CN103087008B - Method for preparing Mepigtlat-chloride - Google Patents
Method for preparing Mepigtlat-chloride Download PDFInfo
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- CN103087008B CN103087008B CN201310055144.2A CN201310055144A CN103087008B CN 103087008 B CN103087008 B CN 103087008B CN 201310055144 A CN201310055144 A CN 201310055144A CN 103087008 B CN103087008 B CN 103087008B
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- exchange resin
- cation exchange
- piperazine
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- piperidines
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Abstract
The invention discloses a method for preparing Mepigtlat-chloride. The method comprises the following steps: dissolving piperidine in ethanol, adding NaOH, stirring, and adding methyl chloride to carry out substitution reaction; and after the reaction finishes, passing the obtained reaction system through a metal cation exchange resin to carry out elution, and collecting the eluate to obtain the Mepigtlat-chloride. By treating with the metal cation exchange resin, the purity of the Mepigtlat-chloride can be enhanced essentially.
Description
Technical field
The present invention relates to pesticide original medicine synthesis field, particularly a kind of method preparing first piperazine.
Background technology
First piperazine is a kind of suppressive piperidines plant-growth regulator, biosynthesizing and the effect of plant materials inner gibberellin can be suppressed, be mainly used in cotton, nourishing and growing of cotton can be controlled, reduce the height of plant, make shortened internodes, branch shortens, plant type is compact, is beneficial to ventilation and penetrating light, reduces cotton buds and bolls exfoliation.After the process of first piperazine, blade face thickeies, and leaf area reduces, and chlorophyll content increases, and improves blade carbon dioxide fixation and assimilative capacity; Increase the ratio of knot bell number and Fu Qiantao, premature ripening; Promote root system development, improve Root Absorption ability, increase the level of calcium and phosphorus in blade.Also can be widely used on the plant materialss such as fruit tree, wheat, paddy rice, beans, tomato, potato; Energy dwarfed plant, improves the stability of cytolemma, increases the resistance of plant.Cotton Production is in critical role in China, and since the nineties, average growth area 5,800,000 hectares, thus, China all needs a large amount of first piperazines every year.
Summary of the invention
The object of this invention is to provide a kind of method preparing first piperazine.
The method preparing first piperazine provided by the invention, add NaOH after comprising the steps: that piperidines is dissolved in ethanol to dissolve, NaoH adds methyl chloride again after dissolving and carries out substitution reaction, after completion of the reaction gained reaction system is crossed metallic cation exchange resin column, collect elutriant, obtain first piperazine.
In aforesaid method, the molar ratio of described piperidines, NaOH and methyl chloride is 1: 1.5-1.9: 2.1-2.3, is specially 1: 1.7: 2.2.
In described dissolving step, temperature is 55-65 DEG C, and the time is 0.5-1 hour, is specially 0.5 hour.
The described methyl chloride that adds carries out in substitution reaction, and temperature is 60-80 DEG C, is specially 65-70 DEG C, and the time is 4-6 hour, is specially 4 hours.After this step reaction, the system that products therefrom is made up of first piperazine and ethanol and NaCl form, and wherein gained NaCl can be carried out refine and reclaim, for industrial production.
Described metallic cation exchange resin column is 001 × 7 strongly acidic styrene type cation exchange resin post, can purchased from Hangzhou Yong Zhou water treatment Science and Technology Ltd..
The described object of metallic cation exchange resin of crossing is for removing sodium ion;
In this step, the elution speed of reaction system is 100 ~ 150L/h, is specially 100 or 120 or 140 or 150 or 100-140 or 120-140 or 140-150L/h;
The number of times crossing post is once.
The blade diameter length ratio of described metallic cation exchange resin column is 1: 3-5, is specially 1: 4;
Column temperature is 20 ~ 25 DEG C;
In reaction system, the mass ratio of piperidines and metallic cation exchange resin is 1: 0.1 ~ 0.15, is specially 1: 0.1 or 1: 0.12 or 1: 0.14 or 1: 0.15 or 1: 0.1-0.14 or 1: 0.1-0.12 or 1: 0.12-0.15 or 1: 0.12-0.14 or 1: 0.14-0.15.
The mass ratio of described piperidines and ethanol is 1: 8-10, is specially 1: 9.
Described method also comprises the steps: after described collection elutriant step, is distilled by elutriant, obtains the first piperazine after purifying.
In this distilation steps, gained ethanol is recyclable carries out recycle.
After the method preparing first piperazine provided by the invention uses the process of metallic cation exchange resin, inherently can improve the purity of first piperazine.
Accompanying drawing explanation
Fig. 1 is the color atlas of first piperazine standard model.
Fig. 2 is the color atlas of embodiment 1 products therefrom.
Fig. 3 is the color atlas of embodiment 2 products therefrom.
Fig. 4 is the color atlas of embodiment 3 products therefrom.
