CN106883196B - A kind of synthetic method of first piperazine raw medicine - Google Patents
A kind of synthetic method of first piperazine raw medicine Download PDFInfo
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- CN106883196B CN106883196B CN201710153270.XA CN201710153270A CN106883196B CN 106883196 B CN106883196 B CN 106883196B CN 201710153270 A CN201710153270 A CN 201710153270A CN 106883196 B CN106883196 B CN 106883196B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/02—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements
- C07D295/037—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements with quaternary ring nitrogen atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/02—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements
- C07D295/023—Preparation; Separation; Stabilisation; Use of additives
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Abstract
The invention discloses a kind of synthetic methods of first piperazine raw medicine.Ethyl alcohol is added to the container first, pyridine mixing is then added, chloromethanes is added after dissolution and carries out heating reaction, obtains N- picoline chloride；N- picoline chloride and catalyst are added in reaction vessel, and are passed through hydrogen, heating is reacted, and N- piperidine hydrochloride system is obtained, and acid binding agent is added in N- piperidine hydrochloride system and carries out neutralization reaction, N- methyl piperidine is obtained by filtration；N- methyl piperidine is dissolved in ethyl alcohol, and chloromethanes is added and carries out heating reaction；Finally reaction system is evaporated, ethyl alcohol and chloromethanes is removed, obtains high purity product first piperazine.The usage amount for reducing acid binding agent in production process of the present invention has saved industrial water cost；Serialization feature is strong simultaneously, effectively save energy consumption, is a kind of novel production technology.Therefore, the present invention has significant economic benefit and social benefit.
Description
One, technical field:
The present invention relates to medicine synthesising process technical fields, and in particular to a kind of synthetic method of first piperazine raw medicine.
Two, background technique:
First piperazine is new plant growth regulator, has preferable uptake and translocation effect to plant；First piperazine can promote
The reproductive growth of plant inhibits cauline leaf overgrowing, controls side shoot, mould ideotype, improve root quantity and vigor；And fruit can be made
Real weight gain, quality improve.First piperazine is widely used in cotton, wheat, rice, peanut, corn, potato, grape, vegetables, beans
The crops such as class and flowers.First piperazine is efficient one kind, low toxicity, without phytotoxicity absorbability medicament.It is difference raw with plant according to dosage
Long-term sprinkling first piperazine, adjustable plant growth make solid resistant to lodging, the improvement color of plant and increase yield.Cotton uses first
Piperazine can promote root system development, leaf color greening, thickeing prevents excessive growth, resistant to lodging, raising Boll probability and increase flower before frost, and make cotton
Flower grade improves, while greatly reduces compact, the superfluous bud of plant type, saves training recruitment.First piperazine can be inhaled by root, spray, blade
It receives, is transmitted to other positions quickly, does not remain, is not carcinogenic.Since China is large agricultural country, so requiring a large amount of first every year
Piperazine.
Currently, the synthesis technology of first piperazine is mainly two-step method: the first step is synthesis N- methyl piperidine, utilizes hexahydro piperidines
With chloromethanes single step reaction, obtain N- methyl piperidine after removing HCl (see formula 1)；N- methyl piperidine under an increased pressure with chloromethane
Alkane reaction generates first piperazine (see formula 2).The technique is highly developed, since the first step needs N- methyl piperidine to separate ability
Next step reaction is carried out, there is the problems such as time-consuming, energy consumption is big.
In order to simplify technique, also occurred a kind of method of one-step synthesis method first piperazine, i.e. piperidines and chlorine in existing literature
Methane is in excessive acid binding agent K2CO3Under effect, one-step synthesis obtains high-purity first piperazine, while KHCO obtained in system3And energy
It is enough utilized, effectively save cost, is reduced energy consumption by calcination cycle (see formula 3).
But at present the methods of all synthesis first piperazines be all using piperidines as raw material, it is at high cost and be not easy to store.
Three, summary of the invention:
The technical problem to be solved by the present invention is it is directed to existing first piperazine synthetic method, the present invention
A kind of method using pyridine for Material synthesis high-purity first piperazine is provided.
