JPH0672146B2 - Method for producing dioxazine compound - Google Patents
Method for producing dioxazine compoundInfo
- Publication number
- JPH0672146B2 JPH0672146B2 JP3610486A JP3610486A JPH0672146B2 JP H0672146 B2 JPH0672146 B2 JP H0672146B2 JP 3610486 A JP3610486 A JP 3610486A JP 3610486 A JP3610486 A JP 3610486A JP H0672146 B2 JPH0672146 B2 JP H0672146B2
- Authority
- JP
- Japan
- Prior art keywords
- parts
- compound
- dichlorobenzene
- added
- washing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
Description
【発明の詳細な説明】 ＜産業上の利用分野＞ 本発明は染顔料ほか機能性色素として用いられるジオキ
サジン化合物の改良された製造法に関する。DETAILED DESCRIPTION OF THE INVENTION <Field of Industrial Application> The present invention relates to an improved method for producing a dioxazine compound used as a functional dye, as well as a dye and pigment.
＜従来の技術＞ 従来、一般式（II） （式中、ＲはC1−C4のアルキル基を表わす） で示される化合物を閉環して、ジオキサジン化合物を得
る方法としては、酸化剤としてベンゼンスルホニルクロ
リドを用いて酸化閉環する方法が知られている。（PBレ
ポート65657参照）また、ｐ−トルエンスルホン酸のよ
うな有機酸を用いて閉環する方法も知られている。<Prior art> Conventional formula (II) As a method for ring-closing the compound represented by the formula (wherein R represents a C 1 -C 4 alkyl group) to obtain a dioxazine compound, there is known a method of ring-closing by oxidation using benzenesulfonyl chloride as an oxidizing agent. ing. (See PB report 65657) Also known is a method of ring closure using an organic acid such as p-toluenesulfonic acid.
（特開昭58−84857号公報参照） ＜発明が解決しようとする問題点＞ しかしながら従来の方法では、閉環反応を行わしめるた
めに用いる酸化剤又は有機酸は、一般式（II）の化合物
に対して、１モル以上必要であり、そのため閉環反応終
了後、生成したジオキサジン化合物を単離する際に、加
えた酸化剤の反応物や未反応の有機酸が相当量生成ジオ
キサジン化合物中にかみこまれており、別する際長時
間を要し、また洗浄に用いる有機溶剤も多量必要とする
などの問題があった。また、その洗浄工程時の有機溶剤
量が不足した場合には、生成したジオキサジン化合物を
染料や特に顔料として用いる際、色相をはじめとして品
質の安定化が難しく、後工程に大きな影響を及ぼすとい
う難点があった。(See JP-A-58-84857) <Problems to be Solved by the Invention> However, in the conventional method, the oxidant or organic acid used for carrying out the ring-closing reaction is the compound of the general formula (II). On the other hand, 1 mol or more is required. Therefore, when the generated dioxazine compound is isolated after completion of the ring-closing reaction, a considerable amount of the reactant of the oxidizing agent or unreacted organic acid is added to the generated dioxazine compound. However, there is a problem that it takes a long time to separate them and a large amount of organic solvent is required for cleaning. Further, when the amount of the organic solvent in the washing step is insufficient, it is difficult to stabilize the quality such as hue when the produced dioxazine compound is used as a dye or particularly a pigment, which has a great influence on the subsequent steps. was there.
＜問題を解決するための手段＞ 本発明者は、一般式（II）の化合物を閉環して生成され
るジオキサジン化合物中に、酸化剤等がかみこまれ、そ
れが故に引き起す従来法の難点を改良すべく、鋭意研究
を行った結果、酸化剤等の代わりに複素環式アミンを用
いることにより、前記の問題が解決できることを見い出
した。<Means for Solving the Problem> The present inventors have found that the dioxazine compound produced by ring-closing the compound of the general formula (II) is bitten by an oxidizing agent or the like, which causes the difficulty of the conventional method. As a result of intensive studies to improve the above, it was found that the above problems can be solved by using a heterocyclic amine instead of an oxidizing agent or the like.
