JPH0830053B2 - Chlorodinitrobenzene derivative and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Field of Application> The present invention provides a compound of formula (I) useful as an intermediate, especially as an intermediate for agricultural chemicals. And a method for producing the same.

<Prior Art> Traditionally, 2- (7-fluoro-4-propargyl-2H-1,4-
Benzoxazin-3 (4H) -on-6-yl) -4,5,
Tetrahydrophthalimide derivatives such as 6,7-tetrahydroisoindole-1,3-dione are known, but the compounds are prepared by using 2-nitro-5-fluorophenoxyacetic acid as a starting material. For this reason, many steps have to be taken, and the operation becomes very complicated, which 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 inventor has shown that the above formula ( The chlorodinitrobenzene derivative represented by I) was successfully developed, and the compound was easily fluorinated, reductively cyclized, alkylated, and then imidized to give a tetrahydrophthalimide derivative. The present invention has been found to be useful, and the present invention has been completed.

<Means for Solving Problems> The present invention provides a chlorodinitrobenzene derivative represented by the above formula (I), and its production method is 1,5-dichloro-2,4-dinitrobenzene. The present invention provides a method for reacting glycerin with glycolonitrile.

In the reaction of 1,5-dichloro-2,4-dinitrobenzene and alcohol (II), glycolonitrile is 1 to 3 equivalent times with respect to 1,5-dichloro-2,4-dinitrobenzene, preferably 1 to Used in 2 equivalents.

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 3 equivalent times, preferably 1 to 2 equivalent times, based on the catalytic amount with respect to 1,5-dichloro-2,4-dinitrobenzene.

It is also possible to use a copper catalyst such as cuprous chloride, cuprous oxide or copper powder or a phase transfer catalyst such as 18-crown-6 or TDA-1 as the catalyst.

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

The reaction temperature is -50 to 200 ° C, preferably -20 to 150 ° C, and the reaction time is generally 1 to 50 hours.

<Effect of the Invention> Thus, according to the method of the present invention, a chlorodinitrobenzene derivative represented by the formula (I), which is a useful intermediate for agricultural chemicals and the like, can be easily obtained in good yield, and the compound is The tetrahydrophthalimide derivative can be easily derived by subjecting this to fluorination, 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 5.0 g of 1,5-dichloro-2,4-dinitrobenzene, 1.81 g of glycolonitrile and 2.19 g of anhydrous potassium carbonate were stirred in 20 g of dimethylformamide at 25 to 30 ° C. for 24 hours.

After the reaction is complete, dilute the reaction mixture with 200 ml of water and wash with ethyl acetate.
It was extracted with 00 ml. The organic layer is washed with water, dried over magnesium sulfate and then concentrated. The precipitated crystals were filtered off and washed with ether to obtain 4.16 g of crude crystals.

The obtained crude crystals were subjected to fractional crystallization with methanol, and the by-product 1,5-bis (cyanomethoxy) -2,4-dinitrobenzene 0.38 g and the target 2,4-dinitro-5-
3.18 g of chlorophenoxyacetonitrile (yield 58.5%)
I got

Melting point 117-118 ° C Elemental analysis C ₈ H ₄ ClN ₃ O ₅ C H N Cl Calculated 37.30 1.57 16.31 13.77% Experimental 37.66 1.66 16.55 13.74% NMR δ CDCl ₃ -DMSO 5.40 (S, 2H), 7.89 (S , 1H),
8.20 (S, 1H) Example 2 5.0 g of 1,5-dichloro-2,4-dinitrobenzene, 1.81 g of glycolonitrile and 3.20 g of triethylamine were stirred in 20 g of dimethylformamide at 25-30 ° C for 24 hours. After completion of the reaction, the same treatment as in Example 1 was carried out to obtain 3.49 g of crude crystals. Recrystallization treatment of the obtained crude crystals with methanol,
2,4-dinitro-5-chlorophenoxyacetonitrile
3.02 g (yield 55.6%) was obtained. The obtained crystal was obtained in Example 1
It was identified by the melting point, NMR, TLC, and GLC with the standard product obtained in.

Reference Example 3 5.0 g of 1,5-dichloro-2,4-dinitrobenzene and 4.2 g of butyl glycolate were dissolved in 15 g of methyl isobutyl ketone, 4.4 g of anhydrous potassium carbonate was added thereto, and the mixture was stirred at room temperature for 7 hours. The reaction solution was poured into water and extracted with toluene, and the organic layer was washed with water and dried. After concentration, methanol was added to the residue, the mixture was cooled, the precipitated crystals were filtered, and 6.0 g of 2,4-
Obtained butyl dinitro-5-chlorophenoxyacetate.

