KR0153588B1 - Process for producing aromatichydroxycarboxylic acid - Google Patents
Process for producing aromatichydroxycarboxylic acid Download PDFInfo
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- KR0153588B1 KR0153588B1 KR1019950022266A KR19950022266A KR0153588B1 KR 0153588 B1 KR0153588 B1 KR 0153588B1 KR 1019950022266 A KR1019950022266 A KR 1019950022266A KR 19950022266 A KR19950022266 A KR 19950022266A KR 0153588 B1 KR0153588 B1 KR 0153588B1
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- aromatic hydroxy
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C65/00—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
- C07C65/01—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups containing hydroxy or O-metal groups
- C07C65/03—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups containing hydroxy or O-metal groups monocyclic and having all hydroxy or O-metal groups bound to the ring
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Abstract
방향족 히드록시 화합물과 알칼리 금속화합물을 소량의 물과 유기용매의 혼합용매에 투입한 후 CO2가스를 4기압 내지 7기압으로 채우고 120 내지 150℃의 온도로 가열하여 1시간내지 3시간 반응시킨 후, 30 내지 50℃로 냉각하고 여기에 산을 투입하여 생성된 방향족 히드록시 카르복실 금속염을 산성화하여 생성된 최종물질인 방향족 히드록시 카르복실산을 여과하여 방향족 히드록시 카르복실산을 수득하고, 또 여액에 녹아나가는 생성물을 회수하기 위하여 여액에 유기용매를 투입하고 30분간 교반한 후 층분리된 유기용매층을 농축하여 여기에 탄화수소류의 용매를 투입, 침전물을 여과하여 방향족 히드록시 카르복실산을 추가로 수득할 수 있는 방향족 히드록시 카르복실산의 제조방법은 용매의 사용을 감소시킬 수 있으며, 반응성이 향상되고, 용매의 양이 거의 없어 조작부피를 크게 증가시킬 수 있으며, 반응 종료후 여액에서 생성물을 회수하여 수율을 증대시키고 폐액의 오염도를 완화시킬 수 있는 우수한 방향족 히드록시 카르복실산의 제조방법이다.After adding the aromatic hydroxy compound and the alkali metal compound to a mixed solvent of a small amount of water and an organic solvent, CO 2 gas was charged to 4 to 7 atm and heated to a temperature of 120 to 150 ℃ to react for 1 hour to 3 hours The resulting mixture was cooled to 30 to 50 ° C. and acid was added thereto, followed by acidification of the aromatic hydroxy carboxyl metal salt. The resulting aromatic hydroxy carboxylic acid was filtered to obtain an aromatic hydroxy carboxylic acid. In order to recover the product dissolved in the filtrate, an organic solvent was added to the filtrate, stirred for 30 minutes, the layer separated organic solvent was concentrated, a solvent of hydrocarbons was added thereto, and the precipitate was filtered to give an aromatic hydroxy carboxylic acid. Further obtainable methods for producing aromatic hydroxy carboxylic acids can reduce the use of solvents, improve reactivity, solvents This amount can be hardly any significant increase in volume of the operation, and is an excellent method of producing an aromatic hydroxy-carboxylic acids after the completion of the reaction to recover the product from the filtrate which can increase the yield and reduce the contamination of the waste liquid.
