JP2849739B2 - Fluorine-containing tertiary polyamine ruthenium complex with nitrogen immobilization ability - Google Patents
Fluorine-containing tertiary polyamine ruthenium complex with nitrogen immobilization abilityInfo
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- JP2849739B2 JP2849739B2 JP26023996A JP26023996A JP2849739B2 JP 2849739 B2 JP2849739 B2 JP 2849739B2 JP 26023996 A JP26023996 A JP 26023996A JP 26023996 A JP26023996 A JP 26023996A JP 2849739 B2 JP2849739 B2 JP 2849739B2
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- Prior art keywords
- nitrogen
- complex
- solvent
- absorbing solution
- fluorinated hydrocarbon
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Description
【0001】[0001]
【発明の属する技術分野】本発明は、1,9−ジアミノ
−3,7−ジアザウンデカン(以下2,3,2−テトラ
アミンとも呼ぶ)を基本骨格としてもつ、フッ化炭化水
素N置換三級テトラアミンを配位子とするルテニウム
(II)錯体、ルテニウム(III)錯体、フッ化炭化
水素N置換三級テトラアミン及びその前駆体と、それら
のルテニウム錯体を用いた窒素吸収性溶液に関するもの
である。The present invention relates to a fluorinated hydrocarbon N-substituted tertiary having 1,9-diamino-3,7-diazaundecane (hereinafter also referred to as 2,3,2-tetraamine) as a basic skeleton. The present invention relates to a ruthenium (II) complex having a tetraamine as a ligand, a ruthenium (III) complex, a fluorinated hydrocarbon N-substituted tertiary tetraamine, a precursor thereof, and a nitrogen-absorbing solution using the ruthenium complex.
【0002】[0002]
【従来の技術】2,3,2−テトラアミンと同じ骨格を
もつtrans−ジクロロ三級テトラアミン錯体は水溶
液中で三塩化チタンと反応させることで水中の溶存窒素
ガスを固定化できることがすでに示されている(T.T
akahashi,K.Hiratami,K.Kas
uga,E.Kimura,Chem.Lett.,1
993,1761)。また、本発明者らによって、上記
の錯体の配位窒素上に炭化水素置換基を導入したルテニ
ウム錯体が、窒素ガス吸収能力をもつことも先に見出さ
れている(特願平7−262147:窒素固定化能をも
つルテニウム三級ポリアミン錯体)。2. Description of the Related Art It has been shown that a trans-dichlorotertiary tetraamine complex having the same skeleton as 2,3,2-tetraamine can fix dissolved nitrogen gas in water by reacting it with titanium trichloride in an aqueous solution. (TT
akahashi, K .; Hiratami, K .; Kas
uga, E .; Kimura, Chem. Lett. , 1
993, 1761). In addition, the present inventors have previously found that a ruthenium complex having a hydrocarbon substituent introduced on the coordinating nitrogen of the above complex has a nitrogen gas absorbing ability (Japanese Patent Application No. Hei 7-262147). : Ruthenium tertiary polyamine complex capable of immobilizing nitrogen).
【0003】[0003]
【発明が解決しようとする課題】本発明の課題は以下の
通りである。 (1)窒素固定化能力をもつ新規なフッ化炭化水素N置
換三級ポリアミンルテニウム錯体を提供すること。 (2)前記錯体の中間体を提供すること。 (3)溶媒に溶かすだけで窒素を固定化できる錯体を提
供すること。 (4)窒素を固定化できる窒素吸収性溶液を提供するこ
と。 本発明の他の課題は以下の記載から明らかに理解される
であろう。The objects of the present invention are as follows. (1) To provide a novel fluorinated hydrocarbon N-substituted tertiary polyamine ruthenium complex having a nitrogen fixing ability. (2) Providing an intermediate of the complex. (3) To provide a complex capable of immobilizing nitrogen simply by dissolving in a solvent. (4) To provide a nitrogen absorbing solution capable of immobilizing nitrogen. Other objects of the present invention will be clearly understood from the following description.
【0004】[0004]
【課題を解決するための手段】本発明者らは前記課題を
解決すべく鋭意研究を重ねた結果、本発明を完成するに
至った。すなわち、本発明によれば、下記式(1)で表
される2,12−ジメチル−5,9−ビスフッ化炭化水
素カルボニル−2,5,9,12−テトラアザトリデカ
ンが提供される。Means for Solving the Problems The inventors of the present invention have made intensive studies to solve the above problems, and as a result, have completed the present invention. That is, according to the present invention, there is provided 2,12-dimethyl-5,9-bisfluorohydrocarboncarbonyl-2,5,9,12-tetraazatridecane represented by the following formula (1).
【化1】 (式中、Rはフッ化炭化水素基を示す) また、本発明によれば、下記式(2)で表される2,1
2−ジメチル−5,9−ジフッ化炭化水素−2,5,
9,12−テトラアザトリデカンが提供される。Embedded image (Wherein, R represents a fluorinated hydrocarbon group) Further, according to the present invention, 2,1 represented by the following formula (2)
2-dimethyl-5,9-difluorohydrocarbon-2,5
9,12-Tetraazatridecane is provided.
【化2】 (式中、Rはフッ化炭化水素基を示す) さらに、本発明によれば、下記式(3)で表されるtr
ans−ジクロロルテニウム(II)(2,12−ジメ
チル−5,9−ジフッ化炭化水素−2,5,9,12−
テトラアザトリデカンン)錯体が提供される。Embedded image (Wherein, R represents a fluorinated hydrocarbon group) Further, according to the present invention, tr represented by the following formula (3)
ans-dichlororuthenium (II) (2,12-dimethyl-5,9-difluorohydrocarbon-2,5,9,12-
Tetraazatridecane) complexes are provided.
