JPS6154790B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention provides a 6,13-diaryl-1-metal complex represented by the general formula () useful as a dye, a redox catalyst, or an organic conductive material.
8-dihydrodibenz [b・i] [1.4.8.
11] Concerning the synthesis method of tetraazacyclotetradecenes. [However, in the formula, R ₁ is an aryl group (this group includes an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, a halogen atom, a nitro group, a cyano group, an acyloxy group, an alkoxy group, a hydroxyl group, a carboxyl group, may be substituted with an alkoxycarbonyl group, carbamoyl group, dialkylamino group, or acylamino group), and X ₁ and X ₂ may be the same or different, and represent a hydrogen atom, a halogen atom, an alkyl group, a substituted It represents an alkyl group, an aryl group, a substituted aryl group, a nitro group, a cyano group, an acyloxy group, an alkoxy group, a hydroxyl group, a carboxyl group, an alkoxycarbonyl group, a carbamoyl group, a dialkylamino group, and an acylamino group. ] 1,8-dihydrodibens [b・i] [1・
4.8.11] Tetraazacyclotetradecenes are important compounds with a structure similar to porphine, and those with hydrogen at the 5, 7, 12, and 14 positions are particularly important because their molecules have a planar structure. It is. Among them, 6,13-diaryl derivatives are compounds that have excellent stability and can be expected to have a wide range of applications, as described by Nishida et al. in Journal of Coordination Chemistry, Vol. 9, pages 161-166. However, as a method for synthesizing 6,13-diaryl derivatives, the 4-aryl-
The only known method is to react a 1,2-dithiolium salt with o-phenylenediamine.
This method uses sulfur and peracetic acid to synthesize the raw material dithiolium salt, so the reaction operation and post-treatment are difficult, and the yield of tetraazaannulene is low, and the resulting compound is also low in purity. It has drawbacks such as being difficult. The present inventors have conducted research to find a new manufacturing method that does not have this drawback and have arrived at the present invention. The present invention relates to β-alkoxy-α-arylacrolein and o-phenylenediamine or its 4 and 5
-It is characterized by reacting with a substituent. The β-alkoxy-α-arylacrolein of the present invention is represented by the formula (). [However, in the formula, R ₁ is an aryl group (this group is an alkyl group, substituted alkyl group, aryl group, substituted aryl group, halogen atom, nitro group, cyano group, acyloxy group, alkoxy group, hydroxyl group, carboxyl group, alkoxy ), and R ₂ represents an alkyl group. ] Specific examples of the aryl group represented by R ₁ include phenyl, naphthyl, and anthracenyl groups, of which phenyl is important. Examples of the alkyl group represented by R ₂ include a methyl group, an ethyl group, a propyl group, a butyl group, and the like. Specific examples of the compound of formula () used in the present invention include β-ethoxy-α-phenylacrolein, β-ethoxy-α-(p-nitrophenyl)
Acrolein, β-ethoxy-α-(p-methoxyphenyl)acrolein, β-ethoxy-α-
(p-tolyl)acrolein, β-ethoxy-α
-[p-(n-butyl)phenyl]acrolein,
β-ethoxy-α-naphthyl acrolein, β-
Ethoxy α-(p-cyanophenyl)acrolein, β-ethoxy-(p-chlorophenyl)acrolein, β-ethoxy-[p-(ethoxycarbonyl)phenyl]acrolein, β-ethoxy-
[p-(carboxyl)phenyl]acrolein,
β-Ethoxy-[p-(carbamoyl)phenyl]
Acrolein, β-ethoxy-(p-hydroxyphenyl)acrolein, β-ethoxy-[p-
(N/N-dimethylamino)phenyl]acrolein, β-ethoxy-α-[p-(ethoxycarbonylmethyl)phenyl]acrolein, β-ethoxy-α-[p-(N/N dimethylaminomethyl)
Phenyl] acrolein, β-ethoxy-α-
(o-nitrophenyl)acrolein, β-ethoxy-α-(o-tolyl)acrolein, β-ethoxy-α-[o-(ethoxycarbonyl)phenyl]acrolein, β-ethoxy-α-(o-methoxyphenyl) Acrolein, β-ethoxy-
α-(m-tolyl)acrolein, β-ethoxy-α-(m-nitrophenyl)acrolein, β
