JPS6169A - Cyanopyrrole derivative - Google Patents

Abstract

NEW MATERIAL:A compound expressed by formula I (X is halogen, lower alkyl or lower haloalkyl; n is 1 or 2). EXAMPLE:3-Cyano-4-(2-chlorophenyl)pyrrole. USE:A compound having improved antimicrobial activity, and a compound obtained by acetylation thereof is useful as an agricultural and horticultural germicide. PREPARATION:A tosylmethyl isocyanide expressed by formula II is reacted with a compound expressed by formula II in the presence of sodium hydride to afford the aimed compound expressed by formula I.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel cyanopyrrole derivative represented by the formula (wherein, X represents a halogen atom, a lower alkyl group, or a lower haloalkyl group, and n represents 1 or 2).

Conventionally, various compounds have been known as phenylpyrrole compounds, including 3-chloro-4-(2-nitro-3-
Chlorphenyl) pyrrole (% Kaisho 5 1-88630
It is becoming known that compounds such as 3-chloro-4-(3-trifluoromethylphenyl)pyrrole (1989-2011) and the like have antibacterial properties against plant pathogens. However, these compounds are unstable to sunlight, have low residual efficacy, and are of little practical use as agricultural fungicides.

The present inventors synthesized a large number of phenylpyrrole crocodile conductors and conducted various studies on their antibacterial properties and efficacy as agricultural and horticultural fungicides. It was found that it has antibacterial activity.

Furthermore, compounds represented by the general formula obtained by acetylating the compounds of the present invention, among which compounds in which Xn is 2-CL, have excellent residual efficacy and are excellent compounds as fungicides for agriculture and horticulture.

The compound of the present invention has Tetra-h as shown in the reaction formula below.
edron Letters (1972) 5337
It can be manufactured by a method similar to that shown in .

Hereinafter, the method for producing the compound of the present invention will be described with reference to Examples.

Example 1 Synthesis of 3-Schiff/-4-(2-10ruphenyl)pyrrole (compound 1): 71 ml of 50% oily sodium hydride was added to 200 liters of anhydrous ether and suspended with stirring. In this, 20? and 239v of tosylmethyl isocyanide in 400ml of anhydrous ether! , anhydrous dimethyl sulfoxide 200Tn1. A solution dissolved in the mixture was added dropwise and stirred. After stirring for another 30 minutes after the dropwise addition, the reaction mixture was poured into ice water for 1 hour.
．． 2 was poured into the solution and the ether layer was separated. The aqueous layer was further extracted twice with 300 g of ethyl acetate. The ether layer and the ethyl acetate layer were combined, washed with brine, dehydrated with anhydrous sodium sulfate, dried under reduced pressure, and the resulting crude crystals were washed with a small amount of benzene and collected separately from F to give 3-cyano- 4-(2-1
16.51 crystals of (0-ruphenyl)pyrrole were obtained.

The physicochemical properties of the obtained compound were as described below.

Properties Slightly grayish green or brown colored crystals Melting point: 137-139°C (around 130°C) Sublimation) Infrared 1 loss 32.40c*'+2210
c+++,'+,1520cn'+1470c
m"+1445cm '+1320cm,'+11
45cm-'+1125cm, ''+1080ca
'+1065cm, '+1030crn'+9
85 cm '+745 cm, -' + high resolution ril=' Mass spectrum analysis results (molecular ion) Example 2 Synthesis of 3-cyano-4-(2,3-dichlorophenyl)pyrrole (compound 3).

8 ml of anhydrous ether was added to 230 ml of 50% oily sodium hydride, and the mixture was stirred and suspended. In this, 2'+3'-
Dichlorocinnamitrile 792mg and tosylmethyl isocyanide 780■ anhydrous ether 133, anhydrous dimethy 7 and sulfoxide 6.7rr+4! A solution dissolved in the mixture was added dropwise and stirred. After the dropwise addition was completed, stirring was continued for an additional 45 minutes, and then the reaction solution was poured into ice water and extracted with ethyl acetate. The ethyl acetate layer was washed with water, dehydrated with anhydrous sodium sulfate, concentrated under reduced pressure, and separated into a preparative thin layer tff'? Thorntail (
Merck Art, 5717. The M crystal obtained was purified with a developing solvent of 4-4-(311) and washed with a mixture of benzene and hexane (1.1) to obtain 2357 ng of 3-no-no-4-(2;3-dichlorophenyl)pyrrole crystals. Ta.