【化3】 (式中、Rはフッ化炭化水素基を示す) さらに、本発明によれば、下記式(4)で表されるtr
ans−ジクロロルテニウム(III)(2,12−ジ
メチル−5,9−ジフッ化炭化水素−2,5,9,12
−テトラアザトリデカン)錯体が提供される。Embedded image (Wherein, R represents a fluorohydrocarbon group) Further, according to the present invention, tr represented by the following formula (4)
ans-dichlororuthenium (III) (2,12-dimethyl-5,9-difluorohydrocarbon-2,5,9,12
-Tetraazatridecane) complexes are provided.
【化4】 (式中、Rはフッ化炭化水素基を示す) さらに、本発明によれば、下記式(3)Embedded image (Wherein, R represents a fluorohydrocarbon group) Further, according to the present invention, the following formula (3)
【化3】 (式中、Rはフッ化炭化水素基を示す)で表されるtr
ans−ジクロロルテニウム(II)(2,12−ジメ
チル−5,9−ジフッ化炭化水素−2,5,9,12−
テトラアザトリデカン)錯体を、溶媒に溶解させてなる
窒素吸収性溶液が提供される。さらにまた、本発明によ
れば、下記一般式(4)Embedded image (Wherein, R represents a fluorohydrocarbon group)
ans-dichlororuthenium (II) (2,12-dimethyl-5,9-difluorohydrocarbon-2,5,9,12-
Provided is a nitrogen-absorbing solution obtained by dissolving a tetraazatridecane) complex in a solvent. Furthermore, according to the present invention, the following general formula (4)
【化4】 (式中、Rはフッ化炭化水素基を示す)で表されるtr
ans−ジクロロルテニウム(III)(2,12−ジ
メチル−5,9−ジフッ化炭化水素−2,5,9,12
−テトラアザトリデカン)錯体を溶媒中で還元してなる
窒素吸収性溶液が提供される。Embedded image (Wherein, R represents a fluorohydrocarbon group)
ans-dichlororuthenium (III) (2,12-dimethyl-5,9-difluorohydrocarbon-2,5,9,12
-Tetraazatridecane) complex in a solvent is provided.
【0005】[0005]
【発明の実施の形態】これまで、すでに下記式(5)DESCRIPTION OF THE PREFERRED EMBODIMENTS Heretofore, the following formula (5)
【化5】 で表される物質の水溶液に三塩化チタンを作用すること
によって、ルテニウム(II)錯体による窒素吸収反応
が起こることが明らかにされている(T.Takaha
shi,K.Hiratami,K.Kasuga,
E.Kimura,Chem.Lett.,1993,
1761)。本発明によって、下記式(3)Embedded image It has been clarified that the action of titanium trichloride on an aqueous solution of a substance represented by the formula (1) causes a nitrogen absorption reaction by a ruthenium (II) complex (T. Takaha).
shi, K .; Hiratami, K .; Kasuga,
E. FIG. Kimura, Chem. Lett. , 1993,
1761). According to the present invention, the following formula (3)
【化3】 (式中、Rはフッ化炭化水素基を示す)で表されるフッ
化炭化水素置換基を導入した化合物が合成できることが
明らかとなった。また、本発明によって、下記式(4)Embedded image (Wherein, R represents a fluorinated hydrocarbon group), it has been found that a compound having a fluorinated hydrocarbon substituent introduced therein can be synthesized. Further, according to the present invention, the following formula (4)
【化4】 (式中、Rはフッ化炭化水素基を示す、以下同じ)で表
されるフッ化炭化水素置換基を導入した化合物も合成で
きることが明らかとなった。Embedded image (Wherein, R represents a fluorinated hydrocarbon group, the same applies hereinafter). It has been clarified that a compound having a fluorinated hydrocarbon substituent introduced therein can also be synthesized.
【0006】前記式(4)の化合物を用いた場合にも、
化合物(5)と場合同様に窒素を固定化し得ることが明
らかとなった。さらに、前記式(3)の化合物を用いた
場合、溶媒に溶解するだけで窒素ガスの固定化が可能で
あることが明らかになった。When the compound of the above formula (4) is used,
It was revealed that nitrogen can be immobilized in the same manner as in the case of compound (5). Further, it was revealed that when the compound of the formula (3) was used, nitrogen gas could be immobilized only by dissolving in a solvent.
【0007】本発明による下記式(1)The following formula (1) according to the present invention:
【化1】 で表される三級テトラアミンジアミド化合物の製造方法
を以下に示す。Embedded image The method for producing the tertiary tetraamine diamide compound represented by the formula is shown below.
【化6】 N,N−ジメチルグリシンエステルと1,3−プロパン
ジアミンとの反応によって2,12−ジメチル−4,1
0−ジオキソ−2,5,9,12−テトラアザトリデカ
ンが製造される。これを、還元剤、好ましくは水素化リ
チウムアルミニウムと反応させることによって、2,1
2−ジメチル−2,5,9,12−テトラアザトリデカ
ンが製造される。これをさらに、(RCO)2Oで表さ
れるカルボン酸無水物もしくはRCOClで表されるカ
ルボン酸塩化物と反応させることによって式(1)で表
される三級テトラアミンジアミド化合物が製造される。Embedded image The reaction of N, N-dimethylglycine ester with 1,3-propanediamine results in 2,12-dimethyl-4,1
0-dioxo-2,5,9,12-tetraazatridecane is produced. This is reacted with a reducing agent, preferably lithium aluminum hydride, to give 2,1
2-Dimethyl-2,5,9,12-tetraazatridecane is produced. This is further reacted with a carboxylic acid anhydride represented by (RCO) 2 O or a carboxylic acid chloride represented by RCOCl to produce a tertiary tetraamine diamide compound represented by the formula (1). .
【0008】本発明による下記式(2)The following formula (2) according to the present invention:
【化2】 で表される三級テトラアミン化合物の製造方法を以下に
示す。Embedded image The method for producing the tertiary tetraamine compound represented by is shown below.