Yield 85.5% Melting point 51.1-51.2 ° C (recrystallized from methanol) NMR δ (CDCl ₃ ) 8.61 (1H, s), 7.10 (1H, s), 4.89
(2H, s), 4.50 (2H, t, J = 6Hz) 1.8 to 1.1 (4H, m), 0.9
2 (3H, t, J = 6Hz) IR (nujol) 1715cm ^-1 (ester group), 1580cm ^-1 (benzene nucleus), 1510 and 1335cm ^-1 (nitro group) Elemental analysis C ₁₂ H ₁₃ ClN ₂ O ₇ C H N Cl calculated value 43.32 3.94 8.42 10.66 (%) Experimental value 43.31 4.04 8.53 11.00 (%) Reference Example 4 3.0 g of 1,5-dichloro-2,4-dinitrobenzene and 1.4 g of methyl glycolate were dissolved in 9 g of acetonitrile, 2.1 g of anhydrous potassium carbonate was added thereto, and the mixture was stirred at room temperature for 2 days.
The reaction solution was poured into ice water and extracted with toluene, and the organic layer was washed with water and dried (MgSO ₄ ). Concentration gave 2.6 g of an oily substance, which was purified by silica gel chromatography (developed with hexane-ethyl acetate) to give 2.3 g of 2,4-dinitro-5-
Methyl chlorophenoxyacetate was obtained.

Yield 62.5% Melting point 119.5-120.5 ° C (recrystallized from methanol) NMR δ (CDCl ₃ ) 8.67 (1H, s), 7.11 (1H, s), 4.90
(2H, s), 3.85 (3H, s), IR (nujol) 1725cm ^-1 (ester group), 1600cm ^-1 (benzene nucleus), 1510 and 1340cm ^-1 (nitro group) Elemental analysis C ₉ H ₇ ClN ₂ O ₇ C H N Cl calculated value 37.19 2.43 9.64 12.20 (%) experimental value 37.10 2.67 9.98 12.16 (%) Reference Example 5 1,5-dichloro-2,4-dinitrobenzene 2.0 g, ethyl glycolate 1.32 g and tris [. 0.27 g of 2- (2-methoxyethoxy) ethyl] amine (TDA-1) was dissolved in 10 g of acetonitrile, 0.88 g of anhydrous potassium carbonate was added thereto, and the mixture was refluxed for 5 hours. After cooling, the reaction solution is 200 ml of 3% hydrochloric acid
And extracted with ethyl acetate. The organic layer was washed with a 5% aqueous sodium carbonate solution, washed with water and dried (MgSO ₄ ). After concentration, the obtained crude crystals were recrystallized from methanol to give 1.9 g.
Of ethyl 2,4-dinitro-5-chlorophenoxyacetate was obtained.

Yield 73.9% Melting point 129-130 ° C (recrystallized from methanol) NMR (CDCl ₃ -DMSO-d ₆ ) 8.68 (1H, s), 7.40 (1H,
s), 5.00 (2H, s), 4.28 (2H, q, J = 8Hz), 1.30 (3H, t, J
= 8Hz) IR (nujol) 1720cm ^-1 (ester group), 1580cm ^-1 (benzene nucleus), 1340cm ^-1 (nitro group) Elemental analysis C ₁₀ H ₉ ClN ₂ O ₇ C H N Cl Calculated value 39.42 2.98 9.20 11.64 (%) Experimental value 39.27 2.99 9.15 11.54 (%) Reference Example 6 5.0 g of 1,5-dichloro-2,4-dinitrobenzene and 4.39 g of ethyl glycolate were dissolved in 20 g of dimethylformamide, and 2.92 g of anhydrous potassium carbonate was added thereto. 2 at 34-37 ° C
It was stirred for 6 hours. The reaction mixture was treated as in Example 5 to give 5.3.
g of ethyl 2,4-dinitro-5-chlorophenoxyacetate was obtained. The crystals obtained were the same as those obtained in Example 5 and GL
It was identified by C, NMR and IR.

Yield 67.5%

Claims (2)

[Claims] 1. A formula A chlorodinitrobenzene derivative represented by. 2. A formula characterized by reacting 1,5-dichloro-2,4-dinitrobenzene with glycolonitrile. A method for producing a chlorodinitrobenzene derivative represented by.