CN108033925A - A kind of benzotriazole compound and preparation method thereof - Google Patents
A kind of benzotriazole compound and preparation method thereof Download PDFInfo
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- CN108033925A CN108033925A CN201711444244.9A CN201711444244A CN108033925A CN 108033925 A CN108033925 A CN 108033925A CN 201711444244 A CN201711444244 A CN 201711444244A CN 108033925 A CN108033925 A CN 108033925A
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- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/16—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms condensed with carbocyclic rings or ring systems
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Abstract
The present invention relates to a kind of benzotriazole compound and preparation method thereof, using o-phenylenediamine or o-phenylenediamine class compound and nitrous acid spy's fourth fat as reaction raw materials, in reaction dissolvent, benzotriazole compound is obtained by the diazo-reaction of intramolecular under room temperature.The preparation method substrate spectrum is extensive, reaction condition is gentle, post processing is simple, the yield of product and purity are high, has opened up new synthetic route and method for benzotriazole compound, has had good application potential and researching value.
Description
Technical field
The invention belongs to organic compound synthesis technical field, more particularly, to a kind of benzotriazole compound and preparation
Method.
Background technology
Benzotriazole (BTA) is a kind of important organic synthesis intermediate, mainly as water treatment agent, preservative and light
Stabilizer, applied in the products such as antirust oil, lipid and copper and copper alloy.Such as：In plating to surface purifying silver,
Copper, zinc, there is Anti- tarnishing effect.BTA is good UV absorbers, and stable work can be played to the product of ultraviolet-sensitive
With, such as prevent diazo colours from fading, it can prevent from becoming with laminates such as BTA processing paper, braid, film, metal coins
Color.In mechanical processing process, BTA is added in grinding oil, cutting oil, the copper piece of processing can be made non-discolouring.The product may be used also
As analytical reagent, shared with ammonium hydroxide and ethylenediamine tetraacetic acid (EDTA), benzotriazole can be used for optionally measuring silver, copper, zinc.Also may be used
As photography antifoggant and organic synthesis intermediate.
So important just because of benzotriazole compound, people, which synthesize it, has carried out numerous studies, at present
Explore a plurality of synthetic route and method：
The first is to use o-phenylenediamine high-pressure process：Using o-phenylenediamine and sodium nitrite as raw material, in high temperature (common 200-
300 °) react under the conditions of high pressure (5-8 atmospheric pressure), then solution is adjusted to PH and obtains benzotriazole for 6, however it is this
Preparation method is there are severe reaction conditions, the defects of low yield, environmental pollution is big.
Second is to use benzimidazolone method：Using benzimidazolone and sodium nitrite as raw material, in water phase, high temperature is high
Benzotriazole is obtained under pressure reaction condition, but raw material benzimidazolone used in this method is expensive to restrict this synthesis
The application of method.
The third is to use adjacent nitro phenylhydrazine method：It is being in ammonium hydroxide, isopropanol and hexylene glycol by raw material of adjacent nitro phenylhydrazine
Mixed solution, under high-temperature and high-pressure conditions reaction obtain 1- hydroxy benzo triazoles, then using copper-chrome green as being catalyzed
Agent synthesizes benzotriazole by deoxidation hydrogenation reaction under elevated pressure conditions, but adjacent nitro phenylhydrazine valency used in this method is high
It is hard to find so that the reaction is difficult to realize industrialize.
Although as described above and as it can be seen that exist in the prior art it is a variety of preparation benzotriazole compounds preparation methods,
But harsh reaction condition of these methods all there are high temperature and pressure, environmental pollution are big, expensive reagents, yield are relatively low, substrate is expanded
The shortcomings such as difference.Therefore, for it is easy, be easily handled, the benzotriazole compounds compound that reaction condition is gentle
Synthetic method, still suffers from the necessity for continuing to study and exploring, this is also medicine intermediate field for benzotriazole
The active demand that compound demand is determined strongly, and one of current research hotspot.
The content of the invention
Goal of the invention：First technical problem to be solved by this invention is the preparation process in benzotriazole compound
In it is complicated the problem of.