Description
[발명의 명칭][Name of invention]
방향족 히드록시 카르복실산의 제조방법Method for producing aromatic hydroxy carboxylic acid
[발명의 상세한 설명]Detailed description of the invention
[발명이 속하는 기술분야][TECHNICAL FIELD OF THE INVENTION]
본 발명은 방향족 히드록시 카르복실산의 제조방법에 관한 것으로서, 더욱 상세하게는 고압의 CO2가스가 채워진 반응용기내에 방향족 히드록시 화합물을 소량의 물과 유기용매에 용해시켜 반응시킴으로써 유기용매가 촉매역할을 하고 접촉면적 및 반응용적을 증가시켜 반응성과 생산성을 증대시키고, 최적의 반응조건에 의하여 반응중 생성되는 부산물을 억제할 수 있어 순도를 향상시킬 수 있으며, 생성물 회수시 효과적인 유기용매를 사용함으로서 산성화 후에 물에 녹아나가는 생성물의 손실을 막아 수율을 현저히 증가시킬 수 있는 방향족 히드록시 카르복실산의 새로운 제조방법에 관한 것이다.The present invention relates to a method for producing an aromatic hydroxy carboxylic acid, and more particularly, an organic solvent is catalyzed by dissolving an aromatic hydroxy compound in a small amount of water and an organic solvent in a reaction vessel filled with a high pressure CO 2 gas. By increasing the contact area and reaction volume, it increases the reactivity and productivity, and can suppress the by-products generated during the reaction by the optimum reaction conditions to improve the purity, and by using an effective organic solvent in product recovery It relates to a new process for producing aromatic hydroxy carboxylic acids which can significantly increase the yield by preventing the loss of the product dissolved in water after acidification.
[종래 기술][Prior art]
방향족 히드록시 카르복실산을 제조하기 위한 종래방법으로서, 일본국 특개소 59-18446호에는 페놀류 화합물과 알칼리를 수용액중에 용해시켜 CO2가스를 통과시키면서 반응시키는 방법이 개시되어 있다. 그러나 이 방법은 생산성(throught put)이 15%로 매우 낮고, 평형의 문제로 인하여 수율도 50% 이하로 저조한 문제점이 있다. 또한 프라크트(J.Prakt, Chem(2).10.89(1874))에서는 페놀과 수산화 나트륨을 수용액에 용해시킨 후 물을 증발시켜 제거하고, 그 잔사를 220 내지 250℃의 온도 및 150기압하에서 CO2와 접촉시켜서 방향족 히드록시 카르복실산을 제조하는 방법을 제안하고 있으나, 이 방법을 사용할 경우에는 에너지 소모량이 너무 많고 고압하에서 반응시키게 되므로 위험할 뿐 아니라 그 수율도 50% 이하로 매우 저조하였다.As a conventional method for producing an aromatic hydroxy carboxylic acid, Japanese Patent Laid-Open No. 59-18446 discloses a method in which a phenol compound and an alkali are dissolved in an aqueous solution and reacted while passing a CO 2 gas. However, this method has a very low productivity (throughput) of 15%, and has a low yield of 50% or less due to the problem of equilibrium. In addition, in J.Prakt, Chem (2) .10.89 (1874), phenol and sodium hydroxide were dissolved in an aqueous solution, and then water was evaporated and the residue was removed at a temperature of 220 to 250 ° C. and 150 atm. It has been proposed a method for producing aromatic hydroxy carboxylic acid by contact with 2 , but this method is not only dangerous because it consumes too much energy and reacts under high pressure, and the yield is also very low at 50% or less.
