JP2012184175A - Method for producing high-purity 3-acetyl-9-ethylcarbazole - Google Patents
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Abstract
Description
本発明は、染料や、電子材料、医農薬中間体として有用な高純度３−アセチル−９−エチルカルバゾールの工業的製造方法を提供する。 The present invention provides an industrial process for producing high-purity 3-acetyl-9-ethylcarbazole useful as a dye, an electronic material, and an intermediate for medical and agricultural chemicals.
カルバゾール類は近年、染料や、電子材料、医農薬中間体として、脚光を浴びている化合物群である。そのうちの一つ、３−アセチル−９−エチルカルバゾールも同様に、染料や、電子材料、医農薬中間体等の原料として期待される化合物である。 Carbazoles are a group of compounds that have recently attracted attention as dyes, electronic materials, and intermediates for medicines and agricultural chemicals. One of them, 3-acetyl-9-ethylcarbazole, is also a compound that is expected as a raw material for dyes, electronic materials, pharmaceutical and agrochemical intermediates, and the like.
３―アセチル−９−エチルカルバゾールは、９−エチルカルバゾールをアセチル化することによって得られるが、染料や電子材料、医農薬中間体等に使用するためには、アセチル化時の副生成物等を効果的に除去し、当該化合物を高純度化することが必須である。しかしながら、既知の高純度３−アセチル−９−エチルカルバゾールの製造法は工業的に適用困難なシリカゲルカラムクロマトグラフィーを用いた精製によるものが知られているだけである（例えば非特許文献１、２）。よって、３−アセチル−９−エチルカルバゾールを染料や、電子材料、医農薬中間体等の原料として工業的規模で使用するために、シリカゲルカラムクロマトグラフィー以外の、工業的に適用可能な高純度３−アセチル−９−エチルカルバゾールの製造方法が求められていた。
本発明が解決しようとする課題は、これら従来技術の欠点を解決し、工業的に利用可能な高純度３−アセチル−９−エチルカルバゾールの製造法を提供することにある。 The problem to be solved by the present invention is to solve the drawbacks of these conventional techniques and to provide a process for producing industrially available high purity 3-acetyl-9-ethylcarbazole.
本発明者らは、前記課題を解決すべく高純度３−アセチル−９−エチルカルバゾールの製造法について、晶析による精製に着眼し様々な有機溶媒による晶析を検討した結果、エステル系溶媒を用いれば特異的に粗３−アセチル−９−エチルカルバゾールの結晶化が可能であることを発見すると同時に、工業的に利用可能な３−アセチル−９−エチルカルバゾールの晶析による精製法を完成させ、さらには、既知のシリカゲルカラムクロマトグラフィーによる精製と同程度、あるいはそれ以上の収率と品質で高純度３−アセチル−９−エチルカルバゾールが製造可能であることを見いだし、本発明を完成するに至った。 In order to solve the above-mentioned problems, the inventors of the present invention have focused on purification by crystallization and studied crystallization with various organic solvents as a method for producing high-purity 3-acetyl-9-ethylcarbazole. When used, it was discovered that it was possible to crystallize crude 3-acetyl-9-ethylcarbazole specifically, and at the same time, a commercially available purification method by crystallization of 3-acetyl-9-ethylcarbazole was completed. Furthermore, the inventors have found that high-purity 3-acetyl-9-ethylcarbazole can be produced in a yield and quality equivalent to or higher than that of purification by known silica gel column chromatography, and the present invention is completed. It came.
本発明は、高純度３−アセチル−９−エチルカルバゾールの工業的に適用可能で、かつ簡便な製造方法を提供する。 The present invention provides an industrially applicable and simple production method for high-purity 3-acetyl-9-ethylcarbazole.