Second technical problem to be solved by this invention is to react bar in the preparation process of benzotriazole compound
The problem of part is not gentle enough
3rd technical problem to be solved by this invention is to make the preparation process of benzotriazole compound be adapted to advise greatly
The problem of mould industrialized production.
The content of the invention：In order to solve the above technical problems, the present invention provides following technical proposals：
A kind of preparation method of benzotriazole compound, with the o-phenylenediamine of structure as shown in formula (I) or adjacent benzene
Diamine compounds, nitrous acid spy's fourth fat are raw material, are obtained in reaction dissolvent by diazo-reaction as shown in formula (II)
Benzotriazole compound；
In formula (I) and (II), R is each independently selected from H, chlorine, bromine, trifluoromethyl, the tert-butyl group and methyl.
Further, the reaction dissolvent is dimethyl sulfoxide (DMSO), n,N-Dimethylformamide, acetonitrile, toluene, tetrahydrochysene furan
Mutter, at least one of ethyl acetate, Isosorbide-5-Nitrae-dioxane, dichloroethanes, NMP, the tert-butyl alcohol, water, preferably water.
Further, o-phenylenediamine or o-phenylenediamine class compound and the molar ratio of the nitrous acid spy fourth fat are 1:(1~
5)。
Further, o-phenylenediamine or o-phenylenediamine class compound and the molar ratio of the nitrous acid spy fourth fat are 1:(1~
3)。
Further, o-phenylenediamine or o-phenylenediamine class compound and the molar ratio of the reaction dissolvent are 1：(150~
1000)。
Further, the reaction temperature of the diazo-reaction is room temperature.
Further, the time of the diazo-reaction is 0.1~0.5h.
Further, the diazo-reaction comprises the following steps：
S1 adds o-phenylenediamine or o-phenylenediamine class compound, nitrous acid spy's fourth fat and reaction dissolvent in reaction vessel,
Then 0.1~0.5h of stirring reaction at normal temperatures, obtains reaction solution after reaction；
S2 adds ethyl acetate after reaction solution is cooled down and the ethyl acetate containing extract is obtained by extraction；
S3 dries the ethyl acetate containing extract by adding excessive anhydrous sodium sulfate, and filtering, is concentrated under reduced pressure, obtains
To concentrate；
S4 by concentrate by pillar layer separation, with petroleum ether and ethyl acetate volume ratio 3:1 is eluant, eluent, collects elution
Liquid, spins off solvent, that is, obtains the benzotriazole compound as shown in formula (II).
Further, the pillar layer separation in step S4 uses 300-400 mesh silica gel.
A kind of benzotriazole compound, the benzotriazole compound is as above-mentioned synthetic method system described in any one
.
Beneficial effect：A kind of benzotriazole compound provided by the invention and preparation method thereof has following beneficial to effect
Fruit：
A) reaction efficiently, high income, post processing it is simple, easy to operate；
B) oxidising agent and catalyst are added without；
C) reaction is carried out in room temperature, mild condition；
D) reaction green, economy；
E) reaction substrate functional group tolerance is high, substrate spectrum is wide and easily prepares；
F) reaction efficiency higher after reaction amplification.
The present invention is using o-phenylenediamine class compound cheap and easy to get and nitrous acid spy's fourth fat as reaction raw materials, in water phase,
Benzotriazole compound is obtained by the diazo-reaction of intramolecular, experimental implementation is simple, and reaction condition is gentle, is adapted to big
Technical scale metaplasia is produced.
Embodiment
In order to illustrate more clearly of the present invention, with reference to preferred embodiment, the present invention is described further.Ability
Field technique personnel should be appreciated that following specifically described content is illustrative and be not restrictive, this should not be limited with this
The protection domain of invention.
A kind of preparation method of benzotriazole compound, with the o-phenylenediamine of structure as shown in formula (I) or adjacent benzene
Diamine compounds and nitrous acid spy's fourth fat are raw material, are obtained in reaction dissolvent by the diazo-reaction of intramolecular such as formula
(II) the benzotriazole compound shown in；
Above-mentioned reaction process, can be represented with following reaction equations：
(I) molar ratio of the o-phenylenediamine of structure shown in formula or phenylenediamine compound and nitrous acid spy's fourth fat is 1:(1~
5), preferably 1:(1~3).
