KR20030018347A - Improved process for preparing 4,4'-bis(2,2-diphenyl-1-vinyl)-1,1'-biphenyl derivatives - Google Patents

Improved process for preparing 4,4'-bis(2,2-diphenyl-1-vinyl)-1,1'-biphenyl derivatives Download PDF

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KR20030018347A
KR20030018347A KR1020010052038A KR20010052038A KR20030018347A KR 20030018347 A KR20030018347 A KR 20030018347A KR 1020010052038 A KR1020010052038 A KR 1020010052038A KR 20010052038 A KR20010052038 A KR 20010052038A KR 20030018347 A KR20030018347 A KR 20030018347A
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biphenyl
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손기남
남궁성건
박선이
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손기남
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/35—Preparation of halogenated hydrocarbons by reactions not affecting the number of carbon or of halogen atoms in the reaction
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
    • C07C17/272—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by addition reactions
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C25/00—Compounds containing at least one halogen atom bound to a six-membered aromatic ring
    • C07C25/18—Polycyclic aromatic halogenated hydrocarbons

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Abstract

PURPOSE: A method for preparing 4,4'-bis(2,2-diphenyl-1-vinyl)-1,1'-biphenyl derivative and a 4,4'-bis(2,2-diphenyl-1-vinyl)-1,1'-biphenyl derivative prepared by the method are provided to improve the purity and the production yield and to simplify the purification process largely. CONSTITUTION: The method comprises the steps of halomethylating the biphenyl derivative of the formula 2 to obtain the 4,4'-bis(halomethyl)-1,1'-biphenyl derivative of the formula 3; reacting the compound of the formula 3 with triethyl phosphite to obtain the 4,4'-bis(diethoxyphosphinylmethyl)-1,1'-biphenyl derivative; and reacting the compound of the formula 4 with benzophenol to obtain 4,4'-bis(2,2-diphenyl-1-vinyl)-1,1'-biphenyl derivative of the formula 1 by the Wittig reaction, wherein X is a halogen atom and R1 and R2 are H, a halogen atom or an alkyl group of C1-C4, respectively. Preferably the halomethylation is carried out in the presence of alkylammonium halide, halogenated alkali metal salt and paraformaldehyde in an organic or inorganic solvent; and the Wittig reaction is carried out in the presence of a base selected from the group consisting of alkoxy alkali metal salt of C1-C4, alkyl alkali metal salt of C1-C4 and alkali hydride.

Description

4,4'-비스(2,2-디페닐-1-비닐)-1,1'-비페닐 유도체의 개선된 제조방법 {Improved process for preparing 4,4'-bis(2,2-diphenyl-1-vinyl)-1,1'-biphenyl derivatives}Improved method for preparing 4,4'-bis (2,2-diphenyl- 1-vinyl) -1,1'-biphenyl derivatives}

본 발명은 다음 화학식 2로 표시되는 비페닐 유도체를 출발물질로 사용하여 다음 화학식 1로 표시되는 4,4'-비스(2,2-디페닐-1-비닐)-1,1'-비페닐 유도체를 합성하는 제조방법에 관한 것으로서, 더욱 상세하게는 다음 화학식 2로 표시되는 비페닐 유도체의 4- 및 4'- 위치에 할로메틸기를 동시에 도입하여 다음 화학식 3로 표시되는 4,4'-비스(할로메틸)-1,1'-비페닐 유도체를 효과적으로 합성하는 과정과, 제조한 화학식 3으로 표시되는 화합물을 트리에틸포스파이트((C2H5O)3P)와 치환 반응시켜 다음 화학식 4으로 표시되는 4,4'-비스(디에톡시포스포릴메틸)-1,1'-비페닐 유도체를 반응중간체로 합성하는 과정이 포함되어 있어 고순도의 4,4'-비스(2,2-디페닐-1-비닐)-1,1'-비페닐 유도체를 높은 수율로 합성할 수 있게 되었고, 특히 그정제과정을 크게 단순화시킨 개선된 제조방법에 관한 것이다.The present invention uses a biphenyl derivative represented by the following formula (2) as a starting material 4,4'-bis (2,2-diphenyl-1-vinyl) -1,1'-biphenyl represented by the following formula (1) The present invention relates to a method for synthesizing a derivative, and more particularly, 4,4'-bis represented by the following Chemical Formula 3 by simultaneously introducing a halomethyl group at the 4- and 4'-positions of the biphenyl derivative represented by the following Chemical Formula 2. A process of effectively synthesizing (halomethyl) -1,1'-biphenyl derivatives and substituting a compound represented by the formula (3) with triethylphosphite ((C 2 H 5 O) 3 P) A process for synthesizing 4,4'-bis (diethoxyphosphorylmethyl) -1,1'-biphenyl derivative represented by 4 as a reaction intermediate includes high purity 4,4'-bis (2,2- Diphenyl-1-vinyl) -1,1'-biphenyl derivatives can be synthesized in high yield, and in particular an improvement that greatly simplifies the purification process. It relates to a process for producing the same.

