CN105859583B - A kind of synthetic method of the cyanophenol of 2,6 dibromo 4 - Google Patents
A kind of synthetic method of the cyanophenol of 2,6 dibromo 4 Download PDFInfo
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- CN105859583B CN105859583B CN201610306903.1A CN201610306903A CN105859583B CN 105859583 B CN105859583 B CN 105859583B CN 201610306903 A CN201610306903 A CN 201610306903A CN 105859583 B CN105859583 B CN 105859583B
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- synthetic method
- bromide
- persulfate
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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 present invention provides a kind of synthetic method of the cyanophenol of 2,6 dibromo 4, and concrete operation step is：Under air or nitrogen atmosphere, in the presence of persulfate and solvent, heating or illumination, react the bromide such as 4-hydroxybenzonitrile and sodium bromide, KBr.The synthetic method of the present invention is safe and reliable, and yield height is pollution-free, and reaction condition is gentle, simple to operate, belongs to green chemical technology, can be used for the preparation of the cyanophenol of 2,6 dibromo 4.
Description
Technical field
The present invention relates to chemical technology field, and in particular to the synthetic method of the bromo- 4- cyanophenols of one kind 2,6- bis-.
Background technology
2,6- bis- bromo- 4- cyanophenols, also known as Brominal, this compound and its form such as caprylate, sodium salt, sylvite are wide
General cauline leaf process contact killing type herbicide after being used as selective bud.Mainly absorbed by blade, by suppressing photosynthetic each mistake
Journey, make necrosis rapidly.Suitable for the crop fields such as wheat, barley, rye, corn, jowar, flax, prevent and kill off broad leaved weed knotweed,
The annual dicotyledonous weeds such as lamb's-quarters, amaranth, conical silene herb, black nightshade, Siberian cocklebur, corn gromwell, salsola collina, field bindweed, corn-bind.Brominal is store
Stabilization is deposited, and other herbicides do not react typically, in addition to alone, can also expand herbicidal spectrum with a variety of herbicide mixtures.
At present, the synthetic method report of existing several bromo- 4- cyanophenols of 2,6- bis-, but many shortcomings are still had,
For example, reaction yield is low, purity is inadequate, and course of reaction operation is dangerous, and reaction environment is seriously polluted etc..Therefore, seek to
A kind of high yield high-purity, synthetic method green, simple to operate and efficient bromo- 4- cyanophenols of 2,6- bis- be in accordance with
People's demand.
Height is promoted culture (study on the synthesis of 3,5- bis- bromo- 4- 4-hydroxy-benzonitriles caprylates, Agriculture of Anhui science, 2009,37 (16)：
Paracresol 7314-7315.) is used as raw material, in the presence of sodium hypochlorite, is reacted generation 2 with bromine, bis- bromo- 4- of 6-
Methylphenol, then 3,5- dibromine-4-hydroxy benzaldehydes are generated under hydrogen peroxide and catalyst action, finally with hydroxylamine hydrochloride and
The formic acid reaction generation bromo- 4- cyanophenols of 2,6- bis-.This method process conditions are complicated, and step is various, and bromine used have compared with
High toxicity and corrosivity, it is higher to equipment requirement, be not suitable for industrialized production.
The content of the invention
Present invention aims at the synthetic method for providing the bromo- 4- cyanophenols of one kind 2,6- bis-, this method solve existing
The problem of 2,6- bis- bromo- 4- cyanophenols synthetic method yields are low, complex operation, feature of environmental protection difference.
The technical proposal for solving the technical problem of the invention is：
The synthetic method of the bromo- 4- cyanophenols of one kind 2,6- bis-, specifically includes following steps：The addition pair in reaction vessel
Cyanophenol, bromide, persulfate and solvent, under air or nitrogen atmosphere, heating or ultraviolet light reaction, reaction terminate
After filter, wash filter cake, the bromo- 4- cyanophenols of 2,6- bis- are produced after drying.Persulfate generates work in the presence of light or heat
Property higher potentiometric titrations and hydroxyl radical free radical, and bromide is further oxidized to bromate, 4-hydroxybenzonitrile is in bromide
With the bromo- 4- cyanophenols of 2,6- bis- are generated under the collective effect of bromate.
Preferably, the persulfate is one kind in sodium peroxydisulfate, potassium peroxydisulfate or ammonium persulfate.
Preferably, the solvent is in water, acetonitrile, ethanol, methanol, tetrahydrofuran and DMF
It is one or more of.
Preferably, the bromide is one kind in sodium bromide, KBr, ammonium bromide or cuprous bromide.
Preferably, the heating-up temperature is 30-80 DEG C, reaction time 4-10h.
It is further preferred that the heating-up temperature is 50 DEG C.
Preferably, the mol ratio of the 4-hydroxybenzonitrile, persulfate and bromide is 1: 1-4: 2-8.
It is further preferred that the mol ratio of the 4-hydroxybenzonitrile, persulfate and bromide is 1: 1: 2.2.
It is further preferred that the solvent is 50% methanol-water solution or 50% ethanol-water solution.
Preferably, the dosage of the solvent is 10-20mL/g 4-hydroxybenzonitriles.
Beneficial effects of the present invention are：
In the bromo- 4- cyanophenols synthetic methods of 2,6- bis- provided by the present invention, step is simple, and product yield and purity is high,
Course of reaction safety and environmental protection, cost is low, high financial profit, belongs to green chemistry process, suitable for industrialized production.
Embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, with reference to embodiments to the present invention
It is further elaborated.It should be appreciated that specific embodiment described herein is not used to limit only to explain the present invention
The fixed present invention.
