TITLE ARTHROPODICIDAL TETRAHYDROPYRIMIDINES The arthropodicidal tetrahydropyrimidines of this invention are characterized by a methyl-substituted alkylene bridge. U.S. 4,831,036 discloses tetrahydropyrimidines not so characterized.

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

wherein:

R ¹ is selected from the group CH ₃ SCH ₂ CH ₂ -,

R ² is selected from the group H; C _j -C o alkyl optionally substituted with

1 or 2 substituents independently selected from the group CN. C(O)R ³ , NO ₂ , OH. SH, C _r C ₄ alkoxy, C _r C ₄ alkylthio, C _r C ₄ haloalkoxy, N(R5)(R6)R7.χ, C _Γ C ₄ alkylamino, C ₂ -Cg dialkylamino and C3-C8 cycloalkyl; C _r C ₂ o haloalkyl:

C _j -Cg alkoxy; C _j -C ₆ alkylthio; C ₂ -Cg alkenyl; C ₂ -C ₆ alkenyloxy; C ₇ -C ₁₀ aralkoxy; C ₂ -C ₆ alkynyl; C(0)R ³ ; N(R ⁵ )R ⁶ ; C ₃ -C ₈ cycloalkyl optionally substituted with 1-3 substituents independently selected from the group halogen, C _j -C ₂ alkyl and Cj-C ₂ haloalkyl; phenyl and C7-C10 aralkyl each ring optionally substituted with a substituent selected from the group halogen, NO , CN, C _| -C alkyl, C _j -C alkoxy, C1-C4 alkylthio, Cι-C haloalkyl, C _] -C ₂ haloalkoxy and Cι-C ₂ haloalkylthio; C1-C3 alkyl substituted with a heteroaromatic ring, the ring optionally substituted with a group selected from halogen, NO ₂ , NH ₂ , CN, C _r C ₄ alkyl, C _r C ₄ alkoxy, C _r C ₄ alkylthio,

Cι-C haloalkyl, C _r C haloalkoxy, C1-C4 haloalkylthio, C _r C alkylamino and C ₂ -Cg dialkylamino; a 3- to 8-membered heterocycle attached through carbon or nitrogen containing 2-7 carbon atoms and 1-4 heteroatoms selected from the group nitrogen, oxygen and sulfur, said heterocycle being fully unsaturated, partially unsaturated or fully saturated; and (CH ₂ CH ₂ O) _q R ⁴ ; R ³ is selected from the group H, NH ₂ , C _r Cg alkyl, OH, Ci-Cg alkoxy,

C1-C4 alkylamino and C ₂ -Cg dialkylamino; R ⁴ is selected from the group H and C _j -C ₅ alkyl; R ⁵ and R ⁶ are independently selected from the group H; C _j -Cg alkyl; and optionally substituted phenyl wherein the substituents are selected from the group halogen, C _j -Cg alkyl and C^-Cg haloalkyl; R ⁷ is selected from the group C _j -Cg alkyl; X is selected from the group halogen and OH; n is 1 or 2; and q is 1, 2, 3, 4 or 5.

Contemplated heteroaromatic rings on the Cj to C3 alkyl R ² group include furyl, imidazolyl, pyrrolyl, thienyl, pyridinyl, pyrazolyl, 1,2.3-triazolyl, 1,2,4- triazolyl, pyrazinyl, pyrimidinyl, oxazolyl, isoxazolyl, 1 ,2,4-oxadiazolyl, 1,3,4- oxadiazolyl, thiazolyl, isothiazolyl, 1,2,5-thiadiazolyl and 1,3,4-thiadiazolyl. Contemplated 3- to 8-membered R ² heterocycles include morpholino, pyrrolidinyl, imidazolidinyl, pyrazolidinyl, pyridinyl, thienyl, pyrrolinyl, and the like.

Preferred Compounds A are compounds of Formula I wherein:

R ² is selected from the group C _j -Cg alkyl; C3~Cg cycloalkyl; C ₂ -C ₆ alkenyl; N(R ⁵ )R ⁶ ; C _r C ₅ alkyl substituted with a group selected from C3-C cycloalkyl, C -Cg dialkylamino and N(R ⁵ )(R ⁶ )R ⁷ *X; and (CH ₂ CH ₂ O) _q R ⁴ ; and n is 1.

Preferred Compounds B are compounds of Preferred A wherein: R ¹ is CH ₃ SCH ₂ CH ₂ -; and R ² is C _r C ₆ alkyl.

Preferred Compounds C are compounds of Preferred A wherein:

R! is

R ² is C _r C ₆ alkyl.

Preferred Compounds D are compounds of Preferred A wherein: R s

R ² is C ₁ -C ₆ alkyl.

Specifically preferred for biological activity are Compounds B and C, respectively, which are:

1 ,2,3 ,5 ,6,7-hexahydro-2 ,6-dimethyl- 1 - [2-(methylthio)ethyl]-8-nitro- imidazo[l,2-c] pyrimidine, and

1 - [ (6-chloro-3-pyridinyl)methyl] - 1 ,2,3 ,5 ,6,7-hexahydro-2,6- dimethyl-8-nitroimidazo [1,2-c] pyrimidine.

Compounds of this invention can exist as one or more stereoisomer. The various stereoisomers include enantiomers, diastereomers and geometric isomers. One skilled in the art will appreciate that one stereoisomer may be more active and how to separate said stereoisomers. Accordingly, the present invention comprises racemic mixtures, individual stereoisomers, and optically active mixtures of compounds of Formula I.

In the above definitions, the term "alkyl", used either alone or in compound words such as "alkythio" or "haloalkyl", denotes straight chain or branched alkyl such as methyl, ethyl, n-propyl, isopropyl or the different butyl isomers.

Alkoxy denotes methoxy, ethoxy, n-propyloxy, isopropyloxy and the various isomers of butoxy, pentoxy and hexyloxy.

Alkenyl denotes straight chain or branched alkenes such as vinyl, 1-propenyl, 2-propenyl, 3-propenyl and the different butenyl, pentenyl and hexenyl isomers.

Alkynyl denotes straight or branched alkynes such as ethynyl, 1-propynyl, 2-propynyl and the different butynyl, pentynyl and hexynyl isomers. Alkylamino denotes methylamino, ethylamino, n-propylamino, isopropylamino and the different butylamino isomers. Dialkylamino denotes nitrogen substituted with two alkyl groups, which may be different. Examples include N,N-dimethylamino and N-ethyl-N-methylamino

Alkylthio denotes methylthio, ethylthio, n-propylthio, isopropylthio and the different butylthio, pentylthio and hexylthio isomers.

Aralkyl denotes a phenyl ring attached to a carbon chain, examples include benzyl and phenethyl. Aralkyl is further defined to include naphthyl.

The term "halogen", either alone or in compound words as "haloalkyl", denotes fluorine, chlorine, bromine or iodine. Further, when used in compound words such as "haloalkyl" said alkyl can be partially or fully substituted with halogen atoms, which can be the same or different. Examples of haloalkyl include CH ₂ CHF ₂ , CF ₂ CF ₃ and CH ₂ CHFC1.

The total number of carbon atoms in a substituent group is indicated by the "C _j -C _j " prefix where i and j are numbers from 1 to 20. For example, C1-C3 alkyl designates methyl through propyl; and C ₂ alkoxy designates OCH ₂ CH3 and C ₃ alkoxy designates OCH ₂ CH ₂ CH ₃ and OCH(CH ₃ ) ₂ .

DETAILS OF THE INVENTION

The compounds of Formula I can be prepared by the reaction of Formula II compounds with one or more equivalents of an amine of Formula III and at least two molar equivalents of formaldehyde in a suitable solvent as depicted in Scheme 1. Substituents depicted in d e following Schemes are as previously defined.

