WO1997005146A1

WO1997005146A1 - Arthropodicidal nitromethylenes

Info

Publication number: WO1997005146A1
Application number: PCT/US1996/011863
Authority: WO
Inventors: David W. Piotrowski
Original assignee: E.I. Du Pont De Nemours And Company
Priority date: 1995-07-27
Filing date: 1996-07-18
Publication date: 1997-02-13
Also published as: AU6499796A

Abstract

Compounds of Formula (I) and their N-oxides and agriculturally suitable salts, are disclosed which are useful as arthropodicides, wherein A is selected from the group C1-C6 alkylene and -(CH2)r-Z-(CH2)t-; Q is selected from the group phenyl, furanyl, furazanyl, thienyl, pyrrolyl, pyrazolyl, oxazolyl, oxadiazolyl, imidazolyl, isoxazolyl, thiazolyl, thiadiazolyl, isothiazolyl, tetrazolyl, pyridinyl, pyrimidinyl, pyridazinyl, pyrazinyl and triazinyl, each ring optionally substitued with 1-3 substituents independently selected from W; X?1, X2 and X3¿ are each independently selected from the group O and NR4; Z is selected from the group O and NR5; n is 0 to 12; r and t are independently 1, 2 or 3; and R1-R5 and W are as defined in the disclosure. Also disclosed are compositions containing the compounds of Formula (I) and a method for controlling arthropods which involves contacting the arthropods or their environment with an effective amount of a compound of Formula (I).

Description

TITLE

ARTHROPODICΓDAL NΓTROMETHYLENES

BACKGROUND OF TJHE INVENTION This invention relates to certain nitromethylene derivatives, their N-oxides, agriculturally suitable salts and compositions, and methods of their use as arthropodicides in both agronomic and nonagronomic environments.

The control of arthropod pests is extremely important in achieving high crop efficiency. Arthropod damage to growing and stored agronomic crops can cause significant reduction in productivity and thereby result in increased costs to the consumer. The control of arthropod pests in forestry, greenhouse crops, ornamentals, nursery crops, stored food and fiber products, livestock, household, and public and animal health is also important. Many products are commercially available for these purposes, but the need continues for new compounds which are more effective, less costly, less toxic, environmentally safer or have different modes of action. U.S. 4,831,036 discloses insectieidal, nematocidal and ectoparasiticidal tetrahydropyrimidine derivatives of Formula i:

This publication does not disclose silyl substitution on the pyrimidine ring as embodied by the present invention.

SUMMARY OF THE INVENTION This invention is directed to compounds of Formula I including all geometric and stereoisomers, N-oxides, and agriculturally suitable salts thereof, agricultural compositions containing them and their use as arthropodicides:

I wherein

A is selected from the group Ci-Cg alkylene and -(CH2)_r-Z-(CH₂)_t-; Q is selected from the group phenyl, furanyl, furazanyl, thienyl, pyrrolyl, pyrazolyl, oxazolyl, oxadiazolyl, imidazolyl, isoxazolyl, thiazolyl, thiadiazolyl, isothiazolyl, tetrazolyl, pyridinyl, pyrimidinyl, pyridazinyl, pyrazinyl and triazinyl, each ring optionally substituted with 1-3 substituents independently selected from W; X¹, X² and X³ are each independently selected from the group O and NR⁴; Z is selected from the group O and NR⁵;

R¹ and R² are each independently selected from the group H and C1-C4 alkyl; or R¹ and R² can be taken together as -CH₂CH2- or -CH2CH2CH2-, each optionally substituted with 1-2 CH₃; each R³ is independently selected from the group C1-C4 alkyl and C1-C4 haloalkyl; each R⁴ is independently selected from the group H and C1-C4 alkyl;

R⁵ is selected from the group H, C_rC₄ alkyl and C(O)R⁶; R⁶ is selected from the group H, C_j-C₄ alkyl; CyC haloalkyl; and phenyl optionally substituted with W¹; each W is independently selected from the group halogen, cyano, nitro, Cι-C₂ alkyl, C_rC₂ haloalkyl, C_rC₂ alkoxy, C_rC₂ haloalkoxy, C_rC₂ alkylthio,

Cι-C₂ haloalkylthio, C_rC₂ alkylsulfinyl, C_rC₂ haloalkylsulfinyl, C_rC₂ alkylsulfonyl, C1-C2 haloalkylsulfonyl, C₁-C4 alkylamino and C2-Cg diaU^lamino; W¹ is selected from the group halogen, cyano, nitro, C_]-C₂ alkyl, C1-C2 haloalkyl, C _l -C₂ alkoxy, C 1 -C₂ haloalkoxy, C 1 -C₂ alkylthio, C _l -C₂ haloalkylthio,

C_rC₂ alkylsulfinyl, C_rC₂ haloalkylsulfinyl, C_rC₂ alkylsulfonyl, C_rC₂ haloalkylsulfonyl, C1-C4 alkylamino and C₂-Cg dialkylamino; n is 0 to 12; and r and t are independently 1, 2 or 3. In the above recitations, the term "alkyl", used either alone or in compound words such as "alkylthio" or "haloalkyl" includes straight-chain or branched alkyl, such as, methyl, ethyl, n-propyl, z^'-propyl, or the different butyl isomers. "Alkylene" denotes a straight-chain or branched alkanediyl. Examples of "alkylene" include CH₂, CH₂CH₂, CH(CH₃), CH₂CH₂CH₂, CH₂CH(CH₃) and the different butylene, pentylene or hexylene isomers. "Alkoxy" denotes methoxy and ethoxy. "Alkylthio" denotes methylthio and ethylthio. "Alkylsulfinyl" includes both enantiomers of an alkylsulfinyl group. Examples of "alkylsulfinyl" are CH₃S(O) and CH₃CH₂S(O). Examples of "alkylsulfonyl" are CH₃S(O)₂ and CH₃CH₂S(O)₂. "Alkylamino" denotes an amino group substituted with one alkyl group. Examples of "alkylamino" include methylamino, ethylamino, n-propylamino, i-propylamino, and the different butylamino isomers. "Dialkylamino" denotes an amino group substituted with two alkyl groups which may be different. Examples of "dialkylamino" include dimethylamino and ethylmethylamino. One skilled in the art will appreciate that not all nitrogen containing heterocycles can form N-oxides since the nitrogen requires an available lone pair for oxidation to the oxide; one skilled in the art will recognize those nitrogen containing heterocycles which can form N-oxides.

The term "halogen", either alone or in compound words such as "haloalkyl", includes 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 F₃C, C1CH₂, CF₃CH₂ and CF₃CC1₂. The terms "haloalkoxy", "haloalkylthio", and the like, are defined analogously to the term "haloalkyl". Examples of "haloalkoxy" include CF₃O, CCl₃CH₂O, HCF₂CF₂O and CF₃CH₂O. Examples of "haloalkylthio" include CC1₃S, CF₃S, CC1₃CH₂S and HCF₂CF₂S. Examples of "haloalkylsulfinyl" include CF₃S(O), CCl₃S(O), CF₃CH₂S(O) and CF₃CF₂S(O). Examples of "haloalkylsulfonyl" include CF₃S(O)₂, CCl₃S(O)₂, CF₃CH₂S(O)₂ and CF₃CF₂S(O)₂.

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 8. For example, Cj-C₂ alkylsulfonyl designates methylsulfonyl through ethylsulfonyl. In the above recitations, when a compound of Formula I is comprised of one or more heterocyclic rings, all substituents are attached to these rings through any available carbon or nitrogen by replacement of a hydrogen on said carbon or nitrogen.

When a group contains a substituent which can be hydrogen, for example R¹ or R⁴, then, when this substituent is taken as hydrogen, it is recognized that this is equivalent to said group being unsubstituted. Compounds of this invention can exist as one or more stereoisomers. The various stereoisomers include enantiomers, diastereomers, atropisomers and geometric isomers. One skilled in the art will appreciate that one stereoisomer may be more active and/or may exhibit beneficial effects when enriched relative to the other stereoisomer(s) or when separated from the other stereoisomer(s). Additionally, the skilled artisan knows how to separate, enrich, and/or to selectively prepare said stereoisomers. Accordingly, the present invention comprises compounds selected from Formula I, N-oxides and agriculturally suitable salts thereof. The compounds of the invention may be present as a mixture of stereoisomers, individual stereoisomers, or as an optically active form. The salts of the compounds of the invention include acid-addition salts with inorganic or organic acids such as hydrobromic, hydrochloric, nitric, phosphoric, sulfuric, acetic, butyric, fumaric, lactic, maleic, malonic, oxalic, propionic, salicylic, tartaric, 4-toluenesulfonic or valeric acids. The salts of the compounds of the invention also include those formed with organic bases (e.g., pyridine, ammonia, or triethylamine) or inorganic bases (e.g., hydrides, hydroxides, or carbonates of sodium, potassium, lithium, calcium, magnesium or barium) when the compound contains an acidic group. Preferred compounds for reasons of better activity and/or ease of synthesis are:

Preferred 1. Compounds of Formula I above, and N-oxides and agriculturally suitable salts thereof, wherein: A is C₃ alkylene;

Q is selected from the group isoxazolyl, thiazolyl and pyridinyl, each ring optionally substituted with 1-3 substituents independently selected from W; X¹, X² and X³ are each O; and R¹ and R² are each independently C_j-C₄ alkyl. Preferred 2. Compounds of Formula I above, and N-oxides and agriculturally suitable salts thereof, wherein:

A is C₃ alkylene;

Q is selected from the group isoxazolyl, thiazolyl and pyridinyl, each ring optionally substitύtedJvkhJ-S^strristituents independently selected from W; X ! , X² and X³ are each O; and

R¹ and R² are taken together as -CH₂CH₂- or -CH₂CH₂CH₂-, each optionally substituted with 1-2 CH₃. Preferred 3. Compounds of Preferred 2 wherein: Q is pyridinyl; W is halogen or C!-C₂ alkyl; and n is O. Preferred 4. Compounds of Preferred 2 wherein: Q is isoxazolyl;

W is halogen or Cι-C₂ alkyl; and n is O. Preferred 5. Compounds of Preferred 2 wherein:

Q is thiazolyl;

W is halogen or C_j-C₂ alkyl; and n is O. Most preferred is the compound of Preferred 3 which is: l-[3-[l-[(6-cUoro-3-pyridinyl)methyl]-l,2,3,7-tetrahydro-8-nitroimidazo[l,2- c]pyrimidin-6(5H)-yl]propyl]-2,8,9-trioxa-5-aza-l-silabicyclo[3.3.3]undecane. This invention also relates to arthropodicidal compositions comprising arthropodicidally effective amounts of the compounds of the invention and at least one of a surfactant, a solid diluent or a liquid diluent. The preferred compositions of the present invention are those which comprise the above preferred compounds.

This invention also relates to a method for controlling arthropods comprising contacting the arthropods or their environment with an arthropodicidally effective amount of the compounds of the invention (e.g., as a composition described herein). The preferred methods of use are those involving the above preferred compounds. DETAILS OF THE INVENTION

The compounds of Formula I can be prepared by one or more of the following methods and variations as described in Schemes 1-19. The definitions of A, Q, X¹ , X², X³, Z, Rϊ-R⁶, W, W¹, n, r and t in the compounds of Formulae I-XXVI below are as defined above in the Summary 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. These reactions are typically carried out at temperatures ranging from 0 °C to the reflux temperature of the solvent, with 0 °C-25 °C being preferred. Scheme 1 reactions are typically complete within one day, however, certain Scheme 1 reactions may require longer reaction times (up to 5 days). Suitable solvents include alcohols such as methanol and ethanol, water, and polar aprotic solvents such as tetrahydrofuran and dimethyl¬ formamide. Formaldehyde can be used in amounts of about 2-10 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 IU can be used.

Scheme 1

π m Compounds of Formula II can be prepared by reaction of compounds of

Formula IV with an amine of Formula V as shown in Scheme 2. Typically, compounds of Formula IV are combined with 1-20 molar equivalents of an amine of Formula V in a suitable solvent at temperatures ranging from 0-100 °C. Scheme 2 reactions typically require 6 to 48 h for completion, however longer reaction times may sometimes be required. Suitable solvents include but are not limited to, alcohols such as methanol, ethanol and isopropanol; water; acetonitrile; dimethylformamide and dimethyiacetamide. Amines of Formula V can also be used as hydrochloride salts; in these cases an equivalent amount of a base (such as sodium hydroxide) is added to the reaction mixtures.

Scheme 2

rv v

G= a suitable leaving group such as halogen, SGH₃ or OC H5.

Alternatively, compounds of Formula II can be prepared by the reaction of

Formula VI compounds with amines of Formula VII as depicted in Scheme 3 using conditions that are completely analogous to those described in Scheme 2. Scheme 3

vi vπ

Compounds of Formula IV can be prepared employing processes known in the art that involve reaction of nitroethene compounds of Formula VIII with amines of Formula VII (Scheme 4). Compounds of Formula VI can be prepared by procedures which are analogous to those for compounds of Formula IV. Typical reaction conditions involve the combination of equimolar amounts of compounds of Formulas VII and VIII in a suitable solvent or solvent mixture at temperatures in the range of about 0-100 °C. Scheme 4 reactions typically require 6 to 48 h for completion. Suitable solvents typically have sufficient polarity to effect solution of compounds of Formulas VII and VIII, and include alcohols such as methanol, ethanol and isopropanol; ethers such as diethyl ether, tetrahydrofuran and dioxane; esters such as ethyl acetate; polar aprotic solvents such as dimethylformamide and dimethyiacetamide; and water, as well as mixtures of solvents.

Scheme 4

Vffl vπ

Alternatively, compounds of Formula I can be prepared by the reaction of tetrahydropyrimidines of Formula DC with amines of Formula VII as depicted in Scheme 5 under conditions analogous to those described in Scheme 2. Scheme 5

LX VTT

Compounds of Formula LX can be prepared by the reaction of Formula IH amines with compounds of Formula VI in the presence of formaldehyde as shown in Scheme 6 using procedures analogous to those described in Scheme 1.

Scheme 6

vi m

Alternatively, as shown in Scheme 7, compounds of Formula I can be prepared by the reaction of compounds of Formula X with an alkylating agent of Formula XI in the presence of a proton acceptor and an optional additive in a suitable solvent. Typical proton acceptors include potassium tert-butoxide, NaH, KH, K2CO , NaHCO , and Cs2CO₃, and optional additives include 18-crown-6, 15-crown-5 and benzo- 18-crown-6. Suitable solvents include DMF, THF, acetonitrile and water. In some cases, Scheme 7 reactions are carried out under phase transfer conditions using solvents that include toluene, dichloromethane, dichloroethane, ether, hexanes, benzene and the like and an aqueous base, including NaOH, KOH, NaHCO₃, Na2CO₃, K₂CO₃, among others. Typical phase transfer catalysts include tetrasubstituted ammonium halide salts, such as tetrabutylammonium iodide, benzyltriethylammonium bromide and the like. Reactions are typically carried out at temperatures ranging from 20-150 °C and are completed in 1 h to 3 days; however, 6 to 24 h is usually preferred. Scheme 7

X XI

Zl = a suitable leaving group such as halogen, tosylate, methanesulfonate, or trifluoromethane sulfonate.

Compounds of Formula X can be prepared by reaction of tetrahydropyrimidines of Formula LX with amines of Formula XII as depicted in Scheme 8 under conditions analogous to those described in Scheme 2.

Scheme 8

rx xπ

Alternatively, compounds of Formula I (where R² is other than H) can be prepared as shown in Scheme 9 using procedures that are completely analogous to those described for Scheme 7 reactions.

Scheme 9

v her ]

I (where R² = H) Xffl The formation of compounds of Formula II (where R and R² are taken together to form a 5-or 6-membered ring) is depicted in Scheme 10. Conditions for carrying out Scheme 10 reactions are analogous to those described for Scheme 7.

Scheme 10

B = Rl and R² taken together to forma 5- or 6- membered ring

Altematively, compounds of Formula II (where R² and R³ are taken together to form a 5- or 6-membered ring) can be prepared as shown in Scheme 11. Typical reactions involve the combination of equimolar amounts of Formula XV and Vm compounds in a suitable solvent or solvent mixture at temperatures in the range of about 0-100 °C for a time ranging from 2 to 48 h. Suitable solvents typically have sufficient polarity to effect solution of Formula XV and VIII compounds and include alcohols such as methanol, ethanol and isopropanol; ethers such as diethyl ether, tetrahydrofuran and dioxane; esters such as ethyl acetate; polar aprotic solvents such as dimethylformamide and dimethyiacetamide; and water, as well as mixtures of solvents.

Scheme 11

B = Rl and R² G = a suitable taken together leaving group Diamines of Formula XV can be formed by reaction of Formula XI compounds with a stoichiometric excess of amines of Formula XVI as depicted in Scheme 12. Typical reactions involve the use of 1.5-10 equivalents of Formula XVI compounds in solvents such as methanol, ethanol, isopropanol, THF, water or acetonitrile, among others. Scheme 12 reactions are sometimes carried out in the absence of solvent. Typical reaction times for Scheme 12 reactions range from 30 min to several days, with 6 to 24 h being generally preferred.

Scheme 12

Zl = a suitable B = Rl and R² leaving group taken together

Altematively, Formula XVI diamines where B is an optionally substituted CH₂CH₂ group can be prepared by the two-step procedure depicted in Scheme 13. In Step i of Scheme 13, amines of Formula VII are treated with potassium cyanide and compounds of Formula XVII in the presence of zero to three equivalents of acid to form aminonitriles of Formula XVIII. One skilled in the art will recognize that compounds of Formula XVII can be formaldehyde, acetaldehyde, or acetone. Other cyanide salts as well as HCN can be used in the procedure as well as hydrohalide and other acid salts of Formula VII. Suitable solvents include methanol, ethanol, isopropanol and water, as well as combinations of solvents. Scheme 13 reactions are usually complete with 24 h. Altemative procedures for the preparation of amino nitriles such as XVIII can be found in the literature (see, e.g., Synth. Commun., (1985), 75, 157; Synthesis, (1979), 127).

In Step ii of Scheme 13, aminonitriles of Formula XVIII are reduced to form diamines of Formula XV. This reduction can usually be achieved using lithium aluminum hydride or borane in amounts ranging from 0.75 to 3 molar equivalents, in a solvent such as diethyl ether or THF. Reactions are carried out at temperatures ranging from -20 °C to the reflux temperature of the solvent for times ranging from 0.5 h to 2 days. Altematively, the reduction of compounds of Formula XVIII to compounds of Formula XV 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 diamines of Formula XV.

