CN120136661A - A method for synthesizing 3-chloropropyne and co-producing p-chlorobenzaldehyde - Google Patents
A method for synthesizing 3-chloropropyne and co-producing p-chlorobenzaldehyde Download PDFInfo
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- CN120136661A CN120136661A CN202510387592.5A CN202510387592A CN120136661A CN 120136661 A CN120136661 A CN 120136661A CN 202510387592 A CN202510387592 A CN 202510387592A CN 120136661 A CN120136661 A CN 120136661A
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- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/16—Preparation of halogenated hydrocarbons by replacement by halogens of hydroxyl groups
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- C07—ORGANIC CHEMISTRY
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- C07—ORGANIC CHEMISTRY
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- C07C17/00—Preparation of halogenated hydrocarbons
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- C07C17/383—Separation; Purification; Stabilisation; Use of additives by distillation
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- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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- C07C45/78—Separation; Purification; Stabilisation; Use of additives
- C07C45/81—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C45/82—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
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Abstract
The invention relates to the technical field of fine chemical product synthesis, in particular to a synthesis method for co-producing p-chlorobenzaldehyde by 3-chloropropion, which comprises the steps of mixing and heating propargyl alcohol, a solvent, an ionic liquid catalyst, a catalyst promoter DMF and a polymerization inhibitor p-tert-butyl catechol, slowly dropwise adding p-chlorobenzylidene dichloride into the mixture, carrying out heat preservation and stirring, collecting a generated 3-chloropropion crude product at a tail gas port, cooling after the reaction is finished, and sequentially decompressing and distilling out the 3-chloropropion, the residual propynyl alcohol and the solvent and a p-chlorobenzaldehyde finished product by a rectifying tower. The invention solves the problems that the existing 3-chlorpropyne production uses toxic dangerous chemicals chlorinating agents and generates a large amount of toxic waste acid gas or low added value byproducts, and the existing direct hydrolysis method of p-chlorobenzaldehyde has low chlorine atom utilization rate, reduces environmental pollution and the like.
Description
Technical Field
The invention relates to the technical field of synthesis of fine chemical products, in particular to a synthesis method for co-producing p-chlorobenzaldehyde by using 3-chloropropionine.
Background
The 3-chlorpropyne is an important chemical raw material, is mainly used for synthesizing an electroplating intermediate, an intermediate of medicines and pesticides, can be used for synthesizing medicine youjiang and pesticide prallethrin, and the like, and is also an excellent metal corrosion inhibitor and antirust agent. The p-chlorobenzaldehyde is mainly used as an intermediate of medicines, pesticides and dyes, the medicines are used for preparing fenamic acid, amino benzene aminobutyric acid and the like, and the pesticides are used for synthesizing bactericides tebuconazole, plant growth regulators uniconazole and pesticide chlorfenapyr.
The chloridizing process of propynyl alcohol is one main production process of 3-chlorpropynyl, and the chlorinating agent includes sulfoxide chloride, phosphorus chloride, carbonyl chloride, etc. CN202849284 refers to the fact that phosphorus trichloride and propargyl alcohol react under the condition that pyridine is used as an acid binding agent, the yield is 85%, pyridine is malodorous liquid, recovery difficulty is high under an acidic condition, and the like, CN99802124.5 refers to the fact that propargyl alcohol and carbonyl chloride are used for preparing propargyl alcohol under the action of an amide catalyst, the yield is only about 65%, carbonyl chloride is a highly toxic substance, and the method is high in equipment requirement and complex in operation. CN 107473930B refers to a method of chlorination using phosphorus trichloride in a tubular reactor, the yield is only 90%, and there is a possibility that the byproduct phosphorous acid is low in quality.
The preparation method of the p-chlorobenzaldehyde mainly comprises a p-chlorotoluene gas-phase oxidation method, a liquid-phase oxidation method, an electrochemical oxidation method and a chlorination hydrolysis method. The oxidation method has low conversion rate and selectivity to the chlorotoluene, and the oxidation degree is difficult to control. At present, the chloridizing hydrolysis method of p-chlorotoluene is mainly used for producing chlorobenzaldehyde in the industrial production process of China. Under the action of light or an initiator, the side chain methyl of the p-chlorotoluene is chloridized, and then the chloridized product is hydrolyzed in the presence of a catalyst to prepare the p-chlorobenzaldehyde. The hydrolysis reaction uses metal halide such as FeCl 3、CuCl2、SnCl2 or zinc salt as catalyst, the catalyst is used in large amount, and residues exist in the product, which affects the color of the product. And the amount of wastewater generated by the process is large, and the safety and environmental protection pressure of the process are large.