すなわち、本発明は、一般式（II） （式中、ＲはC1〜C4のアルキル基を表わす。） で示される化合物を不活性有機溶剤中、複素環式アミン
の存在下に加熱閉環させることを特徴とする一般式
（Ｉ） 〔式中、ＲはC1−C4のアルキル基を表わし、式（Ｉ）
は、X1＝X2＝Cl,X1＝Cl,X2＝ＨおよびX1＝X2＝Ｈの混合
物を表わすものとする〕 で示されるジオキサジン化合物の製造法である。That is, the invention has the general formula (II) (In the formula, R represents a C 1 -C 4 alkyl group.) The compound represented by the formula (I) is characterized in that the compound is ring-closed by heating in an inert organic solvent in the presence of a heterocyclic amine. [Wherein R represents a C 1 -C 4 alkyl group, and is represented by the formula (I)
Is a mixture of X 1 = X 2 = Cl, X 1 = Cl, X 2 = H and X 1 = X 2 = H].
本発明において、不活性溶剤としては、クロルベンゼ
ン、ジクロルベンゼン、トリクロルベンゼン、及びそれ
らの混合物、ニトロベンゼン、沸点が110℃以上のアル
キルベンゼン、あるいはアルキルナフタレン系の高沸点
溶媒があげられ、特に好ましいのはクロルベンゼン類、
ニトロベンゼン、アルキルベンゼン類である。In the present invention, examples of the inert solvent include chlorobenzene, dichlorobenzene, trichlorobenzene, and a mixture thereof, nitrobenzene, an alkylbenzene having a boiling point of 110 ° C. or higher, or an alkylnaphthalene-based high-boiling solvent, and particularly preferable. Is chlorobenzene,
They are nitrobenzene and alkylbenzenes.
本発明において、複素環式アミンとしては、ピリジン及
びその誘導体、ピリミジン及びその誘導体、キノリン及
びその誘導体があげられ、特に、ピリジン、８−ピリジ
ンメタノール、α−ピコリン、β−ピコリン、γ−ピコ
リン、４−エチルピリジンなどのアルキルピリジン、ピ
リミジン、キノリンのようにこれらの中で、特に、液体
を呈する複素環式アミンが好ましく用いられる。In the present invention, examples of the heterocyclic amine include pyridine and its derivatives, pyrimidine and its derivatives, quinoline and its derivatives, and particularly pyridine, 8-pyridinemethanol, α-picoline, β-picoline, γ-picoline, Among them, as alkyl pyridines such as 4-ethyl pyridine, pyrimidine, and quinoline, a heterocyclic amine which exhibits a liquid is particularly preferably used.
複素環式アミンの使用量は、一般式（II）の化合物１モ
ルに対して0.01モル−3.0モル好ましくは0.1モル−1.0
モルである。The amount of the heterocyclic amine used is 0.01 mol-3.0 mol, preferably 0.1 mol-1.0, relative to 1 mol of the compound of the general formula (II).
It is a mole.
反応温度は100℃以上であればよいが、特に100〜200℃
が好ましい。また、加熱時間は、通常3.0〜10.0時間で
ある。The reaction temperature may be 100 ° C or higher, but particularly 100 to 200 ° C.
Is preferred. The heating time is usually 3.0 to 10.0 hours.
反応が完結したら、過を行なって、結晶を分離し、必
要量の溶媒で洗浄を行なう、充分に圧搾した後、乾燥す
れば一般式（Ｉ）で示されるジオキサジン化合物を高収
量で得るができる。When the reaction is completed, the reaction is completed, the crystals are separated, washed with a required amount of solvent, sufficiently squeezed and dried to obtain the dioxazine compound represented by the general formula (I) in high yield. .