Scheme 1

Reactions depicted in Scheme 1 are typically carried out at temperatures ranging from 0°C to the reflux temperature of the solvent, with 0°C to 25°C being preferred. Suitable solvents include alcohols such as methanol and ethanol, water, and polar aprotic solvents such as tetrahydrofuran and dimethylformamide.

Formaldehyde can be used in amounts of about 2 to 10 molar equivalents. Either solid paraformaldehyde or aqueous solutions of formaldehyde can be used. In some cases, it is desirable to use a small amount of a strong, non-oxidizing acid, such as hydrochloric acid, as a catalyst. Alternatively, a hydrohalide or a hydrosulfonic acid salt of amine III can be used.

Compounds of Formula II can be prepared by the reaction of imidazolidines

(n=l) or tetrahydropyrimidines (n=2) of Formula IV with an alkylating agent of Formula V in the presence of a proton acceptor as shown in Scheme 2.

Scheme 2

IV V wherein: X ¹ is a leaving group such as halide or sulfonate

The reactions depicted in Scheme 2 typically involve the mixture of equimolar amounts of IV and V in the presence of one equivalent of a base such as NaH or K ₂ CO3 in a polar, aprotic solvent such as DMF or THF at a temperature ranging from room temperature to 150°C. The product is typically isolated by removal of the solvent followed by column chromatography on silica gel using a suitable solvent such as chloroform, methylene chloride, methanol, ethanol, ethylacetate, triethylamine, saturated aqueous ammonium hydroxide or mixtures of these solvents.

Alternatively, compounds of Formula II can be prepared by the reaction of diamines of Formula VI with compounds of Formula VII as shown in Scheme 3.

Scheme 3

VI VII

wherein: X-- is a leaving group such as SCH3, OC H^ or halogen.

Scheme 3 reactions typically involve the mixture of equimolar amounts of VI and VII (usually l,l-bis(methylthio)-2-nitroethylene) in a polar solvent such as methanol, ethanol, acetonitrile, tetrahydrofuran, water or mixtures thereof at

temperatures up to the reflux temperature of the solvent. A proton acceptor such as NaOH, sodium carbonate or triethylamine can be used.

Alternatively, compounds of Formula II can be prepared by the reaction of diamine VI with a 2,2,2-trihalonitroethane of Formula VM as depicted in Scheme 4 using conditions analogous to those described for Scheme 3 reactions. Scheme 4 reactions typically involve the use of between 1 and 10 molar equivalents of base selected from amines such as triethylamine and pyridine, carbonates such as Na ₂ CO3, K ₂ CO3 and NaHCO3, hydroxides such as LiOH, NaOH and KOH, or like bases.

Scheme 4

VIII wherein: X X and X are halogen.

Formula IV compounds wherein n=l can be prepared by the reaction of 1,2-diaminopropane (IX, n=l) with Formula VII compounds. Compounds of Formula IV wherein n=2 can be prepared by the reaction of 1 ,3-diaminobutane (IX, n=2) with Formula VII compounds in an analogous manner. Conditions for the preparation of Formula IV compounds are analogous to those described for Scheme 3. The preparation of Formula IV compounds is depicted in Scheme 5.

Scheme 5

^{IX (n=1} _' ²⁾

The preparation of diamines VI wherein n=l can be achieved using the two-step procedure shown in Scheme 6.

Scheme 6

In Step i of Scheme 6, amine X is treated with potassium cyanide and acetaldehyde in the presence of one to three equivalents of acid in a solvent to form aminonitrile XI. Other cyanide salts as well as HCN can be used in the procedure as well as hydrohalide and other acid salts of X. Suitable solvents include methanol, ethanol, isopropanol and water, as well as combinations of solvents. Alternative procedures for the preparation of amino nitriles such as XI can be found in the literature (see, e.g., Synth. Commun., (1985), 15, 157; Synthesis, (1979), 127).

In Step ii of Scheme 6, aminonitrile XI is reduced to form diamine VI (n=l). This reduction can usually be achieved using lithium aluminum hydride in amounts ranging from 0.75 to 3 molar equivalents in a solvent such as diethyl ether or THF at a temperature ranging from -20°C to the reflux temperature of the solvent. Alternatively, the reduction of XI to VI can be achieved using catalytic hydrogenation over a catalyst such as palladium on carbon or Raney nickel. The addition of ammonia to the hydrogenation reaction is sometimes useful to maximize the yield of diamine VI.

An alternative procedure for the preparation of diamines VI (n=l) is depicted in Scheme 7.

Scheme 7

XIII XV

Step ii [H]

XV VI (n=l)

wherein: R ⁸ is CH ₃ SCH ₂ , 3-pyridyl, 5-thiazolyl, 2-chloro-5-pyriifyl or 2-chloro-5-thiazolyl,

In Step i of Scheme 7, alanine amide (XIII) is treated with 1 to 2 molar equivalents of acid chloride XIV in the presence of 1 to 3 molar equivalents of a base such as NaOH, KOH, K ₂ CO3, pyridine or triethylamine. Suitable solvents include THF, CH ₂ C1 ₂ , water or pyridine. The product XV can be isolated by extraction or, more conveniently, by removal of solvent and is usually suitable for use in Step ii of Scheme 7 in crude form. Alanine amide XIII can be used either in neutral form as depicted or as the salt form (typically as the HC1 or CF3CO ₂ H salt, among others). When the salt form of XIII is used, an additional one equivalent of base is used in Step i of Scheme 7.

In Step ii of Scheme 7, the amide XV is converted to diamine VI (n=l) by treatment with a reducing agent such as LiAlH ₄ , BH ₃ 'THF or BH3'SMe ₂ in a solvent such as THF or Et O at temperatures ranging from 0°C to the reflux temperature of the solvent. Analogous procedures are well-known in the literature (see e.g. Synthesis, (1981), 441).

The use of either the D- or the L- form of alanine amide XIII or its salt provides a convenient means of obtaining enantiomerically enriched forms of diamine VI (n=l). When compounds of Formula II (n=l) are prepared as described for Scheme 3 reactions using enantiomerically enriched forms of VI (n=l), the products II (n=l) are obtained in enantiomerically enriched form. When compounds of Formula I are prepared as described for Scheme 1 reactions

using enantiomerically enriched forms of II, the products I are obtained in enantiomerically enriched form.

Alternatively, diamines VI can be obtained in enantiomerically enriched forms by resolution with enantiomeric acids, such as tartaric acid. Such resolutions are well-known to one skilled in the art (see e.g. Synthesis, (1991), 789 for a related example).

The preparation of diamines VI wherein n=2 can be achieved using the two- step procedure shown in Scheme 8.

Scheme 8

Step i R ¹

Me NH

CN

R^

CN

Me

XII

Step ii

XII VI (n=2)

In Step i of Scheme 8, aminonitrile XII is formed when amine X and crotononitrile are mixed either neat or in a suitable solvent, including water, methanol, ethanol, THF or mixtures of these solvents at temperatures ranging from 10°C to 150°C. The quantities of X used range from one to ten molar equivalents.

The reduction of aminonitrile XII to form diamine VI (n=2) as depicted in Step ii of Scheme 8 can be achieved using conditions analogous to those previously described for Step ii of Scheme 6. Alkylating agents of Formula V are known and include 2- chloroethylmethylsulfide and 3-(chloromethyl)pyridine. Other representative alkylating agents are described in EP-302,389-A2 and EP-446,913-A.

Amines of Formula X are known and include 2-(methylthio)ethylamine and 3-(aminomethyl)pyridine. Other representative amines are described in EP-302,389-A2.

