JP4837199B2 - Novel biphenyl compound and method for producing the same - Google Patents
Novel biphenyl compound and method for producing the same Download PDFInfo
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- JP4837199B2 JP4837199B2 JP2001245310A JP2001245310A JP4837199B2 JP 4837199 B2 JP4837199 B2 JP 4837199B2 JP 2001245310 A JP2001245310 A JP 2001245310A JP 2001245310 A JP2001245310 A JP 2001245310A JP 4837199 B2 JP4837199 B2 JP 4837199B2
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Description
【０００１】
【発明の属する技術分野】
本発明は、新規なビフェニル化合物とその製造方法に関し、さらに詳しくは、下記式（Ｉ）で示される新規なビフェニル化合物とその製造方法を提供するものである。
【０００２】
【化３】
【従来技術】
本発明に係る４−（シアノメチル）−２−フルオロ−３’−フルオロ−４’−（トリフルオロメチル）ビフェニルは新規な化合物である。よって、この新規化合物を製造する方法も新規である。
【０００４】
【発明が解決しようとする課題】
即ち、本発明は、式（Ｉ）で示される新規な４−（シアノメチル）−２−フルオロ−３’−フルオロ−４’−（トリフルオロメチル）ビフェニルに関するものである。本発明によって提供される式（Ｉ）で示される新規な４−（シアノメチル）−２−フルオロ−３’−フルオロ−４’− （トリフルオロメチル）ビフェニルは、次世代のフラットディスプレ−として近年注目されている有機ＥＬ（エレクトロルミネッセンス）ディスプレ−の発光素子材料などへの利用が期待される有用な化合物である。また、式（Ｉ）で示される４−（シアノメチル）−２−フルオロ−３’−フルオロ−４’−（トリフルオロメチル）ビフェニルは上記の用途として有用であるばかりでなく、反応活性なメチル基を有することからトリフルオロメチル基やフッ素原子を有する医農薬、機能性材料等の中間体としての利用も期待される有用な化合物である。
【０００５】
【課題を解決するための手段】
本発明者らは、多種多様な組合せの中から、式（Ｉ）で示される新規な４−（シアノメチル）−２−フルオロ−３’−フルオロ−４’− （トリフルオロメチル）ビフェニルを式（ＩＩ）で示される４−ハロ−２−フルオロベンゾトリフルオリドと式（ＩＩＩ）で示される１−ハロ−４−（シアノメチル）−２−フルオロベンゼンとをカップリング反応させることにより製造できることを見出した。カップリング反応の収率や経済性を考慮すると、式（ＩＩ）及び式（ＩＩＩ）で示される化合物のハロゲンＸがいずれも臭素であることが、取扱い上好ましく、推奨される。
【０００６】
【化４】
以下、本発明の新規化合物としてのその典型的な臭素化合物の具体的な製造方法を示す。
式（ＩＩ）で示される化合物のハロゲンＸが臭素である４−ブロモ−２−フルオロベンゾトリフルオリドは、比較的入手容易な４−ブロモ−２−フルオロ安息香酸のカルボキシル基を四フッ化硫黄でフッ素化する方法等により製造することができる。
【０００８】
また、式（ＩＩＩ）で示される化合物のハロゲンＸが臭素である１−ブロモ−４−（シアノメチル）−２−フルオロベンゼンは、比較的入手容易な４−ブロモ−３−フルオロトルエンのメチル基をモノブロモ化及びシアノ化する方法等により製造することができる。
【０００９】
式（ＩＩ）で示される化合物のハロゲンＸが臭素である４−ブロモ−２−フルオロベンゾトリフルオリドから調製される有機金属化合物と、式（ＩＩＩ）で示される化合物のハロゲンＸが臭素である１−ブロモ−４−（シアノメチル）−２−フルオロベンゼンとを、金属触媒存在下でカップリング反応させることにより式（Ｉ）で示される新規な４−（シアノメチル）−２−フルオロ−３’−フルオロ−４’−（トリフルオロメチル）ビフェニルを製造することができる。
【００１０】
式（ＩＩ）で示される化合物から調製される有機金属化合物としては、有機亜鉛化合物、有機銅化合物、有機ホウ素化合物、有機アルミニウム化合物などが挙げられる。これら有機金属化合物の調製方法としては、有機リチウム化合物あるいは有機マグネシウム化合物に誘導した後に金属交換反応を行なう方法や直接金属と反応させる方法がある。その一例として式（ＩＩ）で示される化合物のハロゲンＸが臭素である４−ブロモ−２−フルオロベンゾトリフルオリドを溶媒中、攪拌下、所定温度、所定時間で有機リチウム試薬と反応させることにより有機リチウム化合物を含む溶液を調製し、これをハロゲン化亜鉛と攪拌下、所定温度、所定時間で反応させることにより、式（ＩＩ）で示される化合物のハロゲンＸが臭素である４−ブロモ−２−フルオロベンゾトリフルオリドの有機亜鉛化合物を調製することができる。本反応は水分を嫌う反応であるため、反応容器内を窒素等の乾燥不活性ガス雰囲気として行なうことが好ましい。
【００１１】
上記反応のための有機リチウム試薬としては、アルキルリチウム、フェニルリチウムが使用できる。有機リチウム試薬の使用量は、好ましくは原料に対して０．８〜１．２倍モル量である。
【００１２】
有機リチウム試薬を作用させる場合には、一般に低温で行なう必要がある。反応温度としては−７８〜０℃が好ましい。この反応のための溶媒としては、ジエチルエ−テル、テトラヒドロフラン等のエ−テル系溶媒が使用できる。その使用量は、好ましくは原料１ｇに対して１〜１００ミリリットルである。反応時間は、好ましくは０．５〜５時間である。
【００１３】
調製された有機リチウム化合物を含む溶液にハロゲン化亜鉛を添加し、反応させる。ハロゲン化亜鉛としては、塩化亜鉛、臭化亜鉛、ヨウ化亜鉛が使用できる。その使用量は、原料に対して０．５〜３倍モル量である。ハロゲン化亜鉛との反応は、−７８〜＋７０℃の温度で反応させるのが好ましい。反応時間は、０．５〜５時間である。以上のような方法により、式（ＩＩ）で示される化合物のハロゲンＸが臭素である４−ブロモ−２−フルオロベンゾトリフルオリドの有機亜鉛化合物を含む溶液を調製することができる。
【００１４】
式（ＩＩ）で示される化合物のハロゲンＸが臭素である４−ブロモ−２−フルオロベンゾトリフルオリドから調製される有機金属化合物の溶液を、乾燥不活性ガス雰囲気下、式（ＩＩＩ）で示される化合物のハロゲンＸが臭素である１−ブロモ−４−（シアノメチル）−２−フルオロベンゼンの溶液と、金属触媒存在下でカップリング反応させることにより式（Ｉ）で示される新規な４−（シアノメチル）−２−フルオロ−３’−フルオロ−４’−（トリフルオロメチル）ビフェニルを製造することができる。
【００１５】
金属触媒としては、０価または２価のＰｄ系触媒あるいはＮｉ系触媒が使用できる。Ｐｄ系触媒とは、Ｐｄ単体やＰｄ化合物を意味する。Ｐｄ単体の場合、その使用量は好ましくは上記有機金属化合物に対して０．０００１〜０．１倍モル量である。式（ＩＩＩ）で示される化合物のハロゲンＸが臭素である１−ブロモ−４−（シアノメチル）−２−フルオロベンゼンの使用量は、有機金属化合物に対して０．２〜５倍モル量が好ましく、特に好ましくは０．５〜２倍モル量である。式（ＩＩＩ）で示される化合物のハロゲンＸが臭素である１−ブロモ−４−（シアノメチル）−２−フルオロベンゼンの溶媒としては、 ジエチルエ−テル、テトラヒドロフラン等のエ−テル系溶媒が使用できる。溶媒の使用量は、式（ＩＩＩ）で示される化合物のハロゲンＸが臭素である １−ブロモ−４−（シアノメチル）−２−フルオロベンゼン１ｇに対して１〜２０ミリリットルである。式（ＩＩ）で示される化合物のハロゲンＸが臭素である４−ブロモ−２−フルオロベンゾトリフルオリドから調製される有機金属化合物の溶液と式（ＩＩＩ）で示される化合物のハロゲンＸが臭素である１−ブロモ−４−（シアノメチル）−２−フルオロベンゼンの溶液とを混合、反応させる温度は−７８〜＋１００℃が好ましい。反応時間は、混合時間を含めて０．５〜４８時間が好ましい。反応終了後は、通常の後処理、精製を行なうことによりカップリングした式（Ｉ）で示される新規な４−（シアノメチル）−２−フルオロ−３’−フルオロ−４’−（トリフルオロメチル）ビフェニルを製造することができる。
