CN112341392B - Process for preparing 1- (4-chlorophenyl) -pyrazolidin-3-one - Google Patents
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Abstract
The invention relates to the field of bactericide synthesis, and discloses a method for preparing 1- (4-chlorphenyl) -pyrazolidin-3-ketone. The method comprises the following steps: 1) reacting parachloroaniline with acrylic acid to obtain an addition reaction product; 2) purifying the addition reaction product and then carrying out a nitrosation reaction with nitrite, or directly carrying out a nitrosation reaction on the addition reaction product and nitrite to obtain a nitrosation reaction product; 3) reducing by using palladium carbon as a catalyst and hydrogen as a reducing agent to obtain a reduction product; 4) and (3) removing the catalyst from the reduction product, and then carrying out heat treatment to obtain the 1- (4-chlorphenyl) -pyrazolidin-3-ketone. According to the method disclosed by the invention, steps such as diazotization, sodium sulfite reduction and the like are avoided, the reaction safety is high, the amount of three wastes is small, and the method is suitable for industrial production.
Description
Technical Field
The invention relates to the field of bactericide synthesis, and in particular relates to a method for preparing 1- (4-chlorphenyl) -pyrazolidin-3-ketone.
Background
Pyraclostrobin is a novel bactericide which is efficient, low-toxicity, broad-spectrum, safe to non-target organisms and safe and friendly to users and environment, and 1- (4-chlorphenyl) -pyrazolidin-3-one is a key intermediate for synthesizing pyraclostrobin.
CN1190961A discloses a method for synthesizing 1- (4-chlorphenyl) -pyrazolidin-3-ketone by using p-chlorophenylhydrazine and ethyl acrylate as raw materials, which is taken as reference in the published documents and inevitably uses the p-chlorophenylhydrazine. However, the synthesis of p-chlorophenylhydrazine requires reaction steps such as diazotization, sodium sulfite reduction and the like, so that the safety risk is high and the three wastes are large.
Disclosure of Invention
The invention aims to solve the problems of high safety risk, large amount of three wastes and the like caused by using p-chlorophenylhydrazine in the prior art, and provides a novel method for preparing 1- (4-chlorphenyl) -pyrazolidin-3-one, which avoids steps of diazotization, sodium sulfite reduction and the like, has high reaction safety and small amount of three wastes and is suitable for industrial production.
In order to achieve the above object, the present invention provides, in one aspect, a process for preparing 1- (4-chlorophenyl) -pyrazolidin-3-one, which comprises the steps of,
1) performing an addition reaction on p-chloroaniline and acrylic acid to obtain an addition reaction product containing a compound with a structure shown in a formula (1);
2) purifying an addition reaction product containing the compound with the structure shown in the formula (1) and then carrying out a nitrosation reaction with nitrite, or directly carrying out the nitrosation reaction on the addition reaction product containing the compound with the structure shown in the formula (1) and nitrite to obtain a nitrosation reaction product containing the compound with the structure shown in the formula (2);
3) reducing nitroso of the compound with the structure shown in the formula (2) into amino by using palladium-carbon as a catalyst and hydrogen as a reducing agent to obtain a reduction product containing the compound with the structure shown in the formula (3);
4) removing the catalyst from the reduction product containing the compound with the structure shown in the formula (3), performing heat treatment to close the ring of the compound with the structure shown in the formula (3) to obtain 1- (4-chlorphenyl) -pyrazolidin-3-ketone,
preferably, in the step 1), the molar ratio of the p-chloroaniline to the acrylic acid is 1: 1-1.5.
Preferably, step 1) is carried out in the presence of a first organic solvent, which is toluene.
Preferably, the mass ratio of the p-chloroaniline to the first organic solvent is 1: 0.5-10.
Preferably, the conditions of the addition reaction include: the reaction temperature is 20-110 ℃, and the reaction time is 1-24 hours.
Preferably, the molar ratio of the addition reaction product containing the compound having the structure represented by formula (1) to the nitrite based on the compound having the structure represented by formula (1) is 1: 1-1.2.
