JPH0768206B2 - O-diisocyanobenzenes and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention has the general formula (I) (In the formula, R ₁ and R ₂ represent a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxyl group, and a lower alkoxycarbonyl group. However, both R ₁ and R ₂ are not hydrogen atoms. R ₁ and R ₂ may combine to form a naphthalene ring) and an O-diisocyanobenzenes and a method for producing the same.

The O-diisocyanobenzenes represented by the above general formula (I) are not described in the literature at all, and are novel compounds synthesized by the present inventors for the first time, and these compounds are advantageously used as a raw material for producing a conductive polymer. can do.

As a compound similar in production to the O-diisocyanobenzenes represented by the general formula (I), O-diisocyanobenzene in which the substituents R ₁ and R ₂ in the general formula (I) are both hydrogen atoms Are known and are described in CA, 61 , 8243e.

However, such O-diisocyanobenzene is extremely unstable thermally and has already been polymerized at about room temperature to cause tar formation, which is not practically applicable.

However, the O-diisocyanobenzenes represented by the general formula (I), which are the target compounds of the present application, are stable even at room temperature and therefore can be advantageously used as various polymer raw materials. Polymers obtained by polymerizing benzenes have excellent conductivity and are expected to find wide application as conductive polymers.

The O-diisocyanobenzenes represented by the general formula (I) are represented by the general formula (II) (Wherein R ₁ and R ₂ have the same meanings as described above) and can be produced by reacting with a dehydrating agent in the presence of a basic amine.

Here, the formamides used as the starting material for this reaction are prepared from J-Org. Chem., 86 , 3238 (197) using mono- or di-substituted-O-phenylenediamine or 2,3-naphthylenediamine as the starting material.
It can be easily produced by formylating an amino group according to the method described in 1), and specific examples thereof include N, N '-(4-methyl-O-phenylene) diformamide and N, N. ′-(4-Butyl-O-phenylene) diformamide, N, N ′-(4.5-dimethyl-O-phenylene) diformamide, N, N ′-(4-chloro-O-phenylene) diformamide, N, N '-(4-methoxy-O
-Phenylene) diformamide, N, N '-(4-propoxy-O-phenylene) diformamide, N, N'-(4.5
-Dimethoxy-O-phenylene) diformamide, N,
Examples thereof include N '-(4-methoxycarbonyl-O-phenylene) diformamide and N, N'-(2,3-naphthylene) formamide.

In the method of the present invention, phosgene, a phosgene generator (for example, phosgene dimer, trichloromethyl formate), thionyl chloride, phosphorus oxychloride, etc. are used as the dehydrating agent, and preferably phosgene or a phosgene generator. In particular, a phosgene generator is preferably used from the viewpoint of safety in handling.

The amount of the dehydrating agent used is equivalent to or more than the formamide group of the raw material O-diisocyanobenzenes, preferably 1.
It is 1 times equivalent or more, and the upper limit is not particularly limited, but it is generally 5 times equivalent, preferably 3 times equivalent.

In this reaction, the basic amine is used as a neutralizing agent for the acid component produced as a by-product of the reaction, and since this reaction is usually carried out in an organic solvent, the basic amine is compatible with the organic solvent. It is preferably soluble, and examples thereof include organic tertiary amines such as trimethylamine, triethylamine, and pyridine. The amount of the basic amine used is at least a theoretical amount sufficient to capture the acid component produced as a by-product of the reaction, and the upper limit thereof is not particularly limited, but it is generally based on the raw material O-diisosylanobenzenes. 10 mol times.

The solvent can be used without particular limitation as long as it is inert to the reaction. For example, aliphatic hydrocarbons such as n-hexane and n-octane, aromatic hydrocarbons such as benzene, toluene and xylene, methylene chloride, chloroform, Examples thereof include halogenated hydrocarbons such as chlorobenzene and ethers such as methyl ether and ethyl ether, but halogenated hydrocarbons, especially halogenated aliphatic hydrocarbons are preferably used.

The reaction is generally carried out at 40 ° C. or lower, preferably 20 ° C. or lower, more preferably 0 ° C. or lower in view of yield and the like. The lower limit of the reaction temperature is not particularly limited, but is practically about -80 ° C.

When the reaction is carried out at a low temperature, it is natural that the melting point of the solvent used must be carefully considered.

