JPH09241221A - C-substituted tertiary polyamine-ruthenium complex having ability to fix nitrogen - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new complex having ability to fix nitrogen. SOLUTION: This new complex, a trans-dichlororuthenium(III) (2,5,9,12- tetramethyl-7-hydrocarbon-2,5,9,12-tetrazatridecane) complex of formula I (R is H or a hydrocarbon; R' is a hydrocarbon), is obtained by reducing a 2,5,9,12- tetramethyl-6,8-dioxo-7-hydrocarbon-2,5,9,12-tetrazatridecane of formula II into a 2,5,9,12-tetramethyl-7-hydrocarbon-2,5,9,12-tetrazatridecane of formula III, which is then reacted with potassium pentachloroaquoruthenium(III)[K2 RuCl5 (OH)2 ]. For this complex, an aqueous solution containing this complex is incorporated with titanium trichloride followed by bringing the resultant solution into contact with nitrogen gas to effect nitrogen fixation.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a ruthenium (III) complex having a C-substituted tertiary tetraamine as a ligand, C
And a substituted tertiary tetraamine, a precursor thereof, a method for producing them, and a method for immobilizing nitrogen.

[0002]

2. Description of the Related Art It is already known that dissolved nitrogen gas in water can be immobilized by reacting a trans-dichloro tertiary tetraamine ruthenium complex with titanium trichloride in an aqueous solution (T. Takahashi, K. Hira.
Tani, K .; Kasuga, E .; Kimura, Ch
em. Lett. , 1993, 1761). In addition, the present inventors have previously found that a ruthenium complex in which a hydrocarbon substituent is introduced on the coordinated nitrogen of the above complex has a nitrogen gas absorption capacity (Japanese Patent Application No. 7- 2621
47: ruthenium tertiary polyamine complex having nitrogen fixing ability).

[0003]

The problems to be solved by the present invention are as follows. (1) To provide a novel C-substituted tertiary polyamine ruthenium complex having nitrogen fixing ability. (2) To provide a C-substituted tertiary polyamine and its intermediate. (3) To provide a method for producing a C-substituted tertiary polyamine and its intermediate. Other objects of the invention will be clearly understood from the following description.

[0004]

Means for Solving the Problems The present inventors have completed the present invention as a result of intensive studies to solve the above problems. That is, according to the present invention, 2,5,9,12-tetramethyl-6,8-dioxo-7-hydrocarbon-2,5,9,12-tetraazatri represented by the following formula (1) Decane is provided.

Embedded image (In the above formula, R represents hydrogen or a hydrocarbon group, and R'represents a hydrocarbon group) Further, according to the present invention, represented by the following formula (2):
5,9,12-tetramethyl-7-hydrocarbon-2,5
9,12-Tetraazatridecane is provided.

Embedded image (In the above formula, R represents hydrogen or a hydrocarbon group, and R ′ represents a hydrocarbon group) Further, according to the present invention, tr represented by the following formula (3)
ans-dichlororuthenium (III) (2, 5, 9, 1
2-Tetramethyl-7-hydrocarbon-2,5,9,12-
A tetraazatridecane) complex is provided.

Embedded image (In the above formula, R represents hydrogen or a hydrocarbon group, and R ′ represents a hydrocarbon group.) Further, according to the present invention, the following formula (1)

Embedded image In the method for producing a tertiary tetraaminediamide compound represented by the formula (wherein R represents hydrogen or a hydrocarbon group, R ′ represents a hydrocarbon group), N, N, N′-trimethylethylenediamine and the following formula:

Embedded image (Wherein R represents hydrogen or a hydrocarbon group, R'represents a hydrocarbon group, and X represents a hydroxyl group, an alkoxy group or halogen), and a malonic acid derivative represented by the above formula is reacted. A method is provided. Furthermore, according to the present invention, the following formula (2)

Embedded image In the method for producing a tertiary tetraamine compound represented by the formula (wherein R represents hydrogen or a hydrocarbon group and R ′ represents a hydrocarbon group), a tertiary tetraaminediamide compound represented by the following formula (1) and a reducing agent are used. There is provided said method, characterized in that

Embedded image (In the above formula, R represents hydrogen or a hydrocarbon group, and R ′ represents a hydrocarbon group) Further, according to the present invention, the following formula (3)

Embedded image (In the above formula, R represents hydrogen or a hydrocarbon group, and R ′ represents a hydrocarbon group) In the method for producing a trans-dichlororuthenium (III) tertiary tetraamine complex represented by the following formula (2) Tertiary tetraamine and potassium pentachloroacorthenium (III) [K ₂ RuC
l ₅ (OH ₂ )] is provided.