【化7】 前記反応はジエチルエーテル、テトラヒドロフラン等の
エーテル系溶媒中に於いて還元剤と反応させることによ
って行われる。還元剤としては、好ましくは水素化リチ
ウムアルミニウム、水素化ボランのテトラヒドロフラン
コンプレックス等が使用される。Embedded image The reaction is carried out by reacting with a reducing agent in an ether solvent such as diethyl ether or tetrahydrofuran. As the reducing agent, lithium aluminum hydride, tetrahydrofuran complex of borane hydride or the like is preferably used.
【0009】本発明による下記式(3)The following formula (3) according to the present invention:
【化3】 で表されるtrans−ジクロロルテニウム(II)フ
ッ化炭化水素N置換三級テトラアミン錯体は、カリウム
ペンタクロロアコルテニウム(III)(K2RuCl5
(OH2))と下記一般式(2)Embedded image Is a trans-dichlororuthenium (II) fluorinated hydrocarbon N-substituted tertiary tetraamine complex represented by the formula: potassium pentachloroacorthenium (III) (K 2 RuCl 5
(OH 2 )) and the following general formula (2)
【化2】 で表されるフッ化炭化水素N置換三級テトラアミンとの
反応によって合成される。この行程における反応を式で
表すと以下のようになる。Embedded image It is synthesized by a reaction with a fluorinated hydrocarbon N-substituted tertiary tetraamine represented by The reaction in this process is represented by the following equation.
【化8】 上記反応は、50℃から150℃においておこなわれ
る。溶媒としては、エタノール、メタノール、エチレン
グリコール、2−メトキシエタノールなどが用いられ
る。反応後、化合物(3)は溶液中に沈殿し、濾過する
ことによって得ることができる。Embedded image The above reaction is carried out at 50 ° C to 150 ° C. As the solvent, ethanol, methanol, ethylene glycol, 2-methoxyethanol, or the like is used. After the reaction, compound (3) precipitates in the solution and can be obtained by filtration.
【0010】本発明による下記式(4)The following formula (4) according to the present invention:
【化4】 で表されるtrans−ジクロロルテニウム(III)
フッ化炭化水素N置換三級テトラアミン錯体塩化物は、
下記一般式(3)Embedded image Trans-dichlororuthenium (III) represented by the formula:
The fluorinated hydrocarbon N-substituted tertiary tetraamine complex chloride is
The following general formula (3)
【化3】 で表されるtrans−ジクロロルテニウム(II)フ
ッ化炭化水素N置換三級テトラアミン錯体を大気中で塩
酸水溶液に溶かすことによって得ることができる。ま
た、カリウムペンタクロロアコルテニウム(III)
(K2RuCl5(OH2))と下記一般式(2)Embedded image Can be obtained by dissolving a trans-dichlororuthenium (II) fluorinated hydrocarbon N-substituted tertiary tetraamine complex represented by the following formula in an aqueous hydrochloric acid solution in the air. Also, potassium pentachloroacorthenium (III)
(K 2 RuCl 5 (OH 2 )) and the following general formula (2)
【化2】 で表されるフッ化炭化水素N置換三級テトラアミンとの
反応によっても合成される。この行程における反応を式
で表すと以下のようになる。Embedded image The compound is also synthesized by a reaction with a fluorinated hydrocarbon N-substituted tertiary tetraamine represented by The reaction in this process is represented by the following equation.
【化9】 上記反応は、50℃から150℃においておこなわれ
る。溶媒としては、エタノール、メタノール、エチレン
グリコール、2−メトキシエタノールなどが用いられ
る。反応後の溶液を濃縮後、2−プロパノールに溶解す
る成分のみをLH−20カラムクロマトグラフィーを用
いて溶離し、濃塩酸から再結晶によってこの錯体を単離
することができる。Embedded image The above reaction is carried out at 50 ° C to 150 ° C. As the solvent, ethanol, methanol, ethylene glycol, 2-methoxyethanol, or the like is used. After concentration of the solution after the reaction, only the components soluble in 2-propanol are eluted using LH-20 column chromatography, and this complex can be isolated by recrystallization from concentrated hydrochloric acid.
【0011】本発明の前記一般式(2)で表されるフッ
化炭化水素N置換三級テトラアミンは、その分子中に含
まれる4個の三級アミンによってRu(II)やRu
(III)との安定な錯体を形成し、置換基の立体障害
のためにtrans−ジクロロ錯体が選択的にえられ
る。The fluorinated hydrocarbon N-substituted tertiary tetraamine represented by the general formula (2) of the present invention can be converted to Ru (II) or Ru by two tertiary amines contained in the molecule.
A stable complex is formed with (III), and a trans-dichloro complex is selectively obtained due to steric hindrance of the substituent.
【0012】本発明のtrans−ジクロロルテニウム
(II)フッ化炭化水素N置換三級テトラアミン錯体塩
化物は、溶媒に溶かすと、窒素ガスを吸収できるように
なる。 この場合の窒素吸収反応(窒素固定化反応)を
溶液内のイオン反応式で示すと以下のようになる。The trans-dichlororuthenium (II) fluorinated hydrocarbon N-substituted tertiary tetraamine complex chloride of the present invention can absorb nitrogen gas when dissolved in a solvent. The nitrogen absorption reaction (nitrogen fixation reaction) in this case is represented by the following ion reaction formula in the solution.
【化10】 (式中、Rはフッ化炭化水素基、XはCl-,OH-等を
示す) この場合の溶媒としては、水やアルコールあるいはそれ
らの混合物が用いられる。また、この溶媒には塩基性物
質を溶解させるのが好ましい。塩基性物質としては、N
aOH、KOH、LiOH等のアルカリ金属水酸化物
や、Ca(OH)2等のアルカリ土類金属水酸化物、ア
ンモニアの他、(トリエチルアミン)等の有機アミンが
挙げられる。Embedded image (Wherein, R represents a fluorinated hydrocarbon group, X represents Cl − , OH −, etc.) As the solvent in this case, water, alcohol, or a mixture thereof is used. Further, it is preferable that a basic substance is dissolved in this solvent. As the basic substance, N
Examples thereof include alkali metal hydroxides such as aOH, KOH and LiOH, alkaline earth metal hydroxides such as Ca (OH) 2 , ammonia, and organic amines such as (triethylamine).
