A novel method for producing terephthalylidene dicamphorsulfonic acid

Abstract

The present invention relates to a method for producing terephthalylidene dicamphorsulfonic acid, specifically, a method for producing terephthalylidene dicamphorsulfonic acid via a step of producing a terephthalylidene dicamphorsulfuryl intermediate compound from a terephthalylidene dicamphorsulfonic acid salt. The method for producing terephthalylidene dicamphorsulfonic acid of the present invention is carried out through a synthesis reaction, which theoretically achieves a 100% conversion rate from salt to acid. The present invention overcomes the problems of the prior art by not using an ion exchange resin, thereby reducing the cost of ion exchange resins and eliminating the generation of acidic waste during their regeneration. Furthermore, it has the advantages of excellent yield and being capable of mass production.

Description

[Technical Field]

[0001] The present invention relates to a method for producing terephthalylidene dicamphorsulfonic acid, specifically, a method for producing terephthalylidene dicamphorsulfonic acid by hydrolyzing a terephthalylidene dicamphorsulfuryl intermediate compound from a terephthalylidene dicamphorsulfonic acid salt obtained by reacting 10-d,l-camphorsulfonic acid with terephthalaldehyde. [Background technology]

[0002] Ultraviolet rays (UV rays) are electromagnetic waves with wavelengths between 10nm and 400nm, shorter than visible light and longer than X-rays. They are outside the violet range, the shortest wavelength of light visible to humans. They are usually abbreviated as UV. UV rays have high energy, causing sunburn and sterilizing effects, and excessive exposure can even cause skin cancer. Most of the UV rays in sunlight are absorbed by oxygen molecules in the atmosphere, creating ozone, and the ozone layer formed in the upper atmosphere of the Earth absorbs most of this UV light, protecting living things on Earth.

[0003] Ultraviolet rays are classified by wavelength into UVA (400-320nm), UVB (320-280nm), and UVC (280-100nm). Due to the properties of light, the shorter the wavelength, the weaker its penetrating power, while the longer the wavelength, the stronger its penetrating power. UVC cannot pass through the atmosphere due to its short wavelength and is completely absorbed by the ozone layer in the atmosphere. Therefore, it does not reach the Earth's surface, and living organisms on Earth are not normally exposed to UVC. On the other hand, UVB and UVA always reach the Earth's surface and have a significant impact on human skin. UVB is about 1,000 times more intense than UVA at causing burns, and the amount of UVA that reaches the Earth's surface is about 100 times greater than UVB.

[0004] Recently, UV rays have been recognized as the main cause of various aging and wrinkles, and the use of sunscreen is recommended for people of all ages and genders. UV rays not only accelerate skin aging, but are also designated as a Class 1 carcinogen by the World Health Organization (WHO). Sunscreen protects the skin from the UV rays we are exposed to every day. It is important to consider UV protection not only for aesthetic reasons but also for skin health.

[0005] Sunscreens are divided into inorganic and organic compounds. Inorganic compounds include titanium dioxide (TiO2) and zinc oxide (ZnO), which form a film to reflect UV rays and protect the skin. Organic compounds convert UV energy absorbed by the skin into heat, such as infrared rays, and release it outside, preventing skin damage. There are many different chemicals that have UV blocking effects, and the range of blocking effects is also wide, with various combinations of ingredients. The most common chemicals include avobenzone, oxybenzone, and octyl methoxycinnamate. Mixing these two compounds creates a mixed sunscreen.

[0006] Terephthalylidene dicamphor sulfonic acid (TDSA) is an organic compound added to sunscreens to block UVA rays. It has been approved by the US FDA for its UVA blocking properties and is effective in reducing oxidative stress caused by UV rays in daily life, a phenomenon that accelerates skin aging caused by active oxygen.

