CN108129350A - A kind of preparation method of 2,4 dichloro benzene nitrile - Google Patents
A kind of preparation method of 2,4 dichloro benzene nitrile Download PDFInfo
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- CN108129350A CN108129350A CN201810050599.8A CN201810050599A CN108129350A CN 108129350 A CN108129350 A CN 108129350A CN 201810050599 A CN201810050599 A CN 201810050599A CN 108129350 A CN108129350 A CN 108129350A
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- dichlorobenzonitriles
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
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Abstract
The present invention relates to one kind 2, the preparation method of 4 dichlorobenzonitriles, by 2,4 dichlorbenzyl alcohols and nitrogen source are dissolved in glacial acetic acid, are passed through oxygen, add in nitric acid and tetramethyl piperidine nitrogen hopcalite as catalyst, closed reactor, reaction 1 for 24 hours, obtains 2,4 dichlorobenzonitriles at a temperature of 25 100 DEG C.The preparation method of the present invention has used nonmetallic as catalyst, and oxygen avoids the use of metallic catalyst, reduce environmental pollution as oxidant.
Description
Technical field
The present invention relates to industrial chemicals preparing technical fields, and in particular to the preparation method of one kind 2,4- dichlorobenzonitriles.
Background technology
2,4- dichlorobenzonitriles are a kind of widely used pesticide intermediates, available for producing fluorine-containing benzoyl area kind desinsection
Agent, herbicide, water analysis reagent, also have certain application in plastics, dyestuff and electronic material etc..Dihalo cyanophenyl at present
Synthetic method there are many, wherein ammonia oxidation is relatively conventional, and the raw material used is 2,4- dichloro benzene toluenes, with VPO composite oxygens
Compound etc. is catalyst, is reacted under the oxidation of oxygen with ammonia, and 2,4- dichlorobenzonitriles are made.This method route is short, raw material
It is at low cost；But it is difficult to develop stable catalyst, production equipment be required high.In addition, with 2,4- dichlorobenzaldehydes are raw material,
In the presence of oxidant, by being reacted with the reagents such as ammonia, hydroxylamine hydrochloride, 2,4- dichlorobenzonitriles can also be made.The party
Method usually can obtain higher yield, but the aldehydes raw material used is easy to oxidation deterioration, it is difficult to preserve, and higher price.
Document report, for raw material, undergoes dehydration with 2,4- dichloro-benzamides or 2,4- dichloro benzaldoxime, and 2,4- bis- is made
6-chlorophenyl nitrile.Both methods is without using oxidant, and pollution is small, but cost of material is high, is unfavorable for commercial Application.Another kind is
The method of commercial Application is 2,4 dichloro benzene methylamine method.This method undergoes two reaction steps of diazotising and cyaniding, then passes through water
Steam distilled isolates 2,4- dichlorobenzonitrile products.But hypertoxic Cymag is used in cyanation step, has caused serious safety
Hidden danger.
Invention content
The purpose of the present invention is deficiencies to solve above-mentioned technical problem, provide the preparation side of one kind 2,4- dichlorobenzonitriles
Method overcomes the problem of using metallic catalyst or the reaction reagent of danger etc. comprehensive of high cost in existing method.
The deficiency of the present invention to solve above-mentioned technical problem, used technical solution are：A kind of 2,4 dichloro benzene nitrile
2,4-DCBA and nitrogen source are dissolved in glacial acetic acid by preparation method, are passed through oxygen, add in nitric acid and tetramethyl piperidine nitrogen oxygen
The mixture of compound reacts 1-24h as catalyst, closed reactor at a temperature of 25-100 DEG C, obtains 2,4- dichlorobenzonitriles.
The structural formula of 2,4 dichloro benzene nitrile is as follows：
；
Synthetic route is as follows：
；
As a kind of optimization of the preparation method of 2,4 dichloro benzene nitrile of the present invention：The nitrogen source is ammonium acetate, ammonium sulfate or nitric acid
Ammonium, the ratio between nitrogen source and the amount of 2,4-DCBA substance are 1-3:1.
As a kind of optimization of the preparation method of 2,4 dichloro benzene nitrile of the present invention：The pressure of the oxygen is 1-50atm.
As a kind of optimization of the preparation method of 2,4 dichloro benzene nitrile of the present invention：Nitric acid and 2,4- dichloros in the catalyst
The ratio between amount of benzyl alcohol substance is 0.1-0.6:1, the ratio between tetramethyl piperidine nitrogen oxides and the amount of 2,4-DCBA substance
For 0.1-0.6:1.
