Novel method for producing p-xylylene dichorsulfonic acid

Abstract

The present invention relates to a method for producing p-xylylenedicamphor sulfonic acid, and more specifically, to a method for producing p-xylylenedicamphor sulfonic acid from p-xylylenedicamphor sulfonate through a step of producing a p-xylylenedicamphor sulfonyl intermediate compound. The method for producing p-xylylene dichorsulfonic acid according to the present invention is performed by a synthesis reaction and thus theoretically has a conversion rate of 100% from a salt to an acid. According to the method, the problems in the prior art are solved, so that ion exchange resin does not need to be used, the cost of using the ion exchange resin is reduced, and acidic waste generated in the regeneration process of the ion exchange resin is not generated. In addition, the method has the advantages of excellent yield and mass production.

Description

TECHNICAL FIELD

[0001] The present invention relates to a method for producing terephthalylidene dicamphor sulfonic acid, and more particularly, to a method for producing terephthalylidene dicamphor sulfonic acid by reacting 10-d,l-camphor sulfonic acid with p-xylylformaldehyde to obtain terephthalylidene dicamphor sulfonic acid salt, and by hydrolyzing a terephthalylidene dicamphor sulfonic acid intermediate compound. BACKGROUND

[0002] Ultra Violet rays is a long electromagnetic wave having a wavelength of 10 nm to 400 nm, and a wavelength shorter than visible light and longer than X-rays. It is located outside of the violet color (purple color) which is the shortest wavelength among the light that can be seen by human beings. It is usually abbreviated as UV. The UV has a large energy, and thus, can burn the skin or be used for sterilization, and when excessively exposed to the UV, skin cancer can also occur. Most of the UV in the sunlight is absorbed by oxygen molecules in the atmosphere to form ozone, and the ozone layer formed in the upper part of the earth's atmosphere absorbs most of such UV, thereby having an effect of protecting the organisms on the earth.

[0003] The UV is classified into UVA (400 to 320 nm), UVB (320 to 280 nm), and UVC (280 to 100 nm) according to the wavelength. In terms of the characteristics of light, the shorter the wavelength, the weaker the penetration, and the longer the wavelength, the stronger the penetration. Since the UVC has a short wavelength, it cannot pass through the atmosphere, and is entirely absorbed by the ozone layer in the atmosphere. Thus, the UVC cannot reach the earth's surface, and the organisms on the earth are not usually exposed to the UVC. In contrast, the UVB and the UVA directly reach the earth's surface, and have a great influence on the human skin. The UVB causes a burn with an intensity about 1,000 times stronger than that of the UVA, and the amount of the UVA reaching the earth's surface is about 100 times greater than that of the UVB.

[0004] Recently, the UV is considered to cause various aging and wrinkles, and thus, the use of a UV blocking agent is recommended for men and women of all ages. The UV not only accelerates the aging of the skin, but is also designated as a first-class carcinogen in the World Health Organization (WHO) and the like. The UV blocking agent protects our skin from the damage by the UV received every day. It is necessary to preferentially block the UV not only in terms of the aesthetic part, but also in terms of the health of the skin.

[0005] As a kind of ultraviolet blocking agent, there are inorganic compound series and organic compound series. As inorganic compound blocking agent, there are titanium white (titanium dioxide, TiO2) and zinc white (zinc oxide, ZnO), and the inorganic compound component forms a thin film to reflect ultraviolet rays, thereby protecting the skin. The organic compound blocking agent converts the ultraviolet ray energy absorbed by the skin into heat form such as infrared rays to release to the outside, thereby preventing skin damage. There are many chemical substances with ultraviolet blocking effect, so the corresponding blocking range is also very extensive, and the component composition is also various, but the most representative chemical substances are Avobenzone, Oxybenzone and Octyl Methoxycinnamate, etc. Mixing the two becomes a mixed blocking agent.

[0006] Terephthalylidene dicamphor sulfonic acid (TDSA) is an organic compound added to the ultraviolet blocking agent for blocking UVA, and its UVA blocking performance is recognized, so it has been approved by the US FDA, and it is effective for reducing oxidative stress caused by daily ultraviolet rays, i.e. for reducing the skin aging acceleration phenomenon caused by active oxygen generation.

