KR0163344B1 - Process for the preparation of 3-nitro-9-ethyl carbazole - Google Patents
Process for the preparation of 3-nitro-9-ethyl carbazole Download PDFInfo
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- KR0163344B1 KR0163344B1 KR1019960002799A KR19960002799A KR0163344B1 KR 0163344 B1 KR0163344 B1 KR 0163344B1 KR 1019960002799 A KR1019960002799 A KR 1019960002799A KR 19960002799 A KR19960002799 A KR 19960002799A KR 0163344 B1 KR0163344 B1 KR 0163344B1
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/56—Ring systems containing three or more rings
- C07D209/80—[b, c]- or [b, d]-condensed
- C07D209/82—Carbazoles; Hydrogenated carbazoles
- C07D209/88—Carbazoles; Hydrogenated carbazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the ring system
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Abstract
[발명이 해결코저 하는 과제][Problem Solving Invention]
3-니트로-9-에틸카바졸의 제조방법은 영국특허 제65657호에 공개 되어 있는데 이는 하기의 반응식(I)에 나타낸 바와 같이 알반식(II)의 9-에틸카바졸 화합물을 질산과 반응시킬 때 용매로서 클로로벤젠과 같은 불황성용매를 이용하여 합성하고 있다.A process for preparing 3-nitro-9-ethylcarbazole is disclosed in British Patent No. 65657, in which the 9-ethylcarbazole compound of alban formula (II) is reacted with nitric acid, as shown in Scheme (I) below. It is synthesized by using an inert solvent such as chlorobenzene as a solvent.
그러나 상기 방법에서는 반응용매로서 인체에 암을 유발시키는 클로로벤젠을 사용하고 있으며 클로로벤젠을 사용하면 반응생성물의 품위나 최종수율이 반응조건에 따라 편차가 심하여 공업적인 대량생산의 방법으로는 적합치 못한 단점과 폐단이 있다.However, in the above method, chlorobenzene is used as a reaction solvent to cause cancer in the human body. When chlorobenzene is used, the quality or final yield of the reaction product varies widely depending on the reaction conditions, which is not suitable for industrial mass production. There is a dead end.
[과제의 해결방안][Solution Solution]
9-에틸바카졸 화합물을 질산과 반응시킬 때 아세토니트릴을 용매로하여 반응시킴으로서 해결하였음.It was solved by reacting the 9-ethylbaccarzol compound with nitric acid using acetonitrile as a solvent.
Description
본 발명은 특히 아세토니트릴을 반응용매로 사용하여서 3-니트로-9-에틸카바졸을 제조하는 방법에 관한 것이다.The present invention relates in particular to a process for preparing 3-nitro-9-ethylcarbazole using acetonitrile as a reaction solvent.
본 발명의 실시예 의해 제조된 화합물의 구조식은,Structural formula of the compound prepared by the embodiment of the present invention,
와 같은데 R은 알킬기이며 특히 바람직하게는 에틸기이다.R is an alkyl group, and particularly preferably an ethyl group.
상기 구조식으로 표시되는 화합물의 제조방법은 영국 특허 제65657호에 공개되어 있는데 이는 하기의 반응식(I)에 나타낸 바와 같이 일반식(II)의 9-에틸카바졸 화합물을 질산과 반응시킬 때 용매로서 클로로벤젠과 같은 불활성용매를 이용하여 합성하고 있다.A method for preparing a compound represented by the above structural formula is disclosed in British Patent No. 65657, which is used as a solvent when the 9-ethylcarbazole compound of the general formula (II) is reacted with nitric acid, as shown in Scheme (I) below. It is synthesized using an inert solvent such as chlorobenzene.
상기식에서 R은 전술한 바와 동일하다.In which R is the same as described above.
그러나 상기 방법에서는 반응용매로서 인체에 암을 유발시키는 클로로벤젠을 사용하고 있으며 클로로벤젠을 사용하면 반응생성물의 품위나 최종수율이 반응조건에 따라 편차가 심하여 공업적인 대량생산의 방법으로는 적합치 못한 단점과 폐단이 있다.However, in the above method, chlorobenzene is used as a reaction solvent to cause cancer in the human body. When chlorobenzene is used, the quality or final yield of the reaction product varies widely depending on the reaction conditions, which is not suitable for industrial mass production. There is a dead end.
