阅读说明：本技术 一种新的吡蚜酮中间体烟醛合成方法及合成装置 (Novel method and device for synthesizing pymetrozine intermediate nicotinaldehyde ) 是由 徐晓东 王凯 姜育田 朱学军 吴同文 唐素荣 傅晓东 陈建国 万金方 于同锋 王 于 2020-12-24 设计创作，主要内容包括：本发明公开了一种新的吡蚜酮中间体烟醛合成方法,包括如下步骤：制备混合溶液；添加主催化剂和助催化剂；反应、冷却、减压蒸馏、过滤即可制得烟醛溶液,本发明还公开了采用如上述的一种新的吡蚜酮中间体烟醛合成方法的合成设备,包括反应釜、搅拌轴和减压蒸馏器,搅拌轴设置于反应釜的内部,并与反应釜转动连接,减压蒸馏器与反应釜连接,并设置于反应釜的下侧,改进烟醛的合成方法步骤,利用主催化剂和助催化剂的相互配合,并控制实验条件,从而使得工艺步骤简单且能适应大规模的生产,并对烟醛的合成方法步骤的合成装置进行改进,利用反应釜和减压蒸馏器的配合,从而使得产品能自动进行生产,进而使得烟醛能进行大规模的生产。(The invention discloses a novel method for synthesizing pymetrozine intermediate nicotinaldehyde, which comprises the following steps: preparing a mixed solution; adding a main catalyst and a cocatalyst; the invention also discloses synthesis equipment adopting the new pymetrozine intermediate nicotinaldehyde synthesis method, which comprises a reaction kettle, a stirring shaft and a reduced pressure distiller, wherein the stirring shaft is arranged in the reaction kettle and is rotationally connected with the reaction kettle, the reduced pressure distiller is connected with the reaction kettle and is arranged at the lower side of the reaction kettle, the steps of the synthetic method of the nicotinaldehyde are improved, the main catalyst and the cocatalyst are matched with each other, and the experimental conditions are controlled, so that the process steps are simple and can adapt to large-scale production, a synthesis device of the steps of the synthetic method of the nicotinaldehyde is improved, and the reaction kettle and the reduced pressure distiller are matched so that the product can be automatically produced, and further the nicotinaldehyde can be produced on a large scale.)

1. A novel method for synthesizing pymetrozine intermediate nicotinaldehyde is characterized by comprising the following steps:

dissolving 3-methylpyridine in a 10-50% acetic acid solution to prepare a mixed solution;

adding 1-10% of a main catalyst and 1-50% of an auxiliary catalyst into the mixed solution;

sealing and filling oxygen, reacting under a preset condition, cooling to room temperature, evaporating under reduced pressure to remove acetic acid, adding water and an ester solvent into residues for dissolving and filtering, and separating phases of filtrate to obtain a water layer which is a nicotinaldehyde solution.

2. The method for synthesizing the new pymetrozine intermediate nicotinaldehyde according to claim 1, wherein the main catalyst is a nitrogen hydroxyl compound, comprising a compound I, a compound II and a compound III.

3. The method for synthesizing the new pymetrozine intermediate nicotinaldehyde as claimed in claim 2, wherein the formula of the compound I is as follows:

4. the method for synthesizing the new pymetrozine intermediate nicotinaldehyde as claimed in claim 3, wherein the molecular formula of the compound II is as follows:

5. the method for synthesizing the new pymetrozine intermediate nicotinaldehyde as claimed in claim 4, wherein the molecular formula of the compound III is as follows:

6. the method for synthesizing the new pymetrozine intermediate nicotinaldehyde according to claim 1, wherein the predetermined conditions are as follows: the oxygen pressure is 1-10atm, and the reaction is carried out for 2-12 hours at 20-100 ℃.

