JPS62192385A - Production of dioxazine compound - Google Patents
Production of dioxazine compoundInfo
- Publication number
- JPS62192385A JPS62192385A JP3610486A JP3610486A JPS62192385A JP S62192385 A JPS62192385 A JP S62192385A JP 3610486 A JP3610486 A JP 3610486A JP 3610486 A JP3610486 A JP 3610486A JP S62192385 A JPS62192385 A JP S62192385A
- Authority
- JP
- Japan
- Prior art keywords
- parts
- dichlorobenzene
- compound
- formula
- 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.)
- Granted
Links
- -1 dioxazine compound Chemical class 0.000 title claims abstract description 29
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229940117389 dichlorobenzene Drugs 0.000 claims abstract description 11
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 claims abstract description 10
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 10
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 claims abstract description 10
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000003960 organic solvent Substances 0.000 claims abstract description 7
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims abstract description 7
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 claims abstract description 5
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- 150000004996 alkyl benzenes Chemical class 0.000 claims abstract description 4
- 238000009835 boiling Methods 0.000 claims abstract description 4
- 239000007788 liquid Substances 0.000 claims abstract description 3
- 125000000217 alkyl group Chemical group 0.000 claims abstract 3
- 238000000034 method Methods 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims 2
- 150000001875 compounds Chemical class 0.000 abstract description 18
- 238000006243 chemical reaction Methods 0.000 abstract description 14
- 239000000049 pigment Substances 0.000 abstract description 6
- 238000006798 ring closing metathesis reaction Methods 0.000 abstract description 5
- 239000003086 colorant Substances 0.000 abstract description 2
- 230000008030 elimination Effects 0.000 abstract 1
- 238000003379 elimination reaction Methods 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 33
- 238000005406 washing Methods 0.000 description 21
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 13
- 238000001914 filtration Methods 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 238000000921 elemental analysis Methods 0.000 description 10
- 238000003756 stirring Methods 0.000 description 8
- 229940005561 1,4-benzoquinone Drugs 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000007800 oxidant agent Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 238000007796 conventional method Methods 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- CSKNSYBAZOQPLR-UHFFFAOYSA-N benzenesulfonyl chloride Chemical compound ClS(=O)(=O)C1=CC=CC=C1 CSKNSYBAZOQPLR-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 150000005125 dioxazines Chemical class 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 150000007524 organic acids Chemical class 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 2
- 238000007363 ring formation reaction Methods 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- ITQTTZVARXURQS-UHFFFAOYSA-N 3-methylpyridine Chemical compound CC1=CC=CN=C1 ITQTTZVARXURQS-UHFFFAOYSA-N 0.000 description 1
- VJXRKZJMGVSXPX-UHFFFAOYSA-N 4-ethylpyridine Chemical compound CCC1=CC=NC=C1 VJXRKZJMGVSXPX-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000008422 chlorobenzenes Chemical class 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 150000005181 nitrobenzenes Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
Landscapes
- Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
Abstract
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 <Industrial Application Field> The present invention relates to an improved method for producing dioxazine compounds used as dyes and pigments as well as functional dyes.
〈従来の技術〉
従来、一般式（ｎ）
（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。（ＰＲレポー
ト６５６５７参煕）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> Conventionally, as a method for obtaining a dioxazine compound by ring-closing a compound represented by the general formula (n) (in the formula, R represents a C1-C4 alkyl group), benzenesulfonyl chloride was used as an oxidizing agent. A method of oxidative ring closure using is known. (See PR Report 65657) A method of ring closure using an organic acid such as p-toluenesulfonic acid is also known.
（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、炉別する際長
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。(Refer to JP-A-58-84857) <Problems to be solved by the invention> However, in the conventional method, the oxidizing agent or organic acid used to carry out the ring-closing reaction is In contrast, 1 mole or more is required, so when isolating the generated dioxazine compound after the completion of the ring-closing reaction,
A considerable amount of reactants from the added oxidizing agent and unreacted organic acids are included in the dioxazine compound produced, which requires a long time to separate in the furnace and requires a large amount of organic solvent for cleaning. There was a problem. Also, if the amount of organic solvent during the cleaning process is insufficient.
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
工程に大きな影栂を及ぼすという難点があった。When using the produced dioxazine compounds as dyes or especially pigments, it is difficult to stabilize the quality, including the hue, and this has the disadvantage of having a large impact on subsequent processes.
