WO2009139564A2 - Production method for an intermediate for a blue-light-emitting substance using anthrone - Google Patents

Production method for an intermediate for a blue-light-emitting substance using anthrone Download PDF

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WO2009139564A2
WO2009139564A2 PCT/KR2009/002481 KR2009002481W WO2009139564A2 WO 2009139564 A2 WO2009139564 A2 WO 2009139564A2 KR 2009002481 W KR2009002481 W KR 2009002481W WO 2009139564 A2 WO2009139564 A2 WO 2009139564A2
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formula
compound
anthrone
light emitting
blue
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PCT/KR2009/002481
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WO2009139564A3 (en
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안현철
배호기
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주식회사 동진쎄미켐
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/626—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing more than one polycyclic condensed aromatic rings, e.g. bis-anthracene
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1011—Condensed systems
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers

Definitions

  • the present invention relates to a method for producing an intermediate of a blue light emitting material for an organic light emitting device having a specific structure in an improved yield through a novel synthesis method using anthrone.
  • blue light emitting materials for organic light emitting devices those having various structures are known, and 9- (naphthalen-2-yl) anthracene derivatives corresponding to the common structure of blue light emitting materials are most widely used as intermediates of blue light emitting materials.
  • the 9- (naphthalen-2-yl) anthracene derivative which is an intermediate of a blue light emitting material, has been produced by the Suzuki coupling method used for bonding between carbon and carbon. It can be represented by Scheme 1:
  • the conventional Suzuki coupling method has been widely used because the synthesis yield is relatively high, such as 70% or more, but the cost of the reactants, especially the Pd catalyst and 9-bromoanthracene used in the reaction, is high, and the reaction cost is high. It has the disadvantage of going through a 2-step reaction.
  • the synthesis method is practically rarely used due to the disadvantage that the variation in the synthesis yield according to the experimenter is too large and there is a limit in obtaining a synthesis yield of 60% or more.
  • an object of the present invention is to provide a method capable of stably manufacturing intermediates of blue light emitting materials for organic light emitting devices with a constant and improved yield by supplementing disadvantages of the conventional Suzuki coupling and the [Scheme 2] synthesis method. do.
  • a compound of formula 2 is reacted with alkyllithium to prepare a compound of formula 3, and then reacted with anthrone to prepare a compound of formula 4, It provides a method for preparing an intermediate of the blue light emitting substance represented by the following formula (1) comprising reacting a compound with a strong acid:
  • Ar is substituted or unsubstituted C3-50 aryl halide.
  • the intermediate of the blue light emitting material for organic light emitting device can be stably manufactured in a constant and improved yield by supplementing the disadvantages of the existing Suzuki coupling, and the cost of the reactant is inexpensive and the intermediate product is separated. It is possible to achieve the desired reaction through a one-step reaction without the need to produce an intermediate of the blue light emitting material economically and conveniently.
  • the present inventors earnestly studied to improve the existing [Scheme 2] method, in which the variation in the synthesis yield according to the experimenter was too large and limited to obtaining a synthesis yield of 60% or more, and based on the existing [Scheme 2] method
  • the above-mentioned disadvantages can be solved by changing the reaction solvent and the reaction temperature, thereby completing the present invention.
  • a compound of Formula 2 is prepared by reacting a compound of Formula 2 with alkyllithium at a temperature of ⁇ 40 to 20 ° C. in an ethyl ether solvent. And reacting it with anthrone to prepare a compound of Formula 4, and then reacting the compound of Formula 4 with a strong acid.
  • Ar is substituted or unsubstituted C3-50 aryl halide.
  • said Ar is phenyl, naphthyl, anthryl, pyrenyl or phenanthryl, optionally substituted with one or more halogen, and optionally substituted with one or more C1-50 alkyl, C3-30 aryl or C3-30 heteroaryl Can be.
  • the halogen may preferably be bromine or iodine.
  • the preparation of the blue light emitting intermediate of formula 1 according to the present invention can be carried out in an ethyl ether solvent under a nitrogen atmosphere at a temperature near -40 to 20 ° C, preferably -20 to 10 ° C, more preferably near 0 ° C. .
  • the ethyl ether solvent may be used in an amount of 3 to 10 moles, preferably 4 to 7 moles, based on 1 mole of the compound of Formula 2.
  • the compound of formula 2 is reacted with alkyllithium (e.g., n-butyllithium) to prepare a compound of formula 3 and reacted with anthrone to produce a compound of formula 4, and then the compound of formula 4 is prepared with a strong acid (e.g. hydrochloric acid).
  • a strong acid e.g. hydrochloric acid
  • Anthrone and strong acid can be used in amounts of 0.5 to 2 moles and 5 to 15 moles based on 1 mole of the compound of formula 2, respectively.
  • the strong acid is preferably used at a concentration of 4 to 8 M.
  • the cost of the reactants is lower than that of the conventional Suzuki coupling method, and the target compound can be synthesized economically and conveniently through one step reaction without separating intermediate products (50%). Cost reduction effect above), compared to the existing [Scheme 2] method, the target compound can be stably synthesized with a constant and much improved yield (more than 60% synthetic yield gain effect).
  • the yield of the title compound obtained by repeating the reaction of Example 1 three times was 68%, 65% and 69%, respectively, with an average yield of the title compound being 67.3%.
  • the reaction of Example 1 is reproducible and can be applied to mass production.
  • the yield of the title compound obtained by repeating the reaction of Comparative Example 1 three times was 83%, 78% and 75%, respectively, and the average yield of the title compound was 78.7%.
  • the yield obtained in Comparative Example 1 was higher than that of Example 1, but the cost of Pd (PPh3) 4 catalyst and 9-bromoanthracene used in the reaction was higher than that of Example 1, and the reaction cost was higher than that of Example 1. It was much higher and uneconomic.
  • the yield of the title compound obtained by repeating the reaction of Comparative Example 2 three times was 47%, 53% and 51%, respectively, and the average yield of the title compound was 50.3%.
  • the yield obtained in Comparative Example 2 was confirmed to be not only much lower than in Example 1 but also poor reproducibility.
  • Example 1 According to the method disclosed in US Patent Application No. 2006-43858 (Idemitsu Kosan) using 9- (naphthalen-2-yl) anthracene synthesized in Example 1 having the structure of Formula 5 A commercially available blue light emitting material was prepared. A light emitting device having a conventional structure including the prepared blue light emitting material in a light emitting layer was manufactured, and the physical properties of the device were measured, and the physical property measurement results are shown in Table 1 below. At this time, the doping amount of the light emitting layer was changed to 0, 3, 5, 7 and 9%, respectively.
  • the compound prepared according to the present invention has excellent electrical stability, high luminous efficiency and luminous luminance, and can be used as a light emitting material of an organic light emitting diode.
  • the intermediate of the blue light emitting material for organic light emitting device can be stably manufactured in a constant and improved yield by supplementing the disadvantages of the existing Suzuki coupling, and the cost of the reactant is inexpensive and the intermediate product is separated. It is possible to achieve the desired reaction through a one-step reaction without the need to produce an intermediate of the blue light emitting material economically and conveniently.

Abstract

The present invention relates to a production method for an intermediate for a blue-light-emitting substance using anthrone. A characterising feature of the method of the present invention is that an intermediate for a blue-light-emitting substance is produced using anthrone at a temperature of between -40 and 20°C in an ethyl ether solvent. When this method is employed, the target intermediate for a blue-light-emitting substance, which is used in an organic light-emitting element, can be produced in high yield and in a way that is both economical and straightforward, while also being fixed, by compensating for the shortcomings of Suzuki coupling of the prior art.

Description

안트론을 이용한 청색발광물질 중간체의 제조방법Method for preparing blue light emitting intermediate using anthrone
본 발명은 특정 구조를 갖는 유기발광소자용 청색발광물질의 중간체를 안트론을 이용하는 신규한 합성 방법을 통해 향상된 수율로 제조하는 방법에 관한 것이다.The present invention relates to a method for producing an intermediate of a blue light emitting material for an organic light emitting device having a specific structure in an improved yield through a novel synthesis method using anthrone.
유기발광소자용 청색발광물질로서 다양한 구조의 것들이 알려져 있는데, 이러한 청색발광물질의 공통적인 구조에 해당하는 9-(나프탈렌-2-일)안트라센 유도체가 청색발광물질의 중간체로서 가장 널리 사용되고 있다.As blue light emitting materials for organic light emitting devices, those having various structures are known, and 9- (naphthalen-2-yl) anthracene derivatives corresponding to the common structure of blue light emitting materials are most widely used as intermediates of blue light emitting materials.
