WO1994008976A1

WO1994008976A1 - Fungicidal and miticidal aminopyrimidines

Info

Publication number: WO1994008976A1
Application number: PCT/US1993/009163
Authority: WO
Inventors: Renee Marie Lett
Original assignee: E.I. Du Pont De Nemours And Company
Priority date: 1992-10-08
Filing date: 1993-10-01
Publication date: 1994-04-28
Also published as: AU5165093A

Abstract

Compounds having fungicidal and miticidal activity having formula (I) wherein: A is selected from the group CH2, CHCH3, CHCH2CH3, CHCH(CH3)2, CHCH2OH, CH-CH(CH2)2, C(CH2)2 and C(CH3)2; R?1 and R2¿ are independently selected from the group H and CH¿3; R?3 is selected from the group C(CH¿3?)3, Si(CH3)3 and Ge(CH3)3, provided when R?3¿ is Si(CH¿3?)3 or Ge(CH3)3 and R?1¿ is CH¿3?, then A is CH-CH(CH2)2 or C(CH2)2; and R?4¿ is selected from the group H, halogen and CH¿3?.

Description

TITLE FUNGICIDAL AND MITICIDAL AMINOPYRIMIDINES The compounds of this invention are characterized by meta substitution on the aryl ring which is believed to enhance fungicidal activity and contribute to low compound phytotoxicity. This characteristic is not appreciated by art such as U.S. 4,435,402. The specific combination of meta substitution and alkylene bridge substitution distinguishes the fungicidal and miticidal compounds of this invention from those in WO 92/08704.

SUMMARY OF THE INVENTION The invention pertains to compounds of Formula I, including all enantiomers, agriculturally suitable salts thereof, agricultural compositions containing them and their use as fungicides and miticides in both agronomic and nonagronomic environments. The compounds are:

wherein:

A is selected from the group CH₂, CHCH₃, CHCH₂CH₃, CHCH(CH₃)₂, CHCH₂OH, CH-CH(CH₂)₂, C(CH₂)₂ and C(CH₃)₂;

R¹ and R² are independently selected from the group H and CH₃; R³ is selected from the group C(CH₃)₃, Si(CH₃)₃ and Ge(CH₃)₃, provided when R³ is Si(CH₃)₃ or Ge(CH₃)₃ and R¹ is CH₃, then A is CH-CH(CH₂)₂ or C(CH₂)₂; and R⁴ is selected from the group H, halogen and CH₃.

Preferred compounds are those wherein A is selected from the group CHCH₃ and CH₂. Preferred Compound A is the compound wherein A is CHCH₃, R¹ is CH₃, R² is H, R³ is C(CH₃)₃, and R⁴ is H. Preferred Compound B is the compound wherein A is CH₂, R¹ is CH₃, R² is H, R³ is C(CH₃)₃, and R⁴ is H. The term "halogen" denotes fluorine, chlorine, bromine or iodine. The substituent CH-CH(CH₂)₂ is CH-<] and C(CH₂)₂ is C-j . Some of the compounds of this invention can exist as enantiomers. One skilled in the art will appreciate that one enantiomer may be more active than the others and how to separate said enantiomers. Accordingly, the present invention comprises racemic mixtures, individual enantiomers, and optically active mixtures of compounds of Formula I.

DETAILS OF THE INVENTION

Compounds of Formula I can be prepared according to the reaction shown in Scheme 1. In this scheme, Z represents a displaceable group such as a halogen atom, an alkylthio group, or an alkyl-or arylsulfonyloxy group; A, R¹, R², R³, and R⁴ are as previously defined for Formula I.

Schems 1

π m

The reaction of pyrimidine II with amine III is best carried out in the presence of an acid acceptor or base. The base can be triethylamine, pyridine, sodium hydride, or potassium carbonate. The synthetic process can be carried out in the absence or presence of a solvent. Suitable solvents include ethanol, toluene, propanol, xylene, N, N-dimethylformamide, and N, N- dimethylacetamide. Preferred temperatures for this process are about 20°C to 200°C with temperatures between 60°C and 150°C being particularly preferred.

Compounds of Formula I where R² is a CH₃ group can be best prepared by reacting an amine of Formula III where R² is CH₃ with a pyrimidine of Formula II. The amine of Formula III where R² is CH₃ can be prepared by alkylating an amine of Formula III, where R² is equal to hydrogen, using conventional methods known to those skilled in the art.

A particularly useful method for the preparation of some of the amines of Formula III is shown in Scheme 2 where TMS is defined as trimethylsilyl. Scheme 2

R^H, A=CHCH₂CH₃

This process utilizes the method of Hart et al. described in J. Org. Chem., (1983), 48, 289. Amines of Formula III where A is equal to CHCH₂CH₃ are prepared from aldehydes of Formula IV by treatment with lithium hexamethyldisilazide in THF at 0°C followed by addition of ethyl Grignard and refluxing. Aldehydes of Formula IV are either commercially available or can be prepared by reaction of dibromides of Formula V with silver nitrate in refluxing water/dimethoxyethane solvent (Scheme 3).

Scheme 3

rv

The dibromides can, in turn, be prepared from compounds of Formula VI. Aryl methyl compounds of Formula VI are subject to free radical bromination with two equivalents of NBS in the presence of light in refluxing carbon tetrachloride (Scheme 4). Scheme 4

VI

Compounds of Formula VI are either commercially available or can be prepared by conventional methods. Silylated compounds of Formula VI where R³ is equal to trimethylsilyl can be prepared according to the methods described by Habich et al. in Syn., (1979), 841. The compounds of Formula VI where R³ is equal to trimethylgermyl can be made by simple modification of the procedure used for the silylated compounds that will be obvious to one skilled in the art.

Another particularly useful method for the preparation of some amines of Formula m is shown in Scheme 5. Hydrazine exchange on a phthalimide of Formula VII in refluxing methanol efficiently yields amines of Formula El when A is equal to CH₂ or CHMe.

Scheme 5

vn iπ

A=CH₂, CHCH₃ A=CH₂, CHCH₃

The phthalimides of Formula VII are prepared by phthalimide displacement of benzyl bromides of Formula VIII (Scheme 6). Scheme 6

vm vπ

A=CH₂, CHMe A=CH₂, CHMe

The displacement reactions are carried out by heating benzyl bromides of Formula Viπ with potassium phthalimide in a dipolar aprotic solvent like dimethylforamide. The benzyl bromides of Formula VIII can be prepared by free radical halogenation of methyl or ethyl benzenes of Formula LX (Scheme 7).

Scheme 7

IX vm

A=CH , CHMe A=CH₂, CHMe

Bromination of methyl or ethyl benzenes is most efficiently accomplished with one equivalent of Ν-bromosuccinimide (ΝBS) in the presence of light in refluxing carbon tetrachloride.

Another useful method for the preparation of amines of Formula III involves the reduction of oximes of Formula X (Scheme 8). Scheme 8

reducing agent

X m

Q=Me, Et, iPr, cPr A=CHMe, CHEt, CHiPr, CHcPr

This method is especially useful for amines of Formula III where A is equal to CHMe, CHEt, CHiPr, and CHcPr. Oximes of Formula X can be reduced using lithium aluminum hydride or Raney nickel alloy (Obata et. al. Pestic. ScL, (1992), 34, 133) or titanium trichloride/sodium cyanoborohydride (Leeds et al. Syn. Commun., (1988), 18, 777).

Oximes of Formula X are prepared from aryl ketones of Formula XI (Scheme 9).

XI Q=Me, Et, iPr, cPr Q=Me, Et, iPr, cPr

Heating aryl ketones with hydroxylamine hydrochloride in the presence of a buffer (sodium acetate) in an alcohol/water solvent mixture efficiently produces oximes. The aryl ketones of Formula XI are either commercially available or prepared by methods known to those skilled in the art. Amines of Formula III can also be prepared directly from aryl ketones of Formula XI by reductive amination procedures (Borch et al. J. Am. Chem. Soc, (1971), 93, 2897). Another particularly useful method for preparing compounds of this invention where A is equal to CHCH OH is shown in Scheme 10.

Reduction of esters of Formula I with a reducing agent, for example, lithium aluminum hydride, gives an alcohol of Formula I where A is equal to CHCH OH. The reaction is best performed in an ether solvent that dissolves the starting ester (tetrahydrofuran) and at reduced temperatures (0°C). Esters of Formula I where A is equal to CHCO₂Me can be prepared according to Scheme 1 using amines of Formula III where A is equal to CHCO₂Me. These reactions are usually performed in the presence of triethylamine in dimethylformamide at about 100°C. The requisite amine of Formula III can in turn be prepared by the process in Scheme 11.

Scheme 11

Hydrolysis of amine HI, where A is equal to CHCN, with hydrogen chloride in methanol at the reflux temperature of the solvent gives an amine of Formula III where A is equal to CHCO₂Me. Finally, amines of Formula III where A is equal to CHCN can be synthesized from aldehydes of Formula IV according to the reaction in Scheme 12.

Scheme 12

IV m

A=CHCN; R--U

Treatment of aldehydes of Formula IV with trimethylsilyl cyanide in the presence of zinc chloride in methylene chloride at ambient temperature leads to an intermediate which when further treated with ammonia in methanol at 40°C gives the desired amino cyanide product.

Pyrimidines of Formula II can be prepared by a variety of literature methods. Some particularly efficient processes are described by Foster et al. in Org. Syn., (1955), 35, 80 and by JP 58 (83) 222, 070, and EP 370, 391.

