CN114685253A - Preparation method of prothioconazole intermediate 3, 5-dichloro-2-pentanone - Google Patents
Preparation method of prothioconazole intermediate 3, 5-dichloro-2-pentanone Download PDFInfo
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- NOSBOKVYSXXKFL-UHFFFAOYSA-N 3,5-dichloropentan-2-one Chemical compound CC(=O)C(Cl)CCCl NOSBOKVYSXXKFL-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 238000002360 preparation method Methods 0.000 title claims abstract description 38
- MNHVNIJQQRJYDH-UHFFFAOYSA-N 2-[2-(1-chlorocyclopropyl)-3-(2-chlorophenyl)-2-hydroxypropyl]-1,2-dihydro-1,2,4-triazole-3-thione Chemical compound N1=CNC(=S)N1CC(C1(Cl)CC1)(O)CC1=CC=CC=C1Cl MNHVNIJQQRJYDH-UHFFFAOYSA-N 0.000 title claims abstract description 10
- 239000005825 Prothioconazole Substances 0.000 title claims abstract description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 77
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims abstract description 67
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims abstract description 67
- OMQHDIHZSDEIFH-UHFFFAOYSA-N 3-Acetyldihydro-2(3H)-furanone Chemical compound CC(=O)C1CCOC1=O OMQHDIHZSDEIFH-UHFFFAOYSA-N 0.000 claims abstract description 50
- 238000005660 chlorination reaction Methods 0.000 claims abstract description 47
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000000034 method Methods 0.000 claims abstract description 36
- CYCRRRIREKXQTK-UHFFFAOYSA-N 3-acetyl-3-chlorooxolan-2-one Chemical compound CC(=O)C1(Cl)CCOC1=O CYCRRRIREKXQTK-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000006114 decarboxylation reaction Methods 0.000 claims abstract description 21
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000007142 ring opening reaction Methods 0.000 claims abstract description 17
- 239000012043 crude product Substances 0.000 claims abstract description 16
- 239000000047 product Substances 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims description 76
- 239000007789 gas Substances 0.000 claims description 48
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 27
- 239000000460 chlorine Substances 0.000 claims description 27
- 229910052801 chlorine Inorganic materials 0.000 claims description 27
- 230000015572 biosynthetic process Effects 0.000 claims description 15
- 238000003786 synthesis reaction Methods 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 14
- 239000012074 organic phase Substances 0.000 claims description 13
- 238000004821 distillation Methods 0.000 claims description 10
- 239000008346 aqueous phase Substances 0.000 claims description 6
- 239000012295 chemical reaction liquid Substances 0.000 claims description 6
- 238000010907 mechanical stirring Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 238000009776 industrial production Methods 0.000 abstract description 5
- 238000000926 separation method Methods 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 238000005580 one pot reaction Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 description 16
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 8
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- 238000009835 boiling Methods 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000004321 preservation Methods 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 150000007517 lewis acids Chemical class 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 239000002841 Lewis acid Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000003444 phase transfer catalyst Substances 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- 229960000583 acetic acid Drugs 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000012320 chlorinating reagent Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000011968 lewis acid catalyst Substances 0.000 description 1
- 238000010606 normalization Methods 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000001256 steam distillation Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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- 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
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/41—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by hydrogenolysis or reduction of carboxylic groups or functional derivatives thereof
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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
- C07C51/09—Preparation of carboxylic acids or their salts, halides or anhydrides from carboxylic acid esters or lactones
Abstract
The invention provides a preparation method of a prothioconazole intermediate 3, 5-dichloro-2-pentanone. The preparation method comprises the following steps: and carrying out chlorination reaction on the alpha-acetyl-gamma-butyrolactone and chlorine gas under the solvent-free condition to obtain a crude product of the alpha-chloro-alpha-acetyl-gamma-butyrolactone, then carrying out ring-opening and chlorination reaction on the crude product of the alpha-chloro-alpha-acetyl-gamma-butyrolactone in the presence of water and hydrogen chloride, and then carrying out decarboxylation reaction to obtain the 3, 5-dichloro-2-pentanone. The invention adopts a one-pot method to perform chlorination reaction under the condition of no solvent, directly adds catalytic amount of water after the chlorination reaction is finished, can directly perform the next operation without separation, and obtains the target product through ring opening, chlorination and decarboxylation reactions. The preparation method has the advantages of simple process, easy operation, high yield, low cost, economy and environmental protection, and is suitable for industrial production.
Description
Technical Field
The invention belongs to the field of fine chemical engineering, and relates to a preparation method of a prothioconazole intermediate 3, 5-dichloro-2-pentanone.
Background
3, 5-dichloro-2-pentanone is an important intermediate for synthesizing medicines and pesticides, and particularly is a key intermediate for developing the bactericide prothioconazole by Bayer.
At present, the mainstream synthetic route reported in the literature is to use alpha-acetyl-gamma-butyrolactone as a raw material, chlorinate the raw material with chlorine (or sulfonyl chloride), and then perform (or in the presence of lewis acid and a phase transfer catalyst) chlororing opening and decarboxylation reactions on the raw material and hydrochloric acid (or glacial acetic acid as a solvent) to obtain a mixture of 3, 5-dichloro-2-pentanone and hydrochloric acid, wherein the amount of tar is large, and a pure product of 3, 5-dichloro-2-pentanone needs to be obtained by further distillation or steam distillation. The disclosed process has a series of problems of complex flow, high energy consumption, high raw material cost, no good comprehensive utilization of byproducts, large tar yield and the like, and obviously influences the large-scale production of the intermediate.
