A composition and its use

Abstract

The present application discloses a composition comprising A and B, wherein the A is selected from one or more of the following: a compound represented by formula (I) and its salt and / or hexamethylenetetramine, 1,5-diazabicyclo[4.3.0]-non-5-ene, 1,8-diazabicyclo[5.4.0]undec-7-ene; the B is selected from a compound represented by formula II, and a method for preparing a compound of formula VI by using the above composition, wherein the definitions of the substituents in formula III, formula V and formula VI are the same as those in the description. The A and the B in the composition of the present application have a synergistic effect.

Description

Technical Field

[0001] This disclosure relates to a composition and its application, particularly to its application in catalytic etherification reactions (e.g., etherification in the preparation of azoxystrobin). Background Technology

[0002] The use of conventional organic amines in existing etherification reactions is not ideal, and often requires a large amount of catalyst to achieve a certain catalytic effect.

[0003] Existing technical literature, CN109721548B, discloses the etherification reaction of (E)-2-[2-[6-chloropyrimidin-4-yloxy]phenyl]-3-methoxyacrylate and 2-cyanophenol. This document discloses a method for preparing azoxystrobin, achieving good catalytic performance using an aqueous solution of trimethylamine or its salts, or a methanol solution, at an 8 mol% catalyst dosage. However, those skilled in the art know that trimethylamine has a very low boiling point, only 2.9 °C at atmospheric pressure, and even in aqueous solutions, such as a 40% trimethylamine aqueous solution, the boiling point is only 26.0 °C. Typically, in the preparation of azoxystrobin, the relevant industrial etherification reaction temperature is close to 100 °C. At such high temperatures, trimethylamine or its aqueous solutions are highly volatile; therefore, using trimethylamine as a catalyst is not suitable for industrial production. The literature also discloses that N,N,N,N-tetramethylethylenediamine, N,N-dimethylpiperazine, 4-dimethylaminopyridine (DMAP), N,N-dimethylisopropylamine, DBU, and triethylamine have virtually no catalytic effect at the same catalyst dosage. The applicant's experimental research shows that even with increased dosage, the catalytic effect and product yield of these compounds are still unsatisfactory.

[0004] Therefore, there is an urgent need in this field to develop a catalyst with good catalytic effect, low cost and readily available raw materials for the preparation of related etherification reactions, especially for industrial applications such as pyraclostrobin. Summary of the Invention

[0005] To address the shortcomings of existing technologies, such as unsatisfactory catalytic effects or unsuitability for industrial production, the applicant, through years of continuous research, unexpectedly discovered a composition comprising A and B. This composition of A and B can be effectively applied to the catalysis of etherification reactions, achieving good catalytic performance. The combination of components in the composition exhibits a good synergistic effect. Particularly noteworthy is the superior technical performance of this composition in the etherification process of azoxystrobin.

[0006] This application provides a composition comprising A and B. The composition exhibits good catalytic effect in etherification reactions, with A and B showing a synergistic effect.

[0007] Another aspect of this application provides a method for preparing an etherification reaction, in which the synergistic composition of this application is used in the preparation process.

[0008] Specifically, this application provides a composition comprising A and B, wherein A is selected from:

[0009] 1) R1R2R3N represents compounds of formula I and their salts, wherein R1, R2, and R3 are each independently selected from hydrogen atoms, substituted or unsubstituted alkyl groups, substituted or unsubstituted cycloalkyl groups, substituted or unsubstituted heterocyclic groups, substituted or unsubstituted aryl groups, and substituted or unsubstituted heteroaryl groups.

[0010] and / or

[0011] 2) One or more of hexamethylenetetramine, 1,5-diazabicyclo[4.3.0]-non-5-ene, and 1,8-diazabicyclo[5.4.0]undec-7-ene;

[0012] The B is

[0013] The compound represented by formula II, wherein Z1, Z2, Z3, Z4 and Z5 are each independently selected from C or N, and R4 and R5 are each independently selected from hydrogen atom, optionally substituted alkyl, optionally substituted cycloalkyl, optionally substituted heterocyclic, optionally substituted aryl, optionally substituted heteroaryl.

