CN111116363B - Preparation method of carboxylic ester compound - Google Patents
Preparation method of carboxylic ester compound Download PDFInfo
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- CN111116363B CN111116363B CN201911383054.XA CN201911383054A CN111116363B CN 111116363 B CN111116363 B CN 111116363B CN 201911383054 A CN201911383054 A CN 201911383054A CN 111116363 B CN111116363 B CN 111116363B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/307—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of halogen; by substitution of halogen atoms by other halogen atoms
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The inventionBelongs to the technical field of compound synthesis, and particularly relates to a preparation method of a carboxylic ester compound, which comprises the following steps: a) Under the action of a catalyst, reacting a compound with a structure shown in a formula (A) with a compound with a structure shown in a formula (B) to obtain a carboxylic ester compound with a structure shown in a formula (C); in the formulae (A) to (C), R 1 Is selected from C 1 ～C 2 An alkyl group; r 2 ～R 5 Independently selected from hydrogen, halogen, C 1 ～C 3 Alkyl or C 1 ～C 3 A haloalkyl group; the catalyst comprises azobisisobutyronitrile and/or a peroxy catalyst. The compound of formula (A) and the compound of formula (B) are used as reaction raw materials, and the two are directly reacted under the action of a specific catalyst to obtain the carboxylic ester compound. The method has the advantages of high catalytic activity, simple process flow, low post-treatment difficulty and high production efficiency, can avoid the generation of three wastes, and meets the requirement of environmental protection.
Description
Technical Field
The invention belongs to the technical field of compound synthesis, and particularly relates to a preparation method of a carboxylic ester compound.
Background
The halogen-containing 3, 3-dimethyl-heptane carboxylic ester compound is an important intermediate for synthesizing pyrethroids such as lambda-cyhalothrin, tefluthrin, resmethrin, phenothrin, permethrin, cypermethrin, deltamethrin, tetrabromthrin and the like. Global pyrethroid product sales scale is rapidly rising from 20.8 billion dollars in 2009 to 31.6 billion dollars in 2014, with a year compound increase of 8.7%. From the global pesticide product distribution, the pyrethroid accounts for 17.0% in the market, second only to neonicotinoid insecticides. In terms of pyrethroid product scale distribution, the global sale is mostly agricultural pyrethroid in 2015, wherein the sale of high-efficiency cyhalothrin (cyhalothrin) reaches $ 6.3 hundred million, and the sale of bifenthrin in 2015 and 2016 is $ 3.27 hundred million and $ 3.39 hundred million respectively. The market demand of halogen-3, 3-dimethyl-heptane carboxylic ester compounds as important intermediates of the above insecticides has also risen year by year. The annual demand amount breaks through 13000 tons, and the market prospect is good.
At present, the synthesis process of halogen-3, 3-dimethyl-heptane carboxylic ester compounds generally adopts cardia acid ester as a starting material, firstly carries out addition reaction with halogenated alkane under the catalysis of cuprous chloride and monoethanolamine, and finally obtains qualified products with the cis-isomer content of more than 98 percent through five steps of cyclization, saponification, acidification and recrystallization.
In the process, cuprous chloride and ethanolamine are adopted in the addition process, the catalyst activity is low, the reaction time is as long as 20 hours, the catalyst needs to be recovered by standing and precipitating after the addition reaction is finished, the standing time is as long as 8 hours, and the productivity is seriously reduced. In addition, the process also produces a large amount of cuprous chloride heavy metal waste salt which is difficult to treat.
Disclosure of Invention
In view of the above, the present invention aims to provide a preparation method of a carboxylic ester compound, which has the advantages of high catalytic activity, simple process flow, low post-treatment difficulty, high production efficiency, avoidance of three wastes, and compliance with environmental protection requirements.
The invention provides a preparation method of a carboxylic ester compound, which comprises the following steps:
a) Under the action of a catalyst, reacting a compound with a structure shown in a formula (A) with a compound with a structure shown in a formula (B) to obtain a carboxylic ester compound with a structure shown in a formula (C);
in the formulae (A) to (C), R 1 Is selected from C 1 ～C 2 An alkyl group; r is 2 ～R 5 Independently selected from hydrogen, halogen, C 1 ～C 3 Alkyl or C 1 ～C 3 A haloalkyl group;
the catalyst comprises azobisisobutyronitrile and/or a peroxy catalyst.