Scheme 13

vπ(Rⁱ =H) xvπ XVffl

R7 and R⁸ are independently H or CH

XV

An altemative procedure for the preparation of diamines of Formula XV where B is an optionally substituted CH₂CH₂ group is depicted in Scheme 14. In Step i of Scheme 14, amino amides of Formula XIX are treated with 1 to 2 molar equivalents of acid chlorides of Formula XX in the presence of 1 to 3 molar equivalents of a base such as NaOH, KOH, K2CO₃, NaHCO , pyridine or triethylamine. Suitable solvents include THF, CH2CI2, water or pyridine. The products (compounds of Formula XXI) can be isolated by extraction or, more conveniently, by removal of solvent, and are usually suitable for use in Step ii of Scheme 14 in crude form. Amides of Formula XLX can be used either in neutral form as depicted or as the salt form (typically as the HCl or CF₃CO2H salt, among others). When the salt form of XLX is used, an additional one equivalent of base is used in Step i of Scheme 14.

In Step ii of Scheme 14, the amide of Formula XXI is converted into the diamine of Formula XV by treatment with a reducing agent such as LiAlH , BH₃ THF or BH₃-SMe2 in a solvent such as THF or Et₂O at temperatures ranging from 0 °C to the reflux temperature of the solvent. Typical reaction times range from 0.5 h to 2 days.

Analogous procedures are well-known in the literature (see e.g., Synthesis, (1981), 441). When R⁷ is CH₃ and R⁸ is H, then XLX is alanine amide. The use of either the D- or the L- form of alanine amide of Formula XLX or its salt provides a convenient means of obtaining enantiomerically enriched forms of diamines of Formula XV. When compounds of Formula II are prepared as described for Scheme 11 reactions using enantiomerically enriched forms of compounds of Formula XV, the compounds of Formula II are obtained in enantiomerically enriched form. When compounds of Formula I are prepared as described for Scheme 1 reactions using enantiomerically enriched forms of compounds of Formula π, the compounds of Formula I are obtained in enantiomerically enriched form.

Scheme 14

xrx XX XXI

Step ii

XXI [ ^H]

XV

R" = 3-pyridyl, 5-thiazolyl, 6-chloro-3-pyridyl, 2-chloro-5-thia2θlyl, or 5,6-dichloro-3-pyridyl.

Altematively, diamines of Formula XV 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).

Amines of Formula III can be prepared by the reaction of a silyl halide of Formula XXII with an excess of ammonia as shown in Scheme 15. These transformations typically involve the addition of compounds of Formula XXII to anhydrous, liquid ammonia (2 to 100 equivalents) at temperatures ranging from -78 to 100 °C. In cases where temperatures greater than -33 °C are required, the reactions are carried out in a sealed, high pressure apparatus. Usually no solvent is required; however, solvents such as THF or diethyl ether are sometimes used. Reactions generally require 0.5 h to 72 h for completion. Typical work-up procedures usually involve the evaporation of excess ammonia, precipitation of ammonium halide by addition of ether, and removal of solvent. One skilled in the art will recognize that there are many altemative methods for converting halides of Formula XXII into primary amines of Formula HI. References for a variety of procedures can be found in March, Adv. Org.

Chem., 4th Ed., pp 1276-7.

Scheme 15

xxπ

Zl = a suitable leaving group

Compounds of Formula XXII can be prepared by reaction of a silane of Formula XXm with a compound of Formula XXIV as depicted in Scheme 16. Typical solvents can include alcohols, such as methanol or ethanol, or hydrocarbons, such as toluene or xylene. The reaction can be performed in the absence of solvents. The reactions can be performed in the presence of 0.05-5 equivalents of a base such as aqueous NaOH, sodium hydride, or triethylamine. Typical reactions temperatures range from 0 °C to the reflux temperature of the solvent. Analogous procedures are known in the art. For example, see 7. Organomet. Chem., (1982), 1, and U.S. Pat. No. 3,118,921.

Scheme 16

xxm xxrv

Y¹, Y², Y³ = Cl, CJ-C6 alkojy , Cj-C^ dialkylamino, acetojy Zl = a suitable leaving group Altematively, amines of Formula HI can be prepared by reaction of amines of Formula XXV and compounds of Formula XXIV as depicted in Scheme 17 using procedures that are completely analogous to those described for Scheme 16 reactions.

Scheme 17

XXV xx v

Y¹, Y² Y³ = Cl, C_j-Cg alkoxy, C_j-Cg dialkylamino, acetoxy

Alternatively, compounds of Formula I can be prepared by reaction of Formula

XXVI compounds with compounds of Formula XXIV using procedures that are analogous to those described for Scheme 16 reactions. Scheme 18 depicts this transformation.

Scheme 18

XXVI XXIV

Y¹, Y² Y³ = Cl, Cj-Cg alkoxy, C\-C dialkylamino, acetoxy

The compounds of Formula XXVI can be prepared by the reaction of Formula II compounds with one or more equivalents of an amine of Formula XXV and at least two molar equivalents of formaldehyde as depicted in Scheme 19 using procedures that are completely analogous to those described for Scheme 1 reactions. One skilled in the art will recognize that Formula XXVI compounds can also be prepared by analogous procedures described for reactions in Schemes 5, 7, and 9. Scheme 19

π xxv

γl, Y², Y³ = Q, Ci-Cg alkoxy, C^Cg dialkylamino, acetoxy

Procedures for the formation of compounds of Formula XXIII are well-known to one skilled in the art (see, Liebigs Ann. Chem., (1987), 51; 7. Organomet. Chem., (1970), 22, 599).

One skilled in the art will recognize that a wide variety of altemative procedures for the preparation of compounds of Formulae HI, XXII, XXIII and XXV are known in the art. Leading references include, e.g., Fleming, I.., Organosilicon Chemistry, in Comprehensive Organic Chemistry, (1979), 3, 541; Colvin, E., Silicon in Organic Synthesis, Butterworths, Boston, (1981); Pawlenko, S., Organosilicon Chemistry, Walter de Gruyter, New York, (1986); Armitage, D. A., Organosilanes, in Comprehensive Organometallic Chemistry, (1982), 2, 1; Stark, F. O.; Falender, J. R.; Wright, A. P., Silicones, in Comprehensive Organometallic Chemistry, (19), 2, 306; Topics in Current Chemistry, (1979), 84, 1. It is recognized that some reagents and reaction conditions described above for preparing compounds of Formula I may not be compatible with certain functionalities present in the intermediates. In these instances, the incorporation of protection/deprotection sequences or functional group interconversions into the synthesis will aid in obtaining the desired products. The use and choice of the protecting groups will be apparent to one skilled in chemical synthesis (see, for example, Greene, T. W.; Wuts, P. G. M. Protective Groups in Organic Synthesis, 2nd ed.; Wiley: New York, 1991). One skilled in the art will recognize that, in some cases, after the introduction of a given reagent as it is depicted in any individual scheme, it may be necessary to perform additional routine synthetic steps not described in detail to complete the synthesis of compounds of Formula I. One skilled in the art will also recognize that it may be necessary to perform a combination of the steps illustrated in the above schemes in an order other than that implied by the particular sequence presented to prepare the compounds of Formula I. One skilled in the art will also recognize that compounds of Formula I and the intermediates described herein can be subjected to various electrophilic, nucleophilic, radical, organometallic, oxidation, and reduction reactions to add substituents or modify existing substituents. Without further elaboration, it is believed that one skilled in the art using the preceding description can utilize the present invention to its fullest extent. The following Examples are, therefore, to be construed as merely illustrative, and not limiting of the disclosure in any way whatsoever. Percentages are by weight except for chromatographic solvent mixtures or where otherwise indicated. Parts and percentages for chromatographic solvent mixtures are by volume unless otherwise indicated. lH NMR spectra are reported in ppm downfield from tetramethylsilane; s = singlet, d = doublet, t = triplet, m = multiplet, dd = doublet of doublets, br s = broad singlet.

EXAMPLE 1 Preparation of l-[3-P -r(6-chloro-3-pyridinyl)methyll- 1 ,2.3.7-tetrahydro-8- mtroirnida2ori.2-c1pyrimidin-6(5H -yllpropyll-2.8.9-trioxa-5-aza-l- silabicyclor3.3.31undecane A mixture of 4.0 g (15.7 mmol) of 2-chloro-5-[2-(nitromethylene)-l- imidazolidinylmethyl]pyridine (prepared according to U.S. Pat. No. 4,678,795), 3.0 mL (39.8 mmol) of 37% aqueous formaldehyde, 4J g (17.6 mmol) of 2,8,9-trioxa-5-aza-l- silabicyclo [3.3.3]undecane-l -propanamine, and 100 mL of ethanol was stirred at room temperature for 120 h. The resulting mixture was concentrated. The yellow residue was azeotroped twice with ethanol and then was recrystallized from isopropanol/ether to give 1J8 g of the title compound of Example 1, a compound of the invention, as a white solid melting at 152-154 °C. A second crop yielded an additional 4.22 g of the title compound of Example 1 as a yellow solid. ^]Η NMR (300 MHz, CDC1₃) δ 8.38 (sJH), 7.90 (dJH), 7.37 ((UH), 4.83 (s,2H), 3.97 (s,2H), 3.85 (sJH), 3.76 (t,6H), 3.70-3.50 (m,4H), 2.81 (t,6H), 2.53 (dd,2H), 1.70-1.60 (m,2H), 0.40 (dd,2H).

