JPH013158A - N,N'-bicyano-p-benzoquinone bisimine, charge transfer complex compound containing same and radical ion salt thereof - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed Description of the Invention] According to West German Patent Application No. 3437814, N
, ``-bicyano-p-benzoquinone bisimine, its production method, and charge transfer complex compounds derived from this compound and tetrathia/tetraselenafulvalene compounds are known.

Radical ionic salts from tetracyanoquinone dimethane and copper or silver are also known C Appl.

Phys, Let, t, 34 (I979), 4
05; J, Amer.

Chem, Sac, 102 (I980), 365
9; Chem.

61 5 kripta 17 (I981), 219].

Furthermore, in the specification of West German Patent Application Publication No. 206266, N,
Radical ionic salts based on t-bicyanobenzoquinone bisimine are described.

The object of the present invention was to provide new N,N'-bicyano-p-benzoquinone bisimines whose charge transfer complex compounds or radical ionic salts have excellent properties.

The present invention solves this problem, and provides - mathematical formula (in which R1
is a 1- or 2-propyl group, C! l-C2゜-alkyl group, C3-C20-alkenyl group or iodine atom, R2,
R3 and R4 are independently hydrogen atom, chlorine atom, bromine atom, iodine atom, fluorine atom, phenyl group,
01-C20-alkyl group, C3-C20-alkenyl group or 01-C8-alkoxy group).

The present invention further provides a biscyanoimine represented by the formula and a fulvalene compound represented by the formula R7R8 (in these formulas, R1 is 1).
- or 2-propyl group, 05-C20-alkyl group, C
3-C20-alkenyl group or iodine atom, R2, R3 and R4 are independently hydrogen atom, chlorine atom, bromine atom, iodine atom, fluorine atom, phenyl group, 01-
C20-alkyl group, 03-C20-alkenyl group or C1-C8-alkoxy group, R6, R6, R7 and R8
independently represent a hydrogen atom, a methyl group or an ethyl group, or Rli and R6, R7 and R
8, or R5 and R7 or R6 and R8 may together form a residue of the formula (I): (■)
The molar ratio of is 1=1.2:1.6:2.1:2 or 2:3
It is a charge transfer complex compound.

The present invention further provides bicyanobenzoquinone bisimine (
I), especially radical ionic salts derived from the formula - (wherein R1 is a 1- or 2-propyl group, C6-C20-
Alkyl group, C3-C20-alkenyl group or iodine atom, R2, R3 and R4 are independently hydrogen atom, chlorine atom, bromine atom, iodine atom, fluorine atom, phenyl group, 01-C20-alkyl group, C3 ~C20-alkenyl group or C1-C8-alkoxy group, Mm■ is m
-valent alkali metal, alkaline earth metal, transition metal, ammonium or phosphonium ion, k is 1
~Number of Otsu, 1 is the number of 1 to Otsu, m is the number of 1 or 2, n is 1
~The number of Otsu, 2 means the number of 0 to 2, k, l, n and 2
Possible values for also include fractions, and (I+z)
=n*m).

Charge transfer complex compounds and radical ionic salts (III) from biscyanobenzoquinone bisimine (I) and fulvalene CI+) have significantly better properties in use than known charge transfer complex compounds and radical ionic salts.

In bicyanoimine (I), in addition to the above-mentioned groups, R1 includes the following groups as individual examples.

C6-C20-Alkyl, such as n-pentyl, 2-pentyl, 3-pentyl, 6-methyl-1-butyl and -
2-butyl, n-hexyl, isohexyl, heftyl,
Octyl, 2-ethylhexy/L/.

Nonyl, decyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, octadecyl and eicosyl. C3-C20-alkenyl, e.g. allyl, 2
-buten-1-yl and oleyl.

R2, R3 and R4 are hydrogen atoms, chlorine atoms, bromine atoms,
In addition to iodine atoms, fluorine atoms, and phenyl groups, the following groups may be used individually. As 01-C20-alkyl,
For example, methyl, ethyl, n- or 1-propyl, butyl, 1-butyl, tertiary butyl and the alkyls mentioned for R1, C9-C20-alkenyls such as the alkenyls mentioned for R', and C5-C8 -Alkoxy is, for example, nodoxy, ethoxy, 1-propoxy, n- or 1-butoxy, pentoxy, hexoxy, heptoxy, octoxy and 2-ethylhexoxy.

Bicyanoimine (T) in which R2 and R4, or R3 and R4, or R2, R3, and R4 are each a hydrogen atom
is preferred, and a compound (■) in which R2 and R4 are each a hydrogen atom is particularly preferred. Furthermore, biscyanoimine in which R1 is an iodine atom is particularly preferred.

Viscyanoimin (■) is a West German patent application published in 6437.
The method described in No. 814, particularly the method described therein (b
) to convert the quinone of formula QV) to formula (V) in the presence of a catalyst.
is produced by reacting with bistrimethylsilylcarbodiimite.

In the reaction between QV) and (V), 2 or more moles of (V) are used per 1 mole of QV). Preferably the reaction is carried out in an inert organic solvent such as dichloromethane, chloroform, 1
, 1,1-trichloroethane, 1,2-dichloroethane or acetonitrile in the presence of a catalyst.

Examples of suitable catalysts are cesium fluoride, potassium cyanide 7
Crown ethers such as 18-crown-6 or titanium tetrachloride, of which titanium tetrachloride is preferred.

Manufactured by the method described. That is, the hydroquinone compound is oxidized, preferably with chromic acid/sulfuric acid, in an acetone/ether mixture (duration 1-2 hours, yield >90% of theory).

The hydroquinone required for the production of 2-promo-5-dodecyl-p-benzoquinone is available from Chem.

Pb, arm, Bu, ll, 20 (I972), 1
968 by brominating 2-dodecyl-1,4-dimethoxybenzole.

2-hexyl-p-benzoquinone was published in the Journal of
American Chemical Society Volume 87 (I965)
, page 4585.

As the second component for the charge transfer complex compound from A fulvalene compound of formula H in which one of R8 is a hydrogen atom and the other is a methyl group is preferred.

R5 and R6, R7 and R8 together form the following formula
A fullvalene derivative (U) forming a residue of ゛ is also preferred.

= 14 - Fullvalene derivative (II) which is S is preferred.

In the charge transfer complex compound, the ratio of (I):(IT) may be 1:1.2:1.6:2.1:2 or 2:6 molar.

In order to produce the charge transfer complex compound of the present invention, the formula (I
) is reacted with fulvalene of formula (II) in the molar ratios mentioned above in a solvent with or without heating. Examples of suitable solvents are dichloromethane, chloroform, 11L1-trichloroethane, acetonitrile, penzole, toluo-)L', chlorobenzole and dichloropenzole.