Example 1 Step A: 2-r2-(Methylthio)ethylaminolpropanenitrile

A solution of 24.4 g (0.27 moles) of 2-(methylthio) ethylamine and 100 mL of methanol was treated with 294 mL of 1 M aqueous HC1 added dropwise with ice-bath cooling over 15 min at 5-10°C. The resulting solution was treated with a solution of 17.4 g (0.27 moles) of potassium cyanide and 150 mL of water at 5-10°C followed by the addition of 13 g (0.29 moles) of acetaldehyde at 5-10°C. The resulting solution was stirred at room temperature for 6 h and was then poured into a mixture of 1 L of saturated aqueous sodium bicarbonate and 300 mL of CH ₂ C1 ₂ . The aqueous layer was extracted with two additional 200 mL portions of CH ₂ C1 ₂ and the combined organic layers were washed with 500 mL of saturated aqueous NaHCO3, dried over anhydrous MgSO ₄ , filtered and concentrated to give 37.6 g (97%) of a pale yellow oil. - NMR (200 MHz, CDC1 ₃ ) δ 3.78-3.60 (m,lH), 3.17-2.97 (m,lH), 2.94-2.74 (m,lH), 2.71-2.62 (m,2H), 2.12 (s,3H), 1.67 (br S,1H), 1.52 (d,J=7 Hz, 3H).

Step B: N ² -r2-(Methylthio1ethyll- 1.2-propanedi mine

A vigorously stirred (mechanical stirrer) solution of lithium aluminum hydride (84 mL of a 1 M solution in (CH ₃ CH ₂ ) ₂ 0, 0.084 moles) and (CH ₃ CH ₂ ) ₂ O (163 mL) was treated with a solution of 6.04 g (0.042 moles) of the product from Step A and 82 mL of (CH ₃ CH ₂ ) ₂ O was added dropwise at 0°C. The resulting white heterogeneous mixture was stirred at 0°C for 1 h, at room temperature for 1 h and then cooled to 0°C and quenched by the careful, sequential addition of a solution of 3.1 mL H ₂ O in 10 mL of tetrahydrofuran, 3.1 mL of 15% NaOH and 9.3 mL of H ₂ O at 0°C. The resulting mixture was diluted with 155 mL of (CH3CH ₂ ) ₂ O and stirred at room temperature overnight. The resulting mixture was filtered and the filtrate was concentrated to give 6.4 g of a dark yellow oil. *H NMR

(200 MHz, CDCI3) δ 2.97-2.45 (m,7H), 2.11 (s,3H), 1.75 (br s,3H), 1.05 (d,J=6 Hz, 3H).

Step C: 5-Methyl-l-r2-(memylthio ethyll-2-(nitro-methyleneVimidazolidine

A solution of 2.6 g (0.018 moles) of the product from Step B, 2.9 g (0.018 moles) of 2,2-bis-(methylthio)-l-nitroethylene and 18 mL of absolute ethanol was heated at reflux for 5 h, cooled to room temperature and concentrated to give 4.8 g of a brown oil. Flash chromatography of the oil on silica gel using 40:1:0.1 CH ₂ Cl ₂ :CH ₃ CH ₂ OH:48% NH ₄ OH gave 1.8 g of a yellow oil that solidified on standing, m.p. 60-62°C. Trituration of the solid with 1 -chlorobutane gave an off-white solid that melted at 66-68°C. *H NMR (200 MHz, CDC1 ₃ ) δ 8.63 (br s,lH), 6.53 (s,lH), 4.21-4.03 (m,lH), 3.90 (t,lH), 3.40-3.28 (m,3H), 2.78-2.58 (m,2H), 2.16 (s,3H), 1.36 (d,3H).

Step D: 1.2.3.5.6.7 - Hexahydro-2.6-dimethyl-l-r2-(methylthio)ethv11-8-nitro- imιdazo 1.2-clpyrimidine (Compound 1)

A solution of 0.50 g (0.0023 moles) of the product of Step C, 0.22 mL (0.0025 moles) of 40% aqueous methylamine, 0.37 mL (0.005 moles) of 37% aqueous formaldehyde and 2.3 mL of ethanol was stirred at room temperature for 20 h. Silica gel (2 g) was added to the resulting solution and the mixture was concentrated. Flash chromatography of the residue on silica gel using 10:1:0.1 methylene chloride:ethanol:48% aqueous ammonium hydroxide gave 0.60 g of a yellow oil. -H NMR (400 MHz, CDC1 ₃ ) δ 4.40-4.32 (m,lH), 4.08-3.98 (m,2H), 3.96-3.85 (m,2H), 3.79 (apparent s,2H), 3.55-3.45 (m,lH), 3.27 (dd,lH), 2.80-2.65 (m,2H), 2.47 (s,3H), 2.11 (s,3H), 1.39 (d,lH).

Example 2 6-r(6-chloro-3-pyridinyl ^' )methvn-1.2.3.5.6.7-hexahvdro-2-methyl-l-r2- (methylthio)ethyll-8-nitro-imidazo π.2-cl-pyrimidine (Compound 2)

A solution of 1.0 g (0.0046 moles) of the product of Step C, Example 1, 0.7 g (0.0051 moles) of 3-(aminomethyl) 6-chloro-pyridine, 0.7 mL (0.010 moles) of 37% aqueous formaldehyde and 5 mL of ethanol was stirred at room temperature for 3 days. Silica gel (3 g) was added to the resulting solution and the mixture was concentrated. Flash chromatography of the residue on silica gel using 20:1:0.1 methylene chloride:ethanol:48% aqueous ammonium hydroxide gave 0.50 g of a yellow oil. -U NMR (400 MHz, CDC1 ₃ ) δ 8.34 (s,lH), 7.72 (d,lH), 7.35 (d,lH), 4.50-4.42 (m,lH), 4.10-4.02 (m,2H), 3.98-3.82 (m,3H), 3.82-3.70 (m,3H), 3.55-3.45 (m,lH), 3.21-3.15 (m,lH). 2.83-2.67 (m,2H), 2.13 (s,3H), 1.40 (d,3H).

Example 3 Step A: 3- [5-Methyl-2-(nitromethylene)-l-imidazolidinyllmethyllpyridin e

Aqueous hydrochloric acid (1 M _. 326 mL, 326 mmoles) was added over 10 min to a solution of 3-(aminomethyl) pyridine (30.1 mL, 296 mmoles) and methanol (110 mL). The resulting solution was treated with a solution of KCN (19.3 g, 296 mmoles) and water (163 mL) at a temperature below 10°C. Acetaldehyde (18.1 mL, 326 mmoles) was then added at 10°C and the resulting mixture was stirred at 25°C for 3.5 h. The mixture was partitioned between saturated NaHCO3 and CH ₂ C1 ₂ . The aqueous layer was extracted twice with CH ₂ C1 ₂ and the combined organic layers were washed with saturated NaHCO3, dried (MgSO ₄ ) and concentrated to give 38.1 g of a yellow oil.