[0007] Previous patents focused on an acidification process using an ion exchange resin to produce terephthalylidene dicamphorsulfonic acid. Specifically, these patents used an acid resin as a proton source to acidify terephthalylidene dicamphorsulfonic acid salt. However, due to the characteristics of the ion exchange resin, this acidification process cannot achieve a 100% ion exchange rate, i.e., an acid conversion rate. Therefore, to achieve a high conversion rate, the amount of resin used must be increased accordingly. While the resin can be regenerated, it is not permanent and generates acidic wastewater during the regeneration process. Furthermore, the installation of additional equipment requires a high initial investment, making mass production difficult, making this process only suitable for laboratory-scale production. Summary of the Invention [Problem to be solved by the invention]

[0008] Therefore, one aspect of the present invention is to provide a method for efficiently producing terephthalylidene dicamphorsulfonic acid by synthesizing a terephthalylidene dicamphorsulfuryl intermediate compound from a terephthalylidene dicamphorsulfonic acid salt and hydrolyzing the intermediate compound, rather than using an ion exchange resin. [Means for solving the problem]

[0009] According to one aspect of the present invention, (b) mixing terephthalylidene dicamphorsulfonate represented by the following formula 3 with alkyl orthoacetate, alcohol or a halogenating agent to prepare a reaction intermediate, terephthalylidene dicamphorsulfuryl intermediate compound represented by the following formula 4: [Chemical formula 3] [ka] [Chemical formula 4] [ka] (wherein, in the above chemical formula, M is an alkali metal or N(R 1 )(R 2 )(R 3 )(R 4 ) and R 1 ~R 4 are each independently hydrogen or (C1-C7) alkyl, and X is a leaving group; and (c) preparing terephthalylidene dicamphorsulfonic acid represented by the following chemical formula 5 by hydrolysis of the terephthalylidene dicamphorsulfuryl intermediate compound; [Chemical formula 5] [ka] The present invention provides a method for producing terephthalylidene dicamphorsulfonic acid, comprising: [Effects of the Invention]

[0010] The method for producing terephthalylidene dicamphorsulfonic acid of the present invention theoretically has a 100% conversion rate from salt to acid. The present invention solves the problems of the prior art by not using ion exchange resins, thereby reducing the cost required for the resins and eliminating the generation of acidic waste during the regeneration process. Furthermore, the present invention has the advantages of excellent yield and enabling mass production. DETAILED DESCRIPTION OF THE INVENTION

[0011] The present invention will be described in detail below with reference to the accompanying drawings, in which: FIG. 1 is a block diagram of a semiconductor device according to a first embodiment of the present invention; FIG. 2 is a block diagram of a semiconductor device according to a first embodiment of the present invention; FIG. 3 is a block diagram of a semiconductor device according to a first embodiment of the present invention;

[0012] Hereinafter, the present invention will be described in more detail with reference to specific examples, examples, and test examples for carrying out the present invention. However, the present invention may be modified into various different forms, and therefore the scope of the present invention is not limited to the following embodiments.

[0013] Throughout the specification of the present invention, when a part is said to "comprise" a certain component, this does not mean that it excludes other components, but that it may further include other components, unless otherwise specified. Throughout the specification of the present invention, when a step is said to be located "on" or "before" another step, this includes the same rights as when a step is in a direct chronological relationship with another step, as well as when the step is in an indirect chronological relationship where the chronological order of the two steps can be changed, such as a step mixed after each other.

[0014] Terms indicating degrees such as "about," "substantially," and the like used throughout the specification of the present invention are used in the sense of a numerical value or close to a numerical value when tolerances for manufacturing and materials inherent in the referred meaning are presented, and are used to prevent unscrupulous infringers from unfairly exploiting the disclosure in which precise or absolute numerical values ​​are referred to to aid in the understanding of the present invention. The terms "step of (doing)" or "step of" used throughout the specification of this application do not mean "step for."

[0015] The present invention relates to a method for producing terephthalylidene dicamphorsulfonic acid, comprising the steps of: (a) reacting 10-d,l-camphorsulfonic acid and terephthalaldehyde with ROM to produce a terephthalylidene dicamphorsulfonic acid salt; (b) producing a terephthalylidene dicamphorsulfuryl intermediate compound from the terephthalylidene dicamphorsulfonic acid salt; and (c) producing terephthalylidene dicamphorsulfuryl intermediate compound from the terephthalylidene dicamphorsulfuryl intermediate compound by hydrolysis.

