CN101323588A - Preparation of pesticide 2-(2-hydroxyethyl)-piperidine-1-carbonate-1-methyl isopropyl ester - Google Patents
Preparation of pesticide 2-(2-hydroxyethyl)-piperidine-1-carbonate-1-methyl isopropyl ester Download PDFInfo
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- CN101323588A CN101323588A CNA2008101230255A CN200810123025A CN101323588A CN 101323588 A CN101323588 A CN 101323588A CN A2008101230255 A CNA2008101230255 A CN A2008101230255A CN 200810123025 A CN200810123025 A CN 200810123025A CN 101323588 A CN101323588 A CN 101323588A
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Abstract
The invention discloses a method for preparing insecticide Picaridin, which comprises three steps as follows: firstly, 2-ethanolpyridine is dissolved in a polar solvent and reacts with hydrogen under the function of a hydrogenation catalyst and at certain pressure and temperature to obtain a 2-thanolpyridine reaction solution; then the obtained 2-thanolpyridine is dissolved in a non-polar solvent, reaction temperature is controlled, and simultaneously, sec-Butyl chloroformate and sig water is added by dripping; crude Picaridin is obtained after the treatments of acid washing, water washing and desolution, finally the crude Picaridin is distilled under the function of an antioxidant and under the condition of vacuum and high temperature to obtain finished Picaridin. The invention has the advantages of low cost input, few side reaction, high overall yield, simple technique and easy operation.
Description
Technical field
The present invention relates to a kind of sterilant, be meant the preparation method of hydroxyl piperazine ester especially.
Background technology
Hydroxyl piperazine ester is the popular name of 2-(2-hydroxyethyl)-piperidines-1-carbonic acid-1-methyl isopropyl ester.Be a kind of sterilant of safe, effective, environmental protection, can substitute the Metadelphene that the smell is awful, viscosity is big.Hydroxyl piperazine ester has the following advantages: widely applicable, and effective to mosquito, louse, sand fly and horse botfly etc.; To skin gentleness, not sticking, and there is not unpleasant odor; Can not damage plastics, fiber, coating and tamanori; Conceived and can use lactation; Children more than 2 years old can use safely.
Hydroxyl piperazine ester is developed by Bayer A.G the earliest, U.S. Pat 4900834 (1988) application documents disclose the synthetic method of series compounds such as hydroxyl piperazine ester, wherein hydroxyl piperazine ester is that to have adopted 2-ethanol piperidines be starting raw material, through obtaining crude product with the sec-butyl chloroformate condensation, high vacuum rectification obtains hydroxyl piperazine ester finished product.
The weak point of this patent is: (one) starting raw material 2-ethanol piperidines is not reported clear and definite preparation method.(2) the synthetic total recovery of the hydroxyl piperazine ester of this patent report has only 49%, does not spell out wherein impurity and side reaction process.(3) hydroxyl piperazine ester crude product purity is low, needs to arrive hydroxyl piperazine ester finished product by high vacuum rectification, causes production process energy consumption height.(4) the required temperature of reaction is subzero 20 degree, is unfavorable for industrial large-scale operation.
Summary of the invention
The object of the present invention is to provide a kind of reaction conditions gentleness, technology is simple, productive rate is high hydroxyl piperazine ester preparation method.
Technical scheme of the present invention is: select hydrogenation catalyst efficiently, adopt medium-pressure hydrocracking prepared committed step starting raw material 2-ethanol piperidines.Because 2-ethanol piperidines has hydroxyl and two active groups of secondary amine, in the reactions steps of preparation hydroxyl piperazine ester, all there is the possibility that reacts with sec-butyl chloroformate, generate secondary butyl ester of impurity list-(2-piperidines-2-ethyl)-carbonic acid and the secondary butyl ester of 2-(2-(sec-butoxy-carbonyl) ethyl)-piperidines-carbonic acid, greatly reduced content in crude product, and separation difficulty, finally influence the quality of hydroxyl piperazine ester finished product.The present invention adopts sec-butyl chloroformate and diluted alkaline to add reaction with the dropping form, fully reduced impurity growing amount in the reaction process, obviously improve hydroxyl piperazine ester content in crude product, adopt the method for purification of underpressure distillation, one step obtained the hydroxyl piperazine ester finished product of 98% above content, and overall yield of reaction improves more than 35%.
