KR100686204B1 - Process for preparing phenyloxo-1,3-dioxolan-2-one derivatives - Google Patents
Process for preparing phenyloxo-1,3-dioxolan-2-one derivatives Download PDFInfo
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- KR100686204B1 KR100686204B1 KR1020040068044A KR20040068044A KR100686204B1 KR 100686204 B1 KR100686204 B1 KR 100686204B1 KR 1020040068044 A KR1020040068044 A KR 1020040068044A KR 20040068044 A KR20040068044 A KR 20040068044A KR 100686204 B1 KR100686204 B1 KR 100686204B1
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Abstract
본 발명은 페닐옥소-1,3-다이옥소란-2-온 유도체의 제조방법에 관한 것으로서, 더욱 상세하게는 할로에틸렌 카보네이트와 페놀 유도체의 반응 혼합용액의 온도를 40 ∼ 60 ℃로 유지하면서 아민촉매를 0.1 ∼ 0.4 mL/분의 적가속도로 서서히 적가하여 부생성물의 생성을 최소화하고, 아민촉매를 적가한 후에는 70 ∼ 100 ℃의 반응온도에서 환류시켜 결합반응을 수행함으로써 고 수율 및 고 순도로 페닐옥소-1,3-다이옥소란-2-온 유도체를 제조하는 방법에 관한 것이다.The present invention relates to a method for preparing a phenyloxo-1,3-dioxolan-2-one derivative, and more particularly, to an amine catalyst while maintaining the temperature of the reaction mixture solution of haloethylene carbonate and a phenol derivative at 40 to 60 ° C. Is gradually added dropwise at a dropping rate of 0.1 to 0.4 mL / min to minimize the formation of by-products, and after the dropwise addition of the amine catalyst, the reaction is carried out by refluxing at a reaction temperature of 70 to 100 ° C. to achieve high yield and high purity. A method for preparing a phenyloxo-1,3-dioxolan-2-one derivative is disclosed.
상기에서, R1, R2, R3, X1 및 X2는 각각 발명의 상세한 설명에서 정의한 바와 같다.In the above, R 1 , R 2 , R 3 , X 1 and X 2 are each as defined in the detailed description of the invention.
할로에틸렌 카보네이트, 페놀, 페닐옥소-1,3-다이옥소란-2-온 유도체 Haloethylene carbonate, phenol, phenyloxo-1,3-dioxolan-2-one derivative
Description
본 발명은 페닐옥소-1,3-다이옥소란-2-온 유도체의 제조방법에 관한 것으로서, 더욱 상세하게는 할로에틸렌 카보네이트와 페놀 유도체의 반응 혼합용액의 온도를 40 ∼ 60 ℃로 유지하면서 아민촉매를 0.1 ∼ 0.4 mL/분의 적가속도로 서서히 적가하여 부생성물의 생성을 최소화하고, 아민촉매를 적가한 후에는 70 ∼ 100 ℃의 반응온도에서 환류시켜 결합반응을 수행함으로써 고 수율 및 고 순도의 페닐옥소-1,3-다이옥소란-2-온 유도체를 제조하는 방법에 관한 것이다.The present invention relates to a method for preparing a phenyloxo-1,3-dioxolan-2-one derivative, and more particularly, to an amine catalyst while maintaining the temperature of the reaction mixture solution of haloethylene carbonate and a phenol derivative at 40 to 60 ° C. Is slowly added dropwise at a dropping rate of 0.1 to 0.4 mL / min to minimize the formation of by-products, and after the dropwise addition of the amine catalyst, the reaction is carried out by refluxing at a reaction temperature of 70 to 100 ° C. to achieve high yield and high purity. A method for preparing a phenyloxo-1,3-dioxolan-2-one derivative is disclosed.
상기에서, R1, R2 및 R3은 각각 수소원자, 또는 탄소수 1∼4의 탄화수소기이고; X1 은 할로겐원자이고; X2는 수소원자, 할로겐원자, 또는 탄소수 1∼4의 탄화수소기이다.In the above, R 1 , R 2 and R 3 are each a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms; X 1 is a halogen atom; X <2> is a hydrogen atom, a halogen atom, or a C1-C4 hydrocarbon group.
본 발명이 목적하는 페닐옥소-1,3-다이옥소란-2-온 유도체의 제조방법에 관련된 특허는 현재 출원되어 있지 않다.There is no patent application related to the preparation method of the phenyloxo-1,3-dioxolan-2-one derivative for which the present invention is intended.