＜本発明の効果＞ 本発明により、従来法に比べて、反応促進剤の使用が少
量であることから安価ですみ、また過時間の短縮、使
用溶剤の削減が可能になり、その結果、溶剤回収、残渣
処理に費やす労力、エネルギーの消費が少なくてすみ、
省資源、省エネルギーへの効果ある製造法が確立され
た。さらに、顔料などの着色剤として着色力、光沢透明
度などに優れたジオキサジン化合物を供給することも可
能になった。<Effect of the present invention> According to the present invention, the amount of the reaction accelerator used is smaller than that of the conventional method, so the cost is low, and the overtime can be shortened and the solvent used can be reduced. Less labor and energy consumed for collection and residue treatment,
A manufacturing method effective for saving resources and energy has been established. Furthermore, it has become possible to supply a dioxazine compound excellent in coloring power and gloss transparency as a coloring agent such as a pigment.
＜実施例＞ 以下に本発明を実施例により更に詳しく説明する。文
中、部、％は重量部、重量％を表わす。<Example> Hereinafter, the present invention will be described in more detail with reference to Examples. In the text, parts and% represent parts by weight and% by weight.
実施例１ 2,5−ジクロル−3,6−ビス（９−エチル−３−カルバゾ
リルアミノ）−1,4−ベンゾキノン60部をｏ−ジクロル
ベンゼン400部に加え、さらに7.6部のピリジンを加え、
撹拌下155〜160℃まで昇温し、同温度で５時間加熱し
た。次いで、120℃まで冷却し、同温度で過した。反
応マスの過終了後、あらかじめ100℃で保温したｏ−
ジクロルベンゼン300部で洗浄後150部のメタノールで洗
浄し、次いで250部の水で洗浄、圧搾後、ケーキを取出
し乾燥した。50.5部のジオキサジン化合物（一般式
（Ｉ）中、ＲがC2H5）を得た。得られた化合物の元素分
析値は、C;71.0％,H;4.0％、N;9.8％,Cl;9.0％を示し
た。Example 1 60 parts of 2,5-dichloro-3,6-bis (9-ethyl-3-carbazolylamino) -1,4-benzoquinone was added to 400 parts of o-dichlorobenzene, and 7.6 parts of pyridine was added. And add
The temperature was raised to 155-160 ° C with stirring, and the mixture was heated at the same temperature for 5 hours. Then it was cooled to 120 ° C. and passed at the same temperature. After the reaction mass was over, keep the temperature at 100 ℃ in advance.
After washing with 300 parts of dichlorobenzene, 150 parts of methanol, then 250 parts of water, squeezing and pressing, the cake was taken out and dried. 50.5 parts of a dioxazine compound (in the general formula (I), R is C 2 H 5 ) was obtained. The elemental analysis values of the obtained compound were C; 71.0%, H; 4.0%, N; 9.8%, Cl; 9.0%.
上記操作において、反応マスの過、ｏ−ジクロルベン
ゼンでの洗浄は短時間で行うことができ、また洗浄に使
用する溶剤の使用量も従来法に比べ少量で済んだ。In the above operation, the excess reaction mass and the washing with o-dichlorobenzene can be carried out in a short time, and the amount of the solvent used for washing was smaller than that in the conventional method.
実施例２ 2,5−ジクロル−3,6−ビス（９−エチル−３−カルバゾ
リルアミノ）−1,4−ベンゾキノン60部をトリクロルベ
ンゼン400部に加え、さらに3.0部のピリジンを加え、撹
拌下180〜190℃まで昇温し、同温度で５時間加熱した。
次いで、120℃まで冷却し、同温度で過した。反応マ
スの過終了後、あらかじめ100℃で保温したトリクロ
ルベンゼン300部で洗浄後150部のメタノールで洗浄し、
次いで250部の水で洗浄、圧搾後、ケーキを取出し乾燥
することにより、50.5部のジオキサジン化合物（一般式
（Ｉ）中、ＲがC2H5）を得た。得られた化合物の元素分
析値は、C;70.5％、H;4.0％、N;9.8％、Cl;10.0％を示
した。Example 2 60 parts of 2,5-dichloro-3,6-bis (9-ethyl-3-carbazolylamino) -1,4-benzoquinone was added to 400 parts of trichlorobenzene, and 3.0 parts of pyridine was added, The temperature was raised to 180 to 190 ° C. with stirring, and the mixture was heated at the same temperature for 5 hours.
