CN113563287B - Preparation method of epoxy caprylate and preparation method of melonal - Google Patents
Preparation method of epoxy caprylate and preparation method of melonal Download PDFInfo
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- CN113563287B CN113563287B CN202110784639.3A CN202110784639A CN113563287B CN 113563287 B CN113563287 B CN 113563287B CN 202110784639 A CN202110784639 A CN 202110784639A CN 113563287 B CN113563287 B CN 113563287B
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- C07C45/57—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds with oxygen as the only heteroatom
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Abstract
The invention relates to a preparation method of epoxy caprylate and a preparation method of melonal. The preparation method of the epoxy caprylate comprises the following steps: in a solvent, in the presence of a first alkaline substance and a first catalyst, performing a dada reaction on methyl heptenone and alpha-halogenated acetate to obtain a first reaction liquid; separating the first reaction liquid to obtain epoxy caprylate; wherein, the first catalyst comprises transition metal ions and Schiff base ligand combined with the transition metal ions, the structure of the Schiff base ligand is shown in the formula (I),
Description
Technical Field
The invention relates to the technical field of organic chemical synthesis, in particular to a preparation method of epoxy caprylate and a preparation method of melonal.
Background
The cucumis melo aldehyde (English name: melonal) has the chemical name of 2, 6-dimethyl-5-heptenal, is colorless or faint yellow oily liquid, has strong fragrance similar to fresh melons, is mainly used for preparing essences of melons, cucumbers and tropical fruits, is also an important intermediate of a novel medicament, and can be used as a medicinal raw material medicament. The currently reported synthetic methods mainly include the following methods:
patent US2014/128622 discloses that using citral as raw material, using hydrogen peroxide to perform bayer-Villiger (Baeyer-Villiger) oxidation rearrangement reaction, and then performing hydrolysis reaction to prepare cucumis melo aldehyde, wherein the total reaction yield is 70%. However, the scheme has high safety risk, and the used raw and auxiliary materials have high cost and are not suitable for industrial production.
Patent WO2018/069456 discloses the preparation of cucumis melo aldehyde by reacting methyl heptenone, methyl chloroacetate and sodium alkoxide in an organic solvent to obtain epoxy caprylate, and then saponifying, acidifying and decarboxylating. Although the process has wide raw material sources, the raw material sodium alkoxide is dangerous, a reaction system is absolutely anhydrous and is carried out at the temperature of minus 15-20 ℃, and the reaction conditions are harsh.
Patent CN111320540A discloses that methyl heptenone, chloroacetate and acid-binding agent are subjected to a reaction under the presence of a solvent and a phase transfer catalyst to obtain epoxy caprylate, and then saponification, acidification and decarboxylation are performed to prepare cucumis melo aldehyde. The method does not use dangerous raw material sodium alkoxide, the reaction temperature is raised to room temperature, but the phase transfer catalyst cannot be recycled, waste water or waste salt containing the catalyst can be generated, environmental protection treatment is needed, the environmental protection cost is increased, and the purity and the yield of the product still have a space for improvement.
Disclosure of Invention
In view of the above, it is necessary to provide a method for preparing epoxy caprylate and cucumis melo aldehyde, which has the advantages of good safety of raw materials, mild reaction conditions, and excellent purity and yield of prepared cucumis melo aldehyde.
The preparation method of the epoxy caprylate provided by the invention comprises the following steps:
in a solvent, in the presence of a first alkaline substance and a first catalyst, performing a dawning reaction on methyl heptenone and alpha-haloacetate to obtain a first reaction liquid; and
separating the epoxy caprylate from the first reaction liquid;
wherein the first catalyst comprises transition metal ions and Schiff base ligands, the transition metal ions and the Schiff base ligands are combined through transition metal-oxygen coordination bonds and/or transition metal-nitrogen coordination bonds, the structure of the Schiff base ligands is shown in a formula (I),
in the formula (I), p is 2, 3, 4 or 5, n is 0, 1 or 2, m is 0, 1 or 2 1 And R 2 Independently selected from methyl, ethyl, methoxy or ethoxy.
In one embodiment, the transition metal ions comprise Cu 2+ 、Co 2+ 、Ni 2+ 、Ti 4+ Or Fe 2+ At least one of;
and/or the Schiff base ligand comprises at least one of disalicylaldehyde ethylenediamine Schiff base, disalicylaldehyde propylenediamine Schiff base, disalicylaldehyde butanediamine Schiff base, bis-5-methyl salicylaldehyde ethylenediamine Schiff base, bis-5-methyl salicylaldehyde propylenediamine Schiff base, bis-5-methyl salicylaldehyde succinamide Schiff base, bis-o-vanillin ethylenediamine Schiff base, bis-o-vanillin propylenediamine Schiff base or bis-o-vanillin succinamide Schiff base.
In one embodiment, the first alkaline material comprises a carbonate.
In one embodiment, the α -haloacetate comprises at least one of ethyl chloroacetate, methyl chloroacetate, isopropyl chloroacetate, methyl bromoacetate, ethyl bromoacetate, or isopropyl bromoacetate.
In one embodiment, the molar ratio of the methylheptenone to the α -haloacetate is from 2;
and/or the molar ratio of the first basic substance to the α -haloacetate is from 0.8;
and/or the mass ratio of the first catalyst to the α -haloacetate is from 0.005.
In one embodiment, the solvent comprises at least one of toluene, cyclohexane, petroleum ether, or dichloroethane.
In one embodiment, the step of performing a dada reaction on methyl heptenone and an alpha-haloacetate is performed at a temperature of 20 ℃ to 70 ℃.
In the preparation method of the epoxy caprylate, the Schiff base ligand in the first catalyst has the characteristics of small volume, high flexibility and high electronegativity, so that the first catalyst and the first alkaline substance have good adaptability to the substrate of the reaction of the first catalyst and the first alkaline substance. Thus, the first catalyst is capable of increasing the electronegativity of the carbonyl oxygen in methylheptenone as well as in α -haloacetates. Furthermore, on one hand, the electrophilicity of carbonyl carbon in the methyl heptenone can be enhanced, and the carbonyl carbon is more easily attacked by a nucleophilic reagent; on the other hand, the acidity of alpha-carbon of the alpha-haloacetate can be enhanced, so that alpha-H is easier to leave in the presence of a first alkaline substance to form alpha-carbanion, the alpha-carbanion further forms an active complex with a first catalyst, the formation of the active complex not only avoids nucleophilic substitution and condensation side reactions of the alpha-carbanion and the alpha-haloacetate, but also has small steric hindrance and can generate nucleophilic addition reaction with methyl heptenone to form an alkoxy anion, and meanwhile, the first catalyst is also complexed with halogen groups of the alpha-haloacetate to improve the leaving capacity of the halogen groups, and finally the alkoxy anion attacks the alpha-carbon to obtain the epoxy caprylate.