상기 반응식에서 : X는 할로겐원자를 나타내고, R1및 R2는 각각 수소원자, 할로겐원자 또는 C1∼C4의 알킬기를 나타낸다.In the above scheme: X represents a halogen atom, R 1 and R 2 each represent a hydrogen atom, a halogen atom or an alkyl group of C 1 to C 4 .

상기 화학식 1로 표시되는 4,4'-비스(2,2-디페닐-1-비닐)-1,1'-비페닐 유도체는 'DPVBi 유도체'로 약칭되고 있는 유기전계발광 물질이다.The 4,4'-bis (2,2-diphenyl-1-vinyl) -1,1'-biphenyl derivative represented by Chemical Formula 1 is an organic electroluminescent material abbreviated as 'DPVBi derivative'.

4,4'-비스(2,2-디페닐-1-비닐)-1,1'-비페닐의 종래 제조방법으로서, 미국특허 제6,074,734호에서는 4,4'-비스(메틸)-1,1'-비페닐의 메틸기를 브롬화반응시켜 얻어진 4,4'-비스(브로모메틸)-1,1'-비페닐을 벤조페논과 직접 축합반응시켜 합성하는 방법이 공개되어 있다.As a conventional method for producing 4,4'-bis (2,2-diphenyl-1-vinyl) -1,1'-biphenyl, US Pat. No. 6,074,734 discloses 4,4'-bis (methyl) -1, A method of synthesizing by directly condensing 4,4'-bis (bromomethyl) -1,1'-biphenyl obtained by bromination by methyl group of 1'-biphenyl is disclosed.

상기 종래방법에 따르면, 4,4'-비스(메틸)-1,1'-비페닐의 메틸기를 브롬화하는 반응에서 4- 또는 4'- 위치가 동시에 브롬이 치환된 4,4'-비스(브로모메틸)-1,1'-비페닐의 수득율이 저조하며, 또한 부생성물의 분리가 용이하지 않아 벤조페논과 직접 축합반응하게 되면 목적하는 화합물 이외에도 여러 불순물이 함께 생성되고, 이러한 불순물의 존재로 인하여 고도의 정제기술이 요구될 수밖에 없다.According to the conventional method, 4,4'-bis (with 4 or 4'-positions at the same time bromine is substituted in the reaction for brominating the methyl group of 4,4'-bis (methyl) -1,1'-biphenyl) When the yield of bromomethyl) -1,1'-biphenyl is poor and the separation of by-products is not easy, condensation reaction with benzophenone directly produces several impurities in addition to the desired compound, and the presence of such impurities Due to this, a high degree of purification technology is required.

따라서, 상기한 미국특허 제6,074,734호의 제조방법에서는 출발물질로 4- 및4'- 위치가 메틸기(-CH3) 치환된 비페닐 화합물을 브롬화하는 반응 및 최종적으로 생성된 목적물을 공업적으로 적용하는데 한계가 있는 크로마토그라피를 수행하는것에 대한 개선의 필요성이 있다.Therefore, in the above-described method of US Pat. No. 6,074,734, a reaction for bromination of a methyl group (-CH 3 ) -substituted biphenyl compound with 4- and 4'-positions as a starting material and industrial application of the finally produced target product There is a need for improvement in performing limited chromatography.

본 발명에서는 보다 용이하게 상기 화학식 1로 표시되는 DPVBi 유도체를 합성하는 방법을 개발하고자 연구 노력하였고, 그 결과 상기 화학식 2로 표시되는 비페닐 유도체를 직접 할로메틸기(-CH2X)로 치환하여 우수한 수율로 상기 화학식 3로 표시되는 4,4'-비스(할로메틸)-1,1'-비페닐 유도체를 제조하고, 또한 제조한 상기 화학식 3으로 표시되는 화합물을 벤조페논과 직접 축합반응하는 대신에 반응 중간체로 상기 화학식 4으로 표시되는 4,4'-비스(디에톡시포스포릴메틸)-1,1'-비페닐 유도체를 합성한 후에 벤조페논과의 축합반응을 수행하게 되면 할로메틸 치환반응에서 생성되는 부생성물을 반응중간체 합성과정에서 용해도 차이를 이용한 분리 정제방법으로 쉽게 제거할 수 있기 때문에 벤조페논과의 축합반응의 수율 및 순도를 높일 수 있고, 또한 관 크로마토그라피와 같은 복잡한 정제과정을 수행하지 않고 간단한 재결정 방법으로도 분리 정제가 가능함을 알게됨으로써 본 발명을 완성하게 되었다.In the present invention, the research effort to develop a method for synthesizing the DPVBi derivative represented by the formula (1) more easily, and as a result, the biphenyl derivative represented by the formula ( 2 ) is directly substituted with a halomethyl group (-CH 2 X) excellent Instead of directly condensing a 4,4'-bis (halomethyl) -1,1'-biphenyl derivative represented by Formula 3 in the yield and the compound represented by Formula 3, the benzophenone When a condensation reaction with benzophenone is performed after synthesis of 4,4'-bis (diethoxyphosphorylmethyl) -1,1'-biphenyl derivative represented by Chemical Formula 4 as a reaction intermediate, halomethyl substitution reaction is performed. The by-products generated in the process can be easily removed by the separation and purification method using the difference in solubility in the reaction intermediate synthesis process, thereby increasing the yield and purity of the condensation reaction with benzophenone. Whereby without performing a complicated purification procedures such as chromatographic calligraphy simple recrystallisation with separation and purification it is also possible to know, thereby completing the present invention.

