WO1993019054A1 - N-heterocyclic nitro anilines as fungicides - Google Patents

Abstract

Anilino heterocyclic compounds, e.g. 4-bromo-3-(4-fluorophenyl)-N-(2,4-dinitro-6-(trifluoromethyl)-phenyl)isothiazol-5-amine and N-(4-bromo-4-chloro-3-methyl-5(4H)-isothiazolylidene)-2,4-dinitro-6-(trifluoromethyl)benzenamine, exhibit fungicidal activity as well as insecticidal and nematicidal activity.

Description

N-heterocyclic nitro anilines as fungicides

This invention provides new anilino heterocyclic

compounds that are useful as agricultural chemicals. More specifically, the invention provides new anilino heterocyclic compounds that are useful as plant fungicides, new plant fungicide compositions utilizing the new compounds, and new methods of combating plant pathogens utilizing the new

compounds and compositions.

European Patent Application 478, 974A discoses

insecticidal use of compounds of the formula

where hetaryl is thienyl, thiazolyl, isothiazolyl, or

thiadiazolyl. There is no disclosure of fungicidal activity for these compounds. In one aspect, the present invention provides a method of inhibiting plant pathogens which comprises applying an

effective amount of a compound of formula (1) :

or a salt thereof, wherein: Ar is a group of the formula

R¹ and R² are independently H, NO₂, halo, C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₂-C₆ alkenyl, C₂-C₆ alkynyl, C₁-C₄

alkylsulfonyl, phenylsulfonyl, substituted phenylsulfonyl, Sθ₂NR⁵R⁶, C₁-C₄ alkoxy, C₁-C₄ haloalkoxy, C₁-C₄ alkylthio, C₁-C₄ haloalkylthio, COOR⁵, or CN, provided R¹ is not CN, or CONR⁵R⁶, where R⁵ and R⁶ are H, C₁-C₄ alkyl, C₃-C₇ alkenyl, C₃- C₇ cycloalkyl or cycloalkenyl, or R⁵ and R⁶ together with the nitrogen atom to which they are attached form a 5-7 member ring containing up to three additional heteroatoms selected from O, N, and S; R³ is H, halo, NR⁵R⁶, C₁-C₆ haloalkyl, C₁- C₆ alkoxy, C₁-C₆ haloalkoxy, C₁-C₆ alkylthio, C₁-C₆

haloalkylthio, phenoxy, substituted phenoxy, phenylthio, substituted phenylthio, benzyloxy, substituted benzyloxy, benzylthio, or substituted benzylthio; R4 is H, COOR⁷, CONR⁵R⁶, CHO, COR⁷, or SO₂R⁷, SO₂NR⁵R⁶, where R⁵ and R⁶ are as defined above and R⁷ is C₁-C₈ alkyl, C₃-C₈ alkenyl, C₂-C₈ branched alkyl, C₁-C₄ haloalkyl, aralkyl, phenyl, or substituted phenyl;

Het is a group selected from:

where

Q is S or O;

R¹⁰ is H, halo, C₁-C₈ alkyl, C₂-C₈ alkenyl, C₂-C₈

alkynyl, C₃-C₈ branched alkyl or alkenyl, C₃-C₇ cycloalkyl or cycloalkenyl, NO₂ , CΝ, SCΝ, CO₂H, COΝR⁵R⁶ where R⁵ and R⁶ are as defined above, CO₂R⁷ where R⁷ is as defined above, or

S(O)_mR⁷ where m is 0,1, or 2 and R⁷ are as defined above.

.R¹¹ is H, halo, C₁-C₈ alkyl, C₂-C₈ alkenyl, C₂-C₈

alkynyl, C₃-C₈ branched alkyl or alkenyl, C₃-C₇ cycloalkyl or cycloalkenyl, aralkyl, (C₃-C₇ cycloalkyl)methyl, phenyl, substituted phenyl, pyridyl, substituted pyridyl, furyl, substituted furyl, thienyl, substituted thienyl, S(O)_mR⁷, OR⁷, NHR⁷, NR⁵R⁶, NR⁷R⁷, NH₂ ,

,

, , ; where m, Q, R⁵, R⁶, and R⁷ are

as defined above;

R¹² is H, halo, CN, CO₂H, halo C₁-C₃ alkyl, phenyl, substituted phenyl, CONR⁵R⁶, or CO₂R⁷ where R⁵, R⁶, and R⁷ are as defined above;

R¹³ is H, halo, CN, CO₂H, halo C₁-C₃ alkyl, phenyl, substituted phenyl, CONR⁵R⁶, or CO₂R⁷ where R⁵, R⁶ , and R⁷ are as defined above; R¹⁴ is C₁-C₈ alkyl, C₂-C₈ alkenyl, C₂-C₈ alkynyl, C₃-C₈ branched alkyl or alkenyl, C₁-C₈ haloalkyl, phenyl,

substituted phenyl, pyridyl, substituted pyridyl, thienyl, substituted thienyl, furyl, substituted furyl, or aralkyl;

R¹⁵ is H, halo, NO₂, CN, CO₂H, CONR⁵R⁶, or CO₂R⁷ where R⁵, R⁶ , and R⁷ are as defined above;

R¹⁶ is H, halo, C₁-C₈ alkyl, C₂-C₈ alkenyl, C₂-C₈

.alkynyl, C₃-C₆ branched alkyl or alkenyl, C₃-C₇ cycloalkyl or cycloalkenyl, C₁-C₈ haloalkyl, CN, NO₂, C₁-C₈ alkoxy, C₁-C₈ haloalkoxy, C₁-C₈ haloalkylthio, phenyl, substituted phenyl, thienyl, substituted thienyl, furyl, substituted furyl, pyridyl, substituted pyridyl, aralkyl, phenoxy, or substituted phenoxy;

R¹⁷ is H, halo, C₁-C₈ alkyl, C₂-C₈ alkenyl, C₂-C₈

alkynyl, C₃-C₆ branched alkyl or alkenyl, C₃-C₇ cycloalkyl or cycloalkenyl, C₁-C₈ haloalkyl, CN, NO₂, C₁-C₈ alkoxy, C₁-C₈ haloalkoxy, C₁-C₈ haloalkylthio, phenyl, substituted phenyl, thienyl, substituted thienyl, furyl, substituted furyl, pyridyl, substituted pyridyl, aralkyl, phenoxy, or substituted phenoxy; R¹⁸ is H, halo, C₁-C₈ alkyl, C₂-C₈ alkenyl, C₂-C₈

alkynyl, C₃-C₆ branched alkyl or alkenyl, C₃-C₇ cycloalkyl or cycloalkenyl, C₁-C₈ haloalkyl, CN, NO₂, C₁-C₈ alkoxy, C₁-C₈ haloalkoxy, C₁-C₈ haloalkylthio, phenyl, substituted phenyl, thienyl, substituted thienyl, furyl, substituted furyl, pyridyl, substituted pyridyl, aralkyl, phenoxy, or substituted phenoxy, S(O)_nR', where n is 0-3, and R' is H, C₁-C₈ alkyl, C₂-C₈ alkenyl, C₃-_C6 branched alkyl or alkenyl, phenyl,

.substituted phenyl, aralkyl, CF3, or NR⁵R⁶ where R⁵ and R⁶ are as defined above;

R¹⁹ is C₁-C₈ alkyl, C₂-C₈ alkenyl, C₂-C₈ alkynyl, C₃-C₆ branched alkyl or alkenyl, C₃-C₇ cycloalkyl or cycloalkenyl, phenyl, substituted phenyl, or aralkyl;

R²⁰ is H, halo, C₁-C₈ alkyl, C₂-C₈ alkenyl, C₂-C₈

alkynyl, C₃-C₆ branched alkyl or alkenyl, C₃-C₇ cycloalkyl or cycloalkenyl, C₁-C₆ haloalkyl, pyridyl, substituted pyridyl, furyl, substituted furyl, thienyl, substituted thienyl, phenyl, or substituted phenyl;

R²¹ and R²¹' are C₁-C₈ alkyl, C₂-C₈ alkenyl, C3-C8 alkynyl, C₃-C_S branched alkyl or alkenyl, C₃-C₇ cycloalkyl or cycloalkenyl, C₁-C₆ haloalkyl, pyridyl, substituted pyridyl, furyl, substituted furyl, thienyl, substituted thienyl, phenyl, or substituted phenyl, aralkyl, COR⁷, CR^7'R^7'COOR⁷ , CR^7'R^7'CONR⁵R⁶, Or S(O)_mR⁷/ where m and R⁷ are as defined above and R⁷' is H or C₁-C₃ alkyl;

R²² is H, C₁-C₈ alkyl, C₂-C₈ alkenyl, C₂-C₈ alkynyl, C₃- C_δ branched alkyl or alkenyl, C₃-C₇ cycloalkyl or

cycloalkenyl, C₁-C₈ haloalkyl, aralkyl, C₁-C₆ alkoxy, C₁-C₈ haloalkoxy, C₁-C₆ alkylthio, C₁-C₆ haloalkylthio, (C₅-C₇

-cycloalkyl)methyl, halo, CN, SCN, NO₂, NR⁵R⁶, phenyl,

substituted phenyl, phenoxy, substituted phenoxy, pyridyl, substituted pyridyl, furyl, substituted furyl, thienyl, substituted thienyl; and

R²³ is H, halo, C₁-C₈ alkyl, C₂-C₈ alkenyl, C₂-C₈

.alkynyl, C₃-C₈ branched alkyl or alkenyl, C₃-C₇ cycloalkyl or cycloalkenyl, C₁-C₈ haloalkyl, NO₂, CN, SCN, CO₂H, CONR⁵R⁶ where R⁵ and R⁶ are as defined above, CO₂R⁷, S(O)_mR⁷ where m and R⁷ are as defined above, phenyl, substituted phenyl, pyridyl, substituted pyridyl, furyl, substituted furyl, thienyl, substituted thienyl, or aralkyl.

The invention also provides novel compounds of the formula (1):

and salts thereof, wherein: is a group of the formula

R¹ and R² are independently H, NO₂, halo, C₁-C₆ alkyl,

C₁-C₆ haloalkyl, C₂-C₆ alkenyl, C₂-C₆ alkynyl, C₁-C₄

alkylsulfonyl, phenylsulfonyl, substituted phenylsulfonyl, SO₂NR⁵R⁶, C₁-C₄ alkoxy, C₁-C₄ haloalkoxy, C₁-C₄ alkylthio, C₁-C₄ haloalkylthio, COOR⁵, or CN, provided R¹ is not CN, or CONR⁵R⁶;

R³ is H, halo, NR⁵R⁶, C₁-C₈ haloalkyl, C₁-C₈ alkoxy, C₁-C₆ haloalkoxy, C₁-C₆ alkylthio, C₁-C₆ haloalkylthio, phenoxy, substituted phenoxy, phenylthio, substituted phenylthio, benzyloxy, substituted benzyloxy, benzylthio, or substituted benzylthio;

R⁴ is H, COOR⁷, CONR⁵R⁶, CHO, COR⁷, SO₂R⁷, or SO₂NR⁵R⁶;

R⁵ and R⁶ are H, C₁-C₄ alkyl, C₃-C₇ alkenyl, C₃-C₇ cycloalkyl or cycloalkenyl, or R⁵ and R⁶ together with the nitrogen atom to which they are attached form a 5-7 member ring containing up to three additional heteroatoms selected from O, N, and S;

R⁷ is C₁-C₈ alkyl, C₃-C₈ alkenyl, C₃-C₈ branched alkyl, C₁-C₄ haloalkyl, aralkyl, phenyl, or substituted phenyl; Het is a group selected from:

R

where Q is S or O;

R¹² is H, halo, CN, CO₂H, halo C₁-C₃ alkyl, phenyl, substituted phenyl, CONR⁵R⁶, or CO₂R⁷ where R⁵, R⁶, and R⁷ are as defined above;