Preferably, the nitrite salt is sodium nitrite.
Preferably, the conditions of the nitrosation reaction include: the reaction temperature is-10 to 20 ℃, and the reaction time is 1 to 12 hours.
Preferably, the mass ratio of the compound with the structure shown in the formula (2) to the palladium carbon is 1: 0.01-0.2.
Preferably, the reduction is carried out in the presence of a second organic solvent, which is one or more of toluene.
Preferably, the mass ratio of the compound with the structure shown in the formula (2) to the second organic solvent is 1: 0.5-10.
Preferably, the reducing conditions include: the reaction temperature is 10-40 deg.C, the reaction time is 1-24 hr, and the hydrogen partial pressure is 0.3-0.5 MPa.
Preferably, the conditions of the heat treatment include: the heat treatment temperature is 50-110 deg.C, and the heat treatment time is 1-12 hr.
Preferably, 1- (4-chlorophenyl) -pyrazolidin-3-one is obtained by distilling the heat-treated product.
According to the method disclosed by the invention, steps such as diazotization, sodium sulfite reduction and the like are avoided, the reaction safety is high, the amount of three wastes is small, and the method is suitable for industrial production.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
In one aspect, the present invention provides a process for preparing 1- (4-chlorophenyl) -pyrazolidin-3-one, which comprises the steps of,
1) performing an addition reaction on p-chloroaniline and acrylic acid to obtain an addition reaction product containing a compound with a structure shown in a formula (1);
2) purifying an addition reaction product containing the compound with the structure shown in the formula (1) and then carrying out a nitrosation reaction with nitrite, or directly carrying out the nitrosation reaction on the addition reaction product containing the compound with the structure shown in the formula (1) and nitrite to obtain a nitrosation reaction product containing the compound with the structure shown in the formula (2);
3) reducing nitroso of the compound with the structure shown in the formula (2) into amino by using palladium-carbon as a catalyst and hydrogen as a reducing agent to obtain a reduction product containing the compound with the structure shown in the formula (3);
4) removing the catalyst from the reduction product containing the compound with the structure shown in the formula (3), performing heat treatment to close the ring of the compound with the structure shown in the formula (3) to obtain 1- (4-chlorphenyl) -pyrazolidin-3-ketone,
according to the method disclosed by the invention, steps such as diazotization, sodium sulfite reduction and the like are avoided, the reaction safety is high, the amount of three wastes is small, and the method is suitable for industrial production.
The present invention is explained below based on the steps.
Step 1): step of addition reaction
According to the present invention, p-chloroaniline and acrylic acid are subjected to an addition reaction to obtain an addition reaction product containing a compound having a structure represented by formula (1).
Preferably, in the step 1), the molar ratio of the p-chloroaniline to the acrylic acid is 1: 1-1.5; more preferably, the p-chloroaniline and acrylic acid are used in a molar ratio of 1: 1-1.2.
In order to allow the reaction to proceed faster, it is preferable that step 1) is performed in the presence of a first organic solvent. The first organic solvent is preferably one or more of aromatic hydrocarbon, chlorinated hydrocarbon and ether, and more preferably one or more of toluene, chlorobenzene, dichloromethane, trichloromethane, carbon tetrachloride, 1, 2-dichloroethane and methyl tert-butyl ether; toluene and/or chlorobenzene are more preferable, and toluene is particularly preferable.
The amount of the first organic solvent can vary within a wide range, and preferably, the mass ratio of the p-chloroaniline to the first organic solvent is 1: 0.5-10; more preferably, the mass ratio of the p-chloroaniline to the first organic solvent is 1: 0.5-3.
The addition reaction is not particularly limited, and may be carried out according to conditions generally used in the art. For example, the conditions of the addition reaction include: the reaction temperature is 20-110 ℃ (preferably 20-90 ℃), and the reaction time is 1-24 hours; more preferably, the addition reaction is carried out at the reflux temperature of the solvent.