本発明で使用される粗３−アセチル−９−エチルカルバゾールは９−エチルカルバゾールがアセチル化剤を用いてアセチル化されたものであればどのようなものでも良い。アセチル化剤としては塩化アセチル、無水酢酸等が例示されるが、アセチル化反応の選択性を考慮すれば塩化アセチルが好ましい。 The crude 3-acetyl-9-ethylcarbazole used in the present invention may be any as long as 9-ethylcarbazole is acetylated using an acetylating agent. Examples of the acetylating agent include acetyl chloride and acetic anhydride, but acetyl chloride is preferred in view of the selectivity of the acetylation reaction.
本発明において使用される炭素数３〜６のエステル系溶媒は、酢酸メチル、酢酸エチル、酢酸ｎ−プロピル、酢酸ｉｓｏ−プロピル、酢酸ｎ−ブチル、酢酸ｉｓｏ−ブチル、酢酸ｔｅｒｔ-ブチル、酢酸ｓｅｃ-ブチル等の酢酸エステル類、プロピオン酸メチル、プロピオン酸エチル、プロピオン酸プロピル等のプロピオン酸エステル類、酪酸メチル、酪酸エチル等の酪酸エステル類等が例示される。これらの内、工業的に入手し易く、かつ安価な酢酸エステル類が好ましく、この中でも酢酸エチル、酢酸ｎ−プロピル、酢酸ｉｓｏ−プロピル、酢酸ｎ−ブチル、酢酸ｉｓｏ−ブチル、酢酸ｔｅｒｔ-ブチル、酢酸ｓｅｃ-ブチルが更に好ましい。 The ester solvent having 3 to 6 carbon atoms used in the present invention is methyl acetate, ethyl acetate, n-propyl acetate, iso-propyl acetate, n-butyl acetate, iso-butyl acetate, tert-butyl acetate, sec-acetate. Examples include acetate esters such as butyl, propionate esters such as methyl propionate, ethyl propionate, and propyl propionate, butyrate esters such as methyl butyrate and ethyl butyrate. Of these, industrially easily available and inexpensive acetates are preferable, among which ethyl acetate, n-propyl acetate, iso-propyl acetate, n-butyl acetate, iso-butyl acetate, tert-butyl acetate, More preferred is sec-butyl acetate.
本発明において使用される溶媒の使用量は、３−アセチル−９−エチルカルバゾールの使用する溶媒に対する溶解度によって適宜選択され、限定されないが、好ましくは３−アセチル−９−エチルカルバゾールに対し２〜１５重量倍、更に好ましくは２〜７重量倍使用される。 The amount of the solvent used in the present invention is appropriately selected depending on the solubility of 3-acetyl-9-ethylcarbazole in the solvent used, and is not limited, but is preferably 2-15 with respect to 3-acetyl-9-ethylcarbazole. The weight is used, more preferably 2 to 7 times.
本発明において実施される晶析の温度は、使用する溶媒により適宜選択され、限定されない。所望の３−アセチル−９−エチルカルバゾールの収量や純度に合わせ当業者であれば適宜選択可能である。 The temperature of crystallization carried out in the present invention is appropriately selected depending on the solvent used and is not limited. A person skilled in the art can select appropriately according to the yield and purity of the desired 3-acetyl-9-ethylcarbazole.
本発明により製造される高純度３−アセチル−９−エチルカルバゾールの純度は最低９０％以上であれば、染料や電子材料、医農薬中間体の原料として使用可能である。さらには、これらの原料として９５％以上の純度であることが好ましい。また、適宜、必要に応じ、本発明の晶析を複数回繰り返し、更に高純度にすることも可能であり、本願発明において、純度の上限値は１００％も含まれる。なお、本願発明でいう純度とは、後述の条件で分析した高速液体クロマトグラフィー法による面積百分率値を示す。 If the purity of the high purity 3-acetyl-9-ethylcarbazole produced by the present invention is at least 90% or more, it can be used as a raw material for dyes, electronic materials, and pharmaceutical and agrochemical intermediates. Furthermore, it is preferable that these materials have a purity of 95% or more. Further, if necessary, the crystallization of the present invention can be repeated a plurality of times to further increase the purity. In the present invention, the upper limit of purity is 100%. In addition, the purity as used in this invention shows the area percentage value by the high performance liquid chromatography method analyzed on the conditions mentioned later.