청색발광물질의 중간체인 상기 9-(나프탈렌-2-일)안트라센 유도체는 탄소와 탄소 간의 결합시 사용되는 스즈키 커플링(Suzuki coupling) 방법에 의해 예전부터 제조되어 왔는데, 그 제법상 구체적인 일례는 하기 반응식 1로 나타내어질 수 있다:The 9- (naphthalen-2-yl) anthracene derivative, which is an intermediate of a blue light emitting material, has been produced by the Suzuki coupling method used for bonding between carbon and carbon. It can be represented by Scheme 1:
[반응식 1]Scheme 1
Figure PCTKR2009002481-appb-I000001
Figure PCTKR2009002481-appb-I000001
상기 기존의 스즈키 커플링 방법은 합성 수율이 70% 이상으로 비교적 높아 널리 사용되어 왔으나, 반응물질, 특히 반응에 사용되는 Pd 촉매 및 9-브로모안트라센의 원가가 비싸 반응단가가 높고, 두 단계(2-step)의 반응을 거쳐야 한다는 단점을 가졌다.The conventional Suzuki coupling method has been widely used because the synthesis yield is relatively high, such as 70% or more, but the cost of the reactants, especially the Pd catalyst and 9-bromoanthracene used in the reaction, is high, and the reaction cost is high. It has the disadvantage of going through a 2-step reaction.
이에, 상기 스즈키 커플링 방법을 대체할 수 있는 방법으로서, 반응물질의 원가가 저렴하고 중간생성물을 분리할 필요 없이 한 단계(1-step) 반응을 통해 목적하는 반응을 달성할 수 있는, 안트론을 이용하는 합성방법이 소개된 바 있으며, 그 제법상 구체적인 일례는 하기 반응식 2와 같다:Thus, as a method to replace the Suzuki coupling method, anthrone, which is a low cost of the reactants and can achieve the desired reaction through a one-step reaction without having to separate the intermediate product Synthetic method using was introduced, a specific example of the manufacturing method is shown in Scheme 2:
[반응식 2]Scheme 2
Figure PCTKR2009002481-appb-I000002
Figure PCTKR2009002481-appb-I000002
그러나, 상술한 장점에도 불구하고, 상기 합성방법은 실험자에 따른 합성 수율의 변동이 너무 크고 60% 이상의 합성 수율을 얻는 데에 한계가 있다는 단점 때문에 실제로 거의 사용되지 않고 있는 실정이다.However, despite the advantages described above, the synthesis method is practically rarely used due to the disadvantage that the variation in the synthesis yield according to the experimenter is too large and there is a limit in obtaining a synthesis yield of 60% or more.
따라서, 본 발명은 기존의 스즈키 커플링과 [반응식 2] 합성방법의 단점을 보완하여 유기발광소자용 청색발광물질의 중간체를 일정하면서도 향상된 수율로 안정적으로 제조할 수 있는 방법을 제공하는 것을 목적으로 한다.Accordingly, an object of the present invention is to provide a method capable of stably manufacturing intermediates of blue light emitting materials for organic light emitting devices with a constant and improved yield by supplementing disadvantages of the conventional Suzuki coupling and the [Scheme 2] synthesis method. do.
상기 목적을 달성하기 위하여, 본 발명은 In order to achieve the above object, the present invention
에틸에테르 용매 중에서 -40 내지 20 ℃의 온도에서, 하기 화학식 2의 화합물을 알킬리튬과 반응시켜 하기 화학식 3의 화합물을 제조하고 이를 안트론과 반응시켜 하기 화학식 4의 화합물을 제조한 다음, 화학식 4의 화합물을 강산과 반응시키는 것을 포함하는 것을 특징으로 하는 하기 화학식 1로 표시되는 청색발광물질 중간체의 제조방법을 제공한다:At a temperature of -40 to 20 ° C. in an ethyl ether solvent, a compound of formula 2 is reacted with alkyllithium to prepare a compound of formula 3, and then reacted with anthrone to prepare a compound of formula 4, It provides a method for preparing an intermediate of the blue light emitting substance represented by the following formula (1) comprising reacting a compound with a strong acid:
[화학식 1][Formula 1]
Figure PCTKR2009002481-appb-I000003
Figure PCTKR2009002481-appb-I000003
[화학식 2][Formula 2]
Ar-BrAr-Br
[화학식 3][Formula 3]
Ar-LiAr-Li
[화학식 4][Formula 4]
Figure PCTKR2009002481-appb-I000004
Figure PCTKR2009002481-appb-I000004
상기 식에서,Where
Ar은 치환되거나 치환되지 않은 C3-50 아릴 할라이드이다.Ar is substituted or unsubstituted C3-50 aryl halide.
