A method of molybdenum disulfide promoted cobalt catalyzed carbonylation esterification reaction

Abstract

The present application relates to a kind of molybdenum disulfide promoted cobalt catalyzed carbonylation esterification reaction method, which uses cobalt salt as catalyst, molybdenum disulfide as cocatalyst, under mild reaction conditions, in carbon monoxide atmosphere, olefin compound or epoxy compound or chlorohydrocarbon compound is reacted with alcohol, and carboxylic acid ester compound is prepared.The reaction condition of the present application is mild, low in cost, and can avoid using metal powder and sodium thiosulfate as reducing agent, and no other transition metal is introduced in the reaction.

Description

Technical Field

[0001] This invention relates to the field of carbonyl synthesis chemistry, and more particularly to a method for cobalt-catalyzed carbonyl esterification reaction promoted by molybdenum disulfide. Background Technology

[0002] Cobalt-catalyzed carbonyl esterification is a reaction that introduces ester groups into organic compounds. It is an important synthetic method for preparing carboxylic acid esters and has significant industrial application value.

[0003] Currently, cobalt-catalyzed carbonylation and esterification reactions mostly use octacarbonyldicobalt as a catalyst, which is costly, easily decomposed, and highly volatile and toxic. To overcome these problems, cobalt salts, which are less expensive and more stable, are typically used for in-situ synthesis of carbonyl cobalt catalysts. The main methods include: high-temperature and high-pressure method, sodium borohydride method, and metal powder reduction method.

[0004] Patent CN1257140C reports a method for generating a cobalt carbonyl catalyst using cobalt salts such as cobalt formate under syngas (a mixture of hydrogen and carbon monoxide) conditions of 20-30 MPa and 100-200℃, which is used to catalyze the hydroformylation reaction of olefins.

[0005] Patent CN102442904A discloses a one-pot carbonyl esterification method for synthesizing malonic acid esters. Under conditions of 40-80 ℃ and carbon monoxide pressure of 0.5-4 MPa, cobalt salt, zinc powder or iron powder, sodium thiosulfate, chloroacetic acid ester, alcohol and alkali are added to a high-pressure reactor to synthesize malonic acid esters in one pot.

[0006] The above-mentioned methods for preparing cobalt carbonyl either use high temperature and high pressure, which are harsh conditions; or they use metal powder, which introduces other transition metals during the preparation of cobalt catalysts, interfering with subsequent carbonylation and esterification reactions and cobalt recovery. Summary of the Invention

[0007] The technical problem to be solved by the present invention is to provide a method for cobalt-catalyzed carbonylation esterification reaction promoted by molybdenum disulfide with mild reaction conditions and no strong reducing agent.

[0008] To address the aforementioned problems, the present invention provides a method for cobalt-catalyzed carbonyl esterification reaction promoted by molybdenum disulfide, characterized in that: the method uses cobalt salt as a catalyst and molybdenum disulfide as a co-catalyst, and reacts olefin compounds, epoxide compounds, or chlorinated hydrocarbon compounds with alcohols under mild reaction conditions and in a carbon monoxide atmosphere to obtain carboxylic acid ester compounds.

[0009] The cobalt salt is a hydrate or anhydrous compound, selected from one of cobalt acetylacetonate, cobalt chloride, cobalt sulfate, cobalt nitrate, cobalt acetate, cobalt formate, cobalt naphthenate, cobalt octanoate, cobalt oleate, and cobalt carbonate.

[0010] The amount of molybdenum disulfide used is 10% to 100% of the mass of the cobalt salt.

[0011] The reaction conditions refer to a reaction temperature of 60~160 ℃, a carbon monoxide pressure of 1~10 MPa, and a reaction time of 1~24 hours.

[0012] The olefin compound is selected from one of cyclohexene, hexene, octene, and styrene, and its mass is 10 to 200 times that of the cobalt salt.

[0013] The epoxy compound is selected from one of ethylene oxide, propylene oxide, propylene oxide, and phenylene oxide, and its mass is 10 to 200 times that of the cobalt salt.

[0014] The chlorinated hydrocarbon compound is selected from one of methyl chloroacetate, ethyl chloroacetate, propyl chloroacetate, and benzyl chloride, and its mass is 10 to 200 times that of the cobalt salt.

[0015] The alcohol is selected from methanol, ethanol, isopropanol, n-propanol, n-butanol, and isobutanol, and its mass is 50 to 1000 times that of the cobalt salt.