Preparation method of the present invention comprises the steps:
1, the preparation method of sterilant hydroxyl piperazine ester is characterized in that may further comprise the steps:
(1) 2-ethanol piperidines preparation
2-ethanol pyridine is dissolved in the polar solvent that consumption is 1～5 times of its weight, be under the effect of highly effective hydrogenation catalyzer of 2-ethanol pyridine weight 0.1～10% at consumption, under 1～10Mpa hydrogen pressure and 50～120 ℃ of temperature, reacted 6～12 hours, record of the 0.5% o'clock reaction end of 2-ethanol pyridine content less than total amount, after the gained reacting liquid filtering was removed catalyzer, decompression and solvent recovery, residuum were 2-ethanol piperidines;
Described polar solvent is an one of the following: methyl alcohol, ethanol, Virahol, 1, and the 4-dioxane, the best is a methyl alcohol; Optimum amount is 2 times of 2-ethanol pyridine weight;
Described highly effective hydrogenation catalyzer is one of the following: 10%Pd/C, R-Ni (W-5), PtO
2, RuO
2, the best is 10%Pd/C or R-Ni (W-5); Optimum amount is 5% of a 2-ethanol pyridine weight.
Described best hydrogen pressure is 3～5Mpa;
Described optimal reaction temperature is 80～100 ℃;
Described optimum reacting time is 10 hours.
(2) hydroxyl piperazine ester crude product preparation
2-ethanol piperidines is dissolved in the non-polar solvent that consumption is 1～5 times of its weight, control reaction temperature is at 40～80 ℃, drip sec-butyl chloroformate and concentration simultaneously and be 1～20% alkaline solution, and mol ratio is an alkali: sec-butyl chloroformate: 2-ethanol piperidines=1～1.5: 1～1.3: 1, the control dropping time is in 1～6 hour, add and continue to be stirred to the reaction end, branch vibration layer, organic phase concentration is 1～10%, consumption is the weak acid scrubbing secondary of 1～3 times of 2-ethanol piperidines weight, after washing secondary again, decompression and solvent recovery, residuum are hydroxyl piperazine ester crude product;
Described non-polar solvent is an one of the following: hexanaphthene, benzene, toluene, methylcyclohexane, and the best is a toluene; Optimum amount is 2 times of 2-ethanol piperidines weight;
Described alkali is one of the following: sodium hydroxide, potassium hydroxide, yellow soda ash, sodium bicarbonate, and the best is sodium hydroxide or sodium bicarbonate; Optimum concn is 10～15%;
Described diluted acid is an one of the following: hydrochloric acid, sulfuric acid, phosphoric acid; Optimum concn is 5%, and consumption the best is 2 times of 2-ethanol piperidines weight.
Described dropping time optimal is 2～3 hours;
Described temperature of reaction the best is 60～70 ℃;
(3) hydroxyl piperazine ester is refining purifies
Adding consumption in the hydroxyl piperazine ester crude product is the antioxidant of its weight 1～3%, and under the high vacuum less than 5mmHg, distillation obtains the hydroxyl piperazine ester finished product of 98% above content under 140～150 ℃ of high temperature;
Described antioxidant is an one of the following: S-WAT, potassium sulfite; Optimum amount is 1.5% of a hydroxyl piperazine ester crude product weight;
Reaction formula of the present invention is as follows:
The beneficial effect that the present invention realizes is as follows:
1, discloses the preparation method of starting raw material 2-ethanol piperidines, need not to buy 2-ethanol piperidines finished product when making preparation hydroxyl piperazine ester, thereby reduce cost input.
2, diluted alkaline and sec-butyl chloroformate all adopt the dropping form to add, thereby reduce the generation of side reaction, improve reaction yield.
3, total recovery height.
4, technology is simple, easy to operate.
Embodiment
Embodiment 1
(1) 2-ethanol piperidines preparation
200g (99%, mol) 2-ethanol pyridine, 400g methyl alcohol, 10g10%Pd/C drops into 1 rising respectively and presses in the hydrogenation still, uses nitrogen replacement three times, uses hydrogen exchange again three times.Stir down and slowly heat up, keep hydrogen pressure 5Mpa, the still temperature was reacted 10 hours at 90 ℃, and gas chromatographic analysis shows 2-ethanol pyridine content less than 0.5%, finished reaction and was cooled to below 30 ℃.Emptying hydrogen, reaction solution are removed catalyzer after filtration, and filtrate decompression reclaims methyl alcohol and applies mechanically, and residuum is a 2-ethanol piperidines, 202g, content 99.2%.