EXAMPLE 2 Step A: l-[3-(1.2.3.7-tetrahydro-8-nitroirrιidazori.2-clpyrirnidin-6(5H)- yl^"|propyn-2.8.9-trioxa-5-aza-l-silabicyclor3.3.31undecane

A mixture of 0.88 g (6.8 mmol) of 2-nitromethylene-l-imidazolidine, 1.67 g (7.2 mmol) of 2,8,9-trioxa-5-aza-l-silabicyclo[3.3.3]undecane-l-propanamine, 1.3 g (16.0 mmol) of 37% aqueous formaldehyde and 20 mL of ethanol was stirred at room temperature overnight. The solvent was removed and the residue was triturated with diethyl ether to give 2.55 g of the title compound of Step A as a white solid melting at 162-165 °C. !Η NMR (300 MHz, CDC1₃) δ 8.35 (br sJH), 4.06 (s,2H), 3.85 (s,2H), 3.76 (t,6H), 3.80-3.60 (m,4H), 2.80 (t,6H), 2.55 (dd,2H), 1.70-1.50 (m,2H), 0.40 (dd,2H).

Step B: Preparation of l-r3-riJ(4-chlorophenyDmethyll- 2,3,7-tetrahydro-8- nitroimidazof 1.2-clpyrimidin-6(5H)-yl1propyll-2.8,9-trioxa-5-aza- 1 - silabicyclor3.3.3]undecane

A mixture of 0.50 g (1.3 mmol) of the title compound of Step A, 0J6 g (1.43 mmol) of potassium tert-butoxide and 0.05 g (0.2 mmol) 18-crown-6 was heated at reflux in tetrahydrofuran. After one hour, 0.21 g (1.3 mmol) of 4-chlorobenzyl chloride was added and the reaction was heated at reflux for an additional 20 hours. The reaction mixture was cooled, diluted with methanol and concentrated. The residue was purified by column chromatography (neutral alumina, 2% methanol/chloroform) to give 0J7 g of the title compound of Step B, a compound of the invention, as a yellow-orange solid melting at 157-160 °C. ^!Η NMR (300 MHz, CDC1₃) δ 7.40-7.30 (m,4H), 4.83 (s,2H), 3.97 (s,2H), 3.86 (s,2H), 3.76 (t,6H), 3.65-3.50 (m,4H), 2.81 (t,6H), 1.70-1.60 (m,2H), 0.40 (dd,2H).

By the procedures described herein together with methods known in the art, the following compounds of Tables 1 to 12 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.

The following notations have been used in Tables 1-12:

Table 1

Q =

COLUMN

1 2 3 4 5 6

1 Q-1 Q-2 Q-3 Q-4 Q-5 Q-6

2 Q-7 Q-8 Q-9 Q-10 Q-i i Q-12

3 Q-13 Q-14 Q-15 Q-16 Q-17 Q-18

4 Q-19 Q-20 Q-21 Q-22 Q-23 Q-24

5 Q-25 Q-26

Table 2

Q =

COLUMN

1 2 3 4 5 6

6 Q-1 Q-2 Q-3 Q-4 Q-5 Q-6

7 Q-7 Q-8 Q-9 Q-10 Q-l l Q-12

8 Q-13 Q-14 Q-15 Q-16 Q-17 Q-18

9 Q-19 Q-20 Q-21 Q-22 Q-23 Q-24

10 Q-25 Q-26 Table 3

Q =

COLUMN

1 2 3 4 5 6

11 Q-i Q-2 Q-3 Q-4 Q-5 Q-6

12 Q-7 Q-8 Q-9 Q-10 Q-l l Q-12

13 Q-13 Q-14 Q-15 Q-16 Q-17 Q-18

14 Q-19 Q-20 Q-21 Q-22 Q-23 Q-24

15 Q-25 Q-26

Table 4

Q =

COLUMN

1 2 3 4 5 6

16 Q-i Q-2 Q-3 Q-4 Q-5 Q-6

17 Q-7 Q-8 Q-9 Q-10 Q-l l Q-12

18 Q-13 Q-14 Q-15 Q-16 Q-17 Q-18

19 Q-19 Q-20 Q-21 Q-22 Q-23 Q-24

20 Q-25 Q-26 Table 5

Q =

COLUMN

1 2 3 4 5 6

21 Q-i Q-2 Q-3 Q-4 Q-5 Q-6

22 Q-7 Q-8 Q-9 Q-10 Q-l l Q-12

23 Q-13 Q-14 Q-15 Q-16 Q-17 Q-18

24 Q-19 Q-20 Q-21 Q-22 Q-23 Q-24

25 Q-25 Q-26

Table 6

Q =

COLUMN

1 2 3 4 5

26 A = CH₂; X¹ , X², X³ = O; R³ = H; Q-1 Q-2 Q-3 Q-4 Q-5 7 A = CH₂; χl , X², X³ = O; R³ = 3,7,10-trimethyl; Q-1 Q-2 Q-3 Q-4 Q-5 28 A = CH₂; χl, X², X³ = NH; R³ = H; Q-1 Q-2 Q-3 Q-4 Q-5 9 A = CH₂; χl, X² = O; X³ = NH; R³ = H; Q-1 Q-2 Q-3 Q-4 Q-5 0 A = CH₂CH₂; χl, X², X³ = O; R³ = H; Q-1 Q-2 Q-3 Q-4 Q-5 1 A = CH₂CH₂; X¹, X², X³ = O; R³ = 3,7,10-trimethyl; Q-i Q-2 Q-3 Q-4 Q-5 2 A = CH₂CH₂; χl, X², X³ = NH; R³ = H; Q-1 Q-2 Q-3 Q-4 Q-5 3 A = CH₂CH₂; X¹, X² = O; X³ = NH; R³ = H; Q-1 Q-2 Q-3 Q-4 Q-5 4 A = (CH₂)₃ χⁱ, x², x³ = o R³ = 3-methyl; Q-1 Q-2 Q-3 Q-4 Q-5 5 A = (CH₂)₃ χl, X² X³ = 0: R³ = 3,7-dimethyl; Q-i Q-2 Q-3 Q-4 Q-5 6 A = (CH₂)₃ χi, x² X³ = 0 R³ = 4,4-dimethyl; Q-1 Q-2 Q-3 Q-4 Q-5 7 A = (CH₂)₃ χⁱ, x², x³ = o R³ = 3-trifluoromethyl; Q-i Q-2 Q-3 Q-4 Q-5 A = (CH₂)₃;X !, X², X³ = O; R³ = 3,7,10-triethyl; Q-i Q-2 Q-3 Q-4 Q-5 A = (CH₂)₄;X ¹,X²,X³ = 0;R³ = H; Q-i Q-2 Q-3 Q-4 Q-5 A = (CH₂)₄;X 1, X², X³ = O; R³ = 3,7,10-trimethyl; Q-i Q-2 Q-3 Q-4 Q-5 A = (CH₂)₄;X l.X², X³ = NH;R³=H; Q-1 Q-2 Q-3 Q-4 Q-5 A = (CH₂)₄;X ¹,X², = 0;X³ = NH;R³ = H; Q-1 Q-2 Q-3 Q-4 Q-5 A = (CH₂)₄; X l.X² X³ = 0;R³ = 3-methyl; Q-i Q-2 Q-3 Q-4 Q-5 A = (CH₂)₄;X 1, X², X³ = O; R³ = 3,7-dimethyl; Q-i Q-2 Q-3 Q-4 Q-5 A = (CH₂)₄; X !, X², X³ = O; R³ = 4,4-dimethyl; Q-1 Q-2 Q-3 Q-4 Q-5 A = (CH₂)₄;X 1, X², X³ = O; R³ = 3-trifluoromethyl; Q-1 Q-2 Q-3 Q-4 Q-5 A = (CH₂)₄;X 1, X², X³ = O; R³ = 3,7,10-triethyl; Q-1 Q-2 Q-3 Q-4 Q-5 A = (CH₂)₅; X 1,X² X³ = 0;R³ = H; Q-1 Q-2 Q-3 Q-4 Q-5 A = (CH₂)₅; X !, X², X³ = O; R³ = 3,7,10-trimethyl; Q-1 Q-2 Q-3 Q-4 Q-5 A = (CH₂)₆;X 1,X²,X³ = 0;R³ = H; Q-i Q-2 Q-3 Q-4 Q-5 A = (CH₂)₆;X 1, X², X³ = O; R³ = 3,7,10-trimethyl; Q-1 Q-2 Q-3 Q-4 Q-5