The physicochemical properties of the obtained compound were as follows.

Properties Slightly brown colored crystalline powder Melting point 153℃ Infrared absorption: 3250c+++ '+ 2230
cz'-'+1505cm'+1434cm'
+ 1408cm '+ 1145cm, '+1
106cm'+1084cm-'+1050
cm '+1008cm-'+ 780cm,-'+
765 cm-'+Example 3 Synthesis of 3-cyano-4-(12-)suσfluoromethylphenyl)pyronyl (compound 4) Add anhydrous ether of F3 mQ to 230π2 of oil-based sodium hydride and stir Made it muddy. Among these, 0-trifluoromethylcinnamitrile 78-8 and tosimethyl isocyanide 78
A solution prepared by dissolving 0.0 ■ in a mixture of 13 mQ anhydrous ether and 67 mQ anhydrous dimethyl sulfoxide was added dropwise and stirred. After the dropwise addition was completed, stirring was continued for an additional 45 minutes, and then the reaction solution was poured into ice water and extracted with ethyl acetate. Wash the ethyl acetate layer with water,
After dehydration over anhydrous sodium sulfate, the crude crystals were concentrated under reduced pressure and purified by preparative thin layer chromatography. The crude crystals were washed with a small amount of benzene-hegisan mixture to give 200 μm of 3-cyano-4-(
Crystals of virol (2-trifluoromethylphenyl-I) were obtained. Melting point: 105-7℃ Infrared absorption + 3240ctn
-”+2540cm, '+2220cm'+1
602cm, '+1573cm'+1485c
m'+1453cm~'+1435cm'+13
10crn'+1270cm'+1250cm"
+1167cm, '+1111ctn-1+10
31cm7"+987cm'+960cm'+
"752 cm7" + 735 cm "Reference Example 1 1-acetyl-3-cyano-4-(2-chlorophenyl)virol (compound A-1) Nogo JR: 1 () 2 of 3
-cyano-4-(2-chlorophenyl)pyrrole 40
1 rlQ, mixed with acetic anhydride and heated at 140-150 ml for 3 hours.
Heat in an oil bath at °C. After cooling the reaction mixture, it was poured into ice water and thoroughly stirred to decompose excess acetic anhydride. The generated crude crystals were collected in a furnace and crystallized from hot methanol with water washing at 7 Q mf' to obtain crystals of the target compound No. 8.51.

The physicochemical properties of the obtained compound were as described below.

Properties: 5 Slight gray-green colored plate-like crystals Melting point: 106-107°C Infrared absorption: 3080cm'+2220cm
-'+ 1728cm "+1515cm""+
1360cm'+1320cm-"+1260c
m'+1220cm'+1180cm'
+], 61'1OcWL', 945cm'+83
0cm-1+763cm, -1.

High-resolution mass spectrometry analysis results (molecular ions) Representative examples of compounds of the present invention obtained in the same manner and compounds obtained by acetylation (7) are shown in Table 1.

Tables 1 to (1) Tables 1 to (2) When using the compounds of the present invention and the compounds obtained by acetylating them as agricultural and horticultural fungicides, use the forms that can be taken by general agricultural chemicals, i.e., irrigation agents, emulsions. It is used in the form of powder, etc. As additives and carriers, fine mineral powders such as diatomaceous earth, apatite, talc, 'zilophyllite, and clay, or vegetable coarse powders such as soybean flour and wheat flour may be used as solidifying agents. For purposes of formulation, kerosene, mineral oil, petroleum, solvent naphtha, xylene, cyclohexane, cyclohexanone, dimethylformamide,
Alcohol, acetone, water, etc. are used as solvents. A surfactant can be added if necessary to obtain a uniform and stable form in these formulations.