Advantageous effect
（1）The preparation method of the present invention has used nonmetallic as catalyst, and oxygen avoids metallic catalyst as oxidant
Use, reduce environmental pollution.
（2）Product purity is high made from the method for the present invention, and feed stock conversion is high, is effectively improved product quality, drops
Low production cost.
Description of the drawings
Fig. 1 is the product 2,4 dichloro benzene nitrile of embodiment 11H-NMR schemes.
Fig. 2 is the product 2,4 dichloro benzene nitrile of embodiment 113C-NMR schemes.
Specific embodiment
Further technical scheme of the present invention is illustrated below in conjunction with specific embodiment.
Embodiment 1
By magneton, 2mL glacial acetic acid, 0.5mmol 2,4 dichloro benzenes methanol, 1.5mmol ammonium acetates, 0.15mmol nitric acid and
0.15mmol tetramethyl piperidine nitrogen oxides is sequentially added in glass reaction tube（The pressure of oxygen is 1atm）.Reaction tube quilt
After sealing, it is placed into 50 DEG C of heating tank, reacts 12h under magnetic stirring.Once the reaction time is reached, reaction system is cold
But to room temperature, uantitative analytical is carried out to product using gas chromatograph, the yield for obtaining 2,4- dichlorobenzonitrile products is
93%.Then above-mentioned experiment is repeated, separating-purifying is carried out to product by pillar layer separation method, obtains the production of 2,4- dichlorobenzonitriles
Object.It utilizes1H-NMR、13C-NMR determines that product structure is shown in Fig. 1 and 2.
Embodiment 2
By magneton, 2mL glacial acetic acid, 0.5mmol2,4- dichlorbenzyl alcohols, 1.5mmol ammonium acetates, 0.15mmol nitric acid and
0.15mmol tetramethyl piperidine nitrogen oxides is sequentially added in the autoclave with glass-lined.After reaction kettle is sealed,
10atm oxygen is filled with, is put into 50 DEG C of heating tank, reacts 12h under magnetic stirring.Once reaching the reaction time, will react
System is cooled to room temperature, and is carried out uantitative analytical to product using gas chromatograph, is obtained the production of 2,4- dichlorobenzonitrile products
Rate is 77%.
Embodiment 3-4
Ammonium acetate in embodiment 1 is become into ammonium sulfate, ammonium nitrate, other conditions are constant, obtain the yield of product（In gas phase
Mark）Respectively 63%, 52%.
Embodiment 5-9
By the quantitative change of the substance of the ammonium acetate in embodiment 1 be 0.5mmol, 0.7mmol, 1mmol, 1.3mmol, 1.5mmol,
Other conditions are constant, obtain the yield of product（Gas phase internal standard）Respectively 47%, 72%, 91%, 90%, 93%.
Embodiment 10-18
By the oxygen pressure in embodiment 2 become 1atm, 3atm, 10atm, 15atm, 20atm, 25atm, 30atm, 40atm,
50atm, other conditions are constant, obtain the yield of product（Gas phase internal standard）Respectively 93%, 75%, 77%, 69%, 80%, 72%, 75%,
79%、82%。
Embodiment 19-24
By the quantitative change of the substance of the nitric acid in embodiment 1 for 0.05mmol, 0.1mmol, 0.15mmol, 0.2mmol,
0.25mmol, 0.3mmol, other conditions are constant, obtain the yield of product（Gas phase internal standard）Respectively 43%, 81%, 93%, 96%,
90%、98%。
Embodiment 25-30
By the quantitative change of the substance of the tetramethyl piperidine nitrogen oxides in embodiment 1 for 0.05mmol, 0.1mmol, 0.15mmol,
0.2mmol, 0.25mmol, 0.3mmol, other conditions are constant, obtain the yield of product（Gas phase internal standard）Respectively 31%, 73%,
93%、91%、89%、95%。
Embodiment 31-38
Reaction temperature in embodiment 1 is become 25 DEG C, 40 DEG C, 50 DEG C, 60 DEG C, 70 DEG C, 80 DEG C, 90 DEG C, 100 DEG C respectively,
His condition is constant, obtains the yield of product（Gas phase internal standard）Respectively 49%, 77%, 93%, 91%, 86%, 72%, 56%, 32%.
Embodiment 39-47
Reaction time in embodiment 1 is become into 1h, 3h, 6h, 9h, 12h, 15h, 18h, 21h, for 24 hours respectively, other conditions are not
Become, obtain the yield of product（Gas phase internal standard）Respectively 46%, 62%, 69%, 88%, 93%, 96%, 92%, 92%, 95%.
