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 R ³ 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

Q-l Q-2

Q-3

A is Ci-Cs straight or branched chain alkylene or ^ ₃ -Cg cycloalkylene, wherein any one atom of A can be optionally substituted with R ⁷ ; X is Ge or Si;

R ¹ is H, halogen C ₁ -C ₄ -alkyl or C- ~-C haloalkyl; R ² is H, halogen, Cχ- - alkyl, C^Cg haloalkyl, ^c ₂ ~ ^c ₄ cyanoalkyl, C -C alkenyl, C ₂ -C ₄ halo- alkenyl, C ₂ -C ₄ alkynyl, C ₂ -C ₆ alkoxyalkyl or C -Cg alkylthioalkyl; R ³ is H, halogen, CN, N0 ₂ , C0 ₂ R ¹⁶ , C(0)R ¹⁶ ,

C(0)N(R ¹⁶ )R ¹⁷ , OR ¹⁶ , SR ¹⁶ , S(0)R ¹⁶ , S(0) ₂ R ¹⁶ r N(R ¹⁶ )R ¹⁷ , Ci-Cg alkyl, C^Cg haloalkyl, C -Cg haloalkoxy, C ₂ -C ₆ alkenyl, C -C ₆ haloalkenyl, C -Cg alkynyl, ^-C hydroxyalkyl, C -Cg alkoxyalkyl, C ₂ -Cg haloalkoxyalkyl, C -C ₆ cyanoalkyl, C ₂ -Cg alkylthioalkyl, C ₂ -Cg halo- alkylthioalkyl, C ₃ -C ₄ cycloalkyl, SCN or C^-Cg alkyl substituted with N(R ¹⁶ )R ¹⁷ ;

provided that (i) when R ² is H, halogen, C _j^ -C alkyl, Ci-C haloalkyl, C ₂ -C ₆ alkoxyalkyl or C ₂ -C ₆ alkyl¬ thioalkyl then R ³ is other than halogen, Ci-Cg alkyl, C^ _^ -Cg haloalkyl, C ₂ -C ₆ alkoxyalkyl or C ₂ -C ₆ alkyl- thioalkyl and (ii) when R ³ is H, then R ⁵ is other than C^-Cg haloalkylthio, Cx-Cg haloalkylsulfinyl, C^ _^ -C haloalkylsulfonyl, C^Cg alkylsulfonyl, C ₁ -C ₆ alkylsulfinyl or C^C alkylthio;

R ⁴ is H, formyl, C ₂ -C ₆ alkoxyalkyl C ₂ -C ₆ alkyl- carbonyl, C ₂ -C ₆ alkoxycarbonyl, C ₂ -C ₆ haloalkoxycarbonyl, C(0)R ¹⁵ , R ^1:L OC(0)S-, R ^1:L OC(0)N(R ¹² )S-, R ^1] -(R ¹² )NS- or SR ⁸ ; or R ⁴ is C ₁ -C ₆ alkyl optionally substituted with halogen, CN, N0 ₂ , S(0) _n R ^1:L , C(0)R ^1:L , C0 ₂ R ^1:L or ^c ι~ ^c ₃ haloalkoxy; or R ⁴ is phenyl optionally substituted with halogen, CN, and C ₁ -C ₂ halo¬ alkyl; R ⁵ is Ci-Cg alkyl, Ci-Cg alkoxy, C^C haloalkoxy, C ₂ -C ₆ alkoxyalkyl, C ₂ -C ₆ alkoxyalkoxy, C ₂ -Cg alkenyl, C ₂ -Cg haloalkenyl, C ₂ -C ₆ alkynyl, C ₂ -C ₆ alkenyloxy, C ₂ -C ₆ alkynyloxy, C ₃ -C ₆ cycloalkyl, C ₃ -C ₆ cycloalkylalkyl, Ci-Cg alkylthio, C ₂ -C ₆ alkylthioalkyl, Cx-Cg alkylsulfinyl, C^-Cg alkylsulfonyl, Cx-C haloalkylthio, Cx-C haloalkylsulfinyl, Cx-Cg haloalkylsulfonyl, phenyl optionally substituted with W or phenoxy optionally substituted with W; R ⁶ is H, halogen, CN, N0 ₂ , C ₁ -C ₂ alkyl, C _x -C ₂ alkoxy or CF ₃ ; R ⁷ is CN, C(0)R ⁸ , C0 ₂ R ⁸ , C(0)N(R ⁸ )R ⁹ , N ₃ , N0 ₂ , N(R ⁸ )R ⁹ , N(R ⁸ )C(0)R ⁹ , N(R ⁸ )C(0)N(R ¹⁰ )R ⁹ , N(R ⁸ )S(0) ₂ R ¹⁰ , OR ⁸ , OC(0)R ⁸ , OC0 ₂ R ⁸ , OC(0)N(R ⁸ )R ⁹ , OS(0) ₂ R ⁸ , SR ⁸ , S(0)R ⁸ , S(0) ₂ R ⁸ , SCN or 1-3 halogens; R ⁸ and R ¹⁰ are independently H, Ci-Cg alkyl, C^C haloalkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ haloalkenyl,

C ₂ -Cg alkynyl, C ₃ -Cg haloalkynyl, C ₂ -Cg alkoxy¬ alkyl, C ₂ -Cg alkylthioalkyl, Cx-Cg nitroalkyl, C ₂ -C ₆ cyanoalkyl, C ₃ -C ₈ alkoxycarbonylalkyl, C ₃ -C ₆ cycloalkyl, C ₃ -C ₆ halocycloalkyl, phenyl optionally substituted with ; or benzyl optionally substituted with W on the phenyl ring;

R ⁹ is H or Cι~C ₄ alkyl; or

R ⁸ and R ⁹ can be taken together when attached to the same atom as -(CH ₂ ) ₄ -, -(CH ₂ ) ₅ - or

-CH ₂ CH ₂ OCH ₂ CH ₂ -;

R ¹¹ and R ¹² are independently C ₁ -C ₄ alkyl;

R ¹³ is Cχ-C ₄ alkyl, C^^ alkoxyalkyl or phenyl optionally substituted with W; R ¹⁴ is C^-C alkyl, C^-Cg alkoxy, C^Cg haloalkoxy, phenyl or benzyl, each phenyl or benzyl optionally substituted with W on the aryl ring;

R ¹⁵ is

R ¹⁶ and R ¹⁷ are independently H, C _x -C ₄ alkyl or

C ₁ -C ₄ haloalkyl; is CN, N0 ₂ , C _! -C ₂ alkyl, C _! -C ₂ haloalkyl, C _x -C ₂ alkoxy, C-L-C ₂ haloalkoxy, C -C ₂ alkylthio, C- _L -C ₂ haloalkylthio, C ₁ -C ₂ alkylsulfonyl, C ₁ -C haloalkylsulfonyl or 1-5 halogens; and n is 0, 1 or 2. Preferred Compounds A are compounds of Formula I wherein:

A is C^Cs straight or branched alkylene; R ¹ is H;

R ² is C -Cg alkyl, C ₂ -C ₄ cyanoalkyl or C ₁ -C haloalkyl;

R ⁴ is H;

R ⁵ is C^-C alkyl, C^-Cg haloalkoxy, C ₂ -C ₆ alkoxyalkyl, C ₂ -Cg alkoxyalkoxy or phenoxy optionally substituted with W; R ⁶ is H, halogen or C ₁ -C ₂ alkyl;

R ¹¹ , R ¹² and R ¹³ are independently C ₂ -C ₂ alkyl; R ¹⁴ is Cx-C _j alkyl, C _x -C alkoxy or phenyl optionally substituted with ; and is halogen or C _! -C ₂ haloalkyl.

Preferred Compounds B are compounds of Preferred A wherein Q is Q-l. 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 di erent 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. Alkyl¬ sulfinyl, alkylsulfonyl, alkylamino, etc., are defined analogously to i e 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 CH ₂ CH ₂ F, CF ₂ CF ₃ and CH ₂ CHFC1. The terms "halocyclo- alkyl", "haloalkenyl" and "haloalkynyl" are defined analogously to the term "haloalkyl". The total number of carbon atoms in a substituent group is indicated by the "Ci-C _j " prefix where i and j

are numbers from 1 to 8. For example, Cι~C ₃ alkyl¬ sulfonyl designates methylsulfonyl through propyl- sulfonyl; C ₂ alkoxyalkoxy designates OCH2θCH ₃ ; C alkoxyalkoxy designates the various isomers of an alkoxy group substituted with a second alkoxy group containing a total of 4 carbon atoms, examples including OCH ₂ OCH ₂ CH ₂ CH ₃ and OCH ₂ CH ₂ OCH ₂ CH ₃ ; C ₂ cyanoalkyl designates CH ₂ CN and C ₃ cyanoalkyl designates CH ₂ CH ₂ CN and CH(CN)CH ₃ ; C ₂ alkylcarbonyl would designates C(0)CH ₃ and C alkylcarbonyl includes C(0)CH ₂ CH ₂ CH ₃ and C(0)CH(CH ₃ ) ₂ ; and as a final example, C ₃ alkoxycarbonylalkyl designates CH C0 ₂ CH ₃ and C alkoxycarbonylalkyl includes CH ₂ CH ₂ C0 ₂ CH ₃ , CH ₂ C0 ₂ CH ₂ CH ₃ and CH(CH ₃ )C0 ₂ CH ₃ . 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, R ² and R ³ are as previously defined for ^" Formula I.

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-dimethyl- acetamide. 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 R ⁴ is an alkyl or acyl group can be best prepared by reacting an amine of Formula III where R ⁴ is an alkyl or acyl group with a pyrimidine of Formula II. The amine of Formula III where R ⁴ is alkyl or acyl can be prepared by acylating or alkylating an amine of Formula III, where R ⁴ 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

AlCl , LiAlH, QC _H2 CN NH ₂ CH ₂ CH ₂ Q

IV III

=H, A=CH ₂ CH ₂

Amines of Formula III wherein A is equal to CH ₂ CH ₂ 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.

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

NBS (1 eq)

Q-CH ₃ - ► QCH ₂ Br sunlamp

VI V

Aryl methyl groups in compounds of Formula VI are subject to free radical bromination by N-bromo¬ succinimide (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

CH,

CH, ^c a) LiN ( MS) = .CH^

H b) CH ₃ CH ₂ MgBr NH,

VII

III

R*«=H, A=CHCH ₂ CH ₃

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 CHCH ₂ CH ₃ 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

&gN ^Q _{3 |}

Q—CHBr ₂ Q—CHO

H ₂ 0 VIII VII

The dibromides can, in turn, be prepared from compounds of Formula VI. Aryl methyl compounds of Formula VI are subject to free radical bro ination 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.

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, ϋbe Industries in JP 58(83) 222,070, and Lonza Ag in EP 370,391. Some pyrimidines of Formula II where R ³ 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 R ³ is equal to N0 ₂ to a pyrimidine of Formula II where R ³ is equal to NH ₂ with hydrogen and Raney nickel

in ethanol. Another example is displacement of bromide from a compound of Formula I where R ³ is equal to Br with sodium methylthiolate (NaSCH ₃ ) to give a compound of Formula I where R ³ is equal to SCH ₃ . This material may be further oxidized with metachloroperbenzoic acid to give a compound of Formula I where R ³ is equal to S(0)CH ₃ or S(0) ₂ CH ₃ .

Some of the preferred compounds of Formula I may be prepared by Palladium catalyzed reactions as shown in Scheme 9, wherein A, Q and R ² are as originally defined in Formula I.

SCHEME 9

R ⁴ -H,alkyl R ³ -CN,alkenyl,alkynyl

Palladium complexes of triarylphosphines are the preferred catalysts of this reaction. Some examples are tetrakis(triphenylphosphine)palladium(0) , bis(tri- phenylphosphine)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 R ³ . 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 MR ³ 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 R ³ is equal to C0 ₂ R ¹⁶ , C(0)R ¹⁶ , and CHO.

EXAMPLE 1

Step A; 6-ethyl-5-iQdQ-4-pyrimidinol 6-ethyl-4-pyrimidinol (1.2 g, 10 mmole) and N-iodo- succinimide (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. *H NMR (CDC1 ₃ ) : δ 13.12 (brs, IH) , 8.10 (s, IH) , 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 NH ₄ OH solution. After extracting the aqueous solution several times with methylene chloride, the combined organic phases were dried (MgS0 ₄ ) and concentrated. The resultant product was a waxy yellow

solid (1.6 g, 93% yield). ~R NMR (CDC1 ₃ ) : δ 8.74 (s, IH) , 3.04 (q, 2H), 1.31 (t, 3H) .

Step C: 6-ethyl-5-iodo-N-π-T4-ftrimethylsilyl)- phenyllethyl1-4-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 (MgS0 ₄ ) , concentrated, and chromatographed on silica gel with 10% ethyl acetate/ hexane. The resultant product was a waxy solid (1.9 g, 82% yield). -R NMR (CDC1 ₃ ) : δ 8.32 (s, IH), 7.50, 7.35 (ABq, 4H) , 5.75 (brd, IH) , 5.35 (m, IH), 2.88 (q, 2H) , 1.59 (d, 3H) , 1.24 (t, 3H) , 0.26 (s, 9H) .

Step D; β-ethyl-4- i Tl-T4-(fcrimethylsilγHphenyll-

P- hyllamino1-5-pyrimidinecarhonitrile 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 (MgS0 ₄ ) , 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. ^-H NMR (CDC1 ₃ ) : δ 8.59 (s, IH) , 7.52, 7.34 (ABq, 4H) , 5.64 (brd, IH), 5.43 (m, IH) , 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: l-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 NH C1 was added and the reaction mixture partitioned. The aqueous phase was extracted three times with ether, and the combined organic phases were dried (MgS0 ₄ ) and concentrated. The resultant oil (60 g, 93% yield) was used in the next step without further purification. ^X H NMR (CDC1 ₃ ) : δ 7.43, 7.22 (ABq, 4H) , 2.64 (q, 2H) , 1.24 (t, 3H), 0.25 (s, 9H) .

Step B; 1-bromo-l-f -trimethylsilylphenγllethane

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 NaHS0 ₃ . Drying (MgS0 ₄ ) and concentration gave an oil (77 g, 91% yield) which was used in the next step without further purification. ^-H NMR (CDC1 ₃ ) : δ 7.48, 7.43 (ABq, 4H) , 5.20 (q, IH) , 2.07 (d, 3H) , 0.26 (s, 9H) .

Step C: 1 r4-trimethylsilylphenyπ -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 (MgS0 ₄ ) and concentrated to give an oil (91 g, 94% yield) which was used in the next step without further purification. ^X H NMR (CDC1 ₃ ) : δ 7.80 (m, 2H) , 7.69 (m, 2H) , 7.49 (s, 4H) , 5.57 (q, IH), 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 ( 00 mL) and heated to reflux for two hours. After cooling, the reaction mixture was poured into 6% aqueous K ₂ C0 ₃ solution. The aqueous mixture was extracted three times with ether and the combined organic phases were dried (MgS0 ₄ ) and concentrated to give an oil (49 g, 90% yield) which was used in the next step without further purification. ¹ H NMR (CDC1 ₃ ) : δ 7.48, 7.35 (ABq, 4H) , 4.10 (q, IH) , 1.65 (brs, 2H), 1.39 (d, 3H) , 0.26 (s, 9H) .

Step E: 6-ethyl-N-ri-T4-(trimethylsilylϊ henyllethyll- 4-p rimidinamine

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 L) . 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 (MgS0 ₄ ) , 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). ^ ^• H NMR (CDC1 ₃ ) : δ 8.48 (s, IH) , 7.49, 7.32 (ABq, 4H) , 6.04 (s, IH), 5.25 (brd, IH) , 4.85 (m, IH) , 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 (MgS0 ₄ ) , concentrated, and chromatographed on silica gel with 10% methanol/ chloroform. The product was an orange solid (0.85 g, 59% yield). ^-H NMR (CDC1 ₃ ) : δ 8.13 (s, IH) , 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 NH OH 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 (MgS0 ) and concentrated to give a waxy solid product (0.64 g, 68% yield). ¹ H NMR (CDC1 ₃ ) : δ 9.00 (s, IH) , 2.84 (q, 2H), 1.39 (t, 3H) . Step C; 6-ethyl-5-nitro-N-Tl-14-(trimethylsilylϊ- phenyll-ethyll-4-pyrimidinamine The product of Step B (0.80 g, 4.3 mmole), -methyl-4-trimethylsilylbenzenemethanamine (0.91 g,

4.7 mmole), and triethylamine (1.2 mL, 8.6 mmole) were dissolved in toluene (5 L) 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 (MgS0 ₄ ) , concentrated, and chromatographed on silica gel with 5% ethyl acetate/hexane. The product was a yellow oil (1.3 g, 89% yield). -K NMR (CDC1 ₃ ) : δ 8.51 (s, IH) , 8.02 (brd, IH), 7.51, 7.35 (ABq, 4H) , 5.51 (m, IH) , 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.

Key to Tables

K-l K-2

O 0

R-R ⁵ or CR ¹⁴ or X (R ^1:L ) (R ¹² ) (R ¹³ ) R-R ⁵ or CR ¹⁴ or X (R ^1:L ) (R ¹² ) (R ¹³ )

K-3 K-4

R=R ⁵ or CR ¹⁴ or XfR ¹¹ ) (R ¹² ) (R ¹³ ) R=R ⁵ or CR ¹⁴ or X(R ¹³ -) (R ¹² ) (R ¹³ )

The following abbreviations are used in the Tables

tBu «= tert butyl Me - CH,

Table 1

K-K-l

R- =4-tBu R ² -Me; R ³ - R- '4-tBu R ² -Et; R ³ = R- '4-tBu R ² -CF ₃ ; R ³ *= R" ■4-tBu R ² «nPr; R >« R- ■4-tBu, R ² -CH ₂ OMe; R ³ « R« '4-tBu R ² -CH ₂ CN; R ³ - R- ■4-tBu R ² -CHCH ₂ ; R ³ - R- •4-tBu R ² -CCH; R ³ -= R~ ■3-tBu R ² -Me; R ³ = R- -3-tBu, R ² -Efc; R ³ - R- ■3-tBu R ² =CF ₃ ; R « R~ •3-tBu R ² -nPr; R ³ « R- 3-tBu R ² -CH ₂ OMe? R ³ - R- 3-tBu R ² -CH ₂ CN; R ³ - R- 3-tBu R ² -CHCH ₂ ; R ³ « R- 3-tBu R ² -CCH; R ³ « R- ^■ 4-CH ₂ CH ₂ OE R ² -Me; R ³ - R- 4-CH ₂ CH ₂ OEt ₁ R ^2« Et; R ^3« R- ■4-CH ₂ CH ₂ OEt R ² -CF ₃ ; R ³ - R- ■4-CH ₂ CH ₂ OEt R ² — nPr; R ³ — R- 4-CH ₂ CH ₂ OE R ^2« =CH ₂ OMe; R ³ - R- 4-CH ₂ CH ₂ OEt R ² -CH ₂ CN; R ³ = R- ^■ 4-CH ₂ CH ₂ OEt R ² -CHCH ₂ ; R ³ «= R- ■4-CH ₂ CH ₂ OEt R ² -CCH; R ³ - R-4-OCH ₂ CH ₂ OEt; R ² -Me; R ³ - R-4-OCH ₂ CH ₂ OEt; R ² -Et; R ³ - R-4-OCH ₂ CH ₂ OEt? R ² -CF ₃ ; R ³ = R-4-OCH ₂ CH ₂ OEt; R=nPr; R ³ = R-4-OCH ₂ CH ₂ OEt; R ² =CH ₂ OMe; R ³ = R-4-OCH ₂ CH ₂ OEt; R ² -CH ₂ CN; R ³ = R-4-OCH ₂ CH ₂ OEt; R ² -CHCH ₂ ; R ³ =

K-K-l

K-K-l ^« 3-tBu; R ² «=Et; R ³ « ■3-tBu; R ² -=CF ₃ A R ³ = '3-tBu; R ² «nPr; R ³ « ■3-tBu; R ² «CH ₂ OMe; R ³ - ■3-tBu; R ² -CH ₂ CN; R ³ - ■3-tBu R ² -CHCH ₂ R ³ = '3-tBu; R ² -CCH; R ³ = «4-CH ₂ CH ₂ OEt; R ² -*le,* R ³ - ■4-CH ₂ CH ₂ OEt; R ² -Et; R ³ - ■4-CH ₂ CH ₂ OEt; R ² -CF ₃ ; R ³ - ■4-CH ₂ CH ₂ OEt; R ² -nPr; R ³ «= «4-CH ₂ CH ₂ OEt; R ² -CH ₂ OMe; R ³ - ■4-CH ₂ CH ₂ OEt; R ² -CH ₂ CN; R ³ - •4-CH ₂ CH ₂ OEt; R ² -CHCH ₂ ; R ³ = ■4-CH ₂ CH ₂ OEt; R ² -CCH; R ³ - •4-OCH ₂ CH ₂ OEt; R ² -Me; R ³ - »4-OCH ₂ CH ₂ OEt; R ² -Et; R ³ - •4-OCH ₂ CH ₂ OEt; R ² «CF ₃ ,- R ³ - ■4-OCH CH ₂ OEt; R ² -nPr; R ³ - «4-OCH CH ₂ OEt; R ² «CH ₂ QMe; R ³ - >4-OCH ₂ CH ₂ OEt; R ² -CH ₂ CN; R ³ - ■4-OCH ₂ CH ₂ OEt; R ² -CHCH ₂ ; R ³ - ■4-0CH ₂ CH ₂ 0Et; R ² «CCH; R ³ = <4-OCHF ₂ ; R ² -Me R ³ - ■4-OCHF ₂ ; R ² -Et; R ³ «= ■4-OCHF ₂ f R ² -CF ₃ ; R ³ «* ■4-OCHF ₂ ; R ² -nPr; R ³ - <4-OCHF ₂ ? R ² =CH ₂ OMe; R ³ «= ^« 4-OCHF ₂ ; R ² -CH ₂ CN; R ³ =4-OCHF ₂ ; R ² =CHCH ₂ ; R ³ = ^« 4-OCHF ₂ ; R ² -CCH; R ³ = *3-OCHF ₂ ; R ² «Me? R ³ - =3-OCHF ₂ ; R ² «Et; R ³ »

K-K-l

K-K-l

262 R" ■4-CH ₂ CH ₂ OEt; R ² =CH ₂ CN; R ³ = 263 R» ■4-CH ₂ CH ₂ OEt; R ² -CHCH ₂ ; R ³ -= 264 R- ^« 4-CH ₂ CH ₂ OEt; R ² -CCH; R ^3« = 265 R- ■4-0CH ₂ CH ₂ 0Et; R ² -Me; R ³ = 266 R» ■4-OCH ₂ CH ₂ OEtA R ² -Et; R ^3« * 267 R- ^■ 4-0CH ₂ CH ₂ 0Et; R ² -CF ₃ ; R ³ - 268 R- ■4-OCH ₂ CH ₂ OEt; R ^2« nPr; R ³ - 269 R- >4-OCH ₂ CH ₂ OEt; R ² -CH ₂ OMe; R ^3« 270 R- ■4-OCH ₂ CH ₂ OEt; R ² -CH ₂ CN; R ³ - 271 R- ■4-0CH ₂ CH ₂ 0Et; R ² -CHCH ₂ ; R ³ - 272 R= ■4-0CH ₂ CH ₂ 0Et; R ^2» CCH; R ³ = 273 R- ■4-0CHF ₂ R ² -Me; R ³ - 274 R- ■4-0CHF R ² -Et; R ³ - 275 R- =4-0CHF ₂ R ² «CF ₃ Λ R ³ - 276 R- ■4-0CHF ₂ R ² -nPr; R ³ - 277 R- ■4-0CHF ₂ R ² -CH ₂ OMe; R ³ - 278 R- ■4-0CHF ₂ R ² -CH ₂ CN; R ³ « 279 R- >4-0CHF ₂ R ² -CHCH ₂ f R ³ - 280 R- ■4-0CHF ₂ R ² -CCH; R ³ - 281 R- 3-0CHF ₂ R ² -Me; R ³ - ^" 282 R- 3-0CHF ₂ R ² -Et; R ³ - 283 R- ■3-0CHF ₂ R ² -CF ₃ ; R ³ « 284 R- <3-0CHF ₂ R ² — nPr; R ³ — 285 R- =3-OCHF ₂ R ² -CH ₂ OMe; R ³ - 286 R- 3-OCHF ₂ R ² -CH ₂ CN; R ³ - 287 R- ■3-OCHF ₂ R ² -CHCH ₂ ; R ³ «= 288 R- <3-0CHF ₂ R ² -CCH; R ³ « 289 R- ■4-OCH ₂ CF ₃ ; R ² -Me; R ³ - 290 R- '4-OCH ₂ CF ₃ ; R ² -Et; R ³ = 291 R- :4-OCH ₂ CF ₃ ; R ² =CF ₃ ; R ³ = 292 R~ 4-0CH ₂ CF ₃ ; R ² -nPr R ³ = 293 R- <4-0CH ₂ CF ₃ ; R ² =CH ₂ OMe; R ^3« 294 R- 4-OCH ₂ CF ₃ ; R ² -CH ₂ CN; R ³ «=

K-K-l

361 R=4-tBu; R ² -=CH ₂ CN; R ³ -

362 R-4-tBu; R ² ~CHCH ₂ ; R ³ =

363 R-4-tBu; R ² -CCH; R ³ -

364 R-3-tBu; R ² -=CH ₂ CN; R ³ -

365 R=3-tBu; R ² -CHCH ₂ ; R ³ «=

366 R-4-tBu; R ² -CCH; R ³ -

367 R=4-CH ₂ CH ₂ OEt; R ² -CH ₂ CN; R ³ =

368 R-4-CH ₂ CH ₂ OEt; R ² -CHCH ₂ ; R ³ =

369 R-4-CH ₂ CH ₂ OEt; R ² «=CCH; R ³ «=

370 R-4-OCH ₂ CH ₂ OEt; R ² -CH ₂ CN; R ³ -

371 R-4-OCH ₂ CH ₂ OEt; R ² -CHCH ₂ ; R ³ -

372 R-4-OCH ₂ CH ₂ OEt; R ² -CCH; R ³ -

373 R-4-OCHF ₂ ; R ² -CH ₂ CN; R ³ -

374 R-4-OCHF ₂ ; R ² -CHCH ₂ ; R ³ -

375 R-4-OCHF ₂ ; R ² -CCH; R ³ -

376 R-3-OCHF ₂ ; R ² -CH ₂ CN; R ³ -

377 R»3-OCHF ₂ ; R ² «CHCH ₂ ; R ³ -

378 R-3-OCHF ₂ ; R ² -CCH; R ³ -

379 R-4-OCH ₂ F ₃ ; R ² «CH ₂ CN; R ³ -

380 R-4-OCH F ₃ ; R ² -CHCH ₂ ; R ³ =

381 R-4-OCH ₂ F ₃ ; R ² -CCH; R ³ -

382 R-3-OCH ₂ F ₃ ; R ² -CH ₂ CN R ³ -

383 R-3-OCH ₂ F ₃ ; R ² «CHCH ₂ ; R ³ =

384 R-3-OCH ₂ F ₃ ; R ² -CCH; R ³ -

385 R-4-SiMe ₃ R ² -CH ₂ CN; R ³ -

386 R-4-SiMe ₃ R ² =CHCH ₂ ; R ³ «=

387 R-4-SiMe ₃ R ² =CCH; R ³ =

388 R-3-SiMe ₃ R ² -CH ₂ CN; R ³ =

389 R«3-SiMe ₃ R ² =CHCH ₂ ; R ³ =

390 R=3-SiMe ₃ R =CCH; R ³ *=

391 R-4-SiEt ₃ R ² =CH ₂ CN; R ³ =

392 R-4-SlEt ₃ R ² =CHCH ₂ ; R ³ =

Table 2

K-K-2

1 ■4-tBu, R ² -Me; R ³ -

2 ■4-tBu R ² -Et; R ³ -

3 ■4-tBu R ² -CF ₃ ; R ³ -

4 ■4-tBu R ² — nPr; R ³ -

5 •4-tBu R ² -CH ₂ QMe; R ³ -

6 •4-tBu R ² -CH ₂ CN; R ³ -

7 ■4-tBu R ² -CHCH ₂ ; R ³ -

8 •4-tBu R ² -CCH; R ³ <~

9 «3-tBu R ² -Me; R ³ - 0 •3-tBu R ² -Et; R ³ = 1 •3-tB R ² -CF ₃ ; R ³ - 2 =3-tBu R ² «=nPr; R = 3 •3-tBu R ² «CH ₂ OMe; R ³ - 4 *3-tBu R ² »CH ₂ CN; R ³ = 5 =3-tBu R ² -CHCH ₂ ; R ³ = 6 •3-tBu R ² -CCH; R ³ -=

K-K-2 R-4 -CH ₂ CH ₂ OEt; R ² -Me; R ³ = R=4 -CH ₂ CH ₂ OEt; R ² -Et; R ³ = R-4 -CH ₂ CH ₂ OEt; R ² -CF ₃ ; R ³ - R-4 -CH ₂ CH ₂ OEt; R ² -nPr; R ³ - R-4 -CH CH ₂ OEt; R ² -CH ₂ OMe; R ³ = R-4 ^■ CH ₂ CH ₂ OEt; R ² -CH ₂ CN; R ^3« = R-4' ^■ CH ₂ CH ₂ OEt; R ² -CHCH ₂ ; R ³ - R-4' -CH ₂ CH ₂ OEt; R ² -CCH; R ³ - R-4 ^• OCH ₂ CH ₂ OEt; R ² -Me; R ³ - _ R-4' -OCH ₂ CH QEt; R ² -Et; R ³ - R-4' ^■ OCH ₂ CH ₂ OEt; R ² -CF ₃ ; R ³ = R-4' ^■ OCH ₂ CH ₂ OEt; R ² -nPr; R ³ - R-4' ^■ OCH ₂ CH ₂ OEt; R ² -CH ₂ OMe; R ³ - R-4' -OCH ₂ CH ₂ OEt; R ² -CH ₂ CN R ³ - R-4' ^■ OCH ₂ CH ₂ OEt; R ² -CHCH ₂ ; R ³ = R-4- ^■ OCH ₂ CH ₂ OEt; R ² -CCH; R ³ - R-4- -OCHF ₂ R ² -Me; R ³ - R-4- ^■ OCHF ₂ R ² -Et; R ³ - R-4- ^■ OCHF ₂ R -CF ₃ ; R ³ - R-4- ^■ 0CHF ₂ R ² -nPr; R ³ - R-4- ^■ OCHF ₂ R ² -CH ₂ OMe; R ³ - R-4- ^■ OCHF ₂ R ² -CH ₂ CN; R ³ = R-4- ^• 0CHF ₂ R ² -CHCH ₂ ; R ³ - R=4- ^■ 0CHF ₂ R ² «=CCH; R ³ - R-3- ^■ 0CHF ₂ R ² -Me; R ³ - R-3- ^• 0CHF ₂ R ² -Et; R ³ - R=3- ^■ OCHF ₂ R ^2β C ₃ ; R = R-3- ^■ 0CHF ₂ R ² -nPr; R ³ - R-3- ^■ OCHF ₂ R ² -CH ₂ OMe; R ³ «= R-3- ^• OCHF ₂ R ² -CH ₂ CN; R ³ «= R-3- ^• OCHF ₂ R ² -CHCH ₂ ; R ³ = R-3- ^■ 0CHF ₂ R ² -CCH; R ³ = R-4 -0CH ₂ CF ₃ ; R ² -Me; R ³ -

K-K-2

116 «4-C0 ₂ Et; R ² -nPr; R ³ - 117 •4-C0 ₂ Et; R ² -CH ₂ 0Me; R ³ « 118 ■4-C0 Et; R ² -CH ₂ CN; R ³ - 119 ■4-C0 ₂ Et; R ² -CHCH ₂ ; R ³ - 120 >4-C0 ₂ Et; R ² -CCH; R ³ = 121 ■4-tBu R ² -Me; R ³ - 122 '4-tBu R ² -Et; R ³ - 123 ■4-tBu R ² -CF ₃ ; R ³ - 124 ■4-tBu, R ² -nPr; R ³ - 125 ■4-tBu R ² -CH ₂ OMe; R ³ - 126 ■4-tBu R ² -CH ₂ CN; R ³ - 127 ■4-tBu R ² -CHCH ₂ ; R ³ - 128 '4-tBu R ² -CCH; R ³ - 129 ■3-tBu R ² -Me; R ³ - 130 -3-tBu R ² -Et; R ³ - 131 ■3-tBu R ² -CF ₃ ; R ³ - 132 ■3-tBu R ² -nPr; R ³ - 133 3-tBu R ² -CH ₂ CMe; R ³ - 134 3-tBu R ² -CH ₂ CN; R ³ - ^~ 135 3-tBu R ² -CHCH ₂ ; R ³ - 136 <3-tBu R ² -CCH; R ³ - 137 ■4-CH ₂ CH ₂ OEt; R ² -Me; R ³ - 138 =4-CH ₂ CH ₂ OEt; R ² -Etf R ³ = 139 -CH ₂ CH ₂ 0Et; R ² -CF ₃ ; R ³ - 140 <4-CH ₂ CH ₂ OEt; R ² -nPr,- R ³ - 141 ^■ 4-CH ₂ CH ₂ OEt; R ² -CH ₂ OMe; R ³ - 142 ■4-CH ₂ CH ₂ OEt; R ² -CH ₂ CN; R ³ - 143 ■4-CH ₂ CH ₂ OEt; R ² -CHCH ₂ R ³ = 144 =4-CH ₂ CH ₂ OEt; R ² -CCH; R ³ = 145 <4-0CH ₂ CH ₂ 0Et,* R ² -Me; R ³ = 146 ■4-0CH ₂ CH ₂ OEt; R ² -Et; R ³ = 147 ■4-OCH ₂ CH ₂ OEt; R ² -CF ₃ ; R ³ - 148 >4-OCH ₂ CH ₂ OEt; R ² -nPr; R ³ -

K-K-2

149 R> ^■ 4-OCH CH OEt; R ² -CH ₂ OMe; R ³ = 150 R" •4-OCH ₂ CH ₂ OEt; R ² -CH ₂ CN; R ³ - 151 R» ^« 4-OCH ₂ CH ₂ OEt; R ² =CHCH ₂ ; R ³ = 152 R ^« >4-OCH ₂ CH OEt; R ² =CCH; R ³ = 153 R- •4-OCHF ₂ R ² -Me; R ³ - 154 R" ■4-OCHF ₂ R ² -Et; R ³ = 155 R- •4-OCHF ₂ R ² -CF ₃ ; R ³ - 156 R- ■4-OCHF R ² -nPr; R ³ - 157 R- ■4-OCHF R ² -CH ₂ OMe; R ³ - 158 R= »4-OCHF ₂ R ² =CH ₂ CN; R ³ = 159 R- •4-OCHF ₂ R ² -CHCH ₂ ; R ³ - 160 R- =4-OCHF ₂ R ² -CCH; R ³ - 161 R- ^■ 3-OCHF ₂ R ² -Me; R ³ - 162 R- =3-OCHF ₂ R ² -Et; R ³ - 163 R- ■3-OCHF ₂ R ² -CF ₃ ; R ³ - 164 R- ■3-OCHF ₂ R ² -nPr; R ³ - 165 R- ■3-OCHF ₂ R ² -CH ₂ OMe; R ³ - 166 R- >3-OCHF ₂ R ² -CH ₂ CN; R ³ - 167 R- ^■ 3-OCHF R ² -CHCH ₂ ; R ³ - 168 R- >3-OCHF ₂ R ² -CCH; R ³ - 169 R- ■4-OCH ₂ CF ₃ R ² -Me; R ³ - - 170 R- >4-OCH ₂ CF ₃ R ² -Et ; R ³ - 171 R- ■4-OCH ₂ CF ₃ R ² -CF ₃ ; R ³ - 172 R- ■4-OCH ₂ CF ₃ R ² -nPr; R ³ - 173 R- ■4-OCH ₂ CF ₃ R ² -CH ₂ OMe; R ³ - 174 R- ■4-OCH ₂ CF ₃ R ² -CH ₂ CN; R ³ = 175 R- ■4-OCH ₂ CF ₃ R ² -CHCH ₂ ; R ³ - 176 R- ■4-OCH ₂ CF ₃ R ² -CCH; R ³ = 177 R" ■3-OCH ₂ CF ₃ R ² -Me; R ³ = 178 R- •3-OCH ₂ CF ₃ R ² -Et; R ³ = 179 R- ^■ 3-OCH ₂ CF ₃ R"-CF 3' ^' 180 R- <3-OCH ₂ CF ₃ R ² -nPr; R ³ = 181 R- •3-OCH ₂ CF ₃ R ² -CH ₂ OMe; R ³ =

K-K-2

248 R« «4-tBu; R ² -CCH; R ³ -

249 R. ^» 3-tBu; R ² -Me; R ³ -

250 R- ^■ 3-tBu; R ² -Et; R ³ -

251 R- ■3-tBu; R ² -CF ₃ ; R ³ -

252 R> •3-tBu; R ² -nPr; R ³ —

253 R- •3-tBu; R ² -CH ₂ OMe; R ³ - 254. R« "3-tBur R ² -CH CN; R ³ - 255 R" '3-tBu; R ² -CHCH ₂ ; R ³ - 256 R> '3-tBu? R ² -CCH; R ³ - 257 R> ■4-CH ₂ CH ₂ OEt; R ² -Me; R ³ - 258 R> ^■ 4-CH ₂ CH ₂ OEt; R ² -Et; R ³ - 259 R« ^» 4-CH ₂ CH ₂ OEt; R ² -CF ₃ ; R ³ - 260 R« ^« 4-CH ₂ CH ₂ OEt; R ² -nPr; R ³ - 261 R> ■4-CH ₂ CH ₂ OEt; R ² -CH ₂ CMe; R ³ - 262 R- ■4-CH ₂ CH ₂ OEt; R ² -CH ₂ CN; R ³ - 263 R> ^« 4-CH ₂ CH ₂ OEt; R ² -CHCH ₂ ; R ³ - 264 R- ■4-CH ₂ CH ₂ OEt; R ² -CCH; R ³ - 265 R> ^■ 4-OCH ₂ CH ₂ OEt; R ² -Me; R ³ - 266 R- ■4-OCH ₂ CH ₂ OEt; R ² -Et; R ³ - 267 R- ■4-OCH ₂ CH ₂ OEt; R ² -CF ₃ ; R ³ - 268 R« >4-OCH ₂ CH ₂ OEt,- R ² -nPr; R ³ - 269 R- ■4-OCH ₂ CH ₂ OEt; R ² -CH ₂ OMe; R ³ - 270 R- ^■ 4-OCH ₂ CH ₂ OEt; R ² -CH ₂ CN; R ³ = 271 R- ^■ 4-OCH ₂ CH ₂ OEt; R ² -CHCH ₂ ; R ³ - 272 R- ^■ 4-OCH ₂ CH ₂ OEt; R ² -CCH; R ³ - 273 R» ■4-OCHF ₂ ; R ² -Me; R ³ - 274 R ^{« ■} 4-OCHF ₂ ; R ² -Efc; R ³ - 275 R- ■4-OCHF ₂ ; R ² -CF ₃ ; R ³ - 276 R" '4-OCHF ₂ ; R ² -πPr; R ³ = 277 R« =4-0CHF ₂ ; R ² =CH ₂ OMe; R ³ = 278 R- ^■ 4-OCHF ₂ ; R ² -CH ₂ CN; R ³ - 279 R« ■4-OCHF ₂ ; R ² -CHCH ₂ ; R ³ - 280 R' ^4-0CHF ₂ ; R ² -CCH; R ³ -

K-K-2

K-K-2 -Cl-P ) ; R ² -CF ₃ ; R ³ - -Cl-Ph) ; R ² -nPr; R ³ - -Cl-P ) ; R ² -CH ₂ OMe; R ³ > -Cl-Ph) ; R ² -CH ₂ CN; R ³ - -Cl-Ph) ; R ² -CHCH ₂ ; R ³ - -Cl-Ph) ; R -CCH; R ³

R ² -Me; R ³ -

R ² -Et; R ³ -

R ² =CF ₃ ; R ³ -

R -nPr; R ³ -

R ² -CH ₂ OMe; R ³ -

R ² =CH ₂ CN; R ³ -

R ² -CHCH ₂ ; R ³ - R ² -CCH; R ³ -

K-K-2 -tBu; R ² -CH ₂ CN; R ³ - -tBu; R ² -CHCH ₂ ; R ³ - -tBu; R ² -CCH; R ³ - -tBu; R ² -CH ₂ CN; R ³ - -tBu; R ² -CHCH ₂ ; R ³ - tBu; R -CCH; R ³ - -CH ₂ CH ₂ OEt; R ² -CH ₂ CN; R ³ = -CH ₂ CH ₂ OEt; R ² -CHCH ₂ ; R ³ = -CH ₂ CH ₂ OEt; R ² -CCH; R ³ - -OCH ₂ CH ₂ OEt; R ² -CH ₂ CN; R ³ - -OCH ₂ CH ₂ OEt; R ² -CHCH ₂ ; R ³ = -OCH ₂ CH ₂ OEt; R ² -CCH; R ³ - -OCHF ₂ ; R ² -CH ₂ CN; R ³ - -OCHF ₂ ; R ² =CHCH ₂ ; R ³ = -OCHF ₂ ; R ² -CCH; R ³ - ^■ OCHF ₂ ; R ² -CH ₂ CN; R ³ - -OCHF ₂ ; R ² «=CHCH ₂ ; R ³ =

K-K-2

K-K-3 «4-SiMe ₃ ; R ² -Etf R ³ - «4-SiMe ₃ ; R ² -CH ₂ CN; R ³ > »3-SiMe ₃ ; R ² -Me; R ³ - «3-SiMe ₃ ; R ² -Et; R ³ - '3-S±Me ₃ ; R ² -CH ₂ CNr R ³ - »4-tBu; R ² -Me? R ³ - ■4-tBu; R ² -Et; R ³ - •4-tBu; R ² -CH ₂ CN; R ³ - »3-tBu; R ² -Me; R ³ - ■3-tBu; R ² -Et;- R ³ - *3-tBu; R ² -CH CN; R ³ -

«4-OCHF ₂ R ² -Me; R ³ - «4-OCHF ₂ R ² -Et; R ³ - «4-OCHF ₂ R ² -CH CN; R ³ - •3-0CHF ₂ R ² -41e; R ³ - •3-OCHF ₂ R ² -Et; R ³ - ■3-0CHF ₂ R ² -CH ₂ CN; R ³ - ■4-SiMe ₃ R ² -Me; R ³ - ■4-SiMe ₃ R ² -Et; R ³ - ■4-SiMe ₃ R ² -CH ₂ CN; R ³ - 3-SiMe ₃ R ² -Φle; R ³ - ■3-SiMe ₃ R ² -Et; R ³ - ■3-SiMe ₃ R ² -CH ₂ CN; R ³ -

K-K-3 R-4-tBu; R ² -CH ₂ CN; R ³ - R-3-tBu; R ² -CH ₂ CN; R ³ - R-4-0CHF ₂ ; R ² -CH ₂ CN; R ³ - R-3-OCHF ₂ ; R ² -CH ₂ CN; R ³ « R-4-SiMe ₃ ; R ² =CH ₂ CN; R ³ - R-3-SiMe ₃ ; R ² -CH ₂ CN; R ³ -

K-K-4 R-4-tBu,' R ² -CH ₂ CN; R ³ - R-3-tBu,* R ² -CH ₂ CN; R ³ = R-4-0CHF ₂ ; R ² -CH ₂ CN; R ³ > R-3-OCHF ₂ ; R ² -CH ₂ CN,' R ³ = R-4-SiMe ₃ ; R ² -CH ₂ CN; R ³ - R-3-SiMe ₃ ; R ² -CH ₂ CN; R ³ -

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.

Wei ht Percent

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 arsden, 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

Hiςrh Strength πoncentrate

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). Exampl 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 P

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 Eusi 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 _r Phytophthora infestans _r Peronospora tabacina, Pseudoperonospora cubensis _r Pythium aphanidermatum _r Alternaria brassicae, Septoria nodorum _r Cercosporidium personatum _r Cercospora arachidicola _r Pseudo- cercosporella herpotrichoides _r Rhizoctinia Solani _r Cercospora beticola, Botrytis cinerea _r Monilinia fructicola _r Pyricularia oryzae, Podosphaera leucotricha, Venturia inaequalis, Erisyphe graminis, Puccinia recondita, Puccinia graminis _f Hemileia vastatrix, Puccinia striiformis _r 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- viπphos, 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%.

a NMR data given in Example 2. b NMR data given in Example 3. c NMR (CDC1 ₃ ) : δ δ.53(s,lH), 8.02 (br d,lH), 7.50-7.30

(m,4H), 5.52 (g,lH), 2.97 (g,2H), 1.63 (d,3H) 1.32 (t,3H),

0.27 (s,9H). d ^-H NMR (CDC1 ₃ ) : δ 8.49 (s,lH), 8.27 (br d,lH), 7.50-7.35

(ABg,4H), 5.42 (g,lH), 2.84 (g,2H), 2.59 (s,3H), 1.55 (d,3H)

1.33 (t,3H), 0.25 (s,9H). β ^X H NMR (CDC1 ₃ ): δ 8.49 (s,lH), 8.47 (S,1H), 7.49, 7.36

(ABg,4H), 5.45 (m,lH), 3.92 (s,3H), 2.92 (g,2H) 1.57 (d,3H), 1.25 (t,3H), 0.25 (s,9H). f 3-H NMR CCDC1 ₃ ): δ 10.39 (s,lH), 9.52 (b d,lH), 8.55 (s,lH), 7.50, 7.35 (ABg,4H) _r 5.53 Cg,lH), 3.00 (g,2H), 1.60 (d,3H),

1.34 (t,3H), 0.25 (s,9H). g ^-H NMR (CDC1 ₃ ) : δ 8.60 (s,lH), 7.48 (m,2H), 7.35 (m,2H), 5.67

(brd,lH), 5.45 (g,lH), 2.82 (g,2H), 1.62 (d,3H), 1.30 (t,3H),

0.26 (s,9H). 1 NMR (CDC1 ₃ ) : δ 8.56 (s,lH), 7.49 (S,1H), 7.46 (m,lH), 7.34

(m,2H), 5.67 (br d,lH), 5.25 (q,lH) , 2.55 (s,3H), 1.62 (d,3H),

0.28 Cs,9H).

Index Table B

^ ^• H NMR (CDC1 ₃ ) : δ 8.61 (s,lH), 7.40-7.15 (m, 4H) , 5.65 (brd,lH),

5.45 (g,lH), 2.82 (g,2H), 1.62 (d,3H), 1.32 (m,12H).

^ ^• H NMR (CDC1 ₃ ) : δ 8.47 (s,lH), 7.36, 7.27 (ABg,4H), 6.05

(s,lH), 5.21 (brs,lH), 4.86 (brs,lH), 2.54 (g,2H), 1.56

(d,3H), 1.31 (S,9H), 1.17 (t,3H). ^X H NMR (CDC1 ₃ ) : δ 8.48 (S,1H), 7.35-7.25 (m,4H), 6.05 (S,1H),

5.25 (brs,lH), 4.82 (brs,lH), 2.55 (g,2H), 1.58 (d,3H), 1.32

(s,9H), 1.16 (t,3H). ^ ^• H NMR (CDC1 ₃ ) : δ 8.48 (S,1H), 7.34, 7.16 (ABg,4H), 6.15

(S,1H), 4.96 (brs,lH), 3.58 (brs,2H), 2.89 (t,2H), 2.61

(g,2H), 1.39 (s,9H), 1.25 (t,3H) .

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 (polyhydriσ 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 _r 13, 14, 15, 16, 17, 18.

TEST 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 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 Com oun Rate PPM hi Ovicide arvicide 2 50 91 83

20 46 96