WO1993022291A1

WO1993022291A1 - Arthropodicidal and fungicidal aminopyrimidines

Info

Publication number: WO1993022291A1
Application number: PCT/US1993/002757
Authority: WO
Inventors: Renée Marie LETT
Original assignee: E.I. Du Pont De Nemours And Company
Priority date: 1992-04-24
Filing date: 1993-03-22
Publication date: 1993-11-11
Also published as: AU3933493A

Abstract

Aminopyrimidines characterized by various substitution at the 5-position of the pyrimidine ring and agricultural compositions containing them useful for the control of anthropods in both agronomic and nonagronomic environments are disclosed.

Description

TITLE

ARTHROPODICIDAL AND FUNGICIDAL AMINOPYRIMIDINES

This invention relates to aminopyrimidines

characterized by various substitution at the 5-position of the pyrimidine ring useful as arthropodicides and fungicides, their agriculturally suitable compositions, and methods of their use against foliar, aquatic, and soil-inhabiting anthropods and plant pathogens.

U.S. 4,895,849, U.S. 4,985,426, U.S. 4,435,402 and EP 424,125 each disclose aminopyrimidines useful as insecticides having substituents at the claimed R³ position limited to H, halogen or lower alkyl. DE 3,905,364 discloses certain aminopyrimidines as aldose reductase inhibitors.

SUMMARY OF THE INVENTION

This invention comprises compounds of Formula I, including all geometric and stereoisomers,

agriculturally suitable salts thereof, agricultural compositions containing them and their use as

arthropodicides and fungicides in both agronomic and nonagronomic environments. The compounds are

wherein

Q is

,

or

;

A is C₁-C₅ straight or branched chain alkylene or C₃-C₆ cycloalkylene, wherein any one atom of A can be optionally substituted with R⁷; X is Ge or Si;

R¹ is H, halogen, C₁-C₄ -alkyl or C₁-C₄ haloalkyl; R² is H, halogen, C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₂-C₄ cyanoalkyl, C₂-C₄ alkenyl, C₂-C₄ haloalkenyl, C₂-C₄ alkynyl, C₂-C₆ alkoxyalkyl or C₂-C₆ alkylthioalkyl;

R³ is H, halogen, CN, NO₂, CO₂R¹⁶, C(O)R¹⁶,

C(O)N(R¹⁶)R¹⁷, OR¹⁶, SR¹⁶, S(O)R¹⁶, S(O)₂R¹⁶, N(R¹⁶)R¹⁷, C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₁-C₆ haloalkoxy, C₂-C₆ alkenyl, C₂-C₆ haloalkenyl, C₂-C₆ alkynyl, C₁-C₆ hydroxyalkyl, C₂-C₆ alkoxyalkyl, C₂-C₆ haloalkoxyalkyl, C₂-C₆ cyanoalkyl, C₁-C₆ alkylthioalkyl, C₂-C₆ haloalkylthioalkyl, C₃-C₄ cycloalkyl, SCN or C₁-C₆ alkyl substituted with N(R¹⁶)R¹⁷; provided that (i) when R² is H, halogen, C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₂-C₆ alkoxyalkyl or C₂-C₆ alkylthioalkyl then R³ is other than halogen, C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₂-C₆ alkoxyalkyl or C₂-C₆ alkylthioalkyl and (ii) when R³ is H, then R⁵ is other than C₁-C₆ haloalkylthio, C₁-C₆ haloalkylsulfinyl, C₁-C₆ haloalkylsulfonyl, C₁-C₆ alkylsulfonyl, C₁-C₆

alkylsulfinyl or C₁-C₆ alkylthio;

R⁴ is H, formyl, C₂-C₆ alkoxyalkyl C₂-C₆ alkylcarbonyl, C₂-C₆ alkoxycarbonyl, C₂-C₆

haloalkoxycarbonyl, C(O)R¹⁵, R¹¹OC(O)S-, R¹¹OC(O)N(R¹²)S-, R¹¹(R¹²)NS- or SR⁸; or R⁴ is C₁-C₆ alkyl optionally substituted with halogen, CN, NO₂, S(O)_nR¹¹, C(O)R¹¹, CO₂R¹¹ or C₁-C₃ haloalkoxy; or R⁴ is phenyl optionally substituted with halogen, CN, and C₁-C₂ haloalkyl;

R⁵ is C₁-C₆ alkyl, C₁-C₆ alkoxy, C₁-C₆ haloalkoxy, C₂-C₆ alkoxyalkyl, C₂-C₆ alkoxyalkoxy, C₂-C₆ alkenyl, C₂-C6 haloalkenyl, C₂-C₆ alkynyl, C₂-C₆ alkenyloxy, C₂-C₆ alkynyloxy, C₃-C₆ cycloalkyl, C₃-C₆ cycloalkylalkyl, C₁-C₆ alkylthio, C₂-C₆ alkylthioalkyl, C₁-C₆ alkylsulfinyl, C₁-C₆ alkylsulfonyl, C₁-C₆ haloalkylthio, C₁-C₆ haloalkylsulfinyl, C₁-C₆ haloalkylsulfonyl, phenyl optionally substituted with W or phenoxy optionally substituted with W;

R⁶ is H, halogen, CN, NO₂, C₁-C₂ alkyl, C₁-C₂ alkoxy or CF₃;

R⁷ is CN, C(O)R⁸, CO₂R⁸, C(O)N(R⁸)R⁹, N₃, NO₂,

N(R⁸)R⁹, N(R⁸)C(O)R⁹, N (R⁸) C (O) N (R¹⁰) R⁹, N(R⁸)S(O)₂R¹⁰, OR⁸, OC(O)R⁸, OCO₂R⁸,

OC(O)N(R⁸)R⁹, OS(O)₂R⁸, SR⁸, S(O)R⁸, S(O)₂R⁸, SCN or 1-3 halogens;

R⁸ and R¹⁰ are independently H, C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₂-C₆ alkenyl, C₂-C₆ haloalkenyl, C₂-C₆ alkynyl, C₃-C₆ haloalkynyl, C₂-C₆ alkoxyalkyl, C₂-C₆ alkylthioalkyl, C₁-C₆ nitroalkyl, C₂-C₆ cyanoalkyl, C₃-C₈ alkoxycarbonylalkyl, C₃-C₆ cycloalkyl, C₃-C₆ halocycloalkyl, phenyl optionally substituted with W; or benzyl optionally substituted with W on the phenyl ring;

R⁹ is H or C₁-C₄ alkyl; or

R⁸ and R⁹ can be taken together when attached to the same atom as -(CH₂)₄-, -(CH₂)₅- or

-CH₂CH₂OCH₂CH₂-;

R¹¹ and R¹² are independently C₁-C₄ alkyl;

R¹³ is C₁-C₄ alkyl, C₁-C₄ alkoxyalkyl or phenyl

optionally substituted with W;

R¹⁴ is C₁-C₆ alkyl, C₁-C₆ alkoxy, C₁-C₆ haloalkoxy, phenyl or benzyl, each phenyl or benzyl

optionally substituted with W on the aryl ring;

R¹⁵ is

^,

, or ;

R¹⁶ and R¹⁷ are independently H, C₁-C₄ alkyl or

C₁-C₄ haloalkyl;

W is CN, NO₂, C₁-C₂ alkyl, C₁-C₂ haloalkyl, C₁-C₂ alkoxy, C₁-C₂ haloalkoxy, C₁-C₂ alkylthio, C₁-C₂ haloalkylthio, C₁-C₂ alkylsulfonyl, C₁-C₂ haloalkylsulfonyl or 1-5 halogens; and

n is 0, 1 or 2.

Preferred Compounds A are compounds of Formula I

wherein:

A is C₁-C₅ straight or branched alkylene;

R¹ is H;

R² is C₁-C₆ alkyl, C₂-C₄ cyanoalkyl or C₁-C₄ haloalkyl; R⁴ is H;

R⁵ is C₁-C₆ alkyl, C₁-C₆ haloalkoxy, C₂-C₆ alkoxyalkyl, C₂-C₆ alkoxyalkoxy or phenoxy optionally substituted with W; R⁶ is H, halogen or C₁-C₂ alkyl;

R¹¹, R¹² and R¹³ are independently C₂-C₂

alkyl;

R¹⁴ is C₁-C₄ alkyl, C₁-C₄ alkoxy or phenyl

optionally substituted with W; and

W is halogen or C₁-C₂ haloalkyl.

Preferred Compounds B are compounds of Preferred A wherein Q is Q-1. Preferred Compounds C are compounds of Preferred A wherein Q is Q-2. Preferred Compounds D are compounds of Preferred A wherein Q is Q-3.

Specifically preferred for biological activity is the compound of Preferred D which is:

6-ethyl-4-[[1-[4-(trimethylsilyl)phenyl]ethyl]- amino]-5-pyrimidinecarbonitrile.

The present invention further comprises

agricultural compositions containing an effective amount of one or more compounds of Formula I and at least one of (a) a surfactant (b) an organic solvent, and (c) at least one solid or liquid diluent.

The present-invention further comprises a method for controlling foliar, aquatic and soil-inhabiting anthropod pests comprising application of an effective amount of a compound of Formula I or an agricultural composition as described above containing one or more compounds of Formula I to the locus of infestation, area to be protected, or directly onto said pests.

DETAILED DESCRIPTION OF THE INVENTION

Compounds of the instant invention include racemic and optically active stereoisomers. By "stereoisomers" is meant all of the isomers of the Formula I compounds which include enantiomers, diastereomers, and geometric isomers. One skilled in the art will appreciate that one or the other of said stereoisomer (s) will be the more active. It is also known how to separate such enantiomers, diastereomers, and geometric isomers.

Accordingly, the present invention comprises racemic mixtures, individual stereoisomers, and optically active mixtures of compounds of Formula I as well as agriculturally suitable salts thereof.

In the above recitations, the term "alkyl" used either alone or in a compound word such as "alkylthio" or "haloalkyl", denotes straight or branched alkyl, e.g., methyl, ethyl, n-propyl, isopropyl, or the different butyl, pentyl or hexyl isomers. Alkoxy denotes methoxy, ethoxy, n-propyloxy, isopropyloxy and the different butoxy, pentoxy or hexyloxy isomers.

Alkenyl denotes straight or branched chain alkenes such as vinyl, 1-propenyl, 2-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. Alkylthio denotes methylthio, ethylthio and the different propylthio, butylthio, pentylthio and hexylthio isomers. Alkylsulfinyl, alkylsulfonyl, alkylamino, etc., are defined analogously to the above examples. 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 CH₂CH₂F, CF₂CF₃ and CH₂CHFCl. The terms "halocycloalkyl", "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_i-C_j" prefix where i and j are numbers from 1 to 8. For example, C₁-C₃ alkylsulfonyl designates methylsulfonyl through propylsulfonyl; C₂ alkoxyalkoxy designates OCH₂OCH₃; C₄ alkoxyalkoxy designates the various isomers of an alkoxy group substituted with a second alkoxy group containing a total of 4 carbon atoms, examples

including OCH₂OCH₂CH₂CH₃ and OCH₂CH₂OCH₂CH₃; C₂

cyanoalkyl designates CH₂CN and C₃ cyanoalkyl

designates CH₂CH₂CN and CH(CN)CH₃; C₂ alkylcarbonyl would designates C(O)CH₃ and C₄ alkylcarbonyl includes C(O)CH₂CH₂CH₃ and C(O) CH (CH₃)₂; and as a final example, C₃ alkoxycarbonylalkyl designates CH₂CO₂CH₃ and C₄ alkoxycarbonylalkyl includes CH₂CH₂CO₂CH₃, CH₂CO₂CH₂CH₃ and CH(CH₃)CO₂CH₃.

For the sake of convenience, the term "arthropod" as used herein includes insects, mites and nematodes.

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, Q, R² and R³ are as previously defined for Formula I .

SCHEME 1

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, but is not limited to, 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 those that will not participate in the above reaction, for example, toluene, xylene, ethanol, propanol, N,N-dimethylformamide, and N,N-dimethylacetamide. Preferred temperatures for this process are from about 20°C to 200°C with temperatures between 80°C and 150°C being particularly preferred.

Compounds of Formula I where R⁴ is an alkyl or acyl group can be best prepared by reacting an amine of Formula III where R⁴ is an alkyl or acyl group with a pyrimidine of Formula II. The amine of Formula III where R⁴ is alkyl or acyl can be prepared by acylating or alkylating an amine of Formula III, where R⁴ is equal to hydrogen, using conventional methods known to those skilled in the art.

A particularly useful method for preparing some of the amines of Formula III is shown in Scheme 2, wherein Q is as previously defined for Formula I.

SCHEME 2

Amines of Formula III wherein A is equal to CH₂CH₂ can be prepared by reduction of nitriles of Formula IV using alane. In situ formation of alane in ether and then treatment with nitrile IV at 0°C gives the desired primary amines in high yields. Nitriles of Formula IV can in turn be synthesized by the displacement of a bromine atom from a bromide of Formula V with potassium cyanide as in Scheme 3, wherein Q is as previously defined for Formula I. SCHEME 3

This reaction can be accomplished in refluxing ethanol and water as co-solvents. Bromides of Formula V can be prepared according to the process shown in Scheme 4, wherein Q is as previously defined in Formula I, and NBS is N-bromosuccinimide.

SCHEME 4

Aryl methyl groups in compounds of Formula VI are subject to free radical bromination by N-bromosuccinimide (NBS) in the presence of light. The reaction is commonly done in refluxing carbon

tetrachloride with one equivalent of NBS. Compounds of Formula VI are either commercially available or can be prepared by conventional methods. Silylated compounds of Formula VI can be prepared according to the methods described by Habich et al. in Syn . , 1979, 841. The germylated compounds related to Formula VI 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 of the amines of Formula III is shown in Scheme 5, wherein Q is as previously defined for Formula I, and TMS is trimethylsilyl. SCHEME 5

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 VII by treatment with lithium hexamethyldisilazide in tetrahydrofuran at 0°C followed by addition of ethyl Grignard and refluxing. Some aldehydes of Formula VII can be prepared by reaction of dibromides of Formula VIII with silver nitrate in refluxing water/dimethoxyethane solvent according to Scheme 6, wherein Q is as previously defined in

Formula I.

SCHEME 6

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 N-bromosuccinimide in the presence of light in refluxing carbon tetrachloride according to Scheme 7, wherein Q is as previously defined in

Formula I. SCHEME 7

The amines of Formula III prepared in Schemes 2 and 5 can be used in Scheme 1 to prepare preferred

compounds of Formula I of this invention.

Pyrimidines of Formula II can be prepared by a variety of literature methods. Some efficient

processes are described by Foster et al. in Org. Syn . , 1955, 35, 80, Ube Industries in JP 58(83) 222,070, and Lonza Ag in EP 370,391. Some pyrimidines of Formula II where R³ is equal to halogen or nitro can be prepared by the reaction of a 4-pyrimidinol with an electrophile (Scheme 8). Electrophilic reagents that transfer halogen

SCHEME 8

(chlorine and N-iodosuccinimide) and nitro (nitronium tetrafluoroborate) are known. Processes similar to the above are described by Ciba Geigy in EP 470,600.

Some pyrimidines of Formula II can be prepared by simple functional group transformations using

conventional methods known to those skilled in the art. For example, reduction of a pyrimidine of Formula II where R³ is equal to NO₂ to a pyrimidine of Formula II where R³ is equal to NH₂ with hydrogen and Raney nickel in ethanol. Another example is displacement of bromide from a compound of Formula I where R³ is equal to Br with sodium methylthiolate (NaSCH₃) to give a compound of Formula I where R³ is equal to SCH₃. This material may be further oxidized with metachloroperbenzoic acid to give a compound of Formula I where R³ is equal to S(O)CH₃ or S(O)₂CH₃.

Some of the preferred compounds of Formula I may be prepared by Palladium catalyzed reactions as shown in Scheme 9, wherein A, Q and R² are as originally defined in Formula I.

SCHEME 9

Palladium complexes of triarylphosphines are the preferred catalysts of this reaction. Some examples are tetrakis (triphenylphosphine)pallpadium(O), bis (triphenylphosphine)palladium(II)dichloride, and tris- (dibenzylideneacetone)dipalladium(O) with 1,1'-bis

(diphenylphosphino) ferroccene ligand. The reaction can be carried out in a variety of solvents including dimethylsulfoxide, dimethylformamide, triethylamine, tetrahydrofuran, dioxane, and toluene. The temperature of the reaction is determined by the nature of the catalyst and displaceable group R³. Generally the reaction is carried out at temperatures in the range of 25°C to 200°C with temperatures of 60°C to 150°C being preferred. Examples of reagents MR³ are potassium cyanide, cuprous iodide with trimethylsilylacetylene, and vinyltrimethyltin. Detailed procedures are

described by Takagi et al. in Bull . Chem . Soc. Jpn . , 1991, 64, 1118, Sakamoto et al. in Synthesis, 1983, 312, and in "Palladium Reagents in Organic Synthesis" by R. F. Heck (Academic Press, 1985).

Palladium catalyzed carbonylation according to the procedures of Dolle and Kruse (Chem . Comm . , 1987, 904) and Baillargeon and Stille ( J. Amer. Chem . Soc , 1986, 108, 452) may be employed to prepare compounds of

Formula I where R³ is equal to CO₂R¹⁶, C(O)R¹⁶, and CHO.

EXAMPLE 1

Step A: 6-ethyl-5-iodo-4-pyrimidinol

6-ethyl-4-pyrimidinol (1.2 g, 10 mmole) and N-iodosuccinimide (2.2 g, 10 mmole) were heated at 61°C in chloroform (20 mL) for four hours. The reaction mixture was cooled and concentrated under vacuum to a solid residue. The crude solid was treated with hot water and filtered. The moist solid was recrystallized from methanol to give a pure white solid product

(1.5 g, 60% yield), mp 192-3°C. ¹H NMR (CDCl₃): δ 13.12 (brs, 1H), 8.10 (s, 1H), 2.90 (q, 2H), 1.26 (t, 3H).

Step B: 4-chloro-6-ethyl-5-iodopyrimidine

The product of Step A (1.5 g, 6 mmole) was

suspended in phosphorus oxychloride (10 mL) and heated at 100°C for 20 minutes during which the solid

dissolved. The dark solution was cooled and

concentrated under vacuum. The resultant oil was poured onto ice and carefully neutralized with

concentrated NH₄OH solution. After extracting the aqueous solution several times with methylene chloride, the combined organic phases were dried (MgSO₄) and concentrated. The resultant product was a waxy yellow solid (1.6 g, 93% yield). ¹H NMR (CDCl₃): δ 8.74 (s, 1H), 3.04 (q, 2H), 1.31 (t, 3H).

Step C: 6-ethyl-5-iodo-N-[1-[4-(trimethylsilyl)-phenyl]ethyl]-4-pyrimidinamine

The product of Step B (1.5 g, 5.6 mmole), α-methyl-4-trimethylsilylbenzenemethanamine (1.1 g, 5.6 mmole), and triethylamine (1.6 mL, 11 mmole) were dissolved in toluene (5 mL) and heated at 110°C for 24 hours. The reaction mixture was cooled and treated with water and ether. After extraction of the aqueous phase with ether, the combined organic phases were dried (MgSO₄), concentrated, and chromatographed on silica gel with 10% ethyl acetate/ hexane. The resultant product was a waxy solid (1.9 g, 82% yield). ¹H NMR (CDCl₃): δ 8.32 (s, 1H), 7.50, 7.35 (ABq, 4H), 5.75 (brd, 1H), 5.35 (m, 1H), 2.88 (q, 2H), 1.59 (d, 3H), 1.24 (t, 3H), 0.26 (s, 9H).

Step D: 6-ethyl-4-[[1-[4-(trimethylsilyl)phenyl]-ethyl]amino]-5-pyrimidinecarbonitrile

Tetrakis(triphenylphosphine)palladium (0.81 g, 0.7 mmole) and the iodide from Step C (3.0 g,

7.0 mmole) were dissolved in tetrahydrofuran (7 mL). Potassium cyanide (0.68 g, 10 mmole) was added and the slurry was heated at 65°C for 36 hours. Additional palladium catalyst (0.1 g) and potassium cyanide

(0.1 g) was added and the heating continued for another eight hours. After cooling the solution was diluted with water and ether and partitioned. The aqueous phase was extracted three times with ether and the combined organic phases were washed once with water, dried (MgSO₄), and concentrated. The crude residue was chromatographed on silica gel with 10% ethyl

acetate/hexane. The resulting product was a white solid (1.75 g, 77% yield), mp 98-100°C. ¹H NMR

(CDCl₃): δ 8.59 (s, 1H), 7.52, 7.34 (ABq, 4H), 5.64 (brd, 1H), 5.43 (m, 1H), 2.82 (q, 2H), 1.61 (d, 3H), 1.30 (t, 3H), 0.26 (s, 9H). IR (nujol, cm^-1): 2226 (m).

EXAMPLE 2

Step A: 1-ethyl-4-trimethylsilylbenzene

Magnesium (9.5 g, 0.39 mole) was suspended in tetrahydrofuran (THF) (60 mL) at room temperature. A solution of 4-bromo-l-ethylbenzene (49 mL, 0.36 mole) in 300 mL of THF was added dropwise at such a rate as to maintain the temperature between 30 and 60°C. When the addition was complete the reaction mixture was stirred for an additional hour and then cooled to 30°C. Trimethylsilyl chloride (49 mL, 0.39 mole) was added dropwise at such a rate as to maintain the temperature between 30 and 40°C. The thin suspension was stirred overnight at room temperature. Saturated aqueous NH₄Cl was added and the reaction mixture partitioned. The aqueous phase was extracted three times with ether, and the combined organic phases were dried (MgSO₄) and concentrated. The resultant oil (60 g, 93% yield) was used in the next step without further purification. ¹H NMR (CDCl₃): δ 7.43, 7.22 (ABq, 4H), 2.64 (q, 2H), 1.24 (t, 3H), 0.25 (s, 9H).

Step B: 1-bromo-1-[4-trimethylsilylphenyl]ethane

The product of Step A (59 g, 0.33 mole) was

dissolved in carbon tetrachloride (700 mL). To this solution was added N-bromosuccinimide (59 g, 0.33 mole) and benzoyl peroxide (ca. 200 mg) in one portion. The reation mixture was heated to reflux for 2.5 hours while being irradiated with a 275 watt sunlamp. After cooling, the solid succinimide was removed by

filtration and the filtrate was washed with saturated aqueous NaHSO₃. Drying (MgSO₄) and concentration gave an oil (77 g, 91% yield) which was used in the next step without further purification. ¹H NMR (CDCl₃): δ 7.48, 7.43 (ABq, 4H), 5.20 (q, 1H), 2.07 (d, 3H), 0.26 (s, 9H). Step C: 1 [4-trimethylsilylphenyl]-1-N-phthalimido-ethane

The product from Step B (77 g, 0.30 mole) and potassium phthalimide (58 g, 0.31 mole) were dissolved in dimethylformamide (DMF) (300 mL). The reaction mixture was heated to 80°C for one hour and then concentrated under vacuum at 80°C to remove most of the DMF. The residue was taken up in water and extracted three times with ether, dried (MgSO₄) and concentrated to give an oil (91 g, 94% yield) which was used in the next step without further purification. ¹H NMR

(CDCl₃): δ 7.80 (m, 2H), 7.69 (m, 2H), 7.49 (s, 4H), 5.57 (q, 1H), 1.93 (d, 3H), 0.23 (s, 9H).

Step D: α-methyl-4-trimethylsilylbenzenemethanamine The product of Step C (91 g, 0.28 mole) and

hydrazine monohydrate (14 mL, 0.29 mole) were dissolved in methanol (400 mL) and heated to reflux for two hours. After cooling, the reaction mixture was poured into 6% aqueous K₂CO₃ solution. The aqueous mixture was extracted three times with ether and the combined organic phases were dried (MgSO₄) and concentrated to give an oil (49 g, 90% yield) which was used in the next step without further purification. ¹H NMR

(CDCl₃): δ 7.48, 7.35 (ABq, 4H), 4.10 (q, 1H), 1.65 (brs, 2H), 1.39 (d, 3H), 0.26 (s, 9H).

Step E: 6-ethyl-N-[1-[4-(trimethylsilyl)phenyl]ethyl]-4-pyrimidinamine

The product of Step D (1.13 g, 5.8 mmole),

4-chloro-6-ethylpyrimidine (0.83 g, 5.8 mmole), and triethylamine (1.6 mL, 11 mmole) were dissolved in toluene (5 mL). The reaction was heated to 110°C for 48 hours and then cooled. Ether and water were added and the mixture was partitioned. The aqueous phase was extracted two times with ether and the combined organic phases were dried (MgSO₄), concentrated, and chromatographed on silica gel with 50% ethyl acetate/hexane. The resultant viscous oil solidified after standing for several days (0.77 g, 44% yield). ¹H NMR (CDCl₃): δ 8.48 (s, 1H), 7.49, 7.32 (ABq, 4H), 6.04 (s, 1H), 5.25 (brd, 1H), 4.85 (m, 1H), 2.53 (q, 2H), 1.56 (d, 3H), 1.16 (t, 3H), 0.25 (s, 9H).

EXAMPLE 3

Step A: 6-ethyl-5-nitro-4-pyrimidinol

6-ethyl-4-pyrimidinol (1.0 g, 8.5 mmole) was dissolved in 10 mL of tetramethylene sulfone by warming to 30°C. Nitronium tetrafluoroborate (2.5 g, 19 mmole) was added portionwise and the reaction mixture was heated at 60°C for one hour. The reaction was cooled, poured into ice water, and extracted several times with ethyl acetate. The combined organic phases were washed two times with water, dried (MgSO₄), concentrated, and chromatographed on silica gel with 10% methanol/ chloroform. The product was an orange solid (0.85 g, 59% yield). ¹H NMR (CDCl₃): δ 8.13 (s, 1H), 2.37 (q, 2H), 1.11 (t, 3H). IR (nujol, cm^-1): 1581 (m), 1530 (m).

Step B: 4-chloro-6-ethyl-5-nitropyrimidine

The product of Step A (0.85 g, 5.0 mmole) was combined with phosphorus oxychloride (10 mL) and heated at 100°C for one hour, during which the slurry became homogeneous. The mixture was concentrated under vacuum and the residue was added to ice. Concentrated NH₄OH solution was carefully added until the aqueous phase was basic. This solution was extracted several times with ether and the combined organic phases were dried (MgSO₄) and concentrated to give a waxy solid product (0.64 g, 68% yield). ¹H NMR (CDCl₃): δ 9.00 (s, 1H), 2.84 (q, 2H), 1.39 (t, 3H) .

Step C: 6-ethyl-5-nitro-N-[1-[4-(trimethylsilyl)-phenyl]-ethyl]-4-pyrimidinamine

The product of Step B (0.80 g, 4.3 mmole),

α-methyl-4-trimethylsilylbenzenemethanamine (0.91 g, 4.7 mmole), and triethylamine (1.2 mL, 8.6 mmole) were dissolved in toluene (5 mL) and heated at 110°C for 3 hours. After cooling, the mixture was diluted with ether and water and partitioned. The aqueous phase was extracted several times with ether and the combined organic phases were dried (MgSO₄), concentrated, and chromatographed on silica gel with 5% ethyl

acetate/hexane. The product was a yellow oil (1.3 g, 89% yield). ¹H NMR (CDCl₃): δ 8.51 (s, 1H), 8.02 (brd, 1H), 7.51, 7.35 (ABq, 4H), 5.51 (m, 1H), 2.97 (q, 2H), 1.62 (d, 3H), 1.32 (t, 3H), 0.25 (s, 9H).

By the procedures described herein, or obvious modifications thereof, the following compounds of

Tables 1 to 4 can be prepared. The compounds in Table 1, line 1 can be referred to as 1-1, 1-2, 1-3, 1-4 and 1-5 (as designated by line and column). All the other specific compounds covered in these Tables can be designated in an analogous fashion relying on the Table number to help distinguish between compounds 1-1 of Table 1 and 1-1 of Table 2, etc.

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. Useful formulations can be prepared in conventional ways. They include dusts, granules, baits, pellets, solutions, suspensions, emulsions, wettable powders, emulsifiable concentrates, dry flowables and the like. 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 an active ingredient, diluent and a surfactant within the following approximate ranges wherein the active ingredient plus surfactant and/or diluent equals 100 weight percent.

Weight Percent

Active

Ingredient Diluent Surfactant

Wettable Powders 25-90 0-74 1-10

Oil Suspensions, 5-50 40-95 0-15

Emulsions, Solutions,

(Including Emulsifiable

Concentrates)

Dusts 1-25 70-99 0-5

Granules, Baits and 0.01-99 5-99.99 0-15

Pellets

High Strength 90-99 0-10 0-2

Compositions 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 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, 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. Preferably, ingredients should be approved by the U.S. Environmental Protection Agency for the use intended.

Methods for formulating 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 mill or fluid energy mill. Water-dispersible granules can be produced be 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, pages 147 and following, Perry's Chemical

Engineer 's Handbook, 4th Ed., McGraw-Hill, New York, 1963, pages 8 to 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 be prepared as taught in DE 3,246,493.

For further information regarding the art of formulation, see U.S. Patent 3,235,361, Col. 6, line 16 through Col. 7, line 19 and Examples 10 through 41; U.S. Patent 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.

Patent 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 parts are by weight percent. Compound numbers refer to Index Table A.

Example A

High Strength Concentrate

Compound 1 98.5% silica aerogel 0.5% synthetic amorphous fine silica 1.0%

The ingredients are blended and ground in a hammer mill to produce a high strength concentrate,

essentially all particles passing a U.S.S. No. 50 sieve

(0.3.mm openings).

Example B

Wettable Powder

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

The ingredients are thoroughly blended. The liquid surfactant is added by spraying upon the solid

ingredients in the blender. 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).

Example C

Granule

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

25-50 sieves) 90.0%

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 , and the granules are allowed to cool.

Example D

Aqueous Suspension

Compound 1 25.0% hydrated attapulgite 3.0% crude calcium ligninsulfonate 10.0% sodium dihydrogen phosphate 0.5% water 61.5% The ingredients are ground together in a ball mill or roller mill until the solid particles have been reduced to diameters under 10 microns.

Example E

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% 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 can be used directly after drying, or the dried pellets can 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) can be used and the fines recycled.

Example F

Emulsifiable Concentrate

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

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

Example G

Dust

Wettable powder of Example B 10.0% pyrophyllite (powder) 90.0%

The wettable powder and the pyrophyllite diluent are thoroughly blended.

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 insects, 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 Nematoda. The compounds of this invention are also active against pests of the Orders Hymenoptera,

Isoptera, Phthiraptera, Siphonaptera, Blattaria, Thysanura and Pscoptera; pests belonging to the Class of Arachnida and Phylum Platyhelminthes. 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. They provide control of diseases caused by a broad spectrum of fungal plant pathogens in the Basidiomycete, Ascomycete and Oomycete classes. They are effective in controlling a broad spectrum of plant diseases, particularly foliar

pathogens of ornamental, vegetable, field, cereal, and fruit crops. These pathogens include Plasmopara viticola, Phytophthora infestans, Peronospora tabacina, Pseudoperonospora cubensis, Pythium aphanidermatum, Alternaria brassicae, Septoria nodorum, Cercosporidium personatum, Cercospora arachidicola, Pseudocercosporella herpotrichoides, Rhizoctinia Solani, Cercospora beticola, Botrytis cinerea, Monilinia fructicola, Pyricularia oryzae, Podosphaera

leucotricha, Venturia inaequalis, Erisyphe graminis, Puccinia recondita, Puccinia graminis, Hemileia

vastatrix, Puccinia striiformis, Puccinia arachidis, and other species closely related to these pathogens. The compounds of this invention also control seed pathogens.

Compounds of this invention can also be mixed with one or more other insecticides, fungicides,

nematocides, 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. Examples of other

agricultural protectants with which compounds of this invention can be formulated are: insecticides such as monocrotophos, carbofuran, avermectin B, tetrachlor-vinphos, malathion, parathion-methyl, methomyl, chlor- dimeform, diazinon, deltamethrin, oxamyl, fenvalerate, esfenvalerate, permethrin, profenofos, sulprofos, triflumuron, diflubenzuron, methoprene, buprofezin, thiodicarb, acephate, azinphosmethyl, chlorpyrifos, dimethoate, fonophos, isofenphos, methidathion, metha-midophos, 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, penconazole,

propiconazole, uniconzole, flutriafol, prochloraz, pyrifenox, fenarimol, triadimenol, diclobutrazol, copper oxychloride, furalaxyl, folpet and flusilazol; 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 and fenbutatin oxide; and biological agents such as Bacillus thuringiensis, and baculovirus.

In certain instances, combinations with other arthropodicides/fungicides having a similiar spectrum of control but a different mode of action will be particularly advantageous for resistance management.

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 non agronomic 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 with equipment that distributes the compound in the

environment of the pests, on 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 compounds can be applied to the foliage or applied to or

incorporated into the soil. Other methods of

application can also be employed including 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 which entice them to ingest or otherwise contact the compounds.

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, 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 control arthropod 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. In general, application rates of about 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 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 Tables A and B 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%.

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, 5, 7, 8, 9, 10, 12, 13, 14, 15, 16, 17, 18.

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, 5, 7, 8 , 9, 10, 13, 14, 15, 16, 17, 18.

TEST C

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 40 ppm: 1, 2, 3, 5, 8, 9, 10, 12, 13, 14, 1.5, 16, 17, 18.

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, 7, 18.

TEST E

Two spotted Spider Mite

One ince squares (2.54 centimeters) of kidney bean leaves that have been infested on the undersides with 25 to 30 adult mites ( Tetranychus urticae) were sprayed with their undersides facing up on a hydraulic sprayer.

Solutions of each of the test compounds

(acetone/distilled water 75/25 solvent) were sprayed by passing the leaves on a conveyer belt, directly beneath a flat fan hydraulic nozzle which discharged the spray at a rate of 0.5 pounds of active ingredient per acre (about 0.55 kg/ha) at 30 psi (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 hrs., after which time

mortality readings were taken. Of the compounds tested, the following gave levels of 80% or higher: 2 , 5 , 1 , 8, 10, 12, 14, 16, 17, 18. TEST F

Two spotted Spider Mite (Tetranychus urticae)

Ovicide Test

Two week old red kidney bean plants infested with two spotted spider mite eggs were sprayed to run-off using a turntable sprayer. Rates of 50 and 20 ppm active ingredient were applied. Plants were held in a chamber at 25°C and 50% relative humidity. Seven days after spray, mortality readings were conducted for egg and larval mortality and are reported below.

% Mortality 7 Days

Compound Rate PPM AI Ovicide Larvicide

2 50 91 83

20 46 96

Claims

What is claimed is:

1. A compound of Formula I :

wherein

Q is

,

or

;

A is C₂-C₅ straight or branched chain alkylene or C₃-C₆ cycloalkylene, wherein any one atom of A can be optionally substituted with R⁷;

X is Ge or Si;

R¹ is H, halogen, C₁-C₄ alkyl or C₁-C₄ haloalkyl;

R² is H, halogen, C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₂-C₄ cyanoalkyl, C₂-C₄ alkenyl, C₂-C₄ haloalkenyl, C₂-C₄ alkynyl, C₂-C₆ alkoxyalkyl or C₂-C₆ alkylthioalkyl;

R³ is H, halogen, CN, NO₂, CO₂R¹⁶, C(O)R¹6,

C(O)N(R¹⁶)R¹⁷, OR¹⁶, SR¹⁶, S(O)R¹⁶, S (O) ₂R¹⁶, N(R¹⁶)R¹⁷, C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₁-C₆ haloalkoxy, C₂-C₆ alkenyl, C₂-C₆ haloalkenyl, C₂-C₆ alkynyl, C₁-C₆ hydroxyalkyl, C₂-C₆ alkoxyalkyl, C₂-C₆ haloalkoxyalkyl, C₂-C₆ cyanoalkyl, C₂-C₆ alkylthioalkyl, C₂-C₆ haloalkylthioalkyl, C₃-C₄ cycloalkyl, SCN or C₁-C₆ alkyl substituted with N(R¹⁶)R¹⁷; provided that (i) when R² is H, halogen, C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₂-C₆ alkoxyalkyl or C₂-C₆ alkylthioalkyl then R³ is other than halogen, C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₂-C₆ alkoxyalkyl or C₂-C₆ alkylthioalkyl and (ii) when R³ is H, then R⁵ is other than C₁-C₆ haloalkylthio, C₁-C₆ haloalkylsulfinyl, C₁-C₆ haloalkylsulfonyl, C₁-C₆ alkylsulfonyl, C₁-C₆ alkylsulfinyl or C₁-C₆ alkylthio;

haloalkoxycarbonyl, C(O)R¹⁵, R¹¹OC(O)S-, R¹¹OC(O)N(R¹²)S-, R¹¹(R¹²)NS- or SR⁸; or R⁴ is C₁-C₆ alkyl optionally substituted with halogen, CN, NO₂, S(O)_nR¹¹, C(O)R¹¹, CO₂R¹¹ or

C₁-C₃ haloalkoxy; or R⁴ is phenyl optionally substituted with halogen, CN, and C₁-C₂ haloalkyl;

R⁵ is C₁-C₆ alkyl, C₁-C₆ alkoxy, C₁-C₆ haloalkoxy, C₂-C₆ alkoxyalkyl, C₂-C₆ alkoxyalkoxy, C₂-C₆ alkenyl, C₂-C₆ haloalkenyl, C₂-C₆ alkynyl, C₂-C₆ alkenyloxy, C₂-C₆ alkynyloxy, C₃-C₆ cycloalkyl, C₃-C₆ cycloalkylalkyl, C₁-C₆ alkylthio, C₂-C₆ alkylthioalkyl, C₁-C₆ alkylsulfinyl, C₁-C₆ alkylsulfonyl, C₁-C₆ haloalkylthio, C₁-C₆ haloalkylsulfinyl, C₁-C₆ haloalkylsulfonyl, phenyl optionally substituted with W or phenoxy optionally substituted with W;

R⁶ is H, halogen, CN, NO₂, C₁-C₂ alkyl, C₁-C₂ alkoxy or CF₃;

R⁷ is CN, C(O)R⁸, CO₂R⁸, C(O)N(R⁸)R⁹, N₃, NO₂,

N(R⁸)R⁹, N(R⁸)C(O)R⁹, N(R⁸)C(O)N(R¹⁰)R⁹,

N(R⁸)S(O)₂R¹⁰, OR⁸, OC(O)R⁸, OCO₂R⁸,

R⁸ and R¹⁰ are independently H, C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₂-C₆ alkenyl, C₂-C₆ haloalkenyl, C₂-C₆ alkynyl, C₃-C₆ haloalkynyl, C₂-C₆

alkoxyalkyl, C₂-C₆ alkylthioalkyl, C₁-C₆

nitroalkyl, C₂-C₆ cyanoalkyl, C₃-C₈

alkoxycarbonylalkyl, C₃-C₆ cycloalkyl, C₃-C₆ halocycloalkyl, phenyl optionally substituted with W; or benzyl optionally substituted with W on the phenyl ring;

R⁹ is H or C₁-C₄ alkyl; or

-CH₂CH₂OCH₂CH₂-;

R¹¹ and R¹² are independently C₁-C₄ alkyl;

R¹³ is C₁-C₄ alkyl, C₁-C₄ alkoxyalkyl or phenyl

optionally substituted with W;

R¹⁴ is C₁-C₆ alkyl, C₁-C₆ alkoxy, C₁-C₆ alkoxy,

C₁-C₆ haloalkoxy, C₁-C₆ haloalkoxy, phenyl or benzyl, each phenyl or benzyl optionally substituted with W on the aryl ring;

R¹⁵ is

, , or ;

R¹⁶ and R¹⁷ are independently H, C₁-C₄ alkyl or C₁-C₄ haloalkyl;

n is 0, 1 or 2.

2. A compound of Claim 1 wherein:

A is C₁-C₅ straight or branched alkylene;

R¹ is H;

R² is C₁-C₆ alkyl, C₂-C₄ cyanoalkyl or C₁-C₄ haloalkyl;

R⁴ is H;

R¹¹, R¹² and R¹³ are independently C₁-C₂

alkyl;

R¹⁴ is C₁-C₄ alkyl, C₁-C₄ alkoxy or phenyl

optionally substituted with W; and

W is halogen or C₁-C₂ haloalkyl.

3. A compound of Claim 2 wherein Q is

4. A compound of Claim 2 wherein Q is

5. A compound of Claim 2 wherein Q is

6. A compound which is

6-ethyl-4-[[1-4[4-(trimethylsilyl)phenyl]ethyl]- amino]-5-pyrimidinecarbonitrile.

7. An arthropodicidal or fungicidal composition comprising an effective amount of a compound of

Formula I

wherein

Q is ,

or

;

A is C₁-C₅ straight or branched chain alkylene or

C₃-C₆ cycloalkylene, wherein any one atom of A can be optionally substituted with R⁷; X is Ge or Si;

R¹ is H, halogen, C₁-C₄ alkyl or C₁-C₄ haloalkyl; R² is H, halogen, C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₂-C₄ cyanoalkyl, C₂-C₄ alkenyl, C₂-C₄ haloalkenyl, C₂-C₄ alkynyl, C₂-C₆ alkoxyalkyl or C₂-C₆ alkylthioalkyl;

R³ is H, halogen, CN, NO₂, CO₂R¹⁶, C (O) R¹⁶,

C (O) N (R¹⁶) R¹⁷, OR¹⁶, SR¹⁶, S (O) R¹⁶, S (O) ₂R¹⁶, N (R¹⁶) R¹⁷, C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₁-C₆ haloalkoxy, C₂-C₆ alkenyl, C₂-C₆ haloalkenyl, C₂-C₆ alkynyl, C₁-C₆ hydroxyalkyl, C₂-C₆ alkoxyalkyl, C₂-C₆ haloalkoxyalkyl, C₂-C₆ cyanoalkyl, C₂-C₆ alkylthioalkyl, C₂-C₆ haloalky Ithioalkyl, C₃-C₄ cycloalkyl, SCN or C₁-C₆ alkyl substituted with N (R¹⁶) R¹⁷;

provided that (i) when R² is H, halogen, C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₂-C₆ alkoxyalkyl or C₂-C₆ alkylthioalkyl then R³ is other than halogen, C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₂-C₆ alkoxyalkyl or C₂-C₆ alkylthioalkyl and (ii) when R³ is H, then R⁵ is other than C₁-C₆ haloalkylthio, C₁-C₆ haloalkylsulfinyl, C₁-C₆ haloalkylsulfonyl, C₁-C₆ alkylsulfonyl,. C₁-C₆ alkylsulfinyl or C₁-C₆ alkylthio;

R⁴ is H, formyl, C₂-C₆ alkoxyalkyl C₂-C₆ alkylcarbonyl, C₂-C₆ alkoxycarbonyl, C₂-C₆ haloalkoxycarbonyl, C(O)R¹⁵, R¹¹OC(O)S-,

R¹¹OC(O)N(R¹²)S-, R¹¹(R¹²)NS- or SR⁸; or R⁴ is C₁-C₆ alkyl optionally substituted with halogen, CN, NO₂, S(O)_nR¹¹, C(O)R¹¹, CO₂R¹¹ or

R⁵ is C₁-C₆ alkyl, C₁-C₆ alkoxy, C₁-C₆ haloalkoxy, C₂-C₆ alkoxyalkyl, C₂-C₆ alkoxyalkoxy, C₂-C₆ alkenyl, C₂-C₆ haloalkenyl, C₂-C₆ alkynyl, C₂-C₆ alkenyloxy, C₂-C₆ alkynyloxy, C₃-C₆ cycloalkyl, C₃-C₆ cycloalkylalkyl, C₁-C₆ alkylthio, C₁-C₆ alkylthioalkyl, C₁-C₆ alkylsulfinyl, C₁-C₆ alkylsulfonyl, C₁-C₆ haloalkylthio, C₁-C₆ haloalkylsulfinyl, C₁-C₆ haloalkylsulfonyl, phenyl optionally substituted with W or phenoxy optionally substituted with W;

R⁶ is H, halogen, CN, NO₂, C₁-C₂ alkyl, C₁-C₂ alkoxy or CF₃;

R⁷ is CN, C(O)R⁸, CO₂R⁸, C(O)N(R⁸)R⁹, N₃, NO₂,

R⁹ is H or C₁-C₄ alkyl; or

-CH₂CH₂OCH₂CH₂-;

R¹¹ and R¹² are independently C₁-C₄ alkyl;

R¹³ is C₁-C₄ alkyl, C₁-C₄ alkoxyalkyl or phenyl

optionally substituted with W;

R¹⁴ is C₁-C₆ alkyl, C₁-C₆ alkoxy, C₁-C₆ alkoxy,

R¹⁵ is

, , or ;

R¹⁶ and R¹⁷ are independently H, C₁-C₄ alkyl or

C₁-C₄ haloalkyl;

n is 0, 1 or 2.

and at least one of (a) a surfactant, (b) an organic solvent, and (c) at least one solid or liquid diluent.

8. A method for controlling plant pathogens or foliar, aquatic, and soil-inhabiting anthropod pests comprising applying to the locus of infestation, area to be protected or directly onto said pests, an

effective amount of a compound of Formula I

wherein

Q is

or ,

;

A is C₁-C₅ straight or branched chain alkylene or

R¹ is H, halogen, C₁-C₄ alkyl or C₁-C₄ haloalkyl; R² is H, halogen, C₁-C₆ alkyl, C₁-C₆ haloalkyl,

C₂-C₄ cyanoalkyl, C₂-C₄ alkenyl, C₂-C₄ haloalkenyl, C₂-C₄ alkynyl, C₂-C₆ alkoxyalkyl or C₂-C₆ alkylthioalkyl;

R³ is H, halogen, CN, NO₂, CO₂R¹⁶, C(O)R¹⁶,

C(O)N(R¹⁶)R¹⁷, OR¹⁶, SR¹⁶, S(O)R¹⁶, S(O)₂R¹⁶,

N(R¹⁶)R¹⁷, C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₁-C₆ haloalkoxy, C₂-C₆ alkenyl, C₂-C₆ haloalkenyl, C₂-C₆ alkynyl, C₁-C₆ hydroxyalkyl, C₂-C₆ alkoxyalkyl, C₂-C₆ haloalkoxyalkyl, C₂-C₆ cyanoalkyl, C₂-C₆ alkylthioalkyl, C₂-C₆ haloalkylthioalkyl, C₃-C₄ cycloalkyl, SCN or

C₁-C₆ alkyl substituted with N(R¹⁶)R¹⁷; provided that (i) when R² is H, halogen, C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₂-C₆ alkoxyalkyl or C₂-C₆ alkylthioalkyl then R³ is other than halogen, C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₂-C₆ alkoxyalkyl or C₂-C₆ alkylthioalkyl and (ii) when R³ is H, then R⁵ is other than C₁-C₆ haloalkylthio, C₁-C₆ haloalkylsulfinyl, C₁-C₆ haloalkylsulfonyl, C₁-C₆ alkylsulfonyl, C₁-C₆ alkylsulfinyl or C₁-C₆ alkylthio;

R⁶ is H, halogen, CN, NO₂, C₁-C₂ alkyl, C₁-C₂ alkoxy or CF₃; R⁷ is CN, C(O)R⁸, C0₂R⁸, C(O)N(R⁸)R⁹, N₃, NO₂,

N(R⁸)R⁹, N(R⁸)C(O)R⁹, N (R⁸) C (O) N (R¹⁰) R⁹,

N(R⁸)S(O)₂R¹⁰, OR⁸, OC(O)R⁸, OCO₂R⁸,

alkoxyalkyl, C₂-C₆ alkylthioalkyl, C₁-C₆

nitroalkyl, C₂-C₆ cyanoalkyl, C₃-C₈

R⁹ is H or C₁-C₄ alkyl;

-CH₂CH₂OCH₂CH₂-;

R¹¹ and R¹² are independently C₁-C₄ alkyl;

R¹³ is C₁-C₄ alkyl, C₁-C₄ alkoxyalkyl or phenyl

optionally substituted with W;

R¹⁴ is C₁-C₆ alkyl, C₁-C₆ alkoxy, C₁-C₆ alkoxy,

R¹⁵ is , , or ;

R¹⁶ and R¹⁷ are independently H, C₁-C₄ alkyl or

C₁-C₄ haloalkyl;

W is CN, NO₂, C₁-C₂ alkyl, C₁-C₂ haloalkyl, C₁-C₂ alkoxy, C₁-C₂ haloalkoxy, C₁-C₂ alkylthio, C₁-C₂ haloalkylthio, C₁-C₂ alkylsulfonyl, C₁-C₂ haloalkylsulfonyl or 1-5 halogens; and n is 0, 1 or 2.

9. A method for controlling plant pathogens or foliar, aquatic, and soil-inhabiting anthropod pests comprising applying to the locus of infestation, area to be protected, or directly onto said pests an effective amount of a composition of Claim 7.