JP3107547B1 - Novel triazacyclononane compound and its metal complex - Google Patents

Abstract

The present invention provides a novel triazacyclononane compound in which all the α-carbons of the three substituents on nitrogen are tertiary, and a metal complex thereof. A triazacyclononane compound represented by the following general formula (I), and a metal complex comprising the triazacyclononane compound and a metal atom. Embedded image (In the formula, R ¹ represents a hydrogen atom or a hydrocarbon group. All of R ¹ is optionally be the same or different .R ² to R ⁴ each independently represent a hydrocarbon group having 2 or more carbon atoms.
Two R ² , two R ³ , and two R ⁴ are the same, and do not form a ring with each other. )

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 metal complexes have attracted much attention in recent years because the metal complexes have catalytic functions for various chemical reactions. For example, we have proposed J. Am. Chem. Soc. 120, a highly selective oxidative polymerization catalyst for phenol derivatives.
8529-8530 (1998) reports a copper complex of 1,4,7-triisopropyl-1,4,7-triazacyclononane. Among them, in the reaction of the present copper complex with oxygen molecules, μ-η ² :
It is described that it is important that only η ² -peroxo binuclear copper complex can be formed. On the other hand, Acc. Chem. Res.
30, 227-237 (1997) states that in order for a triazacyclononane / copper complex to form only a μ-η ² : η ² -peroxo dinuclear copper complex, α of the substituent on the nitrogen of triazacyclononane is required. It states that all carbons need to be tertiary. When this metal complex is used as a catalyst, solubility in a reaction solvent is required from the viewpoint of catalytic activity. However, the conventional metal complex catalyst has a problem that solubility in an organic solvent is low, a reaction solvent is limited, and thus a reaction substrate is also limited.

[0003]

Accordingly, an object of the present invention is to provide a novel triazacyclononane compound having high solubility in an organic solvent and a metal complex thereof.

[0004]

That is, the present invention provides a triazacyclononane compound represented by the following general formula (I) and a metal complex comprising the triazacyclononane compound and a metal atom. .

[0005]

Embedded image

[0006] (.R ² wherein, ^{R 1} represents a hydrogen atom ~R
⁴ independently represents a hydrocarbon group having 2 or more carbon atoms. Two R ² , two R ³ , and two R
⁴ are the same and do not form a ring with 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).

[0008] Table of ^{R 1} is a hydrogen atom in formula (I)
You.

In the above formula (I), R ^{2 to} R ⁴ each independently represent a hydrocarbon group having 2 or more carbon atoms.
^Two , two R ³ and two R ⁴ are the same, and must not form a ring with each other.

The hydrocarbon group as R ^{2 to} R ^{4 in} the general formula (I) is preferably an alkyl group having 2 to 20 carbon atoms, an aralkyl group or an aryl group, and specifically, an ethyl group, an n-propyl group , An iso-propyl group, an n-butyl group, an iso-butyl group, a t-butyl group, a pentyl group,
Cyclopentyl, hexyl, cyclohexyl, octyl, decyl, benzyl, 2-phenylethyl, 1-phenylethyl, phenyl, 4-methylphenyl, 1-naphthyl, 2-naphthyl, etc. No.

R ^{2 to} R ^{4 in} the general formula (I) are preferably an alkyl group having 2 to 20 carbon atoms, more preferably an alkyl group having 2 to 6 carbon atoms, and further preferably an alkyl group having 2 to 6 carbon atoms. It is an alkyl group having 2 to 4 atoms. Particularly preferred is an ethyl group.

The metal complex of the present invention is a metal complex comprising the triazacyclononane compound and a metal atom.

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. For example, in the case of copper, monovalent or divalent copper can be used.

In the metal complex, the number of metal atoms is preferably one per triazacyclononane compound.

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.

In some cases, the metal complex of the present invention requires a counter ion to maintain electrical neutrality. As the counter anion, a conjugated base of Bronsted acid is usually used, and specific examples include fluoride ion, chloride ion, bromide ion, iodide ion, sulfate ion, nitrate ion, carbonate ion, perchlorate ion, Tetrafluoroborate, hexafluorophosphate, methanesulfonate, trifluoromethanesulfonate, toluenesulfonate, acetate, trifluoroacetate, propionate, benzoate, hydroxide, oxide ion,
Methoxide ions, ethoxide ions and the like can be mentioned. As the counter anion, preferably chloride ion, bromide ion, iodide ion, sulfate ion, nitrate ion, acetate ion, hydroxide ion or methoxide ion, more preferably chloride ion, bromide ion, sulfate ion or It is a nitrate ion. As the counter cation, a cation such as an alkali metal or an alkaline earth metal can be appropriately used.

The metal complex of the present invention is preferably a metal complex represented by the following general formula (II).

