CN111675608A - Process for producing 1-chloro-1' -chloroacetyl-cyclopropane - Google Patents

Process for producing 1-chloro-1' -chloroacetyl-cyclopropane Download PDF

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CN111675608A
CN111675608A CN202010456333.0A CN202010456333A CN111675608A CN 111675608 A CN111675608 A CN 111675608A CN 202010456333 A CN202010456333 A CN 202010456333A CN 111675608 A CN111675608 A CN 111675608A
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reaction
acetyl
chloro
chloroacetyl
butyrolactone
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CN111675608B (en
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沈运河
熊国银
周全全
汪建
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Anhui Jukai Agrochemical Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • 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
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/63—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by introduction of halogen; by substitution of halogen atoms by other halogen atoms
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B7/00—Halogens; Halogen acids
    • C01B7/01—Chlorine; Hydrogen chloride
    • C01B7/012—Preparation of hydrogen chloride from the elements
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • 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
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • 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
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
    • C07C45/673—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by change of size of the carbon skeleton
    • C07C45/676—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by change of size of the carbon skeleton by elimination of carboxyl groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/26—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D307/30—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D307/32—Oxygen atoms
    • C07D307/33—Oxygen atoms in position 2, the oxygen atom being in its keto or unsubstituted enol form
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/02—Systems containing only non-condensed rings with a three-membered ring

Abstract

The invention relates to the technical field of fine chemical engineering, and particularly provides a process for producing 1-chloro-1' -chloroacetyl-cyclopropane, which at least comprises the following steps: (1) primary chlorination reaction: adding alpha-acetyl-gamma-butyrolactone into a reaction container, and introducing first chlorine gas to obtain a chlorinated material; (2) and (3) hydrolysis reaction: continuously adding water into the reaction container, adding a hydrochloric acid solution into the reaction container, and obtaining a hydrolyzed material after the reaction is finished; (3) ring closing reaction: continuously adding alkali liquor into the reaction container to obtain a 1-acetyl-1-chlorocyclopropane mixed solution, then standing for phase splitting, and taking an upper-layer material to obtain a cyclized material; (4) and (3) secondary chlorination reaction: and mixing the cyclized material with a solvent, introducing second chlorine, reacting, and performing aftertreatment to obtain the catalyst. The process can synthesize the needed intermediate in one step, and the primary chlorination, hydrolysis reaction and ring closing reaction are carried out in the same kettle without distilling materials in the middle.

Description

Process for producing 1-chloro-1' -chloroacetyl-cyclopropane
Technical Field
The invention relates to the technical field of fine chemical engineering, in particular to a process for producing 1-chloro-1' -chloroacetyl-cyclopropane.
Background
1-chloro-1' -chloroacetyl cyclopropane is a key intermediate of broad-spectrum triazole fungicide prothioconazole, and the product is obtained by chlorination reaction by generally adopting sulfonyl chloride as a chlorinating agent in the prior art. 1-chloro-1' -chloroacetyl-cyclopropane is used as an important intermediate for synthesizing prothioconazole raw material, and the yield of the prothioconazole can directly influence the annual yield of the prothioconazole if the annual yield is to be reached. The conventional method is to use sulfuryl chloride and the like as chlorination reagents to perform chlorination reaction on alpha hydrogen atoms of substrate carbonyl, but the reaction has violent heat release, serious local overheating problem and heat exchange problem of a reaction system, so that the reaction selectivity is poor and the yield is not ideal; the reaction operation time is too long, and the productivity is not high; and the generated gases such as sulfur dioxide and the like greatly increase the amount of three wastes.
The Chinese patent CN201410520401.X selects 1-chloro-1 '-chloroacetyl-cyclopropane as an initial material to react with sulfonyl chloride, and glacial acetic acid, n-butyl ammonium bromide and other means are added into a system to prepare the 1-chloro-1' -chloroacetyl-cyclopropane, but the overall route has more requirements on equipment, is more complicated, is equivalent to one-step reaction, has more steps and is complicated in post-treatment, so that the yield is also lower. The commonly used step-by-step method is that the intermediate 1-chloro-1, chloroacetyl-cyclopropane is synthesized by alpha-chloro-alpha-acetyl-beta-butyrolactone through chlorination, hydrolytic ring-opening reaction, cyclization reaction and chlorination in four steps, after butyrolactone is chlorinated, hydrolysis reaction is carried out under the condition of acid water, then hydrolysate is distilled out, ring closure reaction is carried out on the hydrolysate under alkaline condition, then ring closure product is distilled out, and then final product 1-chloro-1, chloroacetyl-cyclopropane is obtained through chlorination. However, the intermediate is produced by a step-by-step method, even if a plurality of sets of reaction systems are adopted for full-load production, the yield cannot meet the production requirement, a plurality of matched dropwise adding kettles, a plurality of transfer kettles, a cooling system, a nitrogen system and the like are additionally arranged, the equipment investment is huge, so that the plurality of reaction kettles and the systems occupy huge space and consume energy, the limited space of a production workshop cannot be effectively utilized, the production cost is increased, and in addition, a large amount of manpower and material resources are required to be invested for the operation and maintenance of the equipment, obviously, the step-by-step method cannot meet the production requirement. In addition, in a limited production space, the equipment investment is huge, the production time is long, the yield is low, the efficiency is low, the energy consumption is high, the space utilization rate is low, the potential safety hazard is large, in addition, the equipment investment is large, the maintenance is time-consuming and labor-consuming, more operators are needed, the corrosion is serious, and the damage of the equipment is aggravated.
Disclosure of Invention
In order to solve the above technical problems, the present invention provides a process for producing 1-chloro-1' -chloroacetyl-cyclopropane, which at least comprises the following steps:
(1) primary chlorination reaction: adding alpha-acetyl-gamma-butyrolactone into a reaction container, and introducing first chlorine gas to obtain a chlorinated material; the mol ratio of the alpha-acetyl-gamma-butyrolactone to the first chlorine gas is 1: (0.8-1.5);
(2) and (3) hydrolysis reaction: continuously adding water into the reaction container, adding a hydrochloric acid solution into the reaction container, and obtaining a hydrolyzed material after the reaction is finished;
(3) ring closing reaction: continuously adding alkali liquor into the reaction container to obtain a 1-acetyl-1-chlorocyclopropane mixed solution, then standing for phase splitting, and taking an upper-layer material to obtain a cyclized material;
(4) and (3) secondary chlorination reaction: and mixing the cyclized material with a solvent, introducing second chlorine, reacting, and performing aftertreatment to obtain the catalyst.
As a preferable technical solution, in the present invention, the mass ratio of the α -acetyl- γ -butyrolactone in the step (1) to the water in the step (2) is 1: (0.5-1.5).
As a preferable technical solution, in the present invention, the molar ratio between the cyclized material and the second chlorine gas in the step (4) is 1: (1-1.5).
As a preferable technical scheme, the mass residual quantity of the alpha-acetyl-gamma-butyrolactone in the step (2) of the invention is less than 0.5%.
In a preferred embodiment, the residual amount of 3, 5-dichloro-2-pentanone in the mixed solution of 1-acetyl-1-chlorocyclopropane in step (3) in the present invention is less than 0.5% by mass.
As a preferable technical scheme, the content of the 1-acetyl-1-chlorocyclopropane in the cyclized material in the step (3) in the invention is more than 95 wt%.
As a preferable technical scheme, the mass concentration of the alkali liquor in the step (3) in the invention is 25-35%.
As a preferable technical solution, the molar ratio of α -acetyl- γ -butyrolactone, solute in the alkaline solution, and solute in the hydrochloric acid solution in the present invention is 1: (1.5-2.5): (0.1-0.5).
In a preferred embodiment, the solvent in the present invention is selected from one or more of dichloromethane, dichloroethane, chloroform, acetonitrile, ethylene glycol dimethyl ether, n-hexane, acetone, toluene, chlorobenzene, and xylene.
In a preferred embodiment of the present invention, the alkali solution is at least one selected from the group consisting of an aqueous sodium hydroxide solution, an aqueous potassium carbonate solution, and an aqueous sodium carbonate solution.
Compared with the prior art, the invention has the following excellent beneficial effects:
firstly, the process for producing the 1-chloro-1' -chloroacetyl-cyclopropane provided by the invention can synthesize the needed intermediate at one time, and the primary chlorination, the hydrolysis reaction and the ring closure reaction are carried out in the same kettle without distilling materials in the middle. Secondly, hydrolysis products and ring closing products in the whole process do not need to be distilled out, so that the decomposition of materials caused by high temperature of distillation is avoided, a large amount of tar byproducts which are difficult to treat are formed, and the energy consumption can be greatly reduced without distillation. In addition, the inventor finds that chlorine is adopted, the chlorine is low in cost, easy to obtain, less in waste gas and less in pollution, the chlorine does not need to be degassed in the primary chlorination reaction, the generated hydrogen chloride byproduct is just suitable for hydrogen chloride used in the hydrolysis reaction, complicated distillation and degassing steps are not needed, the purity of the synthesized intermediate transition product is high, and the reaction rate and the purity of the next step can be increased; the influence of sulfur dioxide which is a byproduct of sulfuryl chloride on the reaction is avoided, and if the residual sulfuryl chloride is not evaporated, the second step of sulfuryl chloride can generate a large amount of gas and heat when meeting water, so that the whole reaction effect is influenced. According to the process adopted by the invention, the reaction rate of the first three steps is high, the prepared cyclized material is high in yield and excellent in purity, the efficiency of the secondary chlorination reaction is improved, the influence of byproducts on the reaction is eliminated, high-temperature distillation is not carried out, and the yield is high. Finally, in the whole process, the number of used equipment is reduced, the limited space of a production workshop can be saved, the equipment investment is reduced, the equipment maintenance cost is reduced, the steps are simplified, and the labor cost is greatly reduced.
