KR102166840B1 - Organocatalysts with multi-hydrogen bonds and method of manufacturing cyclic alkylene carbonates using the same - Google Patents

Abstract

상기 화학식 1에서, R¹ 및 R²는 서로 독립적으로 수소 또는 탄소수 C₁ 내지 C₁₀의 알킬기이다.The present invention relates to a novel organic catalyst for preparing a cyclic alkylene carbonate and a method for producing a cyclic alkylene carbonate using the same, and more particularly, a plurality of hydrogen bonds capable of multiple hydrogen bonds in one molecule as shown in Formula 1 below. Using an epoxide compound and carbon dioxide as raw materials by using an ammonium halide salt containing both a hydroxy (OH) group and an ammonium base as a catalyst, selectively producing a cyclic alkylene carbonate in a high yield with a higher conversion rate than the existing catalyst It's about how to do it.
[Formula 1]

In Formula 1, R ¹ and R ² are each independently hydrogen or a C ₁ to C ₁₀ alkyl group.

Description

Organic catalyst having multiple hydrogen bonds and a method of manufacturing cyclic alkylene carbonates using the same {Organocatalysts with multi-hydrogen bonds and method of manufacturing cyclic alkylene carbonates using the same}

The present invention relates to an organic catalyst having multiple hydrogen bonds and a method for producing a cyclic alkylene carbonate using the same.

Cyclic alkylene carbonate is a material with a very wide range of use as an electrolyte solution for lithium ion batteries, a precursor of polycarbonate, an intermediate in various pharmaceutical processes, and a reaction solvent. In addition, cyclic alkylene carbonate made from carbon dioxide has an environmentally friendly advantage in that it is a chemical conversion of carbon dioxide, but when it is synthesized at a high temperature, the carbon dioxide reduction effect is reduced due to additional heat. Therefore, there is a need to develop a catalyst capable of synthesizing cyclic alkylene carbonate at low temperature.

In general, cyclic alkylene carbonate is synthesized and manufactured using an epoxide, carbon dioxide, and a catalyst, as shown in Scheme 1 below.

[Scheme 1]

In Reaction Scheme 1, R is selected from hydrogen, chlorine, a C ₁ to C ₄ alkyl group, an alkoxy or aryloxy group.

In general, a problem arises that a high pressure or high temperature condition is required in order to shorten the reaction time. Accordingly, various organic and organometallic catalysts have been developed in order to mitigate the progression of an incidental reaction such as polymer formation under high pressure or high temperature conditions.

Korean Patent Registration No. 10-1839877 discloses a method of using a catalyst having one OH bonded to a phenyl group in the molecule without OR ² in the formula (1). In the above-described known technology, there is a problem in that a long reaction time of 24 hours has to be applied to obtain cyclic propylene carbonate in an 85% yield at 25°C.

Japanese Patent Laid-Open Publication No. Hei 9-67365 is a method of using organic substances derived from halogenated phosphonium halide, halide imidazolium halide, and ammonium halide as a catalyst. No., Japanese Patent Application Laid-Open No. 59-13776, Japanese Patent Application Laid-Open No. Hei 9-235252, and U.S. Patent No. 2,773,070.

Japanese Patent Laid-Open No. Hei 9-67365 discloses a method of using KI as a catalyst, and Japanese Patent Laid-Open No. 59-13776 discloses tributylmethyl phosphonium iodide and tetrahalogenated salt. Disclosed is a method of using an alkyl phosphonium halide as a catalyst. In addition, Japanese Patent Application Laid-Open No. Hei 9-235252 discloses a method of using a polymer through copolymerization with polystyrene having a halide quaternary phosphonium salt bonded to the terminal.

The known techniques describe that it can be obtained in a yield of 50 to 95% by setting the reaction condition to be performed at a temperature of 100° C. or higher for 1 to 5 hours, but in order to obtain a better yield, the reaction time is extended or the temperature is increased. It has a problem that the execution of the process is not simple, such as the need to change the height conditions.

As described above, the conventional technology requires high temperature conditions in order to industrially manufacture cyclic alkylene carbonates, and requires a long reaction time to be applied, and thus reaction conditions are difficult, and selectivity and yield are low. In particular, when the reaction temperature is lowered, there is a limit to increasing the amount of catalyst used (more than 10 mol%) or increasing the reaction time to 24 hours.