A solution of the above product (38.1 g 236 mmoles) and diethylether (380 mL) was added dropwise at 0°C to a vigorously stirred solution of lithium aluminum hydride (236 mL of a 1.0 M solution in ether, 236 mmoles) and ether (800 mL). The resulting heterogeneous mixture was stirred at 0°C.for 1 h, at 25°C for 1 h and then cooled to 0°C and quenched by the careful, sequential addition of 8.8 mL H ₂ O, 8.8 mL of 15% aqueous NaOH and 26.4 mL H ₂ O. The mixture was diluted with ether (1000 mL) and stirred overnight at 25 °C. The resulting mixture was filtered and concentrated to give 29.2 g of a yellow oil. A solution of the above product (29.2 g, 177 mmoles) and ethanol (177 mL) was treated with 1,1-bis (methylthio)-2-nitroethylene (29.2 g, 177 mmoles) and heated at reflux for 2 h and then stirred overnight at 25°C. The resulting solution was concentrated to give 52.3 g of a brown oil. A 18.3 g aliquot of the crude product was chromatographed on 1 kg of silica gel using 10:1:0.1 CH ₂ Cl ₂ -EtOH-concentrated. NH ₄ OH to give 13.3 g of the title compound as a yellow solid that melted at 116-118°C. H NMR (400 MHz, CDC1 ₃ ) δ 8.75 (s,lH), 8.57 (d,lH), 8.52 (apparent s,lH), 7.60 (d,lH), 7.31 (d,lH), 6.59 (s,lH), 4.39 (ABq,2H), 4.02-3.93 (m,2H), 3.41 (m,lH), 1.33 (d,3H). Step B: 1.2.3.5.6.7-Hexahydro-2.6-dimethyl-8-nitro-l-(3-pyridinylmet hyIV imidazofl .2-c ^" |pyrimidme (Compound 22)

A solution of 1.0 g (4.3 mmoles) of the product from Step A, 0.4 mL (4.7 mmoles) of 40% aqueous methylamine, 0.7 mL (9.4 mmoles) of 37% aqueous formaldehyde and 5 mL of ethyl alcohol was stirred at room temperature for 20 h. The resulting solution was concentrated to give 1.2 g of the title compound as a yellow solid that melted at 143-146°C. ^! H NMR

(400 MHz, CDC1 ₃ ) δ 8.55 (overlapping d and s,2H total), 7.75 (d.lH), 7.29 (m,lH), 5.22 (l/2ABq,lH), 4.66 (l/2ABq,lH), 3.99-3.83 (m,3H), 3.82-3.74 (m,3H), 3.22 (dd,lH), 2.39 (s,3H), 1.29 (d,3H).

Example 4 Step A: Hexahydro-6-methyl-l- 2-(methylthio)ethyll-2-(nitromethylene)- pyrimidine

A solution of 13.5 g (0.15 moles) of 2-(methylthio)ethyl amine and 12.1 mL (0.15 moles) of crotononitrile was heated at reflux for 2 days. The resulting mixture was cooled to room temperature, dissolved in 200 mL EtOAc, dried (MgSO ₄ ) and concentrated to give 19.5 g of an orange oil.

A solution of 19.5 g (0.12 moles) of the above product and 200 mL of diethyl ether was added dropwise with vigorous mechanical stirring to a solution of lithium aluminum hydride (123 mL of a 1.0 M solution in ether) and ether (415 mL) at 0°C. The resulting heterogeneous mixture was stirred at 0°C for 1 h, at 25°C for 1 h and was then cooled to 0°C and quenched by the careful, dropwise sequential addition of 4.6 mL of H ₂ O, 4.6 mL of 15% aqueous NaOH and 13.8 mL of H ₂ O. The resulting mixture was allowed to warm to 25°C, diluted with 500 mL of ether and stirred overnight at 25 °C. The resulting mixture was filtered and the filtrate was dried over MgSO ₄ and concentrated to give 16.7 g of an orange oil.

A solution of 16.7 g (104 mmoles) of the above product, 17.1 g (104 mmoles) of 1,1 -bis (mefhylthio)-2-nitroethylene and 104 mL of ethyl alcohol was heated at reflux for 2 h (effluent gases from the reaction were passed through a bleach scrubber to trap methanethiol). The resulting solution was concentrated to give 26.5 g of a brown oil. A 12 g sample of this oil was chromatographed on 600 g of silica gel using 20: 1 :0.1

CH ₂ Cl ₂ -EtOH-concentrated NH ₄ OH to give 8.0 of the title compound as a brown oil that later solidified. *H NMR (400 MHz, CDC1 ₃ ) δ 10.89 (br s,lH), 6.62 (s,lH), 3.76-3.65 (m,lH), 3.58-3.42 (m,3H), 3.25 (quintet, 1H), 2.80-2.65 (m,3H), 2.17 (s,3H), 2.15-2.05 (m,2H), 1.30 (d,3H).

Step B: 1.3.4.6.7.8-Hexahvdro-2.7-dimethyl-l-r2-(methylthio)ethyll-9 -nitro-2H- pyrimidinori.6-alpyrimidine (Compound 33).

A solution of 0.7 g (3.0 mmoles) of the product from Step A, 0.3 mL (3.3 mmoles) of 40% aqueous methylamine, 0.5 mL (6.6 mmoles) of 37% aqueous formaldehyde and 3 mL of ethyl alcohol was stirred at 25°C for 20 h and

then concentrated. The residue was chromatographed on 50 g silica gel using 15:1:0.1 CH ₂ Cl ₂ -EtOH-concentrated NH ₄ OH to give 0.37 g of the title product as a solid: m.p. 145°C (dec). *H NMR (400 MHz, CDC1 ₃ ) δ 4.18 (br d,lH), 4.02 (d,lH), 3.78-3.57 (m,6H), 3.43-3.39 (m,lH), 2.76 (t,2H), 2.47 (s,3H), 2.30-2.22 (m,lH), 2.07 (s,3H), 1.96-1.86 (m,lH), 1.36 (d,3H).

By die general procedure described herein, or obvious modifications thereof, the compounds of Tables 1 through 10 and Index Tables A through F can be prepared. In Tables 1 through 10 and Index Tables A through F the following notations have been used:

Table 1

Table 2

Table 3

Table 4

R ² R ² R ²

CH ₂ CH ₂ Ph CH ₂ CONMe ₂ (CH ₂ ) ₃ N(Et) ₂ MeI

NHPh CH ₂ CONEt ₂ CH ₂ (2-Cl-Ph) (CH ₂ ) ₂ CONHMe

Table 5

Table 6

(CH ₂ ) ₇ CH ₃ c-heptyl (CH ₂ ) ₃ C1

CH(CH ₃ )(CH ₂ ) ₃ CH(CH ₃ ) ₂ CH ₂ (c-heptyl) (CH ₂ ) ₂ F

CH ₂ CH(CH ₂ CH ₃ )(CH ₂ ) ₃ CH ₃ c-octyl (CH ₂ ) ₂ Br

C(CH ₃ ) ₂ CH ₂ C(CH ₃ ) ₃ CH ₂ (c-octyl) (CH ₂ ) ₃ Br

Table 7

R ² R^ R ²

Table 8

R ² R^ R ²

Table 9

Table 10

R^ R ² R ²

Formulation/Utility

Compounds of this invention will generally be used in formulation with an agriculturally suitable carrier comprising a liquid or solid diluent. Useful formulations include dusts, granules, baits, pellets, solutions, suspensions, emulsions, wettable powders, emulsifiable concentrates, dry flowables and the

like, consistent with the physical properties of the active ingredient, mode of application and environmental factors such as soil type, moisture and temperature. Sprayable formulations can be extended in suitable media and used at spray volumes from about one to several hundred liters per hectare. High strength compositions are primarily used as intermediates for further formulation. The formulations will typically contain effective amounts of active ingredient, diluent and surfactant within the following approximate ranges which add up 100 weight percent.

Weight Percent

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

Typical solid diluents are described in Watkins, et al., Handbook of

Insecticide Dust Diluents and Carriers, 2nd Ed., Dorland Books, Caldwell, New Jersey. Typical liquid diluents and solvents are described in Marsden, Solvents Guide, 2nd Ed., Interscience, New York, 1950. McCutcheon's Detergents and Emulsifiers Annual, Allured Publ. Corp., Ridgewood, New Jersey, as well as Sisely and Wood, Encyclopedia of Surface Active Agents, Chemical Publ. Co., Inc., New York, 1964, list surfactants and recommended uses. All formulations can contain minor amounts of additives to reduce foam, caking, corrosion, microbiological growth, and the like.