[0007] In order to manufacture terephthalylidene dicamphor sulfonic acid, the traditional patent mainly adopts an acidification process using ion exchange resin as the core. That is, the traditional patent uses acid resin as a proton source for acidifying terephthalylidene dicamphor sulfonic acid salt. However, the acidification process using such acid resin cannot achieve 100% ion exchange rate due to the characteristics of ion exchange resin, i.e. cannot obtain complete conversion rate of acid, therefore, in order to obtain high conversion rate, the amount of resin used must be increased accordingly. On the other hand, although the resin can be recycled, the resin is not permanent, and there is a problem of generating acidic wastewater during the recycling process. In addition, since additional equipment needs to be installed, high initial investment cost is required, and mass production is difficult, so it is currently only suitable for laboratory-scale production. SUMMARY

[0008] TECHNICAL PROBLEM

[0009] Therefore, one aspect of the present application provides a method for synthesizing terephthalylidene dicamphor sulfonic acid intermediate compound from terephthalylidene dicamphor sulfonic acid salt and hydrolyzing it to effectively manufacture terephthalylidene dicamphor sulfonic acid, rather than using ion exchange resin.

[0010] TECHNICAL SOLUTION

[0011] According to an aspect of the present application, a manufacturing method of p-xylylenedi-camphorsulfonic acid, includes: (b) a step of mixing a p-xylylenedi-camphor salt represented by Chemical Formula 3 below with an alkyl orthoacetate, an alcohol, or a halogenating agent to manufacture a reaction intermediate, i.e., a p-xylylenedi-camphorsulfonyl intermediate compound represented by Chemical Formula 4 below,

[0012] [Chemical Formula 3]

[0013]

[0014] [Chemical Formula 4]

[0015]

[0016] (wherein, in the chemical formula, M is an alkali metal or N(R 1 )(R 2 )(R 3 )(R 4 ), R 1 to R 4 each independently is hydrogen or (C1-C7)alkyl, and X is a leaving group); and

[0017] (c) a step of manufacturing p-xylylenedi-camphorsulfonic acid represented by Chemical Formula 5 below by performing a hydrolysis reaction on the p-xylylenedi-camphorsulfonyl intermediate compound.

[0018] [Chemical Formula 5]

[0019]

[0020] Effects of Invention

[0021] The manufacturing method of p-xylylenedi-camphorsulfonic acid of the present application has a 100% conversion rate from a salt to an acid in theory. The present application solves the problems of the prior art, thereby not requiring the use of an ion exchange resin, thus reducing the cost of using the same, and not generating acidic waste generated in the regeneration process thereof. In addition, it has the advantages of excellent yield and mass production.

[0022] Best Mode for Carrying Out the Invention

[0023] Hereinafter, preferred embodiments of the present application will be described with reference to the accompanying drawings. However, the embodiments of the present application can be modified in various other forms, and the scope of the present application is not limited to the embodiments described below.

[0024] Next, the present application will be described more specifically by the <Examples> and <Experimental Examples> for embodying the specific contents of the present application, but the scope of the present application is not limited to the following embodiments since the embodiments of the present application can be modified into various different forms.

[0025] In the specification of the present application, when a certain part is described as "including" a certain component, it means that other components can also be included unless otherwise specified, and does not exclude other components. In the specification of the present application, when a certain step is described as being "above" or "before" another step, it includes not only a case where there is a direct time sequence relationship between the certain step and the other step, but also a case where the time sequence of the two steps can be changed, i.e., a case where there is an indirect time sequence relationship between the steps, and the same right is intended.

[0026] In the specification of the present application, the terms "about", "substantially" and the like, when referring to inherent manufacturing errors or material allowable errors, are used to mean the meaning of the numerical value itself or a numerical value close thereto, and the disclosure of the precise or absolute numerical value is intended to prevent improper use by dishonest infringers. The term "(do)ing a step" or "a step of" used in the specification does not mean "a step for".

