WO2010133133A1 - Synthetic method of 2-methyl-6-tert-butyl-4-dicyanomethylene-4h-pyran - Google Patents
Synthetic method of 2-methyl-6-tert-butyl-4-dicyanomethylene-4h-pyran Download PDFInfo
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- WO2010133133A1 WO2010133133A1 PCT/CN2010/072453 CN2010072453W WO2010133133A1 WO 2010133133 A1 WO2010133133 A1 WO 2010133133A1 CN 2010072453 W CN2010072453 W CN 2010072453W WO 2010133133 A1 WO2010133133 A1 WO 2010133133A1
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- C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
- C07D309/34—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
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- the invention belongs to the field of organic synthesis and relates to the synthesis of key intermediates of red light doping material DCJTB, in particular to a method for synthesizing 2-methyl-6-tert-butyl-4-dicyanomethyl- 4H-pyran. Background technique
- Organic electroluminescent devices have high efficiency and are capable of producing luminescent colors that cover the entire visible region, and have great application prospects in flat panel display technology.
- DCM1 and DCJ are high-efficiency red light-emitting devices for guest luminescent materials. Since then, DCM-based red luminescent dyes have been extensively studied and applied to devices. . However, DCM and DCJ have the disadvantage of concentration fragmentation in device applications. To this end, Tang et al. modified DC J, and they were substituted at the C-1 and C-4 positions of julolididine to obtain compound DCJT. Although DCJT has good electroluminescence properties, its synthesis and purification separation process has great problems due to the reaction precursor 2, 6-dimethyl-(4-dicarbonitrile) used in the synthesis process.
- Alkenyl) -4H pyran contains two reactive methyl groups, so DCJT will further condense with the aldehyde during the synthesis to form a dicondensation by-product 4 - dicyanyl- 2,6-bis (julonine -9-vinyl) -4H-pyran (bis-DCJT).
- bis-DCJT dicondensation by-product 4 - dicyanyl- 2,6-bis (julonine -9-vinyl) -4H-pyran
- DCJTB is currently the most successful material in red light materials, and its brightness, efficiency and longevity meet commercial applications.
- a synthetic method of red light doping material DCJTB is provided in U.S. Patent No. 5,935,720, which is formed by docking two intermediates, one being 2-methyl-6-tert-butyl-4-dicyanomethylene-4H-pyran. , one is 1, 1, 7, 7-Tetramethyl-9-juronidine aldehyde. Among them, 1, 1, 7, 7-tetramethyl-9-juronidine has been solved, only 2-methyl-6-tert-butyl-4-dicyanomethyl-4H-pyran intermediate The yield is very low, which makes DCJTB industrialized at a high cost and is limited in OLED preparation applications. Therefore, 2-methyl-6-tert-butyl-4-dicyanomethylene-4H-pyran intermediate becomes DCJTB industrialization. The bottleneck.
- the present invention provides a method for synthesizing 2-methyl-6-tert-butyl-4-dicyanomethyl-4H-pyran, the yield of which is more than half of the literature yield. It is highly pure and can be used directly to prepare DCJTB.
- a method for synthesizing 2-methyl-6-tert-butyl-4-dicyanomethyl- 4H-pyran comprising the following steps:
- the alcohol solvent is one or a mixture of methanol, ethanol, isopropanol, and butanol.
- the step (1) has a reaction time of 6 to 15 hours.
- the reaction time is 8 hours.
- the reaction mechanism of the present invention is a reaction of 2-methyl-6-tert-butyl-pyrone with malononitrile under the action of a water reducing agent acetic anhydride.
- the present invention adopts a reflux temperature control, and the boiling point of acetic anhydride is 1 39 °C.
- the reaction temperature is basically controlled to be above 130 ° C, so that the reaction rate is accelerated, and the TLC method is used to monitor the end point of the reaction, so that the reaction is more complete, so that the post-treatment of the present invention is relatively simple, and the post-treatment of the present invention
- the treatment process is to recrystallize the concentrated residue directly with an alcohol solvent, eliminating the column chromatography process in the original literature, and the yield is high and the purity is very good, reaching 99% or more, and can be used as a red light intermediate material. , Laser material intermediates used.