Solutions are prepared by simply mixing the ingredients. Fine solid compositions are made by blending and, usually, grinding as in a hammer mill or fluid energy mill. Water-dispersible granules can be produced by agglomerating a fine powder composition; see for example, Cross et al., Pesticide Formulations, Washington, D.C., 1988, pp 251-259. Suspensions are prepared by wet-milling; see, for example, U.S. 3,060,084. Granules and pellets can be made by spraying the active material upon preformed granular carriers or by agglomeration techniques. See Browning, "Agglomeration", Chemical Engineering,

December 4, 1967, pp 147-148, Perry's Chemical Engineer's Handbook. 4th Ed., McGraw-Hill, New York, 1963, pages 8-57 and following, and WO 91/13546.

For further information regarding the art of formulation, see U.S. 3,235,361, Col. 6, line 16 through Col. 7. line 19 and Examples 10-41; U.S. 3,309,192, Col. 5, line 43 through Col. 7, line 62 and Examples 8, 12. 15, 39, 41, 52, 53, 58, 132, 138 -140, 162-164, 166, 167 and 169-182; U.S. 2,891,855, Col. 3, line 66 through Col. 5, line 17 and Examples 1-4: Klingman, Weed Control as a Science, John Wiley and Sons, Inc., New York, 1961, pp 81-96; and Hance et al., Weed Control Handbook, 8th Ed., Blackwell Scientific Publications, Oxford, 1989.

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

Example A Wettable Powder

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

Example B Granule

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

25-50 sieves) 90.0%.

Example C Extruded Pellet

Compound 1 25.0% anhydrous sodium sulfate 10.0% crude calcium ligninsulfonate 5.07c sodium alkylnaphthalenesulfonate 1.0% calcium/magnesium bentonite 59.0%.

Example D Emulsifiable Concentrate

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

The compounds of this invention exhibit activity against a wide spectrum of foliar-feeding, fruit-feeding, stem or root feeding, seed-feeding, aquatic and soil-inhabiting arthropods (term "arthropods" 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 growth stages of 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, junveniles and adults of the Phylum Nematoda. The compounds of this invention are also active against pests of the Orders Hymenoptera, Isoptera, Siphonaptera, Blattaria, Thysanura and Psocoptera; pests belonging to the Class Arachnida and Phylum Platyhelminthes. Specifically, the compounds are active against southern corn rootworm (Diabrotica undecimpunctata howardϊ), aster leafhopper (Mascrosteles fascifrons), boll weevil (Anthonomus grandis), two-spotted spider mite (Tetranychus urticae), fall armyworm (Spodoptera frugiperda), black bean aphid (Aphis fabae), tobacco budworm (Heliothis virescens), rice water weevil (Lissorhoptrus oryzophilus), rice leaf beetle (Oulema oryzae), whitebacked planthopper (Sogatella furcifera), green leafhopper (Nephotettix cincticeps), brown planthopper (Nilaparvata lugens), small brown planthopper (Laodelphax striatellus), rice stem borer (Chilo suppressalis), rice leafroller (Cnaphalocrocis medinalis), black rice stink bug (Scotinophara lurida), rice stink bug (Oebalus pugnax), rice bug (Leptocorisa chinensis), slender rice bug (Cletus puntiger), and southern green stink bug (Nezara viridula). The compounds are active on mites, demonstrating ovicidal, larvicidal and chemosterilant activity against such

families as Tetranychidae including Tetranychus urticae, Tetranychus cinnabarinus, Tetranychus mcdanieli, Tetranychus pacificus, Tetranychus turkestani, Byrobia rubrioculus, Panonychus ulmi, Panonychus citri, Eotetranychus carpini borealis, Eotetranychus, hicoriae, Eotetranychus sexmaculatus, Eotetranychus yumensis, Eotetranychus banksi and Oligonychus pratensis; Tenuipalpidae including Brevipalpus lewisi, Brevipalpus phoenicis, Brevipalpus californicus and Brevipalpus obovatus; Eriophyidae including Phyllocoptruta oleivora, Eriophyes sheldoni, Aculus cornutus, Epitrimerus pyri and Eriophyes mangiferae. See WO 90/10623 and WO 92/00673 for more detailed pest descriptions.

Compounds of this invention can also be mixed with one or more other insecticides, fungicides, nematocides, bactericides, acaricides, growth regulators, chemosterilants, 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 avermectin B, monocrotophos, carbofuran, tetrachlorvinphos, malathion, parathion-methyl, methomyl, chlordimeform, diazinon, deltamethrin, oxamyl, fenvalerate, esfenvalerate, permethrin, profenofos, sulprofos, triflumuron, diflubenzuron, methoprene, buprofezin, thiodicarb, acephate, azinphosmethyl, chlorpyrifos, dimethoate, fipronil, flufenprox, fonophos, isofenphos, methidathion, metha-midophos, phosmet, phosphamidon, phosalone, pirimicarb, phorate, terbufos, trichlorfon, methoxychlor, bifenthrin, biphenate, cyfluthrin, tefluthrin, fenpropathrin, fluvalinate, flucythrinate, tralomethrin, imidacloprid, metaldehyde and rotenone; fungicides such as carbendazim, thiuram, dodine, maneb, chloroneb, benomyl, cymoxanil, fenpropidine, fenpropimorph, triadimefon, captan, thiophanate- methyl, thiabendazole, phosethyl-Al, chlorothalonil, dichloran, metalaxyl, captafol, iprodione, oxadixyl, vinclozolin, kasugamycin, myclobutanil, tebuconazole, difenoconazole, diniconazole, fluquinconazole, ipconazole, metconazole, penconazole, propiconazole, uniconzole, flutriafol, prochloraz, pyrifenox, fenarimol, triadimenol, diclobutrazol, copper oxychloride, furalaxyl, folpet, flusilazol, blasticidin S, diclomezine, edifenphos, isoprothiolane, iprobenfos, mepronil, neo-asozin. pencycuron, probenazole, pyroquilon, tricyclazole, validamycin, and flutolanil; nematocides such as aldoxycarb, fenamiphos and fosthietan; bactericides such as oxytetracyline, streptomycin and

tribasic copper sulfate; acaricides such as binapacryl, oxythioquinox, chlorobenzilate, dicofol, dienochlor, cyhexatin, hexythiazox, amitraz, propargite, tebufenpyrad and fenbutatin oxide; and biological agents such as entomopathogenic bacteria, virus and fungi. In certain instances, combinations with other arthropodicides 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, horticultural and specialty crops, animal and human health is achieved by applying one or more of the compounds of this invention, in an effective amount, to the environment of the pests including the agronomic and/or nonagronomic locus of infestation, to the area to be protected, or directly on the pests to be controlled. Thus, the present invention further comprises a method for the control of foliar and soil inhabiting arthropods and nematode pests and protection of agronomic and/or nonagronomic crops, comprising applying one or more of the compounds of Formula I, or compositions containing at least one such compound, in an effective amount, to the environment of the pests including the agronomic and/or nonagronomic locus of infestation, to die area to be protected, or directly on the pests to be controlled. A preferred method of application is by spraying. Alternatively, granular formulations of these compounds can be applied to the plant foliage or the soil. Other methods of application include direct and residual sprays, aerial sprays, seed coats, microencapsulations, systemic uptake, baits, eartags, boluses, foggers, fumigants, aerosols, dusts 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.

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 will depend on such factors as the species of arthropod to be controlled, the pest's life cycle, life stage, its size, location, time of year, host crop or animal, feeding behavior, mating

behavior, ambient moisture, temperature, and the like. Under normal circumstances, application rates of about 0.01 to 2 kg of active ingredient per hectare are sufficient to control pests in agronomic ecosystems, but as little as 0.001 kg/hectare may be sufficient or as much as 8 kg hectare may be required. For nonagronomic applications, effective use rates will range from about 1.0 to 50 mg/square meter but as little as 0.1 mg/square meter may be sufficient or as much as 150 mg/square meter may be required.

The following Tests demonstrate the control efficacy of compounds of this invention on specific pests. The pest control protection afforded by the compounds is not limited, however, to these species. See Index Tables A-F for compound descriptions.

Index Table A

Index Table B

Index Table C

38 39 40 41 42 43

Index Table E

Compound R ² m.p. °C

50 Me 165-169

Index Table F

Compound R ² m.p. °C

51 Me 148-149

Cmpd No. *H NMR Data ¹

8.55 (s,lH), 8.54 (s,lH), 7.74 (dd,lH), 7.30 (dd,lH), 4.44 (dt,lH), 4.10-4.00 (m,2H), 3.95-3.83 (m,3H), 3.80 (s,2H), 3.78 (d,lH), 3.51 (dt,lH), 3.17 (dd,lH), 2.85-2.67 (m,2H), 2.14 (s,3H). 1.39 (d,3H).

4.38-4.28 (m.lH), 4.00 (overlapping s,2H and t,lH), 3.93 (d,lH), 3.83-3.78 (m,2H), 3.47 (apparent quintet,lH), 3.21 (dd,lH), 2.81-2.58 (m,4H), 2.12 (s,3H), 1.39 (d,3H), 1.15 (t,3H).

4.35-4.25 (m,lH), 4.09-3.95 (m,4H), 3.85-3.80 (m,2H), 3.51 (apparent quintet, IH), 3.21 (dd,lH), 2.93 (quintet,lH), 2.82-2.64 (m, 2H), 2.12 (s,3H), 1.92-1.82 (m,2H), 1.80-1.65 (m,2H), 1.63-1.53 (m,2H), 1.50-1.40 (m,2H), 1.39 (d,3H).

4.33-4.24 (m,lH), 4.04-3.97 (m,3H), 3.93 (d,lH), 3.89-3.80 (m,2H), 3.51 (quintet,lH), 3.19 (dd,lH), 2.81-2.64 (m,3H). 2.12 (s,3H), 1.67-1.53 (m,2H), 1.39 (d,3H), 1.07 (dd,3H), 0.90 (t,3H).

4.42-4.34 (m,lH), 4.04-3.93 (m,3H), 3.91 (d,lH), 3.84-3.78 (m,2H), 3.53-3.45 (m,lH), 3.22 (dd,lH), 2.81-2.65 (m,2H). 2.55

(t,2H), 2.11 (s,3H), 1.57-1.47 (m,2H), 1.39 (d,3H), 1.29 (m,6H), 0.89 (t,3H).

4.20-4.11 (m,lH), 4.08 (d,lH), 4.01 (m,lH), 3.97 (d,lH), 3.84 (t,lH), 3.81 (d,lH), 3.59-3.51 (m,lH), 3.20 (dd,lH), 2.84-2.66 (m,2H), 2.14 (s,3H), 1.40 (d,3H), 1.17 (s,9H).

4.43-4.33 (m,lH), 4.21-4.13 (m,2H), 4.08-3.97 (m,2H), 3.86 (t,lH), 3.76 (s,3H), 3.75-3.70 (m,lH), 3.55-3.42 (m,3H), 3.22 (t,lH), 2.80-2.65 (m,2H), 2.11 (s,3H), 1.39 (d,3H).

10 7.38-7.27 (m,5H), 4.43 (dt,lH), 4.07-3.98 (m,2H), 3.96 (s,2H),

3.85 (d,lH), 3.81-3.72 (m,3H), 3.52 (dt,lH), 3.13 (dd,lH), 2.83-2.68 (m,2H), 2.15 (s,3H), 1.38 (d,3H).

11 (Partial, 200 MHz, D ₂ O, HDO=4.68) 1.97 (s,3H), 0.94 (d,3H).

12 4.40 (dt,lH), 4.08-3.97 (m,3H), 3.93 (d,lH), 3.85 (t,lH), 3.63 (t,2H), 3.48 (dt,2H), 3.22 (dd,lH), 2.95 (t,2H), 2.80-2.63 (m,2H), 2.11 (s,3H), 1.39 (d,3H).

13 4.41-4.33 (m,lH), 4.04-3.85 (m,3H), 3.83-3.62 (m,3H), 3.53-3.44 (m,lH), 3.22 (dd,lH), 2.81-2.60 (m,2H), 2.57-2.50 (m,2H), 2.11 (s,3H), 1.5 (m,2H), 1.39 (d,3H), 1.33-1.20 (m,12H), 0.88 (t,3H).

14 4.43-4.35 (m,lH), 4.08 (d,lH), 4.04-3.97 (m,2H), 3.92-3.82

(m,3H), 3.68-3.60 (m,2H), 3.47 (dt,lH), 3.21 (dd,lH), 2.79-2.64 (m,4H), 2.11 (s,3H), 2.02-1.94 (m,2H), 1.39 (d,3H).

15 4.67 (m,lH), 4.57 (m,lH), 4.43-4.35 (m,lH), 4.12 (s,2H), 4.04-3.84 (m,4H), 3.50 (dt,lH), 3.22 (dd,lH), 3.08-2.64 (m,4H),

2.11 (s,3H), 1.39 (d,3H).

16 4.33-4.23 (m,lH), 4.22-4.12 (m,2H), 4.08-3.82 (m,4H), 3.47 (dt,lH), 3.18 (dd,lH), 2.77-2.58 (m,6H), 2.11 (s,3H), 1.6 (m,4H), 1.42- 1.25 (overlapping d and s,5H total).

17 4.30-4.21 (m,lH), 4.08-3.95 (m,4H), 3.87-3.78 (m,2H), 3.51

(quintet,lH), 3.18 (t,lH), 2.92 (quintet,lH), 2.80-2.63 (m,2H), 2.11 (s,3H), 1.38 (d,3H), 1.13 (m,6H).

18 4.40-4.33 (m,lH), 4.09 (s,2H), 4.03-3.98 (m,lH), 3.90 (s,2H), 3.84

(t,lH), 3.49 (dt,lH), 3.21 (dd,lH), 2.81-2.64 (m,4H), 2.52-2.40 (m,2H), 2.25 (s,6H), 2.11 (s,3H), 1.39 (d,3H).

19 4.40-4.33 (m,lH), 4.08 (s,2H), 4.00 (m,lH), 3.92-3.82 (m,3H), 3.51 (dt,lH), 3.21 (dd,lH), 2.81-2.53 (m,10H), 2.11 (s,3H), 1.39

(d,3H), 1.02 (t,6H).

20 4.37 (m,lH), 4.10-3.97 (m,3H), 3.90-3.80 (m,3H), 3.55-3.46 (m,3H), 3.23 (dd,lH), 2.73 (m,4H), 2.11 (s,3H), 2.04 (m,2H), 1.39 (d,3H).

21 (400 MHz, d ₆ DMSO) 4.27-4.00 (4H,m), 3.85-3.65 (m,3H) 3.55-3.42 (m,3H), 3.11 (s,9H), 3.03-2.85 (m,2H), 2.73-2.62 (m,2H), 2.03 (s,3H), 1.26 (d,3H).

23 8.55 (overlapping s and d,2H), 7.78 (d,lH), 7.29 (m,lH), 5.09 (1/2 ABq,lH), 4.68 (1/2 ABq,lH), 3.98 (s,2H), 3.90 (overlapping doublets,2H), 3.77 (overlapping doublets,2H), 3.22 (dd,lH), 2.51 (q,2H), 1.28 (d,3H), 1.13 (t,3H).

24 8.55 (br s,2H), 7.78 (d,lH), 7.29 (m,lH), 5.14 (1/2 ABq,lH), 4.70 (1/2 ABq,lH), 4.07-3.90 (m,4H), 3.78 (overlapping doublets,2H), 3.22 (dd,lH), 2.66 (quintet,lH), 1.87-1.63 (m,4H), 1.62-1.48 (m,2H), 1.47-1.38 (m,2H), 1.27 (d,3H).

25 8.54 (overlapping s and d,2H total), 7.65 (d,lH) ca. 7.27 (m,lH), 5.14 (d,lH), 4.67 (d,lH), 3.99 (s,2H), 3.91-3.75 (m,4H), 3.19 (dd,lH), 2.66-2.58 (m,lH), 1.62-1.45 (m,lH), 1.40-1.28 (m,lH), 1.27 (d,3H), 1.01 (apparent t,3H), 0.89 (t,3H).

26 8.55 (overlaping s and d,2H), 7.75 (d,lH), 7.29 (m,lH), 5.20 (1/2 ABq,lH), 4.66 (1/2 ABq,lH), 4.02-3.84 (m,4H), 3.80-3.68 (m,2H), 3.21 (dd,lH), 2.39 (t,2H), 1.47 (m,2H), 1.35-1.22 (m,9H), 0.88 (t,3H).

27 8.59 (overlapping s and d,2H total), 7.77 (d,lH), 7.37-7.22 (m,6H), 5.22 (1/2 ABq,lH), 4.66 (1/2 ABq,lH), 4.01-3.82 (m,5H), 3.74-3.55 (m,3H), 3.12 (dd,lH), 1.30 (d,3H).

28 ca. 8.58 (overlapping singlets,2H), 7.82 (d,lH), 7.33 (dd,lH), 4.99

(1/2 ABq,lH), 4.79 (1/2 ABq,lH), 4.09 (d,lH), 3.99 (d,lH), 3.95-3.70 (m,4H), 3.19 (apparent t,lH), 1.22 (d,3H), 1.14 (s,9H).

29 ca. 8.54 (overlapping singlets,2H), 7.75 (d,lH), ca. 7.3 (m,lH), 5.19 (1/2 ABq,lH), 4.65 (1/2 ABq,lH), 4.02-3.82 (m,4H),

3.80-3.68 (m,2H), 3.22 (br t,lH), 2.41 (t,2H), 1.45 (m,2H), 1.35-1.18 (m,14H), 0.88 (distorted t,3H).

30 8.54 (br s,2H), 7.78 (d,lH), 7.30 (m,lH), 5.10 (1/2 ABq,lH), 4.71 (1/2 ABq,lH), 4.03 (d,lH), 3.99-3.83 (m,3H), 3.82-3.75 (m,2H),

3.20 (dd,lH), 2.82 (quintet,lH), 1.26 (d,3H), 1.09 (d,6H).

31 8.55 (br s,2H), 7.56 (d,lH), ca. 7.30 (m,lH), 5.12 (1/2 ABq,lH), 4.68 (1/2 ABq,lH), 4.13 (s,2H), 4.01-3.82 (m,3H), 3.80-3.67 (m,4H), 3.36 (ABq,2H), 3.20 (t,lH), 2.17 (s,3H), 1.28 (d,3H).

32 (partial) ca. 7.68 (m,lH), ca. 7.30 (d,lH), 1.34 (d,3H).

34 4.18 (d,lH), 3.97 (d,lH), 3.84 (d,lH), 3.75 (d,lH), 3.70-3.54 (m,4H), 3.44-3.36 (m,lH), 2.76 (t,2H), 2.66-2.59 (m,2H),

2.29-2.21 (m,lH), 2.07 (s,3H), 1.94-1.85 (m,lH), 1.35 (d,3H), 1.15 (t,3H).

35 4.08 (m,lH), 3.93 (d,lH), 3.83-3.50 (m,6H), 3.42 (m,lH), 2.82-2.65 (m,3H), 2.25-2.18 (m,lH), 2.08 (s,3H), 1.92-1.83

(m,lH), 1.68-1.48 (m,lH), 1.42-1.30 (overlapping d and m,4H),. 1.05 (d,3H), 0.91 (distorted t,3H).

36 (partial) 2.10 (s,3H), 1.37 (d,3H), 1.15 (s,9H).

37 4.22 (d,lH), 3.98 (d,lH), 3.82 (d,lH), 3.78-3.53 (m,5H), 3.43-3.35 (m,lH), 2.74 (t,2H), 2.60-2.47 (m,2H), 2.28-2.20 (m,lH), 2.06 (s,3H), 1.92-1.84 (m,lH), 1.55-1.45 (m,2H), 1.35 (d,3H), ca. 1.28 (m,12H), 0.88 (t,3H).

38 4.15 (d,lH), 4.00-3.83 (m,3H), 3.70-3.53 (m,4H), 3.42-3.35 (m,lH), 3.00-2.89 (m,lH), 2.82-2.70 (m,2H), 2.27-2.20 (m,lH), 2.07 (apparent s,3H), 1.92-1.82 (m,3H), 1.80-1.63 (m,2H), 1.62-1.40 (m,4H), 1.35 (m,3H).

39 4.21 (d,lH), 3.98 (d,lH), 3.84 (d,lH), 3.78-3.52 (m,6H), 3.41 (m,lH), 2.75 (dist t,2H), 2.55 (distorted q,2H), 2.24 (m,lH), 2.05 (m,3H), 1.88 (m,lH), 1.50 (m,2H), 1.38-1.22 (m,8H), 0.89 (dist t,3H).

40 7.35-7.27 (m,5H), 4.23 (d,lH), 4.15 (d,lH), 3.82-3.59 (m,7H), 3.48 (m,lH), 3.24 (m,lH), 2.78 (m,2H), 2.25 (m,lH), 2.09 (s,3H), 1.88 (m,lH), 1.36 (m,3H).

41 4.30 (d,lH), 4.18 (d,lH), 4.02 (d,lH), 3.78-3.38 (m,l IH), 2.77

(m,2H), 2.25 (m,lH), 2.07 (s,3H), 1.90 (m,lH), 1.35 (m,3H).

42 (400 MHz, D ₂ O, partial spectrum, HDO=4.66) 1.87 (s,3H), 1.18

(d,3H).

43 (partial spectrum) 2.08 (s,3H), 1.33 (d,3H).

44 8.54 (overlapping s and d,2H), 7.62 (apparent d,lH), 7.29 (m,lH),

4.67 (d,lH), 4.59 (m,lH), 4.14 (d,lH), 3.85 (m,lH), 3.74 (d,lH), 3.63 (d,lH), 3.52-3.38 (m,3H), 2.37 (s,3H), 2.04 (m,lH), 1.93

(m,lH), 1.35 (m,3H).

45 8.53 (m,2H), 7.62 (m,lH), ca. 7.27 (m,2H), 4.67 (d,lH), 4.58 (m,lH), 4.17 (d,lH), 3.83 (m,2H), 3.69 (d,lH), 3.52-3.37 (m,3H), 2.38 (m,2H), 2.05 (m,lH), 1.94 (m,lH), 1.46 (m,2H), 1.36 (m,3H), ca. 1.25 (m,12H), 0.88 (t,3H).

46 ca. 8.53 (overlapping d and s,2H), 7.62 (d,lH), 7.29 (m,lH), 4.67 (d,lH), 4.59 (m,lH), 4.18 (d,lH), 3.84 (apparent d,2H), 3.69 (d,lH), 3.43 (m,3H), 2.39 (m,2H), 2.06 (m,lH), 1.83 (m,lH), 1.48 (m,2H), 1.37 (d,3H), ca. 1.29 (m,6H), 0.88 (distorted t,3H).

