CN113024413B - Synthesis method of salicylonitrile co-produced plant growth regulator - Google Patents
Synthesis method of salicylonitrile co-produced plant growth regulator Download PDFInfo
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- CN113024413B CN113024413B CN201911359993.0A CN201911359993A CN113024413B CN 113024413 B CN113024413 B CN 113024413B CN 201911359993 A CN201911359993 A CN 201911359993A CN 113024413 B CN113024413 B CN 113024413B
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
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- 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
Abstract
The invention relates to the field of pesticides, and discloses a method for synthesizing a salicylonitrile co-produced plant growth regulator, which comprises the following steps of 1) in the presence of an aprotic polar solvent, carrying out contact reaction on 2-methoxybenzonitrile and lithium chloride to obtain salicylonitrile and chloromethane gas; 2) Performing quaternization reaction on the chloromethane gas obtained in the step 1) and a solution containing N-methylpiperidine or a solution containing N-methylmorpholine to obtain the mepiquat chloride or the regulating agent. The method is environment-friendly, mild in reaction conditions and simple and convenient to operate, and can be used for obtaining the salicylaldehyde with high yield and co-producing the mepiquat chloride or regulating the safety, so that the tail gas of the salicylaldehyde is zero in emission.
Description
Technical Field
The invention relates to the field of pesticides, and particularly relates to a synthetic method of a salicylonitrile co-produced plant growth regulator.
Background
2-hydroxybenzonitrile (salicylaldehyde) can be used as an intermediate of Strobilurin bactericidal pesticide azoxystrobin such as methoxy acrylate (Strobilurin) and an intermediate of bucindolol hydrochloride (Ding Bianjing Xinan) for injection of hypertension and angina, and the structural formula of the intermediate is as follows:
the salicylaldehyde is an important intermediate for synthesizing the bactericidal pesticide azoxystrobin, and the market demand of the salicylaldehyde is increased along with the increase of the yield of the azoxystrobin; the current commercial route for the industrial production of salicylaldehyde is mainly the salicylamide dehydration process. The current raw material salicylamide has limited capacity, the price is increased due to the environmental protection pressure, and the influence on the capacity and the cost of the salicylamide is large. Therefore, a new method for searching raw materials with larger market capacity is developed, and the method which is environment-friendly, high in yield, high in added value and simple and convenient to operate is developed, so that the method has important significance for the industrial production of the bactericide.
Disclosure of Invention
The invention aims to overcome the problems in the prior art and provides a synthesis method of a plant growth regulator co-produced with salicylaldehyde, which is environment-friendly, mild in reaction condition and simple and convenient to operate, can obtain the salicylaldehyde at high yield, and co-produces mepiquat chloride or regulating safety at the same time, so that the zero emission of tail gas is realized.
In order to achieve the above objects, the present invention provides a method for synthesizing a salicylonitrile co-produced plant growth regulator, which comprises the following steps,
1) In the presence of an aprotic polar solvent, carrying out contact reaction on 2-methoxybenzonitrile and lithium chloride to obtain salicylonitrile and chloromethane gas;
2) Performing quaternization reaction on the chloromethane gas obtained in the step 1) and a solution containing N-methylpiperidine or a solution containing N-methylmorpholine to obtain mepiquat chloride or chloramphinium.
Preferably, the aprotic polar solvent is one or more of N, N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, N-dimethylacetamide, 1,3-dimethyl-2-imidazolidinone, sulfolane and hexamethylphosphoric triamide.
Preferably, the lithium chloride is used in an amount of 4 to 18 moles with respect to 1 mole of 2-methoxybenzonitrile; more preferably, the lithium chloride is used in an amount of 4 to 12 moles with respect to 1 mole of 2-methoxybenzonitrile.