Step 2): nitrosation reaction
According to the present invention, after the addition reaction is completed, the addition reaction product containing the compound having the structure represented by formula (1) may be purified to obtain the compound having the structure represented by formula (1), and then subjected to a nitrosation reaction with a nitrite to obtain a nitrosation reaction product containing the compound having the structure represented by formula (2) (that is, the addition reaction product containing the compound having the structure represented by formula (1) may be purified and then subjected to a nitrosation reaction with a nitrite to obtain a nitrosation reaction product containing the compound having the structure represented by formula (2), which is hereinafter also referred to as "nitrosation scheme 1"); alternatively, the addition reaction product containing the compound having the structure represented by formula (1) may be subjected to a nitrosation reaction with a nitrite without purification to obtain a nitrosation reaction product containing the compound having the structure represented by formula (2) (that is, the addition reaction product containing the compound having the structure represented by formula (1) may be subjected to a nitrosation reaction with a nitrite to obtain a nitrosation reaction product containing the compound having the structure represented by formula (2), which will be also referred to as "nitrosation scheme 2" hereinafter).
From the viewpoint of suitability for industrialization, it is preferable to subject the addition reaction product containing the compound having the structure represented by formula (1) directly to a nitrosation reaction with a nitrite to obtain a nitrosation reaction product containing the compound having the structure represented by formula (2) (i.e., nitrosation scheme 2).
When conducting the nitrosation reaction according to the above nitrosation scheme 1, the molar ratio of the compound having a structure represented by formula (1) to the nitrite used is preferably 1: 1-1.1, more preferably 1: 1-1.05.
When conducting the nitrosation reaction according to the above nitrosation scheme 2, the molar ratio of the addition reaction product containing the compound having the structure represented by formula (1) to the nitrite salt is preferably 1: 1-1.2, more preferably 1: 1-1.1.
Preferably, the nitrite is sodium nitrite and/or potassium nitrite; more preferably, the nitrite salt is sodium nitrite. In the present invention, the nitrite is preferably used in the form of an aqueous solution, and the content of nitrite in the aqueous solution may be, for example, 20 to 35% by weight.
Preferably, the conditions of the nitrosation reaction include: the reaction temperature is-10 to 20 ℃, and the reaction time is 1 to 12 hours.
Preferably, the nitrosation reaction is carried out in the presence of an acid, which may be, for example, one or more of hydrochloric acid, sulfuric acid and phosphoric acid, preferably hydrochloric acid.
According to the invention, because the nitrosation reaction yield is very high, after the nitrosation reaction is finished, only the nitrosation reaction product needs to be subjected to liquid separation, a water phase is separated, and an organic phase is directly used for the next reaction.
Step 3): reduction step
According to the present invention, in step 3), a nitroso group of the compound having a structure represented by formula (2) is reduced to an amine group using palladium on carbon as a catalyst and hydrogen as a reducing agent to obtain a reduction product containing the compound having a structure represented by formula (3).
In the present invention, the nitrosation reaction product may be purified to obtain a compound having a structure represented by formula (2), and then the purified compound having a structure represented by formula (2) may be used to carry out the above-mentioned reduction; the reduction may be carried out using an organic phase obtained by separating the nitrosation reaction product. Under the condition of directly using the organic phase, the operation is simple, and the method is very suitable for industrial production.
Preferably, the mass ratio of the compound of the structure represented by the formula (2) (also based on the compound of the structure represented by the formula (2) when the organic phase is used) to the palladium carbon is 1: 0.0004-0.2; more preferably, the mass ratio of the compound of the structure represented by formula (2) (also based on the compound of the structure represented by formula (2) when the organic phase is used) to the amount of palladium on carbon is 1: 0.01-0.2.
Preferably, the reduction is carried out in the presence of a second organic solvent. The second organic solvent is preferably one or more of aromatic hydrocarbon, chlorinated hydrocarbon and ether, and more preferably one or more of toluene, chlorobenzene, dichloromethane, trichloromethane, carbon tetrachloride, 1, 2-dichloroethane and methyl tert-butyl ether; toluene and/or chlorobenzene are more preferable, and toluene is particularly preferable.