For example, CN104292089A discloses that in the preparation of α -chloro- α -acetyl- γ -butyrolactone, sulfonyl chloride is reacted with α -acetyl- γ -butyrolactone to prepare α -chloro- α -acetyl- γ -butyrolactone, then reduced pressure distillation is performed to remove a small amount of sulfonyl chloride and residual acid gas, and the crude product is directly used in the next reaction. The method has high cost of raw materials, produces a large amount of byproduct sulfur dioxide, cannot effectively utilize byproduct hydrogen chloride, and increases the environmental protection pressure. In the subsequent chlorination and decarboxylation processes, acetic acid is used as a solvent, the yield is about 88%, and the production cost is high.
CN106565441A discloses that alpha-chloro-alpha-acetyl-gamma-butyrolactone is prepared by a sulfonyl chloride method, and the alpha-chloro-alpha-acetyl-gamma-butyrolactone reacts with hot hydrochloric acid in the presence of Lewis acid and a phase transfer catalyst, and is subjected to reduced pressure distillation to obtain 3, 5-dichloro-2-pentanone. The method simultaneously uses sulfonyl chloride, Lewis acid and other raw materials, thereby not only increasing the production cost, but also greatly increasing the difficulty of wastewater treatment.
CN109265329A discloses the use of sulfonyl chloride method to prepare α -chloro- α -acetyl- γ -butyrolactone, which directly reacts with water, hydrochloric acid, etc. without reduced pressure distillation and low boiling point to obtain a mixture of 3, 5-dichloro-2-pentanone and hydrochloric acid, and then the mixture is subjected to solvent extraction and distillation separation to obtain 3, 5-dichloro-2-pentanone. The method avoids using a large amount of acetic acid as a solvent and partially utilizes hydrogen chloride generated by the reaction, but the scheme needs to add water which is 0.1 to 10 times of the weight of the alpha-acetyl-gamma-butyrolactone to enter a reaction system, extract a crude product by using an organic solvent after the reaction is finished, and further distill to obtain the 3, 5-dichloro-2-pentanone. The scheme has the problems of high cost, large amount of sulfur dioxide and waste acid water generation, and the like when sulfonyl chloride is used.
Therefore, the preparation method of the 3, 5-dichloro-2-pentanone, which is simple in process, economic, environment-friendly and suitable for industrial production, has important significance in the field.
Disclosure of Invention
In view of the problems in the prior art, the invention aims to provide a preparation method of prothioconazole intermediate 3, 5-dichloro-2-pentanone. The preparation method solves the problems of complex process, large amount of waste acid water, high raw material cost and the like in the technology for preparing 3, 5-dichloro-2-pentanone in the prior art, and has the advantages of short process flow, more economy and environmental protection and suitability for industrial production.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a preparation method of a prothioconazole intermediate 3, 5-dichloro-2-pentanone, which comprises the following steps: performing chlorination reaction on the alpha-acetyl-gamma-butyrolactone and chlorine under the solvent-free condition to obtain a crude product of the alpha-chlorine-alpha-acetyl-gamma-butyrolactone;
then, the crude product of the alpha-chlorine-alpha-acetyl-gamma-butyrolactone is subjected to ring opening and chlorination reaction in the presence of water and hydrogen chloride, and then subjected to decarboxylation reaction to obtain the 3, 5-dichloro-2-pentanone;
the reaction occurring in the preparation process of 3, 5-dichloro-2-pentanone is represented by formula I:
the invention adopts a one-pot method to react chlorine with alpha-acetyl-gamma-butyrolactone under the condition of no solvent to obtain a crude product of alpha-chlorine-alpha-acetyl-gamma-butyrolactone, an organic solvent is not needed in the step, a catalytic amount of water is directly added after the chlorination reaction is finished, and the next step of operation can be directly carried out without separation after the water is added; and (3) carrying out ring opening, chlorination and decarboxylation on the alpha-chloro-alpha-acetyl-gamma-butyrolactone crude product in the presence of catalytic water and hydrogen chloride to obtain a prothioconazole intermediate 3, 5-dichloro-2-pentanone.
In the invention, the target product is obtained by the steps of chlorination, ring-opening decarboxylation and the like of the alpha-acetyl-gamma-butyrolactone, and the method has the advantages of simple process, easy operation and higher yield; the chlorine with lower price is used as the chlorinating agent, so that the raw material cost is greatly reduced, and the comprehensive utilization of the chlorine element is realized; meanwhile, sulfuryl chloride is avoided, and sulfur dioxide is not generated. The target product is prepared by the method, and a solvent is not required to be adopted for extraction in the post-treatment process, so that the separation process of the solvent is avoided, the flow is simpler, and the energy consumption in the production process is obviously reduced.
In order to increase the yield of 3, 5-dichloro-2-pentanone and reduce the consumption of raw materials, a preferred embodiment of the present invention is that in the chlorination reaction, the molar ratio of the α -acetyl- γ -butyrolactone to chlorine gas is 1 (1 to 1.5), and may be, for example, 1:1, 1:1.02, 1:1.05, 1:1.1, 1:1.2, 1:1.25, 1:3, 1:35, 1:4, 1:45, or 1: 5; preferably 1 (1-1.05).