An object of the present invention is to solve the above problems, and to provide a method for producing a cyclic alkylene carbonate having a high yield within a short time while using a small amount of an organic catalyst at room temperature. In the present invention, an organic catalyst containing an ammonium salt in the molecule and a hydroxyl group capable of simultaneously forming multiple hydrogen bonds of different types is prepared, and the high temperature used in the conventional method is used as a catalyst. The present invention was completed by finding out that it is possible to prepare cyclic alkylene carbonate in a high yield when the reaction proceeds for a short time using a small amount of catalyst at room temperature (25°C), which is much lower than the conditions.

Accordingly, an object of the present invention is to provide a novel organic catalyst capable of selectively synthesizing cyclic alkylene carbonate by reacting epoxide and carbon dioxide. Another object of the present invention is to provide a method for preparing alkylene carbonate comprising the step of reacting epoxide and carbon dioxide in the presence of the organic catalyst.

The present invention relates to a novel organic catalyst for preparing a cyclic alkylene carbonate and a method for producing a cyclic alkylene carbonate using the same, and more particularly, a plurality of hydrogen bonds capable of multiple hydrogen bonds in one molecule as shown in Formula 1 below. A method of selectively producing cyclic alkylene carbonate in high yield with higher conversion rate than conventional catalysts from raw materials of epoxide compound and carbon dioxide by using an ammonium halide salt containing both hydroxy (OH) group and ammonium base as a catalyst It is about.

[Formula 1]

In Formula 1, R ¹ and R ² are each independently hydrogen or a C ₁ to C ₁₀ alkyl group.

The present invention relates to a novel organic catalyst and a method for producing a cyclic alkylene carbonate using the same, wherein the novel organic catalyst is not only excellent in terms of economy because it is easy to synthesize and is inexpensive And, by using the organic catalyst, the cyclic alkylene carbonate synthesis reaction can proceed at room temperature, which is a more relaxed condition than the conventional method, and the reaction time can be shortened, and a cyclic alkylene carbonate can be produced with a high yield. It can be used for the production of cyclic alkylene carbonates.

1 is a graph showing the reaction yield change according to the reaction time using the compound 5 of the present invention in the absence of a solvent.

Hereinafter, various embodiments of the present document will be described with reference to the accompanying drawings. The examples and terms used therein are not intended to limit the technology described in this document to a specific embodiment, and should be understood to include various modifications, equivalents, and/or substitutes of the corresponding embodiments.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings.

The present invention provides a catalyst for selectively producing cyclic alkylene carbonate from epoxide and carbon dioxide, and the catalyst of the present invention is an organic catalyst represented by the following formula (1).

[Formula 1]

In Formula 1, R ¹ and R ² are each independently hydrogen or a C ₁ to C ₁₀ alkyl group.

The term "alkyl group" in the specification of the present invention refers to a straight-chain or branched hydrocarbon, and includes, but is not limited to, methyl, ethyl, propyl, butyl, pentyl, hexyl, and the like.

Another aspect of the present invention relates to a method for preparing an alkylene carbonate comprising reacting epoxide and carbon dioxide in the presence of an organic catalyst represented by Chemical Formula 1.

In one embodiment of the present invention, the epoxide is ethylene oxide, propylene oxide, epichlorohydrin, butylene oxide, styrene oxide, Glycidol or hexylene oxide may be used. For example, propylene oxide may be used, but the present invention is not limited thereto.

In the method for producing a cyclic alkylene carbonate according to an embodiment of the present invention, the organic catalyst is preferably used in an amount of 0.01 to 10 mol% relative to the epoxide, and when the amount is less than 0.01 mol%, the reaction time is If it is too long and the concentration is increased, the reaction time is shortened, but there is no economic benefit due to an increase in the catalyst unit cost when used in an amount of 10 mol% or more.

In the method for producing a cyclic alkylene carbonate according to an embodiment of the present invention, the reaction temperature is preferably 25 to 150°C, and when the reaction is performed under conditions where the reaction temperature is too low, the reaction time becomes longer, Increasing the temperature has the effect of shortening the reaction time, but it is uneconomical because the reaction time is no longer shortened compared to the additional cost required for this when it is performed under a temperature condition of 150°C or higher.

In the method for producing a cyclic alkylene carbonate according to an embodiment of the present invention, the reaction is carried out under conditions in which carbon dioxide is provided at an atmospheric pressure of 0.1 to 100 bar, 1 to 30 bar, for example, 5 to 10 bar. It may be, but is not limited thereto.

