CN103374025B - Triazines boronic acid derivatives and preparation method thereof - Google Patents
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Abstract
The invention provides triazines boronic acid derivatives and preparation method thereof。Described derivant is Tz-3B, BTAm-3Tz-6B and BTHo-3Tz-6B。Tz-3B is first reacted with n-BuLi by Cyanuric Chloride, then with borate generation nucleophilic substitution, finally obtain with dilute hydrochloric acid acidolysis；BTAm-3Tz-6B is that products therefrom reacts with n-BuLi by Cyanuric Chloride and 1,3,5-benzene triamine, then with borate generation nucleophilic substitution, finally obtain with dilute hydrochloric acid acidolysis；BTHo-3Tz-6B is reacted by Cyanuric Chloride and 1,3,5-benzenetriol, and products therefrom reacts with n-BuLi, then with borate generation nucleophilic substitution, finally obtain with dilute hydrochloric acid acidolysis；The obtained product of this invention is expected to become excellent environment-friendly type organic fire-retardant。
Description
Technical field
The present invention relates to the field of fire-proof technology of organic polymer synthetic material, be specifically related to triazines boronic acid derivatives and preparation method thereof。
Background technology
Along with the development of modern science and technology, macromolecular material plays great function in national economy and people's lives。Due to the inflammability of macromolecular material, fire incident has been increasingly becoming the social problem that people are concerned about, therefore 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, including halogenated flame retardant, organic phosphorus flame retardant etc., but because there is the shortcomings such as the amount of being fuming is big, toxicity big, poor heat stability, therefore seeks new fire retardant imperative。
In view of boronic acid derivatives is the solidifying phase fire proofing that a class is excellent, therefore, the kind and the application that expand triazine boric acid analog derivative are particularly important。
Summary of the invention
The defect not enough in order to solve the existing organic fire-retardant feature of environmental protection, expands kind and the application thereof of boric acid analog derivative simultaneously, and the present invention provides three kinds of triazines boronic acid derivatives and preparation method thereof。
Three kinds of triazines boronic acid derivatives provided by the present invention are 2,4,6-tri-boronate-1,3,5-triazines (Tz-3B), N, N ', N "-three [(4 '; 6 '-hypoboric acid base)-2 '-triazine radical]-1,3,5-benzene triamine (BTAm-3Tz-6B) and 1; 3; 5-tri-[(4 ', 6 '-hypoboric acid)-2 '-triazine radical]-benzenetriol (BTHo-3Tz-6B), there is molecular structure as follows:
The preparation process of 2,4,6-tri-boronate-1,3,5-triazines (Tz-3B) of the present invention is as follows:
Under first step nitrogen protection, in the tetrahydrofuran solution of Cyanuric Chloride, drip n-BuLi, control reaction temperature-78 DEG C, stir 1-5 hour, temperature is risen to 45-60 clock is stirred at room temperature thereafter；
The reactant liquor that the first step is obtained by second step is cooled to-78 DEG C, and drips methyl borate. wherein, stirs 45-70 minute, then heats to room temperature and stir 8-10 hour；
