JPS60188394A - Novel ferrocenophane compound - Google Patents

Abstract

NEW MATERIAL:The compound of formula. USE:An organic electro-conductive material. PREPARATION:For example, ferrocene is used as the starting material, and is made to react with a diazonium salt synthesized from 4-aminobenzoic acid to obtain 1-(4-alkoxycarbonylphenyl)ferrocene, which is made to react again with a diazonium salt synthesized from 4-amino-2,5-dimethoxybenzoic acid ester. The ester group of the resultant 1-(4-alkoxycarboniumphenyl)-1'-(4-alkoxycarbonyl-2,5- dimethoxyphenyl)ferrocene is reduced to hydroxymethyl with lithium aluminum hydride. The product is brominated with chlorotrimethylsilane and lithium bromide, and cyclized with butyl lithium. Finally, the methoxy group is cyclized to a quinone with boron tribromide and silver oxide.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to novel ferrocenophane compounds useful as organic conductive materials.

In recent years, charge transfer complexes such as TTF (tetrathiafulvalene)-TCNQ (tetracyanoquinodimethane) have been actively studied as conductive materials. However, a charge transfer type conductive material in which an acceptor and a donor exist within the same molecule has not yet been found. The present inventors conducted various studies on electrically conductive compounds in which an acceptor group and a donor group are in the same molecule, and arrived at the present invention.

That is, the present invention has the formula [1] This ferrocenophane compound can be produced, for example, by the following method.

That is, 1-(4-alkoxycarbonylphenyl)ferrocene is obtained by using ferrocene as a starting material and reacting it with a diazonium salt synthesized from 4-aminebenzoic acid ester. A diazonium salt synthesized from a benzoic acid ester is reacted to form 1-(4-alkoxycarbonylphenyl)-1'-(4-alkoxycarbonyl-2,5-dimethoxycarbonyl)ferrocene, and then the ester group is removed by 1,000 μm. . Reduced using aluminum hydride,
The compound of the present invention can be synthesized by converting the hydroxymethyl compound into a quinone by total oxidation of the chlorotri groups.

The ferrocenephan compound obtained in the present invention is an intramolecular charge transfer type compound that has both a quinone group as a π-electron accepting group (acceptor) and a ferrocene group as a π-electron donating group (donor) in the same molecule. It has high conductivity. In fact, the specific resistance value of the compound of the present invention was determined at room temperature and showed I x 105 Ωcmf. Because of these properties, this substance can be used as an organic semiconductor and an electromagnetic wave shielding agent. Furthermore, it is expected that compositions in which this substance is mixed and dispersed in other inorganic compounds, organic compounds, or polymeric compounds will have similar conductive properties, and overall, it is expected that compositions in which this substance is mixed and dispersed in other inorganic compounds, organic compounds, or polymeric compounds will have similar conductive properties, and overall, it is possible to It can be used for a wide range of purposes.

Hereinafter, the m IIJ present invention will be explained in further detail in Examples.

Example 1 Ferrocene 24y-(0.1 a mol) and 1150 ml of acetic acid were placed in a 3-day flask and dissolved with stirring at room temperature.

In another flask, add 200 ml of water and 15+++ A of concentrated sulfuric acid!
and methyl 4-aminobenzoate 13.6P (
0.09 mol) was added and heated to completely dissolve.

This was cooled, and 50ml of an aqueous solution containing 6.9ii1-(0.1 mol) of sodium nitrite was added dropwise at 2 to 4C.
, 3-diazonium salt solution was prepared.

This diazonium salt solution was added to the acetic acid solution of ferrocene, stirred at room temperature for 7 hours, and then allowed to stand overnight. After diluting 3 times with water, it was extracted with chloroform, thoroughly washed with water, aqueous sodium bicarbonate, and water to make it neutral, and then dehydrated and dried using anhydrous awn crystals.

After distilling off the solvent, column chromatography (silica gel-
(benzene); ([Purified. Recrystallized with n-hexane to obtain orange crystals 12f (yield: 42%). Melting point 127-128 U, I lit, NMR shows the desired product. This was confirmed.

Example 2 Ethyl 4-amino-2,5-dimethoxybenzoate 15
y-(0.07 mol) 'e 225 ml of water Vc Heat and dissolve in a solution to which 14 ml of concentrated sulfuric acid has been added to form a sulfate.
Sodium nitrite 5.3ψ (0,0'75
70 moles of an aqueous solution containing 70 moles of water were added dropwise. The resulting aqueous 4-diazonium salt solution was converted into Compound 19.2 synthesized in Example 1 above! Vinegar j'll contained in i' (0.06 mol)'
The mixture was immediately added to Solution 125 (1+l) under a nitrogen atmosphere. After stirring at room temperature for 10 hours, it was further left at room temperature overnight. Post-treatment and purification were carried out according to Example 1.