이에 본 발명은 상술한 공지의 제조방법의 단점과 폐단을 해소키 위해 안출된 것으로서 하기 일반식(II)의 에틸카바졸화합물을 아세토니트릴 용매하에서 반응시켜 하기 일반식(I)의 3-니트로-9-에틸카바졸을 얻은 제조방법과 그 화합물을 제공한다.Accordingly, the present invention is designed to solve the disadvantages and disadvantages of the known production method described above, and reacts the ethylcarbazole compound of the following general formula (II) in an acetonitrile solvent to give 3-nitro- of the general formula (I) The preparation method which obtained 9-ethylcarbazole, and its compound are provided.
본 발명에 의한 반응은 아세토니트릴 용매중에서 출발물질(II)과 질산을 실온하에서 3-5시간 반응시킴으로서 이루어지는데 질산은 출발물질(II)에 대하여 1.2당량 이상을 사용하여 반응시킬 수 있으나 약 1.3내지 1.8당량을 사용하는 것이 적당하고 특히 1.5당량이 가장 바람직하다.The reaction according to the present invention is carried out by reacting the starting material (II) with nitric acid in acetonitrile solvent at room temperature for 3-5 hours. The nitric acid can be reacted with the starting material (II) using more than 1.2 equivalents, but it is about 1.3 to 1.8. It is suitable to use the equivalents, in particular 1.5 equivalents most preferred.
여기서 당량이라함은 화학적으로 몰수의 개념을 도입한 것인데 반응몰수에 대한 상대적인 몰수의 비로서 나타낸다.Equivalent here is chemically introduced the concept of moles, expressed as the ratio of the moles to relative moles.
이 개념을 도입함으로써 분자량과 무관한 량으로 표기되는데 출발물질인 9-에틸카바졸 1몰에 대해 질산 1.5몰을 사용하게될 때 이는 에틸카바졸에 대한 질산의 사용량이 1.5당량이 되는 것이다.By introducing this concept, it is expressed in an amount independent of molecular weight. When 1.5 moles of nitric acid is used for 1 mole of 9-ethylcarbazole, the starting material, the amount of nitric acid used for ethyl carbazole is 1.5 equivalents.
질산의 농도는 28-40%가 적당하고 특히 32-36%가 가장 바람직하다.A suitable concentration of nitric acid is 28-40%, most preferably 32-36%.
또한 용매인 아세토니트릴은 다른 용매에 비해 출발물질(II)에 대한 용해성이 크기 때문에 같은 량의 용매로서 더 많은 량의 생성물을 얻을 수 있는 특징이 있다.In addition, acetonitrile, which is a solvent, is more soluble in starting material (II) than other solvents, and thus, a higher amount of product may be obtained as the same amount of solvent.
이하 본 발명의 실시예를 제시한다.Hereinafter, examples of the present invention are presented.
[실시예 1]Example 1
아세토니트릴 40g에 9-에틸카바졸 10g(0.051몰)을 용해시키고 질산 13.45g(36%, 0.076몰)을 섭씨 25-40도를 유지하면서 적가하였다.10 g (0.051 mol) of 9-ethylcarbazole was dissolved in 40 g of acetonitrile, and 13.45 g (36%, 0.076 mol) of nitric acid was added dropwise while maintaining 25-40 degrees Celsius.
적가가 종료되면 섭씨 25-40에서 4시간동안 교반시키고 이를 통해 반응이 완성되면 여과한 후 물에 재분산시켜 세척하고 다시 여과, 건조시켜 11.32g(수율 92%)의 표제화합물을 얻었다.When the addition was completed, the mixture was stirred at 25-40 degrees Celsius for 4 hours, and when the reaction was completed, the resultant was filtered, redispersed in water, washed, filtered and dried again to obtain 11.32 g (yield 92%) of the title compound.