以下、本発明を実施例によりさらに詳細に説明するが、本発明は以下の実施例に限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to a following example.
＜分析条件＞
展開液：水／アセトニトリル、逆相カラム（（株）住化分析センター社製 ＳＵＭＩＰＡＸ ＯＤＳ Ａ−２１２（５μｍ、６．０ｍｍφ×１５０ｍｍ））、カラム温度：４０℃、流量１．０ｍＬ／ｍｉｎを使用した高速液体クロマトグラフ（島津製作所（株）製ＬＣ−２０１０Ｃ）を用い、２４０ｎｍの波長で測定した。なお、特に断りのない限り、以下実施例等に記載の純度は、本条件で分析した高速液体クロマトグラフィーによる面積百分率値を示す。
<Analysis conditions>
Developing solution: water / acetonitrile, reverse phase column (SUMIPAX ODS A-212 (5 μm, 6.0 mmφ × 150 mm) manufactured by Sumika Chemical Analysis Co., Ltd.), column temperature: 40 ° C., flow rate 1.0 mL / min Measured using a high performance liquid chromatograph (LC-2010C, manufactured by Shimadzu Corporation) at a wavelength of 240 nm. Unless otherwise specified, the purity described in the examples and the like below indicates an area percentage value by high performance liquid chromatography analyzed under these conditions.
＜製造例１＞
３００ｍＬの４つ口フラスコに、エチルカルバゾール１０．００ｇ（０．０５ｍｏｌ）、塩化亜鉛８．３８ｇ（０．０６ｍｏｌ）、ニトロベンゼン２００．００ｇを仕込み、攪拌を開始した。攪拌しながら室温で塩化アセチル４．８２ｇ（０．０６ｍｏｌ）を１０分かけて滴下を行い、その後室温で４時間攪拌を行った。その後、得られた反応マスを定法により酸洗浄、中和、水洗を行った後、有機層を濃縮し、粗３−アセチル−９−エチルカルバゾール１２．０７ｇ（０．０５ｍｏｌ）を得た。この粗３−アセチル−９−エチルカルバゾールを高速液体クロマトグラフィーにて分析を行ったところ、純度９４．１％であった。
<Production Example 1>
A 300 mL four-necked flask was charged with 10.00 g (0.05 mol) of ethylcarbazole, 8.38 g (0.06 mol) of zinc chloride and 200.00 g of nitrobenzene, and stirring was started. While stirring, 4.82 g (0.06 mol) of acetyl chloride was added dropwise at room temperature over 10 minutes, and then stirred at room temperature for 4 hours. Thereafter, the obtained reaction mass was subjected to acid washing, neutralization, and water washing by a conventional method, and then the organic layer was concentrated to obtain 12.07 g (0.05 mol) of crude 3-acetyl-9-ethylcarbazole. When this crude 3-acetyl-9-ethylcarbazole was analyzed by high performance liquid chromatography, the purity was 94.1%.
