CN103374025A - Triazine boric acid derivatives and preparation methods thereof - Google Patents
Triazine boric acid derivatives and preparation methods thereof Download PDFInfo
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Abstract
The invention provides triazine boric acid derivatives and preparation methods thereof. The derivatives are Tz-3B, BTAm-3Tz-6B and BTHo-3Tz-6B. The Tz-3B is obtained by firstly enabling cyanuric chloride to react with n-butyl lithium, then performing nucleophilic substitution reaction with borate ester, and finally performing acid hydrolysis by using dilute hydrochloric acid; the BTAm-3Tz-6B is obtained by enabling the cyanuric chloride to react with 1, 3, 5-benzene triamine, then enabling an obtained product to react with the n-butyl lithium, further performing the nucleophilic substitution reaction with the borate ester, and finally performing acid hydrolysis by using dilute hydrochloric acid; and the BTHo-3Tz-6B is obtained by enabling the cyanuric chloride to react with 1, 3, 5-benzene triol, then enabling the obtained product to react with the n-butyl lithium, further performing the nucleophilic substitution reaction with the borate ester, and finally performing acid hydrolysis by using dilute hydrochloric acid. The obtained products are expected to become excellent environment-friendly organic flame retardants.
Description
Technical field
The present invention relates to the flame-retarded technology field of organic polymer synthetic materials, be specifically related to triazines boric acid derivatives and preparation method thereof.
Background technology
Along with the development of modern science and technology, macromolecular material is being brought into play great function in national economy and people's lives.Because the inflammableness of macromolecular material, fire failure become the social concern that people are concerned about day by day, thus fire retardant along with the development of macromolecular material development.Organic fire-retardant is as the most active field of fire retardant, and it is of a great variety, comprises halogenated flame retardant, organic phosphorus flame retardant etc., but the shortcomings such as the amount of being fuming is large because there is, toxicity large, poor heat stability, it is imperative therefore to seek new fire retardant.
In view of boric acid derivatives is the coagulation phase fire retardant material of a class excellence, therefore, the kind and the Application Areas that enlarge triazine boric acid analog derivative seem particularly important.
Summary of the invention
In order to solve the defective of existing organic fire-retardant feature of environmental protection deficiency, enlarge simultaneously kind and the Application Areas thereof of boric acid analog derivative, the invention provides three kinds of triazines boric acid derivatives and preparation method thereof.
Three kinds of triazines boric acid derivatives provided by the present invention are 2,4,6-, three boronate-1,3,5-triazine (Tz-3B), N, N ', N " three [(4 '; 6 '-hypoboric acid base)-2 '-triazinyls]-1,3,5-benzene triamine (BTAm-3Tz-6B) and 1; 3; 5-three [(4 ', 6 '-hypoboric acid)-2 '-triazinyl]-benzenetriol (BTHo-3Tz-6B) has molecular structure as follows:
Of the present invention 2,4, the preparation process of 6-three boronate-1,3,5-triazines (Tz-3B) is as follows:
Under the first step nitrogen protection, drip n-Butyl Lithium in the tetrahydrofuran solution of cyanuric chloride, control temperature of reaction-78 ℃ stirred 1-5 hour, thereafter temperature was risen to stirring at room 45-60 clock;
Second step is cooled to-78 ℃ with the reaction solution that the first step obtains, and to wherein dripping trimethyl borate, stirs 45-70 minute, then is warming up to room temperature and stirs 8-10 hour;
The 3rd step was removed tetrahydrofuran (THF) and unreacted trimethyl borate in the second step reaction solution with Rotary Evaporators, obtained solid product.Dissolve this solid product with methylene dichloride, then add saturated aqueous ammonium chloride and extract, collect organic phase, with anhydrous sodium sulfate drying and filtration, filtrate decompression is removed the crude product that organic solvent obtains 2,4,6-, three boric acid esters-1,3,5-triazines.Take the mixed solvent of sherwood oil and ethyl acetate (preferred volume ratio was as 20: 1) as washing fluid, with chromatographic column separate obtain pure 2,4,6-three boric acid esters-1,3,5-triazines.
