JP5488786B2 - Process for producing azaboracyclopentene compound and synthetic intermediate thereof - Google Patents
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Description
本発明は、例えば、アザボラシクロペンテン（アザボロール）化合物の製造方法に関する。アザボラシクロペンテン化合物は、例えば、金属含有薄膜形成用、重合触媒用、医薬、農薬用等の金属錯体配位子として有用な化合物であり、例えば、重合用触媒としては、オレフィン用重合触媒としての使用が開示されている（例えば、特許文献１参照）。 The present invention relates to a method for producing an azaboracyclopentene (azabolol) compound, for example. The azaboracyclopentene compound is a compound useful as a metal complex ligand for, for example, forming a metal-containing thin film, a polymerization catalyst, a pharmaceutical, and an agrochemical. For example, as a polymerization catalyst, Use is disclosed (for example, refer to Patent Document 1).
従来、アザボラシクロペンテン化合物の製造方法としては、以下の方法が知られている。
（１）アリルアミンのジリチオ体にホウ素化合物を反応させて合成する方法（例えば、非特許文献１参照）。
（２）ジブチルスズジクロリド用いて合成する方法（例えば、非特許文献２参照）。
（３）ジルコノセンジクロリドを用いる方法（例えば、非特許文献３参照）。
Conventionally, the following method is known as a manufacturing method of an azaboracyclopentene compound.
(1) A method in which a boron compound is reacted with a dilithio form of allylamine to synthesize (for example, see Non-Patent Document 1).
(2) A method of synthesis using dibutyltin dichloride (for example, see Non-Patent Document 2).
(3) A method using zirconocene dichloride (for example, see Non-Patent Document 3).
従来の前記（１）の方法においては極端に収率が低いという問題があった。これを解決するために、有機スズ化合物を用いる方法（前記（２）の方法）やジルコノセンジクロリドを使用する方法（前記（３）の方法）が開示されているが、いずれの場合も高価な金属の使用のみでしか収率向上が達成できていないという問題がある上に、極めて毒性の高い有機スズ化合物を用いなければならない等の工業的な製造方法としては問題があった。 The conventional method (1) has a problem that the yield is extremely low. In order to solve this, a method using an organotin compound (method (2) above) and a method using zirconocene dichloride (method (3) above) have been disclosed. In addition to the problem that the yield improvement can be achieved only by the use of No. 1, there is a problem as an industrial production method such as the use of a highly toxic organotin compound.
本発明の課題は、即ち、上記問題点を解決し、特定のジハロゲノ金属化合物を用いる方法にて、特定の中間体（新規な化合物）を経由して、高収率でアザボラシクロペンテン化合物の製造方法を提供することにある。 The object of the present invention is to solve the above-mentioned problems and produce azaboracyclopentene compounds in high yield via a specific intermediate (novel compound) by a method using a specific dihalogeno metal compound. It is to provide a method.
本発明の課題は、一般式（１） The subject of this invention is general formula (1).
（式中、Ｒ１は炭素原子数１〜５の直鎖状又は分岐状のアルキル基、Ｒ２〜Ｒ４は水素原子又は炭素原子数１〜５の直鎖状又は分岐状のアルキル基を示し、Ｍは２価の金属原子を示す。）
で示されるアザメタラシクロペンテン化合物と一般式（２）
(In the formula, R 1 is a linear or branched alkyl group having 1 to 5 carbon atoms, R 2 to R 4 are a hydrogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms. M represents a divalent metal atom.)
Azametallacyclopentene compound represented by the general formula (2)
（式中、Ｒ５は炭素原子数１〜５の直鎖状又は分岐状のアルキル基又は炭素原子数６〜１０のアリール基を示し、Ｘはハロゲン原子を示す。）
で示されるジハロゲノ有機ホウ素化合物とを反応させることを特徴とする、一般式（３）
(In the formula, R 5 represents a linear or branched alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 10 carbon atoms, and X represents a halogen atom.)