＜製造例２＞
３００ｍＬの４つ口フラスコに、エチルカルバゾール１０．００ｇ（０．０５ｍｏｌ）、塩化鉄９．９８ｇ（０．０６ｍｏｌ）、ニトロベンゼン１００．００ｇを仕込み、攪拌を開始した。攪拌しながら室温で塩化アセチル４．８２ｇ（０．０６ｍｏｌ）を１０分かけて滴下を行い、その後室温で２時間攪拌を行った。その後、得られた反応マスを定法により酸洗浄、中和、水洗を行い、有機層を濃縮し、粗３−アセチル−９−エチルカルバゾール１２．４６ｇ（０．０５ｍｏｌ）を得た。この粗３−アセチル−９−エチルカルバゾールを高速液体クロマトグラフィーにて分析を行ったところ、純度８７．５％であった。
<Production Example 2>
A 300 mL four-necked flask was charged with 10.00 g (0.05 mol) of ethylcarbazole, 9.98 g (0.06 mol) of iron chloride and 100.00 g of nitrobenzene, and stirring was started. While stirring, 4.82 g (0.06 mol) of acetyl chloride was added dropwise at room temperature over 10 minutes, and then stirred at room temperature for 2 hours. Thereafter, the obtained reaction mass was subjected to acid washing, neutralization and water washing by a conventional method, and the organic layer was concentrated to obtain 12.46 g (0.05 mol) of crude 3-acetyl-9-ethylcarbazole. When this crude 3-acetyl-9-ethylcarbazole was analyzed by high performance liquid chromatography, the purity was 87.5%.
以下実施例及び比較例、参考例に記載する重量倍は特に断りのない限り、粗３−アセチル−９−エチルカルバゾールに対する重量倍である。また、精製収率は下式にて算出した有姿収率である。
（精製後３−アセチル−９−エチルカルバゾール（ｇ））／（粗３−アセチル−９−エチルカルバゾール（ｇ））×１００
Hereinafter, the weight times described in Examples, Comparative Examples, and Reference Examples are weight times with respect to crude 3-acetyl-9-ethylcarbazole unless otherwise specified. The purification yield is a solid yield calculated by the following formula.
(After purification 3-acetyl-9-ethylcarbazole (g)) / (crude 3-acetyl-9-ethylcarbazole (g)) × 100
（実施例１）
２００ｍＬの４つ口フラスコに、製造例１で得られた粗３−アセチル−９−エチルカルバゾール１２．０７ｇ（純度９４．１％）、酢酸エチル６０．００ｇ（５．０重量倍）を仕込み、６５℃まで昇温した。昇温後、同温度で１時間攪拌し３−アセチル−９−エチルカルバゾールが完溶したことを確認した後、３℃まで冷却後ろ過し、さらに同温度まで冷却した酢酸エチル１１．２０ｇで洗浄を行った。その後、得られた結晶を減圧乾燥したところ、３−アセチル−９−エチルカルバゾール９．０６ｇ（精製収率７５．１％）を得た。得られた３−アセチル−９−エチルカルバゾールを高速液体クロマトグラフィーにて分析を行ったところ、純度９９．３％であった。
Example 1
A 200 mL four-necked flask was charged with 12.07 g (purity 94.1%) of crude 3-acetyl-9-ethylcarbazole obtained in Production Example 1, and 60.00 g (5.0 times by weight) of ethyl acetate. The temperature was raised to 65 ° C. After heating, the mixture was stirred at the same temperature for 1 hour to confirm that 3-acetyl-9-ethylcarbazole was completely dissolved, cooled to 3 ° C., filtered, and further washed with 11.20 g of ethyl acetate cooled to the same temperature. Went. Then, when the obtained crystal was dried under reduced pressure, 9.06 g (purification yield 75.1%) of 3-acetyl-9-ethylcarbazole was obtained. When the obtained 3-acetyl-9-ethylcarbazole was analyzed by high performance liquid chromatography, the purity was 99.3%.