Preferably, the time of the chlorination reaction is 0.5 to 8 hours, for example, 0.5 hour, 1 hour, 1.5 hour, 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours, 5 hours, 5.5 hours, 6 hours, 6.5 hours, 7 hours, 7.5 hours or 8 hours, and preferably 2 to 4 hours.
Preferably, the temperature of the chlorination reaction is 0 to 60 ℃, for example, 0 ℃,5 ℃, 10 ℃, 15 ℃, 20 ℃, 30 ℃, 40 ℃, 50 ℃ or 60 ℃, preferably 0 to 20 ℃. Under the preferred chlorination reaction conditions, α -chloro- α -acetyl- γ -butyrolactone can be obtained in higher yields.
As a preferred technical scheme of the invention, the mixing mode of the alpha-acetyl-gamma-butyrolactone and chlorine gas comprises the following steps: chlorine gas is introduced into the alpha-acetyl-gamma-butyrolactone and/or the alpha-acetyl-gamma-butyrolactone and chlorine gas are introduced into the reactor through a mixer, preferably the chlorine gas is introduced into the alpha-acetyl-gamma-butyrolactone for mixing.
Preferably, the time for introducing the chlorine gas is maintained for 0.5 to 8 hours, for example, 0.5 hour, 1 hour, 1.5 hour, 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours, 5 hours, 5.5 hours, 6 hours, 6.5 hours, 7 hours, 7.5 hours or 8 hours, and preferably 2 to 4 hours.
In the invention, the chlorination reaction process is shown as formula II:
in a preferred embodiment of the present invention, the molar ratio of water to α -acetyl- γ -butyrolactone is (0.1 to 1: 1), and may be, for example, 0.1:1, 0.2:1, 0.3:1, 0.4:1, 0.5:1, 0.6:1, 0.7:1, 0.8:1, 0.9:1, or 1: 1; preferably (0.2-0.8): 1.
Preferably, the hydrogen chloride comprises hydrogen chloride derived from crude alpha-chloro-alpha-acetyl-gamma-butyrolactone and/or hydrogen chloride introduced into the reaction system.
Preferably, the molar ratio of the hydrogen chloride to the alpha-acetyl-gamma-butyrolactone in the crude alpha-chloro-alpha-acetyl-gamma-butyrolactone product is (1.0-1.05): 1. In the preparation method, the molar ratio of the hydrogen chloride byproduct of the chlorination reaction to the alpha-acetyl-gamma-butyrolactone is (1.0-1.05):1, wherein about 40% of the hydrogen chloride remains in the system, and about 60% of the hydrogen chloride escapes from the system, and the escaped hydrogen chloride is directly used in the process of introducing the hydrogen chloride, thereby realizing the recycling of resources.
The byproduct hydrogen chloride can be used for synthesizing 3, 5-dichloro-2-pentanone after being collected by a tail gas collecting device, and in the actual production, tail gas can be introduced into a material system which is subjected to chlorine introduction and water addition for reaction in the synthesis process of alpha-chlorine-alpha-acetyl-gamma-butyrolactone.
Preferably, the molar ratio of the hydrogen chloride to the alpha-acetyl-gamma-butyrolactone introduced into the reaction system is (0.2-5.0): 1, and may be, for example, 0.2:1, 0.5:1, 0.8:1, 1:1, 1.5:1, 2:1, 2.5:1, 3:1, 3.5:1, 4:1, 4.5:1 or 5: 1; preferably (0.4-2.0) 1; more preferably (0.6-1.4): 1.
In order to further improve the yield of 3, 5-dichloro-2-pentanone and the utilization rate of hydrogen chloride, the time for introducing hydrogen chloride is preferably 1 to 20 hours, for example, 1 hour, 2 hours, 2.5 hours, 3 hours, 5 hours, 6 hours, 6.5 hours, 7 hours, 7.5 hours, 9 hours, 9.5 hours, 11 hours, 12 hours, 15 hours, 18 hours, or 20 hours, preferably 2 to 10 hours, and more preferably 4 to 8 hours.
In the invention, in the reaction process of preparing 3, 5-dichloro-2-pentanone from the crude product of alpha-chloro-alpha-acetyl-gamma-butyrolactone, the temperature control is divided into two stages; the temperature of the reaction system when the hydrogen chloride is introduced is 0 to 120 ℃, and may be, for example, 0 ℃,5 ℃, 10 ℃, 15 ℃, 20 ℃, 25 ℃, 30 ℃, 40 ℃, 50 ℃, 55 ℃, 60 ℃, 70 ℃, 80 ℃, 100 ℃, 110 ℃ or 120 ℃, preferably 20 to 60 ℃, and more preferably 30 to 50 ℃.
After the hydrogen chloride is introduced, the method further comprises heating the reaction system to 40-120 deg.C, such as 40 deg.C, 50 deg.C, 60 deg.C, 65 deg.C, 70 deg.C, 75 deg.C, 80 deg.C, 85 deg.C, 90 deg.C, 95 deg.C, 100 deg.C, 110 deg.C or 120 deg.C, preferably 60-90 deg.C.