Tab 7

Q =

COLUMN

1 2 3 4 5 A = CH₂;Xl,X²,X³ = 0;R³ = H; Q-1 Q-2 Q-3 Q-4 Q-5 A = CH₂; X¹, X², X³ = O; R³ = 3,7,10-trimethyl; Q-1 Q-2 Q-3 Q-4 Q-5 A = CH₂;χl,X²,X³=NH;R³=H; Q-1 Q-2 Q-3 Q-4 Q-5 A = CH₂;Xl,X² = 0;X³ = NH;R³ = H; Q-i Q-2 Q-3 Q-4 Q-5 A = CH₂CH₂; X ^l , X², X³ = O; R³ = H; Q-i Q-2 Q-3 Q-4 Q-5 A = CH₂CH₂; X¹, X² X³ = O; R³ = 3,7J0-trimethyl; Q-i Q-2 Q-3 Q-4 Q-5 A = CH₂CH₂; X¹ , X², X³ = NH; R³ = H; Q-i Q-2 Q-3 Q-4 Q-5 A = CH₂CH₂;Xl,X² = 0;X³ = NH;R³ = H; Q-i Q-2 Q-3 Q-4 Q-5 A = (CH₂)₃; X¹, X², X³ = O; R³ = 3-methyl; Q-i Q-2 Q-3 Q-4 Q-5 A = (CH₂)₃; χl, X², X³ = O; R³ = 3,7-dimethyl; Q-1 Q-2 Q-3 Q-4 Q-5 A = (CH₂)₃; X¹, X², X³ = O; R³ = 4,4-dimethyl; Q-i Q-2 Q-3 Q-4 Q-5 A = (CH₂)₃ ; X 1 , X², X³ = O; R³ = 3-trifluoromethyl; Q-1 Q-2 Q-3 Q-4 Q-5 A = (CH₂)₃; X¹, X², X³ = O; R³ = 3,7,10-triethyl; Q-i Q-2 Q-3 Q-4 Q-5 A = (CH₂)₄;χl,X²,X³ = 0;R³ = H; Q-1 Q-2 Q-3 Q-4 Q-5 A = (CH₂)₄; X¹, X², X³ = O; R³ = 3,7,10-trimethyl; Q-1 Q-2 Q-3 Q-4 Q-5 A = (CH₂)₄;X¹,X²,X³ = NH;R³ = H; Q-1 Q-2 Q-3 Q-4 Q-5 A = (CH₂)₄;χl,X², = 0;X³ = NH;R³ = H; Q-i Q-2 Q-3 Q-4 Q-5 A = (CH₂)₄; X¹ , X², X³ = O; R³ = 3-methyl; Q-1 Q-2 Q-3 Q-4 Q-5 A = (CH₂)₄; χl, X², X³ = O; R³ = 3,7-dimethyl; Q-1 Q-2 Q-3 Q-4 Q-5 A = (CH₂)₄; χl, X², X³ = O; R³ = 4,4-dimethyl; Q-i Q-2 Q-3 Q-4 Q-5 A = (CH₂)₄; X¹, X², X³ = O; R³ = 3-trifluoromethyl; Q-i Q-2 Q-3 Q-4 Q-5 A = (CH₂)₄; X¹. X², X³ = O; R³ = 3,7,10-triethyl; Q-i Q-2 Q-3 Q-4 Q-5 A = (CH₂)₅;χl,X², X³ = 0;R³ = H; Q-1 Q-2 Q-3 Q-4 Q-5 A = (CH₂)₅; X¹, X², X³ = O; R³ = 3,7,10-trimethyl; Q-1 Q-2 Q-3 Q-4 Q-5 A = (CH₂)₆;X1,X²,X³ = 0;R³ = H; Q-i Q-2 Q-3 Q-4 Q-5 A = (CH₂)₆; X¹, X², X³ = O; R³ = 3,7,10-trimethyl; Q-i Q-2 Q-3 Q-4 Q-5

Table 8

Q =

COLUMN

1 2 3 4 5 A = CH₂;χl,X²,X³ = 0;R³ = H; Q-i Q-2 Q-3 Q-4 Q-5 A = CH₂CH₂;Xl,X²,X³ = 0;R³ = H; Q-i Q-2 Q-3 Q-4 Q-5 A = (CH₂)₃;χl,X², X³ = 0;R³ = H; Q-1 Q-2 Q-3 Q-4 Q-5 A = (CH₂)₄;χl,X²,X³ = 0;R³ = H; Q-i Q-2 Q-3 Q-4 Q-5 A = CH₂;χl,X² X³=NH;R³ = H; Q-1 Q-2 Q-3 Q-4 Q-5 A = CH₂CH₂;Xl,X² X³ = NH;R³ = H; Q-1 Q-2 Q-3 Q-4 Q-5 A = (CH₂)₃;Xl,X² X³ = NH;R³ = H; Q-i Q-2 Q-3 Q-4 Q-5 A = (CH₂)₄; X ^] , X², X³ = NH; R³ = H; Q-1 Q-2 Q-3 Q-4 Q-5 A = CH₂;χl,X² = Q;X³ = NH;R³ = H; Q-1 Q-2 Q-3 Q-4 Q-5 87 A = CH₂CH₂;X¹,X² = 0;X³ = NH;R³ = H; Q-i Q-2 Q-3 Q-4 Q-5

88 A = (CH₂)₃;X¹.X² = 0;X³ = NH;R³ = H; Q-1 Q-2 Q-3 Q-4 Q-5

89 A = (CH₂)₄;X¹,X² = 0;X³ = NH;R³ = H; Q-i Q-2 Q-3 Q-4 Q-5

90 A = CH₂;X¹,X²,X³ = 0;R³ = CH₃; Q-1 Q-2 Q-3 Q-4 Q-5

91 A = CH₂CH₂;X¹,X²,X³ = 0;R³ = CH₃; Q-1 Q-2 Q-3 Q-4 Q-5

92 A = (CH₂)₃;X¹,X²,X³ = 0;R³ = CH₃; Q-1 Q-2 Q-3 Q-4 Q-5

93 A = (CH₂)₄;X¹,X²,X³ = 0;R³ = CH₃; Q-i Q-2 Q-3 Q-4 Q-5

Table 9

Q =

COLUMN

1 2 3 4 5

94 A = CH₂;X¹,X², X³ = 0;R³ = H; Q-1 Q-2 Q-3 Q-4 Q-5

95 A = CH₂CH₂;X¹,X²,X³ = 0;R³ = H; Q-1 Q-2 Q-3 Q-4 Q-5

96 A = (CH₂)₃;X¹,X²,X³ = 0;R³ = H; Q-1 Q-2 Q-3 Q-4 Q-5

97 A = (CH₂)₄;X¹,X²,X³ = 0;R³ = H; Q-1 Q-2 Q-3 Q-4 Q-5

98 A = CH₂;χl,X²,X³ = NH;R³ = H; Q-i Q-2 Q-3 Q-4 Q-5

99 A = CH₂CH₂;χ!,X²,X³ = NH;R³ = H; Q-1 Q-2 Q-3 Q-4 Q-5

100 A = (CH₂)₃;χl,X² X³=NH;R³=H; Q-1 Q-2 Q-3 Q-4 Q-5

101 A = (CH₂)₄;χl,X² X³=NH;R³ = H; Q-i Q-2 Q-3 Q-4 Q-5

102 A = CH₂;Xl,X² = 0;X³ = NH;R³ = H; Q-1 Q-2 Q-3 Q-4 Q-5

103 A = CH₂CH₂;X¹,X² = 0;X³ = NH;R³ = H; Q-1 Q-2 Q-3 Q-4 Q-5

104 A = (CH₂)₃;X¹.X² = 0;X³ = NH;R³ = H; Q-1 Q-2 Q-3 Q-4 Q-5

105 A = (CH₂)₄;χl,X² = 0;X³ = NH;R³ = H; Q-i Q-2 Q-3 Q-4 Q-5

106 A = CH₂;Xl,X²,X³ = 0;R³ = CH₃; Q-i Q-2 Q-3 Q-4 Q-5

107 A = CH₂CH₂;X¹,X²,X³ = 0;R³ = CH₃; Q-1 Q-2 Q-3 Q-4 Q-5

108 A = (CH₂)₃;χ!,X²,X³ = 0;R³ = CH₃; Q-1 Q-2 Q-3 Q-4 Q-5

109 A = (CH₂)₄;X¹,X²,X³ = 0;R³ = CH₃; Q-1 Q-2 Q-3 Q-4 Q-5 Table 10

Q =

COLUMN

1 2 3 4 5 A = CH₂;χl,X²,X³ = 0;R³ = H; Q-i Q-2 Q-3 Q-4 Q-5 A = CH₂CH₂;χl,X²,X³ = 0;R³ = H; Q-1 Q-2 Q-3 Q-4 Q-5 A = (CH₂)₃; X¹, X², X³ = O; R³ = H; Q-1 Q-2 Q-3 Q-4 Q-5 A = (CH₂)₄;X¹,X²,X³ = 0;R³ = H; Q-1 Q-2 Q-3 Q-4 Q-5 A = CH₂;Xl,X²,X³ = NH;R³ = H; Q-i Q-2 Q-3 Q-4 Q-5 A = CH₂CH₂;X¹,X² X³ = NH;R³ = H; Q-i Q-2 Q-3 Q-4 Q-5 A = (CH₂)₃;X¹,X²,X³ = NH;R³ = H; Q-i Q-2 Q-3 Q-4 Q-5 A = (CH₂)₄;χl,X², X³ = NH;R³ = H; Q-1 Q-2 Q-3 Q-4 Q-5 A = CH₂;Xl,X² = 0;X³ = NH;R³ = H; Q-1 Q-2 Q-3 Q-4 Q-5 A = CH₂CH₂;X¹,X² = 0;X³ = NH;R³ = H; Q-i Q-2 Q-3 Q-4 Q-5 A = (CH₂)₃;X¹,X² = 0;X³ = NH;R³ = H; Q-1 Q-2 Q-3 Q-4 Q-5 A = (CH₂)₄;χl,X² = 0;X³=NH;R³ = H; Q-i Q-2 Q-3 Q-4 Q-5 A = CH₂;X¹,X² X³ = 0;R³ = CH₃; Q-1 Q-2 Q-3 Q-4 Q-5 A = CH₂CH₂;χl,X²,X³ = 0;R³ = CH₃; Q-1 Q-2 Q-3 Q-4 Q-5 A = (CH₂)₃;χl,X², X³ = 0;R³ = CH₃; Q-1 Q-2 Q-3 Q-4 Q-5 A = (CH₂)₄;χl,X² X³ = 0;R³ = CH₃; Q-1 Q-2 Q-3 Q-4 Q-5