[0016] The method for producing terephthalylidene dicamphorsulfonic acid of the present invention particularly includes the steps of: (b) mixing terephthalylidene dicamphorsulfonic acid salt represented by the following Chemical Formula 3 with alkyl orthoacetate, alcohol or a halogenating agent to produce a reaction intermediate, terephthalylidene dicamphorsulfuryl intermediate compound represented by the following Chemical Formula 4; and (c) heating the terephthalylidene dicamphorsulfuryl intermediate compound in the presence of water to produce terephthalylidene dicamphorsulfonic acid represented by the following Chemical Formula 5 by hydrolysis.

[0017] [Chemical formula 3] [ka]

[0018] [Chemical formula 4] [ka]

[0019] [Chemical formula 5] [ka]

[0020] (wherein, in the above chemical formula, M is an alkali metal or N(R 1 )(R 2 )(R 3 )(R 4 ), R is (C1-C7) alkyl, and R 1 ~R 4 are each independently hydrogen or (C1-C7) alkyl, and X is a leaving group.

[0021] The terephthalylidene dicamphorsulfonate represented by Chemical Formula 3 may be provided by further comprising the step of: (a) reacting 10-d,l-camphorsulfonic acid represented by Chemical Formula 1 below and terephthalaldehyde represented by Chemical Formula 2 below with an alkoxy salt (ROM) to prepare the terephthalylidene dicamphorsulfonate represented by Chemical Formula 3:

[0022] [Chemical formula 1] [ka]

[0023] [Chemical formula 2] [ka]

[0024] (In the above ROM, M is an alkali metal or N(R 1 )(R 2 )(R 3 )(R 4 ) and R is (C1-C7) alkyl.

[0025] Meanwhile, the method for preparing the terephthalylidene dicamphorsulfonate salt is not particularly limited, and it can be prepared by a known method known in the art.

[0026] Examples of the alkali metal for M include Li, Na, and K, and Na is preferred from the viewpoint of reaction efficiency.

[0027] The step (b) is a step of preparing a terephthalylidene dicamphor sulfuryl intermediate compound, which is a reaction intermediate represented by the following Chemical Formula 4, from terephthalylidene dicamphor sulfonic acid salt.

[0028] [Chemical formula 4] [ka]

[0029] In the above formula 4, X is a leaving group. The term "leaving groups" generally refers to groups that can be displaced by a nucleophile, and such leaving groups are known in the art. Examples of leaving groups include, but are not limited to, halogens (e.g., I, Br, F, Cl), sulfonates (e.g., mesylate, tosylate), alkoxides (methoxide, ethoxide), sulfides (e.g., SCH), N-hydroxysuccinimide, N-hydroxybenzotriazole, etc.

[0030] In one embodiment of the present invention, the leaving group X in the above Chemical Formula 4 is at least one selected from the group consisting of halogen, a sulfonate compound, a sulfide compound, N-hydroxysuccinimide, N-hydroxybenzotriazole, and an -OR' compound, and the R' may be a lower alkyl having 1 to 6 carbon atoms, such as a halogen group or an alkoxide group.

[0031] Step (b) of preparing the terephthalylidene dicamphor sulfuryl intermediate compound can be carried out by reacting terephthalylidene dicamphor sulfonate with one or more compounds selected from the group consisting of SOCl, PCl, POCl, oxalyl chloride, cyanuric chloride, N-chlorosuccinimide, sulfuryl chloride, PBr, methanol, ethanol, trimethyl orthoacetate, and triethyl orthoacetate.

[0032] More specifically, the method may include a step of mixing a terephthalylidene dicamphorsulfonate represented by Chemical Formula 3 with an alkyl orthoacetate, or mixing a terephthalylidene dicamphorsulfonate with an alcohol in the presence of an acid catalyst to prepare a terephthalylidene dicamphorsulfuryl ester; or a step of mixing a terephthalylidene dicamphorsulfonate represented by Chemical Formula 3 with a halogenating agent to prepare a terephthalylidene dicamphorsulfuryl halide, and in this case, the step (b) of preparing the terephthalylidene dicamphorsulfuryl intermediate compound may be carried out at a temperature of 30 to 110°C, for example, 30 to 55°C, or at room temperature.