다만, 이와 구조적으로 유사한 페닐싸이오-1,3-다이옥소란-2-온 유도체를 원료로 사용하여 플루오로에틸렌 카보네이트(EFC)를 합성하는 방법이 공지되어 있다 [Tetarahedron 57(2001) 9067-9072]. 이 문헌에서는 비닐렌 카보네이트와 싸이오페놀을 아민촉매 하에서 반응시켜 페닐싸이오-1,3-다이옥소란-2-온 유도체를 제조할 수 있음이 언급되어 있을 뿐이다.However, a method of synthesizing fluoroethylene carbonate (EFC) using a similar phenylthio-1,3-dioxolan-2-one derivative as a raw material is known [ Tetarahedron 57 (2001) 9067-9072. ]. It is only mentioned in this document that phenylthio-1,3-dioxolan-2-one derivatives can be prepared by reacting vinylene carbonate with thiophenol under an amine catalyst.
즉, 상기한 문헌에서는 비닐렌 카보네이트, 싸이오페놀 및 아민촉매를 한꺼번에 반응용기에 투입한 후에 테트라하이드로푸란(THF) 용매의 환류온도로 반응시켜 페닐싸이오-1,3-다이옥소란-2-온 유도체를 제조하는 방법이 공지되어 있다. 그러나, 상기한 공지 방법에 의하면 반응 혼합용액으로부터 목적물을 분리하기가 매우 어렵고 실리카켈 컬럼크로마토그래피와 같은 복잡한 정제공정을 수행하여야만 목적물을 겨우 수득할 수 있다. 따라서, 제조수율이 크게 저조하고 정제공정이 까다로워 상업적 규모로 적용하기에는 적합한 방법이 될 수 없다. That is, in the above-mentioned literature, vinylene carbonate, thiophenol, and amine catalyst are added to the reaction vessel at once, and then reacted at the reflux temperature of the tetrahydrofuran (THF) solvent to form phenylthio-1,3-dioxolane-2-. Methods of preparing on derivatives are known. However, according to the above known method, it is very difficult to separate the target object from the reaction mixture solution and only a complicated purification process such as silica gel column chromatography can be performed to obtain the target product. Therefore, the production yield is very low and the purification process is difficult, which is not a suitable method for applying on a commercial scale.
특히, 상기한 공지방법에서 반응물질로서 사용하고 있는 비닐렌 카보네이트 는 매우 불안정한 화합물로 에틸렌 카보네이트를 염소가스와 개시제를 이용하여 염소화시킨 후 다시 탈염산화하는 과정을 거쳐 제조하여 사용하고 있다[J. Am. Chem. Soc. 1953, 75, 1263]. In particular, vinylene carbonate, which is used as a reactant in the above-described known methods are used to prepare through the process of oxidation again desalting was chlorinated using chlorine gas very unstable compound and an initiator of ethylene carbonate to [J. Am . Chem. Soc . 1953, 75 , 1263.
그러나, 본 발명은 페닐옥소-1,3-다이옥소란-2-온 유도체의 제조방법을 목적으로 하는 발명으로서, 상기한 문헌에 공지된 페닐싸이오-1,3-다이옥소란-2-온 유도체의 제조방법과는 그 목적물이 상이하다. 그 뿐만 아니라, 반응원료물질로서는 안정성이 비교적 우수한 할로에틸렌 카보네이트를 선택 사용함과 동시에 아민촉매의 적가온도 및 적가속도 조절을 통하여 보다 안정하게 목적하는 페닐옥소-1,3-다이옥소란-2-온 유도체를 고 수율 및 고 순도로 합성하는 제조방법 발명이라는 점에서 분명하게 구분된다.However, the present invention is an invention for the purpose of producing a phenyloxo-1,3-dioxolan-2-one derivative, and the phenylthio-1,3-dioxolan-2-one derivative known in the above-mentioned document. The object is different from the production method of. In addition, as a reaction raw material, the desired phenyloxo-1,3-dioxolan-2-one derivative is more stably selected by using haloethylene carbonate having excellent stability and controlling the dropping temperature and dropping speed of the amine catalyst. Is clearly distinguished in that it is a production method invention for synthesizing with high yield and high purity.
따라서, 본 발명은 제조수율이 보다 향상되고 안정적으로 반응시키는 것을 주요 특징으로 하는 페닐옥소-1,3-다이옥소란-2-온 유도체의 제조방법을 제공하는데 그 목적이 있다.
