KR0169558B1 - Process for preparation of 2-amino-3,5-dibromobenzaldehyde - Google Patents
Process for preparation of 2-amino-3,5-dibromobenzaldehyde Download PDFInfo
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- KR0169558B1 KR0169558B1 KR1019950043694A KR19950043694A KR0169558B1 KR 0169558 B1 KR0169558 B1 KR 0169558B1 KR 1019950043694 A KR1019950043694 A KR 1019950043694A KR 19950043694 A KR19950043694 A KR 19950043694A KR 0169558 B1 KR0169558 B1 KR 0169558B1
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Abstract
본 발명은 하기 식(Ⅰ)로 표시되는 2-아미노-3, 5-디브로모 벤즈알데히드를 공업적으로 용이하게 제조할 수 있는 방법에 관한 것으로, 좀더 상세하게는 2개의 히드록시기를 갖는 탄소수 C2∼C4의 글리콜, 탄소수 C1∼C4의 알코올 및 물로 이루어진 군으로 부터 선택된 둘 또는 그 이상의 혼합용매 존재하에서 하기 식(Ⅱ)로 표시되는 벤즈하이드라자이드 화합물과 탄산염 및 수산화염을 60∼90℃의 온도범위에서 1∼15시간 동안 반응시켜 하기 식(Ⅰ)로 표시되는 2-아미노-3, 5-디브로모 벤즈알데히드를 제조하는 방법에 관한 것이다.The present invention relates to a method that can be easily produced industrially 2-amino-3, 5-dibromo benzaldehyde represented by the following formula (I), more specifically, to a carbon number having two hydroxyl groups C 2 of ~C 4 glycols, high-benzamide represented by the following formula (ⅱ) under two or more mixed solvents selected from the presence of alcohol and water in the group consisting of carbon atoms C 1 ~C 4 dryer Zaid 60~ the compound and the carbonate and hydroxyl flame It relates to a method for producing 2-amino-3, 5-dibromo benzaldehyde represented by the following formula (I) by reacting for 1 to 15 hours at a temperature range of 90 ° C.
Description
본 발명은 하기 식(Ⅰ)로 표시되는 2-아미노-3, 5-디브로모 벤즈알데히드를 공업적으로 용이하게 제조할 수 있는 방법에 관한 것으로, 좀더 상세하게는 에틸렌글리콜-메탄올-물의 혼합용매하에서 하기 식(Ⅱ)로 표시되는 화합물을 염기로 처리하여 고순도 및 고수율로 하기 식(Ⅰ)로 표시되는 2-아미노-3, 5-디브로모 벤즈알데히드의 제조방법에 관한 것이다.The present invention relates to a method for industrially preparing the 2-amino-3, 5-dibromo benzaldehyde represented by the following formula (I), and more particularly, a mixed solvent of ethylene glycol-methanol-water. The present invention relates to a method for producing 2-amino-3,5-dibromo benzaldehyde represented by the following formula (I) in high purity and high yield by treating a compound represented by the following formula (II) with a base.
상기 식(Ⅰ)로 표시되는 2-아미노-3, 5-디브로모 벤즈알데히드는 기관지 확장제 암브록솔의 마지막 중간체로 사용되는 핵심 원료로서 현재 수요가 급증하고 있는 추세이다. 상기 식(Ⅰ)로 표시되는 2-아미노-3, 5-디브로모 벤즈알데히드는 아미노기와 불안정한 알데히드기를 동시에 갖는 화합물로서 안정성이 떨어져 쉽게 산화되거나 다른 친핵성 작용기와 반응하여 변질되는 경향이 있으므로 비교적 제조 및 분리가 어려운 문제점이 있다.2-amino-3, 5-dibromo benzaldehyde represented by the formula (I) is a key raw material used as the last intermediate of the bronchodilator ambroxol, and the demand is increasing rapidly. 2-amino-3, 5-dibromo benzaldehyde represented by the formula (I) is a compound having an amino group and an unstable aldehyde group at the same time, and is relatively prepared because of poor stability and a tendency to easily oxidize or react with other nucleophilic functional groups. And difficult to separate.
상기 식(Ⅰ)로 표시되는 2-아미노-3, 5-디브로모 벤즈알데히드(이하 목적화합물이라 함)를 제조하는 기존의 선행기술로서 대표적인 두가지 기술이 영국특허 제 GB 2,239,241(A)호와 미합중국 특허 제 4,363,766호에 개시되어 있다.Conventional prior art for preparing 2-amino-3, 5-dibromo benzaldehyde (hereinafter referred to as a target compound) represented by the formula (I) is represented by British Patent No. GB 2,239,241 (A) and the United States of America. Patent 4,363,766 is disclosed.