In addition, the first catalyst has excellent safety and catalytic activity, so that the participating reaction can be carried out under mild conditions, the process requirement is reduced, the self nucleophilic substitution and condensation side reaction of the alpha-haloacetate can be avoided, and the formation of byproducts is effectively reduced.
A preparation method of melonal comprises the following steps:
providing an epoxy octoate solution, wherein the epoxy octoate solution is the first reaction solution or is obtained by dissolving the epoxy octoate obtained by the preparation method in a solvent;
mixing the epoxy caprylate solution with an alkaline solution, and performing saponification reaction to obtain a second reaction solution; separating the epoxy acid from the second reaction solution; and
and performing decarboxylation on the epoxy acid to obtain the cucumis melo aldehyde.
In one embodiment, the alkaline solution comprises a second alkaline substance, the second alkaline substance comprises sodium hydroxide or potassium hydroxide, the mass fraction of the second alkaline substance in the alkaline solution is 10% -30%, and the molar ratio of the second alkaline substance to the α -haloacetate is 1.
In one embodiment, the step of separating the epoxy acid from the second reaction solution comprises:
and firstly, separating the second reaction solution to obtain a first organic phase and a first water phase, acidifying the first water phase, and separating to obtain the epoxy acid.
In an embodiment, after the step of separating into a first organic phase and a first aqueous phase, the first organic phase circulation jacket is used for preparing the epoxy octoate solution.
In one embodiment, the step of performing saponification is performed at a temperature of 5 ℃ to 35 ℃.
In one embodiment, the step of decarboxylating the epoxy acid comprises:
and in the presence of a second catalyst, carrying out reduced pressure decarboxylation on the epoxy acid, wherein the temperature is 70-120 ℃, and the vacuum degree is 500-1000 Pa.
In one embodiment, the second catalyst comprises a copper salt, and the mass ratio of the copper salt to the α -haloacetate is from 0.005 to 0.05.
The preparation method of the cucumis melo aldehyde provided by the invention has the advantages of good raw material safety and mild reaction conditions, and effectively avoids side reactions, so that the prepared cucumis melo aldehyde has excellent purity and yield, the aroma quality of the cucumis melo aldehyde is further improved, and the product competitiveness is improved.
In addition, when the epoxy caprylate solution is the first reaction solution, the first catalyst in the first reaction solution has excellent stability and does not influence the saponification reaction of the epoxy caprylate, so that the first reaction solution can be directly saponified without purification, the operation is simpler and more convenient, the equipment investment is reduced, and the method is suitable for industrial mass production.
Detailed Description
The preparation method of epoxy caprylate and preparation method of melonal provided by the invention are further described below.
The preparation method of the epoxy caprylate provided by the invention comprises the following steps:
s11, in a solvent, carrying out a dawning reaction on methyl heptenone and alpha-haloacetate in the presence of a first alkaline substance and a first catalyst to obtain a first reaction liquid; and
and S12, separating the epoxy caprylate from the first reaction liquid.
In step S11, methylheptenone has the formula
The structural formula of the alpha-haloacetate is
Wherein X is Cl, br or I, R 3 Selected from methyl, ethyl or isopropyl, and the structural formula of the epoxy caprylate generated by the dapsone reaction between methyl heptenone and alpha-halogenoacetate is->
Specifically, the first catalyst comprises transition metal ions and Schiff base ligands, the transition metal ions and the Schiff base ligands are combined through transition metal-oxygen coordination bonds and/or transition metal-nitrogen coordination bonds, the structure of the Schiff base ligands is shown as the formula (I),
in the formula (I), p is 2, 3, 4 or 5, n is 0, 1 or 2, m is 0, 1 or 2 1 And R 2 Independently selected from methyl, ethyl, methoxy or ethoxy.
Therefore, schiff base ligands in the first catalyst have the characteristics of small volume, large flexibility and high electronegativity, so that the first catalyst, the first alkaline substance and a substrate for a dawn reaction have good adaptability, and the first catalyst can improve the electronegativity of carbonyl oxygen in methyl heptenone, further enhance the electrophilicity of carbonyl carbon in the methyl heptenone, and are more easily attacked by a nucleophilic reagent.
Meanwhile, the electronegativity of carbonyl oxygen in the alpha-haloacetate can be improved by the first catalyst, so that the acidity of alpha-carbon of the alpha-haloacetate is enhanced, alpha-H is easy to leave in the presence of a first alkaline substance to form alpha-carbanion, further, the alpha-carbanion and the first catalyst form an active complex, the formation of the active complex can avoid nucleophilic substitution and condensation side reactions of the alpha-carbanion and the alpha-haloacetate on one hand, and on the other hand, the steric hindrance of the active complex is small, so that nucleophilic addition reaction can be smoothly carried out with methylheptenone to form an alkoxy anion, and meanwhile, the first catalyst is also complexed with a halogen group of the alpha-haloacetate to improve the leaving capacity of the halogen group, and finally the alkoxy anion attacks the alpha-carbon to obtain the epoxy caprylate.
In addition, the first catalyst has excellent safety and catalytic activity, so that the parameter reaching reaction can be carried out under mild conditions, the process requirement is reduced, the nucleophilic substitution and condensation side reaction of alpha-haloacetate can be avoided, and the formation of byproducts is effectively reduced.
In one embodiment, to further enhance the catalytic effect of the first catalyst, the transition metal ion comprises Cu 2+ 、Co 2+ 、Ni 2+ 、Ti 4+ Or Fe 2+ Preferably comprises Cu 2+ 、Co 2+ Or Ni 2+ At least one of (1).
In one embodiment, in order to further reduce the steric hindrance of the daemon reaction, the structure of the Schiff base ligand is shown as formula (I-a), formula (I-b) or formula (I-c),
in the formula (I-a), p is 2, 3, 4 or 5;
in the formulae (I-b) and (I-c), p is 2, 3, 4 or 5 1 And R 2 Independently selected from methyl, ethyl, methoxy or ethoxy.
In one embodiment, the schiff base ligand comprises at least one of disalicylaldehyde ethylenediamine schiff base, disalicylaldehyde propylenediamine schiff base, disalicylaldehyde butanediamine schiff base, bis-5-methyl salicylaldehyde ethylenediamine schiff base, bis-5-methyl salicylaldehyde propylenediamine schiff base, bis-5-methyl salicylaldehyde succinamide schiff base, bis-o-vanillin ethylenediamine schiff base, bis-o-vanillin propylenediamine schiff base, or bis-o-vanillin succinamide schiff base; preferably comprising disalicylaldehyde ethylenediamine schiff base.