3rd step Rotary Evaporators removes the oxolane in second step reactant liquor and unreacted methyl borate., obtains solid product。Dissolve this solid product with dichloromethane, be subsequently adding saturated aqueous ammonium chloride and extract, collect organic facies, dry with anhydrous sodium sulfate and filter, filtrate decompression is removed organic solvent and obtains the crude product of 2,4,6-tri-borates-1,3,5-triazines。Using the mixed solvent of petroleum ether and ethyl acetate (preferred volume ratio is for 20: 1) as flushing liquor, it is easily separated by chromatographic column and obtains pure 2,4,6-tri-borates-1,3,5-triazines。
2,4,6-tri-borates-1,3,5-triazines is carried out acidolysis by the 4th step dilute hydrochloric acid, adjusts pH to 3-4 to precipitate out solid, and obtains pure Tz-3B with frozen water cyclic washing。
N, N of the present invention ', N " preparation process of-three [(4 ', 6 '-hypoboric acid base)-2 '-triazine radical]-1,3,5-benzene triamine (BTAm-3Tz-6B) is as follows:
Cyanuric Chloride is dissolved in oxolane by the first step, drips the tetrahydrofuran solution of 1,3,5-benzene triamine at stirring state, drips Bi Jixu and stirs 1-3 hour；Remove solvent and obtain solid product, by ethyl acetate, solid product is carried out recrystallization and obtain pure N, N ', N "-three [(4 ', 6 '-dichloro)-2 '-triazine radical]-1,3,5-benzene triamine；
Second step under nitrogen protection, to N, N ', " in the tetrahydrofuran solution of-three [(4 ', 6 '-dichloro)-2 '-triazine radical]-1,3,5-benzene triamine, dropping n-BuLi, controls reaction temperature-78 DEG C, stirs 1-4 hour N；Drip methyl borate. wherein, stir 50-80 minute, then heat to room temperature and stir 12-15 hour；
3rd step Rotary Evaporators removes the oxolane in second step reactant liquor and unreacted methyl borate., obtains solid product。This solid product is dissolved with dichloromethane, it is subsequently adding saturated aqueous ammonium chloride to extract, collect organic facies, dry with anhydrous sodium sulfate and filter, filtrate decompression being removed organic solvent and obtains N, N ', N " the crude product of-three [(4 '; 6 '-diborate)-2 '-triazine radical]-1,3,5-benzene triamine。Using the mixed solvent of petroleum ether and ethyl acetate (preferred volume ratio is for 5: 1) as flushing liquor, it is easily separated by chromatographic column and obtains pure N, N ', N "-three [(4 ', 6 '-diborate)-2 '-triazine radical]-1,3,5-benzene triamine；
4th step dilute hydrochloric acid is to N, N ', "-three [(4 ', 6 '-diborate)-2 '-triazine radical]-1,3,5-benzene triamine carries out acidolysis to N, adjusts pH to 3-4 to precipitate out solid, and obtains pure BTAm-3Tz-6B with frozen water cyclic washing。3, the preparation process of [(4 ', 6 '-hypoboric acid)-2 '-triazine radical]-benzenetriol (BTHo-3Tz-6B) of the present invention 1,3,5-tri-is as follows:
Between the first step, Cyanuric Chloride is dissolved in oxolane, drips the tetrahydrofuran solution of 1,3,5-benzenetriol under agitation, drip Bi Jixu and stir 1-3 hour；Remove solvent and obtain solid product, by ethyl acetate, solid product carried out recrystallization and obtain pure 1,3,5-tri-[(4 ', 6 '-dichloro)-2 '-triazine radical]-benzenetriol；
Under nitrogen protection, dropping n-BuLi in the tetrahydrofuran solution of [(4 ', 6 '-dichloro)-2 '-triazine radical]-benzenetriol, controls reaction temperature-78 DEG C, stirs 1-4 hour second step to 1,3,5-tri-；Drip methyl borate. wherein, stir 50-80 minute, then heat to room temperature and stir 11-15 hour；