본 발명의 방법에 의하면, 기존의 스즈키 커플링의 단점을 보완하여 유기발광소자용 청색발광물질의 중간체를 일정하면서도 향상된 수율로 안정적으로 제조할 수 있으며, 반응물질의 원가가 저렴하고 중간생성물을 분리할 필요 없이 한 단계(1-step) 반응을 통해 목적하는 반응을 달성할 수 있어 경제적이고 간편하게 청색발광물질의 중간체를 제조할 수 있다.According to the method of the present invention, the intermediate of the blue light emitting material for organic light emitting device can be stably manufactured in a constant and improved yield by supplementing the disadvantages of the existing Suzuki coupling, and the cost of the reactant is inexpensive and the intermediate product is separated. It is possible to achieve the desired reaction through a one-step reaction without the need to produce an intermediate of the blue light emitting material economically and conveniently.
본 발명자들은, 실험자에 따른 합성 수율의 변동이 너무 크고 60% 이상의 합성 수율을 얻는 데에 한계가 있는 기존의 [반응식 2] 방법을 개선하고자 예의연구한 결과, 기존의 [반응식 2] 방법에 근거하되 반응용매와 반응온도를 변화시킴으로써 상술한 단점을 해소시킬 수 있음을 발견하고 본 발명을 완성하게 되었다.The present inventors earnestly studied to improve the existing [Scheme 2] method, in which the variation in the synthesis yield according to the experimenter was too large and limited to obtaining a synthesis yield of 60% or more, and based on the existing [Scheme 2] method However, it was found that the above-mentioned disadvantages can be solved by changing the reaction solvent and the reaction temperature, thereby completing the present invention.
본 발명에 따른 하기 화학식 1로 표시되는 청색발광물질 중간체의 제조방법은, 에틸에테르 용매 중에서 -40 내지 20 ℃의 온도에서, 하기 화학식 2의 화합물을 알킬리튬과 반응시켜 하기 화학식 3의 화합물을 제조하고 이를 안트론과 반응시켜 하기 화학식 4의 화합물을 제조한 다음, 화학식 4의 화합물을 강산과 반응시키는 것을 포함한다.In the method for preparing the blue light emitting intermediate represented by Formula 1 according to the present invention, a compound of Formula 2 is prepared by reacting a compound of Formula 2 with alkyllithium at a temperature of −40 to 20 ° C. in an ethyl ether solvent. And reacting it with anthrone to prepare a compound of Formula 4, and then reacting the compound of Formula 4 with a strong acid.
[화학식 1][Formula 1]
Figure PCTKR2009002481-appb-I000005
Figure PCTKR2009002481-appb-I000005
[화학식 2][Formula 2]
Ar-BrAr-Br
[화학식 3][Formula 3]
Ar-LiAr-Li
[화학식 4][Formula 4]
Figure PCTKR2009002481-appb-I000006
Figure PCTKR2009002481-appb-I000006
상기 식에서,Where
Ar은 치환되거나 치환되지 않은 C3-50 아릴 할라이드이다.Ar is substituted or unsubstituted C3-50 aryl halide.
이러한 본 발명에 따른 화학식 1의 청색발광물질 중간체의 제법을 반응식으로 나타내면 하기 반응식 3과 같다.The preparation method of the blue light emitting substance intermediate of Chemical Formula 1 according to the present invention is represented by the following Scheme 3.
[반응식 3]Scheme 3
Figure PCTKR2009002481-appb-I000007
Figure PCTKR2009002481-appb-I000007
상기 식에서, Ar은 상기에서 정의한 바와 같다. Wherein Ar is as defined above.
바람직하게는, 상기 Ar은 하나 이상의 할로겐으로 치환된, 페닐, 나프틸, 안트릴, 피레닐 또는 페난트릴이며, 임의로 하나 이상의 C1-50 알킬, C3-30 아릴 또는 C3-30 헤테로아릴로 치환될 수 있다. 상기 할로겐은 바람직하게는 브롬 또는 요오드일 수 있다.Preferably, said Ar is phenyl, naphthyl, anthryl, pyrenyl or phenanthryl, optionally substituted with one or more halogen, and optionally substituted with one or more C1-50 alkyl, C3-30 aryl or C3-30 heteroaryl Can be. The halogen may preferably be bromine or iodine.
본 발명에 따른 화학식 1의 청색발광물질 중간체의 제조는 에틸에테르 용매 중에서 -40 내지 20 ℃, 바람직하게는 -20 내지 10 ℃, 더욱 바람직하게는 0 ℃ 근처의 온도에서 질소 분위기 하에 수행할 수 있다. 에틸에테르 용매는 화학식 2의 화합물 1몰을 기준으로 3 내지 10몰, 바람직하게는 4 내지 7몰의 양으로 사용할 수 있다.The preparation of the blue light emitting intermediate of formula 1 according to the present invention can be carried out in an ethyl ether solvent under a nitrogen atmosphere at a temperature near -40 to 20 ° C, preferably -20 to 10 ° C, more preferably near 0 ° C. . The ethyl ether solvent may be used in an amount of 3 to 10 moles, preferably 4 to 7 moles, based on 1 mole of the compound of Formula 2.
화학식 2의 화합물을 알킬리튬(예: n-부틸리튬)과 반응시켜 화학식 3의 화합물을 제조하고 이를 안트론과 반응시켜 화학식 4의 화합물을 제조한 다음, 화학식 4의 화합물을 강산(예: 염산)과 반응시키는데, 안트론 및 강산은 각각 화학식 2의 화합물 1몰을 기준으로 0.5 내지 2몰 및 5 내지 15몰의 양으로 사용할 수 있다. 강산은 4 내지 8M 농도의 것을 사용하는 것이 바람직하다.The compound of formula 2 is reacted with alkyllithium (e.g., n-butyllithium) to prepare a compound of formula 3 and reacted with anthrone to produce a compound of formula 4, and then the compound of formula 4 is prepared with a strong acid (e.g. hydrochloric acid). ), Anthrone and strong acid can be used in amounts of 0.5 to 2 moles and 5 to 15 moles based on 1 mole of the compound of formula 2, respectively. The strong acid is preferably used at a concentration of 4 to 8 M.
본 발명의 방법에 출발물질로서 사용되는 화학식 2의 화합물은 Ar의 종류에 따라 각각 통상적인 방법으로 제조할 수 있다.Compounds of formula (II) used as starting materials in the process of the present invention can be prepared by conventional methods, respectively, depending on the type of Ar.
이와 같이, 본 발명의 방법에 의하면, 기존의 스즈키 커플링 방법에 비해 반응물질의 원가가 저렴하고 중간생성물을 분리할 필요 없이 한 단계 반응을 통해 목적 화합물을 경제적이고 간편하게 합성할 수 있고(50% 이상의 원가 절감 효과), 기존의 [반응식 2] 방법에 비해 목적 화합물을 일정하면서도 훨씬 향상된 수율로 안정적으로 합성할 수 있다(60% 이상의 합성 수율 획득 효과).As described above, according to the method of the present invention, the cost of the reactants is lower than that of the conventional Suzuki coupling method, and the target compound can be synthesized economically and conveniently through one step reaction without separating intermediate products (50%). Cost reduction effect above), compared to the existing [Scheme 2] method, the target compound can be stably synthesized with a constant and much improved yield (more than 60% synthetic yield gain effect).
이하, 본 발명의 이해를 돕기 위하여 바람직한 실시예를 제시하나, 하기 실시예는 본 발명을 예시하는 것일 뿐 본 발명의 범위가 하기 실시예에 한정되는 것은 아니다.Hereinafter, preferred examples are provided to help understanding of the present invention, but the following examples are merely to illustrate the present invention, and the scope of the present invention is not limited to the following examples.
[실시예]EXAMPLE
[실시예 1] 본 발명에 따른 화학식 1a의 9-(나프탈렌-2-일)안트라센의 합성Example 1 Synthesis of 9- (naphthalen-2-yl) anthracene of formula 1a according to the present invention
[반응식 4]Scheme 4
Figure PCTKR2009002481-appb-I000008
Figure PCTKR2009002481-appb-I000008
에틸에테르 용매 중에서 0 ℃의 온도 및 질소 분위기 조건 하에서, 화학식 2a의 2-브로모나프탈렌을 n-부틸리튬과 반응시켜 화학식 3a의 화합물을 제조하고 이를 안트론과 반응시켜 화학식 4a의 화합물을 제조한 다음, 화학식 4a의 화합물을 6M 염산과 반응시켜 화학식 1a의 표제 화합물을 제조하였다. 이때 에틸에테르 용매, 안트론 및 염산을 각각 화학식 2a의 2-브로모나프탈렌 1몰을 기준으로 5몰, 0.83몰 및 10몰의 양으로 사용하였으며, 리튬화반응(0 ℃)에 소요된 반응시간은 60분, 안트론 첨가 후 12시간 동안 실온에서 반응하였다.Under a temperature of 0 ° C. and a nitrogen atmosphere in an ethyl ether solvent, 2-bromonaphthalene of formula 2a was reacted with n-butyllithium to prepare a compound of formula 3a, and reacted with anthrone to prepare a compound of formula 4a. Next, the compound of formula 4a was reacted with 6M hydrochloric acid to prepare the title compound of formula 1a. At this time, ethyl ether solvent, anthrone and hydrochloric acid were used in amounts of 5 moles, 0.83 moles and 10 moles based on 1 mole of 2-bromonaphthalene of Formula 2a, respectively, and the reaction time required for lithiation reaction (0 ° C.). Silver was reacted for 60 minutes at room temperature for 12 hours after the addition of anthrone.