(1) o-phenylenediamine or o-phenylenediamine class compound
O-phenylenediamine or o-phenylenediamine class compound have the structure as shown in formula (I)：
In formula (I), R is each independently selected from H, chlorine, bromine, trifluoromethyl, the tert-butyl group and methyl.
(2) reaction dissolvent
The reaction dissolvent used in the present invention is dimethyl sulfoxide (DMSO), N,N-dimethylformamide, acetonitrile, toluene, tetrahydrochysene furan
Mutter, at least one of ethyl acetate, Isosorbide-5-Nitrae-dioxane, dichloroethanes, NMP, the tert-butyl alcohol, water, preferably water..
(3) reaction temperature
The present invention preparation method in, reaction temperature is room temperature, may be, for example, in non-limiting manner 0 DEG C, 5 DEG C, 10 DEG C, 15
DEG C, 20 DEG C, 25 DEG C, 30 DEG C or 40 DEG C
(4) reaction time
In the preparation process in accordance with the present invention, the reaction time, there is no particular limitation, such as can pass through liquid chromatographic detection mesh
Product or raw material residual percentage and determine the suitable reaction time, it typically is 0.1-0.5 it is small when, example in non-limiting manner
Such as 0.1 it is small when, 0.15 it is small when, 0.2 it is small when, 0.25 it is small when, 0.3 it is small when, 0.35 it is small when or 0.4 it is small when.
(5) isolate and purify
The mixture of gained after reaction can be isolated and purified further, to obtain purer final products.This
The field method well-known to the ordinarily skilled artisan isolated and purified, for example, can use extraction, column chromatography, distillation, decantation, filtering, from
The methods of heart, washing, evaporation, recrystallization, stripping and absorption or its at least two combination, is isolated and purified, such as is extracted
Take, column chromatography.
Certainly, the reaction mixture of acquisition can also be introduced directly into other processes directly reaction if desired to produce
Other products.Optionally, before other processes are incorporated into, can to reaction mixing pre-process, such as concentration, extraction and
One or more in vacuum distillation, to obtain crude product or pure product, are then incorporated into other processes.
In a preferred embodiment, the diazo-reaction comprises the following steps：
S1 adds o-phenylenediamine or o-phenylenediamine class compound, nitrous acid spy's fourth fat and reaction dissolvent in reaction vessel,
Then 0.1~0.5h of stirring reaction at normal temperatures, obtains reaction solution after reaction；
S2 adds ethyl acetate after reaction solution is cooled down and the ethyl acetate containing extract is obtained by extraction；
S3 dries the ethyl acetate containing extract by adding excessive anhydrous sodium sulfate, and filtering, is concentrated under reduced pressure, obtains
To concentrate；
S4 by concentrate by pillar layer separation, with petroleum ether and ethyl acetate volume ratio 3:1 is eluant, eluent, collects elution
Liquid, spins off solvent, that is, obtains the benzotriazole compound as shown in formula (II).
Further, the pillar layer separation in step S4 uses 300-400 mesh silica gel.
Embodiment 1
The synthesis of benzotriazole
At room temperature, o-phenylenediamine (0.3mmol, 1equiv), nitrous acid spy's fourth fat (0.45mmol, 1.5equiv) are added
Enter into reaction tube, add the H of 50mmol2O, 15min is stirred under 25 DEG C of reaction temperatures, obtains reaction solution after reaction；
Then 10ml ethyl acetate is added after reaction solution is cooled down the ethyl acetate containing extract is obtained by extraction；Extract will be contained again
Ethyl acetate dried by adding excessive anhydrous sodium sulfate, filtering, is concentrated under reduced pressure, obtains concentrate；Finally by concentrate
By pillar layer separation (using 300 mesh silica gel), with petroleum ether and ethyl acetate volume ratio 3:1 is eluant, eluent, collects eluent,
Solvent is spun off, obtains white solid, that is, obtains the benzotriazole compound as shown in formula (II), yield 99%.
The data of the nuclear magnetic resonance spectroscopy of products therefrom are as follows：
1HNMR(500MHz,CDCl3)δ7.47(2H,d),7.93(2H,d).
