CA1206966A - 3,4-substituted pyrrole derivatives - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE
This invention relates to novel pyrrole derivatives of the general formula II' II' wherein R1 is a fragment selected from the group consisting of [X,Y,Z(phenyl)], [X,Y,Z(biphenyl)l, [U,V,W(pyridyl)], [U,V,W(furyl)] and [U,V,W(thienyl)], wherein X, Y and Z
are each independently selected from the group consisting of hydrogen, halogen, C1-C4alkyl, Cl-C3haloalkyl, di(Cl-C4alkyl)amino, nitro, cyano, -COO(Cl-C4alkyl), -CON(Cl-C4alkyl)2 and the group -E-R4, where E is -O-, -S-, -SO-or -SO2-, R4 is Cl-C6alkyl which is unsubstituted or sub-stituted by C1-C4alkoxy, C3-C5alkenyl which is unsub-stituted or substituted by halogen, C3-C5alkyoyl which is unsubstituted or substituted by halogen or hydroxy, or is [X,Y,Z(phenyl)] or -CH2-[X,Y,Z(phenyl)]; U, V and W are each independently selected from the group consisting of hydrogen, halogen and Cl-C4alkyl, and R2 is -COO(Cl-C6alkyl), -CO(Cl-C6alkyl), -CO-N(C1-C6alkyl)2, cyano, nitro, -SO2-(Cl-C6alkyl), -P(O)-(C1-C6alkoxy)2, -SO-(Cl-C6alkyl) or -SO2-N(Cl-C3alkyl)2. These compounds are useful intermediates in the preparation of certain correspond-ing N-sulfenylated pyrrole derivatives having microbicidal activity.

Description

12~69~;6 This Application is a Divisional Application from Application Number 417,974, filed December 17, 1982.
Application 417,974 relates to novel N-sulfenylated pyrrole derivatives, to khe preparation thereof, and to micro-bicidal compositions which contain at least one of these novel compounds.
The compounds of Application 417,974 have the general formula I

gl ~ ~ R2 N (I) wherein Rl is a fragment selected from the group consisting of [X,Y,Z(phenyl)], [X,Y,Z(biphenyl)], ~U,V,W(pyridyl)], [U,V,W(furyl)] and [U,V,W(thienyl)], wherein X,Y and Z are each independently selected from the group consisting o hydrogen, halogen, Cl-C4alkyl, Cl-C3haloalkyl, di(Cl-C4alkyl)amino, nitro, cyano, -COO(Cl-C4alkyl), -CON(Cl-C4alkyl)2 and the group -E-R4, where E is -O-, -S-, -SO- or -SO2-, R4 is Cl-C6alkyl which is unsubstituted or substituted by Cl-C4alkoxy~ C3-C5alkenyl which is unsub-stituted or substituted by halogen, C3-C5alkynyl which is unsubstituted or substituted by halogen or hydroxy, or is [X,Y,Z(phenyl)] or -CH2-~X,Y,Z(phenyl)];

~2~ 66 U, V and W are each independentl~ selected from the group consisting of hydrogen, halogen and Cl~C4alkyl, R2 is -COO(Cl-C6alkyl), -CO(Cl-C6alkyl), -CO-N(Cl-C6alkyl)2, cyano, nitro, -S02-(Cl-C6alkyl), -P(O)-(Cl-C6alkoxy)2, -SO-~Cl-C6alkyl) or -S02-N(Cl-C3alkyl)2; and R3 is Cl C3haloalkyl.
Throughout this specification in common with Application 417,974, the symbols ~X,Y,Z(phenyl)], [X,Y,Z(biphenyl)], [U,V,W(pyridyl~], [U,V,W(furyl)~] and [U,V,W(thienyl)] are 10respectively the Eollowing groups:
X X ~

U U
V-~ , V ~ .
W W

Depending on the indicated number of carbon atoms, alkyl by it-self or as moiety of another substituent will be understood as comprising e.g. the following groups: methyl, ethyl, propyl, butyl, pentyl, hexyl etc., and the isomers thereof, e.g. isopropyl, isobutyl, tert-butyl, isopentyl etc. Haloalkyl is a monohalo-, ~,, i6 genated to perhalogenated alk~l substituent such as CH2Cl,CHC12~ CC13~ CH2Br~ CHBr2~ C~3~ CH2F, CHF2~ CF3, CC13F, CC12-CHC12, CH2CH2F, CI3 etc. Throughout this specification, halogen will be understood as signi~ying ~luorine, chlorine, bromine or iodine, with fluorine, chlorine or bromine being preferred. C3-C5Alkenyl denotes an unsaturated aliphatic radical containing one or more double bonds and at most 5 carbon atoms, and is e.g.
propen-l-yl, allyl, buten-1-yl, buten-2-yl, buten-3-yl, CH3CH=CHCH=CH- etc. Pyridyl is 2-pyridyl, 3~pyridyl and 4-pyridyl, and furyl is 2-furyl and 3-furyl. Thienyl is 2-thienyl and 3-thienyl and biphenyl is biphenyl-4-yl, biphenyl-3-yl and biphenyl-

