JPH0657687B2 - Fluorodinitrobenzene derivative and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to intermediates, particularly formulas useful as intermediates for agricultural chemicals. 2,4-dinitro-5-fluorophenoxyacetonitrile and a method for producing the same.

<Prior Art> Conventionally, 2- (7-fluoro-4-propargyl-2H-1,4) has been used as a compound having a particularly strong pesticidal activity.
-Benzoxazin-8 (4H) -on-6-yl)-
Tetrahydrophthalimide derivatives such as 4,5,6,7-tetrahydroisoindole-1,3-dione are known, but these compounds use 2-nitro-5-fluorophenoxyacetic acid as a starting material. Therefore, many steps have to be performed for its production, which is very complicated in terms of operation, and is not sufficiently satisfactory as an industrial production method.

<Problems to be Solved by the Invention> Therefore, as a result of research to develop an intermediate for advantageously producing the above-mentioned tetrahydrophthalimide derivative, the present inventors Succeeded in developing 2,4-dinitro-5-fluorophenoxyacetonitrile shown, which compound undergoes reductive cyclization,
The present invention has been completed by finding that a tetrahydrophthalimide derivative can be easily obtained by alkylation followed by imidization, and that it is extremely useful as an intermediate thereof.

<Means for Solving Problems> The present invention provides 2,4-dinitro-5-fluorophenoxyacetonitrile represented by the above formula,
Further, as its manufacturing method, 1,5-difluoro-2,4-
Provided is a method of reacting dinitrobenzene with glycolonitrile.

In the reaction of 1,5-difluoro-2,4-dinitrobenzene and glycolonitrile, glycolonitrile is used in an amount of 1 to 1.5 equivalent times with respect to 1,5-difluoro-2,4-dinitrobenzene.

A base catalyst is usually used in this reaction, and examples of the catalyst include sodium hydroxide, potassium hydroxide, potassium carbonate, sodium hydrogen carbonate, pyridine, triethylamine, N, N-dimethylaniline, and the like. The amount used is from the catalyst amount to 2 equivalent times, preferably 1 to 1,5-difluoro-2,4-dinitrobenzene.
~ 1.2 equivalent times.

This reaction is usually carried out in a solvent, and as the solvent, toluene, xylene, acetone, tetrahydrofuran, ethyl acetate, methylene chloride, chloroform, chlorobenzene,
An organic solvent such as acetonitrile, N, N'-dimethylformamide, dimethylsulfoxide, or the like, or water or a mixed solvent thereof is used.

The reaction temperature is −50 to 200 ° C., preferably −20 to 15
It is 0 ° C., and the reaction time is generally 1 to 10 hours.

<Effects of the Invention> Thus, according to the method of the present invention, 2,4-dinitro-5-fluorophenoxyacetonitrile, which is a useful intermediate such as an agricultural chemical, can be easily obtained in good yield, and the compound is, for example, The tetrahydrophthalimide derivative can be easily derived by subjecting this to a reductive cyclization, alkylation, or imidization, and therefore its industrial utility value is extremely high.

<Examples> The present invention will be described below with reference to Examples.

Example 1 7.4 g of 1,5-difluoro-2,4-dinitrobenzene
Then, 4.4 g of triethylamine was dissolved in 74 g of toluene, and a mixed solution of 3.1 g of glycolonitrile and 6.2 g of toluene was added dropwise at room temperature. After stirring for another 2 hours at room temperature, 5%
It was poured into an aqueous hydrochloric acid solution and extracted with ethyl acetate. The organic layer was washed with water and then concentrated to give 8.2 g of 2,4-dinitro-5.
-Fluoro-phenoxyacetonitrile was obtained.

Yield: 93.8% Melting point: 112-113 ° C (recrystallized from ethyl acetate-hexane) NMR δ (CDC ₃ -DMSO-d ₆ ) 8.88 (1H, d, J =
8Hz), 7.84 (1H, d, J = 13Hz), 5.40 (2H,
s) 1R (nujol) 1600 cm ⁻¹ (benzene nucleus), 1510 and 1340 cm ⁻¹ (nitro group) EI-MS M / Z241 (M ⁺ ), 186, 169, 97 Example 2 1,5-difluoro-2, 4-dinitrobenzene 3.8g
And anhydrous potassium carbonate 3.1 g acetonitrile 50 m
Suspended in. Glyconitrile 1.5 under stirring at room temperature
A solution of g in 10 ml of acetonitrile was added dropwise.
After stirring at room temperature for 1 hour, the temperature was raised and the mixture was refluxed for 30 minutes (internal temperature 83 ° C.). After cooling, the mixture was poured into water and extracted with ethyl acetate. The organic layer was washed with water and then concentrated to obtain 4.0 g of crystals of 2,4-dinitro-5-fluorophenoxyacetonitrile. (Yield 89.1%) From the melting point, NMR, IR and GLC, it was confirmed that the obtained crystal was the same as the compound obtained in Example 1.

Example 3 2 g of 1,5-difluoro-2,4-dinitrobenzene,
Acetone (20 g) and 50% glycolonitrile aqueous solution (1.2 g) were mixed, and while stirring, a solution prepared by dissolving 0.9 g of sodium hydrogen carbonate in 18 g of water was added to 27 to 30.
The mixture was added dropwise at 5 ° C for 5 minutes. Then, stirring was continued at 27 to 41 ° C. for 4.5 hours.

After completion of the reaction, the reaction solution was poured into 1% hydrochloric acid water, extracted with ethyl acetate, and then the extract solution was concentrated.

The concentrated liquid was filtered to separate precipitated crystals and dried to obtain 2.0 g of 2,4-dinitro-5-fluorophenoxyacetonitrile.

(Yield 83.0%) From the melting point, IR, NMR and GLC, it was confirmed that the obtained crystal was the same as the compound obtained in Example 1.

Claims (2)

[Claims] 1. A formula 2,4-dinitro-5-fluorophenoxyacetonitrile represented by 2. A formula characterized by reacting 1,5-difluoro-2,4-dinitrobenzene with glycolonitrile. A method for producing 2,4-dinitro-5-fluorophenoxyacetonitrile acetonitrile represented by: