Isosorbide-based diepoxide compound and method for preparing same

Abstract

The present application relates to: a novel isosorbide-based diepoxide compound, a salt thereof, a solvate thereof, and a solvate of the salt thereof; a composition comprising same; use thereof; and a method for preparing same. The novel isosorbide-based diepoxide compound of the present application can be used as a monomer for manufacturing bioplastics, and thus is highly applicable as an eco-friendly material. In addition, the preparation method of the present application enables the synthesis of isosorbide-based diepoxide compounds with high efficiency, and thus can be provided as a useful method for providing isosorbide monomers for manufacturing bioplastics.

Description

Isosorbide-based diepoxide compound and method for producing the same

[0001] The present application relates to a novel isosorbide-based diepoxide compound and a salt thereof, a solvate thereof and a solvate of a salt thereof; a composition comprising the same; a use thereof; and a method for preparing the same.

[0002]

[0003] The production of conventional plastics has raised many concerns due to its heavy reliance on petroleum-based feedstocks. For example, the widespread use of petroleum-derived plastics has resulted in significant environmental pollution, with plastic waste persisting in landfills and oceans for extended periods. Consequently, there is a pressing need for extensive research and development of bio-based materials, with a particular focus on environmentally friendly plastics derived from biomass. Therefore, the search for environmentally friendly alternatives to conventional plastics has become increasingly important, leading to active research into the synthesis of bio-based monomers.

[0004] Meanwhile, numerous studies have been conducted on the production of bioplastics based on biomass-derived materials. Among these, isosorbide (ISB), a biomass-derived material with two hydroxyl groups, offers numerous applications and advantages as a sustainable material. In particular, ISB-based compounds functionalized with epoxy groups have been widely utilized in the production of biopolymers. Biopolymer synthesis using ISB-derived monomers containing epoxy groups offers numerous environmental and performance benefits, making them applicable to a wide range of industries seeking more sustainable and high-performance materials. Furthermore, ISB-based units containing epoxides can serve as precursors for building blocks functionalized with cyclic carbonates to form non-isocyanate polyurethanes. Therefore, developing a simple and efficient synthetic method for biomass-derived building blocks containing epoxy groups is essential.

[0005] Applying the epoxidation process to biomass-derived materials is an efficient approach to enhance the value and usability of natural resources in the synthesis of biopolymers. The most widely known method for epoxidation is the method using m-chloroperbenzoic acid (m-CPBA) as an oxidizing agent (e.g., Korean Patent Publication No. KR 10-2001-0098398 A), and its use in ISB has also been reported. However, synthetic methods using m-CPBA require toxic solvents (e.g., CH2C). l2 ), which involves long reaction times, high reaction temperatures, and complex purification processes. Therefore, the development of an efficient method for epoxidation of ISB-based materials is still required.

[0006]

[0007] The present inventors have conducted research efforts to develop a novel compound that can be used as a monomer for bioplastic synthesis and an efficient method for producing the same, and as a result, have identified a simple and efficient method for obtaining an isosorbide-based diepoxide that can be a useful monomer for bioplastic production using DMDO and a novel compound produced therefrom, and completed the present application.

[0008] One object of the present application is to provide an isosorbide-based diepoxide compound represented by the following chemical formula 1, a salt thereof, a solvate thereof, and a solvate of a salt thereof.

[0009] [Chemical Formula 1]

[0010] ,

[0011] In the above chemical formula 1, X is a bond, C 1-6 Alkyl, C 1-6 Alkylene, C 1-6 Heteroalkylene, C 2-6 Alkenylene, C 2-6 Alkynylene or halogen; R1 and R2 are each independently hydrogen, C 1-6 Alkyl, C 1-6 Heteroalkyl, C 1-6 Alkoxy, or halogen.

[0012] Another object of the present application is to provide a method for producing an isosorbide-based diepoxide compound represented by the following chemical formula 1, comprising: a mixing step of producing a mixture of an isosorbide-based allyl derivative represented by the following chemical formula 2, acetone, and a buffer; and an epoxidation step of adding oxone (KHSO5) dropwise to the mixture to react the isosorbide-based allyl derivative with DMDO molecules generated in situ from acetone and oxone to epoxidize the compound.

[0013] [Chemical Formula 1]

[0014] ,

[0015] [Chemical Formula 2]

[0016]

[0017] In the above chemical formulas 1 and 2, X is a bond, C 1-6 Alkyl, C 1-6 Alkylene, C 1-6 Heteroalkylene, C 2-6 Alkenylene, C 2-6 Alkynylene or halogen, and R1 and R2 are each independently hydrogen, C 1-6 Alkyl, C 1-6 Heteroalkyl, C 1-6 Alkoxy, or halogen.

[0018]

[0019] The novel isosorbide-based diepoxide compound disclosed in the present application can be effectively utilized as a monomer for the production of bioplastics, demonstrating its high utility. Furthermore, the manufacturing method disclosed in the present application enables the synthesis of isosorbide-based diepoxide compounds in a simple, environmentally friendly manner, while being highly efficient and short-lived. This provides an efficient method for providing isosorbide monomers for the production of bioplastics.

[0020]

[0021] FIG. 1 is a schematic diagram disclosing a method for producing an isosorbide-based diepoxide compound of the present invention according to one embodiment.

[0022] Figure 2 is a diagram for isosorbide-dipentenyl ether (IPE) synthesized according to an embodiment of the present invention. 1 This diagram shows the H NMR spectrum.

[0023] Figure 3 is a graph showing isosorbide-dipentenyl ether (IPE) synthesized according to an embodiment of the present invention. 13 This diagram shows the C NMR spectrum.

[0024] Figure 4 is a diagram for isosorbide-diallyl ether (IDE) synthesized according to an embodiment of the present invention. 1 This diagram shows the H NMR spectrum.

[0025] Figure 5 is a graph showing the isosorbide-diallyl ether (IDE) synthesized according to an embodiment of the present invention. 13 This diagram shows the C NMR spectrum.

[0026] Figure 6 is a graph showing the isosorbide-dimethyl propenyl ether (IME) synthesized according to an embodiment of the present invention. 1 This diagram shows the H NMR spectrum.

[0027] Figure 7 is a graph showing the isosorbide-dimethyl propenyl ether (IME) synthesized according to an embodiment of the present invention. 13 This diagram shows the C NMR spectrum.

[0028] Figure 8 is a graph showing the isosorbide-dipentyl oxide (IPO) synthesized according to an embodiment of the present invention. 1 This diagram shows the H NMR spectrum.

[0029] Figure 9 is a graph showing the isosorbide-dipentyl oxide (IPO) synthesized according to an embodiment of the present invention. 13 This diagram shows the C NMR spectrum.

[0030] Figure 10 is a schematic diagram showing the design of conditions for changing the epoxidation reaction during the synthesis of isosorbide-dipentyl oxide (IPO) in Example 2 of the present invention.

[0031] FIG. 11 is a diagram showing the conversion rate and yield of isosorbide-dipentyl oxide (IPO) production according to the oxone concentration in an epoxidation reaction according to one embodiment of the present invention.