2-yl. Alkynyl is in particular propargyl.
The compounds of formula I are oils, resins or mainly solids which are stable under normal conditions and have very valuable microbicidal properties. They can be used in agricult-ure or related fields preventively and curatively for controlliny phytopa-thogenic microorganisms. The compounds of the formula I
have excellent fungicidal activity in broad concentration ranges and their use is unproblematical.
On account of their pronounced microbicidal activity, preferred eompounds of the formula I as disclosed in Application 417,494 are those compounds which contain the following substit-uents or combinations -thereof with one another:
for Rl a) [X,Y,Z(phenyl)], [X,Y,Z(biphenyl-4-yl)], [X,Y,Z(biphenyl-3-yl)], [X,Y,Z(biphenyl-2-yl)], [U,V,W(2-pyridyl)], [U,V,W(3-pyridyl)], 12~69G6 [U,V,W(4-pyridyl)~, [U,V,W(2-furyl)]! [U,V,W(3-furyl)~, IU,V!W(2~thienyl)], [U!V,W(3-thienyl)~;
b) [X,Y,Z(phenyl)l, IX,Y!Z(biphenyl-4-yl)]!
[U,VrZ(2-pyridyl)] r ~UrVrW(3-pyridyl)]~
lurvrw( 2-furyl)~, IU~v~w(2-thienyl)];
c) IX,Y,Z(phenyl)], IU~vrw (2-furyl)];
d) [X~YrZ (phenyl)~;
for XrY~Z a) Er halogen, Cl-C3alkylr Cl-C3haloalkylr di(Cl-C3alkyl)aminor nitror cyanor -COO(Cl-C3-alkyl) r ~coN(cl-c3alkyl)2r Cl-C~alkoxyr Cl-C4-alkylthio~ C3-C5alkenyloxy r C3-C5haloalkenyloxy, phenoxy, benzyloxy;
b) H, Fr Clr Brr CH3r C2H5, CF3r -N(CH3)2r ~N(C2Hs)2r -COOCH3 r -COOC2H5, -CON(CH3)2 r - 3a -~2~9696~;

Cl-C4alkoxy, cl-c4alkyl~hio, C3-C5alkenylo~y, C3-C5haloalkenyloxy, phenoxy, benzyloxy;
c) H, Cl, Br, CH3, C2H5, CF3, -N(CH3)2, -COOCH3, -CON(CH3)2, Cl-C~alkoxy, Cl-C4alkylthio, C3alkenyloxy, phenoxy, benzyloxy;
d) H, Cl, ~r, CH3, Cl-C~alkoxy, Cl-C~alkylthio, C3alkenyloxy;
or U,V,W: a) H, halogen, Cl-C~alkyl;
b) H~ Cl, Br, Cl-C2alkyl;
c) H, Cl, Br, CH3;

for R2: a) -COO(Cl-C3alkyl), -CO-(Cl-C3alkyl), -CO-N(Cl-C3alkyl), cyano, nitro, -SO2(Cl-C3alkyl), -P(O)(Cl-C3alkoxy)2, -SO2N(Cl-C3alkyl)2i b) -COOCH3, -COOC2H5, -COCH3, -COC2115, -CON(CI-13)2, -CON(C2H5)2~ cyano, nitro, -S02-CH3, -SO2C2~15, CH3, P(O)(OC113)2, -P(O)(OC2H5)~, -so2-N(cH3)2~ -S2 N(C2H5)2;
c) -COOCH3, -COCH3, -CON(CH3)2, cyano, nitro, -SO2-CH3' ~P()(C2Hs)2~ SO2 ( 3)2 d) -COCH3, CN;
or R3: a) Cl-C3haloalkyli b) Cl-C2haloalkyl;
c) CC13, CC12F, CC12H, CClH2, CF3, CF2H, C2C15, CC12CHC12;
d) CC13, CC12F, CC12CHC12.

The following combinations a) to g) of these types of sub-stituents result a) (Rl-a), (X,Y,Z-a), (U,V,W-a), (R2-a), (R3-a) b) (Rl-b), (X,Y,Z-b), (U,V,W-b), (R2-b), (R3-b) c) (Rl-c), (X,Y,Z-c), (U,V,W-c), (R2-c), (R3-c) d) (Rl-d), (X,Y,Z-d), (R2-d), (R3-d) ~Z~6~6 e) (Rl-a), (X,Y,Z-c), (U,V,W-c), (R2-b), (R3-C) f) (Rl-b), (X,Y,Z-c), (U,V,W-c), (R2-d), (R3-d) g) (Rl-d), (X,Y,Z-d), (R2-a), (R3-a).
Accordingly, preferred groups of compo~mds are:

a) compounds of the formula I, wherein Rl is a fragment selected from the group consisting of ~X,Y,Z(phenyl)], [X,Y,Z(biphenyl-4-yl)], [X,Y,Z(biphenyl-3-yl)], [X,Y,Z(bi-phenyl-2-yl)], [U,V,W(2-pyridyl)], [U,V,W(3-pyrldyl)], [U,V,W(4-pyridyl)], [U,V,W(2-furyl)], [U,V,W(3-furyl)], [U,V,W(2-thienyl)] or [U,V,W-3-thienyl], wherein X,Y and Z
are each independently selected from the group consisting of hydrogen, Cl-C3alkyl, Cl-C3haloalkyl, di(Cl-C3alkyl)amino, nitro, cyano, -COO(Cl-C3alkyl), -CON(Cl-C3alkyl)2, Cl-C4-alkoxy, Cl-C~alkylthio, C3-C5alkenyloxy, C3-C5halo~1kenylo~y, phenoxy and benzyloxy; U,V and W are each independently selected from the group consisting of hydrogen, halogen and Cl-C4alkyl; R2 is -COO(Cl-C3alkyl), -CO-(Cl-C3al.kyl), -CO N(Cl-C3alkyl)2, cyano, nitro, -SO2-(C]-C3alkyl), -P(O)(Cl-C3alkoxy)2 or -SO2-N(Cl-C3alkyl)2; and R3 is Cl-C3haloalkyl;

b) compounds of the formula I, wherein Rl is a fragment selected from the group consisting o~ [X,Y,Z(phenyl)], [X,Y,Z(biphenyl-4-yl)], [U,V,W(2-pyridyl)], [U,V,W(3-pyridyl)], [U,V,W(2-furyl)] or [U,V,W(2-thienyl)], wherein X, Y and Z
are each independently selected from the group consistlng of hydrogen, fluorine, chlorine, bromine, methyl, ethyl, tri-fluoromethyl, -N(C~I3)2, -N(C2H5)2~ 3 2 5 -CON(CH3)2, Cl-C4alkoxy, Cl-C~alkylthio, C3-C5alkenyloxy, C3-C5haloalkenyloxy, phenoxy and benzyloxy; U, V and W are each independently selected from the group consisting of hydrogen, chlorine, bromine and Cl-C2alkyl; R2 is R2-COOCH3, -COOC2H5, -COCH3, -COC2H5, -CON(CH3)2, -CON(C2H5)2, cyano, 12~6~6~i nitrO~ -S2-cH3' -SO2C2H5~ P()(CH3)2 3 P(O)(OC H5)2, -S02-N(CH3)2 or -SO2 ~(C2H5)2; 3 Cl-C2haloalkyl.

Within the subgroup b), particularly preferred compounds of the formula I are those wherein Rl is a fragment selected from the group consisting of [X,Y,Z(phenyl)], [U,V,W(2-pyridyl)], [U,V,W(3-pyridyl)], [U,V,W(2-furyl)] or [U,V,W(2-thienyl)], wherein X, Y and Z are each independently selected from the group consisting of fluorine, chlorine, bromine, methyl, ethyl, trifluoromethyl, Cl-C3alkoxy and Cl-C3alkyl-thio; U, V and W are each independen~:ly selected from the group consisting of hydrogen, chlorine, bromine, methyl and ethyl; R2 is -COOCH3, COCH3, NO2 or CN; and R3 is CFCl2 or CCl3.

c) Compo-mds o:E the formula I, wherein Rl is a fragment selected from the group consisting of [X,Y,Z(phenyl)] and [U,V,W(2-furyl)], wherein X, Y and Z are each independen~ly selected from the group consisting of hydrogen, chlorine, bromine, methyl, ethyl, trifluoromethyl, N(CH3)2, -COOC~13, -CON(CH3)2, Cl-C~ alkoxy, Cl-C4alkylthio, C3alkenyloxy, phenoxy and benzyloxy; U, V and W are each independently selected from the group consisting of hydrogen, chlorine, bromine and Cl-C2alkyl; R2 is -COOCH3, -COC113, -CO~(CH3)2, cyano, nitro, -SO2-CH3' -P(o)(oc2Hs)2 or -SO2-N(CH3)2; and R3 is CC13, CCl2F, CCl2H, CClH2, CF3, CF2H, C2Cl5 or CC12C~IC12 i d~ compounds of the formula I, wherein Rl is the fragment [X,Y,Z(phenyl)], wherein X, Y and Z are each independently selected from the group consisting o:E hydrogen, chlorine, bromine, methyl, Cl-C4alkoxy, Cl-C4alkylthio and C3alkenyloxyi R2 is -COCH3 or cyano; and R3 is CCl3, CCl3F or CCl2CHCl2.

