JPS6233157A - Novel compound, charge-transfer complex of said compound and electron donor and anion or anion radical of said compound - Google Patents

Abstract

NEW MATERIAL:The compound of formula I[X is C(CN)CN, CHCN, C(CO2R1) CO2R2, N-CN or CHCO2R1; one of A and B is group of formula II, III, IV or V and the other is group of formula VI(R1, R2 and R5 are H, alkyl, aryl, etc.; R3, R4 and R6-R8 are H, alkyl, aryl, halogen, nitro, etc.; Y is S or Se)]. EXAMPLE:Benzothiazolo-tetracyanoguinodimethane. USE:An organic electronic material. A charge-transfer complex of the novel compound and an electron donor or a salt of the anion or anionic radical of the novel compound can be produced from the compound. PREPARATION:For example, a tetracyanoquinodimethane derivative can be produced by reacting the corresponding quinone derivative with malononitrile.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a novel compound useful as an organic electronic material, a charge transfer complex between the compound and an electron donor, and a salt of an anion or anion radical of the compound. Regarding.

[Conventional technology]

Tetracyanoanthraquinodimethane and its derivatives have been known as compounds useful as organic electronic materials such as organic semiconductors (for example, JP-A-57-149259).
No. 58-55450, etc.).

These tetracyanoanthraquinodimethanes are compounds having a basic skeleton represented by the following formula and substituted with various substituents.

These tetracyanoanthraquinodimethanes are compounds useful as organic electronic materials such as organic semiconductors, organic photographic materials, organic conductors, and thermistor materials.

In addition, the present inventors succeeded in isolating a charge transfer complex consisting of the tetracyanoquinodimethanes and an electron-donating compound as a pure product that is solid at room temperature. -w? He discovered that the tr Ryodougibushi H Katabushiyoh was also useful as a material for the right tomb thunder beams, and has already applied for a patent (patent application Sho fj?-).
.

The present inventors replaced at least one of the two benzo-fused rings of the above-mentioned tetracyanoanthraquinodimethanes with another heterofused ring, and further modified the two dicyanomethylene groups into various groups. We also conducted extensive research on compounds, believing that they would also be useful as organic electronic materials.

[Problem that the invention seeks to solve]

Therefore, the object of the present invention is to substitute at least one of the two benzo-fused rings of tetracyanoanthraquinodimethanes with a heterofused ring, and optionally substitute two dicyanomethylene groups with other groups. It is an object of the present invention to provide novel compounds that have the following properties.

Another object of the present invention is to provide a charge transfer complex of the novel compound and an electron donor.

Yet another object of the present invention is to provide a salt of the anion or anion radical of the novel compound.

[Means and effects for solving the problem] First aspect of the present invention
is a compound represented by the following general formula (1).

R□, R2 and R5 are each independent of each other and represent H, alkyl, aryl or aryl-substituted alkyl group, and R3, R4, R6, R7 and R8 are each independent of each other. H, alkyl, aryl, aryl-substituted alkyl, alkoxy, halogen, nitro, cyanide, carbo/acid ester group Co2R
1 (in the formula, R1 has the same meaning as above).

Examples of the compounds represented by the above general formula are shown below as structural formulas.

In the formula, lyig represents a methyl group and Et represents an ethyl group.

The compound represented by the general formula (1) according to the present invention can generally be synthesized from the corresponding quinone derivative.

For example, tetracyanoquinodimethane derivative (X=C(CN
) In the case of 2), titanium tetrachloride is added to a solution in which the corresponding quinone derivative is dissolved in a solvent such as chloroform, dioxane, or tetrahydrofuran, and the solution is maintained at a predetermined temperature. Next, a solution of malononitrile (CH2(CN)2) and an optional tertiary organic base in an amount equivalent to or more than the quinone derivative is added to this suspension, and the reaction is carried out at a predetermined temperature. Check the progress and after the reaction is complete,
After concentrating the reaction solution if desired, the product is crystallized by injecting it into a non-solvent, and purified by recrystallization or the like.

Similarly, by replacing malononitrile with other active compounds, compounds other than X:CH2(ON)2 can be obtained.By using silyl)-carbodiimide 9, X=
A compound of NCH is obtained.

The second aspect of the present invention is a charge transfer complex of the compound represented by the general formula (1) and an electron donor. Examples of electron donors include aromatic compounds such as Banze/, naphthalene 1, anthracene, pyrene, perylene, P-phenylenediamine and similar fused ring type aromatic compounds, tetrathiafulvalene (TTF'), tetrathia Tetracene (TTT
) and tetramethylthiafulvalene (TMTSF)
Examples include sulfur-containing electron-donating compounds such as.

These electron donors and other examples are shown below with the structural formula (%).The charge transfer complex of the present invention can be produced by the following method.

