CN111574455A - Preparation method of imidocarb dipropionate and intermediate thereof - Google Patents
Preparation method of imidocarb dipropionate and intermediate thereof Download PDFInfo
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- CN111574455A CN111574455A CN202010411314.6A CN202010411314A CN111574455A CN 111574455 A CN111574455 A CN 111574455A CN 202010411314 A CN202010411314 A CN 202010411314A CN 111574455 A CN111574455 A CN 111574455A
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- imidazoline
- nitrophenyl
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/64—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms, e.g. histidine
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/41—Preparation of salts of carboxylic acids
- C07C51/412—Preparation of salts of carboxylic acids by conversion of the acids, their salts, esters or anhydrides with the same carboxylic acid part
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Abstract
The invention discloses a preparation method of imidocarb dipropionate and an intermediate thereof. Belongs to the technical field of chemical pharmacy. The method comprises the steps of reacting m-nitrobenzonitrile with ethylenediamine by using sodium sulfide as a catalyst, reducing the m-nitrobenzonitrile with palladium ammonium carbonate, carrying out a condensation reaction with urea to obtain imidazole phenylurea dihydrochloride, and reacting the liberated imidazole phenylurea with propionic acid to obtain the dipropionic acid imidazole phenylurea. The method reduces the generation of wastes, has the advantages of cheap and easily obtained raw materials, simple and convenient operation, high product yield, simple and convenient process operation and high safety, and is suitable for industrial production.
Description
Technical Field
The invention belongs to the technical field of chemical pharmacy, and particularly relates to a preparation method of imidocarb dipropionate.
Background
The piriformis disease is a general term for blood protozoal diseases transmitted by hard ticks and caused by protozoa of the families babesidae or theileriaceae of the piriformis, is commonly transmitted in livestock and wild mammals, is very popular in many countries of the world including China, and causes great loss to the world animal husbandry and the world economy.
The sym-diphenylurea diamidine compound imidazole phenylurea (chemical name is N, N' -bis [3- (4, 5-dihydro-1H-imidazol-2-yl) phenyl ] urea) with all substituents as hydrogen is a new generation of best anti-piriformis medicine, and the structural formula is as follows:
developed by Monbijoustrasse, Switzerland, the dihydrochloride of which was first marketed in Switzerland in 1969, has important biological activity. Compared with piriformis resistant medicaments such as quinoline urea sulfate, triazamidine, yellow pigment, trypan blue and the like, the imidazofenoxuron has the advantages of broad spectrum, low toxicity, wide application range, small dosage and the like, has good treatment effect, is long in-vivo retention time, and has good prevention effect. And researches show that the imidazole phenylurea can be used for multiple purposes, and can treat various protozoal diseases such as the pyriform disease, the trichinosis, the eperythrozoonosis, the trypanosomiasis, the hepatic clusteriasis and the like. Therefore, the research on the synthesis process of the imidazole phenylurea has great economic and social benefits.
The current method for synthesizing imidazole phenylurea mainly comprises the following steps: (1) the method comprises the steps of taking ethyl m-nitrobenzoate as a raw material, reacting with ethylenediamine in the presence of trimethylaluminum, reducing nitro by hydrazine hydrate, and finally condensing with phosgene. In the middle of the route, ethyl nitrobenzoate, trimethylaluminum and hydrazine hydrate are expensive, the hydrazine hydrate has strong corrosivity to equipment, and phosgene is a highly toxic gas, so the method is not suitable for industrial production. (2) The method comprises the steps of taking m-nitrobenzoic acid as a raw material, synthesizing m-aminobenzoic acid through palladium-carbon hydrogenation reduction, generating sodium salt with sodium hydroxide, cyclizing with dihydrochloride of ethylenediamine, and finally condensing with urea. The route needs high-pressure hydrogenation reaction, the cyclization with hydrochloride of ethylenediamine needs high-temperature solid-solid reaction, the operation is complex, and the method is not beneficial to industrial production. (3) Uses cyanobenzene as raw material, and makes it undergo the processes of nitration, cyclization with ethylenediamine, iron powder reduction and double-gas condensation to obtain imidazole phenylurea. According to the route, when the sulfur is used as a catalyst for backflow, sublimed sulfur is condensed in the condensation pipe, so that the condensation pipe is blocked, iron powder is reduced to generate a large amount of iron mud, the environment is polluted, the double-phosgene toxicity is high, the green synthesis concept is not met, and the industrial production is not suitable.