~L~0~966 Within the scope of the present invention, the following individual compounds are especially preferred:

a) intermediates of the formula II', in particular on account of their advantageous properties in storage and plant protection:

3-(2-methylthiophenyl)-4-cyanopyrrole, 3-(2-methoxyphenyl)-4-cyanopyrrole;

b) final products of the formula I, in particular on account of their pronounced fungicidal properties:

N-fluorodichloromethylsulfenyl-3-t2-allyloxyphenyl)-4-cyano-pyrrole, N-fluorodichloromethylsulfenyl-3-(2-chlorophenyl)-4-cyano-pyrrole, N-fluorodichloromethylsulfenyl-3-phenyl-4-acetylpyrrole, N-fluorodichloromethylsulfenyl-3-(2-chlorophenyl)-4-acetyl-pyrrole, N-fluorodichloromethylsulfenyl-3-(4-methylphenyl)-~-acetyl-pyrrole, N-fluorodichloromethylsulfenyl-3-(3-chlorophenyl)-4-acetyl-pyrrole, N-fluorodichloromethylsulfenyl-3-(3-methylphenyl)-~-acetyl-pyrrole, N-fluorodichloromethylsulfenyl-3-(3-chlorophenyl)-4-methoxy-carbonylpyrrole, N-fluorodichloromethylsulfenyl-3-(2-chlorophenyl)-4-methoxy-carbonylpyrrole, N-fluorodichloromethylsulfenyl-3-(2-chlorophenyl)-4-nitro-pyrrole, N-fluorodichloromethylsulfenyl-3-(2-furyl)-4-cyanopyrrole, N-trichloromethylsulfenyl-3-(2-pyridyl)-4-cyanopyrrole~
N-fluorodichloromethylsulfenyl-3-(2,3-dichlorophenyl)-4-cyanopyrrole.
. . .

j't3~6 According to Application 417,974 the compounds of formula I are prepared by sulfenylating a free pyrrole of the formula II

R1 ~ R2 (II~
N

at the pyrrole nitrogen, with a reactive acid derivative of a sulfenic acid of the formula III
R3-S-OH (III) in the presence of a base. In the above formulae, Rl, R2 and R3 are as defined for formula I. This reaction is discussed in some detail in Application 417,974.
Some of the pyrroles of the formula II are known Erom the literature. For example, the me-thod of preparing and the chemical properties of 4-cyano-3-phenylpyrrole are described in Tetrahedron Letters No. 52, pp. 5337-5340 (1972). Nothing is reported on the biological properties of the compound.
Differently substituted 3~phenyl-4-cyanopyrrole derivatives are known from the literature. For example, pyrroles of the formula IV

~ ~ - CN (IV), Xn H

lZ~6~66 wherein X is a halogen atom, a lower alkyl group or a lower haloalkyl group, and n is O, 1 or 2, are described in German Offenlegungsschrift 29 27 480 as intermediates having insignificant fungicidal activity.
This invention is concerned with pyrrole derivatives of the formula II' Rl - ~ ~ R2 (II'), N
H

wherein Rl is a fragment selected from the group consisting of [X,Y,Z(phenyl)], [X,Y,Z(biphenyl)l, [U,V,r~(pyridyl)], [U,V,W(furyl)] and [U,V,W(thienyl)], wherein X, Y and ~ are each independently selected from the group consisting of , :

` 12~i966 hydrogen, halogen, Cl-C4alkyl, Cl-C3haloalkyl, di(Cl-C~al1;yl)-amino, nitro, cyano, -COO(Cl-C4alkyl), -CO~(Cl-C4alkyl)2 and the group -~-r~4, wherein E is -O-, -S~ SO- or -S02-, R~
is Cl-C6alkyl ~hich is unsubstituted or substituted by Cl-C~alko~y, C3-C5alkenyl which is insubstiLuted or sub-stituted by halogen, C3-C5alkynyl which is unsubstituted or substituted by halogen or hydroxy, or is [X,Y,~(phenyl)] or -CH2-[~,Y,Z(phenyl)], and U, V and W are each independently selected from the group consisting of hydrogen, halogen or Cl-C4alkyl; R2 is -COO(Cl-C4alkyl), -CO-(Cl-C6alkyl), -CO-N(Cl-C4alkyl)2, nitro, S02-(Cl-C~alkyl), -P(O)(Cl-C6-alkoxy)2, -SO-(Cl-C6alkyl) and -S02-N(Cl-C3alkyl)2, and, where Rl is a fragment [~,Y,Z(biphenyl)], [U,V,W(pyridyl)], [U,V,W(furyl)] or [U,V,W(thienyl)], R2 is additionally cyano.
These compounds are specially developed intermediates Eor obtaining the valuable compounds of the formula I. ~ecause of their structure they can be readily converted by N-sulfen-ylation into the compounds of the formula I. In addition, the compounds of formula II' have fungicidal activity agaiI1st important harmful fungi in plant protection, as well as e~cellent storage protection properties. The novel com-pounds of formula II', including the preparation thereof and use thereof, therefore fall within the province of this invention.

The compounds of formula II, and therefore also those of formula II', can be prepared in alkaline medium by a Michael cycloaddition reaction of a compound of formula V with tosylmethyl isocyanide, accompanied by the elimination of p-toluenesulfinic acid or the salt thereof:

l R21 3 \ / S2 C~l2~~c/b~lse ( V) ~I p R - -- -R
J H3 \ / -so2~ ~ ~ ( II,II ') .

i2C)~966 In the above formulae, Rl and R2 have meanings assigned to them previously.