[0027] The present application relates to a manufacturing method of p-xylylenedi-camphorsulfonic acid, characterized by comprising: (a) a step of reacting 10-d,l-camphorsulfonic acid with p-xylene dialdehyde and ROM to manufacture p-xylylenedi-camphorsulfonic acid salt; (b) a step of manufacturing a p-xylylenedi-camphorsulfonyl intermediate compound from the p-xylylenedi-camphorsulfonic acid salt; and (c) a step of manufacturing p-xylylenedi-camphorsulfonic acid from the p-xylylenedi-camphorsulfonyl intermediate compound by hydrolysis.

[0028] The manufacturing method of p-xylylenedi-camphorsulfonic acid of the present application, in particular, comprises: (b) a step of mixing p-xylylenedi-camphorsulfonic acid salt represented by Chemical Formula 3 below with an alkyl orthoacetate, an alcohol or a halogenating agent to manufacture a reaction intermediate, i.e., a p-xylylenedi-camphorsulfonyl intermediate compound represented by Chemical Formula 4 below; and (c) a step of heating the p-xylylenedi-camphorsulfonyl intermediate compound in the presence of water to manufacture p-xylylenedi-camphorsulfonic acid represented by Chemical Formula 5 below by a hydrolysis reaction.

[0029] [Chemical Formula 3]

[0030]

[0031] [Chemical Formula 4]

[0032]

[0033] [Chemical Formula 5]

[0034]

[0035] (where, in the 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 to R 4 each independently is hydrogen or (C1-C7)alkyl, and X is a leaving group.)

[0036] The p-xylylene biscamphor sulfonic acid salt represented by the chemical formula 3 can be provided by including: (a) a step of reacting 10-d,l-camphor sulfonic acid represented by the following chemical formula 1 with a p-xylene aldehyde represented by the following chemical formula 2 with an alkoxylate salt (ROM) to produce the p-xylylene biscamphor sulfonic acid salt represented by the chemical formula 3.

[0037] [Chemical Formula 1]

[0038]

[0039] [Chemical Formula 2]

[0040]

[0041] (where, in the ROM, M is an alkali metal or N(R 1 )(R 2 )(R 3 )(R 4 ), and R is (C1-C7)alkyl.)

[0042] On the other hand, the method of performing the step of producing the p-xylylene biscamphor sulfonic acid salt of this kind is not particularly limited, and can be produced by a publicly known production method known in the art.

[0043] As an example of the alkali metal of the M, lithium, sodium, potassium, and the like can be given, and from the viewpoint of reaction efficiency, sodium is preferred.

[0044] The step (b) is a step of producing a reaction intermediate, i.e., a p-xylylene biscamphor sulfonic acid intermediate compound, from the p-xylylene biscamphor sulfonic acid salt.

[0045] [Chemical Formula 4]

[0046]

[0047] In the Chemical Formula 4, X is a leaving group. The "leaving group" generally refers to a group which is transferable by a nucleophile, and such leaving groups are well known in the art. Examples of the leaving group include halogen (e.g., iodine, bromine, fluorine, chlorine), sulfonate (e.g., methanesulfonate, p-toluenesulfonate), alkoxy (methoxy, ethoxy), thioether (e.g., methylthio), N-hydroxysuccinimide, N-hydroxybenzotriazole, etc., but are not limited thereto.

[0048] In an embodiment of the present application, the leaving group X in the Chemical Formula 4 is at least one selected from the group consisting of halogen, sulfonate compound, thioether compound, N-hydroxysuccinimide, N-hydroxybenzotriazole, and -OR' compound, wherein R' can be a lower alkyl having a carbon number of 1 to 6, for example, can be a halogen group or an alkoxy group.

[0049] The step (b) of manufacturing the terephthalylidene dicamphor sulfonic acid intermediate compound can be performed by reacting the terephthalylidene dicamphor sulfonic acid salt with one or more compounds selected from the group consisting of thionyl chloride, phosphorus pentachloride, phosphorus oxychloride, oxalyl chloride, cyanuric chloride, N-chlorosuccinimide, sulfuryl chloride, phosphorus pentabromide, methanol, ethanol, trimethyl orthoacetate, triethyl orthoacetate.