Then it was cooled to 120 ° C. and passed at the same temperature. After the reaction mass was over, wash with 300 parts of trichlorobenzene preheated at 100 ° C and then wash with 150 parts of methanol,
Then, after washing with 250 parts of water and pressing, the cake was taken out and dried to obtain 50.5 parts of a dioxazine compound (in the general formula (I), R is C 2 H 5 ). The elemental analysis values of the obtained compound were C; 70.5%, H; 4.0%, N; 9.8%, Cl; 10.0%.
過、洗浄操作について、実施例１と同様の効果が得ら
れた。The same effects as in Example 1 were obtained in the washing and washing operations.
実施例３ 2,5−ジクロル−3,6−ビス（９−エチル−３−カルバゾ
リルアミノ）−1,4−ベンゾキノン60部をｏ−ジクロル
ベンゼン400部に加え、さらに6.0部のキノリンを加え、
撹拌下140〜150℃まで昇温し、同温度で6.0時間加熱し
た。次いで、120℃まで冷却し、同温度で過した。反
応マスの過終了後、あらかじめ100℃で保温したｏ−
ジクロルベンゼン300部で洗浄後150部のメタノールで洗
浄し、次いで250部の水で洗浄、圧搾後、ケーキを取出
し乾燥することにより、49.5部のジオキサジン化合物
（一般式（Ｉ）中、ＲがC2H6）を得た。得られた化合物
の元素分析値は、C;69.8％、H;4.2％,N;9.6％、Cl;10.3
％を示した。Example 3 60 parts of 2,5-dichloro-3,6-bis (9-ethyl-3-carbazolylamino) -1,4-benzoquinone was added to 400 parts of o-dichlorobenzene, and further 6.0 parts of quinoline. And add
The temperature was raised to 140 to 150 ° C. with stirring, and the mixture was heated at the same temperature for 6.0 hours. Then it was cooled to 120 ° C. and passed at the same temperature. After the reaction mass was over, keep the temperature at 100 ℃ in advance.
After washing with 300 parts of dichlorobenzene, 150 parts of methanol, then 250 parts of water, squeezing, squeezing, and drying the cake, 49.5 parts of the dioxazine compound (in the general formula (I), R is C 2 H 6 ) was obtained. The elemental analysis values of the obtained compound are C; 69.8%, H; 4.2%, N; 9.6%, Cl; 10.3
%showed that.
過、洗浄操作について、実施例１と同様の効果が得ら
れた。The same effects as in Example 1 were obtained in the washing and washing operations.
実施例４ 2,5−ジクロル−3,6−ビス（９−エチル−３−カルバゾ
リルアミノ）−1,4−ベンゾキノン60部をｏ−ジクロル
ベンゼン400部に加え、さらに4.0部のα−ピコリンを加
え、撹拌下150〜160℃まで昇温し、同温度で5.0時間加
熱した。次いで、120℃まで冷却し、同温度で過し
た。反応マスの過終了後、あらかじめ100℃で保温し
たｏ−ジクロルベンゼン300部で洗浄後150部のメタノー
ルで洗浄し、次いで250部の水で洗浄、圧搾後、ケーキ
を取出し乾燥することにより、49.5部のジオキサジン化
合物（一般式（Ｉ）中、ＲがC2H5）を得た。得られた化
合物の元素分析値は、C;70.0％、H;4.1％、N;9.7％、C
l;10.0％を示した。Example 4 60 parts of 2,5-dichloro-3,6-bis (9-ethyl-3-carbazolylamino) -1,4-benzoquinone were added to 400 parts of o-dichlorobenzene, and 4.0 parts of α were added. -Picoline was added, the temperature was raised to 150 to 160 ° C with stirring, and the mixture was heated at the same temperature for 5.0 hours. Then it was cooled to 120 ° C. and passed at the same temperature. After the reaction mass was over, washed with 300 parts of o-dichlorobenzene which had been kept at 100 ° C. in advance, washed with 150 parts of methanol, then washed with 250 parts of water, squeezed, and then removing the cake by drying, 49.5 parts of a dioxazine compound (in the general formula (I), R is C 2 H 5 ) was obtained. The elemental analysis values of the obtained compound are C; 70.0%, H; 4.1%, N; 9.7%, C
l; 10.0% was shown.
過、洗浄操作について、実施例１と同様の効果が得ら
れた。The same effects as in Example 1 were obtained in the washing and washing operations.
実施例５ 2,5−ジクロル−3,6−ビス（９−エチル−３−カルバゾ
リルアミノ）−1,4−ベンゾキノン60部をニトロベンゼ
ン400部に加え、さらに2.0部のピリジンを加え、撹拌下
160〜170℃まで昇温し、同温度で5.0時間加熱した。次
いで、120℃まで冷却し、同温度で過した。反応マス
の過終了後、あらかじめ100℃で保温したニトロベン
ゼン300部で洗浄後150部のメタノールで洗浄し、次いで
250部の水で洗浄、圧搾後、ケーキを取出し乾燥するこ
とにより、51.0部のジオキサジン化合物（一般式（Ｉ）
中、ＲがC2H5）を得た。得られた化合物のの元素分析値
は、C;72.0％、H;4.0％、N;9.8％、Cl;8.0％を示した。Example 5 2,5-Dichloro-3,6-bis (9-ethyl-3-carbazolylamino) -1,4-benzoquinone (60 parts) was added to 400 parts of nitrobenzene, and 2.0 parts of pyridine was further added and stirred. under
The temperature was raised to 160 to 170 ° C, and the mixture was heated at the same temperature for 5.0 hours. Then it was cooled to 120 ° C. and passed at the same temperature. After the reaction mass was over, wash with 300 parts of nitrobenzene that had been kept at 100 ° C in advance, then wash with 150 parts of methanol, then
After washing and pressing with 250 parts of water, the cake is taken out and dried to give 51.0 parts of the dioxazine compound (general formula (I)
Among them, R was C 2 H 5 ). The elemental analysis values of the obtained compound were C; 72.0%, H; 4.0%, N; 9.8%, Cl; 8.0%.
過、洗浄操作について、実施例１と同様の効果が得ら
れた。The same effects as in Example 1 were obtained in the washing and washing operations.
実施例６ 2,5−ジクロル−3,6−ビス（９−エチル−３−カルバゾ
リルアミノ）−1,4−ベンゾキノン60部をｏ−ジクロル
ベンゼン400部に加え、さらに3.0部のγ−ピコリンを加
え、撹拌下160〜170℃まで昇温し、同温度で4.5時間加
熱した。次いで、120℃まで冷却し、同温度で過し
た。反応マスの過終了後、あらかじめ100℃で保温し
たｏ−ジクロルベンゼン300部で洗浄後150部のメタノー
ルで洗浄し、次いで250部の水で洗浄、圧搾後、ケーキ
を取出し乾燥することにより、49.5部のジオキサジン化
合物（一般式（Ｉ）中、ＲがC2H5）を得た。得られた化
合物の元素分析値は、C;69.9％,H;4.1％、N;9.8％、Cl;
10.3％を示した。Example 6 60 parts of 2,5-dichloro-3,6-bis (9-ethyl-3-carbazolylamino) -1,4-benzoquinone was added to 400 parts of o-dichlorobenzene, and 3.0 parts of γ was added. -Picoline was added, the temperature was raised to 160 to 170 ° C with stirring, and the mixture was heated at the same temperature for 4.5 hours. Then it was cooled to 120 ° C. and passed at the same temperature. After the reaction mass is over, washed with 300 parts of o-dichlorobenzene which has been kept at 100 ° C. in advance, washed with 150 parts of methanol, then washed with 250 parts of water, squeezed, and by removing the cake and drying, 49.5 parts of a dioxazine compound (in the general formula (I), R is C 2 H 5 ) was obtained. The elemental analysis values of the obtained compound are C; 69.9%, H; 4.1%, N; 9.8%, Cl;
It showed 10.3%.
