WO1992003050A1

WO1992003050A1 - Fungicidal sulfoneoxime esters

Info

Publication number: WO1992003050A1
Application number: PCT/US1991/005508
Authority: WO
Inventors: Richard James Brown
Original assignee: E.I. Du Pont De Nemours And Company
Priority date: 1990-08-16
Filing date: 1991-08-08
Publication date: 1992-03-05
Also published as: IL99194A0; AU8432291A; CN1058880A

Abstract

Fungicidally effective compounds of formula (I) are disclosed.

Description

TITLE

FUNGICIDAL SULFONEOXIME ESTERS CROSS-REFERENCE TO RELATED APPLICATION This application is a continuation-in-part of application U.S.S.N.

07/568,485, filed August 16, 1990.

BACKGROUND OF THE INVENTION

Bellina (U.S. 3,819,700) claims compounds of Formula A

wherein:

n is 1 or 2;

R¹ is C₁-C₁₂ alkyl, C₃-C₁₂ alkyl substituted with Cl, C₃-C₄

alkenyl, C₃-C₈ cycloalkyl, C₆-C₇ cycloalkylalkyl, phenyl, benzyl, or

wherein R², R³ and R² are as defined below, p is 1 or 2, and R⁸ is phenylene, xylylene, or C₂-C₁₈ alkylene; R² and T$ are independently C₁-C₁₂ alkyl, C₃-C₄ alkenyl, C₃-C₁₀ cycloalkyl, C₅-C₈ cycloalkenyl, C₆-C₇ cycloalkylalkyl or benzyl provided that

1) only one of R² and R³ can be benzyl;

2) the sum of carbon atoms in R² and R³ can total no more than 12, except where both R² and R³ are alkyl;

R⁴ is H or (C=O)NHR⁵;

R⁵ is C₁-C₈ alkyl, propargyl, C₃-C₄ alkenyl, C₃-C₈ cycloalkyl,

benzyl, phenyl or phenyl substituted with 1 or 2 substituents selected from halogen, nitro, methoxy and methyl.

The use of these compounds as fungicides is disclosed. The compounds claimed are outside of the scope of the instant application.

EP 0010588 (U.S. equivalents 4,449,999, 4,394,152, 4,451,279 and 4,382,893) discloses the use of compounds of Formula B as herbicide safeners

The compounds disclosed as safeners overlap the compounds claimed in Bellina (U.S. 3,819,700) wherein X is C( =O)NR¹R².

SUMMARY OF THE INVENTION

This invention pertains to a method of controlling fungus disease in plants that comprises treating the locus to be protected with an effective amount of a compound of Formula I:

wherein:

G is C(=L)N R²R³, C(=O)OR⁴, SO₂NR²R³ or S(O)_mR⁵;

L is O or S;

A is H, C(=O)OR6, C(=O)NHR⁷, C(=O)(CH₂)_nR⁸ or SO₂R¹⁴;

R¹ is C₁-C₈ alkyl optionally substituted with C₁-C₂ alkoxy, C₃-C₆ cycloalkyl, cyano, CO₂R¹⁵, or one or more halogen; C₃-C₆ cycloalkyl; C₁-C₂ alkyl substituted with phenyl, naphthalenyl, heteroalicyclic, heteroaromatic or fused heteroaromatic ring systems; or phenyl, naphthalenyl, heteroalicyclic,

heteroaromatic or fused heteroaromatic ring systems; said phenyl, naphthalenyl, heteroaromatic, or fused heteroaromatic rings being optionally substituted with R⁹ and R¹⁰; R² and R³ are independently H; C₁-C₆ alkyl; C₁-C₆ haloalkyl; C₂- C₆ alkoxyalkyl; C₃-C₄ alkenyl; C₃-C₄ haloalkenyl; or R² and R³ may be taken together along with the nitrogen to which they are attached to form a pyrrolidino, piperidino or morpholino group, each optionally substituted with 1-2 methyl groups;

R⁴ is C₁-C₈ alkyl, C₁-C₈ haloalkyl, C₃-C₆ alkoxyalkyl, C₃-C₆

alkenyl or C₃-C₆ haloalkenyl;

R⁵ is C₁-C₆ alkyl; C₁-C₆ haloalkyl; C₂-C₆ alkoxyalkyl; or phenyl or benzyl, said phenyl or benzyl groups being optionally

substituted with methyl, trifluoromethyl, methoxy, cyano, nitro or 1-3 halogen; R⁶ is C₁-C₈ alkyl optionally substituted with C₁-C₆ alkoxy, C₃-C₆ cycloalkyl, cyano or one or more halogen; C₃-C₆ cycloalkyl; or C₁-C₂ alkyl substituted with phenyl, naphthalenyl,

heteroalicyclic, heteroaromatic or fused heteroaromatic ring systems, said phenyl, napthalenyl, heteroaromatic or fused heteroaromatic rings being optionally substituted with R9 and

R¹⁰;

R⁷ is phenyl, benzyl, naphthalenyl, heteroaromatic or fused

heteroaromatic ring system; said phenyl, benzyl, naphthalenyl, heteroaromatic or fused heteroaromatic rings being optionally substituted with R⁹ and R¹⁰;

R⁸ is phenyl, naphthalenyl, heteroaromatic or fused heteroaromatic ring systems, said phenyl, naphthalenyl, heteroaromatic or fused heteroaromatic rings being optionally substituted with R⁹ and R¹⁰;

R⁹ is C₁-C₂ alkyl, C₁-C₂ haloalkyl, C₁-C₂ alkoxy, C₁-C₂

haloalkoxy, cyano, nitro or 1-2 halogen;

R¹⁰ is C₁-C₄ alkyl; C₁-C₄ haloalkyl; C₂-C₄ alkenyl; C₂-C₄ alkynyl;

C₂-C₄ alkoxyalkyl; OR¹¹; C(=O)R¹²; CO₂R¹²; C(=O)NR²R³; NR²R³; NR²C(=O)R¹²; S(O)_mR¹²; SO₂NR²R³;

— O(CH₂)_pO_q— ;— (CH₂)_w— ; halogen; cyano; nitro; or phenyl or phenoxy, said phenyl or phenoxy groups being optionally substituted with R¹³;

R¹¹ is C₁-C₄ alkyl optionally substituted with C₁-C₂ alkoxy, C₃-C₆ cycloalkyl, cyano or one or more halogen; or C₃-C₆ cycloalkyl; R¹² is C₁-C₄ alkyl optionally substituted with C₁-C₂ alkoxy, cyano or one or more halogen;

R¹³ is methyl, methoxy, trifluoromethyl, nitro, cyano or 1-2 halogen; R¹⁴ is C₁-C₆ alkyl; C₁-C₆ haloalkyl; C₂-C₆ alkoxyalkyl; or phenyl or benzyl, said phenyl or benzyl groups being optionally substituted with methyl, trifluoromethyl, methoxy, cyano, nitro or 1-3 halogen; R¹⁵ is C₁-C₈ alkyl, C₁-C₈ haloalkyl, C₃-C₆ alkoxyalkyl, C₃-C₆ alkenyl or C₃-C₆ haloalkenyl;

m is 0, 1 or 2;

n is 0, 1 or 2;

p is 1, 2 or 3;

q is 0 or 1; and

w is 3 or 4; provided that

i) when G is C(=O)NR²R³ _:

1) A is C(=O)(CH₂)_nR⁸ and n is 0; or

2) R¹ is C₁-C₈ alkyl substituted with cyano or 2 or more halogens; or C₂-C₈ alkyl substituted with

CO₂R¹⁵; or

3) R¹ is substituted phenyl or substituted benzyl; ii) R¹ is not methyl.

iii) when R², R³ or R⁴ are alkenyl or haloalkenyl, they must be attached to the heteroatom through an sp³-hybridized carbon; iv) when A is H and R¹ is 4-methylphenyl, G is not

C(=O)N(CH₂CH₃)₂ or C(=O)N(CH₃)₂; and

v) when G is C(=O)N(CH₃)₂ and A is C(=O)-2,4-dichlorophenyl, R¹ is not n-octyl.

In the above recitations, 'heteroaromatic or fused heteroaromatic ring systems" refers to a 5- to 10-membered ring system wherein the heteroatoms consist of:

i) 1-4 nitrogen atoms,

ii) 1-2 nitrogen atoms with 1 oxygen or 1 sulfur atom, or iii) 1-2 oxygen or sulfur atoms.

Examples of 'heteroaromatic" rings include furan, thiophene, pyrrole, oxazole and thiazole. Examples of "fused heteroaromatic" rings include quinoline, indole, isoindole, benzoxazole, benzthiazole,

benzo[b]furan and benzo[b]thiophene. Examples of 'heteroalicyclic" rings include tetrahydrofuran, tetrahydropyran, pyrrolidine, piperidine, dioxane, morpholine,

thiomorpholine and piperazine.

The term "alkyl", used either alone or in compound words such as 'haloalkyl" denotes straight chain or branched alkyl, especially methyl, ethyl, n-propyl, i-propyl, or the different butyl, pentyl, hexyl, heptyl or octyl isomers.

"Alkenyl" denotes straight chain or branched alkenes, especially 1-propenyl, 2-propenyl, 3-propenyl and the different butenyl isomers.

"Alkynyl" denotes straight chain or branched alkynes, especially ethynyl, 1-propynyl, 3-propynyl and the different butynyl isomers.

"Alkoxy" denotes methoxy, ethoxy, n-propyloxy, isopropyloxy and the different butoxy, pentoxy and hesyloxy isomers.

"Cycloalkyl" denotes cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.

The term "halogen", either alone or in compound words such as

"haloalkyl", denotes fluorine, chlorine, bromine or iodine. Further, when used in compound words such as "haloalkyl", said alkyl may be partially or fully substituted with halogen atoms which may be the same or different. Specific examples of "haloalkyl", "haloalkenyl" and "haloalkoxy" include F₃C, ClCH₂, CF₃CH₂, CF₃CF₂, (Cl)2C =CHCH₂, BrCH=CHCH₂, CF₃O, CCI₃CH₂O, and CF₃CH₂O.

The total number of carbon atoms in a substituent group is indicated by the "C_i-C_j" prefix where i and j are numbers from 1 to 8. For example, "C2 alkoxyalkyl" designates CH₃OCH₂, "C₃ alkoxyalkyl" designates CH₃OCH₂CH₂ and CH₃CH₂OCH₂. Other examples of

"alkoxyalkyl" include CH₃CH₂CH₂CH₂OCH₂ and CH₃CH₂OCH₂CH₂.

Preferred embodiments include:

1) A method of controlling fungus disease in plants that comprises treating the locus to be protected with an effective amount of a compound of Formula I wherein:

G is C(=O)NR²R³ or C(=O)OR⁴; R¹ is C₁-C8 alkyl optionally substituted with C1-C2 alkoxy, cyano, CO₂R¹⁵ or one or more halogen;

C₁-C₂ alkyl substituted with phenyl, said phenyl group being optionally substituted with R⁹ and

R¹⁰; or phenyl substituted with R⁹ and R¹⁰; R¹¹ is C₁-C₄ alkyl optionally substituted with C₁-C₂ alkoxy, cyano or one or more halogen; and

R¹² is C₁-C₂ alkyl optionally substituted with one or more halogen. 2) A method of Preferred 1 wherein:

G is C( =O)NR²R³;

R¹ is phenyl or benzyl, said phenyl or benzyl group being optionally substituted with R⁹ and R¹⁰;

R² and R³ are independently H; C₁-C₄ alkyl; C₁-C₄

haloalkyl; or R² and R³ may be taken together along with the nitrogen to which they are attached to form a pyrrolidino, piperidino or morpholino group each optionally substituted with 0-2 methyl;

R⁹ is methyl, trifluoromethyl, methoxy, cyano, nitro or 1-2 Cl or F; and

R¹⁰ is methyl; t-butyl; trifluoromethyl; methoxy; C(=O)CH₃;

CO₂CH₃; N(CH₃)₂; SCH₃; SO₂CH₃; F; Cl; Br; cyano; nitro; or phenyl or phenoxy, said phenyl or phenoxy being optionally substituted with R^3.

3) A method of Preferred 2 wherein:

A is C(=O)OR⁶; and

R⁶ is C₁-C₈ alkyl optionally substituted with C₁-C₆ alkoxy, halogen or cyano; or C₁-C₂ alkyl substituted with phenyl, said phenyl being optionally substituted with

R⁹ and R¹⁰. 4) A method of Preferred 2 wherein:

A is C(=O)NHR⁷; and

R ' is phenyl or benzyl, said phenyl or benzyl groups being optionally substituted with R⁹ and R¹⁰.

5) A method of Preferred 2 wherein:

A is H.

6) A method of Preferred 2 wherein:

A is C(=O)(CH₂)_nR⁸.

7) A method of Preferred 6 wherein:

n is 0; and

R⁸ is phenyl or naphthalenyl, said phenyl or naphthalenyl groups being optionally substituted with R⁹ and R¹⁰.

8) A method of Preferred 7 wherein:

R¹ is phenyl optionally substituted with R¹⁰; and

R⁸ is phenyl optionally substituted with R¹⁰.

9) Compounds of the Formula I and agricultural compositions containing them and their use as fungicides wherein:

G is SO₂NR²R³ or S(O)_mR⁵;

A is H, C(=O)OR⁶, C(=O)NHR⁷, C(=O)(CH₂)_nR⁸ or SO₂R¹⁴; R¹ is C₁-C₈ alkyl optionally substituted with C₁-C₂ alkoxy, C₃-C₆ cycloalkyl, cyano, CO₂R¹⁵, or one or more halogen; C₃-C₆ cycloalkyl; C₁-C₂ alkyl substituted with phenyl, naphthalenyl, heteroalicyclic, heteroaromatic or fused heteroaromatic ring systems; or phenyl, naphthalenyl, heteroalicyclic, heteroaromatic or fused heteroaromatic ring systems; said phenyl, naphthalenyl, heteroaromatic, or fused heteroaromatic rings being optionally substituted with R⁹ and R¹⁰; R² and R³ are independently H; C₁-C₆ alkyl; C₁-C₆

haloalkyl; C₂-C₆ alkoxyalkyl; C₃-C₄ alkenyl; C₃-C₄ haloalkenyl; or R² and R³ may be taken together along with the nitrogen to which they are attached to form a pyrrolidino, piperidino or morpholino group, each optionally substituted with 1-2 methyl groups;

R⁵ is C₁-C₆ alkyl; C₁-C₆ haloalkyl; C₂-C₆ alkoxyalkyl; or phenyl or benzyl, said phenyl or benzyl groups being optionally substituted with methyl, trifluoromethyl, methoxy, cyano, nitro or 1-3 halogen;

R⁶ is C₁-C₈ alkyl optionally substituted with C₁-C₆ alkoxy, C₃-C₆ cycloalkyl, cyano or one or more halogen; C₃-C₆ cycloalkyl; or C₁-C₂ alkyl substituted with phenyl, naphthalenyl, heteroalicyclic, heteroaromatic or fused heteroaromatic ring systems, said phenyl, napthalenyl, heteroaromatic or fused heteroaromatic rings being optionally substituted with R⁹ and R¹⁰;

R⁷ is phenyl, benzyl, naphthalenyl, heteroaromatic or fused heteroaromatic ring system; said phenyl, benzyl, naphthalenyl, heteroaromatic or fused heteroaromatic rings being optionally substituted with R⁹ and R¹⁰; R⁸ is phenyl, naphthalenyl, heteroaromatic or fused

heteroaromatic ring systems, said phenyl,

naphthalenyl, heteroaromatic or fused heteroaromatic rings being optionally substituted with R⁹ and R¹⁰; R⁹ is C₁-C₂ alkyl, C₁-C₂ haloalkyl, C₁-C₂ alkoxy, C₁-C₂ haloalkoxy, cyano, nitro or 1-2 halogen; R¹⁰ is C₁-C₄ alkyl; C₁-C₄ haloalkyl; C₂-C₄ alkenyl; C₂-C₄ alkynyl; C₂-C₄ alkoxyalkyl; OR¹¹; C( =O)R¹²; CO₂R¹²; C(=O)NR2R³; NR²R³; S(O)_mR¹²; SO₂NR²R³;

R¹¹ is C₁-C₄ alkyl optionally substituted with C₁-C₂ alkoxy, C₃-C₆ cycloalkyl, cyano or one or more halogen; or C₃-C₆ cycloalkyl;

R¹² is C₁-C₄ alkyl optionally substituted with C₁-C₂ alkosy, cyano or one or more halogen;

R¹³ is methyl, methoxy, trifluoromethyl, nitro, cyano or 1-2 halogen;

R¹⁴ is C₁-C₆ alkyl; C₁-C₆ haloalkyl; C₂-C₆ alkoxyalkyl; or phenyl or benzyl, said phenyl or benzyl groups being optionally substituted with methyl, trifluoromethyl, methoxy, cyano, nitro or 1-3 halogen;

R¹⁵ is C₁-C₈ alkyl, C₁-C₈ haloalkyl, C₃-C₆ alkoxyalkyl, C₃-C₆ alkenyl or C₃-C₆ haloalkenyl;

m is 0, 1 or 2;

n is 0, 1 or 2;

p is 1, 2 or 3;

q is 0 or 1; and

w is 3 or 4. 10) Compounds of the Formula I and agricultural compositions containing them and their use as fungicides wherein:

G is C(=L)NR²R³ or C(=O)OR⁴; and

L is O or S;

A is H, C(=O)OR⁶, C(=O)NHR⁷, C(=O)(CH₂)_nR⁸ or SO₂R¹⁴; R¹ is C₁-C₈ alkyl substituted with cyano, CO₂R¹⁵ or more than one halogen; or C₁-C₂ alkyl substituted with phenyl, naphthalenyl or heteroaromatic ring systems containing from 5 to 10 atoms, wherein the heteroatoms comprise:

i) 1-3 nitrogen atoms, or

ii) 1-2 nitrogen atoms with 1 oxygen or sulfur atom, or; iii) 1-2 oxygen or sulfur atoms; said phenyl,

naphthalenyl or heteroaromatic ring systems being optionally substituted with R⁹ and R¹⁰;

R² and R³ are independently H; C₁-C₆ alkyl; C₁-C₆

R⁴ is C₁-C₈ alkyl, C₁-C₈ aloalkyl, C₃-C₆ alkoxyalkyl,

C₃-C₆ alkenyl or C₃-C₆ haloalkenyl;

R⁷ is phenyl, benzyl, naphthalenyl, heteroaromatic or fused heteroaromatic ring system; said phenyl, benzyl, naphthalenyl, heteroaromatic or fused heteroaromatic rings being optionally substituted with R⁹ and R¹⁰; R³ is phenyl, naphthalenyl, heteroaromatic or fused

heteroaromatic ring systems, said phenyl, naphthalenyl, heteroaromatic or fused heteroaromatic rings being optionally substituted with R⁹ and R¹⁰; R⁹ is C₁-C₂ alkyl, C₁-C₂ haloalkyl, C₁-C₂ alkoxy, C₁-C₂ haloalkoxy, cyano, nitro or 1-2 halogen;

R¹⁰ is C₁-C₄ alkyl; C₁-C₄ haloalkyl; C₂-C₄ alkenyl; C₂-C₄ alkynyl; C₂-C₄ alkoxyalkyl; ORH; C(=O)R¹²; CO₂R¹²;

C(=O)NR²R³; NR²R³; S(0)_mR¹²; SO₂NR²R³;

R¹l is C₁-C₄ alkyl optionally substituted with C₁-C₂ alkoxy, C₃-C₆ cycloalkyl, cyano or one or more halogen; or C₃-C₆ cycloalkyl;

R¹² is C₁-C₄ alkyl optionally substituted with C₁-C₂ alkoxy, cyano or one or more halogen;

R¹³ is methyl, methoxy, trifluoromethyl, nitro, cyano or 1-2 halogen;

R¹⁵ is C₁-C₈ alkyl, Cχ-C8 haloalkyl, C₃-C₆ alkoxyalkyl, C₃-C₆ alkenyl or C₃-C₆ haloalkenyl;

m is 0, 1 or 2;

n is 0, 1 or 2;

p is 1, 2 or 3;

q is 0 or 1; and

w is 3 or 4; provided that when G is C(=O)NR²R³:

1) A is C(=OXCH₂)_nR⁸ and n is 0;

or 2) R¹ is C₁-C₈ alkyl substituted with cyano or 2 or more halogens; or C₂-C₈ alkyl substituted with

CO₂R¹⁵.

.1) A compound of the Preferred 10 wherein:

G is C(=O)NR²R³;

A is C(=O)(CH₂)_nR⁸; and

R¹ is benzyl substituted with R⁹;

provided that n is 0. Specifically preferred for greatest fungicidal activity and/or ease of synthesis are:

1) 2-[[4-(1,1-diιnethylethyl)phenyl]sulfonyl]-2-(hydroxyimino)- N,N-dimethylacetamide); and

2) 2-[(4-bromophenyl)sulfonyl]-2-[[(3-(Morobenzoyl)oxy]imino]- N,N-dimethylacetamide).

DETAILED DESCRIPTION OF THE INVENTION

Synthesis

The compounds of Formula I can be prepared from compounds of Formula III and an appropriate electrophiUc reagent of Formula E in an inert solvent with or without a base used either as a catalyst or acid scavenger. Suitable solvents include polar aprotic solvents such as acetonitrile, dimethylformamide, or dimethylsulfoxide; ethers such as tetrahydrofuran, dimethoxyethane, or diethyl ether; ketones such as acetone or 2-butanone; hydrocarbons such as toluene or benzene; or halocarbons such as dichloromethane or chloroform. Appropriate bases include alkali metal alkoxides such as sodium methoxide or potassium tert-butoxide. inorganic bases such as sodium hydride or potassium carbonate, or tertiary amines such as triethylamine, pyridine, 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), or triethylenediamine (DABCO). The reaction temperature can vary between 0° and 150°C for periods of 1 to 72 hours depending on the choice of base, solvent, temperature, and substrates.

Compounds of Formulas Ia-d can be prepared from combining an appropriate electrophilic reagent of Formula IIa-d with an oxime of Formula III by several processes which are summarized in the following equations.

>

A novel method of preparation of compounds of Formula Ia-b comprises sequential preparation of the novel chloroformate Ie by reaction of compounds of Formula III with phosgene in the presence of organic bases such as N,N-diethylaniline and pyridine, followed by the appropriate R⁷NH₂ or R⁶OH compound in the presence of a suitable acid scavenger such as N,N-diethylaniline, pyridine or triethylamine.

Compounds of Formula le can be prepared from compounds of Formula III and a carboxylic acid IId in the presence of a coupling auxiliary reagent such as, but not limited to, N,N-dicyclohesylcarbodiimide (DCC) or 2,2'-dipyridyldisulfide (DPDS).

G

The thiocarboxamide compounds of Formula I can be prepared from the carboxamide of Formula I by methods described elsewhere (see S. Scheibye, E.S.Pedersen and S. O. Lawesson, Bull Soc, Chim. Belg. 1978.87:229 and G. Lajore, F. Lepine, L. Maziak and B. Belleau, Tet. Letters. 1983.24:3815).

Compounds of Formula I can also be prepared by conversion of other compounds of Formula I by standard methods of organic reactions, recognizable by those skilled in the art, such as, but not limited to, reduction and oxidation.

The α-sulfone oximes of Formula III can be prepared from thiohydroxamates of Formula IV by oxidation with two equivalents of organic oxidants such as peracetic acid, m-chloroperbenzoic acid

(MCPBA) or monoperoxyphthalic acid magnesium salt (MMPP) or inorganic oxidants such as hydrogen peroxide or potassium

peroxymonosulfate (OXONE®).

The α-sulfone oximes of Formula III can also be prepared by the reaction of alkah metal sulfinate salts with α-chloroaldoximes of Formula

VI.

Sulfinic acids and their salts can be prepared in a number of ways.

(For a review, see K. K. Andersen, in Comprehensive Organic Chemistry;

Barton, D. and Ollis, W. D., Eds.; Pergamon:Oxford, 1979; Vol. 3; pp. 317-

329.)

The α-sulfone oximes of Formula III can also be prepared by the reaction of sulfones of Formula VII with sodium nitrite. Alternatively, the α-sulfoneoximes of Formula III can be prepared by the reactions of sulfones of Formula VII with bases such as sodium alkoxides, followed by reaction with organic nitrites such as isoamyl nitrite, (see O. Touster, Org. Reactions. 1953. 7:327 for general procedures).

Compounds of Formula III may also be prepared from

α-nitrosulfones of Formula VIII by reaction with sodium nitrite, (see J. J. Zeilstra and J.B.F.N. Engberts, Synthesis. 1974. p 49).

Compounds of Formula IV may be prepared by the reaction of α-chloroaldoximes of Formula VI with thiols of Formula IX in the presence of a base such as triethylamine or sodium carbonate (see M. H. Benn, Can. J. Chem. 1964. 42:2393).

The α-chloroaldoximes of Formula VI can be prepared by treating amines of Formula X with sodium nitrite and hydrochloric acid (see G. S.

Skinner, J.Am. Chem. Soc. 1924. 46:731).

The α-chloroaldoximes of Formula VI can also be prepared from aldoximes of Formula XI by treatment with N-chlorosuccinimide (see K. E. Larsen and K B. G. Torsell, Tetrahedron. 1984. 40:2985) or t- butylhypochlorite (see C. J. Peake and J. H. Strickland, Synth, Comm. 1986. 16:763).

Some α-chloroaldoximes of Formula VI may be prepared from amide oximes XII by treatment with sodium nitrite in hydrochloric acid solution (see M.Kocevar, S. Polanc, M. Sollner, M. Tisler and B.Vercek, Synth, Comm. 1988. 18:1427).

The α-chloroaldoximes of Formula VI can be prepared from trichloromethyl compounds of Formula XIII by basic hydrolysis in the presence of hydroxylamine (see A. P. Kozikowski and M. Adamczyk, J. Org. Chem. 1983. 48:366).

The α-chloroaldoximes of Formula VI can be prepared by the reaction of nitrile N-oxides of Formula XIV with hydrochloric acid (see C. Grundmann, V. Mini, J. M. Dean, and H.-D. Frommeld, Justis laebigs Ann. Chem.1965. 687:191).

The nitrile N-oxides of Formula XIV can be prepared by several methods well known in the chemical art (for a summary of methods, see

T. Shimizu, Y.Hayashi, and K Taramura, Bull. Soc. Chem. Jpn. 1984.

57:2531).

The carboxamide and carboxylic acid ester compounds of Formula

VI can be prepared by the procedures taught in the U.S. Patents

3,557,089, 3,557,190, and 3,560,555.

The thiocarboxamide compounds of Formula VI can be prepared from the trihalothioacetamides of Formula XVI which are obtained from the haloimmonium chlorides of Formula XV. See W. Walter and K.-D. Bode, Angew. Chem. Internal Edit. 1966. 5:447 for a review of the syntheses of thiocarboxamides.

The thioalkyl and thioaryl compounds of Formula VI can be prepared from dichloroformaldoxime XVII (see D.Chiarino, M.

Napoletano and A. Sala, Synth, Comm.1988. 18:1171 and D. M. Vyas, Y. Chiang and T.W.Doyle, Tet. Letters. 1984.25:487) by reaction with a thiol and one equivalent of an organic base such as triethylamine (see M. H. Benn, Can. J. Chem. 1964. 42:2393).

The sulfoxide and sulfone compounds of Formula VI can be prepared from compounds of Formula VI (G = R⁵S) by oxidation using one or two equivalents, respectively, of oxidants such as hydrogen peroxide or organic peracids, such as peracetic acid.

The sulfone compounds of Formula Vlb can also be prepared from compounds of Formula XVIII (G = R⁵SO₂) according to methods already reported (see P.A.Wade and H. R. Hinney, J Am Chem. Soc. 1979.

101:1319).

Alternatively, the sulfonylcarbohydroximoyl chlorides of Formula VI can be prepared from α-diazosulfones of Formula XIX and nitrosyl chloride (see J. C. Jagt, I. van Buuren, J. Strating and A. M. van Leusen, Synth, Commun. 1974. 4:311).

The carboxamide compounds of Formula III can be prepared by the procedures taught in U.S. Patent 3,819,700.

The sulfide compounds of Formula III can be prepared by the reaction of chlorooximes of Formula XX with thiols in the presence of base. The sulfoxide and sulfone compounds of Formula III can be prepared by the oxidation of the sulfide compounds of Formula III with one or two equivalents, respectively, of oxidizing agents such as peracetic acid or hydrogen peroxide.

^J

Those skilled in the art will recognize compounds of Formula I are O-substituted oximes which can be of either the syn or anti form. The scope of the specification referring to compounds of Formula I includes both stereoisomeric oxime forms either as a specific stereoisomer, a mixture of stereoisomers, or as any reciprocal mixture ratio of the two stereoisomeric forms.

The examples which follow are representative of the production of the novel oximes of Formula I.

EXAMPLE 1

Ethyl 2-(benzylthio)-2-hydroxyiminoacetate

A solution of 7 mL triethylamine in 50 mL of diethyl ether was added over a 10 minute period to a solution of ethyl chlorooximidoacetate (7.6 g) and benzylmercaptan (5.9 mL) in 300 mL of diethyl ether. A white precipitate formed. After stirring the reaction for 30 minutes, the precipitate was removed by filtration and washed with several portions of ether. The combined filtrate and washings were concentrated in vacuo to give an oil which solidified on standing. The crude solid was triturated in hexane to yield 8.93 g light amber solid; m.p. 90-92°C, 75% yield. EXAMPLE 2

Ethyl 2-(benzylsulfonyl)-2-hydroxyiminoacetate

To a stirred solution of ethyl 2-(ben-zylthio)-2-hydroxyiminoacetate (14.25 g) in 240 mL of methanol was added a solution of OXONE® (55 g) dissolved in 240 mL of water, over a 20 minute period, to form a white heterogeneous reaction mixture. Monitoring the reaction mixture by TLC indicated rapid formation of the sulfoxide within 60 minutes after the addition was complete. Further oxidation to the sulfone required prolonged stirring (72 hours) at room temperature. The reaction volume was reduced by rotary evaporation and the remaining mixture was diluted with 150 mL water. The aqueous mixture was extracted with chloroform (4 × 250 mL) and the extracts were combined and dried (MgSO₄). Filtration and concentration in vacuo afforded a white solid;

12.1 g, m.p. 77-83°C, 75% yield. EXAMPLE 3

2-(4-Chlorobenzylsulfonyl)-2-hydroxyimino-N,N-dimethylacetamide

To a solution of 2-(4-chlorobenzylthio)-2-hydroxyimino-N,N- dimethylacetamide (19.4 g) in 150 mL of dichloromethane was added a

32% weight solution of peracetic acid. A precipitate formed and the mixture was stirred for 24 hours. The solid was removed by filtration, dried in vacuo and recrystallized from acetonitrile to yield 12.1 g white solid; m.p. 175-180°, 53% yield. Additional material was recovered by quenching the reaction filtrate with half-saturated aqueous sodium bisulfite solution and collecting the resulting precipitate. After

recrystallization, 1.9 g white solid was obtained. 8% yield.

EXAMPLE 4

2-(Phenylsulfonyl)-2-hydroxyiminopiperidinoacetamide A solution of 2-chloro-2-hydroxyimino-piperidinoacetamide (7.5 g) and benzenesuhimc acid, sodium salt (12.8 g) in 750 mL of

dichloromethane and 100 mL of methanol was stirred at room

temperature for 3 days. The heterogeneous reaction mixture was filtered through CeliteT and the filtrate was concentrated is vacuo to yield an orange, viscous oil. Purification was accomplished using silica gel flash chromatography, using a gradient elution of 20% ethyl acetate in CH₂CI2 to 25%. Concentration of the appropriate fraction resulted in a white powder which was recrystallized from 1-chlorobutane/ethyl acetate/ hexane with a trace of acetonitrile to yield 3.2 g of white crystalline solid; m.p. 175-176°C.

EXAMPLE 5

N,N-dimethyl-2-(phenylsulfonyl)- 2-[[[3-(trifluoromethyl)benzoyn]oxy]imino]acetamide

To a stirred solution of 2-(phenylsutfonyl)-2-hydroxyimino-N,N-dimethylacetamide (7.7 g) and 3-trifluoromethylbenzoylchloride (4.5 mL) in 130 mL of tetrahydrofuran (THF) was added dropwise a solution of triethylamine (4.2 mL) in 20 mL of THF. A precipitate formed and the reaction mixture was stirred for 2 hours. The precipitate was removed by filtration and the filtrate was concentrated in vacuo to provide 13 g of white solid, which was recrystallized from 1-chlorobutane/hexane to yield 10.2 g granular white solid; m.p. 90-92°C, 80% yield. EXAMPLE 6

2-[(4-Chlorophenyl)sulfonyl]-N,N-dimethyl-

2-[[[3-(trifluoromethyl)benzoyl]oxy]imino]acetamide To a stirred solution of 2-[(4-chlorophenyl)-sulfonyl]-2-hydroxyim--no-N,N-dimethylacetamide (1.45 g) and 3-trifluoromethylbenzoylchloride (1.04 g) in 20 mL of THF was added triethylamine (0.7 mL). A white precipitate formed. After 1 hour, the precipitate was removed by filtration and the filtrate was concentrated in vacuo to yield 2 g of white solid. The material was further purified by recrystallization from 1-chlorobutane to yield white crystalline solid; m.p. 122-125°C. EXAMPLE 7

2-[(4-Bromophenyl)sulfonyl]-2-[[[(3-chlorophenyl)amino]carbonyl]oxy]imino-N,N-dimethylacetamide

To a solution of 2-(4-bromophenylsulfonyl)-2-hydroxyimino-N,N- dimethylacetamide (790 mg) and 3-chlorophenyl isocyanate (0.25 mL) in 20 mL of THF was added one drop of DBU. The clear solution was stirred at room temperature for 3 days. The solvent was removed in vacuo and the residue was triturated in 1-chlorobutane/hexane to yield 960 mg of white solid; m.p. 135-138°C, 98% yield. EXAMPLE 8

2-[(4-Chlorophenyl)sulfonyl]- 2-[[(ethoxycarbopyl)oxy]imino]-N,N-dimethylacetamide To a solution of 2(4-chlorophenylsulfonyl)-2-hydroxyimino-N,N- dimethylacetamide (490 mg) and ethyl chloroformate (0.18 mL) in 15 mL of THF was added 0.24 mL of triethylamine. A white precipitate formed. The reaction mixture was stirred for one hour and the precipitate was removed by filtration. The filtrate was concentrated in vacuo to yield a white solid. The solid was triturated in hexane to give 500 mg white solid. The solid was further purified by recrystallization from acetonitrile to yield 220 mg of white crystalline solid; m.p. 95-98°C, 36% yield.

EXAMPLE 9

1-[2-[[[(3-Chlorophenyl)carbonyl]- oxy]imino]-2-(phenylsulfonyl)acetyl]piperidine A stirred solution of 2-phenylsulfonyl-2-hydroxyimino-piperidinoacetamide (600 mg) in 25 mL of CH₂CI2, cooled to 0°C, was treated sequentially with 0.18 mL of pyridine and 0.22 mL of 3-chlorobenzoyl chloride. The resulting reaction mixture was stirred for 30 minutes at 0°C, then poured into a separatory funnel containing 50 mL of CH₂CI₂ and 20 mL of half-saturated NH₄CI solution. The organic phase was separated, dried with MgSO₄, filtered and concentrated in vacuo to yield a colorless oil which crystallized on standing. Recrystallization from 1-chlorobutane/hexane with a trace of acetonitrile resulted in 320 mg of white crystals; m.p. 167-169°C.

EXAMPLE 10

2-(4-Chlorophenylsulfonyl)-2-hydroxyimino-N,N-dimethylacetamide To a solution of 2(4-cMorophenylthio)-2-hydroxyimino-N,N-dimethylacetamide (19 g) in 150 mL of CH₂CI₂ was added 28.4 mL of

35% peracetic acid solution. The mixture was stirred overnight. The resulting precipitate was removed by filtration and dried in vacuo to yield 18.65 g of white solid; m.p. 165-168°C, 88% yield.

EXAMPLE 11

2-(4-Chlorophenylthio)-2-hydroxyimino-N,-N -dimethylacetamide

To a solution of 2-cMoro-2-hydroxvimino-N,N-dimethylacetamide

(11.25 g) and 4-chlorothiophenol (10.8 g) in 500 mL of THF was added dropwise a solution of triethylamine (10.5 mL) in 50 mL of THF. A precipitate formed. After 2 hours, monitoring by TLC indicated complete reaction. The precipitate was removed by filtration and washed with several portions of THF. The combined filtrate and washings were concentrated in vacuo to yield a crude solid. The solid was triturated in hexane to yield 19.4 g of off-white solid, m.p. 205-207°C.

EXAMPLE 12

2-(4-Bromophenylsulfonyl)-2-hydroxyimino-N,N-dimethylacetamide To a solution of 2-(4-bromophenylthio)-2-hydroxyimino-N,N-dimethylacetamide (11.0 g) in 150 mL of CH₂CI₂ was added 14 mL of

35% peracetic acid solution. The reaction mixture was stirred at room temperature overnight. The solids which had formed were removed by filtration and dried in vacuo to afford 8.57 g of white solid; m.p.

170-173°C, 71% yield. EXAMPLE 13

2-[(2-chlorophenyl)sulfonyl]-N,N-dimethyl- 2-[[[(4-methylphenyl)sulfonyl]oxy]iminolacetamide

To a stirred solution of 2-[(2-chlorophenyl)sulfonyl]-2- hydroxyimino-N,N-dimethyl acetamide (580 mg) and p-toluene- sulfonylchloride (380 mg) in 25 mL of THF was added triethylamine (0.3 mL) in 20 mL of THF dropwise. A white precipitate formed after a short time. The mixture was stirred at room temperature overnight. The precipitate was removed by filtration and the filtrate was concentrated in vacuo. Purification was accomplished using silica gel flash

chromatography, with 1:1 hexane:ethyl acetate as eluent. Concentration of the appropriate fractions and trituration of the residue in cold 1-chlorobutane/hexane yielded 600 mg of white solid; m.p. 125-127°C.

EXAMPLE 14

2-[(3-thienyl)sulfonyl]-2-hydroxyimino-N,N-dimpthyl acetamide

A solution of 3-bromothiophene (7.0 mL) in 150 mL of diethyl ether was cooled to -78°C using a dry ice/acetone bath. A 2.5 M solution of butyllithium in hexane (30 mL) was added dropwise with stirring and continued cooling. The resulting reaction mixture was stirred at -78°C for 30 min to form 3-lithiothiophene. Using a vacuum-jacketed addition funnel cooled with dry ice/acetone, sulfur dioxide gas was condensed (16.7 mL). The liquified sulfur dioxide was added dropwise to the

3-lithiothiophene solution prepared earlier. A white precipitate formed upon adidition. After the addition, the mixture was stirred at -78°C for 30 min. The pale yellow solid was collected by filtration, washed with cold ether and dried to yield 11.5 g crude lithium 3-thienylsulfinate salt; m.p. >200°C.

The crude sulfinate salt was added to a solution of 2-chloro-2-hydroxyimino-N,N-dimethyl acetamide (11.1 g) in 200 mL of methanol. The resulting mixture was stirred at room temperature overnight. The solution was poured into 300 mL of ice-water. The mixture was extracted with dichloromethane (3 × 200 mL). The combined organic phases were dried (MgSO₄), filtered and concentrated in vacuo. The resulting white solid was triturated in hexane and collected by filtration to yield 14.8 g white solid; m.p. 170-173°C.

EXAMPLE 15

2-[(3-thienyl)sulfonyl]-N,N-dimethyl-2-[[[benzoyl]oxy]imino]acetamide

To a solution of 2-[(3-thienyl)sulfonyl]-2-hydroxyimino-N,N-dimethyl acetamide (524 mg) and benzoyl chloride (0.23 mL) in 15 mL of THF at room temperature was added triethylamine (0.28 mL). A white precipitate formed upon addition. The mixture was stirred at room temperature for 1.5 h. The precipitate was removed by filtration and the filtrate concentrated in vacuo. The residue was triturated in

1-chlorobutane/hexane to yield 600 mg of white solid; m.p. 132-135°C.

EXAMPLE 16

2-[4-tert-butylphenyl)sulfonyl]-2-hydroxyimino-N,N-dimethyl acetamide

To a solution of 25.2 g of sodium sulfite in 200 mL of water was added 23.3 g of 4-tert-butylbenzenesulfonyl chloride. The mixture was heated to 75-85°C for 4 h. The initial drop in pH was neutralized by the addition of approximately 25 mL of 20% sodium hydroxide solution. No further drop in pH occurred during the last 2 h of heating. The mixture was cooled in an ice bath and acidified with concentrated sulfuric acid.

The mixture was extracted with methylene chloride (4X) and ethyl acetate (IX). The combined organic extracts were dried (MgSO₄), filtered, and concentrated in vacuo to yield off-white solid. This material was slurried in hexane with a small amount of methylene chloride and refrigerated. The solid was collected by filtration and washed with cold hexane. The solid was dried in the vacuum oven to yield 19.2 g white solid; m.p. 196-200°C. Analysis by 200 MHz NMR indicated the solid to be impure; it was carried on without further purification. To a solution of 15.84 g of the impure 4-tert-butylbenzene sulfinic acid in 150 mL of methanol was added 18.3 mL of 25 weight % sodium methoxide in methanol. The solution was stirred 5 min and then 2-chloro-2- hydroxyimino-N,N-dimethyl acetamide (12.04 g) was added. The mixture was stirred at room temperature overnight. The reaction mixture was poured into approximately 300 mL of water. The resulting precipitate was collected by filtration. The wet solid was redissolved in methylene chloride, dried (MgSO₄) and the solvent removed by rotary evaporation. The residue was triturated in 1-chlorobutane/hexane and collected by filtration to yield 5.9 g white solid; m.p. 180-183°C.

The following Table lists representative compounds of this invention, which can be prepared by one or more of the methods illustrated in the preceding Examples. The Table is not intended to be all-inclusive.

The formula:

used at the head of the Table represents exactly the same compounds as the formula:

used earlier. The use of Formula Ii with the Table is intended to simplify the understanding of structures of compounds represented in that Table. Inspection of Ii and I will readily show that:

X-B of Ii is the same as G of I,

W-Z-Al of Ii is the same as A of I.

Formulations

Useful formulations of the compounds of Formula I can be prepared in conventional ways. They include dusts, granules, pellets, solutions, suspensions, emulsions, wettable powders, emulsifiable concentrates and the like. Many of these may be applied directly.

Sprayable formulations can be extended in suitable media and used at spray volumes of from a few liters to several hundred liters per hectare. High strength compositions are primarily used as intermediates for further formulation. The formulations, broadly, contain about 0.1% to 99% by weight of active ingredient(s) and at least one of (a) about 0.1% to 20% surfactant(s) and (b) about 1% to 99.9% solid or liquid inert diluent(s). More specifically, they will contain these ingredients in the following approximate proportions:

Weight Percent*

Ingredient Diluent(s) Surfactant(s)

Wettable Powders 20-90 0-74 1-10

Oil Suspensions, 3-50 40-95 0-15 Emulsions, Solutions,

(including Emulsifiable

Concentrates)

Aqueous Suspension 10-50 40-84 1-20

Dusts 1-25 70-99 0-5

Granules and Pellets 0.1-95 5-99.9 0-15 High Strength 90-99 0-10 0-2 Compositions

*Active ingredients plus at least one of a surfactant

or a diluent equals 100 weight percent.

Lower or higher levels of active ingredient can, of course, be present depending on the intended use and the physical properties of the compound. Higher ratios of surfactant to active ingredient are sometimes desirable, and are achieved by incorporation into the formulation or by tank mixing.

Typical solid diluents are described in Watkins et aL, "Handbook of Insecticide Dust Diluents and Carriers", 2nd Ed., Dorland Books,

Caldwell, NewJersey, but other solids, either mined or manufactured, may be used. The more absorptive diluents are preferred for wettable powders and the denser ones for dusts. Typical liquid diluents and solvents are described in Marsden, "Solvents Guide", 2nd Ed.,

Interscience, New York, 1950. Solubility under 0.1% is preferred for suspension concentrates; solution concentrates are preferably stable against phase separation at 0°C. "McCutcheon's Detergents and

Emulsifiers Annual", MC Publishing Corp., Ridgewood, NewJersey, as well as Sisely and Wood, "Encyclopedia of Surface Active Agents",

Chemical Pubhshing Co., Inc., NewYork, 1964, list surfactants and recommended uses. All formulations can contain minor amounts of additives to reduce foaming, caking, corrosion, microbiological growth, etc.