따라서, 본 발명은 정제공정을 단순화할 수 있음은 물론 수율 향상 효과까지도 얻고 있는 DPVBi 유도체의 공업적 대량 생산에 유용한 제조방법을 제공하는데 그 목적이 있다.Accordingly, an object of the present invention is to provide a production method useful for industrial mass production of DPVBi derivatives, which can simplify the purification process as well as obtain a yield improving effect.

본 발명에 따른 제조방법은Manufacturing method according to the invention

다음 화학식 2로 표시되는 비페닐 유도체를 할로메틸화 반응시켜 다음 화학식 3으로 표시되는 4,4'-비스(할로메틸)-1,1'-비페닐 유도체를 제조하는 과정;Preparing a 4,4'-bis (halomethyl) -1,1'-biphenyl derivative represented by the following Chemical Formula 3 by halomethylation of the biphenyl derivative represented by the following Chemical Formula 2;

상기 화학식 3로 표시되는 화합물을 트리에틸포스파이트((C2H5O)3P)와 치환반응시켜 다음 화학식 4으로 표시되는 4,4'-비스(디에톡시포스포릴메틸)-1,1'-비페닐 유도체를 제조하는 과정; 및Substituted reaction of the compound represented by the formula (3) with triethyl phosphite ((C 2 H 5 O) 3 P) 4,4'-bis (diethoxyphosphorylmethyl) -1,1 represented by the following formula (4) Preparing a '-biphenyl derivative; And

상기 화학식 4으로 표시되는 화합물을 벤조페논과 비트히 반응(Wittig reaction)시켜 다음 화학식 1로 표시되는 4,4'-비스(2,2-디페닐-1-비닐)-1,1'-비페닐 유도체를 합성하는 과정을 포함한다.By reacting the compound represented by the formula (4) with benzophenone (Wittig reaction) 4,4'-bis (2,2-diphenyl-1-vinyl) -1,1'- ratio represented by the following formula (1) Synthesizing phenyl derivatives.

상기 반응식에서 : X는 할로겐원자를 나타내고, R1및 R2는 각각 수소원자, 할로겐원자 또는 C1∼C4의 알킬기를 나타낸다.In the above scheme: X represents a halogen atom, R 1 and R 2 each represent a hydrogen atom, a halogen atom or an alkyl group of C 1 to C 4 .

이와 같은 본 발명을 더욱 상세히 설명하면 다음과 같다.Referring to the present invention in more detail as follows.

본 발명은 유기전계발광물질로 알려진 상기 화학식 1로 표시되는 DPVBi 유도체의 새로운 제조방법을 그 특징으로 하는데, 본 발명에 따른 제조방법은 상기 화학식 2를 출발물질로 사용하여 할로메틸화 반응하고, 상기 화학식 4으로 표시되는 반응 중간체를 합성 경유한다는데 그 기술구성상에 주요한 특징을 가지고 있다.The present invention is characterized by a novel method for producing a DPVBi derivative represented by the formula (1) known as an organic electroluminescent material, the production method according to the invention is a halomethylation reaction using the formula (2) as a starting material, The synthesis of the reaction intermediate represented by 4 is carried out through the synthesis.

즉, 상술한 바대로 일반적인 제조방법에서와 같이 상기 화학식 3로 표시되는4,4'-비스(할로메틸)-1,1'-비페닐 유도체에 벤조페논을 직접 축합반응시키게 되면 관 크로마토그라피로 최종생성물을 정제함으로써 상업화에 문제가 있는데 반하여, 본 발명의 제조방법에 따라 상기 화학식 4으로 표시되는 반응 중간체를 합성 경유하게 되면 재결정에 의하여 반응 중간체 및 최종생성물의 정제가 용이하며 총수율의 향상 효과가 있다.That is, as described above, when the benzophenone is directly condensed to the 4,4'-bis (halomethyl) -1,1'-biphenyl derivative represented by Chemical Formula 3, as in the general preparation method, tube chromatography is performed. While there is a problem in commercialization by purifying the final product, if the reaction intermediate represented by the formula (4) according to the production method of the present invention via the synthesis, it is easy to purify the reaction intermediate and the final product by recrystallization and improve the overall yield There is.

본 발명에 따른 상기 화학식 1로 표시되는 DPVBi 유도체의 합성과정을 보다 상세히 설명하면 다음과 같다.Hereinafter, the synthesis process of the DPVBi derivative represented by Chemical Formula 1 according to the present invention will be described in detail.

먼저, 상기 화학식 2로 표시되는 비페닐 유도체를 유기산 또는 무기산 용매에서 할로겐화 알킬암모늄염, 할로겐화 알카리금속염 및 파라포름알데히드 존재하에 반응시켜 비페닐의 4- 및 4'- 위치에 할로메틸기(-CH2X)를 치환하여 상기 화학식 3으로 표시되는 화합물을 제조한다. 이때, 반응온도는 40 내지 90 ℃ 범위이며, 반응시간은 대략 48 시간이내이다. 또한, 반응용매로는 황산, 염산, 인산, 질산, 브롬화수소산, 포름산, 아세트산 등을 비롯한 무기산 또는 유기산을 사용하며, 할로겐화 알킬암모늄염으로는 테트라부틸암모늄 아이오다이드, 테트라부틸암모늄 브로마이드, 테트라부틸암모늄 클로라이드 등을 사용하며, 할로겐화 알카리금속염으로는 할로겐화 리튬염, 할로겐화 나트륨염, 할로겐화 칼륨염 등을 사용한다.First, the biphenyl derivative represented by Chemical Formula 2 is reacted in the presence of a halogenated alkylammonium salt, a halogenated alkali metal salt, and paraformaldehyde in an organic acid or an inorganic acid solvent to form a halomethyl group (-CH 2 X) at the 4- and 4'-positions of biphenyl. Substituted) to prepare a compound represented by the formula (3). At this time, the reaction temperature is in the range of 40 to 90 ℃, the reaction time is within about 48 hours. In addition, as the reaction solvent, inorganic acids or organic acids including sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid, hydrobromic acid, formic acid, acetic acid, and the like are used. Chloride and the like, and halogenated alkali metal salts include lithium halide salts, sodium halide salts, and potassium halide salts.

4,4'-비스(할로메틸)-1,1'-비페닐 유도체를 제조하는 종래방법(미국특허 제6,074,734호)이, 비교적 가격이 고가인 4,4'-디메틸-1,1'-비페닐을 사용하여 사염화탄소 용매에서 벤조일 퍼옥사이드 존재하에N-할로숙신이미드와 반응하여 4-및 4'-의 벤질 위치에 동시에 할로치환반응(halogenation)시켜 합성하고 있다. 그러나, 이러한 종래 방법은 생성물인 4,4'-비스(할로메틸)-1,1'-비페닐 유도체 이외에도 부생성물로서 4-할로메틸-1,1'-비페닐 유도체, 4-디할로메틸-1,1'-비페닐 유도체들이 동시에 얻어지므로 원하는 생성물의 정제가 용이하지 않으며, 이로 인하여 최종생성물인 DPVBi 유도체도 관 크로마토그라피를 사용함이 없이는 정제가 곤란한 것이 문제점으로 지적되었다. 이에 반하여, 본 발명에 따른 방법에서는 4,4'-비스(메틸)-1,1'-비페닐 유도체보다는 비교적 가격이 저렴한 비페닐 유도체를 사용하여 상기한 반응조건을 할로메틸 치환반응을 수행하게 되면 우수한 수율로 4,4'-비스(할로메틸)-1,1'-비페닐 유도체를 수득할 수 있었다. 또한, 소량이지만 함께 생성된 부생성물은 다음에서 수행하게 되는 상기 화학식 4로 표시되는 중간체의 합성과정에서 용이하게 제거될 수 있다.Conventional methods for preparing 4,4'-bis (halomethyl) -1,1'-biphenyl derivatives (US Pat. No. 6,074,734) are relatively expensive, 4,4'-dimethyl-1,1'- Biphenyl is used to react with N -halosuccinimide in the presence of benzoyl peroxide in a carbon tetrachloride solvent to simultaneously synthesize halo-substitution at the benzyl positions of 4- and 4'-. However, this conventional method is a 4-halomethyl-1,1'-biphenyl derivative, 4-dihalomethyl as a by-product in addition to the product 4,4'-bis (halomethyl) -1,1'-biphenyl derivative. It is pointed out that the purification of the desired product is not easy because the -1,1'-biphenyl derivatives are obtained at the same time, which makes it difficult to purify the final product without the use of tube chromatography. In contrast, the method according to the present invention uses a biphenyl derivative which is relatively inexpensive rather than a 4,4'-bis (methyl) -1,1'-biphenyl derivative to perform the halomethyl substitution reaction under the above reaction conditions. 4,4'-bis (halomethyl) -1,1'-biphenyl derivative was obtained in excellent yield. In addition, the minor by-products produced together may be easily removed during the synthesis of the intermediate represented by Formula 4 to be carried out in the following.