Disclosure of Invention
The invention mainly aims at the defects of the prior art and provides a preparation method of imidocarb dipropionate suitable for industrial production.
A preparation method of imidocarb dipropionate and an intermediate thereof is characterized by comprising the following steps:
the method comprises the following steps: m-nitrobenzonitrile (compound 2) is taken as a raw material and reacts with ethylenediamine under the action of a catalyst to synthesize 2- (3-nitrophenyl) imidazoline (compound 3);
step two: reducing the compound 3 by palladium ammonium carbonate to obtain 2- (3-aminophenyl) imidazoline (compound 4);
step three: carrying out condensation reaction on the compound 4 and urea to prepare imidazole phenylurea dihydrochloride, and dissociating by NaOH to obtain imidazole phenylurea (a compound 5);
step four: reacting the free imidazole phenylurea with propionic acid to form salt, and obtaining the dipropionic acid imidazole phenylurea (compound 1).
The corresponding reaction equation in the synthesis process is:
in particular, the amount of the solvent to be used,
in the first step: the catalyst used is sodium sulfide in an amount of 0.2 to 1 times, preferably 0.5 times, the molar amount of the compound 1.
In the second step: the nitro reduction method is palladium ammonium carbonate reduction, the solvent is water, and the reaction time is 1-5h, preferably 2 h.
In the second step: palladium on carbon is used in an amount of 1% to 10%, preferably 5%, by weight of compound 3; the amount of the ammonium formate is 1 to 5 times, preferably 3 times of the amount of the compound 3 mol; the amount of water used is 1 to 10 times, preferably 10 times, the weight of compound 3.
In the third step: the synthesis method of the compound 4 and urea is adopted, and the amount of the urea is 0.5-1 times, preferably 0.5 times of the compound 3 molar weight.
Compared with the prior art, the invention has the following advantages: in the first step of the process, sodium sulfide is used as a catalyst to replace sulfur, so that a condensation pipe cannot be blocked, and the solvent can be recycled, thereby realizing clean and green production, shortening the reaction time and improving the yield; the second step of the process is a typical nitro reduction reaction, but in the conditions used in the prior nitro reduction reaction, iron powder reduction and sulfide generation caused by a large amount of solid wastes are eliminated, hydrazine hydrate reduction toxicity is high, safety is low, and palladium-carbon hydrogenation reduction requires high-pressure reaction and is dangerous. The process takes water as a solvent, uses palladium-carbon to catalyze the reduction of ammonium formate, has mild reaction conditions and low pollution, and is suitable for industrial production; in the second step and the third step of the process, a one-pot method is adopted to prepare crude imidazole phenylurea, and the phosgene with high toxicity is replaced by urea; improves the product yield, reduces the cost, has simple and convenient operation and is more suitable for industrial production.
The process improves the yield, reduces the generation of solid wastes, shortens the reaction time, reduces the cost and improves the safety of the synthesis process of the imidocarb dipropionate.
Detailed Description
The present invention will be described in further detail with reference to the following examples, but the present invention is not limited thereto.
Example 1
Synthesis of Compound 3
1L of methanol was added to a 2L three-necked reaction flask, and m-nitrobenzonitrile (100g, 0.67mol), Na and the like were added under stirring2S (26.35g, 0.335mol) and ethylenediamine (48.65g, 0.81mol) were reacted under stirring at elevated temperature to reflux. Reflux reaction is carried out for 8h, heat filtration is carried out, the filtrate is cooled to minus 5 ℃ to 0 ℃, stirring is carried out for crystallization for 2h, filtration is carried out, a small amount of cold methanol is used for washing a filter cake, and the product is dried in vacuum to obtain light yellow solid 2- (3-nitrophenyl) imidazoline (123g, 95.3%).
Example 2
Synthesis of Compound 3
1L of methanol was added to a 2L three-necked reaction flask, and m-nitrobenzonitrile (100g, 0.67mol), Na and the like were added under stirring2S (52.7g, 0.67mol) and ethylenediamine (48.65g, 0.81mol) were reacted under stirring at elevated temperature to reflux. Reflux reaction is carried out for 8h, heat filtration is carried out, the filtrate is cooled to minus 5 ℃ to 0 ℃, stirring is carried out for crystallization for 2h, filtration is carried out, a small amount of cold methanol is used for washing a filter cake, and the product is dried in vacuum to obtain light yellow solid 2- (3-nitrophenyl) imidazoline (120g, 93.2%).