く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、鋭駕研
究を行った結果、酸化剤等の代わりに複索環式アミンを
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 Problems> The present inventor has discovered that an oxidizing agent or the like is incorporated into a dioxazine compound produced by ring-closing the compound of general formula (II),
In order to improve the drawbacks of the conventional method caused by this, in-depth research was conducted and it was discovered that the above-mentioned problems could be solved by using a polycyclic amine instead of an oxidizing agent or the like.
すなわち、本発明は、一般式（Ｕ）
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（１
）
〔式中、ＲはＣ１−Ｃ４のアルキル基を表わし、式（１
） ｌｉ、Ｘｊ＝Ｘｌ ＝ＣＩ、 Ｘｓ ＝Ｃ１、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 present invention provides a compound represented by the general formula (1), which is characterized by subjecting the compound represented by the general formula (U) to ring closure by heating in the presence of a heterocyclic amine in an inert organic solvent.
) [In the formula, R represents a C1-C4 alkyl group, and the formula (1
) li, Xj = Xl = CI, Xs = C1, X2
represents a mixture of =H and X1=X2=H] This is a method for producing a dioxazine compound represented by:
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、及びこれら
の混合物、ニトロベンゼン、沸点が１１０°Ｃ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アル。In the present invention, examples of the inert solvent include chlorobenzene, dichlorobenzene, trichlorobenzene, and mixtures thereof, nitrobenzene, alkylbenzenes with a boiling point of 110°C or higher, and alkylnaphthalene-based high-boiling solvents, which are particularly preferred. These are chlorobenzenes, nitrobenzenes, 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絖導体、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、ｒ−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い（用いられる。In the present invention, heterocyclic amines include pyridine and its derivatives, pyrimidine and its conductors, quinoline and its derivatives, in particular pyridine, 8-pyridinemethanol, α-picoline, β-picoline, r-picoline. Among these, liquid heterocyclic amines such as alkylpyridines such as , 4-ethylpyridine, pyrimidine, and quinoline are particularly preferred (and used).
複素環アミンの使用意は、一般式（ｎ）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 heterocyclic amine to be used is 0.01 mol to 3.0 mol, preferably 0.1 mol to 1.0 mol, per 1 mol of the compound of general formula (n).
反応温度は１００℃以上であればよいが、特に１００〜
２００°Ｃが好ましい。また、加熱時間は、通常８．０
〜ｌＯ０θ時間である。The reaction temperature may be 100°C or higher, but especially 100°C or higher.
200°C is preferred. In addition, the heating time is usually 8.0
~lO0θ time.
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（１）で示されるジオキサジン化合物を高収
量で得ることができる。When the reaction is completed, the crystals are separated by filtration, washed with a necessary amount of solvent, sufficiently compressed, and dried to obtain a high yield of the dioxazine compound represented by the general formula (1). I can do it.
〈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受
承であることから安価ですみ、また濾過時間の短縮、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
。<Effects of the present invention> Compared to conventional methods, the present invention requires less use of a reaction accelerator and is therefore less expensive, and also enables shorter filtration time and reduced solvent use. Less labor and energy consumption is required for solvent recovery and residue treatment.
A manufacturing method that is effective in saving resources and energy has been established.
さらに、顔料などの右色剤として着色力、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。Furthermore, it has become possible to supply dioxazine compounds with excellent coloring power, gloss transparency, etc. as right-coloring agents for pigments and the like.
〈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、チは重量部、重諏チを表わす。<Examples> The present invention will be explained in more detail below using examples. In the text, parts and parts represent parts by weight and parts by weight.
実施例１
２．５−ジクロル−８，６−ビス（９−エチル−８−カ
ルバゾリルアミノ）−１，４−ベンゾキノン６０部を０
−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、攪拌下１５５〜１６０°Ｃまで昇温し
、同温度で５時間加熱した。次いで、１２０°Ｃまで冷
却し、同温度で濾過した。反応マスの濾過終了後、あら
かじめ１００℃で保温したＯ−ジクロルベンゼン８００
部で洗浄後１５０部のメタノールで洗浄し、次いで２５
０部の水で洗浄、圧搾後、ケーキを取出し乾燥した。Example 1 60 parts of 2.5-dichloro-8,6-bis(9-ethyl-8-carbazolylamino)-1,4-benzoquinone was added to 0
- In addition to 400 parts of dichlorobenzene, 7.6 parts of pyridine was added, 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 filtered at the same temperature. After filtration of the reaction mass, O-dichlorobenzene 800, which had been kept warm at 100°C in advance,
Wash with 150 parts of methanol, then 25 parts of methanol.