The data of the carbon-13 nmr spectra of products therefrom are as follows：
13C NMR(125MHz,CDCl3)δ114.72,126.56,138.06.
The theoretical calculation and experimental result analyzed product are as follows：
Anal.Calcd.For C6H5N3:C,60.50；H,4.23；N,35.27；
Found:C,60.51；H,4.24；N,35.28.
Embodiment 2
The synthesis of 5,6- dichloro benzotriazole
At room temperature, by 4,5- dichloros o-phenylenediamine (0.3mmol, 1equiv), nitrous acid spy's fourth fat (1.5mmol,
5equiv) it is added in reaction tube, adds the H of 300mmol2O, stirs 30min under 40 DEG C of reaction temperatures, after reaction
To reaction solution；Then 10ml ethyl acetate is added after reaction solution is cooled down the ethyl acetate containing extract is obtained by extraction；Again will
Ethyl acetate containing extract is dried by adding excessive anhydrous sodium sulfate, and filtering, is concentrated under reduced pressure, obtains concentrate；Most
Afterwards by concentrate by pillar layer separation (using 400 mesh silica gel), with petroleum ether and ethyl acetate volume ratio 3:1 is eluant, eluent,
Eluent is collected, solvent is spun off, obtains white solid, that is, obtain the benzotriazole compound as shown in formula (II), yield
93%.
The data of the nuclear magnetic resonance spectroscopy of products therefrom are as follows：
1HNMR(500MHz,d6-DMSO)δ8.27(2H,s).
The data of the carbon-13 nmr spectra of products therefrom are as follows：
13CNMR(125MHz,d6-DMSO)δ116.98,128.58,138.69.
The theoretical calculation and experimental result analyzed product are as follows：
Anal.Calcd.For C6H3Cl2N3:C,38.33；H,1.61；Cl,37.71；N,22.35；
Found:C,38.34；H,1.62；Cl,37.72；N,22.36.
Embodiment 3
The synthesis of 5- methyl benzotriazazoles
At room temperature, by 5- methyl-o-phenylenediamines (0.3mmol, 1equiv), nitrous acid spy's fourth fat (0.3mmol,
1equiv) it is added in reaction tube, adds the H of 45mmol2O, 6min is stirred under 0 DEG C of reaction temperature, is obtained after reaction
Reaction solution；Then 10ml ethyl acetate is added after reaction solution is cooled down the ethyl acetate containing extract is obtained by extraction；It will contain again
The ethyl acetate for having extract is dried by adding excessive anhydrous sodium sulfate, and filtering, is concentrated under reduced pressure, obtains concentrate；Finally
By concentrate by pillar layer separation (using 325 mesh silica gel), with petroleum ether and ethyl acetate volume ratio 3:1 is eluant, eluent, is received
Collect eluent, spin off solvent, obtain white solid, that is, obtain the benzotriazole compound as shown in formula (II), yield 83%；
The data of the nuclear magnetic resonance spectroscopy of products therefrom are as follows：
1H NMR(500MHz,CDCl3)δ:2.47(s,3H),7.23-7.24(d,1H),7.59(s,1H),7.79-7.82
(d,1H).
The data of the carbon-13 nmr spectra of products therefrom are as follows：
13CNMR(125MHz,CDCl3)δ:21.59,113.07,115.47,122.84,136.81,137.97,138.93.
The theoretical calculation and experimental result analyzed product are as follows：
Anal.Calcd.For C7H7N3:C,63.14；H,5.30；N,31.56；
Found:C,63.15；H,5.31；N,31.55.
Embodiment 4
The synthesis of the bromo- 6- trifluoromethyls benzo triazoles of 4-
At room temperature, by the bromo- 6- trifluoromethyls o-phenylenediamines (0.3mmol, 1equiv) of 4-, nitrous acid spy's fourth fat
(0.45mmol, 1.5equiv) is added in reaction tube, adds the H of 60mmol2O, stirs 24min, instead under 5 DEG C of reaction temperatures
Reaction solution is obtained after answering；Then 10ml ethyl acetate is added after reaction solution is cooled down the acetic acid containing extract is obtained by extraction
Ethyl ester；The ethyl acetate containing extract is dried by adding excessive anhydrous sodium sulfate again, filtering, is concentrated under reduced pressure, obtains
Concentrate；Finally by concentrate by pillar layer separation (using 325 mesh silica gel), with petroleum ether and ethyl acetate volume ratio 3:1
For eluant, eluent, eluent is collected, solvent is spun off, obtains white solid, that is, obtain the benzotriazole chemical combination as shown in formula (II)
Thing, yield 92%.
