JP2560245B2 - Novel crown compound and method for producing the same - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel crown compound and a method for producing the same. More specifically, the present invention is capable of forming a strong complex with various cationic compounds, and is a novel catalyst that can be used for organic synthesis catalysts, metal ion trapping, separation, and separation of optical isomers. The present invention relates to a crown compound and a method for producing the same with high selectivity and high yield.

[0002]

2. Description of the Related Art Conventionally, crown compounds such as macrocyclic polyethers and macrocyclic polyesters can form a strong complex with various cationic compounds, and therefore, for example, catalysts for organic synthesis, trapping and separation of metal ions. It is known to be a compound that is useful in a wide range of industrial fields, such as in the separation of compounds and optical isomers, etc. ["Macrocyclic Polyether Syntheses
ether Syntheses) Springer-
Verlag (1982), "Journal of Synthetic Organic Chemistry"
Volume 47, June issue (1989)].

Such crown compounds have hitherto been known.
It is produced by condensation of an alkyl dihalide with a diol or condensation of a dicarboxylic acid chloride with a diol. However, these production methods generally give (1) a plurality of products having different ring members,
The yield of the target crown compound is low, (2) the reaction under highly diluted conditions is required, (3) an equivalent amount or more of base is required during condensation, and (4) a large amount of salt is by-produced. There were drawbacks such as.

[0004]

DISCLOSURE OF THE INVENTION The present invention has been made for the purpose of providing a novel crown compound suitable for a catalyst for organic synthesis and for capturing and separating metal ions and separating optical isomers. is there.

[0005]

[Means for Solving the Problems] The inventors of the present invention have conducted diligent research in order to develop a novel crown compound having more improved metal capturing and separating performances by containing various functional groups. As a result of repeating, a novel crown compound containing three aromatic six-membered rings can be obtained by trimerizing an aromatic six-membered ring-containing dialdehyde in the presence of a specific catalyst, and the aromatic compound of this compound. It was found that various functional groups can be introduced into the sex 6-membered ring by using a corresponding dialdehyde, and the present invention has been completed based on this finding.

That is, the present invention has the general formula

Embedded image (Wherein X is a carbon atom or a nitrogen atom having one hydrogen atom bonded thereto, n is 0 or 1), and a divalent aromatic 6-membered ring is contained and the aromatic 6-membered ring is a nucleus. The present invention provides a crown compound, which has a chemical structure in which at least three constituent units selected from substituted ones are cyclically linked.

Here, the aromatic six-membered ring means a carbocyclic ring or a nitrogen-containing heterocyclic ring in which π electrons are delocalized to form a stable six-membered ring, such as a benzene ring or a pyridine ring. Say. This novel crown compound is a novel process

Embedded image The aromatic 6-membered ring-containing dialdehyde represented by the formula (wherein X is the same as described above) or a dialdehyde in which the aromatic 6-membered ring is nuclear-substituted is used as a compound of a rare earth metal or a compound of Group 4A of the periodic table. It can be easily produced by performing a cyclization reaction in the presence.

Examples of the nuclear substituent of the general formula (II) include halogen atom such as fluorine atom, chlorine atom and bromine atom, alkyl group such as methyl group, ethyl group, propyl group and isopropyl group, methoxy group. Group, ethoxy group, propoxy group, alkoxy group such as butoxy group, methylthio group, ethylthio group, propylthio group, alkylthio group such as butylthio group, tertiary amino group such as dimethylamino group and diethylamino group. They can be attached to the aromatic or heterocyclic ring as 1 to 4 substituents. When two or more nuclear substituents are present, they may be the same or different from each other.

Therefore, examples of the raw material compound represented by the general formula (II) include isophthalaldehyde and 2-
Chloroisophthalaldehyde, 2-methoxyisophthalaldehyde, 2-dimethylaminoisophthalaldehyde, 2-methylthioisophthalaldehyde, 4,5-dichloroisophthalaldehyde, 2-methylisophthalaldehyde, 4-methylisophthalaldehyde, 5-methylisophthalaldehyde, 4 , 5-dimethylisophthalaldehyde, 4,5,6-trimethylisophthalaldehyde, 4-ethylisophthalaldehyde, 4,5-diethylisophthalaldehyde, 4-ethyl-5-propylisophthalaldehyde, 4-ethyl-6-butylisophthalaldehyde 4-methoxyisophthalaldehyde,
Isophthalaldehyde such as 4-ethoxyisophthalaldehyde, 5-propoxyisophthalaldehyde, 4-chloro-5-ethylisophthalaldehyde, 4-methyl-5-ethoxyisophthalaldehyde and its nuclear substitutes, 2,6-pyridinedialdehyde, 3 -Chloro-2
6-Pyridinedialdehyde, 4-chloro-2,6-pyridinedialdehyde, 3-chloro-4-methyl-2,6-
Pyridinedialdehyde, 3-methyl-5-ethoxy-
Examples thereof include 2,6-pyridinedialdehyde such as 2,6-pyridinedialdehyde and its nuclear substitution products.