그리고 일본국 특개소 62-10043호에는 페놀류의 화합물과 알칼리금속을 유기용매에 용해시켜 CO2가스를 가압하는 방법이 개시되어 있으며, 이 방법은 종래의 방법들에 비해서 수율도 향상되고 반응시간도 단축되기는 하였지만, 방향족 히드록시 화합물이 유기용매에 용해된 상태로 반응하므로 히드록시 방향족 화합물과 CO2가스가 오직 유면에서만 접촉하여 반응하기 때문에 반응시간이 여전히 길고, 수율도 여전히 충분치 못하였으며, 방향족 히드록시 화합물과 CO2의 원활한 접촉을 위해 상기 용액을 교반시켜 준다하여도 역시 반응시간을 크게 단축할 수는 없었고, 수율도 만족스럽지 못한 단점이 있었다. 또한 반응용기의 일정 부피를 액체상태인 방향족 히드록시 화합물의 용액이 차지해야 했고 여기에 CO2가 채워져야 하기 때문에 조작 부피가 20 내지 50% 정도로 매우 작아 생산적이지 못하였다. 그리고 생산물인 방향족 히드록시 카르복실산의 중간물질인 방향족 히드록시 카르복실 금속염이 유기용매에 녹아나가 수율에 막대한 손실을 가져오게 되며 이것을 막기 위하여 중간물질에 묻어 있는 유기용매를 드라이시킬 경우 색상이 크게 변색되어 그 순도를 떨어뜨리는 단점이 있다.In addition, Japanese Patent Application Laid-Open No. 62-10043 discloses a method of dissolving a phenol compound and an alkali metal in an organic solvent to pressurize CO 2 gas, which improves yield and reaction time compared to conventional methods. Although it was shortened, the reaction time was still long and the yield was still insufficient because the hydroxy aromatic compound and CO 2 gas were only in contact with the oil surface because the aromatic hydroxy compound reacted in an organic solvent. Even if the solution was stirred for smooth contact between the oxy compound and CO 2, the reaction time could not be greatly reduced, and the yield was not satisfactory. In addition, a certain volume of the reaction vessel had to be occupied by a solution of an aromatic hydroxy compound in a liquid state, and CO 2 should be filled therein, so that the operation volume was very small, such as 20 to 50%, which was not productive. In addition, the aromatic hydroxy carboxyl metal salt, which is an intermediate of the aromatic hydroxy carboxylic acid, is dissolved in the organic solvent, which causes a great loss in yield. In order to prevent this, the color of the organic solvent buried in the intermediate is greatly dried. There is a disadvantage that the color change is lowered purity.
[발명이 해결하려 하는 과제][Problem to solve the invention]
본 발명은 상기와 같은 종래 기술의 문제점을 해결하기 위하여 안출된 것으로서, 본 발명의 목적은 방향족 히드록시 화합물을 소량의 물과 촉매역할을 하는 유기용매를 사용하고 CO2가스를 가압함으로써 과거 물을 사용하는 방법에서의 단점이었던 반응성과 생산성이 크게 향상되고, 용매로써 물을 사용하므로 유기용매를 사용할 때의 공정상에 어려움을 간단하게 개선한 방향족 히드록시 카르복실산의 제조방법을 제공하고, 또한 반응조건을 개선하여 물을 소량 사용시 항상 생성되던 부산물을 억제할 수 있는 방향족 히드록시 카르복실산의 제조방법을 제공하고, 또한 산성화후 물에 녹아나가는 생성물을 유기용매로 추출해 냄으로써 많은 양의 생성물의 손실을 막을 수 있는 방향족 히드록시 카르복실산의 제조방법을 제공한다. 즉, 본 발명의 목적은 반응공정이 간단하며, 가압과 촉매를 사용하여 수율도 증가되고 적은 용매를 사용하여 생산성을 증대시키고 순도에 지장을 주는 부산물을 억제할 수 있어 매우 경제적이면서도 생산적인 방향족 히드록시 카르복실산의 제조방법을 제공하는데 있다.The present invention has been made to solve the problems of the prior art as described above, an object of the present invention is to use a small amount of water and an organic solvent to catalyze the aromatic hydroxy compound and pressurized CO 2 gas by pressing the CO 2 gas It provides a method for producing aromatic hydroxy carboxylic acid, which greatly improves the reactivity and productivity, which were disadvantages in the method of use, and uses water as a solvent, thereby simplifying the process difficulty when using an organic solvent. Improve the reaction conditions to provide a method for producing aromatic hydroxy carboxylic acid that can suppress the by-products that are always produced when using a small amount of water, and also by extracting the product dissolved in water with an organic solvent after acidification of a large amount of product It provides a method for producing an aromatic hydroxy carboxylic acid that can prevent the loss. That is, the objective of the present invention is that the reaction process is simple, the yield is increased by the use of pressurization and catalyst, and the byproducts which increase productivity and suppress the purity by using a small solvent can be suppressed, which is very economical and productive aromatic hydroxide. It is to provide a process for the preparation of hydroxy carboxylic acid.