エチルカルバゾールの仕込量を１０．００ｇから３０．００ｇとした以外は製造例１と同様の仕込比率、反応方法で粗３−アセチル−９−エチルカルバゾールの合成を行ったところ、粗３−アセチル−９−エチルカルバゾールを４１．２７ｇ（純度９４．０％）得た。３００ｍＬの４つ口フラスコにこの粗３−アセチル−９−エチルカルバゾール全量と酢酸エチル１２３．８０ｇ（３．０重量倍）を仕込、６５℃まで昇温した。昇温後、同温度で１時間攪拌し３−アセチル−９−エチルカルバゾールが完溶したことを確認した。０℃まで冷却後ろ過し、さらに同温度まで冷却した酢酸エチル３０．９０ｇで洗浄を行った。その後、得られた結晶を減圧乾燥したところ、３−アセチル−９−エチルカルバゾール３０．１３ｇ（精製収率７３．０％）を得た。得られた３−アセチル−９−エチルカルバゾールを高速液体クロマトグラフィーにて分析を行ったところ、純度９９．４％であった。 Crude 3-acetyl-9-ethylcarbazole was synthesized by the same charge ratio and reaction method as in Production Example 1 except that the amount of ethylcarbazole was changed from 10.00 g to 30.00 g. 41.27 g (purity 94.0%) of 9-ethylcarbazole was obtained. A 300 mL four-necked flask was charged with the entire amount of crude 3-acetyl-9-ethylcarbazole and 123.80 g (3.0 times by weight) of ethyl acetate, and the temperature was raised to 65 ° C. After raising the temperature, the mixture was stirred at the same temperature for 1 hour, and it was confirmed that 3-acetyl-9-ethylcarbazole was completely dissolved. After cooling to 0 ° C., the mixture was filtered, and further washed with 30.90 g of ethyl acetate cooled to the same temperature. Then, when the obtained crystal | crystallization was dried under reduced pressure, 3-acetyl-9-ethylcarbazole 30.13g (purification yield 73.0%) was obtained. When the obtained 3-acetyl-9-ethylcarbazole was analyzed by high performance liquid chromatography, the purity was 99.4%.
（実施例３）
２００ｍＬの４つ口フラスコに、製造例２で得られた粗３−アセチル−９−エチルカルバゾール１２．４６ｇ（純度８７．５％）、酢酸ｎ−ブチル３７．００ｇ（３．０重量倍）を仕込み、７０℃まで昇温した。昇温後、同温度で１時間攪拌し３−アセチル−９−エチルカルバゾールが完溶したことを確認し、３℃まで冷却後ろ過し、さらに同温度まで冷却した酢酸ｎ−ブチル１２．００ｇで洗浄を行った。その後、得られた結晶を減圧乾燥したところ、３−アセチル−９−エチルカルバゾール８．１２ｇ（精製収率６５．５％）を得た。得られた３−アセチル−９−エチルカルバゾールを高速液体クロマトグラフィーにて分析を行ったところ、純度９５．２％であった。
(Example 3)
In a 200 mL four-necked flask, 12.46 g (purity: 87.5%) of the crude 3-acetyl-9-ethylcarbazole obtained in Production Example 2 and 37.00 g (3.0 times by weight) of n-butyl acetate were added. The temperature was raised to 70 ° C. After heating, the mixture was stirred at the same temperature for 1 hour to confirm that 3-acetyl-9-ethylcarbazole was completely dissolved, cooled to 3 ° C., filtered, and further cooled to the same temperature with 12.00 g of n-butyl acetate. Washing was performed. Then, when the obtained crystal was dried under reduced pressure, 8.12 g (purification yield 65.5%) of 3-acetyl-9-ethylcarbazole was obtained. When the obtained 3-acetyl-9-ethylcarbazole was analyzed by high performance liquid chromatography, the purity was 95.2%.
