CN105461564B - A kind of methyl permethrinate new synthetic method - Google Patents
A kind of methyl permethrinate new synthetic method Download PDFInfo
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- CN105461564B CN105461564B CN201410450101.9A CN201410450101A CN105461564B CN 105461564 B CN105461564 B CN 105461564B CN 201410450101 A CN201410450101 A CN 201410450101A CN 105461564 B CN105461564 B CN 105461564B
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Abstract
The present invention provides a kind of synthetic method of methyl permethrinate, includes the following steps：Under agitation, amines catalyst is put into 3,3 dimethyl, 4,6,6,6 tetrachloro methyl hexyl, obtains raw mixture；Obtained raw mixture is warming up to 20~60 DEG C, and liquid organic base is added dropwise, and makes organic base and 3, and the molar ratio of 3 dimethyl, 4,6,6,6 tetrachloro methyl hexyl is up to 2.0~2.5:1；After being added dropwise, reaction mixture is kept the temperature 0.5~3.0 hour at 20 60 DEG C, waits for stopping reaction when the content of 3,3 dimethyl, 4,6,6,6 tetrachloro methyl hexyl is less than 0.3%, product obtains methyl permethrinate through subsequent processing.The method of the present invention eliminates the solvent needed for methyl permethrinate synthesis, reduce organic base amount, it reduces reaction temperature and shortens the reaction time, reduce the generation of the impurity such as alkynes ester while reacting fully again, methyl permethrinate quality is made obviously to increase.Present invention process is simple, operating aspect, is advantageous to industrialize.
Description
Technical field
The present invention relates to a kind of synthetic methods of compound, and in particular to a kind of new method of methyl permethrinate synthesis.
Background technology
Dichlor chrysanthemic acid pyrethroid pyrethroids is a kind of novel, deinsectization effect non-phosphorus pesticide outstanding, is had with tradition
Machine phosphorus, organo-chlorine pesticide are compared, and dichlor chrysanthemic acid ester pesticides activity is high, Environmental compatibility is good, residence time section, and has to people
Raise the advantage of low toxicity.The especially 3- phenoxy group benzyl esters of dichlor chrysanthemic acid have activity more higher than natural pyrethrin, commodity
The pyrethrin insecticide of change has more than 50 kinds, and 20% is accounted in the insecticide sales in the whole world, therefore studies in synthesis key
Mesosome methyl permethrinate is particularly important.
The method for carrying out industrialized production at present is substantially original with 3,3- dimethyl -4,6,6,6- tetrachloro methyl hexyls
Material in the presence of an organic base, after removing two molecule hydrogen chloride, obtains product methyl permethrinate, correlated response process is substantially such as
Under：
In order to improve the quality and yield of methyl permethrinate, document report has following several method：
1, it is reacted using different organic base and polar solvent, is first cyclized and carries out elimination reaction again and obtain product, it should
Process is relatively complicated, yield also just 70-85%；
2, it using mixing organic base, is reacted using tetrahydrofuran, hexamethylene isopolarity solvent, is divided into two steps and carries out instead
It answers, this method period is long, and although reaction yield reaches 89.9%, but process tedious, solvent separation is difficult, high expensive, no
Conducive to industrialization；
3, it uses methanol and DMF mixtures as reaction dissolvent, sodium methoxide is added dropwise and reacts 2hr, add sodium methoxide and continue instead
16hr is answered, yield is up to 95%, and along inverse ratio 88/12, but still there are subsequent products separation difficulty, DMF to consume the big, reaction time
Long, the limitations such as industrialization difficulty；
4, the method that CN102030650 B are proposed is the collocation nonpolar solvent such as mixed base, by adjusting alkali and nonpolarity
The collocation of solvent adjusts the suitable inverse ratio of product up to 20:80-80:20, yield reaches 94.6%.But the method still needs to use molten
Agent, and alcohol detaches palpus with solvent and puts into more equipment, procedure regulation mix ratio causes technique, and there are certain unstability, and
Due to the addition of nonpolar solvent, reaction speed reduces obviously, and single batch reaction period is longer.
In addition, the above several method synthesis methyl permethrinate elimination process temperature is higher, reach 80-120 DEG C, generally
Crude product is obtained after adding water-soluble salt layering and precipitation, crude product impurity is higher, product content only 80-90%, subsequently takes off light rectifying point
From extremely harsh, and post-processing produces a large amount of high concentration high slat-containing wastewater and more organic coke-like object, entire synthesis and
Processing procedure solvent loss amount is also larger.
Therefore, it is necessary to provide it is a kind of synthesis methyl permethrinate new method, with further increase yield and reduce at
This.
Invention content
It is an object of the invention to：A kind of new method of methyl permethrinate synthesis is provided, synthesis yield is further increased
And product quality, being more conducive to reduces cost, is more advantageous to industrialization.