In the invention, the process of the ring opening and the chlorination reaction is shown as a formula III:
preferably, the temperature of the ring-opening and chlorination reactions is the same as the temperature of the reaction system when hydrogen chloride is introduced, and is 0 to 120 ℃, and for example, may be 0 ℃,5 ℃, 10 ℃, 15 ℃, 20 ℃, 25 ℃, 30 ℃, 40 ℃, 50 ℃, 55 ℃, 60 ℃, 70 ℃, 80 ℃, 100 ℃, 110 ℃ or 120 ℃, preferably 20 to 60 ℃, and more preferably 30 to 50 ℃.
Preferably, the decarboxylation reaction is as shown in formula IV:
preferably, the decarboxylation reaction is carried out at a temperature after the reaction system is raised after the hydrogen chloride introduction is completed, specifically 40 to 120 ℃, and for example, 40 ℃, 50 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃, 95 ℃, 100 ℃, 110 ℃ or 120 ℃, preferably 60 to 90 ℃.
In the step, the ring-opening, decarboxylation and chlorination are carried out by adding catalytic amount of water into the chloride and introducing hydrogen chloride, so that the use of Lewis acid or phase transfer catalyst is avoided.
Preferably, the preparation method further comprises an operation of collecting the off-gas generated by the chlorination reaction.
Preferably, the off-gas produced by the chlorination reaction comprises hydrogen chloride.
Preferably, the preparation method further comprises the operations of standing for layering and separating an aqueous phase and an organic phase after the ring opening, the chlorination and the decarboxylation reaction are finished. The method is direct, and can obtain the crude product of the 3, 5-dichloro-2-pentanone and the water phase with a catalytic amount by directly layering without introducing other organic solvents after the chlorination reaction.
In the invention, the obtained water phase can be used as the water added in the step (2) to enter the reaction system again, and the water is not consumed in the whole process, and water is not generated, so that the water phase can be directly used in the next batch of ring-opening, decarboxylation and chlorination reactions without treatment.
Preferably, the organic phase is subjected to reduced pressure distillation to obtain the 3, 5-dichloro-2-pentanone.
As a preferable technical scheme of the invention, the preparation method comprises the following steps:
(1) synthesis of α -chloro- α -acetyl- γ -butyrolactone: adding alpha-acetyl-gamma-butyrolactone into a reaction bottle provided with a mechanical stirring device, a thermometer and a tail gas trapping device, introducing chlorine gas, and completing the introduction for 2-5 hours, wherein the molar ratio of the alpha-acetyl-gamma-butyrolactone to the chlorine gas is 1 (1-1.5);
after chlorine introduction is finished, preserving heat for 0.5-8 h at 0-60 ℃ until chlorination reaction is finished, and collecting tail gas generated by chlorination reaction to obtain a crude product of alpha-chlorine-alpha-acetyl-gamma-butyrolactone and hydrogen chloride gas;
wherein the chlorination reaction process is shown as formula II:
(2) synthesis of 3, 5-dichloro-2-pentanone: adding water into the reaction liquid obtained in the step (1), introducing hydrogen chloride gas at 0-120 ℃, keeping the temperature for 0.5-2 hours to perform ring opening and chlorination reaction after the hydrogen chloride gas is introduced for 1-20 hours, wherein the reaction process is shown as a formula III:
and then, heating to 40-120 ℃, and carrying out decarboxylation reaction at the temperature for 1-5 hours, wherein the reaction process is shown as a formula IV:
and (3) standing and layering after the reaction is finished, separating an aqueous phase and an organic phase, wherein the aqueous phase is used as water added in the step (2) and re-enters the reaction system, and the organic phase is subjected to reduced pressure distillation to obtain the 3, 5-dichloro-2-pentanone.
Illustratively, the preparation method of the invention can be carried out by adopting the following steps:
(1) synthesis of alpha-chloro-alpha-acetyl-gamma-butyrolactone
Adding alpha-acetyl-gamma-butyrolactone (1.0eq) into a four-mouth reaction bottle provided with a mechanical stirrer, a thermometer and a tail gas trapping device, and cooling to 0 ℃; starting to introduce chlorine gas (1-1.05 eq), controlling the temperature to be not more than 5 ℃ and completing the introduction for about 3-4 hours; after chlorine introduction is finished, continuously preserving heat for 1-2 h, and finishing the reaction;
weighing the obtained alpha-chlorine-alpha-acetyl-gamma-butyrolactone crude product, wherein a certain amount of HCl is contained, and then directly entering the reaction of the next step without transferring materials; in addition, HCl gas obtained by collecting tail gas can be directly used for the next reaction;
(2) synthesis of 3, 5-dichloro-2-pentanone
Adding water (0.1-1 eq) into the reaction system, slowly heating to 20-60 ℃, wherein the heating speed is preferably no gas escapes from the system;
then, slowly introducing hydrogen chloride (0.2-5.0 eq) for about 3-4 hours, and then continuing to perform heat preservation reaction for 1 hour (the tail gas trapping device collects hydrogen chloride gas and can be directly used for the next reaction);
slowly heating to 40-120 ℃, and reacting for 1-3 h in a heat preservation way;
standing and layering after the reaction is finished, and separating out water (containing a small amount of 3, 5-dichloro-2-pentanone) which can be directly applied to the next 3, 5-dichloro-2-pentanone reaction; and distilling the organic phase under reduced pressure to obtain the 3, 5-dichloro-2-pentanone, wherein the yield is calculated according to the alpha-acetyl-gamma-butyrolactone.