The production process of the 3-chloropropionine and p-chlorobenzaldehyde can show that the two products are produced by adopting different production processes respectively, the atom economy of the reaction is low, and by-products with low added value or a large amount of waste acid gas are generated, so that the environmental pollution is easy to cause.
Therefore, a safe and environment-friendly production method of 3-chloropropionine and p-chlorobenzaldehyde is needed to be found, so that the method has a larger industrial application value.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a synthesis method for co-producing 3-chloropropion and p-chlorobenzaldehyde, which takes propargyl alcohol as a raw material, uses p-chlorobenzylidene dichloride to obtain 3-chloropropion and p-chlorobenzaldehyde under the action of a catalyst, solves the problems that a toxic dangerous chemical chlorinating agent is used in the existing 3-chloropropion production, a large amount of toxic waste acid gas or low added value byproducts are generated, and the utilization rate of chlorine atoms is low in the existing direct hydrolysis of the p-chlorobenzaldehyde, and reduces environmental pollution.
The invention is realized by the following technical scheme:
The synthesis process of co-producing p-chlorobenzaldehyde with 3-chloropropene includes mixing propargyl alcohol, solvent, ionic liquid catalyst, promoter DMF and polymerization inhibitor p-tert-butyl catechol, heating, slowly dropping p-chlorobenzylidene dichloride into the mixture, maintaining the temperature while stirring, collecting the produced 3-chloropropionyl crude product in the tail gas port, cooling after the reaction, and successively decompressing and distilling out 3-chloropropionyl, residual propargyl alcohol and solvent and p-chlorobenzaldehyde product in a rectifying tower.
In the invention, chlorine atoms in the p-chlorobenzylidene dichloride are eliminated under nucleophilic conditions to generate carbonium ions, and simultaneously, after the hydroxyl groups of the propargyl alcohol are complexed with the ionic liquid, benzyl sites are attacked to form p-chlorobenzaldehyde and 3-chloropropionine. The nucleophilic of the lone pair electron on the DMF oxygen of the cocatalyst can promote the leaving of chlorine, and the polymerization inhibitor p-tert-butyl catechol can inhibit the side reaction of free radicals (such as the polymerization of 3-chloropropionine) to avoid the decomposition of the product.
Further, in the vacuum rectification, the vacuum degree of 3-chloropropionine is 0.07MPa, the temperature is 30-45 ℃, the vacuum degree of the residual propargyl alcohol and the solvent is 0.09-0.095 MPa, the temperature is 60-90 ℃, and the high vacuum of p-chlorobenzaldehyde is 0.098-0.1 MPa, and the temperature is 105-125 ℃.
The reaction mixed solution is subjected to first-stage vacuum rectification (about 0.07MPa, and the temperature is 30-45 ℃), and 3-chloropropionine (product) +the rest components;
the rest components are subjected to second-stage vacuum rectification (0.09-0.095 MPa, and the temperature is 60-90 ℃), and the mixed solution of the solvent and the propargyl alcohol is added with crude p-chlorobenzaldehyde;
Crude p-chlorobenzaldehyde, vacuum rectification (0.098-0.1 MPa, temperature 105-125 ℃) and p-chlorobenzaldehyde (finished product).
Preferably, the dripping and heat preservation temperature is 80-90 ℃, and the heat preservation and stirring are carried out for 2-4 hours.
The temperature of 80-90 ℃ is lower than the boiling point of propargyl alcohol, so that more propargyl alcohol is prevented from being carried out by tail gas in the process of the dropwise adding reaction.
Further, the molar ratio of the propynyl alcohol to the p-chlorobenzylidene dichloride is 1.1-1.5:1.
Preferably, the molar ratio of the propargyl alcohol to the p-chlorobenzylidene dichloride is 1.2-1.3:1.
Further, the mass ratio of the propargyl alcohol to the solvent, the catalyst, the cocatalyst and the polymerization inhibitor is 1:0.3-0.6:0.05-0.2:0.005-0.01:0.002.
Preferably, the mass ratio of the propargyl alcohol to the solvent, the catalyst, the cocatalyst and the polymerization inhibitor is 1:0.4-0.5:0.1-0.15:0.01:0.002.
Further, the solvent is one or more of chlorobenzene, o-dichlorobenzene and xylene.
The solvent is selected from common solvents, has the functions of dilution, uniform mixing and the like, does not participate in the reaction, has the boiling point higher than that of propargyl alcohol, ensures that tail gas does not run off as much as possible in the reaction process, has a certain melting point in the raw material ionic liquid, is more uniform in reaction liquid mixing after adding the solvent, can not participate in the reaction, and has the melting point of the generated para-aldehyde of about 48 ℃ so as to facilitate the rectification of the 3-chloropropionine at the back.