R¹³ is H, halo, CN, CO₂H, halo C₁-C₃ alkyl, phenyl, substituted phenyl, CONR⁵R⁶, or CO₂R⁷ where R⁵, R⁶ , and R⁷ are as defined above;

R¹⁴ is C₁-C₈ alkyl, C₂-C₈ alkenyl, C₂-C₈ alkynyl, C₃-C₈ branched alkyl or alkenyl, C₁-C₈ haloalkyl, phenyl,

substituted phenyl, pyridyl, substituted pyridyl, thienyl, substituted thienyl, furyl, substituted furyl, or aralkyl;

R¹⁵ is H, halo, NO₂, CN, CO₂H, CONR⁵R⁶, or CO₂R⁷ where R⁵, R⁶, and R⁷ are as defined above;

R¹⁶ is H, halo, C₁-C₈ alkyl, C₂-C₈ alkenyl, C₂-C₈

alkynyl, C₃-C₆ branched alkyl or alkenyl, C₃-C₇ cycloalkyl or cycloalkenyl, C₁-C₈ haloalkyl, CN, NO₂, C₁-C₈ alkoxy, C₁-C₈ haloalkoxy, C₁-C₈ haloalkylthio, phenyl, substituted phenyl, thienyl, substituted thienyl, furyl, substituted furyl, pyridyl, substituted pyridyl, aralkyl, phenoxy, or substituted phenoxy; R¹⁷ is H, halo, C₁-C₈ alkyl, C₂-C₈ alkenyl, C₂-C₈

alkynyl, C₃-C₆ branched alkyl or alkenyl, C₃-C7 cycloalkyl or cycloalkenyl, C₁-C₈ haloalkyl, CN, NO₂, C₁-C₈ alkoxy, C₁-C₈ haloalkoxy, C₁-C₈ haloalkylthio, phenyl, substituted phenyl, thienyl, substituted thienyl, furyl, substituted furyl, pyridyl, substituted pyridyl, aralkyl, phenoxy, or substituted phenoxy; R¹⁸ is H, halo, C₁-C₈ alkyl, C₂-C₈ alkenyl, C₂-C₈

alkynyl, C₃-C₆ branched alkyl or alkenyl, C₃-C₇ cycloalkyl or cycloalkenyl, C₁-C₈ haloalkyl, CN, NO2, C₁-C₈ alkoxy, C₁-C₈ haloalkoxy, C₁-C₈ haloalkylthio, phenyl, substituted phenyl, thienyl, substituted thienyl,. furyl, substituted furyl, pyridyl, substituted pyridyl, aralkyl, phenoxy, or substituted phenoxy, S(O)_nR', where n is 0-3, and R' is H, C₁-C₈ alkyl, C₂-C₈ alkenyl, C₃-C₆ branched alkyl or alkenyl, phenyl, substituted phenyl, aralkyl, CF₃, or NR⁵R⁶ where R⁵ and R⁶ are as defined above; R¹⁹ is C₁-C₈ alkyl, C₂-C₈ alkenyl, C₂-C₈ alkynyl, C₃-C₆ branched alkyl or alkenyl, C₃-C₇ cycloalkyl or cycloalkenyl, phenyl, substituted phenyl, or aralkyl;

R²⁰ is H, halo, C₁-C₈ alkyl, C₂-C₈ alkenyl, C₂-C₈

alkynyl, C₃-C₆ branched alkyl or alkenyl, C₃-C₇ cycloalkyl or cycloalkenyl, C₁-C₈ haloalkyl, pyridyl, substituted pyridyl, furyl, substituted furyl, thienyl, substituted thienyl, phenyl, or substituted phenyl;

R²¹ and R^21' are C₁-C₈ alkyl, C₂-C₈ alkenyl, C₃-C₈ alkynyl, C₃-C₆ branched alkyl or alkenyl, C₃-C₇ cycloalkyl or cycloalkenyl, C₁-C₆ haloalkyl, pyridyl, substituted pyridyl, furyl, substituted furyl, thienyl, substituted thienyl, phenyl, substituted phenyl, aralkyl, COR⁷, CR^7'R^7'COOR⁷,

CR^7'R^7'CONR⁵R⁶, or S(O)_mR⁷, where m, R⁵, R⁶, and R⁷ are as defined above, and R^7' is H or C₁-C₃ alkyl; R²² is H, C₁-C₈ alkyl, C₂-C₈ alkenyl, C₂-C₈ alkynyl, C₃- C₈ branched alkyl or alkenyl, C₃-C₇ cycloalkyl or

cycloalkenyl, C₁-C₆ haloalkyl, aralkyl, C₁-C₆ alkoxy, C₁-C₆ haloalkoxy, C₁-C₆ alkylthio, C₁-C₆ haloalkylthio, (C₅-C₇ cycloalkyl)methyl, halo/ CN, SCN, N02, phenyl, substituted phenyl, phenoxy, substituted phenoxy, pyridyl, substituted pyridyl, furyl, substituted furyl, thienyl, substituted thienyl, or NR⁵R⁶ where R⁵ and R⁶ are as defined above; and

R²³ is H, halo, C₁-C₈ alkyl, C₂-C₈ alkenyl, C₂-C₈

alkynyl, C₃-C₈ branched alkyl or alkenyl, C₃-C₇ cycloalkyl or cycloalkenyl, C₁-C₈ haloalkyl, NO₂, CN, SCN, CO₂H, CONR⁵R⁶, CO₂R⁷, COR⁷, S(O)_mR⁷, phenyl, substituted phenyl, pyridyl, substituted pyridyl, furyl, substituted furyl, thienyl, substituted thienyl, or aralkyl, where m, R⁵, R⁶, and R⁷ are as defined above; provided that the following compounds are excluded: a) 2-methyl-5-(2,4-dinitrophenylamino)-1,3,4-oxadiazole; b) N-methyl-5-trifluoromethyl-2-(2-chloro-4,6-dinitroanilino)-1,3,4-thiadiazole; c) Ν-methyl-5-t-butyl-2-(2-chloro-4,6-dinitroanilino)-1,3,4-thiadiazole; d) 3-(2,4-dinitroanilino)-4-nitro-5-phenylpyrazole; and e) 3-(2,6-dinitro-p-toluidino)-4-nitro-5-phenylpyrazole.

Another aspect of the invention comprises compounds having the following general formula (10):

wherein:

Q is S or O;

R¹ and R² are independently H, NO₂, halo, C₁-C₈ alkyl, C₁-C₆ haloalkyl, C₂-C₆ alkenyl, C₂-C₆ alkynyl, C₁-C₄

alkyIsulfonyl, phenylsulfonyl, substituted phenylsulfonyl,

SO₂NR⁵R⁶, C₁-C₄ alkoxy, C₁-C₄ haloalkoxy, C₁-C₄ alkylthio, C₁-C₄ haloalkylthio, COOR⁵, CONR⁵R⁶,or CN, provided R¹ is not CN; R³ is H, halo, NR⁵R⁶, C₁-C₈ haloalkyl, C₁-C₈ alkoxy, C₁-C₈ haloalkoxy, C₁-C₈ alkylthio, C₁-C₆ haloalkylthio, phenoxy, substituted phenoxy, phenylthio, substituted phenylthio, benzyloxy, substituted benzyloxy, benzylthio, or substituted benzylthio;

R⁵ and R⁶ are H, C₁-C₄ alkyl, C₃-C₇ alkenyl, C₃-C₇

cycloalkyl or cycloalkenyl, or R⁵ and R⁶ together with the. nitrogen atom to which they are attached form a 5-7 member ring containing up to three additional heteroatoms selected from O, N, and S;

R¹¹' is C₁-C₈ alkyl, C₂-C₈ alkenyl, C₂-C₈ alkynyl, C₃-C₈ branched alkyl or alkenyl, C₃-C₇ cycloalkyl or cycloalkenyl, aralkyl, (C₃-C₇ cycloalkyl)methyl, halo C₁-C₈ alkyl, phenyl, substituted phenyl, pyridyl, substituted pyridyl, furyl, substituted furyl, thienyl, substituted thienyl; and

R²⁴ and R^24'are independently Cl or Br.

The invention also provides a method of inhibiting plant pathogens which comprises applying an effective amount of a compound of formula (10) to the locus of the pathogen. The invention also provides a method of inhibiting a nematode population which comprises applying to the locus of a nematode, a nematode inactivating amount of a compound of the formula (1) or (10) as defined above.

The invention also provides a method of inhibiting an insect or mite population which comprises applying to the locus of the insect or arachnid an effective insect or mite inactivating amount of a compound of formula (1) or (10).

Detailed Description of the Invention

Throughout this document, all temperatures are given in degrees Celsius, and all percentages are weight percentages unless otherwise stated.

The term "halo" refers to a F, Cl, Br, or I atom. The term "haloalkyl" refers to straight chain, branched chain, and cyclo groups.

The term "HPLC" refers to a high pressure liquid

chromatography. The term "substituted phenyl" refers to phenyl

substituted with C₁-C₆ alkyl, C₂-C₇ alkenyl, C₂-C₇ alkynyl, C₃-C₇ branched alkyl, C₃-C₇ cycloalkyl, C₁-C₆ alkoxy, C₁-C₆ alkylthio, halo, hydroxy, NO₂, C₁-C₆ haloalkyl, C₁-C₆

haloalkoxy, C₁-C₆ haloalkylthio, CN, phenyl, substituted phenyl, phenoxy, substituted phenoxy, C₁-C₄ alkanoyloxy, benzyloxy, or S(O)_mAlk, where m=0-2.

The terms "substituted benzyl", "substituted benzyloxy", and "substituted benzylthio" refer to such groups that are ring substituted with C₁-C₆ alkyl, C₂-C₇ alkenyl, C₂-C₇ alkynyl, C₃-C₇ branched alkyl, C₃-C₇ cycloalkyl, C₁-C₆ alkoxy, C₁-C₆ alkylthio, halo, hydroxy, NO₂, C₁-C₆ haloalkyl, C₁-C₆ haloalkoxy, C₁-C₆ haloalkylthio, CN, phenyl, substituted phenyl, phenoxy, substituted phenoxy, C₁-C₄ alkanoyloxy, benzyloxy, or S(O)mAlk, where m-=0-2. The terms "substituted phenoxy" and "substituted

phenylthio", and "substituted phenylsulfonyl" refer to such groups that are substituted with C₁-C₆ alkyl, C₂-C₇ alkenyl, C₂-C₇ alkynyl, C₃-C₇ branched alkyl, C₃-C₇ cycloalkyl, C₁-C₆ alkoxy, C₁-C₆ alkylthio, halo, hydroxy, NO₂, C₁-C₆ haloalkyl, C₁-C₆ haloalkoxy, C₁-C₆ haloalkylthio, CN, phenyl, substituted phenyl, phenoxy, substituted phenoxy, C₁-C₄ alkanoyloxy, benzyloxy, or S(O)_mAlk, where m=0-2.

The term "aralkyl" refers to such groups wherein the aryl portion is phenyl or substituted phenyl and the alkyl portion is C₁-C₃ straight chain or C₂-C₃ branched chain, e. g.

, , or

.

Substituted pyridyl, substituted furyl, and substituted thienyl refer to such groups substituted with halo, halo C₁-C₄ alkyl, CN, NO₂, C₁-C₄ alkyl, C₃-C₄ branched alkyl, phenyl, (C₁-C₄ ) alkoxy, or halo (C₁-C₄) alkoxy.