Fig. 5 is the color atlas of embodiment 4 products therefrom.
Fig. 6 is standard model working curve.
Fig. 7 be embodiment 1 gained first piperazine nucleus magnetic resonance (
1h-NMR) spectrogram.
Embodiment
Below in conjunction with specific embodiment, the present invention is further elaborated, but the present invention is not limited to following examples.Described method is ordinary method if no special instructions.Described starting material all can obtain from open commercial sources if no special instructions.Following embodiment metallic cation exchange resin used is 001 × 7 strongly acidic styrene type cation exchange resin, purchased from Hangzhou Yong Zhou water treatment Science and Technology Ltd..
The preparation of embodiment 1, first piperazine
1kg piperidines is dissolved in 9kg ethanol, under stirring, adds the NaOH of 0.8kg, at 55 ~ 65 DEG C, stir 0.5h to NaOH dissolve; In system, pass into the methyl chloride of 1.3kg, stirring reaction 4h at 65 ~ 70 DEG C, obtains first piperazine ethanol system and NaCl; Again by gained filtrate with the elution speed of 100L/h by post high for 20cm, the diameter of post is 5cm, and column temperature is 20 ~ 25 DEG C, resin quality be the metallic cation exchange resin column of 0.1kg once, the Na in removing system
+; After collecting elutriant, distillation obtains first piperazine.
The nuclear-magnetism detected result of this embodiment products therefrom as shown in Figure 7.As seen from the figure, this product structure is correct, is target compound first piperazine.
The preparation of embodiment 2, first piperazine
1kg piperidines is dissolved in 9kg ethanol, under stirring, adds the NaOH of 0.8kg, at 55 ~ 65 DEG C, stir 0.5h; In system, pass into the methyl chloride of 1.3kg, at 60 ~ 80 DEG C, stirring reaction 4h to NaOH dissolves; Gained system will be reacted filter, obtain first piperazine ethanol system and NaCl; Again by gained filtrate with the elution speed of 120L/h by post high for 20cm, the diameter 5 of post is cm, and column temperature is 20 ~ 25 DEG C, resin quality be 0.12kg metallic cation exchange resin column once, the Na in removing system
+; After collecting elutriant, distillation obtains first piperazine.
The nuclear-magnetism detected result of this embodiment products therefrom and Fig. 7, without substantive difference, repeat no more.
The preparation of embodiment 3, first piperazine
1kg piperidines is dissolved in 9kg ethanol, under stirring, adds the NaOH of 0.8kg, at 55 ~ 65 DEG C, stir 0.5h; In system, pass into the methyl chloride of 1.3kg, at 60 ~ 80 DEG C, stirring reaction 4h to NaOH dissolves; Gained system will be reacted filter, obtain first piperazine ethanol system and NaCl; Again by gained filtrate with the elution speed of 140L/h by post high for 20cm, the diameter 5 of post is cm, and column temperature is 20 ~ 25 DEG C, resin quality be 0.14kg metallic cation exchange resin column once, the Na in removing system
+; After collecting elutriant, distillation obtains first piperazine.
The nuclear-magnetism detected result of this embodiment products therefrom and Fig. 7, without substantive difference, repeat no more.
The preparation of embodiment 4, first piperazine
1kg piperidines is dissolved in 9kg ethanol, under stirring, adds the NaOH of 0.8kg, at 55 ~ 65 DEG C, stir 0.5h; In system, pass into the methyl chloride of 1.3kg, at 60 ~ 80 DEG C, stirring reaction 4h to NaOH dissolves; Gained system will be reacted filter, obtain first piperazine ethanol system and NaCl; Again by gained filtrate with the elution speed of 150L/h by post high for 20cm, the diameter 5 of post is cm, and column temperature is 20 ~ 25 DEG C, resin quality be the metallic cation exchange resin column of 0.15kg once, the Na in removing system
+, after collecting elutriant, distillation obtains first piperazine.
The nuclear-magnetism detected result of this embodiment products therefrom and Fig. 7, without substantive difference, repeat no more.
The detection method of embodiment 5, first piperazine and detected result
Select high performance liquid ion-pair chromatography to detect the mass percentage of first piperazine in embodiment 1-4 elutriant, moving phase be by volume ratio be 10: 90 acetonitrile and concentration be that the normal heptane sodium sulfonate aqueous solution of 5mmol/L forms; Solvent is redistilled water, sampling volume 10 μ L, flow velocity 1.0mL/min, determined wavelength 195nm, column temperature 40 DEG C.
Fig. 1 is the color atlas of first piperazine standard model.Utilize this standard model to make the mass concentration of first piperazine and the typical curve of peak area, as shown in Figure 6, corresponding linear equation is gained typical curve: y=0.0000014x+0.019, correlation coefficient r=0.9996, wherein, x is the mass concentration g/L of first piperazine, y is peak area;
Fig. 2 is the color atlas of embodiment 1 products therefrom.