And a dihalogeno organoboron compound represented by the general formula (3):
（式中、Ｒ１〜Ｒ４は前記と同義である。）
で示されるアザボラシクロペンテン化合物の製造方法によって解決される。
(In the formula, R 1 to R 4 are as defined above.)
It solves by the manufacturing method of azaboracyclopentene compound shown by these.
本発明により、安価で毒性の低い金属を用いる方法にて、高収率でアザボラシクロペンテン化合物の製造方法を提供することができる。アザボラシクロペンテン化合物は、例えば、金属含有薄膜形成用、重合触媒用、医薬、農薬用等の金属錯体配位子として有用な化合物である。 According to the present invention, a method for producing an azaboracyclopentene compound can be provided in a high yield by a method using an inexpensive and less toxic metal. The azaboracyclopentene compound is a useful compound as a metal complex ligand for forming a metal-containing thin film, for a polymerization catalyst, for medicine, for agricultural chemicals, and the like.
本発明はアザボラシクロペンテン化合物の新規な製造方法を提供することにあるが、本発明の反応は以下のふたつの反応工程からなる。 Although this invention is providing the novel manufacturing method of an azaboracyclopentene compound, reaction of this invention consists of the following two reaction processes.
（１）一般式（４） (1) General formula (4)
（式中、Ｒ１は炭素原子数１〜５の直鎖状又は分岐状のアルキル基、Ｒ２〜Ｒ４は水素原子又は炭素原子数１〜５の直鎖状又は分岐状のアルキル基を示す。）
で示されるアリルアミンジリチオ体と一般式（５）
(In the formula, R 1 is a linear or branched alkyl group having 1 to 5 carbon atoms, R 2 to R 4 are a hydrogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms. Show.)
Allylamine dilithio compound represented by the general formula (5)
で示されるジハロゲノ金属化合物とを反応させることを特徴とする、一般式（１）
And a dihalogeno metal compound represented by the general formula (1):
（式中、Ｒ１〜Ｒ４及びＭ前記と同義である。）
で示されるアザメタラシクロペンテン化合物を製造する反応工程（以下、環化反応工程と称する。）。
(Wherein R 1 to R 4 and M are as defined above.)
A reaction step for producing an azametallacyclopentene compound represented by (hereinafter referred to as a cyclization reaction step).
（２）一般式（１） (2) General formula (1)
（式中、Ｒ１は炭素原子数１〜５の直鎖状又は分岐状のアルキル基、Ｒ２〜Ｒ４は水素原子又は炭素原子数１〜５の直鎖状又は分岐状のアルキル基を示し、Ｍは２価の金属原子を示す。）
で示されるアザメタラシクロペンテン化合物と一般式（２）
(In the formula, R 1 is a linear or branched alkyl group having 1 to 5 carbon atoms, R 2 to R 4 are a hydrogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms. M represents a divalent metal atom.)
Azametallacyclopentene compound represented by the general formula (2)
（式中、Ｒ５は炭素原子数１〜５の直鎖状又は分岐状のアルキル基又は炭素原子数６〜１０のアリール基を示し、Ｘはハロゲン原子を示す。）
で示されるジハロゲノ有機ホウ素化合物とを反応させることを特徴とする、一般式（３）
(In the formula, R 5 represents a linear or branched alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 10 carbon atoms, and X represents a halogen atom.)
And a dihalogeno organoboron compound represented by the general formula (3):
（式中、Ｒ１〜Ｒ４は前記と同義である。）
で示されるアザボラシクロペンテン化合物を製造する反応工程（以下、ホウ素交換反応工程と称する）。
(In the formula, R 1 to R 4 are as defined above.)
The reaction process which manufactures the azaboracyclopentene compound shown by this (henceforth a boron exchange reaction process).