[실시예 2]Example 2
아세토니트릴 40g에 9-에틸카바졸 10g(0.051몰)을 용해시키고 질산 13.45g(36%, 0.076몰)을 섭씨 25-40도를 유지하면서 적가하였다.10 g (0.051 mol) of 9-ethylcarbazole was dissolved in 40 g of acetonitrile, and 13.45 g (36%, 0.076 mol) of nitric acid was added dropwise while maintaining 25-40 degrees Celsius.
적가가 종료되면 섭씨 25-40도에서 4시간동안 교반시키고 이를 통해 반응이 완성되면 물 10-15g을 붓고 10-20분간 재교반하여 여과하고 물에 재분산시켜 세척한 다음 여과, 건조시켜 표제화합물 12.05g(수율 98%)을 얻었다.After completion of the dropwise addition, the mixture was stirred for 4 hours at 25-40 degrees Celsius, and when the reaction was completed, 10-15 g of water was poured, re-stirred for 10-20 minutes, filtered, redispersed in water, washed, filtered, and dried. g (yield 98%) was obtained.
[실시예 3]Example 3
아세토니트릴 40g에 9-에틸카바졸 15g(0.077몰)을 용해시키고 질산 17.48g(36%, 0.10몰)을 섭씨 25-40도를 유지하면서 적가시켰다.15 g (0.077 mol) of 9-ethylcarbazole was dissolved in 40 g of acetonitrile and 17.48 g (36%, 0.10 mol) of nitric acid was added dropwise while maintaining 25-40 degrees Celsius.
적가가 종료되면 실시예 2와 동일한 과정을 거치게하여 결국 18.13g(수율 98.2%)의 표제화합물을 얻었다.When the dropwise addition was completed, the same procedure as in Example 2 was carried out to thereby obtain 18.13 g (yield 98.2%) of the title compound.
[실시예 4]Example 4
아세토니트릴 40g에 9-에틸카바졸 15g(0.077몰)을 용해시키고 질산 17.48g(32%, 0.10몰)을 섭씨 25-40도를 유지하면서 적가시켰다.15 g (0.077 mol) of 9-ethylcarbazole was dissolved in 40 g of acetonitrile and 17.48 g (32%, 0.10 mol) of nitric acid was added dropwise while maintaining 25-40 degrees Celsius.
적가가 종료되면 실시예2와 동일한 과정을 거치게 하여 결국 18.09g(수율 98%)의 표제화합물을 얻었다.When the dropwise addition was completed, the same procedure as in Example 2 was carried out to thereby obtain 18.09 g (yield 98%) of the title compound.
다음 클로로벤젠을 용매로 사용한 공지기술의 실시예를 제시한다.The following is an example of a known technique using chlorobenzene as a solvent.
[비교실시예 1]Comparative Example 1
전술한 영어특허 제65657호의 제조방법에 의하면, 출발물질인 9-에틸카바졸 200g을 클로로벤젠 180g(출발물질에 대해 무게비로 0.9배 사용)에 용해시키고 질산(35.5%) 305g(1.68 당량)을 첨가하여 섭씨 20-28도에서 5시간 이상 반응시킨다.According to the preparation method of English Patent No. 65657, 200 g of 9-ethylcarbazole, a starting material, was dissolved in 180 g of chlorobenzene (0.9 times the weight ratio of starting material), and 305 g (1.68 equivalents) of nitric acid (35.5%) was dissolved. Add and react for at least 5 hours at 20-28 degrees Celsius.
이러한 방법을 통해 얻은 생성물을 섭씨 50-60도에서 건조하여 결국 78-80%의 수율을 갖는 화합물을 얻는다.The product obtained through this method is dried at 50-60 degrees Celsius to eventually give a compound having a yield of 78-80%.