[0033] The alkyl orthoacetate may be trimethyl orthoacetate or triethyl orthoacetate; the alcohol may be methanol or ethanol; and the halogenating agent may be selected from the group consisting of thionyl chloride (SOCl2), phosphoryl chloride (POCl3), phosphorus pentachloride (PCl5), oxalyl chloride, oxalyl chloride, cyanuric chloride, N-chlorosuccinimide, sulfuryl chloride, and phosphorus pentabromide (PBr5).

[0034] According to one embodiment of the present invention, step (b) of preparing the reaction intermediate terephthalylidene dicamphor sulfuryl intermediate compound involves dissolving terephthalylidene dicamphor sulfonate in a solvent and cooling the solution to 10-15°C with stirring, followed by dropwise addition of a compound having a leaving group. The solution to which the compound having a leaving group has been added dropwise is heated to 30-110°C, e.g., 30-55°C, and stirred for 30 minutes to 6 hours, e.g., 2 hours. After completion of the reaction, the solution is cooled, and the precipitated solid is filtered and dried.

[0035] In this case, the solvent may be at least one selected from the group including methylene chloride (MC), DMSO, dichloroethane, xylene, dioxane, acetone, and acetonitrile, but is not limited thereto.

[0036] The compound having a leaving group may be one or more selected from the group consisting of halogen compounds including SOCl2, PCl5, POCl3, oxalyl chloride, cyanuric chloride, N-chlorosuccinimide, sulfuryl chloride, and PBr5, or methanol, ethanol, trimethyl orthoacetate, and triethyl orthoacetate.

[0037] The compound having the leaving group is preferably added dropwise in an amount corresponding to 1 to 3 equivalents, preferably 2 equivalents, relative to the terephthalylidene dicamphorsulfonate.

[0038] In the above reaction, the leaving group undergoes a nucleophilic substitution reaction with the dicamphor metal sulfonate, resulting in the attachment of the leaving group to the sulfur atom.

[0039] The step (c) is a step of preparing terephthalylidene dicamphorsulfonic acid represented by the following formula 5 by hydrolysis of the terephthalylidene dicamphorsulfuryl intermediate compound obtained in the step (b).

[0040] [Chemical formula 5] [ka]

[0041] According to one embodiment of the present invention, the step (c) of preparing terephthalylidene dicamphorsulfonic acid may be carried out in water, a solvent, or a mixture thereof, and may involve heating. For example, the terephthalylidene dicamphorsulfuryl intermediate compound is dissolved in water, e.g., distilled water, heated to react with water, and then concentrated. In the step (c), the heating for raising the temperature may be carried out at a temperature of 90 to 100°C.

[0042] The solvent may be at least one solvent selected from water-miscible solvents such as alcohols including methanol and ethanol, acetone, dimethylformamide (DMF), dimethyl sulfoxide (DMSO), isopropanol (IPA), and the like.

[0043] On the other hand, the step (c) may be carried out in the presence of an acid catalyst, including the step of adding an acid catalyst.

[0044] The acid catalyst may be at least one selected from the group consisting of solid acid catalysts including sulfonic acid and polysulfonic acid resin; and acid catalysts including sulfuric acid, toluenesulfonic acid, dodecylbenzenesulfonic acid, hydrocarbon sulfate ester, and hydrochloric acid. For example, sulfuric acid (HCl) or acid resin (sulfuric acid functional group) can be used, but is not limited thereto.

[0045] The acid resin used in step (c) of the present invention only serves as an acid catalyst to ensure smooth reaction of the terephthalylidene dicamphorsulfuryl intermediate compound with water, and its function and role are completely different from those of the prior art, which uses it as a proton source for acidifying terephthalylidene dicamphorsulfonate.

[0046] The present invention will be described in detail with reference to the following examples, which are provided for illustrative purposes only and are not intended to limit the scope of the present invention. [Example]

[0047] Example (1) Preparation of terephthalylidene dicamphorsulfonate While stirring 1.0 kg (2.2 eq) of camphorsulfuryl amide and 2.6 L of toluene, 1.7 kg (4.7 eq) of 30 wt% aqueous sodium methoxide solution was added dropwise, and the internal temperature was raised to 70-75°C. 2.6 kg (1.0 eq) of terephthalaldehyde was dissolved in 2.4 L of toluene and added dropwise to the reactor over 2-3 hours while maintaining the internal temperature at 70-75°C. After the addition was complete, the reaction was allowed to proceed for 2-3 hours. After the reaction was complete, 2.4 L of acetic acid and 2.4 L of water were added and the mixture was separated at 60-70°C. The separated aqueous layer was slowly cooled to 0-5°C to precipitate crystals. The precipitated crystals were filtered under reduced pressure and dried at an external temperature of 80°C. The yield of disodium terephthalidene dicamphorsulfonate was 1.0 kg (86.4%).