그런 다음, 상기 화학식 3로 표시되는 4,4'-비스(할로메틸)-1,1'-비페닐 유도체를 용매 겸 반응물로서 트리에틸포스파이트((C2H5O)3P)와 치환 반응시켜 상기 화학식 4으로 표시되는 4,4'-비스(디에톡시포스포릴메틸)-1,1'-비페닐 유도체를 반응중간체로 합성한다. 이때, 반응온도는 실온 내지 환류온도 범위이며, 반응시간은 대략 24 시간이내이다. 반응용매겸 반응물질로 사용되는 트리에틸포스파이트는 화학식 3로 표시되는 화합물에 대하여 1 ∼ 10 몰비 범위로 사용한다.Subsequently, the 4,4'-bis (halomethyl) -1,1'-biphenyl derivative represented by Chemical Formula 3 was substituted with triethylphosphite ((C 2 H 5 O) 3 P) as a solvent and a reactant. By reacting, 4,4'-bis (diethoxyphosphorylmethyl) -1,1'-biphenyl derivative represented by Chemical Formula 4 is synthesized as a reaction intermediate. At this time, the reaction temperature ranges from room temperature to reflux temperature, and the reaction time is within about 24 hours. Triethyl phosphite used as the reaction solvent and the reactant is used in the range of 1 to 10 molar ratio with respect to the compound represented by the formula (3).

한편, 상기 화학식 4로 표시되는 화합물은 흰색 고체로 생성되므로 에틸아세테이트와 헥산의 혼합용매를 사용하여 재결정하면 손쉽게 수득이 가능한 바, 본 발명은 상기 화학식 4로 표시되는 화합물을 반응 중간체로 경유하므로써 다음에서 수행하게 되는 벤조페논 화합물과의 축합반응 생성물을 보다 높은 수율로 수득이 가능할 수 있었던 것이다.On the other hand, since the compound represented by the formula (4) is produced as a white solid, it can be easily obtained by recrystallization using a mixed solvent of ethyl acetate and hexane, the present invention can be obtained by passing the compound represented by the formula (4) as a reaction intermediate Condensation reaction product with the benzophenone compound to be carried out at could be obtained in a higher yield.

다음 과정은 상기 화학식 4으로 표시되는 반응 중간체를 C1∼C4의 알콕시 알카리금속염, C1∼C4의 알킬 알카리금속염, 알카리금속 하이드라이드와 같은 염기의 존재 하에 벤조페논과 비트히 반응(Wittig reaction)시켜 목적하는 상기 화학식 1로 표시되는 DPVBi 유도체를 합성한다. 이때, 반응온도는 실온 내지 60 ℃ 범위이며, 반응시간은 대략 24 시간이내이다. 염기로서는 구체적으로 칼륨 t-부톡사이드, 나트륨 t-부톡사이드, 나트륨 에톡사이드, 나트륨 메톡사이드, 나트륨 하이드라이드, 부틸 리튬 등이 사용될 수 있다.The next step is reacting the reaction intermediate represented by the formula (4) with benzophenone in the presence of a base such as C 1 to C 4 alkoxy alkali metal salts, C 1 to C 4 alkyl alkali metal salts and alkali metal hydrides (Wittig reaction) to synthesize the desired DPVBi derivative represented by Chemical Formula 1. At this time, the reaction temperature is in the range of room temperature to 60 ℃, the reaction time is within about 24 hours. Specifically as the base, potassium t-butoxide, sodium t-butoxide, sodium ethoxide, sodium methoxide, sodium hydride, butyl lithium and the like can be used.

상기한 반응중에 합성되는 상기 화학식 4으로 표시되는 반응 중간체 및 목적하는 상기 화학식 1로 표시되는 DPVBi 유도체는 고체 화합물로서 얻어지므로, 복잡한 정제공정 없이도 간단한 재결정 방법으로 용이하게 수득할 수 있었다. 또한, 본 발명에 따른 제조방법으로 얻어진 DPVBi 유도체는 그 제조수율이 86% 이상이다.The reaction intermediate represented by Chemical Formula 4 and the DPVBi derivative represented by Chemical Formula 1, which are synthesized during the reaction, are obtained as a solid compound, and thus can be easily obtained by a simple recrystallization method without a complicated purification process. In addition, the production yield of the DPVBi derivative obtained by the production method according to the present invention is 86% or more.