The data of the nuclear magnetic resonance spectroscopy of products therefrom are as follows：
1HNMR(500MHz,d6-DMSO)δ8.27(1H,s)；7.76(1H,s)；
The data of the carbon-13 nmr spectra of products therefrom are as follows：
13C NMR(125MHz,d6-DMSO)δ:109.59,113.87,122.61,125.48,125.82,140.96,
142.62；
The theoretical calculation and experimental result analyzed product are as follows：
Anal.Calcd.For C7H3BrF3N3:C,31.61；H,1.14；Br,30.04；F,21.43；N,15.80；
Found:C,31.60；H,1.14；Br,30.05；F,21.44；N,15.80.
Embodiment 5
The synthesis of 5- tert-butyl group benzotriazole
At room temperature, by 4- tert-butyl os phenylenediamine (0.3mmol, 1equiv), nitrous acid spy's fourth fat (0.45mmol,
1.5equiv) it is added in reaction tube, adds the H of 150mmol2O, stirs 18min, after reaction under 10 DEG C of reaction temperatures
Obtain reaction solution；Then 10ml ethyl acetate is added after reaction solution is cooled down the ethyl acetate containing extract is obtained by extraction；Again
Ethyl acetate containing extract is dried by adding excessive anhydrous sodium sulfate, filtering, is concentrated under reduced pressure, obtains concentrate；
Finally by concentrate by pillar layer separation (using 325 mesh silica gel), with petroleum ether and ethyl acetate volume ratio 3:1 is elution
Agent, collects eluent, spins off solvent, obtain white solid, that is, obtain the benzotriazole compound as shown in formula (II), yield
95%.
The data of the nuclear magnetic resonance spectroscopy of products therefrom are as follows：
1HNMR(500MHz,C6D6)δ：1.13(s,9H),7.16–7.62(m,3H)；
The data of the carbon-13 nmr spectra of products therefrom are as follows：
13C NMR(125MHz,C6D6)δ：31.02,34.71,109.77,115.06,123.94,149.03. to product into
The theoretical calculation and experimental result of row analysis are as follows：
Anal.Calcd.For C10H13N3:C,68.54；H,7.48；N,23.98；
Found:C,68.53；H,7.49；N,23.97.
Embodiment 6
The synthesis of 5- Chloro-Benzotriazoles
At room temperature, by 4- chlorine o-phenylenediamine (0.3mmol, 1equiv), nitrous acid spy's fourth fat (0.9mmol, 3equiv)
It is added in reaction tube, adds the H of 200mmol2O, 15min is stirred under 15 DEG C of reaction temperatures, is reacted after reaction
Liquid；Then 10ml ethyl acetate is added after reaction solution is cooled down the ethyl acetate containing extract is obtained by extraction；Extraction will be contained again
The ethyl acetate of thing is taken to be dried by adding excessive anhydrous sodium sulfate, filtering, is concentrated under reduced pressure, obtains concentrate；Finally will be dense
Contracting thing is by pillar layer separation (using 325 mesh silica gel), with petroleum ether and ethyl acetate volume ratio 3:1 is eluant, eluent, and collection is washed
De- liquid, spins off solvent, obtains white solid, that is, obtain the benzotriazole compound as shown in formula (II), yield 99%.
The data of the nuclear magnetic resonance spectroscopy of products therefrom are as follows：
1H NMR(500MHz,d6-DMSO)δ:7.42,7.49(d,1H),7.93–8.03(m,2H).
The data of the carbon-13 nmr spectra of products therefrom are as follows：
13CNMR(100MHz,d6-DMSO)δ:114.73,117.28,126.31,130.53,138.42,139.63.
The theoretical calculation and experimental result analyzed product are as follows：
Anal.Calcd.For C7H7N3:C,46.93；H,2.63；Cl,23.08；N,27.36；
Found:C,46.92；H,2.64；Cl,23.09；N,27.37.