[0050] More specifically, the step of manufacturing the terephthalylidene dicamphor sulfonic acid intermediate compound can be performed by mixing the terephthalylidene dicamphor sulfonic acid salt represented by the Chemical Formula 3 with an alkyl orthoacetate or mixing the terephthalylidene dicamphor sulfonic acid salt with an alcohol under an acid catalyst to manufacture a terephthalylidene dicamphor sulfonic acid ester, or mixing the terephthalylidene dicamphor sulfonic acid salt represented by the Chemical Formula 3 with a halogenating agent to manufacture a terephthalylidene dicamphor sulfonic acid halide, and the step of manufacturing the terephthalylidene dicamphor sulfonic acid intermediate compound can be performed at a temperature of 30°C to 110°C, for example, at a temperature of 30°C to 55°C or at room temperature.

[0051] The alkyl orthoacetate can be trimethyl orthoacetate or triethyl orthoacetate, the alcohol can be methanol or ethanol, and the halogenating agent can be selected from the group consisting of thionyl chloride (SOCl2), phosphorus oxychloride (POCl3), phosphorus pentachloride (PCl5), oxalyl chloride, cyanuric chloride, N-chlorosuccinimide, sulfuryl chloride, and phosphorus pentabromide (PBr5).

[0052] According to an embodiment of the present application, the step (b) of manufacturing the reaction intermediate, i.e., the terephthalylidene dicamphor sulfonic acid intermediate compound, dissolves the terephthalylidene dicamphor sulfonic acid salt in a solvent to cool to 10 to 15°C while stirring, and then adds a compound having a leaving group dropwise. The solution of the compound having a leaving group is warmed to 30 to 110°C, for example, to 30 to 55°C, while stirring for 30 minutes to 6 hours, for example, for 2 hours. After the reaction is completed, cooling is performed, and the precipitated solid is filtered and dried.

[0053] At this time, the solvent can be selected from one or more of the group including dichloromethane (MC), dimethyl sulfoxide (DMSO), dichloroethane, xylene, dioxane, acetone, and acetonitrile, but is not limited thereto.

[0054] The compound having a leaving group can be selected from one or more of the group including a halogen compound such as thionyl chloride (SOCl2), phosphorus oxychloride (POCl3), phosphorus pentachloride (PCl5), oxalyl chloride, cyanuric chloride, N-chlorosuccinimide, sulfuryl chloride, and phosphorus pentabromide, or one or more of the group including methanol, ethanol, trimethyl orthoacetate, and triethyl orthoacetate.

[0055] The compound having a leaving group is added dropwise in an amount corresponding to 1 to 3 equivalents, preferably 2 equivalents, with respect to the terephthalylidene dicamphor sulfonic acid salt.

[0056] In the reaction, the leaving group is bound to the sulfur atom by undergoing a nucleophilic substitution reaction with the metal camphor sulfonate.

[0057] The step (c) is a step of manufacturing terephthalylidene dicamphor sulfonic acid represented by Chemical Formula 5 by a hydrolysis reaction of the terephthalylidene dicamphor sulfonic acid intermediate compound obtained in the step (b).

[0058] [Chemical Formula 5]

[0059]

[0060] According to an embodiment of the present application, the step (c) of manufacturing the terephthalylidene dicamphor sulfonic acid can include a process performed in water, a solvent, or a mixture thereof, and can be accompanied by a heating process. For example, the terephthalylidene dicamphor sulfonic acid intermediate compound can be dissolved in water, such as distilled water, and can be subjected to a heating process for temperature elevation and a reaction process with water, followed by a concentration process. In the step (c), the heating process for temperature elevation can be performed at a temperature of 90 to 100°C.

[0061] The solvent can be at least one solvent selected from the group consisting of alcohols including methanol and ethanol, acetone, dimethylformamide (DMF), dimethyl sulfoxide (DMSO), isopropyl alcohol (IPA), and the like, which can be mixed with water.

[0062] On the other hand, the step (c) can also include a step of adding an acid catalyst to be performed in the presence of the acid catalyst.

[0063] The acid catalyst can be at least one selected from the group consisting of solid acid catalysts including sulfonic acid and poly sulfonic acid resin, and acid catalysts including sulfuric acid, p-toluenesulfonic acid, dodecylbenzenesulfonic acid, hydrocarbyl sulfates, and hydrochloric acid, for example, hydrochloric acid (HCl) or an acid resin (sulfuric acid functional group) can be used, but is not limited thereto.