- the molar ratio of 2-methyl-6-tert-butyl-pyrone to malononitrile is preferably 1:2, since 2-methyl-6-tert-butyl-pyrone is not easily separated from the product, so an excess is employed.
- the malononitrile is completely reacted, and the concentration can remove excess malononitrile and acetic anhydride, so the molar ratio of 2-methyl-6-tert-butyl-pyrone to malononitrile is preferably 1:2.
- 2-methyl-6-tert-butyl-pyrone is completely reacted.
- alcohol can be methanol, ethanol, isopropanol, butanol One or several blends.
- 2-Methyl-6-tert-butyl-pyrone can be prepared according to the method disclosed in U.S. Patent 5,957, 520 (see examples thereof).
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Abstract
A synthetic method of 2-methyl-6-tert-butyl-4-dicyanomethylene-4H-pyran is disclosed. This method includes the following steps: (1) refluxing the solution of 2-methyl-6-tert-butyl-pyrone and malononitrile in acetic anhydride, monitoring the reaction by TLC; (2) condensing, adding the alcohol solvent for recrystallizing and obtaining the target compound.
Description
2-甲基 -6-叔丁基 -4-二氰甲烯基 -4H-吡喃的合成方法 技术领域 Method for synthesizing 2-methyl-6-tert-butyl-4-dicyanomethyl- 4H-pyran
本发明属于有机合成领域，涉及红光搀杂材料 DCJTB关键中间体的合成， 特 别是涉及 2-甲基 -6-叔丁基 -4-二氰甲烯基 -4H-吡喃的合成方法。 背景技术 The invention belongs to the field of organic synthesis and relates to the synthesis of key intermediates of red light doping material DCJTB, in particular to a method for synthesizing 2-methyl-6-tert-butyl-4-dicyanomethyl- 4H-pyran. Background technique
有机电致发光器件具有效率高以及能够产生可覆盖整个可见光区域的发光 颜色， 在平板显示器技术中有巨大的应用前景。 Organic electroluminescent devices have high efficiency and are capable of producing luminescent colors that cover the entire visible region, and have great application prospects in flat panel display technology.
由于有机电致发光二极管突出的性能以及在平板显示器技术中的巨大应用 前景，引起了人们的高度重视。为了实现彩色显示，必须开发一系列发光效率高、 性能优良的三色发光材料。 经过十多年深入研究， 已开发出具有高亮度、 高效率 的绿光、 蓝色材料， 但红光材料满足要求相对少。 在有机电致发光领域中， 最为 广泛运用的分子内电荷转移类红光染料是 DCM系列染料， 1989年 Tang等人报道 了利用 8-羟基喹啉铝 Alq3作主体发光材料 (C. H. Chen, Tang, C. W.， J. Shi, Thin solid Films, 2000, 363, 327-331)， DCM1和 DCJ作客体发光材料的高效红色发光 器件， 自此， DCM类红色发光染料被广泛地研究并应用到器件中。 而 DCM及 DCJ 在器件应用中会有浓度碎灭的缺点， 为此， Tang等人对 DC J进行了修饰， 他们 在久洛尼定的 C-1及 C-4位进行取代得到化合物 DCJT。尽管 DCJT具有良好的电 致发光性能，但其合成及纯化分离过程却存在很大的问题， 这是由于在合成过程 中使用的反应前体 2， 6一二甲基一 (4-二腈甲烯基) -4H吡喃中含有两个活泼甲 基，因此在合成过程中 DCJT会进一步同醛縮合生成二縮合副产物 4一 (二氰甲烯 基- 2， 6-双（久洛尼定 -9-乙烯基 ) -4H-吡喃（bis— DCJT)。 二縮合副产物的生成 不仅导致反应收率的降低， 而且使得产物的分离纯化变得困难。针对合成过程中 存在的问题， Chen等人设计了 DCJTB, 由于改进了合成方法，化合物的合成与纯 化具有良好的红色发光特性 (Chin H. Chen, C. W. Tang, J. Shi, US5935720. Due to the outstanding performance of organic electroluminescent diodes and the great application prospects in flat panel display technology, people have paid great attention to it. In order to realize color display, it is necessary to develop a series of three-color luminescent materials with high luminous efficiency and