The invention includes salts of the compounds of formulas 1, 10 and 10A. Specifically contemplated are compounds of those formulas wherein R⁴ is

(a) an alkali metal or alkaline earth metal ion such as sodium, potassium, calcium, magnesium, barium,

(b) an ammonium ion whose nitrogen can carry up to four C₁-C₄ alkyl, hydroxy C₁-C₄ alkyl, phenyl, substituted phenyl, benzyl, or substituted benzyl substituents,

(c) a phosphonium ion,

(d) a sulfonium ion,

(e) an equivalent of a transition metal cation,

especially manganese, iron, copper, and zinc. As will be apparent to those skilled in the art, for compounds having pyridyl, furyl, or thienyl as an optional substituent, as in the case where R¹⁸, R²⁰, or R²¹ is such a group, a variety of other heteroaryl groups are functionally equivalent to the named heteroaryl groups, and substitution of these equivalents is within the scope of the invention. A preferred heteroaryl group is 2-pyridyl.

Compounds of formula (1) wherein Het is a group of formula (2) are N-(substituted phenyl)-5-isothiazolamines.

Compounds of formula (1) wherein Het is a group of formula (3) and Q is S are N-(substitutedphenyl)-4-isothiazolamines. Compounds of formula (1) wherein Het is a group of formula (3) and Q is O are N-(substituted phenyl)-4-isoxazolamines.

Compounds of formula (1) wherein Het is a group of formula (4) and Q is S are N-(substituted phenyl)-3-isothiazolamines. Compounds of formula (1) wherein Het is a group of formula (4) and Q is O are N-(substituted phenyl)-3-isoxazolamines.

Compounds of formula (1) wherein Het is a group of formula (5) and Q is S are N-(substituted phenyl)-2-thiazolamines. Compounds of formula (1) wherein Het is a group of formula (5) and Q is O are N-(substituted phenyl)-2-oxazolamines.

Compounds of formula (1) wherein Het is a group of formula (6) and Q is S are N-(substituted phenyl)-1,3,4-thiadiazol-5-amines and N-(substituted phenyl)-1,3,4-thiadiazol-2-amines. Compounds of formula (1) wherein Het is a group of formula (6) and Q is O are N-(substituted phenyl)-1,3,4-oxadiazol-5-amines and N-(substituted phenyl)-1,3,4-oxadiazol-2-amines. Compounds of formula (1) wherein Het is a group of formula (7) and Q is S are N-(substituted phenyl)-1,2,5-thiadiazol-3-amines. Compounds of formula (1) wherein Het is a group of formula (7) and Q is O are N-(substituted phenyl)-1,2,5-oxadiazol-3-amines. Compounds of formula (1) wherein Het is a group of formula (8) and Q is S are N-(substituted phenyl)-1,2,4-thiadiazol-5-amines. Compounds of formula (1) wherein Het is a group of formula (8) and Q is O are N-(substituted phenyl)-1,2,4-oxadiazol-5-amines. Compounds of formula (1) wherein Het is a group of formula (9) are N-(substituted phenyl)-5-pyrazolamines.

Preferred Embodiments

The compounds of formulas (1) and (10) have demonstrated useful activity against plant pathogens, however certain classes of these compounds are preferred for reasons of greater efficacy. More specifically, the following classes of compounds are preferred: 1) isothiazole derivatives of formula (1) wherein Het is a group of formula (2);

2) compounds of class 1 wherein R¹⁰ is halo;

3) compounds of class 2 wherein R¹⁰ is bromo; 4) compounds of class 1 wherein R¹⁰ is iodo;

5) compounds of any one of classes 1 to 4 wherein R¹¹ is C₁-C₄ alkyl, C₃-C₄ branched alkyl, C₃-C₇ cycloalkyl, phenyl, or phenyl subsituted with C₁-C₄ alkyl, halo, C₁-C₆ haloalkyl; 6) compounds of any one of classes 1 to 5 wherein Ar is a substituted phenyl group of the formula

wherein n is 1 or 2;

7) compounds of any one of classes 1 to 5 wherein Ar is DTI;

8) compounds of any one of classes 1 to 5 wherein Ar is o-DTI;

9) compounds of formula (10) wherein Ar is DTI;

10) compounds of formula (10) wherein R²⁴ and R^24' are Cl.

The following specific compounds are preferred for their exceptional activity:

3-methyl-N-(2,4-dinitro-6-(trifluoromethyl)phenyl)isothiazol-5-amine;

4-bromo-3-methyl-N-(2,4-dinitro-6-(trifluoromethyl)phenyl)isothiazol-5-amine;

N-(4,4-dichloro-3-methyl-5(4H)-isothiazolylidene)-2,4- dinitro-6-(trifluoromethyl)benzenamine; 4-chloro-3-methyl-N-(2,4-dinitro-6-(trifluoromethyl)phenyl) isothiazol-5-amine;

3-methyl-4-nitro-N-(2,4-dinitro-6-(trifluoromethyl)phenyl)isothiazol-5-amine;

3-(3-methylphenyl)-N-(2,4-dinitro-6-(trifluoromethyl)phenyl)isothiazol-5-amine;

4-bromo-3-ethyl-N-(2,4-dinitro-6-(trifluoromethyl)phenyl)isothiazol-5-amine;

4-bromo-3-(3-methylphenyl)-N-(2,4-dinitro-6- (trifluoromethyl)phenyl)isothiazol-5-amine;

3-t-butyl-N-(2,6-dinitro-4-(trifluoromethyl)phenyl)isothiazol-5-amine;

4-bromo-3-t-butyl-N-(2,4-dinitro-6-(trifluoromethyl)phenyl)isothiazol-5-amine;

4-bromo-3-methyl-N-(2,6-dinitro-4-(trifluoromethyl)phenyl)isothiazol-5-amine;

N-(4-bromo-4-dichloro-3-ethyl-5(4H)-isothiazolyl-idene) 2,4-dinitro-6-(trifluoromethyl)benzenamine;

N-(4,4-dichloro-3-n-butyl-5(4H)-isothiazolylidene)-2,4-dinitro-6-(trifluoromethyl)benzenamine;

N-(4,4-dibromo-3-methyl-5(4H)-isothiazolylidene)-2,4-dinitro-6-(trifluoromethyl)benzenamine;

4-bromo-3-ethyl-N-(2,6-dinitro-4-(trifluoromethyl)phenyl)isothiazol-5-amine;

4-chloro-3-methyl-N-(2,6-dinitro-4-(trifluoromethyl)phenyl)isothiazol-5-amine;

N-(4,4-dichloro-3-t-butyl-5(4H)-isothiazolylidene)-2,6-dinitro-4-(trifluoromethyl)benzenamine;

4-chloro-3-t-butyl-N-(2,6-dinitro-4-(trifluoromethyl)phenyl)isothiazol-5-amine;

3-methyl-4-iodo-N-(2,6-dinitro-4-(trifluoromethyl)phenyl)isothiazol-5-amine;

3-t-butyl-4-bromo-N-(2,6-dinitro-4-(trifluoromethyl)phenyl)isothiazol-5-amine;

4-bromo-3-cyano-N-(2,6-dinitro-4-(trifluoromethyl)phenyl)isothiazol-5-amine;

1-(3-trifluoro-methylphenyl)-4-cyano-N-(2,6-dinitro-4- (trifluoro-methyl)phenyl)pyrazol-5-amine; N-(2,6-dinitro-4-(trifluoromethyl)phenyl)-2-phenyl- 1,2,4-thiadiazol-5-amine;

N-(2,6-dinitro-4-(trifluoromethyl)phenyl)-2-phenyl- 1,3,4-thiadiazol-5-amine;

N-(2,6-dinitro-4-(trifluoromethyl)phenyl)-4-phenylthiazol-2-amine;

N-(2,6-dinitro-4-(trifluoromethyl)phenyl)-3-phenylisoxazol-5-amine;

N-(2,6-dinitro-4-(trifluoromethyl)phenyl)-4-bromo-3- phenylisoxazo1-5-amine;

3-t-butyl-4-bromo-N-(2,6-dinitro-4-cyanophenyl)isothiazol-5-amine;

1-(3-nitrophenyl)-4-phenyl-N-(2,6-dinitro-4-(trifluoromethyl)phenyl)pyrazol-5-amine.

The following tables identify representative compounds of formulas (1) and (10), together with characterizing physical and biological activity. Abbreviations used in the table include the following: ∅ refers to phenyl, Me refers to methyl, Et. refers to ethyl, n-Bu refers to n-butyl, t-Bu refers to t-butyl, Bz refers to benzyl. The term "DTI" refers to the group

The term "o-DTI" refers to the group

An explanation of the biological data reported in the table is given hereinafter in the section titled "Greenhouse Tests."

Synthesis

Compounds of general formula (1) wherein R¹ is H or halo can be prepared using the following general procedure:

wherein one of Y and Z is NH₂ and the other is halo. The reaction is preferrably carried out in the presence of a base such as an alkali metal hydroxide, carbonate, hydride or alkaline earth metal hydroxide or carbonate. Preferred bases are sodium hydride, sodium hydroxide, sodium carbonate, potassium carbonate, potassium t-butoxide, sodium bicarbonate and potassium hydroxide. The reaction is carried out in a nonreactive organic solvent such as tetrahydrofuran, at a temperature in the range from -20 to 200°C. It is preferred for Y to be halo and Z to be NH₂. Compounds of formula (1) wherein Het is

can be synthesized by the foregoing general procedure, using a 4-halo-5-isothiazolamine starting material. Alternatively, they can be prepared by halogenating a compound of formula (1) wherein Het is

Halogenation is typically carried out by reacting the compound of formula (1) with a small excess of elemental bromine, chlorine, or iodine in CH₂CI₂ or CHCI₃. Bromination andchlorination usually proceed rapidly at room temperature.

Iodination may require addition of potassium carbonate or sodium carbonate and brief heating to reflux. Other halogenating agents, such as N-bromosucciriimide and N-chlorosuccinimide may also be used.

Compounds of formula (1) wherein Het is

can be made by nitrating a compound of formula (1) wherein Het is

Nitration is typically carried out by dissolving the compound of formula (1) in concentrated sulfuric acid and adding excess fuming nitric acid at room temperture. If no conversion has occurred within ten minutes, brief heating at 100°C may be used.

Compounds of formula (10) are prepared by halogenating a compound of formula (1) wherein Het is

wherein R^10' is H or halo.

Starting Materials

The starting materials used in preparing compounds of the invention are commercially available or they are readily prepared by known synthetic methods. The following table identifies some of the available sources for the starting materials.

For example, 5-aminoisothiazole starting materials can be prepared by the routes illustrated in the following Schemes 1A-1C:

5-Aminoisoxazole starting materials can be prepared, for example, by the procedure illustrated in Scheme 2.

2-Aminothiazole starting materials can be prepared, for example, by the procedure illustrated in Scheme 3.

2-Amino-1,3,4-oxadiazole starting materials can be prepared, for example, by the procedure illustrated in Scheme 4.

2-Amino-1,3,4-thiadiazole starting materials can be prepared, for example, by the pro.cedure illustrated in Schemes 5A and 5B

5-Aminopyrazole starting materials can be prepared, for example, by the procedures illustrated in Scheme 6A-6D.

5-Amino-1, 2 , 4-thiadiazole starting materials can be prepared, for example, by the procedures illustrated in

Schemes 7A and 7B.

Preparation 1

2-t-Butyl-4,6-dinitrochlorobenzene

To mechanically stirred concentrated nitric acid (750mL), cooled to 0°C, was added 150.2 g (1 mole) of 2-t-butylphenol at such a rate that the reaction temperature never exceded 10°C. The mixture was stirred one-half hour after the

addition of the phenol was completed. Then the mixture was poured upon ice in a 4L beaker and allowed to stand overnight at room temperature. After filtering the mixture, the

precipitate was washed with water and recrystalized from 800 mL of ethanol and cooled in a refrigerator. 2-t-Butyl-4,6- dinitrophenol, in the form of yellow prisms, was collected by suction filtratrion and air dried. Yield 84.0 g. M.P. 125- 128°C.

To a suspension of 60.01 g (0.25 mole) of 2-t-butyl-4,6- dinitrophenol in 125 mL of 1,2-dichloroethane was added 38.3 g (0.275 mole) of 2,4,6-trimethylpyridine. Mechanical stirring was started and 115 g (0.75 mole) of phosphorous oxychloride was added in many small portions, keeping the temperature of the mixture below 50°C. The mixture was then stirred for 40 hours under reflux. The cooled mixture was then poured into hot water (55°C) a little at a time, ice was added whenever the reaction temperature exceeded 65°C. The mixture was extracted with IL of CHCI₃ and again with 500 mL of CHCI₃.

The combined extracts were washed twice with water and dried over anhydrous Na₂SO₄ and filtered. The filtrate was

concentrated in a rotary evaporator to a black oil that crystallized on standing. The solid was dissolved in IL of benzene, treated with 100 g of fϊorisil and filtered. The filtrate was concentrated to a wine colored oil, which was dissolved in 200 mL of Skelly B and chilled. White platelets of the title product formed. Yield 59.2 g. M.P. 62-63°C. Preparation 2

5-amino-4-bromo-3-ethylisothiazole

Sodium hydride (60%, 32.0 g, 0.8 mole) was suspended in dry THF (250 mL) and heated to reflux (70°C) with vigorous stirring. To this suspension was added a mixture of ethyl propionate (30.7 g, 0.3 mole) and acetonitrile (27.0 g, 0.6 mole) over a 2.0 hour period and further refluxed for 9.0 hours. After cooling to 25°C, ethanol (15.0 mL) followed by water (350 mL) was added to the reaction mixture. To the resulting yellowish-brown solution was added hexane (500 mL) and vigorously stirred. The aqueous layer obtained was washed with hexane/ethyl ether (2:1, 400 mL), acidified with 5N HCl (about 130 mL) and then extracted with dichloromethane. The combined organic extracts were dried over sodium sulfate, filtered and concentrated to give 28.0 g of 3-oxopentane nitrile (96%).

Ammonia (about 3.5 g) was bubbled at a steady rate over a 5.0 min period through a solution of 3-oxopentane nitrile (7.09, 72.2 mmol ) in absolute ethanol (130 mL) in a heavy wall tube (Ace Glass Inc.) and immediately sealed with a teflon plug. The sealed tube was then placed in an oven and heated at 110°C for 16 hours. After cooling to 2°C, the solvent was removed under vacuum to give 6.39 of 3-aminopentene nitrile (91%) as red oil.

H₂S (7.2 g) was bubbled at a steady rate over a 4.5 min period through a solution of 3-aminopentene nitrile (11.1 g, 115.6 mmol) in THF (35 mL) and ethyl alcohol (25 mL) at 0°C in a heavy wall tube and immediately sealed with a teflon plug. After the reaction mixture was allowed to warm to 25°C, the sealed tube was placed in an oven and heated 90°C for 3 hours. The sealed tube was allowed to stand at 25°C for 48.0 hours and then removal of solvent under vacuum gave 3-amino-2-pentene thioamide 14.5 g of 1b (96% yield) as thick red oil.

Bromine (2.72g, 17.0 mmol) in dichloromethane (50.0 ml) was added dropwise to a solution of 3-amino-2-pentene

thioamide (1.1g, 8.5 mmol), in dichloromethane (50.0 mL) at 5°C over a 30 min period. The resulting reddish-brown

solution was stirred at ambient temperature for 2 hours.

After the removal of dichloromethane in vacuo, the residue was titrated with ethyl acetate. The white solid obtained was filtered to give and basified, pH between 9 to 10, with ammonium hydroxide and extracted with dichloromethane. The combined organic extracts were dried over sodium sulfate, filtered and concentrated to give 5-amino-4-bromo-3-ethylisothiazole (1.30g, 74%) as a yellow oil.

Example 1

3-methyl-N-[2,6-dinitro-4-(trifluoromethyl)phenyl]isothiazol- 5-amine

To a solution of 1.14 g (.01 mole) of 3-methylisothiazol-5-amine and 2.78 g (.01 mole) of 4-chloro-3,5-dinitrobenzotrifluoride in about 50 mL of anhydrous THF was added 0.7 g of 50% NaH in oil. On the following day TLC showed some starting material remained. A few milliliters ofethyl alcohol were added and the mixture was evaporated to dryness under vaccum providing a black solid. This residue was boiled up in hexane. The resulting black red material was isolated by decanting the hexane and the residue was dissolved in water. When the aqueous mixture was acidified a dark orange oil formed, which was extracted into methylene

chloride. The extract was filtered and concentrated to dryness under vacuum. The resulting material was first purified by chromatography (Siθ₂/3:1 Et₂O/Pentane) then recrystallized in hexane, providing 1.1 g of yellow-orange crystalline powder. M.P. 118-120°C.

Example 2

4-bromo-3-methyl-N-[2,6-dinitro-4-(trifluoromethyl)phenyl]isothiazol-5-amine To a solution of 0.9 g ( .0025 mole) of 3-methyl-N-[2,6-dinitro-4-(trifluoromethyl)phenyl]isothiazol-5-amine in about 50 mL of CHCI₃ was added 0.46 g of Br₂ with swirling. The solution became cloudy and then turned clear orange. The solution was washed with water, filtered, and evaporated to dryness under vacuum to provide 1.14 g of a bright yellow solid. The product was again washed with water, filtered, and dried, providing 0.98 g of. golden-yellow crystals. M.P. 171-172°C.

Example 3

N-(4-bromo-3-methylisothiazol-5-yl)-N-[2,6-dinitro-4- (trifluoromethyl)phenyl]acetamide

To a solution of 0.64 g of 4-bromo-3-methyl-N-[2,6-dinitro-4-(trifluoromethyl)phenyl]-5-isothiazolamine in about 15 mL of acetic anhydride was added about 1 g of granular K₂CO₃. The mixture was heated to near reflux temperature for about 1 minute. The solution was then filtered and the salts were washed with ethyl ether. The solution was concentrated to dryness under vacuum providing a dark oil, which was

equilibrated between ethyl ether and dilute HCl. Hexane was added to the mixture, the aqueous layer was removed, and the organic layer was concentrated under vacuum to provide .72 g of orange oil. Crystallization from Et₂O/hexane providedyellow-brown crystals. Recrystallization from CH₂Cl₂/hexane provided .55 g of the title product. MP 136-139°C. Example 4

3-methyl-4-nitro-N-[2,6-dinitro-4-(trifluoromethyl)phenyl]isothiazol-5-amine

A solution of 0.5 g of 3-methyl-N-[2,6-dinitro-4- (trifluoromethyl)phenyl]isothiazol-5-amine in 10 mL of concentrated sulfuric acid was warmed to 50°C on a steam bath. To this solution was added 2 mL of fuming nitric acid. After swirling, the mixture was allowed to stand for 10 minutes.

The mixture was first diluted with ice water, then flooded with 150 mL of water. The resulting yellow powder was

isolated by filtration and air dried to provide 0.89 g of product, which was purified by recrystallization from

CHCI₃/hexane to provide 0.66 g of the title product.

MP 175-178°C. Example 5

3-ethyl-4-bromo-N-[2,6-dinitro-4-(trifluoromethyl)phenyl]isothiazol-5-amine

To a solution of 0.45 g of 4-bromo-3-ethylisothiazol-5-amine and 0.6 g of 4-chloro-3,5-dinitro-benzotrifluoride in 75 mL of anhydrous THF was added 0.25 g of 50% NaH in oil. On the following day, TLC showed some starting material remained. Two milliliters of ethyl alcohol were added and the mixture was concentrated to dryness under vaccum providing a black solid. This residue was dissolved in water. When the aqueous mixture was acidified with dilute HCl the solution turned a bright yellow. An extraction using hexane/Et₂O was followed by extractions using dilute sodium hydroxide until the organic layer showed only a single product when tested using TLC. The aqueous layer was separated, acidified, and extracted with hexane/Et₂O to provide a material which was recrystallized from pentane to provide 0.5 g of the title product. MP 99-103°C. Example 6

N-(4-bromo-4-chloro-3-methyl-5(4H)-isothiazolylidene)- 2,4-dinitro-6-(trifluoromethyl)benzenamine

Excess chlorine was bubbled into a solution of 0.56 g of 4-bromo-3-methyl-N-[2,6-dinitro-4-(trifluoromethyl)phenyl]isothiazol-5-amine in 50 mL of chloroform. After ten minutes the solution was concentrated to dryness under vacuum to provide 0.52 g of the title product as a yellow solid.

Recfystallization from hexane gave pale yellow crystals. MP 133-137°C.

Example 7

N-(4,4-dichloro-3-n-butyl-5(4H)-isothiazolylidene)-2,4- dinitro-6-(trifluoromethyl)benzenamine

A solution of 0.65 g of 3-n-butyl-N-[2,6-dinitro-4-(trifluoromethyl)phenyl]isothiazol-5-amine in 30 mL of

chloroform was saturated with chlorine. After 3 to 4 minutes TLC indicated that the reaction had progressed to completion. The mixture was concentrated under vacuum to provide 0.82 g of a clear yellow oil. The oil was dissolved in pentane and crystals slowly developed. After cooling the mixture in a freezer, 0.43 g of pale orange crystals were collected. MP 115-120°C.

Example 8

3,N-Dimethyl-N-[2,6-dinitro-4- (trifluoromethyl)phenyl]isothiazol-5-amine

To 3-methyl-N-[2,6-dinitro-4-(trifluoromethyl)phenyl] (1.4 g, .004 mole) in 75 mL of methylethyl ketone was added 3 g of potassium carbonate and 2 g of methyl iodide. The container was stoppered and stirred for 48 hours. The mixture was filtered, then the organic layer was concentrated using a rotary evaporator to give 1.3 g of a red solid, which was purified on a SiO₂/CHCl₃ column, then recrystallized from hexane. Yield .27g. M.P. 147-149°C.

The compounds of the present invention have been found to control fungi, particularly plant pathogens. When employed in the treatment of plant fungal diseases, the compounds are applied to the plants in a disease inhibiting and phytologically acceptable amount. The term "disease

inhibiting and phytologically acceptable amount, " as used herein, refers to an amount of a compound of the invention which kills or inhibits the plant disease for which control is desired, but is not significantly toxic to the plant. This amount will generally be from about 1 to 1000 ppm, with 10 to 500 ppm being preferred. The exact concentration of compound required varies with the fungal disease to be controlled, the type formulation employed, the method of application, the particular plant species, climate conditions and the like. A suitable application rate is typically in the range from .25 to 4 lb/A. The compounds of the invention may also be used to protect stored grain and other non-plant loci from fungal infestation.

Greenhouse Tests

The following screen was used to evaluate the efficacy of the present compounds against a variety of different organisms that cause plant diseases. The test compounds were formulated for application by dissolving 50 mg of the compound into 1.25 ml of solvent . The solvent was prepared by mixing 50 ml of "Tween 20"

(polyoxyethylene (20) sorbitan monolaurate emulsifier) with 475 ml of acetone and 475 ml of ethanol. The solvent/compound solution was diluted to 125 ml with deionized water. The resulting formulation contains 400 ppm test chemical. Lower concentrations were obtained by serial dilution with the solvent-surfactant mixture.

The formulated test compounds were applied by foliar spray. The following plant pathogens and their corresponding plants were employed. Pathogen Designation in Host

Tables 1-9

Erysiphe graminis tritici POWD wheat

(powdery mildew) MDEW

Pyricularia oryzae RICE rice

(rice blast) BLAST

Puccinia recόndita tritici LEAF wheat

(leaf rust) RUST

Septoria nodorum LEAF wheat

(glume blotch) BLOT

Plasmopara viticola DOWN grape

(downy mildew) MDEW

The formulated technical compounds were sprayed on all foliar surfaces of the host plant (or cut' berry) to past run-off. Single pots of each host plant were placed on raised, revolving pedestals in a fume hood. Test solutions were sprayed on all foliar surfaces. All treatments were allowed to dry and the plants were inoculated with the appropriate pathogens within 2-4 hours.

