CA2176501A1 - N-(4-pyrimidinyl)amide pesticides - Google Patents

Abstract

N-(4-pyrimidinyl)amide pesticides of formulas (1, 2) and N-oxides and salts thereof, wherein the variable groups are as defined in the specification, are active against nematodes, insects, mites, and plant pathogens.

Description

~ 76~0 1 ~WO 95/18795 PCTIUS94/14848 N-(4-PYRIMIDINYL)AMIDE PESTICIDES
This invention provides new compounds that are useful as nematicides, insecticides, miticides, and plant fungicides. The invention also provides nematicidal, insecticidal, rniticidal, and fungicidal methods.
There is an acute need for new nematicides, insecticides, miticides, and plant filn~icitlçs Available nematicides typically have high m~mm~ n toxicity and must be used at high rates. A nematicide that can be applied at lower rates and that has lower " ,~" " "~ n toxicity would l~lt;senl a .~i~nific~nt advance.
Mites and insects are developing resistance to the miticides and insecticides in current lo use. Resistance to insecticides in anthropods is widespread, with at least 400 species resistant to one or more insecticides. The development of resistance to some of the older insecticides, such as DDT, the carb~m~tes, and the organophosphates is well known. But resistance has even developed to some of the newer ~ylG~Iroid insecticides and rniticides. Simil~rly, target pathogens are rapidly developing resistance to ~ y used fungicides. At least 50 species of fungi have developed resistance to the b~n7imi(1~701e fungicides. Even recently introduced fungicides, like the acyl~l~nin~s, which initially exhibited excellent control of potato late blight and grape downy mildew in the field, have become less effective because of resistance.
Therefore a need exists for new insecticides, miticides, and fungicides, and particularly for compounds that have new or atypical modes of action.
This invention provides compounds of the formula (1) and (2):

R2` N J~ Y-Z N=C~
~N ~N Y Z
~ N ~ R~N ~ Rl (2) and N-oxides and salts thereof, wherein Rl is H, (Cl-C4)alkyl, (C3-C4) branched aL~yl, (C3-C7) cycloaL~yl, (C2-C4) alkenyl, (C3-C4) branched alkenyl, halo(Cl-C4)aL~yl, (Cl-C4)aLIcoxy, (Cl-C4)aLI~oxy(Cl-C4)aLkyl, halo(Cl-C4)alkoxy, (Cl-C4)aL~ylthio, (Cl-C4)alkylsulfonyl, (Cl-C4)aL~ylsulfinyl, halo, or phenyl;
R2 is H, (Cl-C4)aLl~yl, (C3-C4) branched alkyl, (Cl-C4)aL~anoyl, halo(Cl-C4)alkyl, (Cl-C4)alkoxymethyl, CH2SiR9RlORll, hydro~yl~ l-yl, benzyl, (C3-C6) cycloaL~ylmethyl, T, TR6 or--P~TR7, where R9,R10 and Rll are indepenclently (Cl-C4) aLI~yl, (C3-C4) branched aIkyl, phenyl, or substituted phenyl, each T is independently O or S, and R6 and R7 are independently (Cl-C4) alkyl, (C3-C4) branched aL~yl, phenyl, or substitlltecl phenyl;

WO 95/18795 PCT/US9~/14848 Yis (1) -CH2-, optionally substituted with (Cl-C4) aL~yl, (C2-C4) alkenyl, (C2-C4) alkynyl, branched (C3-C7) aL~yl, (C3-C7) cycloaL~yl, (C3-C7) cycloalkenyl, halo, halo (Cl-C4) aL~yl, halo (Cl-C4) alkoxy, hydroxy, CN, (Cl-C4) alkanoyl, (Cl-C4) alkoxycarbonyl, aryloxycarbonyl, where aryl is as defined below, hydroxy (Cl-C4) alkyl, (Cl-C4) alkoxy (Cl-C4) aL~yl, or --C--(2) R27--C--R28, where R27 and R28 are independently selected from H, (Cl-C4) alkyl, (Cl-C4) alkoxy, SH, S-lower alkyl, NH2, NH-lower alkyl, N,N-di-lower alkyl, O-lower aL~yl, OH, morpholino, piperidinyl, pyrrolidinyl, thiomorpholino, or R27 and R28 combine to form part of a (Cs-C6) saluldlt;d or unsaLu dLt;d ring optionally including 1 or 2 hetero atoms selected from O, S, or NR5, where R5 is H, (Cl-C4)aL~yl, or (Cl-C4)alkanoyl;
zis (1) (C3-Cg) cycloalkyl or cycloalkenyl, optionally substituted with one or more groups independently selected from (Cl-C4) aL~yl, (Cl-C4) alkoxy, halo (Cl-C4) alkyl, halo (Cl-C4) aLIcoxy, halo, hydroxy, or (Cl-C4) aL~anoyl; or (2) aryl, where aryl is (a) a phenyl group optionally ~ul~LiLuLed with one or more groups independently selected from:
halo, (C3-Cg) cycloaLkyl, (C3-Cg) cycloalkenyl, phenoxy, substituted phenoxy, phenylthio, substituted phenylthio, phenyl, substituted phenyl, N02, --C--R8, where R8 is (Cl-C7) alkyl, halo (Cl-C7) aL~yl, (C3-C7) branched aL~yl, halo (C3-C7) I, allched aL~yl, (C3-C7) cycloaL~cyl, halo (C3-C7) cycloaL~yl, (Cl-C7) alkoxy, h3droxy, phenyl, substituted phenyl, phenoxy, or substituted phenoxy, --O-C-R8, wherein R8 is defined as above, except that hydroxy is excluded, OH, CN, ~W095/18795 2 ~ 7 ~ t PCT/US94/14848 SiR9RlOR11 or oSiR9R1OR11, where R9,R10 and R11 are independently (Cl-C4) aL~yl, (C3-C4) branched aL~yl, phenyl, or substituted phenyl, NR12R13, where R12 and R13 are independently H, (Cl-C4) alkyl, or (Cl-C4) aL~anoyl, s S(o)R14, So2Rl4~ or oSO2R14~ where R14 is (Cl-Clo) aL~yl, phenyl, or substituted phenyl;
a (Cl-C12)s~ ed or unsaturated hydrocarbon chain, straight chain or branched optionally including a hetero atom selected from O, S, SO, SO2, NR5, orSiR6R7, where R5, R6 and R7 are as defined above, and optionally substituted with halo, halo (Cl-C4) aL~oxy, hydroxy, (C3-Cg) cycloaLIcyl or cycloaL~enyl, (Cl-C4)aL~anoyl, phenoxy, substituted phenoxy, phenyl, substituted phenyl, phenylthio, substituted phenylthio, or cyano;
(Cl-C7) aL~oxy optionally substituted with halo, phenyl, substituted phenyl, (C3-Cg) cycloalkyl or cycloalkenyl, phenoxy, or substituted phenoxy; or (Cl-C7) alkylthio optionally substituted with halo, phenyl, substituted phenyl, (C3-Cg) cycloaL~yl or cycloaLkenyl, phenoxy or substituted phenoxy;
b) a ~uryl group of formula (3) ~O~ (3) where R15 is H, halo, halomethyl, CN, N02, (Cl-C4) aL~yl, (C3-C4) branched aL~yl, phenyl, (Cl-C4) aL~oxy;
(c) a thienyl group of the formula (4) ~S~ (4) where R16 is H, halo, halomethyl, CN, N02, (Cl-C4) alkyl, (C3-C4) branched aL~yl, phenyl, (Cl-C4) aL~oxy, or thienyl;
2s (d) a group of formula (5) or (6) /--J~ Rl5 ~Q~ Rl5 where R15 is as defined in paragraph (b), J is N or CH, and G is O, NR17, or S, provided that if J is not N then G is NR, where R17 is H, (Cl-C4) aL~yl, (Cl-C4) alkanoyl, phenylsulfonyl, or substituted phenylsulfonyl;
(e) a group selected from optionally substituted naphthyl, dihy~llolld~hthyl, tetrahydrollal~hthyl, and decahydronaphthyl;
optionally snbsti1~lted indolyl;