To solve the above-mentioned problems, the technical solution adopted by the present invention is that:
The present invention provides a kind of synthetic method of first piperazine raw medicine, the synthetic method the following steps are included:
A, ethyl alcohol is added in reaction vessel first, raw material pyridine is then added and is mixed, chloromethanes is added after dissolution；
Then 60~100 DEG C are heated to, pressure when control is reacted is 0.3~1.0MPa, is reacted under this temperature, pressure condition
3~6h obtains N- picoline chloride after reaction；
The mass ratio of additional amount is 1:2.5~5 between the pyridine and ethyl alcohol；Additional amount between the pyridine and chloromethanes
Molar ratio be 1:1.1~1.6；
B, the obtained N- picoline chloride of step a and catalyst are added in reaction vessel, the catalyst adds
Enter amount accounts for N- picoline chloride quality 3~5%；Then it is passed through hydrogen into reactor, is heated to 120~150
DEG C, pressure when control is reacted is 5~7MPa, and 7~15h is reacted under this temperature, pressure condition, obtains N- first after reaction
Propylpiperidine hydrochloride system；
The molar ratio of additional amount is 1:3.0~5.5 between the N- picoline chloride and hydrogen；
C, acid binding agent is added in the N- piperidine hydrochloride system that step b is obtained and carries out neutralization reaction, the N- first
The molar ratio being added between propylpiperidine hydrochloride system and acid binding agent is 1:1.05~1.11；It is filtered after neutralization reaction, mistake
N- methyl piperidine is obtained after filter；
D, the N- methyl piperidine that step c is obtained is dissolved in ethyl alcohol, N- methyl piperidine ethanol solution is obtained, then to reactant
Chloromethanes is added in system, is heated to 25~100 DEG C, control reaction pressure is 0.1~0.4MPa, in this temperature, pressure strip
The part lower reaction time is 3~6h；
The mass ratio of additional amount is 1:2.5~5 between the N- methyl piperidine and ethyl alcohol；The N- methyl piperidine and chloromethane
Molar ratio between alkane is 1:1.1~1.6；
E, the first piperazine system that step d is obtained is evaporated, ethyl alcohol and chloromethanes is evaporated off, obtain the first piperazine of high-purity
.
According to the synthetic method of above-mentioned first piperazine raw medicine, the mass percentage concentration of ethyl alcohol described in step a is 95~
99.5%.
According to the synthetic method of above-mentioned first piperazine raw medicine, the molar ratio described in step a between pyridine and chloromethanes is
1:1.1~1.2.
According to the synthetic method of above-mentioned first piperazine raw medicine, catalyst described in step b is bimetal supported catalyst
Ru-Pd/C or PTP-20 pyridine hydrogenation catalyst.
According to the synthetic method of above-mentioned first piperazine raw medicine, acid binding agent described in step c is sodium ethoxide, NaOH, Na2CO3Or
NaHCO3。
According to the synthetic method of above-mentioned first piperazine raw medicine, the mass percentage concentration of ethyl alcohol described in step d is 95~
99.5%.
According to the synthetic method of above-mentioned first piperazine raw medicine, rubbing between N- methyl piperidine and chloromethanes described in step d
You are than being 1:1.1~1.2.
According to the synthetic method of above-mentioned first piperazine raw medicine, the purity of high-purity first piperazine described in step e is 99.5%.
Positive beneficial effect of the invention:
1, raw material pyridine and chloromethanes that the present invention uses, and the first piperazine generated are all dissolved in ethyl alcohol, can effectively mention
The purity of pure first piperazine raw medicine；Present invention process is easy to operate, and the cost of raw material is cheap, technique waste water is few, and economic cost is low, institute
Product first piperazine purity is high is obtained, is suitble to large-scale continuous, industrialized production, is a kind of synthesis high-purity vegetable growth regulator
The new process of first piperazine.
2, the first piperazine for raw material pyridine, chloromethanes and the generation that the method for the present invention utilizes all is dissolved in ethyl alcohol, while tiing up acid
Agent usage amount greatly reduces, so as to effectively improve the purity of first piperazine raw medicine.It is prepared using technical solution of the present invention
First piperazine purity reach 99.5%.
3, the usage amount for reducing acid binding agent in present invention process production process, has saved industrial water cost；Connect simultaneously
Continuousization feature is strong, effectively save energy consumption, is a kind of novel production technology.Therefore, the present invention have significant economic benefit and
Social benefit.
Four, Detailed description of the invention:
The liquid chromatogram of Fig. 1 first piperazine standard sample；
The liquid chromatogram of 1 products therefrom of Fig. 2 embodiment of the present invention；
The liquid chromatogram of 2 products therefrom of Fig. 3 embodiment of the present invention；
The liquid chromatogram of 3 products therefrom of Fig. 4 embodiment of the present invention；
Fig. 5 first piperazine standard sample working curve.
Nuclear magnetic resonance (1H-NMR) spectrogram of 1 gained first piperazine of Fig. 6 embodiment of the present invention.
Five, specific embodiment:
The present invention is further explained with reference to embodiments, but is not intended to limit protection content of the invention.