한편, 상기 제조방법에 의해 제조된 DPVBi 유도체에 있어 다음 화학식 1a로 표시되는 화합물은 신규 화합물인 바, 이에 본 발명은 신규 화합물을 포함한다,Meanwhile, in the DPVBi derivatives prepared by the preparation method, the compound represented by the following Formula 1a is a novel compound, and thus the present invention includes the novel compound.

상기 화학식 1a에서 : R1및 R2는 각각 수소원자, 할로겐원자 또는 C1∼C4의 알킬기를 나타내고, 단 R1및 R2가 동시에 수소원자인 경우는 제외한다.In Formula 1a: R 1 and R 2 each represent a hydrogen atom, a halogen atom or an alkyl group of C 1 to C 4 , except that R 1 and R 2 are hydrogen atoms at the same time.

이와 같은 본 발명은 다음의 실시예에 의거하여 더욱 상세히 설명하겠는 바, 본 발명이 이에 한정하는 것은 아니다.Such a present invention will be described in more detail based on the following examples, but the present invention is not limited thereto.

실시예 1 : 4,4'-비스(브로모메틸)-1,1'-비페닐의 합성Example 1 Synthesis of 4,4'-bis (bromomethyl) -1,1'-biphenyl

70% 황산 수용액 50 mL에 비페닐 30.8 g(0.2 mol), 파라포름알데히드 36 g(0.4 mol), KBr 48 g(0.4 mol) 및 테트라부틸암모늄 브로마이드 3.22 g(0.01 mol)을 첨가하고 온도를 80 ℃로 유지하면서 혼합용액을 48 시간 동안 교반하였다. 혼합용액을 실온으로 냉각시킨 후, 증류수 100 mL를 첨가하였다. 이 용액에 NaHCO3를 서서히 첨가하여 용액의 pH가 7∼8이 되도록 한 다음, 디클로로메탄 100 mL로 추출하였다. 디클로로메탄 층을 분리하여 무수 황산마그네슘으로 건조한 후, 증류하여 얻은 반응 혼합물을 에틸아세테이트로 재결정하여 흰색 고체의 4,4'-비스(브로모메틸)-1,1'-비페닐 54 g(수율 79%, 녹는점 143∼145℃)을 얻었다.To 50 mL of a 70% aqueous sulfuric acid solution, 30.8 g (0.2 mol) of biphenyl, 36 g (0.4 mol) of paraformaldehyde, 48 g (0.4 mol) of KBr and 3.22 g (0.01 mol) of tetrabutylammonium bromide were added and the temperature was 80 The mixed solution was stirred for 48 hours while maintaining at 占 폚. After cooling the mixed solution to room temperature, 100 mL of distilled water was added. NaHCO 3 was slowly added to the solution to bring the pH of the solution to 7-8, and then extracted with 100 mL of dichloromethane. The dichloromethane layer was separated, dried over anhydrous magnesium sulfate, and the reaction mixture obtained by distillation was recrystallized with ethyl acetate to give 54 g of 4,4'-bis (bromomethyl) -1,1'-biphenyl as a white solid (yield). 79%, melting | fusing point 143-145 degreeC) was obtained.

실시예 2 : 4,4'-비스(클로로메틸)-1,1'-비페닐의 합성Example 2 Synthesis of 4,4'-bis (chloromethyl) -1,1'-biphenyl

상기 실시예 1의 방법에서 KBr과 테트라부틸암모늄 브로마이드 대신에 KCl 30 g(0.4 mol)과 테트라부틸암모늄 클로라이드 2.78 g(0.01 mol)을 사용하였다. 그 결과 흰색 고체의 4,4'-비스(클로로메틸)-1,1'-비페닐 49 g(수율 70%, 녹는점 135∼136℃)을 얻었다.In the method of Example 1, 30 g (0.4 mol) of KCl and 2.78 g (0.01 mol) of tetrabutylammonium chloride were used in place of KBr and tetrabutylammonium bromide. As a result, 49 g (yield 70%, melting point 135-136 degreeC) of 4,4'-bis (chloromethyl) -1,1'-biphenyl of a white solid was obtained.