[0014] This application also provides a method for preparing compound VI, the reaction route of which is as follows:

[0015]

[0016] R6 is selected from halogens, and R7 to R... 19 Each group is independently selected from hydrogen atom, halogen, hydroxyl, amino, cyano, nitro, optionally substituted alkyl, optionally substituted cycloalkyl, optionally substituted heterocyclic, optionally substituted aryl, optionally substituted heteroaryl, and M is a hydrogen atom or a metal ion, wherein the metal ion is preferably sodium, potassium, or calcium.

[0017] Beneficial effects of this application

[0018] 1) The composition of this application exhibits good synergistic catalytic effect in the etherification reaction;

[0019] 2) The catalyst raw materials used in the compositions of this application are readily available and low in cost;

[0020] 3) The catalyst in the composition used in this application can be recycled, and the reaction process of this application is green and environmentally friendly, which is more conducive to industrial production. Detailed Implementation

[0021] Embodiments of the invention are described in detail below. However, these embodiments are exemplary, and the invention is not limited thereto.

[0022] In this document, unless otherwise specifically defined, the following terms used in the specification and claims have the following meanings.

[0023] "Alkyl" refers to a saturated aliphatic group, including branched and branched groups with 1 to 20 carbon atoms, preferably alkyl groups containing 1 to 10 carbon atoms, specifically such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl, etc., and more preferably lower alkyl groups containing 1 to 4 carbon atoms, such as methyl, ethyl, propyl, 2-propyl, n-butyl, isobutyl, or tert-butyl, etc.

[0024] "Cycloalkyl" refers to a 3- to 8-membered monocyclic group containing one or more double bonds. Specific examples include cyclopropyl, cyclobutyl, cyclopentyl, cyclopentene, cyclohexane, cyclohexadiene, cycloheptane, and cyclohepttriene.

[0025] "Heterocyclic groups" refer to 3- to 8-membered monocyclic groups, where one or two ring atoms are selected from nitrogen, oxygen, or S(O)m (where m is an integer from 0 to 2), and the remaining ring atoms are carbon. These rings may also have one or more double bonds. Specific examples include: pyrrolidinyl, piperidinyl, piperazinyl, morpholinyl, thiomorpholinyl, homopiperazinyl, etc.

[0026] "Aryl" refers to a group having at least one aromatic ring structure, that is, an aromatic ring with a conjugated π-electron system, including carbocyclic aryl, heteroaryl, and biaryl.

[0027] "Heteroaryl" refers to an aryl group having 1 to 4 heteroatoms as ring atoms, with the remaining ring atoms being carbon. Heteroatoms include oxygen, sulfur, and nitrogen. The ring can be a 5-membered or 6-membered ring. Examples include furanyl, thiophene, pyridinyl, pyrrole, N-alkylpyrroleyl, pyrimidinyl, pyrazinyl, imidazolyl, tetrazolyl, etc.

[0028] "Alkoxy" refers to -O- (alkyl) and -O- (unsubstituted cycloalkyl). Specific examples include: methoxy, ethoxy, propoxy, butoxy, cyclopropoxy, cyclobutoxy, cyclopentoxy, etc.

[0029] "Optional substitution" means substitution or substitution. When substituted, the substituent is one or more halogens, nitro, cyano, hydroxyl, alkyl, alkoxy, halogen, hydroxyl, amino, cyano, nitro, haloalkyl, or haloalkoxy.

[0030] "Halogenated alkyl" refers to an alkyl group that has been replaced by a halogen.

[0031] "Haloalkoxy" refers to -O- (haloalkyl).

[0032] "Halogen" refers to fluorine, chlorine, bromine, or iodine.

[0033] "Nitro" refers to -NO2.

[0034] "Hydroxy" refers to -OH.

[0035] “Cyano” refers to -CN.

[0036] "M" is a hydrogen or metal ion. The metal ion can replace the hydrogen atom on the phenolic hydroxyl group to obtain a phenolic salt. The preferred metal ion is one of sodium, potassium, or calcium.

[0037] The main catalyst mentioned in this application refers to a catalyst that accounts for more than 50% of the catalyst composition, while the co-catalyst mentioned in this application refers to a catalyst that accounts for less than 50% of the catalyst composition. The above percentages refer to the ratio of the number of moles of catalyst to the total number of moles of the catalyst composition.