Accordingly, an object of the present invention is to provide a method for producing a phenyloxo-1,3-dioxolan-2-one derivative, which is characterized in that the production yield is improved and reacted stably.
본 발명은 다음 화학식 2로 표시되는 할로에틸렌 카보네이트와 다음 화학식 3으로 표시되는 페놀 유도체가 포함된 반응 혼합용액의 온도를 40 ∼ 60 ℃로 유지 하면서 아민촉매를 0.1 ∼ 0.4 mL/분의 속도로 적가하고,The present invention is added dropwise an amine catalyst at a rate of 0.1 ~ 0.4 mL / min while maintaining the temperature of the reaction mixture solution containing a haloethylene carbonate represented by the formula (2) and a phenol derivative represented by the following formula (3) at 40 ~ 60 ℃ and,
상기 아민촉매의 적가가 완료되면 반응용액을 70 ∼ 100 ℃의 온도에서 환류시켜 다음 화학식 1로 표시되는 페닐옥소-1,3-다이옥소란-2-온 유도체를 제조하는 방법을 그 특징으로 한다.When the dropwise addition of the amine catalyst is completed by refluxing the reaction solution at a temperature of 70 ~ 100 ℃ characterized in that the method for producing a phenyloxo-1,3-dioxolan-2-one derivative represented by the following formula (1).
상기 화학식 1, 2 및 3에서, R1, R2 및 R3은 각각 수소원자, 또는 탄소수 1∼4의 탄화수소기이고; X1은 할로겐원자이고; X2는 수소원자, 할로겐원자, 또는 탄소수 1∼4의 탄화수소기이다.In Formulas 1, 2 and 3, R 1 , R 2 and R 3 are each a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms; X 1 is a halogen atom; X <2> is a hydrogen atom, a halogen atom, or a C1-C4 hydrocarbon group.
이와 같은 본 발명을 더욱 상세히 설명하면 다음과 같다.Referring to the present invention in more detail as follows.
본 발명은 할로에틸렌 카보네이트와 페놀 유도체를 결합 반응시킴에 있어 아 민촉매를 한꺼번에 투입하는 대신에 일정 적가속도로 그리고 일정 초기반응 온도가 유지되도록 투입함으로써 부산물의 생성을 최소화하여 제조 수율을 크게 향상시키고, 이로써 증류 또는 재결정과 같은 간단한 정제공정에 의해서도 페닐옥소-1,3-다이옥소란-2-온 유도체를 고 수율 및 고 순도로 수득할 수 있는 제조방법에 관한 것이다.In the present invention, instead of adding the amine catalyst at the same time to combine the haloethylene carbonate and phenol derivatives, the production rate is minimized by minimizing the production of by-products by maintaining the constant initial reaction temperature at a constant acceleration rate. Therefore, the present invention relates to a preparation method in which a phenyloxo-1,3-dioxolan-2-one derivative can be obtained in high yield and high purity even by a simple purification process such as distillation or recrystallization.
다시 말하면, 본 발명은 할로에틸렌 카보네이트와 페놀 유도체를 결합 반응시킬 때 아민촉매의 적가속도 조절을 통하여 부산물의 생성을 최소화한데 기술구성상의 가장 큰 특징이 있다. 아민촉매 하에서 할로에틸렌 카보네이트와 페놀 유도체를 결합 반응시키게 되면 염 또는 타르와 같은 반응부산물이 생성되는 바, 생성된 부산물은 생성물의 반응을 저해함으로써 제조 수율과 목적물의 순도를 저하시키는 원인으로 작용하게 된다. 이에, 본 발명에서는 아민촉매가 적가되는 반응 혼합용액의 온도와 아민촉매의 적가속도 조절을 통하여 상기한 부산물의 생성을 최소화한 것이다.In other words, the present invention has the biggest feature in terms of technology configuration in minimizing the production of by-products through the control of the acceleration of the amine catalyst when combining the haloethylene carbonate and phenol derivatives. When the reaction of the haloethylene carbonate and phenol derivatives under the amine catalyst produces reaction by-products such as salts or tars, the by-products inhibit the reaction of the product, thereby acting as a cause of lowering the yield and purity of the target product. . Thus, in the present invention, the production of the by-products is minimized by controlling the temperature of the reaction mixture solution in which the amine catalyst is added and the dropping speed of the amine catalyst.
상기한 본 발명에 따른 제조방법을 보다 상세히 설명하면 다음과 같다.Referring to the manufacturing method according to the present invention in more detail as follows.