Embodiment 1:
The synthetic method of first piperazine raw medicine of the present invention, the detailed step of the synthetic method are as follows:
A, the ethyl alcohol that mass percentage concentration is 99.5% is added in reaction vessel first, raw material pyridine is then added and carries out
Mixing, is added chloromethanes after dissolution；Then 80 DEG C are heated to, pressure when control is reacted is 0.5MPa, in this temperature, pressure
6h is reacted under the conditions of power, obtains N- picoline chloride after reaction；
The mass ratio of additional amount is 1:2.5 between the pyridine and ethyl alcohol；Additional amount between the pyridine and chloromethanes
Molar ratio is 1:1.2；
B, reaction is added in the obtained N- picoline chloride of step a and bimetal supported catalyst Ru-Pd/C to hold
In device, the additional amount of the catalyst accounts for the 4% of N- picoline chloride quality；Then hydrogen is passed through into reactor, institute
The molar ratio for stating additional amount between N- picoline chloride and hydrogen is 1:3.0；Then 130 DEG C are heated to, control is anti-
Seasonable pressure is 6MPa, and 12h is reacted under this temperature, pressure condition, obtains N- piperidine hydrochloride body after reaction
System；
C, acid binding agent NaOH is added in the N- piperidine hydrochloride system that step b is obtained and carries out neutralization reaction, it is described
The molar ratio being added between N- piperidine hydrochloride system and acid binding agent NaOH is 1:1.08；It is filtered after neutralization reaction,
N- methyl piperidine is obtained after filtering；
D, the N- methyl piperidine that step c is obtained is dissolved in the ethyl alcohol that mass percentage concentration is 99.5%, obtains N- methyl
Piperidine ethanol solution, is then added chloromethanes into reaction system, is heated to 60 DEG C, and control reaction pressure is 0.3MPa,
The reaction time is 5h under this temperature, pressure condition；
The mass ratio of additional amount is 1:2.5 between the N- methyl piperidine and ethyl alcohol；The N- methyl piperidine and chloromethanes
Between molar ratio be 1:1.2；
E, the first piperazine system that step d is obtained is evaporated, ethyl alcohol and chloromethanes is evaporated off, obtaining purity is 99.5%
First piperazine (liquid chromatogram for being detailed in attached drawing 2).
Embodiment 2:
The synthetic method of first piperazine raw medicine of the present invention, the detailed step of the synthetic method are as follows:
A, the ethyl alcohol that mass percentage concentration is 97% is added in reaction vessel first, raw material pyridine is then added and is mixed
It closes, chloromethanes is added after dissolution；Then 100 DEG C are heated to, pressure when control is reacted is 0.7MPa, in this temperature, pressure
4h is reacted under the conditions of power, obtains N- picoline chloride after reaction；
The mass ratio of additional amount is 1:3.5 between the pyridine and ethyl alcohol；Additional amount between the pyridine and chloromethanes
Molar ratio is 1:1.1；
B, the obtained N- picoline chloride of step a and PTP-20 pyridine hydrogenation catalyst are added in reaction vessel,
The additional amount of the catalyst accounts for the 3% of N- picoline chloride quality；Then hydrogen, the N- first are passed through into reactor
The molar ratio of additional amount is 1:3.5 between pyridinum chloride and hydrogen；Then 150 DEG C are heated to, when control is reacted
Pressure is 5MPa, and 8h is reacted under this temperature, pressure condition, obtains N- piperidine hydrochloride system after reaction；
C, acid binding agent NaOH is added in the N- piperidine hydrochloride system that step b is obtained and carries out neutralization reaction, it is described
The molar ratio being added between N- piperidine hydrochloride system and acid binding agent NaOH is 1:1.11；It is filtered after neutralization reaction,
N- methyl piperidine is obtained after filtering；
D, the N- methyl piperidine that step c is obtained is dissolved in the ethyl alcohol that mass percentage concentration is 97%, obtains N- methyl piperazine
Pyridine ethanol solution, is then added chloromethanes into reaction system, is heated to 100 DEG C, and control reaction pressure is 0.2MPa,
This temperature, pressure condition lower reaction time are 4.5h；
The mass ratio of additional amount is 1:3.5 between the N- methyl piperidine and ethyl alcohol；The N- methyl piperidine and chloromethanes
Between molar ratio be 1:1.1；
E, the first piperazine system that step d is obtained is evaporated, ethyl alcohol and chloromethanes is evaporated off, obtaining purity is 99.5%
First piperazine (liquid chromatogram for being detailed in attached drawing 3).