The 4th step was carried out acidolysis with dilute hydrochloric acid to 2,4,6-, three boric acid esters-1,3,5-triazines, transferred pH to 3-4 to separate out solid, and obtained pure Tz-3B with the frozen water repetitive scrubbing.
N of the present invention, N ', N " three [(4 ', 6 '-hypoboric acid base)-2 '-triazinyls]-1,3, the preparation process of 5-benzene triamine (BTAm-3Tz-6B) is as follows:
The first step is dissolved in cyanuric chloride in the tetrahydrofuran (THF), and the tetrahydrofuran solution at stirring state dropping 1,3,5-benzene triamine drips Bi Jixu and stirred 1-3 hour; Desolventizing obtains solid product, with ethyl acetate solid product is carried out recrystallization and obtains pure N, N ', N " three [(4 ', 6 '-dichloro)-2 '-triazinyls]-1,3,5-benzene triamine;
Second step is under nitrogen protection, and " three [(4 ', 6 '-dichloro)-2 '-triazinyls]-1,3 drip n-Butyl Lithium in the tetrahydrofuran solution of 5-benzene triamine, and control temperature of reaction-78 ℃ stirred 1-4 hour for to N, N ', N; To wherein dripping trimethyl borate, stirred 50-80 minute, then be warming up to room temperature and stirred 12-15 hour;
The 3rd step was removed tetrahydrofuran (THF) and unreacted trimethyl borate in the second step reaction solution with Rotary Evaporators, obtained solid product.Dissolve this solid product with methylene dichloride, then adding saturated aqueous ammonium chloride extracts, collect organic phase, with anhydrous sodium sulfate drying and filtration, filtrate decompression is removed organic solvent obtain N, N ', N " three [(4 '; 6 '-hypoboric acid ester)-2 '-triazinyls]-1,3, the crude product of 5-benzene triamine.As washing fluid, separate obtain pure N, N ', N " three [(4 ', 6 '-hypoboric acid ester)-2 '-triazinyls]-1,3,5-benzene triamine take the mixed solvent of sherwood oil and ethyl acetate (preferred volume ratio was as 5: 1) with chromatographic column;
The 4th step, to N, " three [(4 ', 6 '-hypoboric acid ester)-2 '-triazinyls]-1,3,5-benzene triamine carried out acidolysis, transferred pH to 3-4 to separate out solid, and obtained pure BTAm-3Tz-6B with the frozen water repetitive scrubbing for N ', N with dilute hydrochloric acid.3, of the present invention 1,3, the preparation process of 5-three [(4 ', 6 '-hypoboric acid)-2 '-triazinyl]-benzenetriol (BTHo-3Tz-6B) is as follows:
Between the first step cyanuric chloride is dissolved in the tetrahydrofuran (THF), under stirring state, drips the tetrahydrofuran solution of 1,3,5-benzenetriol, drip Bi Jixu and stirred 1-3 hour; Desolventizing obtains solid product, with ethyl acetate to solid product carry out recrystallization obtain pure 1,3,5-three [(4 ', 6 '-dichloro)-2 '-triazinyl]-benzenetriol;
Second step drips n-Butyl Lithium in the tetrahydrofuran solution of 1,3,5-three [(4 ', 6 '-dichloro)-2 '-triazinyl]-benzenetriol under nitrogen protection, control temperature of reaction-78 ℃ stirred 1-4 hour; To wherein dripping trimethyl borate, stirred 50-80 minute, then be warming up to room temperature and stirred 11-15 hour;
The 3rd step was removed tetrahydrofuran (THF) and unreacted trimethyl borate in the second step reaction solution with Rotary Evaporators, obtained solid product.Dissolve this solid product with methylene dichloride, then add saturated aqueous ammonium chloride and extract, collect organic phase, with anhydrous sodium sulfate drying and filtration, filtrate decompression is removed organic solvent obtain 1,3, the crude product of 5-three [(4 ', 6 '-hypoboric acid ester)-2 '-triazinyl]-benzenetriol.Take the mixed solvent of sherwood oil and ethyl acetate (volume ratio was as 4: 1) as washing fluid, with chromatographic column separate obtain pure 1,3,5-three [(4 ', 6 '-hypoboric acid ester)-2 '-triazinyl]-benzenetriol;
The 4th step was carried out acidolysis with dilute hydrochloric acid to 1,3,5-three [(4 ', 6 '-hypoboric acid ester)-2 '-triazinyl]-benzenetriol, transferred pH to 3-4 to separate out solid, and obtained pure BTHo-3Tz-6B with the frozen water repetitive scrubbing.