After washing with 0 parts of water and pressing, the cake was removed and dried.
５０．５部のジオキサジン化合物（一般式（１）中。50.5 parts of a dioxazine compound (in general formula (1)).
ＲがＣ２Ｈ５）を得た。得られた化合物の元素分析値は
、Ｃ１７１，０チ、ＮＦ４．Ｑチ Ｎ ｉ９．８チ、Ｃ
１９，０チを示した。R is C2H5) was obtained. The elemental analysis values of the obtained compound were C171.0, NF4. Qchi N i9.8chi, C
It showed 19.0chi.
上記操作において、反応マスの濾過％〇−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生態で済んだ。In the above operation, the reaction mass can be washed with filtrated %-dichlorobenzene in a short time, and the amount of solvent used for washing is economical compared to conventional methods.
実施例２
２．５−ジクロル−８，６−ビス（９−エチル−８−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８．０部のピ
リジンを加え、攪拌下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、
同温度で濾過した。反応マスの濾過終了後、あらかじめ
１００℃で保温したトリクロルベンゼン８００部で洗浄
後１５０部のメタノールで洗浄し、次いで２６０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（１）中、Ｒ
がＣｚＨｓ） を得た。得られた化合物の元素分析値
は％Ｃ；７０．５％、Ｈ＋４．０％、ＮＦ２．８Ｔｏ、
Ｃ１：１０．０チを示した。Example 2 60 parts of 2.5-dichloro-8,6-bis(9-ethyl-8-carbazolylamino)-1,4-benzoquinone was added to 400 parts of trichlorobenzene, and further 8.0 parts of pyridine was added. The temperature was then raised to 180 to 190°C while stirring, and the mixture was heated at the same temperature for 5 hours. Then, cooled to 120°C,
It was filtered at the same temperature. After filtration of the reaction mass, wash with 800 parts of trichlorobenzene kept at 100°C in advance, wash with 150 parts of methanol, then wash with 260 parts of water, squeeze, and then take out the cake and dry it.
50.5 parts of a dioxazine compound (in general formula (1), R
CzHs) was obtained. The elemental analysis values of the obtained compound were %C; 70.5%, H+4.0%, NF2.8To,
C1: showed 10.0ch.
Ｐ蝙、洗浄操作について、実施例１と同様の効果が得ら
れた。Regarding the cleaning operation, the same effects as in Example 1 were obtained.
実施例８
２．５−ジクロル−８，６−ビス（９−エチル−８−カ
ルバゾリルアミノ）−１，４−ベンゾキノン６０部を０
−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、攪拌下１４０〜１５０°Ｃ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、同温度で濾過した。反応マスの濾過終了後、あ
らかじめ１００°Ｃで保温した０−ジクロルベンゼン８
００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
（り中、ＲがＣ２Ｈ５）を得た。得られた化合物の元素
分析値は、Ｃ；ｓ９．ｓ＊。Example 8 60 parts of 2,5-dichloro-8,6-bis(9-ethyl-8-carbazolylamino)-1,4-benzoquinone was added to 0
- In addition to 400 parts of dichlorobenzene, 6.0 parts of quinoline was added, 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 filtered at the same temperature. After completing the filtration of the reaction mass, add 0-dichlorobenzene 8, which had been kept warm at 100°C in advance.
After washing with 0.00 parts, washing with 150 parts of methanol, then washing with 250 parts of water, and squeezing, the cake was taken out and dried to obtain 49.5 parts of a dioxazine compound (general formula (R is C2H5)). The elemental analysis value of the obtained compound was C; s9.s*.
Ｈ： ４．２％ 、 Ｎ ＋ ９．６ Ｔｏ 、ＣＩ＋
ｌ Ｏ，８％ヲ示した。H: 4.2%, N+9.6To, CI+
It showed l O, 8%.
濾過、洗浄操作について、実施例１と同様の効果が得ら
れた。Regarding the filtration and washing operations, the same effects as in Example 1 were obtained.