3rd step Rotary Evaporators removes the oxolane in second step reactant liquor and unreacted methyl borate., obtains solid product。This solid product is dissolved with dichloromethane, it is subsequently adding saturated aqueous ammonium chloride to extract, collect organic facies, dry with anhydrous sodium sulfate and filter, filtrate decompression is removed organic solvent and obtains 1, the crude product of 3,5-tri-[(4 ', 6 '-diborate)-2 '-triazine radical]-benzenetriol。Using the mixed solvent of petroleum ether and ethyl acetate (volume ratio is for 4: 1) as flushing liquor, it is easily separated by chromatographic column and obtains pure 1,3,5-tri-[(4 ', 6 '-diborate)-2 '-triazine radical]-benzenetriol；
[(4 ', 6 '-diborate)-2 '-triazine radical]-benzenetriol carries out acidolysis to 4th step dilute hydrochloric acid to 1,3,5-tri-, adjusts pH to 3-4 to precipitate out solid, and obtains pure BTHo-3Tz-6B with frozen water cyclic washing。
2,4,6-tri-boronate-1 of the present invention, 3,5-triazine (Tz-3B), N, N ', N "-three [(4 '; 6 '-hypoboric acid base)-2 '-triazine radical]-1; 3,5-benzene triamines (BTAm-3Tz-6B) and 1,3; course of reaction of 5-tri-[(4 ', 6 '-hypoboric acid)-2 '-triazine radical]-benzenetriol (BTHo-3Tz-6B) can be expressed as follows:
The present invention compared with prior art has the advantage that and beneficial effect:
Three kinds of triazines boronic 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, forms into charcoal cover layer on combustible surface, stops the burning of combustible。Therefore these three triazines boronic acid derivatives is expected to become excellent environment-friendly type organic fire-retardant。The present invention it is also possible to solve that the toxicity that existing fire retardant exists is big, the amount of being fuming big, the easy shortcoming such as drippage, poor heat stability。
Detailed description of the invention
Below in conjunction with example, the present invention is described in further detail
The preparation of embodiment 12,4,6-tri-boronate-1,3,5-triazines (Tz-3B):
Under first step nitrogen protection, in the tetrahydrofuran solution of Cyanuric Chloride, drip n-BuLi, control reaction temperature-78 DEG C, stir 1 hour, temperature is risen to be stirred at room temperature 60 minutes thereafter；
The reactant liquor that the first step is obtained by second step is cooled to-78 DEG C, and drips methyl borate. wherein, stirs 70 minutes, then heats to room temperature and stir 8 hours；
3rd step Rotary Evaporators removes the oxolane in second step reactant liquor and unreacted methyl borate., obtains solid product。Dissolve this solid product with dichloromethane, be subsequently adding saturated aqueous ammonium chloride and extract, collect organic facies, dry with anhydrous sodium sulfate and filter, filtrate decompression is removed organic solvent and obtains the crude product of 2,4,6-tri-borates-1,3,5-triazines。Using the mixed solvent of petroleum ether and ethyl acetate (volume ratio is for 20: 1) as flushing liquor, it is easily separated by chromatographic column and obtains pure 2,4,6-tri-borates-1,3,5-triazines。
2,4,6-tri-borates-1,3,5-triazines is carried out acidolysis by the 4th step dilute hydrochloric acid, adjusts pH to 3.2 to precipitate out solid, and obtains pure Tz-3B with frozen water cyclic washing。
Utilizing mass spectrum, nucleus magnetic hydrogen spectrum to characterize obtained product, structural characterization data are as follows:
Mass spectrum: m/z212.6 (M+)
Hydrogen is composed1H-NMR (400MHz, DMSO, ppm): 1.9 (s, 6H, OH)
According to thermogravimetry, recording the product carbon yield when being heated to 800 DEG C is 35%。
The preparation of embodiment 22,4,6-tri-boronate-1,3,5-triazines (Tz-3B):