(2) hydroxyl piperazine ester crude product preparation
Get 100g (99.2%, 0.769mol) 2-ethanol piperidines, 200g toluene drops into and to be equipped with in 1 liter of reaction flask of prolong, is stirred and heated to 60 ℃.Drip simultaneously 111g (99%, the 0.805mol) sodium bicarbonate aqueous solution of sec-butyl chloroformate and 473g15% (0.844mol).The dropping time was controlled at 3 hours, 70 ℃ of controlled temperature.Drip to continue to stir and finished in 1 hour.Leave standstill branch and remove waste water, organic phase is washed secondary with 5% dilute hydrochloric acid, each 200g.And then remove waste water with dividing behind the 200g clear water washing secondary.Organic phase reclaim under reduced pressure toluene solvant cover is used down and is criticized, and residuum is hydroxyl piperazine ester crude product 170g, content 94%.
(3) hydroxyl piperazine ester is refining purifies
(94%, 0.615mol) hydroxyl piperazine ester crude product, 2.2g S-WAT drop into respectively in 250 milliliters the reaction flask, and under the condition of control vacuum less than 5mmHg, heat temperature raising, the cut of collecting 150 ℃ are hydroxyl piperazine ester finished product, 135g, content 98.7% to get 150g.Residuum is that organic high boiling material still is residual, goes to burn harmless processing.
Embodiment 2
(1) 2-ethanol piperidines preparation
200g (99%, mol) 2-ethanol pyridine, 400g ethanol, 10g10%Pd/C drops into 1 rising respectively and presses in the hydrogenation still, uses nitrogen replacement three times, uses hydrogen exchange again three times.Stir down and slowly heat up, keep hydrogen pressure 5Mpa, the still temperature was reacted 10 hours at 90 ℃, and gas chromatographic analysis shows 2-ethanol pyridine content less than 0.5%, finished reaction and was cooled to below 30 ℃.Emptying hydrogen, reaction solution are removed catalyzer after filtration, and filtrate decompression reclaims methyl alcohol and applies mechanically, and residuum is a 2-ethanol piperidines, 200g, content 99.3%.
(2) hydroxyl piperazine ester crude product preparation
Get 100g (99.2%, 0.769mol) 2-ethanol piperidines, the 200g hexanaphthene drops into and to be equipped with in 1 liter of reaction flask of prolong, is stirred and heated to 60 ℃.Drip simultaneously 111g (99%, the 0.805mol) aqueous sodium hydroxide solution of sec-butyl chloroformate and 473g10% (0.844mol).The dropping time was controlled at 3 hours, 70 ℃ of controlled temperature.Drip to continue to stir and finished in 1 hour.Leave standstill branch and remove waste water, organic phase is washed secondary with 5% dilute hydrochloric acid, each 200g.And then remove waste water with dividing behind the 200g clear water washing secondary.Organic phase reclaim under reduced pressure toluene solvant cover is used down and is criticized, and residuum is hydroxyl piperazine ester crude product 169g, content 94.1%.
(3) hydroxyl piperazine ester is refining purifies
(94.1%, 0.615mol) hydroxyl piperazine ester crude product, 2.2g S-WAT drop into respectively in 250 milliliters the reaction flask, and under the condition of control vacuum less than 5mmHg, heat temperature raising, the cut of collecting 150 ℃ are hydroxyl piperazine ester finished product, 136g, content 98.6% to get 150g.Residuum is that organic high boiling material still is residual, goes to burn harmless processing.
Embodiment 3
(1) 2-ethanol piperidines preparation
200g (99%, mol) 2-ethanol pyridine, the 400g Virahol, 10g10%Pd/C drops into 1 rising respectively and presses in the hydrogenation still, uses nitrogen replacement three times, uses hydrogen exchange again three times.Stir down and slowly heat up, keep hydrogen pressure 5Mpa, the still temperature was reacted 10 hours at 90 ℃, and gas chromatographic analysis shows 2-ethanol pyridine content less than 0.5%, finished reaction and was cooled to below 30 ℃.Emptying hydrogen, reaction solution are removed catalyzer after filtration, and filtrate decompression reclaims methyl alcohol and applies mechanically, and residuum is a 2-ethanol piperidines, 204g, content 99.1%.