[0048] 1 H NMR(MeOD,400MHz)δ(ppm):7.58(4H,s),7.22(2H,m),3.45(2H,d),3.16(2H,d) ,2.88(2H,m),2.31(2H,m),1.77(3H,m),1.74(3H,m),1.64(6H,s),0.83(6H,s)

[0049] (2) Preparation of terephthalylidene dicamphor sulfuryl intermediate compound (2-1) Preparation of terephthalylidene dicamphor sulfuryl ester 1. Trimethyl orthoacetate While stirring 1.0 kg (1.0 eq) of disodium terephthalylidene dicamphorsulfonate and 5.0 L of MC, 594.0 g (3.0 eq) of trimethyl orthoacetate was added dropwise at room temperature, and the mixture was stirred for 24 hours. After the reaction was completed, the mixture was concentrated and crystallized. The solid obtained by crystallization was dried at an external temperature of 60°C. The yield of terephthalylidene dicamphor sulfuryl methyl ester was 899.7 g (92.5%).

[0050] 1 H NMR(CDCl3,400MHz)δ(ppm):7.26(1H,s),7.25(4H,m),7.15(1H,s),3.85(6H,s),3.57(2 H,d),3.32(2H,d),2.17(2H,m),1.66~1.63(6H,m),1.38(2H,m),1.20(6H,s),0.83(6H,s)

[0051] 2. Methanol While stirring 1.0 kg (1.0 eq) of disodium terephthalylidene dicamphorsulfonate and 10.0 L of methanol, 1.0 kg (3.0 eq) of hydrochloric acid was bubbled through the mixture, and the mixture was refluxed and stirred for 12 hours or more. After the reaction was completed, crystallization was carried out. The solid obtained by crystallization was dried at an external temperature of 60°C. The yield of terephthalylidene dicamphor sulfuryl methyl ester was 904.5 g (93.0%).

[0052] 3. Triethyl orthoacetate While stirring 1.0 kg (1.0 eq) of disodium terephthalylidene dicamphorsulfonate and 5.0 L of MC, 802.2 g (3.0 eq) of triethyl orthoacetate was added dropwise at room temperature, and the mixture was stirred for 24 hours. After the reaction was completed, the mixture was concentrated and crystallized. The solid obtained by crystallization was dried at an external temperature of 60°C. The yield of terephthalylidene dicamphor sulfuryl ethyl ester was 866.8 g (85.0%).

[0053] 1 H NMR(CDCl3,400MHz)δ(ppm):7.32(1H,s),7.25(4H,m),7.05(1H,s),3.57(6H,m),3.32(2 H,d),2.07(2H,m),1.66~1.63(6H,m),1.38(2H,m),1.25(6H,t),1.30(6H,s),0.83(6H,s)

[0054] 4. Ethanol While stirring 1.0 kg (1.0 eq) of disodium terephthalylidene dicamphorsulfonate and 10.0 L of ethanol, 1.0 kg (3.0 eq) of hydrochloric acid was bubbled through the mixture, and the mixture was refluxed and stirred for 12 hours or more. After the reaction was completed, crystallization was carried out. The solid obtained by crystallization was dried at an external temperature of 60°C. The yield of terephthalylidene dicamphor sulfuryl ethyl ester was 902.5 g (88.5%).

[0055] (2-2) Preparation of terephthalylidene dicamphor sulfuryl halide Terephthalylidene dicamphor sulfuryl halide was prepared from disodium terephthalylidene dicamphor sulfonate by adding different halogen compounds dropwise.