The recitation of numerical ranges herein includes not only the above-recited values, but also any values between any of the above-recited numerical ranges not recited, and for brevity and clarity, is not intended to be exhaustive of the specific values encompassed within the range.
Compared with the prior art, the invention has at least the following beneficial effects:
(1) according to the preparation method of the prothioconazole intermediate 3, 5-dichloro-2-pentanone, alpha-acetyl-gamma-butyrolactone and chlorine are used as raw materials, chlorine is used as a chlorinating agent to replace sulfonyl chloride, so that comprehensive utilization of chlorine is realized, sulfur dioxide is not generated, and the raw material cost and the three wastes are remarkably reduced; meanwhile, the intermediate product is added with catalytic amount of water and introduced with hydrogen chloride to carry out ring-opening, decarboxylation and chlorination, so that Lewis acid and a phase transfer catalyst are avoided, a solvent is not required for extraction in the post-treatment, the separation process of the solvent is avoided, the process is simpler, and the energy consumption in the production process is obviously reduced;
(2) according to the method, only a small amount of water is added as a catalyst for the reaction, the byproduct hydrogen chloride, acidic water and the like are well utilized, a large amount of waste acid water is not generated, the problem of wastewater treatment in the preparation of 3, 5-dichloro-2-pentanone in the prior art can be solved, the raw materials can be fully utilized, the production cost is reduced, and the method is economical, environment-friendly and suitable for industrial production.
Drawings
FIG. 1 is a schematic diagram of the synthetic route of the process for preparing 3, 5-dichloro-2-pentanone described in the present invention.
FIG. 2 is a gas-phase normalized graph of the product obtained in example 1.
Detailed Description
The technical solutions of the present invention are further described in the following embodiments with reference to the drawings, but the following examples are only simple examples of the present invention and do not represent or limit the scope of the present invention, which is defined by the claims.
In the following examples, unless otherwise specified, reagents and consumables were purchased from conventional reagent manufacturers in the field; unless otherwise indicated, all experimental methods and technical means used are those conventional in the art.
Example 1
The embodiment provides a preparation method of 3, 5-dichloro-2-pentanone, which specifically comprises the following steps:
(1) synthesis of alpha-chloro-alpha-acetyl-gamma-butyrolactone
Adding 128.8g of alpha-acetyl-gamma-butyrolactone (1.0mol, 99.5 percent, 1.0eq) into a 500mL four-mouth reaction bottle provided with a mechanical stirring device, a thermometer and a tail gas trapping device, and cooling to 0 ℃;
beginning to introduce 74.5g of chlorine (1.05mol, 99.9 percent, 1.05eq), controlling the temperature to be not more than 5 ℃, and finishing the introduction for 3 hours; after the chlorine introduction is finished, continuously preserving the heat for 1h to finish the reaction;
weighing to obtain 178.4g of reaction liquid (containing 13.4g of HCl and 1.0mol of alpha-chloro-alpha-acetyl-gamma-butyrolactone), and directly carrying out the next reaction without material transfer;
24.9g (0.68mol, 99.0%) of HCl gas is collected by a tail gas trapping device and can be directly used for the next reaction;
(2) synthesis of 3, 5-dichloro-2-pentanone
Adding 9.0g of water (0.5mol, 99.9 percent and 0.5eq) into the reaction system, slowly heating to 40 ℃, and no gas escapes from the system when the temperature is raised;
then, about 40g of hydrogen chloride (1.1mol, 99.0%, 1.1eq) was slowly passed in and over for 3 h; the reaction is continued for 1 hour (15.0 g of hydrogen chloride gas is collected by using a tail gas trapping device and can be directly used for the next batch of reaction), then the temperature is slowly increased to 80 ℃, and the reaction is kept for 2 hours;
standing and layering after the reaction is finished, and separating 9.1g of water (containing a small amount of 3, 5-dichloro-2-pentanone) which can be directly applied to the next 3, 5-dichloro-2-pentanone reaction;
the organic phase was subjected to vacuum distillation to obtain 151.8g of 3, 5-dichloro-2-pentanone (boiling range 71-72 ℃ C., 10mmHg), the content of which was 97.0%, in terms of α -acetyl- γ -butyrolactone, the yield was 95.0%.
The above steps can be represented by fig. 1, that is, after the raw material alpha-acetyl-gamma-butyrolactone is mixed with chlorine gas, the raw material alpha-acetyl-gamma-butyrolactone is subjected to chlorination reaction to obtain alpha-chloro-alpha-acetyl-gamma-butyrolactone; the alpha-chlorine-alpha-acetyl-gamma-butyrolactone is mixed with introduced hydrogen chloride, under the action of catalytic amount of water, the ring is opened and chlorination reaction is carried out, then the temperature is raised for decarboxylation reaction, and CO is released2。
The nuclear magnetic resonance hydrogen spectrum data of the obtained product are as follows:1H NMR(600MHz,CDCl3)：δ＝2.13-2.20(m，1H)，2.31(s，3H)，2.34-2.38(m，1H)，3.63-3.69(m，2H)，4.50(dd,J＝4.3、9.4Hz,1H)ppm.
the gas phase normalization diagram is shown in FIG. 2, wherein the retention time of 3, 5-dichloro-2-pentanone is 2.795min and the content is 97.0%, the other peak is an impurity peak, and the retention time is 3.047 min.