Charge transfer complex compounds are usually isolated by suction filtration. The R1, R2, R3 and R4 may each be substituted as described for (I).

Among the radical ionic salts CIII), those in which R2 and R4, or R3 and R4, or R2, R3, and R4 are each a hydrogen atom are preferred. Particularly preferred is a radical ionic salt (III) in which R2 and R4 are each a hydrogen atom. In addition, compounds Qll) in which R1 is an iodine atom are also preferred. Radical ionic salts of formula (I) in which 'R2=R'=H and z=0 are particularly excellent.

Suitable Mm(f3) is an ion of a metal whose redox potential is lower than that of silver, and an ammonium ion and a phosphonium ion.

Preferred ions of alkali metals are lithium, sodium,
Ions of potassium, rubidium and cesium; preferred ions of alkaline earth metals are calcium, strontium and barium; preferred ions of transition metals are, for example, chromium, manganese, iron, cobalt, nickel, copper,
ions of zinc, silver, cadmium, mercury, tin, lead and thallium.

Examples of suitable ammoniums are:

C3-C4-TeI-raalkylammonium, tetraphenyl-C1-C3-alkylammonium, phenyl-C1-C3-alkyl-tris-C1-C4-alkylammonium, 01-C4-alkylpyridinium,
N-phenyl-01-c3-alkylpyridinium, quinolinium, N-C, ~C4-7/L/kylquinolinium, N-phenyl-C3-C3-alkylquinolinium and corresponding inquinolinium compounds. Suitable phosphonium ions are especially those derived from triphenyl compounds.

Specific examples of Mme are as follows. L12, Na(!
l), ■ ■ Φ 2■ 2@OO
Ω 2■, Rb, Cs, Mg, Ca,
Ba, Sr, Cr, Mn.

2■ θ θ OΦ 2Φ 2Φ
■Fe, Fe, Co, Nl, Cu, Cu
, ,Zn, ,Ag.

. ♂■, H-1♂, mlΦ, pb'■, 7□■, Tlo
o, triphenylmethylphosphonium, tetramethylammonium, tetraethylammonium, tetrapropylammonium, tetrabutylammonium, tetrabenzylammonium, tetra(2-phenylethyl)ammonium, trimethylbenzylammonium, triethylbenzylammonium, pyridinium, N-methyl- and N-ethylpyridinium, N-methyl-2-methylpyridinium, N-methyl-3-methylpyridinium, N-methyl-4-methylpyridinium, N-benzylpyridinium, quinolinium, N-methyl-1N-ethyl- and N- Benzylquinolinium.

Preferred Mm0 ions are as follows. Lithium, sodium, potassium, rubidium, cesium, copper(I)
and ions of silver(I), tetramethylammonium, tetraethylammonium, tetrabenzylammonium, trimethylbenzylammonium, triethylbenzylammonium, quinolinium, pyridinium, N-methylpyridinium, N-methylquinolinium and N-ethylquinolinium. Especially copper (I), silver (■),
The ions of pyridinium, N-methylpyridinium, quinolinium and N-methylquinolinium are preferred.

The complex compound and salt (III) of the present invention exhibit electrical conductivity in a crystalline state. Many compounds (I) are thermally stable at temperatures of about 300°C or higher. The new complex compounds can therefore be used as electrical semiconductors and photoconductors, for example in the antistatic finishing of synthetic resins, as electrodes and storage materials in batteries, in the production of solar cells, in fuel cells, in the conversion of radiation or in electronic Suitable for use in equipment manufacturing. Microcrystalline films made with the radical ionic salts of the present invention can be used in the production of bistable electrical switching elements.

The radical ion salt (@) of the present invention can be produced by various methods. In one method, the following formula (R", R2, R3
and R4 have the meanings given above), optionally heated in a solvent with a halide, preferably iodide, of said cation Mme in a molar ratio of 6:1 to 1:6. and react. As a solvent,
For example, dichloromethane, chloroform, 1,1,1-trichloroethane, acetonitrile, penzole, doluol, chlorbenzole or dichlorpenzole are used. Radical ionic salts are usually separated by suction filtration.

In addition, the radical ionic salt (III) of the present invention has the formula I
N,I-dicyanoquinone diimine and the cation (
It can also be produced by electrolyzing a solution containing a salt of Mm(El 2 ) in the solvent, optionally at a low temperature.

The radical ion salt is separated by suction filtration using a conventional method.

Another method for producing radical ion salt (III) is E
It is described in the specification PA 206266.

The production of microcrystalline films of the radical ionic salts of the invention is carried out in a customary manner by immersing the metal body in a solution of the N2 idicyanoquinone imine in the aforementioned solvent, preferably at elevated temperature.

The yields (%) in the following examples are based on theoretical values. Electrical conductivity was measured on powder presses or single crystals.

1, N,N'-bicyano-p-benzoquinone bisimine (I) Example 1 2-dodecyl-N,■-dicyano 1,4-benzoquinone diimine (I,1) The reaction was carried out in an externally heated flask. Perform in a dry nitrogen atmosphere. TiCl4 in ml pure anhydrous dichloromethane ID
1.90 ji (I D mmol) was charged first, and 0
Bistrimethylsilylcarbodiimide 1.86,9 at °C
(I0 mmol) is added dropwise. Then dichloromethane 6
2-dodecyl-p-benzoquinone 553m9 in ml
A solution of (2 mmol) was gradually added dropwise at 0°C, and after completion of the addition, the mixture was stirred at room temperature for 24 hours.

The reaction mixture was poured onto ice, extracted with dichloromethane,
It is dried over MgSo, filtered and concentrated by evaporation.

The concentrated dichloromethane solution was dissolved in silica gel (0,063
Add 6 vtl of methylcyclohexane to the clear solution F and evaporate until crystallization begins. Filter and dry under vacuum (20 mm Hg). 1.
Yield of 1 380 mg (59%), melting point 97-98°C.

IR (KBr) 2160cm-' Elemental analysis: C20H28N4 (324,5)CHN Calculated value range 1 74.03 8.7 [] 1y, 27 Actual value (%) 74.35 8.97 17.14 Examples 2 to 8 Compounds of the following formula (I)N\,N shown in Table 1 are prepared in the same manner as in Example 1.

R'=H 21-c3u: HCH31207421703A
11yl AILyl H691421704A
11yl HA11yl 90 60
21755 I HCH31
627921706I HH121452
1757I HBr 226
72 2170a I
HI 233 42 214
0 Example 9 Pure anhydrous dichloromethane 50ml! titanium tetrachloride 8,1
0 g (43,0 mmol) of bistrimethylsilylcarbodiimide 7,959 (42,7 mmol) was added at 0 °C.
mol) is gradually added dropwise. 3.08 g (8.54 mmol) of 2-octadecyl-1,4-benzoquinone in 50 ml of dichloromethane are added slowly to the mixture obtained and stirred for 48 hours at room temperature.