In the method for producing a cyclic alkylene carbonate according to an embodiment of the present invention, the reaction is mainly carried out in the absence of a solvent, but a solvent may be used to prevent rapid heat generation during the reaction. As the solvent, any one or more selected from the group consisting of tetrahydrofuran, methylene chloride, diethyl ether, hexane, and water may be used, but is not limited thereto.

In one embodiment of the present invention, the cyclic alkylene carbonate may be represented by Formula 2 below, but is not limited thereto:

[Formula 2]

In Formula 2, R is hydrogen, carbon, chlorine, a C ₁ to C ₄ alkyl group, an alkoxy or aryloxy group.

Hereinafter, the present invention will be described in more detail through examples of the present application, but the following examples are merely illustrative to aid understanding of the present application, and the contents of the present application are not limited to the following examples.

Example

Materials and substances

All experiments were performed in a nitrogen atmosphere using standard Schlenk type glassware (dual manifold Schlenk line). Nitrogen was deoxygenated using an activated Cu catalyst, and a small amount of water was removed with a drierite. All solvents used in the synthesis of ligands and catalysts were distilled using sodium diphenylketyl and stored in an active molecular sieve of 3Å.

Data measurement

¹ H and ¹³ C NMR spectra were obtained with a 400 MHz NMR spectrometer using standard parameters. All chemical shifts were performed with CDCl ₃ (δ 7.24 for ¹ H NMR; δ77.00 for ¹³ C NMR) (CD ₃ ) ₂ S=O (δ 2.50 for ¹ H NMR; δ 39.25 for ¹³ C NMR) and Expressed in ppm for CD ₃ CN (δ 1.94 for ¹ H NMR; δ 1.32 and 118.26 for ¹³ C NMR).

Compound synthesis

Compounds were prepared in order to confirm the effect as a catalyst according to the structure of each compound.

Specifically, compounds 1 to 5 in the following Formula 3 were prepared according to the following Preparation Example.

[Formula 3]

Manufacturing example 1-1. Preparation of compound 1

N,N,N-trimethyl-N',N'-bis(2-hydroxy-3-methoxybenzyl)ethylenediamine iodide (hereinafter, Compound 1) was prepared as shown in Scheme 2 below.

[Scheme 2]

Specifically, compound L1 (1.08 g, 3.0 mmol) was dissolved in acetonitrile (MeCN) (25 mL) solution, methyl iodide (1.7 g, 12 mmol) was added, and then the mixture was prepared at 50°C. Refluxed. After 12 hours, the reaction mixture was cooled to room temperature and all volatiles were removed using a vacuum pump. The obtained solid was washed three times three times with diethyl ether (40 mL) and then dried to obtain the desired product 1 (1.36 g, 90%) as a pale yellow solid.

¹ H NMR (CDCl ₃ ): δ 6.80-6.76 (m, 6H, Ar- H ), 3.83 (s, 6H, ArOC H ₃ ), 3.81 (s, 4H, ArC H ₂ N-), 3.72 (m, 2H, -C H ₂ NMe ₃ ), 3.19 (s, 9H, -N Me ₃ ), 2.93 (m, 2H, -NC H ₂ CH ₂ NMe ₃ ). ¹³ C NMR (CDCl ₃ ): δ 147.2, 144.9, 122.6, 121.7, 119.8, 111.0 (Ar), 63.61 (- C H ₂ NMe ₃ ), 55.94 (-N Me ₃ ), 55.22 (Ar C H ₂ N- ), 55.93 (ArO C H ₃ ), 46.08 (-N C H ₂ CH ₂ NMe ₃ ). HRMS m / z calcd. for [C ₂₁ H ₃₁ N ₂ O ₄ I-I] ⁺ 375.2278. Found 375.2278.

Manufacturing example 1-2. Preparation of compound L2

N,N-dimethyl-N',N'-bis(2,3-dihydroxybenzyl)ethylenediamine (hereinafter, compound L2) was prepared as shown in Scheme 3 below.

[Scheme 3]

Specifically, L1 (3.6 g, 10 mmol) and 20% HBr acetic acid solution (8 mL) were mixed well with 100 mL acetic acid, and then refluxed at 120°C. After 48 hours, all solvents were removed using a vacuum pump. Then, concentrated HCl and ice were added, and NaHCO ₃ was added to neutralize. After extraction with chloroform, water of the extracted solution with MgSO ₄ was removed. When the solution obtained by filtering with filter paper was dried with a vacuum pump, the desired product L2 (2.2 g, 65%) was obtained as a colorless solid.