The structural formula of the disalicylaldehyde ethylene diamine Schiff base is shown as follows
In this case, n and m are both 0, p is 2; the structural formula of the bis 5-methyl salicylidene ethylenediamine Schiff base is represented as->
In this case, n and m are both 1, p is 2 1 And R 2 Are both methyl; the structural formula of the bis-o-vanillin ethylene diamine Schiff base is shown in the specification
In this case, n and m are both 1, p is 2 1 And R 2 Are all methoxy groups.
In one embodiment, the α -haloacetate preferably comprises at least one of ethyl chloroacetate, methyl chloroacetate, isopropyl chloroacetate, methyl bromoacetate, ethyl bromoacetate, or isopropyl bromoacetate.
In one embodiment, the mass ratio of the first catalyst to the α -haloacetate is from 0.005 to 1.0.02, more preferably from 0.008.
In order to better reduce the halogen substitution, ester decomposition and self nucleophilic substitution and condensation side reaction of the α -haloacetate, resulting in a decrease in the yield of the epoxy octanoate, the first basic substance preferably comprises a carbonate, and in one embodiment, the carbonate comprises potassium carbonate or sodium carbonate, and the carbonate preferably comprises potassium carbonate in view of its excellent solubility in the solvent. The molar ratio of the first basic substance to the α -haloacetate is from 0.8 to 1.3, more preferably from 1 to 1.2.
In order to further avoid the condensation side reaction of α -haloacetate itself, thereby increasing the yield and purity of epoxy octanoate, in one embodiment, step S11 comprises:
s111, mixing a first alkaline substance, a first catalyst and a solvent to obtain a first mixed solution, and mixing methyl heptenone and alpha-haloacetate to obtain a second mixed solution; and
and S112, adding the second mixed solution into the first mixed solution to enable methyl heptenone and the alpha-halogenated acetate to perform a reaction in the presence of a first alkaline substance and a first catalyst to obtain a first reaction solution.
In step S112, the addition is preferably carried out in a batch manner, for example, dropwise, and the total time of addition is controlled to be 3 hours to 6 hours, preferably 4 hours to 5 hours, and stirring is carried out during the addition, and the temperature is controlled to be 20 ℃ to 70 ℃.
In order to further reduce the occurrence of side reactions of self-condensation of α -haloacetate and avoid the contamination of incompletely reacted α -haloacetate in the first reaction solution, and to perform saponification, acidification and decarboxylation reactions, which leads to a decrease in the purity of cucumis meloaldehyde, in one embodiment, the molar ratio of methylheptenone to α -haloacetate is from 2.
In one embodiment, the solvent comprises at least one of toluene, cyclohexane, petroleum ether, or dichloroethane.
In one embodiment, the temperature in the step of performing the datuming reaction of methylheptenone with an α -haloacetate is 20 ℃ to 70 ℃, more preferably 40 ℃ to 50 ℃.
In addition, the present invention is not limited to the separation method of the epoxy caprylate, and in one embodiment, the step S12 includes: and washing and rectifying the first reaction liquid to obtain the epoxy caprylate.
The invention also provides a preparation method of cucumis melo aldehyde, which can be carried out on the basis of the preparation method of epoxy caprylate provided by the invention and comprises the following steps:
s21, providing an epoxy caprylate solution;
s22, mixing the epoxy caprylate solution with the alkaline solution, and performing saponification reaction to obtain a second reaction solution;
s23, separating the epoxy acid from the second reaction liquid; and
and S24, carrying out decarboxylation on the epoxy acid to obtain the cucumis melo aldehyde.
Specifically, in step S21, the epoxy caprylate solution is the first reaction solution or the epoxy caprylate obtained by the preparation method described above is dissolved in a solvent.
When the epoxy caprylate solution is the first reaction solution, the first catalyst in the first reaction solution has excellent stability and does not influence the saponification reaction of the epoxy caprylate, so that the first reaction solution can be directly saponified without purification, the operation is simpler and more convenient, the equipment investment is reduced, and the method is suitable for industrial mass production.
In step S22, the alkaline solution comprises a second alkaline substance, and in order to complete the saponification reaction of the epoxy caprylate, in one embodiment, the molar ratio of the second alkaline substance to the α -haloacetate is 1 to 1.2, and the second alkaline substance comprises sodium hydroxide or potassium hydroxide.
In one embodiment, the temperature in the step of performing the saponification reaction is 5 ℃ to 35 ℃, more preferably 15 ℃ to 25 ℃.
In order to avoid too violent saponification in view of the exothermic reaction of saponification, in one embodiment, the second basic substance is present in the alkaline solution in an amount of 10% to 30% by mass.
In one embodiment, mixing the first reaction solution with the alkaline solution comprises: the alkaline solution is added to the first reaction solution, preferably in a batch manner, for example, dropwise, and during the addition, stirring is performed, and the temperature is controlled to be 5 ℃ to 35 ℃.
It will be appreciated that the epoxy acid has the formula
In one embodiment, step S23 includes: and (3) firstly separating the second reaction solution to obtain a first organic phase and a first water phase, acidifying the first water phase, and separating to obtain the epoxy acid.
It will be appreciated that the first aqueous phase resulting from the separation will include a salt corresponding to the epoxy acid.
In one embodiment, the step of acidifying the first aqueous phase and separating to obtain the epoxy acid comprises: and mixing the first water phase with an extracting agent, adding an acidic substance for acidification, then carrying out liquid separation, separating a second organic phase from a second water phase, and washing and distilling the second organic phase to obtain the epoxy acid.
To avoid the introduction of acidic species into the second organic phase, and preferably to separate the epoxy acid from the second organic phase, the acidic species preferably comprises a mineral acid, and in one embodiment, the mineral acid comprises at least one of hydrochloric acid, sulfuric acid, or phosphoric acid.
In the step of adding the acidic substance for acidification, the acidic substance is preferably added in portions, such as dropwise, and stirred during the addition, and the temperature is controlled to be 5-35 ℃.
In one embodiment, the extractant comprises at least one of toluene, cyclohexane, dichloroethane, or petroleum ether, preferably toluene or cyclohexane. It will be appreciated that during distillation the extractant can be separated from the second organic phase and recycled for use in the extraction of the epoxy acid.
In one embodiment, after the step of separating the resulting first organic phase and first aqueous phase, the first organic phase is recycled for use in preparing the epoxy octoate solution.
When the epoxy caprylate solution is the first reaction solution, the first organic phase obtained by liquid separation includes the solvent and the first catalyst, and in one embodiment, the first organic phase further includes unreacted methyl heptenone. The first catalyst still keeps excellent catalytic activity after saponification reaction, so that the first organic phase is circularly sleeved for the reaction to prepare epoxy caprylate, and further prepare epoxy caprylate solution.