7. The synthesis equipment adopting the new synthesis method of the pymetrozine intermediate nicotinaldehyde as claimed in claim 5, is characterized by comprising a reaction kettle, a stirring shaft and a reduced pressure distiller, wherein the stirring shaft is arranged inside the reaction kettle and is rotatably connected with the reaction kettle, and the reduced pressure distiller is connected with the reaction kettle and is arranged at the lower side of the reaction kettle.

8. The new pymetrozine intermediate nicotinaldehyde synthesis equipment as claimed in claim 7, wherein the stirring shaft comprises a stabilizing foot, a shaft rod and a stirring blade, the upper end of the stabilizing foot is fixedly connected with the shaft rod, the lower end of the stabilizing foot is matched with the reaction kettle, and the stirring blade is arranged on the outer peripheral side of the shaft rod.

Technical Field

The invention relates to the technical field of synthesis processes of pesticide intermediates, in particular to a new pymetrozine intermediate nicotinaldehyde synthesis method and a new pymetrozine intermediate nicotinaldehyde synthesis device.

Background

The method is characterized in that the nicotinaldehyde is a key intermediate for synthesizing the pymetrozine, the widely adopted process is to prepare the nicotinaldehyde by taking the cyanamide as an initial material and performing hydrogenation reduction on the nicotinaldehyde by Raney nickel, and the obvious defects of the process comprise that the initial material, namely the cyanamide, is expensive; the reaction is easy to reduce excessively, a large amount of byproducts are generated, and the treatment amount of the subsequent three wastes is increased; the hydrogen used for reduction is inflammable and explosive gas, the Raney nickel also has higher fire risk, higher-level safety measures are needed during production, and in the prior art, the organic complex combination of cobalt and silver is used as a catalyst to prepare the nicotinaldehyde by direct oxidation, but the catalyst is expensive and is not easily available in the market, so that the application of large-scale production of the nicotinaldehyde is limited.

Disclosure of Invention

The invention provides a novel method and a novel device for synthesizing pymetrozine intermediate nicotinaldehyde, aiming at solving the problem that the existing nicotinaldehyde synthesizing process cannot be applied to large-scale production.

A novel method for synthesizing pymetrozine intermediate nicotinaldehyde comprises the following steps:

dissolving 3-methylpyridine in a 10-50% acetic acid solution to prepare a mixed solution;

adding 1-10% of a main catalyst and 1-50% of an auxiliary catalyst into the mixed solution;

sealing and filling oxygen, reacting under a preset condition, cooling to room temperature, evaporating under reduced pressure to remove acetic acid, adding water and an ester solvent into residues for dissolving and filtering, and separating phases of filtrate to obtain a water layer which is a nicotinaldehyde solution.

The main catalyst is a nitrogen hydroxyl compound, and comprises a compound I, a compound II and a compound III.

Wherein the compound I has the molecular formula:

wherein the molecular formula of the compound II is as follows:

wherein the compound III has a molecular formula:

wherein the predetermined condition is: the oxygen pressure is 1-10atm, and the reaction is carried out for 2-12 hours at 20-100 ℃.

The synthesis equipment adopting the new pymetrozine intermediate nicotinaldehyde synthesis method comprises a reaction kettle, a stirring shaft and a reduced pressure distiller, wherein the stirring shaft is arranged in the reaction kettle and is rotationally connected with the reaction kettle, and the reduced pressure distiller is connected with the reaction kettle and is arranged at the lower side of the reaction kettle.

The stirring shaft comprises a stabilizing foot, a shaft rod and stirring blades, the upper end of the stabilizing foot is fixedly connected with the shaft rod, the lower end of the stabilizing foot is matched with the reaction kettle, and the stirring blades are arranged on the outer peripheral side of the shaft rod.

The invention has the beneficial effects that: the synthetic method steps of the nicotinaldehyde are improved, the main catalyst and the auxiliary catalyst are matched with each other, and the experimental conditions are controlled, so that the process steps are simple and can adapt to large-scale production, the synthetic device of the synthetic method steps of the nicotinaldehyde is improved, and the reaction kettle and the reduced pressure distiller are matched with each other, so that the product can be automatically produced, and further the nicotinaldehyde can be produced on a large scale.