[0064] In the present application, the acid resin used in the step (c) only functions as an acid catalyst to smoothly perform a reaction of the terephthalylidene dicamphor sulfonic acid intermediate compound with water, and is completely different from the function and role of a conventional technique used as a proton source for acidifying terephthalylidene dicamphor sulfonic acid salt.

[0065] Hereinafter, the present application will be described in detail through examples. The following examples are merely illustrative as a means of describing the embodiments of the present application, and the content of the present application is not limited to the following examples.

[0066] Embodiments of the present application Example

[0067] (1) Manufacturing terephthalylidene dicamphor sulfonic acid salt

[0068] After stirring 1.0 kg (2.2 eq) of camphorsulfonic acid and 2.6 L of toluene, 1.7 kg (4.7 eq) of 30 wt% sodium methoxide aqueous solution was added dropwise to raise the internal temperature to 70 to 75°C. 2.6 kg (1.0 eq) of p-xylylene formaldehyde was dissolved in 2.4 L of toluene, after which the temperature was maintained at 70 to 75°C inside the reactor, and was added dropwise for 2 to 3 hours. After the dropwise addition was completed, the reaction was performed for 2 to 3 hours. After the reaction was completed, 2.4 L of acetic acid and 2.4 L of water were added, after which the layering was performed at 60 to 70°C. The separated water layer was slowly cooled to 0 to 5°C to precipitate crystals. The precipitated crystals were filtered under reduced pressure, and were dried at an external temperature of 80°C. The yield of disodium p-xylylenedimethylene dicamphorsulfonate was 1.0 kg (86.4%).

[0069] 1 H NMR (MeOD, 400 MHz) 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)

[0070] (2) Manufacturing of p-xylylenedimethylene dicamphorsulfonic acid intermediate compound

[0071] (2-1) Manufacturing of p-xylylenedimethylene dicamphorsulfonic acid ester

[0072] ① Trimethyl orthoacetate

[0073] After stirring 1.0 kg (1.0 eq) of disodium p-xylylenedimethylene dicamphorsulfonate and 5.0 L of dichloromethane, 594.0 g (3.0 eq) of trimethyl orthoacetate was added dropwise at room temperature, and was stirred for 24 hours. After the reaction was completed, it was concentrated to perform crystallization. The solid obtained by the crystallization was dried at 60°C. The yield of p-xylylenedimethylene dicamphorsulfonic acid methyl ester was 899.7 g (92.5%).

[0074] 1 H NMR (CDC13, 400 MHz) δ (ppm): 7.26 (1H, s), 7.25 (4H, m), 7.15 (1H, s), 3.85 (6H, s), 3.57 (2H, 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)

[0075] ② Methanol

[0076] Stir 1.0 kg (1.0 eq) of disodium p-xylylene disulfonate and 10.0 L of methanol, bubble 1.0 kg (3.0 eq) of hydrochloric acid and reflux stir for 12 hours or more. After the reaction is completed, perform crystallization. Dry the solid obtained by crystallization at an external temperature of 60°C. The yield of p-xylylene disulfonate methyl ester is 904.5 g (93.0%).

[0077] ③triethyl orthoacetate

[0078] Stir 1.0 kg (1.0 eq) of disodium p-xylylene disulfonate and 5.0 L of dichloromethane, while adding 802.2 g (3.0 eq) of triethyl orthoacetate dropwise at room temperature, and then stir for 24 hours. After the reaction is completed, concentrate to perform crystallization. Dry the crystal obtained by crystallization at 60°C. The yield of p-xylylene disulfonate ethyl ester is 866.8 g (85.0%).

[0079] 1 H NMR (CDC13, 400 MHz) δ (ppm): 7.32 (1H, s), 7.25 (4H, m), 7.05 (1H, s), 3.57 (6H, m), 3.32 (2H, 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)

[0080] ④ethanol

[0081] Stir 1.0 kg (1.0 eq) of disodium p-xylylene disulfonate and 10.0 L of ethanol, bubble 1.0 kg (3.0 eq) of hydrochloric acid and reflux stir for 12 hours or more. After the reaction is completed, perform crystallization. Dry the crystal obtained by crystallization at 60°C. The yield of p-xylylene disulfonate ethyl ester is 902.5 g (88.5%).

