CN102030650B - Novel process for synthesizing dimethylcyclopropanecarboxylate - Google Patents
Novel process for synthesizing dimethylcyclopropanecarboxylate Download PDFInfo
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Abstract
The invention provides a method for synthesizing dimethylcyclopropanecarboxylate. The method comprises the following steps of: dissolving 3,3-dimethyl-4,6,6,6-methyl tetrachlorocaproate in one part of a nonpolar organic solvent to obtain solution A; mixing organic alkali and the other part of the nonpolar organic solvent to form solution B; mixing the solution A and the solution B in a dripping mode to ensure that a molar ratio of the 3,3-dimethyl-4,6,6,6-methyl tetrachlorocaproate to the organic alkali is 1:(2.0-3.3) and ensure that a mass ratio of the 3,3-dimethyl-4,6,6,6-methyl tetrachlorocaproate to the whole nonpolar organic solvent is 1:(3-10); and reacting at the temperature of between 70 and 120 DEG C to remove HCl and adjusting a ratio of ethanol generated in a reaction system to the nonpolar organic solvent simultaneously to adjust a cis-trans ratio of the generated dimethylcyclopropanecarboxylate so as to obtain the dimethylcyclopropanecarboxylate with the cis-trans ratio of 20:80-80:20. The method provided by the invention can further improve the yield and simplify the process so as to better facilitate industrial production.
Description
Technical field
The present invention relates to a kind of synthetic method of compound, be specifically related to the synthetic novel process of a kind of dichlor chrysanthemic acid methyl esters.
Background technology
Dichlor chrysanthemic acid class pyrethroid is the non-phosphorus agricultural chemicals that a class is novel, deinsectization is remarkably productive, compare with traditional organophosphorus, organochlorine pesticide, dichlor chrysanthemic acid ester pesticides activity is high, Environmental compatibility is good, the residence time is short, and has the advantage low to the person poultry toxicity.Especially the 3-phenoxy group benzyl ester of dichlor chrysanthemic acid; have the activity higher than natural pyrethrin; commercial pyrethroid insectide has more than 50 kind of to account for 20% in the sales volume of the sterilant in the whole world; therefore; the synthetic key intermediate dichlor chrysanthemic acid methyl esters of research, the professional etiquette of going forward side by side modelling is produced particularly important.
The method of carrying out at present suitability for industrialized production is with 3,3-dimethyl-4,6,6 substantially, 6-tetrachloro methyl hexyl be raw material in the presence of organic bases, remove two molecule hydrogenchloride after, obtain product dichlor chrysanthemic acid methyl esters.
Reaction formula:
Different from inverse proportional dichlor chrysanthemic acid methyl esters in order to obtain, bibliographical information is mainly with using different organic bases and polar solvents to react, and first cyclisation is eliminated and obtained product, and process is more loaded down with trivial details, and yield is also low by only 70 ~ 85%; It is solvent that Zhengzhou University's journal first phase Wang Dekun in 2004 etc. " synthesizing of dichlor chrysanthemic acid methyl esters " disclose a kind of tetrahydrofuran (THF), normal hexane, ethanol etc. selected, the mixed base technique of sodium tert-butoxide and sodium ethylate, so that the yield of dichlor chrysanthemic acid methyl esters brings up to 89.9% by 75%, be 50/50 along reverse proportionality.Although this reaction yield is higher, adopted stepwise reaction in its building-up process, the tetrachloro methyl esters reacts first and obtains three chloromethyl esters, obtains the dichlor chrysanthemic acid ester by three chloromethyl esters again, if suitability for industrialized production will need more equipment investment; The polar solvent of wherein selecting in the cyclization is not easily separated with the alcohol that reaction generates, solvent comprehensive utilization trouble, and processing cost is higher, also is unfavorable for suitability for industrialized production.
Summary of the invention
The object of the invention is to: a kind of Novel process for synthesizing dimethylcyclopropanecarboxylate is provided, further improves productive rate, more be conducive to suitability for industrialized production.Can regulate simultaneously the suitable inverse ratio of the dichlor chrysanthemic acid methyl esters of generation, obtain along the dichlor chrysanthemic acid methyl esters of inverse ratio between 20:80 ~ 80:20.