excellent performance. After more than ten years of intensive research, green light and blue materials with high brightness and high efficiency have been developed, but red light materials meet relatively few requirements. In the field of organic electroluminescence, the most widely used intramolecular charge transfer red dye is DCM series dye. In 1989, Tang et al. reported the use of 8-hydroxyquinoline aluminum Alq 3 as the main luminescent material (CH Chen, Tang , CW, J. Shi, Thin solid Films, 2000, 363, 327-331), DCM1 and DCJ are high-efficiency red light-emitting devices for guest luminescent materials. Since then, DCM-based red luminescent dyes have been extensively studied and applied to devices. . However, DCM and DCJ have the disadvantage of concentration fragmentation in device applications. To this end, Tang et al. modified DC J, and they were substituted at the C-1 and C-4 positions of julolididine to obtain compound DCJT. Although DCJT has good electroluminescence properties, its synthesis and purification separation process has great problems due to the reaction precursor 2, 6-dimethyl-(4-dicarbonitrile) used in the synthesis process. Alkenyl) -4H pyran contains two reactive methyl groups, so DCJT will further condense with the aldehyde during the synthesis to form a dicondensation by-product 4 - dicyanyl- 2,6-bis (julonine -9-vinyl) -4H-pyran (bis-DCJT). The formation of the second condensation by-product not only leads to a decrease in the reaction yield, but also makes the separation and purification of the product difficult. For the problems in the synthesis process, Chen Etc. DCJTB was designed. Due to the improved synthesis method, the synthesis and purification of the compound have good red luminescence properties (Chin H. Chen, CW Tang, J. Shi, US5935720.
DCJTB是目前红光材料中最成功的材料， 亮度、 效率、 寿命都满足了商业应 用。在美国专利 US5935720中提供了红光搀杂材料 DCJTB的合成方法， 由两个中 间体对接生成的， 一个是 2-甲基 -6-叔丁基 -4-二氰甲烯基 -4H-吡喃， 一个是 1，
1， 7， 7-四甲基 -9-久络尼定醛。 其中 1， 1， 7， 7-四甲基 -9-久络尼定醛已经被 解决， 只有 2-甲基 -6-叔丁基 -4-二氰甲烯基 -4H-吡喃中间体的产率很低， 致使 DCJTB工业化成本很高，在 0LED制备应用也受到限制，因此 2-甲基 -6-叔丁基 -4- 二氰甲烯基 -4H-吡喃中间体成为 DCJTB工业化的瓶颈。 DCJTB is currently the most successful material in red light materials, and its brightness, efficiency and longevity meet commercial applications. A synthetic method of red light doping material DCJTB is provided in U.S. Patent No. 5,935,720, which is formed by docking two intermediates, one being 2-methyl-6-tert-butyl-4-dicyanomethylene-4H-pyran. , one is 1, 1, 7, 7-Tetramethyl-9-juronidine aldehyde. Among them, 1, 1, 7, 7-tetramethyl-9-juronidine has been solved, only 2-methyl-6-tert-butyl-4-dicyanomethyl-4H-pyran intermediate The yield is very low, which makes DCJTB industrialized at a high cost and is limited in OLED preparation applications. Therefore, 2-methyl-6-tert-butyl-4-dicyanomethylene-4H-pyran intermediate becomes DCJTB industrialization. The bottleneck.
