This invention relates to new arthropodicidal and nematocidal compounds, to methods of preparing these compounds, to new arthropodicidal or nematocidal compositions containing the compounds and to methods of controlling arthropods and/or nematodes using such compositions.

Insecticidal activity has been reported for certain triazolyl sulfonic acid esters in United States Patent 3.966.754. Insecticidal and nematocidal activity has also been described for various pyridyl sulfonic acid esters in United States Patents 4,652.574 and 4.987,141.

The present invention is based on the discovery of high levels of arthropodicidal and nematocidal activity for novel substituted 1.2,4-triazolyl sulfonates.

This invention provides arthropodicidal compounds of Formula I, including all geometric and stereoisomers and all agriculturally suitable salts thereof.

In another aspect, this invention also provides agricultural compositions comprising compounds of Formula I and their use for the control of arthropods and nematodes in both agronomic and non-agronomic uses. The compounds are -

R SO ₂ - O - Q I wherein: Q is selected from the group Q-l to Q-4

Q-l Q-2

Q-3 Q-4

R is selected from the group C C_ alkyl and C C haloalkyl;

R ¹ is selected from the group C,-C ₆ alkyl, C,-C ₆ haloalkyl, C,-C ₅ cyanoalkyl,

C ₂ -C ₆ alkenyl, C ₂ -C ₆ haloalkenyl, C ₂ -C ₆ alkynyl, C ₂ -C ₆ haloalkynyl, C ₃ -C ₆ cycloalkyl, C ₃ - C ₆ halocycloalkyl, C ₄ -C ₇ cycloalkylalkyl, C ₄ -C ₇ halocycloalkylalkyl, optionally substituted phenyl and optionally substituted benzyl;

R ² is selected from the group C,-C ₆ alkylthio, C,.C ₆ alkylsulfmyl, C,-C ₆ alkylsulfonvl, C _: - C ₆ alkenylthio, C ₂ -C ₆ alkenylsulfinyl, C ₂ -C ₆ alkenylsulfonyl, C ₂ -C ₆ alkynylthio. C ₂ -C ₆ alkynylsulfinyl and C ₂ -C ₆ alkynylsulfonyl, each optionally substituted with one or more members independently selected from R ⁵ ; C ₃ -C ₆ cycloalkylthio, C ₃ -C ₆ cycloalkylsulfinyl, C ₃ -C ₆ cycloalkylsulfonyl, C ₄ -C ₇ cycloalkylalkylthio, C ₄ -C ₇ cycloalkylalkylsulfinyl, and C ₄ -C ₇ cycloalkylalkylsulfonyl, each optionally substituted with one or more members independently selected from R ⁵ ; SO ₂ F; optionally substituted heteroarylthio : SO ₂ NfR*)R ⁷ ; C(S)N(R ⁸ )R ⁹ ; and C(O)N(R ⁸ )R ⁹ ;

R ³ is selected from the group C ₂ -C ₆ alkylsulfonyl, C ₂ -C ₆ alkylcarbonyl, C ₃ -C ₆ cycloalkylsulfonyl, C ₄ -C ₇ cycloalkylalkylsulfonyl,

C ₂ -C ₆ alkenylsulfonyl and C ₂ -C ₆ alkynylsulfonyl, each of which is optionally substituted with R ⁵ ; SO ₂ N(R ⁶ )R ⁷ ; C(S)N(R ⁶ )R ⁷ ; and C(O)N(R ⁸ )R ⁹ ;

R ⁴ is selected from the group H, C,-C ₆ alkyl. C,-C ₆ haloalkyl, C,-C ₆ alkoxy. C,- haloalkoxy, C,-C ₆ alkylthio, C,-C ₆ haloalkylthio. C ₂ -C ₆ alkoxycarbonyl. C ₂ -C ₆ alkylcarbonyl, formyl, halogen, amino. C,-C ₆ alkylamino, C,-C ₆ dialkylamino. optionally substituted phenyl. and optionally substituted benzyl;

- _>

R ⁵ is selected from the group halogen. CN. SCN, NO,, OH. OR ^lÏ… . SR ^lÏ… . S(O)R'°. S(O) ₂ R ¹⁰ , OC(O)R'°, OS(O) ₂ R ¹⁰ . CH=N-OR'°, N(COCH ₂ ) ₂ (i.e. succinimidyl). O,CH,.,O. Si(R ^lÏ‹ )(R")(R ^,:! ). CO ₂ R'°, C(O)N(R ⁹ )R'°. C(O)R ¹⁰ , N(R'°)R" and optionally substituted heteroaryl ;

R ⁶ is selected from the group C,-C ₆ alkyl, C,-C ₆ haloalkyl, C,-C _< alkoxy. C -C ₅ alkoxyalkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ haloalkenyl. C ₂ -C ₆ alkynyl. C ₂ -C ₆ haloalkynyl, C _r C ₆ cycloalkyl, C ₄ -C ₇ cycloalkylalkyl, N(R' )R ¹⁴ , phenyl or benzyl optionally substituted with 1 or 2 substituents independently selected from W, and C,-C, alkyl optionally substituted with one or more groups selected from CN, N(R ¹³ )R ¹⁴ and S(O) _n R ¹⁵ ;

R ⁷ is selected from the group H, C C ₂ alkyl, C,-C ₂ haloalkyl, formyl, C ₂ -C ₃ alkylcarbonyl, C ₂ -C ₃ alkoxycarbonyl, C ₃ alkenyl and C ₃ alkynyl; or

R ⁶ and R ⁷ together form -(CH ₂ ) ₄ -, -(CH ₂ ) ₅ - or -CH ₂ CH ₂ -O-CH ₂ CH ₂ -;

R ⁸ is selected from the group C ₂ -C ₆ alkyl, C,-C ₆ haloalkyl, C,-C ₅ alkoxy, C ₂ -C ₅ alkoxyalkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ haloalkenyl, C,-C ₆ alkynyl, C ₂ -C ₆ haloalkynyl, C ₃ -C ₆ cycloalkyl, C ₄ -C ₇ cycloalkylalkyl, N(R ¹³ )R ¹⁴ , phenyl or benzyl optionally substituted with 1 or 2 substituents independently selected from W, and C C_ alkyl optionally substituted with a group selected from CN, N(R ¹³ )R ¹⁴ and S(O) _n R ¹⁵ ;

R ⁹ is selected from the group H, C.-C, alkyl, C C_ alkoxy, C,-C ₂ haloalkyl. formyl, C ₂ -C ₃ alkylcarbonyl, C ₂ -C ₃ alkoxycarbonyl, C ₃ alkenyl, C ₃ alkynyl, and optionally substituted phenyl ; or

R ⁸ and R ⁹ together form -(CH ₂ ) ₄ -, -(CH ₂ ) ₅ - or -CH ₂ CH ₂ -O-CH ₂ CH ₂ -;

R ¹⁰ , R" and R ¹² are independently selected from the group C,-C ₃ alkyl and C,-C ₃ haloalkyl; or

R ⁹ and R ¹⁰ together form -(CH ₂ ) ₄ -, -(CH _{2 5} -, -(CH ₂ ) ₂ O(CH ₂ ) ₂ . or -(CH ,,N(R ⁷ ΪCH ₂ V;

R ^1J and R ¹⁴ are independently selected from the group methyl and ethyl; or

R ¹³ and R ¹⁴ together form -(CH _: ) ₄ -, -(CH,) ₅ - or -CH,CH,-0-CH,CH _: -;

R" is selected from the group C C ₂ alkyl and C,-C-, haloalkyl;

W is selected from the group halogen, C,-C ₂ alkyl, C,-C ₂ alkoxy, CF ₃ and OCF,; and

n is O, 1 or 2:

with the proviso that when Q is Q-2, R and R ¹ are both CH ₃ . then R ² is not cyanomethylthio, 4-chloro-2-butenylthio or methylthioethylthio.

The compounds excluded from the scope of this invention by the above proviso are disclosed in US Patent 3.966,754, being those in which Q is Q-2, R and R ¹ are both CH ₃ i.e. the compounds:

1 -Methyl-5-cyanomethylthio-3-me_hane sulphonyloxy- 1 ,2,4-triazole 1 -Methyl-5-(4-chloro-2-butenylthio)-3-me_hane sulphonyloxy- 1 ,2.4-triazole 1 -Methyl-5-methylthioethylthio-3-methane sulphonyloxy- 1 ,2,4-triazole

Preferred compounds A of the invention are compounds of formula I wherein: R is CH ₃ ; Q is Q-l, Q-2, Q-3 or Q-4.

Preferred compounds B are the compounds of Preferred A wherein Q is selected from Q- 1 and Q-2 and R ¹ is selected from C,-C ₆ alkyl.

Preferred compounds C are the compounds of Preferred A wherein Q is selected from Q- 1 and Q-2. R ² is selected from C,-C ₆ alkylthio and C ₃ -C ₆ alkenylthio each optionally substituted with R ⁵ .

Preferred compounds D are the compounds of Preferred A wherein Q is selected from Q-

1 and Q-2 and R- is selected from SO _:

Preferred compounds E are the compounds of Preferred A wherein Q is selected from Q- l and Q-2 and R ² is selected from C(S) N(R ⁶ )R ⁷ and σθ)N(R")R ⁹

Particularly preferred compounds of the invention are compounds of formula I wherein: R is CH ₃ ; Q is Q-2; R ¹ is CH ₃ ;

R ² is selected from C C ₆ alkylthio and C ₃ -C ₆ alkenylthio each optionally substituted with one or more members independently selected from R ⁵ ; C,-C ₆ alkyl sulfamoyl and C ₂ -C ₆ alkyl carbamoyl.

Specifically preferred compounds for biological activity are the following compounds:

1 -Methyl-N-( 1 -methylethyl)-3-methanesulfonyloxy- 1 ,2,4-triazole-5-sulfonamide; 1 -Methyl-N-( 1 -methylethyl)-3-methanesulfonyloxy- 1 ,2,4-tri_-Zθle-5-carboxamide;

1 -Methyl-3-methanesulfonyloxy-5-(3,4,4-trifluorobut-3-enyl)th io- 1 ,2,4-triazole

1 -Methyl-3-methanesulfonyloxy-5-(N,N-dimethylcarbamoyl)methyl thio- 1 ,2,4- triazole

1 -Isopropyl-3-methanesulfonyloxy-5-(N,N-dimethylcarbamoyl)met hylthio- 1.2,4- triazole

1 -Methyl-3-methanesuifonyloxy-5-(succinimid- 1 -yl)methylthio- 1.2,4-triazole

In all of the above, the terms "optionally substituted phenyl", "optionally substituted benzyl", "optionally substituted heteroaryl" and "optionally substituted heteroarylthio" denote phenyl, benzyl, heteroaryl or heteroarylthio groups which can be substituted by one or more groups independently selected from halo, alkyl, haloalkyl, alkoxy. haloalkoxy, alkylthio, cyano, and nitro.

In all of the above, the term "alkyl" used either alone or in compound words such as "haloalkyl", denotes straight or branched alkyl including methyl, ethyl, /.-propyl. isopropyl, or the different butyl, pentyl or hexyl isomers. Alkoxy denotes methoxy, ethoxy. «-propyloxy, z ^' so-propyloxy and the different butoxy or pentoxy isomers.

"Alkenyl" denotes straight or branched chain alkenes such as vinyl. 1 -propenyl. 2- propenyl, 3-propenyl and the different butenyl, pentenyl and hexenyl isomers. "Alkynyl" denotes straight chain or branched alkynes such as ethynyl. 1 -propynyl. 3-propynyl and the different butynyl, pentynyl and hexynyl 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. Examples of haloalkyl include CH ₂ CH ₂ F, CF ₂ CF ₃ and CH ₂ CHFC1. The terms "haloalkenyl" and "haloalkynyl" are defined analogously to the term "haloalkyl".

The total number of carbon atoms in a substituent group is indicated by the "C,-C." prefix where i and j are numbers from 1 to 7. For example, C ₂ alkylcarbonyl designates C(O)CH ₃ and C ₃ -alkylcarbonyl designates C(O)CH ₂ CH ₃ ; C,-alkoxycarbonyl designates C(O)OCH ₃ and C ₃ -alkoxycarbonyl designates C(O)OCH ₂ CH ₃ and C ₃ - alkoxyalkyl designates CH ₂ OCH ₂ CH ₃ , CH ₂ CH ₂ OCH ₃ and CH(CH ₃ )OCH ₃ .

Examples of compounds within the scope of this invention are given in Tables 1 to 4 which follow. In these tables, the following abbreviations for various alkyl chains and rings have been used.

TABLE 1

TABLE 2

- 9 -

TABLE 2 (continued)

TABLE 2 (continued)

a 3,5-(CH ₃ ) ₂ -isoxazol-4-yl-CH ₂ S b 4-Cl-2-CH ₃ S-6-pyrimidinyl-S

TABLE 3

TABLE 4

H

Compound Synthesis

Compounds of Formula I wherein Q is Q-l, Q-2, Q-3 or Q-4 are prepared from the corresponding 3- or 5-hydroxytriazole by reaction with the appropriate suifonvl halide in the presence of a base such as triethyamine or pyridine in an inert solvent such as dichloromethane.

Compounds of Formula I wherein Q is Q- 1 can be prepared from the hydroxy triazole II A by reaction with a sulfonylhalide of formula R-SO ₂ Hal. wherein R. R ¹ and R ² are as previously defined and Hal represents halogen.

II A I A

The hydroxytriazoles of formula II A can be prepared by a number of different methods and the choice of synthetic route depends to some extent on the particular substituents R ¹ and R ² . When the substituent R ¹ is an alkyl, substituted alkyl, phenyl or substituted phenyl group and the substituent R ² forms a thio ether linkage with the triazole ring the compounds of formula II A can conveniently be prepared from the corresponding mercapto triazoles of formula III A.

HI A IV A

The thio ether IV A formation may be carried out by alkylation of the thiol with the appropriate substituted alkyl, alkenyl or alkynyl halide in the presence of a base.

The compounds of formula II A wherein substituent R ² is a sulfonamide group may be prepared by oxidative chlorination of the corresponding mercapto triazole of formula III A (or a suitable thio ether derivative) to the suifonvl chloride and then reaction with the appropriate amine to give the sulfonamides of formula V A.

5

10 III A V A

It may also be advantageous to convert the intermediate suifonvl chloride to the corresponding sulfonyl fluoride by reaction in situ with potassium hydrogen difluoride. Use of the more stable triazole sulfonyl fluoride may give a better conversion of the 15 mercapto triazole III A to the sulfonamide V A.

The compounds of formula II A wherein substituent R ² is an amide group may be prepared by a number of methods including the reaction of a suitable oxamate ester with a substituted semicarbazide, followed by base-catalysed ring closure to the triazole VI A. 20

R ⁹ (R ⁸ )NC(0)Cθ ₂ Alk + H ₂ NN(R )CONH ₂

VI A

30 In the formulae IV A, V A and VI A, R ⁶ . R ⁷ , R ⁸ and R ⁹ are as previously defined and Alk represents C,-C _ft alkyl, C ₂ -C ₆ alkenyl, C _: -C ₆ alkynyl, each substituted with R ⁵ as previously defined, C ₃ -C ₆ cycloalkyl and cycloalkylalkyl.

Compounds of Formula I wherein Q is Q-2 can be prepared from the hydroxytnazole II B by reaction with a suitable alkylsulfonvl halide of formula RSO ₂ Hal and where R. R'. R ² and Hal are as previously defined.

II B I B

The hvdroxytriazoles of formula II B can be prepared by a variety of different methods including analogous methods to those outlined above for the isomeric compounds of formula II A. Thus, the thio ether derivatives IV B and the sulfonamides V B can each be prepared from the mercapto triazoles III B.

III B IV B

The carboxamide derivatives VI B can be formed from the appropriate

1 -substituted semicarbazide and an oxamate ester as outlined for the analogous compounds VI A above.

V B V1 B

General information about the synthesis of hydroxytriazoles of formula II A and II B is available in the chemical literature. The related hydroxytriazoles II C and II D may also be prepared by various general methods which are described in the literature. For

example, see "The Chemistry of Heterocyclic Compounds". Volume 37. 1.2.4-Triazoles by C Temple, Editor J A Montgomery. Wiley. New York 1981.

ii c Π D

The thio ether triazoles of formulae IV A and IV B can be converted to the corresponding sulfoxides and sulfones by various oxidation conditions which are well known to those skilled in the art.

The compounds of formula I wherein R ² and R ³ are C(S)N(R ⁶ )R ⁷ can be prepared by reaction of the corresponding compounds wherein R ² and R ³ are C(O)N(R )R ⁹ with phosphorous pentasulfide or Lawessons reagent (2,4-bis(methoxyphenyl)-l,3-dithia-2,4- diphosphetane-2,2-disulfide) .

The compounds of the invention, their preparation and properties are illustrated by the following non-limiting examples.

EXAMPLE 1

Preparation of 1 -methyl-N-( 1 -methylethyl)-3-methanesulfonyloxy- 1.2.4-tπazole-5- sulfonamide (Compound No 2-2)

(i) 1 -Methyl-3-hyάroxy- J , 2, 4-triazole-5-sulfonylβuoride

A solution of potassium hydrogen difluoride ( 12 g) and l-methyl-3-hydroxy-5- mercapto-1.2,4-triazole (2.0 g) in water (100 ml) was stirred and cooled in an ice bath. Chlorine gas was bubbled gently through the solution for approximately 30 minutes and the temperature of the solution was maintained between 5° and 10°C.

A small amount of unidentified solid was removed by filtration and the filtrate was concentrated under reduced pressure and then extracted with diethyl ether (2x100 ml). The ether layer was separated, dried (MgSO ₄ ) and evaporated to give the crude sulfonylfluoride product (500 mg) as a white crystalline solid. Infrared spectrum (nujol mull): 1582, 1220, 883, 806 cm ^-1 .

(ii) 1 -Methyl-N-(1 -me thy le thy I) -3-hydroxy- 1 -2-4-triazole-5-sulfonamide

Isopropylamine (1 ml) was added dropwise to a cooled solution of l-methyl-3- hydroxy-l,2,4-triazole-5-sulfonylfluoride (300 mg) in acetonitrile (20 ml). The reaction mixture was left at room temperature for 20 hours and then poured into water (30 ml) and extracted with ethyl acetate. The ethyl acetate layer was separated, dried over magnesium sulfate and then the solvent removed under reduced pressure to give the title sulfonamide as a clear, viscous oil (300 mg). Proton magnetic resonance spectrum (CDC1 ₃ ): δ 1.24 (d, 6H), 3.68 (m. IH), 4.05 (s, 3H), 5.86 (d, IH), 9.0 (broad, IH).

(Hi) l-Methyl-N-(l-methylethyl)-3-methanesulfonyloxy-l,2,4-tria∠‘ole-5-sulfonamide To a solution of l-methyl-N-(l-methylethyl)-3-hydroxy-l,2.4-triazole-5- sulfonamide (440 mg) in dichloromethane (30 ml) was added triethylamine (0.35 ml). The solution was cooled to 5°C and methanesulfonyl chloride (0.18 ml) was added dropwise. The reaction mixture was stirred at room temperature for 24 hours and then washed with cold water and the organic layer separated and dried

over magnesium sulfate. Evaporation of the solvent gave crude product which was purified by chromatography on silica gel. using chloroform as eluent. The title compound was isolated as a white solid, mp 85-86 °C. proton magnetic resonance spectrum (CDC1 ₃ ): δ 1.25 (d. 6H), 3.44 (s, 3H), 3.73 (m. IH), 4.12 (s, 3H), 5.2 (broad, IH).

EXAMPLE 2

Compounds No. 2-32, 2-33, 2-34, and 2-35 were prepared from the 5-sulphonyl fluoride following procedures similar to those described in Example 1. Their proton magnetic resonance spectra or melting point data are given in Example 9.

EXAMPLE 3

Preparation of 1 -methyl-3-methanesulfonyloxy-5-(3-cyanopropyl)mercapto- 1 ,2,4-triazole (Compound No 2-1)

(i) 1 -Methyl-3-hydroxy-5-(3-cyanopropyl)mercapto-l ,2,4-t azole

A solution of l-methyl-3-hydroxy-5-mercapto-l_2,4-triazole ( 1.57 g), 4-bromobutyronitrile (1.19 ml) and triethylamine (1.68 ml) in ethanol (25 ml) was heated under reflux until thin layer chromatography indicated that reaction was complete (5 hours). The solvent was removed under reduced pressure and the residue was dissolved in water (50 ml) and extracted with ethyl acetate (2x100 ml). The organic extracts were combined, dried over magnesium sulfate and then evaporated to give the crude product as a pale yellow semi-solid. Recrystallization from ethanol gave the title compound (1.40 g 64%). as a white powder, mp 130-131 C. proton magnetic resonance spectrum (CDC1.): δ 2.10 (m. 2H), 2.56 (t. 2H), 3.25 (t, 2H). 3.65 (s, 3H).

(ii) I -Methyl-3-methanesulfonyloxy-5-( 3 -cyanopropyh mercapto- 1.2.4-ιrιazolc

A solution of l-methyl-3-hydroxy-5-(3-cyanopropyl)triazole (0.79 g) was treated with triethylamine (0.83 ml) and then cooled in an ice bath. Methanesulfonyl chloride (0.39 ml) was added dropwise to the stirred reaction mixture and after warming to room temperature and stirring for 3 hours, cold water was added. The dichloromethane layer was separated, the aqueous phase extracted with more dichloromethane and the combined organic extracts were dried over sodium sulfate. filtered and evaporated to give the title compound as a light brown oil. On standing for several days the compound solidified to a waxy solid, mp 68-70°C.

Proton magnetic resonance spectrum (CDC1 ₃ ): δ 2.15 (m, 2H). 2.55 (t, 2H). 3.33 (t, 2H), 3.42 (s, 3H), 3.72 (s, 3H).

EXAMPLE 4

Compounds No 2-5, 2-6, 2-7, 2-8, 2-10, 2-1 1, 2-12, 2-13, 2-26, 2-27, 2-28, 2-30, 2-31, 2-36, 2-38 to 2-41, 2-44 to 2-48, 2-50-2-57 and 2-59 to 2-76 were prepared from the appropriate 3-hydroxy-5-mercapto-l,2,4-triazole following a similar procedure to that described in Example 3. Each product was characterized by various spectral methods. Their proton magnetic resonance spectra or melting point data are recorded in Example 9.

EXAMPLE 5

Preparation of l-methyl-3-methanesulfonyloxy-5-(3-cyanopropyl)sulfonyl-l,2, 4-triazole (Compound 2-4)

A solution of Compound No 2-1 (0.34 g) in acetic acid (2 ml) was treated with 30% hydrogen peroxide solution (0.56 ml) and the mixture was heated for 5 hours at 80°C. The cooled mixture was diluted with water (20 ml) and extracted with methvlene chloride (3x30 ml). The organic layers were combined, washed with water, dilute sodium hvdroxide solution, water, and then dried over sodium sulfate. The methvlene chloride

was evaporated to give the sulfone as a viscous oil (220 mg. 60%).

Proton magnetic resonance spectrum (CDC1,): δ 2.3 (m. 2H): 2.68 (t, 2H); 3.49 (s. 3H):

3.70 (t, 2H): 4.19 (s. 3H).

EXAMPLE 6

Compounds No 2-14, 2-29, 2-58, 2-77 and 2-78 were prepared by oxidation of the appropriate thioether following essentially the same procedure described in example 5. Their proton magnetic resonance spectra or melting point data are recorded in Example 9.

EXAMPLE 7

Preparation of 1 -Phenyl-N-( 1 -methylethyl)-3-methanesulfonyloxy- 1 ,2,4-triazole-5- carboxamide (Compound No 2-3)

(i) l-Phenyl-N-(l-methylethyl)-3-hydroxy-l,2,4-triazole-5-carbox amide

A solution of 1-phenylsemicarbazide (3.0 g) and ethyl N-(l-methylethyl)oxamate (3.2 g) in absolute ethanol (100 ml) was heated to 80° with stirring. A solution of sodium metal (0.5 g) in ethanol (30 ml) was added and the mixture then heated at reflux temperature for several hours as a precipitate gradually separated. The reaction mixture was poured into ice-water and the solution acidified with cone, hydrochloric acid. The aqueous solution was extracted with chloroform (2x200 ml) and the organic solution was separated and evaporated to a pale yellow solid.

Purification by chromatography on silica gel (80 g) using chloroform as eluent gave the pure hydroxy triazole in an intermediate fraction as a colourless solid (0.75 g).

Proton magnetic resonance spectrum (CDC1 ₃ ): δ 1.22 (d. 6H); 4.13 (m, IH); 7.0 (bd. IH); 7.50 (s. 5H).

(ii) 1 -Phenyl-N-( 1 -methylethyl)-3-methanesulfonyloxy- 1.2.4-triazole-5-carboxamide

The title compound was prepared from the hydroxytnazole described in part ( i) above and using essentially the same procedure as given in Example 1 , pan (iii). The compound was isolated as a pale orange crystalline solid and was characterized by its spectral properties. Proton magnetic resonance spectrum (CDC1 ₃ ): δ 1.23 (d. 6H);

3.48 (s, 3H); 4.13 (m, IH); 7.08 (bd, IH); 7.52 (s, 5H).

EXAMPLE 8

Compounds No 1-1, 2-9, 2-37, 2-42. 2-43, and 2-49 were prepared from the appropriate semicarbazide by reaction with the appropriate ethyl N-(l -alkDoxamate following a similar pathway to that given in Example 7. The products were purified by chromatography and characterized by their proton magnetic resonance spectra details of which are given in Example 9.

EXAMPLE 9

Many of the compounds of the invention were obtained as oils and were characterized primarily by their nuclear magnetic resonance spectra. The spectra are recorαed below in Table 5:

TABLE 5

TABLE 5 (CONTINUED)

TABLE 5 (CONTINUED)

. ~ι .

TABLE 5 (CONTINUED)

Formulation

The compounds of this invention will generally be used in a formulation with an agriculturally suitable carrier comprising one or more liquid or solid diluent(s) or organic soivent(s). Useful formulations of the compounds of Formula 1 can be prepared in conventional ways. They include dusts, granules, baits, pellets, solutions, suspensions, emulsions, wettable powders, emulsifiable concentrates, dry flowables and the like. Many of these can be applied directly. Sprayable formulations can be extended in suitable media and used at spray volumes of from about one to several hundred liters per hectare. High strength compositions are primarily used as intermediates for fuπher formulation. The formulations, broadly, contain from less than 1% to 99% by weight of active ingredient(s) and at least one of a) about 0.1% to 20% surfactants) and b) about 5% to 99% solid or liquid diluent(s). More specifically, they will contain effective amounts of these ingredients in the following approximate proportions:

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 somewhat 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, New Jersey. The more absoφtive diluents are preferred for wettable powders and the denser ones for dusts. Typical liquid diluents and solvents are described in Marsden, "Solvents Guide". 2nd 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". Allured Publ. Coφ., Ridgewood, New Jersey, as well as Sisely and Wood, "Encyclopedia of Surface Active Agents", Chemical Publ. Co., Inc., New York, 1964. list surfactants and recommended uses. All formulations can contain minor amounts of additives to reduce foam, caking, corrosion, microbiological growth, etc. Preferably, ingredients should be approved by the US Environmental Protection Agency for the use intended.

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. Granules and pellets can 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 147 and following, and "Perry ^' s Chemical Engineer ^' s Handbook", 4th Ed., McGraw-Hill, New York, 1963, pages 8 to 59 and following.

Typical formulations and methods for their manufacture are given below:

FORMULATION A Emulsifiable Concentrate

1 -Methyl-N-( 1 -me.hylethyl)-3-methylsulfonyloxy- 1 ,2.4-triazole-5- sulfonamide (Compound No 2-2) 20% blend of oil soluble sulfonates and polyoxyethylene ethers 10% isophorone 70%

The ingredients are combined and stirred with gentle warming to speed solution. A fine screen filter is included in packaging operation to ensure the absence of any extraneous undissolved material in the product.

FORMULATION B Wettable Powder

Compound No 2-2 30% sodium alkylnaphthalenesulfonate 2% sodium ligninsulfonate 2%

Synthetic amoφhous silica 3% kaolinite 63%

The active ingredient is mixed with the inert materials in a blender. After grinding in a hammermill, the material is re-blended and sifted through a 50 mesh screen.

FORMULATION C Dust

Wettable powder of Example B 10% pyrophyllite (powder) 90%

The wettable powder and the pyrophyllite diluent are thoroughly blended and then packaged. The product is suitable for use as a dust.

FORMULATION D Granule

Compound No 2-2 10% attapulgite granules (low volatile matter. 90%

0.71/0.30 mm; USS No 25-30 sieves)

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The active ingredient is dissolved in a volatile solvent such as acetone and sprayed upon dedusted and pre-warmed attapulgite granules in a double cone blender. The acetone is then driven off by heating. The granules are then allowed to cool and are packaged.

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FORMULATION E Granule

Wettable powder of Example B 15% gypsum 69% 0 5 potassium sulfate 16% 0

The ingredients are blended in a rotating mixer and water sprayed on to accomplish granulation. When most of the material has reached the desired range of 0.1 to 0.42 mm (USS No 18 to 40 sieves), the granules are removed, dried and screened. Oversize 0 material is crushed to produce additional material in the desired range. These granules contain 4.5% active ingredient.

FORMULATION F Aqueous Suspension

5 Compound No 2-2 40% polyacrylic acid thickener 0.3% dodecyclophenol polyethylene glycol ether 0.5% disodium phosphate 1.0% monosodium phosphate 0.5% 0 polyvinyl alcohol 1.0% water 56.7%

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

FORMULATION G Solution

Compound No 2-1 25%

N-methyl-pyrrolidone 75%

The ingredients are combined and stirred to produce a solution suitable for direct, low volume application.

FORMULATION H Oil Suspension

Compound No 2-1 35% blend of polyalcohol carboxylic esters and 6% oil soluble petroleum suifonates xylene range solvent 59%

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

FORMULATION I Bait Granules

Compound No 2-7 3% blend of polyethoxylated nonylphenols and 9% sodium dodecylbenzene suifonates ground up corn cobs 88%

The active incredient and surfactant blend are dissolved in a suitable solvent such as

acetone and sprayed onto the ground corn cobs. The granules are then dried and packaged.

Formulations with other active ingredients

Compounds of Formula I can also be mixed with one or more other insecticides, fungicides, nematocides. bactericides, acaricides or other biologically active compounds to form a multi-component pesticide giving an even broader spectrum of effective agricultural protection. Example of other agricultural protectants with which compounds of this invention can be formulated are:

Insecticides:

3-hydroxy-N-methylcrotonamide(dimethylphosphate)ester (monocrotophos) methylcarbamic acid, ester with 2,3-dihydro-2,2-dimethyl-7-benzofuranol (carbofuran) O-[2,4,5-trichloro-α-(chlorome-hyl)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- -nitrophenyl ester (methyl parathion) methylcarbamic acid, ester with α-naphthol (carbaryl) methyl O-(methylcarbamoyl)thiolacetohydroxamate (methomyl)

N ^, -(4-chloro-o-tolyl)-N,N-dimethylformamidine (chlordimeform)

O,O-diethyul-O-(2-isopropyl-4-methyl-6-pyrimidylphosphoro -thioate (diazinon) octachlorocamphene (toxaphene) O-ethyl-O- -nitrophenyl phenylphosphonothioate (EPN)

(S)-α-cyano-m-phenoxybenzyl ( 1 R,3R)-3-(2,2-dibromovinyl)-2,2- dimethylcyclopropanecarboxylate (deltamethrin)

Methyl-N'N ^, -dimethyl-N-[(methylcarbamoyl)oxy]-l-thioox amimidate (oxamyl) cyano(3-phenoxyphenyl)-methyl-4-chloro-a-(methylethyl)-benze neacetate (fenvalerate) (3-phenoxyphenyl)methyl (±)-c/ ,trα«5-3-(2,2-dichloro ethenyl)2,2- dimethylcyclopropanecarboxylate (permethrin) α-cyano-3-phenoxybenzyl 3-(2.2-dichlorovinyl)-2.2-dimethylcyclopropane carboxylate

(cypermethrin) -cyano-3-phenoxybenzyl 1 -(4-ethoxyphenyl)-2.2-dichlorocyclopropane 1 -carboxylate

(cycloprothxin)

0-ethyl-S-(p-chlorophenyl)ethylphosphonodithioate (pro enofos) phosphorothiolothionic acid, 0-ethyl-0-[4-(methylthio)-phenyl]-S-/7-propyl ester

(sulprofos)

Additional insecticides are listed hereafter by their common names: trifiumuron. diflubenzuron, methoprene. buprofezin, thiodicarb, acephate, azinphosmethyl. chloφyri fos. dimethoate, fonophos, isofenphos, methidathion, methamidiphos, monocrotphos. phosmet, phosphamidon, phosalone, pirimicarb, phorate, terbufos, trichlorfon, methoxychlor, bifenthrin, biphenate, cyfluthrin, fenpropathrin, fluvalinate, flucythrinate. tralomethrin, metal-dehyde and rotenone.

Fungicides methyl 2-benzimidazolec__rbamate (carbendazim) tetramethylthiur-im disulfide (thiuram) n-dodecylguanidine acetate (dodine) manganese ethylenebisdithiocarbamate (maneb) l,4-dichloro-2,5-dimethoxybenzene (chloroneb) methyl l-(butylcarbamoyl)-2-benzimidazoiec__rbamate (benomyl)

1 -[2-(2,4-dichlorophenyl)-4-propyl- 1 ,3-dioxolan-2-ylmethyl]- 1 H- 1 ,2,4-triazole

(propiconazole)

2-cyano-N-ethylcarbomyl-2-methoxyiminoacetamide (cymoxanil) 1 -(4-chlorophenoxy)-3,3-dimethyl- 1 -( 1 H- 1 ,2,4-triazol- 1 -yl)-2-butanone (triadimefon)

N-(trichloromethylthio)tetrahydrophthalimide (captan)

N-(trichloromethylthio)phthalimide (folpet)

1 -[[[bis(4-fluorophenyl)] [methyl]silyl]methyl]- 1 H- 1 ,2,4-triazole

Nematocides:

S-methyl l-(dimethylcarbamoyl)-N-(methylcarbamoyloxy)-thioformimidate S-methyl 1 -carbamoyl-N-(methylcarbamoyloxy)thio-formimidate

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N-isopropylphosphoramidicacidO-ethylO'-[4-(methyl-thio)-w -tolyl]diester( fenamiphos)

Bactericides: tribasic copper sulfate streptomycin sulfate

Acaricides: senecioic acid, ester with 2-sec-butyl-4,6-dinitrophenol (binapacryl)

6-methyl- 1 ,3-cithiolo[4,5-b]quinoxalin-2-one (oxythioquinox) ethyl 4,4'-dichloroben__ilate (chlorobenzilate)

1 , 1 -bis(p-chlorophenyl)-2,2,2-tachloroethanol (dicofol) bis( pentachloro-2,4-cyclopentadien- 1 -yl) (dienochlor) tricyclohexyltin hydroxide (cyhexatin) trans-5-(4-chlorophenyl)-N-cyclohexyl-4-methyl-2-oxothiazoli dine-3-carboxamide (hexythiazox) amitraz propargite fenbutatin-oxide

Utility

The compounds of this invention exhibit activity against a wide spectrum of foliar and soil inhabiting arthropods and nematodes which are pests of growing and stored agronomic crops, forestry, greenhouse crops, ornamentals, nursery crops, stored food and fiber products, livestock, household, and public and animal health. Those skilled in the art will recognize that not all compounds are equally effective against all pests but the compounds of this invention display activity against economically important agronomic, forestry, greenhouse, ornamental food and fiber product, stored product, domestic structure and nursery pests, such as:

larvae of the order Lepidoptera including fall and beet armyworm and other

Spodoptera spp.. tobacco budworm. corn earworm and other Heliothis spp.. European corn borer, navel orangeworm. stalk/stem borers and other pyralids. cabbage and soybean loopers and other loopers. codling moth, grape berry moth and other tortricids. black cutworm, spotted cutworm, other cutworms and other noctuids, diamondback moth, green cioverworm. velvetbean cateφillar. green cloverworm. pink bollworm, gypsy moth, and spruce budworm;

foliar feeding larvae and adults of the order Coleoptera including Colorado potato beetle, Mexican bean beetle, flea beetle, Japanese beetles, and other leaf beetles, boll weevil, rice water weevil, granary weevil, rice weevil and other weevil pests, and soil inhabiting insects such as Western corn rootworm and other Diabrotica spp., Japanese beetle, European chafer and other coleopteran grubs, and wireworms;

adults and larvae of the other Hemiptera and Homoptera including tarnished plant bug and other plant bugs (miridae), aster lea hopper and other leafhoppers (cicadellidae), rice planthopper, brown planthopper, and other planthoppers (fulgoroidea), psylids, whiteflies (aleurodidae), aphids (aphidae), scales (coccidae and diaspididae), lace bugs (tingidae), stink bugs (pentatomidae), cinch bugs and other seed bugs (lygaeidae), cicadas (cicadidae), spittlebugs (cercopids), squash bugs (coreidae), red bugs and cotton stainers (pyrrhocoridae);

adults and larvae of the order Acari (mites) including European red mite, two spotted spider mide, rust mites, McDaniel mite, and foliar feeding mites;

adults and immatures of the order Orthoptera including grasshoppers;

adults and immatures of the order Diptera including leafminers, midges, fruit flies (tephritidae), and soil maggots;

adults and immatures of the class nematoda including;

Awl nematode Doϋchodorus heterocephatus

Banana nematode Pratylenchus musicola

Bud and leaf nematode Aphelenchoides spp.

Burrowing nematode Radopholus simiius

Carrot root nematode Heterodera carotae

Coffee root-knot nematode Meloidogyne exigua

Corn nematode Praylenchus ∑eae

Dagger nematodes Xiphinema spp.

Golden nematode Globodera rostochiensis

Grass nematode Anguina agrosis

Lance nematodes Hoplolaimus spp.

Lesion nematodes Pratylenchus spp.

Northern Root-knot nematode Meloidogyne hapla

Pea root nematode Heterodera gottmgiana

Peanut root-knot nematode Meloidogyne arenaria

Pin nematodes Paratyienchus spp.

Potato rot nematode Ditylenchus destructor

Reinform nematode Rotylenchulus reinformus

Rice nematode Ditylenchus angustus

Ring nematodes Criconemoides spp.

Smooth-headed lesion nematode Pratylenchus brachyurus

Southern root-knot nematode Meloidogyne incognita

Soybean cyst nematode Heterodera giyctnes

Spiral nematodes Helicotyienchus spp.

Stem and bulb nematode Ditylenchus dipsaci

Sting nematodes Beionolaimus spp.

Stubby-root nematodes Trichodorus spp.

Sugar beet nematode Heterodera schachtii

Tobacco cyst nematode Heterodera tabacum

Tobacco stunt nematode Tylenchorhynchus claytoni

Wheat nematode Anguina tritici

adults and immatures of the order Thysanoptera including onion thrips and other foliar feeding thrips.

The compounds are also active against economically important livestock, household, public and animal health pests such as:

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insect pests of the order Hymenoptera including caφenter ants. bees, hornets and wasps;

insect pests of the order Diptera including house flies, stable flies, face flies, horn flies, blow flies, and other muscoid fly pests, horse flies, deer flies and other Brachycera, mosquitoes, black flies, biting midges, sand flies, sciarids. and other Nematocera;

insect pests of the order Orthoptera including cockroaches and crickets;

insect pests of the order Isoptera including the Eastern subterranean termite and other termites;

insect pests of the order Mallophaga and Anoplura including the head louse, body louse, chicken head louse and other sucking and chewing parasitic lice that attack man and animals;

insect pests of the order Siphonoptera including the cat flea, dog flea and other fleas.

The specific species for which control is exemplified are: boll weevil, Anthonomus grandis; aster leafhopper, Macrosteles fascifrons; black bean aphid, (Aphis Fabae); southern com rootworm. Diabrotica undecimpunctata. The pest control protection afforded by the compounds of the present invention is not limited, however, to these species.

Application

Arthropod and nematode pests are controlled and protection of agronomic crops, animal and human health is achieved by applying one or more of the compounds of this invention, in an effective amount, to the environment of the pests including the agronomic

and/or nonagronomic locus of infestation, to the area to be protected, or directly on the pests to be controlled. Because of the diversity of habitat and behavior of these arthropod and nematode pest species, many different methods. of application are employed. A preferred method of application is by spraying with equipment that distributes the compound in the environment of the pests, in the foliage, animal, person, or premise, in the soil or animal, to the plant part that is infested or needs to be protected. Alternatively, granular formulations of these toxicant compounds can be applied to or incoφorated into the soil. Other methods of application can also be employed including direct and residual sprays, aerial sprays, baits, eartags, boluses, foggers. aerosols, and many others. The compounds can be incoφorated into baits that are consumed by the arthropods or in devices such as traps and the like which entice them to ingest or otherwise contact the compounds.

The compounds of this invention can be applied in their pure state, but most often application will be of a formulation comprising one or more compounds with suitable carriers (including diluents and surfactants) and possibly in combination with a food depending on the contemplated end use. A preferred method of application involves spraying a water dispersion or refined oil solution of the compounds. Combinations with spray oils, spray oil concentrates, and synergists such as piperonyl butoxide often enhance the efficacy of the compounds of Formula I.

The rate of application of the compounds of Formula I required for effective control will depend on such factors as the species of arthropod to be controlled, the pest ^' s life cycle, life stage, its size, location, time of year, host crop or animal, feeding behavior, mating behavior, ambient moisture, temperature, etc. In general, application rates of 0.01 to 2 kg of active ingredient per hectare are sufficient to provide large-scale effective control of pests in agronomic ecosystems under normal circumstances, but as little as 0.001 kg/hectare or as much as 8 kg/hectare may be required. For nonagronomic applications, effective use rates will range from about 1.0 to 50 mg/square meter but as little as about 0.1 mg/square meter or as much as 150 mg/square meter may be required.

The following tests demonstrate the control efficacy of compounds of Formula I on

specific pests. Compounds not mentioned were either not screened or gave mortality levels less than 80%.

TEST A Southern Corn Rootworm

The units, each consisting of a 230 mL plastic cup containing 1 sprouted corn seed, were prepared. The test units were sprayed as described in Test A with individual solutions of the test compounds. After the spray on the cups had dried, five third-instar larvae of the southern corn rootworm (Diabrotica undecimpunctata howardϊ) were placed into each cup. A moistened dental wick was inserted into each cup to prevent drying and the cups were then covered. The cups were then held at 27°C and 50% relative humidity for 48 hours, after which time mortality readings were taken. Of the compounds tested, the following gave mortality levels of 80% or higher: 1-1, 2-1, 2-2, 2-3. 2-4, 2-5, 2-6, 2-7, 2-8, 2-9, 2-12, 2-13, 2-26, 2-28, 2-29, 2-30, 2-31, 2-32, 2-33, 2-34, 2-35. 2-36, 2-37, 2- 38, 2-40, 2-41, 2-42, 2-43, 2-44, 2-45, 2-46, 2-47, 2-48, 2-49, 3-17, 4-21, and 4-23.

TEST B Aster Lealhopper

Test units were prepared from a series of 350 mL cups, each containing oat (Avena sativa) seedlings in a 2.5cm layer of sterilised soil. The test units were sprayed as described in Test A with individual solutions of the below-listed compounds. After the oats had dried from the spraying, between 10 and 15 adult aster leafhoppers (Mascrosteles fascifrons) were aspirated into each of the covered cups. The cups were held at 27°C and 50% relative humidity for 48 hours, after which time mortality readings were taken. Of the compounds tested, the following gave mortality levels of 80% or higher: 2-1, 2-2, 2-4, 2-5, 2-7, 2-26 2-29, 2-30, 2-31, 2-32, 2-33. 2-34. 2-35, 2-37, 2-40, 2-41, 2-42, 2-43, 2-44, 2-45, 2-46, 2-47, 2-48, 2-49, 3-17,

TEST C Boll Weevil

Five adult boll weevils (Anthonomus grandis grandis) were placed into each of a series of 260 mL cups. The test procedure employed was then otherwise the same as in Test

A. Mortality readings were taken 48 hours after treatment. Of the compounds tested, the following gave mortality levels of 80% or higher: 2-1. 2-2, 2-4. 2-5, 2-7, 2-13. 2-14. 2- 26. 2-28. 2-29, 2-30. 2-31, 2-32. 2-33. 2-34, 2-35, 2-40. 2-41. 2-42. 2-44. and 2-46.

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TEST D Black Bean Aphid

Individual nasturtium leaves were infested with 5 to 10 aphids (all stages of Aphis Fabae) and sprayed with their undersides facing up on a hydraulic sprayer as described in Test 0 A. The leaves were then set in 1-inch diameter vials containing sugar water solution and covered with a clear plastic 1 ounce-portion cup to prevent escape of aphids that drop from the leaves. The test units were held at 27°C and 50% relative humidity for 48 hours, after which time mortality readings were taken. Of the compounds tested, the following gave mortality levels of 80% or higher: 2-1, 2-2, 2-4, 2-5, 2-7, 2-28, 2-29, 5 2-30, 2-31, 2-32, 2-33, 2-34, 2-35, 2-36, 2-37, 2-39, 2-40, 2-41, 2-42, 2-44, 2-46, 2-47, 2-48, and 3-17.