When the epoxy octoate solution is prepared by dissolving the epoxy octoate obtained by the above preparation method in a solvent, the first organic phase obtained by liquid separation comprises the solvent, and at this time, the first organic phase is circularly used for dissolving the epoxy octoate to prepare the epoxy octoate solution.
Therefore, the operation of first separating liquid and then acidifying can reduce the environmental protection cost; in addition, in the liquid separation process, fat-soluble byproducts enter the first organic phase, and the epoxy acid in the first water phase is primarily purified, so that the purification operation of the cucumis melo aldehyde is simplified.
It should be noted that the present invention does not limit the decarboxylation process of epoxy acid, and in one embodiment, step S23 includes:
s231, in the presence of a second catalyst, carrying out reduced pressure decarboxylation on epoxy acid to obtain a third reaction liquid; and
and S232, separating the cucumis melo aldehyde from the third reaction solution.
In one embodiment, in step S231, the temperature is from 70 ℃ to 120 ℃, more preferably from 90 ℃ to 110 ℃, and the vacuum is from 500Pa to 1000Pa, more preferably from 500Pa to 800Pa.
In one embodiment, the second catalyst comprises a copper salt, such as copper sulfate or copper chloride, and the mass ratio of the copper salt to the α -haloacetate is from 0.005 to 1.05, more preferably from 0.01 to 0.05.
And step S232, rectifying the third reaction liquid to obtain the cucumis melo aldehyde.
In one embodiment, the temperature of the rectification is from 70 ℃ to 90 ℃.
The cucumis melo aldehyde prepared by the preparation method provided by the invention has excellent purity and yield, the aroma quality of the cucumis melo aldehyde is further improved, and the product competitiveness is improved.
Hereinafter, the method for preparing epoxy octanoate and the method for preparing melonal will be further described by the following specific examples.
Example 1
Adding 29g of sodium carbonate and 0.8g of nickel (II) bis (salicylaldehyde) ethylenediamine into 200g of dichloroethane, uniformly mixing, and heating to 40 ℃ to obtain a first mixed solution; mixing 42g of methyl heptenone and 41g of ethyl chloroacetate to obtain a second mixed solution; and dropwise adding the second mixed solution into the first mixed solution, maintaining the temperature at 40 ℃ in the dropwise adding process, keeping the temperature for 6 hours, keeping the temperature for 2 hours after the dropwise adding is finished to ensure that the ginseng completely reacts, and then cooling to room temperature to obtain a first reaction solution, wherein the first reaction solution comprises epoxy ethyl caprylate.
And dropwise adding 130g of aqueous sodium hydroxide solution into the first reaction solution under stirring to perform saponification, controlling the temperature to be 25-35 ℃ in the dropwise adding process, keeping the mass fraction of sodium hydroxide in the aqueous sodium hydroxide solution at 10%, keeping the temperature at 25-35 ℃ for 1 hour after dropwise adding is finished, so that the saponification is complete, and then cooling to room temperature to obtain a second reaction solution.
Standing and separating the second reaction solution, and separating to obtain a first organic phase and a first water phase, wherein the first organic phase comprises nickel (II) bis (salicylaldehyde) ethylenediamine and dichloroethane; the first water phase comprises sodium salt of epoxy acid, the first organic phase is recycled and used for reaction, 200g of dichloroethane is added into the first water phase, then the first water phase is acidified to pH of about 3 by concentrated hydrochloric acid, the temperature is controlled to be 25-35 ℃ in the acidification process, standing and layering are carried out after the acidification is finished, the second water phase is discarded, the second organic phase is washed by water, and dichloroethane is removed by atmospheric distillation, so that residue comprising epoxy acid is obtained.
Adding 0.3g of copper chloride into the residue, and performing reduced pressure decarboxylation reaction, wherein in the process of reduced pressure decarboxylation, the temperature is 70 ℃, the vacuum degree is 500pa, and the reduced pressure decarboxylation reaction is complete, so as to obtain a crude product of the cucumis melo aldehyde; and (3) carrying out rectification purification on the crude product of the cucumis melo aldehyde under reduced pressure, wherein the rectification temperature is 70 ℃, so that 41.09g of product cucumis melo aldehyde is obtained, the yield is 87.59 percent based on ethyl chloroacetate, and the purity is 98.2 percent.
Example 2
Adding 46g of potassium carbonate and 0.3g of bis-salicylaldehyde ethylene diamine cobalt (II) into 200g of toluene, uniformly mixing, and heating to 55 ℃ to obtain a first mixed solution; mixing 84g of methylheptenone and 41g of ethyl chloroacetate to obtain a second mixed solution; and dropwise adding the second mixed solution into the first mixed solution, wherein the temperature is maintained at 55 ℃ in the dropwise adding process, the dropwise adding time is 4 hours, after the dropwise adding is finished, continuously preserving the heat for 2 hours to ensure that the ginseng reacts completely, and then cooling to 5 ℃ to obtain a first reaction solution, wherein the first reaction solution comprises epoxy ethyl caprylate.
And dropwise adding 65g of aqueous sodium hydroxide solution into the first reaction solution under stirring to perform saponification, wherein the temperature is controlled to be lower than 20 ℃ in the dropwise adding process, the mass fraction of sodium hydroxide in the aqueous sodium hydroxide solution is 20%, after dropwise adding is finished, keeping the temperature at 20 ℃ for 1 hour to complete the saponification, and then cooling to room temperature to obtain a second reaction solution.
Standing and separating the second reaction solution, and separating to obtain a first organic phase and a first water phase, wherein the first organic phase comprises salicylaldehyde ethylene diamine cobalt (II), toluene and unreacted methyl heptenone; the first water phase comprises sodium salt and potassium salt of epoxy acid, the first organic phase is recycled and used for the reaction of the ginseng, 200g of toluene is added into the first water phase, then concentrated hydrochloric acid is used for acidification until the pH value is about 4, the temperature is controlled to be 10-25 ℃ in the acidification process, standing and layering are carried out after the acidification is finished, the second water phase is discarded, the second organic phase is washed by water, and the toluene is removed by normal pressure distillation, so that the residue comprising the epoxy acid is obtained.
Adding 2g of copper sulfate into the residue, and performing reduced pressure decarboxylation reaction, wherein in the process of reduced pressure decarboxylation, the temperature is 100 ℃, the vacuum degree is 800pa, and the reduced pressure decarboxylation reaction is complete to obtain a crude product of the cucumis melo aldehyde; and (3) carrying out rectification and purification on the crude product of the cucumis melo aldehyde under reduced pressure, wherein the rectification temperature is 90 ℃, so that 44.63g of product cucumis melo aldehyde is obtained, the yield is 95.13% in terms of ethyl chloroacetate, and the purity is 98.9%.
