JPH0473434B2 - - Google Patents

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention is directed to a novel conductive organic compound, more specifically, as a raw material for conductive paint, conductive ink, resist ink, conductive plastic, conductive rubber, etc. It also relates to conductive organic compounds that can be used in a wide range of applications as constituent materials for electrodes, thick film ICs, liquid crystal display tubes, solar cells, ultra-high density memories, etc. [Prior art] Conductive organic compounds have advantages over metals, such as light weight, anisotropy of conductivity, ease of molding, and ease of chemical modification depending on the application. As the possibility of conduction phenomena is suggested,
It has attracted attention in recent years, and many materials are being developed, both low-molecular and polymeric. Among them, tetracyanoquinodimethane (hereinafter referred to as
"TCNQ") was used as the electron acceptor part.
Those with a TCNQ complex structure generally have high conductivity and are the most well-known. And these conventional
Electron donor moieties of the TCNQ complex include tetra-n-butylammonium, quinoline, acridine, o-phenanthroline, N-methylphenazine (NMP), N-methylbenzothiazine, tetrathiafulvalene (TTF), tetrathia Tetracene (TTT), tetramethyltetraselenafulvalene (TMTSF), etc. have been used ["Synthesis and Application of Organic Semiconductor Materials" CNC (1981); "Modern Chemistry"
No. 141, pp. 12-19, Tokyo Kagaku Dojin (1982); Kagaku Review 42 "Chemistry of Conductive Low-dimensional Materials" Society Publishing Center (1983)]. [Problems to be solved by the invention] However, although many conductive organic compounds with the TCNQ complex structure are known, there are only a few that are satisfactory in terms of conductivity, and those with high conductivity are still lacking. Since most of them have complex chemical structures and are difficult to synthesize, there has been a desire to develop organic compound materials that have high conductivity and are easy to synthesize. [Means for Solving the Problems] As a result of intensive studies to find an organic compound that satisfies the above conditions, the present invention uses cycloheptabenzodiazine, cycloheptabenzoxazine, cycloheptabenzodiazine, and cycloheptabenzodiazine as electron donor moieties. The present invention was completed based on the discovery that a TCNQ complex using a 7-membered ring compound such as benzothiazine has nearly the highest electrical conductivity compared to conventional TCNQ complexes, and can be synthesized extremely easily. That is, the present invention provides the following general formula () (wherein, R represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, X represents HNCH ₃ N, O or S, and n represents a number of 1 or 2) It is something. The conductive organic compound of the present invention can be easily produced, for example, by combining known synthesis methods according to the following formula. (In the formula, Y represents Cl, Br or I, and R and X are the same as above.) That is, by protonating or alkylating cycloheptabenzodiazine, cycloheptabenzoxazine, or cycloheptabenzothiazine, 7 Obtaining member ring system cations [Proceedings of the 47th Spring Annual Meeting of the Chemical Society of Japan, 4F34 (1983); Bulletin of the Chemical Society of Japan.
Bull.Chem.Soc.Japan 51 , 2185
(1978); Ibid., 34 , 146 (1961)]. Next, equivalent amounts of the cation and TCNQ ^- Li ⁺ were mixed in boiling ethanol solution to obtain the 7-membered ring cation TCNQ (1:
1) The complex is further treated with an equivalent amount of TCNQ (1:1) complex.
The TCNQ (1:2) complex is obtained by mixing the respective boiling acetonitrile solutions of TCNQ [Can.J.
Chem.) 43 , 1448 (1965)]. As the 7-membered ring compound/TCNQ complex obtained in this way, cyclohepta[b][1,4]benzodiazinium TCNQ (1:1) complex, cyclohepta[b][1,4]benzodiazinium TCNQ (1:1) complex,
2) Complex; N-methylcyclohepta[b][1,
4] Benzodiazinium TCNQ (1:1) complex,
Same (1:2) complex; N-ethylcyclohepta[b][1,4]benzodiazinium TCNQ (1:
1) Complex, same (1:2) complex; N-propylcyclohepta[b][1,4]benzodiazinium
TCNQ (1:1) complex, TCNQ (1:2) complex; N,
N-dimethylcyclohepta[b][1,4]benzodiazinium TCNQ (1:1) complex;
2) Complex; N-methyl, N-ethyl-cyclohepta[b][1,4]benzodiazinium TCNQ
(1:1) complex, (1:2) complex; cyclohepta[b][1,4]benzoxazinium TCNQ
(1:1) complex, the same (1:2) complex; N-methylcyclohepta[b][1,4]benzoxazinium TCNQ (1:1) complex, the same (1:2) complex;
N-Ethylcyclohepta[b][1,4]benzoxazinium TCNQ (1:1) complex;
2) Complex; cyclohepta[b][1,4]benzothiazinium TCNQ (1:1) complex;
2) Complex; N-methylcyclohepta[b][1,
4] Benzothiazinium TCNQ (1:1) complex,
(1:2) complex, N-propylcyclohepta[b][1,4]benzothiazinium TCNQ (1:
1) complex, the same (1:2) complex, and the like. [Function] After the 7-membered ring compound/TCNQ complex of the present invention and the TTF/TCNQ complex, which has one of the highest conductivity among conventional conductive organic compounds, is pressure-molded by a conventional method, its specific resistance is determined. was measured using the two-terminal method, and the conductivity of these complexes was compared.