Preferably, the halogen is fluorine, chlorine or bromine; said C is 1 ～C 3 The halogen element in the halogenated alkyl is one or more of fluorine, chlorine and bromine.
Preferably, said R is 5 Is chlorine or bromine.
Preferably, the molar ratio of the compound with the structure of formula (A) to the compound with the structure of formula (B) is 1: (1-5).
Preferably, the peroxygen catalyst comprises one or more of dibenzoyl peroxide, di-4-chlorobenzoyl peroxide, diacetyl peroxide, t-butyl peroxyacetate, t-amyl peroxyacetate, t-butyl peroxybenzoate, t-amyl peroxybenzoate, t-butyl peroxyisobutyrate, t-butyl peroxypivalate, t-butyl peroxyneoheptanoate, and t-butyl peroxyneodecanoate.
Preferably, the catalyst is used in an amount of 0.01 to 10wt% based on the mass of the compound of formula (A).
Preferably, the temperature of the reaction is 40 to 80 ℃.
Preferably, the reaction time is 2 to 8 hours.
Preferably, step a) specifically comprises:
adding a compound with a structure shown in a formula (A) into a closed reaction kettle, and heating to a reaction temperature; and then adding a catalyst and the compound with the structure shown in the formula (B) into the closed reaction kettle, and carrying out heat preservation reaction to obtain the carboxylic ester compound with the structure shown in the formula (C).
Preferably, the reaction is carried out in a solvent or without the use of a solvent.
Compared with the prior art, the invention provides a preparation method of a carboxylic ester compound. The preparation method provided by the invention comprises the following steps: a) Under the action of a catalyst, reacting a compound with a structure shown in a formula (A) with a compound with a structure shown in a formula (B) to obtain a carboxylic ester compound with a structure shown in a formula (C); in the formulae (A) to (C), R 1 Is selected from C 1 ～C 2 An alkyl group; r 2 ～R 5 Independently selected from hydrogen, halogen, C 1 ～C 3 Alkyl or C 1 ～C 3 A haloalkyl group; the catalyst comprises azobisisobutyronitrile and/or a peroxy catalyst. The invention takes the compound with the structure of formula (A) and the compound with the structure of formula (B) asAnd reacting the raw materials directly under the action of a specific catalyst to obtain the carboxylic ester compound. The preparation method provided by the invention has the advantages of simple process flow, high catalyst activity, high selectivity, less side reaction and easy control of the reaction process. In addition, the preparation method provided by the invention does not need post-treatment operations such as standing, sedimentation, layering, high vacuum distillation and the like, so that non-metallic salt is not generated, and the environmental protection pressure is reduced. The experimental results show that: the product purity and the product yield of the preparation method are both over 98 percent.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the embodiments or the prior art descriptions will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 is a chromatogram provided in example 1 of the present invention;
FIG. 2 is a mass spectrum provided in example 1 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
The invention provides a preparation method of a carboxylic ester compound, which comprises the following steps:
a) Under the action of a catalyst, reacting a compound with a structure shown in a formula (A) with a compound with a structure shown in a formula (B) to obtain a carboxylic ester compound with a structure shown in a formula (C);
in the formulae (A) to (C), R 1 Is selected from C 1 ～C 2 Alkyl radical, R 2 ～R 5 Independently selected from hydrogen, halogen, C 1 ～C 3 Alkyl or C 1 ～C 3 A haloalkyl group;
the catalyst comprises azobisisobutyronitrile and/or a peroxy catalyst.
