JPH0267279A - Novel electron acceptor and electrically conductive charge-transfer complex containing same acceptor as ingredient - Google Patents

Abstract

NEW MATERIAL:A compound expressed by formula I (X is Cl or Br) or formula II. USE:Useful in synthesizing a charge-transfer complex having high conductivity as an electron acceptor in combination with a electron donor of other ingredient. The complex has remarkable high conductivity and is free from corrosive properties. PREPARATION:For example, a compound expressed by formula III is heated in a solvent in the presence of N-chlorocinnamic imide to give a compound expressed by formula IV. Then the compound expressed by formula IV is heated with tetracyanoethylene oxide in the presence of copper(II)chloride in a solvent to provide the compound expressed by formula I. The compound expressed by formula II is synthesized by reacting a compound expressed by formula V in the presence of N- chlorocinnamic imide in a solvent, reacting the resultant compound in the presence of a peroxide in a solvent and reacting the resultant compound expressed by formula VI with tetracyanoethylene oxide e.g. in the presence of copper(II)chloride. Furthermore, the compound expressed by formula I or formula II is preferably blended with the electron donor at a molar ratio of 1:1.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a novel compound that can serve as an electron acceptor and a highly conductive organic charge transfer complex containing the compound as one component.

(Prior Art) Organic highly conductive substances have been attracting particular attention in recent years because they have excellent advantages such as being lighter than metal materials such as copper and aluminum, and being non-corrosive.

Organic highly conductive materials are also superior to metal materials in that they can be manufactured from abundant organic resources.

Generally, organic substances have properties as electrical insulators, and it is best to form charge transfer complexes to impart conductivity to them. Various electron donors and electron acceptors have been synthesized so far. , these combinations have provided a number of new electrically conductive charge transfer complexes.

For example, the present inventors found that 5,5゛-bis-(dicyanomethylene)-5, represented by the following formula (A>),
5°-dihydro-2,2°-vitaophene was discovered, and the charge transfer complex of this with tetrathiafulvalene or tetrathiotetracene was 2.2X 10'''4 to 3.3X10
-45CIII-1 (J, Chem, Soc, Chem, Coim
un, , 1987.1816>.

(Problems to be Solved by the Invention) The present invention provides a novel electron acceptor in which the electron acceptor compound represented by the above formula (A) is further substituted with an electron-withdrawing group. The object is to provide a charge transfer complex with improved conductivity by combining an electron acceptor with a suitable electron donor.

(Means for Solving the Problems) The present invention provides a compound represented by the following formula (I) or (n) (wherein X represents a chlorine atom or a bromine atom), and the compound as an electron acceptor. It provides a conductive charge transfer complex derived from an electron donor as another component.

The compound of formula (I>) of the present invention can be synthesized by the following reaction formula.

(III) (IV) (V) (Vl) (IV) or (Vl) (I) (However, in the above formula, X represents a chlorine atom or a bromine atom) The above compound (III) was added to N-chlorosuccinic acid in a solvent. Compound (IV) is obtained by heating in the presence of imide. Moreover, compound (Vl) can be obtained by heating compound (V) in the presence of N-bromosuccinimide in a solvent.

Compound (IV) or (Vl') is heated in a solvent with tetracyanoethylene oxide in the presence or absence of cuprous chloride to obtain the target compound (I).

Moreover, compound (IV) or (vl) can also be synthesized by the following method.

(IV) (VI) (■) When thiophene is reacted with sulfuryl chloride in the presence of iron powder, 1q of compound (IV) is produced. Also, 2.2′ −
Compound (Vl) is obtained by reacting bithiophene with N-bromosuccinimide in the presence of a solvent.

The compound of formula (n) of the present invention can be synthesized by the following reaction formula.

(IX) (I[> (However, in the above formula, X represents a chlorine atom or a bromine atom) When the above compound (■) is reacted in the presence of N-chlorosuccinimide or N-70 mosuccinimide in a solvent, Compound (■) is obtained.Compound (IX) is obtained by reacting compound (■) in a solvent in the presence of peroxide.Next, this compound (IX) is reacted in a solvent in the presence of cuprous chloride. Alternatively, the target compound (n) can be obtained by reacting with tetracyanoethylene oxide in the absence of the compound.

The above compound of formula (I> or formula (I)) can be used as an electron acceptor and combined with other electron donors to synthesize a highly conductive charge transfer complex.

The charge transfer complex of the present invention is usually prepared in an organic solvent by the above formula (I
) or synthesized by mixing the compound of formula (II) and an electron donor. Examples of organic solvents include benzene, toluene, chlorobenzene, tetrahydrofuran, acetonitrile, and dichloromethane. In addition to the above method, it can also be synthesized by thoroughly mixing a considerable amount of the compound of formula (I> or formula (II)) and an electron donor in a mortar or the like without using an organic solvent.