Drawings

In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.

FIG. 1 is a process step diagram of the new method for synthesizing pymetrozine intermediate nicotinaldehyde.

Fig. 2 is a schematic structural diagram of a new pymetrozine intermediate nicotinaldehyde synthesis device of the present invention.

10-a reaction kettle, 20-a stirring shaft, 30-a reduced pressure distiller, 11-a stabilizing tank, 12-a connecting opening, 13-a feeding port, 21-a stabilizing foot, 22-a shaft lever, 23-a stirring blade, 31-a negative pressure device, 32-a condensing tube, 33-a collecting tank, 34-a heater and 35-a reaction tank.

Detailed Description

Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to the same or similar elements or elements having the same or similar function throughout. The embodiments described below with reference to the drawings are illustrative and intended to be illustrative of the invention and are not to be construed as limiting the invention.

In the description of the present invention, it is to be understood that the terms "length", "width", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", and the like, indicate orientations or positional relationships based on the orientations or positional relationships illustrated in the drawings, and are used merely for convenience in describing the present invention and for simplicity in description, and do not indicate or imply that the devices or elements referred to must have a particular orientation, be constructed in a particular orientation, and be operated, and thus, are not to be construed as limiting the present invention. Further, in the description of the present invention, "a plurality" means two or more unless specifically defined otherwise.

Referring to fig. 1 and fig. 2, the present invention provides a technical solution:

a novel method for synthesizing pymetrozine intermediate nicotinaldehyde comprises the following steps:

s101: dissolving 3-methylpyridine in a 10-50% acetic acid solution to prepare a mixed solution;

s102: adding 1-10% of a main catalyst and 1-50% of an auxiliary catalyst into the mixed solution;

s103: sealing and filling oxygen, reacting under a preset condition, cooling to room temperature, evaporating under reduced pressure to remove acetic acid, adding water and an ester solvent into residues for dissolving and filtering, and separating phases of filtrate to obtain a water layer which is a nicotinaldehyde solution.

Further, the main catalyst is a nitrogen hydroxyl compound, including a compound I, a compound II and a compound III.

Further, the compound I has a formula as follows:

further, the compound II has a molecular formula as follows:

further, the compound III has a molecular formula as follows:

further, the predetermined condition is: the oxygen pressure is 1-10atm, and the reaction is carried out for 2-12 hours at 20-100 ℃.

Further, the cocatalyst is 10-30% by mass of concentrated nitric acid or fuming nitric acid, and the ester solvent is at least one of ethyl acetate or butyl acetate.

Preparing 10-50% acetic acid solution from 3-methylpyridine, adding 1-10% equivalent of one of the catalysts in 3 and 1-50% of cocatalyst, hermetically charging oxygen to 1-10atm, reacting at 20-100 ℃ for 2-12 hours, cooling to room temperature, evaporating under reduced pressure to remove acetic acid, adding water and esters into residues, dissolving and filtering, separating the phases of the filtrate to obtain a water layer, namely a nicotinaldehyde solution, and an organic phase containing unreacted raw materials and the catalyst.

Further, 3-methylpyridine is prepared into 10-20% acetic acid solution, the main catalyst is 1-5% equivalent (II), the auxiliary catalyst adopts 10-30% mass fraction concentrated nitric acid or fuming nitric acid, the oxygen pressure is 1-3atm, the temperature is 20-50 ℃, the reaction time is 5-8 hours, and the post-treatment ester solvent is ethyl acetate or butyl acetate.