¹ H NMR ((CD ₃ ) ₂ S=O): δ 9.15 (br s, 4H, -O H ) 6.68-6.63 (m, 2H, Ar- H ), 6.58-6.53 (m, 4H, Ar- H) ), 3.57 (s, 4H, ArC H ₂ N-), 2.48 (s, 4H, -C H ₂ C H ₂ NMe ₂ ), 2.09 (s, 6H, -N Me ₂ ). ¹³ C NMR ((CD ₃ ) ₂ S=O): δ 145.3, 144.7, 123.8, 120.5, 118.4, 114.7 (Ar), 55.52 (- C H ₂ NMe ₂ ), 53.60 (Ar C H ₂ N-), 49.29 (-N Me ₂ ), 44.82 (-N C H ₂ CH ₂ NMe ₂ ). HRMS m / z calcd. for [C ₁₈ H ₂₅ N ₂ O ₄ +H] 333.1809. Found 333.1809.

Manufacturing example 1-3. Preparation of compound 2

N,N,N-trimethyl-N',N'-bis(2,3-dihydroxybenzyl)ethylenediamine iodide (hereinafter, Compound 2) was prepared as shown in Scheme 4 below.

[Scheme 4]

Specifically, in the same manner as used for preparing compound 1 of Preparation Example 1-1, compound L2 (1.0 g, 3.0 mmol) and methyl iodide (1.7 g, 12 mmol) were reacted to form a pale yellow solid compound 2 ( 1.2 g, 85%) was prepared.

¹ H NMR ((CD ₃ ) ₂ S=O): δ 9.23 (s, 2H, -OH), 8.73 (s, 2H, -OH) 6.72-6.59 (m, 6H, Ar- H ), 3.65 (s , 4H, ArC H ₂ N-), 3.55 (m, 2H, -C H ₂ NMe ₃ ), 2.96 (s, 9H, -N Me ₃ ), 2.80 (m, 2H, -NC H ₂ CH ₂ NMe ₃ ). ¹³ C NMR ((CD ₃ ) ₂ S=O): δ 145.1, 144.3, 123.8, 120.8, 118.8, 114.6 (Ar), 64.95 (- C H ₂ NMe ₃ ), 55.80 (-N Me ₃ ), 52.50 ( Ar C H ₂ N-), 45.52 (-N C H ₂ CH ₂ NMe ₃ ). HRMS m / z calcd. for [C ₁₉ H ₂₇ N ₂ O ₄ I-I] 347.1965. Found 347.1965.

Manufacturing example 1-4. Preparation of compound 3

N,N,N-trimethyl-N',N'-bis(2-hydroxy-3-methoxy-5-methylbenzyl)ethylenediamine iodide (hereinafter, compound 3 ) was prepared as shown in Scheme 5 below. I did.

[Scheme 5]

Specifically, in the same manner as used for preparing compound 1 of Preparation Example 1-1, compound L3 (1.17 g, 3.0 mmol) and methyl iodide (1.7 g, 12 mmol) were reacted to form a pale yellow solid compound 3 ( 1.27 g, 80%) was prepared.

¹ H NMR (CDCl ₃ ): δ 6.60 (d, 2H, J = 1.2 Hz, Ar- H ), 6.54 (d, 2H, J = 0.8 Hz, Ar- H ), 3.81 (s, 6H, ArOC H ₃ ), 3.75 (s, 4H, ArC H ₂ N-), 3.72 (m, 2H, -C H ₂ NMe ₃ ), 3.20 (s, 9H,- N Me ₃ ), 2.93 (m, 2H, -NC H ₂ CH ₂ NMe ₃ ), 2.22 (s, 6H, Ar-C H ₃ ). ¹³ C NMR (CDCl ₃ ): δ 146.9, 142.5, 129.3, 122.8, 121.3, 112.1 (Ar), 63.89 (- C H ₂ NMe ₃ ), 55.92 (-N Me ₃ ), 55.55 (Ar C H ₂ N- ), 54.01 (ArO C H ₃ ), 46.40 (-N C H ₂ CH ₂ NMe ₃ ), 21.00 (Ar- C H ₃ ). HRMS m / z calcd. for [C ₂₅ H ₃₅ N ₂ O ₄ -I] 403.2591. Found 403.2591.

Manufacturing example 1-5. Preparation of compound L4

N,N-dimethyl-N',N'-bis(2,3-dihydroxy-5-methylbenzyl)ethylenediamine (hereinafter, compound L4 ) was prepared as shown in Scheme 6 below.