Table 11

Q =

COLUMN

1 2 3 4 5 A = CH₂;χl,X²,X³ = 0;R³ = H; Q-1 Q-2 Q-3 Q-4 Q-5 A = CH₂CH₂;χl,X², X³ = 0;R³ = H; Q-1 Q-2 Q-3 Q-4 Q-5 A = (CH₂)₃;χ!,X², X³ = 0;R³ = H; Q-1 Q-2 Q-3 Q-4 Q-5 A = (CH₂)₄;X1,X²,X³ = 0;R³ = H; Q-1 Q-2 Q-3 Q-4 Q-5 A = CH₂;X¹,X²,X³ = NH;R³ = H; Q-1 Q-2 Q-3 Q-4 Q-5 A = CH₂CH₂;X¹,X²,X³ = NH;R³ = H; Q-1 Q-2 Q-3 Q-4 Q-5 A = (CH₂)₃;χl.X²,X³ = NH;R³ = H; Q-i Q-2 Q-3 Q-4 Q-5 A = (CH₂)₄; X¹, X², X³ = NH; R³ = H; Q-1 Q-2 Q-3 Q-4 Q-5 A = CH₂;Xl,X² = 0;X³ = NH;R³ = H; Q-1 Q-2 Q-3 Q-4 Q-5 A = CH₂CH₂;Xl,X² = 0;X³ = NH;R³ = H; Q-1 Q-2 Q-3 Q-4 Q-5 A = (CH₂)₃;X¹,X² = 0;X³ = NH;R³ = H; Q-i Q-2 Q-3 Q-4 Q-5 A = (CH₂)₄;χl,X² = 0;X³ = NH;R³ = H; Q-1 Q-2 Q-3 Q-4 Q-5 A = CH₂;X¹,X²,X³ = 0;R³ = CH₃; Q-i Q-2 Q-3 Q-4 Q-5 A = CH₂CH₂;χl,X²,X³ = 0;R³ = CH₃; Q-1 Q-2 Q-3 Q-4 Q-5 A = (CH₂)₃;Xl,X²,X³ = 0;R³ = CH₃; Q-1 Q-2 Q-3 Q-4 Q-5 A = (CH₂)₄;χl,X²,X³ = 0;R³ = CH₃; Q-i Q-2 Q-3 Q-4 Q-5

Table 12

Q =

COLUMN

1 2 3 4 5

142 A = CH₂;Xl,X²,X³ = 0;R³ = H; Q-1 Q-2 Q-3 Q-4 Q-5

143 A = CH₂CH₂;χ!,X²,X³ = 0;R³ = H; Q-1 Q-2 Q-3 Q-4 Q-5

144 A = (CH₂)₃;χl,X² X³ = 0;R³ = H; Q-i Q-2 Q-3 Q-4 Q-5

145 A = (CH₂)₄;X1,X²,X³ = 0;R³ = H; Q-i Q-2 Q-3 Q-4 Q-5

146 A = CH₂;χl,X² X³=NH;R³ = H; Q-1 Q-2 Q-3 Q-4 Q-5

147 A = CH₂CH₂;χ!,X²,X³ = NH;R³=H; Q-1 Q-2 Q-3 Q-4 Q-5

148 A = (CH₂)₃;χl,X²,X³=NH;R³ = H; Q-1 Q-2 Q-3 Q-4 Q-5

149 A = (CH₂)₄;χl,X², X³=NH;R³=H; Q-1 Q-2 Q-3 Q-4 Q-5

150 A = CH₂;Xl,X² = 0;X³=NH;R³=H; Q-1 Q-2 Q-3 Q-4 Q-5

151 A = CH₂CH₂;X¹,X² = 0;X³ = NH;R³ = H; Q-1 Q-2 Q-3 Q-4 Q-5

152 A = (CH₂)₃;χl,X² = 0;X³ = NH;R³ = H; Q-i Q-2 Q-3 Q-4 Q-5

153 A = (CH₂)4;χ!,X² = 0;X³=NH;R³ = H; Q-i Q-2 Q-3 Q-4 Q-5

154 A = CH₂;X1,X²,X³ = 0;R³ = CH₃; Q-i Q-2 Q-3 Q-4 Q-5

155 A = CH₂CH₂;χl,X², X³ = 0;R³ = CH₃; Q-1 Q-2 Q-3 Q-4 Q-5

156 A = (CH₂)₃; X¹, X², X³ = O; R³ = CH₃; Q-i Q-2 Q-3 Q-4 Q-5

157 A = (CH₂)₄;χl,X²,X³ = 0;R³ = CH₃; Q-i Q-2 Q-3 Q-4 Q-5

Formulation/Utility

Compounds of this invention will generally be used as a formulation or composition with an agriculturally suitable carrier comprising at least one of a liquid diluent, a solid diluent or a surfactant. The formulation or composition ingredients are selected to be consistent with the physical properties of the active ingredient, mode of application and environmental factors such as soil type, moisture and temperature. Useful formulations include liquids such as solutions (including emulsifiable concentrates), suspensions, emulsions (including microemulsions and/or suspoemulsions) and the like which optionally can be thickened into gels. Useful formulations further include solids such as dusts, powders, granules, pellets, tablets, films, and the like which can be water-dispersible ("wettable") or water-soluble. Active ingredient can be (micro)encapsulated and further formed into a suspension or solid formulation; alternatively the entire formulation of active ingredient can be encapsulated (or "overcoated"). Encapsulation can control or delay release of the active ingredient. 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 to 100 percent by weight.

Weight Percent

Active Ingredient Diluent Surfactant

Water-Dispersible and Water-soluble 5-90 0-94 1-15 Granules, Tablets and Powders.

Suspensions, Emulsions, Solutions 5-50 40-95 0-15 (including Emulsifiable Concentrates)

Dusts 1-25 70-99 0-5

Granules and Pellets 0.01-99 5-99.99 0-15

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 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, or thickeners to increase viscosity. Surfactants include, for example, polyethoxylated alcohols, polyethoxylated alkylphenols, polyethoxylated sorbitan fatty acid esters, dialkyl sulfosuccinates, alkyl sulfates, alkylbenzene sulfonates, organosilicones, N,N-dialkyltaurates, lignin sulfonates, naphthalene sulfonate formaldehyde condensates, polycarboxylates, and polyoxyethylene/polyoxypropylene block copolymers. Solid diluents include, for example, clays such as bentonite, montmorillonite, attapulgite and kaolin, starch, sugar, silica, talc, diatomaceous earth, urea, calcium carbonate, sodium carbonate and bicarbonate, and sodium sulfate. Liquid diluents include, for example, water, N,N-dimethylformamide, dimethyl sulfoxide, N-alkylpyrrolidone, ethylene glycol, polypropylene glycol, paraffins, alkylbenzenes, alkylnaphthalenes, oils of olive, castor, linseed, tung, sesame, corn, peanut, cotton-seed, soybean, rape-seed and coconut, fatty acid esters, ketones such as cyclohexanone, 2-heptanone, isophorone and 4-hydroxy-4- methyl-2-pentanone, and alcohols such as methanol, cyclohexanol, decanol and tetrahydrofurfuryl alcohol.

Solutions, including emulsifiable concentrates, can be prepared by simply mixing the ingredients. Dusts and powders can be prepared by blending and, usually, grinding as in a hammer mill or fluid-energy mill. Suspensions are usually prepared by wet-milling; see, for example, U.S. 3,060,084. Granules and pellets can be prepared by spraying the active material upon preformed granular carriers or by agglomeration techniques. See Browning, "Agglomeration", Chemical Engineering, December 4, 1967, pp 147-48, Perry's Chemical Engineer's Handbook, 4th Ed., McGraw-Hill, New York, 1963, pages 8-57 and following, and WO 91/13546. Pellets can be prepared as described in

U.S. 4,172,714. Water-dispersible and water-soluble granules can be prepared as taught in U.S. 4,144,050, U.S. 3,920,442 and DE 3,246,493. Tablets can be prepared as taught in U.S. 5,180,587, U.S. 5,232,701 and U.S. 5,208,030. Films can be prepared as taught in GB 2,095,558 and U.S. 3,299,566. 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 sihcoaluminate 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 5.0% sodium alkylnaphthalenesulfonate 1.0% calcium/magnesium bentonite 59.0%.