Of the present invention 2,4,6-three boronate-1,3,5-triazine (Tz-3B), N, N ', N " three [(4 '; 6 '-hypoboric acid base)-2 '-triazinyls]-1; 3,5-benzene triamine (BTAm-3Tz-6B) and 1,3; reaction process of 5-three [(4 ', 6 '-hypoboric acid)-2 '-triazinyl]-benzenetriol (BTHo-3Tz-6B) can be expressed as follows:
The present invention compared with prior art has following advantage and beneficial effect:
Three kinds of triazines boric acid derivatives provided by the present invention, because containing boric acid base group in its molecular structure, it can be dehydrated into charcoal in combustion processes, is formed into the charcoal tectum on the combustiblematerials surface, stops the burning of combustiblematerials.Therefore these three kinds of triazines boric acid derivatives are expected to become good environment-friendly type organic fire-retardant.The present invention may solve large, the shortcomings such as the amount of being fuming is large, easy drippage, poor heat stability of toxicity that existing fire retardant exists in addition.
Embodiment
Below in conjunction with example, the present invention is described in further detail
Embodiment 12,4, the preparation of 6-three boronate-1,3,5-triazines (Tz-3B):
Under the first step nitrogen protection, drip n-Butyl Lithium in the tetrahydrofuran solution of cyanuric chloride, control temperature of reaction-78 ℃ stirred 1 hour, thereafter temperature was risen to stirring at room 60 minutes;
Second step is cooled to-78 ℃ with the reaction solution that the first step obtains, and to wherein dripping trimethyl borate, stirs 70 minutes, then is warming up to room temperature and stirs 8 hours;
The 3rd step was removed tetrahydrofuran (THF) and unreacted trimethyl borate in the second step reaction solution with Rotary Evaporators, obtained solid product.Dissolve this solid product with methylene dichloride, then add saturated aqueous ammonium chloride and extract, collect organic phase, with anhydrous sodium sulfate drying and filtration, filtrate decompression is removed the crude product that organic solvent obtains 2,4,6-, three boric acid esters-1,3,5-triazines.Take the mixed solvent of sherwood oil and ethyl acetate (volume ratio was as 20: 1) as washing fluid, with chromatographic column separate obtain pure 2,4,6-three boric acid esters-1,3,5-triazines.
The 4th step was carried out acidolysis with dilute hydrochloric acid to 2,4,6-, three boric acid esters-1,3,5-triazines, transferred pH to 3.2 to separate out solid, and obtained pure Tz-3B with the frozen water repetitive scrubbing.
Utilize mass spectrum, nucleus magnetic hydrogen spectrum to characterize resulting product, the structural characterization data are as follows:
Mass spectrum: m/z212.6 (M+)
The hydrogen spectrum
1H-NMR (400MHz, DMSO, ppm): 1.9 (s, 6H, OH)
According to thermogravimetry, recording the carbon yield of product when being heated to 800 ℃ is 35%.