It will be recognized that some reagents and reaction conditions described above for preparing compounds of Formula I may benefit by the incorporation of protection deprotection sequences into the synthesis. The use and choice of the protecting group will be apparent to one skilled in the chemical synthesis.

Example 1 Step A: 1— f 1 -bromoethyl)-3-(^" 1.1 -dimethylethyPbenzene The compound, l-(l,l-dimethylethyl)-3-ethylbenzene (20 g, 0.12 mole), N- bromosuccinimide (22 g, 0.12 mole), and benzoyl peroxide (0.1 g) were combined in carbon tetrachloride (250 mL). The mixture was heated to reflux for three hours while being irradiated with a sunlamp. NMR analysis of an aliquot indicated the reaction was complete (10% dibromide, 80% monobromide, 10% starting material). After filtering the cooled mixture, the filtrate was washed with 10% aqueous sodium sulfite, dried (MgSO₄), and concentrated to give the product (30 g, 80% yield) as a pale yellow oil. lH NMR (CDC1₃): δ 7.42 (m, 1H), 7.29 (m, 3H), 5.21 (q, 1H), 2.05 (d, 3H), 1.33 (s, 9H). Step B : 2-\ 1 -\3-( 1 ■ 1 -dimethylethvDphenvIlethyll- 1 H-isoindole- 1.3.2HVdione

The product of Step A (30 g, 0.12 mole) and potassium phthalimide (24 g, 0.13 mole) were dissolved in dimethylformamide (100 mL) and heated at 80°C for two hours. After concentration under vacuum to remove most of the DMF, the residue was partitioned between diethyl ether and water. The organic phase as washed with water, dried (MgSO^, concentrated, and the resultant residue was chromatographed on silica gel with 10% ethylacetate/hexane. The product was isolated as a viscous oil (29 g, 77% yield). ^lH NMR (CDC1₃): δ 7.80 (m, 2H), 7.66 (m, 2H), 7.54 (m, 1H), 7.40-7.20 (m, 3H), 5.55 (q, 1H), 1.93 (d, 3H), 1.30 (s, 9H).

Step C: 3-(l.l-dimethylethyl)- -methylbenzenemethanamine

The product of Step B (29 g, 0.091 mole) was dissolved in methanol (155 mL) and treated with hydrazine hydrate (4.9 mL, 0.1 mole). The mixture was heated to reflux for two hours during which time a precipitate formed. After cooling and filtration to remove solids, the filtrate was concentrated under vacuum to remove most of the methanol. The residue was partitioned between methylene chloride and 6% aqueous potassium carbonate. The organic phase was dried (MgSO4) and concentrated to give the product as a yellow oil (15 g, 95% yield). --H NMR (CDC1₃): δ 7.36 (s, 1H), 7.26 (m, 2H), 7.18 (m, 1H), 4.12 (q, 1H), 1.95 (brs, 2H), 1.41 (d, 3H), 1.33 (s, 9H).

Step D: 5-chloro-N-r 1 -f3-d .1 -dimethylethvnphenyllethyl1-6-ethyl-4- pyrimidinamine The product of Step C ( 1.5 g, 8.5 mmole), 4,5-dichloro-6-ethylpyrimidine

(1.5 g, 8.5 mmole), and triethylamine (2.4 mL, 17 mmole) were dissolved in toluene (8 mL) and heated to reflux for 24 hours. The mixture was cooled, treated with water and extracted with diethyl ether. The organic phase was dried (MgSO ), concentrated, and chromatographed on silica gel with 5% ethyl acetate/hexane to give the title compound as a colorless oil (2.3 g, 85% yield). ^JH NMR (CDC1₃): δ 8.41 (s, 1H), 7.32 (m, 4H), 5.62 (brd, 1H), 5.36 (q, 1H), 2.78 (q, 2H), 1.61 (d, 3H), 1.32 (s, 9H), 1.25 (t, 3H). Example 2 Step A: 2-(3-bromophenyl)-2-methyl-1.3-dioxolane

The compound, l-(3-bromophenyl)ethanone (35 g, 0.18 mole), ethylene glycol (39 mL, 0.70 mole), and p-toluenesulfonic acid (0.5 g) were dissolved in toluene (300 mL) and heated to reflux in a Dean-Stark appratus. After six hours, water and some ethylene glycol had separated and the mixture was cooled and washed with water and saturated aqueous sodium bicarbonate solution. Drying (MgSO₄) and concentrating the organic phase gave the product as an oil (44 g, 99% yield). ^!H NMR (CDC1₃): δ 7.64 (m, 1H), 7.39 (m, 2H), 7.21 (t, 1H), 4.04 (m, 2H), 3.76 (m, 2H), 1.63 (s, 3H).

Step B: l-[3-(trimethylsilyl phenyllethanone

A flame-dried flask was charged with magnesium pieces (5.3 g, 0.22 mole) and tetrahydrofuran (50 mL) under a nitrogen atmosphere. To this vigorously stirred slurry was added the product of Step A (44 g, 0.18 mole) in THF ( 150 mL) dropwise. The reaction mixture was warmed to 40°C during the additon and then to 65°C for 1.5 hours after addition was complete. After cooling the solution to room temperature, trimethylsilyl chloride (28 mL, 0.22 mole) was added dropwise over 15 minutes and the reaction was allowed to stir for 16 hours. The reaction suspension was cooled to 10°C and treated with saturated aqueous ammonium chloride solution and extracted with diethyl ether. The combined organic phases were dried (MgSO₄) and concentrated to give the intermediate silylated ketal. This crude intermediate was dissolved in acetone (180 mL) and treated with IN hydrochloric acid solution (18 mL) at reflux for 2 hours. After cooling, saturated aqueous sodium bicarbonate solution (180 mL) was added carefully and the mixture extracted with methylene chloride. The combined organic phases were dried (MgSO₄) and concentrated to give the product ketone as a yellow oil (34 g, 99% yield). *H NMR (CDC1₃): δ 8.10 (s, 1H), 7.91 (m, 1H), 7.73 (m, 1H), 7.45 (t, 1H), 2.62 (s, 3H), 0.30 (s, 9H).

Step C: l-r3-(trimethylsilyl)phenyllethanone oxime

The product from Step B (34 g, 0.18 mole) was dissolved in methanol (175 mL) and treated with a solution of hydroxylamine hydrochloride (19 g, 0.28 mole) and sodium acetate (38 g, 0.28 mole) in water (130 mL). The mixture was heated at reflux for 2.5 hours, cooled, and extracted with methylene chloride. The combined organic phases were dried (MgSO4), concentrated, and chromatographed on silica gel with 10% ethyl acetate/hexane. The product was isolated as a colorless oil (30 g, 80% yield). ^lϋ NMR (CDC1₃): δ 9.27 (s, 1H), 7.77 (s, 1H), 7.56 (m, 2H), 7.37 (t, 1H), 2.32 (s, 3H), 0.29 (s, 9H).

Step D: α-methyl-3-(trimethylsilyl)benzenemethanamine

The product of Step C (15 g, 0.07 mole) and ammonium acetate (59 g, 0.75 mole) were dissolved in methanol (600 mL). To this mixture was added sodium cyanaborohydride (13 g, 0.21 mole) in several portions. Then, 170 mL of a 12 wt % solution of titanium trichloride (in 21 wt % HCl) was added dropwise over 2 hours while maintaining the reaction temperature at 22°C with a cold water bath. The dark blue mixture was stirred at room temperature for 16 hours. The reaction was made basic by the addition of 15% aqueous sodium hydroxide solution, concentrated under vacuum to remove most of the methanol and then extracted with methylene chloride. The combined organic phases were dried (MgSO₄) and concentrated to give the amine product as a pale yellow oil (12 g, 92% yield). iH NMR (CDC1₃): δ 7.45 (s, 1H), 7.35 (m, 3H), 4.10 (q, 1H), 1.74 (s, 2H), 1.40 (d, 3H), 0.27 (s, 9H).

Step E: 5-chloro-6-methyl-N-ri-r3-rtrimethylsilvDphenyllethyll-4- pyrimidinamine The product from Step D (1.8 g, 9.2 mmole), 4,5-dichloro-6- methylpyrimidine (1.5 g, 9.2 mmole), and triethylamine (2.6 mL, 18 mmole) were dissolved in toluene (9 mL) and heated to reflux for 16 hours. After cooling to room temperature, the reaction was treated with water and extracted with diethyl ether. The combined organic phases were dried (MgSO₄), concentrated, and chromatographed on silica gel with 10% ethyl acetate/hexane to give the title compound as a colorless oil (2.2 g, 74% yield). ^lH NMR (CDC1₃): δ 8.36 (s, 1H), 7.51 (s, 1H), 7.44 (m. 1H), 7.35 (m, 2H), 5.61 (brd, 1H), 5.38 (q, 1H), 2.46 (s, 3H), 1.61 (d, 3H), 0.27 (s, 9H).

Example 3 Step A: l-(dibromomethyl -3-d.l-dimethylethyl)benzene

The compound, l-(l,l-dimethylethyl)-3-methylbenzene (5 g, 34 mmole), N-bromosuccinimide (13 g, 71 mmole), and benzoyl peroxide (0.05 g) were dissolved/suspended in carbon tetrachloride (350 mL). The mixture was heated at reflux for 3 hours while being irradiated with a sunlamp. After cooling and filtering off suspended solids, the filtrate was washed with 10% aqueous sodium sulfite solution, dried (MgSO₄) and concentrated to give the product as an oil (11 g, 99% yield). ^lH NMR (CDC1₃): δ 7.54 (s, 1H), 7.45-7.25 (m, 3H, 6.66 (s, 1H), 1.34 (s, 9H).

Step B : 3-( 1.1 -dimethylethyllbenzaldehyde

The product of Step A (11 g, 34 mmole) was dissolved in dimethoxyethane (175 mL) and heated to reflux. Silver nitrate (17 g, 0.10 mole) in water (130 mL) was added dropwise while maintaining reflux. A precipitate formed and the mixture was refluxed for 30 more minutes. After cooling and filtering solids, the filtrate was washed with water, dried (MgSO₄), and concentrated. The crude residue was passed through a plug of silica gel with methylene chloride to isolate, after concentration of the solvent, an oil (3.7 g, 66% yield). ^lH NMR (CDC1₃): δ 10.02 (s, 1H), 7.92 (s, 1H), 7.68 (m, 2H), 7.45 (m, 1H), 1.37 (s, 9H).

Step C: 3-(l.l-dimethylethy -^Qg-ethylbenzenemethamine

Hexamethyldisilazane (5.7 mL, 27 mmole) was dissolved in tetrahydrofuran (10 mL), cooled to 0°C, and treated with n-butyllithium (11 mL of 2.5M, 27 mmole). The mixture was warmed to 22°C for 30 minutes and then recooled to 0°C. The product of Step B (3.7 g, 22 mmole) was dissolved in THF (10 mL) in a separate flash and cooled to 0°C. The solution of lithium hexamethyl¬ disilazide was added via cannula to the aldehyde solution and the mixture was stirred cold for 15 minutes. After removal of the cooling bath, ethyl magnesiumbromide (18 mL of 3.0M, 54 mmole) was added dropwise during which the mixture warmed to 25 °C. The reaction was heated to reflux for 16 hours, cooled to 10°C, and treated with saturated aqueous ammonium chloride solution. After extracting with diethyl ether, the combined organic phases were dried (MgSO₄), concentrated, and chromatographed on silica gel with ethyl acetate. The product amine was isolated as a colorless oil (2.1 g, 51 % yield).

!H NMR (CDCI3): δ 7.29 (m, 3H), 7.12 (m, 1H), 3.80 (t, 1H), 1.69 (q, 2H), 1.56 (s, 2H), 1.33 (s, 9H), 0.89 (t, 3H). Step D: 5-chloro-N-ri-r3-ri.l-dimethylethvnphenyllρropyll-6-ethyl-4- pyrimidinamine The product from Step C (0.76 g, 4.0 mmole), 4,5-dichloro-6- ethylpyrimidine (0.70 g, 4.0 mmole), and triethylamine (1.1 mL, 8.0 mmole) were dissolved in toluene (6 mL) and heated to reflux for 16 hours. After cooling, the reaction mixture was treated with water and extracted with ether. The combined organic phases were dried (MgSO₄), concentrated, and chromatographed on silica gel with 10% ethyl acetate/hexane. The title compound was isolated as a viscous oil (0.84 g, 65% yield). --H NMR (CDCI₃): δ 8.39 (s, IH), 7.35 (s, IH), 7.30 (m, 2H), 7.15 (m, IH), 5.65 (brd, IH), 5.15 (q, IH), 2.77 (q, 2H), 1.95 (m, 2H), 1.32 (s, 9H), 1.25 (t, 3H), 0.95 (t, 3H).

By the procedures described herein, the compounds of Table 1 can be prepared. The compounds on line 1 can be referred to as 1-1, 1-2, 1-3, 1-4, 1-5, 1-6, 1-7 and 1-8 (as designated by line and column, respectively). All the other specific compounds covered in the Table can be designated in an analogous fashion. The Table compounds are numbered from 1-1 through 144-8. The following abbreviations have been used in the Table: tBu=tertiary butyl.

Table Compounds

TABLE 1

Formulation/Utility

Compounds of this invention will generally be used in formulation with an agriculturally suitable carrier comprising a liquid or solid diluent or an organic solvent. Use formulations include dusts, granules, baits, pellets, solutions, suspensions, emulsions, wettable powders, emulsifiable concentrates, dry flowables and the like, consistent with the physical properties of the active ingredient, mode of application and environmental factors such as soil type, moisture and temperature. Sprayable formulations can be extended in suitable media and used at spray volumes from about one to several hundred liters per hectare. High strength compositions are primarily used as intermediates for further formulation. The formulations will typically contain effective amounts of active ingredient, diluent and surfactant within the following approximate ranges which add up 100 weight percent.

High Strength Compositions 90-99 0-10 0-2

Typical solid diluents are described in Watkins, et al., Handbook of Insecticide Dust Diluents and Carriers, 2nd Ed., Dorland Books, Caldwell, New Jersey. Typical liquid diluents and solvents are described in Marsden, Solvents Guide, 2nd Ed., Interscience, New York, 1950. McCutcheon's Detergents and Emulsifiers Annual, Allured Publ. Corp., 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.

Solutions are prepared by simply mixing the ingredients. Fine solid compositions are made by blending and, usually, grinding as in a hammer mill or fluid energy mill. Water-dispersible granules can be produced by agglomerating a fine powder composition; see for example, Cross et al., Pesticide Formulations, Washington, D.C., 1988, pp 251-259. Suspensions are prepared by wet-milling; see, for example, U.S. 3,060,084. Granules and pellets can be made by spraying the active material upon preformed granular carriers or by agglomeration techniques. See Browning, "Agglomeration", Chemical Engineering, December 4, 1967, pp 147-148, Perry's Chemical Engineer's Handbook, 4th Ed., McGraw-Hill, New York, 1963, pages 8-57 and following, and WO 91/13546. Pellets can be prepared as described in U.S. 4,172,714. Water-dispersible and water-soluble granules can also be prepared as taught in DE 3,246,493. For further information regarding the art of formulation, see U.S.

3,235,361, Col. 6, line 16 through Col. 7, line 19 and Examples 10-41; U.S. 3,309,192, 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; U.S. 2,891,855, Col. 3, line 66 through Col. 5, line 17 and Examples 1-4; Klingman, Weed Control as a Science, John Wiley and Sons, Inc., New York, 1961, pp 81-96; and Hance et al., Weed Control Handbook, 8th Ed., Blackwell Scientific Publications, Oxford, 1989.

In the following Examples, all percentages are by weight and all formulations are worked up in conventional ways. Compound numbers refer to compounds in Index Table A.

Example A Wettable Powder

Compound 1 65.0% dodecylphenol polyethylene glycol ether 2.0% sodium ligninsulfonate 4.0% sodium silicoaluminate 6.0% montmorillonite (calcined) 23.0%.

Example B Granule Compound 1 10.0% attapulgite granules (low volative matter, 0.71/0.30 mm; U.S.S. No.

25-50 sieves) 90.0%.

Example C Extruded Pellet

Compound 1 25.0% anhydrous sodium sulfate 10.0% crude calcium ligninsulfonate 5.0% sodium alkylnaphthalenesulfonate 1.0% calcium/magnesium bentonite 59.0%.

Example D Emulsifiable Concentrate

Compound 1 20.0% blend of oil soluble sulfonates and polyoxyethylene ethers 10.0% isophorone 70.0%.

The compounds of this invention exhibit activity against a wide spectrum of foliar-feeding, fruit-feeding, seed-feeding, aquatic and soil-inhabiting arthropods (term includes insect, mites 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 appreciate that not all compounds are equally effective against all pests. Nevertheless, all of the compounds of this invention display activity against pests that include: eggs, larvae and adults of the Order Lepidoptera; eggs, foliar-feeding, fruit-feeding, root-feeding, seed-feeding larvae and adults of the Order Coleoptera; eggs, immatures and adults of the Orders Hemiptera and Homoptera; eggs, larvae, nymphs and adults of the Order Acari; eggs, immatures and adults of the Orders Thysanoptera, Orthoptera and Dermaptera; eggs, immatures and adults of the Order Diptera; and eggs, juveniles and adults of the Phylum Nemata. The compounds of this invention are also active against pests of the Orders Hymenoptera, Isoptera, Phthiraptera, Siphonoptera, Blattaria, Thysanaura and Pscoptera; pests belonging to the Class Arachnida and Phylum Platyhelminthes. The compounds are also active on mites, demonstrating ovicidal, larvicidal and chemosterilant activity against such families as Tetranychidae including Tetranychus urticae, Tetranychus cinnabarinus, Tetranychus mcdanieli, Tetranychus pacificus, Tetranychus turkestani, Byrobia rubrioculus, Panonychus ulmi, Panonychus citri, Eotetranychus carpini borealis, Eotetranychus, hicoriae, Eotetranychus sexmaculatus, Eotetranychus yumensis, Eotetranychus banksi and Oligonychus pratensis; Tenuipalpidae including Brevipalpus lewisi, Brevipalpus phoenicis, Brevipalpus calif ornicus and Brevipalpus obovatus; Eriophyidae including Phyllocoptruta oleivora, Eriophyes sheldoni, Aculus cornutus, Epitrimerus pyri and Eriophyes mangiferae. See WO 90/10623 and WO 92/00673 for more detailed pest descriptions.

The compounds of this invention are also useful as plant disease control agents. The present invention therefore further comprises a method for controlling plant diseases caused by fungal plant pathogens comprising applying to the plant or portion thereof to be protected, or to the plant seed or seedling to be protected, an effective amount of a compound of Formula I or a fungicidal composition containing said compound. The compounds and compositions of this invention provide control of diseases caused by a broad spectrum of fungal plant pathogens in the Basidiomycete, Ascomycete, Oomycete and Deuteromycete 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 Plasmopara viticola, Phytophthora infestans, Peronospora tabacina, Pseudoperonospora cubensis, Pythium aphanidermatum, Alternaria brassicae, Septoria nodorum, Cercosporidium personatum, Cercospora arachidicola, Pseudocercosporella herpotrichoides, Cercospora beticola, Botrytis cinerea, Monilinia fructicola, Pyricularia oryzae, Podosphaera leucotricha, Venturia inaequalis, Erysiphe graminis, Uncinula necatur, Puccinia recondita, Puccinia graminis, Hemileia vastatrix, Puccinia striiformis, Puccinia arachidis, Rhizoctonia solani, Sphaerotheca fuliginea, Fusarium oxysporum, Verticillium dahliae, Pythium aphanidermatum, Phytophthora megasperma and other generea and species closely related to these pathogens.

Compounds of this invention can also be mixed with one or more other insecticides, fungicides, nematicides, bactericides, acaricides, semiochemicals, repellants, attractants, pheromones, feeding stimulants or other biologically active compounds to form a multi-component pesticide giving an even broader spectrum of agricultural protection. In certain instances, combinations with other biologically active compounds having a similiar spectrum of control but a different mode of action will be particularly advantageous for resistance management. Examples of other agricultural protectants with which compounds of this invention can be formulated are: insecticides such as monocrotophos, carbofuran, tetrachlorvinphos, malathion, parathion-methyl, methomyl, chlordimeform, diazinon, deltamethrin, oxamyl, fenvalerate, esfenvalerate, permethrin, profenofos, sulprofos, triflumuron, diflubenzuron, methoprene, buprofezin, thiodicarb, acephate, azinphosmethyl, chlorpyrifos, dimethoate, fipronil, flufenprox, fonophos, isofenphos, methidathion, methamidophos, phosmet, phosphamidon, phosalone, pirimicarb, phorate, terbufos, trichlorfon, methoxychlor, bifenthrin, biphenate, cyfluthrin, fenpropathrin, fluvalinate, flucythrinate, tralomethrin, metaldehyde and rotenone; fungicides such as carbendazim, thiuram, dodine, maneb, chloroneb, benomyl, cymoxanil, fenpropidine, fenpropimorph, triadimefon, captan, thiophanate-methyl, thiabendazole, phosethyl-Al, chlorothalonil, dichloran, metalaxyl, captafol, iprodione, oxadixyl, vinclozolin, kasugamycin, myclobutanil, tebuconazole, difenoconazole, diniconazole, fluquinconazole, ipconazole, metconazole, penconazole, propiconazole, uniconzole, flutriafol, prochloraz, pyrifenox, fenarimol, triadimenol, diclobutrazol, copper oxychloride, furalaxyl, folpet, flusilazol, blasticidin S, diclomezine, edifenphos, isoprothiolane, iprobenfos, mepronil, neo-asozin, pencycuron, probenazole, pyroquilon, tricyclazole, validamycin, and flutolanil; nematocides such as aldoxycarb, fenamiphos and fosthietan; bactericides such as oxytetracyline, streptomycin and tribasic copper sulfate; acaricides such as binapacryl, oxythioquinox, chlorobenzilate, dicofol, dienochlor, cyhexatin, hexythiazox, amitraz, propargite, tebufenpyrad and fenbutatin oxide; and biological agents such as Bacillus thuringiensis and baculovirus. Arthropod 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. A preferred method of application is by spraying. Alternatively, granular formulations of these compounds can be applied to the plant foliage or the soil. Other methods of application include direct and residual sprays, aerial sprays, systemic uptake, baits, eartags, boluses, foggers, fumigants, aerosols, and many others. The compounds can be incorporated into baits that are consumed by the arthropods or in devices such as traps and the like. Plant disease control is ordinarily accomplished by applying an effective amount of a compound of this invention either pre — or post — infection, to the portion of the plant to be protected such as the roots, stems, foliage, fruit, seeds, tubers or bulbs, or to the media (soil or sand) in which the plants to be protected are growing. The compounds can also be applied to the seed to protect the seed and seedling. 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 (term includes 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 concentrations, spreader stickers, adjuvants, and synergists and other solvents such as piperonyl butoxide often enhance compound efficacy.

The rate of application required for effective arthropod 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, and the like. Under normal circumstances, application rates of about 0.01 to 2 kg of active ingredient per hectare are sufficient to control pests in agronomic ecosystems, but as little as 0.001 kg/hectare may be sufficient 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 0.1 mg/square meter may be sufficient or as much as 150 mg/square meter may be required.

Rates of application for these compounds as plant disease control agents can be influenced by many factors of the environment and should be determined under actual use conditions. Foliage can normally be protected when treated at a rate of from less than 1 g ha to 10,000 g/ha of active ingredient. 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.

The following tests demonstrate the control efficacy of compounds of Formula I on specific pests and plant pathogens; see Index Table A for compound descriptions. The pest control protection afforded by the compounds of the present invention is not limited, however, to these species. Compounds not included were either not screened or gave pathogen control levels less than 70% or insect control less than 80%. INDEX TABLE A

A: NMR data provided in Example 1 - Step D B: NMR data provided in Example 2 - Step E C: NMR data provided in Example 3 - Step D

TEST A

The test compounds were dissolved in acetone in an amount equal to 3% of the final volume and then suspended at a concentration of 200 ppm in purified water containing 250 ppm of 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 dust of Erysiphe graminis f. sp. tritici (the causal agent of wheat powdery mildew) and incubated growth chamber at 20°C for 7 days, after which disease ratings were made. Of the compounds tested, the following gave 70% disease control or higher: 1, 2, 3, 4.

TEST B

The test compounds were dissolved in acetone in an amount equal to 3% of the final volume and then suspended at a concentration of 200 ppm in purified water containing 250 ppm of the surfactant Trem^® 014 (polyhydric alcohol esters). This suspension was sprayed to the point of run-off on wheat seedlings. The following day, the seedlings were inoculated with a spore suspension of Puccinia recondita (the causal agent of wheat leaf rust) and incubated in a saturated atmosphere at 20°C for 24 hours, and then moved to a growth chamber at 20°C for 6 days, after which disease ratings were made. Of the compounds tested, the following gave 70% disease control or higher: 1, 2, 3, 4.

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 grape seedlings. The following day the seedlings were inoculated with a spore suspension of Plasmopara viticola (the causal agent of grape downey mildew) and incubated in a saturated atmosphere at 20°C for 6 days, and then incubated in a saturated atmosphere at 20°C for 24 hours, after which disease ratings were made. Of the compounds tested, the following gave 70% disease control or higher when tested at 200 ppm: 1, 2, 3, 4.

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 is sprayed to the point of run-off on rice seedlings. The following day the seedlings are inoculated with a spore suspension of Pyricularia oryzae (the causal agent of rice blast) and incubated in a saturated atmosphere at 27°C for 24 h, and then moved to a growth chamber at 30°C for 5 days, after which disease ratings are made. Of the compounds tested, the following gave 70% disease control or higher: 1, 2, 3, 4.

TEST E Two-Spotted Spider Mite

One inch squares (2.54 centimeters) of kidney bean leaves that had been infested on the undersides with 25 to 30 adult mites (Tetranychus urticae) were sprayed with their undersides facing up on a hydraulic sprayer with a solution of the test compound (acetone/distilled water 75/25 solvent). Spraying was accomplished by passing the leaves, on a conveyer belt, directly beneath a flat fan hydraulic nozzle which discharged the spray at a rate of 0.125 pounds of active ingredient per acre (about 0.137 kg/ha) at 30 p.s.i. (207 kPa). The leaf squares were placed underside-up on a square of wet cotton in a petri dish and the perimeter of the leaf square was tamped down onto the cotton with forceps so that the mites cannot escape onto untreated leaf surface. 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 levels of 80% or higher: 1, 2, 3, 4.

Claims

CLAIMS 1. A compound of the formula

wherein:

A is selected from the group CH₂, CHCH₃, CHCH₂CH₃, CHCH(CH₃)₂,

CHCH₂OH, CH-CH(CH₂)₂, C(CH₂)₂ and C(CH₃)₂; R¹ and R² are independently selected from the group H and CH₃; R³ is selected from the group C(CH₃)₃, Si(CH₃)₃ and Ge(CH₃)₃, provided when R³ is Si(CH₃)₃ or Ge(CH₃)₃ and R¹ is CH₃, then A is

CH-CH(CH₂)₂ or C(CH₂)₂; and R⁴ is selected from the group H, halogen and CH₃.

2. A compound according to Claim 1 wherein A is selected from the group CHCH₃ and CH₂.

3. A compound according to Claim 2 wherein A is CHCH₃, R¹ is CH₃, R² is H, R³ is C(CH₃)₃, and R⁴ is H.

4. A compound according to Claim 2 wherein A is CH₂, R¹ is CH₃, R² is H, R³ is C(CH₃)₃, and R⁴ is H.

5. A composition comprising a fungicidally effective amount of a compound according to Claim 1 and a carrier therefor.

6. A composition comprising a jticidally "Tective amount of a compound according to Claim 1 and a carrier therefor.

7. A method for controlling fungi that comprises applying to the fungi or to their environment a fungicidally effective amount of a compound according to Claim 1.

8. A method for controlling mites that comprises applying to the mites or to their environment a miticidally effective amount of a compound according to Claim 1.