CN107043336B - A kind of preparation method of 2- (2- methylphenoxy)-methylene benzoyl cyanide - Google Patents
A kind of preparation method of 2- (2- methylphenoxy)-methylene benzoyl cyanide Download PDFInfo
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- CN107043336B CN107043336B CN201710177386.7A CN201710177386A CN107043336B CN 107043336 B CN107043336 B CN 107043336B CN 201710177386 A CN201710177386 A CN 201710177386A CN 107043336 B CN107043336 B CN 107043336B
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- methylphenoxy
- methylene
- potassium ferrocyanide
- benzoyl cyanide
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/14—Preparation of carboxylic acid nitriles by reaction of cyanides with halogen-containing compounds with replacement of halogen atoms by cyano groups
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Abstract
The present invention relates to the field of chemical synthesis, specifically disclose a kind of preparation method of 2- (2- methylphenoxy)-methylene benzoyl cyanide, this method can be obtained target product 2- (2- methylphenoxy)-methylene benzoyl cyanide using potassium ferrocyanide as cyanidization agent, with 2- (2- methylphenoxy)-methylene-benzene formyl chloride preparation；Compared with prior art, potassium ferrocyanide of the present invention is cheap, nontoxic as cyanidization agent, and end reaction yield reaches 90% or more, reacts safer, and cost of material is low, simple process, it is easy to operate, good condition is provided for industrialized production.
Description
Technical field
The invention belongs to organic synthesis field, in particular to a kind of 2- (2- methylphenoxy)-methylene benzoyl cyanide
Preparation method.
Background technique
Kresoxim-methyl is a kind of efficient, wide spectrum, novel strobilurin fungicide, and the mechanism of action is to act on cell
On pigment compound, the electron transfer process of germ mitochondrial respiratory chain is blocked to make disease to inhibit germ cell energy supply
Bacterium cell lack energy and it is dead.There is good preventive effect for diseases such as powdery mildew, anthracnose, pears scab；It has both simultaneously
There are good protection and therapeutic effect, and other common fungicide no interactions resistances, and it is longer than the conventional sterilization agent lasting period；Tool
There is the selectivity of height, it is substantially pollution-free to environment to crop, people and animals and beneficial organism safety.
2- (2- methylphenoxy)-methylene benzoyl cyanide is the production essential and basic intermediate product of kresoxim-methyl, is closed at present
At 2- (2- methylphenoxy)-methylene benzoyl cyanide method, there are mainly two types of:
2- (2- methylenedioxy phenoxy is synthesized first is that being reacted by 2- (2- methylphenoxy)-methylene-benzene formyl chloride with Cymag
Base)-methylene benzoyl cyanide.Its reaction equation are as follows:
This method is using Cymag as cyanidization agent, and reaction condition is mild, and yield is higher, but Cymag severe toxicity, and reaction is not
Safety, cost of material are higher.
2- (2- methylenedioxy phenoxy is synthesized second is that being reacted by 2- (2- methylphenoxy)-methylene-benzene formyl chloride with cuprous cyanide
Base)-methylene benzoyl cyanide.Its reaction equation are as follows:
This method is using cuprous cyanide as cyanidization agent, and reaction temperature is high, and the reaction time is long, and yield is relatively low.
Therefore how a kind of higher yields and safer 2- (2- methylphenoxy)-methylene benzoyl cyanide are provided
Synthetic method become urgent problem to be solved.
Summary of the invention
The purpose of the present invention is to provide a kind of 2- (2- methylphenoxy)-methylene benzoyl cyanide preparation methods, should
Method can be obtained target using potassium ferrocyanide as cyanidization agent, with 2- (2- methylphenoxy)-methylene-benzene formyl chloride preparation
Product 2- (2- methylphenoxy)-methylene benzoyl cyanide；Compared with prior art, potassium ferrocyanide of the present invention is done
It is cheap, nontoxic for cyanidization agent, and end reaction yield reaches 90% or more, reacts safer, and raw material at
This low, simple process, it is easy to operate, good condition is provided for industrialized production.
The specific technical solution of the present invention is as follows: reaction equation:
The specific steps of which are as follows:
Use potassium ferrocyanide for cyanidization agent, 2- (2- methylphenoxy)-methylene-benzene formyl chloride and potassium ferrocyanide
Molar ratio is 1.0:0.17-1.0:0.19；The specific steps of which are as follows:
Potassium ferrocyanide is dissolved in water first, potassium ferrocyanide mass fraction is 20-22% after dissolution, is added quantitative molten
Agent, solvent and potassium ferrocyanide mass ratio are 5-5.5:1, and phase transfer catalyst is added into above-mentioned system later, is then added dropwise
2- (2- methylphenoxy)-methylene-benzene formyl chloride, is to slowly warm up to 35-38 DEG C, insulation reaction 1-2h after being added dropwise.