由于主要中间体 2-甲基 -6-叔丁基 -4-二氰甲烯基 -4H-吡喃的合成工艺中 (见下式） 每步产率都很低， 合成出的 DCJTB价格很贵， 限制了 DCJTB的使用。 要使 DCJTB得到推广，中间体 2-甲基 -6-叔丁基 -4-二氰甲烯基 -4H-吡喃（式中 E )， 5， 5-二甲基 -2， 4-己二醛 -0， 0-二氟化硼 （式中 B)， 7-二甲基氨基 -2， 2-二甲 基 -6-烯 -3， 5-辛二醛 -0， 0-二氟化硼 （式中 C)， 2-甲基 -6-叔丁基-吡喃酮 （式 中 D) 的合成工艺均有待改善。 Due to the low yield per step of the main intermediate 2-methyl-6-tert-butyl-4-dicyanomethyl-4H-pyran (see below), the price of the synthesized DCJTB is very high. Expensive, limits the use of DCJTB. For the promotion of DCJTB, the intermediate 2-methyl-6-tert-butyl-4-dicyanomethylene-4H-pyran (in the formula E), 5, 5-dimethyl-2, 4-hexyl Dialdehyde-0,0-boron difluoride (in the formula B), 7-dimethylamino-2,2-dimethyl-6-ene-3, 5-octanedialdehyde-0, 0-difluoro The synthesis process of boron (in the formula C) and 2-methyl-6-tert-butyl-pyrone (in the formula D) has to be improved.
在上述专利的基础上， 本发明提供一种 2-甲基 -6-叔丁基 -4-二氰甲烯基 -4H-吡喃的合成方法， 其收率比文献收率高一半以上， 且纯度很高， 可直接用于 制备 DCJTB。 Based on the above patent, the present invention provides a method for synthesizing 2-methyl-6-tert-butyl-4-dicyanomethyl-4H-pyran, the yield of which is more than half of the literature yield. It is highly pure and can be used directly to prepare DCJTB.
2-甲基 -6-叔丁基 -4-二氰甲烯基 -4H-吡喃的合成方法， 包括如下步骤： A method for synthesizing 2-methyl-6-tert-butyl-4-dicyanomethyl- 4H-pyran, comprising the following steps:
( 1 ) 2-甲基 -6-叔丁基 -吡喃酮与丙二腈在乙酸酐的溶液中于回流状态反应，(1) 2-methyl-6-tert-butyl-pyrone is reacted with malononitrile in a solution of acetic anhydride at reflux.
( 2 ) 反应完全后， 浓縮反应液， 加入醇类溶剂重结晶即可。 (2) After the reaction is completed, the reaction solution is concentrated and recrystallized by adding an alcohol solvent.
所述醇类溶剂为甲醇、 乙醇、 异丙醇、 丁醇中的一种或几种混合。 The alcohol solvent is one or a mixture of methanol, ethanol, isopropanol, and butanol.
所述 2-甲基 -6-叔丁基-吡喃酮与丙二腈的摩尔比为 1 : 2。 The molar ratio of 2-methyl-6-tert-butyl-pyrone to malononitrile was 1:2.
所述步骤 （1 ) 反应时间为 6-15小时。 The step (1) has a reaction time of 6 to 15 hours.
优选反应时间为 8小时。 Preferably, the reaction time is 8 hours.
所述反应完全采用 TLC检测。 The reaction was completely tested by TLC.
