JP2849739B2 - Fluorine-containing tertiary polyamine ruthenium complex with nitrogen immobilization ability - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

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]

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]

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]

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).

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.

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.

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.

Embedded image (Wherein, R represents a fluorohydrocarbon group) Further, according to the present invention, the following formula (3)

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)

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]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Heretofore, the following formula (5)

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)

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)

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.

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.

The following formula (1) according to the present invention:

Embedded image The method for producing the tertiary tetraamine diamide compound represented by the formula is shown below.

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). .

The following formula (2) according to the present invention:

Embedded image The method for producing the tertiary tetraamine compound represented by is shown below.

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.

The following formula (3) according to the present invention:

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)

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.

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.

The following formula (4) according to the present invention:

Embedded image Trans-dichlororuthenium (III) represented by the formula:
The fluorinated hydrocarbon N-substituted tertiary tetraamine complex chloride is
The following general formula (3)

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)

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.

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.

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.

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.

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).

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.

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.

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.

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.

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]

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]

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.

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

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 .

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 .

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.

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.

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.

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.

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.

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.

[Brief description of the drawings]

FIG. 1 is a structural explanatory view of a reaction vessel equipped with a burette and a constant pressure funnel.

FIG. 2 is a structural explanatory view of a reaction container with a burette.

FIG. 3 shows the change over time in the volume of absorbed nitrogen.

FIG. 4 shows the change over time of the absorbed nitrogen volume.

──────────────────────────────────────────────────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)

(57) [Claims] An acid amide compound represented by the following formula (1): Embedded image (Wherein, R represents a fluorinated hydrocarbon group) 2. Tertiary tetramine represented by the following formula (2). Embedded image (Wherein, R represents a fluorinated hydrocarbon group) 3. A ruthenium (II) complex represented by the following general formula (3). (Wherein, R represents a fluorinated hydrocarbon group) 4. A ruthenium (II) represented by the following formula (4):
I) complexes. Embedded image (Wherein, R represents a fluorinated hydrocarbon group) 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. 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. 7. The nitrogen-absorbing solution according to claim 5, wherein the solvent is water or alcohol or a mixture thereof. 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. 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. 10. The nitrogen-absorbing solution according to claim 6, wherein the solvent is water or alcohol or a mixture thereof. 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. 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.