[0032] FIG. 12 is a diagram showing the conversion rate and yield of isosorbide-dipentyl oxide (IPO) production according to the oxone injection rate in an epoxidation reaction according to one embodiment of the present invention.

[0033] FIG. 13 is a diagram showing the conversion rate and yield of isosorbide-dipentyl oxide (IPO) production according to the reaction temperature in an epoxidation reaction according to one embodiment of the present invention.

[0034] Figure 14 shows the time evolution of conversion and yield for the in situ generated DMDO epoxidation reaction as determined by GC-FID (a) and 1H NMR spectroscopy (b), respectively (●: double bond, *: epoxide).

[0035] FIG. 15 is a diagram showing the temporal changes of a GC-FID chromatogram during isosorbide-dipentenyl ether (IPE) epoxidation under optimized conditions according to Example 2 of the present invention.

[0036] FIG. 16 is a schematic diagram showing a synthesis test of various epoxy compounds based on ISB using in-situ-generated DMDO according to Example 3 of the present invention.

[0037] Figure 17 is a graph of isosorbide-diallyl oxide (IDO) synthesized according to an embodiment of the present invention. 1 This diagram shows the H NMR spectrum.

[0038] Figure 18 is a graph showing isosorbide-diallyl oxide (IDO) synthesized according to an embodiment of the present invention. 13 This diagram shows the C NMR spectrum.

[0039] Figure 19 is a graph of isosorbide-dimethyl propyl oxide (IMO) synthesized according to an embodiment of the present invention. 1 This diagram shows the H NMR spectrum.

[0040] Figure 20 is for isosorbide-dimethyl propyl oxide (IMO) synthesized according to an embodiment of the present invention. 13 This diagram shows the C NMR spectrum.

[0041] FIG. 21 is a diagram showing (a) comparative results of epoxidation of three different precursors using in-situ-generated DMDO according to an embodiment of the present invention and (b) a schematic diagram of steric hindrance effects using energy-minimized structures of isosorbide-diallyl ether (IDE) and isosorbide-dipentenyl ether (IPE) represented by a space-filling model.

[0042]

[0043] This is explained in detail as follows. Meanwhile, each description and embodiment disclosed in this application can also be applied to each other description and embodiment. That is, all combinations of the various elements disclosed in this application fall within the scope of this application. Furthermore, the scope of this application is not limited by the specific descriptions described below. Furthermore, numerous papers and patent documents are referenced and cited throughout this specification. The disclosures of the cited papers and patent documents are incorporated into this specification in their entirety by reference to more clearly explain the level of the technical field to which this application belongs and the contents of this application.

[0044]

[0045] As a first aspect of the present application, an isosorbide-based diepoxide compound represented by the following chemical formula 1 and a salt thereof, a solvate thereof, and a solvate of a salt thereof are provided:

[0046] [Chemical Formula 1]

[0047] ,

[0048] In the above chemical formula 1, X is a bond, C 1-6 Alkyl, C 1-6 Alkylene, C 1-6 Heteroalkylene, C 2-6 Alkenylene, C 2-6 Alkynylene or halogen, and R1 and R2 are each independently hydrogen, C 1-6 Alkyl, C 1-6 Heteroalkyl, C 1-6 Alkoxy, or halogen.

[0049]

[0050] The term "isosorbide" in this specification refers to a 100% natural biomaterial derived from corn. It is a natural bioplastic material made by extracting starch from corn and then processing it with glucose, sorbitol, etc. Isosorbide is a compound containing two fused furan rings, with the molecular formula C6H 10 It has O4 and is represented by the following chemical formula 3.

[0051] [Chemical Formula 3]

[0052]

[0053] In this application, the term "epoxide" refers to a type of cyclic ether, a compound containing a trigonal ring composed of two carbon atoms and one oxygen atom. Epoxide compounds are typically produced by a process in which the oxygen of an oxidizing agent reacts with a double bond in a reactant, oxidizing the reactant and producing an epoxy.

[0054]

[0055] The term "alkyl" in this application means a straight-chain, branched-chain, or cyclic hydrocarbon radical, each carbon atom of which may be optionally substituted with one or more substituents. Examples of alkyl include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, neopentyl, and hexyl.

[0056] The term "heteroalkyl" in this application means a stable straight or branched chain or a combination thereof comprising at least one carbon atom and at least one heteroatom (e.g., O, N, P, Si and S).

[0057] The term "alkylene" in this application refers to a divalent aliphatic hydrocarbyl group that is straight-chain or branched. Examples of such alkylene include, but are not limited to, methylene (-CH2-), ethylene (-CH2CH2-), n-propylene (-CH2CH2CH2-), iso-propylene (-CH2CH(CH3)-), and the like.

[0058] In this application, the term "heteroalkylene" means a divalent radical derived from heteroalkyl. The heteroalkylene is, for example, -CH2-CH2-S-CH2-CH2- and -CH2-S-CH2-CH2-NH-CH2-

[0059] The term "alkenyl" as used herein refers to a monovalent group derived from a hydrocarbon moiety containing at least two carbon atoms and at least one carbon-carbon double bond. The double bond may or may not be a point of attachment to another group. Examples of such alkenyl groups include, but are not limited to, ethenyl, propenyl, prop-1-en-2-yl, butenyl, 1-methyl-2-buten-1-yl, heptenyl, octenyl, and the like.

[0060] The term "alkynylene" in this application refers to a group having at least two carbon atoms and containing at least one carbon-carbon triple bond.

[0061] The term "alkoxy" in this application means -O-alkyl, wherein alkyl is as defined above. Examples of alkoxy include, but are not limited to, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, t-butoxy, and the like.

[0062] In this application, the term “halo(gen)” means a substituent of fluoro, chloro, bromo or iodo.

[0063]

[0064] Specifically, in the above chemical formula 1, X is C 1-6It can be alkyl, for example, -C- or -CCC.

[0065] For example, in the above chemical formula 1, R1 and R2 can each independently be H or C.

[0066]

[0067] More specifically, the isosorbide-based diepoxide compound may be a compound selected from compounds represented by the following chemical formulae 1-1 to 1-3, but is not limited thereto:

[0068] [Chemical Formula 1-1]

[0069] ,

[0070] [Chemical Formula 1-2]

[0071] ,

[0072] [Chemical Formula 1-3]

[0073] .

[0074] The compound represented by the above chemical formula 1-1 is named isosorbide-dipentyl oxide, and may also be used interchangeably as the abbreviation IPO in this application.

[0075] The compound represented by the above chemical formula 1-2 is named isosorbide-dipropyl oxide, and may also be used interchangeably as the abbreviation IDO in this application.

[0076] The compound represented by the above chemical formula 1-3 is named isosorbide-dimethyl propyl oxide, and may also be used interchangeably with the abbreviation IMO in this application.

[0077]

[0078] The compound of the present invention may exist in the form of a pharmaceutically acceptable salt. Useful salts include acid salts formed with pharmaceutically acceptable free acids. The term "pharmaceutically acceptable salt" as used herein refers to a salt that is relatively nontoxic and harmless at a concentration that provides an effective effect on a patient, and any organic or inorganic addition salt of the compound represented by Chemical Formula 1, wherein the side effects caused by the salt do not diminish the beneficial effects of the compound.