[0082] (2-2) manufacturing p-xylylene disulfonate halide

[0083] By changing the halogenated compound added dropwise, p-xylylene disulfonate halide is manufactured from disodium p-xylylene disulfonate.

[0084] ①thionyl chloride

[0085] Stir 1.0 kg (1.0 eq) of disodium p-xylylene biscamphorsulfonate and 3.0 L of dichloromethane while cooling the internal temperature to 10-15°C. After adding 397.0 g (2.0 eq) of thionyl chloride dropwise, warm to stir for 2 hours at an internal temperature of 30-35°C. After the reaction is complete, add 3.0 L of water to perform extraction, and concentrate the separated oil layer to obtain p-xylylene biscamphorsulfonyl chloride at a yield of 840.2 g (85.0%).

[0086] 1 H NMR (MeOD, 400 MHz) 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)

[0087] ②Phosphorus pentachloride

[0088] Stir 1.0 kg (1.0 eq) of disodium p-xylylene biscamphorsulfonate and 3.0 L of dichloroethane (Dichloroethane) while cooling the internal temperature to 10-15°C. After adding 695.0 g (2.0 eq) of phosphorus pentachloride dropwise, warm to stir for 2 hours at an internal temperature of 30-35°C. After the reaction is complete, add 3.0 L of water to perform extraction, and concentrate the separated oil layer to obtain p-xylylene biscamphorsulfonyl chloride at a yield of 740.4 g (74.9%).

[0089] ③Phosphorus oxychloride

[0090] Stir 1.0 kg (1.0 eq) of disodium p-xylylene biscamphorsulfonate and 3.0 L of xylene while cooling the internal temperature to 10-15°C. After adding 512.0 g (2.0 eq) of phosphorus oxychloride (2.0 eq) dropwise, warm to stir for 2 hours at an internal temperature of 100-110°C. After the reaction is complete, add 3.0 L of water to perform extraction, and concentrate the separated oil layer to obtain p-xylylene biscamphorsulfonyl chloride at a yield of 423.0 g (42.8%).

[0091] ④Oxalyl chloride

[0092] Stir 1.0 kg (1.0 eq) of disodium p-xylylene biscamphorsulfonate and 3.0 L of dioxane while cooling the internal temperature to 10-15°C. After adding 424.0 g (2.0 eq) of oxalyl chloride dropwise, warm to stir for 2 hours at an internal temperature of 30-35°C. After the reaction is complete, add 3.0 L of water to extract, and separate the resulting oil layer to obtain 601.0 g (60.8%) of p-xylylene biscamphorsulfonyl chloride.

[0093] (5) Cyanuric chloride

[0094] Stir 1.0 kg (1.0 eq) of disodium p-xylylene biscamphorsulfonate and 3.0 L of acetone while cooling the internal temperature to 10-15°C. After adding 608.5 g (2.0 eq) of cyanuric chloride and 364.3 g (3.0 eq) of triethylamine dropwise, warm to stir for 2 hours at an internal temperature of 50-55°C. After the reaction is complete, add 3.0 L of water to extract, and separate the resulting oil layer to obtain 325.5 g (32.9%) of p-xylylene biscamphorsulfonyl chloride.

[0095] (6) N-chlorosuccinimide

[0096] Stir 1.0 kg (1.0 eq) of disodium p-xylylene biscamphorsulfonate and 3.0 L of acetonitrile while cooling the internal temperature to 10-15°C. After adding 440.0 g (2.0 eq) of N-chlorosuccinimide dropwise, warm to stir for 2 hours at an internal temperature of 50-55°C. After the reaction is complete, add 3.0 L of water to extract, and separate the resulting oil layer to obtain 463.2 g (46.9%) of p-xylylene biscamphorsulfonyl chloride.