According to the thin layer chromatogram (silica gel, eluent dichloromethane/petroleum ether 4:1 by volume), the reaction is complete. The mixture is poured into ice water, extracted with dichloromethane and the extract is dried over magnesium sulfate. The evaporated and concentrated extract is filtered through silica gel, and 5 ml of methylcyclohexane is added to the filtrate. Dichloromethane is distilled off from the mixture until crystallization begins. Recrystallization from methylcyclohexane ('16 ml for 791 rv of crude product) gives 1.1.2 as a fine yellow precipitate with a melting point of 102° C. 6621n9 (20% of theory).

Elemental analysis: 026H4°N4(409)CHN Calculated value (%) 76.42 9.87 13.71
Actual value (%) 76.05 9.93 13.68I
R (KBr) Niji = 3050cm' (CH), 29
20 (cH), 2850 (CH), 2175 (C'3N
), 1575 (C=C), 1545 (C=N) uv (CH3CN): Cho ax (Igε) = 33
4 nm (4,44) 23 One Example 1O N,N'-dicyano-2-bromo-5-octadecyl-
1,4-quinonediimine (I,3) Titanium tetrachloride in 20 ml of pure 2-dichloromethane: y
5.31 g of bistrimethylsilylcarbodiimide (28
, 5 mmol) was gradually added dropwise, followed by dichloromethane 4
2.51 g (5.70 mmol) of 2-bromo-5-octadecyl-1,4-benzoquinone in 0 ml are added over 45 minutes. The reaction mixture is heated to room temperature and stirred for 48 hours. Thereafter, finishing treatment was carried out in the same manner as in Example 9, the silica gel effluent was evaporated and concentrated until crystals precipitated, 400 ml of petroleum ether was gradually added, and the precipitate was collected at -25°C. 1.52 g of 1.3 as an analytically pure orange solid
(55% of the theoretical value) is obtained. Melting point: 125°C (decomposed).

Elemental analysis: C26H3C26H3 (488) CHN Calculated value (%J 64.05 8.05 11.49 Actual value (%J 63.76 8.06 11.57 Engineering R (KBr) Niji = 304 []]c7n-' (CH
), 2910 (cH), 2840 (CH), 2165 (
C3N), 1560 (c=c), 1545 (C=N) Uv (CH2C12): λmax (""ε) = 355
nm (4,51), 670 (4,41) sh Example 11 N, “-dicyano-2-dodecyl-1,4-quinone diimine (I,4) In the same manner as in Example 9, in 10 ml of pure dichloromethane Titanium tetrachloride: / 1.909 (I O, Om mo/I
) was charged first, and 1.86 g (I0.0 mmol) of bistrimethylsilylcarbodiimide was added to 60 g of bistrimethylsilylcarbodiimide at 0°C.
00 mmol) is added over 60 minutes and the reaction mixture is stirred at room temperature for 24 hours and then worked up as in Example 9. 1.4 is obtained as a fine yellow precipitate with a melting point of 98° C., 680 μm (59% of theory).

Elemental analysis' C20H28N4 (325) CHN Calculated value (%) 74.03 8.70 17.27 Actual value (%) 74.35 8.97 '17.14
IR(xBr) Niji=6045crn-' (CH)
, 210 (cn), 284, 0 (CH), 2160 (
c=N), 157° (c=c), 155o (a=N) UV (CH8CN):λmaX (Igε)=33
4nm (4,44) Example 12 N,cardicyano-2-dodecyl-5-methyl-1,4
-Quinonediimine (T, 5) Proceed as in Example 9, titanium tetrachloride 11.0. 10.49 (56.0 mmol) of bistrimethylsilylcarbodiimide is added to p (58.0 mmol) at 0° C. over 60 minutes. Then, the 2-dob compound in 27 ml of dichloromethane was gradually warmed to room temperature, and 48 ml of dichloromethane was added.
After stirring for a period of time, finishing treatment is carried out in the same manner as in Example 9.

2. The target substance is orange-yellow needle-like crystals with a decomposition point of 114°C.
06 g (76% of theory) are obtained.

Elemental analysis' C2 + HsN4 (339) CHN Calculated value (%) 74.51 8.9316.55 Actual value (%) 74.68 9.20 16.48 Engineering R (KBr) Niji = 3045 crn' (CH), 29
18(CH), 2845(CH), 2185.2172
(C'miN), 1585 (c=c), 1545 (C=N
) UV(CH3CN):λmax(Igε)=344n
m (4,41) Example 16 2-bromo-N,N'-dicyano-5-dodecyl-1
,4-quinonediimine (I,6) In the same manner as in Example 9, pure dichloromethane 6'Oml
71 tofj (58,0111 mol) of tita tetrachloride in the solution, 10.6 of bistrimethylsilylcarbodiimide
g (57.0 mmol) are added at 0°C.

At the same temperature, 2.90 ml of 2-bromo-5-dodecylquinone in 32 ml of dichloromethane! 9 (8,20m
4 mol) was added dropwise and the reaction mixture was warmed to room temperature.
Stir for 8 hours. The finishing treatment is then carried out in the same manner as in Example 1o. The product was precipitated with 200 ml of petroleum ether, -2
Complete precipitation at 5°C. 2.29 g (70% of W theoretical value) of the target substance was obtained as an orange precipitate with a melting point of 115°C.

Elemental analysis: C2oH27BrN, (403)CHN Calculated value (%) 59.55 6.75 13.89
Actual value%) 60.07 721 13.67IR
(KBr) Niji=303[]cm” (CH), 291
5 (CH), 2842 (CH), 2165 (C3N)
, 1555 (C2C), 1545 (cN) UV (CH3CN): (I, gε) = 348 nm
(4,47) Example 14 N,N'-dicyano-2-hexyl-1,4-quinonediimine (C7) In the same manner as in Example 9, first 15 ml of pure dichloromethane
Prepare 1.90 g (I0.0 mmol) of titanium tetrachloride, and add 1.8 g of bistrimethylsilylcarbodiimide to this.
6 g (0.0 mmol of I) are added dropwise at 0° C. over 20 minutes. The orange solution was dissolved in 5 ml of dichloromethane at 0°C.
Hexyl-1,4-penzoginone 385 m? (2,
OOmmol). The resulting solution is then warmed to room temperature and stirred for 24 hours. Thereafter, the finishing treatment was carried out in the same manner as in Example 9, and the crude product was recrystallized from 3 ml of methylcyclohexane at 75°C. 336 mg (70% of the theoretical value) of the target substance was obtained in the form of a pale yellow precipitate with a melting point of 85°G. )can get.

