temperature of reaction is 100～190 ℃, and the reaction times is 5～15h.
2. method for preparing monomer according to claim 1, is characterized in that, lewis acid catalyst is zinc chloride, aluminum chloride or iron trichloride.
3. method for preparing monomer according to claim 1, is characterized in that, in step (2), without solvent, the Benzoyl chloride of take is reactant again in the situation of reaction medium, and the mass ratio of the relative nitrile consumption of its consumption is 8～20.
4. method for preparing monomer according to claim 1, is characterized in that, adopts solvent in step (2), and the mass ratio of the relative nitrile consumption of consumption of Benzoyl chloride is 5～10.
5. method for preparing monomer according to claim 4, is characterized in that, solvent is selected Multi substituted benzenes.
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| CN106866563B (en) * | 2015-12-11 | 2020-02-14 | 中国科学院大连化学物理研究所 | Method for preparing 2, 4-disubstituted-1, 3,5 triazine derivative |
| CN105669578A (en) * | 2016-03-18 | 2016-06-15 | 广东工业大学 | Triazine compound and synthesis method and application thereof |
| JP6794029B2 (en) * | 2016-08-23 | 2020-12-02 | 東ソー株式会社 | Method for Producing Triazine Compound Using Amidine |
| CN106588796B (en) * | 2016-11-03 | 2019-04-16 | 大连理工大学 | A kind of s-triazine structure containing triaryl and the armaticity binary primary amine of ehter bond and preparation method thereof |
| CN108264490B (en) * | 2016-12-30 | 2021-06-01 | 湖北尚赛光电材料有限公司 | 1,3, 5-triazine derivative and preparation method and application thereof |
| JP7175085B2 (en) * | 2018-01-30 | 2022-11-18 | 東ソー株式会社 | Method for producing triazine compound |
| CN110407759A (en) * | 2019-07-04 | 2019-11-05 | 深圳市格物致欣化学技术有限公司 | 1,3,5 replace triaizine compounds and preparation method thereof |
| CN112979945B (en) * | 2021-02-23 | 2022-02-18 | 西安交通大学 | All-triazine covalent skeleton and preparation method thereof, and M-N-C prepared based on all-triazine covalent skeleton and method |
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| US3700665A (en) * | 1969-10-31 | 1972-10-24 | Ciba Geigy Corp | Diamino-s-triazines |
| CN1114314A (en) * | 1994-06-30 | 1996-01-03 | 中国科学院长春应用化学研究所 | Synthesis of monomer containing carbon-to-carbon unsaturated link disymtriazinyl |
| US20030170490A1 (en) * | 2002-01-29 | 2003-09-11 | Xerox Corporation | Organic electroluminescent (EL) devices |
| CN101522857A (en) * | 2006-08-31 | 2009-09-02 | Cdt牛津有限公司 | Compounds for use in opto-electrical devices |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3700665A (en) * | 1969-10-31 | 1972-10-24 | Ciba Geigy Corp | Diamino-s-triazines |
| CN1114314A (en) * | 1994-06-30 | 1996-01-03 | 中国科学院长春应用化学研究所 | Synthesis of monomer containing carbon-to-carbon unsaturated link disymtriazinyl |
| US20030170490A1 (en) * | 2002-01-29 | 2003-09-11 | Xerox Corporation | Organic electroluminescent (EL) devices |
| CN101522857A (en) * | 2006-08-31 | 2009-09-02 | Cdt牛津有限公司 | Compounds for use in opto-electrical devices |
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