実施例４
２．５−ジクロル−８，６−ビス（９−エチル−８−カ
ルバゾリルアミノ）−１，４−ベンゾキノン６０部を０
−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、攪拌下１５０〜１６０°Ｃ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、同温度で濾過した。反応マスの濾過終了後
、あらかじめ１００°Ｃで保温した０−ジクロルベンゼ
ン８００部で洗浄後１５０部のメタノールで洗浄し、次
いで（ｌＯ）
２５０部の水で洗浄、圧搾後、ケーキを取出し乾゛繰す
ることにより、４９．５部のジオキサジン化合物（一般
式（り中、ＲがＣ２Ｈ３）を得た。得られた化合物の元
素分析値は、Ｃ；７０．０％、 ）ｉ ； ４． ｌ慢
、Ｎ；９，７チ、Ｃｌ＋１Ｏ９０％を示した。Example 4 60 parts of 2,5-dichloro-8,6-bis(9-ethyl-8-carbazolylamino)-1,4-benzoquinone was added to 0
- In addition to 400 parts of dichlorobenzene, 4.0 parts of α-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 120℃
and filtered at the same temperature. After filtration of the reaction mass, wash with 800 parts of 0-dichlorobenzene kept at 100°C in advance, wash with 150 parts of methanol, then wash with 250 parts of (lO) water, squeeze, and then remove the cake and dry. By repeating this process, 49.5 parts of a dioxazine compound (general formula (in which R is C2H3) was obtained. The elemental analysis value of the obtained compound was C; 70.0%, )i; 4. It showed arrogance, N; 9.7, Cl+1O 90%.
濾過、洗浄操作について、実施例１と同様の効果が得ら
れた。Regarding the filtration and washing operations, the same effects as in Example 1 were obtained.
実施例５
２．５−ジクロル−８，６−ビス（９−エチル−８−カ
ルバゾリルアミノ）−１ｊ４−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、攪拌下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
、同温度で濾過した。反応マスの濾過終了後、あらかじ
め１００℃で保温したニトロベンゼン８００部で洗浄後
１５０部ノメタノールで洗浄し、次いで２５０部の水で
洗浄。Example 5 60 parts of 2.5-dichloro-8,6-bis(9-ethyl-8-carbazolylamino)-1j4-benzoquinone was added to 400 parts of nitrobenzene, and further 2.0 parts of pyridine was added, followed by stirring. The temperature was raised to 160 to 170° C. and heated at the same temperature for 5.0 hours. It was then cooled to %120°C and filtered at the same temperature. After filtration of the reaction mass, the mass was washed with 800 parts of nitrobenzene kept at 100° C., then washed with 150 parts of nomethanol, and then washed with 250 parts of water.
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Ｃ２Ｈ
５）を得た。得られた化合物の元素分析値は、Ｃ＋７２
．０％、Ｈ；４．Ｏｆ！Ｉ、Ｎ；９．８％、ｃｔ：ｓ、
ｏｑｂを示した。After squeezing, the cake is taken out and dried to give 51.0
dioxazine compound (in the general formula (I), R is C2H)
5) was obtained. The elemental analysis value of the obtained compound is C+72
．． 0%, H;4. Of! I, N; 9.8%, ct:s,
It showed oqb.
濾過、洗浄操作について、実施例１と同様の効果が得ら
れた。Regarding the filtration and washing operations, the same effects as in Example 1 were obtained.
実施例６
２．５−ジクロル−８，６−ビス（９−エチル−８−カ
ルバゾリルアミノ）−１，４−ベンゾキノン６０部を０
−ジクロルベンゼン４００部に加え、さらに８．０部の
ｒ−ピコリンを加え、攪拌下１６０〜１７０°Ｃまで昇
温し、同温度で４．５時間加熱した。次いで、１２０°
Ｃまで冷却し、同温度で濾過した。反応マスの濾過終了
後、あらかじめ１００°Ｃで保温したＯ−ジクロルベン
ゼン８００ｍ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。Example 6 60 parts of 2,5-dichloro-8,6-bis(9-ethyl-8-carbazolylamino)-1,4-benzoquinone was added to 0
- In addition to 400 parts of dichlorobenzene, 8.0 parts of r-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 120°
The mixture was cooled to 30°C and filtered at the same temperature. After the reaction mass was filtered, it was washed with 800ml of O-dichlorobenzene kept at 100°C in advance, and then washed with 150 parts of methanol.
Next, after washing with 250 parts of water and pressing, the cake was taken out and dried to obtain 49.5 parts of dioxazine compound (
In the general formula (I), R is C2H5).
得られた化合物の元素分析値は、Ｃ；６９．９チ、ＨＦ
２．１％、Ｎｕ ９．８優、Ｃ／ｉｌｏ、８チを示した
。The elemental analysis values of the obtained compound were C; 69.9C, HF.
It showed 2.1%, Nu 9.8 excellent, C/ilo 8 H.