Embodiment 7
The synthesis of 5,6- dimethylbiphenyl triazoles
At room temperature, by 4,5- dimethyl o-phenylenediamine (0.3mmol, 1equiv), nitrous acid spy's fourth fat (0.6mmol,
2equiv) it is added in reaction tube, adds the H of 50mmol2O, stirs 12min under 20 DEG C of reaction temperatures, after reaction
To reaction solution；Then 10ml ethyl acetate is added after reaction solution is cooled down the ethyl acetate containing extract is obtained by extraction；Again will
Ethyl acetate containing extract is dried by adding excessive anhydrous sodium sulfate, and filtering, is concentrated under reduced pressure, obtains concentrate；Most
Afterwards by concentrate by pillar layer separation (using 400 mesh silica gel), with petroleum ether and ethyl acetate volume ratio 3:1 is eluant, eluent,
Eluent is collected, solvent is spun off, obtains white solid, that is, obtain the benzotriazole compound as shown in formula (II), yield
91%.
The data of the nuclear magnetic resonance spectroscopy of products therefrom are as follows：
1HNMR(500MHz,CDCl3)δ：2.33(s,6H),7.59(s,2H)；
The data of the carbon-13 nmr spectra of products therefrom are as follows：
13CNMR(125MHz,CDCl3)δ：20.65,114.07,136.12,138.06.
The theoretical calculation and experimental result analyzed product are as follows：
Anal.Calcd.For C8H9N3:C,65.29；H,6.16；N,28.55；
Found:C,65.28；H,6.17；N,28.54.
Embodiment 8
The synthesis of the chloro- 6- fluorine benzotriazole of 5-
At room temperature, by the chloro- 5- fluorine o-phenylenediamines (0.3mmol, 1equiv) of 4-, nitrous acid spy's fourth fat (0.45mmol,
1.5equiv) it is added in reaction tube, adds the H of 100mmol2O, stirs 15min, after reaction under 25 DEG C of reaction temperatures
Obtain reaction solution；Then 10ml ethyl acetate is added after reaction solution is cooled down the ethyl acetate containing extract is obtained by extraction；Again
Ethyl acetate containing extract is dried by adding excessive anhydrous sodium sulfate, filtering, is concentrated under reduced pressure, obtains concentrate；
Finally by concentrate by pillar layer separation (using 325 mesh silica gel), with petroleum ether and ethyl acetate volume ratio 3:1 is elution
Agent, collects eluent, spins off solvent, obtain white solid, that is, obtain the benzotriazole compound as shown in formula (II), yield
83%.
The data of the nuclear magnetic resonance spectroscopy of products therefrom are as follows：
1HNMR(500MHz,d6-DMSO)δ:8.278(s,1H),7.99(s,1H).
The data of the carbon-13 nmr spectra of products therefrom are as follows：
13C NMR(125MHz,d6-DMSO)δ:109.61,113.85,122.66,125.58,125.92,140.85,
142.58.
The theoretical calculation and experimental result analyzed product are as follows：
Anal.Calcd.For C6H3ClFN3:C,42.01；H,1.76；Cl,20.66；F,11.07；N,24.49；
Found:C,42.02；H,1.77；Cl,20.67；F,11.08；N,24.48.
Embodiment 9
The synthesis of 5- trifluoromethyls and triazole
At room temperature, by 4- trifluoromethyls o-phenylenediamine (0.3mmol, 1equiv), nitrous acid spy's fourth fat (0.45mmol,
1.5equiv) it is added in reaction tube, adds the H of 50mmol2O, stirs 6min under 25 DEG C of reaction temperatures, after reaction
To reaction solution；Then 10ml ethyl acetate is added after reaction solution is cooled down the ethyl acetate containing extract is obtained by extraction；Again will
Ethyl acetate containing extract is dried by adding excessive anhydrous sodium sulfate, and filtering, is concentrated under reduced pressure, obtains concentrate；Most
Afterwards by concentrate by pillar layer separation (using 300 mesh silica gel), with petroleum ether and ethyl acetate volume ratio 3:1 is eluant, eluent,
Eluent is collected, solvent is spun off, obtains white solid, that is, obtain the benzotriazole compound as shown in formula (II), yield
98%.