【0013】本発明のtrans−ジクロロルテニウム
(III)フッ化炭化水素N置換三級テトラアミン錯体
塩化物は、水溶液中で還元剤、例えば三塩化チタンと反
応させることによって瞬時に還元を受けてルテニウム
(II)となり、窒素ガスを吸収できるようになる。こ
の反応を溶液内のイオン反応式で示すと以下のようにな
る。The trans-dichlororuthenium (III) fluorinated hydrocarbon N-substituted tertiary tetraamine complex chloride of the present invention is instantaneously reduced by reacting with a reducing agent such as titanium trichloride in an aqueous solution to obtain ruthenium ( II), and nitrogen gas can be absorbed. This reaction is represented by the ion reaction formula in the solution as follows.
【化11】 還元剤としては、前記三塩化チタンの他、金属マグネシ
ウムを用いることができる。また、ルテニウム(III)
の還元は、電気還元により行うこともできる。Embedded image As the reducing agent, metal magnesium can be used in addition to the above-mentioned titanium trichloride. Also ruthenium (III)
Can be reduced by electric reduction.
【0014】本発明のルテニウム(II)錯体を用いて
窒素ガス吸収実験を行うには、図1のような装置中のフ
ラスコに錯体を、その上部の等圧漏斗に窒素ガスを飽和
させた溶媒を入れておき、内部を一定気圧に保つように
ガスビュレットを接続する。そして、等圧漏斗のコック
を開け錯体に溶媒を注ぎ溶解させることにより、窒素ガ
スの吸収がガスビュレットの読みとりより観測されるも
のである。反応は20℃においては2日間で完結する。To conduct a nitrogen gas absorption experiment using the ruthenium (II) complex of the present invention, a complex in a flask in an apparatus as shown in FIG. And connect a gas burette to keep the inside at a constant pressure. Then, by opening the cock of the equal-pressure funnel and pouring the solvent into the complex to dissolve it, the absorption of nitrogen gas is observed by reading the gas burette. The reaction is completed in 2 days at 20 ° C.
【0015】本発明のルテニウム(III)錯体を用い
て窒素ガス吸収実験を行うには、内部を一定気圧に保つ
ようにガスビュレットを接続し、図2のような装置中に
錯体の水溶液を入れたうえであらかじめ溶液中に窒素を
飽和しておき、セラムキャップから三塩化チタン塩化水
素酸溶液を注入することにより、窒素ガスが吸収されて
いることがガスビュレットの読みとりより観測されるも
のである。反応は20℃においては1日以内で完結す
る。In order to conduct a nitrogen gas absorption experiment using the ruthenium (III) complex of the present invention, a gas burette is connected so as to keep the inside at a constant pressure, and an aqueous solution of the complex is placed in an apparatus as shown in FIG. After that, nitrogen was previously saturated in the solution, and the nitrogen gas was absorbed by injecting a titanium trichloride hydrochloride solution from the serum cap. . The reaction is completed within one day at 20 ° C.
【0016】前記における反応終了時に生成する窒素錯
体は結合している窒素分子のtrans位の配位子が塩
化物イオンの錯体、水の錯体、ならびにそれぞれの立体
異性体の混合物となっている(T.Takahash
i,K.Hiratami,E.Kimura,Che
m.Lett.,1993,1329)。In the nitrogen complex formed at the end of the above reaction, the ligand at the trans position of the nitrogen molecule bonded thereto is a chloride ion complex, a water complex, and a mixture of each stereoisomer ( T. Takahash
i, K. Hiratami, E .; Kimura, Che
m. Lett. , 1993, 1329).
【0017】[0017]
【発明の効果】本発明のtrans−ジクロロルテニウ
ム(II)フッ化炭化水素N置換三級ポリアミン錯体
は、溶媒に溶解するだけで窒素ガスを固定することがで
きる。また、本発明のtrans−ジクロロルテニウム
(III)フッ化炭化水素N置換三級ポリアミン錯体
は、そのフッ化炭化水素基のため、窒素ガス溶解度の高
いフッ素系の溶媒への溶解度が高まる。The trans-dichlororuthenium (II) fluorinated hydrocarbon N-substituted tertiary polyamine complex of the present invention can fix nitrogen gas only by being dissolved in a solvent. Further, the trans-dichlororuthenium (III) fluorinated hydrocarbon N-substituted tertiary polyamine complex of the present invention has an increased solubility in a fluorine-based solvent having high nitrogen gas solubility because of its fluorinated hydrocarbon group.
【0018】[0018]
【実施例】次に本発明を実施例によりさらに詳細に説明
する。 実施例1 2,12−ジメチル−4,10−ジオキソ−2,5,
9,12−テトラアザトリデカンの合成 N,N−ジメチルグリシンエチルエステル23.3g
(177mmol)と1,3−ジアミノプロパン6.5
0g(88.6mmol)とを混合し、20時間140
℃加熱する。この反応液から減圧蒸留を行って0.1m
mHg,170℃の留分として2,12−ジメチル−
4,10−ジオキソ−2,5,9,12−テトラアザト
リデカンを得ることができる。この物質は常温では無色
の固体である。収率76%、融点86.7〜87.7
℃。Next, the present invention will be described in more detail with reference to examples. Example 1 2,12-dimethyl-4,10-dioxo-2,5
Synthesis of 9,12-tetraazatridecane N, N-dimethylglycine ethyl ester 23.3 g
(177 mmol) and 1,3-diaminopropane 6.5
0 g (88.6 mmol) for 140 hours for 20 hours.
Heat to ° C. The reaction solution was distilled under reduced pressure to obtain 0.1 m
2,12-dimethyl- as a fraction at mHg, 170 ° C.
4,10-dioxo-2,5,9,12-tetraazatridecane can be obtained. This substance is a colorless solid at room temperature. Yield 76%, melting point 86.7-87.7
° C.