[0097] (7) Sulfuryl chloride

[0098] Stir 1.0 kg (1.0 eq) of disodium p-xylylene biscamphorsulfonate and 3.0 L of dichloromethane while cooling the internal temperature to 10-15°C. After adding 444.6 g (2.0 eq) of sulfuryl chloride dropwise, warm to stir for 2 hours at an internal temperature of 50-55°C. After the reaction is complete, add 3.0 L of water to extract, and separate the resulting oil layer to obtain 513.7 g (52.0%) of p-xylylene biscamphorsulfonyl chloride.

[0099] V. Phosphorus pentabromide

[0100] Stir 1.0 kg (1.0 eq) of disodium terephthalylidene dicamphor sulfonate and 3.0 L of acetone while cooling the internal temperature to 10-15°C. After adding 1,420 g (2.0 eq) of phosphorus pentabromide dropwise, warm to stir for 2 hours at an internal temperature of 30-35°C. After the reaction is complete, add 3.0 L of water to extract, and separate the oil layer to concentrate to obtain terephthalylidene dicamphor sulfonic acid chloride at a yield of 401.2 g (35.5%).

[0101] The yields of the terephthalylidene dicamphor sulfonic acid halides manufactured in ① to ⑧ of the above (2-2) were measured, and the results are shown in Table 1 below.

[0102] [Table 1]

[0103]

[0104]

[0105] As can be confirmed from Table 1, the yield is the best when thionyl chloride is added dropwise as a halogenated compound to manufacture terephthalylidene dicamphor sulfonic acid chloride.

[0106] (3) Synthesis of terephthalylidene dicamphor sulfonic acid from terephthalylidene dicamphor sulfonic acid intermediate compounds

[0107] (3-1) Synthesis of terephthalylidene dicamphor sulfonic acid from terephthalylidene dicamphor sulfonic acid ester

[0108] 3-1-①. Hydrochloric acid

[0109] After putting 500.0 g (1.0 eq) of terephthalylidene dicamphor sulfonic acid methyl ester into 10.0 L of 1.0 N hydrochloric acid, warm to stir for 3 hours at an internal temperature of 90-100°C. After the reaction is complete, concentrate. The yield of terephthalylidene dicamphor sulfonic acid is 443.3 g (93.0%).

[0110] 1 H NMR (MeOD, 400 MHz) 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)

[0111] (3-2) Synthesis of terephthalylidene dicamphor sulfonic acid from terephthalylidene dicamphor sulfonic acid halide

[0112] changing the conditions of the production of the terephthalylidene dicamphor sulfonic acid chloride in the (2-2) to produce terephthalylidene dicamphor sulfonic acid.

[0113] 3-2-①. acid free

[0114] After 840.0 g (1.0 eq) of terephthalylidene dicamphor sulfonic acid chloride was put into 10.0 L of pure water, it was warmed to be stirred for 20 hours at 90 to 100°C. After the reaction was completed, filtration and concentration were performed. The yield of terephthalylidene dicamphor sulfonic acid was 731.0 g (92.7%).

[0115] The yield of terephthalylidene dicamphor sulfonic acid produced from the (3-1) and (3-2) was measured to list the results thereof in the following .

[0116] 3-2-②. hydrochloric acid

[0117] After 840.0 g (1.0 eq) of terephthalylidene dicamphor sulfonic acid chloride was put into 10.0 L of 0.01 N hydrochloric acid, it was warmed to be stirred for 3 hours at 90 to 100°C. After the reaction was completed, concentration was performed. The yield of terephthalylidene dicamphor sulfonic acid was 748.2 g (94.9%).

[0118] 1 H NMR (MeOD, 400 MHz) 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)

[0119] 3-2-③. acid resin (sulfuric acid functional group)

[0120] After 840.0 g (1.0 eq) of terephthalylidene dicamphor sulfonic acid chloride was put into 10.0 L of pure water, it was stirred. After 8.4 g (0.1 w / w) of acid resin was added to the reaction solution, it was warmed to be stirred for 3 hours at an internal temperature of 90 to 100°C. After the reaction was completed, filtration and concentration were performed. The yield of terephthalylidene dicamphor sulfonic acid was 735.0 g (93.2%).