Embodiment 3:
The synthetic method of first piperazine raw medicine of the present invention, the detailed step of the synthetic method are as follows:
A, the ethyl alcohol that mass percentage concentration is 95% is added in reaction vessel first, raw material pyridine is then added and is mixed
It closes, chloromethanes is added after dissolution；Then 60 DEG C are heated to, pressure when control is reacted is 0.9MPa, in this temperature, pressure
Under the conditions of react 6h, obtain N- picoline chloride after reaction；
The mass ratio of additional amount is 1:5 between the pyridine and ethyl alcohol；Additional amount rubs between the pyridine and chloromethanes
You are than being 1:1.2；
B, reaction is added in the obtained N- picoline chloride of step a and bimetal supported catalyst Ru-Pd/C to hold
In device, the additional amount of the catalyst accounts for the 5% of N- picoline chloride quality；Then hydrogen is passed through into reactor, institute
The molar ratio for stating additional amount between N- picoline chloride and hydrogen is 1:3.0；Then 120 DEG C are heated to, control is anti-
Seasonable pressure is 7MPa, and 14h is reacted under this temperature, pressure condition, obtains N- piperidine hydrochloride body after reaction
System；
C, acid binding agent NaOH is added in the N- piperidine hydrochloride system that step b is obtained and carries out neutralization reaction, it is described
The molar ratio being added between N- piperidine hydrochloride system and acid binding agent NaOH is 1:1.05；It is filtered after neutralization reaction,
N- methyl piperidine is obtained after filtering；
D, the N- methyl piperidine that step c is obtained is dissolved in the ethyl alcohol that mass percentage concentration is 95%, obtains N- methyl piperazine
Pyridine ethanol solution, is then added chloromethanes into reaction system, is heated to 50 DEG C, and control reaction pressure is 0.35MPa,
This temperature, pressure condition lower reaction time are 6h；
The mass ratio of additional amount is 1:5 between the N- methyl piperidine and ethyl alcohol；The N- methyl piperidine and chloromethanes it
Between molar ratio be 1:1.2；
E, the first piperazine system that step d is obtained is evaporated, ethyl alcohol and chloromethanes is evaporated off, obtaining purity is 99.5%
First piperazine (liquid chromatogram for being detailed in attached drawing 4).
Embodiment 4:
The synthetic method of first piperazine raw medicine of the present invention, the detailed step of the synthetic method are as follows:
A, the ethyl alcohol that mass percentage concentration is 98% is added in reaction vessel first, raw material pyridine is then added and is mixed
It closes, chloromethanes is added after dissolution；Then 70 DEG C are heated to, pressure when control is reacted is 1.0MPa, in this temperature, pressure
Under the conditions of react 5h, obtain N- picoline chloride after reaction；
The mass ratio of additional amount is 1:2.8 between the pyridine and ethyl alcohol；Additional amount between the pyridine and chloromethanes
Molar ratio is 1:1.3；
B, the obtained N- picoline chloride of step a and PTP-20 pyridine hydrogenation catalyst are added in reaction vessel,
The additional amount of the catalyst accounts for the 4.5% of N- picoline chloride quality；Then hydrogen, the N- are passed through into reactor
The molar ratio of additional amount is 1:3.0 between picoline chloride and hydrogen；Then 140 DEG C, when control is reacted are heated to
Pressure be 6MPa, 12h is reacted under this temperature, pressure condition, obtains N- piperidine hydrochloride system after reaction；
C, acid binding agent sodium ethoxide is added in the N- piperidine hydrochloride system that step b is obtained and carries out neutralization reaction, institute
Stating the molar ratio being added between N- piperidine hydrochloride system and acid binding agent sodium ethoxide is 1:1.08；It is taken out after neutralization reaction
Filter, obtains N- methyl piperidine after filtering；
D, the N- methyl piperidine that step c is obtained is dissolved in the ethyl alcohol that mass percentage concentration is 98%, obtains N- methyl piperazine
Pyridine ethanol solution, is then added chloromethanes into reaction system, is heated to 70 DEG C, and control reaction pressure is 0.3MPa,
This temperature, pressure condition lower reaction time are 5h；
The mass ratio of additional amount is 1:3.0 between the N- methyl piperidine and ethyl alcohol；The N- methyl piperidine and chloromethanes
Between molar ratio be 1:1.3；
E, the first piperazine system that step d is obtained is evaporated, ethyl alcohol and chloromethanes is evaporated off, obtaining purity is 99.5%
First piperazine.
It is composed in addition, having carried out nuclear magnetic resoance spectrum map analysis i.e. (1H-NMR) to 1 products obtained therefrom first piperazine of the embodiment of the present invention
Figure, is detailed in attached drawing 6.
