JPH10324689A - Silicon-containing alfa-diimine compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject new compound having a bulky substitution group and useful as a ligand for a metal complex. SOLUTION: This compound is a silicon-containign α-diimine compound of formula I (R and R<1> are each H, methyl, ethyl, n-propyl, phenyl, etc.; R<2> to R<4> are each a 1-10C monovalent hydrocarbon; R<5> is H, a silicon-containing group of the formula R<2> R<3> R<4> Si-, etc.), e.g. N,N'-bis(2-trimethylsilylphenyl) ethylenediamine. The compound of formula I can be obtained, for example, by mixing the aniline derivative of formula H with α-dicarbonyl compound of formula III in an alcohol, or a mixed solvent of an alcohol and water, and carrying out dehydrating condensation of the mixture. The compound is expected to be used as a ligand for a metal complex because the compound has bulky substituting groups at the ortho position of the amino group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a silicon-containing α-diimine compound which is a novel compound useful as a ligand of a metal complex.

[0002]

2. Description of the Related Art An α-diimine compound is well known as one of chelating ligands, and compounds having various substituents have been synthesized. Further, many studies have been made to form complexes with various metals and evaluate their properties from various aspects.

[0003] In recent years, an interesting report has been made that a transition metal complex of an α-diimine compound functions as an olefin polymerization catalyst (Journal of America).
nChemical Society 1995 November
Vol. 7, No. 23, pp. 6414-6415 and the same magazine, 1996
Vol. 118, No. 1, pp. 267-268, International Publication W
No. O96 / 23010). The metal complex reported in this document has a structure in which a hydrocarbon group bonded to an α-diimine compound covers a metal atom above and below. It is said that this gives a high molecular weight polymer which could not be obtained conventionally, and the properties of the obtained polymer also differ depending on the height of the hydrocarbon substituent. As a specific example of the hydrocarbon group, a methyl group or an isopropyl group is used, but these substituents are not necessarily sufficient in bulkiness, and the α-diimine compound into which a bulkier substituent is introduced is used. Development was desired.

[0004]

An object of the present invention is to provide a novel silicon-containing α-diimine compound having a bulky substituent, which is useful as a ligand of a metal complex.

[0005]

Means for Solving the Problems and Embodiments of the Invention The present inventors have conducted various studies to solve the above-mentioned problems, and as a result, have found that a silicon-containing α-diimine compound represented by the following general formula (1): I came to find.

[0006]

Embedded image (Wherein, R and R ¹ may be the same or different from each other, each represents a hydrogen atom, a methyl group, an ethyl group, selected from n- propyl group and a phenyl group. Or, R and R ¹ are fused two R ² , R ³ , and R ² may form a ring structure together with two adjacent carbon atoms.
⁴ may be the same or different, and each is selected from monovalent hydrocarbon groups having 1 to 10 carbon atoms. R ⁵ is hydrogen atom, R ² R ³ R ⁴ silicon-containing group or a monovalent hydrocarbon group having 1 to 10 carbon atoms represented by Si-. )

Hereinafter, the compounds of the present invention will be described in detail.
In the formula (1), R and R ¹ are substituents independently selected from a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, and a phenyl group. R and R ¹ may be condensed in a dehydrogenated form to form a divalent hydrocarbon group. Specific examples of such a divalent hydrocarbon group include trimethylene, tetramethylene, pentamethylene, hexamethylene, methyltrimethylene, methyltetramethylene, methylpentamethylene, dimethyltrimethylene, Examples include a dimethyltetramethylene group, a trimethyltrimethylene group, a biphenylene group, and a naphthylene group.
These divalent hydrocarbon groups form a ring structure with two adjacent carbon atoms.

In the formula (1), R ² , R ³ and R ⁴ may be the same or different from each other, and each has 1 to 1 carbon atoms.
0 is selected from monovalent hydrocarbon groups. R ² , R ³ and R ⁴ are methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, n -Pentyl, isopentyl, 1-methylbutyl, 1-ethylpropyl, 1,1-dimethylpropyl, cyclopentyl, n-hexyl, texyl, cyclohexyl, n-heptyl, cycloheptyl, n -Octyl group, cyclooctyl group, n-nonyl group, n-decyl group, phenyl group, o-tolyl group, m-
Tolyl group, p-tolyl group, 2,6-dimethylphenyl group, 2,5-dimethylphenyl group, 2,4-dimethylphenyl group, 2,3-dimethylphenyl group, 3,4-dimethylphenyl group, 3, Examples include a 5-dimethylphenyl group, a mesityl group, a 1-naphthyl group, and a 2-naphthyl group.