The technical solution adopted in the present invention is：
A kind of new method of methyl permethrinate synthesis is provided, is included the following steps：
1) under agitation, to 3,3- dimethyl -4,6, amines catalyst is put into 6,6- tetrachloro methyl hexyls；
2) raw mixture that step 1) obtains is warming up to 20~60 DEG C, liquid organic base is added dropwise, makes organic base and 3,
The molar ratio of 3- dimethyl -4,6,6,6- tetrachloro methyl hexyls is up to 2.0~2.5:1；
3) after being added dropwise described in step 2), reaction mixture is kept the temperature 0.5~3.0 hour at 20-60 DEG C, is being reacted
Control in the process, gas-chromatography GC analyses, after deducting solvent, 3,3- dimethyl -4,6, the normalizing of 6,6- tetrachloro methyl hexyls
Content≤0.3% is qualified, stops reaction, and product obtains methyl permethrinate through subsequent processing.
Amines catalyst described in step 1) can be：Four ammonium of hexa-methylene, ammonioformaldehyde, hexamethyl tricresyl phosphate
One or more of ammonium, four ammonium of hexamethyl mixture；Further preferred four ammonium of hexa-methylene or hexamethyl triammonium phosphate
In any one.
The weight ratio of amines catalyst and 3,3- dimethyl -4,6,6,6- tetrachloro methyl hexyls described in step 1) is preferred
It is 1:5000-1:100(W/W).
Organic base described in step 2) can be：The methanol solution (preferred content 1~36%) of sodium methoxide, the first of potassium methoxide
The mixture of one or both of alcoholic solution (preferred content 1~33%).
Compared with prior art, the beneficial effects of the invention are as follows use solventless methods to synthesize methyl permethrinate, and makes anti-
It answers temperature to be reduced to 20-60 DEG C, improved since alkali concentration is opposite and uses amines catalyst so that reaction temperature is relatively low, anti-
Should be very fast, reduce the generation of the impurity such as alkynes ester while reacting abundant again, the methyl permethrinate of generation along inverse ratio 40/60~
60/40, so that methyl permethrinate quality is obviously increased.In the method for the present invention, the solvent very low amount of reaction and single, usually
Only methanol is easily recycled and purifies, and is generated without waste water；The yield of product can reach 97.5%, and the quality of crude product is most
Height can reach 97.6% (far above the content of the 80-90% of prior art), production cost be greatly reduced, compared with prior art phase
Than with the obvious advantage.
In addition, the method synthesis condition of the present invention is mild, reaction process is stable, reaction time is short, the organic no coke of Synthesis liquid
Shape object；Centrifugally operated is carried out after reaction to generate without waste water；It recycles salt NaCl contents and is more than 98.5%, can be used as one after drying
As Nacl sell, produce certain economic benefit.Material steams content more than 98% through separating methanol letter after centrifugation, can directly use
In the next step or sale, saves the input of de- light rectifying device and greatly reduce the energy consumption of product.
In short, the present invention improves product yield and quality, the reaction time is greatly shortened, while further simplifying life
Production. art eliminates the use of other polarity or nonpolar solvent, does not have to the separation for carrying out different solvents, simpler environmental protection.
Due to the reduction of cost and being further simplified for technique, it is more advantageous to industrial-scale production.
Specific implementation mode
It adopts below and explains in detail technical solutions and effects of the present invention in the form of examples, but the present invention is not limited to following
Embodiment.Example 1：
148g (0.5mol) 3,3- dimethyl -4,6,6,6- tetrachloro n-caproic acid first is added in the four-hole boiling flask equipped with stirring
Ester, adds four ammonium 0.03g of hexa-methylene, and raw material is warming up to the methanol solution for starting that sodium methoxide is added dropwise after 20~60 DEG C, makes first
The molar ratio of sodium alkoxide and 3,3- dimethyl -4,6,6,6- tetrachloro methyl hexyls reaches 2.0:1, the entire process that is added dropwise maintains reaction
20-60 DEG C of temperature, be added dropwise Bi Baowen, controlled in sampling, GC analyze four chloromethyl esters content be less than 0.3% after stop reaction, heat preservation
Reaction time total 1.5hr, product is post-treated to obtain methyl permethrinate 110.9g, content 96.5%, yield 96.0%.
Example 2：
148g (0.5mol) 3,3- dimethyl -4,6,6,6- tetrachloro n-caproic acid first is added in the four-hole boiling flask equipped with stirring
Ester, adds four ammonium 1.48g of hexa-methylene, and raw material is warming up to the methanol solution for starting that sodium methoxide is added dropwise after 20~60 DEG C, makes first
The molar ratio of sodium alkoxide and 3,3- dimethyl -4,6,6,6- tetrachloro methyl hexyls reaches 2.5:1, the entire process that is added dropwise maintains reaction
20-60 DEG C of temperature, be added dropwise Bi Baowen, controlled in sampling, GC analyze four chloromethyl esters content be less than 0.3% after stop reaction, heat preservation
The time total 0.5hr of reaction, product is post-treated to obtain methyl permethrinate 111.4g, content 97.6%, yield 97.5%.
