WO2019104850A1

WO2019104850A1 - Method for preparing lactone compound

Info

Publication number: WO2019104850A1
Application number: PCT/CN2018/073177
Authority: WO
Inventors: 李浩然; 汪玲瑶; 袁浩然; 梁程; 李景波
Original assignee: 浙江大学; 浙江新和成股份有限公司
Priority date: 2017-11-28
Filing date: 2018-01-18
Publication date: 2019-06-06
Also published as: CN109836406A; DE112018000088T5; CN109836406B

Abstract

Disclosed is a method for preparing a lactone compound, for which a cyclic ketone compound serves as a raw material; in an oxygen-containing atmosphere, a cyclic organic nitroxide free radical serves as a catalyst, and a certain amount of an aldehyde additive is added for a reaction. Disclosed is a preparation method having mild conditions, a high degree of safeness, and a wide range of options for non-metal catalyzed oxidation; the amount of the aldehyde additive used is greatly reduced, the efficiency and range of the aldehyde additive are increased, and the lactone compound can be acquired with a high yield.

Description

Method for preparing lactone compound

Technical field

The invention relates to the field of organic synthesis, and in particular to a method for preparing a lactone compound.

Background technique

The lactone compound refers to a corresponding compound which is formed by oxidation of a substituted or unsubstituted cyclic ketone compound as a substrate, and among them, ε-caprolactone (ε-CL) is most widely used.

ε-CL is an important organic intermediate and polymer monomer. It is widely used in industrial production in the fields of fine chemicals, petrochemicals, organic synthesis and pharmaceuticals.

ε-CL is a non-toxic new polyester monomer whose polymerization product is biodegradable polycaprolactone (PCL). The copolymerization of caprolactone with various monomers or the blending of PCL with other resins can improve the gloss, transparency, biodegradability and anti-stickiness of the materials, and has an irreplaceable role in the synthesis and modification of polymer materials. Especially in the application of environmental protection and medical materials.

ε-CL is also an excellent organic solvent and an important organic synthesis intermediate. It exhibits good solubility for some poorly soluble resins and can be reacted with various compounds to prepare fine chemicals with unique properties. Since the synthesis of caprolactone involves harsh process operations such as strong oxidation, only a few companies in the United States, Germany, Japan, Switzerland and other countries have been able to produce caprolactone, and all of China relies on imports. In recent years, with the continuous expansion of the use of caprolactone, its market demand has gradually increased, and research on caprolactone has received increasing attention.

The method for synthesizing ε-CL includes a cyclohexanone oxidation method, a 1,6-hexanediol liquid phase catalytic dehydrogenation method, and a 6-hydroxycaproic acid intramolecular condensation method. Considering factors such as raw materials, equipment and reaction conditions, cyclohexanone oxidation is the most effective method, and it is also the current method for industrial production of caprolactone. Among them, the main synthesis method is cyclohexanone Baeyer-Villiger oxidation method. At present, the process of producing caprolactone by using peroxyacid or H ₂ O ₂ as an oxygen source in the industry has the problems of explosion hazard, poor product stability and many by-products.

Mukaiyama conditions avoid the use of explosive or corrosive organic peracids and hydrogen peroxide. However, under most Mukaiyama conditions, the B-V oxidation of cyclohexanone consumed 3 molar equivalents of benzaldehyde as a sacrificial agent, resulting in a large amount of benzoic acid. If ε-caprolactone can be formed by reducing the amount of benzaldehyde or aliphatic aldehyde, the reaction will be more economical and more environmentally friendly.

U.S. Patent No. 3,025,306 discloses the co-oxidation of cyclohexanone and an aldehyde catalyzed by a catalyst such as a transition metal such as Co, Mn, Pt or Pb. U.S. Patent No. 3,843,222 discloses a reaction route for the catalytic oxidation of cyclohexanone with a soluble iron-containing compound in the presence of an aldehyde. However, the methods of these two patents result in too much by-products (such as adipic acid), and the aldehyde efficiency is relatively low.

