Method for catalyzing cycloalkane oxidative carbonylation reaction by metal-based ionic liquid
By catalyzing the oxidative carbonylation reaction of cycloalkanes and alcohols with metal-based ionic liquids, the problems of low reaction selectivity and low yield in the prior art were solved, and efficient preparation of cycloalkane formates was achieved, and the yield was significantly increased to 71.8-99.8%.
Patent Information
- Application Number
- CN202311156795.0
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2023-09-08
- Publication Date
- 2025-03-11
AI Technical Summary
In the prior art, the oxidative carbonylation reaction of cycloalkanes and alcohols has problems with low selectivity and low yield. Especially when using non-precious metal catalysts, the maximum yield of cycloalkane formate is only 85%, which is difficult to meet industrial needs.
The metal-based ionic liquid is used as a catalyst to prepare cycloalkyl formate by mixing the metal-based ionic liquid, peroxide, cycloalkanes and alcohol, and heating it in a carbon monoxide atmosphere.
Under the catalysis of metal-based ionic liquid, the oxidative carbonylation reaction of cycloalkanes and alcohols is significantly improved, and the yield of cycloalkane formate reaches 71.8-99.8%, which is far higher than the yield of traditional non-precious metal catalysts.
Smart Images
Figure QLYQS_1 
Figure QLYQS_2 
Figure BDA0004438859720000021
Abstract
Description
Technical Field
[0001] The invention relates to the technical field of chemical catalysis, and in particular to a method for catalyzing oxidative carbonylation of cycloalkanes using metal-based ionic liquids. Background Art
[0002] Due to its special molecular structure and physicochemical properties, cycloalkyl formate is widely used in the fields of medicine, natural product synthesis, pesticides and high-performance materials. Therefore, the synthesis method of cycloalkyl formate has always attracted much attention. At present, cycloalkyl formate is mainly prepared by the esterification reaction of cycloalkanecarboxylic acid and alcohol, which requires the preparation of cycloalkyl carboxylic acid first, and its yield is limited due to the reversibility of the esterification reaction. Another synthesis method is to directly prepare esters by carbonylation reaction of cycloalkyl halide with carbon monoxide and alcohol under noble metal catalysis. This method has the advantage of using cheap carbon monoxide as a C1 source, but the alkyl halide itself has high biological toxicity and its preparation process is complicated. Therefore, directly using cheap and readily available cycloalkane compounds as raw materials, preparing cycloalkyl formate by oxidative carbonylation reaction with carbon monoxide and alcohol has become a very attractive and highly atom-economical method. However, due to the high activation energy of alkanes, C(sp3)-H is difficult to activate, and a highly active oxidant is often required. However, this easily leads to undesirable oxidation reactions of cycloalkanes and alcohols, which in turn seriously affects the selectivity of the oxidative carbonylation reaction. Therefore, the oxidative carbonylation reaction of cycloalkanes and alcohols remains a challenge.
[0003] In recent years, the oxidative carbonylation of alkanes has mainly relied on noble metal catalysts (such as PdCl2), and usually requires the synergistic action of ligands to react. Due to the scarcity of noble metal resources, the development of non-noble metal catalysts is particularly important. Although there are some reports on non-noble metal-catalyzed oxidative carbonylation reactions, the yield of cycloalkyl carboxylate in these reactions has not yet reached the ideal level, with a maximum of only 85%. Therefore, it is urgent to develop more efficient catalysts for the oxidative carbonylation of cycloalkanes and alcohols. Summary of the invention
[0004] The object of the present invention is to provide a method for catalyzing the oxidative carbonylation reaction of cycloalkanes by using metal-based ionic liquids, so as to achieve efficient catalysis of the oxidative carbonylation reaction of cycloalkanes and alcohols with high selectivity to prepare cycloalkyl formate.
[0005] The present invention provides a method for oxidative carbonylation of cycloalkanes catalyzed by metal-based ionic liquids, comprising the following steps:
[0006] Mix metal-based ionic liquid, peroxide, cycloalkane and alcohol, add 0.5-5Mpa carbon monoxide, heat to 90-150°C, react for 2-12h to obtain cycloalkyl formate.
[0007] The amount of the metal-based ionic liquid is 0.1 to 20 mol% of the alcohol, the molar ratio of cycloalkane to alcohol is 20 to 200:1, and the structural formula of the metal-based ionic liquid is any one of (1) to (3):
[0008]
[0009] n is an integer from 0 to 8.