Accordingly, the compound of formula (1) has a bulky silicon substituent at the ortho position of the amino group. R ² R ³ R
Specific examples of the silicon substituent represented by ⁴ Si— include a trimethylsilyl group, an ethyldimethylsilyl group, n
-Propyldimethylsilyl group, isopropyldimethylsilyl group, cyclopropyldimethylsilyl group, n-butyldimethylsilyl group, isobutyldimethylsilyl group, se
c-butyldimethylsilyl group, tert-butyldimethylsilyl group, cyclobutyldimethylsilyl group, n-pentyldimethylsilyl group, isopentyldimethylsilyl group, (1-methylbutyl) dimethylsilyl group, (1-ethylpropyl) dimethylsilyl Group, (1,1-dimethylpropyl) dimethylsilyl group, cyclopentyldimethylsilyl group, n-hexyldimethylsilyl group, texyldimethylsilyl group, cyclohexyldimethylsilyl group, n
-Heptyldimethylsilyl group, cycloheptyldimethylsilyl group, n-octyldimethylsilyl group, cyclooctyldimethylsilyl group, n-nonyldimethylsilyl group,
n-decyldimethylsilyl group, diethylmethylsilyl group, di-n-propylmethylsilyl group, di-n-butylmethylsilyl group, dicyclopropylmethylsilyl group, triethylsilyl group, phenyldimethylsilyl group, o-tolyldimethyl Silyl group, m-tolyldimethylsilyl group,
p-tolyldimethylsilyl group, 2,6-dimethylphenyldimethylsilyl group, 2,5-dimethylphenyldimethylsilyl group, 2,4-dimethylphenyldimethylsilyl group, 2,3-dimethylphenyldimethylsilyl group, 3,
Examples thereof include a 4-dimethylphenyldimethylsilyl group, a 3,5-dimethylphenyldimethylsilyl group, a mesityldimethylsilyl group, a 1-naphthyldimethylsilyl group, and a 2-naphthyldimethylsilyl group.

R ⁵ in the formula (1) is a substituent on the benzene ring, and is a hydrogen atom, a silicon-containing group represented by R ² R ³ R ⁴ Si—, or a monovalent hydrocarbon having 1 to 10 carbon atoms. Selected from among the groups. Examples of the monovalent hydrocarbon group having 1 to 10 carbon atoms include 1 to 1 carbon atoms exemplified for R ² , R ³ and R ⁴ above.
The same thing as the monovalent hydrocarbon group of 0 can be illustrated.

The α-diimine compound of the present invention can be produced, for example, as follows. That is, an aniline derivative represented by the following general formula (2) and an α-dicarbonyl compound represented by the following general formula (3) are used, for example, in Z.I. Natureforsch. As described in Vol. 36b, 1981, pp. 823 to 832, a method of mixing in an alcohol or a mixed solvent of alcohol and water and performing dehydration condensation can be employed. In addition, it is preferable to use 2 equivalents or more of the aniline derivative of the formula (2) with respect to the α-dicarbonyl compound of the formula (3). The reaction temperature is usually -10C to 100C.

[0012]

Embedded image (In the formula, R ^{2 to} R ⁵ represent the same meaning as in formula (1).)

[0013]

Embedded image (In the formula, R and R ¹ represent the same meaning as in formula (1).)

As described in the above literature, a small amount of formic acid can be added as a catalyst to accelerate the reaction.

[0015]

The present invention will be described below in more detail with reference to Examples, but the present invention is not limited to the following Examples.

Example 1 Synthesis of N, N'-bis (2-trimethylsilylphenyl) ethylenediimine A 100-ml three-necked glass flask equipped with a dropping funnel, a thermometer, and a stirrer was purged with nitrogen. A solution of 1.81 g (11 mmol) of (trimethylsilyl) aniline in 10 ml of methanol was charged. While stirring the contents, 0.80 g of 40% aqueous glyoxal solution was dropped from the dropping funnel.
(5.5 mmol) was added dropwise at 20 ° C. for 5 minutes. 20
After continuing stirring at で 25 ° C. for further 20 hours, the precipitated yellow solid was collected by filtration. This solid was washed with 10 ml of methanol and dried under vacuum to obtain 1.55 g of a yellow powdery solid. From the results of nuclear magnetic resonance spectrum, infrared absorption spectrum and mass spectrum, this solid was found to be N, N'-bis (2-
(Trimethylsilylphenyl) ethylenediimine. The yield was 79.9%.

