CN107417642A - A kind of synthetic method of N methyl piperidines - Google Patents
A kind of synthetic method of N methyl piperidines Download PDFInfo
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- CN107417642A CN107417642A CN201710453597.9A CN201710453597A CN107417642A CN 107417642 A CN107417642 A CN 107417642A CN 201710453597 A CN201710453597 A CN 201710453597A CN 107417642 A CN107417642 A CN 107417642A
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- piperidines
- methyl piperidines
- synthetic method
- methyl
- potassium dihydrogen
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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
- C07D295/027—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 containing only one hetero ring
- C07D295/03—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 containing only one hetero ring with the ring nitrogen atoms directly attached to acyclic carbon atoms
-
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Fertilizers (AREA)
Abstract
The present invention provides a kind of synthetic method of N methyl piperidines, and piperidines is heated into 80 100 DEG C, adds paraformaldehyde and potassium dihydrogen phosphite, the mol ratio of the piperidines, paraformaldehyde and potassium dihydrogen phosphite is 1：1‑1.2：0.5 0.6, after reaction terminates, N methyl piperidines and solid are filtered to obtain, gained solid is heated and distilled, collects distillate, gained distillate is N methyl piperidines；React filtered and distillation obtains N methyl piperidines, purity is high, purified can not directly utilize, remaining solid is potassium dihydrogen phosphate, recyclable directly as fertilizer utilization.
Description
Technical field
The invention belongs to technical field of organic synthesis, and in particular to a kind of synthetic method of N- methyl piperidines.
Background technology
Plant growth regulator first piperazine can promote the reproductive growth of plant, suppress cauline leaf overgrowing, control side shoot, improve
Root quantity and vigor, increase the resistance of plant, particularly used on cotton, effectively can prevent cotton from overgrowing, control
Plant type is compact, reduces the shedding of cotton bolls, promotes ripe, Yield Increase In Cotton, and the toxic residue of first piperazine is small.China is large agricultural country, N-
The important intermediate that methyl piperidine synthesizes as first piperazine, its development for synthesizing for agricultural have huge progradation.
The synthetic method of N- methyl piperidines mainly has following two at present：
First method：Using piperidines, formaldehyde and formic acid, in a heated condition after reaction completely, concentrated hydrochloric acid is added, is steamed
Excessive formaldehyde and formic acid send wastewater treatment, then after sodium hydrate aqueous solution alkalizes, steams the mixing of N- methyl piperidines and water
Thing, after being dried using sodium hydroxide, rectifying obtains N- methyl piperidines (reaction equation is shown in formula 1)；The synthesis technique is more ripe, should
With extensive, but reactant formaldehyde and formic acid are seriously polluted, and post-process and produce a large amount of waste water, and cost for wastewater treatment is high.
Second method：Using piperidines and chloromethanes, react in the basic conditions, N- first is obtained through distillation after reaction completely
The mixture of phenylpiperidines and water, after being dried using sodium hydroxide, rectifying obtains N- methyl piperidines (reaction equation is shown in formula 2)；The technique
Although avoiding using formaldehyde and formic acid, waste water yield obtains a certain degree of reduction, reactant chloromethanes normal temperature and pressure
It is down gas, and it is poisonous, operation is complicated, and industrialization difficulty is high.
Big for energy consumption present in the production of current N- methyl piperidines, low yield is seriously polluted, the problems such as complex operation,
Need badly and find a kind of synthetic method of high-efficiency environment friendly.
The content of the invention
The present invention is big for energy consumption present in the production of current N- methyl piperidines, and low yield is seriously polluted, complex operation etc.
Problem, there is provided a kind of synthetic method of N- methyl piperidines, reaction is filtered and distillation obtains N- methyl piperidines, and purity is high, can not
Purified directly to utilize, remaining solid is potassium dihydrogen phosphate, recyclable directly as fertilizer utilization.
The present invention adopts the following technical scheme that：
A kind of synthetic method of N- methyl piperidines, piperidines is heated to 80-100 DEG C, adds paraformaldehyde and phosphorous acid two
Hydrogen potassium, after reaction terminates, filter to get filtrate and residue, gained filtrate are N- methyl piperidines；
Wherein, the mol ratio of the piperidines, paraformaldehyde and potassium dihydrogen phosphite is 1：1-1.2：0.5-0.6；It is wherein more
The mole of polyformaldehyde is calculated on the basis of monomer molecule quality.