[0010] Compared with the prior art, the invention has the following beneficial effects: the invention adopts metal-based ionic liquid to catalyze the oxidative carbonylation reaction of cycloalkane and alcohol to prepare cycloalkyl formate, effectively avoiding the use of noble metal catalysts, overcoming the problem of low activity of non-noble metal catalysts and the problem of using additional organic ligands. Under the catalysis of the metal-based ionic liquid, the raw alcohol is basically reacted completely, and the yield of cycloalkyl formate is significantly improved, and the yield reaches 71.8-99.8%. DETAILED DESCRIPTION
[0011] In order to make the purpose, technical solution and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with the embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention.
[0012] The present invention provides a method for oxidative carbonylation of cycloalkanes catalyzed by metal-based ionic liquids, comprising the following steps:
[0013] Mix metal-based ionic liquid, peroxide, cycloalkane and alcohol, add 0.5-5Mpa carbon monoxide, heat to 90-150°C, react for 2-12h to obtain cycloalkyl formate.
[0014] The amount of the metal ionic liquid is 0.1-20 mol% of the alcohol, the molar ratio of cycloalkane to alcohol is 20-200:1, and the structural formula of the metal-based ionic liquid is any one of (1)-(3):
[0015]
[0016] n is an integer from 0 to 8.
[0017] Specifically, the reactor can be a high-pressure reactor with a temperature sensor. The cation in the metal-based ionic liquid is a proton-type imidazolium cation; the anion in the metal-based ionic liquid is [CuCl2] - , [FeCl4] - , [CuCl3] - Any one of .
[0018] Specifically, the cycloalkane is any one of cyclopentane, cyclohexane, cycloheptane and cyclooctane.
[0019] Specifically, the alcohol is any one of benzyl alcohol, phenylethyl alcohol, (S)-(-)-1-phenylethyl alcohol, (R)-(+)-1-phenylethyl alcohol, 4-methylbenzyl alcohol, 2-naphthalenemethyl alcohol, and 3-chloro-1-propanol.
[0020] Preferably, the amount of the metal-based ionic liquid is 1-10 mol% of the alcohol, the molar ratio of the cycloalkane to the alcohol is 50-150, and the pressure of the carbon monoxide is 1-2 MPa.
[0021] More preferably, the temperature is heated to 110-130° C. and the reaction is carried out for 4-8 hours.
[0022] Specifically, the peroxide is di-tert-butyl peroxide (DIBP).
[0023] Specifically, the metal ions in the metal-based ionic liquid need to be prepared in two steps: a. Weigh an equal molar amount of n-methylimidazole and 36% hydrochloric acid, add the hydrochloric acid dropwise into the n-methylimidazole, stir and reflux in a 70°C oil bath for 5 hours, and remove excess water by rotary evaporation to obtain a transparent viscous liquid. After the reaction is completed, wash the product with anhydrous ethanol 3 to 5 times to remove the unreacted raw materials, then put it into a vacuum drying oven, and dry it at 80°C for 12 hours to obtain methylimidazole hydrochloride. b. Add a certain amount of methylimidazole hydrochloride to a 20mL glass vial, then add an equal molar amount of anhydrous cuprous chloride or anhydrous ferric chloride or anhydrous cupric chloride, stir at 40°C for 2 hours to obtain a metal-based ionic liquid.
[0024] Preferably, the structural formula of the ionic liquid is (1) and (2),
[0025]
[0026] n is an integer from 0 to 8.
[0027] When the catalyst is an ionic liquid (1) or (2), the monovalent copper ion in (1) and the trivalent iron ion in (2) can coordinate with the alkyl radical activated by the oxidant to form MR, and the carbon monoxide can be inserted into MR on the metal center to form M(=O)-R; the H atom connected to N1 and the H atom connected to C2 in the proton-type imidazolium cation can form a hydrogen bond with the O atom in the alcohol, promoting the activation of the alcohol, and further promoting the alcohol to form the product cycloalkyl formate with M(=O)-R. Therefore, under the synergistic effect of the metal center and the hydrogen-donating group of the cation, cycloalkanes can react with alcohols to form cycloalkyl formate in a highly selective oxidative carbonylation reaction.
[0028] The following specific examples illustrate the method of oxidative carbonylation of cycloalkanes catalyzed by metal-based ionic liquids. The compounds in the following examples can be directly prepared according to existing methods, and of course, in other examples, they can also be directly purchased from the market, but are not limited thereto.