British Patent UK1009773 discloses cyclohexanone and aldehydes in metals (Mn, Fe, Co, Ni, Zn, etc.) and chelating agents, for example, aminocarboxylic acids (EDTA), nitrilotriacetic acid, nitrogen-containing heterocyclic compounds A peroxidation reaction occurs in the presence of (2,2'-bipyridyl) or an organic phosphate. A disadvantage of this process is the low selectivity brought about by high temperatures, and another disadvantage is that the large use of 2,2'-bipyridine leads to low selectivity and uneconomical reaction.

Japanese Patent No. 1,507,337 discloses a soluble metal salt (such as Fe, Pb, Cr and Ce, etc.) and a nitrogen-containing heterocyclic polydentate ligand (2,2'-bipyridyl, 1,10-phenanthroline). Etc.) Catalytic co-oxidation of cyclohexanone and aldehyde. The process conditions are mild, but the reaction efficiency is not high.

Chinese patents CN201110276434.7, 2011102998626.1, 201510037608.6, and 201510726676.3 all disclose a method for preparing ε-caprolactone. In the presence of aldehyde, the catalysts described in each patent are: (1) a Co-loaded catalyst; (2) a metal porphyrin compound; (3) copper chloride or supported copper chloride; (4) a cupric dichroic magnetic nano Fe ₃ O ₄ sphere and TiO ₂ P25 are coated in MCM-41. The patent CN201110276434.7 uses 3 times equivalent of benzaldehyde, and the reaction yield can reach more than 90%, but when 2 times equivalent of benzaldehyde is used, the yield is less than 90%. The reactions involved in these patents are mild in temperature but the catalyst preparation process involved is complex. The catalysts used in the methods of the prior patents all contain transition metals, which cause certain pollution and residue to the environment.

In recent years, there have been several reports that the stoichiometric benzaldehyde stoichiometry is less than 2. In 2012, Sinhamahapatra et al. reported in Catalysis Science and Technology that mesoporous zirconium phosphate was catalyzed by 1.75-fold equivalents of benzaldehyde as an auxiliary. The caprolactone was prepared by oxidizing cyclohexanone, but the yield was 78%. In 2013, Y.F. Li et al. reported in ACS Catalysis that metal-free graphite was used as an auxiliary agent under 1-fold equivalents of benzaldehyde, but the yield of caprolactone was only 65%.

Therefore, it is still challenging and important to explore green and high-efficiency metal-free catalysts for catalyzing the high selectivity of molecular oxygen oxidation of cyclic ketones to the corresponding lactones.

Summary of the invention

The invention discloses a method for preparing a corresponding lactone by a metal-free catalytic oxidation of a cyclic ketone compound with mild conditions, high safety and high selectivity, and co-production of an organic acid. The method uses an organic nitroxide precursor as a catalyst, an aldehyde compound as an auxiliary agent, and an auxiliary efficiency is improved, so that industrial production of a lactone compound by oxygen or air oxidation is possible.

The specific technical solutions are as follows:

A method for preparing a lactone compound, which comprises mixing a cyclic ketone compound, a catalyst and an auxiliary agent, and reacting in an oxygen-containing atmosphere;

The cyclopentanone compound has 0 to 5 substituents, and the cyclohexanone compound has 0 to 6 substituents, and each substituent on the cyclopentanone compound or the cyclohexanone compound It is independently selected from a hydrogen atom or an alkyl group, or at least two substituents are ring-formed; the alkyl group may be selected from a cycloalkyl group or a linear or branched alkyl group having a carbon number of 1 to 10.

Further preferably, the cyclic ketone compound is selected from the group consisting of cyclopentanone, cyclohexanone, 2-methylcyclohexanone, 3-methylcyclohexanone, 4-methylcyclohexanone, norbornone, and adamantane. At least one of the ketones.

The catalyst is selected from the group consisting of cyclic organic nitroxide precursors, and the skeleton of the skeleton is represented by the following formula (I);

In the formula (I), R represents C _n H _m , wherein n = 2 or 3, m = 2n or 2n-2; the R has 0 to n substituents, and the substituents are independently selected from a hydrogen atom, an alkyl group, a cycloalkyl group, an aromatic group, a heterocyclic ring, a hydroxyl group, a nitro group or a halogen, or at least two rings;

For example, when there are two substituents on the R, the two substituents may be substituted by themselves or may form a ring, and the ring may be a saturated ring, which is (e) in the following formula, or may be an unsaturated ring. , (d) in the following formula;

When there are three substituents on the R, the three substituents R may be substituted by themselves or may be ring-formed in two or two, and may be a saturated ring, which may be an unsaturated ring in the following formula (h), and is as follows. (i); the ring may be a carbocyclic ring or a carbon heterocyclic ring, as in the following formula (g).