過、洗浄操作について、実施例１と同様の効果が得ら
れた。The same effects as in Example 1 were obtained in the washing and washing operations.
実施例７ 2,5−ジクロル−3,6−ビス（９−エチル−３−カルバゾ
リルアミノ）−1,4−ベンゾキノン60部をｏ−ジクロル
ベンゼン400部に加え、さらに5.0部のピリミジン、を加
え、撹拌下160〜170℃まで昇温し、同温度で5.0時間加
熱した。次いで、120℃まで冷却し、同温度で過し
た。反応マスの過終了後、あらかじめ100℃で保温し
たｏ−ジクロルベンゼン300部で洗浄後150部のメタノー
ルで洗浄し、次いで250部の水で洗浄、圧搾後、ケーキ
を取出し乾燥することにより、48.5部のジオキサジン化
合物（一般式（Ｉ）中、ＲがC2H5）を得た。得られた化
合物の元素分析値は、C;69.5％,H;4.0％,N;10.0％,;10.
5％を示した。Example 7 60 parts of 2,5-dichloro-3,6-bis (9-ethyl-3-carbazolylamino) -1,4-benzoquinone was added to 400 parts of o-dichlorobenzene, and 5.0 parts of pyrimidine was added. , Was added, the temperature was raised to 160 to 170 ° C. with stirring, and the mixture was heated at the same temperature for 5.0 hours. Then it was cooled to 120 ° C. and passed at the same temperature. After the reaction mass is over, washed with 300 parts of o-dichlorobenzene which has been kept at 100 ° C. in advance, washed with 150 parts of methanol, then washed with 250 parts of water, squeezed, and by removing the cake and drying, There were obtained 48.5 parts of a dioxazine compound (R in the general formula (I) is C 2 H 5 ). The elemental analysis values of the obtained compound are C; 69.5%, H; 4.0%, N; 10.0% ,; 10.
Showed 5%.
過、洗浄操作について、実施例１と同様の効果が得ら
れた。The same effects as in Example 1 were obtained in the washing and washing operations.
比較例１ 2,5−ジクロル−3,6−ビス（９−エチル−３−カルバゾ
リルアミノ）−1,4−ベンゾキノン60部をｏ−ジクロル
ベンゼン400部に加え、115℃まで昇温後、ベンゼンスル
ホニルクロライド19部を加え、175〜180℃に昇温し、同
温度で６時間保温した。120℃まで冷却後、同温度で
過した。次いで、あらかじめ100℃に保温していたｏ−
ジクロルベンゼン400部を用いて、洗浄した。次いで、
同様のｏ−ジクロルベンゼン400部を用いてさらに洗浄
した。その後150部のメタノール、300部の水で洗浄後、
圧搾し、取出したケーキを乾燥した。47.6部のジオキサ
ジン化合物を得た。得られた化合物の元素分析値は、C;
70.0％、H;3.8％,N;9.6％,Cl;11.5％,S;0.3％を示し
た。Comparative Example 1 2,5-Dichloro-3,6-bis (9-ethyl-3-carbazolylamino) -1,4-benzoquinone (60 parts) was added to 400 parts of o-dichlorobenzene, and the temperature was raised to 115 ° C. Then, 19 parts of benzenesulfonyl chloride was added, the temperature was raised to 175 to 180 ° C., and the temperature was kept for 6 hours. After cooling to 120 ° C, the mixture was kept at the same temperature. Next, o-
It was washed with 400 parts of dichlorobenzene. Then
It was further washed with 400 parts of the same o-dichlorobenzene. After washing with 150 parts of methanol and 300 parts of water,
The cake pressed and taken out was dried. 47.6 parts of dioxazine compound was obtained. The elemental analysis value of the obtained compound is C;
70.0%, H; 3.8%, N; 9.6%, Cl; 11.5%, S; 0.3%.