Example 2
The embodiment provides a preparation method of 3, 5-dichloro-2-pentanone, which specifically comprises the following steps:
(1) synthesis of alpha-chloro-alpha-acetyl-gamma-butyrolactone
Adding 128.8g of alpha-acetyl-gamma-butyrolactone (1.0mol, 99.5 percent, 1.0eq) into a 500mL four-mouth reaction bottle provided with a mechanical stirring device, a thermometer and a tail gas trapping device, and cooling to 0 ℃;
introducing 78.1g of chlorine (1.1mol, 99.9 percent and 1.05eq) at the beginning, controlling the temperature to be not more than 5 ℃, and finishing the introduction for 4 hours; after the chlorine introduction is finished, continuously preserving the heat for 1h to finish the reaction;
weighing to obtain 180.0g of reaction liquid (containing 13.4g of HCl and 1.0mol of alpha-chloro-alpha-acetyl-gamma-butyrolactone), and directly carrying out the next reaction without material transfer;
collecting tail gas to obtain 26.9g (0.73mol, 99.0%) of HCl gas, which can be directly used for the next reaction;
(2) synthesis of 3, 5-dichloro-2-pentanone
Adding 9.0g of water (0.5mol, 99.9 percent and 0.5eq) into the reaction system, slowly heating to 40 ℃, and no gas escapes from the system when the temperature is raised;
then about 40g of hydrogen chloride (1.1mol, 99.0%, 1.1eq) was slowly passed in over 4 h; the reaction is continued for 1h under heat preservation (15.0 g of hydrogen chloride gas is collected by a tail gas trapping device and can be directly used for the next reaction), and then the temperature is slowly increased to 80 ℃ for 2h under heat preservation;
standing and layering after the reaction is finished, and separating 9.0g of water (containing a small amount of 3, 5-dichloro-2-pentanone) which can be directly applied to the next 3, 5-dichloro-2-pentanone reaction;
the organic phase was subjected to vacuum distillation to obtain 142.3g of 3, 5-dichloro-2-pentanone (boiling range 71-72 ℃ C., 10mmHg), the content of which was 96.5%, based on α -acetyl- γ -butyrolactone, and the yield was 88.6%.
Example 3
The embodiment provides a preparation method of 3, 5-dichloro-2-pentanone, which specifically comprises the following steps:
(1) synthesis of alpha-chloro-alpha-acetyl-gamma-butyrolactone
Adding 128.8g of alpha-acetyl-gamma-butyrolactone (1.0mol, 99.5 percent, 1.0eq) into a 500mL four-mouth reaction bottle provided with a mechanical stirring device, a thermometer and a tail gas trapping device, and cooling to 0 ℃;
beginning to introduce 74.5g of chlorine (1.05mol, 99.9 percent, 1.05eq), controlling the temperature to be not more than 5 ℃, and finishing the introduction for 4 hours; after the chlorine introduction is finished, continuously preserving the heat for 1h to finish the reaction;
weighing to obtain 178.5g of reaction liquid (containing 13.4g of HCl and 1.0mol of alpha-chloro-alpha-acetyl-gamma-butyrolactone), and directly carrying out the next reaction without material transfer;
collecting tail gas to obtain 24.9g (0.68mol, 99.0%) of HCl gas;
(2) synthesis of 3, 5-dichloro-2-pentanone
Adding 9.0g of water (0.5mol, 99.9 percent and 0.5eq) into the reaction system, slowly heating to 50 ℃, and no gas escapes from the system when the temperature is raised;
then about 40g of hydrogen chloride (1.1mol, 99.0%, 1.1eq) was slowly passed in over for 3.5 h; then the reaction is continued for 1h (16.5 g of hydrogen chloride gas is collected by the tail gas trapping device and can be directly used for the next reaction); then slowly heating to 75 ℃ and reacting for 2h under the condition of heat preservation;
standing and layering after the reaction is finished, and separating 9.2g of water (containing a small amount of 3, 5-dichloro-2-pentanone) which can be directly applied to the next 3, 5-dichloro-2-pentanone reaction;
the organic phase is subjected to reduced pressure distillation to obtain 145.5g of 3, 5-dichloro-2-pentanone (the boiling range is 71-72 ℃ and the boiling range is 10mmHg), the content of the 3, 5-dichloro-2-pentanone is 96.0 percent, and the yield is 90.1 percent based on the alpha-acetyl-gamma-butyrolactone.
