CN105859583A - Method for synthesizing 2, 6-dibromo-4-cyanophenol - Google Patents
Method for synthesizing 2, 6-dibromo-4-cyanophenol Download PDFInfo
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- CN105859583A CN105859583A CN201610306903.1A CN201610306903A CN105859583A CN 105859583 A CN105859583 A CN 105859583A CN 201610306903 A CN201610306903 A CN 201610306903A CN 105859583 A CN105859583 A CN 105859583A
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- synthetic method
- bromide
- cyanophenol
- persulfate
- hydroxybenzonitrile
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
Abstract
The invention provides a method for synthesizing 2, 6-dibromo-4-cyanophenol. The method includes a particular operation step of carrying out reaction on 4-cyanol phenol and bromine such as sodium bromine and potassium bromine in air or nitrogen atmosphere in the presence of persulfate and solvents under heating or illumination conditions. The method has the advantages that the method is safe and reliable, is high in yield, free of pollution and easy to implement, is an environment-friendly chemical process and can be used for preparing the 2, 6-dibromo-4-cyanophenol, and reaction conditions are mild.
Description
Technical field
The present invention relates to chemical technology field, be specifically related to a kind of 2, the synthetic method of 6-bis-bromo-4-cyanophenol.
Background technology
2,6-bis-bromo-4-cyanophenols, also known as Brominal, this compound and caprylate, sodium salt, after the form such as potassium salt is widely used as selectivity bud, stem and leaf processes contact insecticide.Mainly absorbed by blade, by each process of inhibited photosynthesis, make rapidly tissue necrosis.It is applicable to the crop fields such as Semen Tritici aestivi, Fructus Hordei Vulgaris, rye (Secale cereale L.), Semen Maydis, Sorghum vulgare Pers., Caulis et Folium Lini, prevents and kill off broad leaved weed knotweed, Herba chenopodii, Herba Amaranthi tricoloris, Herba Silenes conoideae, Herba Solani Nigri, Herba Xanthii, wheatThe father-in-law, Herba Salsolae Collinae, Herba seu Flos Convolvuli arvensis, the annual dicotyledonous weeds such as corn-bind.Brominal storage is stable, and other herbicides do not react, in addition to alone, it is also possible to and multiple herbicide mixture, expand herbicidal spectrum.
At present, existing several 2, the synthetic method report of 6-bis-bromo-4-cyanophenol, but yet suffer from a lot of shortcoming, such as, reaction yield is low, and purity is inadequate, and course of reaction operation is dangerous, and reaction environment is seriously polluted etc..Therefore, seeking to a kind of high yield high-purity, environmental protection, simple to operate and efficient 2, the synthetic method of 6-bis-bromo-4-cyanophenol is in accordance with people's demand.
Height promotes culture (3, the study on the synthesis of 5-bis-bromo-4-4-hydroxy-benzonitrile caprylate, Agriculture of Anhui science, 2009,37 (16): 7314-7315.) using paracresol is raw material, under the effect of sodium hypochlorite, react generation 2 with bromine, 6-bis-bromo-4-methylphenol, 3 are generated again under hydrogen peroxide and catalyst action, 5-dibromine-4-hydroxy benzaldehyde, finally reacts generation 2,6-bis-bromo-4-cyanophenol with oxammonium hydrochloride. and formic acid.The method process conditions are complicated, and step is various, and bromine used has higher toxicity and corrosivity, higher to equipment requirements, is not suitable for industrialized production.
Summary of the invention
Present invention aim at providing one 2, the synthetic method of 6-bis-bromo-4-cyanophenol, this method solve existing 2,6-bis-bromo-4-cyanophenol synthetic method yield is low, operation is complicated, the problem of feature of environmental protection difference.
The present invention solves the technical scheme that technical problem used:
A kind of 2, the synthetic method of 6-bis-bromo-4-cyanophenol, specifically include following steps: in reaction vessel, add 4-hydroxybenzonitrile, bromide, persulfate and solvent, under air or nitrogen atmosphere, heating or ultraviolet light irradiate reaction, and reaction is filtered after terminating, and washes filter cake, 2 are i.e. obtained, 6-bis-bromo-4-cyanophenol after drying.Persulfate generates the higher potentiometric titrations of activity and hydroxyl radical free radical under the effect of light or heat, and bromide is oxidized to bromate further, and 4-hydroxybenzonitrile generates 2 under the common effect of bromide and bromate, 6-bis-bromo-4-cyanophenol.