Example 3：
148g (0.5mol) 3,3- dimethyl -4,6,6,6- tetrachloro n-caproic acid first is added in the four-hole boiling flask equipped with stirring
Ester, adds four ammonium 0.1g of hexa-methylene, and raw material is warming up to the methanol solution for starting that sodium methoxide is added dropwise after 20~60 DEG C, makes methanol
The molar ratio of sodium and 3,3- dimethyl -4,6,6,6- tetrachloro methyl hexyls reaches 2.2:1, the entire process that is added dropwise maintains reaction temperature
20-60 DEG C of degree is added dropwise Bi Baowen, is controlled in sampling, GC analyze four chloromethyl esters content be less than 0.3% after stop reaction, heat preservation is anti-
The time total 1hr answered, product is post-treated to obtain methyl permethrinate 112.3g, content 97%, yield 97.0%.
Example 4：
148g (0.5mol) 3,3- dimethyl -4,6,6,6- tetrachloro n-caproic acid first is added in the four-hole boiling flask equipped with stirring
Ester, adds hexamethyl triammonium phosphate 0.03g, and raw material is warming up to the methanol solution for starting that potassium methoxide is added dropwise after 20~60 DEG C, makes
The molar ratio of potassium methoxide and 3,3- dimethyl -4,6,6,6- tetrachloro methyl hexyls reaches 2.0:1, the entire process that is added dropwise remains anti-
Answer 20-60 DEG C of temperature, Bi Baowen be added dropwise, is controlled in sampling, GC analyze four chloromethyl esters content be less than 0.3% after stop reaction, protect
The time total 2.5hr of temperature reaction, product is post-treated to obtain methyl permethrinate 111.4g, content 96.9%, yield 96.8%.
Example 5：
148g (0.5mol) 3,3- dimethyl -4,6,6,6- tetrachloro n-caproic acid first is added in the four-hole boiling flask equipped with stirring
Ester, adds hexamethyl triammonium phosphate 1.48g, and raw material is warming up to the methanol solution for starting that potassium methoxide is added dropwise after 20~60 DEG C, makes
The molar ratio of potassium methoxide and 3,3- dimethyl -4,6,6,6- tetrachloro methyl hexyls reaches 2.5:1, the entire process that is added dropwise remains anti-
Answer 20-60 DEG C of temperature, Bi Baowen be added dropwise, is controlled in sampling, GC analyze four chloromethyl esters content be less than 0.3% after stop reaction, protect
The time total 3.0hr of temperature reaction, product is post-treated to obtain methyl permethrinate 111.5g, content 97.5%, yield 97.5%.
Example 6：
148g (0.5mol) 3,3- dimethyl -4,6,6,6- tetrachloro n-caproic acid first is added in the four-hole boiling flask equipped with stirring
Ester, adds four ammonium 0.03g of hexamethyl triammonium phosphate 0.03g and hexamethyl, and raw material starts that first is added dropwise after being warming up to 20~60 DEG C
The methanol solution of sodium alkoxide makes sodium methoxide and 3, the molar ratio of 3- dimethyl -4,6,6,6- tetrachloro methyl hexyls reach 2.0:1,
It is entire that 20-60 DEG C of process maintaining reaction temperature is added dropwise, Bi Baowen is added dropwise, is controlled in sampling, the content that GC analyzes four chloromethyl esters is less than
Stop reaction after 0.3%, the time total 0.5hr of insulation reaction, product is post-treated to obtain methyl permethrinate 111.4g, content
97.3%, yield 97.2%.Example 7：
148g (0.5mol) 3,3- dimethyl -4,6,6,6- tetrachloro n-caproic acid first is added in the four-hole boiling flask equipped with stirring
Ester, adds four ammonium 0.03g of hexamethyl triammonium phosphate 0.03g and ring hexamethyl, and raw material starts to be added dropwise after being warming up to 20~60 DEG C
The mixing methanol solution of potassium methoxide and sodium methoxide makes the total amount of sodium methoxide and potassium methoxide and 3,3- dimethyl -4,6,6,6- tetrachloros
The molar ratio of methyl hexyl reaches 2.5:1, it is entire that 20-60 DEG C of process maintaining reaction temperature is added dropwise, Bi Baowen is added dropwise, in sampling
Control, GC analyze four chloromethyl esters content be less than 0.3% after stop reaction, the time total 0.5hr of insulation reaction, product is post-treated
Obtain methyl permethrinate 111.6g, content 97.0%, yield 97.1%.