실시예 3 : 4,4'-비스(디에톡시포스포릴메틸)-1,1'-비페닐의 합성Example 3: Synthesis of 4,4'-bis (diethoxyphosphorylmethyl) -1,1'-biphenyl

에탄올 100 mL에 4,4'-비스(브로모메틸)-1,1'-비페닐 34 g(0.1 mol), 트리에틸포스파이트 33.2 g(0.2 mol)를 넣은 혼합용액을 24 시간 동안 환류시켰다. 혼합용액을 실온으로 냉각하여 용매를 감압 증류한 후, 반응 혼합물을 에틸아세테이트:헥산(1:1, 부피비)의 혼합용매로 재결정하여 흰색 고체의 4,4'-비스(디에톡시포스피닐메틸)-1,1'-비페닐 43 g(수율 96%, 녹는점 109∼110℃)을 얻었다.A mixed solution of 34 g (0.1 mol) of 4,4'-bis (bromomethyl) -1,1'-biphenyl and 33.2 g (0.2 mol) of triethyl phosphite was refluxed in 100 mL of ethanol for 24 hours. . The mixed solution was cooled to room temperature, the solvent was distilled off under reduced pressure, and the reaction mixture was recrystallized from a mixed solvent of ethyl acetate: hexane (1: 1, volume ratio) to give 4,4'-bis (diethoxyphosphinylmethyl) as a white solid. 43 g of -1,1'-biphenyl (yield 96%, melting point 109-110 degreeC) were obtained.

실시예 4 : 4,4'-비스(2,2-디페닐-1-비닐)-1,1'-비페닐의 합성Example 4 Synthesis of 4,4'-bis (2,2-diphenyl-1-vinyl) -1,1'-biphenyl

질소 존재 하에 4,4'-비스(디에톡시포스포릴메틸)-1,1'-비페닐 9.1 g(0.02 mol)을 테트라하이드로퓨란 200 mL에 녹인 후, 벤조페논 7.3 g(0.04 mol)과 칼륨 t-부톡사이드 5.6 g(0.05 mol)을 첨가하여 40 ℃의 온도에서 24 시간동안 교반하였다. 혼합용액을 실온으로 냉각시켜 증류수 200 mL를 서서히 첨가한 다음, 이용액에 에틸아세테이트 200 mL를 더 넣고 혼합 유기용매 층을 분리하였다. 유기용매 층을 무수 황산마그네슘으로 건조, 증류한 다음, 반응혼합물을 디클로로메탄으로 재결정하여 흰색 고체의 4,4'-비스(2,2-디페닐-1-비닐)-1,1'-비페닐 9.2 g(수율 90%, 녹는점 202∼204℃)을 얻었다.9.1 g (0.02 mol) of 4,4'-bis (diethoxyphosphorylmethyl) -1,1'-biphenyl was dissolved in 200 mL of tetrahydrofuran in the presence of nitrogen, followed by 7.3 g (0.04 mol) of benzophenone and potassium. 5.6 g (0.05 mol) of t-butoxide was added and stirred at a temperature of 40 ° C. for 24 hours. The mixed solution was cooled to room temperature, and 200 mL of distilled water was slowly added thereto. Then, 200 mL of ethyl acetate was added to the solution, and the mixed organic solvent layer was separated. The organic solvent layer was dried over anhydrous magnesium sulfate, distilled, and the reaction mixture was recrystallized from dichloromethane to give 4,4'-bis (2,2-diphenyl-1-vinyl) -1,1'-ratio as a white solid. 9.2 g (yield 90%, melting point 202-204 degreeC) of phenyl were obtained.

이상에서 상세히 설명한 바와 같이, 본 발명에 따른 DPVBi 유도체의 제조법은 기존의 합성법(미국특허 제6,074,734호)과 비교하여 비페닐 유도체에 할로메틸 치환반응 과정 및 화학식 4의 중간체 합성과정을 경유함으로써 재결정과 같은 간단한 분리 및 정제 방법에 의해서도 DPVBi를 수득할 수 있다는 점에 그 우수성이 있다.As described in detail above, the preparation method of the DPVBi derivative according to the present invention is recrystallized by passing through a halomethyl substitution reaction to a biphenyl derivative and a process of synthesizing an intermediate of Formula 4 as compared with the conventional synthesis method (US Pat. No. 6,074,734). It is excellent in that DPVBi can be obtained by the same simple separation and purification method.

따라서, 본 발명은 기존의 공정 및 가격 경쟁력을 비교할 때 대량 생산을 더욱 용이하게 하므로 DPVBi의 산업화에 크게 기여하게 된다.Therefore, the present invention greatly contributes to the industrialization of DPVBi since mass production is more easily compared with existing processes and price competitiveness.