(1) The compound represented by general formula (I) and the electron-donating compound were dissolved in a mixed solvent of a solvent in which both were soluble (for example, methylene chloride, dichloroethane, etc.) and a poor solvent (CCl4, etc.) and reacted. After that, the mixed solvent is removed to obtain the desired complex.

(2) A method in which the compound represented by general formula (1) and an electron-donating compound are dissolved in a solvent in which both are soluble and reacted, and then a poor solvent is added and mixed, and then the solvent is removed to obtain the desired complex.

The third aspect of the present invention is a salt of an anion or an anion radical of the compound represented by the general formula (1).

Examples of the anion or counter cation of the anion radical of the compound of general formula (1) include the following.

Shili3 Ward H3 These salts can be prepared by conventional methods.

Charge transfer complexes of the compound represented by the general formula (1) and salts of anions or anion radicals of the compound represented by the general formula (1) are also organic electronic materials in the same way as the compound represented by the general formula (1) itself. It is useful as

〔Example〕

Example I BTDA-TCNQ (Benzothiadiazo-lotetracyanoquinodimethane) 1 Raw material quinone derivative 2 was prepared by RoNeidlein et al. (Ch
em.

The compound was synthesized according to the method of J. B. Ber-, 115, 2898 (1982)) and sublimated at 250° C. at 4×10-2 Torr (melting point>390° (decomposed)).

Pink powder raw material crushed in a mortar 26.09 (
26,5 rnmol) in 11 ml of dry chloroform (dry-distilled with CaH2) in a three-bottomed round-bottomed flask.
Suspend in 〇-.

Add TLC1412rcl (4 equivalents) and stir vigorously with a mechanical stirrer. Cool to -50°C in a dry ice-methanol bath and add malonitrile (boiling point 10
3-106℃/14mHg) 5.13F (77,7
rnmol.

2, g equivalent) and dry pyridine (dry distilled over CcLH2) 42d (20 equivalents) of dry chloroform 195
1 Solution fi - Add dropwise while maintaining temperature at -50°C.

At this time, the color of the solution changes from orange to purple to yellow.

Keep the flask temperature below -10°C in an ice-salt bath and stir vigorously for 6.5 hours. Next, cooled ether 15
When 0d is added, green-yellow crystals precipitate (at this time, if the temperature is high, there will be many decomposition products (green ones), and it will become tar-like. This may occur if the number of equivalents of malonitrile is large The same is true.

Therefore, it is necessary to process the reaction promptly).

At this time, unreacted 2 remains as orange cubic crystals at the bottom of the flask, but this can be easily separated from the crystals of 1 by decantation (the same applies during recrystallization described later). The solid obtained by separating green-yellow crystals in a Puchner F-Too contains Ti salts, so ether (100 m
After washing with a large amount of water (100sux2)
), washed with hot water (~50°C, 200dX2) and dried under reduced pressure. Crude product yield 7.16 g (84%, melting point 350~
365°C (decomposition)). The crude product (1) was fractionated and recrystallized using A7T.
A mixture of 0.4F is obtained.

At this time, 1 is a pale yellow-green crystal, sublimated (4X10-
2 Torr, 300°C) as a yellow powder (1
) is obtained. Final yield 72 inches. Melting point 375-380℃
(Disassembly). Recrystallization from acetonitrile gives yellow needles.

Original cumulative analysis: Calculated value (chi) as C1□N8S2 C45,00; N 34.98;
S 20.02 actual value (penalty C45,19; N 35
．． 16; S 20.14゜Mass: % (
%) = 320 (M”, 100).

UV: ode”:””/yn(toy t > 384
(4,53), 364C450 Heaven 309 (4,45),
3038h (4,36), 246 (4,04>, 23
9 (4,06).

Engineering R: V mother spoon/Ctn= 2225 (CN), 1
580 (c==c) IH-NMR: No protons observed.

Example 2 TDA-TCNNQ (thiadiazolotetracyanonaphthoquinodimethane) 3 The raw material quinone derivative 4 was prepared by RlNaefe et al. (Chem.

Bar-, 90, 1137 (1957)) and silica gel (G-22) chromatography (
The product was purified using CH2Cl2 as an eluent (melting point 245-248°C (decomposed)).

4 1.10F (5,09 mm 01) is suspended in 50 m dry chloroform in a 200 mJ three-bottle round bottom flask.