먼저, 반응용기에 유기용매를 넣은 후 상기 화학식 2로 표시되는 할로에틸렌 카보네이트와 상기 화학식 3으로 표시되는 페놀 유도체를 1 : 0.8 ∼ 1.2 몰비 범위로 보다 바람직하게는 1 : 0.8 ∼ 1.0 몰비 범위로 넣고 교반한다. 상기 화학식 2로 표시되는 할로에틸렌 카보네이트의 예로는 클로로에틸렌 카보네이트, 브로모에틸렌 카보네이트, 클로로프로필렌 카보네이트, 브로모프로필렌 카보네이트 등이 포함될 수 있다. 그리고, 상기 화학식 3으로 표시되는 페놀 유도체의 예 로는 플루오로페놀, 다이플루오로페놀, 플루오로크레졸, 플루오로다이메틸페놀 등이 포함될 수 있다.First, the organic solvent is added to the reaction vessel, and then the haloethylene carbonate represented by Chemical Formula 2 and the phenol derivative represented by Chemical Formula 3 are added in a range of 1: 0.8 to 1.2 molar ratio, more preferably in a range of 1: 0.8 to 1.0 molar ratio. Stir. Examples of the haloethylene carbonate represented by Formula 2 may include chloroethylene carbonate, bromoethylene carbonate, chloropropylene carbonate, bromopropylene carbonate, and the like. In addition, examples of the phenol derivative represented by Chemical Formula 3 may include fluorophenol, difluorophenol, fluorocresol, fluorodimethylphenol, and the like.
그런 다음, 상기 반응 혼합용액의 온도를 40 ∼ 60 ℃ 보다 바람직하게는 45 ∼ 55 ℃로 유지하면서 아민촉매를 0.1 ∼ 0.4 mL/분 보다 바람직하게는 0.2 ∼ 0.3 mL/분의 속도로 적가한다. 이때, 아민촉매가 적가되는 반응 혼합용액의 온도가 40 ℃ 미만으로 유지되거나 또는 아민촉매의 적가속도가 0.1 mL/분 미만으로 유지되면 장시간의 반응시간이 소요되므로 결코 바람직하다할 수 없고, 반응 혼합용액의 온도가 60 ℃를 초과하거나 아민촉매의 적가속도가 0.4 mL/분을 초과하게 되면 할로에틸렌 카보네이트의 반응성을 저하시켜 생산성 저하의 문제가 있다. 아민촉매는 트리에틸아민, 트리에탄올아민 및 암모니아 중에서 선택 사용할 수 있으며, 상기 화학식 2로 표시되는 할로에틸렌 카보네이트에 대하여 2.6 ∼ 3.5 몰비 범위 보다 바람직하게는 2.7 ∼ 3.0 몰비 범위 내에서 적가한다. 아민촉매의 적가량이 2.6 몰비 미만이면 할로에틸렌 카보네이트의 반응성을 저하시켜 생산성 저하의 문제가 있으며, 3.0 몰비를 초과하게 되면 부산물이 생성되는 문제가 있다.Then, the amine catalyst is added dropwise at a rate of 0.2 to 0.3 mL / minute, more preferably 0.1 to 0.4 mL / minute, while maintaining the temperature of the reaction mixture solution at 40 to 60 ° C., more preferably 45 to 55 ° C. In this case, if the temperature of the reaction mixture solution in which the amine catalyst is added dropwise is maintained below 40 ° C. or the dropping rate of the amine catalyst is kept below 0.1 mL / min, a long reaction time is required, which is never preferable. If the temperature of the solution exceeds 60 ℃ or the dropping rate of the amine catalyst exceeds 0.4 mL / min, there is a problem of lowering the reactivity of the haloethylene carbonate to reduce the productivity. The amine catalyst may be selected from triethylamine, triethanolamine and ammonia, and is preferably added dropwise within the range of 2.7 to 3.0 molar ratio with respect to the haloethylene carbonate represented by the formula (2). If the dropwise addition of the amine catalyst is less than 2.6 molar ratio, there is a problem of lowering the productivity of the haloethylene carbonate, and if it exceeds 3.0 molar ratio, there is a problem that by-products are generated.