Further, the substituent on R may have other substituents, and may be a hydrogen atom, an alkyl group, a cycloalkyl group, a hydroxyl group, an aromatic group, a heterocyclic ring, a nitro group, a halogen or other functional groups.

The auxiliary agent is selected from the group consisting of an aldehyde compound having a structural formula of R'CHO, and R' is selected from a hydrogen atom, an alkyl group or an aromatic group; further preferably, the aldehyde compound is selected from the group consisting of benzaldehyde and m-chlorobenzaldehyde. At least one of isobutyraldehyde and n-heptanal, and further preferred aldehyde compounds are easily oxidized in situ to form peroxyacid, and the oxidation efficiency is high, and the aldehyde compound generates a corresponding acid after the reaction.

The invention firstly finds that an organic nitroxide precursor can cooperate with an aldehyde auxiliary to catalyze the oxidation of a cyclic ketone compound to a corresponding lactone in the presence of oxygen. The organic nitroxide precursor can promote the oxidation of the auxiliary aldehyde molecules to generate peroxy radicals and stabilize the peroxy radicals, which is beneficial to the formation of lactones, thereby greatly reducing the amount of additives and improving the efficiency of the additives. The range also shortens the reaction time and reduces the energy consumption of the reaction; at the same time, the catalyst contains no metal and reduces environmental pollution. Hydroxylamine and hydrazine are the major nitroxyl radical precursors, but cyclic hydroxylamines have better properties.

Preferably, the catalyst is selected from at least one of the following formulas (a) to (i);

Further preferably, the catalyst is selected from N-hydroxysuccinimide (NHS) as shown in formula (a), 1-hydroxypiperidine-2,6-dione (HPD) as shown in formula (c) N-hydroxyphthalimide (NHPI) represented by formula (d), 2-hydroxy-1H-pyrrole [3,4c]-pyridine-1,3- as shown in formula (g) At least one of 2H-diketones (NHQI); more preferably NHPI.

In the present invention, the oxygen-containing atmosphere is not particularly limited, and pure oxygen, oxygen-enriched air, air may be used, or one or more diluted with an inert gas such as nitrogen, helium, argon or carbon dioxide may be used. oxygen. The amount of oxygen used is appropriately selected depending on the cyclic ketone compound, and is preferably an excess amount of oxygen relative to the cyclic ketone compound.

The temperature at which the reaction is carried out is critical, and the reaction temperature may vary between 20 and 100 ° C; the higher the temperature, the higher the conversion of the cyclic ketone compound, however, the higher the temperature will also increase the production of by-products. The selectivity of the corresponding lactone is lowered, and an excessively high temperature may cause catalyst deactivation or product degradation. Preferably, the reaction temperature is 30 to 50 ° C; more preferably 36 to 46 ° C.

The pressure of the reaction is from normal pressure to high pressure. The higher the pressure, the more decomposition of the lactone compound, the more the carboxylic acid is produced, and the preferred reaction pressure is 0.1 to 0.6 MPa. For economic reasons, it is more preferable. Pressure.

The time required for the reaction depends on the rate of supply of the oxygen source, preferably 4 to 18 h.

Preferably, the molar ratio of the cyclic ketone compound, the catalyst and the auxiliary agent is 1:0.05 to 0.2:0.5 to 2.

Further, in the preparation method, an organic solvent is further added, specifically:

After the cycloketone compound, the catalyst, and the auxiliary agent are mixed with an organic solvent, the reaction is carried out in an oxygen-containing atmosphere;

The organic solvent is selected from the group consisting of an alkane (such as hexane, octane, etc.) inert to the oxidation reaction, an aromatic hydrocarbon (such as benzene, toluene, etc.), a halogenated hydrocarbon (such as chloroform, dichloromethane, dichloroethane, Carbon tetrachloride, chlorobenzene, trifluorotoluene, etc.), organic acids (such as acetic acid, propionic acid, etc.), esters (such as ethyl acetate, butyl acetate, etc.), nitriles (such as acetonitrile, propionitrile, benzonitrile, etc.) At least one of; more preferably 1,2-dichloroethane, ethyl acetate, toluene or acetonitrile; most preferably 1,2-dichloroethane.