[0079] Acid addition salts are prepared by conventional methods, for example, by dissolving the compound in an excess of an aqueous acid solution and precipitating the salt using a water-miscible organic solvent such as methanol, ethanol, acetone or acetonitrile. Equimolar amounts of the compound and an acid or alcohol (e.g., glycol monomethyl ether) in water can be heated, and the mixture can then be evaporated to dryness, or the precipitated salt can be filtered off with suction.

[0080] At this time, organic acids and inorganic acids can be used as free acids, and inorganic acids such as hydrochloric acid, phosphoric acid, sulfuric acid, nitric acid, and tartaric acid can be used, and organic acids such as methanesulfonic acid, p-toluenesulfonic acid, acetic acid, trifluoroacetic acid, maleic acid, succinic acid, oxalic acid, benzoic acid, tartaric acid, fumaric acid, mandelic acid, propionic acid, citric acid, lactic acid, glycolic acid, gluconic acid, galacturonic acid, glutamic acid, glutaric acid, glucuronic acid, aspartic acid, ascorbic acid, carbonic acid, vanillic acid, and hydroiodic acid can be used, but are not limited thereto.

[0081] Additionally, pharmaceutically acceptable metal salts can be prepared using bases. Alkali metal salts or alkaline earth metal salts are obtained, for example, by dissolving a compound in an excess alkali metal hydroxide or alkaline earth metal hydroxide solution, filtering out the undissolved compound salt, and evaporating and drying the filtrate. In this case, sodium, potassium, or calcium salts are particularly suitable for pharmaceutical purposes, but are not limited thereto. Furthermore, the corresponding silver salt can be prepared by reacting an alkali metal or alkaline earth metal salt with a suitable silver salt (e.g., silver nitrate).

[0082] Pharmaceutically acceptable salts of the compounds of the present invention include salts of acidic or basic groups that may be present in the compounds of Formula 1, unless otherwise indicated. For example, pharmaceutically acceptable salts may include sodium, calcium, and potassium salts of hydroxyl groups, and other pharmaceutically acceptable salts of amino groups include hydrobromide, sulfate, hydrogen sulfate, phosphate, hydrogen phosphate, dihydrogen phosphate, acetate, succinate, citrate, tartrate, lactate, mandelate, methanesulfonate (mesylate), and p-toluenesulfonate (tosylate) salts, and may be prepared by methods known in the art for preparing salts.

[0083] As the salt of the isosorbide-based diepoxide compound of the present invention, any salt of the isosorbide-based diepoxide compound that is pharmaceutically acceptable and exhibits pharmacological activity equivalent to that of the isosorbide-based diepoxide compound may be used without limitation.

[0084] In addition, the compound represented by the above chemical formula 1 according to the present invention includes, without limitation, not only its pharmaceutically acceptable salts but also solvates such as possible hydrates that can be prepared therefrom and all possible stereoisomers. The solvates and stereoisomers of the compound represented by the above chemical formula 1 can be prepared from the compound represented by the chemical formula 1 using methods known in the art.

[0085] Furthermore, the compound represented by the above chemical formula 1 according to the present invention can be prepared in a crystalline or amorphous form, and when prepared in a crystalline form, can be optionally hydrated or solvated. The present invention may include not only stoichiometric hydrates of the compound represented by the above chemical formula 1, but also compounds containing various amounts of water. The solvates of the compound represented by the above chemical formula 1 according to the present invention include both stoichiometric solvates and non-stoichiometric solvates.

[0086]

[0087] As a second aspect of the present application, a monomer composition for plastic synthesis is provided, comprising a compound represented by the above chemical formula 1, a salt thereof, a solvate thereof, and a solvate of a salt thereof.

[0088] The compound represented by the above chemical formula 1 is defined in the same manner as described above.

[0089] Specifically, the plastic may be a bioplastic.

[0090] The term "bioplastic" in this application refers to plastics made from renewable raw materials, as opposed to plastics made from monomers derived from fossil fuels. The bioplastic may be polycarbonate, polyester, or polyurethane, and is not limited to, for example, non-isocyanate polyurethane.

[0091] The isosorbide-based compound represented by the chemical formula 1 of the present application can serve as a useful monomer for manufacturing bioplastics, and thus has high utility as an eco-friendly material and application.

[0092] Specifically, the monomer composition for plastic synthesis of the present application may additionally include other additives and solvents, and the types of specific additives or solvents are not particularly limited, and any material used in a general bioplastic synthesis process may be used without limitation.

[0093]

[0094] As a third aspect of the present application, a use of a composition comprising a compound represented by the above chemical formula 1 and a salt thereof, a solvate thereof and a solvate of a salt thereof for bioplastic synthesis is provided.

[0095] The above “compound represented by chemical formula 1” and “bioplastic” are defined as described above.

[0096]

[0097] As a fourth aspect of the present application, a method for producing an isosorbide-based diepoxide compound represented by the following chemical formula 1 is provided, comprising a mixing step of producing a mixture of an isosorbide-based allyl derivative represented by the following chemical formula 2, acetone, and a buffer solution, and an epoxidation step of adding oxone (KHSO5) dropwise to the mixture to epoxidize the isosorbide-based allyl derivative by reacting it with DMDO molecules generated in situ from acetone and oxone.

[0098] [Chemical Formula 1]

[0099] ,

[0100] [Chemical Formula 2]

[0101] .

[0102] At this time, in the above chemical formulas 1 and 2, X is a bond, C 1-6 Alkyl, C1-6 Alkylene, C 1-6 Heteroalkylene, C 2-6 Alkenylene, C 2-6 alkynylene or halogen,

[0103] R1 and R2 are each independently hydrogen, C 1-6 Alkyl, C 1-6 Heteroalkyl, C 1-6 Alkoxy, or halogen.

[0104] At this time, the above “isosorbide-based diepoxide compound represented by chemical formula 1” is defined in the same manner as described above.

[0105]

[0106] The present applicants have demonstrated the efficient and simple synthesis of isosorbide-based diepoxide compounds from isosorbide-based allyl derivatives via epoxidation using DMDO as an oxidizing agent, thereby securing a convenient method for producing biomass-derived ISB building blocks in high yield. A schematic diagram of a method for synthesizing an isosorbide-based diepoxide compound according to one embodiment of the present application is shown in FIG. 1.

[0107]

[0108] In the manufacturing method of the present application, the mixing step is a step of mixing an isosorbide-based allyl derivative represented by chemical formula 2, acetone, and a buffer solution.

[0109]

[0110] The compound represented by the above chemical formula 2 is used as a precursor for producing an isosorbide-based diepoxide compound represented by the chemical formula 1 in the method of the present application. The compound represented by the above chemical formula 2 may be manufactured according to a method known in the art, or may be purchased and used as a commercially available compound.

[0111] Specifically, in the above chemical formula 2, X is C 1-6 It can be alkyl, for example, -C- or -CCC.

[0112] For example, in the above chemical formula 2, R1 and R2 can each independently be H or C.