Embedded image (In the above formula, R represents hydrogen or a hydrocarbon group, and R ′ represents a hydrocarbon group) Further, according to the present invention, the following formula (3)

Embedded image (In the above formula, R represents hydrogen or a hydrocarbon group, and R ′ represents a hydrocarbon group) Titanium chloride was added to an aqueous solution of a trans-dichlororuthenium (III) tertiary tetraamine complex represented by the formula and contacted with nitrogen gas. A method for immobilizing nitrogen is provided.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION So far, the following formula (5) has already been used.

Embedded image It has been clarified that a nitrogen absorption reaction by a ruthenium (II) complex occurs by acting titanium trichloride on an aqueous solution of a substance represented by (T. Takahas).
hi, K .; Hiratani, K .; Kasuga, E .;
Kimura, Chem. Lett. , 1993, 17
61). According to the present invention, the following formula (3)

Embedded image (In the above formula, R represents hydrogen or a hydrocarbon group, and R'represents a hydrocarbon group.) It was revealed that a compound having a substituent introduced therein could be synthesized.

Also when the compound of the above formula (3) is used,
It became clear that the same nitrogen immobilization method as that of Compound 4 can be realized.

The following formula (1) according to the present invention

Embedded image (In the above formula, R represents hydrogen or a hydrocarbon group, and R ′ represents a hydrocarbon group), the tertiary tetraaminediamide compound is N, N, N′-trimethylethylenediamine and a malonic acid derivative, preferably It is produced by reacting with an acid chloride. This reaction is represented by the following equation.

[Chemical 6] (In the above formula, R represents hydrogen or a hydrocarbon group, R'represents a hydrocarbon group, X represents a hydroxyl group, an alkoxy group or halogen.) The hydrocarbon groups R and R'bonded to the malonic acid derivative are A chain or cyclic alkyl group, an aryl group, an aralkyl group and the like are included. Examples of the alkyl group include an alkyl group having 1 to 12 carbon atoms, preferably 2 to 4 carbon atoms, and a cyclohexyl group. Examples of the aryl group include a phenyl group and a tolyl group. Examples of the aralkyl group include a benzyl group and a phenethyl group.

The following equation (2)

Embedded image The tertiary tetraamine compound represented by the formula (wherein R represents hydrogen or a hydrocarbon group, and R ′ represents a hydrocarbon group) is a tetraaminediamide compound represented by the formula (1) as a reducing agent, preferably hydrogenated. It is produced by reduction with a boron compound, lithium aluminum hydride, alkylaluminum hydride or the like in an ether solvent. This reaction is represented by the following equation.

Embedded image

The following equation (3)

Embedded image (In the above formula, R represents hydrogen or a hydrocarbon group, and R ′ represents a hydrocarbon group), the trans-dichlororuthenium (III) C-substituted tertiary tetraamine complex is a tertiary tertiary amine of the above formula (2). It is synthesized by the reaction of tetraamine with potassium pentachloroacorthenium (III) [K ₂ RuCl ₅ (OH ₂ )]. The reaction in this process is represented by the following equation.

Embedded image

The trans-dichlororuthenium (III) C-substituted tertiary tetraamine complex of the present invention is instantly reduced to ruthenium (II) by reacting with titanium trichloride in an aqueous solution and absorbs nitrogen gas. Will be able to. This reaction is represented by the ion reaction formula in the solution as follows.

Embedded image (In the formula, X represents water or chloride ion)

[0011]

EFFECTS OF THE INVENTION The trans-dichlororuthenium (III) C-substituted tertiary polyamine complex of the present invention has a hydrocarbon group, so that its solubility in a solvent other than water is enhanced and the trans-dichlororuthenium (III) C-substituted tertiary polyamine complex is accumulated on a micelle interface or a solid surface. Will be easier.