[Scheme 6]

Specifically, in the same manner as used for preparing compound L2 of Preparation Example 1-2, compound L3 (3.9 g, 10 mmol) and 20% HBr acetic acid solution (8 mL) were reacted to form a colorless solid compound L4 (1.6 g, 45%) was prepared.

¹ H NMR (CDCl ₃ ): δ 7.87 (br s, 4H, -O H ) 6.65 (d, 2H, J = 1.5 Hz, Ar- H ), 6.36 (d, 2H, J = 1.4 Hz, Ar- H ), 3.57 (s, 4H, ArC H ₂ N-), 2.59 (s, 4H, -C H ₂ C H ₂ NMe ₂ ), 2.27 (s, 6H, -N Me ₂ ), 2.18 (s , 6H, ArC H ₃ ). ¹³ C NMR (CDCl ₃ ): δ 145.1, 141.0, 128.9, 122.1, 121.4, 115.1 (Ar), 55.97 (- C H ₂ NMe ₂ ), 55.49 (Ar C H ₂ N-), 48.91 (-N Me ₂ ), 44.69 (-N C H ₂ CH ₂ NMe ₂ ), 20.69 (Ar C H ₃ ). HRMS m / z calcd. for [C ₂₀ H ₂₉ N ₂ O ₄ +H] 361.2122. Found 361.2122.

Manufacturing example 1-6. Preparation of compound 4

N,N,N-trimethyl-N',N'-bis(2,3-dihydroxy-5-methylbenzyl)ethylenediamine iodide (hereinafter, Compound 4 ) was prepared as shown in Scheme 7 below.

[Scheme 7]

Specifically, in the same manner as used for preparing compound 1 of Preparation Example 1-1, compound L4 (1.1 g, 3.0 mmol) and methyl iodide (1.7 g, 12 mmol) were reacted to form a pale yellow solid compound 4 ( 1.3 g, 87%) was prepared.

¹ H NMR (CD ₃ CN): δ 6.69 (d, 2H, J = 1.8 Hz, Ar- H ), 6.53 (s, 2H, Ar- H ), 3.81 (s, 4H, ArC H ₂ N-), 3.54 (m, 2H, -C H ₂ NMe ₃ ), 2.97 (m, 2H,- NC H ₂ CH ₂ NMe ₃ ), 2.96 (s, 9H, -N Me ₃ ), 2.18 (s, 6H, ArC H ₃ ). ¹³ C NMR (CD ₃ CN): δ 145.4, 142.6, 130.3, 123.0, 122.6, 116.9 (Ar), 62.84 (- C H ₂ NMe ₃ ), 55.39 (-N Me ₃ ), 54.15 (Ar C H ₂ N -), 46.31 (-N C H ₂ CH ₂ NMe ₃ ), 20.63 (Ar C H ₃ ). HRMS m / z calcd. for [C ₂₁ H ₃₁ N ₂ O ₄ I-I] 375.2278. Found 375.2278.

Manufacturing example 1-7. Preparation of compound L5

N,N-dimethyl-N',N'-bis(2,3-dihydroxy-5-tertiary-butylbenzyl)ethylenediamine (hereinafter, compound L5 ) was prepared as shown in Scheme 8 below.

[Scheme 8]

Specifically, 1,2-dihydroxy-4-tertiary-butylphenol (8.3 g, 50 mmol), N,N-dimethylethylenediamine (2.2 g, 25 mmol), 36% formaldehyde/water ( 4.1 g, 50 mmol) was mixed well with 100 mL of methanol and stirred at room temperature. After 72 hours, all volatiles were removed using a vacuum pump. The obtained colorless solid was washed three times with methanol (40 mL) and then dried to obtain the desired product L5 (9.4 g, 85%) as a colorless solid.

¹ H NMR ((CD ₃ ) ₂ SO): δ 6.69 (d, 2H, J = 2.2 Hz, Ar- H ), 6.56 (d, 2H, J = 2.2 Hz, Ar- H ), 3.57 (s, 4H, ArC H ₂ N-), 2.50 (s, 4H, -C H ₂ C H ₂ NMe ₂ ), 2.12 (s, 6H, -N Me ₂ ), 1.20 (s , 18 H, ArC(C H ₃ ) ₃ ). ¹³ C NMR ((CD ₃ ) ₂ SO): δ 144.6, 142.2, 140.7, 122.8, 117.0, 112.0 (Ar), 55.56 (- C H ₂ NMe ₂ ), 53.76 (Ar C H ₂ N-), 49.22 ( -N Me ₂ ), 44.79 (-N C H ₂ CH ₂ NMe ₂ ), 22.58 (ArC ( C H ₃ ) ₃ ), 31.45 (Ar C (CH ₃ ) ₃ ). HRMS m / z calcd. for [C ₂₆ H ₄₁ N ₂ O ₄ +H] 445.3061. Found 445.3061.