[0016] The carboxylic acid ester compounds include, but are not limited to, one of the following: methyl cyclohexylcarboxylate, methyl heptanoate, ethyl nonanoate, ethyl phenylpropionate, methyl hydroxypropionate, isopropyl 3-hydroxybutyrate, isobutyl 3,4-dihydroxybutyrate, methyl 3-hydroxyphenylpropionate, dimethyl malonate, diethyl malonate, dipropyl malonate, and butyl phenylacetate.

[0017] Compared with the prior art, the present invention has the following advantages:

[0018] 1. This invention utilizes molybdenum disulfide to reduce cobalt salts in situ under a carbon monoxide atmosphere to obtain a cobalt catalyst required for carbonylation-esterification reactions. Molybdenum disulfide is a heterogeneous co-catalyst with stable properties, capable of catalyzing the reduction of cobalt salts by carbon monoxide to generate a cobalt carbonyl catalyst.

[0019] 2. The reaction conditions during the preparation process of this invention are mild, effectively avoiding the use of high temperature and high pressure reaction conditions during cobalt salt reduction.

[0020] 3. This invention uses carbon monoxide as a reducing agent, avoiding the use of metal powder and sodium thiosulfate as reducing agents, and does not introduce other transition metals into the reaction, so that the subsequent carbonylation and esterification reactions and cobalt recovery are not interfered with.

[0021] 4. This invention does not use expensive cobalt carbonyl reagents, which greatly reduces production costs. Detailed Implementation

[0022] A method for cobalt-catalyzed carbonyl esterification reaction promoted by molybdenum disulfide is disclosed. This method uses a cobalt salt as a catalyst and molybdenum disulfide as a co-catalyst. In a carbon monoxide atmosphere at a pressure of 1–10 MPa, olefins, epoxides, or chlorinated hydrocarbons are reacted with alcohols at 60–160 °C for 1–24 hours to yield carboxylic acid esters. The specific process is as follows:

[0023] By weight (in grams), add 1 part cobalt salt and 0.1-1 part molybdenum disulfide co-catalyst to a high-pressure reactor. Add 10-200 parts of olefin, epoxide, or chlorinated hydrocarbon compound, and 50-1000 parts of alcohol. Purge with carbon monoxide at 1-10 MPa, heat to 60-160°C, and react for 1-24 hours. After the reaction time is reached, cool the high-pressure reactor to room temperature, slowly open the vent valve, reduce the pressure to atmospheric pressure, and replace the residual carbon monoxide in the reactor with nitrogen. Open the reactor, remove the reaction mixture, and obtain the carboxylic acid ester compound.

[0024] If the reactants are epoxides or chlorinated hydrocarbons, pre-activation is performed under a carbon monoxide atmosphere and at the appropriate reaction temperature.

[0025] Wherein: the cobalt salt is a hydrate or anhydrous compound, selected from one of cobalt acetylacetonate, cobalt chloride, cobalt sulfate, cobalt nitrate, cobalt acetate, cobalt formate, cobalt naphthenate, cobalt octanoate, cobalt oleate, and cobalt carbonate.

[0026] The olefin compounds are selected from one of cyclohexene, hexene, octene, and styrene.

[0027] Epoxy compounds are selected from one of ethylene oxide, propylene oxide, propylene oxide, and phenylene oxide.

[0028] The chlorinated hydrocarbon compounds are selected from one of methyl chloroacetate, ethyl chloroacetate, propyl chloroacetate, and benzyl chloride.

[0029] The alcohol is selected from one of methanol, ethanol, isopropanol, n-propanol, n-butanol, and isobutanol.

[0030] Carboxylic acid ester compounds include, but are not limited to, one of the following: methyl cyclohexylcarboxylate, methyl heptanoate, ethyl nonanoate, ethyl phenylpropionate, methyl hydroxypropionate, isopropyl 3-hydroxybutyrate, isobutyl 3,4-dihydroxybutyrate, methyl 3-hydroxyphenylpropionate, dimethyl malonate, diethyl malonate, dipropyl malonate, and butyl phenylacetate.

[0031] Example 1

[0032] 1 gram of cobalt acetylacetonate, 1 gram of molybdenum disulfide, 10 grams of cyclohexene, and 50 grams of methanol were added to a 100 mL stainless steel high-pressure reactor. The reactor was then charged with 1 MPa of carbon monoxide to displace the air, and this process was repeated three times. Afterward, 5 MPa of carbon monoxide was introduced into the reactor, and the reaction temperature was controlled at 140 °C with continuous stirring for 6 h. Once the reaction time was reached, the reactor was cooled to room temperature, the vent valve was slowly opened, the pressure was reduced to atmospheric pressure, and residual carbon monoxide was displaced with nitrogen before the reactor was opened. Gas chromatography analysis showed a methyl cyclohexylcarboxylate yield of 84%.