【００１６】
以下にその実施例を示す。本発明における新規物質の製造方法はこれらの実施例により限定されるものではない。
【００１７】
【実施例】
４−（シアノメチル）−２−フルオロ−３’−フルオロ−４’−（トリフルオロメチル）ビフェニルの製造
実施例１
冷却浴、温度計、および圧力平衡管付き滴下ロ−トを備えた３０ｍｌガラス製フラスコに窒素雰囲気下、４−ブロモ−２−フルオロベンゾトリフルオリド１．１４ｇ（４．６７ミリモル）とジエチルエーテル５ｍｌとを仕込んだ。およそ−６０℃に冷却下、攪拌しながらｎ−ブチルリチウムヘキサン溶液（１．５４Ｍ）３．１ｍｌ（４．７４ミリモル）を約２０分間かけて滴下した。滴下終了後、−５０℃程度でさらに２時間攪拌を続けた。その−５０℃の温度条件下で攪拌しながら、塩化亜鉛０．６５ｇ（４．７７ミリモル）のテトラヒドロフラン溶液（４ｍｌ）を約５分間で滴下し、その後約３０分間かけて−２０℃まで昇温して有機亜鉛化合物の溶液を調製した。
【００１８】
冷却浴、温度計、および圧力平衡管付き滴下ロ−トを備えた別の５０ｍｌガラス製フラスコに［１，１’−ビス（ジフェニルホスフィノ）フェロセン］パラジウム（ＩＩ）ジクロリド（ＣＨ2Ｃｌ2１：１錯体）０．０９５ｇ（０．１２ミリモル）と１−ブロモ−４−（シアノメチル）−２−フルオロベンゼン０．５０ｇ（２．３４ミリモル）とテトラヒドロフラン３ｍｌとを仕込んだ。マイナス２０℃に冷却攪拌下、上記に調製した有機亜鉛試薬の溶液を約１０分間で添加し、室温下で１８時間攪拌した。反応終了後、０℃で飽和食塩水５ｍｌを加えて３０分間攪拌後、酢酸エチルエステル（３０ｍｌ×４）で抽出した。有機相を飽和食塩水１００ｍｌで洗浄後、無水硫酸マグネシウムで乾燥し、硫酸マグネシウムを濾別後、溶媒を減圧留去した。得られた粗生成物をシリカゲルカラムクロマトグラフィーにより精製して、４−（シアノメチル）−２−フルオロ−３’−フルオロ−４’−（トリフルオロメチル） ビフェニル０．６０ｇを得た［１−ブロモ−４−（シアノメチル）−２−フルオロベンゼン基準収率８６％］。
【００１９】
生成物の構造は、核磁気共鳴分析等で確認した。核磁気共鳴分析［ＶＡＲＩＡＮ社製、Ｇｅｍｉｎｉ２００］の結果は以下のとおりである。
1Ｈ−ＮＭＲ（溶媒：ＣＤＣｌ3、 標準物質 : テトラメチルシラン）
δ ７．６９（ｍ，１Ｈ，ＡｒＨ）
７．５２〜７．３４（ｍ，３Ｈ，ＡｒＨ）
７．２８〜７．１６（ｍ，２Ｈ，ＡｒＨ）
３．８２（ｓ，２Ｈ，ＡｒＣＨ 2ＣＮ）
19Ｆ−ＮＭＲ（溶媒：ＣＤＣｌ3、標準物質 ：ＣＦＣｌ3）
δ −６１．０９（ｄ，Ｊ＝１２．８Ｈｚ，３Ｆ，ＣＦ 3）
−１１３．５０〜−１１３．９５（ｍ，１Ｆ，ＡｒＦ）
−１１５．４３（ｍ，１Ｆ，ＡｒＦ）
実施例２
［１，１’−ビス（ジフェニルホスフィノ）フェロセン］パラジウム（ＩＩ）ジクロリドの代わりに、［１，１’−ビス（ジフェニルホスフィノ）フェロセン］ニッケル（ＩＩ）ジクロリドを使用した以外は、実施例１と同様に実施した。その結果、４−（シアノメチル）−２−フルオロ−３’−フルオロ−４’−（トリフルオロメチル）ビフェニル０．５６ｇを得た［１−ブロモ−４−（シアノメチル）−２−フルオロベンゼン基準収率８０％］。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method of manufacturing the novel biphenyl compounds, and more specifically, there is provided a a method of manufacturing the novel biphenyl compound represented by the following formula (I).