Tables 1-9 report the activity of typical compounds of the present invention when evaluated in this experiment. The effectiveness of test compounds in controlling disease wasrated using the following scale.

0 = not tested against specific organism - = 0-19% control at 400 ppm

+ 20-89% control at 400 ppm

++ = 90-100% control at 400 ppm

+++ = 90-100% control at 100 ppm

An arabic numeral following this rating gives the control rating at 6.25 ppm on the following scale: rating disease

control

1 0-19%

2 20-29%

3 30-39%

4 40-59%

5 60-74%

6 75-89%

7 90-96%

8 97-99%

9 100%

Phytotoxic effects, if any, observed when the compound was tested at 100 ppm are also reported in the line below the activity rating in Tables 1-9. This rating consists of an arabic numeral and a letter. The arabic numeral reports the degree of chemical injury as rated on the following scale:

rating degree of

injury

1 none

2 slight

3 moderate

4 severe

5 death

The letter reports the type of symptomology observed, using the following code:

letter symptom

S stunting

C chlorosis

G general necrosis

F formative

W wilting

Insecticide and Miticide Utility The compounds of formulas (1) and (10) show activity against a number of insects and mites.

The compounds of formulas (1) and (10) are useful for reducing populations of insects and mites, and are used in a method of inhibiting an insect or mite population which comprises applying to a locus of the insect or mite an effective insect- or mite-inactivating amount of a compound of formulas (1) and (10). The "locus" of insects or mites is a term used herein to refer to the environment in which the insects or mites live or where their eggs are present, including the air surrounding them, the food they eat, or objects which they contact. For example, plant-ingesting insects or mites can be controlled by applying the active compound to plant parts, which the insects or mites eat, particularly the foliage. It is contemplated that the

compounds might also be useful to protect textiles, paper, stored grain, or seeds by applying an active compound to such substance. The term "inhibiting an insect or mite" refers to a decrease in the numbers of living insects or mites; or a decrease in the number of viable insect or mite eggs. The extent of reduction accomplished by a compound depends, of course, upon the application rate of the compound, the

particular compound used, and the target insect or mite species. At least an insect-inactivating or mite-inactivating amount should be used. The terms "insect-inactivating amount" and "mite-inactivating amount" are used to describe the amount, which is sufficient to caμse a measurable reduction in the treated insect or mite population. Generally an amount in the range from about 1 to about 1000 ppm active compound is used.

In a preferred embodiment, the present invention is directed to a method for inhibiting a mite which comprises applying to a plant an effective mite-inactivating amount of a compound of formulas (1) and (10) in accordance with the present invention.

MITE/INSECT SCREEN

The compounds of the foregoing examples were tested for miticidal and insecticidal activity in the following

mite/insect screen. Each test compound was formulated as a 400 ppm solution, and this solution was then diluted with water to give the indicated concentrations. The 400 ppm solution was prepared by combining 19.2 mL of .05% solution of Tween 20 (polyoxyethylene (20) sorbitan monolaurate) in water with a solution of 8 mg of the compound in .8 mL of acetone/EtOH (9/1).

Twospotted spider mites {Tetranychus urticae Koch) and melon aphids (Aphis gossypii Glover) are introduced on squash cotyledons and allowed to establish on both leaf surfaces. Other plants in the same treatment pot are left uninfested. The leaves are then sprayed with test solution using an atomizing sprayer at 17 psi. Both surfaces of the leaves are covered until runoff, and then allowed to dry. Activity of a compound is determined 48 hours after treatment. Activity is rated as a percent based on the mites/aphids present in plants sprayed with solvent alone. An uninfested plant is cut after the spraying and drying steps and placed into a Petri dish containing larval southern armyworm (Spodopetra eridania Cramer). The larvae are checked after 72 to 96 hours for mortality and for antifeedent activity of the compound. The ratings are based on comparison to results on plants sprayed with solvent alone. Activity on Southern corn rootworm (Diabrotica

undecimpuctata howardi Barber) is evaluated by adding one mL of test solution containing a predetermined concentration of test compound to a cup containing a kernel of corn in 16 g of sterile soil. This produces a soil concentration of 24 ppm. After 1.5 to 2 hours of drying, five 4th instar corn rootworm larvae are added to the individual cups. Mortality is measured at 3-4 days by emptying the cup onto a pan and inspecting the soil for live rootworms.

Results for are reported in the following table. The following abbreviations are used in the table:

CRW refers to corn rootworm

SAW refers to Southern armyworm

SM refers to twospotted spider mites

MA refers to melon aphids. Compound CRW CRW SAW SAW SM MA

RATE RESULTS SM & MA RESULTS RESULTS RESULTS

PPM % RATE % % %

2 24.00 100 400 0 90 100 12.00 0 200 0 0 0

3 24.00 0 400 60 90 90 12.00 0 200 0 100 100 4 24 . 00 400 80 100 100

5 24.00 0 400 0 100 100

12.00 0 200 0 90 100

6 24.00 0 400 0 0 0

7 24.00 100 400 0 80 100

12.00 0 200 0 0 0

8 24.00 0 400 0 100 100

12.00 0 200 100 100 100

9 24.00 0 400 0 0 0

11 24.00 0 400 0 80 40

12.00 0 200 0 80 60 12 24.00 0 400 0 20 0

13 24.00 0 400 0 100 100 12.00 200

14 24.00 100 400 0 100 100

12.00 0 200 0 80 80

15 24.00 100 400 0 0 40

12.00 0 200 0 0 80

16 24.00 0 400 0 80 70

12.00 0 200 0 0 0

19 24.00 0 400 0 0 0

48 24.00 0 400 0 0 0

50 24.00 0 400 0 0 0

51 24.00 0 400 0 0 60

55 24.00 0 400 0 90 30

56 24.00 0 400 0 0 0

12.00 0 200 0 90 40

60 24.00 0 400 0 0 0

61 24.00 0 400 0 0 0

63 24. oσ 100 400 0 100 0

12.00 100 200 0 100 0

69 24.00 0 400 0 0 0

71 24.00 0 400 0 0 0

72 24.00 0 400 0 80 80

12.00 0 200 0 80 0

74 24.00 0 400 0 0 0

75 24.00 0 400 0 0 0

78 24.00 0 400 0 0 0

82 24.00 0 400 0 0 0

85 24.00 0 400 0 0 0

86 24.00 0 400 0 0 0

95 24.00 0 400 0 0 0

96 24.00 0 400 0 0 0

101 24.00 0 400 0 0 0

104 24.00 0 400 0 0 0

105 24.00 0 400 0 0 80

12.00 0 200 0 0 0 Compound CRW CRW SAW SAW SM MA

RATE RESULTS SM & MA RESULTS RESULTS RESULTS

PPM % RATE % % %

106 24.00 80 400 0 0 60

12.00 0 200- 0 0 0

107 24.00 0 400 0 100 80

12.00 0 200 0 100 80

123 24.00 0 400 0 0 0

124 24.00 0 400 40 70 90

12.00 0 200 0 0 0

125 24.00 0 400 0 0 0

126 24.00 80 400 60 0 0

12.00 0 200 0 0 0

147 24.00 0 400 0 0 0

148 24.00 0 400 100 0 0

12.00 0 200 0 0 0

149 24.00 0 400 0 0 0

186 24.00 0 400 0 0 0

187 24.00 0 400 0 0 0

188 24.00 0 400 0 100 80

12.00 0 200 0 0 0

189 24.00 0 400 0 0 0

190 24.00 0 400 0 0 90

191 24.00 0 400 0 0 0

192 24.00 0 400 0 100 100

12.00 0 200 0 0 60

193 24.00 0 400 0 0 0

194 24.00 0 400 0 60 20

195 24.00 0 400 0 0 0

196 24.00 0 400 0 100 0

12.00 100 200 0 90 0

0 0 100

197 24.00 0 400 0 0 0

198 24.00 0 400 0 0 0

Nematicide Utility

Some of the compounds of the present invention are also useful for reducing populations of nematodes. Accordingly, another aspect of the invention is a method of inhibiting a nematode population which comprises applying to a locus of a nematode an effective nematode inactivating amount of a compound of formula (1)or (10). The term "inhibiting a nematode" refers to a decrease in the numbers of living nematodes. The extent of reduction accomplished by a compound depends upon the application rate of the compound, the

particular compound used, and the target species. At least a nematode-inactivating amount should be used. The term

"nematode-inactivating amount" is used to describe the amount, which is sufficient to cause a measurable reduction in the treated nematode population.

The method is practiced in accordance with standard techniques for the application of nematicides. In general, good nematicidal activity can be expected at rates of 1-10 lbs/acre. The compound can be formulated as described below in the Compositions section. When formulated as dispersions, nematicides are typically applied as aqueous drenches around growing plants or applied incrementally via irrigation

systems. When applied as granules, nematicides may be

incorporated into the soil before planting, or applied in a band on top of a seed row, or broadcast and then incorporated into the soil, or used as a side dressing to an established crop.

Compositions

The compounds of formulas (1) and (10) are applied in the form of compositions which are important embodiments of the invention, and which comprise a compound of formula (1) or (10) and a phytologically-acceptable inert carrier. The compositions are either concentrated formulations which are dispersed in water for application, or are dust or granular formulations- which are applied without further treatment. The compositions are prepared according to procedures and formulae which are conventional in the agricultural chemical art, but which are novel and important because of the presence therein of the compounds of this invention. Some description of the formulation of the compositions will be given, however, to assure that agricultural chemists can readily prepare any desired composition.

The dispersions in which the compounds are applied are most often aqueous suspensions or emulsions prepared from concentrated formulations of the compounds. Such

water-soluble, water-suspendable or emulsifiable formulations are either solids usually known as wettable powders, or liquids usually known as emulsifiable concentrates or aqueous suspensions. Wettable powders, which may be compacted to form water dispersible granules, comprise an intimate mixture of the active compound, an inert carrier and surfactants. The concentration of the active compound is usually from about 10%to about 90% by weight. The inert carrier is usually chosen from among the attapulgite clays, the montmorillonite clays, the diatomaceous earths, or the purified silicates. Effective surfactants, comprising from about 0.5% to about 10% of the wettable powder, are found among the sulfonated lignins, the condensed naphthalenesulfonates, the naphthalenesulfonates, the alkylbenzenesulfonates, the alkyl sulfates, and non-ionic surfactants such as ethylene oxide adducts of alkyl phenols.

Emulsifiable concentrates of the compounds comprise a convenient concentration of a compound, such as from about 50 to about 500 grams per liter of liquid, equivalent to about 10% to about 50%, dissolved in an inert carrier which is either a water miscible solvent or a mixture of

water-immiscible organic solvent and emulsifiers. Useful organic solvents include aromatics, especially the xylenes, and the petroleum fractions, especially the high-boiling naphthalenic and olefinic portions of petroleum such as heavy aromatic naphtha. Other organic solvents may also be used, such as the terpenic solvents including rosin derivatives, aliphatic ketones such as cyclohexanone, and complex alcohols such as 2-ethoxyethanol. Suitable emulsifiers for emulsifiable concentrates are chosen from conventional nonionic surfactants, such as those discussed above. Aqueous suspensions comprise suspensions of

water-insoluble compounds of this invention, dispersed in an aqueous vehicle at a concentration in the range from about.5% to about 50% by weight. Suspensions are prepared by finely grinding the compound, and vigorously mixing it into a vehicle comprised of water and surfactants chosen from the same types discussed above. Inert ingredients, such as inorganic salts and synthetic or natural gums, may also be added, to increase the density and viscosity of the aqueous vehicle. It is often most effective to grind and mix the compound at the same time by preparing the aqueous mixture, and homogenizing it in an implement such as a sand mill, ball mill, or piston-type homogenizer.