[과제를 해결하기 위한 수단][Means for solving the problem]
상기와 같은 본 발명의 목적을 달성하기 위하여 본 발명은, 방향족 히드록시 화합물과 알칼리 금속화합물을 물과 유기용매의 혼합용매에 용해시키고, 상기 용해시켜 제조한 혼합물을 CO2와 반응시키고, 상기 CO2와 반응한 반응액에 산을 투입하여 중간물질로 생성된 방향족 히드록시 카르복실 금속염을 산성화하는 공정을 포함하는 방향족 히드록시 카르복실산의 제조방법을 제공한다.In order to achieve the object of the present invention as described above, the present invention, the aromatic hydroxy compound and the alkali metal compound is dissolved in a mixed solvent of water and an organic solvent, and the mixture prepared by dissolving and reacting with the CO 2 , the CO Provided is a method for producing an aromatic hydroxy carboxylic acid comprising the step of acidifying the aromatic hydroxy carboxyl metal salt produced as an intermediate by adding an acid to the reaction solution reacted with 2 .
또한 본 발명은 상기한 본 발명에 있어서, 상기 생성된 방향족 히드록시 카르복실산을 여과하고, 상기 여과후 여액에 녹아나가는 생성물을 회수하기 위하여 여액에 유기용매를 투입하고 교반하는 공정과, 상기 교반에 의하여 층분리된 유기용매층을 농축하여 여기에 탄화수소류의 용매를 투입하여 방향족 히드록시 카르복실산 침전물을 여과하는 공정을 더욱 포함하는 방향족 히드록시 카르복실산의 제조방법을 제공한다. 이와 같은 추가적인 공정을 통하여 본 발명은 여액에서 생성물를 회수함으로써 수율을 높일 수 있다.In addition, the present invention, in the present invention, the step of filtering the resulting aromatic hydroxy carboxylic acid, and injecting and stirring the organic solvent in the filtrate to recover the product dissolved in the filtrate after the filtration, and the stirring It provides a method for producing an aromatic hydroxy carboxylic acid further comprising the step of concentrating the organic solvent layer separated by the step of adding a solvent of hydrocarbons to the filtration of the aromatic hydroxy carboxylic acid precipitate. Through such an additional process, the present invention can increase the yield by recovering the product from the filtrate.
상기한 본 발명에 있어서, 상기한 유기용매는 X- (CH2)n-OH(X는 저급알콕시, n은 3∼6) 또는 CH3- (CH2)n-OH (n은 2∼5)로 이루어진 군에서 선택되는 것이 바람직하며, 이들 유기용매는 방향족 히드록시 화합물 1몰에 대하여 0.5몰 이하로 사용하는 것이 바람직하다.In the present invention described above, the organic solvent is X- (CH 2 ) n -OH (X is lower alkoxy, n is 3 to 6) or CH 3- (CH 2 ) n -OH (n is 2 to 5 The organic solvent is preferably used in an amount of 0.5 mol or less with respect to 1 mol of the aromatic hydroxy compound.
또 상기한 혼합용매에서 물과 유기용매의 혼합비는 무게비로 1:0.5∼0.05인 것이 바람직하다.In the mixed solvent, the mixing ratio of water and organic solvent is preferably 1: 0.5 to 0.05 by weight.
그리고 본 발명에 있어서, 상기 용해된 혼합물은 가스압력이 4기압 내지 8기압인 CO2와 40 내지 190℃의 온도에서 반응시키는 것이 바람직하다.In the present invention, the dissolved mixture is preferably reacted at a temperature of 40 to 190 ℃ with CO 2 gas pressure of 4 to 8 atm.