[0002]
[Chemical 3]
[Prior art]
4- (Cyanomethyl) -2-fluoro-3′-fluoro-4 ′-(trifluoromethyl) biphenyl according to the present invention is a novel compound. Therefore, the method for producing this novel compound is also novel.
[0004]
[Problems to be solved by the invention]
That is, the present invention relates to a novel 4- (cyanomethyl) -2-fluoro-3′-fluoro-4 ′-(trifluoromethyl) biphenyl represented by the formula (I). The novel 4- (cyanomethyl) -2-fluoro-3′-fluoro-4 ′-(trifluoromethyl) biphenyl represented by the formula (I) provided by the present invention has recently attracted attention as a next-generation flat display. It is a useful compound expected to be used for a light emitting device material of an organic EL (electroluminescence) display. Further, 4- (cyanomethyl) -2-fluoro-3′-fluoro-4 ′-(trifluoromethyl) biphenyl represented by the formula (I) is not only useful for the above-mentioned use but also a reactive methyl group. Therefore, it is a useful compound expected to be used as an intermediate for medical and agricultural chemicals, functional materials and the like having a trifluoromethyl group or a fluorine atom.
[0005]
[Means for Solving the Problems]
The inventors have prepared a novel 4- (cyanomethyl) -2-fluoro-3′-fluoro-4 ′-(trifluoromethyl) biphenyl represented by the formula (I) from various combinations. It was found that it can be produced by a coupling reaction between 4-halo-2-fluorobenzotrifluoride represented by II) and 1-halo-4- (cyanomethyl) -2-fluorobenzene represented by formula (III) . Considering the yield and economic efficiency of the coupling reaction, it is preferable and recommended for handling that the halogen X of the compounds represented by the formulas (II) and (III) is bromine.
[0006]
[Formula 4]
Hereinafter, the specific manufacturing method of the typical bromine compound as a novel compound of this invention is shown.
4-Bromo-2-fluorobenzotrifluoride in which the halogen X of the compound represented by the formula (II) is bromine is a relatively readily available carboxyl group of 4-bromo-2-fluorobenzoic acid with sulfur tetrafluoride. It can be produced by a method such as fluorination.
[0008]
In addition, 1-bromo-4- (cyanomethyl) -2-fluorobenzene in which the halogen X of the compound represented by the formula (III) is bromine is a relatively easily available methyl group of 4-bromo-3-fluorotoluene. It can be produced by monobromination and cyanation.
[0009]
An organometallic compound prepared from 4-bromo-2-fluorobenzotrifluoride in which the halogen X of the compound represented by the formula (II) is bromine, and 1 in which the halogen X of the compound represented by the formula (III) is bromine A novel 4- (cyanomethyl) -2-fluoro-3′-fluoro represented by the formula (I) is prepared by a coupling reaction of bromo-4- (cyanomethyl) -2-fluorobenzene in the presence of a metal catalyst. -4 '-(trifluoromethyl) biphenyl can be produced.