When the reaction system containing the organic solvent is used, it is more preferred that the molar ratio of the cyclic ketone compound, the catalyst and the auxiliary agent is 1:0.1 to 0.15:1 to 2.

In order to facilitate the recovery of the catalyst and the separation of the catalyst and the product, preferably, the catalyst is a supported catalyst, and the cyclic organic nitroxide precursor is used as an active component, and the carrier used may be two. One or more kinds of carriers such as silica, alumina, zirconia, titania, cerium oxide, and polymer microspheres. For specific fixing methods, reference may be made to the methods disclosed in the prior art such as CN 101626835 B, CN 104069891 B, CN 104148110 B.

Representatively, the specific reaction formula of the present invention is as shown in the following formula (II):

If the substrate is a cyclopentanone compound, the product is a γ-valerolactone compound, and if the substrate is a cyclohexanone compound, the product is an ε-caprolactone compound.

After completion of the reaction, the reaction solution was cooled to room temperature, and the solvent was evaporated under reduced pressure. The residue was separated and purified to give the lactone compound and the corresponding acid. The oxidation product of the cyclic ketone compound can be recovered by distillation and other methods. These treatments can be carried out batchwise, semi-continuously or continuously. A continuous process is preferred.

Compared with the prior art, the present invention has the following advantages:

(1) The present invention uses a cyclic nitroxide radical as a catalyst to greatly improve the efficiency of the auxiliary aldehyde and increase the yield of the lactone compound;

(2) The catalyst system of the invention realizes no metallization, mild reaction conditions, and reduces environmental pollution to avoid operation and safety problems under high temperature and high pressure conditions;

(3) Since the cyclic nitroxide precursor has an excellent property of promoting the oxidation of the auxiliary aldehyde molecule to produce a peroxy radical, the auxiliary agent of the present invention can be extended from the aromatic aldehyde to the cheap and readily available fatty aldehyde, which can be practical. Process needs, comprehensive consideration of input and output and other preferred choices;

(4) The reaction process of the invention is simple, the operability is strong, and the catalyst is cheap and easy to obtain, and the fixed catalyst is easy to be separated and recovered, and has good industrial application prospect.

The mechanism of the excellent results of the present invention is discussed. The reaction mechanism of the cyclic lactones to form the corresponding lactones has two paths of peroxy radicals and peroxyacids. In general, both are heavier, but the peroxy radical path is more favorable for the reaction, and the efficiency is higher. The results of the present invention show that the cyclic nitroxide precursor can promote the oxidation of aldehyde molecules to form corresponding peroxy radicals, and at the same time, the cyclic nitroxide precursors have certain effects on peroxyl radicals in the reaction system. The stabilizing effect, and thus the free radical path, becomes the main route of the reaction of the present invention. In addition, a small amount of peroxyacids generated by peroxy radicals can also attack the carbonyl carbon on the cyclic ketone compound to form the corresponding lactone and organic acid.

Detailed ways

The present invention will be further described below in conjunction with specific embodiments, but the scope of protection of the present invention is not limited to the scope of the embodiments:

Example 1

NHPI 0.0326g (0.2mmol), benzaldehyde 0.4245g (4mmol), cyclohexanone 0.1962g (2mmol), 1,2-dichloroethane (DCE) were sequentially added to a three-necked flask connected to a condenser, thermometer and oxygen bag. ) 20mL. Under normal pressure conditions, the mixture was stirred at a constant temperature of 40 ° C for 6 hours, cooled to room temperature, and analyzed by gas phase internal standard method. The conversion of cyclohexanone was 100%, and the selectivity of ε-caprolactone was 99.9%.