As preferably, described persulfate is the one in sodium peroxydisulfate, potassium peroxydisulfate or Ammonium persulfate..
As preferably, described solvent is selected from one or more in water, acetonitrile, ethanol, methanol, oxolane and DMF.
As preferably, described bromide is the one in sodium bromide, potassium bromide, ammonium bromide or cuprous bromide.
As preferably, described heating-up temperature is 30-80 DEG C, and the response time is 4-10h.
It is further preferred that described heating-up temperature is 50 DEG C.
As preferably, the mol ratio of described 4-hydroxybenzonitrile, persulfate and bromide is 1:1-4:2-8.
It is further preferred that the mol ratio of described 4-hydroxybenzonitrile, persulfate and bromide is 1:1:2.2.
It is further preferred that described solvent is 50% methanol-water solution or 50% ethanol-water solution.
As preferably, the consumption of described solvent is 10-20mL/g 4-hydroxybenzonitrile.
The invention have the benefit that
Provided by the present invention 2,6-bis-bromo-4-cyanophenol synthetic method, step is simple, and product yield and purity is high, course of reaction safety and environmental protection, low cost, and high financial profit belongs to green chemistry process, it is adaptable to industrialized production.
Detailed description of the invention
In order to make the purpose of the present invention, technical scheme and advantage clearer, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not intended to limit the present invention.
Embodiment 1
4 g (0.034mol) 4-hydroxybenzonitrile is added in 100 mL round-bottomed flasks, 9.18 g (0.034mol) potassium peroxydisulfate and 7.6g (0.074mol) sodium bromide, add 50% ethanol water 60 mL, stirring, react 4 hours at 50 DEG C, after reaction terminates, filter, washing filter cake, dry to obtain product 2, 6-bis-bromo-4-cyanophenol, for white solid, productivity is 92%, HPLC purity is 98%, and use Switzerland's Bruker AV-400 nuclear magnetic resonance chemical analyser to carry out nuclear-magnetism test, condition determination is: is dissolved in deuterochloroform by the product after isolated and purified and tests, analysis result is: 1H NMR (400 MHz, CDCl3)
δ 7.78 (s, 2H), 6.38 (s,
1H)；13C NMR (100 MHz, CDCl3)
δ 153.59, 135.65, 116.21,
110.41, 106.55。
Embodiment 2
In 100 mL round-bottomed flasks, add 4 g (0.034mol) 4-hydroxybenzonitrile, 9 g (0.037mol) sodium peroxydisulfate and 10.1g (0.085mol) potassium bromide, add 50% methanol aqueous solution 40 mL, stirring, under uviol lamp, irradiate reaction 8 hours, after reaction terminates, filter, washing filter cake, drying to obtain product 2,6-bis-bromo-4-cyanophenol, for white solid, productivity is 94%, and HPLC purity is 98%.
Embodiment 3
In 100 mL round-bottomed flasks, add 4 g (0.034mol) 4-hydroxybenzonitrile, 31 g (0.136mol) Ammonium persulfate. and 39g (0.272mol) cuprous bromide, add N, dinethylformamide 80 mL, stirring, react 10 hours at 30 DEG C, after reaction terminates, filter, wash filter cake, dry to obtain product 2,6-bis-bromo-4-cyanophenol, for white solid, productivity is 95.2%, and HPLC purity is 97.6%.
Embodiment 4
In 100 mL round-bottomed flasks, add 4 g (0.034mol) 4-hydroxybenzonitrile, 9 g (0.037mol) sodium peroxydisulfate and 10.5g (0.102mol) sodium bromide, add N, dinethylformamide 70 mL, stirring, react 5 hours at 80 DEG C, after reaction terminates, filter, wash filter cake, dry to obtain product 2,6-bis-bromo-4-cyanophenol, for white solid, productivity is 93.8%, and HPLC purity is 96.5%.
Embodiment 5
In 100 mL round-bottomed flasks, add 4 g (0.034mol) 4-hydroxybenzonitrile, 16.2 g (0.068mol) sodium peroxydisulfate and 14g (0.0136mol) sodium bromide, add oxolane 40 mL, stirring, under uviol lamp, irradiate reaction 10 hours, after reaction terminates, filter, washing filter cake, drying to obtain product 2,6-bis-bromo-4-cyanophenol, for white solid, productivity is 95.6%, and HPLC purity is 98.3%.