[0056] 1.SOCl2 1.0 kg (1.0 eq) of disodium terephthalylidene dicamphorsulfonate and 3.0 L of MC were stirred while the internal temperature was cooled to 10-15°C. 397.0 g (2.0 eq) of SOCl2 was added dropwise, and the temperature was raised and the mixture was stirred at an internal temperature of 30-35°C for 2 hours. After the reaction was completed, 3.0 L of H2O was added for extraction, and the separated oil layer was concentrated to obtain terephthalylidene dicamphorsulfuryl chloride in a yield of 840.2 g (85.0%).

[0057] 1 H NMR(MeOD,400MHz)δ(ppm):7.52(4H,s),7.32(2H,s),4.47(2H,d),3.86(2H,d),3.18 (2H,d),2.57(2H,m),2.39(2H,m),1.91(3H,m),1.75(3H,m),1.20(6H,s),0.86(6H,s)

[0058] 2.PCl5 1.0 kg (1.0 eq) of disodium terephthalylidene dicamphorsulfonate and 3.0 L of dichloroethane were stirred while the internal temperature was cooled to 10-15°C. 695.0 g (2.0 eq) of PCl5 was added dropwise, and the temperature was raised and the mixture was stirred at an internal temperature of 30-35°C for 2 hours. After the reaction was completed, 3.0 L of H2O was added for extraction, and the separated oil layer was concentrated to obtain terephthalylidene dicamphorsulfuryl chloride in a yield of 740.4 g (74.9%).

[0059] 3.POCl3 1.0 kg (1.0 eq) of disodium terephthalylidene dicamphorsulfonate and 3.0 L of xylene were stirred while the internal temperature was cooled to 10-15°C. 512.0 g (2.0 eq) of POCl3 was added dropwise, and the temperature was raised and the mixture was stirred at an internal temperature of 100-110°C for 2 hours. After the reaction was completed, 3.0 L of water (HO) was added for extraction, and the separated oil layer was concentrated to obtain terephthalylidene dicamphorsulfuryl chloride in a yield of 423.0 g (42.8%).

[0060] 4. Oxalyl chloride 1.0 kg (1.0 eq) of disodium terephthalylidene dicamphorsulfonate and 3.0 L of dioxane were stirred while the internal temperature was cooled to 10-15°C. 424.0 g (2.0 eq) of oxalyl chloride was added dropwise thereto, and the temperature was raised and the mixture was stirred at an internal temperature of 30-35°C for 2 hours. After the reaction was completed, 3.0 L of HO was added for extraction, and the separated oil layer was concentrated to obtain terephthalylidene dicamphorsulfuryl chloride in a yield of 601.0 g (60.8%).

[0061] 5. Cyanuric chloride 1.0 kg (1.0 eq) of disodium terephthalylidene dicamphorsulfonate and 3.0 L of acetone were stirred while the internal temperature was cooled to 10-15°C. 608.5 g (2.0 eq) of cyanuric chloride and 364.3 g (3.0 eq) of TEA were added dropwise, and the temperature was raised and the mixture was stirred at an internal temperature of 50-55°C for 2 hours. After the reaction was completed, 3.0 L of HO was added for extraction, and the separated oil layer was concentrated. The yield of terephthalylidene dicamphorsulfuryl chloride obtained was 325.5 g (32.9%).

[0062] 6. N-chlorosuccinimide 1.0 kg (1.0 eq) of disodium terephthalylidene dicamphorsulfonate and 3.0 L of acetonitrile were stirred while the internal temperature was cooled to 10-15°C. 440.0 g (2.0 eq) of N-chlorosuccinimide was added dropwise, and the temperature was raised and the mixture was stirred at an internal temperature of 50-55°C for 2 hours. After the reaction was completed, 3.0 L of HO was added for extraction, and the separated oil layer was concentrated to obtain terephthalylidene dicamphorsulfuryl chloride in a yield of 463.2 g (46.9%).

[0063] 7. Sulfuryl chloride 1.0 kg (1.0 eq) of disodium terephthalylidene dicamphorsulfonate and 3.0 L of MC were stirred while the internal temperature was cooled to 10-15°C. 444.6 g (2.0 eq) of sulfuryl chloride was added dropwise thereto, and the temperature was raised and the mixture was stirred at an internal temperature of 50-55°C for 2 hours. After the reaction was completed, 3.0 L of HO was added for extraction, and the separated oil layer was concentrated to obtain terephthalylidene dicamphorsulfuryl chloride in a yield of 513.7 g (52.0%).