상기 실시예 1의 반응을 3회 반복 수행하여 얻어진 표제 화합물의 수율이 각각 68%, 65% 및 69%로서, 표제 화합물의 평균 수율은 67.3%이었다. 3회 실험을 통해 얻어진 수율들의 재현성을 판정해 본 결과, 실시예 1의 반응은 재현성이 있어 대량생산에 적용할 수 있음을 확인하였다.The yield of the title compound obtained by repeating the reaction of Example 1 three times was 68%, 65% and 69%, respectively, with an average yield of the title compound being 67.3%. As a result of judging the reproducibility of the yields obtained through three experiments, it was confirmed that the reaction of Example 1 is reproducible and can be applied to mass production.
[비교예 1] 스즈키 커플링 방법에 근거한 화학식 1a의 9-(나프탈렌-2-일)안트라센의 합성Comparative Example 1 Synthesis of 9- (naphthalen-2-yl) anthracene of Chemical Formula 1a Based on Suzuki Coupling Method
[반응식 5]Scheme 5
Figure PCTKR2009002481-appb-I000009
Figure PCTKR2009002481-appb-I000009
테트라하이드로퓨란(THF) 용매 중에서 -78 ℃의 온도 및 질소 분위기 조건 하에서, 화학식 2a의 2-브로모나프탈렌을 n-부틸리튬과 반응시켜 화학식 3a의 화합물을 제조하고 이를 트리메톡시보론 및 염산과 반응시킨 후 결과적으로 얻어진 생성물을 여과분리 및 정제하여 화학식 5의 화합물을 수득하였다(수율 70 내지 76%). 수득된 화학식 5의 화합물을 톨루엔과 물의 혼합용매 중에서 Pd(PPh3)4 및 K2CO3 촉매 존재 하에서 9-브로모안트라센과 반응시켜 화학식 1a의 표제 화합물을 제조하였다.In a tetrahydrofuran (THF) solvent, under a temperature of −78 ° C. and under nitrogen atmosphere, 2-bromonaphthalene of Formula 2a is reacted with n-butyllithium to prepare a compound of Formula 3a, which is treated with trimethoxyboron and hydrochloric acid. After the reaction, the resultant product was filtered off and purified to obtain a compound of formula 5 (yield 70 to 76%). The title compound of Formula 1a was prepared by reacting the obtained compound of Formula 5 with 9-bromoanthracene in the presence of Pd (PPh 3) 4 and K 2 CO 3 catalyst in a mixed solvent of toluene and water.
상기 비교예 1의 반응을 3회 반복 수행하여 얻어진 표제 화합물의 수율이 각각 83%, 78% 및 75%로서, 표제 화합물의 평균 수율은 78.7%이었다. 비교예 1에서 얻어진 수율은 실시예 1에 비해 높았으나, 반응에 사용된 Pd(PPh3)4 촉매 및 9-브로모안트라센의 원가가 높고 두 단계 반응을 거쳐야 하는 등 반응원가가 실시예 1에 비해 훨씬 높아 비경제적임을 확인할 수 있었다.The yield of the title compound obtained by repeating the reaction of Comparative Example 1 three times was 83%, 78% and 75%, respectively, and the average yield of the title compound was 78.7%. The yield obtained in Comparative Example 1 was higher than that of Example 1, but the cost of Pd (PPh3) 4 catalyst and 9-bromoanthracene used in the reaction was higher than that of Example 1, and the reaction cost was higher than that of Example 1. It was much higher and uneconomic.