（１）環化反応工程
本発明の環化反応工程において使用するアリルアミンジリチオ体は、前記の一般式（４）において示される。その一般式（１）において、Ｒ１は炭素原子数１〜５の直鎖状又は分岐状のアルキル基を示すが、具体的には、例えば、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｔｅｒｔ−ブチル基、ｎ−ペンチル基等の炭素原子数１〜５の直鎖状又は分岐状のアルキル基である。又、Ｒ２〜Ｒ４は水素原子又は炭素原子数１〜５の直鎖状又は分岐状のアルキル基を示すが、具体的には、例えば、水素原子；メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｔｅｒｔ−ブチル基、ｎ−ペンチル基等の炭素原子数１〜５の直鎖状又は分岐状のアルキル基である。
(1) Cyclization reaction step The allylamine dilithio compound used in the cyclization reaction step of the present invention is represented by the general formula (4). In the general formula (1), R 1 represents a linear or branched alkyl group having 1 to 5 carbon atoms. Specifically, for example, methyl group, ethyl group, n-propyl group, isopropyl A linear or branched alkyl group having 1 to 5 carbon atoms, such as a group, an n-butyl group, an isobutyl group, a tert-butyl group, and an n-pentyl group. R 2 to R 4 represent a hydrogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms. Specific examples include a hydrogen atom; a methyl group, an ethyl group, and n-propyl. A linear or branched alkyl group having 1 to 5 carbon atoms such as a group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group.
前記アリルアミンジリチオ体は、アリルアミン（又はその塩）と有機リチウム化合物を反応させることによって得られる（例えば、非特許文献４参照）。前記有機リチウム化合物としては、例えば、メチルリチウム、ｎ−ブチルリチウム、ｓｅｃ−ブチルリチウム、ｔｅｒｔ−ブチルリチウム等が挙げられるが、好ましくはｎ−ブチルリチウムが使用される。なお、これらのリチウム化合物は単独又は二種以上を混合して使用しても良い。 The allylamine dilithio compound is obtained by reacting allylamine (or a salt thereof) with an organolithium compound (see, for example, Non-Patent Document 4). Examples of the organic lithium compound include methyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, and the like. Preferably, n-butyllithium is used. In addition, you may use these lithium compounds individually or in mixture of 2 or more types.
なお、アリルアミンジリチオ体は、一旦合成したものを単離して使用、又は反応系内で合成したものをそのまま使用することができる。 In addition, as the allylamine dilithio compound, a compound once synthesized can be isolated and used, or a compound synthesized in a reaction system can be used as it is.
本発明の環化反応工程において使用するジハロゲノ金属化合物は、その一般式（５）において、Ｍは２価の金属原子（モノアルキル化された３価の金属原子を含む）であり、例えば、亜鉛、マグネシウム、鉄、銅、モノアルキルアルミニウム等が挙げられるが、好ましくは亜鉛、マグネシウムである。又、Ｙはハロゲン原子であり、例えば、フッ素原子、塩素原子、ヨウ素原子、臭素原子である。 The dihalogeno metal compound used in the cyclization reaction step of the present invention is a divalent metal atom (including a monoalkylated trivalent metal atom) in the general formula (5), for example, zinc , Magnesium, iron, copper, monoalkylaluminum and the like, and zinc and magnesium are preferable. Y is a halogen atom, for example, a fluorine atom, a chlorine atom, an iodine atom, or a bromine atom.
前記ジハロゲノ金属化合物の使用量は、アリルアミンジリチオ体１モルに対して、好ましくは０．５〜１．５モル、更に好ましくは０．８〜１．２モルである。 The amount of the dihalogeno metal compound to be used is preferably 0.5 to 1.5 mol, more preferably 0.8 to 1.2 mol, with respect to 1 mol of allylamine dilithio.