[실시예]EXAMPLE
이하 본 발명의 대표적인 실시예를 상세히 설명하면 다음과 같다.Hereinafter, exemplary embodiments of the present invention will be described in detail.
본 발명은 방향족 히드록시 카르복실산을 제조하는데 있어서 교반기가 부착되어 있는 일반 반응기에 방향족 히드록시 화합물과 알칼리 금속화합물을 소량의 물과 유기용매, 바람직하게는 무게비 9:1로 혼합된 유기용매와 함께 투입한 후 CO2가스를 4기압 내지 7기압으로 채우고 120 내지 150℃의 온도로 가열하여 1시간내지 3시간 반응시킨 후, 30 내지 50℃로 냉각하고 여기에 산을 투입하여 생성된 방향족 히드록시 카르복실 금속염을 산성화하여 생성된 최종물질인 방향족 히드록시 카르복실산을 여과하여야 수득하고, 또 여액에 녹아나가는 생성물을 회수하기 위하여 여액에 유기용매를 투입하고 30분간 교반한 후 층분리된 유기용매층을 농축하여 여기에 탄화수소류의 용매를 투입, 침전물을 여과하여 상기에서 얻어진 방향족 히드록시 카르복실산과 함께 건조하여 방향족 히드록시 카르복실산을 수득한다.The present invention relates to an organic solvent in which an aromatic hydroxy compound and an alkali metal compound are mixed with a small amount of water and an organic solvent, preferably in a weight ratio of 9: 1, in a general reactor to which an stirrer is attached to prepare an aromatic hydroxy carboxylic acid. After adding together, the CO 2 gas was charged with 4 to 7 atm and heated to a temperature of 120 to 150 ° C. for 1 hour to 3 hours, then cooled to 30 to 50 ° C. and an acid was added thereto to produce an aromatic hydroxide. Aromatic hydroxy carboxylic acid, which is the final product formed by acidifying the hydroxy carboxyl metal salt, is obtained by filtration, and in order to recover the product that is dissolved in the filtrate, an organic solvent is added to the filtrate, stirred for 30 minutes, and then organically separated. Concentrate the solvent layer, add a solvent of hydrocarbons thereto, filter the precipitate, and obtain the aromatic hydroxy carboxylic acid obtained above. Drying to obtain the aromatic hydroxycarboxylic acid to.
본 발명은 물과 유기용매의 혼합용매를 사용함으로써 용매의 사용을 감소시키면서, 유기용매를 촉매로 사용하므로 본반응의 평면조건을 개선하고 히드록시 방향족 화합물과 CO2가스가 보다 잘 반응되도록 접촉면적을 증가시켜 반응성을 향상시키며, 용매의 양이 거의 없어 조작부피가 크게 증가된다. 반응종료후, 여액에서 생성물을 회수하여 수율을 증대시키고 폐액의 오염도를 완화시킬 수 있다.The present invention reduces the use of a solvent by using a mixed solvent of water and an organic solvent, and uses an organic solvent as a catalyst to improve the planar conditions of the present reaction and to better react the hydroxy aromatic compound with CO 2 gas. It increases the reactivity to improve the reactivity, the operation volume is greatly increased because there is almost no amount of solvent. After completion of the reaction, the product can be recovered from the filtrate to increase the yield and reduce the contamination of the waste liquid.
이하 본 발명의 바람직한 실시예를 기재한다. 그러나 하기한 실시예는 본 발명의 이해를 돕기 위한 본 발명의 바람직한 일 실시예일뿐 본 발명이 하기한 실시예에 한정되는 것은 아니다.Hereinafter, preferred embodiments of the present invention will be described. However, the following examples are only one preferred embodiment of the present invention to aid in understanding the present invention, and the present invention is not limited to the following examples.