[0113] Specifically, the isosorbide-based allyl derivative represented by the above chemical formula 2 may be one compound selected from compounds represented by the following chemical formulas 2-1 to 2-3, but is not limited thereto:

[0114] [Chemical Formula 2-1]

[0115] ,

[0116] [Chemical Formula 2-2]

[0117] ,

[0118] [Chemical Formula 2-3]

[0119] .

[0120] The above acetone is a ketone with the molecular formula CH3COCH3, also known as dimethyl ketone. Acetone is a colorless, transparent, volatile liquid. In the manufacturing method of the present application, the acetone is used as a liquid and solvent to produce dimethyl dioxirane (DMDO), an oxidizing reagent for the precursor compound, together with oxone.

[0121]

[0122] The above buffer is a substance for maintaining the pH of the reactant, and may be, for example, sodium bicarbonate.

[0123] The above sodium bicarbonate is also called sodium hydrogen carbonate. The above sodium bicarbonate is a white, hygroscopic crystal with basic properties, and has a molecular formula of NaHCO3.

[0124] Specifically, the concentration of the sodium bicarbonate may be, for example, 0.01 to 0.1 M, but is not limited thereto.

[0125] Specifically, the pH of the reaction solution can be maintained in the range of 8 to 10, but is not limited thereto.

[0126] In one embodiment, the mixture may additionally comprise one or more selected from the group consisting of a chelating agent, a solvent, and deionized water.

[0127] As above, in the mixing step, a mixture is prepared by mixing an isosorbide-based allyl derivative represented by the following chemical formula 2, acetone, and a buffer solution.

[0128]

[0129] Next, in the manufacturing method of the present application, the epoxidation step refers to a step of adding oxone dropwise to the mixture manufactured in the mixing step to in situ generate dimethyl dioxirane (DMDO), and epoxidizing an isosorbide-based allyl derivative using the DMDO as an oxidizing agent.

[0130] In this application, the term "oxone" is also referred to as potassium peroxymonosulfate. The oxone has a molecular formula of KHSO5 and is a compound represented by the following chemical formula 4.

[0131] [Chemical Formula 4]

[0132]

[0133] In the manufacturing method of the present application, the oxone is used as a material for generating dimethyl dioxirane (DMDO), which is an oxidizing reagent of a precursor compound, together with acetone in the mixture prepared in the above-described mixing step.

[0134] Specifically, the oxone may be added dropwise to the isosorbide-based allyl derivative represented by Chemical Formula 2 so that the equivalent ratio of the isosorbide-based allyl derivative represented by Chemical Formula 2: oxone is 1:3 to 1:8, more specifically, it may be added dropwise so that the equivalent ratio is 1:3 to 1:7, 1:4 to 1:7, 1:3 to 1:6, 1:4 to 1:6, or 1:5 to 1:7, and as an example, it may be added dropwise so that the equivalent ratio is 1:6. When the equivalent ratio of the isosorbide-based allyl derivative represented by Chemical Formula 2: oxone falls within the above range, the appropriate pH range for the epoxidation reaction of the present application can be maintained while reducing the formation of undesired byproducts in the epoxidation reaction, thereby significantly increasing the overall yield.

[0135] Specifically, the oxone may be added dropwise at a flow rate of 10 to 25 mL / min. More specifically, the oxone may be added dropwise at a flow rate of 10 to 23 mL / min, a flow rate of 13 to 23 mL / min, a flow rate of 12 to 20 mL / min, a flow rate of 13 to 20 mL / min, a flow rate of 10 to 18 mL / min, a flow rate of 10 to 17 mL / min, or a flow rate of 13 to 17 mL / min, and as an example, the oxone may be added dropwise at a flow rate of 15 mL / min. When the flow rate of the oxone supplied to the reaction medium falls within the above range, the epoxidation process may be more efficient, and thus the yield may be significantly increased. When the flow rate is slower than the above range, the yield may decrease, and when the flow rate is excessively faster than the above range, decomposition of DMDO formed in situ may be induced, thereby decreasing the yield.

[0136]

[0137] Oxone added dropwise to the mixture prepared in the above mixing step reacts with acetone in the mixture to produce dimethyl dioxirane (DMDO) in situ.

[0138] The term "epoxidation" in this application refers to a reaction that synthesizes an epoxy ring, for example, oxidizing an unsaturated compound with a peracid. For the purposes of this application, the epoxidation may refer to a reaction that oxidizes an isosorbide-based allyl derivative represented by Chemical Formula 2 to produce an isosorbide-based diepoxide compound represented by Chemical Formula 1. Specifically, in this application, the epoxidation may be a reaction in which dimethyl dioxirane generated in situ acts as an oxidizing agent.

[0139] In this application, the term "dimethyldioxirane (DMDO)" has a molecular formula of (CH3)2CO2. Dimethyldioxirane has the property that it is difficult to provide commercially due to its instability, and the properties of the pure substance itself are still not well known. In the manufacturing method of the present application, dimethyldioxirane is produced in situ by dropwise addition of oxone and reacts with an isosorbide-based allyl derivative represented by Chemical Formula 2 in the mixture as an oxidizing agent for producing an epoxide. The dimethyldioxirane is represented by Chemical Formula 5 below.

[0140] [Chemical Formula 5]

[0141]

[0142] The manufacturing method of the present application enables environmentally friendly epoxidation of an isosorbide-based compound without using a toxic solvent such as meta-chloroperoxybenzoic acid (m-CPBA) by using the DMDO as an oxidizing agent.

[0143] Specifically, the epoxidation reaction may be performed at a temperature of -10 to 10°C. More specifically, the epoxidation reaction may be performed at a temperature of -10 to 8°C, -8 to 10°C, -8 to 8°C, -7 to 7°C, -5 to 7°C, -7 to 5°C, -5 to 5°C, -3 to 3°C, and, for example, at 0°C. If the temperature at which the epoxidation reaction is performed is lower than the above range, the reaction rate may decrease, thereby reducing the yield of the product, and if it is higher than the above range, the yield of the product may decrease due to the instability of the DMDO molecule. Thus, the manufacturing method of the present application has one technical advantage in that it is possible to efficiently manufacture an isosorbide-based diepoxide compound without the need for high temperatures.

[0144] Specifically, the epoxidation reaction may be performed by ultrasonic stirring under ultrasonic treatment. In one embodiment of the present application, it was confirmed that when epoxidation using DMDO is performed under ultrasonic treatment, a product can be synthesized with a significantly improved conversion rate and yield compared to a general stirring method.

[0145] Specifically, the ultrasonic treatment may be performed at an output of 500 to 1000 W, and for example, may be performed at an output of 750 W, but is not limited thereto. Specifically, the ultrasonic treatment may be performed at a frequency range of 10 to 30 kHz, and for example, may be performed at a frequency range of about 20 kHz, but is not limited thereto.

[0146] Specifically, the epoxidation reaction may be performed for 0.1 to 2 hours, and more specifically, the epoxidation reaction may be performed for 1 minute or more and less than 45 minutes, and for example, may be performed for 1 minute or more and 35 minutes or less. In one embodiment of the present application, it was confirmed that a high conversion rate and yield for the target compound, an isosorbide-based diepoxide compound, were achieved in just 35 minutes.