本発明の環化反応には溶媒の存在下で行うことが望ましく、使用される溶媒としては反応を阻害しないものならば特に限定されないが、例えば、ジエチルエーテル、テトラヒドロフラン、ジメトキシエタン、ジオキサン等のエーテル類；ヘキサン、シクロヘキサン、メチルシクロヘキサン等の脂肪族炭化水素類；トルエン、キシレン等の芳香族炭化水素類が挙げられるが、好ましいくはエーテル類、更に好ましくはジエチルエーテル、テトラヒドロフランが使用される。なお、これらの溶媒は単独又は二種以上を混合して使用しても良い。 The cyclization reaction of the present invention is preferably carried out in the presence of a solvent, and the solvent used is not particularly limited as long as it does not inhibit the reaction. For example, ethers such as diethyl ether, tetrahydrofuran, dimethoxyethane, dioxane, etc. Aliphatic hydrocarbons such as hexane, cyclohexane and methylcyclohexane; aromatic hydrocarbons such as toluene and xylene, and the like, preferably ethers, more preferably diethyl ether and tetrahydrofuran. In addition, you may use these solvents individually or in mixture of 2 or more types.
前記溶媒の使用量は、反応液の均一性や攪拌性等により適宜調節するが、アリルアミンジリチオ体１ｇに対して、好ましくは０．５〜１００ｇ、更に好ましくは３〜３０ｇである。 Although the usage-amount of the said solvent is suitably adjusted with the uniformity of a reaction liquid, stirring property, etc., Preferably it is 0.5-100g with respect to 1g of allylamine dilithio bodies, More preferably, it is 3-30g.
本発明の環化反応は、例えば、アリルアミンジリチオ体、ジハロゲノ金属化合物及び溶媒を混合して、攪拌しながら反応させる等の方法によって行われる。その際の反応温度は、好ましくは−７８〜５０℃、更に好ましくは−１０〜４０℃あり、反応圧力は特に制限されない。 The cyclization reaction of the present invention is performed, for example, by a method in which an allylamine dilithio compound, a dihalogeno metal compound and a solvent are mixed and reacted with stirring. The reaction temperature at that time is preferably −78 to 50 ° C., more preferably −10 to 40 ° C., and the reaction pressure is not particularly limited.
なお、アリルアミンジリチオ体を反応系内で調製したものをそのまま使用する方法としては、アリルアミン（又はその塩）と有機リチウム化合物とを反応させてアリルアミンジリチオ体を合成した後、それにジハロゲノ金属化合物及び溶媒を加えて反応させる方法もしくは、別途アリルアミン（又はその塩）と有機リチウム化合物とを反応させて得られたアリルアミンジリチオ体を、ジハロゲノ金属化合物及び溶媒中に加えて反応させる方法等が挙げられる。 In addition, as a method of using the allylamine dilithio compound prepared in the reaction system as it is, after synthesizing an allylamine dilithio compound by reacting allylamine (or a salt thereof) with an organolithium compound, a dihalogeno metal compound is then synthesized. And a method of reacting by adding a solvent or a method of separately reacting an allylamine dilithio compound obtained by reacting allylamine (or a salt thereof) with an organolithium compound in a dihalogeno metal compound and a solvent. It is done.
本発明の環化反応工程によって得られるアザメタラシクロペンテン化合物は、一般式（１） The azametallacyclopentene compound obtained by the cyclization reaction step of the present invention has the general formula (1)
（式中、Ｒ１は炭素原子数１〜５の直鎖状又は分岐状のアルキル基、Ｒ２〜Ｒ４は水素原子又は炭素原子数１〜５の直鎖状又は分岐状のアルキル基を示し、Ｍは２価の金属原子を示す。）
で示される新規な化合物である。
(In the formula, R 1 is a linear or branched alkyl group having 1 to 5 carbon atoms, R 2 to R 4 are a hydrogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms. M represents a divalent metal atom.)
It is a novel compound shown by these.
本発明の環化反応によって得られたアザメタラシクロペンテン化合物は、一旦合成したものを単離して、又は反応系内で合成したものをそのままホウ素交換反応工程に使用することができる。 As the azametallacyclopentene compound obtained by the cyclization reaction of the present invention, a compound once synthesized can be isolated, or a compound synthesized in a reaction system can be used as it is in a boron exchange reaction step.
