JPH0261943B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel compound and a method for producing the same. This is a compound and a method for producing the same.

The compound of the present invention is useful as an intermediate for producing 4-phenylpyrrole derivatives useful as medicines, agricultural chemicals, or intermediates thereof. For example, as shown in the reaction formula below, a 4-phenyl-3-chloro-pyrrole derivative useful as a disinfectant can be obtained by reacting the compound of the present invention with a Vilsmeier reagent, such as an adduct of dimethylformamide and phosphorus oxychloride. It will be done.

K0391 The compound of the present invention is produced by reacting a compound represented by the general formula K0392 with ammonia or aqueous ammonia in an organic solvent. Examples of organic solvents include glyme, dioxane,
Ethers such as ethyl ether and isopropyl ether, alcohols such as ethanol and propanol, and inert solvents such as benzene can be used, but ethers are preferred. The reaction is at room temperature ~
The temperature is preferably 50°C, preferably around 40°C, and at high temperatures a pyrrole ring is produced by dehydrochlorination. After completion of the reaction, the solvent is distilled off, dissolved in an appropriate organic solvent, washed with water, and the solvent is distilled off to obtain a crude product of the compound of the present invention. When producing the above-mentioned pyrrole derivative, the obtained crude product can be directly subjected to the next reaction without purifying and isolating the compound of the present invention.

In the case of purification and isolation, hydrogen chloride gas is blown into the organic solvent solution to precipitate crystals as a hydrochloride salt, and after separation, the compound is neutralized to obtain a substantially pure compound of the present invention. However, since the compound of the present invention is relatively unstable, it is desirable to use it in the next step as soon as possible.

The raw material compound () is a new compound and can be produced by reacting the corresponding diazonium salt of aniline with 2,4-dichlorocrotonaldehyde.

The structure of the compound of the present invention was determined from the results of spectrum measurements such as MASS, NMR, and IR.

The manufacturing method of the present invention will be explained in more detail below with reference to Examples.

Example 1 12.8 g of K0393 3-(2.3-dichlorophenyl)-2.2.4-trichlorobutanal was dissolved in 80 ml of glyme,
Ammonia gas was blown into the mixture at 40° C. for 4 hours while stirring. After separating the precipitate, the solvent was distilled off under reduced pressure.
The residue was dissolved in 200 ml of ether, washed with water, and then dried. Hydrogen chloride gas was blown into this ether solution while cooling with ice water, and the precipitate was filtered and washed with ether.
12.1 g of 3.3-dichloro-4-(2,3-dichlorophenyl)-Δ'-pyrroline hydrochloride was obtained. The hydrochloride was suspended in 100 ml of water, and neutralized by adding saturated aqueous sodium bicarbonate solution while cooling. ether
After extraction by adding 200ml of 3.3-dichloro-4-(2.3-
Dichlorophenyl)-Δ'-pyrroline was obtained.

Yield 88% n ^30.5 _D 1.5937 Mass spectrum M ⁺ = 281 IR (cm ^-1 ) 1620, 1580, 1560, 1450, 1420 NMR (CDCl ₃ ) δ = 3.9-4.1ppm (2H), 4.4-4.5ppm (1H ), 6.5-7.0ppm (4H) Example 2 3.2g of K0394 3-(2.3-dichlorophenyl)-2.2.4-trichlorobutanal was dissolved in 60ml of ether,
Ammonia gas was blown in under reflux conditions for 4 hours.
Ether was added to the reaction solution, washed with water, dried, and the ether was distilled off under reduced pressure to obtain 2.8 g of a crude product. This product was purified by silica gel column chromatography (benzene: n-hexane = 1:1 solution) and 2.3g
3,3-dichloro-4-(2,3-dichlorophenyl)
-Δ'-pyrroline was obtained. Yield 81% Example 3 3.2 g of K0395 3-(2.3-dichlorophenyl)-2.2.4-trichlorobutanal was dissolved in 10 ml of glyme.
10 ml of 28% aqueous ammonia was added, and stirring was continued for 2 hours under reflux conditions. Ether was added to the reaction solution to separate the layers, followed by washing with water, drying, and distilling off the solvent to obtain 2.4 g of a crude product. This product was purified by silica gel column chromatography (benzene:n-hexane=1:1 solution) to obtain 1.3 g of 3.3-dichloro-4-(2.3-dichlorophenyl)-Δ'-pyrroline.