The data of the nuclear magnetic resonance spectroscopy of products therefrom are as follows：
1H NMR(500MHz,d6-DMSO)δ8.38(s,1H,),8.07(d,1H),7.68(d,1H)；
The data of the carbon-13 nmr spectra of products therefrom are as follows：
13C NMR(125MHz,DMSO-d6+1drop TFA-d)δ：139.93,138.55,124.57,125.78,
122.45,115.52,114.87.
The theoretical calculation and experimental result analyzed product are as follows：
Anal.Calcd.For C7H4F3N3:C,44.93；H,2.15；F,30.46；N,22.46；
Found:C,44.92；H,2.16；F,30.45；N,22.45.
Embodiment 10
The synthesis of 6- bromine benzotriazole
At room temperature, by 5- bromines o-phenylenediamine (0.3mmol, 1equiv), nitrous acid spy's fourth fat (0.45mmol,
1.5equiv) it is added in reaction tube, adds the H of 50mmol2O, stirs 6min under 25 DEG C of reaction temperatures, after reaction
To reaction solution；Then 10ml ethyl acetate is added after reaction solution is cooled down the ethyl acetate containing extract is obtained by extraction；Again will
Ethyl acetate containing extract is dried by adding excessive anhydrous sodium sulfate, and filtering, is concentrated under reduced pressure, obtains concentrate；Most
Afterwards by concentrate by pillar layer separation (using 325 mesh silica gel), with petroleum ether and ethyl acetate volume ratio 3:1 is eluant, eluent,
Eluent is collected, solvent is spun off, obtains white solid, that is, obtain the benzotriazole compound as shown in formula (II), yield
96%.
The data of the nuclear magnetic resonance spectroscopy of products therefrom are as follows：
1H NMR(500MHz,d6- DMSO) δ=15.81 (bs, 1H), 8.15 (s, 1H), 7.86 (d, 1H), 7.51 (d,
1H)；
The data of the carbon-13 nmr spectra of products therefrom are as follows：
13C NMR (125MHz, DMSO-d6+1drop TFA-d) δ=140.01,138.05,128.56,118.48,
117.55,117.05.；
The theoretical calculation and experimental result analyzed product are as follows：
Anal.Calcd.For C6H4BrN3:C,36.39；H,2.04；Br,40.35；N,21.22；
Found:C,36.38；H,2.05；Br,40.35；N,21.21.
It can be seen that by above-described embodiment 1-10, when preparation method using the present invention, can be obtained with high yield, high-purity
To benzotriazole compound.
Embodiment 11-21
It is roughly the same with specific embodiment 1, differ only in reaction dissolvent difference.Used organic solvent and corresponding production
The yield of thing is as shown in table 1 below.
Table 1
| Numbering | Solvent | Reaction yield (%) |
| Embodiment 11 | Dimethyl sulfoxide (DMSO) | 46 |
| Embodiment 12 | N,N-dimethylformamide | 76 |
| Embodiment 13 | Toluene | 63 |
| Embodiment 14 | Acetonitrile | 53 |
| Embodiment 15 | Tetrahydrofuran | 52 |
| Embodiment 16 | Ethyl acetate | 46 |
| Embodiment 17 | 1,4- dioxane | 32 |
| Embodiment 18 | Dichloroethanes | 68 |
| Embodiment 19 | NMP | 59 |
| Embodiment 20 | The tert-butyl alcohol | 69 |
It can be seen that by upper table 1, when using other organic solvents, such as in intensive polar solvent dimethyl sulfoxide (DMSO), N, N- bis-
Methylformamide, NMP and nonpolar toluene, n-hexane and weak coordination organic solvent acetonitrile, six alkane of dioxy can react,
Yield has obvious reduction compared with water, it was demonstrated that the appropriately selected yield to reaction of solvent has significant impact.
In conclusion can clearly be found out by above-mentioned all embodiments, under Green Water solvent condition, o-phenylenediamine or adjacent benzene
Diamine compounds easily occur to chemically react and obtain benzotriazole with high yield and high-purity with nitrous acid spy's fourth fat
Compound, brand-new synthetic route is provided for the efficient quick synthesis of such compound.