Add TE012.2 rxl (4 equivalents'Ijk) and cool to 0°C in an ice-water bath. 6.70 g (102 mm 01, 20 equivalents - 11) of malonitrile and 50% dry chloroform of dry Viridi 716w1 (70 equivalents) while keeping at 0°C.
Add wJ solution dropwise. After stirring at room temperature for 20 minutes, pour into 100 cups of water, add Ti salt to each room, and add methyl chloride C20d.
Wash thoroughly with X5). The layers were quickly separated, the aqueous layer was extracted with methylene chloride (50mjX 2 ), the organic layers were combined and washed with water (150yLtX 6 ), and Nα2
Dry in S04. Concentrate the solvent at a low temperature (~20°C) (~20d), add 10d of ether, and separate the yellow precipitate. Crude product: 1.01164, melting point: 268-
The product was recrystallized from methylene chloride-hexane to give yellow needles with a melting point of 277-278°C (decomposition). Final yield: 55%.

Elemental analysis: C,, Calculated value as H4N6S (correspondence) C61,53; H1,29; N2
6.90; S 10.27 actual measurement value book) C61,
16; H1,07; N 26.22; S 10.
06°Mass rn/f, ('II = 312 (
M”, 100).

U ■: λjishi moromi 09ε) 357 (4, 44), 296
(4,38).

IR: y:,,,/crn-' 2218 (CN)
, 1558 (C=C).

"H-NMRδCDC137,8~8.1 (2H,su,8.6~8.9Pm (2H,yx).

Example 3 5eDA-TCNNQ (Selenadiazolola 2 tracyanonaphthoquinodimethane) 5 65001W (1,90 mmol) Rough L,
Dry [suspended in 30d of TiC140,8
Add 5 mA' (4 equivalents). Maronitrile 1.3
2 g (~10 eq.) of dry pyridine 6a+1 (40 eq.) in 15d dry methylene chloride solution was slowly added dropwise to ~1
．． 5 hours) and stirred at room temperature for 8 hours while checking by thin layer chromatography. After confirming that the spot of the raw material quinone derivative has disappeared, add 100 d of water to CH2Cl2.
Pour into 50 d of mixture and extract. Water layer is further VcCH
Extract with 2C12 (soixz), combine the organic layers, wash with water (100p x 3), and dry with Nα2SO4.

After distilling off the solvent, 30 cm of ether was added and the crystals were dried separately to obtain 452 cm of crude product (66%). Melting point 33
0-350 (decomposition). This is recrystallized from CH2Cl2-X xane to give a yellow powder. Melting point 335-370℃
(Disassembly).

Elemental analysis: Calculated value as C16H4N6Se (@C53,50; H1,12; N2
3.40 actual value (fishing C53,31; H1,00;
N23.30.

Example 4 TDA-DCNNQ (thiasiazone dicyanonaphthoquinodiimine) 7 Thiadiazolona 7 toquinone 4 100 - (0,463
) to 10. d in dry CE2C12, TiCl2
Add 0.2 mg ('equivalent). N,N'-bis(trimethylsilyl)carbodiimide 830η (9,6 equivalent 1
) and reflux for 8 hours. The mixture is poured into 20-ml water and separated, the aqueous layer is extracted with CH2Cl2 (20d), the organic layers are combined, washed with water (50d), and then dried over Nα2S04. Distill the solvent to 101
091Iv (89 crude product is obtained, which is converted into CH2Cl
Recrystallization from 2-hexane gives a dark yellow powder. Melting point 275-280°C (decomposition).

Elemental analysis: Calculated value as C□2H4N6S (chi) C54,54; H1,53; N
31.80; S 12.13 actual value (@C54,7
1; H1,37; N 31.29; S 11.50
゜Example 5 SgDA-DCNNQ (Selendiazo-Rodicyanonaphthoquinodiimine) 8 Selenodiazolo Naphthoquino 76100 ■ 20d was suspended in dry CH2Cl2 and Tz C140,2pal
(Add 4 tons of →.
Add 1 dry CH2012 solution and reflux for 54 hours. 2
Pour into 0 m water and extract with 30 d CH2Cl2.

The aqueous layer is extracted with CH2C1t2 (20tttt).

The aqueous layer is extracted with CH2Cl2 (20d) and the combined organic layers are washed with water (50iJX2) and dried over Nα2S04. The crude product 118~ obtained by distilling off the solvent was purified by CH2C
Recrystallize from ClCl (2CH2Cl may be used) to obtain a purified product with a melting point of 298-318°C (decomposed).2
8■ (24chi).

Example 5 BTDA-TCNQ, TTT (k/zothiadiazole-tetracyanoquinodimethane-tetrathiatetracene) (1:1) complex BTDA-TCNQ (produced in Example 1) 62779
(0°2 mmol) is dissolved in 130% CH2C71!2, and using a Soxhlet extractor, tetrathiatetracene (TTT)70Tn9 (0.2 mm)1) is dissolved. After all the TTT has been extracted, leave it at room temperature to obtain black needle crystals 132η (~100T). Melting point〉40
0℃.

Engineering R Niji cH = 2173 cm, specific resistance value ρ (measured using the 4-terminal method for a pellet) = 0.14 to 0.1
5Ω muscle.