Note that the measurements were performed at room temperature. The results are shown in Table 1. [Table] The specific resistance of ordinary TCNQ complex compounds is generally 10 ²
~10 ⁸ Ωcm [“Modern Chemistry”, No. 141, No.
13 pages (1982)]. On the other hand, the 7-membered ring compound/TCNQ complex of the present invention, especially the (1:2) complex,
As shown in Table 1, it has very high conductivity. Therefore, the conductive organic compound of the present invention has TTF/
The conductivity of the TCNQ complex is not as good as that of the conventional one.
It has nearly the highest degree of conductivity compared to the TCNQ complex. [Effects of the Invention] As mentioned above, the conductive organic compound of the present invention is one step ahead of the TTF/TCNQ complex in terms of conductivity, but since it is extremely easy to synthesize compared to the TTF/TCNQ complex, the conductive organic compound It is industrially very advantageous as a material. For example, when comparing the synthesis method of TTF and cyclohepta[b][1,4]benzothiazine, which is one of the raw materials of the compound of the present invention, TTF is synthesized in 7 steps from thiophosgene and disodium dimercaptomaleonitrile as shown in the following formula. whereas cyclohepta[b][1,4]benzothiazine is synthesized with 2
-Can be synthesized in one step from chlorotropone and o-aminothiophenol. Synthesis of TTF: [Journal of the American Chemical Society]
Chemical Society) 86 , 5290 (1964);
Communications) 1453 (1970)] Synthesis of cyclohepta[b][1,4]benzothiazine: [Bull.Chem.Soc.Japan]
51, 2185 (1978)] [Example] Next, the present invention will be explained by giving synthesis examples and examples. Synthesis Example 1 Synthesis of N-methylcyclohepta[b][1,4]benzodiazinium hydrochloride: HCl gas was bubbled through 50 ml of absolute ethanol for 30 minutes to prepare a hydrochloric acid acidic ethanol solution. N to this
-Methylcyclohepta[b][1,4]benzodiazine (100 mg, 0.481 mmol) was dissolved and stirred at room temperature for 30 minutes. The solid obtained by distilling off the ethanol was recrystallized from ethanol to give dark green needle crystals N.
95 mg (0.388 mmol) of -methylcyclohepta[b][1,4]benzodiazinium hydrochloride was obtained (yield 80.5%). mp258~260℃ (decomposition). Synthesis Example 2 N,N-dimethylcyclohepta[b][1,4]
Synthesis of benzodiazinium iodide: 208 mg of N-methylcyclohepta[b][1,4]benzodiazine in 5 ml of dry ether (1.00 m
11.4 g of methyl iodide
(80.3 mmol) was added, and the mixture was heated under reflux for 45 hours. As the reaction progressed, the dimethyl compound precipitated as crystals. Ether was added to the residue obtained by distilling off ether and excess methyl iodide to remove the soluble portion (containing unreacted raw materials), and the insoluble portion was recrystallized from ethanol to form a dark green plate. 263 mg (0.75 mmol) of crystalline N,N-dimethylcyclohepta[b][1,4]benzodiazinium iodide was obtained (yield 75
%). mp267-268℃ (decomposition). Example 1 Synthesis of cyclohepta[b][1,4]benzoxazinium TCNQ (1:1) complex: Boiling 59 mg (0.256 mmol) of cyclohepta[b][1,4]benzoxazinium hydrochloride in absolute ethanol TCNQ ^- Li ⁺ 49mg (0.256
mmol) of boiling absolute ethanol (4 ml) was mixed and left at room temperature for 2 hours under _N2 gas atmosphere.
Separate the precipitated crystals, add a small amount of absolute ethanol,
Wash with 3 ml of dry ether to obtain purple needle-like crystals of cyclohepta[b][1,4]benzoxazinium.
55 mg (0.137 mmol) of TCNQ (1:1) complex was obtained (yield 53.4%). The physical properties of this product are shown in Table 2. Example 2 Synthesis of N-methylcyclohepta[b][1,4]benzodiazinium TCNQ (1:1) complex: Synthesis of cyclohepta[b][1,4]benzoxazinium hydrochloride of Example 1 The same procedure as in Example 1 was carried out using 63 mg (0.256 mmol) of N-methylcyclohepta[b][1,4]benzodiazinium hydrochloride instead, and 77 mg of the title compound in the form of blue-purple needles was obtained.