Example 3
Adding 35g of sodium carbonate and 0.4g of bis-salicylaldehyde copper (II) ethylenediamine condensate into 200g of cyclohexane, uniformly mixing, and heating to 65 ℃ to obtain a first mixed solution; mixing 63g of methylheptenone and 42g of ethyl chloroacetate to obtain a second mixed solution; and dropwise adding the second mixed solution into the first mixed solution, wherein the temperature is maintained at 65 ℃ in the dropwise adding process, the dropwise adding time is 3 hours, after the dropwise adding is finished, continuously preserving the heat for 2 hours to ensure that the ginseng reacts completely, and then cooling to 10 ℃ to obtain a first reaction solution, wherein the first reaction solution comprises epoxy ethyl caprylate.
And (2) dropwise adding 41g of sodium hydroxide aqueous solution into the first reaction solution under stirring to perform saponification, controlling the temperature to be lower than 25-35 ℃ in the dropwise adding process, keeping the mass fraction of sodium hydroxide in the sodium hydroxide aqueous solution at 30%, keeping the temperature at 25-35 ℃ for 1 hour after dropwise adding is finished to complete saponification, and then cooling to room temperature to obtain a second reaction solution.
Standing and separating the second reaction solution to obtain a first organic phase and a first water phase; the first water phase comprises sodium salt of epoxy acid, the first organic phase is recovered and circularly used for reaction, 200g of cyclohexane is added into the first water phase, then 30% sulfuric acid is used for acidification until the pH value is about 2, the temperature is controlled to be 25-35 ℃ in the acidification process, standing and layering are carried out after the acidification is finished, the second water phase is discarded, the second organic phase is washed by water, and cyclohexane is removed through atmospheric distillation, so that residue comprising epoxy acid is obtained.
Adding 1.5g of copper sulfate into the residue, and performing reduced pressure decarboxylation reaction, wherein in the process of reduced pressure decarboxylation, the temperature is 120 ℃, the vacuum degree is 1000pa, and the reduced pressure decarboxylation reaction is complete to obtain a melon aldehyde crude product; and (3) carrying out rectification and purification on the crude product of the cucumis melo aldehyde under reduced pressure, wherein the rectification temperature is 90 ℃, so that 43.0g of product cucumis melo aldehyde is obtained, the yield is 89.48 percent based on ethyl chloroacetate, and the purity is 98.5 percent.
Example 4
Adding 50.6g of potassium carbonate and 0.9g of bis-salicylaldehyde copper ethylenediamine (II) into 150g of dichloroethane, uniformly mixing, and heating to 60 ℃ to obtain a first mixed solution; mixing 54.6g of methylheptenone with 36.2g of methyl chloroacetate to obtain a second mixed solution; and dropwise adding the second mixed solution into the first mixed solution, wherein the temperature is maintained at 60 ℃ in the dropwise adding process, the dropwise adding time is 5 hours, after the dropwise adding is finished, continuously preserving the heat for 2 hours to ensure that the ginseng reacts completely, and then cooling to 5 ℃ to obtain a first reaction solution, wherein the first reaction solution comprises epoxy methyl caprylate.
And (2) dropwise adding 120g of potassium hydroxide aqueous solution into the first reaction solution under stirring to perform saponification, wherein in the dropwise adding process, the temperature is controlled to be lower than 5-20 ℃, the mass fraction of potassium hydroxide in the potassium hydroxide aqueous solution is 15%, after dropwise adding is finished, the temperature is kept at 20 ℃ for 1 hour to complete the saponification, and then the temperature is reduced to room temperature to obtain a second reaction solution.
Standing and separating the second reaction solution to obtain a first organic phase and a first water phase; the first water phase comprises potassium salt of epoxy acid, the first organic phase is recycled and used for the reaction, 150g of dichloroethane is added into the first water phase, then the first water phase is acidified to pH value of about 3 by phosphoric acid, the temperature is controlled to be 10-25 ℃ in the acidification process, standing and layering are carried out after the acidification is finished, the second water phase is discarded, the second organic phase is washed by water, and dichloroethane is removed by atmospheric distillation, so that residue comprising epoxy acid is obtained.
Adding 1g of copper sulfate into the residue, and performing reduced pressure decarboxylation reaction, wherein in the process of reduced pressure decarboxylation, the temperature is 85 ℃, the vacuum degree is 600pa, and the reduced pressure decarboxylation reaction is complete to obtain a crude product of the cucumis melo aldehyde; and (3) carrying out rectification and purification on the crude product of the cucumis melo aldehyde under reduced pressure, wherein the rectification temperature is 80 ℃, so that 41.2g of product cucumis melo aldehyde is obtained, the yield is 88.08 percent based on methyl chloroacetate, and the purity is 99.3 percent.
Example 5
Uniformly mixing the first organic phase recovered in example 1 with 47.5g of potassium carbonate, and then heating to 50 ℃ to obtain a first mixed solution; mixing 47g of methylheptenone and 36.2g of methyl chloroacetate to obtain a second mixed solution; and dropwise adding the second mixed solution into the first mixed solution, maintaining the temperature at 50 ℃ in the dropwise adding process, keeping the dropwise adding time for 4.5 hours, keeping the temperature for 2 hours after the dropwise adding is finished to ensure that the ginseng completely reacts, and then cooling to 5 ℃ to obtain a first reaction solution, wherein the first reaction solution comprises epoxy methyl caprylate.
And (2) dropwise adding 130g of sodium hydroxide aqueous solution into the first reaction solution under stirring to perform saponification, controlling the temperature to be lower than 5-20 ℃ in the dropwise adding process, keeping the mass fraction of sodium hydroxide in the sodium hydroxide aqueous solution at 10%, keeping the temperature at 20 ℃ for 1 hour after the dropwise adding is finished to complete the saponification, and then cooling to room temperature to obtain a second reaction solution.
Standing and separating the second reaction solution to obtain a first organic phase and a first water phase; the first aqueous phase comprises sodium salt and potassium salt of epoxy acid, the first organic phase is recovered, 200g of dichloroethane is added into the first aqueous phase, then the mixture is acidified to pH of about 3 by sulfuric acid, the temperature is controlled to be 15-25 ℃ in the acidification process, standing and layering are carried out after the acidification is finished, the second aqueous phase is discarded, and the dichloroethane is removed by washing and atmospheric distillation of the second organic phase, so that residue comprising epoxy acid is obtained.
Adding 1.8g of copper sulfate into the residue, and performing reduced pressure decarboxylation reaction, wherein in the process of reduced pressure decarboxylation, the temperature is 85 ℃, the vacuum degree is 600pa, and the reduced pressure decarboxylation reaction is complete, so as to obtain a crude product of the cucumis melo aldehyde; and (3) carrying out rectification and purification on the crude product of the cucumis melo aldehyde under reduced pressure, wherein the rectification temperature is 90 ℃, so that 42.8g of product cucumis melo aldehyde is obtained, the yield is 91.50 percent based on methyl chloroacetate, and the purity is 98.1 percent.