[0147] In one embodiment, the manufacturing method of the present application may be characterized in that it can achieve a yield of 90% or more of an isosorbide-based diepoxide compound represented by Chemical Formula 1 within a reaction time of 35 minutes or less. As such, the manufacturing method of the present application has a technical advantage in that it enables the synthesis of an isosorbide-based diepoxide compound with high efficiency with only a relatively short reaction time, without the need for a long reaction time.

[0148]

[0149] Specifically, the epoxidation reaction of the present application may be characterized by not using a separate catalyst or oxidizing agent. For example, the epoxidation reaction of the present application may be characterized by not using m-CPBA as an oxidizing agent. The epoxidation reaction of the present application does not cause toxicity or environmental problems due to the use of a catalyst, thereby enabling the synthesis of an environmentally friendly epoxide compound. In addition, in the case of a conventional method using a separate catalyst or oxidizing agent, an additional process of separating the product from the catalyst and / or oxidizing agent after the reaction must be performed. However, in the method of the present application, since the by-product after the reaction is in a salt state without using a separate catalyst or oxidizing agent, separation and purification of the product and the by-product are easy.

[0150] By the process described above, an isosorbide-based diepoxide compound represented by the chemical formula 1 is produced in the epoxidation step.

[0151]

[0152] Specifically, the manufacturing method of the present application may additionally include a step of isolating and / or purifying the produced compound.

[0153] In one embodiment, the separating and / or purifying step may include filtering the reaction product in which the epoxidation reaction is completed to remove solids.

[0154] In one embodiment, the separating and / or purifying step may include separating the product within the solution through liquid-liquid extraction. The manufacturing method of the present application may provide a technical advantage in that the product can be efficiently obtained even through a simple purification process such as simple liquid-liquid extraction. For example, the liquid-liquid extraction may utilize benzene compounds such as ethyl acetate, methylene chloride (MC), ether, benzene, or toluene, but is not limited thereto.

[0155] In one embodiment, the step of separating and / or purifying may further comprise drying and evaporating the organic layer in the product separated by liquid-liquid extraction.

[0156] In addition, the above separation and / or purification step can be performed without limitation using any separation / purification method known in the art.

[0157]

[0158] Hereinafter, the present application will be described in more detail through examples. These examples are intended to more specifically explain the present application, and the scope of the present application is not limited by these examples.

[0159]

[0160] Experimental Example 1. Materials and Analysis Methods

[0161] The materials and analysis methods used in all experimental examples and examples below were performed as follows.

[0162] Potassium hydroxide, allyl bromide, tetrabutylammonium bromide (TBABr), anhydrous magnesium sulfate, potassium peroxymonosulfate (Oxone), and sodium bicarbonate were purchased from Sigma-Aldrich. Acetone, dichloromethane, and ethyl acetate were purchased from Samchun Chemical. 5-Bromo-1-pentene and 1-bromo-3-methyl-2-butene (3,3-dimethylallyl bromide) were purchased from TCI. All chemicals were used as supplied without further purification. Isosorbide (ISB) was purchased from Samyang Corporation. 1 H-NMR and 13 C-NMR was recorded using a Bruker 600 MHz spectrometer in deuterated chloroform (CDC l3 ) was recorded. The reaction mixture was analyzed using an Agilent 7890B gas chromatograph equipped with a flame ionization detector (FID) and an HP-5MS UI capillary column (30 m x 0.25 mm x 0.25 μm). High-resolution electrospray ionization mass spectrometry (ESI-MS) was performed using an Exactive mass spectrometer.

[0163]

[0164] Experimental Example 2. Synthesis of Reactants

[0165] To prepare reactants for epoxidation of isosorbide (ISB)-based compounds, ISB-dipentenyl ether (IPE), ISB-diallyl ether (IDE), and ISB-dimethylpropenyl ether (IME) were synthesized.

[0166] First, isosorbide (ISB) was alkylated using 5-bromo-1-pentene, 3-bromo-1-propene, and 1-bromo-3-methyl-2-butene (3,3-dimethylallyl bromide) as an alkylating agent to synthesize ISB-dipentenyl ether (IPE), ISB-diallyl ether (IDE), and ISB-dimethylpropenyl ether (IME), respectively. After completion of each reaction, liquid-liquid extraction was performed with dichloromethane and distilled water. The organic phase was dried over anhydrous magnesium sulfate, and the solvent was evaporated. The synthetic process of each reactant is described in detail below.

[0167]

[0168] Experimental Example 2-1. Synthesis of ISB-dipentenyl ether (IPE)

[0169] ISB-dipentenyl ether (IPE) was synthesized by referring to a previously published methodology (J. ￡ukaszczyk, B. Janicki, A. Frick, J Mater Sci: Mater Med 2012, 23, 1149). Isosorbide (ISB) (8.11 g, 55.5 mmol) and tetra-n-butylammonium bromide (TBABr) (4.29 g, 13.32 mmol) were placed in a 250 mL three-necked round-bottom flask equipped with an overhead stirrer and a reflux condenser. To the mixture, 50% aqueous KOH solution (18.7 mL) and 5-bromo-1-phenene (39.4 mL, 333 mmol) were sequentially added dropwise with stirring. After reaction at 115°C for 24 hours and completion of the work-up process, a crude mixture was obtained and purified by column chromatography (n-hexane / ethyl acetate (v / v 4:1), silica gel) to obtain IPE as a light yellow oil (yield 66.6%). The obtained compound was analyzed by ESI-MS spectrum, and 1 H-NMR and 13 The C-NMR spectrum was measured and identified, and the results are shown in Figs. 2 and 3, respectively.

[0170] 1H NMR (CDCl3, 600 MHz): δ (ppm) 5.83-5.75 (m, 2H), 5.03-4.94 (m, 4H), 4.61-4.60 (t, 1H), 4.49-4.47 (d, 1H), 3.98 -3.90 (m, 5H), 3.69-3.66(m, 1H), 3.60-3.55(t, 1H), 3.49-3.43(m, 3H).

[0171] 13 C NMR (CDCl3, 600 MHz): δ (ppm) 138.3, 115.0, 96.5, 84.6, 80.5, 73.6, 70.3, 69.9, 69.1, 30.3, 29.0.

[0172] MS(ESI-MS): Calculated m / z 321.15 for C16H26O4Na [M+K]+, observed m / z value 321.76.

[0173]

[0174] Experimental Example 2-2. Synthesis of ISB-diallyl ether (IDE)

[0175] The synthesis of ISB-diallyl ether (IDE) was performed according to a procedure similar to the preparation of IPE in Experimental Example 2-1. A 50% KOH aqueous solution (80.8 mL, 1.44 mol) was added dropwise to a 1 L three-necked round-bottom flask containing ISB (35.08 g, 0.24 mol), TBABr (4.64 g, 0.014 mol), and allyl bromide (124.6 mL, 1.44 mol) to form a mixture, which was stirred at 65°C for 7 hours using a mechanical stirrer. Upon completion of the reaction, IDE was obtained as a pale yellow oil product (yield: 52.3 g (96.3%)) without a separate purification process after the same workup process. The obtained compound was characterized by ESI-MS spectra, and 1 H-NMR and 13 The C-NMR spectrum was measured and identified, and the results are shown in Figs. 4 and 5, respectively.