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

The compounds of this invention exhibit activity against a wide spectrum of foliar-feeding, fruit-feeding, 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, juveniles 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 root worm (Diabrotica undecimpunctata howardi), aster leafhopper (Mascrosteles fascifrons), boll weevil (Anthonomus grandis), two-spotted spider mite (Tetranychus urticae), fall armyworm (Spodoptera frugiperda), black bean aphid (Aphis fabae), green peach aphid (Myzus persica), cotton aphid (Aphis gossypii), Russian wheat aphid (Diuraphis noxia), English grain aphid (Sitobion avenae), tobacco budworm (Heliothis virescens), rice water weevil (Lissorhoptrus oryzophilus), rice leaf beetle (Oulema oryzae), whitebacked planthopper (Sogatellafurcifera), 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, repellents, 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 such agricultural protectants with which compounds of this invention can be formulated are: insecticides such as abamectin, acephate, azinphos-methyl, bifenthrin, buprofezin, carbofuran, chlorpyrifos, chlo yrifos-methyl, cyfluthrin, beta-cyfluthrin, cyhalothrin, lambda-cyhalothrin, deltamethrin, diafenthiuron, diazinon, diflubenzuron, dimethoate, esfenvalerate, fenpropathrin, fenvalerate, fipronil, flucythrinate, tau-fluvalinate, fonophos, imidacloprid, isofenphos, malathion, metaldehyde, methamidophos, methidathion, methomyl, methoprene, methoxychlor, methyl 7-chloro-2,5-dihydro-2-[[N- (methoxycarbonyl)-N- [4- (trifluoromethoxy)phenyl]amino]carbonyl]indeno[l,2-e][l,3,4]oxadiazine-4a(3H)- carboxylate (DPX-JW062), monocrotophos, oxamyl, parathion, parathion-methyl, permethrin, phorate, phosalone, phosmet, phosphamidon, pirimicarb, profenofos, rotenone, sulprofos, tebufenozide, tefluthrin, terbufos, tetrachlorvinphos, thiodicarb, tralomethrin, trichlorfon and triflumuron; fungicides such as azoxystrobin (ICIA5504), benomyl, blasticidin-S, Bordeaux mixture (tribasic copper sulfate), bromuconazole, captafol, captan, carbendazim, chloroneb, chlorothalonil, copper oxychloride, copper salts, cymoxanil, cyproconazole, cyprodinil (CGA 219417), diclomezine, dicloran, difenoconazole, dimethomorph, diniconazole, diniconazole-M, dodine, edifenphos, epoxyconazole (BAS 480F), fenarimol, fenbuconazole, fenoxycarb, fenpiclonil, fenpropidin, fenpropimoφh, fluquinconazole, flusilazole, flutolanil, flutriafol, folpet, fosetyl-aluminum, furalaxyl, hexaconazole, ipconazole, iprobenfos, iprodione, isoprothiolane, kasugamycin, kresoxim-methyl (BAS 490F), mancozeb, maneb, mepronil, metalaxyl, metconazole, myclobutanil, neo-asozin (ferric methanearsonate), oxadixyl, penconazole, pencycuron, probenazole, prochloraz, propiconazole, pyrifenox, pyroquilon, sulfur, tebuconazole, tetraconazole, thiabendazole, thiophanate-methyl, thiram, triadimefon, triadimenol, tricyclazole, triticonazole, uniconazole, validamycin and vinclozolin; nematocides such as aldoxycarb and fenamiphos; bactericides such as streptomycin; acaricides such as amitraz, chinomethionat, chlorobenzilate, cyhexatin, dicofol, dienochlor, fenazaquin, fenbutatin oxide, fenpropathrin, fenpyroximate, hexythiazox, propargite, pyridaben and tebufenpyrad; and biological agents such as Bacillus thuringiensis, Bacillus thuringiensis delta endotoxin, baculovirus, and entomopathogenic bacteria, virus and fungi.

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

Preferred for better control of pests (use rate or spectrum) or resistance management are mixtures of a compound of this invention with an arthropodicide selected from the group bifenthrin, chlorpyrifos, chlorpyrifos-methyl, cyfluthrin and its isomer beta-cyfluthrin, cyhalothrin and its isomer lambda-cyhalothrin, deltamethrin, esfenvalerate, fenoxycarb, fenpropathrin, fenvalerate, flucythrinate, tau-fluvalinate, methomyl, methyl 7-chloro-2,5-dihydro-2-[[N-(methoxycarbonyl)-N-[4- (trifluoromethoxy )phenyl]amino]carbonyl]indeno[ 1 ,2-e] [ 1 ,3 ,4]oxadiazine-4a(3H carboxylate (DPX-JW062), permethrin, tebufenozide, tefluthrin and tralomethrin. Specifically preferred mixtures (compound numbers refer to compounds in Index Table A) are selected from the group: compound 1 and bifenthrin; compound 1 and chlorpyrifos; compound 1 and chlorpyrifos-methyl; compound 1 and cyfluthrin; compound 1 and cyhalothrin; compound 1 and deltamethrin; compound 1 and esfenvalerate; compound 1 and fenoxycarb; compound 1 and fenpropathrin; compound 1 and fenvalerate; compound 1 and flucythrinate; compound 1 and tau-fluvalinate; compound 1 and methomyl; compound 1 and methyl 7-chloro-2,5-dihydro-2-[[N- (methoxycarbonyl)-N- [4-

(trifluoromemoxy)phenyl]amino]carbonyl]indeno[l,2-e][l,3,4]oxadiazine-4a(3H)- carboxylate (DPX-JW062); compound 1 and permethrin; compound 1 and tebufenozide; compound 1 and tefluthrin; and compound 1 and tralomethrin.

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 the invention, 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 the area to be protected, or directly on the pests to be controlled. A preferred method of application is by spraying. Alternatively, granular formulations of these compounds can be applied to the plant foliage or the soil. Other methods of application include direct and residual sprays, aerial sprays, 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, other solvents, and synergists 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 OJ 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. "Control efficacy" represents inhibition of arthropod development (including mortality) that causes significantly reduced feeding. The pest control protection afforded by the compounds is not limited, however, to these species. See Index Table A for compound descriptions. The abbreviation "Ex." stands for "Example" and is followed by a number indicating in which example the compound is prepared.

INDEX TABLE A

wherein R^3a is H or R³

Cmpd No. A Q R! R². g3a m.p. (°C)

1 (Ex. 1) -CH₂CH₂CH₂- 6-Cl-3-pyridinyl -CH₂CH₂- H 152-154

2 -CH₂CH₂CH₂- 6-Cl-3-pyridinyl -CH₂CH₂- CH₃ 137-140

3^a -CH₂CH₂CH₂- 6-Cl-3-pyridinyl -CH(CH₃)CH₂- H 163-165

4 (Ex. 2) -CH₂CH₂CH₂- 4-Cl-phenyl -CH₂CH₂- H 157-160

5 -CH₂CH₂CH₂- 6-Cl-3-pyridinyl -CH₂CH₂CH₂- H 174-175

6 -CH₂CH₂CH₂- 6-Br-3-pyridinyl -CH₂CH₂- H 154-156

7 -CH₂CH₂CH₂- 6-CH₃-3-pyridinyl -CH₂CH₂- H 122-124 ^a Compound is the (R) enantiomer.

BIOLOGICAL EXAMPLES OF THE INVENTION TEST A Fall Armyworm

Test units, each consisting of a H.I.S. (high impact styrene) tray with 16 cells were prepared. Wet filter paper and approximately 8 cm² of lima bean leaf was placed into twelve of the cells. A 0.5-cm layer of wheat germ diet was placed into the four remaining cells. Fifteen to twenty third-instar larvae of fall armyworm (Spodoptera frugiperda) were placed into a 230-mL (8-ounce) plastic cup. Solutions of each of the test compounds in 75:25 acetone-distilled water solvent were sprayed into the tray and cup. Spraying was accomphshed by passing the tray and cup on a conveyer belt directly beneath a flat fan hydraulic nozzle which discharged the spray at a rate of

0J38 kilograms of active ingredient per hectare (about 0J3 pounds per acre) at 207 kPa (30 p.s.i.). The insects were transferred from the 230-mL cup to the H.LS. tray (one insect per cell). The trays were covered and held at 27°C and 50% relative humidity for 48 hours, after which time readings were taken on the twelve cells with lima bean leaves. The four remaining cells were read at 6-8 days for delayed toxicity. Of the compounds tested, the following gave control efficacy levels of 80% or greater: 1, 2, 3, 6 and 7.

TEST B Southern Corn Rootworm

Test units, each consisting of a 230-mL (8-ounce) plastic cup containing a 6.5-cm² (1 -square-inch) plug of a wheatgerm diet, were prepared. The test units were sprayed as described in TEST A with individual solutions of the test compounds. After the spray on the cups had dried, five second-instar larvae of the southern corn rootworm (Diabrotica undecimpunctata howardϊ) were placed into each cup. The cups were held at 27°C and 50% relative humidity for 48 hours, after which time mortality readings were taken. The same units were read again at 6-8 days for delayed toxicity. Of the compounds tested, the following gave control efficacy levels of 80% or greater: 1, 2, 3, 4, 5, 6 and 7.