The ¹ H nuclear magnetic resonance spectrum (C
DCl ₃ solvent) in FIG. 1, ¹³ C nuclear magnetic resonance spectrum (CDCl ₃ solvent) in FIG. 2, also showing the infrared absorption spectrum (KBr) in Figure 3. Mass spectrum (EI) m / z: 352 (M ^<+> ), 33
7 ([M-Me] ⁺ ), 279 ([M-Me ₃ S
i] ⁺ ), 73 ([Me ₃ Si] ⁺ )

Example 2 N, N'-bis [2- (n-
Synthesis of hexyldimethylsilyl) phenyl] ethylenediimine A 100 ml three-neck glass flask equipped with a thermometer and a stirrer was purged with nitrogen, and 3.30 g (14 mmol) of 2- (n-hexyldimethylsilyl) aniline in 15 ml of methanol The solution was charged. 1.0 g (7 mmol) of a 40% aqueous glyoxal solution was added at 21 ° C. 20
After stirring at ２５25 ° C. for 20 hours, the mixture was further reacted under heating and refluxing for 6 hours. The reaction mixture separated into upper and lower layers was cooled to room temperature, and then the upper layer was removed.
After adding 1 and stirring for 5 minutes, the upper methanol layer was removed. After repeating the methanol washing three times, the lower layer oily substance was dried under reduced pressure at 2 mmHg and 50 ° C. to obtain 3.11 g of a red oily substance. From the results of nuclear magnetic resonance spectrum, infrared absorption spectrum, and mass spectrum, this oil was found to contain N,
It was confirmed to be N'-bis [2- (n-hexyldimethylsilyl) phenyl] ethylenediimine. The yield was 90.1%.

The ¹ H nuclear magnetic resonance spectrum (C
DCl ₃ solvent) in FIG. 4, ¹³ C nuclear magnetic resonance spectrum (CDCl ₃ solvent) in FIG. 5, also showing the infrared absorption spectrum (NaCl) in FIG. Mass spectrum (EI) m / z: 492 (M ^<+> ), 47
7 ([M-Me] ⁺ ), 408 ([M-C ₆ H ₁₃ ] ⁺ ),
246

[0020]

Industrial Applicability The silicon-containing α-diimine compound of the present invention has a bulky substituent represented by R ² R ³ R ⁴ Si— at the ortho position of the amino group and is useful as a ligand of a metal complex. It is.

[Brief description of the drawings]

FIG. 1 shows the ¹ H nuclear magnetic resonance spectrum of the compound obtained in Example 1 of the present invention.

FIG. 2 shows a ¹³ C nuclear magnetic resonance spectrum of the compound obtained in Example 1 of the present invention.

FIG. 3 shows the results of the compound obtained in Example 1 of the present invention. Infrared absorption
The spectrum is shown.

FIG. 4 shows the ¹ H nuclear magnetic resonance spectrum of the compound obtained in Example 2 of the present invention.

FIG. 5 shows a ¹³ C nuclear magnetic resonance spectrum of the compound obtained in Example 2 of the present invention.

FIG. 6 shows the results of the compound obtained in Example 2 of the present invention. Infrared absorption
The spectrum is shown.

Claims (2)

[Claims] [Claim 1] The following general formula (1) (Wherein, R and R ¹ may be the same or different from each other, each represents a hydrogen atom, a methyl group, an ethyl group, selected from n- propyl group and a phenyl group. Or, R and R ¹ are fused two R ² , R ³ , and R ² may form a ring structure together with two adjacent carbon atoms.
⁴ may be the same or different, and each is selected from monovalent hydrocarbon groups having 1 to 10 carbon atoms. R ⁵ is hydrogen atom, R ² R ³ R ⁴ silicon-containing group or a monovalent hydrocarbon group having 1 to 10 carbon atoms represented by Si-. A) a silicon-containing α-diimine compound represented by the formula: 2. The silicon-containing α-diimine compound according to claim 1, wherein in formula (1), R and R ¹ are both hydrogen atoms.