Potassium ferrocyanide is usually that aroyl chloride substitution reaction cyanidization agent is used as to use in the prior art, with prior art phase
Than, the present invention uses potassium ferrocyanide to prepare 2- (2- methylphenoxy)-methylene benzoyl cyanide for cyanidization agent for the first time, compared with
Other previously used cyanidization agents, cyanidization agent reaction of the present invention is safer, and yield significantly improves, and yield is compared with existing
There is technology to improve 7-8%, the efficiency for substantially increasing reaction reduces production cost.
Above-mentioned reaction dissolvent is benzene or toluene or dimethylbenzene；The phase transfer catalyst is tetrabutylammonium bromide；Choosing
It can play the role of optimal be adapted to unclassified stores of the invention with above-mentioned substance.
Further, inventor further limits 2- (2- methylphenoxy)-methylene-benzene formyl chloride and ferrocyanide
The molar ratio of potassium is 1.0:0.17-1.0:0.19, and optimal effect can be obtained in above-mentioned ratio range.
Further, potassium ferrocyanide mass fraction is preferably 20% after dissolving in the above process, and quantitative solvent is added
When solvent and potassium ferrocyanide mass ratio be 5.2:1；
Technical solution of the present invention has the advantage that compared with prior art
(1) present invention uses cheap and easy to get, nontoxic potassium ferrocyanide for cyanidization agent, reacts safer, avoids
Safe pressure caused by conventional method.
(2) for the present invention using potassium ferrocyanide as cyanidization agent, 6 CN in potassium ferrocyanide structure can participate in reaction, cyanogen
The atom utilization of base is high, and raw material dosage reduces, and mitigates environmental pressure, meets national environmental protection policy.
(3) synthetic method of the present invention is simple, easy to operate, low in cost, is conducive to industrialized production.
In conclusion the potassium ferrocyanide that the present invention uses is as cyanidization agent, it is cheap, nontoxic and final
Reaction yield reaches 90% or more, reacts safer, and cost of material is low, simple process, easy to operate, is industrialized production
Good condition is provided.
Specific embodiment
It is further described below with reference to the technical solution that embodiment is related to invention, to facilitate reason of the invention
Solution, but not as the limitation to technical solution, in addition to specifically mentioned, component ratio is weight percentage.
Embodiment 1
It weighs 21.5g (0.051mol) potassium ferrocyanide, is added 86g water, 111.8g toluene, 0.69g tetrabutylammonium bromide,
In 20-25 DEG C of dropwise addition 2- (2- methylphenoxy)-methylene-benzene formyl chloride (78.2g, 0.3mol), slowly heating after being added dropwise to complete
It is stirred to react 1-2h to 35-38 DEG C, obtains product 2- (2- methylphenoxy)-methylene benzoyl cyanide 69.9g, content
97.8%, yield 90.8%.
Embodiment 2
26.6g (0.063mol) potassium ferrocyanide is weighed, 103.7g water, 131.6g toluene, 0.78g tetrabutyl phosphonium bromide is added
Ammonium, in 20-25 DEG C of dropwise addition 2- (2- methylphenoxy)-methylene-benzene formyl chloride (88.6g, 0.34mol), after being added dropwise to complete in
35-38 DEG C is stirred to react 1-2h, obtains product 2- (2- methylphenoxy)-methylene benzoyl cyanide 78.7g, and content 98% is received
Rate 90.3%.
Embodiment 3
30.2g (0.071mol) potassium ferrocyanide is weighed, 114.4g water, 160.1g toluene, 0.92g tetrabutyl phosphonium bromide is added
Ammonium, in 20-25 DEG C of dropwise addition 2- (2- methylphenoxy)-methylene-benzene formyl chloride (104.2g, 0.4mol), after being added dropwise to complete in
35-38 DEG C is stirred to react 1-2h, obtains product 2- (2- methylphenoxy)-methylene benzoyl cyanide 92.7g, content 98.2%,
Yield 90.6%.
Embodiment 4
22.9g (0.054mol) potassium ferrocyanide is weighed, 83.2g water, 123.7g toluene, 0.64g tetrabutyl phosphonium bromide is added
Ammonium, in 20-25 DEG C of dropwise addition 2- (2- methylphenoxy)-methylene-benzene formyl chloride (72.9g, 0.28mol), after being added dropwise to complete in
35-38 DEG C is stirred to react 1-2h, obtains product 2- (2- methylphenoxy)-methylene benzoyl cyanide 64.7g, and content 98% is received
Rate 90.2%.