Example 4
The embodiment provides a preparation method of 3, 5-dichloro-2-pentanone, which specifically comprises the following steps:
(1) synthesis of alpha-chloro-alpha-acetyl-gamma-butyrolactone
Adding 128.8g of alpha-acetyl-gamma-butyrolactone (1.0mol, 99.5 percent, 1.0eq) into a 500mL four-mouth reaction bottle provided with a mechanical stirring device, a thermometer and a tail gas trapping device, and cooling to 0 ℃;
beginning to introduce 74.5g of chlorine (1.05mol, 99.9 percent, 1.05eq), controlling the temperature to be not more than 5 ℃, and finishing the introduction for 4 hours; after the chlorine introduction is finished, continuously preserving the heat for 1h to finish the reaction;
weighing to obtain 179.0g of reaction liquid (containing 13.4g of HCl and 1.0mol of alpha-chloro-alpha-acetyl-gamma-butyrolactone), and directly carrying out the next step of reaction without material transfer;
collecting tail gas to obtain 24.2g (0.66mol, 99.0%) of HCl gas;
(2) synthesis of 3, 5-dichloro-2-pentanone
Adding 9.0g of water (0.5mol, 99.9 percent and 0.5eq) into the reaction system, slowly heating to 35 ℃, and no gas escapes from the system when the temperature is raised;
then about 40g of hydrogen chloride (1.1mol, 99.0%, 1.1eq) was slowly passed in and over for 3 h; then the reaction is continued for 1h (15.1 g of hydrogen chloride gas is collected by a tail gas trapping device and can be directly used for the next reaction); slowly heating to 90 ℃, and reacting for 2 hours in a heat preservation way;
standing and layering after the reaction is finished, and separating 8.9g of water (containing a small amount of 3, 5-dichloro-2-pentanone) which can be directly applied to the next 3, 5-dichloro-2-pentanone reaction;
the organic phase was subjected to reduced pressure distillation to obtain 150.4g of 3, 5-dichloro-2-pentanone (boiling range 71-72 ℃ C., 10mmHg), the content of which was 97.1%, in terms of α -acetyl- γ -butyrolactone, and the yield was 94.2%.
Example 5
The difference from example 1 is that the amount of chlorine fed in the preparation process was 85g (1.2mol, 99.9%, 1.2 eq); the rest steps and parameters are consistent with those of the embodiment 1;
in this example 152.4g of 3, 5-dichloro-2-pentanone were obtained with a content of 96.5% and a yield of 94.9% based on α -acetyl- γ -butyrolactone.
Example 6
The difference from example 1 is that the amount of chlorine fed in the preparation process was 106g (1.5mol, 99.9%, 1.5 eq); the rest steps and parameters are consistent with those of the embodiment 1;
in this example 152.0g of 3, 5-dichloro-2-pentanone was obtained with a content of 97.1% and a yield of 95.2% based on α -acetyl- γ -butyrolactone.
Example 7
The difference from the embodiment 1 is that the reaction temperature is adjusted to 20 ℃ after the chlorine introduction is finished in the preparation method; the rest steps and parameters are consistent with those of the embodiment 1;
141.6g of 3, 5-dichloro-2-pentanone are obtained in this example with a content of 95.9% and a yield of 87.6% based on α -acetyl- γ -butyrolactone.
Example 8
The difference from the embodiment 1 is that the reaction temperature is adjusted to 40 ℃ after the chlorine introduction is finished in the preparation method; the rest steps and parameters are consistent with those of the embodiment 1;
in this example, 136.9g of 3, 5-dichloro-2-pentanone was obtained, having a content of 96.8% and a yield of 85.5% based on α -acetyl- γ -butyrolactone.
Example 9
The difference from the example 1 is that the time for introducing the hydrogen chloride in the preparation method is 10 h; the remaining steps and parameters were in accordance with example 1;
147.2g of 3, 5-dichloro-2-pentanone, content 95.4% and yield 90.6% based on α -acetyl- γ -butyrolactone were obtained in this example.
Example 10
The difference from the example 1 is that the time for introducing the hydrogen chloride in the preparation method is 1 h; the rest steps and parameters are consistent with those of the embodiment 1;
146.9g of 3, 5-dichloro-2-pentanone having a content of 96.3% and a yield of 91.3% based on α -acetyl- γ -butyrolactone were obtained in this example.
From the above examples, the yield of 3, 5-dichloro-2-pentanone obtained by the preparation method of the present invention is 85.5% to 95.2%; among them, as can be seen from comparison among examples 1, 5 and 6, in order to increase the yield of 3, 5-dichloro-2-pentanone and reduce the consumption of raw materials, the molar ratio of α -acetyl- γ -butyrolactone to chlorine is preferably 1 (1-1.05), and when it exceeds 1:1.05, the yield is not significantly increased, but the raw materials are wasted; as can be seen from the comparison of examples 1, 9 and 10, the yield of the target product can be improved when the temperature of the chlorination reaction is 0-20 ℃; as is clear from comparison of examples 1, 9 and 10, the yield of 3, 5-dichloro-2-pentanone and the utilization rate of hydrogen chloride can be improved by controlling the time for introducing hydrogen chloride.
In conclusion, the target product is obtained by the steps of chlorination, ring-opening decarboxylation and the like of the alpha-acetyl-gamma-butyrolactone, the process is simple, the operation is easy, the yield is high, and the method is suitable for industrial production.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.