[0038] In this application, etherification refers to the reaction in which the hydrogen atom of the hydroxyl group in an alcohol or phenol molecule is replaced by an alkyl or aryl group, thereby etherifying the alcohol or phenol.

[0039] In this application, solvent refers to the reaction medium used to dilute the reactants in the reaction.

[0040] This application provides a composition comprising A and B, wherein A is selected from:

[0041] 1) Compounds of formula I represented by R1R2R3N and their salts, wherein R1, R2, and R3 are each independently selected from hydrogen atoms, substituted or unsubstituted alkyl groups, substituted or unsubstituted cycloalkyl groups, substituted or unsubstituted heterocyclic groups, substituted or unsubstituted aryl groups, and substituted or unsubstituted heteroaryl groups; more preferably, hydrogen atoms, C1-C 10 The alkyl group, C3-C8 cycloalkyl group, C3-C8 heterocyclic group, and more preferably methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl and decyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclopentene, cyclohexane, cyclohexadiene, cycloheptane, cycloheptanetriene, pyrrolidinyl, piperidinyl, piperazinyl, morpholinyl, thiomorpholinyl, homopiperazinyl; the salt is a hydrochloride, sulfate, phosphate and sulfonate, preferably a hydrochloride;

[0042] and / or

[0043] 2) One or more of hexamethylenetetramine, 1,5-diazabicyclo[4.3.0]-non-5-ene, and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), and salts of the above compounds, wherein the salts are hydrochloride, sulfate, phosphate, and sulfonate, preferably hydrochloride;

[0044] The B is:

[0045] The compound of formula II and its salts are represented, wherein Z1, Z2, Z3, Z4, and Z5 are each independently selected from C or N, and R4 and R5 are each independently selected from hydrogen atoms, optionally substituted alkyl groups, optionally substituted cycloalkyl groups, optionally substituted heterocyclic groups, optionally substituted aryl groups, and optionally substituted heteroaryl groups; further preferably, hydrogen atoms, C1-C 10 Alkyl, C3-C8 cycloalkyl, C3-C8 heterocyclic groups; particularly preferred are methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl and decyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclopentene, cyclohexane, cyclohexadiene, cycloheptane, cycloheptanetriene, pyrrolidinyl, piperidinyl, piperazinyl, morpholinyl, thiomorpholinyl, and homopiperazinyl.

[0046] In the above composition, A is particularly preferably one or more of N,N-dimethylethylamine, N,N-dimethylisopropylamine, N,N-diethylmethylamine, trimethylamine, 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), hexamethylenetetramine, N-methylpyrrolidine, N-methylmorpholine, 1,5-diazabicyclo[4.3.0]non-5-ene, 1,8-diazabicyclo[5.4.0]undec-7-ene, and salts of the above preferred compounds.

[0047] In the above composition, B is preferably DMAP.

[0048] Preferably, in the above composition, A is the main catalyst and B is the co-catalyst.

[0049] Preferably, in the above-described composition, based on the amount of 1 mol of the composition, the amount of B is greater than 0 mol, preferably greater than 0.001 mol, and less than 0.5 mol.

[0050] The applicant's research found that when the amount of B in the composition is greater than 0 mol, the catalytic effect of A can be enhanced.

[0051] In the above composition, the molar ratio of A to B is a synergistic amount, preferably 1:10-500:1, more preferably 80:1, 12.5:1, 6:1, 5:1, 3:1, 2:1, 1:1, 2:5, 1:4. Within the above range, A and B exhibit a good synergistic effect.

[0052] This application also provides a method for preparing a compound of formula IV, comprising subjecting a compound of formula (III) and a compound of formula V or a salt thereof to an etherification reaction catalyzed by the composition of this application.

[0053]

[0054] R6 is selected from halogens, and R7 to R... 19 Each group is independently selected from hydrogen atom, halogen, hydroxyl, amino, cyano, nitro, optionally substituted alkyl, optionally substituted cycloalkyl, optionally substituted heterocyclic, optionally substituted aryl, optionally substituted heteroaryl, and M is a hydrogen atom or a metal ion, wherein the metal ion is preferably sodium, potassium, or calcium.