[0029] Embodiment 1:
[0030] Preparation of benzyl cyclohexanecarboxylate by oxidative carbonylation of cyclohexane and benzyl alcohol catalyzed by 1-ethylimidazole cuprous chloride ionic liquid (Structure 1, where n=1)
[0031] Preparation of 1-ethylimidazole cuprous chloride ionic liquid:
[0032] Add 4.8065g (0.05mol) of ethyl imidazole to a 150mL three-necked flask, add 5.06389g (0.05mol) of 36% hydrochloric acid dropwise, stir and reflux in an oil bath at 70°C for 5h, and obtain a transparent viscous liquid after rotary evaporation. After the reaction, wash the product with anhydrous ethanol for 3 to 5 times to remove the unreacted raw materials, and then put it in a vacuum drying oven and dry it at 80°C for 12h to obtain ethyl imidazole hydrochloride.
[0033] 1-Ethylimidazole hydrochloride was added into a 20 mL glass vial, and then an equimolar amount of anhydrous cuprous chloride was added, and the mixture was stirred at 40° C. for 2 h to obtain 1-ethylimidazole cuprous chloride ionic liquid.
[0034] Oxidative carbonylation reaction of cyclohexane and benzyl alcohol: 2.5 mL of cyclohexane, 0.0216 g (0.2 mmol) of benzyl alcohol, 0.0023 g (0.01 mmol) of 1-ethylimidazole cuprous chloride ionic liquid, and 0.0585 g (0.4 mmol) of oxidant DTBP were added to a 25 mL high-pressure reactor respectively. After replacing the gas in the reactor with carbon monoxide three times, 1.5 MPa of carbon monoxide was charged, the reaction temperature was set at 120°C, the reaction was carried out for 6 hours, and the product was detected by gas chromatography. n-octane was used as the internal standard. The yield of benzyl cyclohexanecarboxylate was 99.8%.
[0035] Embodiment 2:
[0036] Preparation of benzyl cyclohexanecarboxylate by oxidative carbonylation of cyclohexane and benzyl alcohol catalyzed by 1-ethylimidazole ferric chloride ionic liquid (structure 2, where n=1)
[0037] Preparation of 1-ethylimidazole ferric chloride ionic liquid ketone Example 1
[0038] 1-Ethylimidazole hydrochloride was added into a 20 mL glass vial, and then an equimolar amount of anhydrous ferric chloride was added, and the mixture was stirred at 40° C. for 2 h to obtain 1-ethylimidazole ferric chloride ionic liquid.
[0039] Oxidative carbonylation reaction of cyclohexane with benzyl alcohol: 2.5 mL of cyclohexane, 0.0216 g (0.2 mmol) of benzyl alcohol, 0.0029 g (0.01 mmol) of 1-ethylimidazole ferric chloride ionic liquid, and 0.0585 g (0.4 mmol) of oxidant DTBP were added to a 25 mL high-pressure reactor respectively. After replacing the gas in the reactor with carbon monoxide three times, 1.5 MPa of carbon monoxide was charged, the reaction temperature was set to 120°C, the reaction was carried out for 6 hours, and the product was detected by gas chromatography. n-octane was used as the internal standard. The yield of benzyl cyclohexanecarboxylate was 93.6%.
[0040] Embodiment 3:
[0041] Preparation of benzyl cyclohexanecarboxylate by oxidative carbonylation of cyclohexane and benzyl alcohol catalyzed by 1-ethylimidazole copper trichloride ionic liquid (Structure 3, where n=1)
[0042] Preparation of 1-ethylimidazole cupric chloride ionic liquid ketone Example 1
[0043] 1-Ethylimidazole hydrochloride was added into a 20 mL glass vial, and then an equimolar amount of anhydrous copper chloride was added, and the mixture was stirred at 40° C. for 2 h to obtain 1-ethylimidazole copper trichloride ionic liquid.
[0044] Oxidative carbonylation reaction of cyclohexane and benzyl alcohol: 2.5 mL of cyclohexane, 0.0216 g (0.2 mmol) of benzyl alcohol, 0.0029 g (0.01 mmol) of 1-ethylimidazole copper chloride ionic liquid, and 0.0585 g (0.4 mmol) of oxidant DTBP were added to a 25 mL high-pressure reactor respectively. After replacing the gas in the reactor with carbon monoxide three times, 1.5 MPa of carbon monoxide was charged, the reaction temperature was set to 120°C, the reaction was carried out for 6 hours, and the product was detected by gas chromatography. n-octane was used as the internal standard. The yield of benzyl cyclohexanecarboxylate was 89.8%.