[비교실시예 2]Comparative Example 2
클로로벤젠을 용매로 하여 최상의 조건 즉, 최고의 수율을 얻을 수 있는 조건으로서 클로로벤젠 2Kg(출발물질에 대해 무게비로 12배 사용)에 출발물질인 9-에틸카바졸 168.19g을 넣고 용해시킨 후 36% 질산용액 265g(1.76 당량)을 강한 교반과 더불어 적가시킨다.Using chlorobenzene as a solvent, the best condition, that is, the best yield, was obtained by dissolving 168.19 g of 9-ethylcarbazole as the starting material in 2Kg of chlorobenzene (12 times the weight ratio of starting material). 265 g (1.76 equiv) of nitric acid solution is added dropwise with vigorous stirring.
실온에서 약 5시간동안 강하게 교반시켜 반응을 완료하고 산기를 제거하기 위해 물을 채워 교반하고 침전시켜 유기충만 분리한다.The mixture is stirred vigorously at room temperature for about 5 hours to complete the reaction and the organics are separated by stirring with water to precipitate an acid to remove the acid groups.
이러한 공정을 수 차례 거쳐 완전히 산기를 제거시킨다.This process is followed several times to completely remove the acid.
위 유기층을 감압하에 가열하여 클로로벤젠을 증류회수하여 91.8%의 생성물을 얻을 수 있었다.The organic layer was heated under reduced pressure, and chlorobenzene was distilled off to obtain 91.8% of product.
이상의 비교실시예 1에서의 결과는 용매인 클로롤벤젠의 량이 반응물에 비해 상당히 적어 반응시 3-니트로-9-에틸카바졸이 석출되어 교반이 불가능하고 후처리가 곤란해지는 단점이 있다.As a result of Comparative Example 1, the amount of chlorolbenzene, which is a solvent, is considerably less than that of the reactant, so that 3-nitro-9-ethylcarbazole precipitates during the reaction, making stirring impossible and post-treatment difficult.
그리고 비교실시예 2에서의 결과는 용매량이 4배이상 소요되고 질산의 량도 더 많이 소요되어 결국 본 발명의 실시예에서의 결과보다 상당히 불량한 결과가 도출되었다.In addition, the results in Comparative Example 2 required more than four times the amount of solvent and more amount of nitric acid, which resulted in significantly worse results than in the Examples of the present invention.
이상의 실시예와 비교실시예에서의 결과는 다음과 같다.The results in the above Examples and Comparative Examples are as follows.
반응시에 물에 녹아있는 질산은 반응에 첨가되었을 때, 아세토니트릴은 물과 자유롭게 혼화되지만 클로로벤젠은 물에 전혀 녹지도 혼화되지도 않으므로 결국 2액반응이 이루어져야 한다.When nitric acid dissolved in water is added to the reaction, acetonitrile is freely mixed with water, but chlorobenzene is not dissolved or miscible in water.
따라서 반응이 교반의 효과가 영향을 끼치게 되는데 클로로벤젠의 경우 강한 교반력이 수반되어야 하는 문제가 있었다.Therefore, the reaction affects the effect of stirring, in the case of chlorobenzene had a problem that must be accompanied by a strong stirring force.
그러나 아세토니트릴에서는 교반의 영향과 무관하게 결과가 거의 일정하다.However, in acetonitrile, the results are almost constant regardless of the effects of agitation.
또한 용제회수시 클로로벤젠은 생성물이 녹아 있는 상태로 반응기내에서 용제회수가 일어나므로 이 역시 수율에 영향을 미치게 되는 것이다.In addition, chlorobenzene during solvent recovery, so that the solvent recovery in the reactor in the state that the product is dissolved, this also affects the yield.
그러나 아세토니트릴의 경우 생성물이 용제에 대한 용해성이 거의 없기 때문에 용제회수를 분리해서 실시함으로써 생성물의 수율이나 품질에 거의 영향을 끼치지 않는 것이다.However, in the case of acetonitrile, since the product has little solubility in the solvent, the recovery of the solvent is performed separately so that the yield and quality of the product are hardly affected.