[0055] Furthermore, R6 is selected from fluorine, chlorine, bromine, and iodine, and R7 to R... 12， R 15 To R 18， Each is independently selected from hydrogen atoms, and the R mentioned above 13 and R 14 Selected from one of methyl, ethyl, and propyl, preferably methyl, R 19 It is a cyano group.

[0056] Further formula III is preferably formula III'

[0057]

[0058] The further preferred form V is V'. Where M is a hydrogen atom or a metal ion, preferably sodium, potassium, or calcium.

[0059] Further, formula VI is preferably formula VI'.

[0060] Furthermore, in the above preparation method, studies have found that an amount of B greater than 0 mol in the composition can enhance the catalytic effect of A. The ratio of A to B in the composition is not particularly limited, as long as the combination of the two achieves a good catalytic effect. For example, the molar ratio of A to B for synergistic effects is preferably 1:10-500:1, more preferably 80:1, 12.5:1, 6:1, 5:1, 3:1, 2:1, 1:1, 2:5, or 1:4. Within the above molar range, A and B exhibit good synergistic effects. However, the molar ratio of A to B is not limited to these values.

[0061] Furthermore, the amount of the composition used in the above preparation method is not limited, as long as it can achieve a good catalytic effect. For example, the amounts of A and B in the composition are 1-60% of the molar amount of compound III, preferably 5-60%. Within the above range of amounts, a good catalytic effect can be achieved. However, it is not limited to this.

[0062] Furthermore, the preparation method described above is characterized in that a solvent is used in the reaction, and the solvent is selected from one or more of cyclohexane, methylcyclohexane, benzene, toluene, xylene, chlorobenzene, dichlorobenzene, pyridine, methyl tert-butyl ether, anisole, methyl isobutyl ketone and cyclohexanone, N,N-dimethylformamide, N,N-dimethylacetamide, butyl acetate, and isopropyl acetate; preferably, toluene, xylene, N,N-dimethylacetamide, pyridine, methyl isobutyl ketone, cyclohexyl ketone, isopropyl acetate, butyl acetate, or N,N-dimethylformamide. The above solvent meets the temperature requirements of the reaction and is not prone to side reactions with the raw materials.

[0063] Furthermore, the above preparation method is carried out at a certain temperature. Generally, there is no particular limitation on the reaction temperature, as long as a good reaction can be carried out at that temperature. For example, the reaction temperature is between 80-150℃, preferably 100-150℃, and particularly preferably between 100-120℃. However, it is not limited to this.

[0064] Studies have found that when the reaction temperature is below 80℃, the reaction time is significantly prolonged, and when the reaction temperature is above 150℃, excessive impurities are generated.

[0065] Furthermore, the present invention also provides a formula VI'

[0066] Preparation methods, including formula III' Japanese V' The reaction is carried out under the catalysis of the composition of the present invention.

[0067] The composition described above comprises A and B, wherein A is selected from one or more of N,N-dimethylethylamine, N,N-dimethylisopropylamine, N,N-diethylmethylamine, trimethylamine, trimethylamine hydrochloride, 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), hexamethylenetetramine, N-methylpyrrolidine, N-methylmorpholine, 1,5-diazabicyclo[4.3.0]non-5-ene, 1,8-diazabicyclo[5.4.0]undec-7-ene, and salts of the above compounds; the salt is preferably a hydrochloride salt, and B is selected from DMAP.

[0068] Furthermore, A is preferably one or more of N,N-dimethylethylamine, N,N-diethylmethylamine, trimethylamine hydrochloride, 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), hexamethylenetetramine, N-methylpyrrolidine, and N-methylmorpholine.

[0069] Furthermore, in the preparation method of formula VI' above, based on the amount of 1 mol of the composition, the amount of B is greater than 0 mol, preferably greater than 0.001 mol. Studies have found that as long as the amount of B is greater than 0 mol, the catalytic effect of A can be enhanced. The molar ratio of A to B is a synergistic amount, preferably 1:10-500:1, more preferably 80:1, 12.5:1, 6:1, 5:1, 3:1, 2:1, 1:1, 2:5, 1:4. Within the above range, A and B have a good synergistic effect. Of course, the molar ratio of A to B is not limited to this, as long as it can achieve a synergistic effect.