Preferably, the mass ratio of the compound with the structure shown in the formula (2) to the second organic solvent is 1: 0.4-20; more preferably, the mass ratio of the compound with the structure shown in the formula (2) to the second organic solvent is 1: 0.5-10.
Preferably, the reducing conditions include: the reaction temperature is 5-45 ℃, the reaction time is 1-36 hours, and the hydrogen partial pressure is 0.2-0.6 Mpa; more preferably, the reducing conditions include: the reaction temperature is 10-40 deg.C, the reaction time is 1-24 hr, and the hydrogen partial pressure is 0.3-0.5 MPa.
Step 4): closing the ring
According to the present invention, after the reduction reaction is completed, the catalyst is removed from the reduction product containing the compound having the structure represented by formula (3), and then the compound having the structure represented by formula (3) is subjected to heat treatment to close the ring, thereby obtaining 1- (4-chlorophenyl) -pyrazolidin-3-one.
The removal of the catalyst from the reduction product containing the compound having the structure represented by the formula (3) can be carried out by solid-liquid separation, and the catalyst is preferably removed by filtration, more preferably by thermal filtration.
Preferably, the conditions of the heat treatment include: the heat treatment temperature is 50-110 deg.C (preferably 60-90 deg.C), and the heat treatment time is 1-12 hr; more preferably, the heat treatment is performed at the reflux temperature of the solvent.
According to the invention, after the ring closing reaction is finished, the 1- (4-chlorphenyl) -pyrazolidin-3-ketone can be obtained by distilling the heat treatment product, the operation method is simple, the target compound can be obtained with high yield and high purity, and the method is very suitable for industrial production.
In the present invention, it is preferable that steps 1) to 4) are performed in the same solvent, and for example, steps 1) to 4) may be performed in toluene, so that the solvent is replaced differently, and the method is more suitable for industrial production.
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 synthetic route of the following examples is shown below.
Example 1
1) Synthesis of Compound 3
Adding 25.7g of parachloroaniline 1 and 100mL of toluene into a reaction bottle, heating to 80 ℃, dropwise adding 16.0g of acrylic acid 2, continuing to perform heat preservation reaction for 3 hours after the dropwise adding is finished, and finishing the reaction, wherein the reaction solution is directly used for the next reaction, and the reaction yield is 95%. Further, samples were taken after completion of the reaction and subjected to mass spectrometry, and the results thereof were as follows.
MSm/z：200(M+1)。
2) Synthesis of Compound 4
27.7g of hydrochloric acid with the content of 30 wt% is added into a toluene solution containing 37.8g of the compound 3, the temperature is controlled to be 5-10 ℃, an aqueous solution containing 13.9g of sodium nitrite (the content of the sodium nitrite is 33 wt%) is dripped, after the dripping is finished, the heat preservation reaction is continuously carried out for 0.5 hour, a water phase is separated, and an organic phase is directly used for the next reaction, wherein the reaction yield is 98%. Further, the organic phase was sampled and subjected to mass spectrometry, and the results thereof are as follows.
MSm/z：229(M+1)。
3) Synthesis of Compound 5
Adding toluene solution containing 42.5g of compound 4 into an autoclave, adding 0.8g of palladium-carbon with the content of 5 wt%, controlling the temperature at 20-30 ℃, introducing hydrogen, controlling the pressure at 0.4Mpa, reacting for 2 hours, cooling to room temperature, filtering out the catalyst, and directly using the reaction solution for the next reaction, wherein the reaction yield is 90%. The reaction solution after filtration was sampled and subjected to mass spectrometry, and the results thereof are as follows.
MSm/z：215(M+1)。
4) Synthesis of Compound 6 (Synthesis of 1- (4-chlorophenyl) -pyrazolidin-3-one)
Adding a toluene solution containing 35.9g of the compound 5 into a reaction bottle, heating to reflux, reacting for 4 hours, separating water generated in the reaction by a water separator, distilling the toluene by steam after the reaction is finished, cooling to 25 ℃, filtering and drying to obtain the 1- (4-chlorophenyl) -pyrazolidin-3-one with the purity of 98 wt% and the reaction yield of 92%.