(2) hydroxyl piperazine ester crude product preparation
Get 100g (99.1%, 0.769mol) 2-ethanol piperidines, the 200g methylcyclohexane drops into and to be equipped with in 1 liter of reaction flask of prolong, is stirred and heated to 60 ℃.Drip simultaneously 111g (99%, the 0.805mol) aqueous sodium hydroxide solution of sec-butyl chloroformate and 473g10% (0.844mol).The dropping time was controlled at 3 hours, 70 ℃ of controlled temperature.Drip to continue to stir and finished in 1 hour.Leave standstill branch and remove waste water, organic phase is washed secondary with 5% aqueous sulfuric acid, each 200g.And then remove waste water with dividing behind the 200g clear water washing secondary.Organic phase reclaim under reduced pressure toluene solvant cover is used down and is criticized, and residuum is hydroxyl piperazine ester crude product 172g, content 93.9%.
(3) hydroxyl piperazine ester is refining purifies
(93.9%, 0.615mol) hydroxyl piperazine ester crude product, 2.2g S-WAT drop into respectively in 250 milliliters the reaction flask, and under the condition of control vacuum less than 5mmHg, heat temperature raising, the cut of collecting 150 ℃ are hydroxyl piperazine ester finished product, 134g, content 98.8% to get 150g.Residuum is that organic high boiling material still is residual, goes to burn harmless processing.
Embodiment 4
(1) 2-ethanol piperidines preparation
200g (99%, mol) 2-ethanol pyridine, 400g methyl alcohol, 10g10%Pd/C drops into 1 rising respectively and presses in the hydrogenation still, uses nitrogen replacement three times, uses hydrogen exchange again three times.Stir down and slowly heat up, keep hydrogen pressure 5Mpa, the still temperature was reacted 10 hours at 90 ℃, and gas chromatographic analysis shows 2-ethanol pyridine content less than 0.5%, finished reaction and was cooled to below 30 ℃.Emptying hydrogen, reaction solution are removed catalyzer after filtration, and filtrate decompression reclaims methyl alcohol and applies mechanically, and residuum is a 2-ethanol piperidines, 201g, content 99.2%.
(2) hydroxyl piperazine ester crude product preparation
Get 100g (99.2%, 0.769mol) 2-ethanol piperidines, 200g toluene drops into and to be equipped with in 1 liter of reaction flask of prolong, is stirred and heated to 60 ℃.Drip simultaneously 111g (99%, the 0.805mol) sodium bicarbonate aqueous solution of sec-butyl chloroformate and 473g15% (0.844mol).The dropping time was controlled at 3 hours, 70 ℃ of controlled temperature.Drip to continue to stir and finished in 1 hour.Leave standstill branch and remove waste water, organic phase is washed secondary with 5% dilute hydrochloric acid, each 200g.And then remove waste water with dividing behind the 200g clear water washing secondary.Organic phase reclaim under reduced pressure toluene solvant cover is used down and is criticized, and residuum is hydroxyl piperazine ester crude product 168g, content 94.2%.
(3) hydroxyl piperazine ester is refining purifies
(94.2%, 0.616mol) hydroxyl piperazine ester crude product, 2.2g potassium sulfite drop into respectively in 250 milliliters the reaction flask, and under the condition of control vacuum less than 5mmHg, heat temperature raising, the cut of collecting 150 ℃ are hydroxyl piperazine ester finished product, 137g, content 98.5% to get 150g.Residuum is that organic high boiling material still is residual, goes to burn harmless processing.