Finally it should be noted that：The above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations；To the greatest extent
Pipe is described in detail the present invention with reference to foregoing embodiments, it will be understood by those of ordinary skill in the art that：Its according to
Can so modify to the technical solution described in foregoing embodiments, either to which part or all technical characteristic into
Row equivalent substitution；And these modifications or replacement, the essence of appropriate technical solution is departed from various embodiments of the present invention technology
The scope of scheme.
Claims (10)
1. a kind of preparation method of benzotriazole compound, it is characterised in that with the adjacent benzene two with the structure as shown in formula (I)
Amine or o-phenylenediamine class compound, nitrous acid spy's fourth fat are raw material, are obtained in reaction dissolvent by diazo-reaction such as formula
(II) the benzotriazole compound shown in；
In formula (I) and (II), R is each independently selected from H, chlorine, bromine, trifluoromethyl, the tert-butyl group and methyl.
2. the preparation method of a kind of benzotriazole compound according to claim 1, it is characterised in that the reaction is molten
Agent is dimethyl sulfoxide (DMSO), N,N-dimethylformamide, acetonitrile, toluene, tetrahydrofuran, ethyl acetate, 1,4- dioxane, dichloro
At least one of ethane, NMP, the tert-butyl alcohol, water.
A kind of 3. preparation method of benzotriazole compound according to claim 1, it is characterised in that o-phenylenediamine or
O-phenylenediamine class compound and the molar ratio of the nitrous acid spy fourth fat are 1:(1~5).
A kind of 4. preparation method of benzotriazole compound according to claim 1, it is characterised in that o-phenylenediamine or
O-phenylenediamine class compound and the molar ratio of the nitrous acid spy fourth fat are 1:(1~3).
A kind of 5. preparation method of benzotriazole compound according to any one of claims 1 to 4, it is characterised in that
O-phenylenediamine or o-phenylenediamine class compound and the molar ratio of the reaction dissolvent are 1：(150~1000).
A kind of 6. preparation method of benzotriazole compound according to any one of claims 1 to 4, it is characterised in that
The reaction temperature of the diazo-reaction is room temperature.
A kind of 7. preparation method of benzotriazole compound according to any one of claims 1 to 4, it is characterised in that
The time of the diazo-reaction is 0.1~0.5h.
A kind of 8. synthetic method of benzotriazole compound as described in claim 1 to 5, it is characterised in that the diazonium
Change reaction to comprise the following steps：
S1 adds o-phenylenediamine or o-phenylenediamine class compound, nitrous acid spy's fourth fat and reaction dissolvent in reaction vessel, then
0.1~0.5h of stirring reaction at normal temperatures, obtains reaction solution after reaction；
S2 adds ethyl acetate after reaction solution is cooled down and the ethyl acetate containing extract is obtained by extraction；
S3 dries the ethyl acetate containing extract by adding excessive anhydrous sodium sulfate, and filtering, is concentrated under reduced pressure, obtains dense
Contracting thing；
S4 by concentrate by pillar layer separation, with petroleum ether and ethyl acetate volume ratio 3:1 is eluant, eluent, collects eluent,
Solvent is spun off, that is, obtains the benzotriazole compound as shown in formula (II).
A kind of 9. synthetic method of benzotriazole compound as claimed in claim 8, it is characterised in that the column in step S4
Chromatographic isolation uses 300-400 mesh silica gel.
10. a kind of benzotriazole compound, it is characterised in that the benzotriazole compound is by any in claim 1-9
Synthetic method described in one is made.
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| CN109503575B (en) * | 2018-12-20 | 2021-01-29 | 温州大学 | Method for synthesizing [1,2,3] triazole [1,5-a ] pyridine compound by catalyst-free N-N coupling reaction |
| CN111100082A (en) * | 2019-11-18 | 2020-05-05 | 温州大学 | Preparation method of 2-aryl benzotriazole compound |
| TWI825787B (en) * | 2022-06-16 | 2023-12-11 | 利昌電氣工業有限公司 | Method and system for refining 5-chlorobenzotriazole |
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