~oth here and subsequen-tly, the tosyl group stands for a large number of groups which are able to activate the methylene group in the methyl isocyanide radical for a ~lichael addition reaction. Further preferred examples of such activating groups are benzenesulfonyl, p-chlorobenzene-sulfonyl, lower alkylsulfonyl such as mesyl.

The cycloaddition is carried out in the presence of a non-nucleophilic base. Suitable bases are alkali metal hydrides such as sodium hydride, or alkali metal carbonates or alkaline earth metal carbonates such as Na2C03, K2C03, or alkali alcoholates such as (CH3)3C0 ~ K ~ and others. The base is advantageously used in at least equimolar amount, based on the starting materials.

As in all reactions, it is convenient also in this case to conduct the reacti.on in an inert solvent. Examples of preEerably anhydrous solvents suitable :Eor the cycloaddition are: aromatic and aliphatic hydrocarbons such as benzene, toluene, xylenes, petroleum ethers, ligroin, cyclohexane;
ethers and ethereal compounds such as dialkyl ethers (di-ethyl ether, diisopropyl ether, tert-butyl methyl ether etc.) dimethoxymethane, tetrahydrofuran, anisolei sulfones such as dimethylsulfoxide; dimethylformamide; and mixtures of such solvents with one another.

The cycloaddition is normally carried out in the temperature range from -30 to ~120C, preferably from -30 to +50C, or at the boiling point of the solvent of solvent mixture.

When choosing suitable bases, the cycloaddition can also conveniently be carried out in aqueous medium. Suitable bases are water-soluble inorganic and organic bases, in particular all;ali metal hydroxides such as LiO~I, NaOil or KO~I, and ammonium bases, e.g. tetraall;ylammonium hydro~ides such as (CH3)4NO~I. At least an equimolar amount of base is used, based on the starting materials. When using aqueous bases, it is advantageous to conduct the reaction in a heterogeneous two-phase system.

Examples of suitable organic solvents for the organic water-immiscible phase are: aliphatic and aromatic hydrocarbons such as pentane, hexane, cyclohexane, petroleum ether, ligroin, benzene, toluene, xylenes etc.,; halogenated hydro-carbons such as dichloromethane, chloroform, carbon tetra-chloride, ethylene dichloride, 1,2-dichloroethane, tetra-chloroethylene etc.; or aliphatic ethers such as diethyl ether, diisopropyl ether, tert-butylmethyl ether etc.

The presence of a phase transfer catalyst can be of advantage in this mode of carrying out the reaction iTI
order to hasten the rate of reaction. Examp].es of such catalysts are: tetraalkylammonlum halides, hydrogen sulfates or hydroxides such as tetrabutylammonium chloride, tetra-butylammonium bromide or tetrabutylammonium iodide; tri-ethylbenzylammonium chloride or bromide; tetrapropylammonium chloride, bromide or iodide ete. Phosphonium salts are also suitable for use as phase transfer catalysts.

The phase transfer catalysed cycloaddition can be carried out in the temperature range from 0 to +80C, preferably from -10 to +50C or at the boiling point of the solvent mixture. The cycloaddition can be carried out in the described embodiment of the process under normal pressure.
The reaction time is in general from 1 to 16 hours, and in phase transfer catalysis from 12' hour to 10 hours.

~, , :~2e;~6~

The inven-tion will now be described in more de-tail by way of the following examples. In these examples, parts and percentages are by weight. Also included are two typical examples taken from Application 417,974 indicating both how the compounds of this invention are converted into their N-sulfenylated analogs, and the microbicidal activity of these compounds.
Example 1: Preparation of 3-(2-methylthiophenyl)-4-cyano-pyrrole.

~ SCH3 ~SCH3 ~ - CH=CH-CN ---~ ~ CN (compound 24) N

H
A solution of 123 g (0.7 mole) of E/Z-3-(2-thiomethylphenyl)-acrylonitrile and 192 g (0.98 mole) of tosylmethyl isocyanide in 800 ml of tetrahydrofuran is added slowly dropwise a-t -13 to -~8C to a solution of 158 g (1.4 moles) of potassium tert-butylate in 400 ml of tetrahydrofuran. The mixture is then stirred for 2~ hours at room temperature, poured into 3 litres of ice/water and extracted twice with ethyl acetate. The combined extracts are washed 4 times with semi-saturated sodium chloride solution, dried over sodium sulfate, decolorised with silica gel and activated carbon, filtered and the filtrate is concentrated. The residue is crystallised from dichloromethane/
petroleum ether to give 95 g of beige-coloured crystals with a melting point of 121-124C. The mother liquor is worked up to give another 21 g of substance. Repeated recrystallisation ~Zl;)6~)66 Erom dichloromethane/petroleum e-ther yields an almost colourless product with a melting point of 128-134C.
Example 2: Preparation of 3-(2-chlorophenyl)-4-acetylpyrrole.