[0010]
Examples of the organometallic compound prepared from the compound represented by the formula (II) include an organozinc compound, an organocopper compound, an organoboron compound, and an organoaluminum compound. As methods for preparing these organometallic compounds, there are a method of conducting a metal exchange reaction after induction into an organolithium compound or an organomagnesium compound, and a method of reacting directly with a metal. For example, 4-bromo-2-fluorobenzotrifluoride in which the halogen X of the compound represented by the formula (II) is bromine is reacted with an organolithium reagent at a predetermined temperature for a predetermined time in a solvent with stirring. A solution containing a lithium compound is prepared, and this is reacted with zinc halide with stirring at a predetermined temperature and for a predetermined time, whereby 4-bromo-2-bromo-2-bromo-2- wherein the halogen X of the compound represented by the formula (II) is bromine An organozinc compound of fluorobenzotrifluoride can be prepared. Since this reaction is a reaction which dislikes moisture, it is preferable to carry out the inside of the reaction vessel in a dry inert gas atmosphere such as nitrogen.
[0011]
As the organic lithium reagent for the above reaction, alkyl lithium and phenyl lithium can be used. The amount of the organic lithium reagent used is preferably 0.8 to 1.2 times the molar amount of the raw material.
[0012]
When an organolithium reagent is allowed to act, it is generally necessary to carry out at a low temperature. The reaction temperature is preferably -78 to 0 ° C. As a solvent for this reaction, an ether solvent such as diethyl ether or tetrahydrofuran can be used. The amount used is preferably 1 to 100 ml per 1 g of raw material. The reaction time is preferably 0.5 to 5 hours.
[0013]
Zinc halide is added to the solution containing the prepared organolithium compound and allowed to react. As the zinc halide, zinc chloride, zinc bromide, and zinc iodide can be used. The amount used is 0.5 to 3 times the molar amount of the raw material. The reaction with zinc halide is preferably carried out at a temperature of -78 to + 70 ° C. The reaction time is 0.5 to 5 hours. By the method as described above, a solution containing an organozinc compound of 4-bromo-2-fluorobenzotrifluoride in which the halogen X of the compound represented by the formula (II) is bromine can be prepared.
[0014]
A solution of an organometallic compound prepared from 4-bromo-2-fluorobenzotrifluoride in which the halogen X of the compound represented by the formula (II) is bromine is represented by the formula (III) under a dry inert gas atmosphere. A novel 4- (cyanomethyl) represented by the formula (I) is prepared by a coupling reaction in the presence of a metal catalyst with a solution of 1-bromo-4- (cyanomethyl) -2-fluorobenzene in which the halogen X of the compound is bromine. ) -2-fluoro-3'-fluoro-4 '-(trifluoromethyl) biphenyl can be prepared.
[0015]
As the metal catalyst, a zero-valent or divalent Pd-based catalyst or a Ni-based catalyst can be used. The Pd-based catalyst means Pd alone or a Pd compound. In the case of Pd alone, the amount used is preferably 0.0001 to 0.1 times the molar amount relative to the organometallic compound. The amount of 1-bromo-4- (cyanomethyl) -2-fluorobenzene in which the halogen X of the compound represented by the formula (III) is bromine is preferably 0.2 to 5 times the molar amount relative to the organometallic compound. Particularly preferably, the molar amount is 0.5 to 2 times. As a solvent of 1-bromo-4- (cyanomethyl) -2-fluorobenzene in which the halogen X of the compound represented by the formula (III) is bromine, an ether solvent such as diethyl ether or tetrahydrofuran can be used. The amount of the solvent used is 1 to 20 ml with respect to 1 g of 1-bromo-4- (cyanomethyl) -2-fluorobenzene in which the halogen X of the compound represented by the formula (III) is bromine. A solution of an organometallic compound prepared from 4-bromo-2-fluorobenzotrifluoride in which the halogen X of the compound represented by the formula (II) is bromine and the halogen X of the compound represented by the formula (III) are bromine. The temperature for mixing and reacting with the solution of 1-bromo-4- (cyanomethyl) -2-fluorobenzene is preferably −78 to + 100 ° C. The reaction time is preferably 0.5 to 48 hours including the mixing time. After completion of the reaction, a novel 4- (cyanomethyl) -2-fluoro-3′-fluoro-4 ′-(trifluoromethyl) represented by the formula (I), which is coupled by carrying out usual post-treatment and purification. Biphenyl can be produced.