[0176] 1H NMR (CDCl3, 600 MHz): δ (ppm) 5.97-5.85 (m, 2H), 5.31-5.26 (m, 2H), 5.21-5.17 (m, 2H), 4.63-4.62 (t, 1H), 4.51 -4.50 (dd, 1H), 4.21-4.18(m, 1H), 4.06-3.91(m, 8H), 3.60-3.58(t, 1H).

[0177] 13 C NMR (CDCl3, 600 MHz): δ (ppm) 134.6, 117.9, 86.5, 83.9, 80.3, 79.6, 73.6, 71.8, 70.6, 69.9.

[0178] MS(ESI-MS): Calculated m / z 249.11 for C12H18O4Na [M+Na]+, observed m / z value 249.60.

[0179]

[0180] Experimental Example 2-3. Synthesis of ISB-dimethylpropenyl ether (IME)

[0181] ISB (4.05 g, 27.75 mmol) and TBABr (1.07 g, 3.33 mmol) were placed in a 100 mL two-necked round-bottomed flask, and then 50% KOH solution (9.4 mL) and 3,3-dimethylallyl bromide (19.3 mL, 166.5 mmol) were added stepwise. The reaction was carried out under reflux conditions at 90°C for 24 h. Through the same workup process, a crude mixture was obtained, which was purified by column chromatography (n-hexane / ethyl acetate (v / v 4:1), silica gel) to obtain ISB-dimethylpropenyl ether (IME) as a product as a pale yellow oil (yield: 0.82 g (10.5%)). The obtained compound was characterized by ESI-MS spectrum, and 1 H-NMR and 13 The C-NMR spectrum was measured and identified, and the results are shown in Figures 6 and 7, respectively.

[0182] 1H NMR (CDCl3, 600MHz): δ (ppm) 5.37-5.30 (m, 2H), 4.62-4.61 (t, 1H), 4.52-4.51 (d, 1H), 4.21-4.18 (m, 1H), 4.04 -3.91 (m, 8H), 3.59-3.56(m, 1H), 1.74(s, 6H), 1.68-1.66(d, 6H).

[0183] 13C NMR (CDCl3, 600 MHz): δ (ppm) 137.8, 120.9, 86.6, 83.7, 80.2, 79.3, 73.5, 69.9, 66.9, 66.1, 25.9, 18.1.

[0184] MS(ESI-MS): Calculated m / z 305.17 for C16H26O4Na [M+Na]+, observed m / z value 305.36.

[0185]

[0186] Example 1. Production of isosorbide dipentyl oxide (IPO) using DMDO

[0187] To synthesize isosorbide dipentyl oxide (IPO), an ISB-based diepoxy compound, a mixture of isosorbide-dipentenyl ether (IPE), an isosorbide-based allyl compound, and acetone containing sodium bicarbonate, which acts as a buffer to maintain the pH of the reaction solution, was prepared. To the mixture, a solution of oxone (KHSO5) was added dropwise using a syringe pump to induce the in-situ generation of DMDO molecules as an oxidizing reagent for the allyl moiety, and the reaction was performed using an ultrasound-assisted synthesis method. A schematic diagram of the reaction is shown in Figure 1. After the reaction was completed, the mixture was filtered to remove solids, and the product in the solution was separated through liquid-liquid extraction using ethyl acetate. The organic layer was then dried over MgSO4 and evaporated. The obtained compound was characterized by ESI-MS spectra, and 1 H-NMR and 13 The C-NMR spectrum was measured and identified, and the results are shown in Figs. 8 and 9.

[0188] As a result, it was confirmed that the synthesized compound was isosorbide dipentyl oxide (IPO).

[0189] [NMR and ESI-MS data of IPO]

[0190] 1 H NMR (CDCl3, 600 MHz):δ(ppm) 4.60-4.58 (m, 1H), 4.47-4.46 (m, 1H), 3.98-3.88 (m, 5H), 3.75-3.66 (m, 1H), 3.57-3.46 (m, 4H), 2.94-2.89 (m, 2H), 2.74-2.72 (t, 2H), 2.47-2.44 (m, 2H), 1.90-1.62 (m, 6H), 1.59-1.50(m, 2H).

[0191] 13C NMR (CDCl3, 600 MHz): δ (ppm) 86.4, 84.5, 80.5, 80.3, 73.5, 70.3, 70.2, 70.0, 69.9, 69.2, 69.2, 52.1, 47.1, 29.3, 26.4.

[0192] MS (ESI-MS): calculatedm / z337.16 for C 16 H 26 O6Na [M+Na] + , observed m / z value of 337.72.

[0193] These results confirm that isosorbide-dipentyl oxide (IPO), an isosorbide-based diepoxy compound, can be produced in an environmentally friendly and simple manner through epoxidation using DMDO. Furthermore, the method of the present invention enabled effective yield of IPO with only a relatively simple purification process (liquid-liquid extraction).

[0194]

[0195] Example 2. Adjustment of reaction parameters for epoxidation reaction

[0196] Next, in the production of ISB-based epoxy compounds using DMDO, the yield and conversion rate according to the conditions of the epoxidation reaction were evaluated, and a schematic diagram of Example 2 is shown in Fig. 10.

[0197] For the epoxidation reaction, IPE was first selected as the reactant and epoxidation was performed. To obtain an ISB-based epoxy compound with high conversion and yield, various reaction parameters, including the concentration of KHSO5, the flow rate via a syringe pump, and the reaction temperature, were selected and investigated. The overall conversion and yield of the epoxidation reaction of the allyl-isosorbide compound were monitored by GC-FID analysis.

[0198]

[0199] Example 2-1. Conversion rate and yield of ISB-based epoxy compound production according to oxone concentration

[0200] First, the effect of oxone (KHSO5) concentration on the epoxidation of IPE was investigated. The flow rate was fixed at 15 mL / min, and the equivalents of oxone were added dropwise as 2, 4, and 6 based on IPE, and the epoxidation reaction was otherwise performed in the same manner as the experimental method of Example 1. Accordingly, the conversion rate and yield of the converted ISB-based epoxy compound after 35 minutes were measured and shown in Fig. 11. When the equivalents of oxone were added dropwise in an excessively high amount based on IPE, the pH of the solution could not be maintained in the appropriate pH range of 8-10 for the reaction, and therefore the experiment was performed only up to 6 equivalents.

[0201]

[0202] Since IPE contains two double bonds in one molecule, 2 equivalents of oxone are required to oxidize two unsaturated hydrocarbons in 2 equivalents of IPE molecules, but as can be seen in Fig. 11, the highest yield was obtained in the group using 6 equivalents of oxone. Although 4 equivalents of oxone also showed excellent IPO conversion, the GC-FID analysis results showed that the group using 6 equivalents of oxone reduced the formation of unwanted by-products during epoxidation, minimizing the generation of by-products that occupy a certain portion of the reaction medium, resulting in a relatively excellent yield.