wo 95/18795 2 1 7 ~ 5 0 1 PCTIUS9~/14848 ~
1 ,3 -benzodioxolyl;
2,6-dimethyl-4-morpholinyl; and l-adarnantyl;
(f) a group of the formula R2om ~=¦=\~O-Het s ~
wherein m is 4; each R20 is independently H, halo, lower aLI~yl, lower alkoxy, haloaLkyl, haloaLkoxy, N02, CN, lower aLkyl c~l,ollyl, S(o)Rl4, So2Rl4~ or oSO2Rl4~ phenoxy, or substituted phenoxy, where R14 is (Cl-Clo) aLkyl, phenyl, or substituted phenyl; provided that at least two Of R20 are selected from H and F; and Het is pyridinyl, pyrazinyl, 0 pyrimidinyl, or pyridazinyl, optionally ~.ub~ u~ed with one or more groups selected from halo, lower aLkyl, lower aLkoxy, haloaLkyl, haloaLkoxy, N02, CN, and lower aLIcyl carbonyl;
(g~ a group of the formula X2.X3 wherein one of x2 and X3 is N and the other is CR23;
R21 is -T-R22, phenyl, substituted phenyl, (Cl-Clo) aLkyl, halo, or halo (Cl-Cg)aLkyl, where TisOorS,and R22 is (Cl-C4) aLI~yl, (C3-C7) branched aL~cyl, halo (Cl-C7) aLl~yl, halo (C3-C7) branched aL~yl, (Cl-C4) aLkoxy (Cl-C4) aL~cyl, or naphthyl or phenyl, either of which may be optionally substituted with up to three groups selected from: ~lo, (Cl-Clo) aLkyl, b,dllclled (C3-C7) aLkyl, halo (Cl-C7) aLkyl, hydroxy (Cl-C7) aLkyl, (Cl-C4) aLI~oxy, halo (Cl-C4) alkoxy, phenoxy, substituted phenoxy, phenyl, substituted phenyl, CN, N02, OH, (Cl-C4) aLkanoyloxy, or benzyloxy;
R23 is:
H, halo, (C3-Cg) cycloalkyl, (C3-Cg) cycloaL~cenyl, phenoxy, substituted phenoxy, phenylthio, snbst~ t~l phenylthio, phenyl, substituted phenyl, N2.

~WO 95/18795 PCT/US94/14848 o --C--R8, where R8 is (Cl-C7) aL~cyl, halo (Cl-C7) aL~yl, (C3-C7) branched aL~yl, halo (C3-C7) branched aL~yl, (C3-C7) cycloaL~yl, halo (C3-C7) cycloaL~yl, (Cl-C7) aL~oxy, phenyl, substituted phenyl, or hydroxy, acetoxy, s OH, CN, SiR9R10R1l or OSiR9R10Rl1, where R9,R10 and R11 are independently (Cl-C4) aL~yl, (C3-C4) branched aL~yl, phenyl, or substituted phenyl, 0 NR12R13, where Rl2 and R13 are independently H, (Cl-C4) aL~cyl, or (Cl-C4) alkanoyl, S(o)R14, or So2Rl4~ where R14 is (Cl-Clo) aL~yl, phenyl, or substituted phenyl;
a (Cl-C12) saturated or unsaturated hydrocarbon chain, straight chain or branched optionally including a hetero atom selected from O, S, SO, S02, NR5, orSiR6R7, where R5, R6 and R7 are as defined above, and optionally substituted with halo, halo (Cl-C4) aLI~oxy, hydru~y, (C3-Cg) cycloaLIcyl or cycloalkenyl, (Cl-C4) aL~anoyl, phenoxy, substituted phenoxy, phenyl, substituted phenyl, phenylthio, substitl-tecl phenylthio, or cyano;
(Cl-C7) aLkoxy optionally substituted with halo, phenyl, substituted phenyl, (C3-Cg) cycloalkyl or cycloaL~enyl, phenoxy, or ~ub~Liluled phenoxy; or (Cl-C7) aL~ylthio optionally substituted with halo, phenyl, substituted phenyl, (C3-Cg) cycloalkyl or cycloaLIcenyl, phenoxy or substituted phenoxy;
or Y-Z together form a (C2-C11) s~t~lr~ted or unsaturated hydrocarbon chain, straight chain or branched;
W is O, S(O)y, wherein y is an integer from 0 to 2, or NR24, where R24 is H, OH,(Cl-C4) alkyl, (Cl-C4) alkoxy, aryl, (Cl-C4) aL~anoyl, NR25R26, benzyl, or benzyl optionally substituted with (Cl-C4) aL~yl, (Cl-C4) alkoxy, halo, halo (Cl-C4) aLIcyl, and R25 and R26 are independently H, (Cl-C4) aL~yl, aryl, alkanoyl, or together form with nitrogen a saturated (C3-C7) ring such as morpholino, piperidinyl, pyrrolidinyl;
G is (Cl-C4) alkyl, aryl, (Cl-C4) aL~canoyl, NR25R26, deuterio (Cl-C4) aL~yl, halo (Cl-C4) aL~yl, benzyl, or benzyl optionally substituted with (Cl-C4) alkyl, (Cl-C4) aL~oxy, halo, or halo (Cl-C4) aL~yl, where R25 and R26 are as defined above; or 3s W-G together are halo, SH, or NR25R26 where R25 and R26 are as defined above;

_5_ 2~ 5~

provided that the following compound is excluded:
(l) the compound of formula l wherein Rl and R2 are H, and Y-Z together form t-butyl.
The invention also provides a method of inhibl~ g a nematode population which s comprises applying to the locus of a nematode, a nematode inactivating amount of a compound of the formula (l) or (2) as defined above.
The invention also provides a method of inhibiting an insect or mite population which c-~mpri~es applying to the locus of the insect or arachnid an effective insect or mite inactivating amount of a compound of formula (l) or (2).
The invention also provides a method of inhibiting plant pathogens which comprises applying an effective amount of a compound of form~ l) or (2) to a locus of the pathogen.
Throughout this document, all temperatures are given in degrees Celcius, and allpercentages are weight percentages unless otherwise stated.
The term "halo" refers ~ ~, Cl, Br, or I atom.
s The terms "alkoxy", "h .~yl", "aL~ylsulfinyl", and "aL~ylsulfonyl" refer to straight chain and branched chain groups.
The terms "substituted phenyl", "substituted phenoxy", "subshr~ted phenylthio", and "subslituted phenylsulfonyl", refer to such groups wherein the phenyl .ng is substituted with up to three groups independently selected from halo, (Cl-Clo) aL~yl, branched (C3-C6) aL~yl, halo (Cl-C7) aLI~yl, hydro~y (Cl-C7) aL~yl, (Cl-C7) aL~oxy, halo (Cl-C7) aL~oxy, phenoxy, substituted phenoxy, phenyl, substituted phenyl, N02, OH, CN, (Cl-C4) aL~canoyl, benzoyl, (Cl-C4) aL~anoyloxy, (Cl-C4)aLkoxycarbonyl, phenoxycarbonyl, or benzoyloxy, provided that a substituted phenyl, substituted phenyoxy, substituted phenylthio, or substituted phenylsulfonyl group that - ;tself substituted with a g1 ~ from this list shall not include a total of more than three phenyl rings. Thus, for example, a phenyl group that is substituted in the 4-position with a 4-chlorophenoxy group is inc111~1ed in the cl~finiti~n of ~ub~lilu~d phenyl.
The terrns "substituted naphthyl", and "s~1bst~ tecl indolyl" refer to these ring systems substituted with one or more groups independently selected from halo, halo (Cl-C4) aL~cyl, CN, N02, (Cl-C4) aLkyl, (C3-C4) branched aLI~yl, phenyl, (Cl-C4) aL~oxy, or halo (Cl-C4) alkoxy.
The term "carbocyclic ring" refers to a ~ lr~te~ or unsalu,aled carbocyclic ringcont~inin~ five or six carbon atoms.
The term "unsaluldled hydrocarbon chain" refers to a hydrocarbon chain co"l;1i"i,~g one or more sites of nn~ r~tion The term "HPLC" refers to a high pressure liquid cl~u,-lalograph~.

2 ~ 7650 1 ~WO 95/1879S PCT/US94/14848 The term ''sllbstit~lted amino" refers to an amino group that is substituted with one or two (Cl-C4) aLkyl groups or one (Cl-C4) aLI~anoyl group.
The term "lower alkyl" refers to Cl to C6 straight hydrocarbon chains and C3 to C6 branched and cyclic hydrocarbon groups.
s The terms "lower alkenyl" and "lower alkynyl" refer to C2 to C6 straight hydrocarbon chains and C3 to C6 branched hydrocarbon groups cont~ining at least one unsaturated bond.
The terms "lower alkoxy" and "lower aL~cylthio" refer to O-lower alkyl and S-lower aLkyl groups.
The term "haloaLkyl" refers to lower aLkyl groups substituted with one or more halo lo atoms.
The term "haloaLIcoxy" refers to lower aLkoxy groups substituted with one or more halo atoms.
Unless otherwise intli~aterl, when it is stated that a group may be substituted with one or more substitll~nt~ selected from an identified class, it is intended that the substituents may be independently selected from the class.
Preferred compounds of formula (1) include the following classes:
a) compounds of formula (1) wllGIGill Y is -CH2-;
b) compounds of formulas (1) wherein Z is aryl;
c) compounds of form~ (1) wherein Z is a phenyl group sllbstitl~ted with a halo(C2-C4) aLkoxy group;
d) compounds of formnl:l~ (1) wherein Z is a phenyl group sllkstihlted with a phenoxy or ~ubsliLu~Gd phenoxy group;
e) compounds of any of the foregoing groups c) and d) wherein the phenyl group is monosubstituted in the 4-position;
f) compounds of the formula lA

HN J~CH2~O~R29 ~N
~N~Rl (lA) where Rl is aLkyl and R29 is an electron withdrawing group, such as halo, halo(Cl-C4)aLkyl;
(Cl-C4) aLkanoyl, CN, N02, or CF3.
Particularly plG~t~llGd are Compounds of formula (lA) wllGlGil~ Rl is ethyl and R29 is 30 CF3, CN, or Cl.

2~ 765~
WO 95tl8795 PCT/ltJS9~/14848 Synthesis The compounds of this invention are made using well known chemic~l procedures.
The required starting materials are commercially available, or they are readily synthe~i7ed ng standard procedures.
5Compounds of Formula (1) can be prepared using the process illustrated in the following schemes:
Scheme 1 O

11 Me3AI
r N ~ CH30--C--Y-Z ~ ~ N
~ N R~ ) toluene N ~ Rl ~1) In the procedure illustrated in Scheme 1, the trimethy~ ,.-i.. -- solution is added to a nixture of the aminopyrimi~in~- (7) in toluene under nitrogen at room ~ Ult~. The solution is warmed and a solution of the ester in toluene is added. The resulting mixture is refluxed, then allowed to cool to room temperature and quenched by dropwise addition of lM
HCl. The mixture is then poured into 1 ~odium hydroxide and e~l-d~;lt;d with a solution of diethyl ether/dichlorometh~ne, dried ov ~ydrous sodium sulfate and concentrated. Scheme 2 Il (COC1)2 1l ~ Rl(7) HO--C--Y-Z ' [ ~l-C--Y-Z] ~ ~Ng`Rl (1) In the procedure illustrated in Scheme 2, a slight excess of oxalyl chloride is added dropwise to a solution of the carboxylic acid (8) in a suitable organic solvent, such as THF, methylene chloride, or xylenes, under nitrogen, at room Is~mp~l~Lu~e. The mixture may also 20 include 1-2 equivalents of pyridine or triethylamine. After stirring the mixture for 30 ~ es to 2 hours, the amine (7), in solution in a suitable organic solvent, such as THF, methylene chloride, or xylene, is added dropwise. The mixture is heated to reflux for 8 to 24 hours, then allowed to cool to room temperature and partitioned beLw~n lN sodium hydroxide and ethyl ether. The aqueous phase is extracted with ethyl ether. The combined organics are washed 25 with water and saturated sodium chloride solution, then dried, filtered, and conren Scheme 3 HO--C--Y-Z S ~ [ Cl-C--Y-Z] ~N 1~ Rl (l) ~WO 95/18795 ~ ~ ~ 6 sa 1, PCT/US9~/14848 In the procedure illustrated in Scheme 3, an acid derivative (8) is heated to reflux in excess thionyl chloride for about two hours. The excess thionyl chloride is then removed by reducing ~les~iul~. To the residue is then added a solution of the amine (7), and optionally about two equivalents of triethylamine, in a suitable organic solvent, such as acetonitrile, 5 toluene, or xylene. The mixture is heated to reflux for 8 to 24 hours, then allowed to cool to room l;;m~ lul~ and partitioned between lN sodium hydroxide and ethyl ether. Theaqueous phase is extracted with ethyl ether. The combined organics are washed with water and saturated sodium chloride solution, then dried, filtered, and concentrated.
Compounds of formula R2~NJ~c~z ~N CR27R28 l~N ~Rl (lA) can be prepared by using the processes illustrated in Scheme 4:
Scheme 4 R4N~ CH2 CH~O ~N-C-C-Z
(10) N ~ Rl toluene (11) H N(CH3)2 1. base \ R R NH

3 aLkylhalide ~ \C(O-loweraL~yl)3 ~ orR24NH
R4 ol N~NC-C-Z ~R~ Oo N~N-C-,C-Z (13) Ri H ~O-loweraL~yl R(l~N H \NE~25R26 (14) aL~cyl-S S-alkyl NHR24 HA BH R4 o N~N C-C-Z
(15) Rl A,CB
~J
Methylene derivatives (11) whef~ the methylene is ~ub~lilul~d with N(CH3)2 may be 15 prepared by treating the N-(4-pyrimidinyl)amide (10) with the a~rol)liate N,N-dialkylcarbrx~mille di-alkylacetal in the presence of toluene with hto~tin~ The N,N-dialkyl derivatives (11) can be converted to their NED~24 derivatives by treating with the ~r~liate amine to give (12). Treating the N-(4-pylimidinyl)amides (10) with trialkyl-orthocarboxylates gives additional methylene derivatives (13). The N-(4-pyrimidinyl)amides (10) can also be 20 converted to S,S-ketene acetals (14) and optionally, to cyclic systems (15).
Compounds of Forrnula (2) where W = O, S, or NR24 can be prepared using the process illusl~ d in Scheme 5:
g W 0 95/18795 2 1 7 6 5 O 1 PCTrUS94/14848 Scheme 5 X ,W-G
HN--C-Y-Z N=C~ N=C
d`N ~. ~N Z , ~N Y Z
(7) l`N~R1 l'N~R1 (2) ~NlRl The carbonyl derivative (7) is converted to the corresponding imidoyl halide (8) by treatment with reagents such as PCls, PBrs, POC13, POBr3, ox ~ 1 chloride, or SOC12. The imidoyl s halide (8) can then be reacted with nucleophiles such dS, for example, H2S, OR-, SR-, NH2R24, NHR25R26, or NHR24NR25R26 to give the desired compounds of Formula (2).
Compounds of Formula (2) where W-G is SH, or W is S and G is aLkyl or benzyl canbe prepared using the process illustrated in Scheme 6:
Scheme 6 o S ~W-G
HN--C--Y-Z -- HN-C--Y--Z N=C~
~N ~N ~N Y Z
o ( ) l~N~R1 (9) ~N~Rl (2) ~N~R1 The carbonyl derivative (7) is treated with Lawesson's reagent or P2Ss to give the corresponding thione (9). The thione can then be aLI~ylated with an aLkyl halide or benzyl halide to give the desired compounds of Formula (2).
~t~r~ing Materials 15 Pyrimidin-4-amine starting m~t~ri~ of formula (7) can be prepared using the procedure illustrated in the following scheme 7:
Sch~mt. 7 HCI MeO H2N HCl 1. N~oCH3 NH2 R-CN , )cNHHcl NH3' )--NH 2.EtocH=CHCN N R

Carboxylic acids of formula (8) are also readily prepared using conventional 20 procedures, for example the classic chain-lengthening procedure illustrated in the following scheme 8:

2 1 ~650 1 ~WO 95/18795 PCT/US94/14848 Scheme 8 NC ~ R , HOOC ~ R ~ HOCH

HooccH2~R ' NCCH2~R XCH2~

In step 1, KOH hydrolysis of the nitrile produces the corresponding carboxylic acid. In step 2, lithium ~ " ,i ~ n hydride reduction of the carboxylic acid produces the alcohol.
- 5 Alternatively, the alcohol can be obtained by sodium borohydride reduction of the corresponding aldehyde. The halogenation illustrated in step 3 may be~ for example, chlorination with thionyl chloride. Tre~tm~.nt of the halide with NaCN in step 4 gives the nitrile. In step 5, hydrolysis of the nitrile gives the phenylacetic acid derivative.
Carboxylic acid derivatives of formula (8) whelcill Z is a group of the formula ~R21 x2.x3 can be prepared using an analogous procedure. Carboxylic acid derivatives of formula (8) wherein Z is a group of the formula ~1 ~O-Het can be prepared by reacting p-hy~v~y~henyl acetic acid with the a~p,u~lia~ chloro-15 substit--te~ heterocyclic compound.
The N-oxides and salts of compounds of formula (1) are obtained in the usual way.
Examples The following tables identify compounds of formula (1) that were prepared by theprocesses illu~tr~tecl in the foregoing scllçm~s- Detailed examples illustrating preparation of 20 exçmrl~ry compounds follow the tables 2 ~ 765Q t W O 95/18795 PCTrUS94114848 TABLE I
R2~ N J' Y-Z
~N
N ~Rl (1) Compound ~ Z Rl R2 MP C
CH2 ~O~Cl CH3 H 111-112 2 CH2{~--O~CN CH3 ~ r 3 CH2~OCH2CF3 CH3 H 154-155 4 CH2{~OCH2CF3 SCH3 H 124-126 S CH2~OCH2CF3 Ph H 147-149 6 CH2 ~-O~F SCH3 H 130-132 7 CH2 ~}o ~F Ph H 106-108 8 CH2 ~F5 ~ CH3 H oil 9 CH2~OCH2CF3 Et H 82-84 CH2 ~} {~F Et H 84-86 11 CH2 _O-O~CF3 Et H wa~c 12 CH2 ~o~3CN Et H glass 13 CH2~} ~ CN Et H 167-169 N

14 CH2 ~-O~ ~Br Et H 193-194 CH2 ~OCH2CF3 c-Pr H93-94 16 CH2 ~3O~}F c-Pr H oil 17 CH2 ~O~Cl Et H88-89 18 CH2 ~OCH2CF3 n-Pr H 106 19 CH2 ~O~F n-Pr H81-83 CH2 ~OCH2CF3 n-Bu H92-94 21 CH2 ~o~3F n-Bu H87-88 æ CH2 ~ O C H2CF3 c-Bu H105-106 23 CH2 ~ O ~ F c-Bu H77-78 24 CH2 ~ O C H2CF3 t-Bu H120-122 21 76~01 Compound Y Z Rl R2MP C
CH2~ O ~ F t-Bu H wax 26 CH2~ O C H2CF3 H H 95 27 CH2~ O ~ CH2 28 CH2~ OC H2CF3 H H 163 29 CH2~ O ~ Cl c-Pr H oil CH2~ 0 C H2CF3 i-Pr H 93-95 31 CH2~ O ~ F i-Pr H 77-79 32 CH2 F Et H oil ~ O ~ C F3 33 ~ C H3 Et H oil 34* n-C17H35 Et H 82-83 CH2~ O-C H2CF3 Et H119-121 36 CH2~ O ~ S 02C H3 Et H 61-62 37 CH2~O~Cl Et H oil 38 CH2~ O C H2CF3 CH20CH3 H oil 39 CH2~ O ~ F CH20CH3 H oil CH2 ~ Et H113-115 41 CH2~ C H3 Et H 64-65 42 CH2~ O C H F2 Et H 64-66 43 CH2~ C H2 C F2-C F2H Et H oil 44 CH2~ O -(n-C4Hg) Et H 64-66 CH2~ C H(C H3)2 Et H oil 46 CH2- o ~ C H(C H3)2 Et H oil 47 CH2~ O ~ Et H oil 48 CH2~ (t-B u) Et H 87-89 49 CH2 0 Et H oil ~ O ~ C H3 * Not a claimed co~ )c~ulld O I

Compound Y Z Rl R2 MP C
CH2 ~ Et H
s 1 CH2~ O ~ Cl c-Pr CH3 T~i3LE II
~W--G
N=C
,J~ ~ Z
N ~` Rl (2) Compound Y Y-Z W~ Rl MP C
s2 CH2--CH2~~Cl O-CH3 c-Pr oil T~BLE rl R2~NJ~y-z ~N
N~Rl (1) Compound Y Z Rl R2 MP C

53 CH2 ~---~N2 C2H5 H gl~ss s4 CH2 ~O~F Cl H 154-156 CH2~O-CF2CF2H C2H5 H 108-lo9 s6 CH2~O-CH2cF3 C2H5 CH3 s7 CH2~O-CH2CF3 C2H5 C2H5 58 CH2 ~O~Cl C2H5 CH3 59 CH2 ~o~Cl t-Bu H 121-122 CH2 ~O~CN t-Bu H 67-68 61 CH2 ~O~Cl C2H5 C2H5 62 CH2 ~o{~CF3 t-Bu H 108-111 63 CH2 ~O~CF3 CH3 H 110-112 64 CH2~O-CF2CF2H C2H5 CH3 CH2 ~}O~CF3 n-Bu H 68-72 66 CH2 ~O~CF3 c-Bu H 64~69 -1~

~WO 95/1879S2 ~ 7 6 ~ I PCT/US94/14848 Compound Y Z Rl R2MP C
67 CH2 ~O~CF3 c-Pr H <72 68 CH2 ~O~CF3 H H

~ ~0~
CH2~--O~CF3 CH20CH3 H
71 CH2 CF3 c-Bu H
~0~
72 CH2 ~O~CF3 i-Pr H oil TABLE IV

HN J~C ' ,OI~N HC_NR25R26 ~N ~C2Hs (12A) C.oml o~ln~i R25R26 z MP C
73 CH3CH3 ~3-o~3cF3 74 CH3CH3 ~OCF2CF2H oil HC2Hs{~-OCF2CF2H oil 76 CH3CH3 ~}O~Cl 77 HC2Hs ~-O~Cl 78 CH3CH3 ~30~CN 80-82 79 HC2Hs ~O~CN
HCH2CH(CH3)2 ~o~CN oil 2 1 7~5~ ~
WO 9~./18795 PCT/US9~114848 Fx~rnple I
(Compound 1) O
N~2 HN--C-CH2~0~CI
~t CH30--C-CH~O~C~ Me3AI

A 2.0M solution of trimethyl~ lli.l in hexane (2.0 mL, 4.0 mmoL) was added s dropwise to a mixture of 4-amino-2-methylpyrimif1ine (0.394 g, 3.6 mmoL) in 15 mL of toluene, under a nitrogen atmosphere, at room temperature. The resultant mixture was stirred at room temperature for 15 minlltt~s" warmed slightly with a heat gun, treated with a solution of the ester in 2 mL of toluene and then heated to reflux. After refluxing overnight ~ 17h), the reaction mixture was allowed to cool to room tempOEature, quenched by the cautious, 1 o dropwise addition of 8 mL of IM HCl, poured into lN sodium hydroxide (75 mL) and extracted with a 2:1 solution of diethyl ether/dichlolu-llt;Lhane (3 x 100 mL). The combined organic extracts were washed with water ( 1 x 100 mL), ~.aLu.aLed sodium chloride (l x 100 mL), dried over anhydrous sodium sulfate and concentrated under reduced pressure to give 1.12 g of a yellow oil. The crude product was purified by clho~ Lography on silica gel (mplc) eluting with 70% hexane/30% ethyl acetate. This gave 0.583 g of the product as a white solid (46% yield).