Example 3
Synthesis of Compound 4
Adding 1L of water, 2- (3-nitrophenyl) imidazoline (120g, 0.63mol) into a 3L reaction bottle, carefully adding 3.6g of 10% wet palladium carbon, slowly heating and stirring until refluxing, slowly dropwise adding a water (240mL) solution of ammonium formate (119.7g, 1.89mol), keeping the temperature for reacting for 2h after about 0.5h is finished, filtering to obtain a light yellow clarified liquid, and directly feeding the filtrate to the next step.
Synthesis of Compound 5
And (3) sequentially adding the reaction liquid in the previous step, hydrochloric acid (134mL, 1.6mol) and urea (19.2g, 0.32mol) into a 2L three-opening reaction bottle, heating and stirring to reflux under the protection of nitrogen, preserving the temperature for reaction for 8h, cooling the reaction liquid to room temperature, adjusting the pH of the reaction liquid to 9-10 by using 2mol/L sodium hydroxide aqueous solution, precipitating a large amount of white solid, stirring for 0.5h at room temperature, filtering, washing a filter cake by a small amount of water, and drying by air blasting a product to obtain the white-like solid imidazole phenylurea (71.43g, 65.2% yield in two steps).
Example 4
Synthesis of Compound 4
Adding 1L of water, 2- (3-nitrophenyl) imidazoline (120g, 0.63mol) into a 3L reaction bottle, carefully adding 6g of 10% wet palladium carbon, slowly heating and stirring until refluxing, slowly dropwise adding a water (240mL) solution of ammonium formate (119.7g, 1.89mol), keeping the temperature for reacting for 2h after about 0.5h is finished, filtering to obtain a light yellow clear solution, and directly feeding the filtrate to the next step.
According to the synthesis of compound 5 in example 3, an off-white solid imidazophenylurea was obtained (88.2g, two-step yield 80.5%).
Example 5
Synthesis of Compound 4
Adding 1L of water, 2- (3-nitrophenyl) imidazoline (120g, 0.63mol) into a 3L reaction bottle, carefully adding 8.4g of 10% wet palladium carbon, slowly heating and stirring until refluxing, slowly dropwise adding a water (240mL) solution of ammonium formate (119.7g, 1.89mol), keeping the temperature for reacting for 2h after about 0.5h is finished, filtering to obtain a light yellow clarified liquid, and directly feeding the filtrate to the next step.
According to the synthesis of compound 5 in example 3, an off-white solid imidazophenylurea was obtained (88.5g, two-step yield 80.7%).
Example 6
Synthesis of Compound 4
Adding 1L of water, 2- (3-nitrophenyl) imidazoline (120g, 0.63mol) into a 3L reaction bottle, carefully adding 6g of 10% wet palladium carbon, slowly heating and stirring until refluxing, slowly dropwise adding a water (240mL) solution of ammonium formate (59.85g, 0.945mol), keeping the temperature for reaction for 2h after about 0.5h is finished, filtering to obtain a light yellow clear solution, and directly feeding the filtrate into the next step.
According to the synthesis of compound 5 in example 3, an off-white solid imidazophenylurea was obtained (58g, two-step yield 53%).
Example 7
Synthesis of Compound 4
Adding 1L of water, 2- (3-nitrophenyl) imidazoline (120g, 0.63mol) into a 3L reaction bottle, carefully adding 6g of 10% wet palladium carbon, slowly heating and stirring until refluxing, slowly dropwise adding a water (240mL) solution of ammonium formate (199.5g, 3.15mol), keeping the temperature for reacting for 2h after about 0.5h is finished, filtering to obtain a light yellow clear solution, and directly feeding the filtrate to the next step.
According to the synthesis of compound 5 in example 3, an off-white solid imidazophenylurea was obtained (85g, two-step yield 77.6%).
Example 8
Synthesis of Compound 4
Adding 0.5L of water and 2- (3-nitrophenyl) imidazoline (120g, 0.63mol) into a 3L reaction bottle, carefully adding 6g of 10% wet palladium carbon, slowly heating and stirring until refluxing, slowly dropwise adding a water (120mL) solution of ammonium formate (199.5g, 3.15mol), keeping the temperature for reacting for 2 hours after 15min is finished, filtering to obtain a light yellow clear solution, and directly feeding the filtrate to the next step.
According to the synthesis of compound 5 in example 3, an off-white solid imidazophenylurea (81g, 74% yield in two steps) was obtained.