【0019】実施例2 2,12−ジメチル−2,5,9,12−テトラアザト
リデカンの合成 2,12−ジメチル−4,10−ジオキソ−2,5,
9,12−テトラアザトリデカン16.2g(66.5
mmol)をあらかじめリチウムアルミニウムヒドリド
19.5g(513mmol)を懸濁してある脱水エー
テル500mlに徐々に加え、窒素気流下室温で16時
間撹拌を行う。反応後、水37g(2.06mol)、
炭酸カリウム35g(254mmol)を加え、50℃
で1時間加熱撹拌する。反応液中に析出する固体を濾過
によって除き、溶媒を留去した後、減圧蒸留を行って
0.1mmHg、100℃の留分として2,12−ジメ
チル−2,5,9,12−テトラアザトリデカンを得る
ことができる。収率47%Example 2 Synthesis of 2,12-dimethyl-2,5,9,12-tetraazatridecane 2,12-dimethyl-4,10-dioxo-2,5
16.2 g of 9,12-tetraazatridecane (66.5)
mmol) is added to 500 ml of dehydrated ether in which 19.5 g (513 mmol) of lithium aluminum hydride is suspended in advance, and the mixture is stirred at room temperature for 16 hours under a nitrogen stream. After the reaction, 37 g (2.06 mol) of water,
35 g (254 mmol) of potassium carbonate was added, and 50 ° C
For 1 hour. After the solid precipitated in the reaction solution was removed by filtration and the solvent was distilled off, distillation under reduced pressure was carried out to obtain 2,12-dimethyl-2,5,9,12-tetraaza as a fraction at 0.1 mmHg and 100 ° C. Tridecane can be obtained. 47% yield
【0020】実施例3 2,12−ジメチル−5,9−ビス(トリフルオロアセ
チル)2,5,9,12−テトラアザトリデカン(式
(1)の化合物1)の合成 2,12−ジメチル−2,5,9,12−テトラアザト
リデカン1.5g(6.9mmol)をピリジン100
mlに溶解し、この溶液を氷冷しながらトリフルオロ酢
酸無水物5.4g(25.7mmol)を溶媒の温度が
上がりすぎないように注意しながらゆっくりと滴下す
る。滴下後さらに約16時間室温にて撹拌を続ける。反
応後、溶媒を減圧留去し、残液を3規定水酸化カリウム
水溶液に溶かしてジクロロメタンによる抽出物を溶媒留
去した後、減圧蒸留によって0.1mmHg160℃の
留分として化合物1を得ることができる。収率85%。
この化合物1はNMR、IRによってその構造を確認し
た。 1H NMR(CDCl3)δ=1.96(2H,qu
intet,NCH2CH2 CH2N),2.26(12
H,s,NCH3 ),2.49(4H,t,NCH2 CH
2CH2 N),3.45−3.52(8H,m,NCH2
CH2 N)ppm(TMS)。IR(neat)294
8,2826,2774,1685、1459,119
4,1141,1095,1062,758cm-1。Example 3 Synthesis of 2,12-dimethyl-5,9-bis (trifluoroacetyl) 2,5,9,12-tetraazatridecane (compound 1 of formula (1)) 2,12-dimethyl 1.5 g (6.9 mmol) of -2,5,9,12-tetraazatridecane was added to pyridine 100
Then, 5.4 g (25.7 mmol) of trifluoroacetic anhydride is slowly added dropwise while paying attention not to raise the temperature of the solvent excessively while cooling the solution with ice. After the addition, stirring is continued at room temperature for about 16 hours. After the reaction, the solvent is distilled off under reduced pressure, the residue is dissolved in a 3N aqueous potassium hydroxide solution, and the extract with dichloromethane is distilled off, and then the compound 1 is obtained as a fraction of 0.1 mmHg at 160 ° C. by vacuum distillation. it can. Yield 85%.
The structure of Compound 1 was confirmed by NMR and IR. 1H NMR (CDCl 3 ) δ = 1.96 (2H, qu)
intet, NCH 2 C H 2 CH 2 N), 2.26 (12
H, s, NC H 3) , 2.49 (4H, t, NC H 2 CH
2 C H 2 N), 3.45-3.52 (8H, m, NC H 2
C H 2 N) ppm (TMS ). IR (neat) 294
8, 2826, 2774, 1685, 1459, 119
4,1141,1095,1062,758 cm -1 .
【0021】実施例4 2,12−ジメチル−5,9−ビス(2′,2′,2′
−トリフルオロエチル)2,5,9,12−テトラアザ
トリデカン(式(2)の化合物2)の合成 2,12−ジメチル−5,9−ビス−トリフルオロアセ
チル−2,5,9,12−テトラアザトリデカン(化合
物1)2.2g(5.4mmol)を、BH3 -テトラヒ
ドロフランコンプレックスのテトラヒドロフラン溶液
(1.06mol/l)40mlに徐々に加え、窒素気
流下室温で6日間撹拌を行う。反応後、反応液を氷冷し
てメタノール5mlを徐々に加え、溶媒を留去した。残
液をメタノールに溶かして溶媒の留去を2回繰り返し、
14%アンモニア水50mlに溶かし、塩化メチレンで
抽出、溶媒留去した。残液を3mol/lの塩化水素酸
水溶液に溶かし、室温で一晩撹拌した。溶媒を留去後、
残さをメタノールに溶かして溶媒留去を二回繰り返し、
これを28%アンモニア水100mlに溶かして塩化メ
チレンで抽出、溶媒留去した。残液を減圧蒸留して0.