Elemental analysis' Cl4H16N4 (240) CHN Calculated value (%) 69.97 6.71 25.61 Actual value) 69.41 6.72 23.42IR
(KBr): ν=3045c1rL-' (CH)
, 2920 (CH), 2850 (CH), 2160 (
C King N), 157D (c=c), 1545 (C=N) uv (CH3CN): Cho ax (Gε) = 334
nm (4,44)・Example 15 N,N'-dicyano-2-hexyl-5-methyl-1,
4-Quinonediimine Working as in Example 9, tita tetrachloride 712. Og (65,0 mmol),
Bistrimethylsilylcarbodiimide 11.4 at 0°C
g (61.2 mmol) are added dropwise.

A solution of 2.50.9 (I2, 1 mmol) of 2-hexyl-5-methyl-1,4-benzoquinone is then added slowly and the reaction mixture is stirred at room temperature for 24 hours. After work-up, 2.51 g (82% of theory) of the target substance are obtained as analytically pure orange needles with a decomposition point of 98° C.

Elemental analysis' C15HI8N4 (254) CHN Calculated value (%) 70,84 7.13 22.0
3 Actual measurement value (%) 7[1,447,2521,65I
R (KBr) Niji = 3040cm' (CH), 292
0 (CH), 2850 (CH), 217o (c N),
1580 (C=C), 1540 (C=N) uv (CH3CN) :λmax (・1gε)=3
46 nm (4,48) Example 16 N, “-dicyano-2-bromo-5-hexyl-1,4
-Quinonediimine (I,8) In the same manner as in Example 9, first 5.50 g of titanium tetrachloride was added.
(29.0 mmol) was added to 15 ml of pure dichloromethane, and 5.31.9 mmol of bistrimethylsilylcarbodiimide was added to 15 ml of pure dichloromethane.
(28.5 mmol) is slowly added dropwise at 0°C. Then 1.55 g (5.70 mmol) of 2-bromo-5-hexyl-1,4-benzoquinone in 20 ml of dichloromethane
was added dropwise and the reaction mixture was stirred for 24 hours, followed by finishing treatment in the same manner as in Example 9. The target substance had a melting point of 114°C.
(decomposition) gives 1.37 g (75% of theory) of an analytically pure orange solid.

Elemental analysis: C,4H,5BrN4 (319)CHN Calculated value ((4) 52.6B 4.74 17.55
Actual value (%) 52.83 4.70 17.36
IR (KBr) Niji = 3 [130cm' (CH)
, 2915 (CH), 2840 (CH), 2162 (C
3N), 1555 (c=c), 1540 (C'=N) uv (CH3CN): Odor aX (Igε) = 35
0 nm (4,49), 368 (4,36), sh Example 17 N,t-dicyano-2,6-diprobyl-1,4-benzoquinone diimine (I,9) 2,3-dipropyl-1,4 -Benzoquinone 5957n
9 (3.10 mmol) was dissolved in 15 ml of pure dichloromethane, and 2.46 ml of titanium tetrachloride was added to the solution at 0°C. ? (I
3.0 mmol) and further dichloromethane 5 m
Bistrimethylsilylcarposi in l! 3.16 g (7.0 mmol I) of thiimide are added.

After stirring for 2 hours at room temperature (monitored by thin layer chromatography), the reaction mixture was poured into ice water, the mixture was extracted 6 times with 60 ml portions of dichloromethane, and the combined organic layers were extracted with Mg
Dry over SO2.

After removing the solvent, 50 ml of methylchlorohexane are added and the mixture is sonicated for 5 minutes at room temperature. The brown insoluble matter is filtered out and the solution is cooled to -78°C. 198 m9 (27% of theory) of orange crystals of 1.9 are obtained, which melt at 77°C and decompose at 125°C.

Elemental analysis: C14HI6N4 (236)CHN Calculated value ((6) 69.97 6.71 23.32 Actual value (%) 70°26 6.76 22.93IR (K
Br) Niji-3060crn-' (-〇-H), 29
70 (C-H), 2170 (C':N), 1560 (
C=C'), 1540 (C=N) UV (CH3CN) :λmax(Igε)=33
2nm (4,36), 343sb (4,33), 395
sb (3,73) Example 18 N,N'-dicyano-2,5-dipropyl-1,4-benzoquinone diimine (I,11) 2,5-zig-copyru 1 dissolved in pure dichloromethane'1Ornl , 4-benzoquinone 875■ (4,55
3.45 g of titanium tetrachloride (I8,2 mmol) at room temperature
3.39 mmol of bistrimethylsilylcarbodiimide & (I8,2
mmol) is added. After 8 hours (followed by thin layer chromatography).

The reaction mixture was poured into 200 m, l of ice water, the mixture was extracted three times with each IDD mJ of dichloromethane, the combined extracts were dried over magnesium sulfate, part of the solvent was removed, and petroleum ether was added. and precipitate. Methylcyclohexane (5 Q rnl for 750 m9 of crude product
), the target substance is obtained in crystalline form at ~730°C (67% of theory), which decomposes at 148°C.

Elemental analysis: C14HI6N4 (240)CHN Calculated value (%) 69.97 6. ．． 71 23.3
2N), 1580 (C=C), 1535 (C=N) uv
(CH3CN) :λmax(:1gε)=344n
m(4,44)■, Charge Transfer Complex Compound Example 19 In a hot solution of N, d-dicyano-2-improbyl-5-methyl-p-benzoquinone bisimine in acetonitrile, in the form of a hot solution in acetonitrile. equimolar amounts of tetrathiafulvalene are mixed. After suction filtration, washing with a small amount of ether, and drying, the donor:acceptor composition is 1=
A charge transfer complex compound of No. 1 is obtained.

Yield: 41% of theoretical value, melting point 104°C0 electrical conductivity (
Io7Sscfn' (powder press).

Example 20 Using 2 moles of bisimine and 6 moles of tetrathiafulvalene in the same manner as in Example 19, the donor:acceptor ratio was 2.
:6 charge transfer complex compound is obtained. Yield: Theoretical value of 3
7%, melting point 86°C0 electrical conductivity t OX 10-2S
-cfn-' (powder press).

Example 21 Analogously to Example 19, N,N'-dicyano-2-iobi-5-methyl-p-benzoquinone diimine is reacted with tetrathiafulvalene in a molar ratio of 1:1 in methylene chloride. Yield: 75% of theory (I:1 complex)
.

Melting point 144°C1 Electrical conductivity 3 x 10-2S -c
m-' (powder press).

Examples 22-24 Operate as in Example 19, except that N, N'-di'/
When the compounds shown in the following table are used as the 7/-p-benzoquinone diimine, the corresponding charge transfer complex compounds are obtained.