The rare earth or Group 4A metal compound used in the present invention may have any structure, for example, the following general formula (III) LnR ¹ R ² R ³ (III) (in the formula, R ¹ is a hydrogen atom, a hydrocarbon group, an alkoxyl group or a silyl group, and R ² and R ³ are a hydrogen atom, a halogen atom, a hydrocarbon group, an alkoxyl group, a silyl group, an acyloxy group or a sulfonyloxy group, respectively. They may be the same or different, and Ln is any rare earth metal) or the general formula (IV) Ln′R ² R ³ (IV) (wherein R ² and R ³ have the same meanings as described above). , Ln ′ is any one of samarium, europium and ytterbium) or the general formula (V) MR ¹ R ² R ³ R ⁴ (V) (wherein R ¹ has the same meaning as described above, R ² , R ³ and R ⁴
Is a hydrogen atom, a halogen atom, a hydrocarbon group, an alkoxyl group, a silyl group, an acyloxy group or a sulfonyloxy group, which may be the same or different, and M is titanium, zirconium or hafnium. A) or a complex thereof is used. Note that these complexes may be adducts of neutral ligands such as tetrahydrofuran and diethyl ether.

The ligand R ¹ in this complex will be described more concretely. An alkyl group such as methyl, tert-butyl, neopentyl and bis (trimethylsilyl) methyl, an aralkyl group such as phenylmethyl and naphthylmethyl, vinyl and styryl. Alkenyl groups such as, alkynyl groups such as phenylethynyl, aryl groups such as phenyl and tolyl, alkoxy groups such as methoxy, tert-butoxy, isopropoxy, benzyloxy and acetylacetonato,
Examples thereof include silyl groups such as trimethylsilyl and triphenylsilyl, cyclopentadienyl-based ligands such as cyclopentadienyl, pentamethylcyclopentadienyl and indenyl. Further, these ligands may be further substituted with a substituent that does not inhibit the reaction.

Specific examples of the ligands R ³ , R ⁴ and R ⁵ include those listed for R ¹ , halogen atoms such as iodine and bromine, acyloxy groups such as acetoxy and benzoyloxy, and trifluoromethanesulfonyl. A sulfonyloxy group such as oxy and toluenesulfonyloxy can be mentioned. In addition, these ligands are
It may be further substituted with a substituent that does not inhibit the reaction.

More concrete examples of the complex used here are (C ₅ Me ₅ ) ₂ LnH and [(C ₅ Me ₅ ) ₂ LnH].
₂ , (C ₅ Me ₅ ) ₂ LnMe, (C ₅ Me ₅ ) ₂ Lnt-B
_{u, (C 5 Me 5)} 2 LnCH 2 t-Bu, (C 5 Me 5) 2
_{LnCH (SiMe 3) 2, (} C 5 Me 5) 2 LnCH 2 P
h, (C ₅ Me ₅ ) ₂ LnC≡CPh, (C ₅ Me ₅ ) ₂ Ln
_{Ph, (C 5 Me 5)} 2 LnCl, (C 5 Me 5) 2 LnOM
_{e, (C 5 Me 5)} 2 LnOCH 2 Ph, (C 5 Me 5) 2 L
nOt-Bu, (C ₅ Me ₅ ) ₂ LnSiMe ₃ , (C
_{5 H 5) 2 LnH, [} (C 5 H 5) 2 LnH] 2, (C 5 H 5) 2
LnMe, (C ₅ H ₅ ) ₂ Lnt-Bu, (C ₅ H ₅ ) ₂ Ln
CH ₂ t-Bu, (C ₅ H ₅ ) ₂ LnCH (SiMe ₃ ) ₂ ,
(C ₅ H ₅ ) ₂ LnCH ₂ Ph, (C ₅ H ₅ ) ₂ LnC≡CP
_{h, (C 5 H 5)} 2 LnPh, (C 5 H 5) 2 LnCl, (C
_{5 H 5) 2 LnOMe, (} C 5 H 5) 2 LnOCH 2 Ph,
(C ₅ H ₅ ) ₂ LnOt-Bu, Ln (OMe) ₃ , Ln
(Oiso-Pr) ₃ , Ln (OCH ₂ Ph) ₃ , (C ₅ M
_{e 5) 2 LnSiMe 3, (} C 5 H 5) 3 Ln, (C 5 Me 5)
₂ Ln ′, Me ₂ Si (C ₅ H ₄ ) ₂ Ln ′, Ln′I ₂ (T
HF) ₂ , (C ₅ Me ₅ ) ₂ MH ₂ , (C ₅ Me ₅ ) ₂ MM
_{e 2, (C 5 Me 5} ) 2 M (OCH 2 Ph) 2, (C 5 H 5) 2
_{MH 2, (C 5 H 5} ) 2 MMe 2, (C 5 H 5) 2 M (OCH 2
Ph) ₂ , (C ₅ H ₅ ) ₂ M (CH ₂ Ph) ₂ , [(CH ₃ )
C = CPh] ₄ M, M (Oiso-Pr) _{4 and the} like (provided that Ln, Ln ′ and M are the same as the above. T-B
u represents a tert-butyl group, Ph represents a phenyl group, iso-Pr represents an isopropyl group, and THF represents tetrahydrofuran. The reaction of the present invention is generally carried out at -30 ° C to 250 ° C, more preferably 20 ° C to 200 ° C.