Claims (10)
1. A preparation method of 3, 5-dichloro-2-pentanone as a prothioconazole intermediate, which is characterized by comprising the following steps of:
the alpha-acetyl-gamma-butyrolactone and chlorine gas are subjected to chlorination reaction under the condition of no solvent to obtain a crude product of the alpha-chlorine-alpha-acetyl-gamma-butyrolactone;
then, the crude product of the alpha-chlorine-alpha-acetyl-gamma-butyrolactone is subjected to ring opening and chlorination reaction in the presence of water and hydrogen chloride, and then subjected to decarboxylation reaction to obtain the 3, 5-dichloro-2-pentanone;
the reaction occurring in the preparation process of 3, 5-dichloro-2-pentanone is represented by formula I:
2. the process according to claim 1, wherein the molar ratio of α -acetyl- γ -butyrolactone to chlorine is 1 (1-1.5), preferably 1 (1-1.05);
preferably, the chlorination reaction time is 0.5-8 h, preferably 2-4 h;
preferably, the temperature of the chlorination reaction is 0-60 ℃, and preferably 0-20 ℃.
3. The method according to claim 1 or 2, wherein the α -acetyl- γ -butyrolactone is mixed with chlorine in a manner comprising: introducing chlorine gas into the alpha-acetyl-gamma-butyrolactone and/or introducing the alpha-acetyl-gamma-butyrolactone and the chlorine gas into a reactor through a mixer, preferably introducing the chlorine gas into the alpha-acetyl-gamma-butyrolactone for mixing;
preferably, the time for introducing the chlorine gas is maintained for 0.5-8 hours, preferably 3-4 hours.
4. The preparation method according to any one of claims 1 to 3, wherein the chlorination reaction is as shown in formula II:
5. the preparation method according to any one of claims 1 to 4, wherein the molar ratio of water to α -acetyl- γ -butyrolactone is (0.1 to 1:1, preferably (0.2 to 0.8: 1;
preferably, the hydrogen chloride comprises hydrogen chloride from a crude product of the alpha-chloro-alpha-acetyl-gamma-butyrolactone and/or hydrogen chloride introduced into the reaction system;
preferably, the molar ratio of the hydrogen chloride to the alpha-acetyl-gamma-butyrolactone in the crude alpha-chloro-alpha-acetyl-gamma-butyrolactone product is (1.0-1.05): 1;
preferably, the molar ratio of the hydrogen chloride to the alpha-acetyl-gamma-butyrolactone introduced into the reaction system is (0.2-5.0): 1, preferably (0.4-2.0): 1, and more preferably (0.6-1.4): 1.
6. The preparation method according to claim 5, wherein the time for introducing the hydrogen chloride is 1-20 hours, preferably 2-10 hours, and more preferably 4-8 hours;
preferably, the temperature of the reaction system is 0-120 ℃, preferably 20-60 ℃ and further preferably 30-50 ℃ when the hydrogen chloride is introduced;
preferably, after the hydrogen chloride introduction is finished, the method further comprises the operation of heating the reaction system, wherein the temperature after heating is 40-120 ℃, and preferably 60-90 ℃.
7. The preparation method according to any one of claims 1 to 6, wherein the ring opening and chlorination reaction process is represented by formula III:
preferably, the temperature of the ring opening and chlorination reaction is 0-120 ℃, preferably 20-60 ℃, and further preferably 30-50 ℃;
preferably, the decarboxylation reaction is as shown in formula IV:
preferably, the temperature of the decarboxylation reaction is 40-120 ℃, and preferably 60-90 ℃.
8. The preparation method according to any one of claims 1 to 7, further comprising an operation of collecting a tail gas generated by the chlorination reaction;
preferably, the off-gas produced by the chlorination reaction comprises hydrogen chloride.
9. The preparation method according to any one of claims 1 to 8, characterized by further comprising operations of standing for layering, and separating an aqueous phase and an organic phase after the decarboxylation reaction is finished;
preferably, the organic phase is distilled under reduced pressure to obtain the 3, 5-dichloro-2-pentanone.
10. The method according to any one of claims 1 to 9, characterized by comprising the steps of:
(1) synthesis of α -chloro- α -acetyl- γ -butyrolactone: adding alpha-acetyl-gamma-butyrolactone into a reaction bottle provided with a mechanical stirring device, a thermometer and a tail gas trapping device, introducing chlorine gas, and completing the introduction for 2-5 hours, wherein the molar ratio of the alpha-acetyl-gamma-butyrolactone to the chlorine gas is 1 (1-1.5);
after chlorine introduction is finished, preserving heat for 0.5-8 h at 0-60 ℃ until chlorination reaction is finished, and collecting tail gas generated by chlorination reaction to obtain a crude product of alpha-chlorine-alpha-acetyl-gamma-butyrolactone and hydrogen chloride gas;
wherein the chlorination reaction process is shown as formula II:
(2) synthesis of 3, 5-dichloro-2-pentanone: adding water into the reaction liquid obtained in the step (1), introducing hydrogen chloride gas at 0-120 ℃, keeping the temperature for 0.5-2 hours to perform ring opening and chlorination reaction after the hydrogen chloride gas is introduced for 1-20 hours, wherein the reaction process is shown as a formula III:
and then, heating to 40-120 ℃, and carrying out decarboxylation reaction at the temperature for 1-5 hours, wherein the reaction process is shown as a formula IV:
and (3) standing and layering after the reaction is finished, separating an aqueous phase and an organic phase, wherein the aqueous phase is used as water added in the step (2) and re-enters the reaction system, and the organic phase is subjected to reduced pressure distillation to obtain the 3, 5-dichloro-2-pentanone.
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