Drawings
FIG. 1 is a schematic flow diagram of a process for producing 1-chloro-1' -chloroacetyl-cyclopropane.
Detailed Description
The technical features of the technical solutions provided by the present invention will be further clearly and completely described below with reference to the specific embodiments, and it should be apparent that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It will be understood by those skilled in the art that, unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the prior art and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.
The words "preferred", "preferably", "more preferred", and the like, in the present invention, refer to embodiments of the invention that may provide certain benefits, under certain circumstances. However, other embodiments may be preferred, under the same or other circumstances. Furthermore, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, nor is it intended to exclude other embodiments from the scope of the invention.
The invention provides a process for producing 1-chloro-1' -chloroacetyl-cyclopropane, which at least comprises the following steps:
(1) primary chlorination reaction: adding alpha-acetyl-gamma-butyrolactone into a reaction container, and introducing first chlorine gas to obtain a chlorinated material; the mol ratio of the alpha-acetyl-gamma-butyrolactone to the first chlorine gas is 1: (0.8-1.5);
(2) and (3) hydrolysis reaction: continuously adding water into the reaction container, adding a hydrochloric acid solution into the reaction container, and obtaining a hydrolyzed material after the reaction is finished;
(3) ring closing reaction: continuously adding alkali liquor into the reaction container to obtain a 1-acetyl-1-chlorocyclopropane mixed solution, then standing for phase splitting, and taking an upper-layer material to obtain a cyclized material;
(4) and (3) secondary chlorination reaction: and mixing the cyclized material with a solvent, introducing second chlorine, reacting, and performing aftertreatment to obtain the catalyst.
In some preferred embodiments, the process for producing 1-chloro-1' -chloroacetyl-cyclopropane comprises at least the following steps:
(1) primary chlorination reaction: adding alpha-acetyl-gamma-butyrolactone into a reaction container, controlling the temperature to be-10-5 ℃, and introducing first chlorine gas to obtain a chlorinated material for later use; the mol ratio of the alpha-acetyl-gamma-butyrolactone to the first chlorine gas is 1: (0.8 to 1.5);
(2) and (3) hydrolysis reaction: continuously adding water into the reaction container, controlling the temperature to be 0-80 ℃, dropwise adding a hydrochloric acid solution into the reaction container, and after the completion, keeping the temperature for 20-50 minutes to obtain a hydrolyzed material;
(3) ring closing reaction: controlling the temperature to be 65-80 ℃, continuously dripping alkali liquor into the reaction container, keeping the temperature for 5-25 minutes after finishing dripping alkali liquor to obtain a 1-acetyl-1-chlorocyclopropane mixed solution, then standing for phase splitting, and taking an upper-layer material to obtain a cyclized material;
(4) and (3) secondary chlorination reaction: and cooling the cyclized material to 20-30 ℃, mixing the cyclized material with a solvent, introducing second chlorine, degassing and desolventizing after chlorine introduction is finished, and obtaining a chlorinated material.
In some more preferred embodiments, the process for producing 1-chloro-1' -chloroacetyl-cyclopropane comprises at least the steps of:
(1) primary chlorination reaction: adding alpha-acetyl-gamma-butyrolactone into a reaction container, controlling the temperature to be-5-2 ℃, and introducing first chlorine gas to obtain a chlorinated material for later use; the mol ratio of the alpha-acetyl-gamma-butyrolactone to the first chlorine gas is 1: (0.9 to 1.2);
(2) and (3) hydrolysis reaction: continuously adding water into the reaction container, controlling the temperature to be 60-80 ℃, dropwise adding a hydrochloric acid solution into the reaction container, and keeping the temperature for 25-40 minutes after finishing adding the hydrochloric acid solution to obtain a hydrolyzed material;
(3) ring closing reaction: controlling the temperature to be 70-80 ℃, continuously dripping alkali liquor into the reaction container, preserving the temperature for 10-20 minutes after finishing dripping alkali liquor to obtain a 1-acetyl-1-chlorocyclopropane mixed solution, then standing for phase splitting, and taking an upper-layer material to obtain a cyclized material;
(4) and (3) secondary chlorination reaction: and cooling the cyclized material to 20-25 ℃, mixing the cyclized material with a solvent, introducing second chlorine, degassing and desolventizing after chlorine introduction is finished, and obtaining a chlorinated material.