Yield 46% Example 4 K0396 3-phenyl-2.2.4-trichlorobutanal
4.5 g was dissolved in 60 ml of glyme, and ammonia gas was blown into the solution at 38° C. for 4.5 hours while stirring. After separating the precipitate, the solvent was distilled off under reduced pressure. Ether the residue
It was dissolved in 70 ml, washed with water, and then dried. While cooling with ice water, hydrogen chloride gas was blown into this ether solution, and the precipitate was filtered and washed with ether to give 3.8 g of 3.3
-dichloro-4-phenyl-Δ'-pyrroline hydrochloride was obtained. This material was suspended in 50 ml of water and neutralized by adding saturated sodium bicarbonate solution while cooling. After extraction with 80ml of ether, wash with water, dry,
The solvent was distilled off to obtain 2.8 g of 3.3-dichloro-4-phenyl-Δ'-pyrroline. Yield 73% n ²⁸ _D =
1.5748 IR (cm ^-1 ) = 1620, 1605, 1585, 1500, 1455 Example 5 K0397 3-(2-trifluoromethylphenyl)-
2.2.4 - 4.5 g of trichlorbutanal in 60 grams of glyme
ml, and ammonia gas was blown into the solution at 40° C. for 4 hours while stirring. Hereafter, the same process as in Example 4 was carried out.
2.9 g of 3.3-dichloro-4-(2-trifluoromethylphenyl)-Δ'-pyrroline was obtained.

Yield 74%, n ²⁹ _D 1.5112 IR (cm ^-1 ) = 1625, 1605, 1585, 1310 Example 6 5.0 g of K0398 3-(2-chlorophenyl)-2.2.4-trichlorobutanal was dissolved in 60 ml of glyme. Ammonia gas was blown into the mixture at 40° C. for 4 hours while stirring. Thereafter, the same procedure as in Example 4 was carried out to obtain 2.2 g of 3.3-dichloro-4-(2-chlorophenyl)-Δ'-pyrroline. Yield 51%, n ²⁵ _D 1.5815 IR (cm ^-1 ) = 1620, 1595, 1570, 1480, 1440 Example 7 K0399 10.0 g of 3-(2-nitrophenyl)-2.2.4-trichlorobutanal was added to 80 ml of grime. The mixture was dissolved and ammonia gas was blown into the mixture at 36° C. for 4 hours while stirring.
Thereafter, the same procedure as in Example 4 was carried out to obtain 5.6 g of 3.3-dichloro-4-(2-nitrophenyl)-Δ'-pyrroline. Yield 64%, n ²⁸ _D 1.5861 IR (cm ^-1 )=1620, 1610, 1580, 1530, 1350 Next, production examples showing the usefulness of the compounds of the present invention and production examples of raw material compounds will be shown.

Production example 1 K0400 3-(2.3-dichlorophenyl)-2.2.4-trichlorobutanal 3.2g was dissolved in 60ml of glyme,
Ammonia gas was blown into the mixture at 40° C. for 4 hours while stirring. After distilling off the solvent under reduced pressure, the residue was dissolved by adding ether and water, separated into layers, washed with water, and dried. Concentration gave 2.8g of oil.