上記操作において、反応マスの過、ｏ−ジクロルベン
ゼンでの洗浄には長時間を要した。In the above operation, it took a long time to pass the reaction mass and wash with o-dichlorobenzene.
また、ｏ−ジクロルベンゼンでの１回目の洗浄終了後、
２回目の洗浄を行なわずに、メタノール洗浄以降同様の
処理をして得られたジオキサジン化合物の元素分析値
は、C;70.0％,H;4.0％,N;9.0％,Cl;11.3％,S;1.5％を示
し、Ｓ分の含有量が多く、洗浄不十分であった。After the first washing with o-dichlorobenzene,
The elemental analysis values of the dioxazine compound obtained by performing the same treatment after methanol washing without performing the second washing are C; 70.0%, H; 4.0%, N; 9.0%, Cl; 11.3%, S It was 1.5%, the content of S was large, and the cleaning was insufficient.
比較例２ 2,5−ジクロル−3,6−ビス（９−エチル−３−カルバゾ
リルアミノ）−1,4−ベンゾキノン60部をｏ−ジクロル
ベンゼン300部に加え、さらにｐ−トルエンスルホン酸2
6部を加え80〜85℃に保温した。この懸濁液を、別途175
〜180℃に保温しておいたｏ−ジクロルベンゼン100部中
へ、撹拌下、３時間要して加えた。加え終った後、さら
に175〜180℃で６時間保温した。その後120℃まで冷却
し、過した。次いで、あらかじめ100℃に保温してい
たｏ−ジクロルベンゼン400部を用いて洗浄した。同様
の操作をさらに３回行なった。次いで、150部のメタノ
ール、300部の水で洗浄後、圧搾し、取出したケーキを
乾燥した。38.7部のジオキサジン化合物を得た。得られ
た化合物の元素分析値は、C;66.0％、H;4.0％,N;7.8％,
Cl;6.5％,S;3.3％でＳ分が多かった。Comparative Example 2 60 parts of 2,5-dichloro-3,6-bis (9-ethyl-3-carbazolylamino) -1,4-benzoquinone was added to 300 parts of o-dichlorobenzene, and p-toluenesulfone was further added. Acid 2
Six parts were added and the temperature was kept at 80 to 85 ° C. Separately add this suspension to 175
It was added to 100 parts of o-dichlorobenzene kept at ˜180 ° C. under stirring for 3 hours. After the addition was completed, the temperature was further kept at 175 to 180 ° C for 6 hours. Then, it cooled to 120 degreeC and passed. Then, it was washed with 400 parts of o-dichlorobenzene which had been kept at 100 ° C. in advance. The same operation was repeated three times. Next, the cake was washed with 150 parts of methanol and 300 parts of water, squeezed, and the cake taken out was dried. 38.7 parts of dioxazine compound was obtained. The elemental analysis values of the obtained compound are C; 66.0%, H; 4.0%, N; 7.8%,
The Cl content was 6.5% and the S content was 3.3%.
上記操作において、反応マスの過、ｏ−ジクロルベン
ゼンでの洗浄には長時間を要した。In the above operation, it took a long time to pass the reaction mass and wash with o-dichlorobenzene.
