JPS58185559A - Production of 3-phenylpyrole derivative - Google Patents

Abstract

PURPOSE:Novel halogeno-3-phenylbutyraldehyde, which is readily available, is used as a starting material in the reaction with ammonia or water in an organic solvent to produce 3-phenyl-pyrole derivative used as a bactericidal agent or its intermediate through a shortened process. CONSTITUTION:A novel compound of formula I (X is halogen, nitro, haloalkyl; n is 0, 1, 2; Y is H, halogen) such as 2,2,4-trichloro-3-(2,3-dichlorophenyl)butyraldehyde is made to react with ammonia or water in an organic solvent such as ethanol or methanol to give a 3-phenylpyrole derivattive of formula II (Z is H, Cl). The compound of formula I is obtained by reaction of a diazonium salt of a corresponding aniline and 2,4-dichlorocrotonaldehyde.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel manufacturing method for a 3-phenylpyrrole brocade conductor, and more specifically, the present invention relates to a novel manufacturing method for a 3-phenylpyrrole brocade conductor, and more particularly, the present invention relates to a novel method for manufacturing a 3-phenylpyrrole brocade conductor, and more particularly, the present invention relates to a method of manufacturing a 3-phenylpyrrole brocade conductor using the general formula Halodan atom, n is 0,1
or 2. ) with ammonia or ammonia hydrate in an organic solvent (wherein, X and no have the same meanings as above, and 2 represents a water bulk atom or a chlorine atom. ) is a method for producing a compound represented by

The compound represented by the Mayuki general formula (1) is a compound useful as a monocide or an intermediate thereof (Japanese Patent Application Laid-open No. 54-10
3865.55-157565.56-18960,
55-160760),.

In particular, when the 4-position is substituted with chlorine, in view of the reactivity of pyrrole, the method for producing it is to protect both α-positions of pyrrole O with a retaining group that is easily eliminated, and then chlorinate the β-position. There are known ways to do it.

However, these known methods require a large number of steps and are complicated to operate, so they cannot be said to be industrially preferred.

jjoli, 0OOOH.

(41111154-103865) cooct.

RR The present inventors have completed the present invention through repeated research on a method for industrially advantageous production of 3-phenylpyrroles with a small number of steps.

゛The method of the present invention aims to significantly shorten the steps by using the novel butyraldehyde represented by the above general formula (1) as a raw material.

In carrying out the present invention, the compound represented by the general formula (1) is heated without a solvent or in an appropriate organic solvent to react with ammonia or aqueous ammonia, thereby simultaneously performing a ring-closing reaction and a dehalonation reaction. Let it happen.

As the organic solvent, ethanol, methanol, ethylene glycol methyl ether (glyme), diethylene glycol dimethyl ether (noblime), etc. are used. The reaction takes place between temperature °C and the boiling point of the solvent,
It is also possible to improve the yield by heating the reaction for 3 to 5 hours, cooling it to room temperature, adding a base, and leaving it at room temperature for an additional several hours to 10 hours.

As the base, bases such as triethylamine and 1,8-notodebicyclo(5,4,0:]-]7-unodecene are used.

After the reaction is complete, the ammonium chloride produced when reacting with ammonia gas is separated by F, the P solution is concentrated to obtain a crude product, which is then reacted with aqueous ammonia and then extracted with an appropriate organic solvent. is distilled off to obtain a crude product. The target product can be obtained in good yield by purifying the obtained nine crude products by column chromatography.

The raw material compound represented by the general formula (1) is a new compound that has not been described in any literature, and can be easily produced, for example, by reacting the corresponding soryzonium salt of aniline with 2,4-dichlorocrotonaldehyde.

Hereinafter, the method of the present invention will be explained in more detail with reference to Examples.

Example 1 2.2.4-Trichloro-3-(2,3-dichlorophenyl)f-thylaldehyde was dissolved in 1.6 fl of Noglyme 5-, added with 28 ml of aqueous ammonia, and heated at about 100°C for 3 hours. Stirred. Two times more 28Is aqueous ammonia was added, and the mixture was further heated and stirred for 1 hour, and then allowed to stand overnight at room temperature.

After extraction with ethyl ether and drying over magnesium sulfate, the enal ether was distilled off to obtain a brown oil '11J-3. This oil was poured into a silica powder.

Purify by column chromatography to obtain the target product 0.54 f
(obtained) Melting point: 59-0°C Yield: 438cm Example 2
Addition of water was added, and the mixture was heated and stirred at -C90°C for 3 hours. 6- Add A/Moni T water 5-, and then add 3
After heating and stirring for an hour, the mixture was kept at a temperature of 'M' for 14 hours. After distilling off Nooxa/, it was extracted with ethyl acetate, washed with saturated brine, dried over magnosulfate, and the solvent was distilled off.
Ta. The obtained crude #IJ was purified by 7 liter column chromatography to obtain 0.65 f of the target product.

%p"' 1.6343 'iL Rate 48.5 Example 3 I 2.2.4- ) Dichloro-3-(2-chlorophenyl)butyraldehyde 1.5 t was dissolved in Nooxa/10- and 25Is Add ammonia water 5- dropwise and heat at 90℃.
The mixture was heated and stirred for hours. Add 5-25% ammonia water,
After further heating and stirring for 3 hours, the mixture was left undisturbed at room temperature for 16 hours.

After distilling off dioxane, the mixture was extracted with ethyl acetate, washed with saturated brine, dried over magnesium sulfate, and then the solvent was distilled off. The obtained composition was purified by silica dull column chromatography to obtain the target product of 0.75V. Melting point 68-70°C Yield 67.5-Example 4 Otori 2.2.4-Trichloro-3-(2-nitrophenyl)
1.52 kg of butyraldehyde was dissolved in 10 mg of dioxane, and the same procedure as in Example 3 was carried out to obtain 0.8 f of the target product. 1) 111-113°C Yield 64-Example 5 az oz 4h 2.2.4-) Rechloro 3-(2,3-sochlorophenyl)butyraldehyde 3.2f was added to grime 40s
After cooling the reaction solution to room temperature, the resulting precipitate was separated from P, and the P solution was mixed with 1.8-noadebicyclo[5゜4-0]-7.
-0.8 t of undecene was added and stirred at room temperature overnight. Insoluble matter was separated from P and Ft was concentrated (under reduced pressure), and the resulting residue was purified by 7 liter column chromatography to obtain the target product 2f. Melting point 59-60°C Yield 81-% Example 6 2.2.4-) LichloroC1-3-(2-trichloromethyl)! Chill Ryoruhito 3.1f was dissolved in grime lead, and anno4nia gas was blown into it for 3 hours at Koen temperature, and the temperature was further heated at 40°C.
So I blew Anmine Niagasu for 3 hours.

After cooling to room temperature, it was heated in the same manner as in Example 5 to obtain the target object 1.5.
Get an F. Melting point 43-52℃ Yield 63 - Patent applicant Nippon Ikken Co., Ltd.

Claims (1)

[Claims] (1) A compound represented by the general formula (in the formula, 2 represents a halodane atom, a nitro group, or a haloalphalytic group, n represents 0.1 or 2, and Y represents a hydrogen atom or a halodane atom). , ammonia or aqueous ammonia in an organic solvent, and is represented by the general formula (wherein ! and n have the same meanings as above, and 2 represents a hydrogen atom or a chlorine atom). Method of manufacturing the compound.