Meanwhile, 3.08 g of phosphorus oxychloride was gradually added to 10 ml of N,N-dimethylformamide while cooling with ice water.
Thereafter, the Vilsmeier reagent was prepared by stirring at room temperature for 20 minutes. The previously obtained oil was gradually added to this solution while cooling with ice water, and then stirring was continued at 96°C for 7 hours. The mixture was extracted with 100 ml of ethyl acetate, washed with water, dried, and concentrated to obtain a crude product. It was purified by silica gel chromatography (benzene: n-hexane = 1:1 solution) to obtain 2.03 g of 3-chloro-4-(2.3-dichlorophenyl)-1-formylpyrrole.

Yield 74% Production example 2 K0401 2,3-dichloroaniline 8.2g (0.05 mol),
A solution of 3.8 g of sodium nitrite dissolved in 8 ml of water was added dropwise to a solution of 10 ml of water and 15 ml of concentrated hydrochloric acid at 0 to 2°C. After stirring for 20 minutes, the mixture was filtered to obtain an aqueous solution of diazonium salt.

2,4-dichlorocrotonaldehyde 4.7g
(0.033 mol), 20 ml of acetone, and potassium chloride
The previously prepared diazonium salt aqueous solution was added to 9.2 g of the mixed solution at 0 to 5°C. Adjust the pH to 2 with a saturated aqueous solution of sodium acetate, add 1 g of cupric chloride, and raise the pH to 15-20.
The reaction was allowed to take place at ℃ for 18 hours. After the reaction is complete, add 30 ml of ether.
The extract was extracted three times with water, washed with saturated brine, dried over magnesium sulfate, and then the ether was distilled off. The obtained oil was distilled to obtain 4.8 g of the desired product.

Yield 45%, melting point 76℃, boiling point 140-148℃/0.3mmHg Production example 3 K0402 K0403 Add 1.3g of sodium nitrite to a solution consisting of 1.7g (0.018 mol) of aniline, 8ml of water, and 6ml of concentrated hydrochloric acid.
A diazonium salt aqueous solution was prepared in the same manner as in Production Example 2 by adding dropwise the solution dissolved in 1 mL of the solution.

2,4-dichlorocrotonaldehyde 7.5g
(0.053 mol), acetone 18 ml and sodium acetate 1.9 g
The previously prepared diazonium salt aqueous solution was added to the mixed solution at 0 to 5°C. To this, 1.2g of lithium chloride,
0.35 g of cupric chloride was added and reacted at 15 to 20°C for 18 hours. Distill acetone from the reaction solution to ether 40
After extracting twice with ml, the extract was dried over magnesium sulfate and the ether was distilled off. The remaining oil was distilled to obtain 1.9 g of the desired product.

Yield 41.4%, boiling point 96-97℃/0.15mmHg Production example 4 K0404 K0405 2-chloroaniline 2g (0.0156 mol), water 9
ml of sodium nitrite and 6 ml of concentrated hydrochloric acid.
A solution of 1.2 g dissolved in 4 ml of water was added dropwise to prepare a diazonium salt aqueous solution in the same manner as in Production Example 2.

2.4-dichlorocrotonaldehyde 6.5g
(0.0467 mol), acetone 18 ml and sodium acetate 1.7
The previously prepared diazonium salt aqueous solution was added to the mixture of g at 0 to 5°C. This includes lithium chloride
0.9 g of cupric chloride and 0.2 g of cupric chloride were added, and the mixture was reacted at 15 to 20°C for 22 hours. The target product is prepared in the same manner as in Production Example 2.
2.2g was obtained. Boiling point 110-115℃/0.1mmHg, yield 49.0%.

Claims (1)

[Claims] 1 General formula K0387 (wherein, X is a halogen atom, a nitro group, or a trifluoromethyl group, and n is 0, 1, or 2)
A compound represented by 2 General formula K0388 (However, X represents a halogen atom, a nitro group, or a trifluoromethyl group, and n represents 0, 1 or 2.)
A method for producing a compound represented by the general formula K0389 (wherein X and n are the same as above), which comprises reacting the compound represented by the above with ammonia gas or aqueous ammonia in an organic solvent.