[0019]

Embedded image

(Wherein, R ^{1 to} R ⁴ have the same definition as those of the above general formula (I). M is a metal atom, X is a counter anion, n is the number of X, R ^{1 to} R ⁴ in the general formula (II) are the same as those in the general formula (I). In the general formula (II), the structure other than the above is not particularly limited, and a solvent or the like may be coordinated. The triazacyclononane compound having an N-substituent represented by the general formula (I) in the present invention is, for example, a compound having a skeleton corresponding to the formula (I) and having no substituent on a nitrogen atom, Starting from a triazacyclononane compound in which all of the groups on the atom are hydrogen atoms, a hydrocarbon group having a predetermined number of carbon atoms is introduced into this nitrogen atom (J. Chem. 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. 1).
379-1381 (1980)) to easily obtain the metal complex.

[0021]

The present invention will be described in more detail with reference to the following examples, but the scope of the present invention is not limited by these examples.

Example 1 (i) Synthesis of 1,4,7-tris (3-pentyl) -1,4,7-triazacyclononane 0.950 g (7.36 mmol) of 1,4,7-triazacyclononane Was dissolved in toluene 40 mL, and 3-bromopentane 6.67 g (44.2 mmol)
And 2.48 g (44.2 mmol) of potassium hydroxide, and added at 110 ° C.
Stirred for 6 hours. After the completion of the reaction, the salt was filtered and toluene 10m
After washing three times with L, 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 0.1 mmHg. (Yield 1.69
g, yield 68%) The present triazacyclononane compound was identified from the following data. ¹ H-NMR (ppm / 600 MHz, DMF-d7): 0.94 (t, 18H), 1.29 (m, 6
H), 1.41 (m, 6H), 2.12 (quintet, 3H), 2.67 (s, 12H), 13C
-NMR (ppm / 150 MHz, DMF-d7): 12.8, 23.9, 53.5, 69.3, I
R (cm ^-1 ): 2957, 2931, 2874, 1463, 1370, 1153, elemental analysis: (C ₂₁ H ₄₅ N ₃ ) calculated values C (74.27%), H (13.36%), N (1
2.37%) / Measured value C (75.03%), H (14.07%), N (12.40%)

(Ii) (1,4,7-tris (3-pentyl) -1,4,7
Synthesis of -triazacyclononane) CuCl ₂ complex In 0.47 g of 1,4,7-tris (3-pentyl) -1,4,7-triazacyclononane, 10 mL of methanol and 6 mL of methylene chloride are uniformly dissolved. After that, cupric chloride dihydrate 0.22
10 mL of a methanol solution containing g was added and stirred at room temperature for 1 hour. After completion of the reaction, the solvent was distilled off in vacuo, washed successively with anhydrous methanol, anhydrous diethyl ether and anhydrous methanol, and dried under vacuum to obtain a complex. (Yield 0.45g,
This complex was identified by elemental analysis and yielded (C ₂₁ H
₄₅ N ₃ CuCl ₂ ) Calculated: C (53.21%), H (9.57%), N (8.86%),
For Cl (14.96%), measured values: C (53.30%), H (9.56%), N
(8.71%) and Cl (14.98%). (Solubility test) Am. Chem. Soc. 120,
8529-8530 (1998), (1,4,7-triisopropyl-1,4,7-triazacyclononane) CuCl ₂ was synthesized. This metal complex is B, and the metal complex obtained in Example 1 is A.

Complexes A and B were each dissolved in 0.5 g of ethanol in an amount of 1 mg, and n-hexane was added little by little with stirring. Complex A remained uniform even when 60 g of n-hexane was added, whereas complex B was precipitated when 1.6 g of n-hexane was added.

[0025]

The triazacyclononane compound of the present invention corresponds to a precursor of the metal complex. The metal complex of the present invention has high solubility in an organic solvent and can be used as a reaction catalyst in the synthesis of an phenol oxidized polymer.

──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Yoshihiko Morooka 2-41, Fujigaoka 2-chome, Aoba-ku, Yokohama-shi, Kanagawa Prefecture 404 Tokyo Tech Dormitory 404 (72) Inventor Shiro Kobayashi 1-1-1 Higashi, Tsukuba-shi, Ibaraki Pref. Examiner in the Industrial Technology Research Institute Shunichi Yokoo (56) References JP-A-10-45904 (JP, A) JP-A-10-45899 (JP, A) ANGE WANDTE CHEMIE int. ed. , Vol. 38 (No. 1/2) p207-210 (1999) Chem. Soc. Dalton trans. 1993 (No. 1) p83-90 (58) Fields investigated (Int. Cl. ⁷ , DB name) C07D 255/02 CA (STN) REGISTRY (STN)

Claims (2)

(57) [Claims] 1. A triazacyclononane compound represented by the following general formula (I). Embedded image (Wherein, ^{R 1} represents a represents .R ² to R ⁴ carbon atoms are each independently 2 or more hydrocarbon radicals a hydrogen atom. Two R
^Two , two R ³ and two R ⁴ are:
Each is the same and does not form a ring with each other. ) 2. A metal complex comprising the triazacyclononane compound according to claim 1 and a metal atom.