Claims (9)
1, the preparation method of sterilant hydroxyl piperazine ester is characterized in that may further comprise the steps:
(1) 2-ethanol piperidines preparation
2-ethanol pyridine is dissolved in the polar solvent that consumption is 1～5 times of its weight, be under the effect of highly effective hydrogenation catalyzer of 2-ethanol pyridine weight 0.1～10% at consumption, under 1～10Mpa hydrogen pressure and 50～120 ℃ of temperature, reacted 6～12 hours, record of the 0.5% o'clock reaction end of 2-ethanol pyridine content less than total amount, after the gained reacting liquid filtering was removed catalyzer, decompression and solvent recovery, residuum were 2-ethanol piperidines;
Described polar solvent is an one of the following: methyl alcohol, ethanol, Virahol, 1,4-dioxane;
Described highly effective hydrogenation catalyzer is one of the following: 10%Pd/C, R-Ni (W-5), PtO
2, RuO
2
(2) hydroxyl piperazine ester crude product preparation
2-ethanol piperidines is dissolved in the non-polar solvent that consumption is 1～5 times of its weight, control reaction temperature is at 40～80 ℃, drip sec-butyl chloroformate and concentration simultaneously and be 1～20% alkaline solution, and mol ratio is an alkali: sec-butyl chloroformate: 2-ethanol piperidines=1～1.5: 1～1.3: 1, the control dropping time is in 1～6 hour, add and continue to be stirred to the reaction end, branch vibration layer, organic phase concentration is 1～10%, consumption is the weak acid scrubbing secondary of 1～3 times of 2-ethanol piperidines weight, after washing secondary again, decompression and solvent recovery, residuum are hydroxyl piperazine ester crude product;
Described non-polar solvent is an one of the following: hexanaphthene, benzene, toluene, methylcyclohexane;
Described alkali is one of the following: sodium hydroxide, potassium hydroxide, yellow soda ash, sodium bicarbonate;
Described diluted acid is an one of the following: hydrochloric acid, sulfuric acid, phosphoric acid;
(3) hydroxyl piperazine ester is refining purifies
Adding consumption in the hydroxyl piperazine ester crude product is the antioxidant of its weight 1～3%, and under the high vacuum less than 5mmHg, distillation obtains the hydroxyl piperazine ester finished product of 98% above content under 140～150 ℃ of high temperature;
Described antioxidant is an one of the following: S-WAT, potassium sulfite.
2, the preparation method of sterilant hydroxyl piperazine ester as claimed in claim 1 is characterized in that the polar solvent described in the step (1) is a methyl alcohol; Consumption is 2 times of 2-ethanol pyridine weight.
3, the preparation method of sterilant hydroxyl piperazine ester as claimed in claim 1 is characterized in that the highly effective hydrogenation catalyzer described in the step (1) is 10%Pd/C or R-Ni (W-5); Consumption is 5% of a 2-ethanol pyridine weight.
4, the preparation method of sterilant hydroxyl piperazine ester as claimed in claim 1 is characterized in that the hydrogen pressure described in the step (1) is 3～5Mpa; Temperature of reaction is 80～100 ℃; Time in reaction times is 10 hours.
5, the preparation method of sterilant hydroxyl piperazine ester as claimed in claim 1 is characterized in that the non-polar solvent described in the step (2) is a toluene; Consumption is 2 times of 2-ethanol piperidines weight.
6, the preparation method of sterilant hydroxyl piperazine ester as claimed in claim 1 is characterized in that the alkali described in the step (2) is sodium hydroxide or sodium bicarbonate; Concentration is 10～15%.
7, the preparation method of sterilant hydroxyl piperazine ester as claimed in claim 1 is characterized in that the acid described in the step (2) is that concentration is 5%, and consumption is 2 times of 2-ethanol piperidines weight.
8, the preparation method of sterilant hydroxyl piperazine ester as claimed in claim 1 is characterized in that the dropping time described in the step (2) is 2～3 hours; Temperature of reaction is 60～70 ℃.
9, the preparation method of sterilant hydroxyl piperazine ester as claimed in claim 1 is characterized in that the antioxidant consumption described in the step (3) is 1.5% of a hydroxyl piperazine ester crude product weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008101230255A CN101323588A (en) | 2008-07-14 | 2008-07-14 | Preparation of pesticide 2-(2-hydroxyethyl)-piperidine-1-carbonate-1-methyl isopropyl ester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008101230255A CN101323588A (en) | 2008-07-14 | 2008-07-14 | Preparation of pesticide 2-(2-hydroxyethyl)-piperidine-1-carbonate-1-methyl isopropyl ester |
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| Publication Number | Publication Date |
|---|---|
| CN101323588A true CN101323588A (en) | 2008-12-17 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2008101230255A Pending CN101323588A (en) | 2008-07-14 | 2008-07-14 | Preparation of pesticide 2-(2-hydroxyethyl)-piperidine-1-carbonate-1-methyl isopropyl ester |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102167681A (en) * | 2010-12-30 | 2011-08-31 | 常州药物研究所 | Method for preparing insect repellant icaridin |
-
2008
- 2008-07-14 CN CNA2008101230255A patent/CN101323588A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102167681A (en) * | 2010-12-30 | 2011-08-31 | 常州药物研究所 | Method for preparing insect repellant icaridin |
| CN102167681B (en) * | 2010-12-30 | 2012-10-24 | 常州药物研究所有限公司 | Method for preparing insect repellant icaridin |
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Open date: 20081217 |