그런 다음, 아민촉매의 적가가 완료되면, 반응용액을 70 ∼ 100 ℃ 보다 바람직하게는 80 ∼ 90 ℃의 반응온도에서 10 ∼ 20 시간 가열 환류 반응시키면 상기 화학식 1로 표시되는 페닐옥소-1,3-다이옥소란-2-온 유도체와 안정한 할로겐화 아민염이 생성된다. 이때, 반응온도 조절을 위하여 오일 중탕을 사용하였다. 또한, 반응온도가 70 ℃ 보다 낮을 때는 반응의 진행 속도가 느리고, 반응온도가 100 ℃를 초과하여 유지되면 수율 저하를 초래한다.Then, when the dropwise addition of the amine catalyst is completed, the reaction solution is heated to reflux for 10 to 20 hours at a reaction temperature of 70 to 100 ° C., preferably 80 to 90 ° C., and phenyloxo-1,3 represented by Formula 1 above. -Dioxoran-2-one derivatives and stable halogenated amine salts are produced. At this time, an oil bath was used to control the reaction temperature. In addition, when the reaction temperature is lower than 70 ℃, the progress of the reaction is slow, if the reaction temperature is maintained above 100 ℃ causes a decrease in yield.
또한, 상기한 본 발명의 제조방법에서는 반응용매로서 유기용매를 사용하고, 상기 유기용매는 테트라하이드로푸란, 다이에틸 에테르 등이 포함될 수 있다. 유기용매는 상기 화학식 2로 표시되는 할로에틸렌 카보네이트에 대하여 무게비로 7 ∼ 10 배 보다 바람직하게는 8.5 ∼ 9.5 배 사용한다. 상기 유기용매가 7 배 미만으로 소량 사용되면 반응 시 교반에 문제가 있고, 10 배를 초과하게 되면 생산성 저하의 문제가 있다.In addition, in the above-described method of the present invention, an organic solvent is used as a reaction solvent, and the organic solvent may include tetrahydrofuran, diethyl ether, or the like. The organic solvent is more preferably 7 to 10 times more preferably 8.5 to 9.5 times by weight relative to the haloethylene carbonate represented by the formula (2). If the organic solvent is used in a small amount of less than 7 times, there is a problem in the stirring during the reaction, if more than 10 times, there is a problem of reduced productivity.
이상의 제조방법을 수행하여 얻어지는 상기 화학식 1로 표시되는 목적 화합물은 컬럼 크로마토그래피, 증류 또는 재결정화와 같은 통상적인 방법에 의하여 분리 및 정제될 수 있다. 특히 본 발명의 제조방법에 의해 얻어지는 목적물의 수율 및 순도가 우수하여 증류 또는 재결정화와 같은 비교적 간단한 정제공정에 의해서도 99% 이상의 순수한 목적물을 얻을 수 있다. The target compound represented by Chemical Formula 1 obtained by performing the above preparation method may be separated and purified by conventional methods such as column chromatography, distillation or recrystallization. In particular, since the yield and purity of the target product obtained by the production method of the present invention are excellent, a pure target product of 99% or more can be obtained even by a relatively simple purification process such as distillation or recrystallization.
이상에서 설명한 바와 같은 본 발명은 다음의 실시예에 의거하여 더욱 상세히 설명하겠는 바, 본 발명이 이에 한정되는 것은 아니다.The present invention as described above will be described in more detail based on the following examples, but the present invention is not limited thereto.
실시예 1 : 4-플루오로페닐옥소-1,3-다이옥소란-2-온의 합성 Example 1 Synthesis of 4-fluorophenyloxo-1,3-dioxolan-2-one
250 mL 유리제 3구 플라스크에 클로로에틸렌 카보네이트 0.1 mol를 넣고, 용매로 테트라하이드로푸란(THF)을 130 mL를 넣었다. 여기에 4-플루오로페놀 0.1 mol를 넣었다. 트리에틸아민(TEA) 0.3 mol를 20 mL의 THF에 희석하여 얻은 용액을 0.3 mL/분의 속도로 4시간 동안 반응기내로 적가하였다. 이때 반응기의 온도는 50 ℃를 유지하였다. 적가가 끝난 후엔 반응용액의 온도를 82℃로 승온 시켜 17 시간동안 환류반응시켰다. 반응의 종료 여부를 확인하기 위하여 가스 크로마토그래피(GC)와 NMR로 분석하여 반응물이 남아 있는지 확인하였다.0.1 mol of chloroethylene carbonate was added to a 250 mL glass three-necked flask, and 130 mL of tetrahydrofuran (THF) was added as a solvent. 0.1 mol of 4-fluorophenol was added thereto. A solution obtained by diluting 0.3 mol of triethylamine (TEA) in 20 mL of THF was added dropwise into the reactor for 4 hours at a rate of 0.3 mL / min. At this time, the temperature of the reactor was maintained at 50 ℃. After the addition was completed, the reaction solution was heated to 82 ° C. and refluxed for 17 hours. In order to confirm the completion of the reaction, the reaction was analyzed by gas chromatography (GC) and NMR to determine whether the reaction remains.
반응이 끝나면 여과를 통해서 생성된 염을 제거하고, 에테르와 물에 의한 추출로 부 반응물들을 제거하였다. 용매를 건조하고, 증류를 통하여 분리하였다. 또한 활성탄을 이용하여 남아있는 색깔을 제거하여 미색의 고체생성물을 얻을 수 있었다. 이 생성물의 순도는 99.9% 이상이며 90%의 수율이었다. At the end of the reaction, the salt produced through filtration was removed, and the side reactants were removed by extraction with ether and water. The solvent was dried and separated through distillation. In addition, the off-white solid product was obtained by removing the remaining color using activated carbon. The purity of this product was at least 99.9% and a yield of 90%.
비교예 1 : 4-플루오로페닐옥소-1,3-다이옥소란-2-온의 합성 Comparative Example 1: Synthesis of 4-fluorophenyloxo-1,3-dioxoran-2-one
250 mL 유리제 3구 플라스크에 클로로에틸렌 카보네이트 0.1 mol를 넣고, 용매로 테트라하이드로푸란(THF)을 130 mL를 넣었다. 여기에 4-플루오로페놀 0.1 mol를 넣었다. 상온에서 트리에틸아민(TEA) 0.3 mol를 위의 내용물에 즉시 혼합하였다. 즉시 혼합이 끝난 후엔 반응용액의 온도를 82 ℃로 승온시켜 17 시간동안 환류반응시켰다. 반응의 종료 여부를 확인하기 위하여 가스 크로마토그래피(GC)와 NMR로 분석하여 반응물이 남아 있는지 확인하였다.0.1 mol of chloroethylene carbonate was added to a 250 mL glass three-necked flask, and 130 mL of tetrahydrofuran (THF) was added as a solvent. 0.1 mol of 4-fluorophenol was added thereto. 0.3 mol of triethylamine (TEA) was immediately mixed with the contents at room temperature. Immediately after mixing, the temperature of the reaction solution was raised to 82 ℃ and refluxed for 17 hours. In order to confirm the completion of the reaction, the reaction was analyzed by gas chromatography (GC) and NMR to determine whether the reaction remains.
반응이 끝나면 여과를 통해서 생성된 염을 제거하고, 에테르와 물에 의한 추출로 부 반응물들을 제거하였다. 용매를 건조하고, 증류를 통하여 분리하였다. 또한 활성탄을 이용하여 남아있는 색깔을 제거하여 미색의 고체생성물을 얻을 수 있었다. 이 생성물의 순도는 99% 이상이며 60%의 수율이었다. At the end of the reaction, the salt produced through filtration was removed, and the side reactants were removed by extraction with ether and water. The solvent was dried and separated through distillation. In addition, the off-white solid product was obtained by removing the remaining color using activated carbon. The product had a purity of at least 99% and a yield of 60%.
비교예 2 : 4-플루오로페닐옥소-1,3-다이옥소란-2-온의 합성 Comparative Example 2: Synthesis of 4-fluorophenyloxo-1,3-dioxolan-2-one
250 mL 유리제 3구 플라스크에 클로로에틸렌 카보네이트 0.041 mol를 넣고, 용매로 테트라하이드로푸란(THF)을 35 mL를 넣었다. 여기에 4-플루오로페놀 0.041 mol를 넣었다. 트리에틸아민(TEA) 0.122 mol를 20 mL의 THF에 희석하여 얻은 용액을 0.3 mL/분의 속도로 4시간 동안 반응기내로 적가하였다. 이때 반응기의 온도는 상온을 유지하였다. 적가가 끝난 후엔 반응용액의 온도를 82 ℃로 승온시켜 17 시간동안 환류반응시켰다. 반응의 종료 여부를 확인하기 위하여 가스 크로마토그래피(GC)와 NMR로 분석하여 반응물이 남아 있는지 확인하였다. In a 250 mL glass three neck flask, 0.041 mol of chloroethylene carbonate was added, and 35 mL of tetrahydrofuran (THF) was added as a solvent. 0.041 mol of 4-fluorophenol was added thereto. A solution obtained by diluting 0.122 mol of triethylamine (TEA) in 20 mL of THF was added dropwise into the reactor for 4 hours at a rate of 0.3 mL / min. At this time, the temperature of the reactor was maintained at room temperature. After the addition was completed, the reaction solution was heated to 82 ° C. and refluxed for 17 hours. In order to confirm the completion of the reaction, the reaction was analyzed by gas chromatography (GC) and NMR to determine whether the reaction remains.