The present invention realizes that the technical scheme of above-mentioned purpose is:
A kind of synthetic method of dichlor chrysanthemic acid methyl esters is provided, may further comprise the steps:
1) with 3,3-dimethyl-4,6,6,6-tetrachloro methyl hexyl is dissolved in a part of non-polar organic solvent, obtains solution A;
2) organic bases and the described non-polar organic solvent of another part are mixed the formation solution B;
3) solution A and step 2 that step 1) are obtained) solution B of gained mixes mutually with the dropping form, make 3,3-dimethyl-4,6,6, the mol ratio of 6-tetrachloro methyl hexyl and organic bases reaches 1:2.0 ~ 3.3,3,3-dimethyl-4,6,6,6-tetrachloro methyl hexyl and total non-polar solvent mass ratio are 1:3 ~ 10, take off HCl 70 ~ 120 ℃ of lower reactions, the alcohol that generates in the conditioned reaction system simultaneously and the ratio of non-polar organic solvent, to regulate the suitable inverse ratio of the dichlor chrysanthemic acid methyl esters that generates, finally obtain along the dichlor chrysanthemic acid methyl esters of inverse ratio between 20:80 ~ 80:20.
The described non-polar organic solvent of step 1) can be benzene, toluene, hexanaphthene, methylcyclohexane, 2-methyl hexane, 3-methyl hexane, 2, the mixture of one or more in 3-dimethylpentane, heptane, the sherwood oil.
Step 2) described organic bases can be selected from one or more the mixture in sodium methylate, sodium ethylate, sodium tert-butoxide, the potassium tert.-butoxide.
Described organic bases is the mixture of one or more in solid sodium methylate, solid sodium ethanol, solid sodium tert-butoxide or solid potassium tert-butoxide preferably.
Described organic bases also can be preferably be dissolved in one or more mixture in the solution that corresponding alcohol obtains from sodium methylate, sodium ethylate, sodium tert-butoxide or potassium tert.-butoxide; Further certainly preferred, by weight percentage, content at 2% ~ 35% methanol solution of sodium methylate, content at 1% ~ 20% alcohol sodium alcohol solution, content at 1% ~ 20% sodium tert-butoxide t-butanol solution or one or more the mixture in the potassium tert.-butoxide t-butanol solution of content 1% ~ 20%.
More preferably 80 ~ 120 ℃ of the described temperature of reaction of step 3).
The alcohol that generates in the described conditioned reaction system of step 3) and the ratio of non-polar organic solvent can be by adding or extraction alcohol or non-polar organic solvent or their mixed solution are realized, preferably the mode of extraction.
There is substantial connection in the suitable inverse ratio of the final dichlor chrysanthemic acid methyl esters that generates of the inventive method with the ratio of the pure and mild non-polar organic solvent that generates in the reaction system, take following several solvent systems as example, can clearly know the relation between them:
Methyl alcohol/non-polar solvent system
| Methyl alcohol: non-polar solvent mass ratio | The dichlor chrysanthemic acid methyl esters is along inverse ratio |
| 25.5:74.5 | 20.5:79.5 |
| 15.2:84.8 | 27.5:72.5 |
| 9.9:90.1 | 34.9:65.1 |
| 5.7:94.3 | 44.1:55.9 |
| 2.5:97.5 | 49.9:50.1 |
The trimethyl carbinol/non-polar solvent system
| The trimethyl carbinol: non-polar solvent mass ratio | The dichlor chrysanthemic acid methyl esters is along inverse ratio |
| 24.5:75.5 | 79.9:20.1 |
| 16.5:83.5 | 70.2:29.8 |
| 10.5:89.5 | 63.3:36.7 |
| 5.5:94.5 | 57.1:42.9 |
| 3.3:96.7 | 50.9:49.1 |
The non-polar organic solvent that obtains through described extraction, preferably through dewatering qualified after, be cycled to used in above-mentioned steps 1) and/or step 2).