Ex~n~le 2 (Compound 4) O, O
HO C-CH2~O-CH2Cp3 SOCl2 , Cl-c-cH2~o-cH2cF3 reflu~c e~NI`SCE~3 ~ N-c-cH2~o-cH2cF3 PhflcH~3 N ~SCH3 A solution of the phenylacetic acid (1.288 g, 5.5 rnmoL) and excess thionyl chloride (10 mL) was refluxed for sixty minutes. The excess thionyl chloride was removed under reduced pressure. The acid chloride was taken up in dichlulu~ e and then concc,~ ~d to remove any residual thionyl chloride (two times). The acid chloride was then treated with a 2s solution of 4-amino-2---t;11lyl~-iopyrimitline (0.706 g, 5.0 mmoL) in 10 mL of toiuene and the resultant mixture was heated to reflux. After lrllllxi~ ovemight (16h), the reaction mixture was allowed to cool to room l~ , poured into lN sodium hydroxide (75 mL) and then P.xtr?~ctecl with a 2:1 solution of diethyl ether/dichloLun-rtl~n~o (3 x 100 mL). The combined organic extracts were washed with water ( 1 x 100 mL), s~tnr~ted sodium chloride ( 1 x 100 mL), dried over anhydrous sodium sulfate and then concenlldled under reduced ~rt;S~ulc; to WOg5/18795 2 l 7 6 S a 1 PCT/US94/14848 give 2.20 g of a yellow solid. The crude product was purified by chromatographing on silica gel (mplc), eluting with 75% hexane/25% ethyl acetate. This gave 1.583 g of the product as a yellow solid (89% yield).
Example 3 (Compound 13) 1. (COCl)2/CHCl3 HN--C-CH2~0~CN
HO--C-CH2~0~CN 2 N 2 ~N~Et N~Et toluer~e~
renux A solution of the phenylacetic acid (1.398 g, 5.5 mmoL) in 10 mL of chloroform was treated with an excess of oxalyl chloritl~. (5 mL) and the resultant mixture was heated to reflux.
After refluxing for sixty minnt~s, the reaction mixture was concentrated under reduced 10 pressure. The acid chloride was taken up in chlol~fi)lm and con~entr~ted again.
A solution of the acid chloride in 10 mL of toluene was treated in one portion with ~amino-2-ethylpyrirnidine and the resultant mixture was heated to reflux. After l~;lluxillg overnight (17 h), the reaction mixture was allowed to cool to room temperature, poured into 1 N sodium hydroxide ( 100 mL) and extracted with a 2:1 solution of diethyl ether/dichlorom~.th~nto (3 x 15 100 mL). The comhine~l organic extracts were washed with water ( 1 x 100 mL), saturated sodium chloride ( 1 x 100 mL), driëd over anhydrous sodium sulfate and then concentrated under reduced pressure to give 1.65 g of a brown oil. The crude product was purified by chromatographing on silica gel (mplc), eluting with 70% hexane/30% ethyl acetate. This gave 0.819 g of the product as a yellow solid (46% yield).
Example 4 (Compound 52) HN-C-CH2~0~Cl N=C-CH2~0~Cl ~c-Pr l.PCIs/PhCH3 ~c-Pr 2. NaOCH3 / MeOH
Phosphorus pentachloride was added to a solution of the amide in 10 mL of toluene and the resultant mixture was warmed to 45C. After stirring at 45-50C for 60 minutes, the 2s mixture was concellLlaled in vacuo. A solution of the imidoyl chloride in 5 mL of methanol was added to solution of sodium methoxide in 5 mL of methanol and the resultant mixture was heated to reflux. After lçll~x;,~g about 18 hours the mixture was poured into 50 mL of water, brought to a pH of 5-6 with lM HCl, and extracted with methylene chloride (2 X 50 mL) and ethyl acetate (1 X 50 mL). The combinçd organics were washed with saturated sodium W095/18795 2 1 7 6 5 Q ~ PCT/US9-~/14848 chloride solution (1 X 50 rnL), dried (sodium sulfate), filtered, and concentrated to give 0.57--g of a yellow oil, which was purified on a preparative HPLC (Clg column), eluting with 90%
CH3CN/10% H2O. This gave 63 mg of the product as a colorless oil.
Tn~cticide and Miticide Utility The compounds of formulas (1) and (2) show activity against a number of insects and mites. More specifically, the compounds show activity against melon aphid, which is a member of the insect order Homoptera. Other members of the Homoptera include leafhoppers, planthoppers, pear pyslla, apple sucker, scale insects, whiteflies, spittle bugs as well as numerous other host speci~lc aphid species. Activity- has also been observed against lo greenhouse thrips, which are members of the order Thysanoptera. The compounds also show activity against Southern al,llywol,ll, which is a member of the insect order Lepidoptera.
Other typical members of this order are codling moth, cutworm, clothes moth, Tn~ nme~l moth, leaf rollers, corn e~ wollll, European corn borer, cabbage worm, cabbage looper, cotton bollworm, bagworm, eastern tent caterpillar, sod webwol~ll, and fall armyworm.
The col"poullds of formulas (1) and (2) are useful for reducing populations of insects and mites, and are used in a method of inhibiting an insect or mite population which comprises applying to a locus of the insect or mite an effective insect- or mite-inactivating amount of a compound of formula (1). The "locus" of insects or mites is a term used herein to refer to the en vi~`~nnlel~t in which the insects or mites live or where their eggs are present, including the air surrounding them, the food they eat, or objects which they contact. For example, plant-ingesting insects or mites can be controlled by applying the active colllpoulld to plant parts, which the insects or mites eat, particularly the foliage. It is con~lllplated that the compounds might also be useful to protect textiles, paper, stored grain, or seeds by applying an active compound to such snbst~n~e. The term "inhibiting an insect or mite" refers to a decrease in the llulllbel~ of living insects or mites; or a decrease in the number of viable insect or mite eggs. The extent of reduction accomplished by a compound depends, of course, upon the application rate of the compound, the particular compound used, and the target insect or mite species. At least an insect-inactivating or mite-inactivating amount should be used. The terms "insect-inactivating amount" and "mite-inactivating amount" are used to describe the amount, which is sufficient to cause a l~lea~ulable reduction in the treated insect or mite population. Generally an amount in the range from about 1 to about 1000 ppm active compound is used.
Some of the above irl~.ntifi~cl compounds were tested for insecticidal, miticidal and nematicidal activity against eight species. Results are reported in the following table, wherein the following abbreviations are used:
ALH refers to aster leafhopper BAW refers to beet ~Illy CA refers to cotton aphid ~wo 95/18795 2 ~ 7 6 5 ~ 1 PCTIUS94/14848 NEM refers to peanut rootknot nematode SCRW refers to southern corn rootworm TBW refers to tobacco budworm TSSM refers to two spotted spider mite GECR refers to German cockroach In conducting evaluations of insecticidal activity, each test compound was fnrm~ ted as a 400 ppm solution, and this solution was then diluted with water to give lesser concentrations. The 400 ppm solution was prepared by comhining 19.2 mL of .05%
solution of Tween 20 (polyoxyethylene (20) sorbitan monolaurate) in water with a solution of 8 mg of the compound in .8 mL of acetone/EtOH (9/1).
Activity against aster leafhopper (Macrosteles fascifrons) was tested as follows. The test was run using concentrations of 400 ppm and 50 ppm. One ounce plastic cups cont~ining a cotton wick was sprayed with 0.4 mL of fnrm~ tç(l m~tPri~l using a flat-fan nozzle. The excess moisture was allowed to evaporate. Then five to ten carbon dioxide anestheti7e~ adult leafhoppers were added to each cup. The cups were capped and held at room L~ elalule for 24 hours. Percent mortality was then delr~ ;Ile~
Activity against beet ~ulllywolln (Spodoptera exiqua) was evaluated as follows. The test is run using concentrations of 400 ppm and 50 ppm. A general purpose lepidoptera artificial diet was diluted to half strength with a 5% non nutritive agar. 8 mL of this diet m~t~Pri~l was dispensed into one ounce diet cups. One hour prior to tre~tmPnt, 35 to 40 eggs were dispensed onto the diet surface. The cups were then sprayed with form~ ted m~tPri~l through a flat-fan nozzle. Treated cups were air dried prior to sealing with plastic caps. The cups were held for 6 days at room Lem~ Lule. Activity was then rated based on the total number of live and dead laIvae, and on the size of live larvae.
Activity against cotton aphid (Aphis gossypii) and two spotted spider mite (Tetranychus urticae) was evaluated as follows. Golden crookneck squash plants were grown to the e~r~n(1P~ cotyledon stage (about 6 to 8 days). The plants were infested with cotton aphids and two spotted spider mites 16 to 24 hours before application of the test m~tPri~l by transfer of infested foliage cut from a stock colony. TmmP~ tPly prior to spray application of 2s the test m~tPri~l the transfer foliage is removed from the squash plants. The test is run using concentrations of 400 ppm and 50 ppm. The plants are sprayed with test solution using an atomizing sprayer at 17 psi. Both surfaces of the leaves are covered until runoff, and then allowed to dry. Activity of each compound was dr,lrl ."i"~ three days after LI~II~PII;.
Activity was rated as a percent based on the mites/aphids present in plants sprayed with solvent alone.
Activity against peanut root knot nematode (Meloidogyne arenaria) was evaluated as follows. Five u~ ;aL~d ~;u~:umbel seeds are placed into the bottom of a clear one ounce cup, 20 g of clean white sand is added, and the cups were sprayed while rotating on a pedestal allowing 1.0 mL of a 400 ppm solution to be deposited on the sand. To each cup was WO 95/18795 2 ~ 7 6 5 0 ~ PCT/IJS94/14848 dispensed 2.5 to 3.0 m~ of deionized water containing 300 to 500 nematodes. The cups wer~
held for 10 to 12 days in an envi, om~ a/ .-wth chamber at a temperature of 76 to 85 F and ambient humidity of 50 to 60%. After 10 to 12 days the cups were evaluated by inverting the cup and observing nematode mortality and feeding damage to the cucumber plants.
s Activity on Southern corn rootworm (Diabro~ca undecimpuctata howardi Barber) was evaluated by adding one mL of test solution cont~ining a predetermined concentration of test compound to a cup con~ g a kernel of corn in 16 g of sterile soil. This produces a soil concentratio: ,rf 24 ppm. After 1.5 to 2 hours - ~ying, five 4th instar corn rootworm larvae were added to the individual cups. Mortality was measured at 3-4 days by emptying the cup onto a pan and inspecting the soil for live rootworms.
Activity against tobacco budworm (Heliothis virescens) was evaluated as follows. A
general purpose lepidoptera artificial diet was diluted to half strength with a 5% non nutritive agar. 8 mL of this diet m~t~.ri~l was dispensed into e. ~I one ounce diet cup. One hour prior to ~l~at~-e,l~t 18 to 20 eggs were dispensed onto the diet suIface. The cups were then sprayed with f~rm~ t~,d m~tt~ri~l through a flat-fan nozzle. The test was run using concentrations of 400 ppm and 50 ppm. Treated cups were air dried prior to sealing with plastic caps. The cups were held for 6 days at room tt~ t;ld~ulC;. Activity was then rated based on the total number of live and dead larvae, and on the size of live larvae.
Activity against German cockroach (Blattella gennanicus) was evaluated as follows. 8 mL of alfalfa based green insect diet m~teri~l was dispensed into a one ounce diet cup. The cups were then sprayed with formulated m~t~ri~l through a flat-fan nozzle. The test was run using concentrations of 400 ppm and 50 ppm. Treated cups were air dried for 24 hours and infested with five late third or early fourth instar Gerrnan cockroaches. The cups were capped and held for ten days in an envil o~ r~ l growth ch~mbto,r at a temperature of 76-85C.
2s Activity was then rated based on the total number of live and dead insects.