（２）ホウ素交換反応工程
本発明のホウ素交換反応において使用するジハロゲノ有機ホウ素化合物は、前記の一般式（２）で示される。その一般式（２）において、Ｒ５は炭素原子数１〜５の直鎖状又は分岐状のアルキル基又は炭素原子数６〜１０のアリール基を示すが、具体的には、例えば、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基、ｎ−ペンチル基等の炭素原子数１〜５の直鎖状又は分岐状のアルキル基；フェニル基、トリル基、ナフチル基等の炭素原子数６〜１０のアリール基を示す。又、Ｘはハロゲン原子を示すが、フッ素原子、塩素原子、臭素原子、ヨウ素原子である。
(2) Boron exchange reaction process The dihalogeno organoboron compound used in the boron exchange reaction of the present invention is represented by the general formula (2). In the general formula (2), R 5 represents a linear or branched alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 10 carbon atoms. Specifically, for example, a methyl group A linear or branched alkyl group having 1 to 5 carbon atoms such as ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group and n-pentyl group; An aryl group having 6 to 10 carbon atoms such as a phenyl group, a tolyl group and a naphthyl group is shown. X represents a halogen atom, which is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.
前記ジハロゲノ有機ホウ素化合物の使用量は、アザメタラシクロペンテン化合物１モルに対して、好ましくは０．５〜１．５モル、更に好ましくは０．８〜１．２モルである。 The amount of the dihalogenoorganoboron compound used is preferably 0.5 to 1.5 mol, more preferably 0.8 to 1.2 mol, per 1 mol of the azametallacyclopentene compound.
本発明の環化反応は、例えば、アザメタラシクロペンテン化合物、ジハロゲノ有機ホウ素化合物（必要ならばその溶媒溶液）及び溶媒を混合して、攪拌しながら反応させる等の方法によって行われる。その際の反応温度は、好ましくは−７８〜５０℃、更に好ましくは−３０〜４０℃あり、反応圧力は特に制限されない。 The cyclization reaction of the present invention is performed by, for example, a method of mixing an azametallacyclopentene compound, a dihalogenoorganoboron compound (a solvent solution thereof if necessary) and a solvent and reacting them with stirring. The reaction temperature at that time is preferably −78 to 50 ° C., more preferably −30 to 40 ° C., and the reaction pressure is not particularly limited.
本発明の環化反応により目的物であるアザボラシクロペンテン化合物が得られるが、反応終了後、中和、抽出、濾過、濃縮、蒸留、再結晶、カラムクロマトグラフィー等の公知の方法によって単離・精製される。 The target product, azaboracyclopentene compound, is obtained by the cyclization reaction of the present invention. After completion of the reaction, the compound is isolated by a known method such as neutralization, extraction, filtration, concentration, distillation, recrystallization, column chromatography, etc. Purified.
又、本発明において環化反応とホウ素交換を連続的に行う場合において、その好ましい態様としては、例えば、リチウム化合物、アリルアミン及び溶媒を混合してアリルアミンジリチオ体を含む溶液を合成した後、次いで、ジハロゲノ金属化合物（必要ならばその溶媒溶液）を反応させて反応系中にアザメタラシクロペンテン化合物を含む溶液を調製する。更に、当該反応液にジハロゲノ有機ホウ素化合物（必要ならばその溶媒溶液）を加えて反応させることによって、アザボラシクロペンテン化合物を製造する方法が挙げられる。 In the present invention, when the cyclization reaction and the boron exchange are continuously performed, as a preferred embodiment, for example, a lithium compound, allylamine and a solvent are mixed to synthesize a solution containing an allylamine dilithio compound, and then Then, a dihalogeno metal compound (a solvent solution thereof if necessary) is reacted to prepare a solution containing an azametallacyclopentene compound in the reaction system. Furthermore, a method of producing an azaboracyclopentene compound by adding a dihalogenoorganoboron compound (if necessary, a solvent solution thereof) to the reaction solution and reacting it.