- CH=CH-COCH ~ ~ COCH3 H (compound 49 A solution of 60 g (0.33 mole) of E/Z-4-(2-chlorophenyl)-3-buten-2-one and 75 g (0.38 mole) of tosylmethyl isocyanide in 400 ml of tetrahydrofuran is slowly added dropwise at -10 to ~30C to a solution of 48 g (0.43 mole) of potassium tert-butylate in 100 ml of tetrahydrofuran. The reaction mixture is stirred for 2~ hours at 5-10C, -then warmed to room temperature, poured into 2 litres of ice/water and extracted twice with ethyl acetate. The combined extracts are washed 4 times with semi-saturated sodium chloride solution, dried over sodium sulfa-te, decolorised with silica gel and Euller's earth, fil-tered and the filtrate is concentrated. The residue is digested in dichloromethane under reflux, cooled and filtered.
Yield: 40 g of beige-coloured crystals with a melting point of 198-201C.
Example 3: Preparation of 3-(3-chlorophenyl)-4-nitropyrrole.

;6 Cl Cl ( ~ CH=CH-N02 ~ N02 N (compound 41) H

1.6 g (0.036 mole) of an approximately 55~ dispersion of sodium hydride in mineral oil are digested under nitrogen twice with petroieum ether and then 50 ml of diethyl ether are added. With efficient stirring, a solution of 5.5 g (0.03 mole) of 2-(3-chlorophenyl)-l-nitroethene and 5.9 g (0.03 mole) of tosylmethyl isocyanide in 20 ml of dimethylsulfoxide and 40 ml of diethyl ether is added dropwise to the above mixture such that the reaction mixture constantly boils under reflux. After the exothermic reaction has subsided, s-tirring is continued for 15 minutes at room -temperature. First ice/water is cautiously added to the mixture, followed by the addition of saturated sodium chloride solution~ The batch is extracted twice with ethyl acetate and the combined extracts are washed 4 times with semi-saturated sodium chloride solution, dried over sodium sulfate, filtered and the filtrate is concentrated. ~he residue is recrystallised from dichloromethane/petroleum ether to give yellow crystals with a melting point of 133-135C.
Example 4: Preparation of 3-(3-methylphenyl)-4-cyanopyrrole.
. .
CH CH

~ CH=CH-CN ~ -- ~ ~ CN ~compound 10 H

.. , ~2~6~)t;6 6.1 g of a 55% dispersion of sodium hydride in mineral oil are washed with petroleum ether and then 60 ml of dimethoxyethane and lO ml of dimethylsulfoxide are added. With stirring, a solution of 14.3 g of 3-methylcinnamonitrile and 21.5 g of tosylmethyl isocyanide in 60 ml of dimethoxyethane and 10 ml of dimethylsulfoxide are added slowly dropwise at -25 to -20C.
The mixture is stirred for 1~ hours in a thawing ice bath, then poured onto ice and extracted twice with ethyl acetate. The organic phase is washed with aqueous sodium chloride solution, dried over sodium sulfate, filtered and the filtrate is con-centrated, to give 19 g of a viscous oil which, after recrystall-isation from dichloromethane/petroleum ether, yields crystalline 3-(3-methylphenyl)-4-cyanopyrrole with a melting point of 109-111C.
Example 5: Preparation of 3-(3-chlorophenyl)-4-cyanopyrrole.

Cl Cl ~ CH=CH-CN _ D ~CN (compound 1) N

H
a) 10.5 g of a 55% dispersion of sodium hydride in mineral oil are washed with petroleum e-ther and then 120 ml of tetrahydro-furan are added. A solution of 30.7 g of 3-chlorocinnamonitrile and 41 g of tosylmethyl isocyanide in 180 ml of tetrahydrofuran and 20 ml of dimethylsulfoxide is then added dropwise at -25 to -20C, and the mixture is stirred for 2 hours in a thawed ice lZt)6966 bath. The mixture is then poured onto ice and extracted -twice with ethyl acetate. I'he organic phase is washed repeatedly with aqueous sodium chloride solution, dried over sodium sulfate and filtered. The filtrate is concentrated and the residue is re-crystallised from dichloromethane, affording crystalline 3-(3-chlorophenyl)-4-cyanopyrrole with a melting point of 138-130C.
_ample 6: Preparation of 3-(3-chlorophenyl)-4-methyloxycar-bonylpyrrole.