Example 6
Uniformly mixing the first organic phase (containing about 43g of unreacted methylheptenone) recovered in example 2 with 47.5g of potassium carbonate, and heating to 50 ℃ to obtain a first mixed solution; mixing 40g of methyl heptenone and 41.1g of ethyl chloroacetate to obtain a second mixed solution; and dropwise adding the second mixed solution into the first mixed solution, wherein the temperature is maintained at 55 ℃ in the dropwise adding process, the dropwise adding time is 5 hours, after the dropwise adding is finished, continuously preserving the heat for 2 hours to ensure that the ginseng reacts completely, and then cooling to 5 ℃ to obtain a first reaction solution, wherein the first reaction solution comprises epoxy ethyl caprylate.
And (2) dropwise adding 130g of potassium hydroxide aqueous solution into the first reaction solution under stirring to perform saponification, wherein the temperature is controlled to be lower than 5-20 ℃ in the dropwise adding process, the mass fraction of potassium hydroxide in the potassium hydroxide aqueous solution is 15%, after dropwise adding is finished, the temperature is kept at 20 ℃ for 1 hour to complete the saponification, and then the temperature is reduced to room temperature to obtain a second reaction solution.
Standing and separating the second reaction solution to obtain a first organic phase and a first water phase; the first aqueous phase comprises potassium salt of epoxy acid, the first organic phase is recovered, 200g of toluene is added into the first aqueous phase, then the first aqueous phase is acidified to pH of about 4 by sulfuric acid, the temperature is controlled to be 15-30 ℃ in the acidification process, standing and layering are carried out after the acidification is finished, the second aqueous phase is discarded, the second organic phase is washed by water, and the toluene is removed by atmospheric distillation, so that residue comprising epoxy acid is obtained.
Adding 1.8g of copper sulfate into the residue, and performing reduced pressure decarboxylation reaction, wherein in the process of reduced pressure decarboxylation, the temperature is 90 ℃, the vacuum degree is 700pa, and the reduced pressure decarboxylation reaction is complete to obtain a melon aldehyde crude product; and (3) carrying out rectification purification on the crude product of the cucumis melo aldehyde under reduced pressure, wherein the rectification temperature is 90 ℃, so that 41.8g of product cucumis melo aldehyde is obtained, the yield is 88.89% based on ethyl chloroacetate, and the purity is 98.7%.
Example 7
Uniformly mixing the first organic phase (containing about 20g of unreacted methylheptenone) recovered in example 3 with 42g of sodium carbonate, and heating to 50 ℃ to obtain a first mixed solution; mixing 44g of methylheptenone and 41.1g of ethyl chloroacetate to obtain a second mixed solution; and dropwise adding the second mixed solution into the first mixed solution, maintaining the temperature at 55 ℃ in the dropwise adding process, keeping the temperature for 5 hours, keeping the temperature for 2 hours after the dropwise adding is finished to ensure that the ginseng completely reacts, and then cooling to 5 ℃ to obtain a first reaction solution, wherein the first reaction solution comprises epoxy ethyl caprylate.
And dropwise adding 130g of aqueous sodium hydroxide solution into the first reaction solution under stirring to perform saponification, wherein the temperature is controlled to be lower than 5-20 ℃ in the dropwise adding process, the mass fraction of sodium hydroxide in the aqueous sodium hydroxide solution is 10%, after dropwise adding is finished, keeping the temperature at 20 ℃ for 1 hour to complete the saponification, and then cooling to room temperature to obtain a second reaction solution.
Standing and separating the second reaction solution to obtain a first organic phase and a first water phase; the first water phase comprises sodium salt of epoxy acid, the first organic phase is recovered, 200g of toluene is added into the first water phase, then concentrated hydrochloric acid is used for acidification until the pH value is about 2, the temperature is controlled to be 15-30 ℃ in the acidification process, standing and layering are carried out after the acidification is finished, the second water phase is discarded, the second organic phase is washed by water, and the toluene is removed by atmospheric distillation, so that the residue comprising the epoxy acid is obtained.
Adding 1.6g of copper chloride into the residue, and performing reduced pressure decarboxylation reaction, wherein in the process of reduced pressure decarboxylation, the temperature is 90 ℃, the vacuum degree is 700pa, and the reduced pressure decarboxylation reaction is complete, so as to obtain a crude product of the cucumis melo aldehyde; and (3) carrying out rectification purification on the crude product of the cucumis melo aldehyde under reduced pressure, wherein the rectification temperature is 85 ℃, so that 41.2g of product cucumis melo aldehyde is obtained, the yield is 87.61 percent based on ethyl chloroacetate, and the purity is 98.0 percent.
Example 8
Adding 40g of potassium carbonate and 0.2g of bis-salicylaldehyde nickel (II) ethylenediamine into 150g of toluene, uniformly mixing, and heating to 60 ℃ to obtain a first mixed solution; mixing 57.2g of methylheptenone with 36.2g of methyl chloroacetate to obtain a second mixed solution; and dropwise adding the second mixed solution into the first mixed solution, wherein the temperature is maintained at 60 ℃ in the dropwise adding process, the dropwise adding time is 4 hours, after the dropwise adding is finished, continuously preserving the heat for 2 hours to ensure that the ginseng reacts completely, and then cooling to 5 ℃ to obtain a first reaction solution, wherein the first reaction solution comprises epoxy methyl caprylate.
And (2) dropwise adding 70g of sodium hydroxide aqueous solution into the first reaction solution under stirring to perform saponification, controlling the temperature to be lower than 5-20 ℃ in the dropwise adding process, keeping the mass fraction of sodium hydroxide in the sodium hydroxide aqueous solution at 20%, after dropwise adding, keeping the temperature at 20 ℃ for 1 hour to complete saponification, and then cooling to room temperature to obtain a second reaction solution.
Standing and separating the second reaction solution to obtain a first organic phase and a first water phase; the first aqueous phase comprises sodium salt and potassium salt of epoxy acid, the first organic phase is recovered, 200g of dichloroethane is added into the first aqueous phase, then the mixture is acidified to pH of about 3 by sulfuric acid, the temperature is controlled to be 25-35 ℃ in the acidification process, standing and layering are carried out after the acidification is finished, the second aqueous phase is discarded, and the dichloroethane is removed by washing and atmospheric distillation of the second organic phase, so that residue comprising epoxy acid is obtained.