[0016]
Examples are shown below. The production method of the novel substance in the present invention is not limited by these examples.
[0017]
【Example】
Preparation of 4- (cyanomethyl) -2-fluoro-3′-fluoro-4 ′-(trifluoromethyl) biphenyl
Example 1
In a 30 ml glass flask equipped with a cooling bath, a thermometer, and a dropping funnel with a pressure balance tube, under nitrogen atmosphere, 1.14 g (4.67 mmol) of 4-bromo-2-fluorobenzotrifluoride and 5 ml of diethyl ether And charged. While cooling to about −60 ° C., 3.1 ml (4.74 mmol) of n-butyllithium hexane solution (1.54M) was added dropwise over about 20 minutes with stirring. After completion of the dropping, stirring was further continued at about −50 ° C. for 2 hours. While stirring under the temperature condition of −50 ° C., a solution of 0.65 g (4.77 mmol) of zinc chloride in tetrahydrofuran (4 ml) was added dropwise over about 5 minutes, and then the temperature was raised to −20 ° C. over about 30 minutes. Thus, a solution of the organozinc compound was prepared.
[0018]
[1,1′-bis (diphenylphosphino) ferrocene] palladium (II) dichloride (CH 2 Cl 2 1) in a separate 50 ml glass flask equipped with a cooling bath, thermometer, and dropping funnel with pressure balance tube. : 1 complex) 0.095 g (0.12 mmol), 1-bromo-4- (cyanomethyl) -2-fluorobenzene 0.50 g (2.34 mmol) and tetrahydrofuran 3 ml were charged. The solution of the organozinc reagent prepared above was added in about 10 minutes under cooling to −20 ° C. and stirred for 18 hours at room temperature. After completion of the reaction, 5 ml of saturated brine was added at 0 ° C. and stirred for 30 minutes, followed by extraction with ethyl acetate (30 ml × 4). The organic phase was washed with 100 ml of saturated brine, dried over anhydrous magnesium sulfate, the magnesium sulfate was filtered off, and the solvent was distilled off under reduced pressure. The obtained crude product was purified by silica gel column chromatography to obtain 0.60 g of 4- (cyanomethyl) -2-fluoro-3′-fluoro-4 ′-(trifluoromethyl) biphenyl [1-bromo -4- (cyanomethyl) -2-fluorobenzene standard yield 86%].
[0019]
The structure of the product was confirmed by nuclear magnetic resonance analysis and the like. The results of nuclear magnetic resonance analysis [manufactured by VARIAN, Gemini 200] are as follows.
1 H-NMR (solvent: CDCl 3 , Standard substance: Tetramethylsilane)
δ 7.69 (m, 1H, Ar H )
7.52 to 7.34 (m, 3H, Ar H )
7.28~7.16 (m, 2H, Ar H )
3.82 (s, 2H, ArC H 2 CN)
19 F-NMR (solvent: CDCl 3 , standard substance: CFCl 3 )
δ−61.09 (d, J = 12.8 Hz, 3F, C F 3 )
−113.50 to −113.95 (m, 1F, Ar F )
−115.43 (m, 1F, Ar F )
Example 2
Example except that [1,1′-bis (diphenylphosphino) ferrocene] nickel (II) dichloride was used instead of [1,1′-bis (diphenylphosphino) ferrocene] palladium (II) dichloride 1 was carried out. As a result, 4- (cyanomethyl) -2-fluoro-3′-fluoro-4 ′-(trifluoromethyl) biphenyl (0.56 g) was obtained [1-bromo-4- (cyanomethyl) -2-fluorobenzene standard yield. Rate 80%].
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