Embodiment 22,4, the preparation of 6-three boronate-1,3,5-triazines (Tz-3B):
Under the first step nitrogen protection, drip n-Butyl Lithium in the tetrahydrofuran solution of cyanuric chloride, control temperature of reaction-78 ℃ stirred 5 hours, thereafter temperature was risen to stirring at room 45 minutes;
Second step is cooled to-78 ℃ with the reaction solution that the first step obtains, and to wherein dripping trimethyl borate, stirs 45 minutes, then is warming up to room temperature and stirs 8 hours;
The 3rd step was removed tetrahydrofuran (THF) and unreacted trimethyl borate in the second step reaction solution with Rotary Evaporators, obtained solid product.Dissolve this solid product with methylene dichloride, then add saturated aqueous ammonium chloride and extract, collect organic phase, with anhydrous sodium sulfate drying and filtration, filtrate decompression is removed the crude product that organic solvent obtains 2,4,6-, three boric acid esters-1,3,5-triazines.Take the mixed solvent of sherwood oil and ethyl acetate (volume ratio was as 20: 1) as washing fluid, with chromatographic column separate obtain pure 2,4,6-three boric acid esters-1,3,5-triazines.
The 4th step was carried out acidolysis with dilute hydrochloric acid to 2,4,6-, three boric acid esters-1,3,5-triazines, transferred pH to 3.9 to separate out solid, and obtained pure Tz-3B with the frozen water repetitive scrubbing.
Embodiment 3N, N ', N " three [(4 ', 6 '-hypoboric acid base)-2 '-triazinyls]-1,3, the preparation of 5-benzene triamine (BTAm-3Tz-6B):
The first step is dissolved in cyanuric chloride in the tetrahydrofuran (THF), drips the tetrahydrofuran solution of 1,3,5-benzene triamine under stirring state, drips Bi Jixu and stirs 1 hour; Desolventizing obtains solid product, with ethyl acetate solid product is carried out recrystallization and obtains pure N, N ', N " three [(4 ', 6 '-dichloro)-2 '-triazinyls]-1,3,5-benzene triamine;
Second step is under nitrogen protection, and " three [(4 ', 6 '-dichloro)-2 '-triazinyls]-1,3 drip n-Butyl Lithium in the tetrahydrofuran solution of 5-benzene triamine, and control temperature of reaction-78 ℃ stirred 1 hour for to N, N ', N; To wherein dripping trimethyl borate, stirred 80 minutes, then be warming up to room temperature and stirred 12 hours;
The 3rd step was removed tetrahydrofuran (THF) and unreacted trimethyl borate in the second step reaction solution with Rotary Evaporators, obtained solid product.Dissolve this solid product with methylene dichloride, then adding saturated aqueous ammonium chloride extracts, collect organic phase, with anhydrous sodium sulfate drying and filtration, filtrate decompression is removed organic solvent obtain N, N ', N " three [(4 '; 6 '-hypoboric acid ester)-2 '-triazinyls]-1,3, the crude product of 5-benzene triamine.As washing fluid, separate obtain pure N, N ', N " three [(4 ', 6 '-hypoboric acid ester)-2 '-triazinyls]-1,3,5-benzene triamine take the mixed solvent of sherwood oil and ethyl acetate (volume ratio was as 5: 1) with chromatographic column;
The 4th step, to N, " three [(4 ', 6 '-hypoboric acid ester)-2 '-triazinyls]-1,3,5-benzene triamine carried out acidolysis, transferred pH to 3.5 to separate out solid, and obtained pure BTAm-3Tz-6B with the frozen water repetitive scrubbing for N ', N with dilute hydrochloric acid.
Utilize mass spectrum, nucleus magnetic hydrogen spectrum to characterize resulting product, the structural characterization data are as follows:
Mass spectrum: m/z623.3 (M+)
The hydrogen spectrum
1H-NMR (400MHz, DMSO, ppm): 1.8 (s, 6H, OH), 4.0 (s, 3H, NH), 5.1 (s, 3H)
According to thermogravimetry, recording the carbon yield of product when being heated to 800 ℃ is 47%.