~ ~ ~ COOCH3 Cl CH=CH-COOCH3 Cl (compound 40) ~N J
H

With stirring, a solution of 136 g of methyl E/Z-3-(3-chloro-phenyl)-acrylate and 155 g of tosylmethyl isocyanide in 500 ml of tetrahydrofuran and a solution of 109 g of potassium tert-butylate in 700 ml of tetrahydrofuran are each added dropwise simultaneously at 0-10C from two drip funnels to 400 ml of tetrahydrofuran. The mixture is stirred for 1~ hours at 0-5C
and for ~ hour at 25C, then poured onto ice and extracted twice with ethyl acetate. The extracts are washed 4 times with semi-saturated sodium chloride solution, dried over sodium sulfate, decolorised with silica gel and activated carbon, filtered and the filtrate is concentrated. The residue is digested with dichloromethane under reflux and the mixture is left to s-tand overnight at -18C and filtered, yielding 131 g of colourless product with a melting point of 187-189C.

-` ~2~ 66 Example 7: Preparation of 3~(2-pyridyl)-4-cyanopyrrole.
1~1, ~ ~
N N ~ CN
CH=CH-CN

(compound 63) N

H
With stirring, a solution of 128.8 g of 3-(2-pyridyl)-prop-2-ene nitrile and 200 g of tosylmethyl isocyanide in 1500 ml of tetrahydrofuran and a solution o 140 g of potassium tert-butylate in 1500 ml of te-trahydrofuran are each added dropwise simultaneously from two drip funnels at -10 to 0C to 200 ml of tetrahydrofuran. The mixture is stirred for 1 hour at 0-5C
and for 1 hour at 25C, then poured onto ice and extracted twice with ethvl acetate. The organic phase is washed twice with aqueous sodium chloride solution, dried over sodium sulfate, stirred with silica gel and activated carbon, filtered and the filtrate i9 concentrated. The dark residue is crystallised from dichloromethane at -20C, affording 75.5 g of brown crystals with a melting point of 148-151C.
All of the compounds listed in the table, can be prepared in corresponding manner. The compounds 8, 9, 11, 13 to 76 marked with an asterisk (*) are novel and some have fungicidal properties. Compounds 16 and 24 in particular are very active against Deuteromycetes, especially Botrytis fungi, as well as against harmful microorganisms in storage protection. These novel compounds constitute an important embodiment of the present invention.

i;~O6966 Table of intermediates of the form~lla . _ >< / 11 11 ' pound n R m . p- [ C]
._ 1 3-Cl CN 138-140 2 2 4-Cl CN 150-152 3 4-Cl CN 153-155

4 2-Cl CN 136-138 6 3-F . CN 138-139 7 3-Br CN 132-134 8* 4-N(CH3)2 CN 180-lS2 9.~. 3-N(CH3)2 CN 144-146 11* 3-N02 CN 232-234 13~; 3-OC6H5 CN 124-126 14* 3-OCH3 CN 125-128 15* 3-OCHF2 CN 95-97 16~; 2-OCH3 CN 135-13G
17~ 2-OCHF2 CN 105-107 18* 2-OC2H5 CN 134-135 19* 2-oCH(CH3)~ CN 80-S1 20~i 2-ocll2cH=cH2 CN 83-86 21~; 2-ocil2c6ll5 CN 91-93 22* 2-OH CN 130-132 23* 3-SCH3 CN 115-117 ~Z~)6~66 . _ ~
pOmund Rn R m, p .[C]
.. _ _ . _ .

25 * 2-SO-C1~3 Ci~ 168-171 26 ^ 2 3 C~l 150-152 27 '; 2-SC21l5 CN 121-123 2S '; 2-SO-C 1l CN 144-145 29 * 2-SO -C ~1 . C~ 1'il-143 30 ~; 2-S-CII(CH3) 2 CN 121-123 31 ~; 2-So2-CH(CH3)2 CN 139-141 32 :; 4 9 CN 61-65 33 ^ 2-SO-C4Hg-n CN 120-123 34 * 2-S02C4Hg-n CN 151-152 35 * 2-COOC2H5 CN 130-132 36 ~'; 3-C-C-C(O~I) (CH3)2 CN oil 37 `~ 3-C-C-H CN 132-134 38 * - 2-C--C-C(OH)(CH3)2 CN 140-143 39 ~; 2-C_C-H C~l 109-115 40 `~ 3-Cl CO-OC~13 187-189 41 `'; 3-Cl ~2 133-135 42 ~; 2-Cl l~2 137-139 43 `~; 3-Cl P(O) (OC2H5)2 102-104 44 `'; 3-Cl P(O) (OCII3)2 120-122 45 `^ 2-Cl P(O) (OC2H5)2 129-131 46 `~'; 2-Cl P(O) (OCII3)2 1~i6-148 47 * 2 4-Cl ~(0) (OC2~15)2 S9-~0 48 * 3-Cl CO-C~13 193-195 49 ~; 2-Cl CO-CH3 198-201 50 * 2 4-Cl CO-CH3 lS4-lS6 51 ^ H CO-CH3 156-15 52`^` 3-C~13 CO-C~3 1~0-123 12~6~