영국특허 제 GB 2,239,241(A)호에서는 상기 식(Ⅱ)로 표시되는 벤조일하이드라자이드 화합물을 전구체로 사용하여 상기 식(Ⅰ)의 화합물을 제조하는 방법으로서, 상기 특허에 따르면, 하기 식(Ⅲ)으로 표시되는 화합물을 에틸렌글리콜과 물의 혼합용매하에서 120∼125℃로 승온 시킨 다음, 상기 온도범위에서 상기 식(Ⅱ)의 화합물을 첨가하고, 1시간 동안 고온반응을 수행하여 상기 식(Ⅰ)의 목적화합물을 순간적으로 제조하였다. 제조된 상기 식(Ⅰ)의 목적화합물은 분리과정없이 이미 첨가된 하기 식(Ⅲ)의 화합물과 반응하여 하기 식(Ⅳ)로 표시되는 화합물로 전환되었다.In GB 2,239,241 (A), a method of preparing a compound of formula (I) using a benzoylhydrazide compound represented by formula (II) as a precursor, according to the above patent, ) Is heated to 120 ~ 125 ℃ under a mixed solvent of ethylene glycol and water, and then the compound of formula (II) is added in the above temperature range, and a high temperature reaction is carried out for 1 hour to the formula (I) The desired compound was prepared instantaneously. The prepared target compound of formula (I) was converted into a compound represented by the following formula (IV) by reacting with a compound of the following formula (III), which was already added without separation.
상기특허에서는 120℃ 이상의 고온을 유지해야 하는 문제점과, 주용매인 에틸렌 글리콜의 인화점(115℃) 이상에서 출발물질인 상기 화합물(Ⅱ)를 주입하고 1시간 동안 고온반응을 수행하여 상기 목적화합물(Ⅰ)을 분리하지 않고, 즉시 다음 반응으로 진행하였으므로 상기 목적 화합물(Ⅰ)의 제조 결과는 언급되어 있지 않다.In this patent, the problem of maintaining a high temperature of 120 ℃ or more, and the injection of the compound (II) as a starting material above the flash point (115 ℃) of the main solvent ethylene glycol and performing a high temperature reaction for 1 hour to the target compound ( The result of the preparation of the target compound (I) was not mentioned since I proceeded to the next reaction immediately without separating I).
한편, 미합중국 특허 제 4,363, 766호에서는 하기 식(Ⅴ)로 표시되는 벤즈아닐라이드 화합물을 전구체로 사용하여 상기 목적화합물(Ⅰ)을 제조하는 방법으로서, 벤즈아닐라이드 화합물을 테트라하이드로 퓨란 용매하에서 유기금속 환원제인 리튬알루미늄하이드라이드(Ⅵ)로 상온에서 처리한 다음, 묽은 황산으로 가수분해하여 60%수율로 목적화합물(Ⅰ)을 제조하였다. 그러나, 상기 특허에서는 환원제로 리튬알루미늄 하이드라이드를 사용하게 되는데, 이러한 가연성이 높은 유기금속 환원제는 안전성면에서 공업적으로 사용하기 어렵고, 사용후 별도의 회수공정이 요구되므로 공업화에 적용하기 어려운 문제점이 있었다. 또한 목적화합물외의 부산물로서 과환원된 하기 식(Ⅶ)로 표시되는 알코올 화합물이 생성되므로 침전을 통해 이를 분리, 제거해야 하는 문제점이 있었다.On the other hand, U.S. Patent Nos. 4,363 and 766 disclose a method for preparing the target compound (I) using a benzanilide compound represented by the following formula (V) as a precursor, wherein the benzanilide compound is prepared in a tetrahydrofuran solvent. Treatment with lithium aluminum hydride (VI), a metal reducing agent, at room temperature, followed by hydrolysis with dilute sulfuric acid to prepare the target compound (I) in 60% yield. However, in the above patent, lithium aluminum hydride is used as a reducing agent. The highly flammable organometallic reducing agent is difficult to be industrially used in terms of safety, and since a separate recovery process is required after use, it is difficult to apply to industrialization. there was. In addition, since the alcohol compound represented by the following formula (Ⅶ) over-reduced as a by-product other than the target compound was produced, there was a problem of separating and removing it through precipitation.
