JP2000302767A - Triazacyclononane compound having high water solubility and its metal complex - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new triazacyclononane compound having a high water solubility having a substituted hydrocarbon group containing a hetero atom, and useful as an intermediate or the like for the synthesis of fine chemicals, high functional catalysts or the like. SOLUTION: A compound of the formula (R1 and R2 are H or a hydrocarbon group; R3 is a hydrocarbon group; and n>=1), for example, 1,4,7-tris(2- methoxyethyl)-1,4,7-triazacyclononane (L). The compound of the formula can be obtained by introducing a hydrocarbon group having an ether-type oxygen such as alkoxyethyl onto a nitrogen atom of a compound (e.g. 1,4,7- triazacyclononane) which has a corresponding skeleton and in which the nitrogen atom is not substituted. The compound can be converted into a metal complex by reacting with a metal salt such as cupric chloride. The compound has a high water solubility, and has no limitation on a reaction substrate or a reaction solvent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel triazacyclononane compound and a metal complex thereof.

[0002]

2. Description of the Related Art 1,4,7-Triazacyclononane derivatives and their metal complexes, which are macrocyclic tridentate ligand compounds, are not only interested in their complex structure when coordinated to a central metal, but also for their metal structures. In recent years, the complex has attracted much attention because it has a catalytic function for various chemical reactions. For example, for derivatives in which the N-substituent of triazacyclononane is a hydrocarbon group, J. Am. Chem.
Soc. 114, 3169-70 (1992), 1,4,7-trimethyl-1,4,7-
Rhodium complexes of triazacyclononane have been reported. In addition, the present inventors reported in J. Am. Chem. Soc. 120,8529-8530 (1998) that 1,4,7-
A copper complex of triisopropyl-1,4,7-triazacyclononane has been reported. On the other hand, the triazacyclononane N-
Derivatives in which the substituent is a substituted hydrocarbon group containing a hetero atom are expected to have particularly improved water solubility. For example,
Nature, 369, 637-639 (1994) describes 1,4,7-tris (hydroxyethyl) -1,4,7-triazacyclononane derivatives. Also, J. Chem. Soc., Chem. Commu
n., 1252-1253 (1991) reports 1,4,7-tris (methoxymethyl) -1,4,7-triazacyclononane derivatives. However, in these triazacyclononane derivatives, for example, since a hydroxyethyl group has active hydrogen, it easily reacts with an electrophilic functional group, and a methoxymethyl group easily reacts with a nucleophilic functional group. There is a drawback, and there is a problem that a reaction substrate and a reaction solvent are limited.

[0003]

An object of the present invention is to provide a compound having a substituted hydrocarbon group containing a heteroatom, having a low reactivity of the substituted hydrocarbon group, and a water solubility which can be used as a reaction substrate or a reaction solvent. It is to provide a high N-substituted triazacyclononane compound and a metal complex thereof.

[0004]

Under these circumstances, the present inventors have conducted intensive studies to achieve the above object, and as a result, have found a novel triazacyclononane compound and a metal complex thereof. The present invention has been completed. That is,
The present invention provides a triazacyclononane compound represented by the following general formula (I). General formula (I)

[0005]

Embedded image

(Wherein, R ¹ and R ² represent a hydrogen atom or a hydrocarbon group; R ³ represents a hydrocarbon group; n represents an integer of 1 or more; all R ¹ , R ² , and R ³⁾ And n may be the same or different from each other.)

[0007]

Next, the present invention will be described in detail. The triazacyclononane compound of the present invention is a triazacyclononane compound represented by the above general formula (I).

In the general formula (I), when R ^{1 to} R ³ are a hydrocarbon group, the hydrocarbon group has 1 to 1 carbon atoms.
20, more preferably 1 to 12, even more preferably 1 to
6, an alkyl group, an aralkyl group or an aryl group. The alkyl group for R ^{1 to} R ³ may be any of a linear hydrocarbon group or a monocyclic or polycyclic alicyclic group.
For example, methyl group, ethyl group, n-propyl group, iso
-Propyl group, cyclopropyl group, n-butyl group, is
o-butyl, t-butyl, cyclobutyl, pentyl, iso-pentyl, neo-pentyl, cyclopentyl, hexyl, cyclohexyl, methylcyclohexyl, cyclohexenyl, cyclohexadienyl, menthyl , Pinanyl group, bicycloheptyl (norbonyl) group, bicyclooctyl group, bicyclodecanyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, 1-adamantyl group, 2-adamantyl group and the like. Can be Examples of the aralkyl group or the aryl include a 1-phenylethyl group,
2-phenylethyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, benzyl group,
Phenyl, xylyl, mesityl, cumyl, 1-
Examples include a naphthyl group and a 2-naphthyl group.