Preferably, the aprotic polar solvent is used in an amount of 4 to 25 parts by weight, relative to 1 part by weight of 2-methoxybenzonitrile; more preferably, the aprotic polar solvent is used in an amount of 4 to 20 parts by weight relative to 1 part by weight of 2-methoxybenzonitrile; further preferably, the aprotic polar solvent is used in an amount of 4 to 15 parts by weight relative to 1 part by weight of 2-methoxybenzonitrile.
Preferably, the conditions of the contact reaction include: the temperature of the contact reaction is 120-200 ℃, and the time of the contact reaction is more than 10 hours.
Preferably, the methyl chloride gas and the solution containing N-methylpiperidine or the solution containing N-methylmorpholine are subjected to a quaternization reaction in a circulating shower apparatus.
Preferably, the circulation shower device includes:
a cooling unit for cooling the gaseous product obtained in step 1) to obtain a liquid aprotic polar solvent and gaseous methyl chloride gas;
a spraying unit for spraying the solution containing N-methylpiperidine or the solution containing N-methylmorpholine to cause the quaternization reaction of the methyl chloride gas and the liquid droplets of the solution containing N-methylpiperidine or the solution containing N-methylmorpholine;
the circulating liquid buffer storage reaction unit is used for storing the circulating liquid and performing the quaternization reaction on the circulating liquid;
and the circulating unit is used for driving the solution containing the N-methyl piperidine or the solution containing the N-methyl morpholine to circulate in the circulating liquid buffer storage reaction unit and the spraying unit.
Preferably, the circulation shower device further includes: and the solvent storage unit is used for storing the solvent obtained by cooling by the cooling unit.
Preferably, the molar ratio of the methyl chloride gas to the solution containing N-methylpiperidine in terms of N-methylpiperidine is 1:1.1-1.2; or the molar ratio of the methyl chloride gas to the solution containing the N-methyl morpholine calculated as the N-methyl morpholine is 1:1.1-1.2.
Preferably, the content of N-methylpiperidine in the solution containing N-methylpiperidine is 20 to 25% by weight.
Preferably, the content of N-methylmorpholine in the solution containing N-methylmorpholine is 20-25 wt%.
Preferably, the temperature of the quaternization reaction is from 40 to 48 ℃.
Through the technical scheme, the method for synthesizing the salicylonitrile co-produced plant growth regulator is environment-friendly, mild in reaction condition and simple and convenient to operate, can obtain the salicylonitrile at high yield, and co-produces mepiquat chloride or regulates safety, so that zero emission of tail gas is achieved.
Drawings
Fig. 1 is a schematic view of a circulating shower apparatus used in the present invention.
Description of the reference numerals
1: a cooling unit; 2: a spraying unit; 3: a circulating liquid buffer storage reaction unit; 4: a circulation unit; 5: a solvent storage unit; a, gaseous products.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and these ranges or values should be understood to encompass values close to these ranges or values. For numerical ranges, each range between its endpoints and individual point values, and each individual point value can be combined with each other to give one or more new numerical ranges, and such numerical ranges should be construed as specifically disclosed herein.
The invention provides a method for synthesizing a salicylonitrile co-produced plant growth regulator, wherein the method comprises the following steps,
1) In the presence of an aprotic polar solvent, carrying out contact reaction on 2-methoxybenzonitrile and lithium chloride to obtain salicylonitrile and methyl chloride gas;
2) Performing quaternization reaction on the chloromethane gas obtained in the step 1) and a solution containing N-methylpiperidine or a solution containing N-methylmorpholine to obtain the mepiquat chloride or the regulating agent.
Step 1) and step 2) will be described below.
Step 1): demethylation reaction
According to the invention, step 1) comprises the step of carrying out contact reaction on 2-methoxybenzonitrile and lithium chloride in the presence of an aprotic polar solvent to obtain salicylanitrile and methyl chloride gas.
Preferably, the aprotic polar solvent is one or more of N, N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, N-dimethylacetamide, 1,3-dimethyl-2-imidazolidinone (DMI), sulfolane, and hexamethylphosphoric triamide (HMPA); more preferably, the aprotic polar solvent is one or more of N, N-dimethylformamide, dimethyl sulfoxide, 1,3-dimethyl-2-imidazolidinone (DMI), and N-methylpyrrolidone.