濾過、洗浄操作について、実施例１と同様の効果が得ら
れた。Regarding the filtration and washing operations, the same effects as in Example 1 were obtained.
実施例７
２．５−ジクロル−８，６−ビス（９−エチル−８−カ
ルバゾリルアミノ）−１，４−ベンゾキノン６０部を０
−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、攪拌下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、同温度で濾過した。反応マスの濾過終了後、
あらかじめ１００℃で保温した０−ジクロルベンゼン８
００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Ｃ２Ｈ３） を得た。得られた化合物
の元素分析値は、Ｃ；６９．５％。Example 7 60 parts of 2,5-dichloro-8,6-bis(9-ethyl-8-carbazolylamino)-1,4-benzoquinone was added to 0
- In addition to 400 parts of dichlorobenzene, 5.0 parts of pyrimidine was added, and the temperature was raised to 160-170°C with stirring, and heated at the same temperature for 5.0 hours. Then, it was cooled to 120°C and filtered at the same temperature. After filtration of the reaction mass,
0-Dichlorobenzene 8 kept warm at 100℃ in advance
After washing with 00 parts of methanol, washing with 150 parts of methanol, washing with 250 parts of water, and pressing, the cake was taken out and dried to obtain 48.5 parts of a dioxazine compound (in the general formula (I), R is C2H3). ) obtained. The elemental analysis value of the obtained compound was C; 69.5%.
Ｈ＋４．１チ、Ｎ＋１０．０％、 ＋１０．５チを示
した。It showed H+4.1ch, N+10.0%, and +10.5ch.
濾過、洗浄操作について、実施例１と同様の効果が得ら
れた。Regarding the filtration and washing operations, the same effects as in Example 1 were obtained.
比較例１
２．５−ジクロル−８，６−ビス（９−エチル−８−カ
ルバゾリルアミノ）−１，４−ベンツキノン６０部を０
−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、１７
５〜１８０℃に昇温し、同温度で６時間保温した。１２
０℃まで冷却後、同温度で濾過した。次いで、あらかじ
め１００°Ｃに保温していた０−ジクロルベンゼン４０
０部を用いて、洗浄した。次いで、同様の０−ジクロル
ベンゼン４００部を用いてさらに洗浄した。Comparative Example 1 60 parts of 2.5-dichloro-8,6-bis(9-ethyl-8-carbazolylamino)-1,4-benzquinone was added to 0
- Add 400 parts of dichlorobenzene, heat up to 115°C, add 19 parts of benzenesulfonyl chloride, and add 17 parts of benzenesulfonyl chloride.
The temperature was raised to 5 to 180°C and kept at the same temperature for 6 hours. 12
After cooling to 0°C, it was filtered at the same temperature. Next, 0-dichlorobenzene 40 which had been kept warm at 100°C in advance
0 parts was used for washing. Then, it was further washed using 400 parts of the same 0-dichlorobenzene.
その後１５０部のメタノール、８００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。After washing with 150 parts of methanol and 800 parts of water,
The cake was pressed and removed and dried. 47.6 parts of dioxazine compound were obtained.
得られた化合物の元素分析値はｓｃ＋７ｏ、。The elemental analysis value of the obtained compound was sc+7o.
チ、Ｈ；３．８％、Ｎｉ９．６チ、Ｃ／Ｆ ｔ １
．５ ％ 。Chi, H; 3.8%, Ni9.6 Chi, C/F t 1
．． 5%.
Ｓ；０，８％を示した。S: showed 0.8%.
上記操作において、反応マスの濾過、０−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 filter the reaction mass and wash it with 0-dichlorobenzene.
また、０−ジクロフレベンゼンでの１回目の洗浄終了後
、２回目の洗浄を行なわずに、メタノール洗紗以降同様
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％ Ｃｆ７０．０％、）ｉ；４．０チ、Ｎ＋９．Ｏチ
、Ｃｆ；１１．８チ、Ｓｉ１．５チを示し、８分の含有
量が多く、洗浄不十分であった。In addition, after the first washing with 0-dicloflbenzene, the elemental analysis value of the dioxazine compound obtained by performing the same treatment after washing with methanol without performing the second washing was %Cf70.0% ,)i;4.0chi,N+9. O, Cf: 11.8, Si: 1.5, the content of 8 was high, and cleaning was insufficient.