なお、本発明の目的物であるアザボラシクロペンテン化合物及びその合成中間体であるアザメタラシクロペンテン化合物は、大気中の水分や酸素に対して必ずしも安定ではない場合が多いため、無水条件下や不活性ガス条件下にて、反応、操作、後処理等を行うことが望ましい。 The azaboracyclopentene compound, which is the object of the present invention, and the azametallacyclopentene compound, which is a synthetic intermediate thereof, are often not always stable with respect to moisture and oxygen in the atmosphere. It is desirable to perform reaction, operation, post-treatment, etc. under gas conditions.
本発明によって製造されるアザボラシクロペンテン化合物は、例えば、以下の式（６）〜（６５）によって示される化合物が挙げられる。 Examples of the azaboracyclopentene compound produced by the present invention include compounds represented by the following formulas (6) to (65).
等が挙げられる。 Etc.
次に、実施例を挙げて本発明を具体的に説明するが、本発明の範囲はこれらに限定されるものではない。 Next, the present invention will be specifically described with reference to examples, but the scope of the present invention is not limited thereto.
実施例１（４−ｔｅｒｔ−ブチル−３−フェニル−４−アザ−３−ボラシクロペンテンの合成）
（ｔｅｒｔ−ブチルアミンジリチオ体の合成）
攪拌装置、温度計及び滴下漏斗を備えた内容積１００ｍｌのフラスコに、アルゴン雰囲気下、ｔｅｒｔ−ブチルアリルアミン２．３ｇ（２０ｍｍｏｌ）及びジエチルエーテル２０ｍｌの混合溶液に、反応液を０℃付近に維持しながら、１．６ｍｏｌ／ｌのｎ−ブチルリチウムへキサン溶液（２５ｍｌ（４０ｍｍｏｌ）をゆるやかに滴下した。次いで、反応液を攪拌させながら２５℃まで２０時間反応させた（この時点でｔｅｒｔ−ブチルアミンジリチオ体が生成）。この反応液にジエチルエーテル５０ｍｌを加えｔｅｒｔ−ブチルアミンジリチオ体のジエチルエーテル溶液を調整した。
Example 1 (Synthesis of 4-tert-butyl-3-phenyl-4-aza-3-boracyclopentene)
(Synthesis of tert-butylamine dilithio compound)
The reaction solution was maintained at around 0 ° C. in a mixed solution of 2.3 g (20 mmol) of tert-butylallylamine and 20 ml of diethyl ether under an argon atmosphere in a 100-ml flask equipped with a stirrer, thermometer and dropping funnel. Then, a 1.6 mol / l n-butyllithium hexane solution (25 ml (40 mmol) was slowly added dropwise. Then, the reaction solution was allowed to react for 20 hours with stirring to 25 ° C. (at this point, tert-butylamine diyl). A 50 ml of diethyl ether was added to this reaction solution to prepare a diethyl ether solution of a tert-butylamine dilithio compound.
（反応工程１：環化反応工程）
攪拌装置、温度計及び滴下漏斗を備えた内容積２００ｍｌのフラスコに、アルゴン雰囲気にて、無水ヨウ化亜鉛６．４ｇ（２０ｍｍｏｌ）をジエチルエーテル２５ｍｌに溶解させた溶液を加え、先に調製したｔｅｒｔ−ブチルアミンジリチオ体のジエチルエーテル溶液の溶液を０℃でゆるやかに滴下した後、反応液を攪拌させながら２５℃まで２時間反応させた（この時点で４−ｔｅｒｔ−ブチル−４−アザ−３−ジンカシクロペンテンが生成。）
(Reaction step 1: cyclization reaction step)
A solution prepared by dissolving 6.4 g (20 mmol) of anhydrous zinc iodide in 25 ml of diethyl ether in an argon atmosphere was added to a 200-ml flask equipped with a stirrer, a thermometer, and a dropping funnel. -A solution of a diethyl ether solution of butylamine dilithio compound was slowly added dropwise at 0 ° C, and the reaction solution was allowed to react for 2 hours while stirring the reaction solution (at this time, 4-tert-butyl-4-aza-3 -Zincacyclopentene is produced.)