22 I HH1045+ 2100 1:1
3-1cr423 I HBr 127 5
5 2110 1:1 0.0224 I HI
192 65 2080 1:1 6・10″
1DCNQI = N, d-dicyano-p-benzoquinone imine compound TTF-tetrathiafulvalene Example 25 N, "-Reaction of dicyano-2,5-dipropyl-1,4-benzoquinone diimine and tetrathiafulvalene Niacetonitrile 5 rnl N inside, sojicyano-2,5-
Dipropyl-1,4-benzoquinone diimine 72.0■
(500 μmol) and a solution of 61.0 μmol (300 μmol) of tetrathiafulvalene in 3 ml of acetonitrile are mixed. The solution immediately turned green, and when cooled to -25°C, 90 mg of moss green crystals of the charge transfer complex were obtained.
(68% of theory) crystallizes. This compound has a molar ratio of 1:
1ON, Gordicyano-2,5-dipropyl-1,4-
It consists of benzoquinone diimine and tetrathiafulvalene and decomposes at 139°C.

Elemental analysis: C20H20N4S4 (444)CHN Calculated value (%) 54.02 4.53 12.60 Actual value) 54.08 4.56 12.96IR
(xBr) Rainbow=2155cm-' (C3N) uv
(CH3CN) :λmax (Igε)=362
sh(4,36), 343(4,47), 324nm(
4,47) Example 26 N, “-dicyano-2-bromo-5-dodecyl-1,4
- Reaction of quinonediimine with tetrathiafulvalene: In a vibrating reaction tube heated under reduced pressure, N,N' - To this are added at room temperature 50.0 to (250 μmol) of tetrathiafulvalene in 2 ml of dichloromethane. The solution turns black immediately. After 5 minutes, gradually cool the solution to 0°C.
After 1.5 hours, quickly remove the black solid. When dried on silica gel, the 1:1 charge transfer complex is present in the form of black needles with a melting point of 86°C (decomposed).
24 mg (86% of theory) are obtained, which gradually decomposes at room temperature.

Elemental analysis: C26H31BrN4S4 (608)C
HN Calculated value (%) 51.39 5.14 9.22 Actual value (51.54 5.60 9.58IR (KB
r): 2110cIn-' (CEN, broa
d) uv (CH3CN): odor ax (Lgε) = 3
48 nm (4,52), 365 (4,42) sh, 42
5 (3,60), 576 (3,23), 620 (3,3
8), 686 (3,41) Example 27 N, “-dicyano-2 to bromo-5-hexyl-1,4
-Reaction of quinonediimine and tetrathiafulvalene N in 2 ml of dichloromethane, ``-dicyano-2-bromo-5-hexyl-1,4-quinonediimine 96.0
1n9 (300 μmol) in dichloromethane'l at room temperature.
61.0 m9 of tetrathiafulvalene in ml (3D
When a solution of 0.08 mol) is added, a black precipitate immediately forms. After 5 minutes the mixture is cooled to 0° C. and the fine precipitate is filtered and washed dropwise with ether. Drying on silica gel gives 927119 (59% of theory) a 1:1 charge transfer complex with a melting point of 87° C. (decomposed).

Elemental analysis: C2(,H,,BrN484 (524)
CHN Calculated value (Piece 45.88 3.66 10.70 Actual value (Piece 45.64 3.69 10.44IR (K
Br) :2120cm-' (CEN, broad
) uv (CH3CN) :λ (Igε)=324
nm (4,37) ah, ax 349 (4,48), 364 (4,35) sh, '42
8 (3,61), 577 (6,26), 61B (3,3
4), 686 (3,35) mmol) is dissolved in acetonitrile and mixed with copper iodide (IN 33 mg (0,7+n mo#) at 55°G.

The dark precipitate is filtered off with suction and washed with acetonitrile. This salt does not contain halogens (negative Pylestein test).

Melting point: 96°C (decomposition), IR (KBr): 2147c
m-'(CEN).

Example 29 The procedure is as in Example 28, except that 2 moles of copper(I) iodide are used for 6 moles of N,N'-dicyano-2-isopropyl-5-methyl-p-benzoquinone diimine. . Yield: 25% of the theoretical value of the radical ion salt of the following formula.

Melting point 109℃, electrical conductivity near XID-2S-CIn'
(powder press).

Example 30 The procedure is as in Example 28, except that N,N'-dicyano-2-iobi-5-methyl-p-benzoquinone diimine and copper(I) iodide are used in a molar ratio of 2:1. yield:
The radical ion salt of the following formula is 88% of the theoretical value.

Melting point: 190°C, electrical conductivity: 20 os-Cm' (
single crystal).

Example 61 Production of a radical ion salt by electrolysis: Electrolysis is carried out in an a Oml electrolytic cell divided into 6 chambers by two 04 glass frits. Each gate can be filled or discharged under protective gas independently.

Place the electrodes in the outer electrolysis chamber. By dividing the chamber into three chambers, by-products generated on the anode are prevented from entering the cathode chamber.

The picture electrode consists of two platinum plates with a size of 20×10 10×1. Before use, the electrodes and electrolyzer are cleaned with a mixture of 65% hydrogen peroxide and concentrated sulfuric acid. After washing with water, the electrolytic cell 9. in distilled water
Leaving it in the sun will remove any remaining traces of acid.

The electrolytic cell is then dried at 120°C.

The current is supplied from a stable power supply whose output can vary between 0 and 250μ. By placing the electrolytic cell in a thermally stable bath, electrolysis can be carried out at a constant temperature.

To start the electrolysis, a solution of N,N'-dicyano-2-methyl-5-impropyl-1,4-benzoquinone diimine (6 mol) and acetonitrile 6
Silver nitrate (2 mol) in 0 ml is charged and a current to 3 μ is conducted at room temperature. A needle crystal with a length of 3 Crn is formed on the cathode. After 80 hours, a silver salt of the following formula is separated.

Melting point: 150℃ (decomposed), electrical conductivity: 4 x 10-2S
-cIn-1 (powder press).

During electrolysis, do not completely electrolyze the solution to avoid excessive reduction.

43 Example 62 Operate in the same manner as Example 31, except that N, merge cyanogen
2-iobi-5-methyl-p-benzoquinone diimine and silver nitrate are used in a 2:10 molar ratio.

Yield: following formula 32% radical ion salt.

Example 66 N,N'-dicyano-2,5-diglobyl-1,4-benzoquinone diimine reaction with copper(I) iodide N,N'-dicyano-2°5-dipropyl-1 in 5 rnl of niacetonitrile , 4-benzoquinone diimine 72■ (600
acetonitrile/l/3 ml in a boiling solution of
Add a solution of Cub 95m9 (500 μmol) in the solution. A black-blue precipitate forms immediately. After cooling, the precipitate is filtered. The yield of radical anion salt is 66 mg (43% of theory). This compound has a receptor/copper composition of 3:2 and decomposes at 155°C.