Under first step nitrogen protection, in the tetrahydrofuran solution of Cyanuric Chloride, drip n-BuLi, control reaction temperature-78 DEG C, stir 5 hours, temperature is risen to be stirred at room temperature 45 minutes thereafter；
The reactant liquor that the first step is obtained by second step is cooled to-78 DEG C, and drips methyl borate. wherein, stirs 45 minutes, then heats to room temperature and stir 8 hours；
3rd step Rotary Evaporators removes the oxolane in second step reactant liquor and unreacted methyl borate., obtains solid product。Dissolve this solid product with dichloromethane, be subsequently adding saturated aqueous ammonium chloride and extract, collect organic facies, dry with anhydrous sodium sulfate and filter, filtrate decompression is removed organic solvent and obtains the crude product of 2,4,6-tri-borates-1,3,5-triazines。Using the mixed solvent of petroleum ether and ethyl acetate (volume ratio is for 20: 1) as flushing liquor, it is easily separated by chromatographic column and obtains pure 2,4,6-tri-borates-1,3,5-triazines。
2,4,6-tri-borates-1,3,5-triazines is carried out acidolysis by the 4th step dilute hydrochloric acid, adjusts pH to 3.9 to precipitate out solid, and obtains pure Tz-3B with frozen water cyclic washing。
Embodiment 3N, N ', N " preparation of-three [(4 ', 6 '-hypoboric acid base)-2 '-triazine radical]-1,3,5-benzene triamine (BTAm-3Tz-6B):
Cyanuric Chloride is dissolved in oxolane by the first step, drips the tetrahydrofuran solution of 1,3,5-benzene triamine under agitation, drips Bi Jixu and stirs 1 hour；Remove solvent and obtain solid product, by ethyl acetate, solid product is carried out recrystallization and obtain pure N, N ', N "-three [(4 ', 6 '-dichloro)-2 '-triazine radical]-1,3,5-benzene triamine；
Second step under nitrogen protection, to N, N ', " in the tetrahydrofuran solution of-three [(4 ', 6 '-dichloro)-2 '-triazine radical]-1,3,5-benzene triamine, dropping n-BuLi, controls reaction temperature-78 DEG C, stirs 1 hour N；Drip methyl borate. wherein, stir 80 minutes, then heat to room temperature and stir 12 hours；
3rd step Rotary Evaporators removes the oxolane in second step reactant liquor and unreacted methyl borate., obtains solid product。This solid product is dissolved with dichloromethane, it is subsequently adding saturated aqueous ammonium chloride to extract, collect organic facies, dry with anhydrous sodium sulfate and filter, filtrate decompression being removed organic solvent and obtains N, N ', N " the crude product of-three [(4 '; 6 '-diborate)-2 '-triazine radical]-1,3,5-benzene triamine。Using the mixed solvent of petroleum ether and ethyl acetate (volume ratio is for 5: 1) as flushing liquor, it is easily separated by chromatographic column and obtains pure N, N ', N "-three [(4 ', 6 '-diborate)-2 '-triazine radical]-1,3,5-benzene triamine；
4th step dilute hydrochloric acid is to N, N ', "-three [(4 ', 6 '-diborate)-2 '-triazine radical]-1,3,5-benzene triamine carries out acidolysis to N, adjusts pH to 3.5 to precipitate out solid, and obtains pure BTAm-3Tz-6B with frozen water cyclic washing。
Utilizing mass spectrum, nucleus magnetic hydrogen spectrum to characterize obtained product, structural characterization data are as follows:
Mass spectrum: m/z623.3 (M+)
Hydrogen is composed1H-NMR (400MHz, DMSO, ppm): 1.8 (s, 6H, OH), 4.0 (s, 3H, NH), 5.1 (s, 3H)
According to thermogravimetry, recording the product carbon yield when being heated to 800 DEG C is 47%。
Embodiment 4N, N ', N " preparation of-three [(4 ', 6 '-hypoboric acid base)-2 '-triazine radical]-1,3,5-benzene triamine (BTAm-3Tz-6B):