상술한 선행 특허들은 모두 공업화에 적용하기 어려운 문제점이 있으므로 이를 극복하기 위하여 본 발명자들은 광범위한 연구를 수행하였고, 그 결과 본 발명에 이르게 되었다.Since all of the above-described prior patents are difficult to apply to industrialization, the present inventors have conducted extensive research to overcome them, and as a result, the present invention has been achieved.
따라서, 본 발명의 목적은 적절한 용매조성을 개발함으로서 반응조건을 순화시켜 반응온도를 대폭 낮추고, 원료물질을 상온에서 주입할 수 있게 하여 안전성을 높이며, 동시에 간단한 여과과정만을 통해 불안정한 목적화합물(Ⅰ)을 고순도, 고수율로 분리함으로서 공업화에 적용하기 유리한 제조방법을 제공하는데 있다.Therefore, the object of the present invention is to purify the reaction conditions by developing a suitable solvent composition, significantly lower the reaction temperature, increase the safety by allowing the injection of raw materials at room temperature, and at the same time to stabilize the unstable target compound (I) through a simple filtration process. It is to provide a manufacturing method that is advantageous to apply to industrialization by separating in high purity, high yield.
상기 목적을 달성하기 위한 본 발명의 하기 식(Ⅰ)로 표시되는 2-아미노-3, 5-디브로모 벤즈알데히드의 제조방법은 2개의 히드록시기를 갖는 탄소수 C2∼C4의 글리콜, 탄소수 C1∼C4의 알코올 및 물로 이루어진 군으로 부터 선택된 둘 또는 그 이상의 혼합용매 존재하에서 하기식(Ⅱ)로 표시되는 벤즈하이드라자이드 화합물과 탄산염 및 수산화염을 60∼90℃의 온도 범위에서 1∼15시간 동안 반응시키는 것으로 이루어진다.Method for producing 2-amino-3, 5-dibromo benzaldehyde represented by the following formula (I) of the present invention for achieving the above object is a C 2 -C 4 glycol having two hydroxyl groups, C 1 from the group consisting of ~C 4 alcohol and water in the benz hydrazide compound and the carbonate and hydroxyl flame represented by the following formula (ⅱ) under the selected two or more mixed solvent present in the temperature range of 60~90 1~15 ℃ Reaction for time.
이하 본 발명의 제조방벙을 더욱 상세히 설명하면 다음과 같다.Hereinafter, the manufacturing method of the present invention will be described in more detail.
본 발명에 따르면, 상기 목적화합물(Ⅰ)을 에틸렌글리콜, 디에닐렌글리콜, 메탄올, 에탄올, 프로판올 및 물로 이루어진 군으로 부터 선택된 둘 또는 그 이상의 혼합용매 존재하에서 상기 식(Ⅱ)로 표시되는 벤즈하이드라자이드 화합물(이하 출발물질이라 함)과 탄산염 및 수산화염을 60∼90℃의 온도범위에서 1∼15시간 동안 반응시키고, 반응완료후 상온까지 냉각하여 여과 및 세척하여 고순도(99% 이상까지), 고수율(75% 까지)로 제조한다.According to the present invention, benzhydra represented by the formula (II) in the presence of two or more mixed solvents selected from the group consisting of ethylene glycol, dienylene glycol, methanol, ethanol, propanol and water. Zide compounds (hereinafter referred to as starting materials), carbonates and hydroxides are reacted for 1 to 15 hours in the temperature range of 60 ~ 90 ℃, cooled to room temperature after completion of the reaction, filtered and washed to high purity (up to 99% or more), Prepared in high yield (up to 75%).
한편, 본 발명에 사용되는 반응용매는 2개의 히드록시기를 갖는 탄소수 C2∼C4의 글리콜, 탄소수 C1∼C4의 알코올 및 물로 이루어진 군으로 부터 선택된 둘 또는 그 이상의 혼합용매를 사용한다. 상기 2개의 히드록시기를 갖는 탄소수 C2∼C4의 글리콜은 예를 들어, 에틸렌글리콜, 프로필렌글리콜, 부틸렌글리콜, 또는 디에틸렌글리콜 등이 있으며, 상기 C1∼C4의 알코올은 예를 들어, 메탄올, 에탄올, 프로판올 또는 부탄올 등이 있다.On the other hand, the reaction solvent used in the present invention uses two or more mixed solvents selected from the group consisting of C 2 -C 4 glycols, C 1 -C 4 alcohols and water having two hydroxyl groups. Examples of the C 2 -C 4 glycol having two hydroxyl groups include ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, and the like, and the C 1 -C 4 alcohol is, for example, Methanol, ethanol, propanol or butanol and the like.