According to the present invention, it is preferable that the lithium chloride is used in an amount of 2 to 18 moles per 1 mole of 2-methoxybenzonitrile from the viewpoints of improvement of reaction yield and reduction of cost; more preferably, the lithium chloride is used in an amount of 4 to 12 moles with respect to 1 mole of 2-methoxybenzonitrile; further preferably, the lithium chloride is used in an amount of 4 to 10 moles with respect to 1 mole of 2-methoxybenzonitrile.
According to the present invention, the aprotic polar solvent may be used in an amount such that 2-methoxybenzonitrile and lithium chloride are well dissolved. For example. The aprotic polar solvent is used in an amount of 4 to 25 parts by weight relative to 1 part by weight of 2-methoxybenzonitrile; preferably, the aprotic polar solvent is used in an amount of 4 to 20 parts by weight, relative to 1 part by weight of 2-methoxybenzonitrile; more preferably, the aprotic polar solvent is used in an amount of 4 to 15 parts by weight relative to 1 part by weight of 2-methoxybenzonitrile.
According to the present invention, preferably, the conditions of the contact reaction include: the temperature of the contact reaction is 120-200 ℃, and the time of the contact reaction is more than 10 hours; more preferably, the conditions of the contact reaction include: the temperature of the contact reaction is 150-165 ℃, and the time of the contact reaction is 18-25 hours.
According to the present invention, preferably, the method further comprises a step of removing the solvent from the product after the contact reaction and then adding water for acidification.
The method for removing the solvent is not particularly limited, and the solvent can be removed by a method generally used in the art, for example, by a method such as concentration under reduced pressure.
The amount of water added in the above acidification with water is usually 3 to 4 volumes based on the reaction solvent, and the pH after acidification may be, for example, 2 to 3. The acid used for acidification may be, for example, one or more of hydrochloric acid, sulfuric acid, and phosphoric acid.
According to the invention, after acidification, solid-liquid separation is carried out to obtain the solid salicylonitrile, and the obtained solid can be washed and dried as required.
Step 2): quaternization reaction
In the present invention, the chloromethane gas obtained in step 1) is subjected to quaternization with a solution containing N-methylpiperidine or a solution containing N-methylmorpholine to obtain a mepiquat chloride or a prohexadione, and the reaction formula involved in the present invention is as follows.
The reaction formula for demethylating o-methoxybenzonitrile and lithium chloride to prepare salicylonitrile is as follows:
the reaction formula for preparing the mepiquat chloride by absorbing chloromethane with N-methylpiperidine is as follows:
n-methylmorpholine absorbs chloromethane to prepare the modified amine according to the reaction formula:
according to the present invention, by subjecting the methyl chloride gas obtained in step 1) to quaternization with a solution containing N-methylpiperidine or a solution containing N-methylmorpholine, in the production of salicylaldehyde, not only is no methyl chloride gas discharged, but also chloromethane gas can be sufficiently utilized to produce mepiquat chloride or chlorambucil, thereby achieving zero emission, and a high value-added mepiquat chloride or chlorambucil can be obtained, which is very useful economically.
According to the present invention, the mode of carrying out the quaternization reaction of the methyl chloride gas obtained in step 1) and the solution containing N-methylpiperidine or the solution containing N-methylmorpholine is not particularly limited, and various modes for carrying out the contact reaction of a liquid and a gas, which are generally used in the art, can be employed. Preferably, the methyl chloride gas and the solution containing N-methylpiperidine or the solution containing N-methylmorpholine are subjected to a quaternization reaction in a circulating shower apparatus.