[0045] Embodiment 4:
[0046] Oxidative carbonylation of cyclopentane and benzyl alcohol to prepare benzyl cyclopentanecarboxylate using cuprous chloride ionic liquid as catalyst
[0047] The preparation of 1-ethylimidazole cuprous chloride ionic liquid is the same as in Example 1
[0048] Oxidative carbonylation reaction of cyclopentane and benzyl alcohol: 2.5 mL of cyclopentane, 0.0216 g (0.2 mmol) of benzyl alcohol, 0.0023 g (0.01 mmol) of 1-ethylimidazole cuprous chloride ionic liquid, and 0.0585 g (0.4 mmol) of oxidant DTBP were added to a 25 mL high-pressure reactor respectively. After replacing the gas in the reactor with carbon monoxide three times, 1.5 MPa of carbon monoxide was charged, the reaction temperature was set to 120°C, the reaction was carried out for 6 hours, and the product was detected by gas chromatography. n-octane was used as the internal standard. The yield of benzyl cyclopentanecarboxylate was 85.4%.
[0049] Embodiment 5:
[0050] Oxidative carbonylation of cycloheptane and benzyl alcohol to prepare benzyl cycloheptanecarboxylate catalyzed by 1-ethylimidazole cuprous chloride ionic liquid
[0051] The preparation of 1-ethylimidazole cuprous chloride ionic liquid is the same as in Example 1
[0052] Oxidative carbonylation reaction of cycloheptane with benzyl alcohol: 2.5 mL of cycloheptane, 0.0216 g (0.2 mmol) of benzyl alcohol, 0.0023 g (0.01 mmol) of 1-ethylimidazole cuprous chloride ionic liquid, and 0.0585 g (0.4 mmol) of oxidant DTBP were added to a 25 mL high-pressure reactor respectively. After replacing the gas in the reactor with carbon monoxide three times, 1.5 MPa of carbon monoxide was charged, the reaction temperature was set to 120 ° C, the reaction was carried out for 6 hours, and the product was detected by gas chromatography. n-octane was used as the internal standard. The yield of benzyl cycloheptane was 71.8%.
[0053] Embodiment 6:
[0054] Oxidative carbonylation of cyclooctane with benzyl alcohol to prepare benzyl cyclooctane carboxylate using 1-ethylimidazole cuprous chloride ionic liquid
[0055] The preparation of 1-ethylimidazole cuprous chloride ionic liquid is the same as in Example 1
[0056] Oxidative carbonylation reaction of cyclooctane with benzyl alcohol: 2.5 mL of cyclooctane, 0.0216 g (0.2 mmol) of benzyl alcohol, 0.0023 g (0.01 mmol) of 1-ethylimidazole cuprous chloride ionic liquid, and 0.0585 g (0.4 mmol) of oxidant DTBP were added to a 25 mL high-pressure reactor respectively. After replacing the gas in the reactor with carbon monoxide three times, 1.5 MPa of carbon monoxide was charged, the reaction temperature was set to 120°C, the reaction was carried out for 6 hours, and the product was detected by gas chromatography. n-octane was used as the internal standard. The yield of cyclooctane benzyl carboxylate was 77.6%.
[0057] Example 7
[0058] Oxidative carbonylation of cyclohexane and phenylethanol to prepare phenylethyl cyclohexanecarboxylate using cuprous chloride ionic liquid as catalyst
[0059] The preparation of 1-ethylimidazole cuprous chloride ionic liquid is the same as in Example 1
[0060] Oxidative carbonylation reaction of cyclohexane and phenylethanol: 2.5 mL of cyclohexane, 0.0244 g (0.2 mmol) of phenylethanol, 0.0023 g (0.01 mmol) of 1-ethylimidazole cuprous chloride ionic liquid, and 0.0585 g (0.4 mmol) of oxidant DTBP were added to a 25 mL high-pressure reactor respectively. After replacing the gas in the reactor with carbon monoxide three times, 1.5 MPa of carbon monoxide was charged, the reaction temperature was set at 120°C, the reaction was carried out for 6 hours, and the product was detected by gas chromatography. n-octane was used as the internal standard. The yield of phenylethyl cyclohexanecarboxylate was 96.4%.