Manufacturing example 1-8. Preparation of compound 5

N,N,N-trimethyl-N',N'-bis(2,3-dihydroxy-5-tertiary-butylbenzyl)ethylenediamine iodide (hereinafter, Compound 5 ) was prepared as shown in Scheme 9 below. Was prepared.

[Scheme 9]

Specifically, in the same manner as used for preparing compound 1 of Preparation Example 1-1, compound L5 (1.3 g, 3.0 mmol) and methyl iodide (1.7 g, 12 mmol) were reacted to form a pale yellow solid compound 5 ( 1.6 g, 93%) was prepared.

¹ H NMR (CD ₃ CN): δ 6.95 (d, 2H, J = 2.3 Hz, Ar- H ), 6.74 (d, 2H, J = 2.3 Hz, Ar- H ), 3.82 (s, 4H, ArC H ₂ N-), 3.54 (m, 2H, -C H ₂ NMe ₃ ), 2.96 (s, 9H, -N Me ₃ ), 2.93 (m, 2H, -NC H ₂ CH ₂ NMe ₃ ), 1.24 (s, 18H, ArC(C H ₃ ) ₃ ). ¹³ C NMR (CD ₃ CN): δ 145.1, 144.0, 142.5, 122.8, 119.3, 113.6 (Ar), 62.98 (- C H ₂ NMe ₃ ), 55.30 (-N Me ₃ ), 54.16 (Ar C H ₂ N -), 46.16 (-N C H ₂ CH ₂ NMe ₃ ), 34.65 (ArC( C H ₃ ) ₃ ), 31.70 (Ar C (CH ₃ ) ₃ ). HRMS m / z calcd. for [C ₂₇ H ₄₃ N ₂ O ₄ I-I] 459.3217. Found 459.3217.

Manufacturing example 1-9. Preparation of compound 6

N,N,N-trimethyl-N',N'-bis(2,3-dihydroxy-5-tertiary-butylbenzyl)ethylenediamine bromide (hereinafter Compound 6 ) was prepared as shown in Scheme 10 below. .

[Scheme 10]

Specifically, silver bromide (0.41 g, 2.2 mmol) was added to a solution of THF (25 mL) containing compound 5 (1.17 g, 2.0 mmol) at room temperature, and the mixture was stirred for 3 hours. Then, the reaction mixture was filtered through Celite. All volatiles were removed under vacuum and the residue was washed with diethyl ether. After vacuum drying, compound 6 (0.86 g, 80%) was obtained as a beige powder.

¹ H NMR ((CD ₃ ) ₂ SO): δ 9.10 (s, 2H, -OH), 8.49 (s, 2H, -OH), 6.74 (s, 2H, Ar- H ), 6.68 (s, 2H, Ar- H ), 3.60 (s, 4H, ArC H ₂ N-), 3.52 (m, 2H, -C H ₂ NMe ₃ ), 2.94 (s, 9H, -N Me ₃ ), 2.51 (m, 2H, -NC H ₂ CH ₂ NMe ₃ ), 1.21 (s, 18H, ArC(C H ₃ ) ₃ ). ¹³ C NMR (CD ₃ CN): δ 144.5, 141.8, 141.1, 123.1, 117.3, 111.7 (Ar), 61.20 (- C H ₂ NMe ₃ ), 52.50 (-N Me ₃ ), 52.19 (Ar C H ₂ N -), 45.85 (-N C H ₂ CH ₂ NMe ₃ ), 33.63 (ArC( C H ₃ ) ₃ ), 31.43 (Ar C (CH ₃ ) ₃ ). HRMS m / z calcd. for [C ₂₇ H ₄₃ N ₂ O ₄ Br-Br] 459.3217. Found 459.3217.

Manufacturing example 1-10. Preparation of compound 7

N,N,N-trimethyl-N',N'-bis(2,3-dihydroxy-5-tertiary-butylbenzyl)ethylenediamine chloride (hereinafter compound 7 ) was prepared as shown in Scheme 11 below. .