Cyanuric Chloride is dissolved in oxolane by the first step, drips the tetrahydrofuran solution of 1,3,5-benzene triamine under agitation, drips Bi Jixu and stirs 3 hours；Remove solvent and obtain solid product, by ethyl acetate, solid product is carried out recrystallization and obtain pure N, N ', N "-three [(4 ', 6 '-dichloro)-2 '-triazine radical]-1,3,5-benzene triamine；
Second step under nitrogen protection, to N, N ', " in the tetrahydrofuran solution of-three [(4 ', 6 '-dichloro)-2 '-triazine radical]-1,3,5-benzene triamine, dropping n-BuLi, controls reaction temperature-78 DEG C, stirs 4 hours N；Drip methyl borate. wherein, stir 50 minutes, then heat to room temperature and stir 13 hours；
3rd step Rotary Evaporators removes the oxolane in second step reactant liquor and unreacted methyl borate., obtains solid product。This solid product is dissolved with dichloromethane, it is subsequently adding saturated aqueous ammonium chloride to extract, collect organic facies, dry with anhydrous sodium sulfate and filter, filtrate decompression being removed organic solvent and obtains N, N ', N " the crude product of-three [(4 '; 6 '-diborate)-2 '-triazine radical]-1,3,5-benzene triamine。Using the mixed solvent of petroleum ether and ethyl acetate (volume ratio is for 5: 1) as flushing liquor, it is easily separated by chromatographic column and obtains pure N, N ', N "-three [(4 ', 6 '-diborate)-2 '-triazine radical]-1,3,5-benzene triamine；
4th step dilute hydrochloric acid is to N, N ', "-three [(4 ', 6 '-diborate)-2 '-triazine radical]-1,3,5-benzene triamine carries out acidolysis to N, adjusts pH to 3.6 to precipitate out solid, and obtains pure BTAm-3Tz-6B with frozen water cyclic washing。
The preparation of embodiment 51,3,5-tri-[(4 ', 6 '-hypoboric acid)-2 '-triazine radical]-benzenetriol (BTHo-3Tz-6B):
Cyanuric Chloride is dissolved in oxolane by the first step, drips the tetrahydrofuran solution of 1,3,5-benzenetriol under agitation, drips Bi Jixu and stirs 1 hour；Remove solvent and obtain solid product, by ethyl acetate, solid product carried out recrystallization and obtain pure 1,3,5-tri-[(4 ', 6 '-dichloro)-2 '-triazine radical]-benzenetriol；
Under nitrogen protection, dropping n-BuLi in the tetrahydrofuran solution of [(4 ', 6 '-dichloro)-2 '-triazine radical]-benzenetriol, controls reaction temperature-78 DEG C, stirs 1 hour second step to 1,3,5-tri-；Drip methyl borate. wherein, stir 80 minutes, then heat to room temperature and stir 12 hours；
3rd step Rotary Evaporators removes the oxolane in second step reactant liquor and unreacted methyl borate., obtains solid product。This solid product is dissolved with dichloromethane, it is subsequently adding saturated aqueous ammonium chloride to extract, collect organic facies, dry with anhydrous sodium sulfate and filter, filtrate decompression is removed organic solvent and obtains 1, the crude product of 3,5-tri-[(4 ', 6 '-diborate)-2 '-triazine radical]-benzenetriol。Using the mixed solvent of petroleum ether and ethyl acetate (volume ratio is for 4: 1) as flushing liquor, it is easily separated by chromatographic column and obtains pure 1,3,5-tri-[(4 ', 6 '-diborate)-2 '-triazine radical]-benzenetriol；
[(4 ', 6 '-diborate)-2 '-triazine radical]-benzenetriol carries out acidolysis to 4th step dilute hydrochloric acid to 1,3,5-tri-, adjusts pH to 3.1 to precipitate out solid, and obtains pure BTHo-3Tz-6B with frozen water cyclic washing。
Utilizing mass spectrum, nucleus magnetic hydrogen spectrum to characterize obtained product, structural characterization data are as follows:
Mass spectrum: m/z626.2 (M+)
Hydrogen is composed1H-NMR (400MHz, DMSO, ppm): 1.8 (s, 6H, OH), 5.8 (s, 3H)