According to the invention, it is preferred that in the circulating shower apparatus shown in fig. 1, as shown in fig. 1, the circulating shower apparatus includes:
a cooling unit 1 for cooling the gaseous product obtained in step 1) to obtain a liquid aprotic polar solvent and gaseous methyl chloride gas;
a spray unit 2 for spraying the solution containing N-methylpiperidine or the solution containing N-methylmorpholine to cause the quaternization reaction of the methyl chloride gas and the liquid droplets of the solution containing N-methylpiperidine or the solution containing N-methylmorpholine;
and the circulating liquid buffer storage reaction unit 3 is used for storing the circulating liquid and performing the quaternization reaction on the circulating liquid.
And the circulating unit 4 is used for driving the solution containing the N-methyl piperidine or the solution containing the N-methyl morpholine to circulate in the circulating liquid buffer storage reaction unit and the spraying unit.
Preferably, the circulating spray device further comprises: and the solvent storage unit 5 is used for storing the solvent cooled by the cooling unit.
The cooling unit 1 may be various means for cooling generally used in the art, and for example, the cooling unit may be a cooling tower, a cooling bottle, or the like.
The spraying means 2 may be a means for sufficiently absorbing a gas with a liquid, which is generally used in the art, and may be, for example, a spray tower.
The circulating liquid buffer storage reaction unit 3 may be various means commonly used in the art for storing liquid, and may be, for example, a storage tank, a storage bottle, or the like.
The circulating means 4 may be any means capable of circulating the solution containing N-methylpiperidine or the solution containing N-methylmorpholine through the circulating liquid buffer reaction means and the spraying means, and may be, for example, a pump.
The solvent storage unit may be various means commonly used in the art for storing liquid, and may be, for example, a storage tank, a storage bottle, etc.
According to the present invention, the amount of the solution containing N-methylpiperidine to be used may be selected depending on the amount of methyl chloride gas, and preferably, the molar ratio of the methyl chloride gas to the solution containing N-methylpiperidine in terms of N-methylpiperidine is 1:1.0-1.2; more preferably; the molar ratio of the methyl chloride gas to the solution containing N-methylpiperidine in terms of N-methylpiperidine is 1:1.1-1.2. In this case, the amount of the solvent to be used,
according to the invention, the amount of the solution containing N-methylmorpholine to be used may be selected according to the amount of methyl chloride gas, preferably in a molar ratio of 1:1.0-1.2; more preferably; the molar ratio of the methyl chloride gas to the solution containing N-methylmorpholine calculated as N-methylmorpholine is 1:1-1.1.
The content of N-methylpiperidine in the above-mentioned solution containing N-methylpiperidine may vary within a wide range, and may be, for example, 10 to 30% by weight, preferably 20 to 25% by weight.
The content of N-methylmorpholine in the N-methylmorpholine-containing solution may vary within wide limits and may, for example, be in the range of from 10 to 30% by weight, preferably from 20 to 25% by weight.
According to the present invention, the solvent in the above-mentioned solution containing N-methylpiperidine and solution containing N-methylmorpholine may be, for example, one or more of methanol, ethanol and isopropanol; preferably, the solvent in the solution containing N-methylpiperidine and the solution containing N-methylmorpholine is methanol.
The temperature of the quaternization may be 25 to 60 ℃ and preferably 40 to 48 ℃. The contact time is not particularly limited, and may be, for example, the reaction time of the demethylation reaction.
After the quaternization reaction is finished, removing the solvent by adding one or more of n-butyl alcohol, sec-butyl alcohol and n-amyl alcohol into the contact reaction product, so that the product is separated out, and then filtering, leaching and drying to obtain the target product. The eluting solvent may be, for example, one or more of n-butanol, sec-butanol and n-pentanol.
The present invention will be described in detail below by way of examples, but the present invention is not limited to the following examples.
The reagents used in the following examples are commercially available unless otherwise specified.
Example 1
2-methoxybenzonitrile (29g, 0.218mol), DMF120g, and anhydrous lithium chloride 37.0g (0.872 mol) were added to a 500ml four-necked flask, and after refluxing under heating for 25 hours, a sample was taken, whereupon the reaction was terminated.