In the preparation method provided by the invention, the compound with the structure of formula (A) and the compound with the structure of formula (B) are used as reaction raw materials. Wherein R in the compound with the structure of the formula (A) 1 The group is methyl or ethyl, namely the compound with the structure shown in the formula (A) can be methyl cardiate or ethyl cardiate; r in the compound with the structure of the formula (B) 2 ～R 5 The radicals are independently selected from hydrogen, halogen, C 1 ～C 3 Alkyl or C 1 ～C 3 A haloalkyl group; the halogen may be in particular fluorine, chlorine or bromine; said C is 1 ～C 3 Alkyl may be specifically methyl, ethyl or propyl; said C is 1 ～C 3 Haloalkyl may be specifically C 1 ～C 3 Fluoroalkyl radical, C 1 ～C 3 Chloroalkyl group, C 1 ～C 3 Bromoalkyl or C 1 ～C 3 Mixing the halogenated alkyl groups. In one embodiment of the present invention, R of the compound of formula (B) 5 The radical is preferably chlorine or bromine. In another embodiment provided by the present invention, the structural compound of formula (B) may specifically be CF 3 CCl 3 (R 2 ＝-CF 3 、R 3 ～R 5 ＝-Cl)、CH 2 Cl 2 (R 2 ～R 3 ＝-H、R 4 ～R 5 ＝-Cl)、CBr 4 Or CH 3 CH 2 CHCl 2 (R 2 ＝-CH 2 CH 3 、R 3 ＝-H、R 4 ～R 5 = Cl). In the present invention, the molar ratio of the compound of formula (a) to the compound of formula (B) is preferably 1: (1-5) of the total weight of the composition,more preferably 1: (1.03-1.5), most preferably 1: (1.05 to 1.3), specifically 1, 1.05, 1.1, 1.25, 1.3, 1.4, 1.
In the preparation method provided by the invention, azobisisobutyronitrile and/or a peroxy catalyst are used as a catalyst for the reaction, wherein the peroxy catalyst comprises one or more of dibenzoyl peroxide, di-4-chlorobenzoyl peroxide, diacetyl peroxide, tert-butyl peroxyacetate, tert-amyl peroxyacetate, tert-butyl peroxybenzoate, tert-amyl peroxybenzoate, tert-butyl peroxyisobutyrate, tert-butyl peroxypivalate and tert-butyl peroxyneodecanoate. In the present invention, the catalyst preferably employs tert-butyl peroxyisobutyrate and/or tert-butyl peroxypivalate. In the present invention, the catalyst is preferably used in an amount of 0.01 to 10wt%, more preferably 0.05 to 5wt%, most preferably 0.1 to 2wt%, and specifically may be 0.01wt%, 0.02wt%, 0.03wt%, 0.04wt%, 0.05wt%, 0.1wt%, 0.2wt%, 0.3wt%, 0.4wt%, 0.5wt%, 0.6wt%, 0.7wt%, 0.8wt%, 0.9wt%, 1wt%, 1.1wt%, 1.2wt%, 1.3wt%, 1.4wt%, 1.5wt%, 1.6wt%, 1.7wt%, 1.8wt%, 1.9wt%, 2wt%, 2.5wt%, 3wt%, 3.5wt%, 4wt%, 4.5wt%, 5wt%, 6wt%, 7wt%, 8wt%, 9wt%, or 10wt% of the amount of the structural compound of formula (A).
In the preparation method provided by the invention, the reaction of the compound with the structure shown in the formula (A) and the compound with the structure shown in the formula (B) under the action of the catalyst is preferably carried out in a protective gas atmosphere, and the protective gas is preferably nitrogen; the reaction may be carried out in a solvent such as tert-butanol, or may be carried out without using a solvent, preferably without using a solvent; the reaction temperature is preferably 40-80 ℃, and specifically can be 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃ or 80 ℃; the reaction time is preferably 2-8 h, and specifically can be 2h, 2.5h, 3h, 3.5h, 4h, 4.5h, 5h, 5.5h, 6h, 6.5h, 7h, 7.5h or 8h; the reaction is carried out in a solvent or without a solvent, preferably tert-butanol.
In the preparation method provided by the invention, the specific process of reacting the compound with the structure of formula (a) and the compound with the structure of formula (B) under the action of the catalyst preferably comprises the following steps:
adding a compound with a structure shown in a formula (A) into a closed reaction kettle, and heating to a reaction temperature; and then adding a catalyst and the compound with the structure shown in the formula (B) into the closed reaction kettle, and carrying out heat preservation reaction.
In the reaction process provided by the invention, the time consumption for adding the catalyst and the compound with the structure shown in the formula (B) into the closed reaction kettle is preferably 0.5-3 h, and specifically can be 0.5h, 1h, 1.5h, 2h, 2.5h or 3h; the time of the heat preservation reaction is preferably 2-6 h, and specifically can be 2h, 2.5h, 3h, 3.5h, 4h, 4.5h, 5h, 5.5h or 6h.
In the preparation method provided by the invention, after the compound with the structure of the formula (A) and the compound with the structure of the formula (B) react under the action of the catalyst, the excessive reactants are recovered under reduced pressure, and the remaining reaction product is the carboxylic ester compound with the structure shown in the formula (C) prepared by the invention.
The preparation method provided by the invention has the advantages of high catalytic activity, simple process flow, low post-treatment difficulty and high production efficiency, can avoid the generation of three wastes, and meets the requirement of environmental protection. More specifically, the method comprises the following advantages:
1) The preparation method has the advantages that the compound with the structure shown in the formula (A) and the compound with the structure shown in the formula (B) are used as reaction raw materials and directly react under the action of a specific catalyst to obtain the carboxylic ester compound, the preparation method is simple and convenient to operate, the catalyst is high in selectivity, few in side reactions, easy to control in reaction process, high in product yield and purity and easy to implement;
2) The method has mild reaction conditions, does not need operations such as standing, sedimentation, filtration, layering and the like in the middle, simplifies the process flow, shortens the reaction time, improves the production efficiency, has simple post-treatment, directly removes excessive reactants, is convenient for separation and purification, has no treatment burden of waste copper salt catalyst, reduces three wastes, reduces the production cost, meets the requirement of environmental protection, and is more suitable for industrial production;
3) The carboxylic ester compound prepared by the invention has high purity and yield which are both over 98 percent, and high vacuum distillation is avoided.
For the sake of clarity, the following examples are given in detail.
Example 1
Synthesizing the carboxylic ester compound according to the following chemical equation:
the specific process comprises the following steps:
1) Under the protection of nitrogen, 145.1g of methyl cardiate is added into a 500ml autoclave, the autoclave is tightly closed, the temperature is raised to 60 ℃, a mixed solution of 0.71g of tert-butyl peroxyneodecanoate and 283.4g of trifluorotrichloroethane is pumped in through a feed inlet, and the pumping is finished after 2 hours. The reaction is continued for 4h under heat preservation.
2) The temperature is reduced to 30 ℃, the reaction solution is transferred to a four-neck flask, and excess trifluorotrichloroethane is recovered under reduced pressure to obtain 330.2g of product, the product content is 99.0 percent by GC analysis, and the yield is 99.2 percent.
The product prepared in this example was analyzed by gas chromatography and mass spectrometry, wherein the results of the chromatography are shown in fig. 1 and table 1, and fig. 1 is the chromatogram provided in example 1 of the present invention; the mass spectrometry results are shown in fig. 2, and fig. 2 is a mass spectrum provided in example 1 of the present invention.
TABLE 1 chromatographic analysis data sheet
| Retention time | Starting time | At the end ofWorkshop | M/Z | Peak area | Peak area, percent |
| 10.707 | 10.66 | 10.933 | TIC | 13723235 | 0.14 |
| 12.35 | 12.307 | 12.42 | TIC | 5155175 | 0.05 |
| 13.176 | 12.867 | 13.213 | TIC | 9775620866 | 99.00 |
| 13.227 | 13.213 | 13.26 | TIC | 15863222 | 0.16 |
| 13.302 | 13.28 | 13.34 | TIC | 34228195 | 0.15 |
| 13.479 | 13.407 | 13.573 | TIC | 43079059 | 0.23 |
| 15.452 | 15.38 | 15.62 | TIC | 27186354 | 0.27 |
Example 2
Synthesizing the carboxylic ester compound according to the following chemical equation:
the specific process comprises the following steps:
1) Under the protection of nitrogen, 156.2g of ethyl cardiate is added into a 500ml autoclave, the autoclave is closed, the temperature is raised to 40 ℃, a mixed solution of 2.84g of azobisisobutyronitrile and 169.5g of dichloromethane is pumped in through a feed inlet, and the pumping is finished after 2 h. The reaction is continued for 4h under heat preservation.
2) The temperature is reduced to 30 ℃, the reaction solution is transferred to a four-mouth flask, excessive dichloromethane is recovered under reduced pressure, 241.2g of product is obtained, the product content is 98.0 percent by GC analysis, and the yield is 98.1 percent.
Example 3
Synthesizing the carboxylic ester compound according to the following chemical equation:
the specific process comprises the following steps:
1) Under the protection of nitrogen, 145.1g of methyl pentenoate is added into a 500ml autoclave, the autoclave is tightly closed, the temperature is raised to 80 ℃, a mixed solution of 0.07g of dibenzoyl peroxide and 331.6g of carbon tetrabromide is pumped in through a feed inlet, and the pumping is finished after 2 hours. The reaction is continued for 4h under heat preservation.
2) The temperature is reduced to 30 ℃, the reaction liquid is transferred to a four-neck flask, and excess carbon tetrabromide is recovered under reduced pressure to obtain 473.4g of product, the product content is 98.0 percent by GC analysis, and the yield is 98.3 percent.
Example 4
Synthesizing the carboxylic ester compound according to the following chemical equation:
the specific process comprises the following steps:
1) Under the protection of nitrogen, 145.1g of methyl pentenoate was added into a 500ml autoclave, the autoclave was closed, the temperature was raised to 80 ℃, a mixed solution of 0.10g of diacetyl peroxide and 171.2g of 1, 1-dichloropropane was pumped in through a feed port, and the pumping was completed after 2 hours. The reaction is continued for 4h under heat preservation.
2) The temperature is reduced to 30 ℃, the reaction solution is transferred to a four-neck flask, and the excessive 1, 1-dichloropropane is recovered under reduced pressure to obtain 256.5g of product, the product content is 97.6 percent by GC analysis, and the yield is 98.1 percent.
Comparative example
600kg of methyl cardia-pavilionate, 700kg of tertiary butanol, 18kg of monoethanolamine and 8kg of cuprous chloride are sequentially put into a reaction kettle, stirring is started, the temperature is increased, 1200kg of trifluorotrichloroethane is dropwise added when the reflux state is achieved, after the addition is finished, the reflux reaction is kept for 12-18 hours, after the reaction is finished, the materials are transferred to a settling tank and are kept stand, the cuprous chloride is settled at the bottom of the tank, the supernatant is subjected to decompression desolventizing treatment, and finally the low-boiling-point substances are removed under the pressure of-0.095 MPa. 1000-1200 kg of crude product is obtained, the content is more than 95%, and the yield is 69-83%.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and amendments can be made without departing from the principle of the present invention, and these modifications and amendments should also be considered as the protection scope of the present invention.
Claims (8)
1. A preparation method of a carboxylic ester compound comprises the following steps:
a) Under the action of a catalyst, reacting a compound with a structure shown in a formula (A) with a compound with a structure shown in a formula (B) to obtain a carboxylic ester compound with a structure shown in a formula (C);
in the formulae (A) to (C), R 1 Is selected from C 1 ～C 2 An alkyl group; r is 2 ～R 5 Independently selected from hydrogen, halogen, C 1 ～C 3 Alkyl or C 1 ～C 3 A haloalkyl group;
the catalyst comprises azobisisobutyronitrile and/or a peroxy catalyst; the peroxy catalyst comprises one or more of di-4-chlorobenzoyl peroxide, diacetyl peroxide, tert-butyl peroxyacetate, tert-amyl peroxyacetate, tert-butyl peroxybenzoate, tert-amyl peroxybenzoate, tert-butyl peroxyisobutyrate, tert-butyl peroxypivalate, tert-butyl peroxyneoheptanoate and tert-butyl peroxyneodecanoate;
no solvent is used during the reaction.
2. The method of claim 1, wherein the halogen is fluorine, chlorine or bromine; said C is 1 ～C 3 The halogen element in the halogenated alkyl is one or more of fluorine, chlorine and bromine.
3. The method of claim 1, wherein R is 5 Is chlorine or bromine.
4. The method according to claim 1, wherein the molar ratio of the compound having a structure represented by formula (a) to the compound having a structure represented by formula (B) is 1: (1-5).
5. The method according to claim 1, wherein the catalyst is used in an amount of 0.01 to 10wt% based on the amount of the compound having the structure of formula (A).
6. The method according to claim 5, wherein the reaction temperature is 40 to 80 ℃.
7. The method according to claim 6, wherein the reaction time is 2 to 8 hours.
8. The method according to claim 1, wherein step a) comprises in particular:
adding a compound with a structure shown in a formula (A) into a closed reaction kettle, and heating to a reaction temperature; and then, adding a catalyst and the compound with the structure shown in the formula (B) into the closed reaction kettle, and carrying out heat preservation reaction to obtain the carboxylic ester compound with the structure shown in the formula (C).
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