Elemental analysis: c42H48cu21'JI2 (848
)CHN Calculated value (%) 59.49 5.70' 19.8
2 Actual measurement value (59.91 5.97 19.28IR
(KBr): 2115 cm-' (C=N).

Example 64 Reaction of 2,5-diallyl-N,mercyano-1,4-benzoquinonediimine (2,5-DA-DCNQI) with copper(I) iodide 2,5-diallyl- N.

y-dicyano-1,4-benzoquinone diimine 71,0
m9 (300 μmol) of copper(I) iodide in 3 ml of acetonitrile/l/95.0 m at room temperature.
g (500 μmol) of solution is added. A brown precipitate forms immediately. After leaving it at -25°C for 12 hours,
The green, finely divided precipitate is filtered and dried on silica gel.

Yield: 78 μg of green powder that absorbs heat and melts at 267℃ (
75% of the theoretical value). Beilstein test is positive.

The isolated product is (2,5-DA, -DCNQI)+
-It has a composition of Cu5.

Elemental analysis: CCs+H+□1+ ・Cu,, ICHN
I Calculated value (%) 48.40 3.4B 16.13
9.13 Actual value (%) 4a, io 3.50
16.06 9.20IR(KBr): 30101
-'(C-H), 2890(C-H), 2180(CA
N), 1490 (CmN) Example 65 N, "Reaction of -dicyano-2-octadecyl-1,4-quinonediimine (C2) and copper(I) iodide 2N,N'-
Dicyano 2-octadecyl-1,4-quinone diimine 204 m? Copper(I) iodide (0.50 mmol) was dissolved in a mixture of 30 ml of acetonitrile and 12 ml of dichloromethane and 133 mmol of copper(I) iodide was dissolved in 7 ml of acetonitrile.
(700 amol) of degassed solution is added. The mixture quickly turns blue and a dark green precipitate forms. 75
After stirring for 10 minutes at 0.degree. C., the flask containing the solution is immersed in a sonication bath, and the mixture becomes a uniform blue-black color. The mixture is gradually cooled to room temperature, filtered and the precipitate is washed with 1 ml of acetonitrile.

When dried on silica gel, (I,2)·Cu(I:1
) is an amorphous solid with a melting point of 101°C (decomposition) at 265
mg (99% of theory).

Elemental analysis: C2aH4゜N4Cu (472)CHN Calculated value (%) 66.14 8.54 11.87 Actual value (death) 65.87 8.38 11.65IR (K
Br): ν=2920 Cm'(CH), 2850
(C'H), 2155 (C'N) Example 36 2-promo N, merged cyano 5-octadecyl-1
,4-quinonediimine (I,3) and copper(I) iodide: 2-bromo-N,N'-dicyano-5-octadefluor 114-ki/7diimine/(I,3) 244m9 (500
133 m9 of copper(I) iodide in 8 ml of pure acetonitrile was dissolved in 40 ml of boiling pure acetonitrile.
700 amol) of degassed solution are added. The reaction mixture quickly becomes dark and cloudy. This was stirred at boiling point for 10 minutes and then left to cool gradually. 0 after 1 hour
Cool to °C, separate the solids and wash with cold acetonitrile until the washings turn blue-green. When dried on silica gel, (C3)·Cu (s
: 263 mg (4) as an amorphous black-blue solid (
95% of theory) is obtained.

Elemental analysis: c133HI95Br5cu4”20 (
2692) CE (N calculated value) 58.01 7.30 10.41 Actual value (%) 5B, 39 7.45 10.33 Engineering R (K
Br): ν=2910Crn-'(CH), 284
0 (CH), 2150 (C3N) Example 67 162 mg (500 a mol) of N,N'-dicyano-2-dodecyl-1,4-quinonediimine (C4) was dissolved in 15 ml of hot acetonitrile, and 7 mL of acetonitrile was dissolved in this.
A solution of 163 to 0.70 mmol of copper(I) iodide in ml is added. A black-blue precipitate forms immediately. The reaction mixture is stirred at 60° C. for 10 minutes, then allowed to cool gradually, and the solids are filtered and washed with 3 ml of acetonitrile. (I,4)・Cu(I:1) is present as a purple-black amorphous precipitate with a melting point of 96°C (decomposition) at 115cm (59% of the theoretical value).
)can get.

Elemental analysis: CHH28CuN4 (388)CHN Calculated value (%) 61.91 7.27 14.44 Actual value (%) 61.92 7.53 14.49IR (K
Br) Niji = 2920 cm −' (CH), 285
0 (CH), 2j55 (C Xie) Example 68 2-bromo-N, ■-dicyano-5-dodecyl 1.4
-Reaction of quinone diimine (I,6) and copper (I) iodide: 2-promo N,N'-dicyano-5-dodecyl-1,
202 μmol (500 μmol) of 4-quinonediimine (IJ) was dissolved in 1:1 of acetonitrile and dichloromethane at room temperature.
1 mixture in 1 oml and heat the solution to 75°C.

This was added to 163m9 of copper(I) iodide in acetonitrile (
After 60 minutes of removal of 700 μmol), it is cooled to 0°C. Filter the solids and add 2 m chloromethane/acetonitrile.
When washed with l, (A,,6)-Cu (I: 1
) as an amorphous precipitate with a melting point of 125°C (decomposition).
(6% of the theoretical value of 8) is obtained.

Elemental analysis: C2oH27Br CuN, (467)
CHN Calculated value (e)l 5t45 5.83 7,2.00
Actual value (%) 51.74 /), 12 12.2
8IR(KBr): C=2915Crn-'(CH
), 2845 (CH), 2158 (C-N) Example 69 Reaction of N, cardicyano-2-hexyl-1,4-quinone diimine (I,7) and European copper (I): N, N'-
Dicyano-2-hexyl-1,4-quinonediimine (I
, 7) 1201 ng (500 μmol) are dissolved in 10 ml of acetonitrile and a degassed solution of 1337 V (700 μmol) of copper(I) iodide in 5 ml of acetonitrile/l is added at 55°C. A dark precipitate forms immediately. After 10 minutes, the mixture is slowly cooled to 0° C. and the blue-black precipitate is filtered and washed with 1 ml of acetonitrile. 73 mg (49%) of (C7).Cu (I:1) with a melting point of 88° C. (decomposed) is obtained as an amorphous precipitate.