C om - n R m . p, [ C ]
p o und ._ . _ . . . .. .. __ 53~' 4-Cl CO-CII 170-] 74

5~ 3 4-Cl CO-C~13 162-16~i 55* 4-OC~13 CO-C~13 179-182 56*. 4-C~13 CO-C~13 1$1-184 57* 3-Cl SO -C~l 125-127 58~ 4-Cl SO-Cl~ 154-156 59* 2,4-C12 SO -CH 174-177 60-'; 3-'~'2 SO -C~I 133-135 61* 2-Cl, 4-~102 SO-C~I 197-200 6Z^ 2-Cl SO -CH 178-180 63* 4-C6H5 I CN 249-254 - - 64* H I CN 120-123 65* H ¦ 2 3 Tabie of intermediates oE the formula . _ R- ~ CN

Com- R m . p . [ C]
p ounc _ 66* 2 -pyridyl 148-151 67* 3-pyridy 1 160-162 68* 4-pyridy 1 200-203 69~!~ 2- (5-chloropyridyl) 20',-206 70* 3- ( 2 -chloropyri dyl) 217-220 71* 2 - (3 ,5-dichloropy~idyl` 176-179 72* 2- thienyl 122-124 73* 2 -furyl 98-100 74* 2 - (.~1-me thylpyrrole) 174-175 75* 2-(6-methylthienyl) loS-110 7~ 2-(3-methylthien 1) ¦ 132-l37 ~l~0~366 Example 8: Prepara-tion of N-fluoroclichloromethylsulfenyl-3-(2-chlorophenyl)-4-acetylpyrrole.

Cl Cl 3 ~ ~ COCH3 I (compound ].24) A solution of 6 ml (0.0575 mole) of fluorodichloromethyl-sulfenyl chloride in 20 ml of tetrahydrofuran is initially added dropwise at 3-5C to a solution of 11 g (0.05 mole) of 3-(2-chlorophenyl)-4-acetylpyrrole in 100 ml of tetrahydrofuran, followed by the dropwise addition of 8 ml (0.0575 mole) of triethylamine in 20 ml of tetrahydrofuran at 5-8C. The mixture is then stirred for 16 hours in a thawing ice bath and filtered. The filtrate is concentrated and the residue is recrystallised from diethyl ether/petroleum ether. Yield: 9.4 g of beige crystals with a melting point of 85-87C. A further crop of beiye crystals (4.5 g) with a melting point of 84-86C
is obtained after purification by chromatography over silica gel with dichloromethane/petroleum ether (4:1) as eluant, concentr-ation of the mother liquor and recrystallisation from diethyl ether/petroleum ether.
Example 9: Systemic action.
Barley plants about 8 cm in height are treated with a spray mixture (0.00~ %, based on the volume of the soil) prepared from the active ingredient formulated as wettable powder. Care is taken that the spray mixture does not come in contact with the parts of the plants above the soil. The treated plants are ~Z~6~6~

infected 48 hours later with a conidia suspension of the fungus.
The infected barley plants are then stood in a greenhouse at about 22C and evaluation of fungus a-ttack is made after 10 days.
Compounds of the formula I are very effective agains-t Erysiphe fungi. Erysiphe attack is 100% on untreated and infected controls.
The compounds 1.24 and 1.36 are found to strongly inhibit fungus attack.

~3 - COCH 3 ~COCH 3 FC12 S-CCl 2F
1.24 1.36

Claims (3)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A pyrrole derivative of the formula II' (II') wherein R1 is a fragment selected from the group consisting of [X,Y,Z(phenyl)], [X,Y,Z(biphenyl)], [U,V,W(pyridyl)], [U,V,W(furyl)] or [U,V,W(thienyl)], wherein X, Y and Z are each independently selected from the group consisting of hydrogen, halogen, Cl-C4alkyl, Cl-C3haloalkyl, di[(Cl-C4)-alkyl] amino, nitro, cyano, -COO(Cl-C4alkyl), -CON(Cl-C4-alkyl)2 and the group -E-R4, wherein E is -O-, -S-, -SO- or -SO2-, R4 is Cl-C6alkyl which is unsubstituted or substituted by Cl-C4alkoxy, C3-C5alkenyl which is unsubstituted or substituted by halogen, C3-C5alkynyl which is unsubstituted or substituted by halogen or hydroxy, or is [X,Y,Z(phenyl)] or -CH2-[X,Y,Z(phenyl)], and U, V
and W are each independently selected from the group consisting of hydrogen, halogen and Cl-C4alkyl; R2 is -COO(Cl-C4alkyl), -CO-(Cl-C6alkyl), -CO-N(Cl-C4alkyl)2, nitro, -SO2-N(Cl-C6-alkyl), -P(O)(Cl-C6alkoxy)2, -SO-(Cl-C6alkyl) or -SO2-N-(Cl-C3alkyl)2, and, where R1 is a fragment [X,Y,Z(biphenyl)], [U,V,W(pyridyl)], [U,V,W(furyl)] or [U,V,W(thienyl)], R2 is additionally cyano.

2. 3-(2-Methylthiophenyl)-4-cyanopyrrole.

3. 3-(2-Methoxyphenyl)-4-cyanopyrrole.