Embodiment 4N, N ', N " three [(4 ', 6 '-hypoboric acid base)-2 '-triazinyls]-1,3, the preparation of 5-benzene triamine (BTAm-3Tz-6B):
The first step is dissolved in cyanuric chloride in the tetrahydrofuran (THF), drips the tetrahydrofuran solution of 1,3,5-benzene triamine under stirring state, drips Bi Jixu and stirs 3 hours; Desolventizing obtains solid product, with ethyl acetate solid product is carried out recrystallization and obtains pure N, N ', N " three [(4 ', 6 '-dichloro)-2 '-triazinyls]-1,3,5-benzene triamine;
Second step is under nitrogen protection, and " three [(4 ', 6 '-dichloro)-2 '-triazinyls]-1,3 drip n-Butyl Lithium in the tetrahydrofuran solution of 5-benzene triamine, and control temperature of reaction-78 ℃ stirred 4 hours for to N, N ', N; To wherein dripping trimethyl borate, stirred 50 minutes, then be warming up to room temperature and stirred 13 hours;
The 3rd step was removed tetrahydrofuran (THF) and unreacted trimethyl borate in the second step reaction solution with Rotary Evaporators, obtained solid product.Dissolve this solid product with methylene dichloride, then adding saturated aqueous ammonium chloride extracts, collect organic phase, with anhydrous sodium sulfate drying and filtration, filtrate decompression is removed organic solvent obtain N, N ', N " three [(4 '; 6 '-hypoboric acid ester)-2 '-triazinyls]-1,3, the crude product of 5-benzene triamine.As washing fluid, separate obtain pure N, N ', N " three [(4 ', 6 '-hypoboric acid ester)-2 '-triazinyls]-1,3,5-benzene triamine take the mixed solvent of sherwood oil and ethyl acetate (volume ratio was as 5: 1) with chromatographic column;
The 4th step, to N, " three [(4 ', 6 '-hypoboric acid ester)-2 '-triazinyls]-1,3,5-benzene triamine carried out acidolysis, transferred pH to 3.6 to separate out solid, and obtained pure BTAm-3Tz-6B with the frozen water repetitive scrubbing for N ', N with dilute hydrochloric acid.
Embodiment 51,3, the preparation of 5-three [(4 ', 6 '-hypoboric acid)-2 '-triazinyl]-benzenetriol (BTHo-3Tz-6B):
The first step is dissolved in cyanuric chloride in the tetrahydrofuran (THF), drips the tetrahydrofuran solution of 1,3,5-benzenetriol under stirring state, drips Bi Jixu and stirs 1 hour; Desolventizing obtains solid product, with ethyl acetate to solid product carry out recrystallization obtain pure 1,3,5-three [(4 ', 6 '-dichloro)-2 '-triazinyl]-benzenetriol;
Second step drips n-Butyl Lithium in the tetrahydrofuran solution of 1,3,5-three [(4 ', 6 '-dichloro)-2 '-triazinyl]-benzenetriol under nitrogen protection, control temperature of reaction-78 ℃ stirred 1 hour; To wherein dripping trimethyl borate, stirred 80 minutes, then be warming up to room temperature and stirred 12 hours;
The 3rd step was removed tetrahydrofuran (THF) and unreacted trimethyl borate in the second step reaction solution with Rotary Evaporators, obtained solid product.Dissolve this solid product with methylene dichloride, then add saturated aqueous ammonium chloride and extract, collect organic phase, with anhydrous sodium sulfate drying and filtration, filtrate decompression is removed organic solvent obtain 1,3, the crude product of 5-three [(4 ', 6 '-hypoboric acid ester)-2 '-triazinyl]-benzenetriol.Take the mixed solvent of sherwood oil and ethyl acetate (volume ratio was as 4: 1) as washing fluid, with chromatographic column separate obtain pure 1,3,5-three [(4 ', 6 '-hypoboric acid ester)-2 '-triazinyl]-benzenetriol;
The 4th step was carried out acidolysis with dilute hydrochloric acid to 1,3,5-three [(4 ', 6 '-hypoboric acid ester)-2 '-triazinyl]-benzenetriol, transferred pH to 3.1 to separate out solid, and obtained pure BTHo-3Tz-6B with the frozen water repetitive scrubbing.
Utilize mass spectrum, nucleus magnetic hydrogen spectrum to characterize resulting product, the structural characterization data are as follows:
Mass spectrum: m/z626.2 (M+)
The hydrogen spectrum
1H-NMR (400MHz, DMSO, ppm): 1.8 (s, 6H, OH), 5.8 (s, 3H)
According to thermogravimetry, recording the carbon yield of product when being heated to 800 ℃ is 51%.