2~ 765~1 INSECTICIDE, ~TICIDE, AND NEMATICIDE DATA
(perce lt mortal ty) Al,H BAW CA RKN SCRWTBW TSSM GECR
Compound 400 400 400 400 400 400 400400 ppm ppm ppm ppm ppm ppm ppmppm æ loo loo loo loo o loo80 21 7G5at WO 9S/18795 PCTrUS94/14848 79 80 lO0 100 100 100 100.100 100 Nematicide Utility The compounds of the present invention are useful for reclllcing populations of nematodes. Accordingly, a ~ignific~nt aspect of the invention is a method of inhi~iting a nematode population which co,~ ises applying to a locus of a nematode an effective s nematode inactivating amount of a compound of formula (1) or (2). The term "inhibiting a nematode" refers to a decrease in the nllmhe.rs of living nematodes. ~he extent of reduction ~wo 95/18795 2 T 7 6 5 ~ t PCT/USg1/l4848 accomplished by a compound depends upon the application rate of the compound, the particular compound used, and the target species. At least a nematode-inactivating amount should be used. The term "nematode-inactivating amount" is used to describe the amount, which is sufficient to cause a measurable reduction in the treated nematode population.
The method is practiced in accordance with standard techniques for the application of nematicides. In general, good nematicidal activity can be expected at rates of 1-10 lbs/acre.
The compound can be formnl~t~d as described below in the Compositions section. When formul~tecl as ~i~p~r~ions, ~m~ticides are typically applied as aqueous drenches around growing plants or applied incle-llelllally via irrig~tinn systems. When applied as granules, nematicides may be incorporated into the soil before planting, or applied in a band on top of a seed row, or broadcast and then incorporated into the soil, or used as a side dressing to an established crop.
Fun~icide Utility The compounds of the present invention have been found to control fungi, particularly plant pathogens. When employed in the treatm~nt of plant fungal diseases, the compounds are applied to the plants in a disease inhihiting and phytologically acceptable amount. The term "disease inhibiting and phytologically acceptable amount," as used herein, refers to an amount of a compound of the invention which ki~ls or inhibits the plant disease for which control is desired, but is not cignific:~ntly tox* to the plant. This amount will generally be from about 1 to 1000 ppm, with 10 to 500 ppm being p~c;r~ll ;d. The exact concentration of compound required varies with the fungal disease to be controlled, the type fnrmlll~tion employed, the method of application, the particular plant species, climate conditions and the like. A suitable application rate is typically in the range from .25 to 4 lb/A. The compounds of the invention may also be used to protect stored grain and other non-plant loci from fungal --re~ion.
Greenhouse Tests The following e~url; Inrl ,l.~ were performed in the laboratory to determine thefungici(l~l efficacy of the compounds of the invention.
The test compounds are formnl~tPcl for application by dissolving 8 mg of the compound into 2 mL of acetone, using ultrasonication if necessary. A O.S mL aliquot of (8mg/2mL) sample is removed to a second cont~in~r, leaving 6mg/l.S mL in the first cont~iner 1.5 mL of acetone is added to the second container, the contents are mixed, and a O.S mL aliquot of (2mg/2mL) sample is removed to a third container, leaving 1.5mg/1.5mL in the second c-)nt~in~r. l.S mL of acetone is added to the third container, the contents are mixed, and a 0.5 mL aliquot of (O.Smg/2mL) sample is removed to a fourth container, leaving 0.375mg/l.SmL in the third container. l.S mL of acetone is added to the fourth container, the contents are mixed, and a 0.5 mL aliquot is removed and discarded, leaving 0.09375 mg/l.SmL in the fourth container. To each of the four contS~iners is added 13.5 mL of a 2 ~ 7G5 Q ~
WO 95/1879~ PCItUS94/14848 110ppm solution of Triton X 100 in water. Final formulations contain 10% acetone, 100 pp Triton X 100, and 400, 100, 25, and 6.25 ppm of test compound.
The form~ te-1 test compounds were applied by foliar s~ ly. The following plant pathogens and their co,le~onding plants were employed.
Pathogen Design~tiQn Host in following Table Erysiphegraministritici (powderymildew)ERYSGT wheat Pyriculariaoryzae (rice blast) PYRIOR rice Puccinia recondita tritici (leaf rust) PUCCRT wheat Leptosphaeria nodorum (glume blotch) LEPINO wheat Plasmopara viticola (downy mildew) PLASVI grape The formnl~te~ teçhnic~l compounds were sprayed on all foliar surfaces of the host plants (or cut berry) to past run-off. Single pots of each host plant were placed on raised, revolving pedestals in a fume hood. Test solutions were sprayed on all foliar snrf~ps All e~ were allowed to dry and the plants were inoculated with the a~lu~"iate pathogens within 2-4 hours.
The following table ~re~;~ the activity of typical compou"ds of the present invention when evaluated in this exp~rim~nt The effectiveness of test compounds in controlling disease was rated using the following scale.
0 = not tested against specific organism - = 0-19% control at 400 ppm + = 20-89% control at 400 ppm ++ = 90-100% control at 400 ppm +++ = 90-100% control at 100 ppm ~UNGIC~D~ DATA
COMPOUND ERYSGT PYRIOR PUCCRT LEPI-NO P,. ~SVI
NUl!~ER
+ + + +
+ + ++ ++ ++
+++ + ++ ++ ++
+ + +++ +++ +
+ + +
++++ + +++ ++
+ + + +++
+++++ + +++ +++
+++ +++ ++ ++ +++
:. ~ +++ +++ ++ ++ +++
::+++ ++ ++ +++ +
:,. +++ ++ ++ +++ +++

~+ + + + + + +

W095/1879S 2 ~ 7 6 ~ 3 I PCT~S94/14848 COMPOUND ERYSGT PYRIOR PUCCRT LEPTNO PLASVI
NI~L ER
:' ++ + + ++ ++
:
,. + + ++ ++ +++
+ ++ ++ ++ ++
o ++ ++ ++ +
a ++ ++ ++ ++
2l~ ++
+ + + + + + +
_. .
', O O O O
,, " + ++ +~ +
,, ~, + ++ ++ ++

+ +
+ + + ++ +_+
~ ~)+++ ++ ++ +
:: ++ + + +
: ~ ++ ++ ++ +++ ~, :: - +
. ~ + +++ ++ +
+ ++ ++
+ + +
~ ++ +++ +++
~ ~ +++ +++ ++ ~, ~- . + + ++ ++
+++ ++ ++
~- ++ ++ ++ ++
~ +++ ++ ++ +
,, +++ ++ ++ + "
~ +++ ++ ++ +
~ + ~
+++ ++ ++ ++
+++ + ++ + ., + + ++ +
+++ ++ ++ ++
~' O O O O
: ++ ++ ++ +++ +++
~, + +++
, +++ ++ ++ +++ ++
: ~ + + ++ +++ +++
+ + ++ ++ +++
~ ++ ++ ++ +++ +++
t~ +++ +++ ++ +++ +++
~ + ++ O ++ ++
6~ +++ + ++ +++ +++
+++ + ++ +++ +++
+ + +
., +++ +++ ++ ++ +++
+++ +++ ++ +++ +++
_. +++ +++ ++ +++ +++
_, +++ ++ ++ +++ +++

WO 95/18795 ~? l 7 6 5 0 tPCT/US94/14848 COMPOUND ERYSGT PYR7.0R PUCCRT LEEYrNO PLASVI
N~ER
_, ++ + ++ +++ +++
_ +

+ + ++ +
+ + + + + + + + + + +
Compositions The c- ~lpounds of formula (1) or (2) are applied in the form of compositions which are important embo-7imçnt~ of the invention, and which comprise a compound of formula (1) or (2) and a phytologica7,1y-accep ~ inert carrier. The compositions are either concenL aled s forn7lllslt70ns which are dispersec ~ lter for application, or are dust or granular forml7l;7tion~
which are applied without further tre~tm~-nt The compositions are prepared according to procedures and formulae which are conventional i- -e agricultural chemical art. but which are novel and important because of the presence there . ~f the compounds of thi~ ntion.
Some description of the formulation of the compositions will be given, howe~ ~ ~ assnre 10 that agricultural chçmi~tc can readily prepare any desired composition.
The dispersions in which the compounds are applied are most often aqueous suspensions or emulsions prepared from concentrated fnrmnls7tions of the compounds. Such water-soluble, water-su~pen-lS ble or ~-mnl~ifislble fnrmnlsltit)ns are either solids usually known as wettable powders, or liquids usually known as çmnl~ifislhle concenLl~tes or aqueous ls suspen~ic ns Wettable powders, which may be compacted to form water dispersible grslnlllçc, comprise an i.~l;,..~lr mixture of the active compound, an inert carrier and surfactants. The concentration of the active compound is usually fromi about 10% to about 90% by weight. The inert carrier is usually chosen from among the attapulgite clays, th~
montmnrillonite clays, the ~lisltomslreous earths, or the purified ~ilicsltes Effective sl~rfactsint 20 comprising from about 0.5% to about 10% of the wettable powder, are found among the sulfonated lignins, the con-lçn~e~l naphths lençslllfonates~ the naphthS~leneslllfonates, the alkylbçn7çnçsl-lfonates, the alkyl sulfates, and non-ionic surfactants such as ethylene oxide adducts of alkyl phenols.
Fmnl~ifi~ble concenLI~Les of the compounds comprise a convenient concentration of a 2s compound, such as from about 50 to about 500 grams per liter of liquid, equivalent to about 10% to about 50%, dissolved in an inert carrier which is either a water miscible solvent or a mixture of water-immiscible organic solvent and em--l~ifi~rs. Useful organic solvents include aromatics, especially the xylenes, and the petroleum fractions, especially the high-boiling naphth~lenic and olefinic portions of petroleum such as heavy aromatic naphtha. Other 30 organic solvents may also be used, such as the terpenic solvents incllltlin~ rosin derivatives, aliphatic ketones such as cycloheY~n- ne, and complex alcohols such as 2-ethoxyethanol.
Suitable ~mnl~ifiers for omnl~ifi~le concentr~t~s are chosen from conventional nonionic surfactants, such as those discussed above.

2 ~ 765~ 1 ~WO 95/18795 PCT/US94114848 Aqueous suspensions comprise suspensions of water-insoluble compounds of this invention, dispersed in an aqueous vehicle at a concentration in the range from about 5% to about 50% by weight. Suspensions are prepared by finely grinding the compound, and vigorously mixing it into a vehicle comprised of water and s surfactants chosen from the same types discussed above. Inert ingredients, such as inorganic salts and synthetic or natural gums, may also be added, to increase the density and viscosity of the aqueous vehicle. It is often most effective to grind and mix the compound at the same time by pr~a.illg the aqueous mixture, and homogenizing it in an implement such as a sand mill, ball mill, or piston-type homogeniær.
The compounds may also be applied as granular compositions, which are particularly useful for applications to the soil. Granular compositions usually contain from about 0.5% to about 10% by weight of the compound, dispersed in an inert carrier which consists entirely or in large part of clay or a sirnilar inexpensive sllhst~nce Such compositions are usually prepared by dissolving the compound in a suitable solvent, and applying it to a granular carrier which has been pre-formed to the ~ opliate particle size, in the range of from about 0.5 to 3 mm. Such compositions may also be form~ tçd by making a dough or paste of the carrier and compound, and crushing and drying to obtain the desired granular particle size.
Dusts cont~ining the compounds are prepared simply by intim:~tçly mixing the compound in powdered form with a suitable dusty agricultural carrier, such as kaolin clay, ground volcanic rock and the like. Dusts can suitably contain from about 1% to about 10% of the compound.
It is equally practical, when desirable for any reason, to apply the compound in the form of a solution in an ~ liale organic solvent, usually a bland petroleum oil, such as the spray oils, which are widely used in agricultural chemistry.
2s Insecticides and mitici~es are generally applied in the form of a (li~p-orci(ln of the active ingredient in a liquid carrier. It is conventional to refer to application rates in terms of the concentration of active ingredient in the carrier. The most widely used carrier is water.
The compounds of formula (1) and (2) can also be applied in the form of an aerosol composition. In such compositions the active compound is dissolved or dispersed in an inert carrier, which is a pressure-gen~,ldLillg propellant mixture. The aerosol composition is pa~k~gçd in a container from which the mixture is tli~p~n~çcl through an aL~ ing valve.
Propellant lni~LulGs comprise either low-boiling halocarbons, which may be mixed with organic solvents, or aqueous suspensions pressurized with inert gases or gaseoushydrocarbons.
The actual amount of compound to be applied to loci of insects and mites is not critical and can readily be ~irlr~ d by those skilled in the art in view of the çY~mrlçs above. In general, concentrations of from 10 ppm to 5000 ppm of colll~oulld are expected to provide good control. With many of the compounds, concçntr~tions of from 100 to 1500 ppm will suffice. For field crops, such as soybeans and cotton, a suitable application rate for the 2 1 ~5q 1 WO 95/18795 PCT/US9~/14848 compounds is about 0.5 to 1.5 lb/A, typically applied in 50 gal/A of spray ft~rm~ tion containing 1200 to 3600 ppm of compound. For citrus crops, a suitable application rate is from about 100 to 1500 gaVA spray formulation, which is a rate of 100 to 1000 ppm.
The locus to which a compound is applied can be any locus inhabited by an insect or 5 arachnid, for example, vegetable crops, fruit anc - t trees, grape vines, and orn~nlent~l plants. Tn~m~ch as many mite species are speciI~-; to a particular host, the foregoing list of mite species provides exemplification of the wide range of settings in which the present compounds can be used.
Because of the unique ability of mi eggs to resist toxicant action, repeated 10 applications may be desirable to control ne ~. ~y emerged larvae, as is true of other known acaricides.
The following formulations of compounds of the invention are typical of compositions useful in the practice of the present invention.
A. 0.75 Emulsifiable Concentrate Compound of formula (1) or (2) 9.38%
"TOXIMUL D" (nonionic/anionic slmf~t:~nt blend) 2.50%
"TOXIMUL H" (nonionic/anionic surfactant blend) 2.50%
"EXXON 200"( n~phth~l~nic solvent) 85.62%