Example 2

NHS 0.0230g (0.2mmol), benzaldehyde 0.4245g (4mmol), cyclohexanone 0.1962g (2mmol), 1,2-dichloroethane (DCE) were sequentially added to a three-necked flask connected to a condenser, thermometer and oxygen bag. ) 20mL. Under normal pressure conditions, the mixture was stirred at a constant temperature of 40 ° C for 6 hours, cooled to room temperature, and analyzed by gas phase internal standard method. The conversion of cyclohexanone was 82.0%, and the selectivity of ε-caprolactone was 99.9%.

Example 3

NHQI 0.0328g (0.2mmol), benzaldehyde 0.4245g (4mmol), cyclohexanone 0.1962g (2mmol), 1,2-dichloroethane (DCE) were sequentially added to a three-necked flask connected to a condenser, thermometer and oxygen bag. ) 20mL. Under normal pressure conditions, the mixture was stirred at a constant temperature of 40 ° C for 6 h, cooled to room temperature, and analyzed by gas phase internal standard method. The conversion of cyclohexanone was 87.0%, and the selectivity of ε-caprolactone was 99.9%.

Example 4

HPD 0.0258g (0.2mmol), benzaldehyde 0.4245g (4mmol), cyclohexanone 0.1962g (2mmol), 1,2-dichloroethane (DCE) were sequentially added to a three-necked flask connected to a condenser, thermometer and oxygen bag. ) 20mL. Under normal pressure conditions, stirring at 40 ° C for 6 h, cooling to room temperature, by gas phase internal standard detection and analysis, cyclohexanone conversion was 85.0%, and the selectivity of ε-caprolactone was 99.0%.

Comparative example 1

Example 1 was repeated without adding a catalyst, and the conversion of cyclohexanone was 3.0%, and the selectivity of ε-caprolactone was 99.9%.

As can be seen from the comparison, the catalyst is essential in the reaction system of the present invention.

Comparative example 2

N,N-diethylhydroxylamine (DEHA) 0.0178 g (0.2 mmol), benzaldehyde 0.4245 g (4 mmol), cyclohexanone 0.1962 g (2 mmol) were sequentially added to a three-necked flask connected to a condenser, a thermometer and an oxygen gas bag. 1,2-Dichloroethane (DCE) 20 mL. Under normal pressure conditions, the mixture was stirred at a constant temperature of 40 ° C for 6 hours, cooled to room temperature, and analyzed by gas phase internal standard method. The conversion of cyclohexanone was 8.7%, and the selectivity of ε-caprolactone was 99.9%.

Comparative Examples 1, 2, 3, 4 and Comparative Example 2 show that the cyclic structure of the organic nitroxide precursor is more suitable for the present invention, and the NHPI has the best catalytic effect.

Table 1

^[a] Benzaldehyde efficiency = ε-caprolactone yield / benzaldehyde conversion rate / 2

Examples 5-7

Example 1 was repeated by replacing the 1,2-dichloroethane with a solvent of acetonitrile (MeCN), ethyl acetate (EtOAc) and toluene, and the results are shown in Table 2 below.

From Examples 1, 4 to 6, it can be seen that cyclohexanone conversion and ε-caprolactone in a 1,2-dichloroethane solvent system compared to acetonitrile, ethyl acetate, toluene solvent The highest selectivity.

Table 2

Example 8

NHPI 0.0326g (0.2mmol), m-chlorobenzaldehyde 0.5623g (4mmol), cyclohexanone 0.1962g (2mmol), 1,2-dichloroethane were sequentially added to a three-necked flask connected to a condenser, thermometer and oxygen bag. (DCE) 20 mL. Under normal pressure conditions, the mixture was stirred at a constant temperature of 40 ° C for 6 h, cooled to room temperature, and analyzed by gas phase internal standard method. The conversion of cyclohexanone was 94.5%, and the selectivity of ε-caprolactone was 95.6%.

Example 9

NHPI 0.0326g (0.2mmol), isobutyraldehyde 0.2884g (4mmol), cyclohexanone 0.1962g (2mmol), 1,2-dichloroethane were sequentially added to a three-necked flask connected to a condenser, thermometer and oxygen bag. DCE) 20 mL. Under normal pressure conditions, the mixture was stirred at a constant temperature of 40 ° C for 18 hours, cooled to room temperature, and analyzed by gas phase internal standard method. The conversion of cyclohexanone was 93.3%, and the selectivity of ε-caprolactone was 91.1%.