Embodiment 61,3, the preparation of 5-three [(4 ', 6 '-hypoboric acid)-2 '-triazinyl]-benzenetriol (BTHo-3Tz-6B):
The first step is dissolved in cyanuric chloride in the tetrahydrofuran (THF), drips the tetrahydrofuran solution of 1,3,5-benzenetriol under stirring state, drips Bi Jixu and stirs 3 hours; Desolventizing obtains solid product, with ethyl acetate to solid product carry out recrystallization obtain pure 1,3,5-three [(4 ', 6 '-dichloro)-2 '-triazinyl]-benzenetriol;
Second step drips n-Butyl Lithium in the tetrahydrofuran solution of 1,3,5-three [(4 ', 6 '-dichloro)-2 '-triazinyl]-benzenetriol under nitrogen protection, control temperature of reaction-78 ℃ stirred 4 hours; To wherein dripping trimethyl borate, stirred 50 minutes, then be warming up to room temperature and stirred 14 hours;
The 3rd step was removed tetrahydrofuran (THF) and unreacted trimethyl borate in the second step reaction solution with Rotary Evaporators, obtained solid product.Dissolve this solid product with methylene dichloride, then add saturated aqueous ammonium chloride and extract, collect organic phase, with anhydrous sodium sulfate drying and filtration, filtrate decompression is removed organic solvent obtain 1,3, the crude product of 5-three [(4 ', 6 '-hypoboric acid ester)-2 '-triazinyl]-benzenetriol.Take the mixed solvent of sherwood oil and ethyl acetate (volume ratio was as 4: 1) as washing fluid, with chromatographic column separate obtain pure 1,3,5-three [(4 ', 6 '-hypoboric acid ester)-2 '-triazinyl]-benzenetriol;
The 4th step was carried out acidolysis with dilute hydrochloric acid to 1,3,5-three [(4 ', 6 '-hypoboric acid ester)-2 '-triazinyl]-benzenetriol, transferred pH to 3.7 to separate out solid, and obtained pure BTHo-3Tz-6B with the frozen water repetitive scrubbing.
Claims (4)
1. the triazines boric acid derivatives it is characterized in that 2,4,6-three boronate-1,3,5-triazines (Tz-3B), N, N ', N " three [(4 ', 6 '-hypoboric acid base)-2 '-triazinyls]-1; 3; 5-benzene triamine (BTAm-3Tz-6B) or 1,3,5-three [(4 '; 6 '-hypoboric acid)-2 '-triazinyl]-benzenetriol (BTHo-3Tz-6B) has following molecular structure:
2. prepare the preparation method of the described Tz-3B of claim 1, it is characterized in that comprising following step:
Under the first step nitrogen protection, drip n-Butyl Lithium in the tetrahydrofuran solution of cyanuric chloride, control temperature of reaction-78 ℃ stirred 1-5 hour, thereafter temperature was risen to stirring at room 45-60 clock;
Second step is cooled to-78 ℃ with the reaction solution that the first step obtains, and to wherein dripping trimethyl borate, stirs 45-70 minute, then is warming up to room temperature and stirs 8-10 hour;
The 3rd step was removed tetrahydrofuran (THF) and unreacted trimethyl borate in the second step reaction solution with Rotary Evaporators, obtained solid product; Dissolve this solid product with methylene dichloride, then add saturated aqueous ammonium chloride and extract, collect organic phase, with anhydrous sodium sulfate drying and filtration, filtrate decompression is removed the crude product that organic solvent obtains 2,4,6-, three boric acid esters-1,3,5-triazines; With the mixed solvent of sherwood oil and ethyl acetate as washing fluid, with chromatographic column separate obtain pure 2,4,6-three boric acid esters-1,3,5-triazines;
The 4th step was carried out acidolysis with dilute hydrochloric acid to 2,4,6-, three boric acid esters-1,3,5-triazines, transferred pH to 3-4 to separate out solid, and obtained pure Tz-3B with the frozen water repetitive scrubbing.