[0033] Comparative example (without molybdenum disulfide)

[0034] 1 g of cobalt acetylacetonate, 10 g of cyclohexene, and 50 g of methanol were added to a 100 mL stainless steel high-pressure reactor. The reactor was then charged with 1 MPa of carbon monoxide to displace the air, and this process was repeated three times. Afterward, 5 MPa of carbon monoxide was introduced into the reactor, and the reaction temperature was controlled at 140 °C with continuous stirring for 6 h. Once the reaction time was reached, the reactor was cooled to room temperature, the vent valve was slowly opened, the pressure was reduced to atmospheric pressure, and residual carbon monoxide was displaced with nitrogen before the reactor was opened. Gas chromatography analysis showed no detection of methyl cyclohexylcarboxylate. This demonstrates that molybdenum disulfide can promote the formation of cobalt carbonyl catalysts and plays an important role in carbonylation-esterification reactions.

[0035] Example 2

[0036] 1 gram of cobalt acetate, 0.1 gram of molybdenum disulfide, 200 grams of hexene, and 1000 grams of methanol were added to a 2000 mL stainless steel high-pressure reactor. The reactor was then charged with 1 MPa of carbon monoxide to displace the air, and this process was repeated three times. Afterward, 10 MPa of carbon monoxide was introduced into the reactor, and the reaction temperature was controlled at 130 °C with continuous stirring for 24 h. Once the reaction time was reached, the reactor was cooled to room temperature, the vent valve was slowly opened, the pressure was reduced to atmospheric pressure, and residual carbon monoxide was displaced with nitrogen before the reactor was opened. Gas chromatography analysis showed that the yield of methyl heptanoate was 91%.

[0037] Example 3

[0038] 1 g of cobalt formate, 0.5 g of molybdenum disulfide, 20 g of octene, and 100 g of ethanol were added to a 250 mL stainless steel high-pressure reactor. The reactor was then charged with 1 MPa of carbon monoxide to displace the air, and this process was repeated three times. Afterward, the reactor was charged with 1 MPa of carbon monoxide, and the reaction temperature was controlled at 160 °C with continuous stirring for 1 h. Once the reaction time was reached, the reactor was cooled to room temperature, the vent valve was slowly opened, the pressure was reduced to atmospheric pressure, and residual carbon monoxide was displaced with nitrogen before the reactor was opened. Gas chromatography analysis showed that the yield of ethyl nonanoate was 65%.

[0039] Example 4

[0040] 1 g of cobalt naphthenate, 0.5 g of molybdenum disulfide, 10 g of styrene, and 100 g of ethanol were added to a 250 mL stainless steel high-pressure reactor. The reactor was then charged with 1 MPa of carbon monoxide to displace the air, and this process was repeated three times. Afterward, 5 MPa of carbon monoxide was introduced into the reactor, and the reaction temperature was controlled at 100 °C with continuous stirring for 6 h. Once the reaction time was reached, the reactor was cooled to room temperature, the vent valve was slowly opened, the pressure was reduced to atmospheric pressure, and residual carbon monoxide was displaced with nitrogen before the reactor was opened. Gas chromatography analysis showed that the yield of ethyl phenylpropionate was 78%.

[0041] Example 5

[0042] 1 g of cobalt octanoate, 0.5 g of molybdenum disulfide, and 50 g of methanol were added to a 250 mL stainless steel high-pressure reactor. The reactor was then purged with 1 MPa of carbon monoxide to displace the air; this process was repeated three times. Next, 5 MPa of carbon monoxide was introduced, and the reaction was heated to 60 °C with continuous stirring for 12 h. While maintaining the reaction temperature at 60 °C, 10 g of ethylene oxide and 50 g of methanol were added using a plunger pump, and the reaction continued for another 12 hours. After the reaction was complete, the high-pressure reactor was cooled to room temperature, the vent valve was slowly opened, the pressure was reduced to atmospheric pressure, and residual carbon monoxide was displaced with nitrogen before the reactor was opened. Gas chromatography analysis showed a yield of methyl 3-hydroxypropionate of 71%.