Further, the ionic liquid catalyst is one or more of 1-butyl-3-methylimidazole chloride, 1-butyl-2, 3-dimethylimidazole chloride, 1-butyl-3-methylimidazole bromide and 1-butyl-2, 3-dimethylimidazole bromide.
The ionic liquid has the property of Lewis acid, can accept electrons on chloride ions to form negatively charged protons, promotes the formation of p-chlorobenzylidene dichloride carbanion, and is complexed with propynyl alcohol, and the ionic liquid has lower oxidizing property than the conventional inorganic Lewis acid, so that the excessive oxidation of p-chlorobenzaldehyde is prevented.
Preferably, the ionic liquid catalyst is 1-butyl-3-methylimidazole chloride or 1-butyl-3-methylimidazole bromide.
Furthermore, the ionic liquid catalyst remained at the bottom of the rectifying still can be used for the next batch of synthesis.
The ionic liquid catalyst remained after rectification is applied for 5 to 12 times, thereby realizing cyclic utilization and reducing waste.
The invention has the beneficial effects that:
The process is clean, adopts low-toxicity solvents and catalysts, adopts p-chlorobenzylidene dichloride, avoids the use of dangerous chlorinating agents such as thionyl chloride, phosphorus chloride, carbonyl chloride and the like, reduces the health risk to operators, has high ionic liquid biodegradation rate, ensures that the reaction is carried out in an ionic liquid acidic environment, directly participates in substitution, completely converts the p-chlorobenzylidene dichloride into p-chlorobenzaldehyde, avoids Persistent Organic Pollutants (POPs) residues, ensures that the solvents can be recycled in a circulating system, realizes zero emission, ensures that the activity of the catalyst is maintained to be more than 95% after being recycled for 5-12 times, reduces the generation of wastes, and meets the requirements of green chemistry and sustainable development. In the aspect of economy, the co-production can reduce raw material consumption, and the preparation of the p-chlorobenzaldehyde is synchronously completed during the synthesis of 3-chloropropionine, because the two products are simultaneously produced in the same reaction step, the atom utilization rate is improved. The efficient use and recycling of the catalyst reduces the production cost. By optimizing the separation process, the high-purity p-chlorobenzaldehyde and 3-chloropropionine are obtained, and the p-chlorobenzaldehyde and 3-chloropropionine obtained by the reaction have high yields, so that the method has greater industrial application value.
The invention solves the problems that a toxic dangerous chemical chlorinating agent is used in the production of 3-chloropropionine and a large amount of toxic waste acid gas or low added value byproducts are generated in the prior art, solves the problem that the utilization rate of chlorine atoms is not high in the direct hydrolysis of the p-chlorobenzaldehyde, reduces environmental pollution, and reduces the emission of the waste acid gas by more than 75 percent compared with the prior main industrial production process of 3-chloropropionine and p-chlorobenzaldehyde.
The synthesis method realizes zero emission of toxic chlorinating agent waste gas through the green solvent and high-efficiency ionic liquid catalysis and co-production design, remarkably improves the utilization rate of chlorine atoms compared with the traditional hydrolysis method, and realizes triple targets of high-efficiency resource utilization, environment-friendly emission and remarkable economic benefit due to full closed-loop utilization (propiolic alcohol circulation, solvent recovery and catalyst repeated use) of byproducts.
Drawings
FIG. 1 is a process flow diagram of the present invention.
FIG. 2 is a table showing the yields of 3-chloropropionine and p-chlorobenzaldehyde for the different ionic liquid catalysts of example 2 of the present invention.
Detailed Description
In order to clearly illustrate the technical characteristics of the scheme, the scheme is explained below through a specific embodiment.
The test materials used in the examples of the present invention are all conventional in the art and are commercially available.
Example 1:
To a 1000ml reaction flask were added 184.8g of propargyl alcohol, 56g of chlorobenzene, 9.3g of 1-butyl-3-methylimidazole chloride, 1.8g of DMF, 0.37g of p-tert-butylcatechol, and the mixture was stirred and heated to 80℃to slowly dropwise add 586.5g of p-chlorobenzylidene dichloride, and the mixture was stirred at 80℃until the p-chlorobenzylidene dichloride reaction was completed.
In the scheme, the boiling points of the products are greatly different, the 3-chloropropionine is 58 ℃, the propynyl alcohol is 114.5 ℃, the solvent is 130-180 ℃, and the aldehyde is 213 ℃, so that the rectification is relatively easy. And (3) evaporating 3-chloropropionine from the reaction mixed solution under the conditions of vacuum degree of 0.07MPa and temperature of 30-45 ℃, evaporating the mixed solution of solvent and residual propargyl alcohol under the conditions of 0.09MPa and temperature of 60-80 ℃, and finally evaporating p-chlorobenzaldehyde under the conditions of 0.1MPa and temperature of 105-125 ℃.