[Scheme 11]

Specifically, silver chloride (0.32 g, 2.2 mmol) was added to a solution of THF (25 mL) containing compound 5 (1.17 g, 2.0 mmol) at room temperature, and the mixture was stirred for 3 hours. Then, the reaction mixture was filtered through Celite. All volatiles were removed under vacuum and the residue was washed with diethyl ether. After vacuum drying, compound 7 (0. g, 83%) was obtained as a beige powder.

¹ H NMR ((CD ₃ ) ₂ SO): δ 9.15 (s, 2H, -OH), 8.55 (s, 2H, -OH), 6.76 (s, 2H, Ar- H ), 6.68 (s, 2H, Ar- H ), 3.61 (s, 4H, ArC H ₂ N-), 3.54 (m, 2H, -C H ₂ NMe ₃ ), 2.94 (s, 9H, -N Me ₃ ), 2.78 (m, 2H, -NC H ₂ CH ₂ NMe ₃ ), 1.21 (s, 18H, ArC(C H ₃ ) ₃ ). ¹³ C NMR (CD ₃ CN): δ 144.6, 141.8, 141.1, 123.3, 117.3, 111.7 (Ar), 61.21 (- C H ₂ NMe ₃ ), 52.40 (-N Me ₃ ), 52.16 (Ar C H ₂ N -), 45.90 (-N C H ₂ CH ₂ NMe ₃ ), 33.63 (ArC( C H ₃ ) ₃ ), 31.43 (Ar C (CH ₃ ) ₃ ). HRMS m / z calcd. for [C ₂₇ H ₄₃ N ₂ O ₄ Cl-Cl] 459.3217. Found 459.3217.

Experimental example 1: Confirmation of the effect of catalytic effect on structural change

The effect of the structure of the compound on the activity of the catalyst was investigated. The prepared compounds have substituents independent of each other in the phenyl ring, which can affect the degree of hydrogen bonding and catalytic activity due to different electron and steric effects of the substituent. In order to compare the activity of the catalyst, the reaction yield was confirmed by reacting each compound with 0.20 mmol of each compound at 25° C. with 10 mmol of PO under a pressure of 10 bar of CO ₂ , and the results are shown in Table 1.

At this time, the conversion rate and selectivity were calculated using the following equation.

Conversion of the reactants (conversion, C) (%) = [(number of moles of reactants converted)/(number of moles of reactants used)] x 100;

Selectivity of product formation (S) (%) = [(number of moles of reactant converted to product)/(number of moles of reactant converted)] x 100;

Product yield (yield, Y) (%) = (S·C)/100;

Turnover number (TON) = [(number of moles of reactant converted)/(number of moles of catalyst used)] x 100;

Turnover frequency (TOF) (h-1) = TON/h.

[Formula 3]

[Scheme 12]

number compound Time (h) yield(%) TON TOF(h ^-1 ) One One 8 29 15 2 2 2 56 28 4 3 3 34 17 2 4 4 70 35 4 5 5 93 47 6 6 6 12 6 0.8 7 7 3 1.5 0.2 8 One 14 51 26 2 9 3 59 30 2 10 2 4 28 14 4 11 6 42 21 4 12 11 77 39 4 13 14 98 49 4 14 4 4 34 17 4 15 6 51 26 4 16 11 96 48 4 17 5 2 24 12 6 18 4 47 24 6 19 6 69 35 6 20 7 81 41 6

As can be seen in Chemical Formula 3, Scheme 10, and Table 1, the compound 5 having two hydroxy groups (OH) and tertiary-butyl groups in each of the two phenyl rings present in the molecule is the shortest time in 8 hours. It was found that it showed the best activity with a yield of 93%. That is, it was shown that the activity increased as the number of hydroxy groups of the phenyl group increased in the structure of the compound of Formula 3.

In addition, there was a difference in catalytic activity between compounds having the same number of hydroxy groups. That is, as the electron effect and steric hindrance effect of the substituent introduced at the 5th carbon position of the phenyl group increase, the activity increases. In particular, for compounds 2 , 4 , and 5 , which are compounds in which two hydroxy groups are present in one phenyl group, the yield of the obtained product gradually increased with time. Finally, Compound 2 showed a yield of 98% in 14 hours, Compound 4 showed a yield of 96% in 11 hours, and Compound 5 showed a yield of 93% in 8 hours.

In addition, a compound substituted with bromine ion and chloride ion instead of iodine ion, which is the counter anion of ammonium cations, was synthesized to investigate its catalytic activity. However, it showed a very low conversion rate compared to the salt containing iodine anion.