Adding 0.5g of copper sulfate into the residue, and performing reduced pressure decarboxylation reaction, wherein in the process of reduced pressure decarboxylation, the temperature is 100 ℃, the vacuum degree is 800pa, and the reduced pressure decarboxylation reaction is complete, so as to obtain a crude product of the cucumis melo aldehyde; the crude product of the cucumis melo aldehyde is purified by rectification under reduced pressure, the rectification temperature is 88 ℃, 42.63g of the product cucumis melo aldehyde is obtained, the yield is 91.14 percent based on methyl chloroacetate, and the purity is 98.9 percent.
Example 9
Referring to the reaction conditions and operation method of example 8, except that "40 g of potassium carbonate and 0.2g of nickel (II) bis-salicylaldehyde ethylene diamine were added to 150g of toluene" was replaced by "the first organic phase recovered in example 8 was uniformly mixed with 40g of potassium carbonate", and the solvent and the first catalyst in example 8 were used repeatedly for 9 times, and the specific reaction results are shown in table 1.
TABLE 1
Example 10
Adding 42g of potassium carbonate and 0.5g of nickel (II) succinamide disalicylate into 200g of toluene, uniformly mixing, and heating to 50 ℃ to obtain a first mixed solution; mixing 58.5g of methyl heptenone and 36.8g of methyl chloroacetate to obtain a second mixed solution; and dropwise adding the second mixed solution into the first mixed solution, wherein the temperature is maintained at 50 ℃ in the dropwise adding process, the dropwise adding time is 4.5 hours, after the dropwise adding is finished, continuously preserving heat for 2 hours to ensure that the ginseng reacts completely, and then cooling to 5 ℃ to obtain a first reaction solution, wherein the first reaction solution comprises epoxy methyl caprylate.
And dropwise adding 68g of sodium hydroxide aqueous solution into the first reaction solution under stirring for saponification, controlling the temperature to be lower than 20-25 ℃ in the dropwise adding process, keeping the mass fraction of sodium hydroxide in the sodium hydroxide aqueous solution at 20%, keeping the temperature at 25 ℃ for 1 hour after dropwise adding is finished, completing the saponification reaction, and then cooling to room temperature to obtain a second reaction solution.
Standing and separating the second reaction solution to obtain a first organic phase and a first water phase; the first water phase comprises sodium salt and potassium salt of epoxy acid, the first organic phase is recovered, 200g of toluene is added into the first water phase, then the first water phase is acidified to pH value of about 4 by sulfuric acid, the temperature is controlled to be 25-35 ℃ in the acidification process, standing and layering are carried out after the acidification is finished, the second water phase is discarded, the second organic phase is washed by water, and the toluene is removed by reduced pressure distillation, so that residue comprising the epoxy acid is obtained.
Adding 0.8g of copper sulfate into the residue, and performing reduced pressure decarboxylation reaction, wherein in the process of reduced pressure decarboxylation, the temperature is 100 ℃, the vacuum degree is 800pa, and the reduced pressure decarboxylation reaction is complete, so as to obtain a crude product of the cucumis melo aldehyde; and (3) carrying out rectification and purification on the crude product of the cucumis melo aldehyde under reduced pressure, wherein the rectification temperature is 90 ℃, so that 40.63g of product cucumis melo aldehyde is obtained, the yield is 85.45 percent based on methyl chloroacetate, and the purity is 98.7 percent.
Example 11
Adding 40g of sodium carbonate and 0.8g of bis (5-methylsalicylaldehyde) propanediamine copper (II) into 220g of cyclohexane, uniformly mixing, and heating to 70 ℃ to obtain a first mixed solution; mixing 65g of methylheptenone and 44g of ethyl chloroacetate to obtain a second mixed solution; and dropwise adding the second mixed solution into the first mixed solution, maintaining the temperature at 70 ℃ in the dropwise adding process, keeping the dropwise adding time for 5 hours, keeping the temperature for 2 hours after the dropwise adding is finished to ensure that the ginseng completely reacts, and then cooling to 10 ℃ to obtain a first reaction solution, wherein the first reaction solution comprises epoxy ethyl caprylate.
And dropwise adding 40g of 20% sodium hydroxide aqueous solution into the first reaction solution under stirring to perform saponification, controlling the temperature to be lower than 25-35 ℃ in the dropwise adding process, keeping the mass fraction of sodium hydroxide in the sodium hydroxide aqueous solution at 30%, keeping the temperature at 25-35 ℃ for 1 hour after dropwise adding is finished, so that the saponification is complete, and then cooling to room temperature to obtain a second reaction solution.
Standing and separating the second reaction solution to obtain a first organic phase and a first water phase; the first water phase comprises sodium salt of epoxy acid, the first organic phase is recycled and used for the reaction of ginseng, 200g of cyclohexane is added into the first water phase, then 30% sulfuric acid is used for acidification until the pH value is about 4, the temperature is controlled to be 25-35 ℃ in the acidification process, standing and layering are carried out after the acidification is finished, the second water phase is discarded, the second organic phase is washed by water, and the cyclohexane is removed through atmospheric distillation, so that the residue comprising the epoxy acid is obtained.
Adding 1.5g of copper chloride into the residue, and performing reduced pressure decarboxylation reaction, wherein in the process of reduced pressure decarboxylation, the temperature is 110 ℃, the vacuum degree is 900pa, and the reduced pressure decarboxylation reaction is complete, so as to obtain a crude product of the cucumis melo aldehyde; and (3) carrying out rectification purification on the crude product of the cucumis melo aldehyde under reduced pressure, wherein the rectification temperature is 90 ℃, so that 41.8g of product cucumis melo aldehyde is obtained, the yield is 83.03 percent based on ethyl chloroacetate, and the purity is 98.5 percent.
Example 12
Adding 38g of sodium carbonate and 1.2g of bis-o-vanillin ethylenediamine copper (II) into 220g of dichloroethane, uniformly mixing, and heating to 60 ℃ to obtain a first mixed solution; mixing 64g of methylheptenone and 48g of isopropyl chloroacetate to obtain a second mixed solution; and dropwise adding the second mixed solution into the first mixed solution, wherein the temperature is maintained at 60 ℃ in the dropwise adding process, the dropwise adding time is 4.5 hours, after the dropwise adding is finished, the temperature is kept for 2 hours continuously to ensure that the ginseng completely reacts, and then the temperature is reduced to 10 ℃ to obtain a first reaction solution, wherein the first reaction solution comprises epoxy octyl isopropyl ester.
And dropwise adding 43g of sodium hydroxide aqueous solution into the first reaction solution under stirring for saponification, controlling the temperature to be lower than 25-30 ℃ in the dropwise adding process, keeping the mass fraction of sodium hydroxide in the sodium hydroxide aqueous solution at 30%, keeping the temperature at 25-30 ℃ for 1 hour after dropwise adding is finished, so that the saponification is complete, and then cooling to room temperature to obtain a second reaction solution.