参考例 実施例１の条件で得られたジオキサジン化合物100部及
び、300メッシュスルーの粒度を持つ食塩700部、エチレ
ングリコール150部を実験用双腕型ニーダーで、70〜75
℃を維持しながら、７時間摩砕し、そのマスを2,000部
の温水（80℃）中へ入れ、撹拌後、過し、4,000部の
水で洗浄後、ケーキを取出し、乾燥した。この乾燥ケー
キを顔料として、ニトロセルローズ〜ポリアミド系グラ
ビアインキを作成し評価した。その際、比較例−１の条
件で得られたジオキサジン化合物も同様に顔料化し、評
価時の標準とした。Reference Example 100 parts of the dioxazine compound obtained under the conditions of Example 1, 700 parts of salt having a particle size of 300 mesh through, and 150 parts of ethylene glycol were used in an experimental double-arm kneader to obtain 70 to 75
The mixture was ground for 7 hours while maintaining the temperature at ℃, put into 2,000 parts of warm water (80 ℃), stirred, passed, washed with 4,000 parts of water, the cake was taken out and dried. Using this dried cake as a pigment, nitrocellulose to polyamide gravure ink was prepared and evaluated. At that time, the dioxazine compound obtained under the conditions of Comparative Example-1 was similarly pigmented and used as a standard for evaluation.
結果 result
Claims (4)
の存在下に加熱閉環させることを特徴とする一般式
（Ｉ） 〔式中、ＲはC1−C4のアルキル基を表わし、式（Ｉ）
は、X1＝X2＝Cl、X1＝Cl,X2＝ＨおよびX1＝X2＝Ｈの混
合物を表わすものとする。〕 で示されるジオキサジン化合物の製造法。1. General formula (II) (In the formula, R represents a C 1 -C 4 alkyl group.) The compound represented by the formula (I) is characterized in that the compound is ring-closed by heating in an inert organic solvent in the presence of a heterocyclic amine. [Wherein R represents a C 1 -C 4 alkyl group, and is represented by the formula (I)
Denotes a mixture of X 1 = X 2 = Cl, X 1 = Cl, X 2 = H and X 1 = X 2 = H. ] The manufacturing method of the dioxazine compound shown by these.
びその誘導体、ピリミジン及びその誘導体またはキノリ
ン及びその誘導体である特許請求の範囲第１項記載の方
法。2. The method according to claim 1, wherein the heterocyclic amine is pyridine and its derivatives, pyrimidine and its derivatives, or quinoline and its derivatives, which are liquid.
許請求の範囲第１項記載の方法。3. The method according to claim 1, wherein the heating temperature is in the range of 120 ° C. to 200 ° C.
ジクロルベンゼン、トリクロルベンゼン及びこれらの混
合物、沸点が110℃以上のアルキルベンゼン類またはニ
トロベンゼンを用いる特許請求の範囲第１項記載の方
法。4. An inert organic solvent such as chlorobenzene,
The method according to claim 1, wherein dichlorobenzene, trichlorobenzene, a mixture thereof, an alkylbenzene having a boiling point of 110 ° C. or higher, or nitrobenzene is used.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3610486A JPH0672146B2 (en) | 1986-02-19 | 1986-02-19 | Method for producing dioxazine compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3610486A JPH0672146B2 (en) | 1986-02-19 | 1986-02-19 | Method for producing dioxazine compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62192385A JPS62192385A (en) | 1987-08-22 |
| JPH0672146B2 true JPH0672146B2 (en) | 1994-09-14 |
Family
ID=12460461
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3610486A Expired - Fee Related JPH0672146B2 (en) | 1986-02-19 | 1986-02-19 | Method for producing dioxazine compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0672146B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19643344A1 (en) * | 1996-10-21 | 1998-04-23 | Clariant Gmbh | Process for the preparation of dioxazine compounds |
-
1986
- 1986-02-19 JP JP3610486A patent/JPH0672146B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62192385A (en) | 1987-08-22 |
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