It is main reaction system that method of the present invention adopts non-polar solvent, ratio by the alcohol that generates in the conditioned reaction system, the maleinoid body content that the demand of can looking is adjusted the dichlor chrysanthemic acid methyl esters reaches the desirable value between 20% ~ 80%, can be directly used in the synthetic downstream pyrethroid product that dichlor chrysanthemic acid is had particular demands along inverse ratio.Method reaction yield of the present invention can reach more than 90%, and the non-polar solvent component in the reaction system is easy to recycling, so just effectively reduce the wastewater discharge in the production process, estimate that by industrialized unit 1 ton of dichlor chrysanthemic acid methyl esters of every production can reduce discharging about 2.5 tons of waste water.
As everyone knows, when the cyclisation elimination occurs the tetrachloro methyl esters, there is the cis-trans isomerization phenomenon in different solvents.Key of the present invention is the suitable inverse proportional needs according to the dichlor chrysanthemic acid methyl esters, use different SOLID ORGANIC alkali or its alcoholic solution, the amount of control reaction system Semi-polarity solvent, namely control mixing solutions azeotropic produced quantity, obtained different suitable inverse proportional dichlor chrysanthemic acid methyl esters, product yield is up to 94.6%, greatly reduces production cost, compared with prior art, with the obvious advantage.
Realize separating of polar solvent and non-polar solvent in engineering; and recycling is thing easily; this technique had both improved product yield; also simplified simultaneously production technique; reduced solvent consumption; effectively reduce the wastewater discharge in the production process, greatly improved the large-scale production level.
Embodiment
The below explains technical scheme of the present invention and effect in detail with the form of embodiment, but the present invention is not limited to following examples.
Embodiment 1:
In the four-hole boiling flask of stirring is housed, add 450g hexanaphthene and 67.5g(1.25mol) solid sodium methylate, be warmed up to 80 ℃ of backflows, begin to drip 148g(0.5mol) 3,3-dimethyl-4,6,6,6-tetrachloro methyl caproate is dissolved in the solution of 100g hexanaphthene, the mixed solution of extraction hexanaphthene and methyl alcohol in reaction, after dripping, continuous slow extraction hexanaphthene is until methyl alcohol in the reaction system: the hexanaphthene mass ratio is 2.8:97.2, and holding temperature is at 100 ℃, insulation reaction 2 ~ 5h, control in the sampling, GC analyzes tetrachloro methyl esters content less than 1% rear stopped reaction, and the cooling aftertreatment gets dichlor chrysanthemic acid methyl esters 117.1g, content 89.31%, yield 93.8%.
Embodiment 2:
In being housed, the four-hole boiling flask of stirring adds 3 of 450g hexanaphthene and 148g, 3-dimethyl-4,6,6,6-tetrachloro methyl caproate is warmed up to 80 ℃ of backflows, begins to drip methanol solution of sodium methylate and the 100g hexanaphthene mixed solution of 225g 30% mass concentration, the mixed solution of while extraction hexanaphthene and methyl alcohol, after dripping, continuous slow extraction hexanaphthene is until methyl alcohol in the reaction system: the hexanaphthene mass ratio is 3.7:96.3, and holding temperature is at 100 ℃, insulation reaction 1 ~ 5h, control in the sampling, GC analyzes tetrachloro methyl esters content less than 1%, and the cooling aftertreatment gets dichlor chrysanthemic acid methyl esters 116.8g, content 89%, yield 93.2%.
Embodiment 3:
In being housed, the four-hole boiling flask of stirring adds 3 of 450g methylcyclohexane and 148g, 3-dimethyl-4,6,6,6-tetrachloro methyl caproate, be warmed up to 80 ℃ of backflows, begin to drip 57.6g solid sodium tert-butoxide and 67.2g solid potassium tert-butoxide and be dissolved in the solution of 200g methylcyclohexane, the mixed solution of extraction methylcyclohexane and ethanol in reaction, after dripping, continuous slow extraction methylcyclohexane is until the trimethyl carbinol in the reaction system: the methylcyclohexane mass ratio is 3.6:96.4, and holding temperature is 120 ℃ of material temperatures, insulation reaction 1 ~ 5h, control in the sampling, GC analyzes tetrachloro methyl esters content less than 1%, and the cooling aftertreatment gets dichlor chrysanthemic acid methyl esters 117.6g, content 89.66%, yield 94.6%.