In addition, a solvent is not always necessary in the reaction of the present invention, but it is also one of the advantageous embodiments of the present invention that the use of a solvent prevents an increase in viscosity as the reaction proceeds. Examples of the solvent used include aromatic compounds such as toluene, benzene and pyridine, ether compounds such as diethyl ether, tetrahydrofuran and dioxane, and aliphatic hydrocarbon compounds such as pentane, hexane and decane.

Further, in this reaction, the above metal compounds may be used alone or in combination of two or more kinds. The amount used may be a so-called catalyst amount,
Generally, it is 0.0 with respect to 1 mol of the raw material dialdehyde.
5 mol or less is sufficient.

The product of this reaction has a general formula depending on the manner of attachment of the groups connecting the aromatic rings.

Embedded image Or general formula

[Chemical 6] (X in the formula is the same as the above) and has two kinds of chemical structures. These can be easily purified by a usual method such as column chromatography, distillation and recrystallization to isolate each component. In this way,
The crown compound of the present invention represented by the general formula (I) can be efficiently obtained.

[0017]

INDUSTRIAL APPLICABILITY The crown compound of the present invention is a novel compound which has not been published in the literature, and is useful as a catalyst for organic synthesis, or as a separating material for capturing / separating metal ions and separating optical isomers. . Further, according to the method of the present invention, the crown compound does not need to be highly diluted and can be produced with high selectivity and in high yield under mild conditions without salt by-products. .

[0018]

The present invention will be described in more detail by way of examples, which should not be construed as limiting the invention thereto.

Example 1 A solution of 0.009 mmol of bis (pentamethylcyclopentadienyl) [bis (trimethylsilyl) methyl] lanthanum in 1.0 ml of benzene was added with 1.07 of isophthalaldehyde at 60 ° C. under a nitrogen atmosphere. The mmol was added and stirred for 7 days. Then, the solvent is distilled off,
Purification by column chromatography gave a crown compound [1] consisting of a trimer with a yield of 86%. The melting point of this crown compound [1] was 140 ° C. The analysis results are shown below.

High-resolution mass spectrometry: Calculated value 402.1098 Measured value 402.1136 IR (KBr): ν (C = O) 1707, 1717 cm
^{-1 11} H-NMR (CDCl ₃ ): δ5.43-5.46
_{(M, 6H, -CH 2 -} ), 7.26-8.80 (m, 1
2H, aromatic ring) ¹³ C-NMR (CDCl ₃ ): δ 66.01, 66.6
_{0,66.86 (-CH 2 -), 126.5-136} .
18 peaks (aromatic ring), 165.41, 165.5 in 7
1, 166.05 (CO) Elemental analysis: C ₂₄ H ₁₈ O ₆ calculated value C = 71.57, H =
4.51 measured value C = 71.58, H = 4.50

Example 2 A solution of 0.01 mmol of bis (pentamethylcyclopentadienyl) [bis (trimethylsilyl) methyl] neodymium in 1.0 ml of benzene was added to isophthalaldehyde 1.10 at 60 ° C. under a nitrogen atmosphere. The mmol was added and stirred for 7 days. Then, the same treatment as in Example 1 was carried out to obtain a crown compound [1] in a yield of 41%.

Example 3 To a solution of 0.01 mmol of samarium (II) iodide in 1.0 ml of tetrahydrofuran was added 1.04 mmol of isophthalaldehyde at 60 ° C. under a nitrogen atmosphere, and the mixture was stirred for 24 hours. Thereafter, by the same treatment as in Example 1, the yield of the crown compound [1] is 40%.
Obtained in%.

Example 4 To a solution prepared by dissolving 0.01 mmol of triisopropoxylanthanum in 1.0 ml of benzene was added 1.09 mmol of isophthalaldehyde at 60 ° C. under a nitrogen atmosphere, and the mixture was stirred for 24 hours. Then, the same treatment as in Example 1 was carried out to obtain a crown compound [1] in a yield of 41%.

Example 5 In place of 1.07 mmol of isophthalaldehyde in Example 1, 1.00 mmol of 4-butyl-2,6-pyrpyridineidinedialdehyde was used and treated in the same manner as in Example 1, The crown compound [2] consisting of a monomer could be obtained with a yield of 82%.

Claims (2)

(57) [Claims] 1. A compound of the general formula (Wherein X is a carbon atom or a nitrogen atom having one hydrogen atom bonded, and n is 0 or 1) and a divalent aromatic 6-membered ring-containing group and its aromatic 6-membered ring are A crown compound, which has a chemical structure in which three structural units selected from nuclear-substituted ones are cyclically linked. 2. A general formula: An aromatic six-membered ring-containing dialdehyde represented by the formula (wherein X is a carbon atom or a nitrogen atom having one hydrogen atom bonded) or a dialdehyde in which the aromatic six-membered ring is nuclear-substituted, The method for producing a crown compound according to claim 1, wherein the cyclization reaction is carried out in the presence of a compound of a rare earth metal or a metal of Group 4A of the periodic table.