47 (partial spectrum) 8.55 (s,lH), 8.52 (s,lH), 1.34 (distorted d,3H), 1.12 (distorted t,3H).

48 8.55 (d,lH), 8.51 (s,lH), 7.64 (d,lH), 7.29 (m,lH), 4.69-4.52 (m,2H), 4.13 (m,lH), 4.00-3.80 (m,2H), 3.72 (m,lH), 3.47

(m,3H), 2.64 (m,lH), 2.00 (m,lH), 1.86 (m,lH), 1.63-1.45 (m,lH), 1.43-1.28 (m,4H), 1.03 (m,3H), 0.88 (m,3H).

49 (partial spectrum) 8.56 (d,lH), 8.52 (s,lH), 2.82 (m,lH), 1.33 (d,3H), 1.10 (apparent s,6H).

50 8.32 (s,lH), 7.82 (d,lH), 7.34 (d,lH), 5.05 (1/2 ABq,lH), 4.75 (1/2 ABq,lH), 3.94-3.72 (m,6H), 3.22 (dd,lH), 2.42 (s,3H), 1.26 (d,3H).

51 7.44 (s,lH), 5.18 (1/2 ABq,lH), 4.79 (1/2 ABq,lH), 3.98-3.74 (m,6H), 3.22 (dd,lH), 2.43 (s,3H), 1.30 (d,3H).

¹ Unless indicated otherwise, spectra were obtained in CDC1 ₃ at 400 MHz. s = singlet, d = doublet, t = triplet, m = multiplet, coupling constants (J) are in Hertz.

TEST A Southern Corn Rootworm

Test units consisting of an 8-ounce (230 mL) plastic cup containing 1 one- inch square of a soybean-wheatgerm diet were prepared. Solutions of each of the test compounds (acetone/distilled water 75/25 solvent) were sprayed into the cup. Spraying was accomplished by passing the cup, on a conveyor 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). After the spray on the cups had dried, five second-instar larvae of the southern corn rootworm (Diabrotica undecimpunctata howardi) were placed into each cup. The cups were then covered and held at 27 °C and 50% relative humidity for 48 h, after which time mortality readings were taken. Of the compounds tested, the following gave mortality levels of 80% or higher after 48 h: 1*,2,3,4,5,6,7,8,10, 11,12,13,14,15,16,18,19,20,21,22,23,24,25,26,27,28,29,30,33, 36,37,42,47,50,51. * test concentration was 250 ppm

TEST B Boll Weevil

Five adult boll weevils (Anthonomus grandis grandis) were placed into each of a series of 9-ounce (260 mL) cups. The test units were sprayed as described in Test A with individual solutions of the below-listed compounds. Each cup was then covered with a vented lid and held at 27 °C. and 50% relative humidity for 48 h, after which time mortality readings were taken. Of the compounds tested, the following gave mortality levels of 80% or higher: 1*,3,5,6,11,12, 14,15, 16, 28,50,51. * test concentration was 250 ppm

TEST C Black Bean Aphid

Individual nasturtium leaves were infested with 10 to 15 aphids (all stages of Aphis fabae) and sprayed with their undersides facing up as described in Test A. The leaves were then set in three 8-inch diameter vials containing 4 mL of sugar water solution and covered with a clear plastic 1 -ounce portion cup to prevent escape of aphids that drop from the leaves. The test units were held at 27 °C and 50% relative humidity for 48 h, after which time mortality readings were taken. Of the compounds tested, the following gave mortality levels of 80%

or higher: 1*,2,3,5,6,7,8,9,10,12,13, 14,15,16,17,18,19,20,21,22,23,24,25,26, • 27,31,36,38,39,40,42,44,45,46,47,48,49,51. * test concentration was 250 ppm

TEST D Aster Leafhopper

Test units were prepared from a series of 12-ounce (350 mL) cups, each containing oat (Avena sativa) seedlings in a 1-inch (2.5 cm) layer of sterilized soil and a 1/2 inch layer of sand. The test units were sprayed as described in Test A with individual solutions of the compounds. After the oats had dried from the spraying, between 10 and 15 adult aster leafhoppers (Mascrosteles fascifrons) were aspirated into each of the cups covered with vented lids. The cups were held at 27°C and 50% relative humidity for 48 hours, after which time mortality readings were taken. Of the compounds tested, the following gave mortality levels of 80% or higher: 2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,19,20,21,36,38,40 ,47.

TEST E Solution Systemic Activity Against the Rice Water Weevil Adults

The test compound is added directly to 50 mL of distilled water and dissolved completely to yield a concentration of 100 ppm. This chemical solution is poured into a scintillation vial. Three or four rice {Oryza sativa) seedlings, 1.5 to 2.0 leaf stage and about 7 to 9 cm tall, are then positioned in the unit by a nonabsorbent cotton plug at the vial collar. This allows complete immersion of the seedling root systems in the chemical solution, while the aerial portion of the plant is isolated above the solution. The cotton also prevents the test insects from accidentally contacting the chemical solution beneath the cotton. Care is taken to avoid accidental chemical contamination of the cotton. A clear, 1-inch diameter, plastic tube is positioned over the vial. The rice seedlings are allowed to absorb the chemical from the solution for 24 h in the laboratory at 22°C under continuous light. Five feral adult rice water weevils (Lissorhoptrus oryzophilus kuschel) that have been starved for about 24 h are then transferred into the test units. The top of the tube is sealed with a plastic cap to prevent the test insects from escaping. The infested units are held at 27°C and 65% relative humidity. Counts of the number of live and dead adults are taken at 48 and 72 h postinfection. Insects which do not respond to being probed or pinched with

forceps are classified as dead. Of the compounds tested, the following gave mortality levels of 80% or higher at 72 h: 1,2,5,6,7.

TEST F ■ Solution Systemic Activity Against Green Leafhopper Nymphs The test chemical is added directly to 10 mL of distilled water and dissolved completely. This chemical solution is poured into a conical shaped test unit. Three rice seedlings are then positioned in the unit by a notched sponge disk. The sponge disk allows a complete immersion of the seedling root systems in the chemical solution, while the aerial portion of the plant is isolated above the solution. The sponge also prevents the test nymphs from accidentally contacting the test solution. A 7 to 10 mm space, between the surface of the chemical solution and the bottom of the sponge disk, prevents accidental chemical contamination of the sponge. The concentration of the test chemical in the chemical solution is 100 ppm. The rice seedlings are allowed to absorb the chemical from the solution for 24 h in a growth chamber held at 27°C and 65% relative humidity. Eight to ten 3rd-instar nymphs of the green leafhopper (Nephotettix cincticeps) are transferred into the test units using an aspirator. The infested units are held under the same temperature and humidity conditions described above. Counts of the number of live and dead nymphs are taken at 24 and 48 h post-infestation. Insects which cannot walk are classified as dead. Of the compounds tested, the following gave mortality levels of 80% or higher at 48 h post-infestation. 1,2,3,4,5,6,7,8,9,10,12,13,14,15,16,18,19,33,36,38,39,40, 41,50,51.

TEST G Solution Systemic Activity Against Brown Planthopper Nymphs

Same methods as used for Solution Systemic Activity against green leafhopper nymphs, except that the brown planthopper (Nilaparvata lugens) is the test species. Of the compounds tested, the following gave mortality levels of 80% or higher at 48 h post-infestation: 1,2,3,4,5,6,7,8,9,10,13,14,15,16,18,19,22,23, 24,25,26,27,29,30,31 ,41 ,45,46,47,48,49,50,51.