比較例２
２．５−ジクロル−８，６−ビス（９−エチル−８−カ
ルバゾリルアミノ）−１，４−ベンゾキノン６０Ｍを０
−ジクロルベンゼン８００部に加え、さらにｐ−）ルエ
ンスルホン酸２６部を加え８０〜８５℃に保温した。Comparative Example 2 2.5-dichloro-8,6-bis(9-ethyl-8-carbazolylamino)-1,4-benzoquinone 60M
- In addition to 800 parts of dichlorobenzene, 26 parts of p-)luenesulfonic acid was added and kept at 80 to 85°C.
この懸濁液を、別途１７５〜１８０°Ｃに保温しておい
た０−ジクロルベンゼン１００部中へ、攪拌下、８時間
要して加えた。加え終った後、さらに１７５〜１８０°
Ｃで６時間保温した。その後１２０°Ｃまで冷却し、濾
過した。This suspension was added to 100 parts of 0-dichlorobenzene, which had been separately kept at a temperature of 175 to 180°C, over a period of 8 hours while stirring. After adding, further 175-180°
It was kept warm at C for 6 hours. Thereafter, it was cooled to 120°C and filtered.
次いで、あらかじめ１００℃に保温していた０−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８回行なった。Next, washing was performed using 400 parts of 0-dichlorobenzene, which had been kept at 100°C in advance. The same operation was repeated eight more times.
次いで、１５０部のメタノール、８００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。Next, after washing with 150 parts of methanol and 800 parts of water, the cake was squeezed and the taken out cake was dried. 38.7 parts of dioxazine compound were obtained.
得られた化合物の元素分析値は、Ｃ；６６．０チ、Ｈ；
４．ｏチ、Ｎ；７，８％、Ｃ／＋６．５チ。The elemental analysis values of the obtained compound were C; 66.0, H;
4. ochi, N; 7.8%, C/+6.5chi.
Ｓｉ８．８チで８分が多かった。Si8.8chi had 8 minutes.
上記繰作において、反応マスの濾過、〇−ジクロルベン
ゼンでの洗浄には長時間を要した。In the above-mentioned repeated operations, it took a long time to filter the reaction mass and wash it with 0-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、８００メツシユ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−
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、攪拌後
、濾過し、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
。Reference Example 100 parts of the dioxazine compound obtained under the conditions of Example 1, 700 parts of common salt having a particle size of 800 mesh through, and 150 parts of ethylene glycol were added to an experimental double-arm kneader.
The mass was ground for 7 hours while maintaining a temperature of 70 to 75°C, and the mass was poured into 2,000 parts of warm water (80°C), stirred, filtered, and washed with 4,000 parts of water. The cake was removed and dried. Using this dried cake as a pigment, a nitrocellulose-polyamide gravure ink was prepared and evaluated.
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。At that time, the dioxazine compound obtained under the conditions of Comparative Example-1 was also made into a pigment in the same way and used as a standard for evaluation.
結果 （１７完）result (17 completed)
Claims (4)
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 ） ▲数式、化学式、表等があります▼（ I ） 〔式中、ＲはＣ＿１−Ｃ＿４のアルキル基を表わし、式
（ I ）は、Ｘ＿１＝Ｘ＿２＝Ｃ＿ｌ、Ｘ＿１＝Ｃ＿ｌ
、Ｘ＿２＝ＨおよびＸ＿１＝Ｘ＿２＝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) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) (In the formula, R represents an alkyl group of C_1 to C_4.)
The general formula (
I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) [In the formula, R represents an alkyl group of C_1-C_4, and the formula (I) is X_1=X_2=C_l, X_1=C_l
, X_2=H and X_1=X_2=H. ] A method for producing a dioxazine compound shown by.
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 a liquid pyridine and its derivatives, pyrimidine and its derivatives, or quinoline and its derivatives.
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.
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) Chlorobenzene, dichlorobenzene, trichlorobenzene and mixtures thereof as inert organic solvents;
The method according to claim 1, wherein an alkylbenzene or nitrobenzene having a boiling point of 110° C. or higher 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 true JPS62192385A (en) | 1987-08-22 |
| JPH0672146B2 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) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0837107A1 (en) * | 1996-10-21 | 1998-04-22 | Clariant GmbH | Process for the manufacture of dioxazine compounds |
-
1986
- 1986-02-19 JP JP3610486A patent/JPH0672146B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0837107A1 (en) * | 1996-10-21 | 1998-04-22 | Clariant GmbH | Process for the manufacture of dioxazine compounds |
| US5932727A (en) * | 1996-10-21 | 1999-08-03 | Clariant Gmbh | Process for the preparation of dioxazine compounds |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0672146B2 (en) | 1994-09-14 |
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