Embodiment 4:
In being housed, the four-hole boiling flask of stirring adds 3 of 250g methylcyclohexane and 148g, 3-dimethyl-4,6,6,6-tetrachloro methyl caproate, be warmed up to 80 ℃ of methanol solution of sodium methylate and 100g methylcyclohexane mixed solutions that begin to drip 225g 30% mass concentration, the mixed solution of while extraction methylcyclohexane and methyl alcohol is after dripping, continuous slow extraction methylcyclohexane is until methyl alcohol in the reaction system: the methylcyclohexane mass ratio is 16:84, holding temperature is at 120 ℃, and insulation reaction 1 ~ 5h is controlled in the sampling, GC analyzes tetrachloro methyl esters content less than 1%, the cooling aftertreatment gets dichlor chrysanthemic acid methyl esters 114.1g, content 88.13%, yield 90.2%.
Embodiment 5:
In being housed, the four-hole boiling flask of stirring adds 120g solid sodium tert-butoxide and 450g hexanaphthene, be warmed up to reflux state, begin to drip 3 of 100g hexanaphthene and 148g, 3-dimethyl-4,6,6,6-tetrachloro methyl caproate mixed solution, the mixed solution of while extraction hexanaphthene and the trimethyl carbinol, after dripping, continuous slow extraction hexanaphthene is until the trimethyl carbinol in the reaction system: the hexanaphthene mass ratio is 5.2:94.8, and holding temperature is 100 ℃ of material temperatures, insulation reaction 1 ~ 5h, control in the sampling, GC analyzes the tetrachloro methyl esters less than 1%, and the cooling aftertreatment gets dichlor chrysanthemic acid methyl esters 113.7g, content 89.02%, yield 90.8%.
Embodiment 6:
In being housed, the four-hole boiling flask of stirring adds 3 of 150g toluene and 148g, 3-dimethyl-4,6,6,6-tetrachloro methyl caproate is warmed up to reflux state, begins to drip 640g18% potassium tert.-butoxide trimethyl carbinol liquid and 250g toluene mixture liquid, the mixed solution of while extraction toluene and the trimethyl carbinol, after dripping, continuous slow extraction toluene is until the trimethyl carbinol in the reaction system: the toluene mass ratio is 16.9:83.1, and holding temperature is 120 ℃ of material temperatures, insulation reaction 1 ~ 5h, control in the sampling, GC analyzes the tetrachloro methyl esters less than 1%, and the cooling aftertreatment gets dichlor chrysanthemic acid methyl esters 114.5g, content 88.23%, yield 90.6%.
The embodiment data statistics is as follows:
| ? | Tetrachloro methyl esters g | Receive dichlor chrysanthemic acid methyl esters g | Along inverse ratio | Yield % |
| Embodiment 1 | 148 | 117.1 | 49:51 | 93.8 |
| Embodiment 2 | 148 | 116.8 | 48.5:51.5 | 93.2 |
| Embodiment 3 | 148 | 117.6 | 51.1:48.9 | 94.6 |
| Embodiment 4 | 148 | 114.1 | 26.5:63.5 | 90.2 |
| Embodiment 5 | 148 | 113.7 | 56.2:43.8 | 90.8 |
| Embodiment 6 | 148 | 114.5 | 71.1:38.9 | 90.6 |
Claims (8)
1. the synthetic method of a dichlor chrysanthemic acid methyl esters may further comprise the steps:
1) with 3,3-dimethyl-4,6,6,6-tetrachloro methyl hexyl is dissolved in a part of non-polar organic solvent, obtains solution A;
2) organic bases and the described non-polar organic solvent of another part are mixed the formation solution B;
3) solution A and step 2 that step 1) are obtained) solution B of gained mixes mutually with the dropping form, make 3,3-dimethyl-4,6,6, the mol ratio of 6-tetrachloro methyl hexyl and organic bases reaches 1:2.0 ~ 3.3,3,3-dimethyl-4,6,6,6-tetrachloro methyl hexyl and total non-polar solvent mass ratio are 1:3 ~ 10, take off HCl 70 ~ 120 ℃ of lower reactions, the alcohol that generates in the conditioned reaction system simultaneously and the ratio of non-polar organic solvent, to regulate the suitable inverse ratio of the dichlor chrysanthemic acid methyl esters that generates, obtain along the dichlor chrysanthemic acid methyl esters of inverse ratio between 20:80 ~ 80:20; The alcohol that generates in the described conditioned reaction system and the ratio of non-polar organic solvent are to realize by extraction alcohol or non-polar organic solvent or their mixed solution.