Meanwhile, FIG. 1 is a graph showing a change in reaction yield by reaction time using Compound 5 of the present invention in the absence of a solvent. Referring to FIG. 1, in the method for producing cyclic alkylene carbonate, when compound 5 is used as a catalyst in the absence of a solvent, it can be seen that the yield of the obtained product gradually increases as time increases.

Experimental example 2: Confirmation of yield change according to various functional groups

Compound 5 (0.20 mmol) was used as a catalyst to investigate the range of epoxide substrates. The reaction yield was confirmed under the reaction conditions of CO ₂ 10 bar and 10 mmol of epoxide, and the results are shown in Table 2.

[Scheme 13]

number R ¹ R ² R ³ Temperature(℃) Time (h) yield(%) TON TOF(h ^-1 ) One Me H H 25 8 93 47 6 2 CH ₂ Cl H H 25 4 90 45 11 3 CH ₂ OH H H 25 4 91 46 12 4 CH ₂ OMe H H 25 8 95 48 6 5 CH ₂ O ^t Bu H H 25 8 94 47 6 6 CH ₂ OPh H H 25 8 93 47 6 7 H Me Me 120 9 99 50 6 8 Me Me H 120 11 90 45 4 9 CH ₂ CH ₂ CH ₂ CH ₂ 120 12 93 47 4 10 CH ₂ CH ₂ CH ₂ 120 12 99 50 4

As can be seen in Scheme 11 and Table 2, it was found that the catalytic activity greatly differs depending on whether the epoxide is terminal or internal. In the case of the terminal epoxide (No. 1-6), the type of epoxide did not inhibit the catalytic activity. In particular, when epichlorohydrin (No. 2) and glycidol (No. 3) were applied, all were converted within a shorter reaction time (4 hours) than other epoxides. In the case of other types of terminal epoxides, all desired products could be obtained within 8 hours. In the case of the internal epoxide (No. 7-10) having low reactivity, the reaction was carried out by raising the reaction temperature to 120°C. In this case, all internal epoxides could be converted to the desired cyclic alkylene carbonate within 9 to 12 hours.

Experimental example 3: Check the reusability of the catalyst

In order to confirm the reusability of 10 mol% of compound 5 relative to PO, the cyclic addition reaction was performed for 3 hours at room temperature and 10 bar CO ₂ pressure conditions as shown in Scheme 13 below. Compound 5 was easily recovered by simple filtration (ammonium salt compound is insoluble in diethyl ether) and reused in the next cycle.

[Scheme 14]

Number of reactions Yield (%) One 99 2 98 3 99 4 97 5 98

As can be seen in Scheme 12 and Table 3, it was found that the catalyst 5 (Compound 5) can be reused up to 5 times without losing catalytic activity. After the reaction was completed, as confirmed based on the results of ¹ H NMR analysis, the selectivity of the reaction product was maintained at 99%.

So far, the present invention has been looked at around its preferred embodiments. Those of ordinary skill in the art to which the present invention pertains will be able to understand that the present invention can be implemented in a modified form without departing from the essential characteristics of the present invention. Therefore, the disclosed embodiments should be considered from an illustrative point of view rather than a limiting point of view. The scope of the present invention is shown in the claims rather than the foregoing description, and all differences within the scope equivalent thereto should be construed as being included in the present invention.

Claims (8)

An organic catalyst represented by the following formula (1) and used to prepare cyclic alkylene carbonate by reacting epoxide and carbon dioxide:
[Formula 1]

In Formula 1, R ¹ is a C ₁ to C ₁₀ alkyl group,
R ² is hydrogen.
The method of claim 1,
The organic catalyst is an organic catalyst, characterized in that any one of the following formula.

delete Including the step of reacting epoxide and carbon dioxide under an organic catalyst,
The organic catalyst is a method for producing a cyclic alkylene carbonate, characterized in that the organic catalyst of claim 1 or 2.
The method of claim 4,
The epoxide is any one selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide, hexylene oxide, and styrene oxide. , Method for producing cyclic alkylene carbonate.
The method of claim 4,
The organic catalyst is a method for producing a cyclic alkylene carbonate, characterized in that used in an amount of 0.01 to 10 mol% based on the epoxide.
The method of claim 4,
In the step of reacting, the reaction temperature is 25 to 150 °C, the reaction pressure is 1 to 20 bar, characterized in that for producing a cyclic alkylene carbonate.
The method of claim 4,
The reaction in the reacting step is a method for producing a cyclic alkylene carbonate, characterized in that neat.

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