According to thermogravimetry, recording the product carbon yield when being heated to 800 DEG C is 51%。
The preparation of embodiment 61,3,5-tri-[(4 ', 6 '-hypoboric acid)-2 '-triazine radical]-benzenetriol (BTHo-3Tz-6B):
Cyanuric Chloride is dissolved in oxolane by the first step, drips the tetrahydrofuran solution of 1,3,5-benzenetriol under agitation, drips Bi Jixu and stirs 3 hours；Remove solvent and obtain solid product, by ethyl acetate, solid product carried out recrystallization and obtain pure 1,3,5-tri-[(4 ', 6 '-dichloro)-2 '-triazine radical]-benzenetriol；
Under nitrogen protection, dropping n-BuLi in the tetrahydrofuran solution of [(4 ', 6 '-dichloro)-2 '-triazine radical]-benzenetriol, controls reaction temperature-78 DEG C, stirs 4 hours second step to 1,3,5-tri-；Drip methyl borate. wherein, stir 50 minutes, then heat to room temperature and stir 14 hours；
3rd step Rotary Evaporators removes the oxolane in second step reactant liquor and unreacted methyl borate., obtains solid product。This solid product is dissolved with dichloromethane, it is subsequently adding saturated aqueous ammonium chloride to extract, collect organic facies, dry with anhydrous sodium sulfate and filter, filtrate decompression is removed organic solvent and obtains 1, the crude product of 3,5-tri-[(4 ', 6 '-diborate)-2 '-triazine radical]-benzenetriol。Using the mixed solvent of petroleum ether and ethyl acetate (volume ratio is for 4: 1) as flushing liquor, it is easily separated by chromatographic column and obtains pure 1,3,5-tri-[(4 ', 6 '-diborate)-2 '-triazine radical]-benzenetriol；
[(4 ', 6 '-diborate)-2 '-triazine radical]-benzenetriol carries out acidolysis to 4th step dilute hydrochloric acid to 1,3,5-tri-, adjusts pH to 3.7 to precipitate out solid, and obtains pure BTHo-3Tz-6B with frozen water cyclic washing。
Claims (4)
1. triazines boronic acid derivatives, it is characterised in that be 2,4,6-tri-boronate-1,3,5-triazines (Tz-3B), N, N ', N "-three [(4 ', 6 '-hypoboric acid base)-2 '-triazine radical]-1; 3; 5-benzene triamine (BTAm-3Tz-6B) or 1,3,5-tri-[(4 '; 6 '-hypoboric acid)-2 '-triazine radical]-benzenetriol (BTHo-3Tz-6B), there is following molecular structure:
2. the preparation method of Tz-3B described in preparation claim 1, it is characterised in that comprise the following steps that
Under first step nitrogen protection, in the tetrahydrofuran solution of Cyanuric Chloride, drip n-BuLi, control reaction temperature-78 DEG C, stir 1-5 hour, temperature is risen to 45-60 clock is stirred at room temperature thereafter；
The reactant liquor that the first step is obtained by second step is cooled to-78 DEG C, and drips methyl borate. wherein, stirs 45-70 minute, then heats to room temperature and stir 8-10 hour；
3rd step Rotary Evaporators removes the oxolane in second step reactant liquor and unreacted methyl borate., obtains solid product；Dissolve this solid product with dichloromethane, be subsequently adding saturated aqueous ammonium chloride and extract, collect organic facies, dry with anhydrous sodium sulfate and filter, filtrate decompression is removed organic solvent and obtains the crude product of 2,4,6-tri-borates-1,3,5-triazines；Using the mixed solvent of petroleum ether and ethyl acetate as flushing liquor, it is easily separated by chromatographic column and obtains pure 2,4,6-tri-borates-1,3,5-triazines；
2,4,6-tri-borates-1,3,5-triazines is carried out acidolysis by the 4th step dilute hydrochloric acid, adjusts pH to 3-4 to precipitate out solid, and obtains pure Tz-3B with frozen water cyclic washing。