Preferably, residue obtained heating is distilled, collects distillate, gained distillate is N- methyl piperidines.
The route map of above-mentioned synthetic method is as shown in Figure 1.
The chemical equation of above-mentioned synthetic method is as follows：
Preferably, the temperature of the heating distillation is 110-120 DEG C.
Preferably, it is added portionwise after paraformaldehyde and the potassium dihydrogen phosphite mixing, total time control that adds is in 0.5-
1.5 hours, after being added completely into, the reaction time of reaction system was controlled in 1-3h；The batch mode is：It is divided into 3-6 batches to add
Enter, every batch of interval time is 10-15 minutes；
Beneficial effects of the present invention are as follows：
The synthetic method reaction time of the present invention is short, simple to operate, energy consumption is low, and reaction impurities are few, and yield is high, and reaction is secondary
Product can be recycled, and not have " three wastes " generation, and environment will not be polluted.And reaction terminate after, it is filtered and
Distillation can obtain N- methyl piperidines, and (piperidines reaction is complete, does not remain and accessory substance；The effect of paraformaldehyde is to provide first
Base, water can be generated after reaction, the water generated can be consumed again during the course of the reaction；Paraformaldehyde has a little excess, can
There can be a small amount of residual, but paraformaldehyde does not dissolve in piperidines and N- methyl piperidines, so being remained in filtrate without paraformaldehyde), yield
Up to more than 93%, post processing is simple, and obtained N- methyl piperidines purity is high, purified can not directly utilize, distillation is remaining
Residue is mainly potassium dihydrogen phosphate, recyclable directly as fertilizer utilization.
Brief description of the drawings
Fig. 1 is the synthetic route chart of the present invention；
Fig. 2 is the nucleus magnetic hydrogen spectrum figure of filtrate；
Fig. 3 is the nucleus magnetic hydrogen spectrum figure of distillate.
Embodiment
In order that the technical purpose of the present invention, technical scheme and beneficial effect are clearer, below in conjunction with the accompanying drawings and specifically
Embodiment is further illustrated to technical scheme.
Embodiment 1
170g piperidines is weighed in churned mechanically 500mL there-necked flasks, oil bath heating weighs poly respectively to 80 DEG C
Formaldehyde 72g, potassium dihydrogen phosphite 144g, and be well mixed, then it is added portionwise in piperidines, total time control that adds is in 1h
It is interior, 4 batches are divided into, every batch added at intervals of 15 minutes, paid attention to preventing slug during charging；2h, thin layer are reacted after charging
After chromatogram detection piperidines reaction completely, room temperature is cooled to, filters to obtain filtrate 130g and residue, will filter and residue obtained be placed in reaction
110 DEG C are heated in bottle to be distilled, untill no liquid distillates, it is potassium dihydrogen phosphate 128g to distill remaining solid, recovery
As Fertilizer application, distillate 54g, the composition of filtrate and distillate is that (nucleus magnetic hydrogen spectrum of filtrate is shown in figure to N- methyl piperidines
2, the nucleus magnetic hydrogen spectrum of distillate is shown in Fig. 3), common 184g.
Embodiment 2
170g piperidines is weighed in churned mechanically 500mL there-necked flasks, oil bath heating weighs poly respectively to 90 DEG C
Formaldehyde 72g, potassium dihydrogen phosphite 144g, and be well mixed, then it is added portionwise in piperidines, total time control that adds exists
In 1.5h, 6 batches are divided into, every batch added at intervals of 15 minutes, paid attention to preventing slug during charging；Reacted after charging
1.5h, after thin-layer chromatography detection piperidines reaction completely, room temperature is cooled to, filters to obtain filtrate 140g and residue；It is residual gained will to be filtered
Slag, which is placed in reaction bulb, to be heated to 115 DEG C and is distilled, and untill no liquid distillates, it is biphosphate to distill remaining solid
Potassium 126g, recovery are used as Fertilizer application, distillate 46g, and the composition of filtrate and distillate is N- methyl piperidines, common 186g.