[0064] 8. PBr5 1.0 kg (1.0 eq) of disodium terephthalylidene dicamphorsulfonate and 3.0 L of acetone were stirred while the internal temperature was cooled to 10-15°C. 1,420 g (2.0 eq) of PBr5 was added dropwise, and the temperature was raised and the mixture was stirred at an internal temperature of 30-35°C for 2 hours. After the reaction was completed, 3.0 L of H2O was added for extraction, and the separated oil layer was concentrated to obtain terephthalylidene dicamphorsulfuryl bromide in a yield of 401.2 g (35.5%).

[0065] The yields of the terephthalylidene dicamphorsulfuryl halides produced from 1. to 8. in (2-2) above were measured, and the results are shown in Table 1 below.

[0066] [Table 1]

[0067] From Table 1 above, it can be seen that the yield is the best when terephthalylidene dicamphor sulfuryl chloride is prepared by dropwise adding SOCl2 as a halogen compound.

[0068] (3) Synthesis of terephthalylidene dicamphorsulfonic acid from terephthalylidene dicamphorsulfuryl intermediate compound (3-1) Synthesis of Terephthalylidene Dicamphorsulfonic Acid from Terephthalylidene Dicamphorsulfuryl Ester 3-1-1.HCl 500.0 g (1.0 eq) of terephthalylidene dicamphor sulfuryl methyl ester was added to 10.0 L of 1.0 N HCl, and the mixture was heated and stirred at an internal temperature of 90-100°C for 3 hours. After the reaction was completed, the mixture was concentrated. The yield of terephthalylidene dicamphorsulfonic acid was 443.3 g (93.0%).

[0069] 1H NMR(MeOD,400MHz)δ(ppm):7.58(4H,s),7.22(2H,s),3.45(2H,d),3.16(2H,d),2.88(2H,m),2.31(2H,m),1.71(6H,m),1.20(6H,s),0.83(6H,s)

[0070] (3-2) Synthesis of Terephthalylidene Dicamphorsulfonic Acid from Terephthalylidene Dicamphorsulfuryl Halogen Terephthalylidene dicamphorsulfuryl chloride prepared in (2-2) above was used to prepare terephthalylidene dicamphorsulfonic acid under different conditions.

[0071] 3-2-1. Acid free 840.0 g (1.0 eq) of terephthalylidene dicamphorsulfuryl chloride was added to 10.0 L of purified water, and the mixture was heated and stirred at an internal temperature of 90-100°C for 20 hours. After the reaction was completed, the mixture was filtered and concentrated. The yield of terephthalylidene dicamphorsulfonic acid was 731.0 g (92.7%).

[0072] The yield of terephthalylidene dicamphorsulfonic acid produced from (3-1) and (3-2) above was measured, and the results are shown in Table 2 below.

[0073] 3-2-2.HCl 840.0 g (1.0 eq) of terephthalylidene dicamphorsulfuryl chloride was added to 10.0 L of 0.01 N HCl, and the mixture was heated and stirred at an internal temperature of 90-100°C for 3 hours. After the reaction was completed, the mixture was concentrated. The yield of terephthalylidene dicamphorsulfonic acid was 748.2 g (94.9%).

[0074] 1 H NMR(MeOD,400MHz)δ(ppm):7.58(4H,s),7.22(2H,s),3.45(2H,d),3.16(2H,d),2.88(2H,m),2.31(2H,m),1.71(6H,m),1.20(6H,s),0.83(6H,s)

[0075] 3-2-3. Acid resin (sulfuric acid functional group) 840.0 g (1.0 eq) of terephthalylidene dicamphorsulfuryl chloride was added to 10.0 L of purified water and stirred. 8.4 g (0.1 w / w) of acid resin was added to the reaction solution, which was then heated and stirred at an internal temperature of 90-100°C for 3 hours. After the reaction was completed, the solution was filtered and concentrated. The yield of terephthalylidene dicamphorsulfonic acid was 735.0 g (93.2%).