Next, some formulation examples of the agricultural and horticultural repellents of the present invention will be shown, but the additives and their addition ratios are not limited to the present formulation examples and can be varied over a wide range.

Formulation example 1 Hydrating agent compound 1 20 parts Cane soil
73 parts or more of higher alcohol sulfate ester Natowau 15 salt 7 parts or more were mixed uniformly and finely ground to obtain a water target J agent containing 20% of the active ingredient.

Formulation example 2 Emulsion synthesis! I102 Part 10
42 parts Dimesenluorumamide 30 parts; J? +) 8 parts or more of oxyethylene argyl allyl ether.

Totsu agent example 3 Powder compound 1 2 parts
98 Mix and grind the two parts uniformly to make a powder containing two parts of the active ingredient.

Product A Example 4 Granule Compound 3 5 parts Melt
40 copies -
39 part bentonite
After uniformly mixing 10 parts or more of 6 parts or more of alkyl sulfate soda and pulverizing it finely, use a granulator to make a powder with a diameter of Q, 5-
The mixture was granulated into 1 mm granules to obtain granules containing 5 active ingredients.

Irrigation preparations and emulsions obtained as in the above formulation examples can be diluted with water to form suspensions or emulsions, and powders and granules can be used as they are in areas where plant diseases have occurred or are expected to occur. Applies where applicable. In other words, it can be used to treat diseases such as blast, sheath blight, gray mold, and scab by applying directly to plants by spraying or coating, or to treat diseases such as seedling blight by treating the soil. Diseases can be effectively controlled. Furthermore, by coating plant seeds directly with irrigation agents and powders, or by immersing the seeds in a chemical solution prepared by diluting hydrating agents and emulsions with water, it is possible to treat rice blast, sesame leaf blight, melon blight, It can also control diseases such as smut. Furthermore, the effective compound of the present invention can be added to various conventional forms of fungicides, insecticides, plant regulators, etc. to impart fungicidal properties.

Next, some test examples regarding the efficacy of the fungicide of the present invention will be shown.

Test Example 1 Botrytis disease leaf test The leaves of green bean seedlings grown for about 3 weeks were cut and immersed in a chemical solution of a predetermined concentration of the hydrating agent of the compound of the present invention for about 30 seconds, and air-dried. Bot-rytis
After inoculating the mycelium of C. cinerea and keeping it in a greenhouse at 20°C for 4 days, the degree of disease onset was investigated, and the control value was calculated based on the degree of disease onset in the untreated control plot.

The results are shown in Table 2.

Table 2 *Control 1°3-Chloro-4-(2~nitro-3=chlorophenyl)pyrrole*ltReference2°Eunoξlene:N'-(dichlorofluoromethylthio)-N,N-dimethyl-N/ - Phenylsulfamide Test Example 2 Gray mold residual effect test A potted green bean seedling that had been grown for about 3 weeks was sprayed with a chemical solution of the water use agent of the present invention compound at a predetermined concentration, and after being placed in a greenhouse for one week, Cut the treated leaves and place them in a greenhouse petri dish.
After inoculating the mycelium of Botrytiscinerea and keeping it at 20°C for 4 days, the degree of disease onset was investigated, and the control value was calculated based on the degree of disease onset in the untreated control plot. The results are shown in Table 3.

Table 3 *Control 1. Pyrrolnidoline: 3-chloro-4-(2-
Nitro-3-chlorophenyl) Pyrrole * Control 2° Eunoglene: N'-(dichlorofluoromethylthio), -N,N-dimethyl-'N'N tnylsulfamide

Claims (3)

[Claims] (1) A compound represented by the general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, X represents a halogen atom, a lower alkyl group, or a lower haloalkyl group, and n represents 1 or 2.) (2) The compound according to claim 1, wherein X is a chlorine atom, a bromine atom, a methyl group, or a trifluoromethyl group. (3) The compound according to claim 2, wherein X is a chlorine atom.