아세토니트릴의 용해성이 우수한 이유와 근거로서는, 유전율과 극성모멘트의 값이 클로로벤젠(ε=5.62, μ=1.69 debye)에 비해 아세토니트릴(ε=36.2, μ=3.92 debye)이 휠씬 크므로 여러 극성유기물질에 대한 용해성이 크게 되고 용제로서 더 작합한 것이다.The reason for the excellent solubility of acetonitrile and the grounds are that acetonitrile (ε = 36.2, μ = 3.92 debye) is much larger than that of chlorobenzene (ε = 5.62, μ = 1.69 debye). It is more soluble in organic matter and more suitable as a solvent.
즉, 유전율과 극성모멘트의 값이 크다는 의미는 용제의 극성이 크다는 것을 의미하고 용제의 극성이 클수록 극성물질에 대한 용해도는 증가하기 때문이다.In other words, the large value of dielectric constant and polar moment means that the polarity of the solvent is large and the solubility of the polar material increases as the polarity of the solvent increases.
따라서 본 발명의 아세토니트릴은 표제의 화합물을 얻는데 가장 바람직한 용매인 것이다.Thus, the acetonitrile of the present invention is the most preferred solvent for obtaining the title compound.
본 발명의 제조방법은 아세토니트릴은 사용함으로써 출발물질에 대한 용해성이 크기 때문에 같은 용량으로 종래의 방법보다 더 많은 량의 생성물을 얻을 수 있는 특징이 있으며 낮은 용점(아세토니트릴=섭씨 81.6도, 클로로벤젠=섭씨 132도)을 가지는 특성으로 인해 용제회수시 에너지소비가 적고 용제회수가 주반응기에서 분리되어 실시되므로 회수율이 높은 장점이 있다.Since the acetonitrile has a high solubility in starting materials by using acetonitrile, the production method of the present invention has a feature that a higher amount of the product can be obtained at the same capacity than the conventional method. = 132 degrees Celsius) has the advantage of high recovery rate because the energy consumption during solvent recovery is low and solvent recovery is performed separately from the main reactor.
그러므로 전체의 공정이 단축되는 경제적인 효과가 수반되는 것이다.Therefore, the economic effect of shortening the whole process is accompanied.
또한 아세토니트릴은 반응시 교반과 전혀 무관하여 일정한 품질과 고품위의 질을 유지하는 생서물을 얻을 수 있는 효과가 있으며 질산의 사용량은 반응물에 대해 1.8당량에서 1.5당량으로 감소시킬 수 있음으로서 산폐수에 대한 부담이 크게 줄어드는 효과가 있어 유용하며 반응수율이 높기 때문에 경제성이 매우 양호한 등의 특징을 갖는 것이다.In addition, acetonitrile has no effect on agitation, and thus it has the effect of obtaining raw materials that maintain a constant quality and high quality, and the amount of nitric acid can be reduced from 1.8 equivalents to 1.5 equivalents to the wastewater. It is useful because the effect on the burden is greatly reduced, and the economical efficiency is very high because the reaction yield is high.
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| KR1019960002799A KR0163344B1 (en) | 1996-02-02 | 1996-02-02 | Process for the preparation of 3-nitro-9-ethyl carbazole |
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| KR1019960002799A KR0163344B1 (en) | 1996-02-02 | 1996-02-02 | Process for the preparation of 3-nitro-9-ethyl carbazole |
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| KR0163344B1 true KR0163344B1 (en) | 1998-12-01 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103254117A (en) * | 2013-05-27 | 2013-08-21 | 南通龙翔化工有限公司 | Method for extracting nitration product from N-ethyl carbazole nitration solvent distillation residue |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| DE19705466A1 (en) * | 1997-02-13 | 1998-08-20 | Clariant Gmbh | Process for the preparation of N-alkylcarbazoles |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103254117A (en) * | 2013-05-27 | 2013-08-21 | 南通龙翔化工有限公司 | Method for extracting nitration product from N-ethyl carbazole nitration solvent distillation residue |
| CN103254117B (en) * | 2013-05-27 | 2016-03-09 | 南通龙翔化工有限公司 | A kind of method extracting nitration product from the nitrated solvent distillation residue of N-ethyl carbazole |
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