本发明的反应机理是 2-甲基 -6-叔丁基-吡喃酮与丙二腈在縮水剂乙酸酐的 作用下反应， 本发明采用回流温度控制， 乙酸酐的沸点为 1 39 °C， 因为有水生 成， 因此反应温度基本控制成 130°C以上， 使反应速度加快， 同时采用 TLC法 来监测反应的终点， 因此反应更完全， 使得本发明的后处理比较简单， 本发明的 后处理过程是将浓縮后的残余物直接用醇类溶剂来重结晶，省去了原文献中柱层 析过程， 收率高且纯度非常好， 达到 99%以上， 可作为红光中间体材料、 激光材 料中间体使用。 The reaction mechanism of the present invention is a reaction of 2-methyl-6-tert-butyl-pyrone with malononitrile under the action of a water reducing agent acetic anhydride. The present invention adopts a reflux temperature control, and the boiling point of acetic anhydride is 1 39 °C. Because water is generated, the reaction temperature is basically controlled to be above 130 ° C, so that the reaction rate is accelerated, and the TLC method is used to monitor the end point of the reaction, so that the reaction is more complete, so that the post-treatment of the present invention is relatively simple, and the post-treatment of the present invention The treatment process is to recrystallize the concentrated residue directly with an alcohol solvent, eliminating the column chromatography process in the original literature, and the yield is high and the purity is very good, reaching 99% or more, and can be used as a red light intermediate material. , Laser material intermediates used.
2-甲基 -6-叔丁基 -吡喃酮与丙二腈的摩尔比优选为 1 : 2, 由于 2-甲基 -6- 叔丁基 -吡喃酮不易与产物分离， 因此采用过量的丙二腈使之反应完全， 浓縮能 将多余的丙二腈和乙酸酐去除， 因此 2-甲基 -6-叔丁基-吡喃酮与丙二腈的摩 尔比优选为 1 : 2, 使 2-甲基 -6-叔丁基 -吡喃酮完全反应。 The molar ratio of 2-methyl-6-tert-butyl-pyrone to malononitrile is preferably 1:2, since 2-methyl-6-tert-butyl-pyrone is not easily separated from the product, so an excess is employed. The malononitrile is completely reacted, and the concentration can remove excess malononitrile and acetic anhydride, so the molar ratio of 2-methyl-6-tert-butyl-pyrone to malononitrile is preferably 1:2. , 2-methyl-6-tert-butyl-pyrone is completely reacted.
本发明工艺按如下进行： The process of the invention proceeds as follows:
2-甲基 -6-叔丁基-吡喃酮、 丙二腈、 乙酸酐回流反应 6~15小时， 浓縮后用 醇纯化； 醇可以是甲醇、 乙醇、 异丙醇、 丁醇中的一种或几种混合。 2-methyl-6-tert-butyl-pyrone, malononitrile, acetic anhydride reflux reaction for 6~15 hours, concentrated and purified with alcohol; alcohol can be methanol, ethanol, isopropanol, butanol One or several blends.
本专利提供的合成工艺， 与美国专利文献提供工艺相比较， 具有以下特点： The synthetic process provided by this patent has the following characteristics compared with the process provided by the U.S. patent document:
( 1 )、 本专利提供的工艺产率比文献高一半以上， 产品纯度达 99%以上。(1) The process yield provided by this patent is more than half of the literature, and the purity of the product is over 99%.
( 2 )、 反应条件温和， 工艺简单、 容易生产化、 成本低。
( 3)、 得到的产物 E纯度较高， 可直接用于制备 DCJTB。 具体实施方式 (2) The reaction conditions are mild, the process is simple, the production is easy, and the cost is low. (3) The obtained product E has high purity and can be directly used for preparing DCJTB. detailed description
下面结合实施例对本发明作进一步的详细说明。 The present invention will be further described in detail below with reference to the embodiments.
2-甲基 -6-叔丁基-吡喃酮可以根据 US5935720 公开的方法制备 （见其实例 2-Methyl-6-tert-butyl-pyrone can be prepared according to the method disclosed in U.S. Patent 5,957, 520 (see examples thereof).
3)。 3).