Standing and separating the second reaction solution to obtain a first organic phase and a first water phase; the first water phase comprises sodium salt of epoxy acid, the first organic phase is recycled and used for the reaction of the epoxy acid, 200g of dichloroethane is added into the first water phase, then the mixture is acidified to pH of about 4 by 30% sulfuric acid, the temperature is controlled to be 25-30 ℃ in the acidification process, standing and layering are carried out after the acidification is finished, the second water phase is discarded, and the second organic phase is washed by water and distilled under normal pressure to remove dichloroethane, so that residue comprising epoxy acid is obtained.
Adding 1.5g of copper sulfate into the residue, and performing reduced pressure decarboxylation reaction, wherein in the process of reduced pressure decarboxylation, the temperature is 110 ℃, the vacuum degree is 900pa, and the reduced pressure decarboxylation reaction is complete, so as to obtain a crude product of the cucumis melo aldehyde; and (3) carrying out rectification purification on the crude product of the cucurbitaldehyde under reduced pressure at the rectification temperature of 90 ℃ to obtain 41.7g of product cucurbitaldehyde, wherein the yield is 84.62 percent based on isopropyl chloroacetate, and the purity is 98.7 percent.
Comparative example 1
Adding 29g of sodium carbonate into 200g of dichloroethane, uniformly mixing, and heating to 40 ℃ to obtain a third mixed solution; mixing 42g of methylheptenone and 41g of ethyl chloroacetate to obtain a second mixed solution; and dropwise adding the second mixed solution into the third mixed solution, wherein the temperature is maintained at 40 ℃ in the dropwise adding process, the dropwise adding time is 6 hours, after the dropwise adding is finished, the temperature is kept for 2 hours, and no epoxy ethyl caprylate is generated through detection.
Comparative example 2
With reference to the reaction conditions and the operation method of example 1, except for replacing "0.8g of nickel (II) disalicylaldehyde ethylenediamine)" with "0.8g of nickel (II) disalicylaldehyde cyclohexyldiamine", rectification was conducted to obtain 12.61g of cucumis melo aldehyde as a product in a yield of 26.88% in terms of ethyl chloroacetate and a purity of 97.2%.
Comparative example 3
Referring to the reaction conditions and operation method of example 1, except for replacing "0.8g of bis-salicylaldehyde ethylenediamine (II)" with "1.3g of bis-o-vanillin hexamethylenediamine (II)", 25.9g of product melonal was obtained through rectification, with a yield of 55.21% in terms of ethyl chloroacetate and a purity of 95.9%.
Comparative example 4
With reference to the reaction conditions and the operation method of example 3, except that "0.4g of copper (II) ethylenediamine bissalicylaldehyde was replaced with" 0.9g of copper (II) propylenediamine bis 3.5-di-t-butylsalicylaldehyde, 18.89g of the product cucumis melo aldehyde was obtained by rectification, the yield was 39.31% in terms of ethyl chloroacetate, and the purity was 96.7%.
The technical features of the above embodiments can be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the above embodiments are not described, but should be considered as the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above examples only show several embodiments of the present invention, and the description thereof is specific and detailed, but not to be construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (12)
1. The preparation method of the epoxy caprylate is characterized by comprising the following steps:
in a solvent, in the presence of a first alkaline substance and a first catalyst, performing a dawning reaction on methyl heptenone and alpha-haloacetate to obtain a first reaction solution, wherein the first alkaline substance comprises carbonate; and
separating the first reaction liquid to obtain epoxy caprylate;
wherein the first catalyst comprises a transition metal ion and a Schiff base ligand, the transition metal ion and the Schiff base ligand are combined through a transition metal-oxygen coordination bond and/or a transition metal-nitrogen coordination bond, and the transition metal ion comprises Cu 2+ 、Co 2+ Or Ni 2+ The Schiff base ligand comprises disalicylaldehyde ethylene diamine Schiff base.
2. The method of claim 1, wherein the α -haloacetate comprises at least one of ethyl chloroacetate, methyl chloroacetate, isopropyl chloroacetate, methyl bromoacetate, ethyl bromoacetate, or isopropyl bromoacetate.
3. The process for the preparation of epoxy octanoate according to claim 1, wherein the molar ratio of said methyl heptenone to said α -haloacetate ester is from 2;
and/or the molar ratio of the first basic substance to the α -haloacetate is from 0.8;
and/or the mass ratio of the first catalyst to the α -haloacetate is from 0.005.
4. The method of claim 1, wherein the solvent comprises at least one of toluene, cyclohexane, petroleum ether, or dichloroethane.
5. The method for preparing epoxy caprylate according to claim 1, wherein the reaction between methyl heptenone and α -haloacetate is carried out at a temperature of 20 ℃ to 70 ℃.
6. A preparation method of melonal is characterized by comprising the following steps:
providing an epoxy octanoate solution, wherein the epoxy octanoate solution is the first reaction solution according to any one of claims 1 to 5, or is obtained by dissolving the epoxy octanoate obtained by the production method according to any one of claims 1 to 5 in a solvent;
mixing the epoxy caprylate solution with an alkaline solution, and performing saponification reaction to obtain a second reaction solution;
separating the epoxy acid from the second reaction liquid; and
and performing decarboxylation on the epoxy acid to obtain the cucumis melo aldehyde.
7. The method for preparing melonal according to claim 6, wherein the alkaline solution comprises a second alkaline substance, the second alkaline substance comprises sodium hydroxide or potassium hydroxide, the mass fraction of the second alkaline substance in the alkaline solution is 10% -30%, and the molar ratio of the second alkaline substance to the α -haloacetate is 1-1.2.
8. The method for producing melonal according to claim 6, wherein the step of separating the epoxy acid from the second reaction solution comprises:
and firstly, separating the second reaction solution to obtain a first organic phase and a first water phase, acidifying the first water phase, and separating to obtain the epoxy acid.
9. The method of preparing cantaloupe aldehyde as claimed in claim 8, wherein said first organic phase circulation is used for preparing said epoxy caprylate solution after said step of separating to obtain a first organic phase and a first aqueous phase.
10. A process for the preparation of meloxal according to any one of the claims 6 to 9, wherein in said step of performing a saponification reaction the temperature is between 5 ℃ and 35 ℃.
11. A process for the preparation of melonal according to any one of claims 6 to 9, wherein the step of decarboxylation of the epoxy acid comprises:
and in the presence of a second catalyst, carrying out reduced pressure decarboxylation on the epoxy acid, wherein the temperature is 70-120 ℃, and the vacuum degree is 500-1000 Pa.
12. The method for preparing melonal according to claim 11, wherein the second catalyst comprises a copper salt, and the mass ratio of the copper salt to the α -haloacetate is 0.005-0.05.
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