이와 같은 혼합용매 중에서 에틸렌글리콜을 주용매로 하고, 저급알코올(특히, 메탄올)과 물을 혼합한 혼합용매일 때 가장 바람직한 결과를 얻었다. 즉, 주용매로는 수율, 순도 및 여과의 용이성 등을 고려할 때 에틸렌글리콜이 가장 바람직하였고, 여기에 첨가되는 다른 혼합용매로서 물을 사용하면 염기로 사용되는 탄산염이나 수산화염 등의 제거가 용이해져 순도 및 수율이 다소 향상되었다. 그리고, 또 다른 혼합용매로서 메탄올을 에틸렌글리콜 및 물과 함께 사용하게 되면 수율이 다소 떨어지나 순도가 향상되고, 반응모액의 현탁상태가 좋아져 여과과정이 용이한 잇점이 있다. 그러나 에틸렌글리콜 외에 다른 용매를 지나치게 많이 첨가하면, 반응속도가 떨어질 뿐만 아니라 오히려 부산물이 더 생성되는 역효과가 있으므로 이들의 조성비 조정이 매우 중요하다.The most preferable result was obtained when the mixed solvent which mixed ethylene glycol as a main solvent and lower alcohol (especially methanol) and water among such mixed solvents. In other words, ethylene glycol is most preferred as the main solvent in consideration of yield, purity, and ease of filtration. When water is used as another mixed solvent, it is easy to remove carbonates and hydroxides used as bases. Purity and yield improved somewhat. In addition, when methanol is used together with ethylene glycol and water as another mixed solvent, the yield is somewhat reduced, but the purity is improved, and the suspension state of the reaction mother liquor is improved, thereby facilitating the filtration process. However, if too much solvent other than ethylene glycol is added, not only the reaction rate is lowered, but also the adverse effects of more by-products are generated.
본 발명에 따른 목적화합물(Ⅰ)의 수율, 순도 및 여과과정 등을 종합적으로 검토해 볼 때, 혼합용매의 사용량은 출발물질(Ⅱ)를 기준으로 3∼8배(중량비)가 가장 효과적이고, 다른 혼합용매로서 메탄올 및 물의 첨가량은 에틸렌글리콜 기준으로 각각0∼0.3배(중량비) 및 0∼0.5배(중량비)가 가장 바람직하였다. 좀 더 바람직한 혼합용매의 사용양은 출발물질(Ⅱ)를 기준으로 4∼5배(중량비), 다른 혼합용매로서 매탄올 및 물의 첨가량은 에틸렌글리콜 기준으로 각각 0.05∼0.2배(중량비) 및 0.05∼0.3배(중량비)이다.When comprehensively examining the yield, purity and filtration process of the target compound (I) according to the present invention, the amount of the mixed solvent is 3 to 8 times (weight ratio) based on the starting material (II). As the mixed solvent, the addition amount of methanol and water was most preferably 0 to 0.3 times (weight ratio) and 0 to 0.5 times (weight ratio), respectively, based on ethylene glycol. The more preferable use amount of the mixed solvent is 4 to 5 times (weight ratio) based on the starting material (II), and the addition amount of methanol and water as other mixed solvents is 0.05 to 0.2 times (weight ratio) and 0.05 to 0.3, respectively, based on ethylene glycol. It is a pear (weight ratio).
본 발명에 따르면, 탄산염은 탄산칼륨, 탄산나트륨, 탄산수소칼륨 또는 탄산수소 나트륨 등을 사용할 수 있고, 수산화염으로는 수산화나트륨 또는 수산화 칼륨 등을 사용할 수 있다. 이중에서 탄산염으로는 탄산칼륨이, 수산화염으로는 수산화칼륨이 가장 바람직하다. 이들의 적정한 사용량은 출발물질(Ⅱ)를 기준으로 탄산칼륨 0.3∼1.0배(중량비)이고, 수산화칼륨 0∼0.05배(중량비)이다. 단, 수산화칼륨은 반응 속도에는 영향을 미치나, 반응 결과는 큰 차이가 없었다.According to the present invention, the carbonate may be used potassium carbonate, sodium carbonate, potassium hydrogen carbonate or sodium hydrogen carbonate, and the like, and sodium hydroxide or potassium hydroxide may be used as the hydroxide. Of these, potassium carbonate is most preferred as carbonate, and potassium hydroxide is most preferred as hydroxide. Suitable amounts of these are potassium carbonate 0.3 to 1.0 times (weight ratio) and potassium hydroxide 0 to 0.05 times (weight ratio) based on the starting material (II). However, potassium hydroxide affected the reaction rate, but the reaction result was not significantly different.
본 발명에 있어서, 반응온도는 50℃ 이하에서는 반응이 거의 진행되지 않았고, 140℃ 이상에서는 거의 부반응으로 이어져 목적화합물(Ⅰ)이 얻을 수 없었다. 결론적으로, 60∼90℃ 사이의 반응온도가 가장 바람직한 결과를 나타내었다.In the present invention, the reaction temperature hardly proceeded at the reaction temperature of 50 ° C. or lower, and almost the side reaction was carried out at 140 ° C. or higher, and the target compound (I) could not be obtained. In conclusion, reaction temperatures between 60 and 90 ° C. showed the most desirable results.
이것은 영국특허 제 GB 2,239,241(A)호의 방법에서 언급된 반응온도 120℃ 이상보다 낮은 온도에서의 반응이고, 동시에 주용매인 에틸렌글리콜의 인화점(115℃)보다 훨씬 낮은 온도에서의 반응이므로 안전성이나 공업화 측면에서 볼 때 본 발명의 장점이라 하겠다.This is a reaction at a temperature lower than the reaction temperature of 120 ° C. or higher mentioned in the method of GB 2,239,241 (A), and at the same time a reaction at a temperature much lower than the flash point (115 ° C.) of ethylene glycol as the main solvent. In terms of aspect it will be an advantage of the invention.
반응시간의 경우는 1시간부터 15시간 범위에서 수행 가능하지만, 반응온도나 염기의 사용량 등과 밀접한 관계가 있으므로, 이에 따라 반응시간은 3∼9시간이 가장 바람직하였다.In the case of the reaction time, it can be carried out in the range of 1 hour to 15 hours, but since the reaction time and the amount of base used are closely related, the reaction time is most preferably 3 to 9 hours.
전술한 바와 같이, 용매조성, 염기 사용량, 반응온도, 반응시간 등의 요소를 종합적으로 고려하여 가장 바람직한 반응조건을 설정할 수 있었다.As described above, the most preferable reaction conditions could be set in consideration of factors such as solvent composition, base usage amount, reaction temperature, reaction time, and the like.
본 발명에 따른 목적화합물(Ⅰ)은 불안정한 알데히드기와 아미노기를 동시에 가지고 있으므로 주변 환경에 따라 변질되거나 산화되어 다른 물질로 전환되기 쉬우므로, 고순도로 분리하기가 매우 어려운 문제점이 있다. 그럼에도 불구하고, 본 발명에 따라 설정된 상기 조건에서는 부반응물의 생성이 최소로 억제되므로 그 만큼 분리과정이 용이해지는 장점이 있다. 실제로, 분리과정에 있어서는 추출법과 여과법을 적용하였는데, 반응완료후 상온까지 냉각하여 여과하는 간단한 여과법을 통해 고순도로 목적화합물(Ⅰ)을 안정하게 분리할 수 있었다.Since the target compound (I) according to the present invention has an unstable aldehyde group and an amino group at the same time, since it is easily deteriorated or oxidized depending on the surrounding environment and converted to other substances, there is a problem that it is very difficult to separate with high purity. Nevertheless, in the above conditions set according to the present invention, since the production of side reactions is minimized, there is an advantage in that the separation process becomes easier. In fact, in the separation process, extraction and filtration were applied, and the target compound (I) could be stably separated with high purity through a simple filtration method that was cooled to room temperature and filtered after completion of the reaction.
상술한 바와 같이, 본 발명에서는 적절한 혼합용매를 적용하므로서 상대적으로 반응온도가 낮아지는 등의 반응조건이 순화되어 부반응물 생성이 최소화되었다. 이에 따라, 간편한 여과과정만을 통해 목적화합물(Ⅰ)을 고순도(99% 이상까지), 고수율(75% 까지)로 제조 및 분리하는 방법을 제공하게 되었다.As described above, in the present invention, by applying an appropriate mixed solvent, the reaction conditions such as the lowering of the reaction temperature are reduced to minimize side reactions. Accordingly, a method of preparing and separating the target compound (I) with high purity (up to 99% or more) and high yield (up to 75%) through a simple filtration process has been provided.
이하 실시예를 통하여 본 발명을 좀 더 구체적으로 살펴보지만, 하기예에 본 발명의 범주가 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to the following examples, but the scope of the present invention is not limited to the following examples.
[실시예 1]Example 1
기계적 교반기, 냉각기 및 온도계가 장착된 250㎖ 4구 플라스크에 에틸렌글리콜 90g과 메탄올 8G 및 물 15g을 첨가하여 교반하였다. 그 다음, 탄산칼륨 13g과 수산화칼륨 0.25g 및 출발물질(Ⅱ) 20g을 투입하고 교반하면서 승온하였다. 반응액의 온도를 90℃까지 승온시킨 다음, 70∼80℃를 유지시키면서, 약 5시간 동안 반응시켰다. 반응완료 후 상온까지 냉각시킨 다음, 반응물을 여과하고 다시 물 30g으로 세척하여 상기 목적화합물(Ⅰ) 9.03g을 얻었다. 수득율은 75%, 순도는 99.0%이었다. 순도는 액체크래마토그래피(L/C)로 측정하였다.90 g of ethylene glycol, 8 g of methanol, and 15 g of water were added to a 250 ml four-necked flask equipped with a mechanical stirrer, a cooler, and a thermometer. Then, 13 g of potassium carbonate, 0.25 g of potassium hydroxide, and 20 g of starting material (II) were added thereto, and the temperature was increased while stirring. The temperature of the reaction solution was raised to 90 ° C, and then reacted for about 5 hours while maintaining 70 to 80 ° C. After the reaction was completed and cooled to room temperature, the reaction was filtered and washed again with 30 g of water to obtain 9.03 g of the target compound (I). Yield was 75%, purity 99.0%. Purity was measured by liquid chromatography (L / C).
[실시예 2]Example 2
실시예 1과 동일한 방법으로 반응을 수행하고, 단 에틸렌글리콜 대신에 디에틸렌글리콜을 사용하였다. 그 결과, 수득율은 60%, 순도는 98.5%(L/C)이었다.The reaction was carried out in the same manner as in Example 1, except that diethylene glycol was used instead of ethylene glycol. As a result, the yield was 60% and the purity was 98.5% (L / C).
[실시예 3]Example 3
실시예 1과 동일한 방법으로 반응을 수행하고, 단 혼합용매로서 에틸렌글리콜과 메타올만을 사용하였다. 그 결과, 수득율은 60%, 순도는 99.1%(L/C)이었다.The reaction was carried out in the same manner as in Example 1, except that only ethylene glycol and metaol were used as mixed solvents. As a result, the yield was 60% and the purity was 99.1% (L / C).
[실시예 4]Example 4
실시예 1과 동일한 방법으로 반응을 수행하고, 단 혼합용매로서 에틸렌글리콜과 물만을 사용하였다. 그 결과, 수득율은 68%, 순도는 98.0%(L/C)이었다.The reaction was carried out in the same manner as in Example 1 except that only ethylene glycol and water were used as mixed solvents. As a result, the yield was 68% and the purity was 98.0% (L / C).
[실시예 5]Example 5
실시예 1과 동일한 방법으로 반응을 수행하고, 단 수산화칼륨을 사용하지 않고 반응을 수행하였다. 그 결과, 수득율은 75%, 순도는 99.0%(L/C)이었다.The reaction was carried out in the same manner as in Example 1 except that the reaction was carried out without using potassium hydroxide. As a result, the yield was 75% and the purity was 99.0% (L / C).
[실시예 6]Example 6
실시예 1과 동일한 방법으로 반응을 수행하고, 단 탄산칼륨 대신에 탄산나트륨을 사용하였다. 그 결과, 수득율은 71%, 순도는 98.7%(L/C)이었다.The reaction was carried out in the same manner as in Example 1 except that sodium carbonate was used instead of potassium carbonate. As a result, the yield was 71% and the purity was 98.7% (L / C).
[실시예 7]Example 7
실시예 1과 동일한 방법으로 반응을 수행하고, 단 탄산칼륨 대신에 탄산나트륨, 수산화칼륨 대신에 수산화나트륨을 사용하여 반응을 수행하였다. 그 결과, 수득율은 68%, 순도는 98.4%(L/C)이었다.The reaction was carried out in the same manner as in Example 1 except that sodium carbonate instead of potassium carbonate and sodium hydroxide instead of potassium hydroxide were carried out. As a result, the yield was 68% and the purity was 98.4% (L / C).
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