JPS5978158A - 3,3-dichloro-4-phenylpyrroline derivative and its preparation - Google Patents

Abstract

NEW MATERIAL:A compound shown by the formula I (X is halogen, nitro, or CF3; n is 0-2). EXAMPLE:3,3-Dichloro-4-(2,3-dichlorophenyl)-DELTA'-pyrroline. USE:An intermediate for preparing a 4-phenylpyrrole derivative such as a compound shown by the formula II, etc. useful as a drug, agricultural chemical, or its intermediate. PROCESS:A compound (novel substance) shown by the formula III obtained from a diazonium salt of an aniline and 2,4-dichlorocrotonaldehyde is reacted with ammonia gas or ammonia water in an organic solvent such as glyme, ether, etc. at room temperature -50 deg.C, to give a compound shown by the formula I .

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel compound and a method for producing the same. The represented compounds and their production methods.

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, by reacting the compound of the present invention with a Vilsmeier reagent, such as an adduct of dimethylformamide and phosphorus oxychloride,
4-Phenyl/l/-3-chloro- useful as a fungicide
A virol derivative is obtained.

The compound of the present invention is produced by reacting a compound represented by the general formula IHO with ammonia or aqueous ammonia in an organic solvent. As the organic solvent, ethers such as glyme, dioxane and ethyl ether isopropyl ether, alcohols such as ethanol and propanol, and inert solvents such as benzene can be used, but ethers are preferred. The reaction is carried out at room temperature to 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 virol 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 (10) is a new compound and can be produced by reacting the corresponding diazonium salt of anilines with 2,4-dichlorocrotonaldehyde.

The structure of the compound of the present invention was determined from the results of spectrum measurements such as MASS and NMRS Il'.

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

Example 1゜3-(2,3-dichlorophenyl)-2,2,4-)
Riff Four Luptanal 12.8N Grime 80WLIK
The mixture was dissolved and ammonia gas was blown into the solution 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 erthyl solution under cooling with ice water, and the precipitate was filtered and washed with ether to obtain the solution in 3. of 12.151.
3-dichloro-4(-2,3-dichlorophenyl)-Δ
'-pyrroline hydrochloride was obtained. The hydrochloride was suspended in water 1001, and neutralized by adding a saturated aqueous sodium bicarbonate solution while cooling. After extraction by adding 200 Wll of ether,
Wash with water, dry, and remove the solvent under reduced pressure to obtain 10.0 g of 3.
3-dichloro-4-(2,3-dichlorophenyl)-△
I-pyrroline was obtained.

Yield 88%, n, 1.5937 Mass spectrum M”=281 4.5 ppm (IH), 6.5-7.0 ppm (
4H) Example 2゜3-(2,3-dichlorophenyl)-2,2,4-)
Lichlorputanal 3,21 was dissolved in ether 6o-, and ammonia gas was blown into the solution 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 material was collected using silica gel column chromatography (benzene: n
- Hexane = 1 = 1 solution) to purify with 3.3 of 2.3.9
-dichloro-4-(2,3-dichlorophenyl)-I
- Obtained vilorin. Yield 81% Example 3 3.21 of 3-(2,3-dichlorophenyl)-2,2,4-trichlorobutanal was dissolved in glyme H)rug, and 10 m/28% aqueous ammonia was added. , 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. 2.4. 9 crude product was obtained. This product was purified by silica gel column chromatography (benzene:n-hexane=x:1 solution), and 1.3I of 3
．． 3-dichloro-4-(2,3-dichlorophenyl)-
I got △z-Birorin.

Yield 46% Example 4゜3-PhenyA/-2,2,4-)lichlorputanal 4
．． 511 was dissolved in Grime 60d, and ammonia gas was blown into the solution at 38° C. for 4.5 hours while stirring. After separating the precipitate from P, the solvent was distilled off under reduced pressure. The residue was dissolved in ether 701, washed with water, and then dried. Hydrogen chloride gas was blown into the ether solution under cooling with ice water, and the precipitate was filtered and washed with ether to obtain 3.8 g of 3.3-dichloro-4-phenyl-Δ'-hyroline hydrochloride.

This material was suspended in 50 d of water and neutralized by adding saturated sodium bicarbonate solution while cooling. After extraction by adding 8 Qm/ of ether, washing with water, drying, and distilling off the solvent, 2.81 of 3.3-dichloro-4-phenyl-ΔI-pyrroline was obtained. Yield 73% n2D' = 1.5748IR (cm
-' ) = 1620, 1605, 1585, 1500,
455 Example 5゜3-(2-)lifluoromethylphenyl) -2゜2.
4-) Dichlorobutanal 4.5 Ii to Glyme 60
The mixture was dissolved in water, and ammonia gas was blown into the mixture at 40° C. for 4 hours while stirring. Hereinafter, the same treatment as in Example 4 was carried out to obtain 2.9 I
3,3-dichloro-4-(2F)lifluoromethyl7-el)-ΔI-pyrroline of I was obtained.