In some most preferred embodiments, the process for producing 1-chloro-1' -chloroacetyl-cyclopropane comprises at least the following steps:
(1) primary chlorination reaction: adding alpha-acetyl-gamma-butyrolactone into a reaction container, controlling the temperature to be 0 +/-1 ℃, and introducing first chlorine gas to obtain a chlorinated material for later use; the mol ratio of the alpha-acetyl-gamma-butyrolactone to the first chlorine gas is 1: 1;
(2) and (3) hydrolysis reaction: continuously adding water into the reaction container, controlling the temperature to be 75 +/-2 ℃, dropwise adding a hydrochloric acid solution into the reaction container, and keeping the temperature for 30 minutes after the completion to obtain a hydrolyzed material;
(3) ring closing reaction: controlling the temperature to be 75 +/-2 ℃, continuously dripping alkali liquor into the reaction container, keeping the temperature for 15 minutes after finishing dripping alkali liquor to obtain a 1-acetyl-1-chlorocyclopropane mixed solution, then standing for phase splitting, and taking an upper-layer material to obtain a cyclized material;
(4) and (3) secondary chlorination reaction: cooling the cyclized material to 23 +/-1 ℃, mixing the cyclized material with a solvent, introducing second chlorine, degassing and desolventizing after chlorine introduction is finished, and obtaining a chlorinated material.
In some embodiments, the process of degassing and desolventizing in step (4) is a technique well known to those skilled in the art.
In some embodiments, the mass ratio of the α -acetyl- γ -butyrolactone in step (1) to the water in step (2) is 1: (0.5-1.5); preferably, the mass ratio of the alpha-acetyl-gamma-butyrolactone in the step (1) to the water in the step (2) is 1: (0.8-1.2); more preferably, the mass ratio of the α -acetyl- γ -butyrolactone in step (1) to the water in step (2) is 1: 1.
in some embodiments, the molar ratio between the cyclization feed and the second chlorine gas in step (4) is 1: (1-1.5); preferably, the molar ratio between the cyclized feed and the second chlorine gas in step (4) is 1: (1-1.3); more preferably, the molar ratio between the cyclized feed and the second chlorine gas in step (4) is 1: 1.1.
in some embodiments, the residual amount of α -acetyl- γ -butyrolactone by mass in step (2) is less than 0.5%.
The method for detecting the mass residual amount of α -acetyl- γ -butyrolactone in the step (2) is not particularly limited, and preferably, a gas chromatograph is used for the detection.
The method for detecting the mass residual quantity of the alpha-acetyl-gamma-butyrolactone in the step (2) of the invention has the following conditions:
1.1 instruments and reagents
Gas chromatograph: FID; a hue workstation; a chromatographic column: RTX-50.32 mm × 30m × 0.25Um chromatography column; microsyringe: 10 mu l of the mixture; dichloromethane: and (5) analyzing and purifying.
1.2 chromatographic operating conditions
Temperature of the column box: the initial temperature is 120 ℃, the holding time is 2min, the rising rate is 10 ℃/min, and the final temperature is 230 ℃; vaporization chamber temperature: 250 ℃; detection chamber temperature: 250 ℃; sample introduction amount: 0.2 μ l; the split ratio is as follows: 5:1.
In some embodiments, the residual amount of 3, 5-dichloro-2-pentanone in the 1-acetyl-1-chlorocyclopropane mixture in step (3) is less than 0.5% by mass.
The method for detecting the mass residual amount of 3, 5-dichloro-2-pentanone in the 1-acetyl-1-chlorocyclopropane mixed solution in the step (3) is not particularly limited, and preferably, the mass residual amount is detected by using a gas chromatograph.
The method for detecting the mass residual quantity of the 3, 5-dichloro-2-pentanone in the 1-acetyl-1-chlorocyclopropane mixed solution in the step (3) comprises the following conditions:
1.1 instruments and reagents
Gas chromatograph: FID; a hue workstation; a chromatographic column: RTX-50.32 mm × 30m × 0.25Um chromatography column; microsyringe: 10 mu l of the mixture; dichloromethane: and (5) analyzing and purifying.
1.2 chromatographic operating conditions
Gas phase conditions: temperature of the column box: the initial temperature is 80 ℃, the holding time is 2min, the rising speed is 40 ℃/min, and the final temperature is 250 ℃; vaporization chamber temperature: 260 ℃; detection chamber temperature: 260 ℃; carrier gas (N2) flow rate: 5 ml/min; hydrogen flow rate: 45 ml/min; air flow rate: 300 ml/min; sample introduction amount: 0.2 μ l; the split ratio is as follows: 5: 1;
in some embodiments, the content of 1-acetyl-1-chlorocyclopropane in the cyclized mass in step (3) is greater than 95 wt%; preferably, the content of 1-acetyl-1-chlorocyclopropane in the cyclized material in the step (3) is more than 97% by weight.
The method for detecting the content of 1-acetyl-1-chlorocyclopropane in the cyclized material in the step (3) is not particularly limited, and preferably, the content is detected by using a gas chromatograph.
The method for detecting the content of the 1-acetyl-1-chlorocyclopropane in the cyclized material in the step (3) in the invention has the following conditions:
1.1 instruments and reagents
Gas chromatograph: FID; a hue workstation; a chromatographic column: RTX-50.32 mm × 30m × 0.25Um chromatography column; microsyringe: 10 mu l of the mixture; dichloromethane: and (5) analyzing and purifying.
1.2 chromatographic operating conditions
Gas phase conditions: temperature of the column box: the initial temperature is 120 ℃, the holding time is 2min, the rising speed is 40 ℃/min, and the final temperature is 250 ℃; vaporization chamber temperature: 260 ℃; detection chamber temperature: 260 ℃; carrier gas (N2) flow rate: 5 ml/min; hydrogen flow rate: 45 ml/min; air flow rate: 300 ml/min; sample introduction amount: 0.2 μ l; the split ratio is as follows: 5: 1;
in some embodiments, the concentration of the alkali liquor in the step (3) is 25-35% by mass; preferably, the mass concentration of the alkali liquor in the step (3) is 30%.
In some embodiments, the lye is selected from at least one of aqueous sodium hydroxide, aqueous potassium carbonate, aqueous sodium carbonate; preferably, the alkali liquor is at least one of sodium hydroxide aqueous solution and potassium hydroxide aqueous solution; more preferably, the alkali liquor is an aqueous sodium hydroxide solution.
In some embodiments, the molar ratio between the α -acetyl- γ -butyrolactone, the solute in the alkaline solution, the solute in the hydrochloric acid solution is 1: (1.5-2.5): (0.1-0.5); preferably, the mole ratio of the alpha-acetyl-gamma-butyrolactone to the solute in the alkali liquor to the solute in the hydrochloric acid solution is 1: 1.5: 0.22.
in some embodiments, the concentration of the hydrochloric acid solution is 25-35%; more preferably, the concentration of the hydrochloric acid solution is 31%.
In some embodiments, the solvent is selected from the group consisting of dichloromethane, dichloroethane, chloroform, acetonitrile, ethylene glycol dimethyl ether, n-hexane, acetone, toluene, chlorobenzene, xylene, and combinations of one or more thereof; more preferably, the solvent is selected from one or more of dichloromethane, dichloroethane and chloroform; further preferably, the solvent is dichloromethane.
In some embodiments, the mass ratio of cyclized mass to solvent in step (4) is (1.5-2.5): 1; preferably, the mass ratio of the cyclized material to the solvent in the step (4) is 2: 1.
the present invention is specifically illustrated by the following examples, which are intended to be purely exemplary of the invention and are not to be construed as limiting the scope of the invention, and insubstantial modifications and adaptations of the invention, as would be apparent to those skilled in the art based on the teachings set forth herein, are intended to be covered thereby.
Example 1
A process for the production of 1-chloro-1' -chloroacetyl-cyclopropane, comprising at least the steps of:
(1) primary chlorination reaction: adding alpha-acetyl-gamma-butyrolactone into a reaction container, controlling the temperature to be 0 +/-1 ℃, and introducing first chlorine gas to obtain a chlorinated material for later use; the mol ratio of the alpha-acetyl-gamma-butyrolactone to the first chlorine gas is 1: 1;
(2) and (3) hydrolysis reaction: continuously adding water into the reaction container, controlling the temperature to be 75 +/-2 ℃, dropwise adding a hydrochloric acid solution into the reaction container, and keeping the temperature for 30 minutes after the completion to obtain a hydrolyzed material;
(3) ring closing reaction: controlling the temperature to be 75 +/-2 ℃, continuously dripping alkali liquor into the reaction container, keeping the temperature for 15 minutes after finishing dripping alkali liquor to obtain a 1-acetyl-1-chlorocyclopropane mixed solution, then standing for phase splitting, and taking an upper-layer material to obtain a cyclized material;
(4) and (3) secondary chlorination reaction: cooling the cyclized material to 23 +/-1 ℃, mixing the cyclized material with a solvent, introducing second chlorine, degassing and desolventizing after chlorine introduction is finished, and obtaining a chlorinated material.
The mass ratio of the alpha-acetyl-gamma-butyrolactone in the step (1) to the water in the step (2) is 1: 1.
the mol ratio of the cyclized material to the second chlorine gas in the step (4) is 1: 1.1.
the mass residual quantity of the alpha-acetyl-gamma-butyrolactone in the step (2) is less than 0.5%. The mass residual quantity of the 3, 5-dichloro-2-pentanone in the mixed solution of the 1-acetyl-1-chlorocyclopropane in the step (3) is less than 0.5 percent. The content of 1-acetyl-1-chlorocyclopropane in the cyclized material in the step (3) is more than 98 wt%.
And (3) the mass concentration of the alkali liquor in the step (3) is 30%, and the alkali liquor is a sodium hydroxide aqueous solution. The mol ratio of the alpha-acetyl-gamma-butyrolactone to the solute in the alkali liquor to the solute in the hydrochloric acid solution is 1: 1.5: 0.22. the concentration of the hydrochloric acid solution is 31%.
The solvent is dichloromethane, and the mass ratio of the cyclized material to the solvent in the step (4) is 2: 1.
example 2
A process for the production of 1-chloro-1' -chloroacetyl-cyclopropane, comprising at least the steps of:
(1) primary chlorination reaction: adding alpha-acetyl-gamma-butyrolactone into a reaction container, controlling the temperature to be minus 4 +/-1 ℃, and introducing first chlorine gas to obtain a chlorinated material for later use; the mol ratio of the alpha-acetyl-gamma-butyrolactone to the first chlorine gas is 1: 0.9;
(2) and (3) hydrolysis reaction: continuously adding water into the reaction container, controlling the temperature to be 60 +/-2 ℃, dropwise adding a hydrochloric acid solution into the reaction container, and after finishing, keeping the temperature for 25 minutes to obtain a hydrolyzed material;
(3) ring closing reaction: controlling the temperature to be 70 +/-2 ℃, continuously dripping alkali liquor into the reaction container, keeping the temperature for 10 minutes after finishing dripping alkali liquor to obtain a 1-acetyl-1-chlorocyclopropane mixed solution, then standing for phase splitting, and taking an upper-layer material to obtain a cyclized material;
(4) and (3) secondary chlorination reaction: cooling the cyclized material to 20 +/-1 ℃, mixing the cyclized material with a solvent, introducing second chlorine, degassing and desolventizing after chlorine introduction is finished, and obtaining a chlorinated material.
The mass ratio of the alpha-acetyl-gamma-butyrolactone in the step (1) to the water in the step (2) is 1: 0.8.
the mol ratio of the cyclized material to the second chlorine gas in the step (4) is 1: 1.
the mass residual quantity of the alpha-acetyl-gamma-butyrolactone in the step (2) is less than 0.5%. The mass residual quantity of the 3, 5-dichloro-2-pentanone in the mixed solution of the 1-acetyl-1-chlorocyclopropane in the step (3) is less than 0.5 percent. The content of 1-acetyl-1-chlorocyclopropane in the cyclized material in the step (3) was 96% by weight.
And (4) the mass concentration of the alkali liquor in the step (3) is 25%, and the alkali liquor is a potassium carbonate aqueous solution. The mol ratio of the alpha-acetyl-gamma-butyrolactone to the solute in the alkali liquor to the solute in the hydrochloric acid solution is 1: 1.5: 0.1. the concentration of the hydrochloric acid solution is 25%.
The solvent is dichloromethane, and the mass ratio of the cyclized material to the solvent in the step (4) is 1.5: 1.
example 3
A process for the production of 1-chloro-1' -chloroacetyl-cyclopropane, comprising at least the steps of:
(1) primary chlorination reaction: adding alpha-acetyl-gamma-butyrolactone into a reaction container, controlling the temperature to be minus 4 +/-1 ℃, and introducing first chlorine gas to obtain a chlorinated material for later use; the mol ratio of the alpha-acetyl-gamma-butyrolactone to the first chlorine gas is 1: 1.2;
(2) and (3) hydrolysis reaction: continuously adding water into the reaction container, controlling the temperature to be 80 +/-2 ℃, dropwise adding a hydrochloric acid solution into the reaction container, and after finishing, keeping the temperature for 40 minutes to obtain a hydrolyzed material;
(3) ring closing reaction: controlling the temperature to be 80 +/-2 ℃, continuously dripping alkali liquor into the reaction container, keeping the temperature for 20 minutes after finishing dripping alkali liquor to obtain a 1-acetyl-1-chlorocyclopropane mixed solution, then standing for phase splitting, and taking an upper-layer material to obtain a cyclized material;
(4) and (3) secondary chlorination reaction: cooling the cyclized material to 25 +/-1 ℃, mixing the cyclized material with a solvent, introducing second chlorine, degassing and desolventizing after chlorine introduction is finished, and obtaining a chlorinated material.
The mass ratio of the alpha-acetyl-gamma-butyrolactone in the step (1) to the water in the step (2) is 1: 1.2.
the mol ratio of the cyclized material to the second chlorine gas in the step (4) is 1: 1.3.
the mass residual quantity of the alpha-acetyl-gamma-butyrolactone in the step (2) is less than 0.5%. The mass residual quantity of the 3, 5-dichloro-2-pentanone in the mixed solution of the 1-acetyl-1-chlorocyclopropane in the step (3) is less than 0.5 percent. The content of 1-acetyl-1-chlorocyclopropane in the cyclized material in the step (3) is more than 97 wt%.
And (4) the mass concentration of the alkali liquor in the step (3) is 35%, and the alkali liquor is a potassium hydroxide aqueous solution. The mol ratio of the alpha-acetyl-gamma-butyrolactone to the solute in the alkali liquor to the solute in the hydrochloric acid solution is 1: 2.5: 0.5. the concentration of the hydrochloric acid solution is 25%.
The solvent is dichloromethane, and the mass ratio of the cyclized material to the solvent in the step (4) is 2.5: 1.
comparative example 1
A process for the production of 1-chloro-1' -chloroacetyl-cyclopropane, comprising at least the steps of:
(1) primary chlorination reaction: adding alpha-acetyl-gamma-butyrolactone into a reaction container, controlling the temperature to be 0 +/-1 ℃, and introducing sulfonyl chloride to obtain a chlorinated material for later use; the mol ratio of the alpha-acetyl-gamma-butyrolactone to the first chlorine gas is 1: 1;
(2) and (3) hydrolysis reaction: continuously adding water into the reaction container, controlling the temperature to be 75 +/-2 ℃, dropwise adding a hydrochloric acid solution into the reaction container, and keeping the temperature for 30 minutes after the completion to obtain a hydrolyzed material;
(3) ring closing reaction: controlling the temperature to be 75 +/-2 ℃, continuously dripping alkali liquor into the reaction container, keeping the temperature for 15 minutes after finishing dripping alkali liquor to obtain a 1-acetyl-1-chlorocyclopropane mixed solution, then standing for phase splitting, and taking an upper-layer material to obtain a cyclized material;
(4) and (3) secondary chlorination reaction: cooling the cyclized material to 23 +/-1 ℃, mixing the cyclized material with a solvent, introducing second chlorine, degassing and desolventizing after chlorine introduction is finished, and obtaining a chlorinated material.
The mass ratio of the alpha-acetyl-gamma-butyrolactone in the step (1) to the water in the step (2) is 1: 1.
the mol ratio of the cyclized material to the second chlorine gas in the step (4) is 1: 1.1.
and (3) the mass concentration of the alkali liquor in the step (3) is 30%, and the alkali liquor is a sodium hydroxide aqueous solution. The mol ratio of the alpha-acetyl-gamma-butyrolactone to the solute in the alkali liquor to the solute in the hydrochloric acid solution is 1: 1.5: 0.22. the concentration of the hydrochloric acid solution is 31%.
The solvent is dichloromethane, and the mass ratio of the cyclized material to the solvent in the step (4) is 2: 1.
comparative example 2
A process for the production of 1-chloro-1' -chloroacetyl-cyclopropane, comprising at least the steps of:
(1) primary chlorination reaction: adding alpha-acetyl-gamma-butyrolactone into a reaction container, controlling the temperature to be 0 +/-1 ℃, and introducing first chlorine gas to obtain a chlorinated material for later use; the mol ratio of the alpha-acetyl-gamma-butyrolactone to the first chlorine gas is 1: 1;
(2) and (3) hydrolysis reaction: continuously adding water into the reaction container, controlling the temperature to be 75 +/-2 ℃, dropwise adding a hydrochloric acid solution into the reaction container, and keeping the temperature for 30 minutes after the completion to obtain a hydrolyzed material;
(3) ring closing reaction: controlling the temperature to be 75 +/-2 ℃, continuously dripping alkali liquor into the reaction container, keeping the temperature for 15 minutes after finishing dripping alkali liquor to obtain a 1-acetyl-1-chlorocyclopropane mixed solution, then standing for phase splitting, and taking an upper-layer material to obtain a cyclized material;
(4) and (3) secondary chlorination reaction: cooling the cyclized material to 23 +/-1 ℃, mixing the cyclized material with a solvent, introducing second chlorine, degassing and desolventizing after chlorine introduction is finished, and obtaining a chlorinated material.
The mass ratio of the alpha-acetyl-gamma-butyrolactone in the step (1) to the water in the step (2) is 1: 1.
the mol ratio of the cyclized material to the second chlorine gas in the step (4) is 1: 1.1.
and (4) the mass concentration of the alkali liquor in the step (3) is 25%, and the alkali liquor is a sodium hydroxide aqueous solution. The mol ratio of the alpha-acetyl-gamma-butyrolactone to the solute in the alkali liquor to the solute in the hydrochloric acid solution is 1: 1.5: 0.22. the concentration of the hydrochloric acid solution is 31%.
The solvent is dichloromethane, and the mass ratio of the cyclized material to the solvent in the step (4) is 2: 1.
performance testing
The purity of the cyclized material obtained in step (3) in examples 1 to 5 was measured, that is, the content of 1-acetyl-1-chlorocyclopropane in the cyclized material was measured, and the residual amount of 1-acetyl-1-chlorocyclopropane in step (4) was measured, and the measurement results are shown in table 1, and the measurement methods were as follows:
(1) method for analyzing purity of cyclized material in step (3)
1.1 instruments and reagents
Gas chromatograph: FID; a hue workstation; a chromatographic column: RTX-50.32 mm × 30m × 0.25Um chromatography column; microsyringe: 10 mu l of the mixture; dichloromethane: and (5) analyzing and purifying.