[0043] Example 6

[0044] 1 g of cobalt oleate, 0.5 g of molybdenum disulfide, and 200 g of isopropanol were added to a 2000 mL stainless steel high-pressure reactor. The reactor was then purged with 1 MPa of carbon monoxide to displace the air, and this process was repeated three times. Next, 5 MPa of carbon monoxide was introduced into the reactor, and the reaction was heated to 100 °C with continuous stirring for 2 h. After cooling to 80 °C, 200 g of propylene oxide and 800 g of isopropanol were added using a plunger pump, and the reaction continued for 12 hours. After the reaction was complete, the high-pressure reactor was cooled to room temperature, the vent valve was slowly opened, the pressure was reduced to atmospheric pressure, and residual carbon monoxide was displaced with nitrogen before the reactor was opened. Gas chromatography analysis showed that the yield of isopropyl 3-hydroxybutyrate was 58%.

[0045] Example 7

[0046] 1 g of cobalt carbonate, 0.5 g of molybdenum disulfide, and 50 g of isobutanol were added to a 250 mL stainless steel high-pressure reactor. The reactor was then purged with 1 MPa of carbon monoxide to displace the air, and this process was repeated three times. Next, 5 MPa of carbon monoxide was introduced, and the reaction was heated to 160 °C with continuous stirring for 2 h. After cooling to 80 °C, 30 g of glycidol and 50 g of isobutanol were added using a plunger pump, and the reaction continued for 12 hours. After the reaction was complete, the high-pressure reactor was cooled to room temperature, the vent valve was slowly opened, the pressure was reduced to atmospheric pressure, and residual carbon monoxide was displaced with nitrogen before the reactor was opened. Gas chromatography analysis showed that the yield of isopropyl 3,4-hydroxybutyrate was 37%.

[0047] Example 8

[0048] 1 g of cobalt chloride, 0.5 g of molybdenum disulfide, and 50 g of methanol were added to a 250 mL stainless steel high-pressure reactor. The reactor was then purged with 1 MPa of carbon monoxide to displace the air, and this process was repeated three times. Next, 5 MPa of carbon monoxide was introduced into the reactor, and the reaction was heated to 150 °C with continuous stirring for 2 h. After cooling to 80 °C, 50 g of phenylene oxide and 50 g of methanol were added using a plunger pump, and the reaction continued for 8 hours. After the reaction was complete, the high-pressure reactor was cooled to room temperature, the vent valve was slowly opened, the pressure was reduced to atmospheric pressure, and residual carbon monoxide was displaced with nitrogen before the reactor was opened. Gas chromatography analysis showed a yield of methyl 3-hydroxyphenylpropionate of 79%.

[0049] Example 9

[0050] Add 1 gram of cobalt acetate, 0.5 grams of molybdenum disulfide, and 20 grams of methanol to a 50 ml stainless steel reactor. Purge the reactor with 1 MPa of carbon monoxide to displace the air inside, repeating this process three times. Then, purge the reactor with 6 MPa of carbon monoxide, heat to 100 °C, and stir continuously for 2 hours.

[0051] A 250 mL stainless steel reactor containing 30 g methyl chloroacetate, 100 g methanol, and 30 g sodium carbonate was charged with 1 MPa of carbon monoxide to displace the air inside the reactor. This process was repeated three times. Afterward, a high-pressure reactor was charged with 5 MPa of carbon monoxide.

[0052] Using a pressure differential, the liquid in a 50 mL reactor was transferred to a 250 mL stainless steel reactor via a stainless steel pipeline. The temperature was raised to 90°C, and the reaction continued for 8 hours. After the reaction, the high-pressure reactor was cooled to room temperature, the vent valve was slowly opened, the pressure was reduced to atmospheric pressure, and residual carbon monoxide in the reactor was replaced with nitrogen. The reactor was then opened. Gas chromatography analysis showed that the yield of dimethyl malonate was 96%.

[0053] Example 10

[0054] Add 1 gram of cobalt sulfate, 0.5 grams of molybdenum disulfide, and 20 grams of ethanol to a 50 ml stainless steel reactor. Purge the reactor with 1 MPa of carbon monoxide to displace the air inside, repeating this process three times. Then, purge the reactor with 6 MPa of carbon monoxide, heat to 100 °C, and stir continuously for 2 hours.

[0055] A 250 mL stainless steel reactor containing 10 g ethyl chloroacetate, 30 g ethanol, and 9 g sodium carbonate was charged with 1 MPa of carbon monoxide to displace the air inside the reactor. This process was repeated three times. Afterward, a high-pressure reactor was charged with 5 MPa of carbon monoxide.

[0056] Using a pressure differential, the liquid in a 50 mL reactor was transferred to a 250 mL stainless steel reactor via a stainless steel pipeline. The temperature was raised to 90°C, and the reaction continued for 8 hours. After the reaction, the high-pressure reactor was cooled to room temperature, the vent valve was slowly opened, the pressure was reduced to atmospheric pressure, and residual carbon monoxide in the reactor was replaced with nitrogen. The reactor was then opened. Gas chromatography analysis showed that the yield of diethyl malonate was 78%.