TEST C Aster Leafhopper

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

TEST D Boll Weevil

Test units consisting of 260-mL (9-ounce) cups containing five adult boll weevils (Anthonomus grandis) were prepared. Spraying was accomplished by passing the tray and cup on a conveyer belt directly beneath a flat fan hydraulic nozzle which discharged the spray at a rate of 28 grams of active ingredient per hectare (about 0.03 pounds per acre) at 207 kPa (30 p.s.i.). Each cup was covered with a vented lid and held at 27°C and 50% relative humidity for 48 hours, after which time mortality readings were taken. Of the compounds tested, the following gave mortality levels of 80% or higher: 1 and 2. TEST E

Contact Test Against Black Bean Aphid

Individual nasturtium leaves were infested with 10 to 15 aphids (all morphs and growth stages oi Aphis fabae) and sprayed with their undersides facing up as described in TEST A. The leaves were then set in 0.94-cm (3/8-inch) diameter vials containing 4 mL of sugar solution (approximately 1.4 g per liter) and covered with a clear plastic 29-mL (1 -ounce) cup to prevent escape of the aphids that drop from the leaves. The test units were held at 27°C and 50% relative humidity for 48 hours, after which time mortality readings were taken. Of the compounds tested, the following gave mortality levels of 80% or higher: 1, 2, 3, 4, 5, 6 and 7. TEST F

Contact Activity Against Green Leafhopper Nymphs

Three rice (Oryza sativa) seedlings at the 1.5-leaf stage and about 10-cm tall were transplanted into a 14-mL (1/2-ounce) plastic cup containing Kumiai Brown artificial soil. Seven milliliters of distilled water was then added to the cup. The test chemical was prepared by first dissolving the chemical in acetone and then adding water to produce a final test concentration of 75:25 (acetone- water). Four plastic cups, each cup serving as a replicate, were then placed on a spray chamber turntable. The cups were sprayed for 45 seconds with 50 mL of the chemical solution at a pressure of 2.0 kg/cm² with air-atomizing spray nozzles. The turntable completed 7.5 rotations during the 45-second spray interval. After chemical application, the treated cups were held in a vented enclosure to dry for about 2 h. After drying, the cups were placed into conical-shaped test units and the surface of the soil covered with 2 to 3 mm of quartz sand. Eight to ten 3rd-instar nymphs of the green leafhopper (Nephotettix cincticeps) were transferred into the test units using an aspirator. The test units were held at 27°C and 65% relative humidity. Counts of the number of live and dead nymphs were taken at 24 and 48 h post-infestation. Insects unable to walk were classified as dead. Of the compounds tested, the following gave mortality levels of 80% or higher at 48 h at an application rate equivalent to 28 grams per hectare: 1, 2 and 3. TEST G Contact Activity Against Brown Planthopper Nymphs

Three rice (Oryza sativa) seedlings at the 1.5-leaf stage and about 10-cm tall were transplanted into a 14-mL (1/2 ounce) plastic cup containing Kumiai Brown artificial soil. Seven milliliters of distilled water was then added to the cup. The test chemical was prepared by first dissolving the chemical in acetone and then adding water to produce a final test concentration of 75:25 (acetone- water). Four plastic cups, each cup serving as a replicate, were then placed on a spray chamber turntable. The cups were sprayed for 45 seconds with 50 mL of the chemical solution at a pressure of 2.0 kg/cm² with air-atomizing spray nozzles. The turntable completed 7.5 rotations during the 45-second spray interval. After chemical application, the treated cups were held in a vented enclosure to dry for about 2 h. After drying, the cups were placed into conical-shaped test units and the surface of the soil covered with 2 to 3 mm of quartz sand. Eight to ten 3rd-instar nymphs of the brown planthopper (Nilaparvata lugens) were then transferred into the test units using an aspirator. The test units were held at 27°C and 65% relative humidity. Counts of the number of live and dead nymphs were taken at 24 and 48 h post-infestation. Insects unable to walk were classified as dead. Of the compounds tested, the following gave mortality levels of 80% or higher at 48 h at an application rate equivalent to 28 grams per hectare: 1, 2 and 3. TEST H

Solution Systemic Activity Against Green Leafhopper Nymphs

The test chemical was added directly into 10 mL of distilled water and dissolved completely. This chemical solution was poured into a conical-shaped test unit. Three rice seedlings were then positioned in the unit by a notched sponge disk. The sponge disk allowed complete immersion of the seedling root systems in the chemical solution, while isolating the aerial portion of the plant above the solution. The sponge also prevented 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 prevented accidental chemical contamination of the sponge. The rice seedlings were 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) were then transferred into the test units using an aspirator. The infested units were held under the same temperature and humidity conditions described above. Counts of the number of live and dead nymphs were taken at 24 and 48 h post-infestation. Insects unable to walk were classified as dead. Of the compounds tested, the following gave mortality levels of 80% or higher at 48 h at an application rate equivalent to 28 grams per hectare: 1, 2 and 3.

TEST I Solution Systemic Activity Against Brown Planthopper Nymphs The test chemical was added directly to 10 mL of distilled water and dissolved completely. This chemical solution was poured into a conical-shaped test unit. Three rice seedlings were then positioned in the unit by a notched sponge disk. The sponge disk allowed complete immersion of the seedling root systems in the chemical solution, while isolating the aerial portion of the plant above the solution. The sponge also prevented 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 prevented accidental chemical contamination of the sponge. The rice seedlings were 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 brown planthopper (Nilaparvata lugens) were then transferred into the test units using an aspirator. The infested units were 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 unable to walk were classified as dead. Of the compounds tested, the following gave mortality levels of 80% or higher at 48 h at an application rate equivalent to 28 grams per hectare: 1, 2 and 3.

Claims

CLAIMS What is claimed is:

1. A compound selected from Formula I, N-oxides and agriculturally suitable salts thereof,

I wherein

A is selected from the group Ci-Cg alkylene and -(CH₂)_r-Z-(CH₂)_t-;

Q is selected from the group phenyl, furanyl, furazanyl, thienyl, pyrrolyl, pyrazolyl, oxazolyl, oxadiazolyl, imidazolyl, isoxazolyl, thiazolyl, thiadiazolyl, isothiazolyl, tetrazolyl, pyridinyl, pyrimidinyl, pyridazinyl, pyrazinyl and triazinyl, each ring optionally substituted with 1-3 substituents independently selected from W; χl, X² and X³ are each independently selected from the group O and ΝR ; Z is selected from the group O and ΝR⁵; Rl and R² are each independentiy selected from the group H and CJ-C4 alkyl; or

Rl and R² can be taken together as -CH₂CH - or -CH₂CH₂CH₂-, each optionally substituted with 1-2 CH₃; each R³ is independently selected from the group C1-C4 alkyl and C_]-C₄ haloalkyl; each R⁴ is independently selected from the group H and C1-C4 alkyl; R⁵ is selected from the group H, C_rC₄ alkyl and C(O)R⁶;

R⁶ is selected from the group H, C1-C4 alkyl; C1-C4 haloalkyl; and phenyl optionally substituted with W¹; each W is independently selected from the group halogen, cyano, nitro, C_j-C₂ alkyl, C_rC₂ haloalkyl, C_rC₂ alkoxy, C_rC₂ haloalkoxy, C_rC₂ alkylthio, C_rC₂ haloalkylthio, C _j -C₂ alkylsulfinyl, C _j -C₂ haloalkylsulfinyl, C _} -C₂ alkylsulfonyl, Cι-C₂ haloalkylsulfonyl, C1-C4 alkylamino and C₂-C₈ dialkylamino; Wl is selected from the group halogen, cyano, nitro, C C₂ alkyl, C C₂ haloalkyl,

C_j-C₂ alkoxy, C C₂ haloalkoxy, Cj-C₂ alkylthio, C_rC₂ haloalkylthio, C ! -C₂ alkylsulfinyl, C γ -C₂ haloalkylsulfinyl, C _j -C₂ alkylsulfonyl, C _j -C₂ haloalkylsulfonyl, C1-C4 alkylamino and C -Cg dialkylamino; n is 0 to 12; and r and t are independently 1, 2 or 3.

2. A compound of Claim 1 wherein: A is C₃ alkylene; Q is selected from the group isoxazolyl, thiazolyl and pyridinyl, each ring optionally substituted with 1-3 substituents independently selected from W; χl, X² and X³ are each O; and Rl and R² are each independentiy C_j-C4 alkyl.

3. A compound of Claim 1 wherein: A is C₃ alkylene;

Q is selected from the group isoxazolyl, thiazolyl and pyridinyl, each ring optionally substituted with 1-3 substituents independently selected from W; Xl, X² and X³ are each O; and

R^l and R² are taken together as -CH₂CH₂- or -CH₂CH₂CH₂-, each optionally substituted with 1-2 CH₃.

4. A compound of Claim 3 wherein: Q is pyridinyl;

W is halogen or C -C₂ alkyl; and n is O.

5. A compound of Claim 3 wherein:

Q is isoxazolyl;

W is halogen or Cj-C₂ alkyl; and n is O.

6. A compound of Claim 3 wherein: Q is thiazolyl;

W is halogen or C_j-C alkyl; and n is O.

7. The compound of Claim 4 which is:

1 -[3-[ 1 -[(6-chloro-3-pyridinyl)methyl]- 1 ,2,3,7-tetrahydro-8-nitroimidazo[ 1 ,2- c]pyrimidin-6(5H)-yl]propyl]-2,8,9-trioxa-5-aza- 1 -silabicyclo[3.3.3]undecane.

8. An arthropodicidal composition comprising an arthropodicidally effective amount of a compound of Claim 1 and at least one of a surfactant, a solid diluent or a hquid diluent.

9. A method for controlling arthropods comprising contacting the arthropods or their environment with an arthropodicidally effective amount of a compound of Claim 1.