（反応工程２：ホウ素交換反応工程）
次いで、前記反応液に、反応液の温度を０℃付近に維持しながらジクロロフェニルボラン３．２ｇ（２０ｍｍｏｌ）のトルエン溶液２０ｍｌをゆるやかに滴下し、攪拌しながら２５℃で２時間反応させた。反応終了後、反応液をアルゴン雰囲気にて濾過し、濾液を濃縮した後に濃縮物を減圧下で蒸留（８０℃、５．２Ｐａ）し、無色液体として、４−ｔｅｒｔ−ブチル−３−フェニル−４−アザ−３−ボラシクロペンテン２．０ｇを得た（単離収率；５０％）。
なお、４−ｔｅｒｔ−ブチル−３−フェニル−４−アザ−３−ボラシクロペンテンの物性値は以下の通りであった。
(Reaction process 2: boron exchange reaction process)
Next, 20 ml of a toluene solution of 3.2 g (20 mmol) of dichlorophenylborane was gently dropped into the reaction solution while maintaining the temperature of the reaction solution at around 0 ° C., and the mixture was reacted at 25 ° C. for 2 hours with stirring. After completion of the reaction, the reaction solution was filtered in an argon atmosphere, the filtrate was concentrated, and the concentrate was distilled under reduced pressure (80 ° C., 5.2 Pa) to give 4-tert-butyl-3-phenyl- as a colorless liquid. 2.0 g of 4-aza-3-boracyclopentene was obtained (isolation yield; 50%).
The physical properties of 4-tert-butyl-3-phenyl-4-aza-3-boracyclopentene were as follows.
１Ｈ−ＮＭＲ（ＤＭＳＯ−ｄ６，δ（ｐｐｍ））；１．２６（９Ｈ，ｓ），４．０４（２Ｈ，ｔ），６．６７（１Ｈ，ｍ），７．１３（１Ｈ，ｍ），７．３３（２Ｈ，ｍ），７．３５（３Ｈ，ｍ）
ＭＳ（ｍ／ｚ）；１９９
1 H-NMR (DMSO-d 6 , δ (ppm)); 1.26 (9H, s), 4.04 (2H, t), 6.67 (1H, m), 7.13 (1H, m ), 7.33 (2H, m), 7.35 (3H, m)
MS (m / z); 199
実施例１−２（４−ｔｅｒｔ−ブチル−４−アザ−３−ジンカシクロペンテンの合成）
実施例１と同様な方法で環化反応にて得られた溶液を濃縮乾固させ、ヘキサン抽出の後、溶媒を除去して１Ｈ−ＮＭＲで確認したところ、下記式で示される４−ｔｅｒｔ−ブチル−４−アザ−３−ジンカシクロペンテンが生成していた。
Example 1-2 (Synthesis of 4-tert-butyl-4-aza-3-zincacyclopentene)
The solution obtained by the cyclization reaction in the same manner as in Example 1 was concentrated to dryness, and after extraction with hexane, the solvent was removed and confirmed by 1H-NMR. As a result, 4-tert- Butyl-4-aza-3-zincacyclopentene was produced.
なお、４−ｔｅｒｔ−ブチル−４−アザ−３−ジンカシクロペンテンは下記の物性値で示される新規な化合物である。 4-tert-butyl-4-aza-3-zincacyclopentene is a novel compound represented by the following physical property values.