[0057] Example 11

[0058] Add 1 gram of cobalt nitrate, 0.5 grams of molybdenum disulfide, and 20 grams of n-propanol to a 50 ml stainless steel reactor. Purge the reactor with 1 MPa of carbon monoxide to displace the air inside, repeating this process three times. Then, purge the reactor with 6 MPa of carbon monoxide, heat to 100 °C, and stir continuously for 2 hours.

[0059] A 2000 mL stainless steel reactor containing 200 g propyl chloroacetate, 500 g n-propanol, and 150 g sodium carbonate was charged with 1 MPa of carbon monoxide to displace the air inside the reactor. This process was repeated three times. Afterward, a high-pressure reactor was charged with 5 MPa of carbon monoxide.

[0060] Using a pressure differential, the liquid in a 50 mL reactor was transferred to a 2000 mL stainless steel reactor via a stainless steel pipeline. The temperature was raised to 90°C, and the reaction continued for 8 hours. After the reaction, the high-pressure reactor was cooled to room temperature, the vent valve was slowly opened, the pressure was reduced to atmospheric pressure, and residual carbon monoxide in the reactor was replaced with nitrogen. The reactor was then opened. Gas chromatography analysis showed that the yield of dipropyl malonate was 43%.

[0061] Example 12

[0062] 1 gram of cobalt acetylacetonate, 0.5 grams of molybdenum disulfide, and 20 grams of n-butanol were added to a 50 mL stainless steel reactor. The reactor was then charged with 1 MPa of carbon monoxide to displace the air; this process was repeated three times. Afterward, the reactor was charged with 6 MPa of carbon monoxide, and the reaction was heated to 100 °C with continuous stirring for 2 h.

[0063] A 250 mL stainless steel reactor containing 30 g benzyl chloride, 100 g n-butanol, and 27 g sodium carbonate was charged with 1 MPa of carbon monoxide to displace the air inside the reactor. This process was repeated three times. Afterward, a high-pressure reactor was charged with 5 MPa of carbon monoxide.

[0064] Using a pressure differential, the liquid in a 50 mL reactor was transferred to a 250 mL stainless steel reactor via a stainless steel pipeline. The temperature was raised to 60°C, and the reaction continued for 8 hours. After the reaction, the high-pressure reactor was cooled to room temperature, the vent valve was slowly opened, the pressure was reduced to atmospheric pressure, and residual carbon monoxide in the reactor was replaced with nitrogen. The reactor was then opened. Gas chromatography analysis showed that the yield of butyl phenylacetate was 97%.

Claims

1. A method of molybdenum disulfide promoted cobalt catalyzed carbonylation esterification reaction, characterized by: The method uses cobalt salt as catalyst, molybdenum disulfide as cocatalyst, reacts olefin compound with alcohol in carbon monoxide atmosphere under mild reaction condition to prepare carboxylic acid ester compound; the cobalt salt is one of cobalt acetylacetonate, cobalt chloride, cobalt sulfate, cobalt nitrate, cobalt acetate, cobalt formate, cobalt naphthenate, cobalt octanoate, cobalt oleate and cobalt carbonate; the olefin compound is one of cyclohexene, hexene, octene and styrene; the alcohol is one of methanol, ethanol, isopropanol, n-propanol, n-butanol and isobutanol; the reaction condition refers to that the reaction temperature is 60-160 DEG C and the carbon monoxide pressure is 1-10 MPa.

2. A process for molybdenum disulfide promoted cobalt catalyzed carbonylation esterification reaction as claimed in claim 1 wherein: The amount of molybdenum disulfide is 10-100% of the mass of cobalt salt.

3. A process for molybdenum disulfide promoted cobalt catalyzed carbonylation esterification reaction as claimed in claim 1 wherein: The reaction time is 1-24 hours.

4. A process for molybdenum disulfide promoted cobalt catalyzed carbonylation esterification reaction as claimed in claim 1 wherein: The mass of olefin compound is 10-200 times of the mass of cobalt salt.

5. A process for molybdenum disulfide promoted cobalt catalyzed carbonylation esterification reaction as claimed in claim 1 wherein: The mass of alcohol is 50-1000 times of the mass of cobalt salt.

6. A process for molybdenum disulfide promoted cobalt catalyzed carbonylation esterification reaction as claimed in claim 1 wherein: The carboxylic acid ester compound includes one of cyclohexyl formate, heptanoic acid methyl ester, nonanoic acid ethyl ester and phenylpropionic acid ethyl ester.