반응이 끝나면 여과를 통해서 생성된 염을 제거하고, 에테르와 물에 의한 추출로 부 반응물들을 제거하였다. 용매를 건조하고, 증류를 통하여 분리하였다. 또한 활성탄을 이용하여 남아있는 색깔을 제거하여 미색의 고체생성물을 얻을 수 있었다. 이 생성물의 순도는 99% 이상이며 65%의 수율이었다. At the end of the reaction, the salt produced through filtration was removed, and the side reactants were removed by extraction with ether and water. The solvent was dried and separated through distillation. In addition, the off-white solid product was obtained by removing the remaining color using activated carbon. The product had a purity of at least 99% and a yield of 65%.
비교예 3 : 4-플루오로페닐옥소-1,3-다이옥소란-2-온의 합성 Comparative Example 3: Synthesis of 4-fluorophenyloxo-1,3-dioxolan-2-one
250 mL 유리제 3구 플라스크에 클로로에틸렌 카보네이트 0.041 mol를 넣고, 용매로 테트라하이드로푸란(THF)을 35 mL를 넣었다. 여기에 4-플루오로페놀 0.041 mol를 넣었다. 상온에서 트리에틸아민(TEA) 0.122 mol를 위의 내용물에 즉시 혼합하였다. 즉시 혼합이 끝난 후엔 반응용액의 온도를 82 ℃로 승온시켜 17 시간동안 환류반응시켰다. 반응의 종료 여부를 확인하기 위하여 가스 크로마토그래피(GC)와 NMR로 분석하여 반응물이 남아 있는지 확인하였다. In a 250 mL glass three neck flask, 0.041 mol of chloroethylene carbonate was added, and 35 mL of tetrahydrofuran (THF) was added as a solvent. 0.041 mol of 4-fluorophenol was added thereto. 0.122 mol of triethylamine (TEA) was immediately mixed with the above contents at room temperature. Immediately after mixing, the temperature of the reaction solution was raised to 82 ℃ and refluxed for 17 hours. In order to confirm the completion of the reaction, the reaction was analyzed by gas chromatography (GC) and NMR to determine whether the reaction remains.
반응이 끝나면 여과를 통해서 생성된 염을 제거하고, 에테르와 물에 의한 추출로 부 반응물들을 제거하였다. 용매를 건조하고, 증류를 통하여 분리하였다. 또한 활성탄을 이용하여 남아있는 색깔을 제거하여 미색의 고체생성물을 얻을 수 있었다. 이 생성물의 순도는 99% 이상이며 48%의 수율이었다. At the end of the reaction, the salt produced through filtration was removed, and the side reactants were removed by extraction with ether and water. The solvent was dried and separated through distillation. In addition, the off-white solid product was obtained by removing the remaining color using activated carbon. The purity of this product was at least 99% and a yield of 48%.
상기 실시예 1과 비교예 1-3은 4-플루오로페닐옥소-1,3-다이옥소란-2-온을 합성하되, 다만 트리에틸아민(TEA)의 적가속도 및 적가온도를 변화시키면서 반응을 수행한 합성예이며, 얻어진 목적물의 순도 및 수율 변화를 확인하여 다음 표 1에 나타내었다.In Example 1 and Comparative Examples 1-3, 4-fluorophenyloxo-1,3-dioxolan-2-one was synthesized, but the reaction was performed while changing the dropping speed and dropping temperature of triethylamine (TEA). Synthesis Example was carried out, and the purity and yield change of the obtained target product was confirmed and shown in Table 1 below.
상기 표 1에 의하면 아민촉매의 적가온도 및 적가속도에 따라 목적 생성물의 순도 및 수율이 크게 변화됨을 알 수 있다.According to Table 1, it can be seen that the purity and yield of the desired product are greatly changed depending on the dropping temperature and dropping speed of the amine catalyst.