Gaseous products containing methyl chloride generated in the reaction process are sent into a circulating spray device shown in figure 1 to be subjected to circulating absorption reaction with 86g of methanol solution of N-methylpiperidine (the content of N-methylpiperidine is 25 weight percent), and the specific process comprises the following steps: sending a gaseous product A containing methyl chloride into a cooling unit 1 (specifically a cooling bottle) for cooling to obtain methyl chloride gas and a cooled liquid solvent, sending the liquid solvent into a solvent storage unit 5 (specifically a storage bottle), sending the methyl chloride gas into a spray unit 2 (specifically a spray tower with a spray head), carrying out contact reaction with sprayed droplets of an N-methylpiperidine methanol solution (keeping the contact temperature at 40 ℃), sending the liquid in the spray unit 2 into a circulating liquid buffer storage reaction unit 3 (specifically a buffer bottle), circulating the liquid stored in the circulating liquid buffer storage reaction unit 3 between the spray unit 2 and the circulating liquid buffer storage reaction unit 3 through a circulating unit 4 (specifically a pump) connected with the circulating liquid buffer storage reaction unit 3 at one section and the spray unit 2 at the other end, fully absorbing and distilling out the methyl chloride gas in the tail gas of the demethylation reaction, adding N-butyl alcohol (65 g) into the circulating absorption liquid after the reaction is finished, then distilling out the methyl alcohol at normal pressure, stopping the distillation to the internal temperature of 65g, and heating. The distillate was cooled to room temperature and filtered to obtain 63.5g of mother liquor, the solid was rinsed with n-butanol (15 g) to obtain a wet white solid, which was dried with an infrared lamp to obtain 29.28g of a dry mepiquat chloride with a purity of 99% by weight and a yield of 90.12%.
The nuclear magnetism of the mepiquat chloride dry product is as follows: 1 H-NMR(500MHz,D 2 O):δ3.181-3.158(t,4H),2.926.(s,6H,)1.712-1.703(t,4H),1.499-1.450(m,2H)。
in addition, after the solvent was removed from the liquid product, 85g of water was added, and hydrochloric acid was added to adjust the pH to 3, to precipitate a solid. The solid was filtered, rinsed and dried to yield a white-like solid with a content of 99 wt% of 24.9g (the solid product was identified as salicylaronitrile by nuclear and mass spectrometry data, as follows), yield: 96 percent.
1 H-NMR(500MHz,d6-DMSO):δ11.036(s,1H),7.594-7.576(dd,1H,)7.501-7.466(m,1H),7.002-7.019(d,1H)，6.934-6.903(t,1H)。
LCMS(M+1)：120.04。
Example 2
2-methoxybenzonitrile (100g, 0.736mol), DMF500g, and anhydrous lithium chloride 190.0g (4.416 mol) were charged into a 1000ml four-necked flask, and the mixture was refluxed for 22 hours, followed by sampling to terminate the reaction.
Gaseous products containing methyl chloride generated in the reaction process are sent into a circulating spraying device shown in figure 1 to be subjected to circulating absorption reaction with 293g of methanol solution of N-methylpiperidine (the content of the N-methylpiperidine is 24.9 weight percent), and the specific process comprises the following steps: sending a gaseous product A containing methyl chloride into a cooling unit 1 (specifically a cooling bottle) for cooling to obtain methyl chloride gas and a cooled liquid solvent, sending the liquid solvent into a solvent storage unit 5 (specifically a storage bottle), sending the methyl chloride gas into a spray unit 2 (specifically a spray tower with a spray head), carrying out contact reaction (keeping the contact temperature at 48 ℃) with sprayed liquid drops of an N-methylpiperidine methanol solution, sending the liquid in the spray unit 2 into a circulating liquid buffer storage reaction unit 3 (specifically a buffer bottle), circulating the liquid stored in the circulating liquid buffer storage reaction unit 3 between the spray unit 2 and the circulating liquid buffer storage reaction unit 3 through a circulating unit 4 (specifically a pump) connected with the circulating liquid buffer storage reaction unit 3 at one section and connected with the spray unit 2 at the other end so as to sufficiently absorb the methyl chloride gas, adding N-butyl alcohol into the circulating absorption liquid after the reaction is finished (220 g), then desolventizing the methyl alcohol at normal pressure, stopping heating to 110 ℃, and heating to evaporate 220g of the methyl alcohol. The distillate is cooled to room temperature and is filtered to obtain 218g of mother liquor, n-butanol (49 g) is used for leaching the solid to obtain a wet white solid, and the wet white solid is dried by an infrared lamp to obtain 101g of a dry mepiquat chloride (the structure is the mepiquat chloride identified by nuclear magnetic and mass spectrum data), the purity is 99 weight percent, and the yield is 90.12 percent.