实施例 1、 2-甲基 -6-叔丁基 -4-二氰甲烯基 -4H-吡喃 Example 1. 2-Methyl-6-tert-butyl-4-dicyanomethyl- 4H-pyran
在 25mL三颈烧瓶中加入 2-甲基 -6-叔丁基-吡喃酮 2. 21g (0. Olmo)、 丙二睛 2. 04g (0. 02mo) , 乙酸酐 5mL 混合搅拌， 加热回流， TLC 检测原料反应完毕 （8 小时）， 停止加热， 旋干混合物， 加入甲醇重结晶两次， 得到 2. 089浅黄色固体 (80%)， HPLC检测纯度 99%。 (US5935720报道产率 50%) In a 25 mL three-necked flask, 2-methyl-6-tert-butyl-pyrone was added. 21 g (0. Olmo), propylene diacetate 2. 04 g (0. 02 mo), acetic anhydride 5 mL was stirred and heated, refluxed. After the TLC was tested, the reaction was completed (8 hours), the heating was stopped, the mixture was spun, and the mixture was recrystallized twice with methanol to give 2. 089 pale yellow solid (80%). (US5935720 reports a yield of 50%)
熔点： 108-110°C Melting point: 108-110 ° C
HMNR (CDC13， 400Hz) : 1. 31 (9H， s) ; 2. 35 (3H, s) ; 6. 57 (2H, d)
HMNR (CDC1 3 , 400Hz) : 1. 31 (9H, s) ; 2. 35 (3H, s) ; 6. 57 (2H, d)
Claims
1、 2-甲基 -6-叔丁基 -4-二氰甲烯基 -4H-吡喃的合成方法， 包括如下步骤：1. A method for synthesizing 2-methyl-6-tert-butyl-4-dicyanomethyl- 4H-pyran, comprising the following steps:
( 1 ) 2-甲基 -6-叔丁基 -吡喃酮与丙二腈在乙酸酐的溶液中于回流状态反应，(1) 2-methyl-6-tert-butyl-pyrone is reacted with malononitrile in a solution of acetic anhydride at reflux.
(2) 反应完全后， 浓縮反应液， 加入醇类溶剂重结晶即可。 (2) After the reaction is completed, the reaction solution is concentrated and recrystallized by adding an alcohol solvent.
2、 根据权利要求 1所述的合成方法， 所述醇类溶剂为甲醇、 乙醇、 异丙醇、 丁 醇中的一种或几种混合。 The synthesis method according to claim 1, wherein the alcohol solvent is one or a mixture of methanol, ethanol, isopropanol, and butanol.
3、根据权利要求 1所述的合成方法，所述 2-甲基 -6-叔丁基-吡喃酮与丙二腈的摩 尔比为 1： 2。 The method according to claim 1, wherein the molar ratio of the 2-methyl-6-tert-butyl-pyrone to malononitrile is 1:2.
4、 根据权利要求 1所述的合成方法， 所述步骤 （1 ) 反应时间为 6-15小时。 4. The method according to claim 1, wherein the step (1) has a reaction time of 6 to 15 hours.
5、 根据权利要求 4所述的合成方法， 所述反应时间为 8小时。 5. The method of synthesis according to claim 4, wherein the reaction time is 8 hours.
6、 根据权利要求 1所述的合成方法， 所述反应完全采用 TLC检测。
6. The method of synthesis according to claim 1, wherein the reaction is completely detected by TLC.
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| CN200910084513.4 | 2009-05-20 | ||
| CN2009100845134A CN101891724A (en) | 2009-05-20 | 2009-05-20 | Synthesis method of 2-methyl-6-tert-butyl-4-dicyano methylene-4H-pyrane |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6867309B2 (en) * | 2002-01-08 | 2005-03-15 | Chi Mei Optoelectronics Corporation | Red-emitting organic electroluminescent compound |
| WO2007136588A1 (en) * | 2006-05-15 | 2007-11-29 | Nitto Denko Corporation | Light emitting devices and compositions |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6867309B2 (en) * | 2002-01-08 | 2005-03-15 | Chi Mei Optoelectronics Corporation | Red-emitting organic electroluminescent compound |
| WO2007136588A1 (en) * | 2006-05-15 | 2007-11-29 | Nitto Denko Corporation | Light emitting devices and compositions |
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|---|---|
| CN101891724A (en) | 2010-11-24 |
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