-Ethoxy-α-(m-methoxyphenyl)acrolein, and compounds in which β-ethoxy in the above compounds is changed to β-methoxy, β-propoxy, or β-butoxy can also be used in exactly the same way. . These β-alkoxy-α-allylacroleins can be easily derived from the corresponding malonaldehydes, and are easier to synthesize than 1,2-thiolium salts, which are the raw materials for conventional methods, and a wide range of derivatives can be synthesized. It is. The o-phenylenediamine or 4,5-substituted product thereof used in the present invention is represented by the formula (). [However, in the formula, X ₁ and X ₂ may be the same or different, and include a hydrogen atom, a halogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, a nitro group, a cyano group, an alkoxy group, and a hydroxyl group. group, carboxyl group, alkoxycarbonyl group,
Represents a carbamoyl group, dialkylamino group, or acylamino group. ] Specific examples of ortho-phenylene diamines used in the present invention include o-phenylene diamine, 4-methyl-o-phenylene diamine, 4-methyl-o-phenylene diamine,
-Chlor-o-phenylenediamine, 4,5-dimethyl-o-phenylenediamine, 4,5-dichloro-o-phenylenediamine, 4-nitro-o
-phenylenediamine, 4-methoxy-o-phenylenediamine, 4-carbamoyl-o-phenylenediamine, 4-phenyl-o-phenylenediamine, 4-carboxyl-o-phenylenediamine, 4-ethoxycarbonyl- o-phenylenediamine, 4-cyano-o-phenylenediamine, 4-dimethylamino-o-phenylenediamine, 4-[(ethoxycarbonyl)methyl]-o-
phenylenediamine, 4-(methoxymethyl)-o
-Phenylenediamine and the like. β-alkoxy- represented by the general formula ()
The reaction between α-arylacroleins and o-phenylenediamines represented by the general formula () is carried out without a solvent or in a solvent by heating to 50°C to 250°C. Suitable solvents include, for example, alcohols, phenols, cyclic ethers and N.
Examples include aprotic polar solvents such as N-dimethylformamide, dimethylsulfoxide, hexamethylphosphortriamide, and N-methylpyrrolidone. In particular, it is preferable to proceed with the reaction near the boiling point of N.N-dimethylformamide using the polar solvent described below, since the yield is high and the product precipitates out as clean crystals after cooling. The fact that the structure of the product is represented by formula () was confirmed by elemental analysis, ultraviolet spectrum, mass spectrum, infrared spectrum, nuclear magnetic resonance method, etc. The _yield by this method _is
If they are the same, it is in the range of 20% to 35%, which is extremely high. When X ₁ and X ₂ are different, the yield tends to decrease. As mentioned above, compared to the conventional method, this method has
It is an excellent method that allows easy synthesis of raw materials and provides the desired product in high yield and purity. The present invention will be described below with reference to Examples, but the present invention is not limited thereto. Example 1 0.02 mol of the raw material (A) of the reaction formula () and 0.02 mol of the raw material (B) of the reaction formula () are dissolved in 25 ml of N.N-dimethylformamide and heated under reflux for 5 hours. Cool to room temperature, filter out the precipitated tetraazaannulene, wash with methanol, and dry. Substituents R ₁ , X ₁ , X ₂ and yields are listed in Table 1.

【table】

【table】

[Table] Example 2 0.02 mol of the raw material (C) in reaction formula () and 2.16 g (0.02 mol) of orthophenylenediamine were mixed with 25 ml of N.
Dissolve in N-dimethylformamide and heat under reflux for 5 hours. After cooling to room temperature, filtering out the precipitated tetraazaannulene and washing with methanol,
dry. Substituents R ₂ and yields are listed in Table 2.

【table】

Claims (1)

[Claims] 1 General formula () [However, in the formula, R ₁ is an aryl group (this group includes an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, a halogen atom, a nitro group, a cyano group, an acyloxy group, an alkoxy group, a hydroxyl group, a carboxyl group, ), and R ₂ represents an alkyl group. ] β-alkoxy-α-arylacrolein represented by and the general formula () (However, in _{the formula, X 1 and} The general formula (2) is characterized by reacting with an ortho-phenylenediamine derivative represented by (However, in the formula, R ₁ , X ₁ , and X ₂ each represent the same as those described above.) A method for synthesizing a tetraazaannulene derivative represented by the following.