The compounds may also be applied as granular

compositions, which are particularly useful for applications to the soil. Granular compositions usually contain from about 0.5% to about 10% by weight of the compound, dispersed in an inert carrier which consists entirely or in large part of clay or a similar inexpensive substance. Such compositions are usually prepared by dissolving the compound in a suitable solvent, and applying it to a granular carrier which has been pre-formed to the appropriate particle size, in the range of from about 0.5 to 3 mm. Such compositions may also be

formulated by making a dough or paste of the carrier and compound, and crushing and drying to obtain the desired granular particle size.

.Dusts containing the compounds are prepared simply by intimately mixing the compound in powdered form with a suitable dusty agricultural carrier, such as kaolin clay, ground volcanic rock and the 'like. Dusts can suitably contain from about 1% to about 10% of the compound. It is equally practical, when desirable for any reason, to apply the compound in the form of a solution in an

appropriate organic solvent, usually a bland petroleum oil, such as the spray oils, which are widely used in agricultural chemistry.

Insecticides and miticides are generally applied in the form of a dispersion of the active ingredient in a liquid carrier. It is conventional to refer to application rates in terms of the concentration of active ingredient in the

carrier. The most widely used, carrier is water.

The compounds of formula (1) and (10) can also be applied in the form of an aerosol composition. In such compositions the active compound is dissolved or dispersed in an inert carrier, which is a pressure-generating propellant mixture. The aerosol composition is packaged in a container from which the mixture is dispensed through an atomizing valve.

Propellant mixtures comprise either low-boiling halocarbons, which may be mixed with organic solvents, or aqueous suspensions pressurized with inert gases or gaseous hydrocarbons. The actual amount of compound to be applied to loci of insects and mites is not critical and can readily be

determined by those skilled in the art in view of the examples above. In general, concentrations of from 10 ppm to 5000 ppm of compound are expected to provide good control. With many of the compounds, concentrations of from 100 to 1500 ppm will suffice. For field crops, such as soybeans and cotton, a suitable application rate for the compounds is about 0.5 to 1.5 lb/A, typically applied in 50 gal/A of spray formulation containing 1200 to 3600 ppm of compound. For citrus crops, a suitable application rate is from about 100 to 1500 gal/A spray formulation, which is a rate of 100 to 1000 ppm.

The locus to which a compound is applied can be any locus inhabited by an insect or arachnid, for example, vegetable crops, fruit and nut trees, grape vines, and ornamental plants. Inasmuch as many mite species are specific to a particular host, the foregoing list of mite species provides exemplification of the wide range of settings in which the present compounds can be used.

Because of the unique ability of mite eggs to resist toxicant action, repeated applications may be desirable to control newly emerged larvae, as is true of other known acaricides.

The following formulations of compounds of the invention are typical of compositions useful in the practice of the present invention.

A. Emulsifiable Concentrate

Compound of Formula (1) or (10) 9.38%

"TOXIMUL D" 2.50%

(nonionic/anionic surfactant blend)

"TOXIMUL H" 2.50%

(nonionic/anionic surfactant blend)

"EXXON 200" 85.62%

(naphthalenic solvent) B. Emulsifiable Concentrate

Compound of Formula (1) or (10) 18.50%

"TOXIMUL D" 2.50%

"TOXIMUL H" 2.50%

"EXXON 200" 76.50%

C. Emulsifiable Concentrate

Compound of Formula (1) or (10) 12.50%

N-methylpyrrolidone 25.00%

"TOXIMUL D" 2.50%

"TOXIMUL H" 2.50%

"EXXON 200" 57.50% D. Aqueous Suspension Compound of Formula (1) or (10) 12.00% "PLURONIC P-103" 1.50% (block copolymer of propylene oxide

and ethylene oxide, surfactant)

"PROXEL GXL" .05%

(biocide/preservative)

"AF-100" .20%

(silicon based antifoam agent)

"REAX 88B" 1.00%

(lignosulfonate dispersing agent)

propylene glycol 10.00% veegum .75% xanthan .25% water 74.25%

E. Aqueous Suspension

Compound of Formula (1) or (10) 12.50% "MAKON 10" (10 moles ethyleneoxide 1.00% nonylphenol surfactant)

"ZEOSYL 200" (silica) 1.00%

"AF-100" 0.20%

"AGRIWET FR" (surfactant) 3.00%

2% xanthan hydrate 10.00% water 72.30%

F. Aqueous Suspension

Compound of Formula (1) or (10) 12.50% "MAKON 10" 1.50% "ZEOSYL 200" (silica) 1.00%

"AF-100" 0.20%

"POLYFON H" 0.20% (lignosulfonate dispersing agent)

2% xanthan hydrate 10.00% water 74.60% G. Suspension Concentrate

Compound of Formula (1) or (10) 10.20%

"TERGITOL TMN-6" 3.40%

"ZEOSYL 200" 0.90%

2% "KELZAN" solution 8.60%

"AF-100" 0.20% water 76.70%

G. Wettable Powder

Compound of Formula (1) or (10) 25.80%

"POLYFON H" 3.50%

"SELLOGEN HR" 5.00%

"STEPANOL ME DRY" 1.00% gum arabic 0.50% "HISIL 233" 2.50%

Barden clay 61.70%

H. Granules

Compound of Formula (1) or (10) 5.0% propylene glycol 5.0% Exxon 200 5.0%

Florex 30/60 granular clay 85.0%

Claims

Claims

1. A method of inhibiting plant pathogens which comprises applying an effective amount of a compound of formula (1):

or a salt thereof, wherein:

Ar is a group of the formula

R¹ and R² are independently H, NO₂, halo, C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₂-C₆ alkenyl, C₂-C₆ alkynyl, C₁-C₄

alkylsulfonyl, phenylsulfonyl, substituted phenylsulfonyl, SO₂NR⁵R⁶, C₁-C₄ alkoxy, C₁-C₄ haloalkoxy, C₁-C₄ alkylthio, C₁-C₄ haloalkylthio, COOR⁵, or CN, provided R¹ is not CN, or CONR⁵R⁶; R³ is H, halo, NR⁵R⁶, C₁-C₅ haloalkyl, C₁-C₆ alko-xy, C₁-C₈ haloalkoxy, C₁-C₆ alkylthio, C₁-C₆ haloalkylthio, phenoxy, substituted phenoxy, phenylthio, substituted phenylthio, benzyloxy, substituted benzyloxy, benzylthio, or substituted benzylthio; R⁴ is H, COOR⁷, CONR⁵R⁶, CHO, COR⁷, SO₂R⁷, or SO₂NR⁵R⁶;

R⁵ and R⁶ are H, C₁-C₄ alkyl, C₃-C₇ alkenyl, C₃-C₇ cycloalkyl or cycloalkenyl, or R⁵ and R⁵ together with the nitrogen, atom to which they are attached form a 5-7 member ring containing up to three additional heteroatoms selected from O, N, and S; R⁷ is C₁-C₈ alkyl, C₃-C₈ alkenyl, C₃-C₈ branched alkyl, C₁-C₄ haloalkyl, aralkyl, phenyl, or substituted phenyl;

Het is a group selected from:

where

Q is S or O;

R¹⁰ is H, halo, C₁-C₈ alkyl, C₂-C₈ alkenyl, C₂-C₈

alkynyl, C₃-C₈ branched alkyl or alkenyl, C₃-C7 cycloalkyl or cycloalkenyl, NO₂, CN, SCN, CO₂H, CONR⁵R⁶, CO₂R⁷, or S(O)_mR⁷ where m is 0,1, or 2 and R⁵, R⁶, and R⁷ are as defined above.

R¹¹ is H, halo, C₁-_C8 alkyl, C₂-C₈ alkenyl, C₂-C₈

alkynyl, C₃-C₈ branched alkyl or alkenyl, C₃-C₇ cycloalkyl or cycloalkenyl, aralkyl, (C₃-C₇ cycloalkyl)methyl, phenyl, substituted phenyl, pyridyl, substituted pyridyl, furyl, substituted furyl, thienyl, substituted thienyl, S(O)_mR⁷, OR⁷,

NHR⁷ , NR5R6 , NR⁷R⁷ , NH₂ ,

— ,

,

, ; where m, Q, R⁵ , R⁶ , and R⁷ are

as defined above;

R¹² is H, halo, CN, CO₂H, halo C₁-C₃ alkyl, phenyl, substituted phenyl, CONR⁵R⁶, or CO₂R⁷ where R⁵, R⁶, and R⁷ are as defined above; R¹³ is H, halo, CN, CO₂H, halo C₁-C₃ alkyl, phenyl, substituted phenyl, CONR⁵R⁶, or CO₂R⁷ where R⁵, R⁶ , and R⁷ are .as defined above;

R¹⁴ is C₁-C₈ alkyl, C₂-C₈ alkenyl, C₂-C₈ alkynyl, C₃-C₈ branched alkyl or alkenyl, C₁-C₈ haloalkyl, phenyl,

substituted phenyl, pyridyl, substituted pyridyl, thienyl, substituted thienyl, furyl, substituted furyl, or aralkyl;

R¹⁵ is H, halo, NO₂, CN, CO₂H, CONR⁵R⁶, or CO₂R⁷ where R⁵, R⁶, and R⁷ are as defined above; R¹⁶ is H, halo, C₁-C₈ alkyl, C₂-C₈ alkenyl, C₂-C₈

alkynyl, C₃-C₆ branched alkyl or alkenyl, C₃-C₇ cycloalkyl or cycloalkenyl, C₁-C₈ haloalkyl, CN, NO₂, C₁-C₈ alkoxy, C₁-C₈ haloalkoxy, C₁-C₈ haloalkylthio, phenyl, substituted phenyl, thienyl, substituted thienyl, furyl, substituted furyl, pyridyl, substituted pyridyl, aralkyl, phenoxy, or substituted phenoxy;

R¹⁷ is H, halo, C₁-C₈ alkyl, C₂-C₈ alkenyl, C₂-C₈

alkynyl, C₃-C₆ branched alkyl or alkenyl, C3-C7 cycloalkyl or cycloalkenyl, C₁-C₈ haloalkyl, CN, NO₂, C₁-C₈ alkoxy, C₁-C₈ haloalkoxy, C₁-C₈ haloalkylthio, phenyl, substituted phenyl, thienyl, substituted thienyl, furyl, substituted furyl, pyridyl, substituted pyridyl, aralkyl, phenoxy, or substituted phenoxy;

R¹⁸ is H, halo, C₁-C₈ alkyl, C₂-C₈ alkenyl, C₂-C₈

alkynyl, C₃-C₆ branched alkyl or alkenyl, C₃-C7 cycloalkyl or cycloalkenyl, C₁-C₈ haloalkyl, CN, NO₂, C₁-C₈ alkoxy, C₁-C₈ haloalkoxy, C₁-C₈ haloalkylthio, phenyl, substituted phenyl, thienyl, substituted thienyl, furyl, substituted furyl, pyridyl, substituted pyridyl, aralkyl, phenoxy, or substituted phenoxy, S(O)_nR', where n is 0-3, and R' is H, C₁-C₈ alkyl, C₂-C₈ alkenyl, C₃-C₆ branched alkyl or alkenyl, phenyl, substituted phenyl, aralkyl, CF3, or NR⁵R⁶ where R⁵ and R⁶ are as defined above; R¹⁹ is C₁-C₈ alkyl, C₂-C₈ alkenyl, C₂-C₈ alkynyl, C₃-C₆ branched alkyl or alkenyl, C₃-C₇ cycloalkyl or cycloalkenyl, phenyl, substituted phenyl, or aralkyl;

R²⁰ is H, halo, C₁-C₈ alkyl, C₂-C₈ alkenyl, C₂-C₈

alkynyl, C₃-C₆ branched alkyl or alkenyl, C₃-C₇ cycloalkyl or cycloalkenyl, C₁-C₆ haloalkyl, pyridyl, substituted pyridyl, furyl, substituted furyl, thienyl, substituted thienyl, phenyl, or substituted phenyl;

R²¹ and R²¹' are C₁-C₈ alkyl, C₂-C₈ alkenyl, C₃-C₈ alkynyl, C₃-C₆ branched alkyl or alkenyl, C₃-C₇ cycloalkyl or cycloalkenyl, C₁-C₈ haloalkyl, pyridyl, substituted pyridyl, furyl, substituted furyl, thienyl, substituted thienyl, phenyl, substituted phenyl, aralkyl, COR⁷, CR^7'R^7'COOR⁷,

CR^7'R^7'CONR⁵R⁶, or S(O)_mR⁷, where m, R⁵, R⁶, and R⁷ are as defined above, and R^7' is H or C₁-C₃ alkyl;

R²² is H, C₁-C₈ alkyl, C₂-C₈ alkenyl, C₂-C₈ alkynyl, C₃- C₈ branched alkyl or alkenyl, C3-C7 cycloalkyl or

cycloalkenyl, C₁-C₆ haloalkyl, aralkyl, Ci-Cβ alkoxy, Ci-Cβ haloalkoxy, C₁-C₆ alkylthio, C₁-C₆ haloalkylthio, (C5-C7 -cycloalkyl)methyl, halo, CN, SCN, NO2, phenyl, substituted phenyl, phenoxy, substituted phenoxy, pyridyl, substituted pyridyl, furyl, substituted furyl, thienyl, substituted thienyl, or NR⁵R⁶ where R⁵ and R⁶ are as defined above; and

R²³ is H, halo, C₁-C₈ alkyl, C₂-C₈ alkenyl, C₂-C₈

-alkynyl, C₃-C₈ branched alkyl or alkenyl, C₃-C₇ cycloalkyl or cycloalkenyl, C₁-C₈ haloalkyl, NO₂, CN, SCN, CO₂H, CONR⁵R⁶, CO₂R⁷, COR⁷, S(O)_mR⁷, phenyl, substituted phenyl, pyridyl, substituted pyridyl, furyl, substituted furyl, thienyl, substituted thienyl, or aralkyl, where m, R⁵, R⁶, and R⁷ are as defined above.

2. The method of inhibiting plant pathogens of claim 1 wherein the compound of formula (1) is one wherein:

R¹ and R² are independently H, NO₂, halo, C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₂-C₆ alkenyl/ C₂-C₆ alkynyl, C₁-C₄. alkylsulfonyl, phenylsulfonyl, substituted phenylsulfonyl, SO₂NR⁵R⁶, C₁-C₄ alkoxy, C₁-C₄ haloalkoxy, C₁-C₄ alkylthio, C₁-C₄ haloalkylthio, COOR⁵, or CN, provided R¹ is not CN, or C0NR⁵R⁶, where R⁵ and R⁶ are H, C₁-C₄ alkyl, C₃-C₇ cycloalkyl; R³ is H, halo, C₁-C₆ haloalkyl, C₁-C₈ alkoxy, C₁-C₈ haloalkoxy, C₁-C₆ alkylthio, C₁-C₆ haloalkylthio, phenoxy, substituted phenoxy, phenylthio, substituted phenylthio, benzyloxy, substituted benzyloxy, benzylthio, or substituted benzylthio; R⁴ is H, COOR⁷, CONR⁵R⁶, CHO, COR⁷, or SO₂R⁷, where R⁵ and

R⁵ are as defined above and R⁷ is C₁-C₄ alkyl, C₁-C₄ haloalkyl, benzyl, substituted benzyl, phenyl, or substituted phenyl;

R¹⁰ is H, halo, C₁-C₈ alkyl, C₃-C₅ branched alkyl, C₃-C₆ cycloalkyl, NO₂, CN, CO₂H, CO₂Alk, CONR⁵R⁶, where Alk is C₁-C₆ alkyl or halo C₁-C₈ alkyl, and where R⁵ and R⁵ are H, C₁-C₄ alkyl, or C₃-C₇ cycloalkyl;

R¹¹ is halo, C₁-C₆ alkyl, C₃-C₅ branched alkyl, C₃-C₆ cycloalkyl, aralkyl, cyclohexylmethyl, phenyl, substituted phenyl, phenoxy, substituted phenoxy, pyridyl, furyl, or thienyl;

R¹² is H, CO₂H, CO₂Alk, or CONR⁵R⁶, where Alk, R⁵ and R⁶ are as defined above; R¹³ is CN, CO₂H, CO₂Alk, or CONR⁵R⁶, where Alk, R⁵ and R⁶ are as defined above; R¹⁴ is C₁-C₆ alkyl, C₁-C₈ haloalkyl, phenyl, substituted phenyl, or aralkyl;

R¹⁵ is H, halo, NO₂, CN, CO₂H, CO₂Alk, CONR⁵R⁶, where Alk, R⁵ and R⁶ are as defined above; R¹⁶ is H, halo, C₁-C₈ alkyl, C₃-C₆ branched alkyl, C₃-C₆ cycloalkyl, C₁-C₈ haloalkyl, CN, NO₂, C₁-C₈ alkoxy, C₁-C₈ haloalkoxy, C₁-C₈ haloalkylthio, phenyl, substituted phenyl, aralkyl, phenoxy, or substituted phenoxy;

R¹⁷ is H, halo, C₁-C₈ alkyl, C₃-C₆ branched alkyl, C₃-C₆ cycloalkyl, C₁-C₆ haloalkyl, CN, NO₂, C₁-C₈ alkoxy, C₁-C₆ haloalkoxy, phenyl, substituted phenyl, aralkyl, phenoxy, or substituted phenoxy;

R¹⁸ is H, halo, C₁-C₈ alkyl, C₃-C₆ branched alkyl, C₃-C₆ cycloalkyl, C₁-C₈ haloalkyl, CN, NO₂, C₁-C₆ alkoxy, C₁-C₆ haloalkoxy, phenyl, substitued phenyl, pyridyl, furyl, thienyl, aralkyl, phenoxy, substituted phenoxy, S(O)_nR', where n is 0-3, and R¹ is H, C₁-C₈ alkyl, C₃-C₆ branched alkyl, phenyl, substituted phenyl, CF₃, or NR⁵R⁶ and R⁵ and R⁶ are as defined above; R¹⁹ is C₁-C₈ alkyl, C₃-C₆ branched alkyl, C₃-C₆

cycloalkyl, phenyl, substituted phenyl, or aralkyl;

R²⁰ is H, halo, C₁-C₈ alkyl, C₁-C₆ alkenyl, C₁-C₆ alkynyl, C₃-C₆ branched alkyl, C₃-C₆ cycloalkyl, C₁-C₈ haloalkyl, pyridyl, furyl, thienyl, phenyl, or substituted phenyl; R²¹ is C₁-C₈ alkyl, C₃-C₆ branched alkyl, C₃-C₆

cycloalkyl, C₁-C₈ haloalkyl, pyridyl, furyl, thienyl, phenyl, 'substituted phenyl, aralkyl, or S(O)_mAlk, where m and Alk are as defined above;

R²² is C₁-C₆ alkyl, C₃-C₆ branched alkyl, C₃-C₆

cycloalkyl, aralkyl, C₁-C₈ alkoxy, C₁-C₈ haloalkoxy, C₁-C₆ alkylthio, C₁-C₈ haloalkylthio, cyclohexylmethyl, halo, NO₂, NR⁵R⁶, phenyl, substituted phenyl, phenoxy, substituted phenoxy, pyridyl, furyl, thienyl; and

R²³ is H, halo, C₁-C₆ alkyl, C₃-C₆ branched alkyl, C₃-C₆ cycloalkyl, NO₂, CN, CO₂H, -CO₂Alk, where Alk is C₁-C₆ alkyl or halo C₁-C₆ alkyl, or CONR⁵R⁶,where R⁵ and R⁶ are as defined above.

3. The method of inhibiting plant pathogens of claim 1 wherein the compound of formula (1) is one wherein Het is a group of formula (2). 4. The method of inhibiting plant pathogens of claim 1 wherein the compound of formula (1) is selected from 4-bromo-3-methyl-N-(2,6-dinitro-4-(trifluoromethyl)phenyl)-5-isothiazolamine, 3-t-butyl-4-bromo-Ν-(2,6-dinitro-4- (trifluoromethyl)phenyl)isothiazol-5-amine,

4-bromo-3-cyano-N- (2,6-dinitro-4-(trifluoromethyl)phenyl)isothiazol-5-amine, 3-methyl-4-iodo-N-(2,6-dinitro-4- (trifluoromethyl)phenyl)isothiazol-5-amine, 3-t-butyl-4-bromo-N-(2,6-dinitro-4-cyanophenyl)isothiazol-5-amine. 1-(3-nitrophenyl)-4-phenyl-N-(2,6-dinitro-4-(trifluoromethyl)phenyl)pyrazol-5-amine, 1-(3-trifluoro-methylphenyl)-4-cyano-N-(2,6-dinitro-4-(trifluoro-methyl)phenyl)pyrazol-5-amine, 1-(3-trifluoro-methylphenyl)-4-cyano-N-(2,6-dinitro-4- (trifluoro-methyl)phenyl)pyrazol-5-amine.

5. A compound of the formula (1):

or a salt thereof, wherein:

Ar is a group of the formula

R¹ and R² are independently H, NO₂, halo, C₁-C₆ alkyl, C₁-C₈ haloalkyl, C₂-C₆ alkenyl, C₂-C₆ alkynyl, C₁-C₄

alkylsulfonyl, phenylsulfonyl, substituted phenylsulfonyl, SO₂NR⁵R⁶, C₁-C₄ alkoxy, C₁-C₄ haloalkoxy, C₁-C₄ alkylthio, C₁- C₄ haloalkylthio, COOR⁵, or CN, provided R¹ is not CN, or CONR⁵R⁶;

R³ is H, halo, NR⁵R⁶, C₁-C₈ haloalkyl, C₁-C₆ alkoxy, C₁-C₈ haloalkoxy, C₁-C₈ alkylthio, C₁-C₈ haloalkylthio, phenoxy, substituted phenoxy, phenylthio, substituted phenylthio, benzyloxy, substituted benzyloxy, benzylthio, or substituted benzylthio;

R⁴ is H, COOR⁷, CONR⁵R⁶, CHO, COR⁷, SO₂R⁷, or SO₂NR⁵R⁶;

R⁵ and R⁶ are H, C₁-C₄ alkyl, C₃-C₇ alkenyl, C₃-C₇ cycloalkyl or cycloalkenyl, or R⁵ and R⁶ together with the nitrogen atom to which they are attached form a 5-7 member ring containing up to three additional heteroatoms selected from O, N, and S;

R⁷ is C₁-C₈ alkyl, C₃-C₈ alkenyl, C₃-C₈ branched alkyl, C₁-C₄ haloalkyl, aralkyl, phenyl, or substituted phenyl; Het is a group selected from:

where

Q is S or O; R¹² is H, halo, CN, CO₂H, halo C₁-C₃ alkyl, phenyl, substituted phenyl, COΝR⁵R⁶, or CO₂R⁷ where R⁵, R⁶, and R⁷ are as defined above;

R¹³ is H, halo, CN, CO₂H, halo C₁-C₃ alkyl, phenyl, substituted phenyl, CONR⁵R⁶, or CO₂R⁷ where R⁵, R⁶ , and R⁷ are as defined above;

R¹⁴ is C₁-C₈ alkyl, C₂-C₈ alkenyl, C₂-C₈ alkynyl, C₃-C₈ branched alkyl or alkenyl, C₁-C₈ haloalkyl, phenyl,

substituted phenyl, pyridyl, substituted pyridyl, thienyl, substituted thienyl, furyl, substituted furyl, or aralkyl;

R¹⁵ is H, halo, N0₂, CN, CO₂H, CONR⁵R⁶, or CO₂R⁷ where R⁵, R⁶, and R⁷ are as defined above;