[0012]

Next, the present invention will be described in more detail with reference to examples. Example 1 Synthesis of 2,5,7,7,9,12-hexamethyl-6,8-dioxo-2,5,9,12-tetraazatridecane (Compound 1 of formula (1)) Dimethylmalonic acid chloride 2 g (11.4 mmol)
Was dissolved in 200 ml of benzene and triethylamine was dissolved in 200 ml of benzene.
35 g (35.2 mmol) was added and stirred. In addition, N, N, N'-trimethylethylenediamine 3.5
6 g (34.8 mmol) was added, and the mixture was stirred at 20 ° C. for 18 hours. After the reaction, the solvent was distilled off under reduced pressure, dissolved in an aqueous sodium hydroxide solution, and extracted with ether. After distilling off the ether under reduced pressure, distillation under reduced pressure was carried out to obtain 2.79 g (9.3 mmol) of Compound 1 as a fraction at 0.1 mmHg and 140 ° C. 79% yield. This substance is a pale yellow liquid at room temperature. The structure of Compound 1 was confirmed by NMR and IR. ¹ H NMR (CDCl ₃ ) d = 1.41 (6H, s, C (C
_{H 3) 2), 2.25 (} 12H, s, N (C H 3) 2), 2.4
4 (4H, t, (CH 3) 2 NC H 2 CH 2 N), 2.94
(6H, s, CH ₂ N (CH ₃ ) CO), 3.47 (4
_{H, t, (CH 3)} 2 NCH 2 C H 2 N) ppm (TM
S). IR (KBr) 3554, 2938, 2770, 162
4 (nCO), 1466, 1403, 1362, 108
5,936,665 cm ^-1 .

Example 2 2,5,7,7,9,12-hexamethyl-2,5
Synthesis of 9,12-tetraazatridecane (Compound 2 of Formula (2)) 2,5,7,7,9,12-hexamethyl-6,8-dioxo-2,5,9,12-tetraazatri 2.0 g (6.8 mmol) of decane (Compound 1) was previously mixed with 2.7 g (71.2 mm) of lithium aluminum hydride.
ol) was gradually added to 150 ml of suspended diethyl ether, and the mixture was stirred at room temperature for 21 hours. After the reaction, water5.
1 g (285 mmol), potassium carbonate 4.9 g (3
(5.6 mmol), and the mixture is heated and stirred at 50 ° C. for about 1 hour. The solid precipitated in the reaction solution was removed by filtration, and the solvent was distilled off under reduced pressure.
1.50 g of compound 2 was obtained as a fraction at 80 ° C. Yield 80%. This substance is a colorless and transparent liquid at normal temperature.
The structure of Compound 2 was confirmed by NMR and IR. ¹ H NMR (CDCl ₃ ) d = 0.86 (6H, s, C
_{(C H 3) 2),} 2.17 (4H, s, NC H 2 C (CH 3) 2
C H ₂ N), 2.24 (12H, s, N (C H ₃ ) ₂ ),
_{2.28 (6H, s, CH 2} N (C H 3) CH 2), 2.3
5 (8H, quintet, (CH 3) 2 NC H 2 CH
₂ N) ppm (TMS). IR (KBr) 2947, 2817, 2767, 146
6, 1382, 1262, 1151, 1120, 84
1,665 cm ^-1 .