1mmHg、160℃の留分として化合物2を得ること
ができる。収率83%。この化合物2はNMR、IRに
よってその構造を確認した。 1H NMR(CDCl3)δ=1.60(2H,qu
intet,NCH2CH2 CH2N),2.23(12
H,s,NCH3 ),2.36−2.41,2.71−
2.76(8H,m,NCH2 CH2 N),2.66(4
H,t,NCH2 CH2CH2 N),3.08(4H,
q,CF3CH2 N)ppm(TMS)。IR(nea
t)2947,2822,2771,1466,127
2,1139,1100,1043,832,665c
m-1。Example 4 2,12-dimethyl-5,9-bis (2 ', 2', 2 '
Synthesis of -trifluoroethyl) 2,5,9,12-tetraazatridecane (compound 2 of formula (2)) 2,12-dimethyl-5,9-bis-trifluoroacetyl-2,5,9, 12-tetraazacyclododecane tridecane (compound 1) 2.2g (5.4mmol), BH 3 - slowly added to a tetrahydrofuran solution (1.06 mol / l) 40 ml of tetrahydrofuran complex, stirred at room temperature for 6 days under nitrogen flow Do. After the reaction, the reaction solution was ice-cooled, 5 ml of methanol was gradually added, and the solvent was distilled off. The remaining solution was dissolved in methanol and the solvent was distilled off twice.
It was dissolved in 50 ml of 14% aqueous ammonia, extracted with methylene chloride, and the solvent was distilled off. The remaining solution was dissolved in a 3 mol / l aqueous solution of hydrochloric acid and stirred at room temperature overnight. After distilling off the solvent,
Dissolve the residue in methanol and repeat the solvent distillation twice,
This was dissolved in 100 ml of 28% aqueous ammonia, extracted with methylene chloride, and the solvent was distilled off. The residual liquid was distilled under reduced pressure to obtain 0.1 ml.
Compound 2 can be obtained as a fraction at 1 mmHg and 160 ° C. Yield 83%. The structure of Compound 2 was confirmed by NMR and IR. 1H NMR (CDCl 3 ) δ = 1.60 (2H, qu)
intet, NCH 2 C H 2 CH 2 N), 2.23 (12
H, s, NC H 3) , 2.36-2.41,2.71-
2.76 (8H, m, NCH 2 CH 2 N), 2.66 (4
H, t, NC H 2 CH 2 C H 2 N), 3.08 (4H,
q, CF 3 C H 2 N ) ppm (TMS). IR (nea
t) 2947, 2822, 2771, 1466, 127
2,1139,1100,1043,832,665c
m -1 .
【0022】実施例5 trans−ジクロロルテニウム(II)(2,12−
テトラメチル−5,9−ビス(2′,2′,2′−トリ
フルオロエチル)2,5,9,12−テトラアザトリデ
カン)錯体(式(3)の化合物3)の合成 前記生成物(化合物2)1.5g(3.9mmol)
を、あらかじめカリウムペンタクロロアコルテニウム
(III)塩を脱水エタノール250mlに懸濁してあ
る容器に加え、激しく撹拌しながらアルゴン気流下で6
7時間加熱環流する。反応液を冷却後濾過すると化合物
3が赤褐色針状晶として得られる。収率28%。この化
合物は、エックス線構造解析によってその構造を確認し
た。Example 5 trans-dichlororuthenium (II) (2,12-
Synthesis of tetramethyl-5,9-bis (2 ', 2', 2'-trifluoroethyl) 2,5,9,12-tetraazatridecane) complex (compound 3 of formula (3)) (Compound 2) 1.5 g (3.9 mmol)
Is added to a container in which potassium pentachloroacorthenium (III) salt is suspended in 250 ml of dehydrated ethanol in advance, and the mixture is stirred under vigorous stirring under a stream of argon.
Heat to reflux for 7 hours. After the reaction solution is cooled and filtered, compound 3 is obtained as reddish brown needles. Yield 28%. The structure of this compound was confirmed by X-ray structure analysis.
【0023】本発明の、trans−ジクロロルテニウ
ム(II)三級テトラアミン錯体は、溶媒に溶解させる
だけで窒素ガスを吸収する能力を有する。The trans-dichlororuthenium (II) tertiary tetraamine complex of the present invention has the ability to absorb nitrogen gas only by being dissolved in a solvent.
【0024】実施例6 trans−ジクロロルテニウム(III)(2,12
−テトラメチル−5,9−ビス(2′,2′,2′−ト
リフルオロエチル)2,5,9,12−テトラアザトリ
デカン)錯体塩化物(式(4)の化合物4)の合成 前記実施例5の反応液を濾過した後の濾液を濃縮乾固し
て、残さに2−プロパノールを加え、析出する塩を濾過
によって取り除き、溶媒を留去する。残さを少量のメタ
ノールに溶かし、LH−20ゲル濾過カラムクロマトグ
ラフィーによってメタノールで展開し、緑色のフラクシ
ョンを集める。集めた溶液を濃縮後約50℃に暖めなが
ら最小量の濃塩酸に溶解し、これを冷ましたときに析出
する黄色針状晶(化合物4)を濾過によって集め、室温
にて減圧乾燥する。収率9%。この化合物は、UVスペ
クトル、サイクリックボルタンメトリーによってtra
ns−ジクロロルテニウム(III)錯体であることを
確認した。Example 6 trans-dichlororuthenium (III) (2,12
Of -tetramethyl-5,9-bis (2 ', 2', 2'-trifluoroethyl) 2,5,9,12-tetraazatridecane) complex chloride (compound 4 of formula (4)) The filtrate obtained after filtering the reaction solution of Example 5 was concentrated to dryness, 2-propanol was added to the residue, the precipitated salt was removed by filtration, and the solvent was distilled off. The residue is dissolved in a small amount of methanol, developed with methanol by LH-20 gel filtration column chromatography, and a green fraction is collected. After concentration, the collected solution is dissolved in a minimum amount of concentrated hydrochloric acid while warming to about 50 ° C., and the yellow needles (compound 4) which precipitate when cooled are collected by filtration and dried at room temperature under reduced pressure. 9% yield. This compound was identified by UV spectrum, cyclic voltammetry as tra.
It was confirmed to be an ns-dichlororuthenium (III) complex.