56.4 G of generated 3-chloropropionine crude product is collected at a tail gas port in the reaction process, the purity is 91.2%, 179.8 g of 3-chloropropionine is distilled out from the reaction liquid under reduced pressure, the purity is 99.3%, and 416.4g of p-chlorobenzaldehyde is distilled out, and the purity is 99.4%. The total yield of 3-chloropropionine is 93.6 percent and the yield of p-chlorobenzaldehyde is 98.2 percent.
Example 2:
The procedure and the amounts of the materials used in this example were the same as in example 1, but the ionic liquid catalyst was replaced with 1-butyl-2, 3-dimethylimidazole chloride, 1-butyl-3-methylimidazole bromide, 1-butyl-2, 3-dimethylimidazole bromide or a combination, respectively. The results of the yields of 3-chloropropionine and p-chlorobenzaldehyde are shown in FIG. 2.
Example 3:
The catalyst remaining after the rectification in example 1 was used as a catalyst, 184.8g of propargyl alcohol, 56g of chlorobenzene, 1.8g of DMF, 0.37g of p-tert-butylcatechol were added to a 1000ml reaction flask, the temperature was raised to 80℃with stirring, 586.5g of p-chlorobenzylidene dichloride was slowly added dropwise, and the mixture was kept warm until the reaction of p-chlorobenzylidene dichloride was completed. 53.8 g of the generated 3-chloropropionine crude product is collected, the purity is 92.4%, 179.1 g of the 3-chloropropionine is distilled out from the reaction solution under reduced pressure, the purity is 99.5%, 418.5g of p-chlorobenzaldehyde is distilled out, and the purity is 99.3%. The total yield of 3-chloropropionine is 92.7 percent and the yield of p-chlorobenzaldehyde is 98.6 percent.
It should be understood that the foregoing embodiments and the accompanying drawings are only for illustrating the technical aspects of the present invention, but not for limiting the present invention, and that the present invention is not limited to the preferred embodiments, and that the changes, modifications, additions or substitutions made by those skilled in the art within the spirit and scope of the present invention will not depart from the spirit and scope of the present invention as defined in the appended claims.
Claims (8)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202510387592.5A CN120136661B (en) | 2025-03-31 | A synthetic method for the co-production of p-chlorobenzaldehyde from 3-chloropropyne |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202510387592.5A CN120136661B (en) | 2025-03-31 | A synthetic method for the co-production of p-chlorobenzaldehyde from 3-chloropropyne |
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| CN120136661A true CN120136661A (en) | 2025-06-13 |
| CN120136661B CN120136661B (en) | 2025-12-30 |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH0753418A (en) * | 1993-08-09 | 1995-02-28 | Ihara Nikkei Kagaku Kogyo Kk | Production of long-chain alkyl halides |
| US6291731B1 (en) * | 1998-03-09 | 2001-09-18 | Basf Aktiengesellschaft | Continuous method for producing propargyl chloride |
| CN1440958A (en) * | 2003-04-03 | 2003-09-10 | 华东师范大学 | Conversion process of primary alcohol, hexamethylene glycol, tertiary amyl alcohol or cyclohexanol into halohydrocarbon in acid ionic liquid [Hmim] X,X==Cl,Br or I) |
| CN1849281A (en) * | 2003-09-08 | 2006-10-18 | 巴斯福股份公司 | Method for producing haloalkanes from alcohols |
| CN101768045A (en) * | 2010-01-12 | 2010-07-07 | 郑州大学 | Method for preparing halogenated hydrocarbons from strongly acidic ionic liquids |
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Patent Citations (6)
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| JPH0753418A (en) * | 1993-08-09 | 1995-02-28 | Ihara Nikkei Kagaku Kogyo Kk | Production of long-chain alkyl halides |
| US6291731B1 (en) * | 1998-03-09 | 2001-09-18 | Basf Aktiengesellschaft | Continuous method for producing propargyl chloride |
| CN1440958A (en) * | 2003-04-03 | 2003-09-10 | 华东师范大学 | Conversion process of primary alcohol, hexamethylene glycol, tertiary amyl alcohol or cyclohexanol into halohydrocarbon in acid ionic liquid [Hmim] X,X==Cl,Br or I) |
| CN1849281A (en) * | 2003-09-08 | 2006-10-18 | 巴斯福股份公司 | Method for producing haloalkanes from alcohols |
| CN101768045A (en) * | 2010-01-12 | 2010-07-07 | 郑州大学 | Method for preparing halogenated hydrocarbons from strongly acidic ionic liquids |
| CN118146068A (en) * | 2024-01-30 | 2024-06-07 | 南京工业大学 | Method for preparing (substituted) benzyl alcohol/aldehyde by rapid phase transfer hydrolysis of benzyl chloride |
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