[0203] From these results, it was confirmed that when oxone was added dropwise so that the equivalent ratio of isosorbide-based allyl derivative: oxone was 1:3 to 1:7, more specifically, 1:5 to 1:7, the production of by-products was minimized while the yield of the isosorbide-based diepoxy compound was greatly increased.

[0204]

[0205] Example 2-2. Conversion rate and yield of ISB-based epoxy compound production according to oxone injection flow rate

[0206] Next, to determine the optimal conditions for efficient epoxidation, the flow rate of the oxone solution supplied to the reaction medium was varied. While the remaining conditions were fixed, oxone was added dropwise at flow rates of 5, 15, and 30 (mL / min) in an amount of 6 equivalents based on IPE. Otherwise, the procedure was the same as in Example 1, and the results after 35 minutes are shown in Figure 12.

[0207]

[0208] As can be seen in the above Figure 12, the conversion rate did not differ significantly depending on the flow rate, but it was confirmed that the final yield was significantly increased to close to 92.2% at a flow rate of 15 mL / min.

[0209] From these results, it was determined that, especially when oxone (KHSO5) was added dropwise at a flow rate of 10 to 20 mL / min, the production amount of DMDO was appropriate, while not causing DMDO decomposition due to excessive injection, resulting in a high final yield. Therefore, it was confirmed that the efficient epoxidation of ISB-based allyl materials could be ensured and undesirable side reactions minimized by adjusting the oxone addition flow rate as described above.

[0210]

[0211] Example 2-3. Conversion and yield of ISB-based epoxy compound production according to reaction temperature

[0212] Finally, the effect of reaction temperature on the production of IISB-based epoxy compounds using in situ-generated DMDO was investigated. Six equivalents of oxone (based on IPE) were added dropwise at a fixed flow rate of 15 mL / min, and the reaction temperature was adjusted to -20, 0, and 20°C. Otherwise, the procedure was the same as in Example 1. The results after 35 minutes are shown in Figure 13.

[0213]

[0214] As can be seen in Fig. 13, the yield of the ISB-based epoxy compound was most significantly increased when the reaction temperature was 0℃. From this, it was confirmed that the reaction temperature in the range of -10 to 10℃ is the range in which both the conversion efficiency from the double bond to the epoxide ring and the stability of DMDO are appropriately exhibited, thereby minimizing the spontaneous decomposition of DMDO molecules and maximizing the reactivity of the substrate, thereby obtaining a high conversion rate and yield of the ISB-based epoxy compound. This suggests that setting a specific range of reaction temperatures can have a significant impact on the epoxidation reaction of DMDO-mediated ISB-based compounds.

[0215]

[0216] Example 2-4. Experimental production of ISB-based epoxy compounds under optimized conditions.

[0217] After securing the optimal reaction conditions as an example through the above Examples 2-1 to 2-3, IPO production was observed using DMDO produced in situ, and the results are shown in Figures 14 and 15. Specifically, 6 equivalents of oxone aqueous solution was added to a mixture containing IPE and NaHCO3 in acetone at a constant flow rate of 15 mL / min, and the reaction was performed at 0°C using ultrasound.

[0218]

[0219] As shown in Fig. 14(a), more than 90% of the reactant was consumed within 5 minutes after the completion of the addition of oxone. The relatively slow rate of IPO production compared to the consumption rate of IPE suggests that the epoxidation of IPE proceeds via a reaction intermediate, which is a mono-epoxidized precursor. As confirmed by 1H NMR spectroscopy in Fig. 14(b) and the GC-FID spectrum in Fig. 15, a substance presumed to be the intermediate was first formed at 5 minutes. Thereafter, the substance presumed to be the intermediate gradually disappeared as the reaction progressed and was confirmed to have completely disappeared in the later stages of the reaction. In addition, the proton signal at 5-6 ppm, which represents the double bond of IPE, was confirmed to have a significantly decreased intensity in the early stage and gradually disappeared as the reaction progressed. The three peaks at 2.91, 2.72 and 2.46 ppm originate from the epoxy ring region of IPO, and the intensity of these peaks increases with increasing reaction time, indicating an increase in yield.

[0220] Finally, the conversion rate of IPO of 90 or more was confirmed in this reaction, confirming that the method of the present invention enables high-yield conversion of IPO, and thus enables efficient production of isosorbide-based diepoxy compounds.

[0221]

[0222] Example 3. Production of various epoxy compounds based on ISB using in-situ-generated DMDO.

[0223]

[0224] In addition to the IPO compounds confirmed above, we attempted to conduct synthetic tests on various epoxy compounds based on ISB using in-situ-generated DMDO. Specifically, the ISB-diallyl ether (IDE) and ISB-dimethylpropenyl ether (IME) obtained in Experimental Example 1 were prepared as reaction precursors, and the epoxidation reaction was performed under the same conditions as Example 1. The compounds obtained through this process were analyzed by ESI-MS spectra, and 1 H-NMR and 13 The C-NMR spectrum was measured and identified, and the results are shown in Figures 17 to 20.

[0225] As a result, it was confirmed that the compound synthesized from the above IDE was ISB-diallyl oxide (IDO), and the compound synthesized from the above IME was ISB-dimethyl propenyl ether (IME).

[0226]

[0227] [NMR and ESI-MS data of IDO]

[0228] 1 H NMR (CDCl3, 600 MHz):δ(ppm) 4.68-4.63 (m, 1H), 4.53-4.49 (m, 1H), 4.04-3.90 (m, 4.5H), 3.85-3.78 (m, 1.5H), 3.64-3.58 (m, 1.5H), 3.46-3.36 (m, 1.5H), 3.20-3.16 (m, 1H), 3.14-3.11 (m, 1H), 2.81-2.78 (m, 2H), 2.63-2.57 (m, 2H).

[0229] 13 C NMR (CDCl3, 600 MHz): δ (ppm) 96.4, 85.1, 80.9, 80.6, 80.3, 73.6, 73.4, 71.9, 71.2, 70.5, 70.4, 70.3, 70.0, 51.0, 50.8, 50.7, 44.4, 44.2.

[0230] MS (ESI-MS): calculatedm / z281.10 for C 12 H 18 O6Na [M+Na] + , observed m / z value of 281.36.

[0231]

[0232] [NMR and ESI-MS data of IMO]

[0233] 1 H NMR (CDCl3, 600 MHz):δ(ppm) 4.69-4.65 (m, 1H), 4.55-4.50 (dd, 1H), 4.13-4.05 (m, 1H), 4.03-3.92 (m, 4.5H), 3.77-3.59 (m, 3H), 3.57-3.50 (m, 1.5H), 3.02-2.91 (d, 1H), 2.94-2.92 (q, 1H), 1.33 (s, 6H), 1.29-1.27 (d, 6H).

[0234] 13 C NMR (CDCl3, 600 MHz): δ (ppm) 96.4, 85.1, 80.7, 80.5, 80.4, 80.3, 80.3, 73.7, 73.4, 70.4, 69.9, 69.8, 69.7, 69.6, 69.8, 69.7, 62.5, 62.0, 61.9, 58.0, 57.7, 24.9, 19.1.