참고예 : 페닐싸이오-1,3-다이옥소란-2-온의 합성 Reference Example: Synthesis of Phenylthio-1,3-dioxoran-2-one
문헌(Tetarahedron 57(2001) 9067-9072)에 공지된 방법에 의하여 다음과 같은 방법으로 페닐싸이오-1,3-다이옥소란-2-온을 합성하였다. Phenylthio -1,3-dioxoran-2-one was synthesized by the method known from Tetarahedron 57 (2001) 9067-9072 in the following manner.
100 mL 유리제 2구 플라스크에 테트라하이드로푸란(THF) 30 mL, 비닐렌 카보 네이트 15 mmol, 벤젠싸이올 20 mmol, 및 트리에틸아민(TEA) 0.3 mol를 투입한 후에, 반응용액의 온도를 80 ℃로 승온시켜 4 시간동안 반응시켰다. 반응의 종료 여부를 확인하기 위하여 가스 크로마토그래피(GC)와 NMR로 분석하여 반응물이 남아 있는지 확인하였다.30 mL of tetrahydrofuran (THF), 15 mmol of vinylene carbonate, 20 mmol of benzenethiol, and 0.3 mol of triethylamine (TEA) were added to a 100 mL glass two-neck flask, and the reaction solution was heated to 80 ° C. It heated up and reacted for 4 hours. In order to confirm the completion of the reaction, the reaction was analyzed by gas chromatography (GC) and NMR to determine whether the reaction remains.
반응이 끝나면 건조를 통해서 용매를 제거하고, 실리카겔 칼럼(EA:n-Hex=1:5)을 이용하여 생성물을 얻을 수 있다. 이 생성물의 순도는 95% 이며 40.8%의 수율로 얻어진다. After the reaction is completed, the solvent is removed by drying, the product can be obtained by using a silica gel column (EA: n-Hex = 1: 5). The purity of this product is 95% and is obtained in a yield of 40.8%.
전술한 바와 같이, 본 발명은 상기 화학식 2로 표시되는 할로에틸렌 카보네이트와 상기 화학식 3으로 표시되는 페놀 유도체를 결합반응시켜 상기 화학식 1로 표시되는 페닐옥소-1,3-다이옥소란-2-온 유도체를 제조하는 방법을 수행함에 있어 아민촉매를 일정 적가온도 및 속도로 적가하여 보다 안정하게 고 수율 및 고 순도로 목적하는 옥소란류를 경제적으로 합성할 수 있다. As described above, the present invention is a phenyloxo-1,3-dioxolan-2-one derivative represented by the formula (1) by combining the haloethylene carbonate represented by the formula (2) and the phenol derivative represented by the formula (3) In carrying out the method for preparing the amine catalyst can be added dropwise at a constant dropping temperature and speed to more stably economically synthesize the desired oxolanes in high yield and high purity.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62290071A (en) | 1986-06-09 | 1987-12-16 | Matsushita Electric Ind Co Ltd | Organic electrolyne secondary battery |
| JPH069610A (en) * | 1993-02-02 | 1994-01-18 | Neos Co Ltd | Production of substituted 1,3-dioxolan-2-one derivative |
| US6010806A (en) | 1995-06-09 | 2000-01-04 | Mitsui Chemicals, Inc. | Fluorine-substituted cyclic carbonate electrolytic solution and battery containing the same |
| JP2000309583A (en) | 1999-04-28 | 2000-11-07 | Kanto Denka Kogyo Co Ltd | Production of 4-fluoro-1,3-dioxolan-2-one |
| US6265592B1 (en) | 1998-04-30 | 2001-07-24 | Basf Aktiengesellschaft | Method for the continuous production of 1,3-dioxolan-2-ones |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62290071A (en) | 1986-06-09 | 1987-12-16 | Matsushita Electric Ind Co Ltd | Organic electrolyne secondary battery |
| JPH069610A (en) * | 1993-02-02 | 1994-01-18 | Neos Co Ltd | Production of substituted 1,3-dioxolan-2-one derivative |
| US6010806A (en) | 1995-06-09 | 2000-01-04 | Mitsui Chemicals, Inc. | Fluorine-substituted cyclic carbonate electrolytic solution and battery containing the same |
| US6265592B1 (en) | 1998-04-30 | 2001-07-24 | Basf Aktiengesellschaft | Method for the continuous production of 1,3-dioxolan-2-ones |
| JP2000309583A (en) | 1999-04-28 | 2000-11-07 | Kanto Denka Kogyo Co Ltd | Production of 4-fluoro-1,3-dioxolan-2-one |
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