JPH02215763A - 1-amino-3,3-dimethylguanidium-7,7,8,8-tetracyanoquinodimethane complex salts and production thereof - Google Patents

Abstract

NEW MATERIAL:The compound of formula I (m is 0.5-1.5). USE:An organic semiconductor. PREPARATION:The compound of formula I can be produced by mixing a 1- amino-3,3-dimethylguanidium.quaternary ammonium salt of formula II and 7,7,8,8-tetracyanoquinodimethane of formula III in the form of hot acetonitrile solutions, allowing the mixture to cool and collecting the precipitated crystal by filtration. The reaction is carried out in an inert gas atmosphere under atmospheric pressure at the boiling point of inert solvent such as DMF or THF.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to an organic semiconductor that is attracting attention as a conductive material in the field of electronic equipment or electronic materials, and in particular, relates to an organic semiconductor that is attracting attention as a conductive material in the field of electronic equipment or electronic materials. 3,3-
The present invention relates to dimethylguanidium/7.7,8.8-tetracyanoquinodimethane complex salts and a method for producing the same.

[Summary of the invention] More specifically, 1-amino-3,3-dimethylguanidium 7,7°8.8-tetracyano as a novel organic semiconductor (new compound) represented by the following formula [1] The present invention provides quinodimethane complex salts and a method for producing the same.

However, 1 m in formula [1] is a positive number (0,5 to 1.5 ) means.

In addition, for convenience of explanation, 7.7.8.8-tetracyanoquinodimethane is hereinafter referred to as TCNQ.

Next, the compound shown by the above formula [1] can be converted to the compound shown by the following formula [2].
1-Amino-3,3-dimethylguanidium quaternary ammonium salts represented by the following formula [3] can be produced by reacting with TCNQ represented by the following formula [3].

m in formula [1] is preferably 0.5 to 1.5, more preferably about 1.

[Synthesis method] As described above, l-amino-3,3-dimethylguanidium TC, which is a novel compound of formula E1 according to the present invention.
NQ#I salts can be easily produced in a preferred yield by reacting 1-amino-3,3-dimethylguanidium quaternary ammonium salts of formula [2] with TCNQ of formula [3]. can. Below, l-amino-3,3
- A method for producing dimethylguanidium TCNQII salt will be described.

The 1-amino-3,3-dimethylguanidium quaternary ammonium salts of formula [2] are already known compounds, and can be prepared by a method known per se from 1-amino-3,3-dimethylguanidium. can be easily synthesized using The synthesis example of this 1-amino-3,3-dimethylguanidium quaternary ammonium salt is shown in the first example.
Shown in the table.

Table 1 Synthetic examples of 1-amino-3,3-dimethylguanidium quaternary ammonium salts TCNQ of formula [31] and its various salts and methods for producing the same are already known; M
J, Am, Chem, Soc, 84.3 of elby et al.
No. 374 (1962) and Patent Application Publication No. 191414 of 1988.

Next, one embodiment of producing the compound of formula [1] from the compound of formula [2] and TCNQ of formula [3] will be described in detail,
For example, a hot acetonitrile solution of 1-amino-33-dimethylguanidium quaternary ammonium salt as formula [2] and a hot acetonitrile solution of TCNQ as formula [3] are mixed at a hot temperature and then allowed to cool, and crystals are precipitated. filter. On this occasion.

A large excess of ether may be added to the reaction solution to precipitate the reaction product.The reaction product may be recrystallized with hot acetonitrile, or washed with cold absolute ethanol until the coloring of the same ethanol disappears. An example of 1-amino-3,3-dimethylguanidium TCNQm salt in formula [11] containing no inorganic salts can be obtained in a preferable yield.

By the way, the reaction between the compound of formula [2] and TCNQ of formula [3] is carried out, for example, under normal pressure, preferably in an inert gas atmosphere such as nitrogen gas or argon gas, using acetonitrile, dimethylformamide, etc. The amount of TCNQ of formula [3] used in the reaction is preferably carried out at the boiling point of an inert organic solvent such as , tetrahydrofuran, alkyl cellosolve, or a suitable mixture thereof. For example, the amount used may be about 1 to 3 mol per 1 mol. Further, the amount of the inert organic solvent to be used can be appropriately selected, and is about 10 to 20 times the amount of the compound of formula [2], and about 5 times the amount of TCNQ of the formula [3].
An example of the usage amount is 0 to 120 times.

[Example] Further, an example of a specific method for synthesizing 1-amino-3,3-dimethylguanidium TCNQ salts of formula [1] according to the present invention will be described.

TCNQo, 002
5 mol was dissolved in 35 ml of acetonitrile while hot and poured, mixed and refluxed for an additional 30 minutes. Thereafter, it is left at 5° C. for about 10 hours. After filtering the precipitated crystals, they were washed with acetonitrile, methanol, and ether in this order, and recrystallized twice with acetonitrile. When this is further dried, l-amino-3,3-dimethylguanidium/quaternary ammonium/TCNQ complex salt, melting point 194~
Needle crystals at 196° C. can be obtained with a preferred yield of 55%. The specific resistance was 2.38Ω·Cm.

[Application example 1 1-amino-3,3- of formula [1] obtained as described above
Regarding the uses of dimethylguanidium/TCNQCN, for example, TCNQCN can be used as a solid electrolyte in a solid electrolytic capacitor consisting of a capacitor element made of two sheets of aluminum foil wound with a separator in between, or as a solid electrolyte in a tanker powder sintered body. It can be used as a solid electrolyte for solid electrolytic capacitors consisting of capacitor elements.

Claims (2)

[Claims] (1) 1-amino-3,3 represented by the following formula [1]
-Dimethylguanidium/7,7,8,8-tetracyanoquinodimethane complex salts. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [1] In formula [1], m is neutral 7, 7, contained in 1 mole of complex salt,
It means a positive number (0.5 to 1.5) corresponding to the number of moles of 8,8-tetracyanoquinodimethane. (2) 1-amino-3,3 represented by the following formula [2]
-Dimethylguanidium quaternary ammonium salts are reacted with 7,7,8,8-tetracyanoquinodimethane represented by the following formula [3]. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [3] 1-amino-3,3-dimethylguanidium 7,7,8,8-tetracyanoquinodimethane complex salts represented by the following formula [1] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [1] Production of 1-amino-3,3-dimethylguanidium/7,7,8,8-tetracyanoquinodimethane complex salts characterized by obtaining Method. In formula [2], X represents halogen. In formula [1], m is neutral 7, 7, contained in 1 mol of complex salt,
It means a positive number (0.5 to 1.5) corresponding to the number of moles of 8,8-tetracyanoquinodimethane.