Claims (6)
1. a kind of synthetic method of first piperazine raw medicine, which is characterized in that the synthetic method the following steps are included:
A, ethyl alcohol is added in reaction vessel first, raw material pyridine is then added and is mixed, chloromethanes is added after dissolution；Then
It is heated to 60~100 DEG C, pressure when control reaction is 0.3~1.0MPa, react 3 under this temperature, pressure condition~
6h obtains N- picoline chloride after reaction；
The mass ratio of additional amount is 1:2.5~5 between the pyridine and ethyl alcohol；Additional amount rubs between the pyridine and chloromethanes
You are than being 1:1.1~1.6；The mass percentage concentration of the ethyl alcohol is 95~99.5%；
B, the obtained N- picoline chloride of step a and catalyst are added in reaction vessel, the additional amount of the catalyst
Account for the 3~5% of N- picoline chloride quality；Then it is passed through hydrogen into reactor, is heated to 120~150 DEG C, control
Pressure when system reaction is 5~7MPa, and 7~15h is reacted under this temperature, pressure condition, obtains N- methyl piperazine after reaction
Thiamine hydrochloride system；
The molar ratio of additional amount is 1:3.0~5.5 between the N- picoline chloride and hydrogen；
C, acid binding agent is added in the N- piperidine hydrochloride system that step b is obtained and carries out neutralization reaction, the N- methyl piperazine
The molar ratio being added between thiamine hydrochloride system and acid binding agent is 1:1.05~1.11；It is filtered after neutralization reaction, after filtering
Obtain N- methyl piperidine；
D, the N- methyl piperidine that step c is obtained is dissolved in ethyl alcohol, N- methyl piperidine ethanol solution is obtained, then into reaction system
Chloromethanes is added, is heated to 25~100 DEG C, control reaction pressure is 0.1~0.4MPa, under this temperature, pressure condition
Reaction time is 3~6h；
The mass ratio of additional amount is 1:2.5~5 between the N- methyl piperidine and ethyl alcohol；The N- methyl piperidine and chloromethanes it
Between molar ratio be 1:1.1~1.6；The mass percentage concentration of the ethyl alcohol is 95~99.5%；
E, the first piperazine system that step d is obtained is evaporated, ethyl alcohol and chloromethanes is evaporated off, obtain the first piperazine of high-purity.
2. the synthetic method of first piperazine raw medicine according to claim 1, it is characterised in that: pyridine described in step a and chlorine
Molar ratio between methane is 1:1.1~1.2.
3. the synthetic method of first piperazine raw medicine according to claim 1, it is characterised in that: catalyst described in step b is
Bimetal supported catalyst Ru-Pd/C or PTP-20 pyridine hydrogenation catalyst.
4. the synthetic method of first piperazine raw medicine according to claim 1, it is characterised in that: acid binding agent described in step c is
Sodium ethoxide, NaOH, Na2CO3Or NaHCO3。
5. the synthetic method of first piperazine raw medicine according to claim 1, it is characterised in that: N- methyl piperazine described in step d
Molar ratio between pyridine and chloromethanes is 1:1.1~1.2.
6. the synthetic method of first piperazine raw medicine according to claim 1, it is characterised in that: high-purity first described in step e
The purity of piperazine is 99.5%.
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| CN110128374A (en) * | 2019-06-05 | 2019-08-16 | 南通金陵农化有限公司 | A kind of production of the absorbability of piperazine containing first plant growth regulator and synthesis technology |
| CN115403513A (en) * | 2022-09-01 | 2022-11-29 | 安徽国星生物化学有限公司 | Continuous synthesis process of N-methylpyridine chloride |
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| CN1034921A (en) * | 1988-11-18 | 1989-08-23 | 军事医学科学院毒物药物研究所 | The synthetic method that plant-growth regulator " helps strong plain " |
| EP0573177A2 (en) * | 1992-06-04 | 1993-12-08 | Micro-Flo Company | Mepiquat chloride |
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| JPH04282375A (en) * | 1991-03-08 | 1992-10-07 | Kawaken Fine Chem Co Ltd | Production of high-purity 1-methylpiperazine |
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| CN1034921A (en) * | 1988-11-18 | 1989-08-23 | 军事医学科学院毒物药物研究所 | The synthetic method that plant-growth regulator " helps strong plain " |
| EP0573177A2 (en) * | 1992-06-04 | 1993-12-08 | Micro-Flo Company | Mepiquat chloride |
| CN103087008A (en) * | 2013-02-21 | 2013-05-08 | 安阳市小康农药有限责任公司 | Method for preparing Mepigtlat-chloride |
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