[실시예1 2,4-디히드록시 벤조산의 제조]Example 1 Preparation of 2,4-dihydroxy benzoic acid
온도계, 리본형태의 교반기가 부착되어 있는 300ml의 고압반응기에 50ml의 물과 5g의 tert-부탄올을 투입하고 1시간동안 질소로 불어준다. 그런후 레조르시놀 49g(0.45몰)과 탄산나트륨 38G(0.36몰)을 투입하고 반응온도를 120±5℃로 유지한다. 그리고 반응기에 CO2압력이 4기압이 되도록 유지하며 3시간 반응시킨다. 반응 종료후 30℃로 교반하면서 냉각한다. 여기에 물을 50ml 가량 첨가투입후 35% 염산 110g을 1시간동안 적가하면 침전이 생성되고 시 침전을 여과하면 흰색고체인 2,4-디히드록시벤조산 53.4g(수율:77%)을 얻었다. 또한 여과액에 에틸아세테이트 50g을 넣어 30분간 교반후 상층액을 농축시키고 여기에 헥산을 투입하면 흰색고체가 침전으로 생성되고 이것을 여과하여 2,4-디히드록시벤조산 10g을 얻었다. 그리하여 최종적으로 2,4-디히드록시벤조산 63.5g(수율:91%)을 얻었다.50 ml of water and 5 g of tert-butanol are added to a 300 ml high pressure reactor equipped with a thermometer and a ribbon stirrer and blown with nitrogen for 1 hour. Then, 49 g (0.45 mol) of resorcinol and 38 G (0.36 mol) of sodium carbonate were added thereto, and the reaction temperature was maintained at 120 ± 5 ° C. Then, the reactor is kept at 4 atmospheres of CO 2 pressure and reacted for 3 hours. After completion of the reaction, the mixture is cooled while stirring at 30 ° C. After adding 50 ml of water, 110 g of 35% hydrochloric acid was added dropwise for 1 hour, and precipitate was formed. When the precipitate was filtered, 53.4 g of a white solid 2,4-dihydroxybenzoic acid (yield: 77%) was obtained. In addition, 50 g of ethyl acetate was added to the filtrate, followed by stirring for 30 minutes, the supernatant was concentrated, and hexane was added thereto. A white solid was formed as a precipitate, which was filtered to obtain 10 g of 2,4-dihydroxybenzoic acid. Thus, 63.5 g (yield: 91%) of 2,4-dihydroxybenzoic acid was finally obtained.
[실시예2 4-히드록시 벤조산의 제조]Example 2 Preparation of 4-Hydroxybenzoic Acid
온도계, 교반기가 장착되어 있는 300ml의 고압반응기에 50ml의 물과 5g의 이소프로판올을 투입하고 1시간동안 질소로 불어준다. 그런후 페놀60g(0.6몰)을 투입하고 반응온도를 140±5℃로 하면서 CO2압력을 6기압으로 유지하면서 3시간 반응한 후 상온으로 냉각하였다. 그런후 반응물에 물 30ml를 첨가투입후 35% 염산 60g 적가하여 산성화시킨 후 생성된 고체를 여과하면 흰색고체인 4-히드록시 벤조산 61.6g(수율:75%, 융점:214∼215℃)을 얻었다.50 ml of water and 5 g of isopropanol are introduced into a 300 ml high pressure reactor equipped with a thermometer and a stirrer and blown with nitrogen for 1 hour. Then, 60 g (0.6 mol) of phenol was added thereto, and the reaction temperature was 140 ± 5 ° C., and the reaction was performed for 3 hours while maintaining the CO 2 pressure at 6 atm, and then cooled to room temperature. Then, 30 ml of water was added to the reaction mixture, followed by acidification by dropwise addition of 60 g of 35% hydrochloric acid, and the resulting solid was filtered to give 61.6 g of a white solid 4-hydroxy benzoic acid (yield: 75%, melting point: 214-215 ° C.). .