Example 3 trans-dichlororuthenium (III) (2,5
7,7,9,12-Hexamethyl-2,5,9,12-
Tetraazatridecane) chloride (compound 3 of formula (3))
Synthesis of 2,5,7,7,9,12-hexamethyl-2,5
9,12-Tetraazatridecane (Compound 2) 0.20
g (0.67 mmol) was previously added to potassium pentachloroacorthenium (III) [K ₂ RuCl ₅ (O
H ₂ )] 0.25 g (0.67 mmol) was added to the suspension in 60 ml of ethanol, and the mixture was refluxed for 45 hours while stirring. After the reaction, the mixture is filtered to remove unreacted substances, the solvent is distilled off, and dissolved in a small amount of 2-propanol to precipitate a salt. This salt is also removed by filtration, the solvent is distilled off, a small amount of methanol is added and dissolved, and diethyl ether is added. The precipitate was filtered, a small amount of concentrated hydrochloric acid was added to the precipitate, and the precipitate was allowed to stand at room temperature.
When crystals were grown, they were filtered and washed with diethyl ether to obtain 0.22 g of yellow needle-shaped compound 3. Yield 41%. The composition of this compound 3 was confirmed by elemental analysis. The redox potential E1 / 2 of the complex measured by UV spectrum and cyclic voltammetry
(Ru (II) / Ru (III)) by trans
-Confirmed to have a structure as a dichlororuthenium (III) complex. Elemental analysis, C ₁₅ H ₃₉ Cl ₃ N ₄ O _1.5 R
As u ₁ , measured value (calculated value) = C35.58 (35.53), H7.61
(7.75), N10.88 (11.05)%, absorption spectrum (1MH
Cl) l = 372 (e3300), 317sh (e800)
nm. Redox potential (1M HCl) E1 / 2 (Ru (I
I) / Ru (III)) 71 mV vs Ag / AgC
l. IR (KBr) 3413, 2927, 1624, 1
466, 1189, 1056, 1006, 947, 82
3,778 cm ^-1 .

Trans-dichlororuthenium (II
I) The tertiary tetraamine complex chloride (compound 4 of formula (4)) has already been shown to absorb nitrogen gas in an aqueous solution by reaction with titanium trichloride (T.
Takahashi, K .; Hiratani, K .; Ka
suga, E .; Kimura, Chem. Lett. ,
1993, 1761). Tr having a tertiary tetraamine ligand in which a substituent is introduced on C-obtained by the present invention
Similarly, the ans-dichlororuthenium (III) complex also has a property of absorbing nitrogen gas in water, and in order to prove this, the following nitrogen gas immobilization test was performed.

(Nitrogen gas immobilization test) As a test device, a device in which a gas buret was connected to a reaction solvent having a serum cap so that the internal pressure was kept constant was used. FIG. 1 shows a structural view of the device. To conduct the nitrogen gas immobilization test, trans-dichlororuthenium (I
II) (2,5,7,9,12-hexamethyl-2,
A solution prepared by dissolving 63.5 mg of 5,9,12-tetraazatridecane) chloride 1.5 hydrate in 20 ml of water was placed in a container, and nitrogen gas was blown into the solution to previously saturate the solution with nitrogen gas. Then, the internal space is sealed and the container is kept at 20 ° C. Next, titanium trichloride (0.19M) saturated with nitrogen gas was passed through a serum cap in the container.
Immediately after injecting 1.00 ml (0.213 mM) of a 0.2 M hydrochloric acid solution of the above, immediately after that, the liquid level of a 10% sodium sulfate aqueous solution that rises according to the decrease in internal pressure due to absorption of nitrogen gas is related to time. Let me record it. In this case, in order to keep the pressure in the container constant, the height of the liquid reservoir was adjusted to the rising liquid level. The results of the nitrogen gas immobilization test are shown in FIG.

The nitrogen immobilization rate shown in the table is defined as follows. (Nitrogen fixation rate) This complex fixes a maximum of one molecule of nitrogen gas per molecule. As a result of the above test, it is found that 73% of the charged complex absorbs nitrogen when the above complex is used as a precursor. The half-life of the reaction was 161 minutes.

[Brief description of drawings]

FIG. 1 is a structural explanatory view of a reaction vessel with a buret.