[비교예 2] 기존 [반응식 2] 방법에 근거한 화학식 1a의 9-(나프탈렌-2-일)안트라센의 합성Comparative Example 2 Synthesis of 9- (naphthalen-2-yl) anthracene of formula 1a based on the existing Scheme 2 method
[반응식 6]Scheme 6
Figure PCTKR2009002481-appb-I000010
Figure PCTKR2009002481-appb-I000010
테트라하이드로퓨란(THF) 용매 중에서 -78 ℃의 온도 및 질소 분위기 조건 하에서, 화학식 2a의 2-브로모나프탈렌을 n-부틸리튬과 반응시켜 화학식 3a의 화합물을 제조하고 이를 안트론과 반응시켜 화학식 4a의 화합물을 제조한 다음, 화학식 4a의 화합물을 6M 염산과 반응시켜 화학식 1a의 표제 화합물을 제조하였다. 이때 에틸에테르 용매, 안트론 및 염산을 각각 화학식 2a의 2-브로모나프탈렌 1몰을 기준으로 5몰, 0.83몰 및 10몰의 양으로 사용하였으며, 리튬화반응(-78 ℃)에 소요된 반응시간은 30분, 안트론 첨가 후 12시간 동안 실온에서 반응하였다.In a tetrahydrofuran (THF) solvent, under a temperature of −78 ° C. and a nitrogen atmosphere, 2-bromonaphthalene of Formula 2a is reacted with n-butyllithium to prepare a compound of Formula 3a, which is reacted with anthrone to react with Formula 4a. The compound of formula 4a was then reacted with 6M hydrochloric acid to prepare the title compound of formula 1a. At this time, ethyl ether solvent, anthrone and hydrochloric acid were used in amounts of 5 moles, 0.83 moles and 10 moles based on 1 mole of 2-bromonaphthalene of Chemical Formula 2a, respectively. The time was reacted for 30 minutes at room temperature for 12 hours after the addition of anthrone.
상기 비교예 2의 반응을 3회 반복 수행하여 얻어진 표제 화합물의 수율이 각각 47%, 53% 및 51%로서, 표제 화합물의 평균 수율은 50.3%이었다. 비교예 2에서 얻어진 수율은 실시예 1에 비해 훨씬 낮을 뿐만 아니라 재현성 또한 좋지 않음을 확인할 수 있었다.The yield of the title compound obtained by repeating the reaction of Comparative Example 2 three times was 47%, 53% and 51%, respectively, and the average yield of the title compound was 50.3%. The yield obtained in Comparative Example 2 was confirmed to be not only much lower than in Example 1 but also poor reproducibility.
[참조예] 청색발광물질 및 발광소자의 제조Reference Example Manufacture of Blue Emitting Material and Light Emitting Device
상기 실시예 1에서 합성된 9-(나프탈렌-2-일)안트라센을 사용하여 미국 특허출원 제2006-43858호(이데미쯔 코산(Idemitsu Kosan)사)에 개시된 방법에 따라 하기 화학식 5의 구조를 갖는 상용되는 청색발광물질을 제조하였다. 제조된 청색발광물질을 발광층에 포함하는 통상적인 구조의 발광소자를 제작하고, 소자의 물성을 측정하여 하기 표 1에 물성 측정결과를 나타내었다. 이때 발광층의 도핑량을 0, 3, 5, 7 및 9%로 각각 변화시켰다. According to the method disclosed in US Patent Application No. 2006-43858 (Idemitsu Kosan) using 9- (naphthalen-2-yl) anthracene synthesized in Example 1 having the structure of Formula 5 A commercially available blue light emitting material was prepared. A light emitting device having a conventional structure including the prepared blue light emitting material in a light emitting layer was manufactured, and the physical properties of the device were measured, and the physical property measurement results are shown in Table 1 below. At this time, the doping amount of the light emitting layer was changed to 0, 3, 5, 7 and 9%, respectively.
[화학식 5][Formula 5]
Figure PCTKR2009002481-appb-I000011
Figure PCTKR2009002481-appb-I000011
[표 1]TABLE 1
Figure PCTKR2009002481-appb-I000012
Figure PCTKR2009002481-appb-I000012
상기 표 1에 나타낸 바와 같이, 본 발명에 따라 제조된 화합물은 전기적 안정성이 우수하고 높은 발광효율과 발광휘도를 가져, 유기전계발광소자의 발광물질로 사용될 수 있음을 확인하였다.As shown in Table 1, it was confirmed that the compound prepared according to the present invention has excellent electrical stability, high luminous efficiency and luminous luminance, and can be used as a light emitting material of an organic light emitting diode.