2. the synthetic method of dichlor chrysanthemic acid methyl esters claimed in claim 1, it is characterized in that: the described non-polar organic solvent of step 1) is benzene, toluene, hexanaphthene, methylcyclohexane, 2-methyl hexane, 3-methyl hexane, 2, the mixture of one or more in 3-dimethylpentane, heptane, the sherwood oil.
3. the synthetic method of dichlor chrysanthemic acid methyl esters claimed in claim 1 is characterized in that: step 2) described organic bases is selected from one or more the mixture in sodium methylate, sodium ethylate, sodium tert-butoxide, the potassium tert.-butoxide.
4. the synthetic method of dichlor chrysanthemic acid methyl esters claimed in claim 3 is characterized in that: described organic bases is selected from one or more the mixture in solid sodium methylate, solid sodium ethanol, solid sodium tert-butoxide or the solid potassium tert-butoxide.
5. the synthetic method of dichlor chrysanthemic acid methyl esters claimed in claim 3 is characterized in that: described organic bases is selected from sodium methylate, sodium ethylate, sodium tert-butoxide or potassium tert.-butoxide and is dissolved in one or more mixture in the solution that corresponding alcohol obtains.
6. the synthetic method of dichlor chrysanthemic acid methyl esters claimed in claim 5, it is characterized in that: described organic bases is selected from, by weight percentage, content at 2% ~ 35% methanol solution of sodium methylate, content at 1% ~ 20% alcohol sodium alcohol solution, content at 1% ~ 20% sodium tert-butoxide t-butanol solution or one or more the mixture in the potassium tert.-butoxide t-butanol solution of content 1% ~ 20%.
7. the synthetic method of dichlor chrysanthemic acid methyl esters claimed in claim 1, it is characterized in that: the described temperature of reaction of step 3) is 70 ~ 120 ℃.
8. the synthetic method of dichlor chrysanthemic acid methyl esters claimed in claim 1 is characterized in that: through non-polar organic solvent that described extraction obtains through dewatering qualified after, be cycled to used in step 1) and/or step 2).
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| CN105461564B (en) * | 2014-09-04 | 2018-08-03 | 江苏扬农化工股份有限公司 | A kind of methyl permethrinate new synthetic method |
| CN106928051A (en) * | 2015-12-31 | 2017-07-07 | 江苏优士化学有限公司 | A kind of synthetic method of cis lanbda-cyhalothric acid |
| CN114426485B (en) * | 2020-10-28 | 2023-06-13 | 中国科学院大连化学物理研究所 | Synthetic method of dichlorochrysanthemic acid compound |
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| 富顺式二氯菊酸甲酯合成新工艺;杨新宇等人;《农药》;200404;第43卷(第4期);第163-164页 * |
| 杨新宇等人.富顺式二氯菊酸甲酯合成新工艺.《农药》.2004,第43卷(第4期),第163-164页. |
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Effective date of registration: 20190308 Address after: 225009 No. 39, Wenfeng Road, Yangzhou, Jiangsu Patentee after: Yangnong Chemical Co., Ltd., Jiangsu Address before: 211400 No. 3 Dalian Road, Yizheng City, Yangzhou City, Jiangsu Province Co-patentee before: Yangnong Chemical Co., Ltd., Jiangsu Patentee before: Jiangsu Youth Chemical Co., Ltd. |