FIG. 2 shows changes in nitrogen absorption rate over time.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Internal reference number FI Technical indication location C07F 15/00 C07F 15/00 A (72) Inventor Kazuhisa Hiratani 1-chome Higashi 1-chome, Tsukuba-shi, Ibaraki Institute of Technology, Institute of Materials Science and Technology (72) Inventor Toshikazu Takahashi, 1-1, Higashi, Tsukuba, Ibaraki Prefecture Institute of Industrial Science and Technology, Institute of Materials and Engineering (72) Kazuyuki Kasuga, 1-1, Higashi, Tsukuba, Ibaraki Institute of Materials Science and Technology (72) Inventor Takayoshi Adachi 2-4-11 Tsubomotocho, Nishi-ku, Osaka City, Osaka Prefecture Daiyo Toyo Oxygen Co., Ltd. (72) Inventor Makoto Uchino 2-chome, Tsubumotocho, Nishi-ku, Osaka City, Osaka Prefecture No. 4-11 Taiyo Toyo Oxygen Co., Ltd. (72) Inventor Taizo Ichida 2-4-11 Tsubuhoncho, Nishi-ku, Osaka City, Osaka Prefecture Taiyo Toyo Oxygen Co., Ltd. Inside the company (72) Inventor Riichi Nakatsuji 1-16-7 Nishishimbashi, Minato-ku, Tokyo Japan Oxide Co., Ltd. (72) Inventor Ichiro Nakayama 1-16-7 Nishishimbashi, Minato-ku, Tokyo (72) Inventor Ayumu Okamoto 1-16-7 Nishishimbashi, Minato-ku, Tokyo Japan Oxide Co., Ltd. (72) Inventor Hiroshi Kawakami 1-16-7 Nishi-shinbashi, Minato-ku, Tokyo Incorporated (72) Inventor Nobuyoshi Ito 1-16-7 Nishishimbashi, Minato-ku, Tokyo Within Nihon Oxygen Co., Ltd.

Claims (7)

[Claims] 1. 2, 5, 9, 1 represented by the following formula (1)
2-Tetramethyl-6,8-dioxo-7-hydrocarbon-
2,5,9,12-Tetraazatridecane. Embedded image (In the above formula, R represents hydrogen or a hydrocarbon group, and R ′ represents a hydrocarbon group) 2. A 2, 5, 9, 1 represented by the following formula (2):
2-Tetramethyl-7-hydrocarbon-2,5,9,12-
Tetraazatridecane. Embedded image (In the above formula, R represents hydrogen or a hydrocarbon group, and R ′ represents a hydrocarbon group) 3. A trans-dichlororuthenium (III) (2,5,9,12-tetramethyl-7-hydrocarbon-2,5,9,12-tetraazatridecane represented by the following formula (3): ) Complex. Embedded image (In the above formula, R represents hydrogen or a hydrocarbon group, and R ′ represents a hydrocarbon group) 4. The following formula (1): In the method for producing a tertiary tetraaminediamide compound represented by the formula (wherein R represents hydrogen or a hydrocarbon group, R ′ represents a hydrocarbon group), N, N, N′-trimethylethylenediamine and the following formula: [Chemical 4] (Wherein R represents hydrogen or a hydrocarbon group, R'represents a hydrocarbon group, and X represents a hydroxyl group, an alkoxy group or halogen), and a malonic acid derivative represented by the above formula is reacted. Method. 5. The following formula (2): In the method for producing a tertiary tetraamine compound represented by the formula (wherein R represents hydrogen or a hydrocarbon group and R ′ represents a hydrocarbon group), a tertiary tetraaminediamide compound represented by the following formula (1) and a reducing agent are used. And the reaction with. Embedded image (In the above formula, R represents hydrogen or a hydrocarbon group, and R ′ represents a hydrocarbon group) 6. The following formula (3): (In the above formula, R represents hydrogen or a hydrocarbon group, and R ′ represents a hydrocarbon group) In the method for producing a trans-dichlororuthenium (III) tertiary tetraamine complex represented by the following formula (2) Tertiary tetraamine and potassium pentachloroacorthenium (III) [K ₂ RuCl
₅ (OH ₂ )] is reacted. Embedded image (In the above formula, R represents hydrogen or a hydrocarbon group, and R ′ represents a hydrocarbon group) 7. The following formula (3): (In the above formula, R represents hydrogen or a hydrocarbon group, and R ′ represents a hydrocarbon group) Titanium trichloride was added to an aqueous solution of trans-dichlororuthenium (III) tertiary tetraamine complex, and nitrogen gas was added. A method for immobilizing nitrogen, which comprises contacting.