Example 10

NHPI 0.0326g (0.2mmol), n-heptanal 0.4568g (4mmol), cyclohexanone 0.1962g (2mmol), 1,2-dichloroethane were sequentially added to a three-necked flask connected to a condenser, thermometer and oxygen bag. DCE) 20 mL. Under normal pressure conditions, the mixture was stirred at a constant temperature of 40 ° C for 18 hours, cooled to room temperature, and analyzed by gas phase internal standard method. The conversion of cyclohexanone was 81.6%, and the selectivity of ε-caprolactone was 99.6%.

Example 11

NHPI 0.0326g (0.2mmol), benzaldehyde 0.3182g (3mmol), cyclohexanone 0.1962g (2mmol), 1,2-dichloroethane (DCE) were sequentially added to a three-necked flask connected to a condenser, thermometer and oxygen bag. ) 20mL. Under normal pressure conditions, stirring at 40 ° C for 8 h, cooling to room temperature, by gas phase internal standard detection and analysis, cyclohexanone conversion was 93.4%, and the selectivity of ε-caprolactone was 99.8%.

Example 12

NHPI 0.0326g (0.2mmol), benzaldehyde 0.2122g (2mmol), cyclohexanone 0.1962g (2mmol), 1,2-dichloroethane (DCE) were sequentially added to a three-necked flask connected to a condenser, thermometer and oxygen bag. ) 20mL. Under normal pressure conditions, stirring at 40 ° C for 8 h, cooling to room temperature, by gas phase internal standard detection and analysis, cyclohexanone conversion was 84.6%, and the selectivity of ε-caprolactone was 99.5%.

Example 13

NHPI 0.0326g (0.2mmol), benzaldehyde 0.1011g (1mmol), cyclohexanone 0.1962g (2mmol), 1,2-dichloroethane (DCE) were sequentially added to a three-necked flask connected to a condenser, thermometer and oxygen bag. ) 20mL. Under normal pressure conditions, the mixture was stirred at a constant temperature of 40 ° C for 8 hours, cooled to room temperature, and analyzed by gas phase internal standard method. The conversion of cyclohexanone was 50.0%, and the selectivity of ε-caprolactone was 98.0%.

Examples 7 to 12 show the effects of different aldehydes and amounts on the reaction. The results are summarized in Table 3.

table 3

^[a] aldehyde efficiency = ε-caprolactone yield / aldehyde conversion rate / aldehyde dosage

Examples 14-17

These examples illustrate that the reaction temperature has a certain effect on the reaction. Repeat with different temperatures

Example 1, the results are shown in Table 4.

Table 4

Example 18

To a 50 ml three-necked glass flask equipped with a stirrer, an inlet tube, and a water-cooled reflux condenser, 20 mL of 1,2-dichloroethane, 0.1962 g (2 mmol) of cyclohexanone, 0.4245 g (4 mmol) of benzaldehyde and 0.0326 g ( 0.2 mmol) NHPI. Under normal pressure, air was introduced into the reaction vessel at a rate of 20 ml/min. The mixture was stirred at 40 ° C for a period of 6 hours (300 rpm), cooled to room temperature, and analyzed by gas phase internal standard method. The conversion of cyclohexanone was 100. The selectivity of %, ε-caprolactone was 99.9%.

Examples 19-24

Example 1 was repeated using different reaction substrates, and only the reaction time was different, and the results are shown in Table 5.

table 5

Example 25

To a 50 ml three-necked glass flask equipped with a stirrer, an inlet tube, and a water-cooled reflux condenser, 4.9 g (0.05 mol) of cyclohexanone, 10.7 g (0.10 mol) of benzaldehyde and 0.8 g (0.005 mol) of NHPI were added. Under normal pressure conditions, oxygen was introduced into the reaction vessel at a rate of 20 ml/min. The mixture was stirred at 40 ° C for a period of 8 hours (300 rpm), cooled to room temperature, and analyzed by gas phase internal standard method. The conversion of cyclohexanone was 27.0. The selectivity of %, ε-caprolactone was 96.0%.