또한 여과액에 메틸렌 클로라이드 50g을 넣어 30분간 교반후 상층액을 농축시키고 여기에 헵탄을 투입하면 흰색고체가 침전으로 생성되고 이것을 여과하여 4-히드록시벤조산 6g을 얻었다. 그리하여 최종적으로 4-히드록시벤조산 67.6g(수율:82%)을 얻었다.In addition, 50 g of methylene chloride was added to the filtrate, followed by stirring for 30 minutes, the supernatant was concentrated, and heptane was added thereto. A white solid formed as a precipitate, which was filtered to obtain 6 g of 4-hydroxybenzoic acid. Thus, 67.6 g (yield: 82%) of 4-hydroxybenzoic acid was finally obtained.
[실시예3 2,4-디히드록시 벤조산의 제조]Example 3 Preparation of 2,4-dihydroxy benzoic acid
온도계와 리본형태의 교반기가 부착되어 있는 500ml 고압반응기에 100ml 물과 10ml의 1-메톡시-2-프로판올을 투입한 후 질소로 1시간 불어준다. 그런후 레조르시놀 95g(0.86몰)과 탄산칼륨 142g(1.03몰)을 투입하고 반응온도를 90±5℃로 하였다. CO2압력을 5기압이 되도록 유지하면서 3시간 반응하였다. 반응종료후 30℃로 교반하면서 냉각한다. 여기에 물을 50ml 가량 첨가투입후 35% 염산 200g을 1시간동안 적가하면 침전이 생성되고 이 침전을 여과하면 흰색고체인 2,4-디히드록시벤조산 99.3g(수율:75%)을 얻었다. 또한 여과액에 메틸렌 클로라이드 100g을 넣어 30분간 교반후 상층액을 농축시키고 여기에 n-헵탄을 투입하면 흰색고체가 침전으로 생성되고 이것을 여과하여 2,4-디히드록시벤조산 15g을 얻었다. 그리하여 최종적으로 2,4-디히드록시벤조산 114.3g(수율:86%)을 얻었다.Into a 500ml high pressure reactor equipped with a thermometer and a ribbon stirrer, 100ml of water and 10ml of 1-methoxy-2-propanol are added and blown with nitrogen for 1 hour. Then, 95 g (0.86 mol) of resorcinol and 142 g (1.03 mol) of potassium carbonate were added thereto, and the reaction temperature was 90 ± 5 ° C. The reaction was carried out for 3 hours while maintaining the pressure of CO 2 at 5 atmospheres. After completion of the reaction, the mixture is cooled to 30 ° C while stirring. After adding 50 ml of water, 200 g of 35% hydrochloric acid was added dropwise for 1 hour to precipitate, and the precipitate was filtered to obtain 99.3 g (yield: 75%) of white solid 2,4-dihydroxybenzoic acid. In addition, 100 g of methylene chloride was added to the filtrate, followed by stirring for 30 minutes, the supernatant was concentrated, and n-heptane was added thereto. A white solid formed as a precipitate, which was filtered to obtain 15 g of 2,4-dihydroxybenzoic acid. Thus, 114.3 g (yield: 86%) of 2,4-dihydroxybenzoic acid was finally obtained.