【0025】trans−ジクロロルテニウム(II
I)三級テトラアミン錯体は5位、9位の窒素上の置換
基が炭化水素基の場合に、TiCl3との反応によって
水溶液中で窒素ガスを吸収することがすでに明らかとな
っている。本発明によって得られたN上にフッ化炭化水
素置換基を導入した三級テトラアミン配位子をもつtr
ans−ジクロロルテニウム(III)錯体も同様に水
中で窒素ガスを吸収する性質を有する。Trans-dichlororuthenium (II
I) It has already been clarified that a tertiary tetraamine complex absorbs nitrogen gas in an aqueous solution by reaction with TiCl 3 when the substituent on the nitrogen at the 5- and 9-positions is a hydrocarbon group. Tr having a tertiary tetraamine ligand obtained by introducing a fluorohydrocarbon substituent on N obtained by the present invention
The ans-dichlororuthenium (III) complex also has the property of absorbing nitrogen gas in water.
【0026】試験例1 trans−ジクロロルテニウム(II)(2,12−
ジメチル−5,9−ビス(2′,2′,2′−トリフル
オロエチル)2,5,9,12−テトラアザトリデカ
ン)錯体塩化物47mg(0.085mmol)を反応
容器に入れ、上部の等圧漏斗に1mol/lの水酸化ナ
トリウム水溶液を50ml入れた。ガスビュレットを接
続して、内部を窒素ガスで置換したのち、密閉して20
℃に静置する。この状態で等圧漏斗のコックを開け、そ
の直後からの気体の体積の変化を時間を追って追跡する
ことによって窒素吸収反応を確認することができる。
(図3)この実験の結果、上記の錯体を前駆体とした場
合、仕込み錯体の約20%が窒素を吸収することがわか
る。Test Example 1 trans-dichlororuthenium (II) (2,12-
47 mg (0.085 mmol) of dimethyl-5,9-bis (2 ′, 2 ′, 2′-trifluoroethyl) 2,5,9,12-tetraazatridecane) complex chloride is placed in a reaction vessel, and 50 ml of a 1 mol / l aqueous solution of sodium hydroxide was put into the isobaric funnel. After connecting a gas buret and replacing the inside with nitrogen gas, it is sealed and closed.
Leave at 0 ° C. In this state, the cock of the isobaric funnel is opened, and the nitrogen absorption reaction can be confirmed by tracking the change in the gas volume immediately after that with time.
(FIG. 3) As a result of this experiment, it was found that when the above-mentioned complex was used as a precursor, about 20% of the charged complex absorbed nitrogen.
【0027】試験例2 trans−ジクロロルテニウム(III)(2,12
−ジメチル−5,9−ビス(2′,2′,2′−トリフ
ルオロエチル)2,5,9,12−テトラアザトリデカ
ン)錯体塩化物26mg(0.041mmol)を水4
0mlに溶かした溶液を、セラムキャップをもちガスビ
ュレットに接続した容器に入れ、これに窒素ガスを飽和
させたのち、密閉して20℃に静置する。この溶液にセ
ラムキャップを貫いてTiCl3塩酸溶液2.00ml
(0.38mmol)をすばやく注入し、その直後から
の気体の体積の変化を時間を追って追跡することによっ
て窒素吸収反応を確認することができる。(図4) この実験の結果、上記の錯体を前駆体とした場合、仕込
み錯体の約50%が窒素を吸収することがわかる。Test Example 2 trans-dichlororuthenium (III) (2,12
-Dimethyl-5,9-bis (2 ', 2', 2'-trifluoroethyl) 2,5,9,12-tetraazatridecane) complex chloride (26 mg, 0.041 mmol) was added to water 4
The solution dissolved in 0 ml is put into a container having a serum cap and connected to a gas burette, and after saturating the container with nitrogen gas, the container is closed and allowed to stand at 20 ° C. 2.00 ml of TiCl 3 hydrochloric acid solution was passed through the serum cap
(0.38 mmol) is quickly injected, and the change in gas volume immediately after that is followed over time to confirm the nitrogen absorption reaction. (FIG. 4) As a result of this experiment, it is found that when the above complex is used as a precursor, about 50% of the charged complex absorbs nitrogen.
【図1】ビュレット・等圧漏斗付き反応容器の構造説明
図。FIG. 1 is a structural explanatory view of a reaction vessel equipped with a burette and a constant pressure funnel.
【図2】ビュレット付き反応容器の構造説明図。FIG. 2 is a structural explanatory view of a reaction container with a burette.
【図3】吸収窒素体積の経時変化を示す。FIG. 3 shows the change over time in the volume of absorbed nitrogen.