Dark red crystals 3.3P (yield: 10.4) were obtained with a melting point of 112-113C (7). The target substance was confirmed by TR, NMR, and mass spectra.

Example 3 Compound 10.4i91-( obtained by the method of Example 2)
0,019 mol) was dissolved in 300 ml of dry benzene. [l, lithium aluminum ramno1 hydride 1.8
Anhydrous ether 3Q in which y-(0,047 mol) was suspended
The mixture was added dropwise into Qm/ over 2 hours, and after the addition was completed, the mixture was further heated under reflux for 4 hours. Water was added to decompose unreacted lithium aluminum hydride, and the product was extracted with chloroform. The subsequent operations were carried out in the same manner as in Actual Flow Side 1, yielding 8.59 centimeters of orange crystals (yield: 98). Melting point 119-119
．． 5CoI R%NM 11. The target substance was confirmed by mass spectrometry.

Example 1 Anhydrous lithium bromide 5.717' (0.07
After dissolving 8.3% (0.77 mol) of chlorotrimethylsilane in 210 ml of total anhydrous acetonitrile over 5 minutes, 5.0 ml of the compound obtained in Example 3 was dissolved. (
0,011 mol) and stirred at 70-72C for 30 minutes. After cooling with ice water, ether was added, and the organic layer was washed twice with water and twice with a saturated aqueous solution of sodium bicarbonate, and then recrystallized from a benzene-hexane mixed solvent to give a solution with a melting point of 66-6.
3.57 (yield: 55%) of 8C yellow crystals were obtained. IR
,NMR,, elemental analysis confirmed that it was the target product.

Example 5 An anhydrous ether solution containing 1.0 g (0.13 mol) of metallic lithium flakes (r- added to 30 ml of anhydrous ether in a nitrogen stream, containing 9.2 P (0.168 mol) of butyl bromide) 15 ml was gradually added dropwise at -10 to -15C.

After dropping, the temperature was gradually raised to 5.0C over 3 hours. In another flask, 4.5 SL (0,008 mol) of the bromomethyl compound obtained by the method of Example 4 and 450 ml of anhydrous tetrahydrofuran were placed and cooled to -50 C under a nitrogen stream, and the above butyllithium solution was added thereto. The temperature rose gradually. After 1 hour, the temperature was at -35C, after 2 hours at -30tr, and after 4 hours at 15C, the temperature was cooled again, and 50ml of water was added dropwise with OC [7].After adding 70ml of 1N hydrochloric acid, the mixture was extracted with chloroform (7). The subsequent operations were carried out in accordance with Example 1, and the melting point was 210-211Cf7) red-orange crystals 0.
67 (yield: 19) was obtained. IR, NMII, elemental analysis confirmed that it was the target product.

-7= Example 6 Boron tribromide 2. o? Example 5
The compound obtained with 0.5 ? 50 ml of a dichloromethane solution of (0,0012 mol) was added dropwise over 30 minutes at -5 to OC. After the dropwise addition was completed, the temperature was gradually raised and the mixture was stirred at 20C for 1.5 hours. After confirming that all the raw materials have been consumed by thin layer chromatography (benzene solvent), cool again and O~
Water was added dropwise at 5C to decompose excess boron tribromide. Ether extraction was then performed, and the organic layer was washed with saturated brine, dried over anhydrous magnesium sulfate, and then the solvent was removed. Dissolve this in 70 ml of acetone and add 1.3P silver oxide (0005
2 mol) was added thereto, and the mixture was stirred at room temperature for 1 hour and then at 50C for 1 hour. After filtration of insoluble matter, the residue was purified by silica gel column chromatography (benzene solvent) and recrystallized from benzene to obtain dark green crystals of 0.254 (yield: 54). It had a melting point of 250 to 252C, -8=I RlNMR, and the measurement results of elemental analysis were as follows, and it was confirmed that it was a compound of the present invention.

IR (KBr): 1650.1640.1570 (quinone ring), 1600.15001850 (benzene ring),
3100.800 (ferrocene ring) cm-' NMR, (CD C7h, δ): 2.98-3.
22 (m.

4[(,-CH2-1,4,14(m,2H,Fc),
4.36 (m, 2H, Fc), 4.51 (m11H1F
C), 4.58 (m, IH, Fc), 4.83 (m.

IH, Fc), 5.56 (m, 1-H, Fc), 5.8
5 (s, 1 f(,Q), 6.22(s, IHlQ
), 6.77-7.11 (m, 4 H, Ph)p
pm (Fc stands for ferrocene ring, Q stands for quinone ring, and Ph stands for benzene ring.) Elemental analysis: Measured value C73,28, H4,74 calculated value
C73,]1, H4,60

Claims (1)

[Claims] (1) Formula [1] Ferrocenophane compound represented by