[0076] [Table 2]

[0077] From Table 2 above, it can be seen that the yield was the best when terephthalylidene dicamphorsulfuryl halogen was used to produce terephthalylidene dicamphorsulfonic acid using HCl as an acid catalyst (Example 3-2-2).

[0078] Although the present invention has been described in detail above with reference to examples and test examples, it is clear that the present invention is not limited to the above examples and can be modified in various forms, and that various modifications can be made by a person skilled in the art within the technical concept of the present invention. Furthermore, various substitutions, modifications, and alterations can be made by a person skilled in the art within the scope of the claims without departing from the technical concept of the present invention, and these also fall within the scope of the present invention.

Claims

1. (b) mixing terephthalylidene dicamphorsulfonic acid salt represented by the following Chemical Formula 3 with alkyl orthoacetate, alcohol or a halogenating agent to prepare a reaction intermediate, terephthalylidene dicamphorsulfuryl intermediate compound represented by the following Chemical Formula 4: [Chemical formula 3] 【Chemistry 1】 [Chemical formula 4] 【Chemistry 2】 (wherein, in the above chemical formula, M is an alkali metal or N(R １ ) (R ２ ) (R ３ ) (R ４ ) and R １ ~R ４ are each independently hydrogen or (C １ -C ７ ) alkyl and X is a leaving group; and (c) hydrolyzing the terephthalylidene dicamphorsulfuryl intermediate compound to prepare terephthalylidene dicamphorsulfonic acid represented by the following formula 5: [Chemical formula 5] 【Transformation 3】 A method for producing terephthalylidene dicamphorsulfonic acid, comprising:

2. The step (b) of preparing the terephthalylidene dicamphor sulfuryl intermediate compound comprises: Mixing a terephthalylidene dicamphorsulfonate represented by Chemical Formula 3 with an alkyl orthoacetate, or mixing a terephthalylidene dicamphorsulfonate with an alcohol in the presence of an acid catalyst to prepare a terephthalylidene dicamphor sulfuryl ester; or 2. The method for preparing terephthalylidene dicamphorsulfonic acid according to claim 1, comprising mixing a terephthalylidene dicamphorsulfonic acid salt represented by Chemical Formula 3 with a halogenating agent to prepare terephthalylidene dicamphorsulfuryl halide.

3. 3. The method for producing terephthalylidene dicamphorsulfonic acid according to claim 2, wherein the alkyl orthoacetate is trimethyl orthoacetate or triethyl orthoacetate.

4. The method for producing terephthalylidene dicamphorsulfonic acid according to claim 2 , wherein the alcohol is methanol or ethanol.

5. The halogenating agent is thionyl chloride (SOCl ２ ), phosphoryl chloride (POCl ３ ), phosphorus pentachloride (PCl ５ ), oxalyl chloride, oxalyl chloride, cyanuric chloride, N-chlorosuccinimide, sulfuryl chloride, and phosphorus pentabromide (PBr ５ 2. The method for producing terephthalylidene dicamphorsulfonic acid according to claim 1, wherein the compound is selected from the group consisting of:

6. 2. The method for producing terephthalylidene dicamphorsulfonic acid according to claim 1, wherein in Formula 4, the leaving group X is at least one selected from the group consisting of halogen, a sulfonate compound, a sulfide compound, N-hydroxysuccinimide, N-hydroxybenzotriazole, and an —OR′ compound, and R′ is a lower alkyl having 1 to 6 carbon atoms.

7. 2. The method for producing terephthalylidene dicamphorsulfonic acid according to claim 1, wherein the step (c) of producing terephthalylidene dicamphorsulfonic acid comprises adding an acid catalyst.

8. 8. The method for producing terephthalylidene dicamphorsulfonic acid according to claim 7, wherein the acid catalyst is at least one selected from the group consisting of solid acid catalysts containing sulfonic acid and polysulfonic acid resin; and acid catalysts containing sulfuric acid, toluenesulfonic acid, dodecylbenzenesulfonic acid, hydrocarbon sulfate, and hydrochloric acid.

9. 2. The method of claim 1, wherein the step (c) of preparing terephthalylidene dicamphorsulfonic acid is carried out in water or a mixture of water and a solvent.

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