Comparative example
148g (0.5mol) 3,3- dimethyl -4,6,6,6- tetrachloro n-caproic acid first is added in the four-hole boiling flask equipped with stirring
Ester, is not added with catalyst, and raw material is warming up to the methanol solution for starting that sodium methoxide is added dropwise after 20~60 DEG C, process maintaining reaction temperature
20-60 DEG C, be added dropwise finish insulation reaction, controlled in sampling, GC analyze four chloromethyl esters content be less than 0.3% after stop reaction, heat preservation
Reaction has carried out 8hr, and post-processing obtains methyl permethrinate 108.9g, content 94.5%, yield 92.29%.
Claims (4)
1. a kind of synthetic method of methyl permethrinate, which is characterized in that include the following steps：
1) under agitation, to 3,3- dimethyl -4,6, amines catalyst is put into 6,6- tetrachloro methyl hexyls, obtains original
Expect mixture；
2) raw mixture that step 1) obtains is warming up to 20~60 DEG C, liquid organic base is added dropwise, makes organic base and 3,3- bis-
The molar ratio of methyl -4,6,6,6- tetrachloro methyl hexyls is up to 2.0~2.5:1；
3) after being added dropwise described in step 2), reaction mixture is kept the temperature 0.5~3.0 hour at 20-60 DEG C, waits for 3,3- diformazans
Base -4,6, the content of 6,6- tetrachloro methyl hexyls stop reaction when being less than 0.3%, and product obtains dichlor chrysanthemic acid through subsequent processing
Methyl esters；
Any one or two kinds of amines catalyst described in step 1) in hexa, hexamethylphosphoric acid triamide
Mixture.
2. the synthetic method of methyl permethrinate according to claim 1, it is characterised in that：Amine described in step 1) is urged
Agent and the weight ratio of 3,3- dimethyl -4,6,6,6- tetrachloro methyl hexyls are 1:5000-1:100.
3. the synthetic method of methyl permethrinate according to claim 1, it is characterised in that：Organic base described in step 2)
The methanol solution of methanol solution or potassium methoxide selected from sodium methoxide.
4. the synthetic method of methyl permethrinate according to claim 1, it is characterised in that：Organic base described in step 2)
Selected from content be 1~36% sodium methoxide methanol solution or content be 1~33% potassium methoxide methanol solution in one kind
Or two kinds of mixture.
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| US4424166A (en) * | 1980-03-12 | 1984-01-03 | Bayer Aktiengesellschaft | Preparation of 1,1-dihalogeno-alkenes |
| US4960922A (en) * | 1989-03-15 | 1990-10-02 | Fmc Corp | Process to dehydrohalogenate esters of pentahalopropyldimethylcyclopropanecarboxylic acids using a catalytic amount of 1,8-diazabicyclo[(5.4.0]Undecene-7-Ene in combination with stoichiometric amounts of base |
| CN102030650A (en) * | 2010-12-17 | 2011-04-27 | 江苏优士化学有限公司 | Novel process for synthesizing dimethylcyclopropanecarboxylate |
| CN102718648A (en) * | 2011-04-02 | 2012-10-10 | 南通天泽化工有限公司 | Preparation technology of DV-chrysanthemyl chloride with cis-trans ratio of 80:20-25:75 |
-
2014
- 2014-09-04 CN CN201410450101.9A patent/CN105461564B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4424166A (en) * | 1980-03-12 | 1984-01-03 | Bayer Aktiengesellschaft | Preparation of 1,1-dihalogeno-alkenes |
| US4960922A (en) * | 1989-03-15 | 1990-10-02 | Fmc Corp | Process to dehydrohalogenate esters of pentahalopropyldimethylcyclopropanecarboxylic acids using a catalytic amount of 1,8-diazabicyclo[(5.4.0]Undecene-7-Ene in combination with stoichiometric amounts of base |
| CN102030650A (en) * | 2010-12-17 | 2011-04-27 | 江苏优士化学有限公司 | Novel process for synthesizing dimethylcyclopropanecarboxylate |
| CN102718648A (en) * | 2011-04-02 | 2012-10-10 | 南通天泽化工有限公司 | Preparation technology of DV-chrysanthemyl chloride with cis-trans ratio of 80:20-25:75 |
Non-Patent Citations (1)
| Title |
|---|
| A convenient synthesis of ethyl 3-(2,2dihaloethenyl)-2,2-dimethylcyclopropanecarboxylates and its modifications for cis-isomer enrichment;kiyohide matsui等;《Bulletin of the Chemical Society of Japan》;19860131;第59卷(第1期);参见223页左栏第1段，222页表2，225页左栏倒数第1段，224页左栏倒数第2段，224页表4，223页右栏第1段，224页左栏第1段 * |
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