R^ιe is H, halo, C₁-C₈ alkyl, C₂-C₈ alkenyl, C₂-C₈

alkynyl, C₃-C₆ branched alkyl or alkenyl, C₃-C7 cycloalkyl or cycloalkenyl, C₁-C₈ haloalkyl, CN, NO₂, C₁-C₈ alkoxy, C₁-C₈ haloalkoxy, C₁-C₈ haloalkylthio, phenyl, substituted phenyl, thienyl, substituted thienyl, furyl, substituted furyl, pyridyl, substituted pyridyl, aralkyl, phenoxy, or substituted phenoxy; R¹⁷ is H, halo, C₁-C₈ alkyl, C₂-C₈ alkenyl, C₂-C₈

alkynyl, C₃-C₆ branched alkyl or alkenyl, C₃-C₇ cycloalkyl or cycloalkenyl, C₁-C₈ haloalkyl, CN, NO₂, C₁-C₈ alkoxy, C₁-C₈ haloalkoxy, C₁-C₈ haloalkylthio, phenyl, substituted phenyl, thienyl, substituted thienyl, furyl, substituted furyl, pyridyl, substituted pyridyl, aralkyl, phenoxy, or substituted phenoxy;

R¹⁸ is H, halo, C₁-C₈ alkyl, C₂-C₈ alkenyl, C₂-C₈

alkynyl, C₃-C₆ branched alkyl or alkenyl, C₃-C₇ cycloalkyl or cycloalkenyl, C₁-C₈ haloalkyl, CN, NO₂, C₁-C₆ alkoxy, C₁-C₈ haloalkoxy, C₁-C₈ haloalkylthio, phenyl, substituted phenyl, thienyl, substituted thienyl, furyl, substituted furyl, pyridyl, substituted pyridyl, aralkyl, phenoxy, or substituted phenoxy, S(O)_nR', where n is 0-3, and R ' is H, C₁-C₈ alkyl, C₂-C₈ alkenyl, C₃-C₆ branched alkyl or alkenyl, phenyl, substituted phenyl, aralkyl, CF₃, or NR⁵R⁶ where R⁵ and R⁶ are as defined above;

R¹⁹ is C₁-C₈ alkyl, C₂-C₈ alkenyl, C₂-C₈ alkynyl, C₃-C₆ branched alkyl or alkenyl, C₃-C₇ cycloalkyl or cycloalkenyl, phenyl, substituted phenyl, or aralkyl;

R²⁰ is H, halo, C₁-C₈ alkyl, C₂-C₈ alkenyl, C₂-C₈ alkynyl, C₃-C₆ branched alkyl or alkenyl, C₃-C7 cycloalkyl or cycloalkenyl, C₁-C₆ haloalkyl, pyridyl, substituted pyridyl, furyl, substituted furyl, thienyl, substituted thienyl, phenyl, or substituted phenyl;

R²¹ and R²¹' are C₁-C₈ alkyl, C₂-C₈ alkenyl, C₃-C₈ alkynyl, C₃-C₆ branched alkyl or alkenyl, C₃-C₇ cycloalkyl or cycloalkenyl, C₁-C₆ haloalkyl, pyridyl, substituted pyridyl, furyl, substituted furyl, thienyl, substituted thienyl, phenyl, substituted phenyl, aralkyl, COR⁷, CR^7'R^7'COOR⁷, CR^7'R^7'CONR⁵R⁶, or S(O)_mR⁷, where m, R⁵, R⁶, and R⁷ are as defined above, and R^7' is H or C₁-C₃ alkyl;

R²² is H, C₁-C₈ alkyl, C₂-C₈ alkenyl, C₂-C₈ alkynyl, C₃-C₈ branched alkyl or alkenyl, C₃-C₇ cycloalkyl or

cycloalkenyl, C₁-C₆ haloalkyl, aralkyl, C₁-C₆ alkoxy, C₁-C₆ haloalkoxy, C₁-C₆ alkylthio, C₁-C₆ haloalkylthio, (C₅-C₇ cycloalkyl )methyl, halo, CN, SCN, NO₂, phenyl, substituted phenyl, phenoxy, substituted phenoxy, pyridyl, substituted pyridyl, furyl, substituted furyl, thienyl, substituted thienyl, or NR⁵R⁶ where R⁵ and R⁶ are as defined above; and

R²³ is H, halo, C₁-C₆ alkyl, C₂-C₈ alkenyl, C₂-C₈ alkynyl, C₃-C₈ branched alkyl or alkenyl, C₃-C₇ cycloalkyl or cycloalkenyl, C₁-C₆ haloalkyl, NO₂, CN, SCN, CO₂H, C0NR⁵R⁶, CO₂R⁷, COR⁷, S(O)_mR⁷, phenyl, substituted phenyl, pyridyl, substituted pyridyl, furyl, substituted furyl, thienyl, substituted thienyl, or aralkyl, where m, R⁵, R⁶, and R⁷ are as defined above; provided that the following compounds are excluded: a) 5-methyl-2-(2,4,6-trinitroanilino)thiazole; b) N,4-dimethyl-2-(2,4,6-trinitroanilino)thiazole; c) 2-methyl-5-(2,4-dinitrophenylamino)-1,3,4-oxadiazole; d) N-methyl-5-trifluoromethyl-2-(2-chloro-4,6-dinitroanilino)-1,3,4-thiadiazole; e) N-methyl-5-t-butyl-2-(2-chloro-4,6-dinitroanilino)-1,3,4-thiadiazole; f) N-acetyl-5-methyl-2-(4-bromo-2-nitroanilino)-1,3,4-thiadiazole; g) N-acetyl-5-methyl-2-(4-methyl-2-nitroanilino)-1,3,4-thiadiazole; h) 3-(2,4-dinitroanilino)-4-nitro-5-phenylpyrazole; and i) 3-(2,6-dinitro-p-toluidino)-4-nitro-5-phenylpyrazole.

6. A compound of claim 5 wherein R¹ and R² are independently H, NO₂, halo, C₁-C₆ alkyl, C₁-C₈ haloalkyl, C₂-C₆ alkenyl, C₂-C₆ alkynyl, C₁-C₄

alkylsulfonyl, phenylsulfonyl, substituted phenylsulfonyl, SO₂NR⁵R⁶, C₁-C₄ alkoxy, C₁-C₄ haloalkoxy, C₁-C₄ alkylthio, C₁-C₄ haloalkylthio, COOR⁵, or CN, provided R¹ is not CN; R³ is H, halo, C₁-C₆ haloalkyl, C₁-C₆ alkoxy, C₁-C₆ haloalkoxy, C₁-C₈ alkylthio, C₁-C₆ haloalkylthio, phenoxy, substituted phenoxy, phenylthio, substituted phenylthio, benzyloxy, substituted benzyloxy, benzylthio, or substituted benzylthio; R⁴ is H, COOR⁷, CONR⁵R⁶, CHO, COR⁷, or SO₂R⁷;

R⁵ and R⁶ are H, C₁-C₄ alkyl, or C₃-C₇ cycloalkyl;

R⁷ is C₁-C₄ alkyl, C₁-C₄ haloalkyl, benzyl, substituted benzyl, phenyl, or substituted phenyl; Het is a group of the formula

where

R²¹ is C₁-C₆ alkyl, C₃-C₆ branched alkyl, C₃-C₆

cycloalkyl, C₁-C₆ haloalkyl, pyridyl, furyl, thienyl, phenyl, substituted phenyl, aralkyl, or S(O)_mAlk, where m is 0-2 and Alk is as defined above;

R²² is C₁-C₈ alkyl, C₃-C₆ branched alkyl, C₃-C₆

cycloalkyl, aralkyl, C₁-C₆ alkoxy, C₁-C₈ haloalkoxy, C₁-C₆ alkylthio, C₁-C₆ haloalkylthio, cyclohexylmethyl, halo, NO₂, NR⁵R⁶, phenyl, substituted phenyl, phenoxy, substituted phenoxy, pyridyl, furyl, or thienyl; and

R²³ is H, halo, C₁-C₆ alkyl, C₃-C₆ branched alkyl, C₃-C₆ cycloalkyl, NO₂, CN, CO₂H, CO₂Alk, where Alk is C₁-C₆ alkyl or halo C₁-C₈ alkyl, or CONR⁵R⁶,where R⁵ and R⁶ are as defined above.

7. A compound of the formula (10):

wherein:

Q is S or O;

R¹ and R² are independently H, NO₂, halo, C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₂-C₆ alkenyl, C₂-C₆ alkynyl, C₁-C₄

alkylsulfonyl, phenylsulfonyl, substituted phenylsulfonyl, SO₂NR⁵R⁶, C₁-C₄ alkoxy, C₁-C₄ haloalkoxy, C₁-C₄ alkylthio, C₁-C₄ haloalkylthio, COOR⁵, CONR⁵R⁶,or CN, provided R¹ is not CN; R³ is H, halo, NR⁵R⁶, C₁-C₆ haloalkyl, C₁-C₆ alkoxy, C₁-C₆ haloalkoxy, C₁-C₆ alkylthio, C₁-C₆ haloalkylthio, phenoxy, substituted phenoxy, phenylthio, substituted phenylthio, benzyloxy, substituted benzyloxy, benzylthio, or substituted benzylthio;

R⁵ and R⁶ are H, C₁-C₄ alkyl, C₃-C₇ alkenyl, C₃-C₇

cycloalkyl or cycloalkenyl, or R⁵ and R⁵ together with the nitrogen atom to which they are attached form a 5-7 member ring containing up to three additional heteroatoms selected from O, N, and S;

R^11' is C₁-C₈ alkyl, C₂-C₈ alkenyl, C₂-C₈ alkynyl, C₃-C₈ branched alkyl or alkenyl, C₃-C₇ cycloalkyl or cycloalkenyl, aralkyl, (C₃-C₇ cycloalkyl)methyl, halo C₁-C₈ alkyl, phenyl, substituted phenyl, pyridyl, substituted pyridyl, furyl, substituted furyl, thienyl, substituted thienyl; and

R²⁴ and R^24'are independently Cl or Br.

8. A compound of claim 7 having the formula (10A)

wherein:

R¹ and R² are independently H, NO₂, halo, C₁-C₆ alkyl,

C₁-C₆ haloalkyl, C₂-C₆ alkenyl, C₂-C₆ alkynyl, C₁-C₄

alkylsulfonyl, phenylsulfonyl, substituted phenylsulfonyl, SO₂NR⁵R⁶, C₁-C₄ alkoxy, C₁-C₄ haloalkoxy, C₁-C₄ alkylthio, C₁-C₄ haloalkylthio, COOR⁵, or CN, provided R¹ is not CN, or CONR⁵R⁶, where R⁵ and R⁵ are H, C₁-C₄ alkyl, C₃-C₇ cycloalkyl;

R³ is H, halo, C₁-C₆ haloalkyl, C₁-C₆ alkoxy, C₁-C₆ haloalkoxy, C₁-C₆ alkylthio, C₁-C₆ haloalkylthio, phenoxy, substituted phenoxy, phenylthio, substituted phenylthio, benzyloxy, substituted benzyioxy, benzylthio, or substituted benzylthio; R^11' is C₁-C₆ alkyl, C₃-C₆ branched alkyl, C₃-C₆

cycloalkyl, aralkyl, cyclohexylmethyl, phenyl, substituted phenyl, pyridyl, furyl, or thienyl; and

R²⁴ and R^24'are independently Cl or Br.

9. A method of inhibiting plant pathogens which

comprises applying an effective amount of a compound of any one of claims 5 to 8 to a locus of the pathogen.

10. A method of inhibiting a nematode population which comprises applying to the locus of a nematode, a nematode inactivating amount of a compound of any one of claims 5 to 8.

11. A method of inhibiting an insect or mite population which comprises applying to the locus of the insect or

arachnid an effective insect or mite inactivating amount of a compound of any one of claims 5 to 8.

12. A pesticidal composition comprising a compound of any one of claims 5 to 8 in combination with an agriculturally acceptable carrier.