본 발명의 방법에 의하면, 기존의 스즈키 커플링의 단점을 보완하여 유기발광소자용 청색발광물질의 중간체를 일정하면서도 향상된 수율로 안정적으로 제조할 수 있으며, 반응물질의 원가가 저렴하고 중간생성물을 분리할 필요 없이 한 단계(1-step) 반응을 통해 목적하는 반응을 달성할 수 있어 경제적이고 간편하게 청색발광물질의 중간체를 제조할 수 있다.According to the method of the present invention, the intermediate of the blue light emitting material for organic light emitting device can be stably manufactured in a constant and improved yield by supplementing the disadvantages of the existing Suzuki coupling, and the cost of the reactant is inexpensive and the intermediate product is separated. It is possible to achieve the desired reaction through a one-step reaction without the need to produce an intermediate of the blue light emitting material economically and conveniently.

Claims (9)

  1. 에틸에테르 용매 중에서 -40 내지 20℃의 온도에서, 하기 화학식 2의 화합물을 알킬리튬과 반응시켜 하기 화학식 3의 화합물을 제조하고 이를 안트론과 반응시켜 하기 화학식 4의 화합물을 제조한 다음, 화학식 4의 화합물을 강산과 반응시키는 것을 포함하는,At a temperature of -40 to 20 ° C. in an ethyl ether solvent, a compound of formula 2 is reacted with alkyllithium to prepare a compound of formula 3, and then reacted with anthrone to prepare a compound of formula 4, Comprising reacting a compound of with a strong acid,
    하기 화학식 1로 표시되는 청색발광물질 중간체의 제조방법:Method for preparing a blue light emitting intermediate represented by the following formula (1):
    [화학식 1][Formula 1]
    Figure PCTKR2009002481-appb-I000013
    Figure PCTKR2009002481-appb-I000013
    [화학식 2][Formula 2]
    Ar-BrAr-Br
    [화학식 3][Formula 3]
    Ar-LiAr-Li
    [화학식 4][Formula 4]
    Figure PCTKR2009002481-appb-I000014
    Figure PCTKR2009002481-appb-I000014
    상기 식에서,Where
    Ar은 치환되거나 치환되지 않은 C3-50 아릴 할라이드이다.Ar is substituted or unsubstituted C3-50 aryl halide.
  2. 제1항에 있어서,The method of claim 1,
    상기 Ar이 하나 이상의 할로겐으로 치환된, 페닐, 나프틸, 안트릴, 피레닐 또는 페난트릴이며, 임의로 하나 이상의 C1-50 알킬, C3-30 아릴 또는 C3-30 헤테로아릴로 치환되는 것임을 특징으로 하는 제조방법.Ar is phenyl, naphthyl, anthryl, pyrenyl or phenanthryl, substituted with at least one halogen, optionally substituted with at least one C1-50 alkyl, C3-30 aryl or C3-30 heteroaryl Manufacturing method.
  3. 제2항에 있어서,The method of claim 2,
    상기 할로겐이 브롬 또는 요오드임을 특징으로 하는 제조방법.Wherein said halogen is bromine or iodine.
  4. 제1항에 있어서,The method of claim 1,
    상기 온도가 -20 내지 10 ℃의 범위임을 특징으로 하는 제조방법.The temperature method is characterized in that the range of -20 to 10 ℃.
  5. 제1항에 있어서,The method of claim 1,
    상기 방법이 질소 분위기 하에서 수행되는 것을 특징으로 하는 제조방법.The process is characterized in that the method is carried out under a nitrogen atmosphere.
  6. 제1항에 있어서,The method of claim 1,
    상기 에틸에테르 용매를 화학식 2의 화합물 1몰을 기준으로 3 내지 10몰의 양으로 사용하는 것을 특징으로 하는 제조방법.The ethyl ether solvent is used in an amount of 3 to 10 moles based on 1 mole of the compound of Formula 2.
  7. 제1항에 있어서,The method of claim 1,
    상기 안트론을 화학식 2의 화합물 1몰을 기준으로 0.5 내지 2몰의 양으로 사용하는 것을 특징으로 하는 제조방법.The anthrone is prepared using an amount of 0.5 to 2 moles based on 1 mole of the compound of Formula 2.
  8. 제1항에 있어서,The method of claim 1,
    상기 강산을 화학식 2의 화합물 1몰을 기준으로 5 내지 15몰의 양으로 사용하는 것을 특징으로 하는 제조방법.Method for using the strong acid in an amount of 5 to 15 moles based on 1 mole of the compound of Formula 2.
  9. 제1항에 있어서,The method of claim 1,
    상기 강산이 4 내지 8 M 염산인 것을 특징으로 하는 제조방법.The strong acid is characterized in that 4 to 8 M hydrochloric acid.
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