Various types of electron donors can be used as the electron donor, but in the present invention, 2,2°, 5,5'-tetrathiafulvalene, 5,6,11,12-tetrathiotetracene, hexamethylenetetrathiaful A compound selected from valene, hexamethylenetetratellahfulvalene, tetraphenylbipyranylidene, N,N'-tetramethyl-〇-7enylenediamine, acenaphthene ditelluride and bisethylenedithiotetrathiafulvalene is highly It is preferable as an electron donor component that provides conductivity.

The complex of the present invention is preferably composed of the compound of formula (I) or formula (II) and the electron donor in a molar ratio of 1:1 or 1:2.

EXAMPLES The present invention will be specifically explained below with reference to Examples, but the present invention is not limited to these Examples.

(Examples) Example 1 Comparative Example 1 The compound of formula (I[I), i.e., 5.5'-dichloro-
235 mg of 2,2'-dithiophene and 2Ildl of acetic acid
and 4 Inl of chloroform were added thereto, 291 mo of N-chlorosuccinimide was added thereto, and the mixture was gently refluxed for 20 hours.

The reaction mixture was poured into water and extracted with chloroform, and the organic layer was washed with water, 5% sodium chloride water, and water in that order, dried over anhydrous magnesium sulfate, and concentrated. The obtained solid was passed through a silica gel column using hexane, then concentrated and recrystallized from hexane to obtain 116 m (1
849. The compound of formula (IV) 2.43 (J, tetracyanoethylene oxide 11.5
(1, cuprous chloride 5.5 alumina treated 1,3
- 130 d of dibromopropane was added and heated under reflux for 6 hours. The reaction solution was developed twice using dichloromethane using silica gel chromatography, and the red component of Rfo, 5 was collected and concentrated, and further recrystallized from acetonitrile to obtain the target compound, the above formula (I>compound (X=α) 880
mg was obtained.

Melting point 300℃ or higher IR (Br) νc8 2217cm-4M5
m/e 360 (M”) Elemental analysis HN Theoretical value (%) 46.53 0.55 15.5
1 Actual value (%) 46.55 0.57 15.
42 Cyclic Voltammetry Ey20.18. -0.06V (VS, ^I
IJ/A11l (1'.

0, 18 Bo3 NCe0 a , CH2Cl2
) A solution of 10 mg of the compound of formula (I) obtained above (X=α) dissolved in 3 Inl of acetonitrile and 2,2°,5,5″-tetrathiafulvalene (
A solution of 68 mg of TTF) dissolved in 5d of acetonitrile is mixed with a solution of 5d of acetonitrile, and the resulting precipitate is filtered to obtain a compound of formula (I>compound (
12 mg of a 1:1 (mol) complex of X=α) and TTF were obtained.

TTF 5, 6, 11.1 shown by the following chemical formula using the formula (I) compound (X = α) as an electron acceptor in the same manner as above.
2-tetrathiotetracene (TTT), hexamethylenetetraterrafulvalene (HMTTeF), tetraphenylbipyranylidene (TPBP), tetramethyl-p
A 1:1 (mol) complex was obtained using -7 enylene diamine (TMPDA) and acenaphthene dithyllide (80Te> as electron donors and the solvents shown in Table 1).

TPBP TMPDA TTT HMTTeF DTe Table 1 shows the physical properties of each charge transfer mirror obtained above.

As Comparative Example 1, the electrical conductivity of a complex (1:1 (mol)) obtained using the conventionally known compound of formula (A) as an electron acceptor and TTF and TTT as electron donors was
It is also shown in the table.

In Table 1, A and C of the synthesis solvents represent acetonitrile and monochlorobenzene, respectively. Further, the electrical conductivity was measured using the 4-point method using a compression-molded pellet.

Table 1 Example 2 Compound of formula (V), i.e. 3.3'-dibromo-2
Vinegar M5d and chloroform 5rnIl were added to 30 g of ,2'-bithiophene 1 and stirred at room temperature. 1.50 (l) of N-bromosuccinimide was added to this and heated under reflux for 5 hours. The reaction mixture was poured into water and extracted with chloroform, and the organic layer was extracted with water, 5% heavy water, and water in that order. After washing,
It was dried over anhydrous magnesium sulfate and concentrated. The obtained solid was recrystallized from chloroform-hexane to give the formula (Vl
) 1.57 g of compound was obtained.

25 d of anhydrous 1,3-dibromopropane was added to 679 mg of this compound and 1.63 g of tetracyanoethylene oxide, and after heating under reflux for 3 hours, 4 g of tetracyanoethylene oxide was added.
06 mg was added and the mixture was further heated under reflux for 1 hour. This was returned to room temperature, passed twice through a silica gel column using methylene chloride, the red band was fractionated, concentrated, and recrystallized from acetonitrile to obtain the target compound, the compound of formula (I) (X
=Br) 65m (J was obtained.