Embodiment 3
170g piperidines is weighed in churned mechanically 500mL there-necked flasks, oil bath heating weighs more respectively to 100 DEG C
Polyformaldehyde 72g, potassium dihydrogen phosphite 144g, and be well mixed, then it is added portionwise in piperidines, total time control that adds exists
In 50 minutes, 5 batches are divided into, every batch added at intervals of 10 minutes, paid attention to preventing slug during charging；Reacted after charging
2.5h, after thin-layer chromatography detection piperidines reaction completely, 60 DEG C are cooled to, filters to obtain filtrate 152g and residue；It is residual gained will to be filtered
Slag, which is placed in reaction bulb, to be heated to 120 DEG C and is distilled, and untill no liquid distillates, it is biphosphate to distill remaining solid
Potassium 122g, recovery are used as Fertilizer application, distillate 36g, and the composition of filtrate and distillate is N- methyl piperidines, common 188g.
Embodiment 4
212g piperidines is weighed in churned mechanically 500mL there-necked flasks, oil bath heating weighs poly respectively to 90 DEG C
Formaldehyde 82g, potassium dihydrogen phosphite 165g, and be well mixed, then it is added portionwise in piperidines, total time control that adds is 40
In minute, 4 batches are divided into, every batch added at intervals of 10 minutes, pays attention to preventing slug during charging, reacts 3h after charging,
After thin-layer chromatography detection piperidines reaction completely, 50 DEG C are cooled to, filters to obtain filtrate 185g and residue；Residue obtained put will be filtered
It is heated to 110 DEG C in reaction bulb to be distilled, untill no liquid distillates, it is potassium dihydrogen phosphate to distill remaining solid
155g, recovery are used as Fertilizer application, distillate 50g, and the composition of filtrate and distillate is N- methyl piperidines, common 235g.
It should be noted last that：Above-described embodiment is merely to illustrate the technical scheme being not intended to limit the present invention, any right
The equivalent substitution and do not depart from the modification of spirit and scope of the invention or local replacement that the present invention is carried out, it all should cover at this
Within the scope of invention right is claimed.
Claims (4)
- A kind of 1. synthetic method of N- methyl piperidines, it is characterised in that：Piperidines is heated to 80-100 DEG C, add paraformaldehyde and Potassium dihydrogen phosphite, after reaction terminates, filter to get filtrate and residue, gained filtrate are N- methyl piperidines；Wherein, the mol ratio of the piperidines, paraformaldehyde and potassium dihydrogen phosphite is 1：1-1.2 ：0.5-0.6.
- 2. the synthetic method of N- methyl piperidines according to claim 1, it is characterised in that：Residue obtained heating is distilled, Distillate is collected, gained distillate is N- methyl piperidines.
- 3. the synthetic method of N- methyl piperidines according to claim 1, it is characterised in that：It is described heating distillation temperature be 110-120℃。
- 4. the synthetic method of N- methyl piperidines according to claim 1, it is characterised in that：The paraformaldehyde and phosphorous acid It is added portionwise after potassium dihydrogen mixing, total time control that adds is in 0.5-1.5 hours, after being added completely into, during the reaction of reaction system Between control in 1-3h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201710453597.9A CN107417642A (en) | 2017-06-15 | 2017-06-15 | A kind of synthetic method of N methyl piperidines |
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| CN201710453597.9A CN107417642A (en) | 2017-06-15 | 2017-06-15 | A kind of synthetic method of N methyl piperidines |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109180562A (en) * | 2018-10-25 | 2019-01-11 | 南京红太阳生物化学有限责任公司 | A kind of preparation method of N- methyl piperidine |
| CN111675677A (en) * | 2020-07-13 | 2020-09-18 | 江苏富比亚化学品有限公司 | Synthesis process of N-methylmorpholine |
-
2017
- 2017-06-15 CN CN201710453597.9A patent/CN107417642A/en active Pending
Non-Patent Citations (3)
| Title |
|---|
| MAHMOOD TAJBAKHSH ET AL.,: "Catalyst-Free One-Pot Reductive Alkylation of Primary and Secondary Amines and N,N-Dimethylation of Amino Acids Using Sodium Borohydride in 2,2,2-Trifluoroethanol", 《SYNTHESIS》 * |
| 张建伟 等: "氮杂环类化合物的反应研究", 《首都医科大学学报》 * |
| 张想竹 等: "N-甲基吗啉的合成研究", 《精细石油化工》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109180562A (en) * | 2018-10-25 | 2019-01-11 | 南京红太阳生物化学有限责任公司 | A kind of preparation method of N- methyl piperidine |
| CN111675677A (en) * | 2020-07-13 | 2020-09-18 | 江苏富比亚化学品有限公司 | Synthesis process of N-methylmorpholine |
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Application publication date: 20171201 |
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