Yield 74%, n2♂1.5112 IR(Cm-1) = 1625.1605.1585
．． 1310 Example 6 5.0 g of 3-(2-chlorophenyl)-2,2,4-)dichlorobutanal was dissolved in 60 WL of glyme, and ammonia gas was blown into the solution at 40° C. for 4 hours while stirring. Thereafter, the same procedure as in Example 4 was carried out to obtain 2.29 3,3-dichloro-4-(2-ri-tetralphenyl)-ΔI-pyrroline. Yield 51%, ns+D1.5815IR(cm
-' ) = 1620.1595.1570.1480
．． 144゜Example 7゜3-(2-nitrophenyl)-2,2,4-)dichlorobutanal 10. ON was dissolved in Glyme 80-, and ammonia gas was blown into the solution at 36° C. for 4 hours while stirring.

Thereafter, the same procedure as in Example 4 was carried out to obtain 5.611 3.3-dichloro-4-(2-nitrophenyl)-Δl-viroline. Yield 64%, rl”71.58611 R(
cm') = 1620.1610.1580. 15
30. 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゜■ CHo・3-(2,3-dichlorophenyl)-2,2,4-trichlorobutanal 3.21 was dissolved in glyme 60d,
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 2.8 g of oil.

Meanwhile, 10 m of N,N-dimethylformamide was added under cooling with ice water.
A Vilsmeier reagent was prepared by gradually adding 3.08.9% of phosphorus oxychloride into 1 and then stirring at room temperature for 20 minutes. The previously obtained oil was gradually added to this solution while cooling with ice water, and stirring was then continued at 96° C. for 7 hours. The mixture was extracted with 100 d of ethyl acetate, washed with water, dried, and concentrated to obtain a crude product. Silica gel chromatography method (benzene: n-hexane = 1
= 1 solution) to produce 2.03 g of 3-chloro-4-(
2,3-dichlorophenyl)-1-formylvirol was obtained.

Yield 74% Production Example 2 A solution of 3.81 sodium nitrite dissolved in 8 tnl of water in a solution consisting of 8.2 F (0.05 mol) of 2.3-dichloroaniline, 10 of water and 15 ml of concentrated hydrochloric acid. 0-2
It was added dropwise at ℃. After stirring for 20 minutes, the mixture was filtered to obtain an aqueous solution of diazonium salt.

=11-2.4-dichlorocrotonaldehyde 4.71(0,0
33 moles), acetone 20+1J, and potassium chloride 9.
Add the previously prepared diazonium salt aqueous solution to 2 g of the mixed solution.
Added at ~5°C. The pH was adjusted to 2 with a saturated aqueous sodium acetate solution, cupric chloride I11 was added, and the mixture was reacted at 15 to 20°C for 18 hours. After the reaction was completed, it was extracted three times with ether 30-
After washing with saturated brine and drying over magnesium sulfate, the ether was distilled off. The obtained oil was distilled to obtain 4.8 g of the target product.
I got it.

Yield 45%, melting point 76°C, boiling point 140-148° (70
, 3MH# Production Example 3゜ Add 1.31 mol of sodium nitrite to a solution consisting of 1.7 N (0,018 mol) of aniline, 81 mol of water and 5 rxl of concentrated hydrochloric acid.
A diazonium salt aqueous solution was prepared by preparing 12= of water.

2.4-dichlorocrotonaldehyde 7.5g (0,0
Add the previously prepared diazonium salt aqueous solution to a mixture of 53 mol), acetone 18-, and 1.9 g of sodium acetate at 0 to 5°C.
I added it. To this, lithium chloride 1.211 cupric chloride 0
．． 3 gM' was added and reacted at 15-20°C for 18 hours.

Acetone was distilled off from the reaction solution, extracted twice with 40 ml of ether, and then the extract was dried over magnesium sulfate and the ether was distilled off. Distill the remaining oily substance to obtain 1.9g of the target product.
I got it.

Yield 41.4%, boiling point 96-97'C10, 15mH
Preparation Example 4 2.9 (0,0156 mol) of 2-chloroaniline and a diazonium salt aqueous solution was prepared in the same manner as in the case of water extraction.

2.4-dichlorocrotonaldehyde 6.5 g (0,0
467 mol), acetone isy and sodium acetate 1.71
The previously prepared diazonium salt aqueous solution was added to the mixed solution at 0 to 5°C. This gave 2°211 of lithium chloride. Boiling point 110-115 °C 10,1 m) (II.

Yield 49.0% Applicant: 2 Nippon Soda Co., Ltd. Agent: Haruyuki Ito Same: Yoshimi Yokoyama 15-

Claims (2)

[Claims] (1) A compound represented by the general formula (wherein, X is a halogen atom, a nitro group, or a trifluoromethyl group, and n is 0.1 or 2). (2) A compound represented by the general formula (wherein, X represents a halogen atom, a nitro group, or a trifluoromethyl group, and n represents 0.1 or 2) is reacted with ammonia gas or aqueous ammonia in an organic solvent. A method for producing a compound represented by the general formula (wherein X and n are the same as above), characterized by: