WO1994012491A1

WO1994012491A1 - Arthropodicidal nitroethylene diamines

Info

Publication number: WO1994012491A1
Application number: PCT/US1993/011164
Authority: WO
Inventors: Stephen Frederick Mccann
Original assignee: E.I. Du Pont De Nemours And Company
Priority date: 1992-11-24
Filing date: 1993-11-22
Publication date: 1994-06-09
Also published as: AU5611094A; CN1088913A

Abstract

Arthropodicidally active compounds, compositions and a method for their use, the compounds having formula (I), wherein Q, Y and R2-R4 are as defined in the text.

Description

TITLE

ARTHROPODICIDAL NITROETHYLENE DIAMINES

The present invention comprises nitroethylene diamines useful as arthropodicides. The compounds of this invention are characterized by methylene substitution of the nitroethylene moiety and are distinguished from those of EP 437,784, U.S. 4,845,106, GB 1,483,633 and WO 91/17659.

SUMMARY OF THE INVENTION

This 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:

Q is selected from the group

CH₃SCH₂-

-

Y is selected from the group halogen and R¹X;

X is selected from the group S(O)_n, O and NR⁵;

R¹ is selected from the group C₁-C₂₀ alkyl, C₃-C₁₀ cycloalkyl, C₄-C₇

cycloalkylalkyl, C₂-C₆ alkenyl and C₂-C₆ alkynyl each of which is optionally substituted with 1 or 2 groups independently selected from

CN, NO₂, OH, C₁-C₄ alkoxy, OC(O)R⁶, OCO₂R⁶, OS(O)₂R⁶, SH, C₁-C₄ alkylthio, C(O)R⁶, C(O)OR⁶, CO₂H, SO₃H, N(R⁷)R⁸, C(O)N(R⁷)R⁸, OS(O)₂N(R⁷)R⁸, C(S)N(R⁷)R⁸, C₁-C₄ alkylamino, C₂-C₆ dialkylamino, S(O)₂N(R⁷)R⁸, Si(R⁹)(R¹⁰)R¹¹, C₁-C₄ alkylsulfinyl, C₁-C₄ alkylsulfonyl, phenyl optionally substituted with

R¹², and a 5- or 6- membered saturated, partially unsaturated or fully unsaturated heterocyclic ring containing 1-4 heteroatoms independently selected from the group 0-1 O, 0-1 S and 0-4 N, each heterocyclic ring optionally substituted with R¹²; H; C₁-C₆ haloalkyl; C₃-C₇ halocycloalkyl; C₄-C₇ halocycloalkylalkyl; C(O)N(R⁷)R⁸; SO₂R⁶;

SO₂N(R⁷)R⁸; C(S)N(R⁷)R⁸; C(O)R⁶; CO₂R⁶; C(S)R⁶; C(S)OR6; C(S)SR⁶; C(O)SR⁶; phenyl optionally substituted with R¹²; 5- or 6- membered saturated, partially saturated or fully unsaturated heterocyclic ring containing 1-4 heteroatoms independently selected from the group 0-1 O, 0-1 S and 0-4 N, each heterocyclic ring optionally substituted with R¹²; provided that (i) when X is NR⁵, R¹ and R⁵ can optionally be taken together as -CH₂CH₂CH₂CH₂-, -CH₂CH₂OCH₂CH₂- or -CH₂CH₂CH₂CH₂CH₂- and (ii) when X is S(O)_n and n=1 or 2, then R- is other than H, C(S)N(R⁷)R⁸, C(O)R⁶, CO₂R⁶, C(S)R⁶, C(S)OR⁶, C(S)SR⁶, C(O)SR⁶, C(O)N(R⁷)R⁸,

SO₂N(R⁷)R⁸ or S(O)₂R⁶;

R² is selected from the group H and C₁-C₃ alkyl;

R³ is selected from the group H and CH₃; or

R² and R³ are taken together to form a group selected from CH₂CH₂,

CH(CH₃)CH₂, CH₂CH₂CH₂ and CH(CH₃)CH₂CH₂, the group being

CH(CH₃)CH₂ or CH(CH₃)CH₂CH₂ when Q is Q-2, Q-3, Q-4 or Q-5;

R⁴ is selected from the group H, CH₂CN, C₁-C₄ alkyl, C₁-C₄ haloalkyl, formyl, C₂-C₄ alkylcarbonyl, C₂-C₄ alkoxycarbonyl, C₂-C₄

alkoxyalkyl, C₃-C₆ dialkoxyalkyl, C₁-C₃ alkoxy, C₁-C₃ alkylsulfonyl, C₂-C₄ alkenyl, C₂-C₄ alkynyl, C₁-C₄ alkylamino, C₂-C₄ dialkylamino and benzyl optionally substituted with R¹²;

R⁵ is selected from the group H, C₁-C₆ alkyl, CHO, C₂-C₄ alkylcarbonyl, C₂-C₄ alkoxy carbonyl and C₁-C₄ alkylsulfonyl provided that when R⁵ is H, then R², R³ and R⁴ are other than H;

R⁶ is selected from the group C₁-C₁₅ alkyl, C₂-C₆ alkenyl and C₁-C₆

haloalkyl each of which can be optionally substituted with phenyl optionally substituted with R¹²; phenyl optionally substituted with R¹²; 5- or 6-membered saturated, partially saturated or fully unsaturated heterocyclic ring containing 1-4 heteroatoms independently selected from the group 0-1 O, 0-1 S and 0-4 N, each heterocyclic ring optionally substituted with R¹²;

R⁷ and R⁸ are independently selected from the group H, C₁-C₆ alkyl and C₃-C₆ cycloalkyl;

R⁹, R¹⁰ and R¹¹ are independently selected from the group C₁-C₄ alkyl, C₁-C₄ alkoxy and phenyl;

R¹² is selected from the group 1-5 halogens, C₁-C₂ alkyl, C₁-C₂ haloalkyl, C₁-C₂ alkoxy, C₁-C₂ alkylthio, C₁-C₂ haloalkylthio, C₁-C₂ haloalkoxy, NO₂ and CN; and

n is 0, 1, or 2.

Preferred Compounds A are compounds of Formula I wherein:

Y is R¹X;

X is S;

R¹ is selected from the group C₁-C₆ alkyl, C₃-C₇ cycloalkyl, C₄-C₇ cycloalkylalkyl, C₂-C₃ alkenyl and C₂-C₃ alkynyl each optionally substituted with a group selected from CN, C₁-C₄ alkylthio and C(O)OR⁶; and

R⁴ is selected from the group H and CH₃.

Preferred Compounds B are compounds of Formula I wherein

Y is R¹X;

X is S;

R¹ is a 5- or 6-membered saturated, partially unsaturated or fully unsaturated heterocyclic ring containing 1-4 heteroatoms independently selected from the group 0-1 O, 0-1 S and 0-4 N, each heterocyclic ring optionally substituted with R¹²; and

R¹² is selected from the group 1-5 halogens, C₁-C₂ alkyl and C₁-C₂ alkylthio.

Preferred Compounds C are Compounds A wherein Q is Q-1. Preferred

Compounds D are Compounds B wherein Q is Q-1. Preferred Compounds E are Compounds A wherein Q is selected from the group Q-2, Q-3, Q-4 and Q-5, and R² and R³ are taken together to form a group selected from CH(CH₃)CH₂ and CH(CH₃)CH₂CH₂, wherein the terminal CH₂ carbon is attached to the nitrogen atom bearing R⁴. Preferred Compounds F are Compounds B wherein Q is selected from the group Q-2, Q-3, Q-4 and Q-5, and R² and R³ are taken together to form a group selected from CH(CH₃)CH₂ and CH(CH₃)CH₂CH₂, wherein the terminal CH₂ carbon is attached to the nitrogen atom bearing R⁴.

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

In the above 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, and the different isomers containing 4-20 carbons. Alkoxy denotes methoxy, ethoxy, n-propyloxy and the different isomers containing 4 carbons. Alkenyl denotes straight chain or branched alkenes such as vinyl, 1-propenyl, 2-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. Alkylthio denotes methylthio, ethylthio, n-propylthio, isopropylthio and the different butylthio isomers.

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 CH₂CHF₂, CF₂CF₃ and CH₂CHFCl. The term "heterocyclic ring" is defined as a 5- or 6-membered ring which can be fully unsaturated, partially unsaturated or fully saturated and contains 1 to 4 heteroatoms selected from the group 0-4 N, 0-2 O and 0-2 S. One of the carbon atoms of the ring can optionally be substituted with O to form carbonyl. Examples of heterocyclic rings include pyrrolidinyl, imidazolinyl, imidazohdinyl, pyrazolinyl, pyrazolidinyl, piperidyl, piperazinyl, oxazolinyl, oxazolidinyl, dioxolanyl, isoxazinyl, furyl, furazanyl, thienyl, pyrrolyl, pyrazolyl, oxazolyl, oxadiazolyl, imidazolyl, isoxazolyl, thiazolyl, thiadiazolyl isothiazolyl, tetrazolyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl and triazinyl with said rings attached through any available carbon or nitrogen, for example, when the ring is furyl, it can be 2-furyl or 3-furyl, for pyrrolyl, the heterocyclic ring is 1-pyrrolyl, 2-pyrrolyl or 3-pyrrolyl, for pyridyl, the heterocyclic ring is 2-pyridyl, 3-pyridyl or 4-pyridyl and similarly for the other rings.

The total number of carbon atoms in a substituent group is indicated by the "C_i-C_j" prefix where i and j are numbers from 1 to 20. For example, C₁-C₃ alkyl designates methyl through propyl; and C₂ alkoxy designates OCH₂CH₃ and C₃ alkoxy designates OCH₂CH₂CH₃ and OCH(CH₃)₂.

DETAILS OF THE INVENTION

The compounds of Formula I where Y is R¹X and X is equal to S and R¹ is other than H can be prepared by the reaction of Formula II compounds with a Formula III compound in the presence of formaldehyde in a suitable solvent as depicted in Scheme 1. Substituents depicted in the following Schemes are as previously defined except where otherwise noted.

Scheme 1

II (X = S,R¹≠H)

Conditions for the reactions depicted in Scheme 1 typically involve use of equal stoichiometric amounts of II, III and formaldehyde although, in some cases, a slight stoichiometric excess of formaldehyde is preferred. Reactions depicted in Scheme 1 are typically carried out at temperatures ranging from 0°C to the reflux temperature of the solvent, with 0-25°C being preferred. Suitable solvents include alcohols such as methanol and ethanol, water, and polar aprotic solvents such as tetrahydrofuran and dimethylformamide. 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. One skilled in the art will recognize that Formula IIl compounds include mercaptans, thiocarboxylic acids, dithiocarboxylic acids and dithiocarbamic acids.

Compounds of Formula I where Y is R-X and X is equal to SO₂ can be prepared by the reaction of Formula II compounds with sulfinic acids or sulfinic acid salts of Formula IV and paraformaldehyde in a suitable solvent as depicted in Scheme 2.

Scheme 2

HCHO I

II + R¹SO₂M

(X=SO₂)

IV

wherein: M=H, Li, Na or K

Suitable solvents include dimethylformamide and N, N-dimethyl acetamide and typical reaction temperatures range from room temperature to the reflux temperature of the solvent. Equimolar amounts of II, IV and paraformaldehyde are typically used. When IV is a sulfinic acid salt (M=Li, Na or K), then between 1 and 10 molar equivalents of an organic acid such as acetic acid is used. Examples of procedures analogous to those depicted in Scheme 2 can be found in

Chem. Ber., (1965), 98, 638.

Compounds of Formula I where Y is R¹X and X is equal to NR⁵ can be prepared by the reaction of compounds of Formula II with compounds of

Formula V and formaldehyde as depicted in Scheme 3. Conditions for Scheme 3 reactions are analogous to those described for Scheme 1 reactions. One skilled in the art will recognize that reactions depicted by Scheme 3 are variations of the Mannich reaction [Org. React., 1, 303 (1942), Synthesis, 703 (1973); Angew. Chem., 69, 463 (1957).] Scheme 3

HCHO I

II + R¹R⁵NH

(X=NR⁵)

V

Compounds of Formula I where Y is R¹X and X is equal to O can be prepared by the reaction of Formula II compounds with formaldehyde and a Formula VI compound as depicted in Scheme 4. One skilled in the art will recognize that Formula VI compounds include water, alcohols and carboxylic acids.

Scheme 4

HCHO I

II + R¹OH

(X=O)

VI

VI is typically used as the reaction solvent and between 1 and 20 molar equivalents of formaldehyde is used (either as an aqueous solution or as solid paraformaldehyde). Typically, the reactions depicted in Scheme 4 are run at temperatures ranging from room temperature to 200°C. When VI is an alcohol, the reactions are generally run between 100° and 200°C and between 0 to 5 equivalents of a base such as potassium carbonate can be used. When VI is either water or a carboxylate acid, the reactions depicted in Scheme 4 are usually carried out at temperatures ranging from room temperature to 100°C. Between 0 and 10 equivalents of a base such as K₂CO₃, triethylamine or 1,4-diazabicyclo- [2.2.2]octane (DABCO) can be used. Analogous reaction procedures are found in J. Am. Chem. Soc, (1959), 81, 2521; Synthesis, (1986), 857; Synth. Commun., (1987), 17, 291; and bid. J. Chem., (1988), 278, 537.

Compounds of Formula I where Y is a halogen atom can be prepared by the reaction of Formula II compounds with formaldehyde and a hydrohalic acid of Formula VII as depicted in Scheme 5. Scheme 5

HCHO

II I

YH VII

wherein: Y is halogen

The reactions depicted in Scheme 5 typically involve the combination of a stoichiometric excess of VII with II and between 1 and 5 equivalents of formaldehyde. A polar solvent such as water or acetic acid can be used.

Sometimes, a Lewis acid such as ZnCl₂ or ZnBr₂ is added. Scheme 5 reactions are generally carried out at temperatures between 0° and 30°C. Analogous reaction procedures are found in J. Org. Chem., (1946), 68, 2002 and J. Am. Chem. Soc, (1942), 64, All.

Alternatively, compounds of Formula I where Y is R¹X and X is S(O)_n and n equals 1 or 2 can be prepared using the three-step procedure depicted in Scheme 6.

Scheme 6

Step i

R¹SH

III

HCHO

VIII IX

Step ii

IX oxidant

X

QCH₂- Y¹

Step iii

XXIV X I

base

(X=S(O)_n , n=1 or 2) wherein: R³ and R⁴≠ H and R¹ is an optionally substituted alkyl

or phenyl, Y¹ is a leaving group such as halogen and Q is as previously defined

In Step i of Scheme 6, Compound IX is formed using conditions analogous to those described for the reactions depicted in Scheme 1. In Step ii of Scheme 6, the sulfide IX is treated with an oxidizing reagent such as hydrogen peroxide, m-chloroperbenzoic acid, NaIO₄ or potassium peroxymonosulfate in solvents such as water, alcohols such as methanol, ethanol or isopropanol, ethyl acetate, methylene chloride, chloroform, acetone or mixtures of solvents. The reaction temperature is generally between 0°C and the reflux temperature of the solvent and the reaction time typically ranges from 1 to 72 h.

In the reaction depicted by Step ii of Scheme 6, when the oxidizing reagent is used in one molar equivalent, Compound X where n is equal to 1 can be obtained, and when two or more molar equivalents of an oxidizing reagent is used,

Compound X where n is equal to 2 can be obtained. The reactions to form

Compound X where n is 2 may require higher temperatures between 30°C and reflux, than analogous reactions where n = 1. In Step iii of Scheme 6, Compound X is treated with an alkylating agent of Formula XXIV in the presence of a base in a suitable solvent at temperatures between 20 and 150°C, with 50-100°C being generally preferred. Typical bases include K₂CO₃ or NaH and suitable solvents include polar aprotic solvents such as DMF, THF or CH₃CN. 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.

The syntheses of compounds of Formula II or Formula VIII have been described previously (see WO 91/17659).

Alternatively, compounds of Formula II where R² and R³ are taken together to form CH₂CH₂, CH(CH₃)CH₂, CH₂CH₂CH₂ or CH(CH₃)CH₂CH₂ can be prepared by the reaction of diamines of Formula XI with compounds of

Formula XII as shown in Scheme 7.

Scheme 7

(R² and R³ taken together to form a substituted alkylene, R⁴=H) wherein: X¹is a leaving group such as SCH₃, OC₆H₅

or halogen, X² is H or Me and q is 1 or 2.

Scheme 7 reactions typically involve the mixture of equimolar amounts of XI and XII (usually 1,1-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. The preparation of diamines XI wherein q=1 can be achieved using the two-step procedure shown in Scheme 8.

Scheme 8

Step i

X²CHO

QCH₂NH₂ XVI

KCN

H+

XIII XIV

Step ii

[H]

(q=1)

XIV XI wherein X² = H or Me

In Step i of Scheme 8, primary amine XIII is treated with potassium cyanide and aldehyde XVI (either formaldehyde or acetaldehyde) in the presence of one to three equivalents of acid in a solvent to form aminonitrile XIV. Other cyanide salts as well as HCN can be used in the procedure as well as hydrohalide and other acid salts of XIII. Suitable solvents include methanol, ethanol, isopropanol and water, as well as combinations of solvents. Alternative procedures for the preparation of amino nitriles such as XIV can be found in the literature (Synth. Commun., (1985), 15, 157; Synthesis, (1979), 127).

In Step ii of Scheme 8, aminonitrile XIV is reduced to form diamine XI (q=1). 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 XIV to XI can be achieved using diborane or by 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 XI. An alternative procedure for the preparation of diamines XI (q=1) is depicted in Scheme 9.

Scheme 9

Step i

QCOCl

XIX

brase

XX XXI

Step ii

XXI [H] XI

(q=1)

In Step i of Scheme 9, amide XX is treated with 1 to 2 molar equivalents of acid chloride XIX in the presence of 1 to 3 molar equivalents of a base such as NaHCO₃, NaOH, KOH, K₂CO₃, pyridine or triethylamine. Suitable solvents include THF, CH₂CI₂, water or pyridine. The products XXI can be isolated by extraction or, more conveniently, by removal of solvent and is usually suitable for use in Step ii of Scheme 9 in crude form. Amide XX can be used either in neutral form as depicted or as the salt form (typically as the HCI or CF₃CO₂H salt, among others). When the salt form of XX is used, an additional one equivalent of base is used in Step i of Scheme 9.

In Step ii of Scheme 9, the amide XXI is converted to diamine XI(q=1) by treatment with a reducing agent such as LiAlH₄, 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. Analogous procedures are well-known in the literature (see e.g. Synthesis, (1981), 441).

Alternatively, compounds of Formula XXI can be prepared from esters XXII using the two step procedure depicted in Scheme 10. Scheme 10

Step i

XIX

base

XXII XXIII

Step ii

NH₃

XXIII

XXI

MeOH wherein: R¹³=C₁-C₅ alkyl or benzyl

In Step i of Scheme 10, one to 10 stoichiometric equivalents of ester XXII (either as the free base or the hydrohalide salt) is combined with acid chloride XIX in the presence of a base such as, but not limited to triethylamine, pyridine or NaHCO₃.

Step ii of Scheme 10 involves reation of ester XXIII with an excess of anhydrous ammonia (2-100 equivalents) in anhydrous methanol to give the amide XXI. Such reactions are usually carried out at temperatures ranging from 15°C to 65°C.

The use of either the D- or the L- form of alanine amide XX or alanine ester XXII or their salts in Scheme 9 and Scheme 10 reactions provides a convenient means of obtaining enantiomerically enriched forms of diamine XI (q=1, X²=Me). When compounds of Formula II (q=1) are prepared as described for Scheme 7 reactions using enantiomerically enriched forms of XI (q=1), the products II (q=1) are obtained in enantiomerically enriched form. When compounds of Formula I are prepared as described in Schemes 1 through 5 using enantiomerically enriched forms of II, the products I are obtained in enantiomerically enriched form.

Alternatively, diamines XI can be enantiomerically enriched 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 XI wherein q=2 can be achieved using the two-step procedure shown in Scheme 11. Scheme 11

Step i XIII

XXV

Step ii

[H]

XXV XI (q=2)

In Step i of Scheme 11, aminonitrile XXV is formed when amine XIH and nitrile XV (either acrylonitrile or crotononitrile) are mixed either neat or in a suitable solvent, including water, methanol, ethanol, THF or mixtures of these solvents at temperatures ranging from 0-150°C. The quantities of Xm used range from one to ten molar equivalents.

The reduction of aminonitrile XXV to form diamine XI (q=2) as depicted in Step ii of Scheme 11 can be achieved using conditions analogous to those previously described for Step ii of Scheme 8.

Alternatively, compounds of Formula I where Y is R¹X and X is O, S or NR⁵ and R¹ is other than H can be prepared by the reaction of Formula I compounds where Y is R¹X and X is O, S or NR⁵ and R¹ is H with a compound of Formula XVII as depicted in Scheme 12.

Scheme 12

R¹- X³

XVII

I

proton acceptor

I (R ¹≠R X=O, S or NR⁵)

(R¹=R X=O,S or NR⁵) wherein: X³ is a leaving group such as halogen

Typical Scheme 12 reactions involve the use of greater than one

stoichiometric equivalent of XVII and greater than one stoichiometric equivalent of a proton acceptor in a suitable solvent at temperatures ranging from 0°C to the reflux temperature of the solvent. Typical proton acceptors include amines such as pyridine, triethylamine, DBU and DABCO, and inorganic bases such as NaHCO₃, K₂CO₃, NaOH and KOH. Suitable solvents include acetonitrile, CH₂Cl₂, THF and EtOAc. In certain cases, the proton acceptor can be used as the solvent (e.g. pyridine, Et₃N or other liquid amines). One skilled in the art will recognize that XVII includes alkyl halides, allyl halides, propargyl halides, acyl halides, haloformates, anhydrides, sulfonyl halides, carbamoyl halides, halothioformates and halodithioformates.

Alternatively, compounds of Formula I where Y is R¹X and X is O, S or NR⁵ and R¹ is C(O)NHR⁸ or C(S)NHR⁸ can be prepared by proccedures depicted in Scheme 13.

Scheme 13

(R¹=C(O)NHR⁸ or C(S)NHR⁸ wherein: X⁴is OorS and X=O, S orNR⁵)

In reactions depicted in Scheme 13, a compound of Formula I where R- is H and X is equal to O, S or NR⁵ is combined with one equivlanet of an isocyanate or isothiocyanate of Formula XVIII. A solvent such as THF, EtOAc or DMF can be used for Scheme 13 reactions. The reactions are generally run at temperatures between 0 and 50°C.

Compounds of Formula I where Y is R¹X and R¹ is H and X is S can be prepared by the hydrolysis of a Formula I compound where R¹ is an acyl group (e.g. R⁶(C)O) and X is S as depicted in Scheme 14. These reactions are typically performed using a base such as NaOH, KOH, NaOMe and NaOEt in a polar solvent such as THF, MeOH, EtOH and sometimes water.

Scheme 14

(R1=R⁶C(O), X=S) (R¹=H, X=S)

The syntheses of the starting materials (I) for Scheme 14 reactions were described in Scheme 1. EXAMPLE 1

Step A: 2-(Nitromethylene)-imidazolidine

A solution of 4.0 mL (0.06 mol) of ethylene diamine, 10 g (0.06 mol) of 2,2 bis(methylthio)nitroethylene and 60 mL of ethanol was heated at reflux for 12 h and then concentrated to give 7.6 g of a beige solid. ¹H NMR

(200 MHz, (CH₃)₂SO-d₆) δ 6.33 (s,1H), 3.58 (s,4H).

Step B: 1-[2-(Methylthio)ethyl]-2-(nitroethylene)imidazolidine

The product from Step A (2.0 g, 0.016 mol) was added to a suspension of 60% sodium hydride (0.7 g, 0.017 mol) and 31 mL of DMF at room temperature. The resulting mixture was stirred for 10 min and then 1.5 mL (0.016 mol) of 2-chloroethyl methyl sulfide was added. The resulting mixture was heated at 100°C for 12 h and then cooled to room temperature. Ethanol, 20 mL, was added and the reaction was concentrated at 70°C. The residue was dissolved in 50 mL of EtOH; 5 g of silica gel was added, and the mixture was concentrated. The residue was chromatographed on 100 g silica gel eluting with CH₂Cl₂-EtOH-48% NH₄OH (20:1:0.1) to give 1.0 g of a brown oil that solidified on standing. Trituration of the solid with MeOH gave a light yellow solid; mp = 102-104°C. ¹H NMR (400 MHz, CDCl₃) 6 8.65 (br s,1H), 6.55 (s,1H), 3.78 (m,4H), 3.38 (t,2H), 2.70 (t,2H), 2.16 (s,3H).

Step C: Methyl[2-[1-[2-(methylthio)ethyl]-2-imidazolidinylidene]-2- nitroethyl]thio]acetate (Compound 1)

A solution of 0.5 g (0.0025 moles) of the product from Step B, 0.2 mL (0.0025 mol) of methyl thioglycolate, 0.2 mL (0.003 mol) of 37% aqueous formaldehyde and 15 mL of ethanol was heated at reflux for 4 h, then cooled to room temperature and concentrated. The resulting crude product (0.8 g) was dissolved into methylene chloride, treated with about 3 g of silica gel, and concentrated. The resulting residue was purified using flash chromatography using silica gel (50 g) and 20:1:0.1 CH₂Cl₂-EtOH-48% NH₄OH to give 0.5 g of a viscous oil that later solidified; mp = 44-47°C. ¹H NMR (400 MHz, CDCl₃) b 9.64 (br s,1H), 4.05 (s,2H), 3.85-3.78 (m,6H), 3.75 (s,3H), 3.45 (s,2H), 2.81 (t,2H), 2.19 (s,3H).

EXAMPLE 2

Step A: 2-[2-(Methylthio)ethylaminolpropanenitrile

A solution of 24.4 g (0.27 mol) of 2-(methylthio) ethylamine and 100 mL of methanol was treated with 294 mL of 1 M aqueous HCI 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 mol) of potassium cyanide and 150 mL of water at 5-10°C followed by the addition of 13 g (0.29 mol) 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 CH₂Cl₂. The aqueous layer was extracted with two additional 200 mL portions of CH₂Cl₂ and the combined organic layers were washed with 500 mL of saturated aqueous NaHCO₃, dried over anhydrous MgSO₄, filtered and concentrated to give 37.6 g (97%) of a pale yellow oil. ¹H NMR (200 MHz, CDCl₃) δ 3.78-3.60 (m,1H), 3.17-2.97 (m,1H), 2.94-2.74 (m,1H), 2.71-2.62 (m,2H), 2.12 (s,3H), 1.67

(br s,1H), 1.52 (d,J=7 Hz,3H).

Step B: N²-[2-(Methylthio)ethyl]-1,2-propanediamine

A vigorously stirred (mechanical stirrer) solution of lithium aluminum hydride (84 mL of a 1 M solution in (CH₃CH₂)₂O, 0.084 mol) and (CH₃CH₂)₂O (163 mL) was treated with a solution of 6.04 g (0.042 mol) of the product from Step A in

82 mL of (CH₃CH₂)₂O 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 H₂O in 10 mL of tetrahydrofuran, 3.1 mL of 15% NaOH and 9.3 mL of H₂O at 0°C. The resulting mixture was diluted with 155 mL of (CH₃CH₂)₂O 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. ¹H NMR (200 MHz, CDCl₃) 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-1-[2-(methylthio)ethyl]-2-(nitromethylene)-imidazolidine

A solution of 2.6 g (0.018 mol) of the product from Step B, 2.9 g

(0.010 0000 000,2-bis-(methylthio)-1-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 CH₂Cl₂:CH₃CH₂OH:48% NH₄OH gave 1.8 g of a yellow oil that solidified on standing, mp 60-62°C. Trituration of the solid with 1-chlorobutane gave an off-white solid that melted at 66-68°C. -E NMR (200 MHz, CDCl₃) δ 8.63

(br s,1H), 6.53 (s,1H), 4.21-4.03 (m,1H), 3.90 (t,1H), 3.40-3.28 (m,3H),

2.78-2.58 (m,2H), 2.16 (s,3H), 1.36 (d,3H). Step D: Methyl[[2-[5-methyl-1-[2-(methylthio)ethyl]-2-imidazolidinylidene]-2- nitroethyl]thio]acetate (Compound 2)

A solution of 0.5 g (2.3 mmol) of the product from Step C, 0.2 mL

(2.3 mmol) of methylthioglycolate, 0.2 mL (2.8 mmol) of 37% aqueous formaldehyde and 14 mL of ethanol was heated at reflux for 4 h. The resulting solution was cooled to room temperature and concentrated to give 0.8 g of a dark brown oil. ¹H NMR (200 MHz, d₆-DMSO) δ 9.18 (br s,1H), 4.12-4.00 (m,1H), 3.85 (s,2H), 3.80-3.70 (m,2H), 3.64 (s,3H), ca. 3.6-3.2 (m,3H), 3.41 (s,2H), 2.70 (q,2H), 2.09 (s,3H), 1.22 (d,3H).

EXAMPLE 3

Step A: Methyl N-[(6-chloro-3-pyridinyl)carbonyl]-alanine

A solution of 50.5 g (0.29 mol) of 6-chloronicotinyl chloride and 290 mL of CH₂Cl₂ was added to a solution of 60 g (0.43 mol) of DL-alanine methyl ester hydrochloride and 290 mL of saturated aqueous sodium bicarbonate solution. 5 mL of aliquat 336 (Aldrich) was then added and the resulting two-phase mixture was stirred rapidly at 25°C for 24 h. The resulting mixture was partitioned between CH₂Cl₂ and saturated NaHCO₃. The aqueous layer was extracted with three portions of CH₂Cl₂. The combined organics were washed twice with saturated NaHCO₃, dried over MgSO₄ and concentrated to give 56.1 g of the title compound as a viscous yellow oil. ¹H NMR (300 MHz, CDCl₃) δ 8.82

(d,J=2.4Hz,1H), 8.10 (dd,1H), 7.41 (d,1H), 7.10 (br d,1H), 4.78 (quintet,1H),

3.80 (s,3H), 1.53 (d,3H).

Step B: 6-Chloro-N-[1 -(aminocarbonyl)-ethyl]-3-pyridine carboxamide

A solution of 50.5 g (0.21 mol) of the product from Step A and 150 mL of anhydrous MeOH was added to 575 mL of 15% anhydrous ammonia in anhydrous methanol. The resulting solution was stirred at room temperature for 48 h. The solid product was removed by filtration, washed with ethanol and dried under vacuum to give 43.5 g of the title compound as a white solid; mp.>220°C.

1H NMR (400 MHz, (CH₃)₂SO-d₆) δ 8.87 (apparent s,1H), 8.79 (d,1H), 8.29 (d,1H), 7.65 (d,1H), 7.45 (br s,1H), 7.03 (br s,1H), 4.41 (quintet, 1H), 1.33 (d,3H). Step C: N²-[(6-chloro-3-pyridinyl)-methyl]-1,2-propanediamine

Borane-methyl sulfide complex (18.7 mL, 0.19 mol) was added dropwise to a mechanically stirred mixture of 8.5 g (0.04 mol) of the product from Step B and 112 mL of THF at 50-60°C. The resulting orange-yellow suspension was refluxed for 2 h, cooled to room temperature and quenched by the careful dropwise addition of 62 mL of 6 N HCI (exothermic with vigorous H₂ evolution!) The resulting pale yellow mixture was stirred at room temperature for 24 h and then was washed with three portions of ether. The aqueous layer was basified with 25 mL of 50% NaOH (added with cooling) and extracted with 3 x 150 mL of 2:1 methylene chloride- chloroform solution. Combined organic layers were dried (K₂CO₃) and concentrated to give 3.5 g of the title compound as a yellow oil.

1H NMR (400 MHz,CDCl₃) δ 8.33 (apparent s,1H), 7.69 (d,1H), 7.30 (d,1H), 3.78 (ABq,2H), 2.75 (d,1H), 2.63 (dd,1H), 2.53 (dd,1H), ca. 1.50 (br s,3H), 1.07 (d,3H).

Step D: 2-Chloro-5-[[5-methyl-2-(nitromethylene)-1- imidazolidinyl]methyl]pyridine

A suspension of 2.5 g (0.013 mol) of the product from Step C, 1.6 g (0.009 mol) of 1,1-bis(methylthio)-2-nitroethylene and 63 mL of anhydrous EtOH was heated at reflux for 3 h and was then allowed to stand at 24°C for 72 h. The resulting mixture was concentrated and chromatographed on silica gel using

15:1:0.1 CH₂Cl₂-EtOH-30% NH₄OH to give 0.70 g of the title compound as a yellow solid; mp=127-131°C. ¹H NMR (400 MHz,CDCl₃) δ 8.70 (br s,1H), 8.27 (s,1H), 7.56 (d,1H), 7.35 (d,1H), 6.56 (s,1H), 4.33 (ABq,2H), 3.95-3.85 (m,2H), 3.45-3.35 (m,1H), 1.33 (d,3H).

Step E: 2-Chloro-5-[[5-methyl-2-[1-nitro-2-(propylthio)ethylidene]-1- imidazolidinyl]methyllpyridine (Compound 7)

A solution of 0.5 g (0.002 mol) of the product from Step D and 12 mL EtOH was treated sequentially with 0.17 mL (0.002 mol) of 1-propanethiol and 0.16 mL (0.002 mol) of 37% aqueous formaldehyde. The resulting mixture was sitrred at 25°C for 18 h and concentrated. Flash chromatography on silica gel using 15:1:0.1 CH₂Cl₂-EtOH-30% NH₄OH gave 0.17 g of the title compound as a yellow solid; mp=127-129°C. ¹H NMR (300 MHz,CDCl₃) δ 9.87 (br s,1H), 8.37 (s,1H), 7.63 (d,1H), 7.39 (d,1H), 4.92 (ABq,2H), 4.00-3.82 (m,3H), 3.46 (d,1H), 3.36 (t,1H), 2.50 (t,2H), 1.55-1.43 (m,2H), 1.32 (d,3H), 0.90 (t,3H). By the general procedures described herein, or obvious modifications thereof, the compounds of Tables 1 through 15 and Index Tables A-C can be prepared. In Tables 1 through 15 and Index Tables A-C the following notations have been used:

^Me = ^CH ₃

Et = CH₂CH₃ CH₂(4-Cl-Ph) = CH₂

n-Pr = (CH₂)₂CH₃

i-Pr = CH(CH₃)₂

n-Bu ₌ (CH₂)₃CH₃ (CH₂)₂-2-Cl-Ph = CH₂CH₂

i-Bu = CH₂CH(CH₃)₂

s-Bu = CH(CH₃)CH₂CH₃

t-Bu = C(CH₃)₃ (CH₂)₂-3-Cl-Ph = CH₂CH₂

n-pentyl = (CH₂)₄CH₃

n-hexyl = (CH₂)₄CH₃ (CH₂)₂-4-Cl-Ph = CH₂CH₂

c-Pr =

2-Cl-Ph =

c-Bu =

c-pentyl =

3-Cl-Ph =

c-hexyl = 4-Cl-Ph =

c-heptyl =

Ac = CH₃ c-octyl = 2-floryl-CH₂ =

2-pyr-CH₂ =

CH₂(2-Cl-Ph) = CH₂

pyrazine-CH₂ =

CH₂(3-Cl-Ph) = CH₂

2-thienyl-CH₂ . Y-6 =

Y-1 = Y-7 =

Y-2 = Y-8 =

Y-3= Y-9= MeS

Y-4 = Y-10 =

Y-5 = Y-11=

Tables 1-15 specifically name compounds by listing values for Y corresponding with the structures in the key above. The compounds in Tables 1-15 can be referred to by line number and column number. For example, in Table 1, the four compounds named in line 1, can be referred to as 1-1, 1-2, 1-3 and 1-4 (as designated by line number-column number). All other specific compounds covered in Tables 1-15 can be designated in an analogous fashion.

Formulation/Utility

The present invention further comprises agricultural compositions containing one or more compounds of Formula I as previously defined. 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

Active

Ingredient Diluent Surfactant

Wettable Powders 5-90 0-74 1-10

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

Solutions, (including Emulsifiable

Concentrates)

Dusts 1-25 70-99 0-5

Granules, Baits 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 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), pp 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 5.0% 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, 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 howardi), 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 (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, 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 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, 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 and B for compound descriptions.

Index Table A

Compound Y mp °C

1 MeO₂CCH₂S 44-47 Index Table B

Compound R¹X mp °C

2 MeO₂CCH₂S oil

3 c-hexyl S oil

4 n-PrS oil

5 (EtO)₃Si(CH₂)₂S oil

6 NaO₂CCH₂S tacky solid

Index Table C

Compound R¹X mp °C

7 n-PrS 127-129

Cmpd No. ¹H NMR Data^(a)

3^(b) 9.22 (s,1H), 2.82-2.65 (m,3H), 2.11(s,3H), 1.98-1.89 (m,2H),

1.32-1.19 (overlapping m and d, 7H total), 1.06 (apparent t, 4H).

4^(b) 9.22 (s,1H), 2.82-2.75 (m,1H), 2.74-2.64 (m,1H), 2.51 (t,2H),

2.11 (s,3H), 1.55 (sextet, 2H), 1.23 (d,3H), 0.92 (t,3H).

5^(b) 9.22 (s,1H), 2.10 (s,3H), 1.23 (d,3H), 1.15 (t,9H), 1.06 (t,2H). 6^(b) (in D₂O, HDO=δ 4.66) 1.98 (s,3H), 1.05 (d,3H). a Unless indicated otherwise, spectra were obtained in CDC1₃ at 400 MHz. s = singlet, d = doublet, t = triplet, m = multiplet, coupling constants (J) are in Hertz.

b Partial data.

TEST A

Southern Corn Rootworm

Test units, each consisting of an 8-ounce (230 mL) plastic cup containing 1 one-inch square of soybean-wheatgerm diet, were prepared. Solutions of each of the test compounds (acetone/distilled water 75/25 solvent) were sprayed into the cups. Spraying was accomplished by passing the cups, on a conveyer belt, directly beneath a flat fan hydraulic nozzle which discharged the spray at a rate of 0.5 pounds of active ingredient per acre (about 0.55 kg/ha) at 30 psi (207 kPa). 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. The units were then covered and held at 27°C and 50% relative humidity for 6 additional days, after which time mortality readings were taken. Of the compounds tested, the following resulted in greater than or equal to 80% mortality after 48 h at 1000 ppm: 1, 2, 5, 6.

Of the compounds tested, the following gave mortality levels of 80% or higher after a total of 8 days at 1000 ppm: 1, 2, 4, 5, 6.

TEST B

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 (2.54 cm) layer of sterilized soil and a 1/2-inch (1.27 cm) layer of sand. The test units were sprayed as described in TEST A with individual solutions of the below-listed compounds. After the oats had dried from the spraying, between 10 and 15 adult aster leafhoppers

(Mascrosteles fascifrons) were aspirated into each of the covered cups equipped with vented lids. The cups 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 resulted in greater than or equal to 80% mortality at 1000 ppm: 1, 3, 4, 5, 6. TEST C

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 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 resulted in greater than or equal to 80% mortality at 1000 ppm: 2.

TEST D

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 3/8-inch (0.94 cm) diameter vials containing 4 mL of sugar water solution and covered with a clear plastic 1 -ounce (29 mL) 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 resulted in greater than or equal to 80% mortality at 1000 ppm: 2, 3.

TEST E

Contact Activity Against Green Leafhopper Nymphs

Three rice (Oryza sativa) seedlings, 1.5 leaf stage and about 10 cm tall are transplanted into a 1/2 oz. plastic cup containing Kumiai Brown artificial soil. Seven milliliters of distilled water is then added to the cup. The test chemical is 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, are then placed on a spray chamber turntable. The cups are 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 completes 7.5 rotations during the 45 second spray interval. After chemical application, treated cups are held in a vented enclosure to dry for about 2 h. After drying, the cups are 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) are transferred into the test units using an aspirator. The test units are held at 27°C and 65% relative humidity. 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 at 100 ppm: 1, 2, 3, 4, 5, 6.

TEST F

Contact Activity Against Brown Planthopper Nymphs

Three rice (Oryza sativa) seedlings, 1.5 leaf stage and about 10 cm tall are transplanted into a 1/2 oz. (14 mL) plastic cup containing Kumiai Brown artificial soil. Seven milliliters of distilled water is then added to the cup. The test chemical is 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, are then placed on a spray chamber turntable. The cups are 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 completes 7.5 rotations during the 45 second spray interval. After chemical application, treated cups are held in a vented enclosure to dry for about 2 h. After drying, the cups are 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) are transferred into the test units using an aspirator. The test units are held at 27°C and 65% relative humidity, 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 at 100 ppm: 2, 3, 4, 5, 6.

TEST G

Solution Systemic Activity Against Green Leafhopper Nymphs

The test chemical is added directly into 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 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 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. Inspects which cannot walk are classified as dead. Of the compounds tested, the following gave mortality levels of 80% or higher at 48 h at 100 ppm: 1, 2, 3, 4, 5, 6.

TEST H

Solution Systemic Activity Against Brown Planthopper Nymphs

The test chemical is added directly into 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 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 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 brown planthopper (Nilaparvata lugens) 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. Inspects which cannot walk are classified as dead. Of the compounds tested, the following gave mortality levels of 80% or higher at 48 h at 100 ppm: 2, 3, 4, 5, 6.