[0061] Example 8
[0062] Oxidative carbonylation of cyclohexane with (S)-(-)-1-phenylethanol to prepare cyclohexanecarboxylic acid-(S)-(-)-1-phenylethyl ester catalyzed by 1-ethylimidazole cuprous chloride ionic liquid
[0063] The preparation of 1-ethylimidazole cuprous chloride ionic liquid is the same as in Example 1
[0064] Oxidative carbonylation reaction of cyclohexane and (S)-(-)-1-phenylethanol: 2.5 mL of cyclohexane, 0.0244 g (0.2 mmol) of (S)-(-)-1-phenylethanol, 0.0023 g (0.01 mmol) of 1-ethylimidazole cuprous chloride ionic liquid, and 0.0585 g (0.4 mmol) of oxidant DTBP were added to a 25 mL high-pressure reactor respectively. After replacing the gas in the reactor with carbon monoxide three times, 1.5 MPa of carbon monoxide was introduced. The reaction temperature was set at 120° C. and the reaction was carried out for 6 hours. The product was detected by gas chromatography. n-octane was used as the internal standard. The yield of cyclohexanecarboxylic acid-(S)-(-)-1-phenylethyl ester was 86.4%.
[0065] Example 9
[0066] Oxidative carbonylation of cyclohexane with (R)-(+)-1-phenylethanol to prepare cyclohexanecarboxylic acid-(R)-(+)-1-phenylethyl ester catalyzed by 1-ethylimidazole cuprous chloride ionic liquid
[0067] The preparation of 1-ethylimidazole cuprous chloride ionic liquid is the same as in Example 1
[0068] Oxidative carbonylation reaction of cyclohexane and (R)-(+)-1-phenylethanol: 2.5 mL of cyclohexane, 0.0244 g (0.2 mmol) of (R)-(+)-1-phenylethanol, 0.0023 g (0.01 mmol) of 1-ethylimidazole cuprous chloride ionic liquid, and 0.0585 g (0.4 mmol) of oxidant DTBP were added to a 25 mL autoclave, and the gas in the autoclave was replaced with carbon monoxide three times. Then, 1.5 MPa of carbon monoxide was introduced, the reaction temperature was set at 120° C., the reaction was carried out for 6 h, and the product was detected by gas chromatography. n-octane was used as the internal standard. The yield of cyclohexanecarboxylic acid-(R)-(+)-1-phenylethyl ester was 87.1%.
[0069] Example 10
[0070] Oxidative carbonylation of cyclohexane with 4-methylbenzyl alcohol to prepare 4-methylbenzyl cyclohexanecarboxylate using cuprous chloride ionic liquid as catalyst
[0071] The preparation of 1-ethylimidazole cuprous chloride ionic liquid is the same as in Example 1
[0072] Oxidative carbonylation reaction of cyclohexane with 4-methylbenzyl alcohol: 2.5 mL of cyclohexane, 0.0244 g (0.2 mmol) of 4-methylbenzyl alcohol, 0.0023 g (0.01 mmol) of 1-ethylimidazole cuprous chloride ionic liquid, and 0.0585 g (0.4 mmol) of oxidant DTBP were added to a 25 mL high-pressure reactor respectively. After replacing the gas in the reactor with carbon monoxide three times, 1.5 MPa of carbon monoxide was charged, the reaction temperature was set at 120°C, the reaction was carried out for 6 hours, and the product was detected by gas chromatography. n-octane was used as the internal standard. The yield of cyclohexanecarboxylic acid-4-methylbenzyl ester was 92.6%.
[0073] Embodiment 11
[0074] Oxidative carbonylation of cyclohexane and 2-naphthylmethanol to prepare 2-naphthyl cyclohexanecarboxylate using 1-ethylimidazole cuprous chloride ionic liquid
[0075] The preparation of 1-ethylimidazole cuprous chloride ionic liquid is the same as in Example 1
[0076] Oxidative carbonylation of cyclohexane with 2-naphthylmethanol: 2.5 mL of cyclohexane, 0.0316 g (0.2 mmol) of 2-naphthylmethanol, 0.0023 g (0.01 mmol) of 1-ethylimidazole cuprous chloride ionic liquid, and 0.0585 g (0.4 mmol) of oxidant DTBP were added to a 25 mL autoclave, and the gas in the autoclave was replaced with carbon monoxide three times. Then, 1.5 MPa of carbon monoxide was introduced, the reaction temperature was set at 120°C, the reaction was carried out for 6 hours, and the product was detected by gas chromatography. n-octane was used as the internal standard. The yield of cyclohexanecarboxylic acid-2-naphthyl ester was 90.8%.