The methods of making such compositions are well known.

Solutions are prepared by simply mixing the ingredients. Fine solid compositions are made by blending and, usually, grinding as in a hammer or fluid energy mill. Suspensions are prepared by wet milling (see, for example, Littler, U.S. Patent 3,060,084). Granules and pellets may be made by spraying the active material upon preformed granular carriers or by agglomeration techniques. See J.E.Browning,

"Agglomeration", Chemical Engineering, December 4, 1967, pp. 147ff and "Perry's Chemical Engineer's Handbook", 5th Ed., McGraw-Hill, New York, 1973, pp. 8-59ff.

For further information regarding the art of formulation, see for example:

H. M. Loux, U.S. Patent 3,235,361, February 15, 1966, Col. 6, line

16 through Col. 7, line 19 and Examples 10 through 41; R. W. Luckenbaugh, U.S. Patent 3,309,192, Marchl4, 1967, Col. 5, line 43 through Col. 7, line 62 and Examples 8, 12, 15, 39, 41, 52, 53, 58, 132, 138-140, 162-164, 166, 167 and 169-182;

H. Gysin and E. Knusli, U.S. Patent 2,891,855, June 23, 1959, Col. 3, line 66 through Col. 5, line 17 and Examples 1-4;

G. C. Klingman, "Weed Control as a Science", John Wiley & Sons,

Inc., New York, 1961, pp. 81-96; and

J. D. Fryer and S. A. Evans, "Weed Control Handbook", 5th Ed., Blackwell Scientific Publications, Oxford, 1968, pp. 101-103.

In the following examples, all parts are by weight unless otherwise indicated.

Example A

Wettable Powder

2-[(4-cmorophenyl)sulfonyl]-N,N-dimethyl-2-[[[3-(trifluoromethyl)benzoyl]oxy]imino]acetamide 80%

sodium alkylnaphthalenesulfonate 2%

sodium liginsulfonate 2%

synthetic amorphous silica 3%

kaolinite 13%

The ingredients are blended, hammer-milled until all the solid are essentially under 50 microns, reblended, and packaged.

Example B

Wettable Powder

2-[(4-chlorophenyl)sulfonyl]-N,N-dimethyl-2-[[[3-(trifluoromethyl)benzoyl]oxy]imino]acetamide 50%

sodium alkylnaphthalenesulfonate 2%

low viscosity methyl cellulose 2%

diatomaceous earth 46%

The ingredients are blended, coarsely hammer-milled and then airmilled to produce particles essentially all below 10 microns in diameter. The product is reblended before packaging. Example C

Granule

Wettable Powder of Example 13 5%

attapulgite granules 95%

(U.S.S. 20-40 mesh; 0.84-0.42 mm)

A slurry of wettable powder containing 25% solids is sprayed on the surface of attapulgite granules in a double-cone blender. The granules are dried and packaged.

Example D

Extruded Pellet

2-[(4-chlorophenyl)sulfonyl]-N,N-dimethyl-2-[[[3-(trifiuoromethyl)benzoyl]oxy]imino]acetamide 25%

anhydrous sodium sulfate 10%

crude calcium liginsulfonate 5%

sodium alkylnaphthalenesulfonate 1%

calcium/magnesium bentonite 59%

The ingredients are blended, hammer-milled and then moistened with about 12% water. The mixture is extruded as cylinders about 3 mm diameter which are cut to produce pellets about 3 mm long. These may be used directly after drying, or the dried pellets may be crushed to pass a U.S.S. No. 20 sieve (0.84 mm openings). The granules held on a U.S.S. No. 40 sieve (0.42 mm openings) may be packaged for use and the fines recycled.

Example E

Oil Suspension

2-[(4-chlorophenyl)sulfonyl]-N,N-dimethyl-2-[[[3-(trifluoromethyl)benzoyl]oxy]

imino]acetamide 25%

polyoxyethylene sorbitol hexaoleate 5%

highly aliphatic hydrocarbon oil 70% The ingredients are ground together in a sand mill until the solid particles have been reduced to under about 5 microns. The resulting thick suspensions may be applied directly, but preferably after being extended with oils or emulsified in water.

Example F

Wettable Powder

2-[(4-chlorophenyl)sulfonyl]-N,N-dimethyl-2-[[[3-(trifluoromethyl)benzoyl]oxy]imino]acetamide 20%

sodium alkylnaphthalenesulfonate 4%

sodium liginsulfonate 4%

low viscosity methyl cellulose 3%

attapulgite 69%

The ingredients are thoroughly blended. After grinding in a hammer-mill to produce particles essentially all below 100 microns, the material is reblended and sifted through a U.S.S. No. 50 sieve (0.3 mm opening) and packaged.

Example G

Low Strength Granule

2-[(4-chlorophenyl)sulfonyl]-N,N-dimethyl-2-[[[3-(trifluoromethyl)benzoyl]oxy]imino]acetamide 1%

N,N-dimethylformamide 9%

attapulgite granule 90%

(U.S.S. 20-40 sieve)

The active ingredient is dissolved in the solvent and the solution is sprayed upon dedusted granules in a double cone blender. After spraying of the solution has been completed, the blender is allowed to run for a short period and then the granules are packaged. Example H

Aqueous Suspension

2-[(4-chlorophenyl)sulfonyl]-N,N-dimethyl-2-[[[3-(trifluoromethyl)benzoyl]oxy]imino]acetamide 40%

polyacrylic acid thickener 0.3% dodecylphenol polyethylene glycol 0.5% ether

disodium phosphate 1%

monosodium phosphate 0.5% polyvinyl alcohol 1.0%

water 56.7%

The ingredients are blended and ground together in a sand mill to produce particles essentially all under 5 microns in size.

Example I

Low Strength Granule

2-[(4-chlorophenyl)sulfonyl]-N,N-dimethyl-2-[[[3-(trifluoromethyl)benzoyl]oxy]imino]acetamide 0.1%

attapulgite granules 99.9%

(U.S.S. 20-40 mesh)

The active ingredient is dissolved in a solvent and the solution is sprayed upon dedusted granules in a double cone blender. After spraying of the solution has been completed, the material is warmed to evaporate the solvent. The material is allowed to cool and then packaged. Example J

2-[(4-chlorophenyl)sulfonyl]-N,N-dimethyl-2-[[[3-(trifluoromethyl)benzoyl]oxy]imino]acetamide 80%

wetting agent 1%

crude ligninsulfonate salt 10%

(containing 5-20% of the natural

sugars) attapulgite clay 9%

The ingredients are blended and milled to pass through a 100 mesh screen. This material is then added to a fluid bed granulator, the air flow is adjusted to gently fluidize the material, and a fine spray of water is sprayed onto the fluidized material. The fluidization and spraying are continued until granules of the desired size range are made. The spraying is stopped, but fluidization is continued, optionally with heat, until the water content is reduced to the desired level, generally less than 1%. The material is then discharged, screened to the desired size range, generally 14-100 mesh (1410-149 microns), and packaged for use.

Example K

High Strength Concentrate

2-[(4-chlorophenyl)sulfonyl]-N,N-dimethyl-2-[[[3-(trifluoromethyl)benzoyl]oxy]imino]acetamide 99%

silica aerogel 0.5%

synthetic amorphous silica 0.5%

The ingredients are blended and ground in a hammer-mill to produce a material essentially all passing a U.S.S. No. 50 screen (0.3 mm opening). The concentrate may be formulated further if necessary.

Wettable Powder

2-[(4-chlorophenyl)sulfonyl]-N,N-dimethyl-2-[[[3-(trifluoromethyl)benzoyl]oxy]imino]acetamide 90%

dioctyl sodium sulfosuccinate 0.1%

synthetic fine silica 9.9%

The ingredients are blended and ground in a hammer-mill to produce particles essentially all below 100 microns. The material is sifted through a U.S.S. No. 50 screen and then packaged. Example M

Wettable Powder

sodium ligninsulfonate 20%

montmorillonite clay 40%

The ingredients are thoroughly blended, coarsely hammer-milled to produce particles essentially all below 10 microns in size. The material reblended and then packaged.

Example N

Oil Suspension

2-[(4-chlorophenyl)sulfonyl]-N,N-dimethyl-2-[[[3-(trifluoromethyl)benzoyl]oxy]imino]acetamide 35%

blend of polyalcohol carboxylic esters and oil 6%

soluble petroleum sulfonates

xylene 59%

The ingredients are combined and ground together in a sand mill to produce particles essentially all below 5 microns. The product can be used directly, extended with oils, or emulsified in water.

Example O

Emulsifiable Concentrate

chlorobenzene 74%

sorbitan monostearate and polyoxyethylene 6%

condensates thereof

The ingredients are combined and stirred to produce a solution which can be emulsified in water for application. UTILITY

The compounds of this invention are useful as plant disease control agents. They provide control of diseases caused by a broad spectrum of fungal plant pathogens in the Basidiomycete, Ascomycete Oomycete classes. They are effective in controlling a broad spectrum of plant diseases, particularly foliar pathogens of ornamental, vegetable, field, cereal, and fruit crops. These pathogens include, Venturia inaequalis, Cercosporidium personatum, Cercospora arachidicola, Cercospora beticola, Pseudocercosporella herpotrichoides, Puccinia recondita,

Puccinia gramminis, Hemileia yastatrix, Puccinia striiformis, Puccinia arachidis, Pyricularia oryzae, Phytophthora infestans, Plasmopara viticola, Peronospora tabacina, Pseudoperonospora cubensis, Pythium aphanidermatum, Botrytis cinerea, and other species closely related to these pathogens. They also control seed pathogens. In particular the compounds of this invention are exceptional in their ability to provide control of diseases for an extended period of time after application.

The compounds of this invention can be mixed with fungicides, bactericides, acaricides, nematicides, insecticides or other biologically active compounds in order to achieve desired results with a minimum of expenditure of time, effort and material. Suitable agents of this type are well-known to those skilled in the art. Some are listed below:

Fungicides

methyl 2-benzimidazolecarbamate (carbendazim)

tetramethylthiuram disulfide (thiuram)

n-dodecylguanidine acetate (dodine)

manganese ethylenebisdithiocarbamate (maneb)

1,4-dicMoro-2,5-dimethoxybenzene (chloroneb)

methyl 1-(butylcarbamoyl)-2-benzimidazolecarbamate (benomyl)

2-cyano-N-ethylcarbanιoyl-2-methoxyiminoacetamide (cymoxanil)

N-trichloromethylthiotetrahydrophthalamide (captan)

N-trichlorometiiylthiophthalimide (folpet)

dimethyl 4,4'-(o-phenylene)bis(3-thioallophanate) (thiophanate-methyl) 2-(thiazol-4-yl)benzimidazole (thiabendazole)

aluminum tris(O-ethyl phosphonate)(phosethyl aluminum)

tetrachloroisophthalonitrile (chlorothalonil)

2,6-dichloro-4-nitroaniline (dichloran)

N-(2,6-dimethylphenyl)-N-(methoxyacetyl)alanine methyl ester (metalaxyl)

cis-N-[1,1,2,2-tetrachloroethyl)thio]cyclohex-4-ene-1,2-dicarbioximide (captafol)

3-(3,5-dichlorophenyl)-N-(1-methylethyl)-2,4-dioxo-1-imidazolidine carboxamide (iprodione)

3-(3,5-dichlorophenyl)-5-ethenyl-5-methyl-2,4-oxazolidinedione

(vinclozolin)

kasugamycin

O-ethyl-S,S-diphenylphosphorodithioate (edifenphos)

4-(3-(4-(1,1-dimethyl-ethyl)phenyl)-2-methyl)propyl-2,6-dimethylmorpholine (fenpropimorph)

4-(3-4(1,1-dimethyl-ethyl)phenyl)-2-methyl)propylpiperidine

(fenpropidine)

1-(4-chlorophenoxy)-3,3-dimethyl-1-1H-1,2,4-triazol-1-yl)butanone

(triadimefon)

2-(4-chlorophenyl)-2-(1H-1,2,4-triazol-1-yl-methyl)hexanenitrile

(myclobutanil)

α-[2-(4-chlorophenyl)ethyl]-a-(1,1-dimethylethyl)-1H-1,2,4-triazole- 1-ethanol (tebuconazol)

3-chloro-4-[4-methyl-2-(1H-1,2,4-triazol)-1-ylmethyl)-1,3-dioxolan- 2-yl]phenyl-4-chlorophenyl ether (difenoconazole)

1-[2-(2,4-dichlorophenyl)pentyl]1H-1,2,4-triazole (penconazole)

(RS)-2,4'-difluoro-a-(1H-1,2,4-triazole-1-ylmethyl)benzhydryl alcohol (flutriafol)

1-[[bis(4-fluorophenyl)methylsilyl)methyl]-1H-1,2,4-triazole (flusilazol) N-propyl-N-[2-(2,4,6-trichlorophenoxy)ethyl]imidazole-1-carboxamide (prochloraz) (±)-1-[2-(2,4-dichlorophenyl)-4-propyl-1,3-dioxolan-2-ylmethyl]-1H-1,2,4- triazole (propiconazole)

α-(2-chlorophenyl)-a-(4-chlorophenyl)-5-pyrinιidinemethanol (fenarimol) 1-(4-Chlorophenoxy)-3,3-dimethyl-1-(1H-1,2,4-triazole-1-yl)butan-2-ol

(triadiminol)

(2RS,3RS)-1-(2,4-dichlorophenyl)-4,4-dimethyl-2-(1H-1,2,4-triazol-1- yl)pentan-3-ol (diclobutrazol)

copper oxychloride

methyl N-(2,6-diιnethylphenyl)-N-(2-furanylcarbonyl)-DL-alaninate

(furalaxyl)

Bactericides

tribasic copper sulfate

streptomycin sulfate

oxytetracycline

Agaricides

senecioic acid, ester with 2-sec-butyl-4,6-dinitro-phenol (binapacryl) 6-methyl-1,3-dithiolo[2,3-B]quinonolin-2-one (oxythio-quinox)

2,2,2-trichloro-1,1-bis(4-chlorophenyl)ethanol (dicofol)

bis(pentachloro-2,4-cyclopentadien-1-yl) (dienochlor)

tricyclohexyltin hydroxide (cyhexatin)

hexakis(2-methyl-2-phenylpropyl)distaιmoxane (fenbutatin oxide)

Nematicides

2-[diethoxyphosphinyliιnino]-l,3-diethietane (fosthietan)

S-methyl-1-(dimethylcarbamoyl)-N-(methylcarbamoyloxy)thioformimidate (oxamyl)

S-methyl-1-carbamoyl-N-(methylcarbanιoyloxy)thioformimidate

N-isopropylphosphoramidic acid, O-ethyI-O'-[4-(methylthio)-m-tolyl]- diester (fenamiphos) Insecticides

3-hydroxy-N-methylcrotonamide(dimethylphosphate)ester

(monocrotophos)

methylcarbamic acid, ester with 2,3-dihydro-2,2-dimethyl-7-benzofuranol (carbofiiran)

O-[2,4,5-trichloro-a-(chloromethyl)benzyl]phosphoric acid, O',O'-dimethyl ester (tetrachlorvinphos)

2-mercaptosuccinic acid, diethyl ester, S-ester with thionophosphoric acid, dimethyl ester (malathion)

phosphorothioic acid, O,O-dimethyl, O-p-nitrophenyl ester (methyl parathion)

methylcarbamic acid, ester with a-naphthol (carbaryl)

methyl N-[[(methylanιino)carbonyl]oxy]ethanimidothioate (methomyl) N'-(4-chloro-o-tolyl)-N,N-dimethylformamidine (chlordimeform)

O,O-diethyl-O-(2-isopropyl-4-methyl-6-pyrimidyl)phosphorothioate (diazinon)

octachlorocamphene (toxaphene)

O-ethyl O-p-nitrophenyl phenylphosphonothioate (EPN)

cyano(3-phenoxyphenyl)-methyl 4-chloro-α-(1-methylethyl)benzeneacetate (fenvalerate)

(3-phenoxyphenyl)methyl (+)-cis,trans-3-(2,2-dichloroethenyl)-2,2- dimethylcyclopropanecarbo-sylate (permethrin)

dimethyl N,N'-[thiob-b(N-methylimmo)carbonyloxy]]bis[ethanimidothioate] (thiodicarb)

phosphorothiolothionic acid, O-ethyl-O-[4-(methylthio)phenyl]-S-n-propyl ester (sulprofos)

α-cyano-3-phenoxybenzyl 3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropane carboxylate (cypermethrin)

cyano(3-phenoxyphenyl)methyl 4-(difluoromethoxy)-α-(methylethyl)- benzeneacetate (flucythrinate)

O,O-diethyl-O-(3,5,6-trichloro-2-pyridyl)phosphorothioate (chlorpyrifos) O,O-dimethyl-S-[(4-oxo-1,2,3-benzotriazin-3-(4H)-yl)-methyl]phosphorodithioate (azinphos-methyl) 5,6-dimethyl-2-dimethylamino-4-pyrimidinyl dimethyl carbamate

(piiimicarb)

S-(N-formyl-N-niethylcarbamoylniethyI)-O,O-diniethylphosphorodithioate

(formothion)

S-2-(ethylthioethyl)-O,O-dimethyl phosphiorothioate (demeton-S-methyl) α-cyano-3-phenoxybenzyl cis-3-(2,2-dibromovinyl)-2,2-dimethylcyclopropane carboxylate (deltamethrin)

cyano(3-phenoxyphenyl)methyl ester of N-(2-chloro-4-trifluoromethylphenyl)alanine (fluvalinate) APPLICATION

Disease control is ordinarily accomplished by applying an effective amount of the compound pre-infection to the portion of the plant to be protected such as the roots, stems, fohage, fruit, seeds, tubers or bulbs, or to the media (soil or sand) in which the plants to be protected are growing. The compound may also be applied to the seed, to protect the seed and seedling.

Rates of application for these compounds can be influenced by many factors of the environment and should be determined under actual use conditions. Fohage can normally be protected when treated at a rate of from less than 10 g/ha to 10,000 g/ha of active ingredient. Plants growing in soil treated at a concentration from 0.1 to about 20 kg/ha can be protected from disease. Seed and seedlings can normally be protected when seed is treated at a rate of from 0.1 to 10 g per kilogram of seed. Test A

The test compounds were dissolved in acetone in an amount equal to 3% of the final volume and then suspended at a concentration of 200 ppm in purified water containing 250 ppm of ihe surfactant Trem 014 (polyhydric alcohol esters). This suspension was sprayed to the point of run-off on apple seedlings. The following day the seedlings were inoculated with a spore suspension of Venturia inaequalis (the causal agent of apple scab) and incubated in a saturated atmosphere at 20°C for 24 hr, and then moved to a growth chamber at 22°C for 11 days, after which disease ratings were made.

The test compounds were dissolved in acetone in an amount equal to 3% of the final volume and then suspended at a concentration of 200 ppm in purified water containing 250 ppm of the surfactant Trem 014 (polyhydric alcohol esters). This suspension was sprayed to the point of run-off on peanut seedlings. The following day the seedlings were inoculated with a spore suspension of Cercosporidium personatum (the causal agent of peanut late leafspot) and incubated in a saturated atmosphere at 22°C for 24 hr, a high humidity atmosphere at 22 to 30°C for 5 days, and then moved to a growth chamber at 29°C for 6 days, after which disease ratings were made. Test C

The test compounds were dissolved in acetone in an amount equal to 3% of the final volume and then suspended at a concentration of 200 ppm in purified water containing 250 ppm of the surfactant Trem 014 (polyhydric alcohol esters). This suspension was sprayed to the point of run-off on wheat seedlings. The following day the seedlings were inoculated with a spore suspension of Puccinia recondita (the causal agent of wheat leaf rust) and incubated in a saturated atmosphere at 20°C for 24 hr, and then moved to a growth chamber at 20°C for 6 days, after which disease ratings were made.

Test D

The test compounds were dissolved in acetone in an amount equal to 3% of the final volume and then suspended at a concentration of 200 ppm in purified water containing 250 ppm of the surfactant Trem 014 (polyhydric alcohol esters). This suspension was sprayed to the point of run-off on rice seedlings. The following day the seedlings were inoculated with a spore suspension of Pyricularia oryzae (the causal agent of rice blast) and incubated in a saturated atmosphere at 27°C for 24 hr, and then moved to a growth chamber at 30°C for 5 days, after which disease ratings were made.

Test E

The test compounds were dissolved in acetone in an amount equal to 3% of the final volume and then suspended at a concentration of 200 ppm in purified water containing 250 ppm of the surfactant Trem 014 (polyhydric alcohol esters). This suspension was sprayed to the point of run-off on tomato seedlings. The following day the seedlings were inoculated with a spore suspension of Phytophthora infestans (the causal agent of potato and tomato late blight) and incubated in a saturated atmosphere at 20°C for 24 hr, and then moved to a growth chamber at 20°C for 5 days, after which disease ratings were made.

Test F

The test compounds were dissolved in acetone in an amount equal to 3% of the final volume and then suspended at a concentration of 200 ppm in purified water containing 250 ppm of the surfactant Trem 014 (polyhydric alcohol esters). This suspension was sprayed to the point of run-off on grape seedlings. The following day the seedlings were inoculated with a spore suspension of Plasmopara viticola (the causal agent of grape downy mildew) and incubated in a saturated atmosphere at 20°C for 24 hr, moved to a growth chamber at 20°C for 6 days,and then incubated in a saturated atmosphere at 20°C for 24 hr, after which disease ratings were made.

Test G

The test compounds were dissolved in acetone in an amount equal to 3% of the final volume and then suspended at a concentration of 200 ppm in purified water containing 250 ppm of the surfactant Trem 014 (polyhydric alcohol esters). This suspension was sprayed to the point of run-off on cucumber seedlings. The following day the seedlings were inoculated with a spore suspension of Botrytis cinerea (the causal agent of gray mold on many crops) and incubated in a saturated atmosphere at 20°C for 48 hr, and moved to a growth chamber at 20°C for 5 days, after which disease ratings were made. Results for Tests A to G are given in Table A. In the table, a rating of 100 indicates 100% disease control and a rating of 0 indicates no disease control (relative to the carrier sprayed controls). NT indicates that no test was performed.

200MHz NMR FOR FOOTNOTED COMPOUNDS

1. δ 8.24 (t, J=1.8 Hz, 1H), 8.19 (d, J=8.2 Hz, 2H), 8.08 (dd, J=1.8, 8.0 Hz, 1H), 7.83 (d, J=8.2 Hz, 2H), 7.80 (d, fine coupling, J=8 Hz, 1H), 7.46 (t, J=8.0 Hz, 1H), 3.24 (s, 3H, NCH₃), 3.09 (s, 3H, NCH₃).

2. δ 8.38 (m, 1H), 7.9 (m, 3H), 7.7 (m, 2H), 7.23 (d, J=B.1 Hz, 2H), 3.93 (s, 3H, CO₂CH₃), 3.33 (s, 3H, NCH₃), 2.92 (s, 3H, NCH₃), 2.40 (s, 3H, ArCH₃).

3. δ 8.0-8.4 (m, 4H), 7.9 (d, J=8 Hz, 1H), 7.7 (m, 3H), 3.26 (s, 3H,

NCH₃), 3.10 (s, 3H, NCH₃).

4. δ 8.33 (s, 1H), 8.26 (d, J=8 Hz, 1H), 7.91 (d, J=7.8 Hz, 1H), 7.72 (m, 3H), 7.43 (t, J-8 Hz, 1H), 7.17 (d, J=8 Hz, 1H), 3.75 (s, 3H, OCH₃),

3.22 (s, 3H, NCH₃), 3.08 (s, 3H, NCH₃).

5. δ 8.21 (s, 1H), 8.07 (d, J=7.8 Hz, 1H), 7.87 (d, J=7.8 Hz, 1H), 7.60 (t,

J=7.8 Hz, 1H), 7.35 (d, J=8.7 Hz, 2H), 6.59 (d, J=8.7 Hz, 2H), 4.65 (s, 2H, -CH₂-), 3.48 (s, 3H, OCH₃), 3.09 (s, 6H, N(CH₃)₂).

6. δ 7.85 (d, J =8.2 Hz, 2H), 7.33, (d, J= 8.6 Hz, 2H), 7.25 (d, J=8.2 Hz, 2H), 6.69 (d, J=8.7 Hz, 2H), 4.63 (s, 2H, -CH₂-), 3.56 (s, 3H, OCH₃),

3.05 (s, 3H, NCH₃), 3.03 (s, 3H, NCH₃), 2.41 (s, 3H, ArCH₃).

7. δ 8.21 (d, J=7.2 Hz, 1H), 7.8 (m, 4H), 7.2-7.6 (m, 6H), 5.33 (s, 2H, OCH₂-), 3.22 (s, 3H, NCH₃), 3.06 (s, 3H, NCH₃). TABLE A

TEST TEST TEST TEST TEST TEST TES¹

Cmpd A B C D E F G No.

1 30 0 NT 0 0 NT 0

2 100 97 94 89 100 100 74

3 100 37 78 9 100 100 10

4 100 97 99 40 100 100 10

5 100 97 97 53 100 97 0

6 100 65 91 9 100 100 0

7 61 0 NT 0 24 NT 0

8 100 96 99 98 100 100! 3

9 100 96 93 98 100 100! 44

10 100 100 93 92 100 100! 3

11 100 96 54 0 100 100! 0

12 100 62 NT 0 100 95! 3

13 100 96 46 0 99 100! 3

14 0 0 NT 0 0 NT 0

15 56! 64 28 0 71 70! 0

16 100! 95 58 98 98 100! 10

17 100! 76 41 82 99 80! 0

18 100! 76 64 96 100 NT 0

19 93! 95 41 62 98 94! 0

20 100! 82 58 96 100 99! 0

21 100! 63 72 96 99 95! 0

22 93! 83 37 23 46 97! 0

23 100! 82 72 97 100 100! 11

24 100! 68 18 41 100 87! 0

25 100! 62 67 95 100 100! 0

26 100! 46 41 23 92 95! 0

27 95! 94 67 90 97 100! 0

28 100! 99 76 96 100 100! 0 TEST TEST TEST TES:r TES:r TEST TES

Cmpd A B C D E F G

No.

29 93! 97 73 90 96 99! 0

30 100! 99 82 98 100 100! 0

31 100! 92 96 98 100 100! 0

32 100! 96 74 89 100 100! 0 33 55! 15 1 19 91 90! 0 34 99! 47 19 28 99 90! 0 35 96! 88 50 86 100 99! 11 36 75! 0 10 28 72 97! 0 37 100! 98 80 100 100 100! 11 38 69! 95 22 61 87 94! 0 39 10! 82 22 41 94 100! 0 40 27! 94 43 96 100 100! 0 41 76! 40 51 61 99 79! 0 42 83! NT 43 80 90 100! 0 43 100! 90 84 97 100 94! 0 44 99! 97 63 90 100 100! 0 46 95 0 NT 0 76 NT 49 47 100! 88 44 49 92 99! 0 48 100! 96 83 99 100 97! 0 49 100! 95 83 86 100 99! 10 56 13 13 0 0 0 NT 057 24 62 NT 0 26 94! 0 58 83! 51 51 0 83 79! 0 59 100! 89 95 93 95 100! 0 60 100! 100 51 73 86 100! 061 100! 85 45 38 88 100! 062 100! 70 51 81 100 99! 0 63 100! 51 82 84 100 100! 064 100! 99 82 96 100 100! 0 TEST TEST TEST TEST TEST TEST TES

Cmpd A B C D E F G

No.

65 100! 99 78 88 98 100! 3

66 100! 94 92 94 98 100! 10

67 100! NT 100 100 100 100! 0

68 51! NT 46 26 100 82! 0

69 100! NT 98 98 100 100! 0

70 100! NT 90 0 100 100! 0

71 100! NT 93 99 100 100! 0

72 100! NT 61 92 100 96! 0

73 99! NT 65 97 100 87! 0

74 100! NT 90 26 100 100! 0

75 100! NT 99 99 100 100! 0

76 93! NT 43 80 89 100! 0

77 100! 100 88 99 100 100! 0

78 61! NT 22 0 93 63! 0

79 83! NT 22 0 99 88! 0

80 100! 96 84 97 99 100! 0

81 100! 69 93 97 100 100! 0

82 100! 93 84 99 100 100! 0

83 90! 74 27 28 100 98! 5

84 79! 74 18 0 99 88! 5

85 83! 64 18 41 96 98! 5

86 100! 61 99 99 100 100! 0

87 63 28 NT 0 0 NT 0

88 100! NT 90 99 100 100! 0

89 100! NT 99 100 100 100! 0

90 100 .! NT 95 99 100 97! 0

91 100! . NT 96 100 100 100! 0

92 100! . NT 98 99 100 100! 0

93 100! . NT 91 98 100 100 !! 0 TEST TEST TEST TEST TEST TEST TEST

Cmpd A B C D E F G

No.

94 100! NT 93 99 100 100! 0

95 100! NT 91 99 100 100! 0

96 100! NT 93 0 100 100! 0

97 NT NT 95^a 98^a 99^a 100^b 0^a

98 NT NT NT 0 100 67! 0

99 NT NT NT NT 53^b 99b NT

100 NT NT 88 99 100 100! 0

101 NT NT NT 99 100 100! 0

102 NT NT 98 98 99 100! 0

103 NT NT 98 99 99 100! 0

104 NT NT NT 0 96 97! 0

105 100! 98 99 98 100 95! 4

106 91! 93 51 36 91 98! 0

107 100! 93 82 93 96 100! 0

108 100! 98 82 84 100 100! 0

109 95 87 58 63 98 100! 0

110 100! 87 82 94 95 88! 8

111 100! 100 91 96 100 100! 0

112 99! 92 91 96 98 95! 0

113 100! NT 90 99 100 992 0

114 100 NT NT 0 100 100! 0

115 100! NT 99 100 100 100! 0

116 100! NT NT 0 0 100! 0

117 100! NT NT 26 100 100! 0

118 100! NT 99 99 100 99! 0

120 100! NT 56 100 100 100! 0

121 100! 59 87 94 99 85! 3

122 100! 0 57 58 91 85! 0

123 100! 59 89 83 100 100! 0 TEST TEST TEST TEST TEST TEST TES

Cmpd A B C D E F G No.

124 100! 98 89 94 100 100! 7

125 100! 84 NT 90 100 99! 0

126 100! 98 92 88 99 97! 9

127 100! 99 86 90 100 100! 9

128 99! 98 NT 67 98 83! 9

129 NT NT 0 71 100 100! 0

130 NT NT 0 0 100 100! 0

131 NT NT 44 0 99 100! 0

132 NT NT 98 91 100 100! 0

133 NT NT 99 NT 100 100! NT

134 NT NT 0 0 23 72! 0

135 NT NT 0 18 68 91! 0

136 NT NT 52 69 99 56 0

137 NT NT 87 69 96 100! 0

138 NT NT 94 83 100 100! 0

139 NT NT 94 86 99 100! 0

140 NT NT 87 80 97 100! 0

141 NT NT 76 67 100 100! 0

142 NT NT 24 19 99 99! 0

143 NT NT 42 0 73 100! 0

144 NT NT 90 19 100 100 0

145 NT NT 0 0 24 97 0

146 NT NT 96 100 100 100! 97

147 NT NT 96 100 100 100! 4

148 NT NT 48 99 100 100! 4

149 NT NT 62 97 100 100! 0

150 NT NT 43 89 100 91! 4

151 NT NT 62 27 100 83! 4

152 NT NT 91 97 100 100! 4 TEST TEST TEST TEST TEST TEST TEST

Cmpd A B C D E F G

No.

153 NT NT 14 27 98 69 ! 4

154 NT NT 43 80 100 100! 0

155 NT NT 0 0 47 99! 0

156 NT NT 49 86 97 94! 0

157 NT NT 87 94 97 100! 0

158 NT NT 64 90 99 100! 9

159 NT NT 46 98 97 100! 0

160 NT NT 46 87 92 100! 0

161 NT NT 10 88 97 100! 9

162 NT NT 56 91 97 100! 0

163 NT NT 87 99 97 100! 48

164 99! 8 98 85 96 89! 0

! Percent control at 40 ppm the highest concentration tested,

a Tested at 100 ppm.

b Tested at 20 ppm.

Claims

What is claimed is:

1. A method for controlling fungus disease in plants that comprises treating the locus to be protected with an effective amount of a compound of Formula I

wherein:

G is C(=L)NR²R³, C(=O)OR⁴ SO₂NR²R³ or S(O)_mR⁵;

L is O or S;

A is H, C(=O)OR⁶, C( =O)NHR⁷, C(=O)(CH₂)_nR⁸ or SO₂R¹⁴;

heteroaromatic or fused heteroaromatic ring systems; said phenyl, naphthalenyl, heteroaromatic, or fused heteroaromatic rings being optionally substituted with R⁹ and R¹⁰; R² and R³ are independently H; C₁-C₆ alkyl; C₁-C₆ haloalkyl;

C₂-C₆ alkoxyalkyl; C₃-C₄ alkenyl; C₃-C₄ haloalkenyl; or R² and R³ may be taken together along with the nitrogen to which they are attached to form a pyrrolidino, piperidino or morpholino group, each optionally substituted with 1-2 methyl groups;

R⁴ is C₁-C₈ alkyl, C₁-C₈ haloalkyl, C₃-C₆ alkoxyalkyl, C₃-C₆

alkenyl or C₃-C₆ haloalkenyl;

substituted with methyl, trifluoromethyl, methoxy, cyano, nitro or 1-3 halogen;

R⁶ is C₁-C₈ alkyl optionally substituted with C₁-C₆ alkoxy, C₃-C₆ cycloalkyl, cyano or one or more halogen; C₃-C₆ cycloalkyl; or C₁-C₂ alkyl substituted with phenyl, naphthalenyl,

heteroalicyclic, heteroaromatic or fused heteroaromatic zing systems, said phenyl, napthalenyl, heteroaromatic or fused heteroaromatic rings being optionally substituted with R9 and

R¹⁰;

R⁷ is phenyl, benzyl, naphthalenyl, heteroaromatic or fused

R⁹ is C₁-C₂ alkyl, C₁-C₂ haloalkyl, C₁-C₂ alkoxy, C₁-C₂

haloalkoxy, cyano, nitro or 1-2 halogen;

C₂-C₄ alkoxyalkyl; OR¹¹; C(=O)R¹²; CO₂R¹²; C(=O)NR²R³;

NR²R³; NR²C(=O)R¹²; S(O)_mR¹²; SO₂NR²R³;

— O(CH₂)_pO_q— ;— (CH₂)_w— ; halogen; cyano; nitro; or phenyl or phenoxy, said phenyl or phenoxy groups being optionally substituted with R¹³; R¹¹ is C₁-C₄ alkyl optionally substituted with C₁-C₂ alkoxy, C₃-C₆ cycloalkyl, cyano or one or more halogen; or C₃-C₆ cycloalkyl; R¹² is C₁-C₄ alkyl optionally substituted with C₁-C₂ alkoxy, cyano or one or more halogen;

R¹³ is methyl, methoxy, trifluoromethyl, nitro, cyano or 1-2 halogen; R¹⁴ is C₁-C₆ alkyl; C₁-C₆ haloalkyl; C₂-C₆ alkoxyalkyl; or phenyl or benzyl, said phenyl or benzyl groups being optionally substituted with methyl, trifluoromethyl, methoxy, cyano, nitro or 1-3 halogen;

R¹⁵ is C₁-C₈ alkyl, C₁-C₈ haloalkyl, C₃-C₆ alkoxyalkyl, C₃-C₆

alkenyl or C₃-C₆ haloalkenyl;

m is 0, 1 or 2;

n is 0, 1 or 2;

p is 1, 2 or 3;

q is 0 or 1; and

w is 3 or 4; provided that

i) when G is C(=O)NR²R³:

1) A is C(=O)(CH₂)_nR⁸ and n is 0; or

2) R¹ is C₁-C₈ alkyl substituted with cyano or 2 or

more halogens; or C₂-C₆ alkyl substituted with

CO₂R¹⁵; or

3) R¹ is substituted phenyl or substituted benzyl;

ii) R¹ is not methyl.

iii) when R², R³ or R⁴ are alkenyl or haloalkenyl, they must be attached to the heteroatom through an sp3-hybridized carbon; iv) when A is H and R¹ is 4-methylphenyl, G is not

C(=O)N(CH₂CH₃)₂ or C(=O)N(CH₃)₂; and

2. The method according to Claim 1 wherein:

G is C(=O)NR²R³ or C(=O)OR⁴;

R¹ is C₁-C₈ alkyl optionally substituted with C₁-C₂

alkoxy, cyano, CO₂R¹⁵ or one or more halogen;

R¹² is C₁-C₂ alkyl optionally substituted with one or more halogen.

3. The method according to Claim 2 wherein:

G is C(=O)NR²R³;

R² and R³ are independently H; C₁-C₄ alkyl; C₁-C₄

R⁹ is methyl, trifluoromethyl, methoxy, cyano, nitro or 1-2 Cl or F; and

R¹⁰ is methyl; t-butyl; trifluoromethyl; methoxy; C(=O)CH₃;

CO₂CH₃; N(CH₃)₂; SCH₃; SO₂CH₃; F; Cl; Br; cyano; nitro; or phenyl or phenoxy, said phenyl or phenoxy being optionally substituted with R¹³.

4. The method according to Claim 3 wherein:

A is C(=O)OR⁶; and

R⁹ and R¹⁰.

5. The method according to Claim 3 wherein:

A is C( =O)NHR⁷; and

R⁷ is phenyl or benzyl, said phenyl or benzyl groups being optionally substituted with R⁹ and R¹⁰.

6. The method according to Claim 3 wherein:

A is H.

7. The method according to Claim 3 wherein:

Ais C( =O)(CH₂)_nR⁸.

8. The method according to Claim 7 wherein:

n is 0; and

9. The method according to Claim 8 wherein:

R¹ is phenyl optionally substituted with R¹⁰; and

R⁸ is phenyl optionally substituted with R¹⁰.

10. Compounds of the Formula I

wherein:

G is SO₂NR²R³ or S(O)_mR5;

A is H, C(=O)OR⁶, C(=O)NHR⁷, C(=O)(CH₂)_nR⁸ or SO₂R¹⁴; R¹ is C₁-C₈ alkyl optionally substituted with C₁-C₂ alkoxy, C₃-C₆ cycloalkyl, cyano, CO₂R¹⁵, or one or more halogen; C₃-C₆ cycloalkyl; C₁-C₂ alkyl substituted with phenyl, naphthalenyl, heteroalicyclic, heteroaromatic or fused heteroaromatic ring systems; or phenyl, naphthalenyl, heteroalicyclic, heteroaromatic or fused heteroaromatic ring systems; said phenyl, naphthalenyl, heteroaromatic, or fused heteroaromatic rings being optionally substituted with R⁹ and R¹⁰;

R² and R³ are independently H; C₁-C₆ alkyl; C₁-C₆ haloalkyl;

C₂-C₆ alkoxyalkyl; C₃-C₄ alkenyl; C₃-C₄ haloalkenyl; or

R² and R³ may be taken together along with the nitrogen to which they are attached to form a pyrrolidino, piperidino or morpholino group, each optionally

substituted with 1-2 methyl groups;

R⁵ is C₁-C₆ alkyl; C₁-C₆ haloalkyl; C₂-C₆ alkoxyalkyl; or

phenyl or benzyl, said phenyl or benzyl groups being optionally substituted with methyl, trifluoromethyl, methoxy, cyano, nitro or 1-3 halogen;

R⁷ is phenyl, benzyl, naphthalenyl, heteroaromatic or fused

R⁸ is phenyl, naphthalenyl, heteroaromatic or fused

heteroaromatic ring systems, said phenyl, naphthalenyl, heteroaromatic or fused heteroaromatic rings being optionally substituted with R⁹ and R¹⁰;

R⁹ is C₁-C₂ alkyl, C₁-C₂ haloalkyl, C₁-C₂ alkoxy, C₁-C₂

haloalkoxy, cyano, nitro or 1-2 halogen;

R¹⁰ is C₁-C₄ alkyl; C₁-C₄ haloalkyl; C₂-C₄ alkenyl; C₂-C₄ alkynyl; C₂-C₄ alkoxyalkyl; OR¹¹; C(=O)R¹²; CO₂R¹²; C(=O)NR²R³; NR²R³; S(O)_mR¹²; SO₂NR²R³;

R¹2 is C₁-C₄ alkyl optionally substituted with C₁-C₂ alkoxy, cyano or one or more halogen;

R¹³ ig methyl, methoxy, trifluoromethyl, nitro, cyano or 1-2 halogen;

m is 0, 1 or 2;

n is 0. 1 or 2;

p is 1, 2 or 3;

q is 0 or 1; and

w is 3 or 4.

11. Compounds of the Formula 1

wherein:

G is C(=L)NR²R³ or C(=O)OR⁴; and

L is O or S;

A is H, C(=O)OR⁶, C(=O)NHR⁷, C(=O)(CH₂)_nR⁸ or SO₂R¹⁴; R¹ is C₁-C₈ alkyl substituted with cyano, CO₂R¹⁵ or more than one halogen; or C₁-C₂ alkyl substituted with phenyl, naphthalenyl or heteroaromatic ring systems containing from 5 to 10 atoms, wherein the heteroatoms comprise: i) 1-3 nitrogen atoms, or

ii) 1-2 nitrogen atoms with 1 oxygen or sulfur atom, or; iii) 1-2 oxygen or sulfur atoms;said phenyl, naphthalenyl or heteroaromatic ring systems being optionally

substituted with R⁹ and R¹⁰;

R² and R³ are independently H; C₁-C₆ alkyl; C₁-C₆ haloalkyl;

C₂-C₆ alkoxyalkyl; C₃-C₄ alkenyl; C₃-C₄ haloalkenyl; or R² and R³ may be taken together along with the nitrogen to which they are attached to form a pyrrolidino,

piperidino or morpholino group, each optionally

substituted with 1-2 methyl groups;

R⁴ is C₁-C₈ alkyl, C₁-C₈ haloalkyl, C₃-C₆ alkoxyalkyl, C₃-C₆ alkenyl or C₃-C₆ haloalkenyl; R⁵ is C₁-C₆ alkyl; C₁-C₆ haloalkyl; C₂-C₆ alkoxyalkyl; or phenyl or benzyl, said phenyl or benzyl groups being optionally substituted with methyl, trifluoromethyl, methoxy, cyano, nitro or 1-3 halogen;

R⁹ is C₁-C₂ alkyl, C₁-C₂ haloalkyl, C₁-C₂ alkoxy, C₁-C₂

haloalkoxy, cyano, nitro or 1-2 halogen;

R¹⁰ is C₁-C₄ alkyl; C₁-C₄ haloalkyl; C₂-C₄ alkenyl; C₂-C₄ alkynyl; C₂-C₄ alkoxyalkyl; OR¹¹; C(-O)R¹²; CO₂R¹²;

C(=O)NR²R³; NR²R³; S(O)_mR¹²; SO₂NR²R³;

— O(CH₂)_pO_q— ;— (CH₂)_w— ; halogen; cyano; nitro; or phenyl or phenoxy, said phenyl or phenoxy groups being optionally substitut d with R¹3;

R¹² is C₁-C₄ alkyl optionally substituted with C₁-C₂ alkoxy, cyano or one or more halogen; R¹³ is methyl, methoxy, trifluoromethyl, nitro, cyano or 1-2 halogen;

m is 0, 1 or 2;

n is 0, 1 or 2;

p is 1, 2 or 3;

q is 0 or 1; and

w is 3 or 4; provided that when G is C(=O)NR²R³:

1) A is C(=OXCH₂)_nR⁸ and n is 0;

or

2) R¹ is C₁-C₈ alkyl substituted with cyano or 2 or more halogens; or C₂-C₆ alkyl substituted with CO₂R¹⁵.

12. Compounds of Claim 11 wherein:

G is C(=O)NR²R³;

A is C(=O)(CH₂)_nR⁸; and

R¹ is benzyl substituted with R⁹;

provided that n is 0.

13. An agriculturally suitable composition comprising a fungicidally effective amount of a compound of any of Claims 10 to 12 and at least one of the following: surfactant, solid diluent or liquid diluent.

14. The method of Claim 6 wherein said compound is: 2-[[4-(1,1-di-methylethyl)phenyl]suffonyl]-2-(hydroxyimino)- N,N-dimethylacetamide).

15. The method of Claim 9 wherein said compound is:

2-[(4-bromophenyl)suffonyl]-2-[[(3-chlorobenzoyl)oxy]imino]- N,N-dimethylacetamide).