[0070] Furthermore, in the preparation method of formula VI' described above, the amount of the composition is not particularly limited, as long as it can achieve a good catalytic effect. For example, the amounts of A and B in the composition are 1-60% of the molar amount of the compound of formula (III), preferably 5-60%. Within the above molar amount range, a good catalytic effect can be achieved. However, the amount of the composition is not limited to this.

[0071] Furthermore, in the preparation method of formula VI' above, the reaction is carried out in a solvent, which is selected from one or more of cyclohexane, methylcyclohexane, benzene, toluene, xylene, chlorobenzene, dichlorobenzene, pyridine, methyl tert-butyl ether, anisole, methyl isobutyl ketone and cyclohexanone, N,N-dimethylformamide, N,N-dimethylacetamide, butyl acetate, and isopropyl acetate; preferably, one or more of methyl isobutyl ketone, cyclohexyl ketone, isopropyl acetate, butyl acetate, or N,N-dimethylformamide. The above solvent meets the temperature requirements of the reaction and is not prone to side reactions with the raw materials, making it suitable for industrial applications.

[0072] Furthermore, in the preparation method of formula VI' described above, the reaction needs to be carried out at a certain temperature. The reaction temperature is not particularly limited, as long as it can effectively complete the relevant reaction. However, the preferred reaction temperature is 80-150℃, more preferably 100-150℃, and most preferably 100-120℃. Studies have found that when the reaction temperature is below 80℃, the reaction time is significantly prolonged, and when the reaction temperature is above 150℃, excessive impurities are generated.

[0073] The invention is illustrated in more detail below with reference to examples; however, these examples are not to be construed as limiting the scope of the invention in any way.

[0074] Example

[0075] Example 1: Preparation of azoxystrobin

[0076] In a 500ml four-necked flask, 67.37g (0.2mol, 95%) of E-2-[2-[6-chloropyrimidin-4-yloxy]phenyl]-3-methoxyacrylate, 27.27g (0.22mol, 96%) of salicylate, 34.02g (0.24mol, 98%) of potassium carbonate, 200ml of butyl acetate, and a certain amount of N,N-dimethylethylamine and DMAP were added. The mixture was heated to 120℃ and maintained at 120℃ for 5 hours. After the reaction, the solvent was removed by vacuum distillation, and the product was obtained by recrystallization with methanol.

[0077] The preparation process of Examples 1-1 to 1-20 below is the same as that of Example 1, except that the amount of N,N-dimethylethylamine and DMAP and their molar ratio are adjusted.

[0078] Table 1 shows the reaction results under different amounts of N,N-dimethylethylamine and DMAP and different molar ratios of the two.

[0079] Table 1. Reaction results using different amounts of N,N-dimethylethylamine and DMAP and their molar ratios.

[0080]

[0081]

[0082]

[0083] Example 2: Preparation of azoxystrobin

[0084] In a 500 ml four-necked flask, 67.37 g (0.2 mol, 95%) of E-2-[2-[6-chloropyrimidin-4-yloxy]phenyl]-3-methoxyacrylate, 27.27 g (0.22 mol, 96%) of salicylate, 34.02 g (0.24 mol, 98%) of potassium carbonate, 200 ml of toluene, and a certain amount of N-methylmorpholine / DMAP were added. The mixture was heated to 100 °C and maintained at 100 °C for 5 h.

[0085] The preparation methods of Examples 2-1 to 2-2 are the same as those of Example 2, except that the amount and molar ratio of N-methylmorpholine and DMAP are adjusted.

[0086] Table 2 shows the reaction results for different amounts of N-methylmorpholine and DMAP and their molar ratios.

[0087] Table 2 shows the reaction results using different amounts of N-methylmorpholine and DMAP and their molar ratios.