After completion of the reaction, the target compound can be taken out from the reaction solution by, for example, treating the reaction solution with an alkaline aqueous solution such as a sodium carbonate aqueous solution and then separating the solution, and further separating the separated oil layer with a sodium carbonate aqueous solution or the like. It is carried out by concentrating this after carrying out, and if necessary, it can be further purified by column chromatography or the like.

Thus, according to the method of the present invention, O-diisocyanobenzenes represented by the general formula (I), which are novel compounds, can be obtained in a good yield and can be used as a raw material of a conductive polymer. For use as such a polymer raw material, it is preferable that the substituent R ₁ is substituted at the 4-position as shown in the following formula.

Hereinafter, the present invention will be described with reference to examples.

Example 1 N, N '-(4-methyl-O-phenylene) diformamide 1.62 g (9.1 mmol), triethylamine 5.2 g (51.7)
(Mmol) and 7.2 ml of methylene chloride are cooled to -78 ° C under a nitrogen atmosphere and stirred. 2.75 g (13.9 mmol) of phosgene dimer and 25.2 m of methylene chloride were added.
The solution consisting of 1 was added dropwise over 30 minutes. After the dropping is completed,
The vessel wall was washed with 5 ml of methylene chloride. -78 ℃ → 0
After stirring at ℃ for 12 hours, the temperature was slowly raised to room temperature. After completion of the reaction, 10% Na ₂ CO ₃ aqueous solution was added to the reaction solution to quench the reaction, and after separation, washing with the 10% Na ₂ CO ₃ aqueous solution was repeated 3 times. The organic layer was dried over anhydrous magnesium sulfate, concentrated, and purified using a Florisil short column.

At this time, 30 g of florisil (60 to 100 mesh) was used, and 300 ml of a 1: 1 mixed solvent of hexane: methylene chloride was used as a developing solvent. The developing solution was concentrated, and the produced crystals were washed with hexane to obtain 0.66 g (yield 50.7%) of 3.4-diisocyanotoluene.

Melting point 78-80 ° C (with black decomposition) NMR (CDCl ₃ ) δ2.42 (3H singlet) 7.16-7.50 (3H multiplet) Mass (GC) M ⁺ = 142 m / e = 115: M ⁺ -HC Elemental analysis value C ₉ H ₆ M ₂ Theoretical value C (%) 76.04 H (%) 4.25 N (%) 19.71 Experimental value C (%) 76.10 H (%) 4.15 N (%) 19.76 Example 2 N, N '-(4.5-Dimethyl-O-phenylene) in place of N, N'-(4-methyl-O-phenylene) diformamide
Reaction and post-treatment were carried out in the same manner as in Example 1 except that 1.76 g (9.2 mmol) of diformamide was used, and 1.26 g of 1,2-diisocyano-4,5-dimethylbenzene (yield 87.8%).
Got

Melting point 112-113 ° C (with black decomposition) NMR (CDCl ₃ ) δ 2.30 (6H singlet) 7.56 (2H singlet) Elemental analysis value C ₁₀ H ₈ N ₂ theoretical value C (%) 76.90 H (%) 5.16 N (%) 17.94 experimental value C (%) 76.99 H (%) 5.01 N (%) 17.70 Examples 3 to 6 N, The reaction and post-treatment were carried out in the same manner as in Example 1 except that the formamides shown in Table 1 were used instead of N '-(4-methyl-O-phenylene) diformamide, and the results shown in Table 1 were obtained. Obtained.

Claims (2)

[Claims] 1. A general formula (In the formula, R ₁ and R ₂ represent a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxyl group, and a lower alkoxycarbonyl group. However, both R ₁ and R ₂ are not hydrogen atoms. R ₁ and R ₂ may combine to form a naphthalene ring). 2. General formula (In the formula, R ₁ and R ₂ represent a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxyl group, and a lower alkoxycarbonyl group. However, both R ₁ and R ₂ are not hydrogen atoms. R ₁ and R ₂ may combine to form a naphthalene ring.) A general formula characterized by reacting a formamide represented by the formula (1) with a dehydrating agent in the presence of a basic amine. (In the formula, R ₁ and R ₂ have the same meanings as described above.) A method for producing O-diisocyanobenzenes.