【図4】吸収窒素体積の経時変化を示す。FIG. 4 shows the change over time of the absorbed nitrogen volume.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 平谷 和久 茨城県つくば市東1丁目1番 工業技術 院物質工学工業技術研究所内 (72)発明者 春日 和行 茨城県つくば市東1丁目1番 工業技術 院物質工学工業技術研究所内 (72)発明者 足立 貴義 大阪府大阪市西区靱本町二丁目4番11号 大陽東洋酸素株式会社内 (72)発明者 内野 誠 大阪府大阪市西区靱本町二丁目4番11号 大陽東洋酸素株式会社内 (72)発明者 市田 泰三 大阪府大阪市西区靱本町二丁目4番11号 大陽東洋酸素株式会社内 (72)発明者 中辻 利一 東京都港区西新橋一丁目16番7号 日本 酸素株式会社内 (72)発明者 岡本 歩 東京都港区西新橋一丁目16番7号 日本 酸素株式会社内 (72)発明者 仲山 一郎 東京都港区西新橋一丁目16番7号 日本 酸素株式会社内 (72)発明者 川上 浩 東京都港区西新橋一丁目16番7号 日本 酸素株式会社内 (72)発明者 伊東 延義 東京都港区西新橋一丁目16番7号 日本 酸素株式会社内 審査官 高堀 栄二 (56)参考文献 特開 平9−241221(JP,A) 特開 平9−77785(JP,A) Chem.Lett.(1993)No. 8,p.1329−1332 J.Chem.Soc.,Chem. Commun.(1989)No.13,p. 879−881 (58)調査した分野(Int.Cl.6,DB名) CA(STN) REGISTRY(STN)──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Kazuhisa Hiratani 1-1-1, Higashi, Tsukuba, Ibaraki Pref. Institute of Industrial Science and Technology (72) Inventor Kazuyuki Kasuga 1-1-1, Higashi, Tsukuba, Ibaraki Pref. (72) Inventor Takayoshi Adachi 2-4-1-11 Ushimotocho, Nishi-ku, Osaka-shi, Osaka Inside (72) Inventor Makoto Uchino 2-4-2 Ushimotocho, Nishi-ku, Osaka-shi, Osaka No. 11 Taiyo Toyo Oxygen Co., Ltd. (72) Inventor Taizo Ichida 2-4-1 Ushimotocho, Nishi-ku, Osaka-shi, Osaka Prefecture Within Taiyo Toyo Oxygen Co., Ltd. (72) Inventor Toshikazu Nakatsuji Minato-ku, Tokyo 1-16-7 Nishi-Shimbashi Japan Oxygen Co., Ltd. (72) Inventor Ayumu Okamoto 1-16-7 Nishi-Shimbashi, Minato-ku, Tokyo Japan Oxygen Co., Ltd. (72) Inventor Nakayama Ichiro 1-16-7 Nishi-Shimbashi, Minato-ku, Tokyo Japan Oxygen Co., Ltd. (72) Inventor Hiroshi Kawakami 1-16-7 Nishi-Shimbashi, Minato-ku, Tokyo Japan Oxygen Co., Ltd. (72) Inventor Nobuyoshi Ito 1-16-7 Nishi-Shimbashi, Minato-ku, Tokyo Japan Oxygen Co., Ltd. Examiner Eiji Takahori (56) Reference JP-A-9-241221 (JP, A) JP-A 9-77785 (JP, A) Chem . Lett. (1993) No. 8, p. 1329-1332. Chem. Soc. , Chem. Commun. (1989) No. 13, p. 879-881 (58) Fields investigated (Int. Cl. 6 , DB name) CA (STN) REGISTRY (STN)
Claims (12)
物。 【化1】 (式中、Rはフッ化炭化水素基を示す)An acid amide compound represented by the following formula (1): Embedded image (Wherein, R represents a fluorinated hydrocarbon group)
ン。 【化2】 (式中、Rはフッ化炭化水素基を示す)2. Tertiary tetramine represented by the following formula (2). Embedded image (Wherein, R represents a fluorinated hydrocarbon group)
(II)錯体. 【化3】 (式中、Rはフッ化炭化水素基を示す)3. A ruthenium (II) complex represented by the following general formula (3). (Wherein, R represents a fluorinated hydrocarbon group)
I)錯体。 【化4】 (式中、Rはフッ化炭化水素基を示す)4. A ruthenium (II) represented by the following formula (4):
I) complexes. Embedded image (Wherein, R represents a fluorinated hydrocarbon group)
ans−ジクロロルテニウム三級テトラアミン(II)錯体
を、溶媒に溶解してなる窒素吸収性溶液。5. The following formula (3): (Wherein, R represents a fluorohydrocarbon group)
A nitrogen-absorbing solution obtained by dissolving ans-dichlororuthenium tertiary tetraamine (II) complex in a solvent.
ans−ジクロロルテニウム(III)三級テトラアミン錯
体を溶媒中で還元してなる窒素吸収性溶液。6. The following formula (4): (Wherein, R represents a fluorohydrocarbon group)
A nitrogen-absorbing solution obtained by reducing ans-dichlororuthenium (III) tertiary tetraamine complex in a solvent.
らの混合物である請求項5の窒素吸収性溶液。7. The nitrogen-absorbing solution according to claim 5, wherein the solvent is water or alcohol or a mixture thereof.
らの混合物に塩基性物質を溶かしたものである請求項5
の窒素吸収性溶液。8. The solvent according to claim 5, wherein the solvent is obtained by dissolving a basic substance in water, alcohol or a mixture thereof.
Nitrogen absorbing solution.
アルカリ土類金属水酸化物、アンモニア、アミン類また
はそれらの混合物である請求項8の窒素吸収性溶液。9. The basic substance is an alkali metal hydroxide,
9. The nitrogen-absorbing solution according to claim 8, which is an alkaline earth metal hydroxide, ammonia, an amine or a mixture thereof.
れらの混合物である請求項6の窒素吸収性溶液。10. The nitrogen-absorbing solution according to claim 6, wherein the solvent is water or alcohol or a mixture thereof.
えるか又は電気的に還元する方法でなる請求項6の窒素
吸収性溶液。11. The nitrogen absorbing solution according to claim 6, wherein the reducing method is a method of adding a reducing agent to the solution of the complex or electrically reducing the solution.
塩化チタン水溶液あるいはそれらの混合物である請求項
11の窒素吸収性溶液。12. The nitrogen-absorbing solution according to claim 11, wherein the reducing agent is magnesium metal, an aqueous solution of titanium trichloride, or a mixture thereof.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP26023996A JP2849739B2 (en) | 1996-09-09 | 1996-09-09 | Fluorine-containing tertiary polyamine ruthenium complex with nitrogen immobilization ability |
Applications Claiming Priority (1)
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JP26023996A JP2849739B2 (en) | 1996-09-09 | 1996-09-09 | Fluorine-containing tertiary polyamine ruthenium complex with nitrogen immobilization ability |
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JPH1087588A JPH1087588A (en) | 1998-04-07 |
JP2849739B2 true JP2849739B2 (en) | 1999-01-27 |
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1996
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Non-Patent Citations (2)
Title |
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Chem.Lett.(1993)No.8,p.1329−1332 |
J.Chem.Soc.,Chem.Commun.(1989)No.13,p.879−881 |
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