1H NMR(300MHz，CDCl3)δ8.48(s，1H)，7.35-6.99(m，4H)，3.94(t，J＝7.8Hz，2H)，2.57(t，J＝7.8HZ，2H)。
MSm/z：197(M+1)。
Example 2
1) Synthesis of Compound 3
Adding 25.7g of parachloroaniline 1 and 13mL of chlorobenzene into a reaction bottle, keeping the temperature at 20 ℃, dropwise adding 21.8g of acrylic acid 2, continuing to perform heat preservation reaction for 24 hours after the dropwise adding is finished, and finishing the reaction, wherein the reaction solution is directly used for the next reaction, and the reaction yield is 90%. Further, samples were taken after completion of the reaction and subjected to mass spectrometry, and the results thereof were as follows.
MSm/z：200(M+1)。
2) Synthesis of Compound 4
Adding 26.3g of hydrochloric acid with the content of 30 wt% into chlorobenzene solution containing 35.8g of the compound 3, controlling the temperature to be minus 10-0 ℃, dropwise adding aqueous solution containing 15.1g of sodium nitrite (the content of the sodium nitrite is 35 wt%), continuously carrying out heat preservation reaction for 0.5 hour after the dropwise adding is finished, separating out a water phase, and directly using the organic phase for the next reaction, wherein the reaction yield is 95%. Further, the organic phase was sampled and subjected to mass spectrometry, and the results thereof are as follows.
MSm/z：229(M+1)。
3) Synthesis of Compound 5
Adding chlorobenzene solution containing 39.0g of compound 4 into an autoclave, adding 7.8g of palladium-carbon with the content of 5 weight percent, controlling the temperature at 10-20 ℃, introducing hydrogen, controlling the pressure at 0.3Mpa, reacting for 24 hours, filtering out a catalyst, and directly using reaction liquid for the next reaction, wherein the reaction yield is 80%. The reaction solution after filtration was sampled and subjected to mass spectrometry, and the results thereof are as follows.
MSm/z：215(M+1)。
4) Synthesis of Compound 6 (Synthesis of 1- (4-chlorophenyl) -pyrazolidin-3-one)
Adding a chlorobenzene solution containing 29.3g of the compound 5 into a reaction bottle, heating to reflux, reacting for 2 hours, separating water generated by the reaction through a water separator, distilling chlorobenzene by steam after the reaction is finished, cooling to 25 ℃, filtering, drying, and obtaining the 1- (4-chlorophenyl) -pyrazolidin-3-ketone through nuclear magnetic and mass spectrometry data, wherein the purity is 96 wt%, and the reaction yield is 95%.
Example 3
1) Synthesis of Compound 3
Adding 25.7g of parachloroaniline 1 and 257mL of dichloroethane into a reaction bottle, heating to reflux, dropwise adding 14.7g of acrylic acid 2, continuing to perform heat preservation reaction for 1 hour after the dropwise adding is finished, and finishing the reaction, wherein the reaction solution is directly used for the next reaction, and the reaction yield is 90%. Further, samples were taken after completion of the reaction and subjected to mass spectrometry, and the results thereof were as follows.
MSm/z：200(M+1)。
2) Synthesis of Compound 4
26.3g of hydrochloric acid with the content of 30 weight percent is added into dichloroethane solution containing 35.8g of the compound 3, the temperature is controlled between 10 and 20 ℃, aqueous solution containing 16.9g of sodium nitrite (the content of the sodium nitrite is 20 weight percent) is dripped, after the dripping is finished, the heat preservation reaction is continued for 0.5 hour, the water phase is separated, and the organic phase is directly used for the next reaction, and the reaction yield is 85 percent. Further, the organic phase was sampled and subjected to mass spectrometry, and the results thereof are as follows.