The above described is only a preferred embodiment of the present invention, not make limitation in any form to the present invention, though
So the present invention is disclosed above with preferred embodiment, however is not limited to the present invention, any technology people for being familiar with this profession
Member, without departing from the scope of the present invention, when the technology contents using the disclosure above make a little change or modification
For the equivalent embodiment of equivalent variations, as long as being without departing from technical solution of the present invention content, technical spirit pair according to the present invention
Any simple modification, equivalent change and modification that above example is made, in the range of still falling within technical solution of the present invention.
Claims (4)
1. one kind 2, the preparation method of 4- dichlorobenzonitriles, it is characterised in that：2,4 dichloro benzene methanol and nitrogen source are dissolved in glacial acetic acid
In, oxygen is passed through, adds in nitric acid and tetramethyl piperidine nitrogen hopcalite as catalyst, closed reactor, in 25-
1-24h is reacted at a temperature of 100 DEG C, 2,4- dichlorobenzonitriles are made.
2. a kind of preparation method of 2,4- dichlorobenzonitriles according to claim 1, it is characterised in that：The nitrogen source is acetic acid
Ammonium, ammonium sulfate or ammonium nitrate, the ratio between nitrogen source and the amount of 2,4-DCBA substance are 1-3:1.
3. a kind of preparation method of 2,4- dichlorobenzonitriles according to claim 1, it is characterised in that：The pressure of the oxygen
For 1-50atm.
4. a kind of preparation method of 2,4- dichlorobenzonitriles according to claim 1, it is characterised in that：Nitre in the catalyst
The ratio between acid and the amount of 2,4 dichloro benzene methanol substance are 0.1-0.6:1, tetramethyl piperidine nitrogen oxides and 2,4-DCBA
The ratio between amount of substance is 0.1-0.6:1.
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| CN201810050599.8A CN108129350B (en) | 2018-01-18 | 2018-01-18 | Preparation method of 2, 4-dichlorobenzonitrile |
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| CN201810050599.8A CN108129350B (en) | 2018-01-18 | 2018-01-18 | Preparation method of 2, 4-dichlorobenzonitrile |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113845442A (en) * | 2021-09-30 | 2021-12-28 | 孙国伟 | Method for preparing p-bromobenzonitrile |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5336811A (en) * | 1993-08-18 | 1994-08-09 | Shell Oil Company | Process for the preparation of aldehydes |
| JP2015040203A (en) * | 2013-08-23 | 2015-03-02 | 国立大学法人 千葉大学 | Method for producing nitrile compound |
| CN106866326A (en) * | 2017-03-07 | 2017-06-20 | 浙江工业大学 | A kind of method that primary alconol prepares nitrile |
| KR101774148B1 (en) * | 2016-03-23 | 2017-09-12 | 인천대학교 산학협력단 | AEROBIC OXIDATIVE CONVERSION OF PRIMARY ALCOHOLS TO NITRILES USING A NITROXYL/NOx CATALYST SYSTEM |
-
2018
- 2018-01-18 CN CN201810050599.8A patent/CN108129350B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5336811A (en) * | 1993-08-18 | 1994-08-09 | Shell Oil Company | Process for the preparation of aldehydes |
| JP2015040203A (en) * | 2013-08-23 | 2015-03-02 | 国立大学法人 千葉大学 | Method for producing nitrile compound |
| KR101774148B1 (en) * | 2016-03-23 | 2017-09-12 | 인천대학교 산학협력단 | AEROBIC OXIDATIVE CONVERSION OF PRIMARY ALCOHOLS TO NITRILES USING A NITROXYL/NOx CATALYST SYSTEM |
| CN106866326A (en) * | 2017-03-07 | 2017-06-20 | 浙江工业大学 | A kind of method that primary alconol prepares nitrile |
Non-Patent Citations (2)
| Title |
|---|
| HIROYUKI SHIMOJO等: "Simple one-pot conversion of alcohols into nitriles", 《SYNTHESIS》 * |
| JI-HYUN NOH等: "Aerobic Oxidative Conversion of Aromatic Aldehydes to Nitriles Using a Nitroxyl/NOx Catalyst System", 《J.ORG.CHEM.》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113845442A (en) * | 2021-09-30 | 2021-12-28 | 孙国伟 | Method for preparing p-bromobenzonitrile |
| CN113845442B (en) * | 2021-09-30 | 2023-09-29 | 孙国伟 | Method for preparing p-bromobenzonitrile |
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