R ¹ and R ² are each independently preferably a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and more preferably a hydrogen atom. Or a methyl group is more preferred. Most preferably, R ¹ and R ² are all hydrogen. Further, R ³ has 1 to 2 carbon atoms.
An alkyl group having 0 carbon atoms is preferable, an alkyl group having 1 to 6 carbon atoms is more preferable, and an alkyl group having 1 to 3 carbon atoms is further preferable. Most preferably, R ³ is a methyl group.

[0010] In the general formula (I), n is not particularly limited as long as it is an integer of 1 or more, preferably 1 to 100, more preferably 1 to 20, and further preferably 1 to 6. is there. Particularly preferably, it is 1. The triazacyclononane compound of the present invention is characterized by having, as its N-substituent, a hydrocarbon group having a specific ether-type oxygen atom as shown in the formula (I).
2-methoxyethyl group, 2-ethoxyethyl group, 2-propoxyethyl group when = 1; 2 ′ when n = 2
A-(2-methoxyethoxy) ethyl group, a 2 '-(2-ethoxyethoxy) ethyl group, a 2'-(2-propoxyethoxy) ethyl group and the like are exemplified as preferred.
Particularly preferred is a 2-methoxyethyl group. In any case, the hydrocarbon group bonded to N has an ethyl group as a main chain.

The metal complex of the present invention is a metal complex comprising the above triazacyclononane compound and a metal atom, wherein one metal atom per triazacyclononane compound. The structure of the metal complex is not particularly limited, but is preferably a metal complex in which a triazacyclononane compound is coordinated as a ligand to a central metal as represented by the general formula (II). General formula (II)

[0012]

Embedded image

In the formula (II), R ^{1 to} R ³ and n have the same meanings as defined in the general formula (I). M is a metal atom, X is a counter anion, m is the number of X, and is an integer of 0 or 1 or more, usually 1 to 6, and the compound of the general formula (II) is electrically charged by the counter anion X. It is determined appropriately so as to neutralize it. It is determined by the valences of M and X.

The metal atom in the metal complex is not particularly limited as long as it is a metal element atom.
PAC inorganic chemistry nomenclature revised edition 1989) is preferably a metal atom of Group 1 to 12, more preferably a metal atom of Group 3 to 12, and still more preferably a metal atom of the first transition metal series. In some cases, a metal belonging to the lanthanum series or the actinium series may be used. For example, Li,
Na, K, Rb, Cs, Fr, Be, Mg, Ca, S
r, Ba, Ra, Sc, Ti, V, Cr, Mn, Fe,
Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, T
c, Ru, Rh, Pd, Ag, Cd, Lu, Hf, T
a, W, Re, Os, Ir, Pt, Au, Hg, Lr, etc., and preferably Sc, Ti, V, Cr, M
n, Fe, Co, Ni, Cu and Zn, and particularly preferably a Cu atom.

The valence of the metal atom in the metal complex can be appropriately selected from those usually present in the natural world, and for example, in the case of copper, monovalent or divalent copper can be used.

In the metal complex of the present invention, the structure other than the triazacyclononane compound and the metal atom is not particularly limited, and a solvent or the like may be coordinated around the complex.

In some cases, the metal complex of the present invention requires a counter ion to maintain electrical neutrality. As the counter anion, a conjugate base of Bronsted acid is usually used. For example, fluoride ion, chloride ion, bromide ion, iodide ion, sulfate ion, nitrate ion, carbonate ion, perchlorate ion, tetrafluoroborate ion, hexafluorophosphate ion, methanesulfonic acid ion, trifluoromethanesulfone Acid ion, toluenesulfonic acid ion, acetate ion, trifluoroacetate ion, propionate ion, benzoate ion, hydroxide ion, oxide ion, methoxide ion, ethoxide ion and the like. Among them, preferred are chloride ions, bromide ions, iodide ions, sulfate ions, nitrate ions, acetate ions, hydroxide ions or methoxide ions, and more preferred are chloride ions, bromide ions, sulfate ions or nitrate ions. It is an ion. As the counter cation, a cation such as an alkali metal or an alkaline earth metal can be appropriately used.

The triazacyclononane compound having an N-substituent represented by the general formula (I) in the present invention is obtained, for example, by starting from a triazacyclononane compound having a corresponding skeleton, wherein N is not substituted. A hydrocarbon group having an ether oxygen atom such as an alkoxyethyl group is introduced into this nitrogen atom by a usual method (J. Ch.
em. Soc. Dalton Trans. 83-90
(1993)). Further, the triazacyclononane compound is reacted with a salt of a metal to be a central metal in a suitable solvent by a known means (Inorg. Chem. 1379-1381 (19)
80)) to easily obtain the metal complex.
This is described in more detail from the method for producing the compound represented by the general formula (I).

[0019]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the present invention.