[0088]

[0089] Example 3: Preparation of azoxystrobin

[0090] In a 500ml four-necked flask, add 67.37g (0.2mol, 95%) of E-2-[2-[6-chloropyrimidin-4-yloxy]phenyl]-3-methoxyacrylate, 27.27g (0.22mol, 96%) of salicylate, 34.02g (0.24mol, 98%) of potassium carbonate, 200ml of N,N-dimethylformamide, and a certain amount of N,N-dimethylisopropylamine / DMAP. Heat to 80℃ and maintain the temperature at 80℃ for 5h.

[0091] The preparation methods of Examples 3-1 to 3-2 are the same as those of Example 3, except that the amount and molar ratio of N,N-dimethylisopropylamine and DMAP are adjusted.

[0092] Table 3 shows the reaction results for different amounts of N,N-dimethylisopropylamine and DMAP and their molar ratios.

[0093] Table 3. Reaction results using different amounts of N,N-dimethylisopropylamine and DMAP, and their molar ratios.

[0094]

[0095] Example 4: Preparation of azoxystrobin

[0096] In a 500 ml four-necked flask, 67.37 g (0.2 mol, 95%) of E-2-[2-[6-chloropyrimidin-4-yloxy]phenyl]-3-methoxyacrylate, 27.27 g (0.22 mol, 96%) of salicylate, 34.02 g (0.24 mol, 98%) of potassium carbonate, 200 ml of xylene, and a certain amount of hexamethylenetetramine / DMAP were added. The mixture was heated to 150 °C and maintained at 150 °C for 5 h.

[0097] The preparation methods of Examples 4-1 to 4-2 are the same as those of Example 4, except that the amount and molar ratio of hexamethylenetetramine and DMAP are adjusted.

[0098] Table 4 shows the reaction results using different amounts of hexamethylenetetramine and DMAP and their molar ratios.

[0099]

[0100] Example 5: Preparation of azoxystrobin

[0101] In a 500ml four-necked flask, add 67.37g (0.2mol, 95%) of E-2-[2-[6-chloropyrimidin-4-yloxy]phenyl]-3-methoxyacrylate, 27.27g (0.22mol, 96%) of salicylate, 34.02g (0.24mol, 98%) of potassium carbonate, 200ml of N,N-dimethylacetamide, and a certain amount of N-methylpyrrolidine / DMAP. Heat to 100℃ and maintain the temperature at 100℃ for 4 hours.

[0102] The preparation methods of Examples 5-1 to 5-2 are the same as those of Example 5, except that the amount and molar ratio of N-methylpyrrolidine and DMAP are adjusted.

[0103] Table 5 shows the reaction results for different amounts of N-methylpyrrolidine and DMAP and their molar ratios.

[0104] Table 5 shows the reaction results using different amounts of N-methylpyrrolidine and DMAP and their molar ratios.

[0105]

[0106] Example 6: Preparation of azoxystrobin

[0107] In a 500 ml four-necked flask, 67.37 g (0.2 mol, 95%) of E-2-[2-[6-chloropyrimidin-4-yloxy]phenyl]-3-methoxyacrylate, 27.27 g (0.22 mol, 96%) of salicylate, 34.02 g (0.24 mol, 98%) of potassium carbonate, 200 ml of pyridine, and a certain amount of DBU / DMAP were added. The mixture was heated to 110 °C and maintained at 110 °C for 4 h.

[0108] The preparation methods of Examples 6-1 to 6-2 are the same as those of Example 6, except that the amount and molar ratio of DBU and DMAP are adjusted.

[0109] Table 6 shows the reaction results for different amounts of DBU and DMAP used and their molar ratios.

[0110] Table 6. Reaction results using different amounts of DBU and DMAP and their molar ratios.

[0111]

[0112] Example 7 Preparation of azoxystrobin

[0113] In a 500 ml four-necked flask, 67.37 g (0.2 mol, 95%) of E-2-[2-[6-chloropyrimidin-4-yloxy]phenyl]-3-methoxyacrylate, 27.27 g (0.22 mol, 96%) of salicylate, 34.02 g (0.24 mol, 98%) of potassium carbonate, 200 ml of methyl isobutyl ketone, and a certain amount of trimethylamine hydrochloride / DMAP were added. The mixture was heated to 100 °C and maintained at 100 °C for 4 h.

[0114] The preparation methods of Examples 7-1 to 7-2 are the same as those of Example 7, except that the amount and molar ratio of trimethylamine hydrochloride and DMAP are adjusted.