Elemental analysis: C14H16CuN4 (304)CHN Calculated value (%) 55.34 5.31 18.44 Actual value (%) s4.6o 5.35 18. '26IR
(KBr): ν=2918 cm-' (CH), 2
850 (C'H), 214o (cmiN) Example 4O N, merged cyano-2-hexyl-5-methyl-1,4
-Reaction of quinone diimine (I,10) and copper (I) iodide: N, cardicyano-2-hexyl-5-methyl-1,4
-Quinone diimine (I, 10) 127m9 (500μ
Copper(I) iodide 2 in 16 rnl of acetonitrile is dissolved while boiling in 10 rnl of acetonitrile.
85 m9 (I, 50 mmol) are added. After 30 minutes, the solution is slowly cooled, and after 2 hours it is cooled to -25 DEG C., and the dark precipitate is filtered off, washed with 2 ml of acetonitrile, and then with 3 ml of ether until the washings are colorless. Melting point 7
(I,10) ・Cu(I:1) at 4°C (decomposition) is 7
2.0 m9 (45% of the theoretical value) is obtained.

Elemental analysis: C1,H,8N4Cu(318)CHN Calculated value ((6) 56.68 5.71 17.63 Actual value (%) 56.40 5.83 17.27IR
(KBr) Niji = 2920 Crn' (CH), 28
50 (CH), 2150 (C3N) Example 41 2-bromo-N, cordicyano-5-hexyl-1,4
-Quinonediimine (I,8) Reaction of copper(I) toiodide: 2-bromoN,111'-cyano5-hexyl-1,4-*N:ydiimine (I,8) 160 mg (5
00 μmol) in 30 ml of pure acetonitrile and 133 m of copper(I) iodide in 10 rnl of pure acetonitrile.
A solution of 9 (700 μmol) is added dropwise at 50°C. After 5 minutes, the solution was allowed to cool, and after a further 90 minutes, it was brought to 0°C, then to 12°C.
Cool to 5°C. The solid matter is filtered, washed with acetonitrile until the washings turn blue, and then dried. Melting point 87°
C (decomposition) (I,8)-cu (I: 1) is obtained as a reddish-purple amorphous solid in an amount of 165 μ (86% of theory).

Elemental analysis: C14HBBrCuN4 (313+)C
HN Calculated value (Wholesale 43.93 3.95 14.64 Actual value (%) 44.15 4.12 14.92IR (K
Br) : l'=291 [lCrn-' (CH
), 2840 (CH), 2150 (c=N) Examples 42 to 44 By operating in the same manner as in Example 41, N,N'-dicyano-1,4-quinone diimine of the following formula /CN N shown in the following table use. The isolated radical ion salt is iodine-free (negative by Beilstein test).

Example 45 Proceed as in Example 62, except that N, sodium cyano-
2-iobi 5-methyl-1,4-benzoquinone diimine and silver nitrate are used. A radical imine of the following formula having a melting point of 164° C. is obtained. IR(KBr) 21
70Crn"-'.

Example 46 N, cyano-2-iobi-5-methyl-1°4-
Electrolysis of benzoquinone diimine (I, 12) and copper bromide (It) N, sodicyano-2 in 60 ml of nitrile
-Yobi 5-methyl-1,4-benzokiffu decomposes (1 mm diameter platinum wire cathode, current density 18 7, 5
μAα-2). 10mm on the cathode after 49 hours! :
The black needles with a metallic luster precipitated at lengths are filtered off with suction, washed with acetonitrile and dried on silica gel. This compound has a ratio of 2:1 ON, Gordicyano-2
- Consisting of 5-methyl-1,4-benzoquinone diimine and copper.

Melting point: 190°C (decomposed), yield: 1 3. 0 m9 (13% of theoretical value).

Elemental analysis: c18Htocu 2N8 (656)C
H N Calculated value (%) 32.97 1.54 17.0
9 Actual value (%) 36, 66 1.41 17.12
IR (KBr): No strong absorption band Example 47 N,N'-dicyano-2-iobi-5-methyl-1.

4-penzoquinone diimine and N, eedicyano-2.

Electrolysis of 5-dimethyl-1,4-benzoquinonediimine in the presence of copper(H) bromide in niacetonitrile 60 m
N, Sodicyano-2-iodo-5-methyl-1 in 1
,4-benzoquinone diimine 59. 2m9C 2
00 nmol), N, sodicyano-2.5-dimethyl-1,4-benzoquinone diimine 37.8~(2
0 μA mol) and copper(II) bromide 6 6. 9 meters?
(300 μmol) solution is electrolyzed using a constant current of 50 μA. After 93 hours, the black needle crystals with a metallic luster and having a length of 1 om or less deposited on the cathode are suction filtered, washed with acetonitrile, and then dried on silica gel.

This compound has a ratio of 2:4:3 of N,N'-dicyano-2
,5-dimethyl-1,4-benzoquinonediimine, N
, N'-dicyano-2-iobi-5-methyl-1,4-
Consists of benzoquinone diimine and copper.

Melting point: 177°C (decomposed), yield: 2 5. 3 m9 (33% of theoretical value), electrical conductivity 200 S-cm-'
.

Elemental analysis'C56HsI]Cu3I4. N24 (
f 7 4 3) C H
N Calculated value (%) 38.58 2.08 19.2
8 Actual value (%+ 38.19 1.96 18.
86IR (KBr): No strong absorption band Example 48 N, "-dicyano-2-iobi-5-methyl-1.

Electrolysis of 4-benzoquinone diimine in the presence of lithium perchlorate Niacetonitrile 60 ml! N inside, ``-dicyano-2-
A solution of 106 mg (1,00 μmol) of 5-methyl-1,4-benzoquinone diimine and lithium perchlorate was incubated at −25 °C with a current of 10 μA.
Electrolyze for 6 hours (platinum plate cathode, 2,8 Crn2, current density 3,6 μAcrn-2). Black crystals with metallic luster are deposited on the cathode. The crystals are separated, washed with ether and dried on silica gel. This product has a ratio of 2:1 ON.

It consists of I-dicyano-2-iobi-5-methyl-1,4-benzoquinone diimine and lithium.

Yield 19.0Tv (62% of theory), melting point 156'C
(decomposition), electrical conductivity 7 X 1 0-23*Crn
'.