Embodiment 1
4g (0.034mol) 4-hydroxybenzonitrile, 9.18g (0.034mol) potassium peroxydisulfate are added into 100mL round-bottomed flasks
With 7.6g (0.074mol) sodium bromide, 50% ethanol water 60mL is added, stirring, is reacted 4 hours at 50 DEG C, reaction knot
Shu Hou, filtering, filter cake is washed, dries to obtain product 2, the bromo- 4- cyanophenols of 6- bis- are white solid, yield 92%, HPLC
Purity is 98%, and carries out nuclear-magnetism test using Switzerland's Bruker AV-400 nuclear magnetic resonance chemical analysers, and condition determination is：It will divide
It is dissolved in deuterochloroform and is tested from product after purification, analysis result is：1H NMR (400MHz, CDCl3)δ 7.78
(s, 2H), 6.38 (s, 1H)；13C NMR (100MHz, CDCl3) δ 153.59,135.65,116.21,110.41.106.55.
Embodiment 2
Into 100mL round-bottomed flasks add 4g (0.034mol) 4-hydroxybenzonitrile, 9g (0.037mol) sodium peroxydisulfates and
10.1g (0.085mol) KBr, 50% methanol aqueous solution 40mL is added, stirring, reaction 8 hours is irradiated under uviol lamp, instead
After should terminating, filtering, filter cake to be washed, dries to obtain product 2, the bromo- 4- cyanophenols of 6- bis- are white solid, yield 94%,
HPLC purity is 98%.
Embodiment 3
Into 100mL round-bottomed flasks add 4g (0.034mol) 4-hydroxybenzonitrile, 31g (0.136mol) ammonium persulfates and
39g (0.272mol) cuprous bromide, DMF 80mL is added, stirring, is reacted 10 hours at 30 DEG C, reaction knot
Shu Hou, filtering, filter cake is washed, dries to obtain product 2, the bromo- 4- cyanophenols of 6- bis- are white solid, yield 95.2%, HPLC
Purity is 97.6%.
Embodiment 4
Into 100mL round-bottomed flasks add 4g (0.034mol) 4-hydroxybenzonitrile, 9g (0.037mol) sodium peroxydisulfates and
10.5g (0.102mol) sodium bromide, DMF 70mL is added, stirring, is reacted 5 hours at 80 DEG C, reaction knot
Shu Hou, filtering, filter cake to be washed, dries to obtain product 2, the bromo- 4- cyanophenols of 6- bis- are white solid, yield 93.8%,
HPLC purity is 96.5%.
Embodiment 5
4g (0.034mol) 4-hydroxybenzonitrile, 16.2g (0.068mol) sodium peroxydisulfate are added into 100mL round-bottomed flasks
With 14g (0.0136mol) sodium bromide, tetrahydrofuran 40mL, stirring, irradiation reaction 10 hours under uviol lamp, reaction knot are added
Shu Hou, filtering, filter cake to be washed, dries to obtain product 2, the bromo- 4- cyanophenols of 6- bis- are white solid, yield 95.6%,
HPLC purity is 98.3%.
Embodiment 6
Into 100mL round-bottomed flasks add 4g (0.034mol) 4-hydroxybenzonitrile, 9g (0.037mol) sodium peroxydisulfates and
10.1g (0.085mol) KBr, 50% acetonitrile solution 60mL is added, stirring, reaction 4 hours is irradiated under uviol lamp, instead
After should terminating, filtering, filter cake is washed, dries to obtain product 2, the bromo- 4- cyanophenols of 6- bis-, are white solid, and yield is
96.2%, HPLC purity are 97.3%.
It is above-mentioned to understand：The present invention is under air or nitrogen atmosphere, and appropriate heating or illumination can react, and raw material is simply easy
Safety non-pollution is obtained, charging sequence is any, easy to operate.In addition, this inventive method yield high-purity is high, green, operation
Simple and efficiently, whole course of reaction also safety and environmental protection, cost is low, high financial profit, belongs to green chemistry process, can be applied to
Prepare the bromo- 4- cyanophenols of 2,6- bis-.
Claims (9)
1. one kind 2, the synthetic method of the bromo- 4- cyanophenols of 6- bis-, it is characterised in that the synthetic method specifically includes following step
Suddenly：4-hydroxybenzonitrile, bromide, persulfate and solvent are added in reaction vessel, under air or nitrogen atmosphere, heating or purple
Outer photo-irradiation reaction, reaction are filtered after terminating, and wash filter cake, the bromo- 4- cyanophenols of 2,6- bis- are produced after drying；
The persulfate is one kind in sodium peroxydisulfate, potassium peroxydisulfate or ammonium persulfate.
2. synthetic method according to claim 1, it is characterised in that the solvent is selected from water, acetonitrile, ethanol, methanol, four
One or more in hydrogen furans and N,N-dimethylformamide.
3. synthetic method according to claim 1, it is characterised in that the bromide be sodium bromide, KBr, ammonium bromide or
One kind in cuprous bromide.
4. synthetic method according to claim 1, it is characterised in that the heating-up temperature is 30-80 DEG C, heating or ultraviolet
The photo-irradiation reaction time is 4-10h.
5. synthetic method according to claim 4, it is characterised in that the heating-up temperature is 50 DEG C.
6. synthetic method according to claim 1, it is characterised in that the persulfate, 4-hydroxybenzonitrile and bromide
Mol ratio is 1：1-4：2-8.
7. synthetic method according to claim 6, it is characterised in that the persulfate, 4-hydroxybenzonitrile and bromide
Mol ratio is 1：1：2.2.
8. synthetic method according to claim 2, it is characterised in that the solvent is 50% methanol-water solution or 50% second
Alcohol-water solution.
9. synthetic method according to claim 1, it is characterised in that the dosage of the solvent is 10-20mL/g to cyano group
Phenol.
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