[0235] MS (ESI-MS): calculatedm / z337.16 for C 16 H 26 O6Na [M+Na] + , observed m / z value of 337.25.

[0236]

[0237] Next, the yield and conversion rate of each compound, including the IPO compound synthesized in Example 2-4, are shown in Figure 21.

[0238]

[0239] As can be seen in Fig. 21, it was confirmed that ISB-dipentenyl oxide (IPO), ISB-diallyl oxide (IDO), and ISB-dimethylpropenyl ether (IME) were successfully produced by the epoxidation reaction, respectively. In the case of producing IPO and IMO using IPE and IME, excellent yields of 92% and 87.9% were achieved, respectively, while epoxidation using IDE showed a yield of 44.8%.

[0240] Since epoxidation occurs via the electrophilic oxygen-transfer reagent DMDO, we hypothesized that a more nucleophilic ISB-based precursor would be advantageous for epoxidation. In other words, we confirmed that utilizing a highly nucleophilic isosorbide precursor compound may be a key factor in achieving particularly high yields in the production of various ISB-based epoxy compounds using in-situ-generated DMDO.

[0241] These results suggest the importance of careful reaction design considering functional aspects such as precursor structure to achieve high yields in the production of biomass-derived ISB building blocks for bioplastics.

[0242]

[0243] Example 4. Comparison of ISB-based epoxy compound production using in-situ-generated DMDO under ultrasonic and conventional stirring.

[0244] Next, the effect of ultrasonic treatment during the synthesis process on the yield in the production of ISB-based epoxy compounds using ISB in-situ-generated DMDO was investigated.

[0245]

[0246] Specifically, an aqueous solution of oxone (6 equivalents) was added dropwise to a mixture of substrates (2.5 mmol) of IPE and IDE and NaHCO3 (4 g) in 60 mL of acetone solution. The addition was performed at a constant flow rate of 15 mL / min at 0°C, and the reaction was allowed to proceed for 35 min under ultrasonic treatment or conventional stirring.

[0247] The ultrasonic treatment conditions were as follows: 750 W, 20 kHz, 13 mm diameter sonotrode, pulse type (3 s on, 2 s off), and response time of 35 min.

[0248]

[0249] After purification, the conversion rate and yield were analyzed by GC-FID, and the results are shown in Table 1 below.

[0250] SubstrateMethodConversion (%)Yield (%)IPEUltrasound>99.992.2IPEStirring99.773.4IDEUltrasound97.744.8IDEStirring77.819.4

[0251] As a result, as shown in Table 1 above, the yields of both compounds were significantly increased when synthesized using ultrasonic treatment compared to the conventional stirring method. These results confirmed that introducing ultrasonic treatment maximizes the efficiency of DMDO-based epoxidation of ISB-based allyl compounds compared to performing only the stirring step.

[0252] From the above description, those skilled in the art will understand that the present application can be implemented in other specific forms without altering its technical concept or essential characteristics. In this regard, it should be understood that the embodiments described above are illustrative in all respects and not restrictive. The scope of this application should be interpreted to include all changes or modifications derived from the meaning and scope of the following claims and their equivalents, rather than the detailed description above.

Claims

1. An isosorbide-based diepoxide compound represented by the following chemical formula 1, a salt thereof, a solvate thereof, and a solvate of a salt thereof: [Chemical Formula 1] , In the above chemical formula 1, X is a bond, C 1-6 Alkyl, C 1-6 Alkylene, C 1-6 Heteroalkylene, C 2-6 Alkenylene, C 2-6 alkynylene or halogen; R1 and R2 are each independently hydrogen, C 1-6 Alkyl, C 1-6 Heteroalkyl, C 1-6 Alkoxy, or halogen.

2. In the first paragraph, the isosorbide-based diepoxide compound represented by the chemical formula 1 is a compound selected from compounds represented by the following chemical formulas 1-1 to 1-3, a salt thereof, a solvate thereof, and a solvate of a salt thereof: [Chemical Formula 1-1] , [Chemical Formula 1-2] , [Chemical Formula 1-3] .

3. A monomer composition for bioplastic synthesis comprising the compound of claim 1 or 2 and a salt thereof, a solvate thereof and a solvate of a salt thereof.

4. A method for producing an isosorbide-based diepoxide compound represented by the following chemical formula 1, A mixing step for producing a mixture of an isosorbide-based allyl derivative represented by the following chemical formula 2, acetone and a buffer; A manufacturing method comprising an epoxidation step of adding oxone (KHSO5) dropwise to the above mixture to react the isosorbide-based allyl derivative with DMDO molecules generated in situ from acetone and oxone to epoxidize it. [Chemical Formula 1] , [Chemical Formula 2] In the above chemical formulas 1 and 2, X is a bond, C 1-6 Alkyl, C 1-6 Alkylene, C 1-6 Heteroalkylene, C 2-6 Alkenylene, C 2-6 alkynylene or halogen; R1 and R2 are each independently hydrogen, C 1-6 Alkyl, C 1-6 Heteroalkyl, C 1-6 Alkoxy, or halogen.

5. In the fourth paragraph, the isosorbide-based diepoxide compound represented by the chemical formula 1 is one selected from compounds represented by the following chemical formulas 1-1 to 1-3, the manufacturing method: [Chemical Formula 1-1] , [Chemical Formula 1-2] , [Chemical Formula 1-3] .

6. In the fourth paragraph, the isosorbide-based allyl derivative represented by the chemical formula 2 is one selected from compounds represented by the following chemical formulas 2-1 to 2-3, the manufacturing method: [Chemical Formula 2-1] , [Chemical Formula 2-2] , [Chemical Formula 2-3] .

7. A manufacturing method according to claim 4, wherein the buffer is sodium bicarbonate.

8. In the fourth paragraph, the oxone (KHSO5) is added dropwise to the isosorbide-based allyl derivative represented by the chemical formula 2 so that the equivalent ratio of the isosorbide-based allyl derivative represented by the chemical formula 2: oxone is 1:5 to 1:

7.

9. In the fourth paragraph, the oxone (KHSO5) is added dropwise to the isosorbide-based allyl derivative represented by the chemical formula 2 so that the equivalent ratio of the isosorbide-based allyl derivative represented by the chemical formula 2: oxone is 1:

6.

10. A manufacturing method in the fourth paragraph, wherein the oxone (KHSO5) is added dropwise at a flow rate of 10 to 20 mL / min.

11. A manufacturing method according to claim 4, wherein the epoxidation step is performed at -10 to 10°C.

12. A manufacturing method according to claim 4, wherein the epoxidation step is performed under ultrasonic treatment.

13. A manufacturing method according to claim 4, wherein the epoxidation step is performed for 0.1 to 2 hours.

14. In the fourth paragraph, the manufacturing method is a manufacturing method in which the yield of the isosorbide-based diepoxide compound represented by the chemical formula 1 is 90% or more within a reaction time of 35 minutes or less.

15. A manufacturing method according to claim 4, characterized in that the epoxidation step does not use a separate catalyst.

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