1.2 chromatographic operating conditions: temperature of the column box: the initial temperature is 120 ℃, the holding time is 2min, the rising speed is 40 ℃/min, and the final temperature is 250 ℃; vaporization chamber temperature: 260 ℃; detection chamber temperature: 260 ℃; carrier gas (N2) flow rate: 5 ml/min; hydrogen flow rate: 45 ml/min; air flow rate: 300 ml/min; sample introduction amount: 0.2 μ l; the split ratio is as follows: 5:1.
(2) Method for analyzing residual quantity of 1-acetyl-1-chlorocyclopropane in step (4)
1.1 instruments and reagents
Gas chromatograph: FID; a hue workstation; a chromatographic column: RTX-50.32 mm × 30m × 0.25Um chromatography column; microsyringe: 10 mu l of the mixture; dichloromethane: and (5) analyzing and purifying.
1.2 chromatographic operating conditions; temperature of the column box: the initial temperature is 80 ℃, the holding time is 2min, the rising speed is 40 ℃/min, and the final temperature is 250 ℃; vaporization chamber temperature: 260 ℃; detection chamber temperature: 260 ℃; carrier gas (N2) flow rate: 5 ml/min; hydrogen flow rate: 45 ml/min; air flow rate: 300 ml/min; sample introduction amount: 0.2 μ l; the split ratio is as follows: 5:1.
TABLE 1 Performance test results
Figure BDA0002509367470000121
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in other forms, and any person skilled in the art may modify or change the technical content disclosed above into an equivalent embodiment with equivalent changes, but all those simple modifications, equivalent changes and modifications made on the above embodiment according to the technical spirit of the present invention still belong to the protection scope of the present invention.

Claims (10)

1. A process for the production of 1-chloro-1' -chloroacetyl-cyclopropane, comprising at least the steps of:
(1) primary chlorination reaction: adding alpha-acetyl-gamma-butyrolactone into a reaction container, and introducing first chlorine gas to obtain a chlorinated material; the mol ratio of the alpha-acetyl-gamma-butyrolactone to the first chlorine gas is 1: (0.8-1.5);
(2) and (3) hydrolysis reaction: continuously adding water into the reaction container, adding a hydrochloric acid solution into the reaction container, and obtaining a hydrolyzed material after the reaction is finished;
(3) ring closing reaction: continuously adding alkali liquor into the reaction container to obtain a 1-acetyl-1-chlorocyclopropane mixed solution, then standing for phase splitting, and taking an upper-layer material to obtain a cyclized material;
(4) and (3) secondary chlorination reaction: and mixing the cyclized material with a solvent, introducing second chlorine, reacting, and performing aftertreatment to obtain the catalyst.
2. The process for producing 1-chloro-1' -chloroacetyl-cyclopropane according to claim 1, wherein the mass ratio of the α -acetyl- γ -butyrolactone in the step (1) to the water in the step (2) is 1: (0.5-1.5).
3. The process for producing 1-chloro-1' -chloroacetyl-cyclopropane according to claim 1, wherein the molar ratio between the cyclized feed and the second chlorine gas in step (4) is 1: (1-1.5).
4. The process for producing 1-chloro-1' -chloroacetyl-cyclopropane according to claim 1, wherein the α -acetyl- γ -butyrolactone in step (2) has a residual amount by mass of less than 0.5%.
5. The process for producing 1-chloro-1' -chloroacetyl-cyclopropane according to claim 1, wherein the residual amount by mass of 3, 5-dichloro-2-pentanone in the mixed solution of 1-acetyl-1-chlorocyclopropane in step (3) is less than 0.5%.
6. The process for producing 1-chloro-1' -chloroacetyl-cyclopropane according to claim 1, wherein the content of 1-acetyl-1-chlorocyclopropane in the cyclized material in the step (3) is more than 95% by weight.
7. The process for producing 1-chloro-1' -chloroacetyl-cyclopropane according to claim 1, wherein the concentration of the alkali solution in the step (3) is 25 to 35% by mass.
8. The process for producing 1-chloro-1' -chloroacetyl-cyclopropane according to claim 1 or 7, wherein the molar ratio between α -acetyl- γ -butyrolactone, solute in the alkali solution, solute in the hydrochloric acid solution is 1: (1.5-2.5): (0.1-0.5).
9. The process for producing 1-chloro-1' -chloroacetyl-cyclopropane of claim 1, wherein the solvent is selected from the group consisting of dichloromethane, dichloroethane, chloroform, acetonitrile, ethylene glycol dimethyl ether, n-hexane, acetone, toluene, chlorobenzene, xylene, and combinations thereof.
10. The process for producing 1-chloro-1' -chloroacetyl-cyclopropane according to claim 1 or 7, wherein the alkali solution is at least one selected from the group consisting of an aqueous sodium hydroxide solution, an aqueous potassium carbonate solution and an aqueous sodium carbonate solution.
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