Detailed description of the preferred embodiment 1

93g (1mol) of 3-methylpyridine is dissolved in 1L of acetic acid to prepare 10% acetic acid solution, the 10% acetic acid solution is added into a 2L high-pressure reaction kettle 10, then 25g (0.1mol, 10% equivalent) of catalyst (I) and 9g of 68% concentrated nitric acid are sequentially added into the kettle, the reaction kettle 10 is sealed and air is replaced by oxygen, the temperature is raised to 100 ℃ under the oxygen pressure of 1atm, the temperature is kept for 2h, the temperature is reduced to room temperature, acetic acid is removed under negative pressure, 200ml of water and 100ml of ethyl acetate are added into residue, after stirring for 0.5h, a small amount of black insoluble substances are filtered, filtrate is layered, the upper layer is a product layer, the yield of quantitative analysis is 70%, and the organic layer is desolventized to recover raw materials and catalysts.

Examples 2 to 5

A nicotinaldehyde product was prepared according to the procedure of example 1, except that the kinds of the main catalyst and the co-catalyst, temperature, pressure, etc. used were as shown in table 1, and the results are shown in table 1.

TABLE 1

The invention also provides a synthesis device adopting the new pymetrozine intermediate nicotinaldehyde synthesis method, which comprises a reaction kettle 10, a stirring shaft 20 and a reduced pressure distiller 30, wherein the stirring shaft 20 is arranged inside the reaction kettle 10 and is rotationally connected with the reaction kettle 10, and the reduced pressure distiller 30 is connected with the reaction kettle 10 and is arranged at the lower side of the reaction kettle 10.

In the present embodiment, the reaction vessel 10 is used as a reaction vessel, the stirring shaft 20 is used for mixing 3-methylpyridine and an acetic acid solution, the vacuum distiller 30 is used for preparing a final nicotinaldehyde solution, and the vacuum distiller 30 is used for matching the production of a final product.

Further, the stirring shaft 20 includes a stabilizing leg 21, a shaft 22 and a stirring blade 23, the upper end of the stabilizing leg 21 is fixedly connected to the shaft 22, the lower end of the stabilizing leg 21 is engaged with the reaction kettle 10, and the stirring blade 23 is disposed on the outer peripheral side of the shaft 22.

In this embodiment, the stabilizing foot 21 is used for improving the stability of the shaft lever 22, so that the shaft lever 22 can effectively improve the stability in the rotating process, and the stirring blade 23 can more fully stir the material, thereby improving the final product yield.

Further, reation kettle 10 has stable trough 11, connection opening 12 and pan feeding mouth 13, stable trough 11 is the ring shape, and encircles connection opening 12 sets up, pan feeding mouth 13 set up in reation kettle 10's upside, connection opening 12 set up in reation kettle 10's downside, and with vacuum distillation ware 30 intercommunication.

In this embodiment, the stabilizing groove 11 is used for matching with the stabilizing leg 21, and the mutual fit between the stabilizing groove 11 and the stabilizing leg 21 is utilized to limit the moving path of the stabilizing leg 21, so as to promote the supporting of the stabilizing leg 21 on the shaft rod 22, the connecting opening 12 is used for sending out the product after the mixed solution is mixed with the main catalyst and the cocatalyst and reacts out of the reaction kettle 10, and the feeding port 13 is used for adding raw materials.

Further, vacuum distillation ware 30 includes negative pressure vessel 31, condenser pipe 32, collection tank 33, heater 34 and retort 35, retort 35 pass through the pipeline with reation kettle 10 intercommunication, condenser pipe 32 set up in the upside of retort 35, and communicate retort 35 with collection tank 33, heater 34 set up in the inside of retort 35, negative pressure vessel 31 with collection tank 33 communicates, and passes through collection tank 33 with retort 35 communicates.

In this embodiment, the negative pressure device 31 is configured to provide negative pressure to the vacuum distillation device 30, the condensation pipe 32 is configured to condense fractions in the reaction tank 35 to become products, the heater 34 is configured to heat the fractions, and further raise the temperature of the reaction tank 35, so as to control reaction products, the reaction tank 35 is used as a container for vacuum distillation to assist in distillation, and the collection tank 33 is configured to collect the finally condensed fractions, so as to produce finished products.

While the invention has been described with reference to a preferred embodiment, it will be understood by those skilled in the art that various changes in form and detail may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.