Fig. 3 is the color atlas of embodiment 2 products therefrom.
Fig. 4 is the color atlas of embodiment 3 products therefrom.
Fig. 5 is the color atlas of embodiment 4 products therefrom.
Detected result is in table 1.
Table 1, first piperazine Content Test result
| Embodiment | Interventions Requested | Detected value |
| 1 | First piperazine content | 99.41％ |
| 2 | First piperazine content | 99.48％ |
| 3 | First piperazine content | 99.56％ |
| 4 | First piperazine content | 99.52％ |
As can be seen from Table 1, utilize preparation method provided by the invention, the mass percentage of gained first piperazine can reach more than 99.4%, is wherein good with elution speed 140L/h.
Claims (11)
1. prepare the method for first piperazine for one kind, add NaOH after comprising the steps: that piperidines is dissolved in ethanol to dissolve, NaOH adds methyl chloride again after dissolving and carries out substitution reaction, after completion of the reaction gained reaction system is crossed metallic cation exchange resin column, collect elutriant, obtain first piperazine;
The molar ratio of described piperidines, NaOH and methyl chloride is 1:1.5-1.9:2.1-2.3;
In described substitution reaction step, temperature is 60-80 DEG C, and the time is 4-6 hour;
Described metallic cation exchange resin is 001 × 7 strongly acidic styrene type cation exchange resin;
In the described step of metallic cation exchange resin excessively, the elution speed of reaction system is 100 ~ 150L/h;
The blade diameter length ratio of described metallic cation exchange resin column is 1:3-5;
Column temperature is 20 ~ 25 DEG C;
The mass ratio of described piperidines and metallic cation exchange resin is 1:0.1 ~ 0.15.
2. method according to claim 1, is characterized in that: the molar ratio of described piperidines, NaOH and methyl chloride is 1:1.7:2.2.
3. method according to claim 1, is characterized in that: in described dissolving step, and temperature is 55-65 DEG C, and the time is 0.5-1 hour.
4. method according to claim 3, is characterized in that: in described dissolving step, and the time is 0.5 hour.
5. method according to claim 1, is characterized in that: in described substitution reaction step, and temperature is 65-70 DEG C, and the time is 4 hours.
6. method according to claim 1, is characterized in that: in the described step of metallic cation exchange resin excessively, the elution speed of reaction system is 140L/h; Or the number of times crossing post is once.
7. method according to claim 1, is characterized in that: the blade diameter length ratio of described metallic cation exchange resin column is 1:4.
8. method according to claim 1, is characterized in that: the mass ratio of described piperidines and metallic cation exchange resin is 1:0.15.
9. method according to claim 1, is characterized in that: the mass ratio of described piperidines and ethanol is 1:8-10.
10. method according to claim 9, is characterized in that: the mass ratio of described piperidines and ethanol is 1:9.
11. methods according to any one of claim 1-10, is characterized in that: described method also comprises the steps: after described collection elutriant step, are distilled by elutriant, obtain the first piperazine after purifying.
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| CN201310055144.2A CN103087008B (en) | 2013-02-21 | 2013-02-21 | Method for preparing Mepigtlat-chloride |
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| CN201310055144.2A CN103087008B (en) | 2013-02-21 | 2013-02-21 | Method for preparing Mepigtlat-chloride |
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| CN106883196B (en) * | 2017-03-15 | 2019-03-22 | 中棉小康生物科技有限公司 | A kind of synthetic method of first piperazine raw medicine |
| CN109796395B (en) * | 2019-03-08 | 2020-10-16 | 鹤壁全丰生物科技有限公司 | Preparation method of N, N-dimethylpiperidine chloride salt |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5705648A (en) * | 1992-06-04 | 1998-01-06 | Micro Flo Co. | Mepiquat chloride |
| CN102584681A (en) * | 2011-01-12 | 2012-07-18 | 中国科学院过程工程研究所 | Synthesis of high-purity mepiquat chloride serving as plant growth regulator with one-step method |
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2013
- 2013-02-21 CN CN201310055144.2A patent/CN103087008B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5705648A (en) * | 1992-06-04 | 1998-01-06 | Micro Flo Co. | Mepiquat chloride |
| CN102584681A (en) * | 2011-01-12 | 2012-07-18 | 中国科学院过程工程研究所 | Synthesis of high-purity mepiquat chloride serving as plant growth regulator with one-step method |
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Address after: 455100 Anyang, Henan, North District Industrial Park Road, No. 8 Patentee after: A cotton Biotechnology Co. Ltd. Address before: 455000 Henan City, Anyang Province Industrial Park, North Road, the number of venture capital of the city of Anyang on the well-being of the limited liability company, the 8 Patentee before: Anyang Xiaokang Pesticide Co., Ltd. |
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