（実施例４）
製造例２と同様の方法で粗３−アセチル−９−エチルカルバゾールの合成を行ったところ、粗３−アセチル−９−エチルカルバゾールを１２．６３ｇ（純度８７．９％）得た。２００ｍＬの４つ口フラスコに、この粗３−アセチル−９−エチルカルバゾール全量と、酢酸ｉｓｏ―ブチル８５．００ｇ（６．７重量倍）を仕込み、９０℃まで昇温した。昇温後、同温度で１時間攪拌し３−アセチル−９−エチルカルバゾールが完溶したことを確認した。３℃まで冷却後ろ過し、さらに同温度まで冷却した酢酸ｉｓｏ―ブチル１１．５０ｇで洗浄を行った。その後、得られた結晶を減圧乾燥したところ、３−アセチル−９−エチルカルバゾール７．１８ｇ（精製収率５６．８％）を得た。得られた３−アセチル−９−エチルカルバゾールを高速液体クロマトグラフィーにて分析を行ったところ、純度９８．３％であった。
Example 4
When crude 3-acetyl-9-ethylcarbazole was synthesized in the same manner as in Production Example 2, 12.63 g (purity 87.9%) of crude 3-acetyl-9-ethylcarbazole was obtained. A 200 mL four-necked flask was charged with the whole amount of the crude 3-acetyl-9-ethylcarbazole and 85.00 g (6.7 times by weight) of iso-butyl acetate, and the temperature was raised to 90 ° C. After raising the temperature, the mixture was stirred at the same temperature for 1 hour, and it was confirmed that 3-acetyl-9-ethylcarbazole was completely dissolved. After cooling to 3 ° C., the mixture was filtered, and further washed with 11.50 g of iso-butyl acetate cooled to the same temperature. Then, when the obtained crystal was dried under reduced pressure, 7.18 g (purification yield 56.8%) of 3-acetyl-9-ethylcarbazole was obtained. When the obtained 3-acetyl-9-ethylcarbazole was analyzed by high performance liquid chromatography, the purity was 98.3%.
（比較例１）
製造例１と同様の方法で粗３−アセチル−９−エチルカルバゾールの合成を行った所、粗３−アセチル−９−エチルカルバゾールを１２．０１ｇ（純度９３．９％）得た。２００ｍＬの４つ口フラスコにこの粗３−アセチル−９−エチルカルバゾール全量とメタノール５０．００ｇ（４．２重量倍）を仕込み、６０℃まで昇温した。昇温後、同温度で１時間攪拌し３−アセチル−９−エチルカルバゾールが完溶したことを確認した。この溶液を３℃まで冷却したが、冷却中反応マスが２層分離し、結晶は析出しなかった。
(Comparative Example 1)
When crude 3-acetyl-9-ethylcarbazole was synthesized in the same manner as in Production Example 1, 12.01 g (purity 93.9%) of crude 3-acetyl-9-ethylcarbazole was obtained. A 200 mL four-necked flask was charged with the whole amount of crude 3-acetyl-9-ethylcarbazole and 50.00 g (4.2 times by weight) of methanol, and the temperature was raised to 60 ° C. After raising the temperature, the mixture was stirred at the same temperature for 1 hour, and it was confirmed that 3-acetyl-9-ethylcarbazole was completely dissolved. This solution was cooled to 3 ° C., but during the cooling, the reaction mass separated into two layers, and crystals did not precipitate.
（比較例２）
製造例１と同様の方法で粗３−アセチル−９−エチルカルバゾールの合成を行ったところ、粗３−アセチル−９−エチルカルバゾールを１２．１１ｇ（純度９４．２％）を得た。２００ｍＬの４つ口フラスコにこの粗３−アセチル−９−エチルカルバゾール全量とトルエン３０．００ｇ（２．５重量倍）を仕込み、８０℃まで昇温した。昇温後、同温度で１時間攪拌し３−アセチル−９−エチルカルバゾールが完溶したことを確認した。この溶液を３℃まで冷却したが、反応マスが白濁するだけで結晶の析出は認められなかった。
(Comparative Example 2)
When crude 3-acetyl-9-ethylcarbazole was synthesized in the same manner as in Production Example 1, 12.11 g (purity 94.2%) of crude 3-acetyl-9-ethylcarbazole was obtained. A 200 mL four-necked flask was charged with the whole amount of crude 3-acetyl-9-ethylcarbazole and 30.00 g (2.5 times by weight) of toluene, and the temperature was raised to 80 ° C. After raising the temperature, the mixture was stirred at the same temperature for 1 hour, and it was confirmed that 3-acetyl-9-ethylcarbazole was completely dissolved. Although this solution was cooled to 3 ° C., no precipitation of crystals was observed because the reaction mass only became cloudy.