Example 26

To a 50 ml three-necked glass flask equipped with a stirrer, an inlet tube, and a water-cooled reflux condenser, 4.9 g (0.05 mol) of cyclohexanone, 10.7 g (0.10 mol) of benzaldehyde and 0.8 g (0.005 mol) of NHPI were added. Under normal pressure, air was introduced into the reaction vessel at a rate of 20 ml/min. The mixture was stirred at 40 ° C for a period of 8 hours (300 rpm), cooled to room temperature, and analyzed by gas phase internal standard method. The conversion of cyclohexanone was 18.5. The selectivity of %, ε-caprolactone was 90.0%.

Claims

A method for preparing a lactone compound, which comprises mixing a cyclic ketone compound, a catalyst and an auxiliary agent, and reacting in an oxygen-containing atmosphere, wherein:

The cyclic ketone compound is a cyclopentanone compound or a cyclohexanone compound, wherein:

The cyclopentanone compound has 0 to 5 substituents, and the cyclohexanone compound has 0 to 6 substituents, and each substituent on the cyclopentanone compound or the cyclohexanone compound Independently selected from a hydrogen atom or an alkyl group, or at least two substituents are ring-forming;

The catalyst is selected from the group consisting of cyclic organic nitroxide precursors, and the skeleton of the skeleton is represented by the following formula (I);

In the formula (I), R represents C n H m , wherein n = 2 or 3, m = 2n or 2n-2; the R has 0 to n substituents, and the substituents are independently selected from a hydrogen atom, an alkyl group, a cycloalkyl group, an aromatic group, a heterocyclic ring, a hydroxyl group, a nitro group or a halogen, or at least two rings;

The adjuvant is selected from the group consisting of aldehyde compounds.
The method for producing a lactone compound according to claim 1, wherein the catalyst is at least one selected from the group consisting of the following formulas (a) to (i);
The method for producing a lactone compound according to claim 2, wherein the catalyst is selected from the group consisting of N-hydroxysuccinimide represented by the formula (a), and 1- for the formula (c) Hydroxypiperidine-2,6-dione, N-hydroxyphthalimide as shown in formula (d), 2-hydroxy-1H-pyrrole [3, 4c] as shown in formula (g) At least one of -pyridine-1,3-2H-dione.
The method for producing a lactone compound according to claim 1, wherein the cyclic ketone compound is selected from the group consisting of cyclopentanone, cyclohexanone, 2-methylcyclohexanone, and 3-methylcyclohexane. At least one of a ketone, 4-methylcyclohexanone, norbornene, and adamantanone.
The method for producing a lactone compound according to claim 1, wherein the aldehyde compound has a structural formula of R'CHO, and R' is selected from a hydrogen atom, an alkyl group or an aromatic group.
The method for producing a lactone compound according to claim 5, wherein the aldehyde compound is at least one selected from the group consisting of benzaldehyde, m-chlorobenzaldehyde, isobutyraldehyde, and n-heptanal.
The method for preparing a lactone compound according to claim 1, wherein the molar ratio of the cyclic ketone compound, the catalyst and the auxiliary agent is 1:0.05 to 0.2:0.5 to 2;

The reaction temperature is 30 to 50 ° C, and the reaction pressure is 0.1 to 0.6 MPa.
The method for producing a lactone compound according to any one of claims 1 to 7, wherein a cycloketone compound, a catalyst, an auxiliary agent and an organic solvent are mixed, and then reacted in an oxygen-containing atmosphere;

The organic solvent is selected from at least one of an alkane, an aromatic hydrocarbon, a halogenated hydrocarbon, an organic acid, an ester, and a nitrile which are inert to the oxidation reaction.
The method for preparing a lactone compound according to claim 8, wherein the molar ratio of the cyclic ketone compound, the catalyst and the auxiliary agent is 1:0.1 to 0.15:1 to 2;

The reaction temperature is 36 to 46 ° C, the reaction pressure is normal pressure, and the reaction time is 4 to 18 hours.
The method of preparing a lactone compound according to claim 1, wherein the catalyst is a supported catalyst, and the cyclic organic nitroxide precursor is used as an active component.