3. the preparation method of described BTAm-3Tz-6B according to claim 1 is characterized in that comprising following step:
The first step is dissolved in cyanuric chloride in the tetrahydrofuran (THF), drips the tetrahydrofuran solution of 1,3,5-benzene triamine under stirring state, drips Bi Jixu and stirs 1-3 hour; Desolventizing obtains solid product, with ethyl acetate solid product is carried out recrystallization and obtains pure N, N ', N " three [(4 ', 6 '-dichloro)-2 '-triazinyls]-1,3,5-benzene triamine;
Second step is under nitrogen protection, and " three [(4 ', 6 '-dichloro)-2 '-triazinyls]-1,3 drip n-Butyl Lithium in the tetrahydrofuran solution of 5-benzene triamine, and control temperature of reaction-78 ℃ stirred 1-4 hour for to N, N ', N; To wherein dripping trimethyl borate, stirred 50-80 minute, then be warming up to room temperature and stirred 12-15 hour;
The 3rd step was removed tetrahydrofuran (THF) and unreacted trimethyl borate in the second step reaction solution with Rotary Evaporators, obtained solid product; Dissolve this solid product with methylene dichloride, then adding saturated aqueous ammonium chloride extracts, collect organic phase, with anhydrous sodium sulfate drying and filtration, filtrate decompression is removed organic solvent obtain N, N ', N " three [(4 '; 6 '-hypoboric acid ester)-2 '-triazinyls]-1,3, the crude product of 5-benzene triamine; As washing fluid, separate obtain pure N, N ', N " three [(4 ', 6 '-hypoboric acid ester)-2 '-triazinyls]-1,3,5-benzene triamine take the mixed solvent of sherwood oil and ethyl acetate (volume ratio was as 5: 1) with chromatographic column;
The 4th step, to N, " three [(4 ', 6 '-hypoboric acid ester)-2 '-triazinyls]-1,3,5-benzene triamine carried out acidolysis, transferred pH to 3-4 to separate out solid, and obtained pure BTAm-3Tz-6B with the frozen water repetitive scrubbing for N ', N with dilute hydrochloric acid.
4. the preparation method of described BTHo-3Tz-6B according to claim 1 is characterized in that comprising following step:
The first step is dissolved in cyanuric chloride in the tetrahydrofuran (THF), drips the tetrahydrofuran solution of 1,3,5-benzenetriol under stirring state, drips Bi Jixu and stirs 1-3 hour; Desolventizing obtains solid product, with ethyl acetate to solid product carry out recrystallization obtain pure 1,3,5-three [(4 ', 6 '-dichloro)-2 '-triazinyl]-benzenetriol;
Second step drips n-Butyl Lithium in the tetrahydrofuran solution of 1,3,5-three [(4 ', 6 '-dichloro)-2 '-triazinyl]-benzenetriol under nitrogen protection, control temperature of reaction-78 ℃ stirred 1-4 hour; To wherein dripping trimethyl borate, stirred 50-80 minute, then be warming up to room temperature and stirred 11-15 hour;
The 3rd step was removed tetrahydrofuran (THF) and unreacted trimethyl borate in the second step reaction solution with Rotary Evaporators, obtained solid product; Dissolve this solid product with methylene dichloride, then add saturated aqueous ammonium chloride and extract, collect organic phase, with anhydrous sodium sulfate drying and filtration, filtrate decompression is removed organic solvent obtain 1,3, the crude product of 5-three [(4 ', 6 '-hypoboric acid ester)-2 '-triazinyl]-benzenetriol; With the mixed solvent of sherwood oil and ethyl acetate as washing fluid, with chromatographic column separate obtain pure 1,3,5-three [(4 ', 6 '-hypoboric acid ester)-2 '-triazinyl]-benzenetriol;
The 4th step was carried out acidolysis with dilute hydrochloric acid to 1,3,5-three [(4 ', 6 '-hypoboric acid ester)-2 '-triazinyl]-benzenetriol, transferred pH to 3-4 to separate out solid, and obtained pure BTHo-3Tz-6B with the frozen water repetitive scrubbing.
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