[0115] Table 7 shows the reaction results for different amounts of trimethylamine hydrochloride and DMAP and their molar ratios.

[0116] Table 7. Reaction results using different amounts of trimethylamine hydrochloride and DMAP and their molar ratios.

[0117]

[0118]

[0119] The data in Tables 1 to 7 show that the compositions of this application exhibit a good synergistic effect in the etherification reaction, especially in the preparation of azoxystrobin.

[0120] Although the invention has been described in conjunction with what is now regarded as a practical example, it should be understood that the invention is not limited to the disclosed embodiments, but rather is intended to cover various modifications and equivalent substitutions contained within the spirit and scope of the appended claims.

Claims

1. A composition for etherification reactions, characterized in that, Includes A and B, wherein A is selected from one or more of the following: N,N-dimethylethylamine, N,N-dimethylisopropylamine, N,N-diethylmethylamine, trimethylamine, 1,8-diazabicyclo[5.4.0]undec-7-ene, hexamethylenetetramine, N-methylpyrrolidine, N-methylmorpholine, and salts of the above compounds; The B is The compounds of formula (II) and their salts are represented, wherein Z1 is N, Z2, Z3, Z4 and Z5 are each independently selected from C, and R4 and R5 are each independently selected from hydrogen atoms or C1-C. 10 Alkyl group; the molar ratio of A to B is a synergistic ratio of 1:10-500:1; the amount of B is greater than 0 mol based on 1 mol of the composition.

2. The composition according to claim 1, characterized in that, The R4 and R5 mentioned therein are each independently selected from hydrogen atoms, hydrogen atoms, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl or decyl.

3. The composition according to claim 2, characterized in that, Wherein B is 4-dimethylaminopyridine.

4. The composition according to any one of claims 1 to 3, characterized in that, Based on the amount of 1 mol of the composition, the amount of B is greater than 0.001 mol.

5. The composition according to claim 4, characterized in that, The molar ratio of A to B in the composition is 80:1 to 1:

4.

6. The composition according to claim 5, characterized in that, The molar ratio of A to B in the composition is 80:1, 12.5:1, 6:1, 5:1, 3:1, 2:1, 1:1, 2:5 or 1:

4.

7. A method for preparing a compound of formula VI', characterized in that, The reaction involves the etherification of compounds of formula III' and V' under the catalysis of the composition. The structures of formulas VI', III', and V' are as follows: VI', III', V', Where M is a hydrogen atom or a metal ion. The composition is the composition according to any one of claims 1-6.

8. The preparation method according to claim 7, characterized in that, M is hydrogen, sodium, potassium, or calcium.

9. The preparation method according to 7, characterized in that, The amount of A used is 1-60% of the molar amount of compound III'.

10. The preparation method according to 9, characterized in that, The amount of A is 5-60% of the molar amount of compound III'.

11. The preparation method according to claim 7, characterized in that, The amount of B used is 1-60% of the molar amount of compound III'.

12. The preparation method according to claim 11, characterized in that, The amount of B used is 5-60% of the molar amount of compound III'.

13. The preparation method according to claim 7, characterized in that, A solvent is added during the reaction, and the solvent is selected from one or more of the following: cyclohexane, methylcyclohexane, benzene, toluene, xylene, chlorobenzene, dichlorobenzene, pyridine, methyl tert-butyl ether, anisole, methyl isobutyl ketone and cyclohexanone, N,N-dimethylformamide, N,N-dimethylacetamide, butyl acetate, and isopropyl acetate.

14. The preparation method according to claim 13, characterized in that, A solvent is added to the reaction, and the solvent is selected from one or more of methyl isobutyl ketone, cyclohexanone, isopropyl acetate, butyl acetate, or N,N-dimethylformamide.

15. The preparation method according to claim 7, characterized in that, The reaction is carried out at a certain temperature, which is 80-150℃.

16. The preparation method according to claim 15, characterized in that, The reaction is carried out at a certain temperature, which is 100-150℃.

17. The preparation method according to claim 16, characterized in that, The reaction is carried out at a certain temperature, which is 100-120℃.

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