Embodiment 5
31.2g (0.074mol) potassium ferrocyanide is weighed, 119.3g water, 165.4g toluene, 0.98g tetrabutyl phosphonium bromide is added
Ammonium, in 20-25 DEG C of dropwise addition 2- (2- methylphenoxy)-methylene-benzene formyl chloride (112g, 0.43mol), in 35- after being added dropwise to complete
38 DEG C are stirred to react 1-2h, obtain product 2- (2- methylphenoxy)-methylene benzoyl cyanide 99.6g, content 97.9%, yield
90.3%.
Comparative example
28.6g (0.58mol) Cymag is weighed, 88.4g water, 103.7g methylene chloride, 0.69g tetrabutyl chlorination is added
Ammonium, in 20-25 DEG C of dropwise addition 2- (2- methylphenoxy)-methylene-benzene formyl chloride (78.2g, 0.3mol), in 35- after being added dropwise to complete
38 DEG C are stirred to react 1-2h, obtain product 2- (2- methylphenoxy)-methylene benzoyl cyanide 68.3g, content 91.3%, yield
82.8%.
It can be seen that the yield and content using Cymag as cyanidization agent are far below technical solution of the present invention, in addition, cyanogen
Change sodium and belong to toxic articles, operated as cyanidization agent and react dangerous, and to do the potassium ferrocyanide used then nontoxic by the present invention
It is harmless, and potassium ferrocyanide is cheap, raw material is easy to get, it is more particularly suitable as cyanidization agent, and be specifically chosen with the present invention molten
Agent and phase transfer catalyst are used cooperatively, and effect is more preferable.
Claims (1)
1. a kind of 2-(2- methylphenoxy) preparation method of-methylene benzoyl cyanide, it is characterised in that: use potassium ferrocyanide
For cyanidization agent, 2-(2- methylphenoxy) molar ratio of-methylene-benzene formyl chloride and potassium ferrocyanide is 1.0:0.17-1.0:
0.19；The specific steps of which are as follows:
Potassium ferrocyanide is dissolved in water first, potassium ferrocyanide mass fraction is 20-22% after dissolution, and quantitative solvent is added, molten
Agent and potassium ferrocyanide mass ratio are 5-5.5:1, and phase transfer catalyst is added into above-mentioned system later, 2-(2- is then added dropwise
Methylphenoxy)-methylene-benzene formyl chloride, 35-38 DEG C is to slowly warm up to after being added dropwise, insulation reaction 1-2h；
The solvent is benzene or toluene or dimethylbenzene；
The phase transfer catalyst is tetrabutylammonium bromide.
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| CN114380713A (en) * | 2021-09-29 | 2022-04-22 | 辽宁众辉生物科技有限公司 | Synthesis method of o-methyl benzoyl cyanide |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013144924A1 (en) * | 2012-03-29 | 2013-10-03 | Rallis India Ltd. | An improved process for the synthesis of strobilurin fungicides viz trifloxystrobin and kresoxim-methyl |
| CN105884651A (en) * | 2016-04-25 | 2016-08-24 | 山东理工大学 | Preparation apparatus and method of kresoxim-methyl intermediate |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013144924A1 (en) * | 2012-03-29 | 2013-10-03 | Rallis India Ltd. | An improved process for the synthesis of strobilurin fungicides viz trifloxystrobin and kresoxim-methyl |
| CN105884651A (en) * | 2016-04-25 | 2016-08-24 | 山东理工大学 | Preparation apparatus and method of kresoxim-methyl intermediate |
Non-Patent Citations (2)
| Title |
|---|
| 以亚铁氰化钾作为环境友好氰化试剂所进行的氰化反应的研究;冯旭;《中国优秀硕士论文 工程科技I辑》;20100615(第06期);第22-27页 |
| 苯氧菌酯的合成研究;刘卫东等;《精细化工中间体》;20030831;第33卷(第4期);10-11页 |
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Address after: 256500 Boxing County Economic Development Zone, Binzhou, Shandong Patentee after: JINGBO AGROCHEMICALS TECHNOLOGY Co.,Ltd. Address before: 256500 Boxing County Economic Development Zone, Binzhou, Shandong Patentee before: JINGBO AGROCHEMICALS TECHNOLOGY Co.,Ltd. |
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