[0077] Example 12
[0078] Oxidative carbonylation of cyclohexane with 3-chloro-1-propanol to prepare 3-chloro-1-propyl cyclohexanecarboxylate using 1-ethylimidazole cuprous chloride ionic liquid
[0079] The preparation of 1-ethylimidazole cuprous chloride ionic liquid is the same as in Example 1
[0080] Oxidative carbonylation reaction of cyclohexane with 3-chloro-1-propanol: 2.5 mL of cyclohexane, 0.0189 g (0.2 mmol) of 3-chloro-1-propanol, 0.0023 g (0.01 mmol) of 1-ethylimidazole cuprous chloride ionic liquid, and 0.0585 g (0.4 mmol) of oxidant DTBP were added to a 25 mL high-pressure reactor respectively. After replacing the gas in the reactor with carbon monoxide three times, 1.5 MPa of carbon monoxide was introduced, the reaction temperature was set at 120°C, the reaction was carried out for 6 hours, and the product was detected by gas chromatography. n-octane was used as the internal standard. The yield of 3-chloro-1-propyl cyclohexanecarboxylate was 93.4%.
[0081] The results of Examples 1 to 12 are shown in Table 1.
[0082] Table 1
[0083]
[0084]
[0085]
[0086] The above embodiments are only exemplary embodiments of the present invention and are not intended to limit the present invention. The protection scope of the present invention is defined by the claims. Those skilled in the art may make various modifications or equivalent substitutions to the present invention within the essence and protection scope of the present invention, and such modifications or equivalent substitutions shall also be deemed to fall within the protection scope of the present invention.
Claims
1. A method for oxidative carbonylation of cycloalkanes catalyzed by metal-based ionic liquids, characterized in that: The steps include: Mix metal-based ionic liquid, peroxide, cycloalkane and alcohol, add 0.5-5Mpa carbon monoxide, heat to 90-150°C, react for 2-12h to obtain cycloalkyl formate. The amount of the metal-based ionic liquid is 0.1 to 20 mol% of the alcohol, the molar ratio of cycloalkane to alcohol is 20 to 200:1, and the structural formula of the metal-based ionic liquid is any one of (1) to (3): n is an integer from 0 to 8.
2. The method for oxidative carbonylation of cycloalkanes catalyzed by metal-based ionic liquids according to claim 1, characterized in that: The structural formula of the ionic liquid is (1) or (2). n is an integer from 0 to 8.
3. The method for oxidative carbonylation of cycloalkanes catalyzed by metal-based ionic liquids according to claim 1 or 2, characterized in that: The n is 1 or 2.
4. The method for oxidative carbonylation of cycloalkanes catalyzed by metal-based ionic liquids according to claim 1, characterized in that: The cation in the metal-based ionic liquid is a proton-type imidazolium cation.
5. The method for oxidative carbonylation of cycloalkanes catalyzed by metal-based ionic liquids according to claim 1, characterized in that: The anion in the metal-based ionic liquid is [CuCl2] - , [FeCl4] - , [CuCl3] - Any one of .
6. The method for oxidative carbonylation of cycloalkanes catalyzed by metal-based ionic liquids according to claim 1, characterized in that: The cycloalkane is any one of cyclopentane, cyclohexane, cycloheptane and cyclooctane.
7. The method for oxidative carbonylation of cycloalkanes catalyzed by metal-based ionic liquids according to claim 1, characterized in that: The alcohol is any one of benzyl alcohol, phenylethyl alcohol, (S)-(-)-1-phenylethyl alcohol, (R)-(+)-1-phenylethyl alcohol, 4-methylbenzyl alcohol, 2-naphthalenemethyl alcohol, and 3-chloro-1-propanol.
8. The method for oxidative carbonylation of cycloalkanes catalyzed by metal-based ionic liquids according to claim 1, characterized in that: The amount of the ionic liquid used is 1 to 10 mol% of the alcohol.
9. The method for oxidative carbonylation of cycloalkanes catalyzed by metal-based ionic liquids according to claim 1, characterized in that: The molar ratio of the cycloalkane to the alcohol is 50-150:1.