[0121]

Table 2

[0122] distinguish 3-1-① hydrochloric acid 3-2-① no acid 3-2-② hydrochloric acid 3-2-③ acid resin yield (%) 93.0 93.7 94.9 93.2

[0123] From the above Table 2, it can be confirmed that the yield of the production of terephthalylidene dicamphor sulfonic acid from terephthalylidene dicamphor sulfonic acid halide using hydrochloric acid as an acid catalyst (Example 3-2-ii) is the best.

[0124] The present application has been described in detail by the above examples and test examples, but the present application is not limited to the examples, and can be modified in various ways, and it is obvious that various modifications can be made by those skilled in the art without departing from the scope of the technical idea of the present application. Furthermore, various substitutions, modifications and changes can be made by those skilled in the art within the scope of the technical idea recited in the claims of the present application, and these should be considered to belong to the scope of protection of the present application.

Claims

1. A method for manufacturing terephthaloethylene dicamphor sulfonic acid, comprising: (b) The step of mixing the terephthalimide dicamphor salt represented by the following chemical formula 3 with an alkyl orthoacetate, an alcohol or a halogenated agent to produce the reaction intermediate represented by the following chemical formula 4, namely the terephthalimide dicamphor sulfonyl intermediate compound; [Chemical Formula 3] [Chemical Formula 4] (wherein, in the chemical formula, M is an alkali metal or N(R) 1 (R) 2 (R) 3 (R) 4 ), R 1 To R 4 Each is independently hydrogen or (C1-C7) alkyl, where X is a leaving group; and (c) The step of hydrolyzing the terephthalimide dicamphorsulfonyl intermediate compound to produce terephthalimide dicamphorsulfonic acid represented by the following chemical formula 5. [Chemical Formula 5] 2. The method for manufacturing terephthaloyl dicamphor sulfonic acid according to claim 1, wherein, Step (b) of manufacturing the terephthalimide dicamphorsulfonyl intermediate compound includes: The step of preparing terephthalimide dicamphor sulfonate by mixing terephthalimide dicamphor sulfonate (represented by chemical formula 3) with an alkyl orthoacetic acid ester, or by mixing terephthalimide dicamphor sulfonate with an alcohol under an acid catalyst; or The step of mixing terephthalimide dicamphor sulfonate, represented by chemical formula 3, with a halogenating agent to produce terephthalimide dicamphor sulfonyl halogen.

3. The method for manufacturing terephthaloethylene dicamphor sulfonic acid according to claim 2, wherein, The orthoacetic alkyl ester is trimethyl orthoacetic acid or triethyl orthoacetic acid.

4. The method for manufacturing terephthaloyl dicamphor sulfonic acid according to claim 2, wherein, The alcohol is methanol or ethanol.

5. The method for manufacturing terephthaloethylene dicamphor sulfonic acid according to claim 1, wherein, The halogenated agent is selected from the group consisting of thionyl chloride, phosphoryl chloride, phosphorus pentachloride, oxalyl chloride, cyanuric chloride, N-chlorosuccinimide, sulfonyl chloride, and phosphorus pentabromide.

6. The method for manufacturing terephthaloethylene dicamphor sulfonic acid according to claim 1, wherein, In the chemical formula 4, the leaving group X is selected from at least one of the group consisting of halogens, sulfonates, thioethers, N-hydroxysuccinimide, N-hydroxybenzotriazole, and -OR' compounds, wherein R' is a lower alkyl group having 1 to 6 carbon atoms.

7. The method for manufacturing terephthaloyl dicamphorsulfonic acid according to claim 1, wherein, The step (c) in the production of terephthalic dimethyl camphor sulfonic acid includes the step of adding an acid catalyst.

8. The method for manufacturing terephthaloyl dicamphor sulfonic acid according to claim 7, wherein, The acid catalyst is selected from at least one of the following groups: solid acid catalysts including sulfonic acid and polysulfonic acid resins; and acid catalysts including sulfuric acid, p-toluenesulfonic acid, dodecylbenzenesulfonic acid, hydrocarbon sulfates and hydrochloric acid.

9. The method for manufacturing terephthaloethylene dicamphor sulfonic acid according to claim 1, wherein, The step (c) in the manufacture of terephthalic dimethyl camphor sulfonic acid is carried out in water or a mixture of water and a solvent.

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