Claims (4)

다음 화학식 2로 표시되는 비페닐 유도체를 할로메틸화 반응시켜 다음 화학식 3으로 표시되는 4,4'-비스(할로메틸)-1,1'-비페닐 유도체를 제조하는 과정;Preparing a 4,4'-bis (halomethyl) -1,1'-biphenyl derivative represented by the following Chemical Formula 3 by halomethylation of the biphenyl derivative represented by the following Chemical Formula 2; 상기 화학식 3로 표시되는 화합물을 트리에틸포스파이트((C2H5O)3P)와 치환 반응시켜 다음 화학식 4으로 표시되는 4,4'-비스(디에톡시포스피닐메틸)-1,1'-비페닐 유도체를 제조하는 과정; 및Substituted reaction of the compound represented by the formula (3) with triethyl phosphite ((C 2 H 5 O) 3 P) 4,4'-bis (diethoxy phosphinylmethyl) -1,1 represented by the following formula (4) Preparing a '-biphenyl derivative; And 상기 화학식 4으로 표시되는 화합물을 벤조페논과 비트히 반응(Wittig reaction)시켜 다음 화학식 1로 표시되는 4,4'-비스(2,2-디페닐-1-비닐)-1,1'-비페닐 유도체를 합성하는 과정을 포함하는 것을 특징으로 하는 제조방법.By reacting the compound represented by the formula (4) with benzophenone (Wittig reaction) 4,4'-bis (2,2-diphenyl-1-vinyl) -1,1'- ratio represented by the following formula (1) Method for producing a phenyl derivative comprising the step of synthesizing. 화학식 2Formula 2 화학식 3Formula 3 화학식 4Formula 4 화학식 1Formula 1 상기 화학식에서 : X는 할로겐원자를 나타내고, R1및 R2는 각각 수소원자, 할로겐원자 또는 C1∼C4의 알킬기를 나타낸다.In the formula: X represents a halogen atom, R 1 and R 2 each represent a hydrogen atom, a halogen atom or an alkyl group of C 1 to C 4 . 제 1 항에 있어서, 상기 할로메틸화 반응은 알킬암모늄 할라이드, 할로겐화 알칼리금속염 및 파라포름알데히드 존재 하에 유기산 또는 무기산의 용매를 사용하여 반응을 수행하는 것을 특징으로 하는 제조방법.The method according to claim 1, wherein the halomethylation reaction is carried out using a solvent of an organic acid or an inorganic acid in the presence of an alkylammonium halide, a halogenated alkali metal salt and paraformaldehyde. 제 1 항에 있어서, 상기 비트히 반응 반응은 C1∼C4의 알콕시 알카리금속염, C1∼C4의 알킬 알카리금속염 및 알카리금속 하이드라이드 중에서 선택된 염기존재하에 반응을 수행하는 것을 특징으로 하는 제조방법.The method of claim 1, wherein the Wittsch reaction is carried out in the presence of a base selected from C 1 to C 4 alkoxy alkali metal salts, C 1 to C 4 alkyl alkali metal salts and alkali metal hydrides Way. 다음 화학식 1a로 표시되는 것임을 특징으로 하는 4,4'-비스(2,2-디페닐-1-비닐)-1,1'-비페닐 유도체.4,4'-bis (2,2-diphenyl-1-vinyl) -1,1'-biphenyl derivative, characterized in that represented by the following formula (1a). 화학식 1aFormula 1a 상기 화학식 1a에서 : R1및 R2는 각각 수소원자, 할로겐원자 또는 C1∼C4의 알킬기를 나타내고, 단 R1및 R2가 동시에 수소원자인 경우는 제외한다.In Formula 1a: R 1 and R 2 each represent a hydrogen atom, a halogen atom or an alkyl group of C 1 to C 4 , except that R 1 and R 2 are hydrogen atoms at the same time.
KR1020010052038A 2001-08-28 2001-08-28 Improved process for preparing 4,4'-bis(2,2-diphenyl-1-vinyl)-1,1'-biphenyl derivatives KR20030018347A (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04275268A (en) * 1991-03-01 1992-09-30 Idemitsu Kosan Co Ltd Styryl compound, production thereof and electroluminescent element comprising the same compound
US5536949A (en) * 1992-08-28 1996-07-16 Idemistu Kosan Co., Ltd. Charge injection auxiliary material and organic electroluminescence device containing the same
JPH0987214A (en) * 1995-09-19 1997-03-31 Nippon Steel Chem Co Ltd Production of 4,4'-bis(chloromethyl)biphenyl
US6074734A (en) * 1995-01-19 2000-06-13 Idemitsu Kosan Co., Ltd. Organic electroluminescence device, organic thin film, and triamine compound

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04275268A (en) * 1991-03-01 1992-09-30 Idemitsu Kosan Co Ltd Styryl compound, production thereof and electroluminescent element comprising the same compound
US5536949A (en) * 1992-08-28 1996-07-16 Idemistu Kosan Co., Ltd. Charge injection auxiliary material and organic electroluminescence device containing the same
US6074734A (en) * 1995-01-19 2000-06-13 Idemitsu Kosan Co., Ltd. Organic electroluminescence device, organic thin film, and triamine compound
JPH0987214A (en) * 1995-09-19 1997-03-31 Nippon Steel Chem Co Ltd Production of 4,4'-bis(chloromethyl)biphenyl

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