１Ｈ−ＮＭＲ（ＴＨＦ−ｄ８，δ（ｐｐｍ））；１．１３（９Ｈ，ｓ），３．２０（２Ｈ，ｍ），６．３５（１Ｈ，ｍ），６．５８（１Ｈ，ｍ） 1 H-NMR (THF-d 8 , δ (ppm)); 1.13 (9H, s), 3.20 (2H, m), 6.35 (1H, m), 6.58 (1H, m )
実施例２〜５、比較例１〜４（４−ｔｅｒｔ−ブチル−３−フェニル−４−アザ−３−ボラシクロペンテンの合成）
実施例１において、ジハロゲノ金属化合物を変えたこと以外は実施例１と同様に反応を行った。その結果を実施例１と併せて表１に示す。
Examples 2 to 5 and Comparative Examples 1 to 4 (Synthesis of 4-tert-butyl-3-phenyl-4-aza-3-boracyclopentene)
In Example 1, the reaction was performed in the same manner as in Example 1 except that the dihalogeno metal compound was changed. The results are shown in Table 1 together with Example 1.
以上の結果から、本発明のアリルアミンジリチオ体と２価の金属原子を含むジハロゲノ金属化合物とを反応させて生成する２価の金属原子を含むアザメタラシクロペンテン化合物を経由してアザボラシクロペンテン化合物を製造することで、高い収率でアザボラシクロペンテン化合物を得ることができることが判明した。 From the above results, an azaboracyclopentene compound is obtained via an azametallacyclopentene compound containing a divalent metal atom produced by reacting the allylamine dilithio compound of the present invention with a dihalogeno metal compound containing a divalent metal atom. It has been found that an azaboracyclopentene compound can be obtained in a high yield by the production.
本発明はアザボラシクロペンテン化合物の製造方法に関する。アザボラシクロペンテン化合物は、例えば、金属含有薄膜形成用、重合触媒用、医薬、農薬用等の金属錯体配位子として有用な化合物である。 The present invention relates to a method for producing an azaboracyclopentene compound. The azaboracyclopentene compound is a useful compound as a metal complex ligand for forming a metal-containing thin film, for a polymerization catalyst, for medicine, for agricultural chemicals, and the like.
Claims (7)
で示されるアザメタラシクロペンテン化合物と一般式（２）
で示されるジハロゲノ有機ホウ素化合物とを反応させることを特徴とする、一般式（３）
で示されるアザボラシクロペンテン化合物の製造方法。 General formula (1)
Azametallacyclopentene compound represented by the general formula (2)
And a dihalogeno organoboron compound represented by the general formula (3):
The manufacturing method of the azabora cyclopentene compound shown by these.
で示されるアリルアミンジリチオ体と一般式（５）
で示されるジハロゲノ金属化合物とを反応させて得られることを特徴とする請求項１記載のアザボラシクロペンテン化合物の製造方法。 The azametallacyclopentene compound represented by the general formula (1) is represented by the general formula (4)
Allylamine dilithio compound represented by the general formula (5)
The method for producing an azaboracyclopentene compound according to claim 1, which is obtained by reacting with a dihalogeno metal compound represented by the formula:
で示されるアリルアミンジリチオ体と一般式（５）
で示されるジハロゲノ有機ホウ素化合物とを反応させることを特徴とする、一般式（３）
で示されるアザボラシクロペンテン化合物の製造方法。 General formula (4)
Allylamine dilithio compound represented by the general formula (5)
And a dihalogeno organoboron compound represented by the general formula (3):
The manufacturing method of the azabora cyclopentene compound shown by these.
で示されるアザメタラシクロペンテン化合物。 General formula (1)
An azametallacyclopentene compound represented by:
で示されるアリルアミンジリチオ体と一般式（５）
で示されるジハロゲノ金属化合物とを反応させることを特徴とする、一般式（１）
で示される請求項５記載のアザメタラシクロペンテン化合物の製造方法。 General formula (4)
Allylamine dilithio compound represented by the general formula (5)
And a dihalogeno metal compound represented by the general formula (1):
The manufacturing method of the azametallacyclopentene compound of Claim 5 shown by these.
The method for producing an azaboracyclopentene compound according to claim 6, wherein M is a zinc atom or a magnesium atom.
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