Example 7 BTDA-TCNQ-N, N, N, N −
TMPD (indithiadiazolotetracyanoquinodimethane N,N,N',N'-tetramethylparaphenylenediamide 7) (1:1) complex BTDA-TCNQ 6
2■ (0.2 mmol) in 60 grams of boiling dry CH2Cl
Dissolve in
my(0,2mrno1) dry CH2Cl! Add all of the 21d solution and leave the entire solution at room temperature. Black powder 50η (5
Section 2). Melting point 225-230°C (decomposed).

Engineering R Niji CN = 2171 cm, ρ = 8.66
Ωcrn (measured using the two-terminal method for a pellet).

Example s (NMP”) (BTDA-TCNQ)
7 [(N-methylzenadinium) (indithiadiazolotetracyanoquinodimethane anion radical)]
(1:I) BTDA-TCNQ and 3 equivalents of Li in salt anhydrous CH3CN
LL” (BTDA-TCNQ) T2 prepared from I and
Dissolve O5"9 (0,63mrrLo1) in 300-boiled dry CH30N and N-methylzenadinium methyl sulfate 192"! 1 of (0,63 mmo1)
Add 0 mJ dry CH3CN solution. Leave it at room temperature and separate the blackish brown needle-like crystals.

Yield: 174cm (61cm). Melting point 219-220°C (decomposed).

Engineering R Niji cN = 2172cW10ρ = 1.66Ω Sono (measured using the two-terminal method for Barrett).

Elemental analysis” C25H1lNl. Calculated value as S2 (@
C58,24; H2,15; N27.17; S 12
．． 94 actual measurement value (@C58°20; H1,96; N
26.96; S 12.33° Example 9 B
Electrical conductivity of charge transfer complexes of TDA-TCNQ and electron donors The results of specific resistance values determined by the two-terminal method or the four-terminal method using charge transfer complexes of BTDA-TCNQ and various electron donors as pellets are shown below. Shown in detail.

Claims (1)

[Claims] 1) A compound represented by the following general formula (I). ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) [In the formula, X is ▲There are mathematical formulas, chemical formulas, tables, etc.▼, CH
CN, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, Represents N-CN or CHCO_2R_1 group, ▲Mathematical formulas, chemical formulas,
Either ▼ There are tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ indicates the heterocycle shown by ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, When one represents this heterocycle, the other is ▲mathematical formula,
Chemical formulas, tables, etc.▼ are also acceptable, Y represents S or Se, R_1, R_2 and R_5 are mutually independent and represent H, alkyl, aryl or aryl-substituted alkyl group, R_3, R_4, R_
6, R_7 and R_8 are independent of each other,
H represents an alkyl, aryl, aryl-substituted alkyl, alkoxy, halogen, nitro, cyano or carboxylic acid ester group CO_2R_1 (wherein R_1 has the same meaning as above); ] 2) The following general formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) [In the formula, X is ▲There are mathematical formulas, chemical formulas, tables, etc.▼, CH
CN, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, Represents N-CN or CHCO_2R_1 group, ▲Mathematical formulas, chemical formulas,
There are tables, etc. ▼ and ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ Either one is ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
or ▲There are mathematical formulas, chemical formulas, tables, etc.▼ indicates a heterocycle, and if one represents this heterocycle, the other ▲There are mathematical formulas, chemical formulas, tables, etc.▼ may be used, and Y is S or Se, R_1, R_2 and R_
5 are independent of each other and represent H, alkyl, aryl or aryl-substituted alkyl group, R_3, R
_4, R_6, R_7 and R_8 are each independently H, alkyl, aryl, aryl-substituted alkyl, alkoxy, halogen, nitro, cyano or carboxylic acid ester CO_2R_1 (wherein R_1 has the same meaning as above) ). A charge transfer complex between a compound represented by ] and an electron donor. 3) The following general formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) [In the formula, X is ▲There are mathematical formulas, chemical formulas, tables, etc.▼, CH
CN, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, represents NCN or CHCO_2R_1 group, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, and ▲There are mathematical formulas, chemical formulas, tables, etc.▼ Either one of them is ▲Mathematical formula, There are chemical formulas, tables, etc.▼
or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ indicates a heterocycle, and if one side represents this heterocycle, the other may be ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, and Y is S or Se, R_1, R_2 and R
_5 are independent of each other and represent H, alkyl, aryl or aryl-substituted alkyl group, R_3,
R_4, R_6, R_7 and R_8 are each independent of each other, and include H, alkyl, aryl, aryl-substituted alkyl, alkoxy, halogen, nitro, cyano or carboxylic acid ester group CO_2R_1 (wherein R_1 has the same meaning as above) ). ] Salts of anions or anion radicals of the compounds shown.