[비교예1 2,4-디히드록시벤조산의 제조]Comparative Example 1 Preparation of 2,4-dihydroxybenzoic acid
온도계와 일반 터어빈 형태의 교반기가 부착되어 있는 300ml 고압 반응기에 1-메톡시-2-프로판을 180ml를 투입한 후 질소로 1시간 불어준다. 그런 후 레조르시놀 31g(0.28몰)과 탄산칼륨 55.2g(0.4몰)을 투입하고, 반응온도를 90±5℃로 하였다. CO2압력을 4기압으로 유지하며 4시간 반응후 상온으로 냉가하여 여과하였다. 여과된 고체를 물 150ml에 녹인후 35% 염산 60g을 적가하여 중화시킨 후 생성된 고체를 여과하면 흰색고체인 2,4-디히드록시 벤조산 22g(수율:51%, 순도:85%)를 얻었다.180 ml of 1-methoxy-2-propane was added to a 300 ml high pressure reactor equipped with a thermometer and a general turbine type stirrer and blown with nitrogen for 1 hour. Thereafter, 31 g (0.28 mol) of resorcinol and 55.2 g (0.4 mol) of potassium carbonate were added thereto, and the reaction temperature was set to 90 ± 5 ° C. The CO 2 pressure was maintained at 4 atm and filtered after cooling for 4 hours to room temperature. The filtered solid was dissolved in 150 ml of water, neutralized by adding dropwise 60 g of 35% hydrochloric acid, and the resulting solid was filtered to give 22 g of a white solid 2,4-dihydroxy benzoic acid (yield: 51%, purity: 85%). .
[비교예2 2,4-디히드록시벤조산의 제조]Comparative Example 2 Preparation of 2,4-dihydroxybenzoic acid
온도계, 리본형태의 교반기가 부착되어 있는 300ml의 일반반응기에 230ml의 물을 투입하고 1시간동안 질소로 불어준다. 그런후 레조르시놀 49g(0.45몰)과 탄산나트륨 81g(0.59몰)을 투입하고 반응온도를 90±5℃로 유지한다. 그리고 반응기에 CO2를 bubbling하며 3시간 반응시킨다. 반응종료후 30℃로 교반하면서 냉각한다. 여기에 35% 염산 110g을 1시간동안 적가하면 침전이 생성되고 이 침전을 여과하면 흰색고체인 2,4-디히드록시벤조산 36g(수율:52%)을 얻었다.230ml of water is added to 300ml of general reactor equipped with thermometer and ribbon stirrer and blown with nitrogen for 1 hour. Then, 49 g (0.45 mol) of resorcinol and 81 g (0.59 mol) of sodium carbonate are added thereto, and the reaction temperature is maintained at 90 ± 5 ° C. And reacted for 3 hours while bubbling CO 2 in the reactor. After completion of the reaction, the mixture is cooled to 30 ° C while stirring. When 110 g of 35% hydrochloric acid was added dropwise for 1 hour, a precipitate was formed, and the precipitate was filtered to obtain 36 g of a white solid 2,4-dihydroxybenzoic acid (yield: 52%).
[효과][effect]
상기한 실시예 및 비교예로부터 알 수 있는 바와 같이, 본 발명에 따라 물과 유기용매의 혼합용매를 사용하여 방향족 히드록시 카르복실산을 제조하는 실시예 1 내지 3의 방향족 히드록시 카르복실산의 제조방법은 종래의 물 또는 유기용매만을 사용하여방향족 히드록시 카르복실산을 제조하는 비교예 1 및 2의 방향족 히드록시 카르복실산의 제조방법에 비하여 용매의 사용을 감소시킬 수 있으며, 반응성이 향상되고, 용매의 양이 거의 없어 조작부피를 크게 증가시킬 수 있으며, 반응 종료후 여액에서 생성물을 회수하여 수율을 증대시키고 폐액의 오염도를 완화시킬 수 있는 우수한 방향족 히드록시 카르복실산의 제조방법이다.As can be seen from the above-described examples and comparative examples, the aromatic hydroxy carboxylic acids of Examples 1 to 3, which prepare aromatic hydroxy carboxylic acids using a mixed solvent of water and an organic solvent according to the present invention. The preparation method can reduce the use of the solvent compared to the preparation method of the aromatic hydroxy carboxylic acid of Comparative Examples 1 and 2 using only water or an organic solvent of the prior art, improving the reactivity It is possible to increase the operation volume greatly because there is little amount of solvent, and after the reaction is a good method of producing an aromatic hydroxy carboxylic acid that can increase the yield by reducing the product from the filtrate to reduce the contamination of the waste liquid.
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