Elemental analysis: C+sH+oI2LiN6 (599)C
HN Calculated value (%) 36.09 1.68 18.70 Actual value (%) 36.45 1.68 19.011R (K
Br): 2150cnn-' (c=N) Example 49 N, "-dicyano-2-iobi-5-methyl-1°4-
Electrolysis of benzoquinone diimine in the presence of sodium perchlorate N, sodicyano-2-iobi-5-methyl-1,4-benzoquinone diimine 59 in 60 ml of niacetonitrile
．． A solution of 2 mg (200 R mol) and perchloric acid (126 μmol) (I, 00 μmol) was heated at -25°C for 50 min.
Electrolyze for 276 hours using a current of μA. Meanwhile, black crystals with a metallic luster are deposited on the cathode. The crystals are separated, washed with ether and dried on silica gel. The product consists of N,N'-dicyano-2-iobi-5-methyl-1,4-benzoquinone diimine and Na in a 2:1 ratio. Yield 18.2 m9 (theoretical value 29
%), melting point 137°C (decomposition), electrical conductivity 0.1S-
Crn-1° elemental analysis: CuH+o 12NaN8CHN Calculated value (%J 35.15 1.6418.22 Actual value ((6) 35.17 1.71 18.18IR(
KBr): 2150 cm-' (C=N) Example 5O N, "-dicyano-2-iobi-5-methyl-1°4-
Electrolysis of benzoquinone diimine in the presence of potassium perchlorateN, Sodicyano-2- in 60rnl of niacetonitrile
Youbi 5-methyl-1,4-benzoquinone diimine 5
9.2 mg (200R mol) and potassium perchlorate 13
A solution of 9 mg (I, oo μmol) was heated to 5 μA at −25°C.
Electrolyze for 276 hours using a current of . Meanwhile, black crystals with a metallic luster are deposited on the cathode. The crystals are separated, washed with ether and dried on silica gel. This product has a 2:1 ratio of N,N'-dicyano=
61- Consists of -2-iobi-5-methyl-1,4-benzoquinone diimine and K. Yield 24.1■ (38% of theoretical value)
, melting point 131℃ (decomposed), electrical conductivity 7×1O-28-
I:m-1゜Elemental analysis: C18HIO'l2KN8CHN Calculated value (%) 34.25 1.60 17.75 Actual value (%J 34.81 1.57 18.14 Engineering R
(xBr): 2150 tyn-' (c=N) Example 51 Electrolysis of N,t-dicyano-2,5-dimethyl-1,4-benzoquinone diimine in the presence of thallium nitrate 55 ml of niacetonitrile and 5 ml of dimethyl sulfoxide
N,N'-dicyano-2,5-dimethyl-1, in ml
4-Benzoquinone diimine 36.9 mg (200m
mol) and talic nitrate L, 26.5 m9 (Io.

A solution of 8 mol) is electrolyzed for 26 hours at -25°C using a current of 20μ. Meanwhile, black crystals with a metallic luster are deposited on the cathode. The crystals are separated, washed with ether and dried on silica gel. This product has a ratio of 2:1ON, N'-dicyano-2,5-dimethyl-
Consists of 1,4-benzoquinone diimine and thallium.

Yield: 24% of theory, melting point: 161°C (decomposed), electrical conductivity: 0.128-cm-'.

Elemental analysis' 020 HI6 N8T ICHN Calculated value ((4) 41.932.82 19.57 Actual value (%> 41.84 2.87 19.64IR(
KBr): 212 Qcrn-', 2080 (CA
N) Applicant Beeninisf Akchengesellschaft Agent Patent Attorney Masao Kobayashi Procedural Amendment (Voluntary) July 1, 1988

Claims (13)

[Claims] 1. General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R^1 is 1- or 2-propyl group, C_5 ~ C_
2_0-alkyl group, C_3-C_20-alkenyl group or iodine atom, R^2, R^3 and R^4 are independently hydrogen atom, chlorine atom, bromine atom, iodine atom, fluorine atom, phenyl group, C_1-C_20-alkyl group, C_3-C_20-alkenyl group or C_1-C
_8-Alkoxy group) bicyanoimine. 2. R^2 and R^4, or R^3 and R^4, or R
The first where ^2, R^3 and R^4 are each hydrogen atoms
Bicyanoimine according to the claims. 3. The biscyanobenzimine according to claim 1, wherein R^2 and R^4 are each hydrogen atoms. 4. The biscyanobenzimine according to the first, second or third claim, wherein R^1 is an iodine atom. 5. Biscyanoimine represented by the general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ and fulvalene compounds represented by the general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In these formulas, R^1 is 1- or 2- Propyl group, C_5-C_20-alkyl group, C_3-C_20-alkenyl group or iodine atom, R
^2, R^3 and R^4 are independently hydrogen atom, chlorine atom, bromine atom, iodine atom, fluorine atom, phenyl group, C_1-C_20-alkyl group, C_3-C
_20-alkenyl group or C_1-C_8-alkoxy group, R^5, R^6, R^7 and R^8 each independently mean a hydrogen atom, a methyl group or an ethyl group, or R^5 and R^6, R^7 and R^8, or R^5 and R^7 and R^6 and R^8 together form the following formula ▲ There is a mathematical formula, chemical formula, table, etc. ▼ or ▲ Mathematical formula, There are chemical formulas, tables, etc. ▼ may form a residue, x and y each independently mean S or Se), (I): (II)
molar ratio of 1:1, 2:1, 3:2, 1:2 or 2:3
A charge transfer complex compound. 6. 6. The charge transfer complex compound according to claim 5, wherein X and Y are the same. 7. The charge transfer complex compound according to claim 5 or 6, wherein R^5, R^6, R^7 and R^8 are each hydrogen atoms. 8. The charge transfer complex compound according to claim 6 or 7, wherein X and Y are each S. 9. General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R^1 is 1- or 2-propyl group, C_5 ~ C_
20-alkyl group, C_3-C_20-alkenyl group or iodine atom, R^2, R^3 and R^4 are independently hydrogen atom, chlorine atom, bromine atom, iodine atom, fluorine atom, phenyl group, C_1-C_20-alkyl group, C_3-C_20-alkenyl group or C_1-C_
8-Alkoxy group, M^m^■ is m-valent alkali metal, alkaline earth metal, transition metal, ammonium-
or phosphonium-ion, k is a number from 1 to 3, l is a number from 1 to
The number 3, m is the number 1 or 2, n is the number 1 to 3, z is 0 to
2, possible values for k, l, n and z also include fractions, and the relationship (l+z)=n·m). 10. M^m^■ is lithium, sodium, potassium,
Rubidium, cesium, thallium, copper (I) or silver ion, or tetramethylammonium group, tetraethylammonium group, tetrabenzylammonium group, trimethylbenzylammonium group, triethylbenzylammonium group, quinolinium group, pyridinium group, N
- The radical ion salt according to claim 9, which is a methylpyridinium group, an N-methylquinolinium group, or an N-ethylquinolinium group. 11. The radical ionic salt according to claim 9 or 10, wherein R^2 and R^4 are each a hydrogen atom, and z is 0. 12. The radical ionic salt according to claim 9 or 10, wherein M^m^■ is Cu^■ or Ag^■. 13. The charge transfer complex compound according to any one of claims 5 to 8 or the radical ion salt according to any one of claims 9 to 12 is used for antistatic finishing of synthetic resins and electrodes and storage devices in batteries. Methods for use as materials, in the production of solar cells, in fuel cells, in the conversion of radiation, or in the production of electronic devices.