3. the preparation method of BTAm-3Tz-6B according to claim 1, it is characterised in that comprise the following steps that
Cyanuric Chloride is dissolved in oxolane by the first step, drips the tetrahydrofuran solution of 1,3,5-benzene triamine under agitation, drips Bi Jixu and stirs 1-3 hour；Remove solvent and obtain solid product, by ethyl acetate, solid product is carried out recrystallization and obtain pure N, N ', N "-three [(4 ', 6 '-dichloro)-2 '-triazine radical]-1,3,5-benzene triamine；
Second step under nitrogen protection, to N, N ', " in the tetrahydrofuran solution of-three [(4 ', 6 '-dichloro)-2 '-triazine radical]-1,3,5-benzene triamine, dropping n-BuLi, controls reaction temperature-78 DEG C, stirs 1-4 hour N；Drip methyl borate. wherein, stir 50-80 minute, then heat to room temperature and stir 12-15 hour；
3rd step Rotary Evaporators removes the oxolane in second step reactant liquor and unreacted methyl borate., obtains solid product；This solid product is dissolved with dichloromethane, it is subsequently adding saturated aqueous ammonium chloride to extract, collect organic facies, dry with anhydrous sodium sulfate and filter, filtrate decompression being removed organic solvent and obtains N, N ', N " the crude product of-three [(4 '; 6 '-diborate)-2 '-triazine radical]-1,3,5-benzene triamine；Using the mixed solvent of petroleum ether and ethyl acetate (volume ratio is for 5: 1) as flushing liquor, it is easily separated by chromatographic column and obtains pure N, N ', N "-three [(4 ', 6 '-diborate)-2 '-triazine radical]-1,3,5-benzene triamine；
4th step dilute hydrochloric acid is to N, N ', "-three [(4 ', 6 '-diborate)-2 '-triazine radical]-1,3,5-benzene triamine carries out acidolysis to N, adjusts pH to 3-4 to precipitate out solid, and obtains pure BTAm-3Tz-6B with frozen water cyclic washing。
4. the preparation method of BTHo-3Tz-6B according to claim 1, it is characterised in that comprise the following steps that
Cyanuric Chloride is dissolved in oxolane by the first step, drips the tetrahydrofuran solution of 1,3,5-benzenetriol under agitation, drips Bi Jixu and stirs 1-3 hour；Remove solvent and obtain solid product, by ethyl acetate, solid product carried out recrystallization and obtain pure 1,3,5-tri-[(4 ', 6 '-dichloro)-2 '-triazine radical]-benzenetriol；
Under nitrogen protection, dropping n-BuLi in the tetrahydrofuran solution of [(4 ', 6 '-dichloro)-2 '-triazine radical]-benzenetriol, controls reaction temperature-78 DEG C, stirs 1-4 hour second step to 1,3,5-tri-；Drip methyl borate. wherein, stir 50-80 minute, then heat to room temperature and stir 11-15 hour；
3rd step Rotary Evaporators removes the oxolane in second step reactant liquor and unreacted methyl borate., obtains solid product；This solid product is dissolved with dichloromethane, it is subsequently adding saturated aqueous ammonium chloride to extract, collect organic facies, dry with anhydrous sodium sulfate and filter, filtrate decompression is removed organic solvent and obtains 1, the crude product of 3,5-tri-[(4 ', 6 '-diborate)-2 '-triazine radical]-benzenetriol；Using the mixed solvent of petroleum ether and ethyl acetate as flushing liquor, it is easily separated by chromatographic column and obtains pure 1,3,5-tri-[(4 ', 6 '-diborate)-2 '-triazine radical]-benzenetriol；
[(4 ', 6 '-diborate)-2 '-triazine radical]-benzenetriol carries out acidolysis to 4th step dilute hydrochloric acid to 1,3,5-tri-, adjusts pH to 3-4 to precipitate out solid, and obtains pure BTHo-3Tz-6B with frozen water cyclic washing。
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