TEST I

Solution Systemic Activity Against Green Peach Aphid

The units, each consisting of a 2- week old turnip plant (7-13 cm in height) grown in Oasis^® wedges (available from Smithers-Oasis, Kent, Ohion), were prepared. Plants were trimmed of all immature leaves, leaving the two primary leaves. Plants were infested with 30-40 aphids, Myzus persicae (Say), of mixed age. Plants were infested by placing aphid infested leaves from the stock culture, on the top of and between the two leaves to be used in the test. The plants were held in this manner for 24 h, in a controlled environment chamber at 22°C, 50% relative humdity, and 16 h light: 8 h dark, light cycle. The infesting leaves were then removed. Each plant was a replicate with four plants making up one treatment. Plants were then removed from the growing tray and the Oasis^® wedges squeezed to remove excess water. Stock solutions of each of the test compounds were prepared by dissolving the test compound in 10 mL of distilled water and sonicating if the compound was not immediately dissolved. Dilutions from the stock solution were made using distilled water. Plants were then placed in vials containing 10 mL of test solution of a given concentration. The treated plants were then held for 48 h in the controlled environment described above. Mortality readings were taken 48 h after treatment, by counting the number of dead and live aphids on the leaf surface and filter papers. Aphids that are able to move their appendages, but cannot walk, or are dark-colored, or show distortions in body shape are considered dead. Mortality is expressed as the percentage of dead compared to the total number of aphids present. The percent control for the four replicates was averaged for each treatment. Of the compounds tested, the following gave mortality levels of 80% or higher after 48 h at 100 ppm: 1.

Claims

1. A compound of the formula

wherein:

Q is selected from the group

CH₃SCH₂-

Y is selected from the group halogen and R¹X;

X is selected from the group S(O)_n, O and NR⁵;

R¹ is selected from the group C₁-C₂₀ alkyl, C₃-C₁₀ cycloalkyl, C₄-C₇ cycloalkylalkyl, C₂-C₆ alkenyl and C₂-C₆ alkynyl each of which is optionally substituted with 1 or 2 groups independently selected from CN, NO₂, OH, C₁-C₄ alkoxy, OC(O)R⁶, OCO₂R⁶, OS(O)₂R⁶, SH, C₁-C₄ alkylthio, C(O)R⁶, C(O)OR⁶, CO₂H, SO₃H, N(R⁷)R⁸, C(O)N(R⁷)R⁸, OS(O)₂N(R⁷)R⁸, C(S)N(R⁷)R⁸, C₁-C₄ alkylamino, C₂-C₆ dialkylamino, S(O)₂N(R⁷)R⁸, Si(R⁹)(R¹⁰)R¹¹, C₁-C₄ alkylsulfinyl, C₁-C₄ alkylsulfonyl, phenyl optionally substituted with R¹², and a 5- or 6- membered saturated, partially unsaturated or fully unsaturated heterocyclic ring containing 1-4 heteroatoms independently selected from the group 0-1 O, 0-1 S and 0-4 N, each heterocyclic ring optionally substituted with R¹²; H; C₁-C₆ haloalkyl; C₃-C₇ halocycloalkyl; C₄-C₇ halocycloalkylalkyl; C(O)N(R⁷)R⁸; SO₂R⁶;

SO₂N(R⁷)R⁸; C(S)N(R⁷)R⁸; C(O)R⁶; CO₂R⁶; C(S)R⁶; C(S)OR⁶; C(S)SR⁶; C(O)SR⁶; phenyl optionally substituted with R¹²; 5- or 6- membered saturated, partially saturated or fully unsaturated heterocyclic ring containing 1-4 heteroatoms independently selected from the group 0-1 O, 0-1 S and 0-4 N, each heterocyclic ring optionally substituted with R¹²; provided that (i) when X is NR⁵, R¹ and R⁵ can optionally be taken together as -CH₂CH₂CH₂CH₂-, -CH₂CH₂OCH₂CH₂- or -CH₂CH₂CH₂CH₂CH₂- and (ii) when X is S(O)_n and n=1 or 2, then R¹ is other than H, C(S)N(R⁷)R⁸, C(O)R6, CO₂R⁶, C(S)R⁶, C(S)OR6, C(S)SR⁶, C(O)SR⁶, C(O)N(R⁷)R⁸,

SO₂N(R⁷)R⁸ or S(O)₂R⁶;

R² is selected from the group H and C₁-C₃ alkyl;

R³ is selected from the group H and CH₃; or

R² and R³ are taken together to form a group selected from CH₂CH₂,

CH(CH₃)CH₂, CH₂CH₂CH₂ and CH(CH₃)CH₂CH₂, the group being

CH(CH₃)CH₂ or CH(CH₃)CH₂CH₂ when Q is Q-2, Q-3, Q-4 or Q-5;

alkoxyalkyl, C₃-C₃ dialkoxyalkyl, C₁-C₃ alkoxy, C₁-C₃ alkylsulfonyl, C₂-C₄ alkenyl, C₂-C₄ alkynyl, C₁-C₄ alkylamino, C₂-C₄ dialkylamino and benzyl optionally substituted with R¹²;

R⁵ is selected from the group H, C₁-C₆ alkyl, CHO, C₂-C₄ alkylcarbonyl, C₂-C₄ alkoxycarbonyl and C₁-C₄ alkylsulfonyl provided that when R⁵ is H, then R², R³ and R⁴ are other than H;

R⁹, R¹⁰ and R¹ - are independently selected from the group C₁-C₄ alkyl,

C₁-C₄ alkoxy and phenyl;

n is 0, 1, or 2.

2. A compound according to Claim 1 wherein:

Y is R¹X;

X is S;

R⁴ is selected from the group H and CH₃.

3. A compound according to Claim 1 wherein:

Y is R¹X;

X is S;

4. A compound according to Claim 2 wherein Q is Q-1.

5. A compound according to Claim 3 wherein Q is Q-1.

6. A compound according to Claim 2 wherein Q is selected from the group Q-2, Q-3, Q-4 and Q-5, and R² and R³ are taken together to form a group selected from CH(CH₃)CH₂ and CH(CH₃)CH₂CH₂, wherein the terminal CH₂ carbon is attached to the nitrogen atom bearing R⁴.

7. A compound according to Claim 3 wherein Q is selected from the group Q-2, Q-3, Q-4 and Q-5, and R² and R³ are taken together to form a group selected from CH(CH₃)CH₂ and CH(CH₃)CH₂CH₂, wherein the terminal CH₂ carbon is attached to the nitrogen atom bearing R⁴.

8. An arthropodicidal composition comprising an arthropodicidally effective amount of a compound according to any one of Claims 1-7 and a carrier therefor.

9. A method for controlling arthropods comprising contacting the arthropods or their environment with an arthropodicidally effective amount of a compound according to any one of Claims 1-7.