Embodiment 6
In 100 mL round-bottomed flasks, add 4 g (0.034mol) 4-hydroxybenzonitrile, 9 g (0.037mol) sodium peroxydisulfate and 10.1g (0.085mol) potassium bromide, add 50% acetonitrile solution 60 mL, stirring, under uviol lamp, irradiate reaction 4 hours, after reaction terminates, filter, washing filter cake, drying to obtain product 2,6-bis-bromo-4-cyanophenol, for white solid, productivity is 96.2%, and HPLC purity is 97.3%.
Knowable to above-mentioned: the present invention is under air or nitrogen atmosphere, and appropriate heating or illumination can be reacted, raw material safety non-pollution simple and easy to get, charging sequence is any, easy to operate.Additionally, this invented partyMethod is producedRate high-purity height, environmental protection, simple to operate and efficient, whole course of reaction also safety and environmental protection, low cost, high financial profit, belong to green chemistry process, can be applicable to prepare 2,6-bis-bromo-4-cyanophenol.
The foregoing is only presently preferred embodiments of the present invention, not in order to limit the present invention, all any amendment, equivalent and improvement etc. made within the spirit and principles in the present invention, should be included within the scope of the present invention.
Claims (10)
1. one kind 2, the synthetic method of 6-bis-bromo-4-cyanophenol, it is characterized in that, described synthetic method specifically includes following steps: add 4-hydroxybenzonitrile, bromide, persulfate and solvent in reaction vessel, and under air or nitrogen atmosphere, heating or ultraviolet light irradiate reaction, reaction is filtered after terminating, washing filter cake, i.e. obtains 2,6-bis-bromo-4-cyanophenol after drying.
Synthetic method the most according to claim 1, it is characterised in that described persulfate is the one in sodium peroxydisulfate, potassium peroxydisulfate or Ammonium persulfate..
Synthetic method the most according to claim 1, it is characterised in that one or more in water, acetonitrile, ethanol, methanol, oxolane and DMF of described solvent.
Synthetic method the most according to claim 1, it is characterised in that described bromide is the one in sodium bromide, potassium bromide, ammonium bromide or cuprous bromide.
Synthetic method the most according to claim 1, it is characterised in that described heating-up temperature is 30-80 DEG C, heating or ultraviolet light irradiation response time are 4-10h.
Synthetic method the most according to claim 5, it is characterised in that described heating-up temperature is 50 DEG C.
Synthetic method the most according to claim 1, it is characterised in that the mol ratio of described persulfate, 4-hydroxybenzonitrile and bromide is 1:1-4:2-8.
Synthetic method the most according to claim 7, it is characterised in that the mol ratio of described persulfate, 4-hydroxybenzonitrile and bromide is 1:1:2.2.
Synthetic method the most according to claim 3, it is characterised in that described solvent is 50% methanol-water solution or 50% ethanol-water solution.
Synthetic method the most according to claim 1, it is characterised in that the consumption of described solvent is 10-20mL/g 4-hydroxybenzonitrile.
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| CN201610306903.1A CN105859583B (en) | 2016-05-11 | 2016-05-11 | A kind of synthetic method of the cyanophenol of 2,6 dibromo 4 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110143852A (en) * | 2019-06-28 | 2019-08-20 | 福建医科大学 | A method of photocatalytic synthesis is at more bromophenol compounds in water phase |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102333758A (en) * | 2009-02-25 | 2012-01-25 | 科学与工业研究委员会 | A process for the eco-friendly preparation of 3, 5-dibromo-4-hydroxybenzonitrile |
| CN103787918A (en) * | 2014-01-23 | 2014-05-14 | 安徽华润涂料有限公司 | Production technology for synthesizing bromoxynil |
-
2016
- 2016-05-11 CN CN201610306903.1A patent/CN105859583B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102333758A (en) * | 2009-02-25 | 2012-01-25 | 科学与工业研究委员会 | A process for the eco-friendly preparation of 3, 5-dibromo-4-hydroxybenzonitrile |
| CN103787918A (en) * | 2014-01-23 | 2014-05-14 | 安徽华润涂料有限公司 | Production technology for synthesizing bromoxynil |
Non-Patent Citations (1)
| Title |
|---|
| 廖道华 等: "3,5-二卤代-4-羟基苯甲腈的合成", 《华东理工大学学报》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110143852A (en) * | 2019-06-28 | 2019-08-20 | 福建医科大学 | A method of photocatalytic synthesis is at more bromophenol compounds in water phase |
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