Example 1 (i) Synthesis of 1,4,7-tris (2-methoxyethyl) -1,4,7-triazacyclononane (L) 0.950 g of 1,4,7-triazacyclononane (L) 7.36 mmol) was dissolved in 40 ml of toluene, and 2-methoxyethoxybromide 4.31 was dissolved.
g (31.0 mmol) and 1.74 g (31.0 mmol) of potassium hydroxide were added, and the mixture was stirred at 80 ° C. for 6 hours. After completion of the reaction, the mixture was cooled to room temperature, 1.74 g of potassium hydroxide was added, and the mixture was stirred at room temperature overnight. The salt was filtered from the reaction mixture, and
After washing twice, the filtrate and the washing solution were concentrated by an evaporator.
This was subjected to Kugel distillation to obtain a triazacyclononane compound as a fraction at about 185 ° C. under 0.2 mmHg. The yield was 1.98 g, 89%.

From the following data, the target triazacyclononane compound was identified. 1H-NMR (ppm / 600 MHz, CDCl3): 2.73 (t, 6H), 2.79 (s, 12
H), 3.34 (s, 9H), 3.46 (t, 6H) 13C-NMR (ppm / 150 MHz, CDCl3): 56.7, 58.1, 58.9, 71.
7 IR (cm ^-1): 2925,2874,2814,1456,1359,1120 Elemental _{analysis: L / 0.5H 2 O (C} 15 H 34 N 3 O 3.5) Calculated C (57.64
%), H (10.99%), N (13.44%) / measured value C (57.97%), H (11.45%)
%), N (13.57%)

(Ii) (1,4,7-tris (2-methoxyethyl)
Synthesis of -1,4,7-triazacyclononane) CuCl ₂ complex (LCuCl ₂ ) 1,4,7-tris (2-methoxyethyl) -1, synthesized in (i)
10 ml of methanol was added to 0.36 g of 4,7-triazacyclononane to make the mixture homogeneous, and then 10 ml of a methanol solution containing 0.19 g of cupric chloride dihydrate was added, followed by stirring at room temperature for 2 hours.
After the completion of the reaction, the solvent was distilled off in vacuo and washed three times with anhydrous diethyl ether to obtain a copper complex. Yield 0.39 g,
The yield was 71%. The copper complex was identified by elemental analysis. _{LCuCl 2 /0.5MeOH/0.5H 2 O (C 15.5} H 36 N 3 O 4 CuCl 2) Calculated: C (40.22%), H (7.84%), N (9.08%), Cl (15.32%) measurements : C (40.38%), H (7.36%), N (9.42%), Cl (15.60%)

(Iii) Water solubility test First, 5 mg of the (1,4,7-tris (2-methoxyethyl) -1,4,7-triazacyclononane) CuCl ₂ complex synthesized in (ii)
When 5 μL of distilled water was added to the mixture, the complex was completely dissolved. Comparative Example 1 (1,4,7-Triisopropyl-1,4,7-triazacyclononane) CuCl synthesized by the method described in J. Am. Chem. Soc., 120, 8529-8530 (1998). ₂ Distilled water (5 μL) was added to 5 mg of the complex, but the complex hardly dissolved.

[0024]

As described above, according to the present invention,
To provide a novel triazacyclononane compound and a metal complex thereof having an N-substituent on its ring but having low reactivity with reaction components and the like even when used as a reaction catalyst and the like, and having high water solubility. Can be. Therefore, the triazacyclononane compound of the present invention has high water solubility and does not have a hydroxyalkyl group or an alkoxymethyl group as in the conventional case, so that the reaction substrate and the reaction solvent are not limited, so that various fine chemicals are used. It is useful as an intermediate or starting material for synthesizing a product or a highly functional catalyst.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Kiyoshi Fujisawa 4-201-706, Azuma, Tsukuba, Ibaraki Prefecture (72) Inventor Yoshihiko Morooka 2-41-21, Fujigaoka, Aoba-ku, Yokohama-shi, Kanagawa 404 (72) Inventor Shiro Kobayashi 1-1-1 Higashi, Tsukuba City, Ibaraki Pref. F-term in the Institute of Materials Science and Technology, Institute of Industrial Science 4H048 AA01 AB84 VA20 VA32 VA56 VB10 4J005 AA14 BB02 BD04 BD05

Claims (2)

[Claims] 1. A triazacyclononane compound represented by the general formula (I). General formula (I) (In the formula, R ¹ and R ² represent a hydrogen atom or a hydrocarbon group. R ³ represents a hydrocarbon group. N represents an integer of 1 or more. All R ¹ , R ² , R ³ and n represent They may be the same or different.) 2. A metal complex of a triazacyclononane compound represented by the general formula (II). General formula (II) (Wherein, R ^{1 to} R ³ represent the same meaning as defined in the general formula (I). M is a metal atom, X is a counter anion, m is the number of X, and 0 or 1 or more. It is an integer.