Melting point 300℃ or higher IR (N8") νCN 2224cm-1M5
m/e 450 (M+) Elemental analysis CHN Theoretical value (%) 37.34 0.44 12.4
5 Actual value (%) 37.30 0.43 12.
37 Cyclic Voltammetry Ey20.20.0.03V (vs, Aa
/A(lcf.

0, 18 Bo3 NCe04, Ct12(f'
2) Using the compound of formula (I> compound (X=Br) obtained above as an electron acceptor and using the electron donor and synthetic solvent shown in Table 1, the compound of formula (1) ( X=B
r) and electron donor in 1:1 (mol) or 1:2 (
mole) complex) is q.

Table 2 shows the physical properties of each charge transfer complex obtained.

Note that the synthesis solvents A and C in Table 2 are the same as in Table 1, and the complexes marked with * indicate that the ratio of electron acceptor to electron donor is 1:2 (mol). Also, the electron donor in Table 2)-I
MTTF (hexamethylenetetrathiafulvalene) is a compound represented by the chemical formula below.

Table 2 Example 3 Compound of formula (Vl), i.e. thienodiophene 87
1 fl of acetic acid and 5 II dl of chloroform were added to 1 mg, and the mixture was stirred at room temperature. 1.58 g of N-bromosuccinimide was added to this, and the mixture was heated at room temperature for 1 hour and at 50 to 60°C for 1 hour.
Stir for hours. Next, carbon disulfide was added until the precipitated solid was dissolved, and the mixture was washed with water, 5% sodium bicarbonate solution, and water in that order, dried over anhydrous magnesium sulfate, and concentrated. The above formula (■) compound (X
=Br) 1.36g was obtained.

177+ng of the above formula (■) compound (X=Br) was added to 15rIJ of methylene chloride! A solution of 216 mO of tochloroperbenzoic acid in 5 d of methylene chloride was added thereto, and the mixture was heated under reflux for 2 days. The reaction solution was poured into a concentrated aqueous sodium bisulfite solution, and then extracted with methylene chloride. The organic layer was washed with 5% sodium bisulfate water, water, dried, and concentrated. The obtained solid was developed on a silica gel column using methylene chloride, and a portion of RfO,7 was collected. The solvent was distilled off under reduced pressure to obtain 90 mg of the compound (IX) (X=Br).

5 mL of 1,2-dibromoethane was added to the above formula (IX) compound (X = Br> 89 mo and 63 mg of tetracyanoethylene oxide, and the mixture was heated under reflux for 2 days. Then, it was cooled to room temperature and developed on a silica gel column using methylene chloride. Then, the red part of Rfo, 15 was collected.

The solvent was distilled off under reduced pressure to obtain 5 mg of the target compound, the compound of formula (II).

Melting point: 300°C or higher IR (Br) 1. IcN 2222Cnl”M
S m/e 354 (M+) Elemental analysis HN Theoretical value (%) 47.43 0.56 15.8
1 Actual value (%) 47.51 0.55 15.
79 Cyclic Voltammetry E% 0.28. -0.05V (vs, A
g/＾aC1゜0.1HBo3 NciPo 4,
CH2Cl2) Using the compound of formula (II) obtained above as an electron acceptor, the reaction between the compound of formula (II) and the electron donor was carried out in the same manner as in Example 1 using the electron donor and synthetic solvent shown in Table 3. 1:1 (mol) or 1:2 (mol) complexes were obtained.

Table 3 shows the physical properties of each charge transfer complex subjected to iFi.

In Table 3, synthetic solvents 8 and C are the same as in Table 1, and complexes marked with * indicate that the ratio of electron acceptor to electron donor is 1:2 (mol).

Table 1 (Effects of the Invention) The compound of formula (I> or (II)) of the present invention and the charge transfer complex using this compound as an electron acceptor are all new substances, and the above compounds are conventionally known as electron acceptors. Since the basic skeleton of the compound is substituted with a specific electron-withdrawing group, the mirror body obtained from this structure is characterized by significantly higher conductivity than conventional mirror bodies.

Claims (4)

[Claims] (1) Formula (I) or (II) below ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (I) (X in formula (I) represents a chlorine atom or bromine atom) ▲ There are mathematical formulas, chemical formulas, tables, etc. A compound represented by ▼(II). (2) A conductive charge transfer complex derived from a compound represented by formula (I) or (II) of claim 1 as an electron acceptor and an electron donor as another component. (3) The electron donor is 2,2',5,5'-tetrathiafulvalene, 5,6,11,12-tetrathiotetracene, hexamethylenetetrathiafulvalene, hexamethylenetetraterrafulvalene, tetraphenyl bi Claim 2 which is a compound selected from pyranylidene, N,N'-tetramethyl-p-phenylenediamine, acenaphthene ditelluride and bisethylene dithiotetrathiafulvalene.
The electrically conductive charge transfer complexes described. (4) The molar ratio of electron acceptor and electron donor is 1:1 to 2
The conductive charge transfer complex according to claim 2 or 3.