(0.186 mmol) was obtained (yield 72.9%). The physical properties of this product are shown in Table 2. Example 3 N,N-dimethylcyclohepta [b] [1,4]
Synthesis of benzodiazinium TCNQ (1:1) complex: N,N-dimethylcyclohepta[b][1,4] in place of cyclohepta[b][1,4]benzoxazinium hydrochloride in Example 1 ] Using 90 mg (0.256 mmol) of benzodiazinium iodide, the same procedure as in Example 1 was carried out, and 90 mg of the title compound in the form of purple needle-like crystals was obtained.
(0.210 mmol) was obtained (yield 82.0%). The physical properties of this product are shown in Table 2. Example 4 Synthesis of N-methylcyclohepta[b][1,4]benzoxazinium TCNQ (1:1) complex: Synthesis of cyclohepta[b][1,4]benzoxazinium hydrochloride of Example 1 The same procedure as in Example 1 was carried out using 63 mg (0.256 mmol) of N-methylcyclohepta[b][1,4]benzoxazinium hydrochloride instead, and 84 mg of the title compound in the form of reddish-purple needles was obtained.
(0.202 mmol) was obtained (yield 78.9%). The physical properties of this product are shown in Table 2. Example 5 Synthesis of cyclohepta[b][1,4]benzothiazinium TCNQ (1:1) complex: Cyclohepta[b][1,4]benzoxazinium hydrochloride in Example 1 was replaced with cyclohepta[b][1,4]benzoxazinium hydrochloride. b] [1,4]benzothiazinium hydrochloride 63mg
(0.256 mmol) in the same manner as in Example 1,
59 mg (0.142 mmol) of the title compound in the form of purple needles was obtained (yield 55.6%). The physical properties of this product are shown in Table 2. [Table] [Table] Example 6 Synthesis of cyclohepta[b][1,4]benzoxazinium TCNQ (1:2) complex: Cyclohepta[b][1,4] obtained in Example 1
Benzoxazinium TCNQ (1:1) complex 50mg
(0.125 mmol) was added to a boiling dry acetonitrile solution (3 ml) of 25.5 mg (0.125 mmol) of TCNQ and left at room temperature for 2 hours under _N2 gas atmosphere. Separate the precipitated crystals and wash with a small amount of dry acetonitrile and 3 ml of dry ether to obtain purple needle-like crystals of cyclohepta[b][1,4]benzoxazinium TCNQ.
51 mg (0.0894 mmol) of a (1:2) complex was obtained (yield 67.5%). The physical properties of this product are shown in Table 3. Example 7 N,N-dimethylcyclohepta [b] [1,4]
Synthesis of benzodiazinium TCNQ (1:2) complex: N,N obtained in Example 3 in place of the cyclohepta[b][1,4]benzoxazinium TCNQ (1:1) complex of Example 6 -dimethylcyclohepta[b][1,4]benzodiazinium TCNQ (1:
1) Using 53 mg (0.125 mmol) of the complex, Example 6
Proceed in the same manner as above to obtain 65 mg of the title compound in the form of blue-purple needles.
(0.103 mmol) (yield 82.4%). The physical properties of this product are shown in Table 3. Example 8 Synthesis of N-methylcyclohepta[b][1,4]benzoxazinium TCNQ(1:2) complex: Cyclohepta[b][1,4]benzoxazinium TCNQ(1:2) complex of Example 6 :1) N-methylcyclohepta [b] obtained in Example 4 instead of the complex
[1,4]Benzoxazinium TCNQ (1:1)
The same procedure as in Example 6 was carried out using 52 mg (0.125 mmol) of the complex, and 67 mg (0.108 mmol) of the title compound in the form of purple needles was obtained.
mmol) (yield 86.7%). The physical properties of this product are shown in Table 3. Example 9 Synthesis of cyclohepta[b][1,4]benzothiazinium TCNQ (1:2) complex: Cyclohepta[b][1,4]benzoxazinium TCNQ (1:1) complex of Example 6 52 mg of cyclohepta[b][1,4]benzothiazinium TCNQ (1:1) complex obtained in Example 5 instead of
(0.125 mmol) in the same manner as in Example 6,
57 mg (0.091 mmol) of the title compound in the form of purple needles was obtained (yield 72.5%). The physical properties of this product are shown in Table 3. 【table】

Claims (1)

[Claims] First-order general formula () (In the formula, R represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, X represents HNCH ₃ N, O or S, and n represents a number of 1 or 2).