Example 9
Synthesis of Compound 5
Compound 4 was synthesized according to example 4, by charging the reaction solution of Compound 4, hydrochloric acid (134mL, 1.6mol), and urea (38.4g, 0.63mol) into a 2L three-necked reaction flask, heating and stirring under nitrogen protection to reflux, maintaining the temperature for 8 hours, cooling the reaction solution to room temperature, adjusting the pH to 9-10 with 2mol/L aqueous sodium hydroxide solution, precipitating a large amount of white solid, stirring at room temperature for 0.5 hours, filtering, washing the filter cake with a small amount of water, and drying the product by air blowing to obtain a white-like solid imidazophenylurea (82.4g, 75.2% yield in two steps).
Example 10
Synthesis of Compound 1
Adding 340mL of crude imidazole phenylurea (85g, 0.24mol) and 340mL of ethyl acetate into a 1L three-necked bottle in sequence, heating and stirring until the mixture flows back, dissolving the solid completely, adding 4.3g of activated carbon, stirring for 0.5h, filtering, stirring the filtrate to cool to room temperature, dropwise adding propionic acid (39.2g, 0.53mol), dropping for about 0.5h, precipitating a large amount of white solid, cooling to 5-10 ℃, stirring and crystallizing for 2h, filtering, washing the filter cake with a small amount of ethyl acetate, and drying the product in vacuum to obtain white solid imidazole phenylurea dipropionate (110.8g, 93%).
Claims (5)
1. A preparation method of imidocarb dipropionate and an intermediate thereof is characterized by comprising the following steps:
the method comprises the following steps: m-nitrobenzonitrile is taken as a raw material and reacts with ethylenediamine under the action of a catalyst to synthesize 2- (3-nitrophenyl) imidazoline;
step two: reducing 2- (3-nitrophenyl) imidazoline by palladium ammonium carbonate to obtain 2- (3-aminophenyl) imidazoline;
step three: 2- (3-aminophenyl) imidazoline and urea are subjected to condensation reaction to prepare imidocarb dihydrochloride, and the imidocarb is obtained through NaOH dissociation;
step four: reacting the free imidazole phenylurea with propionic acid to form salt so as to obtain the imidazole phenylurea dipropionate.
2. The method for preparing imidocarb dipropionate and the intermediate thereof according to claim 1, characterized in that: the catalyst used in the first step is sodium sulfide, and the dosage of the sodium sulfide is 0.2 to 1 time of the mole number of the m-nitrobenzonitrile, and the preferred dosage is 0.5 time.
3. The method for preparing imidocarb dipropionate and the intermediate thereof according to claim 1, characterized in that: the nitro reduction method adopted in the second step is palladium ammonium carbonate reduction, the solvent is water, and the reaction time is 1-5h, preferably 2 h.
4. The method for preparing imidocarb dipropionate and the intermediate thereof according to claim 1, characterized in that: in the second step, the dosage of the palladium-carbon is 1-10 percent of the weight of the 2- (3-nitrophenyl) imidazoline, and the optimal dosage is 5 percent; the amount of the ammonium formate is 1 to 5 times, preferably 3 times of the mole number of the 2- (3-nitrophenyl) imidazoline; the amount of water used is 1 to 10 times, preferably 10 times, the weight of 2- (3-nitrophenyl) imidazoline.
5. The method for preparing imidocarb dipropionate and the intermediate thereof according to claim 1, characterized in that: and step three, adopting a synthesis method of condensing 2- (3-aminophenyl) imidazoline and urea, wherein the using amount of the urea is 0.5-1 time, preferably 0.5 time of the mole number of the 2- (3-nitrophenyl) imidazoline.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111892541A (en) * | 2020-08-31 | 2020-11-06 | 山东久隆恒信药业有限公司 | Recovery and purification method of imidocarb |
| CN114773270A (en) * | 2022-04-13 | 2022-07-22 | 山东省药学科学院 | Production and preparation method of imidocarb dipropionate |
| CN116813551A (en) * | 2023-08-28 | 2023-09-29 | 齐鲁晟华制药有限公司 | Preparation method of imidazole phenylurea dipropionate |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111892541A (en) * | 2020-08-31 | 2020-11-06 | 山东久隆恒信药业有限公司 | Recovery and purification method of imidocarb |
| CN114773270A (en) * | 2022-04-13 | 2022-07-22 | 山东省药学科学院 | Production and preparation method of imidocarb dipropionate |
| CN116813551A (en) * | 2023-08-28 | 2023-09-29 | 齐鲁晟华制药有限公司 | Preparation method of imidazole phenylurea dipropionate |
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