TTTT.

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;

R ¹ is Cχ-Ci2 alkyl, C3-C12 alkyl substituted with Cl, C3-C4 alkenyl, C3-C8 cycloalkyl, C6-C7 cycloalkylalkyl, phenyl, benzyl, or

wherein R^, R3 and R^ are as defined below, p is 1 or 2, and R^ is phenylene, xylylene, or C2-C18 alkylene;

2 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 Bx- and ^ can be benzyl;

2) the sum of carbon atoms in R2 and $ can total no more than 12, except where both R^ and B& are alkyl;

R is H or (C=0)NHR5; 5 is Ci-Cg 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 β as herbicide safeners

Ar-SO -C-X

N-O-Q

£

The compounds disclosed as safeners overlap the compounds claimed in Bellina (U.S. 3,819,700) wherein X is C(-=0)NRlR2.

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)NR2R3, C(=0)OR ⁴ , S0 ₂ NR ² R ³ or S(0) _m R5;

L is O or S;

A is H, C(=0)OR6, C(=0)NHR7, C(=0)(CH ₂ ) _n R ⁸ or S0 ₂ R ¹⁴ ; * is Ci-Cs alkyl optionally substituted with C -C2 alkoxy, C3-C6 cycloalkyl, cyano, Cθ2R^^, or one or more halogen; C3-Cg 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 R^ and R*0; R2 and B are independently H; Ci-Cg alkyl; C -Cβ haloalkyl; C2-

CQ alkoxyalkyl; C3-C4 alkenyl; C3-C4 haloalkenyl; or Ηs- and 3 m 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; R ⁴ is Ci-Cs alkyl, Ci-Cs haloalkyl, C3-C6 alkoxyalkyl, C3-C6 alkenyl or C3-C6 haloalkenyl; R^ is Ci-Cg alkyl; Cj-Cg haloalkyl; C2-Cg alkoxyalkyl; or phenyl or benzyl, said phenyl or benzyl groups being optionally substituted with methyl, trifluoromethyl, methoxy, cyano, nitro or 1-3 halogen;

6 is Ci-Cg alkyl optionally substituted with Ci-Cg alkoxy, C3-C cycloalkyl, cyano or one or more halogen; C3~C 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

RlO; ' is phenyl, benzyl, naphthalenyl, heteroaromatic or fused heteroaromatic ring system; said phenyl, benzyl, naphthalenyl, heteroaromatic or fused heteroaromatic rings being optionally substituted with ^ and R*0;

Rδ is phenyl, naphthalenyl, heteroaromatic or fused heteroaromatic ring systems, said phenyl, naphthalenyl, heteroaromatic or fused heteroaromatic rings being optionally substituted with R^ and R ¹⁰ ; R ⁹ s C1-C2 alkyl, C1-C2 haloalkyl, C1-C2 alkoxy, C1-C2 haloalkoxy, cyano, nitro or 1-2 halogen; R ¹⁰ is C1-C4 alkyl; C1-C4 haloalkyl; C2-C4 alkenyl; C2-C4 alkynyl;

C2-C4 alkoxyalkyl; OR**; C(=0)R* ² ; C0 R ¹² ; C(=0)NR ² R3; NR ² R3; NR ² C(=0)Rl ² ; S(0) _m R ¹² ; S0 ₂ NR ² R ³ ; — 0(CH2) Oq— ; — (CH2) _W — ; halogen; cyano; nitro; or phenyl or phenoxy, said phenyl or phenoxy groups being optionally substituted with Rl ; R11 is C1-C4 alkyl optionally substituted with C -C2 alkoxy, C3-Cg cycloalkyl, cyano or one or more halogen; or C3-Cg cycloalkyl; R* ² is C1-C4 alkyl optionally substituted with C1-C2 alkoxy, cyano or one or more halogen; Rl3 i _s methyl, methoxy, trifluoromethyl, nitro, cyano or 1-2 halogen; RI ⁴ is Ci-Cg alkyl; C -Cg haloalkyl; C2-Cg alkoxyalkyl; or phenyl or benzyl, said phenyl or benzyl groups being optionally substituted with methyl, trifluoromethyl, methoxy, cyano, nitro or 1-3 halogen;

Rl5 is Ci-Cg alkyl, Ci-Cβ haloalkyl, C3-C alkoxyalkyl, C3-Cg alkenyl or C3-C 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(=0)NR ² R3 _: 1) A is C(=0)(CH2) _n R ⁸ and n is 0; or

2) I is Cι»C8 alkyl substituted with cyano or 2 or more halogens; or C2-C alkyl substituted with

CO2R ¹⁵ ; or

3) RI is substituted phenyl or substituted benzyl; ϋ) R^ s not methyl. iii) when R ² , R or R ⁴ are alkenyl or haloalkenyl, they must be attached to the heteroatom through an sp^-hybridized carbon; iv) when A is H and R* is 4-methylphenyl, G is not C(=0)N(CH ₂ CH ₃ )2 or C(=0)N(CH ₃ ) ₂ ; and v) when G is C(=0)N(CH3)2 and A is C(=0)-2,4-dichlorophenyl, I 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 F ₃ C, C1CH ₂ , CF ₃ CH ₂ , CF ₃ CF _2> (C1)2C--=CHCH ₂ , BrCH=CHCH ₂ , CF3O, CCI3CH2O, and CF3CH2O.

The total number of carbon atoms in a substituent group is indicated by the "Ci-Cj" prefix where i and j are numbers fro 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(--=0)NR ² R3 or C(=0)OR ⁴ ;

R is Ci-Cs alkyl optionally substituted with C1-C2 alkoxy, cyano, CO2 I or one or more halogen; C -C2 alkyl substituted with phenyl, said phenyl group being optionally substituted with R ⁹ and R ¹⁰ ; or phenyl substituted with R ⁹ and R ¹⁰ ; U is C1-C4 alkyl optionally substituted with C1-C2 alkoxy, cyano or one or more halogen; and l s C -C2 alkyl optionally substituted with one or more halogen.

2) A method of Preferred 1 wherein:

G is C(:=0)NR ² R3; RI is phenyl or benzyl, said phenyl or benzyl group being optionally substituted with R^ and R*0; R and 3 are independently H; C1-C4 alkyl; C1-C4 haloalkyl; or R ² and R may be taken together along with the nitrogen to which they are attached to form a pyrroHdino, piperidino or morpholino group each optionally substituted with 0-2 methyl; 9 is methyl, trifluoromethyl, methoxy, cyano, nitro or 1-2 Cl or F; and

RlO is methyl; *-butyl; trifluoromethyl; methoxy; C(=0)CH3; C0 ₂ CH ₃ ; N(CH ₃ ) ₂ ; SCH3; S0 ₂ CH ₃ ; 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(=0)OR ⁶ ; and

R6 is C -Cs alkyl optionally substituted with Cj-Cg alkoxy, halogen or cyano; or C -C2 alkyl substituted with phenyl, said phenyl being optionally substituted with

R9 and RlO.

4) A method of Preferred 2 wherein: A is C(=0)NHR7; and ' is phenyl or benzyl, said phenyl or benzyl groups being optionally substituted with ^ and lO.

5) A method of Preferred 2 wherein: A is H.

6) A method of Preferred 2 wherein: A is C(=0)(CH ₂ ) _n R ⁸ .

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 R® and R*0.

8) A method of Preferred 7 wherein: I is phenyl optionally substituted with R*0; and R8 is phenyl optionally substituted with R*0.

9) Compounds of the Formula I and agricultural compositions containing them and their use as fungicides wherein: G is S0 ₂ NR R3 or S(0) _m R5;

A is H, C(=0)OR6, C(=0)NHR7, C(=0)(CH ₂ ) _n R ⁸ or S0 ₂ R ¹⁴ ; I is Ci-Cs alkyl optionally substituted with C1-C2 alkoxy,

Ctø-Cg cycloalkyl, cyano, Cθ2R^, or one or more halogen; C3-Cg cycloalkyl; C -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 R ⁹ and R*0; R ² and R ³ are independently H; Ci-Cg alkyl; Ci-Cg haloalkyl; C2-C alkoxyalkyl; C3-C4 alkenyl; C3-C4 haloalkenyl; or R ² and R ³ 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; R ⁵ is Ci-Cg alkyl; Ci-Cg haloalkyl; C2-Cg alkoxyalkyl; or phenyl or benzyl, said phenyl or benzyl groups being optionally substituted with methyl, trifluoromethyl, methoxy, cyano, nitro or 1-3 halogen; Ro is C -Cs alkyl optionally substituted with Ci-Cg alkoxy, C3-Cg cycloalkyl, cyano or one or more halogen; C3-Cg cycloalkyl; or C -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 R ⁹ and R*0; ' is phenyl, benzyl, naphthalenyl, heteroaromatic or fused heteroaromatic ring system; said phenyl, benzyl, naphthalenyl, heteroaromatic or fused heteroaromatic rings being optionally substituted with R ⁹ and R^O; R° is phenyl, naphthalenyl, heteroaromatic or fused heteroaromatic ring systems, said phenyl, naphthalenyl, heteroaromatic or fused heteroaromatic rings being optionally substituted with R ⁹ and *0; R ⁹ is C1-C2 alkyl, C1-C2 haloalkyl, C -C2 alkoxy, C1-C2 haloalkoxy, cyano, nitro or 1-2 halogen;

R ¹⁰ is C1-C4 alkyl; C1-C4 haloalkyl; C2-C4 alkenyl; C2-C4 alkynyl; C2-C4 alkoxyalkyl; OR ¹¹ ; C(«=0)R ¹² ; C0 ₂ R ¹² ; C(=0)NR2R ³ ; NR ² R ³ ; S(0) _m R ¹² ; S0 ₂ NR ² R ³ ; — 0(CH2)pOq — ; — (CH2 — ; halogen; cyano; nitro; or phenyl or phenoxy, said phenyl or phenoxy groups being optionally substituted with * ³ ;

RI! is C1-C4 alkyl optionally substituted with C1-C2 alkoxy, C3-Cg cycloalkyl, cyano or one or more halogen; or C3-Cg cycloalkyl; Rl2 is C1-C4 alkyl optionally substituted with C -C2 alkosy, cyano or one or more halogen;

Rl3 is methyl, methoxy, trifluoromethyl, nitro, cyano or 1-2 halogen; R ¹⁴ is Ci-Cg alkyl; Ci-Cg haloalkyl; C2-C alkoxyalkyl; or phenyl or benzyl, said phenyl or benzyl groups being optionally substituted with methyl, trifluoromethyl, methoxy, cyano, nitro or 1-3 halogen; R ¹⁵ is C1-C8 alkyl, Ci-Cβ haloalkyl, C3-Cg alkoxyalkyl, C3»Cg alkenyl or C3-Cg 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)NR ² R ³ or C(=0)OR ⁴ ; and L is O or S;

A is H, C(=0)OR6, C(=0)NHR7, C(=0)(CH ₂ ) _n R ⁸ or S0 ₂ R ¹⁴ ; RI is Cj-Cs alkyl substituted with cyano, Cθ2R^ or more than one halogen; or C -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; ϋi) 1-2 oxygen or sulfur atoms; said phenyl, naphthalenyl or heteroaromatic ring systems being optionally substituted with R ⁹ and *0; and 3 are independently H; Ci-Cg alkyl; Ci-Cg haloalkyl; C2-Cg alkoxyalkyl; C3-C4 alkenyl; C3-C4 haloalkenyl; or R ² and R ³ 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; R ⁴ is C1-C8 alkyl, Ci-Cg haloalkyl, C3-Cg alkoxyalkyl, C3-Cg alkenyl or C3-Cg haloalkenyl;

R ⁵ is Ci-Cg alkyl; Ci-Cg haloalkyl; C2-Cg alkoxyalkyl; or phenyl or benzyl, said phenyl or benzyl groups being optionally substituted with methyl, trifluoromethyl, methoxy, cyano, nitro or 1-3 halogen; R^ is C1-C8 alkyl optionally substituted with Ci-Cg alkoxy,

C3-Cg cycloalkyl, cyano or one or more halogen; C3-C cycloalkyl; or C -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 R ⁹ and B.---*; B.~ is phenyl, benzyl, naphthalenyl, heteroaromatic or fused heteroaromatic ring system; said phenyl, benzyl, naphthalenyl, heteroaromatic or fused heteroaromatic rings being optionally substituted with R ⁹ and *0;

R is phenyl, naphthalenyl, heteroaromatic or fused heteroaromatic ring systems, said phenyl,

5 naphthalenyl, heteroaromatic or fused heteroaromatic rings being optionally substituted with R ⁹ and R^O; R ⁹ is C1-C2 alkyl, C1-C2 haloalkyl, C1-C2 alkoxy, C1-C2 haloalkoxy, cyano, nitro or 1-2 halogen; R!0 is C1-C4 alkyl; C1-C4 haloalkyl; C2-C4 alkenyl; C2-C4

10 alkynyl; C2-C4 alkoxyalkyl; ORH; C(=0)R ¹² ; C0 ₂ R ¹² ;

C(=0)NR R3; NR ² R3; S(0) _m R ¹² ; S0 ₂ NR ² R ³ ; — 0(CH2)pOq — ; — (CH2) _W — ; halogen; cyano; nitro; or phenyl or phenoxy, said phenyl or phenoxy groups being optionally substituted with R^ ; 15 Rll is C -C4 alkyl optionally substituted with C1-C2 alkoxy,

C3-Cg cycloalkyl, cyano or one or more halogen; or Ctø-Cg cycloalkyl; RI is C -C4 alkyl optionally substituted with C1-C2 alkoxy, cyano or one or more halogen; 20 i methyl, methoxy, trifluoromethyl, nitro, cyano or 1-2 halogen; R ¹⁴ is Ci-Cg alkyl; Ci-Cg haloalkyl; C2-Cg alkoxyalkyl; or phenyl or benzyl, said phenyl or benzyl groups being optionally substituted with methyl, trifluoromethyl, 25 methoxy, cyano, nitro or 1-3 halogen;

R ¹⁵ is Ci-Cs alkyl, Cχ-C8 haloalkyl, C3~Cg alkoxyalkyl, C3-Cg alkenyl or C3-Cg haloalkenyl; m is 0, 1 or 2; n is 0, 1 or 2; 30 p is 1, 2 or 3; q is 0 or 1; and w is 3 or 4;

provided that when G is C(=0)NR ² R ³ : or

2) RI is Ci-Cs alkyl substituted with cyano or 2 or more halogens; or C2-C8 alkyl substituted with

C0 ₂ R ¹⁵ -

11) A compound of the Preferred 10 wherein: G is C(=0)NR ² R3;

A is C(=0)(CH ₂ ) _n R ⁸ ; and

RI is benzyl substituted with R ⁹ ; provided that n is 0.

Specifically preferred for greatest fungicidal activity and/or ease of synthesis are:

1) 2-[[4-( 1 , l-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 IH 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 Ila-d with an oxime of Formula ffl by several processes which are summarized in the following equations.

SO2R ¹ SO2R ¹

ffi Da la

+ C1C(=0)0R ⁶ G-C=N-0-C(=0)OR6

I SO2R ¹

lib lb

ffl + Cl(0=)C(CH ₂ ) _n R ⁸ > G-C=N-0-C(=0)(CH ₂ ) _n R ⁸

I SO2R ¹

m + C1S0 ₂ R ¹⁴ G-C=N-OS0 R ¹⁴

I SO2R ¹

Hd Id

A novel method of preparation of compounds of Formula Ia-b comprises sequential preparation of the novel chloroformate I§ by reaction of compounds of Formula ffi with phosgene in the presence of organic bases such as N,N-diethylaniline and pyridine, followed by the appropriate R ⁷ NH2 or R^OH compound in the presence of a suitable acid scavenger such as N,N-diethylaniline, pyridine or triethylamine.

R ⁷ NH2 or

COCl ₂ R ⁶ OH

G-C=NOH -> G-CNOC(=0)Cl > G-C=NO-A I Base I Base I

SO2R ¹ SO2R ¹ SO2R ¹

ffl e la. l

A = C(=0)NHR ⁷ or

C(=0)OR ⁶

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

DCC or ∑ PDS

G-C=NOH + HOC(=0)(CH ₂ ) _n R ⁸ > G-C-=NOC(=0)(CH ₂ ) _n R ⁸

I I

SO2R ¹ SO2R ¹

DI lid Ic

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, Pu l So , Cihim. ^" Rely. 1978. ≤2:229 and G. Lajore, F. Lepine, L. Maziak and B. Belleau, JsL Letters. 1983.24:3815).

G-C=NO-A s G-C-=NO-A

I I

S02R ¹ S02 ¹

I, G = C(=0)NR R ³ , I, G - C(=S)NR ² R ³ ,

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 HE can be prepared from thiohydroxamates of Formula I . 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®).

^2e q- - .

G-C=NOH ■> G-C=NOH

I I

SRl SO2R ¹

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

YL

G-C=NOH + RlS0 ₂ M > G-C---NOH I I

Cl SO2 ¹

yj M -= Ii, Na, K in

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

(For a review, see K Andersen, in Comprehensive Org? ? flh .τr.-sf-τv;

Barton, D. and Ollis, W. D., Eds.; PergamonrOxford, 1979; Vol. 3; pp. 317-

329.) The α-sulfone oximes of Formula HI can also be prepared by the reaction of sulfones of Formula VII with sodium nitrite. Alternatively, the α-sulfoneoximes of Formula ffl can be prepared by the reactions of sulfones of Formula VΩ with bases such as sodium alkoxides, followed by reaction with organic nitrites such as isoamyl nitrite, (see O. Touster, Org. Reactions. 1953. 2:327 for general procedures).

NaN02

RlS0 ₂ CH ₂ G > G-C=NOH or I RONO SO2R ¹ wherein R=alkyl vπ ffi

Compounds of Formula HI 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).

NaN02

G-CHSO2R ¹ > G-C=NOH

I I

N0 ₂ SO2R ¹

H in

Compounds of Formula E may be prepared by the reaction of α-chloroaldoximes of Formula 2 with thiols of Formula E£ in the presence of a base such as triethylamine or sodium carbonate (see M. H. Benn, Can. J. Chem. 1964. 42:2393).

base

G-C=NOH + RlSH > G-C=NOH I I

Cl SRl

32 IY

The α-chloroaldoximes of Formula 32 can be prepared by treating amines of Formula 2 with sodium nitrite and hydrochloric acid (see G. S.

Skinner, J.Am. Chem. Soc. 1924. 4g:731).

G-CH ₂ NH ₂ NaN0 ₂ G-C=NOH I

H ₂ 0 Cl

HCl

X 32

The α-chloroaldoximes of Formula 32 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. 4Q:2985) or t- butylhypochlorite (see C. J. Peake and J. H. Strickland, Pyp . C-PTT ¹ 1986. Ifi:763).

Some α-chloroaldoximes of Formula 32 may be prepared from amide oximes XH by treatment with sodium nitrite in hydrochloric acid solution (see M.Kocevar, S. Polanc, M. Sollner, M. Tisler and B.Vercek, fi .h Crm-ny 1988. 1&1427).

The α-chloroaldoximes of Formula 3 can be prepared from trichloromethyl compounds of Formula ^"~ ~il by basic hydrolysis in the presence of hydroxylamine (see A. P. Kozikowski and M. Adamczyk, _J Pry. Chem. 1983. 4£:366).

NH ₂ OH

G-CCI3 > G-C=NOH

NaOH I

Cl

xm 32

The α-chloroaldoximes of Formula 32 can be prepared by the reaction of nitrile N-oxides of Formula XTV with hydrochloric acid (see C. Grundmann, V. Mini, J. M. Dean, and H.-D. Frommeld, Justis laebigs Ann Clht>jr. 1965. 687:191).

+ - HCl G-CsN-O G-C=NOH

I

Cl

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, .-l^ Sine.. Chem. Jpn. 1984.

£7:2531). The carboxamide and carboxyHc 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.

G-C=NOH G = C(=0)NR ² R3, C0 R ⁴

I

Cl

VI

The thiocarboxamide compounds of Formula 3 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.

+

X ₃ C-C _S :NR ² R H ₂ S X ₃ CC(-=S)NR R3 NH ₂ OH G-C*NOH

I > > I

Cl Cl Cl- NaOH

XY X32 SI

X = halogen G = C(=S)NR R ³

The thioalkyl and thioaryl compounds of Formula VJE can be prepared from dichloroformaldoxime XVII (see D.Chiarino, M. Napoletano and A. Sala, fiyr' , < τ" 1988. 1£: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,

The sulfoxide and sulfone compounds of Formula VI can be prepared from compounds of Formula 32 (G = R^S) by oxidation using

one or two equivalents, respectively, of oxidants such as hydrogen peroxide or organic peracids, such as peracetic acid.

[ O ] G-C=NOH -> G-C=NOH I I

Cl Cl

32 32

G -= RδS G = R5S0, R S0 ₂

The sulfone compounds of Formula Vlb can also be prepared from compounds of Formula XVHI (G = R^S02) according to methods already reported (see P.A.Wade and H. R. Hinney, Am πhem. Soc. 1979. 1111:1319).

GCH ₂ N0 ₂ > G-C=NOH

I X

XYHE 32h

G = R ⁵ S0 ₂ X = Br

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, fi nt CpTnmun. 1974. 4:311).

NOC1 GCH ₂ N ₂ > G-C=-NOH

I Cl

XIX 32

G = RδS0 ₂

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

G-C=NOH

I S02R ¹

IH

G = C(=0)NR ² R3

The sulfide compounds of Formula HI can be prepared by the reaction of chlorooximes of Formula 2Ω£ with thiols in the presence of base. The sulfoxide and sulfone compounds of Formula HI can be prepared by the oxidation of the sulfide compounds of Formula HE with one or two equivalents, respectively, of oxidizing agents such as peracetic acid or hydrogen peroxide.

Base

K ¹ SOoC--:NOH + R ^δ SH G-C---NQH-

I

Cl SO ₂ R

xx HI G-=R ⁵ S

CO]

III G --- R ^δ SO, R ⁵ SO ₂

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 foUow are representative of the production of the novel oximes of Formula I.

EXAMPLE 1

Et.bvl 2-fbPTi9-v1tbin .2-bvdrΛwiτn-nnflCfttfltfi

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 jn vacuo to S- ^{ve an} o l which solidified on standing. The crude solid was triturated in hexane to yield 8.93 g Hght amber soHd; m.p. 90-92°C, 75% yield.

EXAMPLE 2

Ethvl 2-fbenzvlsulfonvl)-2-hvdroxvi iτ nar»At _f - ₁ t.A To a stirred solution of ethyl 2-(ben-zylthio)-2-hyo oxyiιninoacetate (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 x 250 mL) and the extracts were combined and dried (MgSθ4). Filtration and concentration m vacuo afforded a white solid;

12.1 g, m.p. 77-83°C, 75% yield.

2-r-l-rb1ornb ^p nτvls»1fnτιvn-2- v^rn rtπτninn-.N.N-dimethvlacetamide

To a solution of 2-(4-cUorobenzylthio)-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 soHd was removed by filtration, dried ia vacuo and recrystalHzed 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 soHd was obtained. 8% yield.

EX MPLE 4 2-(Phenylsulfonyl)-2-hvdroχv-τn-innpip<a7 ^ip >aretqmidp 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 CeHteT and the filtrate was concentrated s vacuo to yield an orange, viscous oil. Purification was accompHshed using siHca 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 soHd; m.p. 175-176°C.

EXAMPLE 5 N,N-dimethyl-2-(phenylsulfonyl)- 2-πT3-(trifluoromethvl)benzovnoxv ^' Kτn r n1arfttflτni>-P

To a stirred solution of 2-(phenylsutfonyl)-2-hyάτoxyimino-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 221 vacuo to provide 13 g of white soHd, which was recrystallized from 1-chlorobutane hexane to yield 10.2 g granular white soHd; m.p. 90-92°C, 80% yield.

EXAMPLE 6

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

Σ-rrrS-ftrifluoromethvDben^oYll ^ylimi lff^tPTPi l* ³ To a stirred solution of 2-[(4-chlorophenyl)-sulfonyl]-2- hydroxyim--no-N,N-diπιethylacetamide (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 soHd. The material was further purified by recrystallization from 1-chlorobutane to yield white crystalline soHd; m.p. 122-125°C.

EXAMPLE 7

2-[(4-Bromophenyl)sulfonyl]-2-[[[(3-chloro- benvl _fl minn1 ^fifl rl-nπ mr Ηττ.i lo.N.N-dim h^f^^ " ^ττl ^ ^fi

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

EXAMPLE 8

2-[(4-Chlorophenyl)sulfonyl]- To a solution of 2(4-chlorophenylsulfonyl)-2-hyό oxyimino-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 soHd was triturated in hexane to give 500 mg white solid. The soHd was further purified by recrystallization from acetonitrile to yield 220 mg of white crystalline solid; m.p. 95-98°C, 36% yield.

EXAMPLE 9 l-[2-[[[(3-Chlorophenyl)carbonyl]- Q'Tlτmino1-2- ⁽ phenylsulfonyl ⁾ acetyπpiperidine 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 mT- of half-saturated NH4CI solution. The organic phase was separated, dried with M Sθ4, filtered and concentrated n vacuo to yield a colorless oil which crystallized on standing. Recrystallization

from 1-chlorobutane hexane with a trace of acetonitrile resulted in 320 g of white crystals; m.p. 167-169°C.

EXAMPLE lQ 2-(4-Chlorophenvlsulfonvl)-2-hvdro-rviτr -nn- N-dimetbv1flrP flmide To a solution of 2(4-cMorophenylthio)-2-hyάτoxyimino-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 soHd; m.p. 165-168°C, 88% yield.

EXAMPLE U 2- 4-Chlorophenvl -Ho)-2-hvdroχ iττι^τιn-. _r -N -^ τriPt^γ^ ptppι dp

To a solution of 2-cMoro-2-hydrox imino-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 ia vacuo to yield a crude soHd. The soHd was triturated in hexane to yield 19.4 g of off-white soHd, m.p. 205-207°C.

EXAMPLE 13 To a solution of 2-(4-bromophenylthio)-2-hydro:---yimino-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 soHds 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-cMorophenyl)sulfonyl]-N,N-dimet-hyl- 2-rrr(4-methvlphenvl sulfoτ γno^γlJm po1«^ptflτrii<l

To a stirred solution of 2-[(2-chlorophenyl)sulfonyl]-2- hydro:∑yi-α_ύno-N,N-dimethyl acetamide (580 mg) and p-toluene- Bulfonylchloride (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 ΪB vacuo. Purification was accompHshed using siHca gel flash chromatography, with 1:1 hexane:ethyl acetate as eluent. Concentration of the appropriate fractions and trituration of the residue in cold 1-chloro- butane hexane yielded 600 mg of white soHd; m.p. 125-127°C.

EXAMPLE 14 2-r ⁽ 3-thienvl ⁾ sulfonvn-2-hvdroxvimino-N.N- im ^p t γl flft tflff" ¹ *?

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 butylHthium 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-Hthiothiophene. Using a vacuum-jacketed addition funnel cooled with dry ice/acetone, sulfur dioxide gas was condensed (16.7 mL). The Hquified sulfur dioxide was added dropwise to the 3-Hthiothiophene solution prepared earHer. A white precipitate formed upon adidition. After the addition, the mixture was stirred at -78°C for 30 min. The pale yeUow 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 tnT ^, of ice-water. The mixture was extracted with dichloromethane (3 x 200 mL). The combined organic phases were

dried (MgSθ4), filtered and concentrated ia vacuo. The resulting white solid was triturated in hexane and collected by filtration to yield 14.8 g white soHd; m.p. 170-173°C.

EXAMPLE 15

To a solution of 2-[(3-thienyl)sτ-ιlfonyl]-2-hydroxyim-ino-N^- dimethyl acetamide (524 mg) and benzoyl chloride (0.23 mL) in 15 mL of THF at room temperature was added triethylamine (0.28 L). 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 ia vacuo. The residue was triturated in 1-chlorobutane hexane to yield 600 mg of white soHd; m.p. 132-135°C.

EXAMPLE 16

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 (MgS04), filtered, and concentrated in vacμio to yield off-white soHd. This material was slurried in hexane with a smaU amount of methylene chloride and refrigerated. The soHd was coUected by filtration and washed with cold hexane. The soHd was dried in the vacuum oven to yield 19.2 g white soHd; m.p. 196-200°C. Analysis by 200 MHz NMR indicated the soHd 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 w.T. of methanol was added 18.3 L 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 soHd was redissolved in methylene chloride, dried (MgS04) 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 soHd; m.p. 180-183°C.

The following Table Hsts 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:

X-B-C=N-0-W-Z-Al,

I S02R ¹

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

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

X-B of H s the same as G of I, W-Z-Al of H is the same as A of I.

XΔBLE-1

SO2R ¹

£ E- ¹

OEt CO CH P H - -

(Mβ) ₂ -N CO Ph CO - 3 CF ₃ -Ph

(Mβ) ₂ -N CO Ph CO - 1 -naphthyl

(Me) ₂ -N CO 4 Cl-Ph H

(Mβ) ₂ -N CO 4 Cl-Ph CO -

(Mβ) ₂ -N CO 4 Cl-Ph CO -

(Me) -N CO 4 Cl-Ph CO -

(Mβ) ₂ -N CO 3 Br-Ph CO -

(Me) ₂ -N CO 3 Br-Ph CO -

(Me) ₂ -N CO 3 Br-Ph CO -

(Mβ) ₂ ~N CO 3 Br-Ph CO -

<Me) ₂ -N CO 3 Br-Ph CO -

(Me) ₂ -N CO 3 Br-Ph CO -

(Mβ) ₂ -N CO 2 OCH ₃ -Ph CO -

(Mβ) ₂ -N CO 2 OCH ₃ -Ph CO -

(Me) ₂ -N CO 2 OCH ₃ -Ph CO -

(Me) ₂ -N CO 2 OCH ₃ -Ph CO -

(Mβ) ₂ -N CO 2 OCH ₃ -Ph CO -

E & ¹ H ¹

£ & ¹ h~

pyrrolidine pyrrolidine pyrrolidine pyrrolidinβ pyrrolidine morpholinβ morpholine morpholinβ morpholinβ morpholine morpholine morpholine morpholine morpholine 3 Me-piperidine

3 Me-piperidine

3 Me-piperidine

3 Me-piperidine 3 Me-piperidine

3 Me-piperidine

3 Me-piperidine

3 Me-piperidine

2,6 Me ₂ -morpholine

2,6 Mβ2-morpholine

2,6 Me2~morpholine

2,6 Mβ2-morpholine

2,6 Me2~morpholine

2,6 Mβ2-morpholine

2,6 Mβ2-morpholine

2,6 Me ₂ -morpholine

£ E- H Δ ^α

£ H z-

MeO CO Ph CO NH 2,6 Cl ₂ -Ph MeO CO Ph CO NH 4 OCH ₃ -Ph MβO CO Ph CO NH CH ₂ (4 Cl-Ph)

(Me) -N CS Ph CO 3 Cl-Ph (Mβ) -N CS Ph CO 2 OCH ₃ -Ph

NH ₂ CO Ph CO 4 OCH ₃ -Ph

NH ₂ CO Ph CO Ph

NH-. CO Ph CO 4 CN-Ph

NH, CO Ph CO 4 Nθ -Ph H CO Ph CO 4 CF ₃ -Ph

NH, CO Ph CO 4 Me-Ph

NH, CO Ph CO 3 CF ₃ -Ph

NH ₂ CO Ph CO 4 SCH ₃ -Ph

NH ₂ CO Ph CO 4 Cl-Ph

NH ₂ CO Ph CO 3 Cl-Ph

MeNH CO Ph CO 4 Cl-Ph

MeNH CO Ph CO Ph

MeNH CO Ph CO 4 Me-Ph

MeNH CO Ph CO 3 Cl-Ph

MeNH CO Ph CO 4 CN-Ph MeNH CO Ph CO 3 CF ₃ -Ph

MeNH CO Ph CO 4 Nθ ₂ -Ph

MeNH CO Ph CO 4 CF ₃ -Ph

MeNH CO Ph CO 4 SCH ₃ -Ph

£ &~ H h-

£ E-

£ E- &-

(Mβ) ₂ -N CO 4 Cl-Ph CO O CH ₂ Ph (Me) ₂ -N CO 4 Cl-Ph CO O CH ₂ CH ₂ Ph

(Me) ₂ -N CO 4 Cl-Ph CO O CH ₂ (1-naphthyl)

(Mβ) ₂ -N CO 4 Cl-Ph CO O CH (2-naphthyl)

(Mβ) -N CO 4 Cl-Ph CO O furfuryl

(Me) -N CO 4 Cl-Ph CO O CH ₂ (3-thiophβnβ)

(Me) ₂ -N CO 4 Cl-Ph CO O tβtrahydrofurfuryl

(Me) ₂ -N CO 4 Cl-Ph CO O CH ₂ (2-tetrahydropyran)

(Me) ₂ -N CO 4 Cl-Ph CO O CH ₂ (2-quinoline)

(Me) ₂ -N CO 4 Cl-Ph CO O CH ₂ (4 Cl-Ph)

(Mβ) -N CO 4 Cl-Ph CO O CH ₂ (3 Cl-Ph)

(Me) ₂ -N CO 4 Cl-Ph CO O CH ₂ (4 Mβ-Ph)

(Me) ₂ -N CO 4 Cl-Ph CO O CH ₂ (2 SCH ₃ -Ph)

(Me) ₂ -N CO 4 Cl-Ph CO O CH ₂ (2 Sθ ₂ CH ₃ -Ph)

(Me) ₂ -N CO 4 Cl-Ph CO O CH ₂ (4 OCH ₃ -Ph)

(Me) ₂ -N CO 4 Cl-Ph CO O CH ₂ (3 CF3-PI1)

(Me) ₂ -N CO 4 Cl-Ph CO O CH (4 Cθ ₂ Me-Ph)

(Mβ) -N CO 4 Cl-Ph CO O CH ₂ (3,4,5 Cl ₃ -Ph)

(Me) ₂ -N CO 4 Cl-Ph CO O CH ₂ (3,4 OMe ₂ -Ph)

(Me) ₂ -N CO 4 Cl-Ph CO O CH (4 allyl-Ph)

(Me) ₂ -N CO 4 Cl-Ph CO O CH ₂ (2 CH ₂ OCH ₃ -Ph)

(Me) ₂ -N CO 4 Cl-Ph CO O CH ₂ (4 t-Bu-Ph)

(Mβ) ₂ -N CO 4 Cl-Ph CO O CH ₂ (3 propargyl-Ph)

<Me) ₂ -N CO 4 Cl-Ph CO O CH ₂ (4 CN-Ph)

(Mβ) ₂ -N CO 4 Cl-Ph CO O CH ₂ (2 Sθ ₂ NMe ₂ -Ph)

(Me) ₂ -N CO 4 Cl-Ph CO O CH ₂ (4 NMe ₂ -Ph)

(Me) ₂ -N CO 4 Cl-Ph CO O CH ₂ (2 CONEt ₂ -Ph)

(Mβ) ₂ -N CO 4 Cl-Ph CO O CH ₂ (4 Nθ ₂ -Ph)

(Me ₂ )-N CO 4 Me-Ph CO CH ₂ Ph

£ E- H h~

£

(Me) ₂ -N CO

(Me) ₂ -N CO

(Mβ) ₂ -N CO

(M ^β ) ₂ -N CO

(Me) ₂ -N CO

(Me) ₂ -N so ₂

(Me) ₂ -N so ₂

(Me) ₂ -N so ₂

(Mβ) ₂ -N so ₂

(Me) ₂ -N so ₂

(Me) ₂ -N so ₂

(Me) -N so ₂

(Me) ₂ -N so ₂

(Mβ) -N so ₂

(Me) ₂ -N so ₂

(Me) ₂ -N so ₂

(Me) ₂ -N so ₂

(Me) -N so ₂

(Me) ₂ -N so ₂

(Me) ₂ -N so ₂

(Me) ₂ -N so ₂

(Me) -N so ₂

(Me) ₂ -N so ₂

(Me) ₂ -N so ₂

(Me) ₂ -N so ₂

(Me) ₂ -N so ₂

(Me) -N so ₂

(Me) -N so ₂

(Me) ₂ -N so.

£ E ¹ h~

£ E ^J H A ¹

(Me) ₂ -N CO CF ₃ CO O CH ₂ (4 Mβ-Ph)

(Me) ₂ -N CO CF ₃ CO O cyclohexyl

(Mβ) ₂ -N CO CF ₃ CO O CH ₂ CH ₂ (1-pyrrolidinβ)

(Mβ) ₂ -N CO CF ₃ CO O CH (3,4,5 Cl ₃ -Ph)

(Mβ) ₂ -N CO CF ₃ CO O piperonyl

(Me) -N CO CFi CO NH 3 Cl-Ph

(Me) ₂ -N CO CF ₃ ^' CO NH 3,5 Cl ₂ -Ph

(Mβ) ₂ -N CO CF ₃ CO NH 3 CF ₃ -Ph

(Me) ₂ -N CO CF ₃ CO NH 4 OCH ₃ -Ph

(Me) ₂ -N CO CF ₃ CO NH 3 CN-Ph

(Me) ₂ -N CO CF. CO NH 2 Cθ Me-Ph

NH 2,6 Mβ ₂ -Ph

NH 2 Et-Ph

NH 4 t-Bu-Ph

NH CH ₂ Ph

NH 2,6 Cl ₂ -Ph

NH 2-naphthyl

NH 2-thiazole

4 OCH ₃ -Ph

Ph

4 Me-Ph

3 Cl-Ph

4 CN-Ph

3 CF ₃ -Ph

4 NO _z -Ph 4 CF ₃ -Ph

4 Sθ ₂ CH ₃ -Ph 2 naphthyl O Et

E E- H ^Λ

£ E- S ¹

£ E- fi Δ ^α

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 Diluentfs ⁾ Surfa<?tant(g)

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

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. G sin 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.

Exam le A

Wettable Powder

2-[(4-cmorophenyl)sulfonyl]-N,N-dimethyl-2-[[[3-(tri- fluoromethyl)benzoyl]oxy]im o]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.

F,yflτn 1p Wettable Powder 2-[(4-chlorophenyl)sulfonyl]-N,N-dimethyl-2-[[[3-(tri- fluoromethyl)benzoyl]o-^]imino]acetamide 50% sodium alkylnaphthalenesulfonate 2% low viscosity methyl cellulose 2% diatomaceous earth 46% The ingredients are blended, coarsely hammer-milled and then air- milled to produce particles essentially all below 10 microns in diameter. The product is reblended before packaging.

F'Xflmpfc 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.

tompfe P

Extruded Pellet

2-[(4-chlorophenyl)sulfonyl]-N,N-dimethyl-2-[[[3-(tri- fiuoromethyl)be-αzoylJoxy]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.

Ex mple E

Oil Suspension

2-[(4-chlorophenyl)sulfonyl]-N,N-dimethyl-2-[[[3-(tri- fluoromethyl)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.

Wettable Powder

2-[(4-chlorophenyl)sulfonyl]-N,N-dimethyl-2-[[[3-(tri- fluoromethyl)benzoyl]o---y]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.

.yflτn 1g fi Low Strength Granule 2-[(4-cUorophenyl)sulfonyl]-N,N-dimethyl-2-[[[3-(tri- fluoromethyl)be:αzoyl]oxy]im--no]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^-dimethyl-2-[[[3-(tri- fluoromethyl)benzoyl]o-^]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.

Fxpmple T Low Strength Granule

2-[(4-chlorophenyl)sulfonyl]-N,N-dimethyl-2-[[[3-(tri- fluoromethyl)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.

Exampl J

2-[(4-chlorophenyl)sulfonyl]-N,N-dimethyl-2-[[[3-(tri- fluoromethyl)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.

Exampl

High Strength Concentrate

2-[(4-chlorophenyl)sulfonyl]-N,N-dimethyl-2-[[[3-(tri- fluoromethyl)benzc d]o-^]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^r-dimethyl-2-[[[3-(tri- fluoromei^yl)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

Wettable Powder

2-[(4-chlorophenyl)sulfonyl]-N^-dimethyl-2-[[[3-(tri- fluoromethyl)benzoyl]oxy]imino]acetamide 40% sodium Hgninsulfonate 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.

Fgflm IP

Oil Suspension

2-[(4-chlorophenyl)sulfonyl]-N^-dimethyl-2-[[[3-(tri- fluoromethyl)benzoyl]oxy]imino]acetamide 35% blend of polyalcohol carboxyHc 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

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

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 Basidiomvcete. Ascomycete Oomvcete 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. C' r FP TJdwm PFrmwl ¹ - Cercospora arachidicola. Cercos ^p ora beticola. Pseudocercosporella herpotrichoides. Puccinia recondita. iific nifl arachidis. Pvricularia orvzae. Phvtophthora infestans. Plasmopara viticola. Peronospora tabacina. Pseudoperonospora cubensis. Pvthinm fl Ηflni ff mntnτrι 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) l,4-dicMoro-2,5-diπιethoxybenzene (chloroneb) methyl l-(butylcarbamoyl)-2-benzimidazolecarbamate (benomyl)

2-cyano-N-ethylcarbanιoyl-2-nιethθ2-yinώnoacetanύde (cynιoxa-nil) N-trichloromethylthiotetrahydrophthalamide (captan)

N-trichlorometiiylthiophthalimide (folpet) dimethyl 4,4'-(o-phenylene)bis(3-thioallophanate) (thiophanate-methyl)

2-(thiazol-4-yl)benzimidazole (thiabendazole) aluminum tris(0-ethyl phosphonateKphosethyl aluminum) tetrachloroisophthalonitrile (chlorothalonil) 2,6-dichloro-4-nitroaniline (dichloran)

N-(2,6-dimethylphenyl)-N-(methoxyacetyl)alanine methyl ester (metalaxyl) s-N-[l,l,2,2-tetracUoroethyl)thio](^clohex-4-ene-l,2-dicarbi oximide

(captafol) 3-(3,5-dic^orophenyl)-N-(l-methylethyl)-2,4-ωoxo-l-imidazol idine carboxamide (iprodione) 3-(3 ,5-dichlorophenyl)-5-ethenyl-5-methyl-2 ,4-oxazolidinedione

(vinclozolin) kasugamycin

0-ethyl-S,S-diphenylphosphorodithioate (edifenphos) 4-(3-(4-(l,l-dimethyl-ethyl)phenyl)-2-methyl)propyl-2,6-dime thyl- morpholine (fenpropimorph)

4-(3-4(l,l-dimethyl-ethyl)phenyl)-2-methyl)propylpiperidi ne

(fenpropidine) l-(4-chlorophenoxy)-3,3-dimethyl-l-lH-l,2,4-triazol-l-yl)but anone

(triadimefon) 2-(4-chlorophenyl)-2-(lH-l,2,4-triazol-l-yl-methyl)hexanenit rile

(myclobutanil) α-[2-(4-chlorophenyl)ethyl]-a-(l,l-dimethylethyl)-lH-l,2,4- triazole-

1-ethanol (tebuconazol) 3-chloro-4-[4-methyl-2-(lH-l,2,4-triazol)-l-ylmethyl)-l,3-di oxolan- 2-yl]phenyl-4-chlorophenyl ether (difenoconazole) l-[2-(2,4-dichlorophenyl)pentyl]lH-l,2,4-triazole (penconazole) (RS)-2,4'-difluoro-a-(lH-l,2,4-triazole-l-ylmethyl)benzhydry l alcohol (flutriafol) l-[[bis(4-fluorophenyl)methylsilyl)methyl]-lH-l,2,4-triazole (flusilazol) N-propyl-N-[2-(2,4,6-trichloropheno-sy)ethyl]imidazole-l-car boxamide (prochloraz)

(±)-l-[2 2,4-dichlorophenyl)-4-proρyl-l,3-dioxolan-2-ylmethyl]-lH-l, 2,4- triazole (propiconazole) α-(2-chlorophenyl)-a-(4-chlorophenyl)-5-pyrinιidinemethano l (fenariιnol) l-(4-Chlorophenoxy)-3,3-dimethyl-l-(lH-l,2,4-triazole-l-yl)b utan-2-ol

(triadin aol) (2RS,3RS l-(2,4-dichlorophenyl)-4,4-dimethyl-2-(lH-l,2,4-triazol-l- yl)pentan-3-ol (diclobutrazol) copper oxychloride nιethyl N-(2,6-diιnethylphenyl)-N-(2-n-u'anylcarbonyl)-DL-alaninate

(furalaxyl)

actericideg tribasic copper sulfate streptomycin sulfate oxytetracycline

Ag rjcjdeg senecioic acid, ester with 2-sec-butyl-4,6-dinitro-phenol (binapacryl) 6-methyl-l,3-dithiolo[2,3-B]quinonolin-2-one (o-^hio-qtιinox) 2,2,2-trichloro-l,l-bis(4-chlorophenyl)ethanol (dicofol) bis(pentachloro-2,4-cyclopentadien-l-yl) (dienochlor) tricyclohexyltin hydroxide (cyhexatin) hexakis(2-methyl-2-phenylpropyl)distaιmoxane (fenbutatin oxide)

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

S-methyl-l-(dimethylcarbamoyl)-N-(methylcarbamoyloxy)tiι io- formimidate (oxamyl) S-methyl-l-carbaπιoyl-N-(methylcarbanιoyloxy)thioformimid ate N-isopropylphosphoramidic acid, 0-ethyI-0'-[4-(methylthio)-m-tolylJ- diester (fenamiphos)

Insecticides

3-hydroxy-N-methylcrotonamide(dimethylphosphate)ester (monocrotophos) methylcarbamic acid, ester with 2,3-dihydro-2,2-dimethyl-7-benzofuranol (carbofiiran) 0-[2,4,5-trichloro-a-(chloromethyl)benzyl]phosphoric acid, 0',0'-dimethyl ester (tetrachlorvinphos) 2-mercaptosuccinic acid, diethyl ester, S-ester with thionophosphoric acid, dimethyl ester (malathion) phosphorothioic acid, 0,0-dimethyl, O-p-nitrophenyl ester (methyl parathion) methylcarbamic acid, ester with a-naphthol (carbaryl) methyl N-[[(methylanιino)carbonyl]o--iy]ethaninύdothioate (methomyl) N'-(4-cUoro-o-tolyl)-N,N-dimethylformamidine (chlordi-meform) 0,0-diethyl-0-(2-isopropyl-4-methyl-6-pyrimidyl)phosphorothi oate (diazinon) octachlorocamphene (toxaphene)

O-ethyl O-p-nitrophenyl phenylphosphonothioate (EPN) cyano(3-pheno^rphenyl)-methyl 4-chloro-α-(l-methylethyl)benzene- acetate (fenvalerate) (3-phenoxyphenyl)methyl (+)-cis,trans-3-(2,2-dichloroethenyl)-2,2- dimethylcyclopropanecarbo-sylate (permethrin) dimethyl N,N'-[thiob-b(N-methyliπm thioate] (thiodicarb) phosphorothiolothionic acid, 0-ethyl-0-[4-(methylthio)phenyl]-S-n-propyl ester (sulprofos) α-cyano-3-phenoxybenzyl 3-(2,2-dicUorovinyl)-2,2-dimethylcyclopropane carboxylate (cypermethrin) cyano(3-phenoxyphenyl)methyl 4-(difluoromethoxy)-α-(methylethyl)- benzeneacetate (flucythrinate) 0,0-diethyl-0-(3,5,6-trichloro-2-pyridyl)phosphorothioate (chlorpyrifos) 0,0-dimethyl-S-[(4-oxo-l,2,3-benzotriazin-3-(4H)-yl)-methyl] phosphoro- dithioate (azinphos-methyl)

5,6-α methyl-2-dimethylan-uno-4-pyrimidinyl dimethyl carbamate (piiimicarb) S-(N-formyl-N-niethylcarbamoylniethyI)-0,0-diniethylphosphor odithioate

(formothion) S-2-(ethylthioethyl)-0,0-dimethyl phosphiorothioate (demeton-S-methyl) α-cyano-3-phenoxybenzyl cis-3-(2,2-dibromovinyl)-2,2-dimethyl- cyclopropane carboxylate (deltamethrin) cyano(3-phenoxyphenyl)methyl ester of N-(2-chloro-4-trifluoromethyl- phenyDalanine (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.

Tegt 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 ofVenturia 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 Cercospnr JVF p rp ^p πfltr TT ¹ (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 Euc l-ύa 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 orvzae (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 Phvtophthora jnfejψ p (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.

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 ofBotrytis cjnerea (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.

TWDEX TO TABLE A X-B-ON-O-W-Z-A ¹

S02R ¹

¹ mp CO

160-162

4 OCH ₃ -Ph 120-125

Ph 128-132

4 CN-Ph 140-144

4 Nθ ₂ -Ph 90-93

4 Me-Ph oil ²

3 CF ₃ -Ph 108-110

4 CF ₃ -Ph 146-149

93-95

4 CF ₃ -Ph 139-141

4 OCH ₃ -Ph 69-73

Ph 118-121

4 CN-Ph 132-135

4 N0 ₂ -Ph 159-162

4 Me-Ph 96-98

3 CF-a-Ph βil3 158-162

4 OCH ₃ -Ph 120-124

Ph 106-109

4 CN-Ph 179-181

4 Nθ ₂ -Ph 164-168 4 Me-Ph 90-93

Cmpd

£ E ^J II - "■p t -c ⁾

81 (Mβ) ₂ -N CO 3 OCH ₃ -Ph CO 3 CF ₃ -Ph oil* 82 (Mβ) ₂ -N CO 3 OCH ₃ -Ph CO 4 CF ₃ -Ph 118-120 83 (Mβ) ₂ -N CO 4 Br-Ph CO 3 Cl-Ph 126-129 84 (Mβ) ₂ -N CO 4 Br-Ph CO 3 CF ₃ -Ph 107-111 85 (Mβ) ₂ -N CO 4 Br-Ph CO 3 CH ₃ -Ph 125-128 86 (Me) ₂ -N CO 4 Br-Ph CO 2-naphthyl 118-121 87 (Mβ) ₂ -N CO 4 Br-Ph CO p-biphβnyl 165-170 88 (Me) ₂ -N CO 4 CF ₃ -Ph CO 89 (Me) ₂ -N CO 4 CF ₃ -Ph H

90 (Me) ₂ -N CO 4 CF ₃ -Ph CO

91 (Mβ) ₂ -N CO 4 CF ₃ -Ph CO

92 (Me) ₂ -N CO 4 CF ₃ -Ph CO

93 (Mβ) ₂ -N CO 4 CF ₃ -Ph CO

94 (Me) ₂ -N CO 4 CF ₃ -Ph CO

95 (Me) ₂ -N CO 4 CF ₃ -Ph CO

96 (Mβ) ₂ -N CO 4 Cl-Ph CO

97 4 t-Bu-Ph H 98 4 t-Bu-Ph CO 99 4 t-Bu-Ph CO 100 4 t-Bu-Ph CO 101 4 t-Bu-Ph CO 102 4 t-Bu-Ph CO 103 4 t-Bu-Ph CO 104 4 t-Bu-Ph CO 105 CH ₂ (4 OCH ₃ -Ph) H 106 CH ₂ (4 OCH ₃ -Ph) CO 107 CH ₂ (4 OCH ₃ -Ph) CO 108 CH ₂ (4 OCH ₃ -Ph) CO

p CO

4 Nθ -Ph 136-139

3 CF ₃ -Ph oil ⁵

4 CF ₃ -Ph 103-106 4 Me-Ph oil*

4 OCH ₃ -Ph 108-112

Ph 54-58

3 CF ₃ -Ph 85-88

4 CF ₃ -Ph 93-97

4-CN-Ph 132-135

4 Me-Ph 77-81

2-benzo- 160-165 thiophβne

175-180

4 OCH ₃ -Ph 78-82

Ph 100-104

4 CN-Ph 138-142

4 Nθ ₂ -Ph 146-150

4 Me-Ph 80-85

3 CF ₃ -Ph 110-112

4 CF ₃ -Ph 130-134 -naphthyl 107-112 2-naphthyl 113-116 2-naρhthyl 147-150 2-methyl- oil? naphthyl

Cmpd £_ X £ E ¹ H Z h ¹ CO

162 (Mβ) ₂ -N CO 3-thiophene CO - 3 CF ₃ -Ph 88-92

163 (Mβ) ₂ -N CO 3-thiophβne CO - 4 CF ₃ -Ph 126-128

164 (ciβ-2,6-Me ₂ CO 4 Cl-Ph H - - 184-186 morpholine

200MH NMR FOR FOOTNOTED COMPOUNDS

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

2. δ 8.38 (m, IH), 7.9 (m, 3H), 7.7 (m, 2H), 7.23 (d, J--B.1 Hz, 2H), 3.93 (s, 3H, C0 ₂ CH ₃ ), 3.33 (s, 3H, NCH3), 2.92 (s, 3H, NCH3), 2.40 (s, 3H, ArCH ₃ ).

3. δ 8.0-8.4 (m, 4H), 7.9 (d, J=8 Hz, IH), 7.7 (m, 3H), 3.26 (s, 3H, NCH3), 3.10 (s, 3H, NCH3).

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

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

5. δ 8.21 (ε, IH), 8.07 (d, J=7.8 Hz, IH), 7.87 (d, J=7.8 Hz, IH), 7.60 (t,

J=7.8 Hz, IH), 7.35 (d, J=8.7 Hz, 2H), 6.59 (d, J=8.7 Hz, 2H), 4.65 (s, 2H, -CH ₂ -), 3.48 (s, 3H, OCH3), 3.09 (s, 6H, N(CH ₃ )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, -CH ₂ -), 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, IH), 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 TEST

TEST TEST TEST TEST TEST TEST TEST

! Percent control at 40 ppm the highest concentration tested, a Tested at 100 ppm. ^b Tested at 20 ppm.