（比較例３）
製造例２と同様の方法で粗３−アセチル−９−エチルカルバゾールの合成を行ったところ、粗３−アセチル−９−エチルカルバゾール１２．６７ｇ（純度８９．０％）を得た。２００ｍＬの４つ口フラスコにこの粗３−アセチル−９−エチルカルバゾール全量とアセトン８５．０ｇ（６．７重量倍）を仕込み、５０℃まで昇温した。昇温後、同温度で１時間攪拌し、３−アセチル−９−エチルカルバゾールが完溶したことを確認した。この溶液を５℃まで冷却したが結晶が殆ど析出しない為、さらに上水４０．０ｇ（３．２重量倍）を仕込み、再度５０℃まで昇温、同温度で１時間攪拌後、３−アセチル−９−エチルカルバゾール完溶したことを確認し、この溶液を５℃まで冷却後ろ過した。結晶量が少なかった為、洗浄を行うことなく得られた結晶を減圧乾燥したところ、３−アセチル−９−エチルカルバゾール０．９１ｇ（精製収率７．２％）を得た。得られた３−アセチル−９−エチルカルバゾールを高速液体クロマトグラフィーにて分析を行ったところ、純度８４．２％であった。
(Comparative Example 3)
Crude 3-acetyl-9-ethylcarbazole was synthesized in the same manner as in Production Example 2 to obtain 12.67 g (purity 89.0%) of crude 3-acetyl-9-ethylcarbazole. A 200 mL four-necked flask was charged with the whole amount of crude 3-acetyl-9-ethylcarbazole and 85.0 g (6.7 times by weight) of acetone, and the temperature was raised to 50 ° C. After heating, the mixture was stirred at the same temperature for 1 hour, and it was confirmed that 3-acetyl-9-ethylcarbazole was completely dissolved. This solution was cooled to 5 ° C, but almost no crystals were precipitated. Therefore, 40.0 g of clean water (3.2 times by weight) was further added, the temperature was raised again to 50 ° C, and stirred for 1 hour at the same temperature. After confirming that -9-ethylcarbazole was completely dissolved, the solution was cooled to 5 ° C and filtered. Since the amount of crystals was small, the crystals obtained without washing were dried under reduced pressure to obtain 0.91 g of 3-acetyl-9-ethylcarbazole (purification yield 7.2%). When the obtained 3-acetyl-9-ethylcarbazole was analyzed by high performance liquid chromatography, the purity was 84.2%.
（参考例）
製造例２と同様の方法で粗３−アセチル−９−エチルカルバゾールの合成を行ったところ、粗３−アセチル−９−エチルカルバゾール１２．３９ｇ（純度８９．２％）を得た。このうち０．６０ｇを取り、和光純薬工業社製シリカゲル、ワコーゲル（登録商標）Ｃ３００を充填したシリカゲルカラムクロマトグラフィー（展開液：酢酸エチル：石油エーテル＝１：９）にて精製したところ、３−アセチル−９−エチルカルバゾール０．３５ｇ（精製収率５８．３％）を得た。得られた３−アセチル−９−エチルカルバゾールを高速液体クロマトグラフィーにて分析を行ったところ、純度９８．１％であった。
(Reference example)
Crude 3-acetyl-9-ethylcarbazole was synthesized in the same manner as in Production Example 2 to obtain 12.39 g (purity 89.2%) of crude 3-acetyl-9-ethylcarbazole. 0.60 g of this was taken and purified by silica gel column chromatography (developing solution: ethyl acetate: petroleum ether = 1: 9) packed with silica gel manufactured by Wako Pure Chemical Industries, Ltd. and Wakogel (registered trademark) C300. There was obtained 0.35 g of acetyl-9-ethylcarbazole (purification yield: 58.3%). When the obtained 3-acetyl-9-ethylcarbazole was analyzed by high performance liquid chromatography, the purity was 98.1%.
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