In addition, after the solvent was removed from the liquid product, 300g of water was added, and hydrochloric acid was added to adjust the pH to 3, to precipitate a solid. The solid was filtered, rinsed and dried to give 98.02 wt% off-white solid (solid product identified by nuclear and mass spectral data as salicylaldehyde) 85.86g, yield: 95.99 percent.
Example 3
2-methoxybenzonitrile (100g, 0.736mol), DMF500g, and anhydrous lithium chloride 190.0g (4.416 mol) were charged into a 1000ml four-necked flask, and the mixture was refluxed for 22 hours, followed by sampling to terminate the reaction.
Gaseous products containing methyl chloride generated in the reaction process are sent into a circulating spraying device shown in figure 1 to be subjected to circulating absorption reaction with methanol solution of N-methylmorpholine (the content of the N-methylmorpholine is 24.83 weight percent) 300, and the specific process is as follows: sending a gaseous product A containing methyl chloride into a cooling unit 1 (specifically a cooling bottle) for cooling to obtain methyl chloride gas and a cooled liquid solvent, sending the liquid solvent into a solvent storage unit 5 (specifically a storage bottle), sending the methyl chloride gas into a spraying unit 2 (specifically a spraying tower with a spraying head), carrying out contact reaction with sprayed liquid drops of the N-methylmorpholine methanol solution (the contact temperature is kept at 48 ℃), sending the liquid in the spraying unit 2 into a circulating liquid buffer storage reaction unit 3 (specifically a buffer bottle), circulating the liquid stored in the circulating liquid buffer storage reaction unit 3 between the spraying unit 2 and the circulating liquid buffer storage reaction unit 3 through a section of circulating unit 4 (specifically a pump) connected with the circulating liquid buffer storage reaction unit 3 and the other end connected with the spraying unit 2 to fully absorb the methyl chloride gas, adding N-butyl alcohol (225 g) into the circulating absorption liquid after the reaction is finished, then desolventizing the methyl alcohol at normal pressure, evaporating the methanol, stopping heating to 110 ℃, and stopping heating the methanol, and evaporating the methyl alcohol evaporating. The distillate was cooled to room temperature and filtered to obtain 221g of mother liquor, the solid was rinsed with n-butanol (49 g) to obtain a wet white solid, which was dried with an infrared lamp to obtain An Ganpin 103.8.8 g (the structure was identified as "adjusted" by nuclear magnetic and mass spectrometry data), 99 wt% purity and 92.08% yield.