MSm/z：229(M+1)。
3) Synthesis of Compound 5
Adding dichloroethane solution containing 34.9g of compound 4 into an autoclave, adding 0.3g of palladium-carbon with the content of 5 wt%, controlling the temperature at 30-40 ℃, introducing hydrogen, controlling the pressure at 0.5Mpa, reacting for 1 hour, filtering out the catalyst while the catalyst is hot, and directly using the reaction solution for the next reaction, wherein the reaction yield is 90%. The reaction solution after filtration was sampled and subjected to mass spectrometry, and the results thereof are as follows.
MSm/z：215(M+1)。
4) Synthesis of Compound 6 (Synthesis of 1- (4-chlorophenyl) -pyrazolidin-3-one)
Adding dichloroethane solution containing 29.5g of the compound 5 into a reaction bottle, heating to reflux, reacting for 12 hours, separating water generated by the reaction through a water separator, distilling by using steam to evaporate toluene after the reaction is finished, cooling to 25 ℃, filtering, drying, and obtaining the 1- (4-chlorphenyl) -pyrazolidin-3-ketone through nuclear magnetic and mass spectrometry data, wherein the purity is 98 weight percent, and the reaction yield is 90 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 (14)
1. A process for the preparation of 1- (4-chlorophenyl) -pyrazolidin-3-one, characterized in that it comprises the steps of,
1) performing an addition reaction on p-chloroaniline and acrylic acid to obtain an addition reaction product containing a compound with a structure shown in a formula (1);
2) purifying an addition reaction product containing the compound with the structure shown in the formula (1) and then carrying out a nitrosation reaction with nitrite, or directly carrying out the nitrosation reaction on the addition reaction product containing the compound with the structure shown in the formula (1) and nitrite to obtain a nitrosation reaction product containing the compound with the structure shown in the formula (2);
3) reducing nitroso of the compound with the structure shown in the formula (2) into amino by using palladium-carbon as a catalyst and hydrogen as a reducing agent to obtain a reduction product containing the compound with the structure shown in the formula (3);
4) removing the catalyst from the reduction product containing the compound with the structure shown in the formula (3), performing heat treatment to close the ring of the compound with the structure shown in the formula (3) to obtain 1- (4-chlorphenyl) -pyrazolidin-3-ketone,
2. the method according to claim 1, wherein in the step 1), the p-chloroaniline and the acrylic acid are used in a molar ratio of 1: 1-1.5.
3. The process of claim 1, wherein step 1) is carried out in the presence of a first organic solvent, which is toluene.
4. The method according to claim 3, wherein the dosage mass ratio of the parachloroaniline to the first organic solvent is 1: 0.5-10.
5. The method of claim 1, wherein the conditions of the addition reaction comprise: the reaction temperature is 20-110 ℃ and the reaction time is 1-24 hours.
6. The method according to any one of claims 1 to 5, wherein the molar ratio of the addition reaction product containing the compound having the structure represented by formula (1) to the nitrite in step 2) is 1: 1-1.2.
7. The method of claim 6, wherein the nitrite salt is sodium nitrite.
8. The method of claim 7, wherein the conditions of the nitrosation reaction include: the reaction temperature is-10 to 20 ℃, and the reaction time is 1 to 12 hours.
9. The method according to any one of claims 1 to 5, wherein the compound having the structure represented by formula (2) and palladium on carbon are used in an amount by mass ratio of 1: 0.01-0.2.
10. The method of claim 1, wherein the reduction is performed in the presence of a second organic solvent, the second organic solvent being toluene.
11. The method according to claim 10, wherein the mass ratio of the compound having the structure represented by formula (2) to the second organic solvent is 1: 0.5-10.
12. The method of claim 1, wherein the reducing conditions comprise: the reaction temperature is 10-40 deg.C, the reaction time is 1-24 hr, and the hydrogen partial pressure is 0.3-0.5 MPa.
13. The method of claim 1, wherein the conditions of the heat treatment comprise: the heat treatment temperature is 50-110 deg.C, and the heat treatment time is 1-12 hr.
14. The process according to claim 1, wherein 1- (4-chlorophenyl) -pyrazolidin-3-one is obtained by distilling the heat-treated product.
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