In addition, after the solvent was removed from the liquid product, 300g of water was added, and hydrochloric acid was added to adjust the pH to 3, to precipitate a solid. The solid was filtered, rinsed and dried to give 98.00 wt% off-white solid (solid product identified by nuclear and mass spectral data as salicylaldehyde) 84.86g, yield: 94.95 percent.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (12)
1. A synthetic method of salicylonitrile co-produced plant growth regulator is characterized in that the method comprises the following steps,
1) In the presence of an aprotic polar solvent, carrying out contact reaction on 2-methoxybenzonitrile and lithium chloride to obtain salicylonitrile and methyl chloride gas;
2) A step of carrying out quaternization reaction on the chloromethane gas obtained in the step 1) and a solution containing N-methylpiperidine or a solution containing N-methylmorpholine in a circulating spray device to obtain mepiquat chloride or regulating the concentration of ammonia,
wherein, circulation spray set includes:
a cooling unit for cooling the gaseous product obtained in step 1) to obtain a liquid aprotic polar solvent and gaseous methyl chloride gas;
a spraying unit for spraying the solution containing N-methyl piperidine or the solution containing N-methyl morpholine to enable the chloromethane gas and the liquid drops of the solution containing N-methyl piperidine or the solution containing N-methyl morpholine to carry out quaternization reaction;
the circulating liquid buffer storage reaction unit is used for storing the circulating liquid and performing the quaternization reaction on the circulating liquid;
and the circulating unit is used for driving the solution containing the N-methyl piperidine or the solution containing the N-methyl morpholine to circulate in the circulating liquid buffer storage reaction unit and the spraying unit.
2. The process of claim 1, wherein the aprotic polar solvent is one or more of N, N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, N-dimethylacetamide, 1,3-dimethyl-2-imidazolidinone, sulfolane, and hexamethylphosphoric triamide.
3. The method according to claim 1, wherein the lithium chloride is used in an amount of 4 to 18 moles with respect to 1 mole of 2-methoxybenzonitrile.
4. The method according to claim 1, wherein the lithium chloride is used in an amount of 4 to 12 moles with respect to 1 mole of 2-methoxybenzonitrile.
5. The method according to claim 1, wherein the aprotic polar solvent is used in an amount of 4 to 25 parts by weight relative to 1 part by weight of 2-methoxybenzonitrile.
6. The method according to claim 5, wherein the aprotic polar solvent is used in an amount of 4 to 20 parts by weight relative to 1 part by weight of 2-methoxybenzonitrile.
7. The method according to claim 6, wherein the aprotic polar solvent is used in an amount of 4 to 15 parts by weight relative to 1 part by weight of 2-methoxybenzonitrile.
8. The method of claim 1, wherein the conditions of the contact reaction comprise: the temperature of the contact reaction is 120-200 ℃, and the time of the contact reaction is more than 10 hours.
9. The method of claim 1, wherein the circulating spray device further comprises: and the solvent storage unit is used for storing the solvent obtained by cooling by the cooling unit.
10. The method of claim 1, wherein the molar ratio of the methyl chloride gas to the solution containing N-methylpiperidine, calculated as N-methylpiperidine, is 1:1.1-1.2;
or the molar ratio of the methyl chloride gas to the solution containing the N-methylmorpholine calculated by the N-methylmorpholine is 1:1.1-1.2.
11. The method according to claim 1, wherein the content of N-methylpiperidine in the solution containing N-methylpiperidine is 20 to 25% by weight; the content of N-methylmorpholine in the solution containing N-methylmorpholine is 20-25 wt%.
12. The method of claim 1, wherein the temperature of the quaternization reaction is from 40 to 48 ℃.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3585233A (en) * | 1967-09-21 | 1971-06-15 | May & Baker Ltd | Process for the preparation of hydroxybenzonitriles |
| GB1587925A (en) * | 1976-11-15 | 1981-04-15 | Basf Ag | Manufacture of n,n-dimethylpiperidinium chloride and n,n-dimethylmorpholinium chloride |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10242080A1 (en) * | 2002-09-11 | 2004-03-25 | Degussa Ag | Process for the catalyst-free production of cyanophenols comprises reaction of a substituted methoxybenzonitrile with an alkali metal alcoholate at a specified temperature |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3585233A (en) * | 1967-09-21 | 1971-06-15 | May & Baker Ltd | Process for the preparation of hydroxybenzonitriles |
| GB1587925A (en) * | 1976-11-15 | 1981-04-15 | Basf Ag | Manufacture of n,n-dimethylpiperidinium chloride and n,n-dimethylmorpholinium chloride |
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