B. 1.5 Emulsifiable Concentrate Compound of formula (l)or (2) 18.50%
"TOX[MUL D" 2.50%
"TOXIMUL H" 2.50%
"EXXON 200" 76.50%

C. 1.0 Emnl~ifiable Concentrate Compound of formula (1) or (2) 12.50%
N~ ;lllyl~yllolidone 25.00%
"TOXIMUL D" 2.50%
"TOXIMUL H" 2.50%
"EXXON 200" 57-50%

o~
~WO 95/18795 PCT/US94/14848 D. l.Q Aqueous Suspension Compound of formula (1) or (2) 12.00 "PLURONIC P-103" 1.50%
(block copolymer of propylene oxide and ethylene oxide, surfactant) s "PROXEL GXL" (biocide/preservative) .05%
"AF-100" (siliconbasedantifoamagent) .20%
"REAX 88B" (lignosulfonate dispersing agent) 1.00%
propylene glycol 10.00 veegum .75%
x~nth~n .25%
water 74.2 E. 1.0 A~ueous Sus~ension Compound of formula (1) or (2) 12.50 "MAKON 10" (10 moles ethyleneoxide nonylphenol surfactant) 1.00%
"ZEOSYL 200" (silica) 1.00%
"AF-100" . 0.20%
"AGRIWETFR" (surfactant) 3.00%
2% xanthan hydrate 10.00 water 72.30 F. 1.0 A~ueous Suspension Compound of formula (1) or (2) 12.50 "MAKON 10" 1.50%
2s "ZEOSYL 200" (silica) 1.00%
"AF-100" 0.20%
"POLYFON H" 0.20%
(lignosulfonate dispersing agent) 2% xanthan hydrate 10.00 water 74.60 G. Wettable Powder Compound of formula (1) or (2) 25.80 "POLYFON H" 3.50%
"SELLOGEN HR" 5.00%
"STEPANOL ME DRY" 1.00%
gum arabic 0.50%
"HISIL 233" 2.50%
Barden clay 61.70 ~ 1 7650 1 H. Granules Compound of formula (l)or (2) 5.0%
propylene glycol 5.0%
Exxon 200 5.0%
Florex 30/60 granular clay 85.0%

Claims (13)

1. A compound of the formula (1) or (2):

and N-oxides and salts thereof, wherein R1 is H, (C1-C4)alkyl, (C3-C4) branched alkyl, (C3-C7) cycloalkyl, (C2-C4) alkenyl, (C3-C4) branched alkenyl, halo(C1-C4)alkyl, (C1-C4)alkoxy, (C1-C4)alkoxy(C1-C4)alkyl, halo(C1-C4)alkoxy, (C1-C4)alkylthio, (C1-C4)alkylsulfonyl, (C1-C4)alkylsulfinyl, halo, or phenyl;
R2 is H, (C1-C4)alkyl, (C3-C4) branched alkyl, (C1-C4)alkanoyl, halo(C1-C4)alkyl, (C1-C4)alkoxymethyl, CH2SiR9R10R11, hydroxymethyl, benzyl, (C3-C6) cycloalkylmethyl, or , where R9,R10 and R11 are independently (C1-C4) alkyl, (C3-C4) branched alkyl, phenyl, or substituted phenyl, each T is independently O or S, and R6 and R7 are independently (C1-C4) alkyl, (C3-C4) branched alkyl, phenyl, or substituted phenyl;
Y is (1) -CH2-, optionally substituted with (C1-C4) alkyl, (C2-C4) alkenyl, (C2-C4)alkynyl, branched (C3-C7) alkyl, (C3-C7) cycloalkyl, (C3-C7) cycloalkenyl, halo, halo (C1-C4) alkyl, halo (C1-C4) alkoxy, hydroxy, CN, (C1-C4) alkanoyl, (C1-C4) alkoxycarbonyl, aryloxycarbonyl, where aryl is as defined below, hydroxy (C1-C4) alkyl, (C1-C4) alkoxy (C1-C4) alkyl, or (2) , where R27 and R28 are independently selected from H, (C1-C4) alkyl, (C1-C4) alkoxy, SH, S-lower alkyl, NH2, NH-lower alkyl, N,N-di-lower alkyl, O-lower alkyl, OH, morpholino, piperidinyl, pyrrolidinyl, thiomorpholino, or R27 and R28 combine to form part of a (C5-C6) saturated or unsaturated ring optionally including 1 or 2 hetero atoms selected from O, S, or NR5, where R5 is H, (C1-C4)alkyl, or (C1-C4)alkanoyl;
Z is (1) (C3-C8) cycloalkyl or cycloalkenyl, optionally substituted with one or more groups independendy selected from (C1-C4) alkyl, (C1-C4) alkoxy, halo (C1-C4) alkyl, halo (C1-C4) alkoxy, halo, hydroxy, or (C1-C4) alkanoyl; or (2) aryl, where aryl is (a) a phenyl group optionally substituted with one or more groups independently selected from:
halo, (C3-C8) cycloalkyl, (C3-C8) cycloalkenyl, phenoxy, substituted phenoxy, phenylthio, substituted phenylthio, phenyl, substituted phenyl, NO2, O
¦
--C-R8,where R8 is (C1-C7) alkyl, halo (C1-C7) alkyl, (C3-C7) branched alkyl, halo (C3-C7) branched alkyl, (C3-C7) cycloalkyl, halo (C3-C7) cycloalkyl, (C1-C7) alkoxy, hydroxy, phenyl, substituted phenyl, phenoxy, or substituted phenoxy, O
¦
--O-C-R8, wherein R8 is defined as above, except that hydroxy is excluded, OH, CN, SiR9R10R11 or OSiR9R10R11, where R9, R10 and R11 are independently (C1-C4) alkyl, (C3-C4) branched alkyl, phenyl, or substituted phenyl, NR12R13, where R12 and R13 are independently H, (C1-C4) alkyl, or (C1-C4) alkanoyl, S(O)R14, SO2R14, or OSO2R14, where R14 is (C1-C10) alkyl, phenyl, or substituted phenyl;
a (C1-C12)saturated or unsaturated hydrocarbon chain, straight chain or branched optionally including a hetero atom selected from O, S, SO, SO2, NR5, orSiR6R7, where R5, R6 and R7 are as defined above, and optionally substituted with halo, halo (C1-C4) alkoxy, hydroxy, (C3-C8) cycloalkyl or cycloalkenyl, (C1-C4) alkanoyl, phenoxy, substituted phenoxy, phenyl, substituted phenyl, phenylthio, substituted phenylthio, or cyano;
(C1-C7) alkoxy optionally substituted with halo, phenyl, substituted phenyl, (C3-C8) cycloalkyl or cycloalkenyl, phenoxy, or substituted phenoxy; or (C1-C7) alkylthio optionally substituted with halo, phenyl, substituted phenyl, (C3-C8) cycloalkyl or cycloalkenyl, phenoxy or substituted phenoxy;
b) a furyl group of formula (3) (3) where R15 is H, halo, halomethyl, CN, NO2, (C1-C4) alkyl, (C3-C4) branched alkyl, phenyl, (C1-C4) alkoxy;
(c) a thienyl group of the formula (4) (4) where R16 is H, halo, halomethyl, CN, NO2, (C1-C4) alkyl, (C3-C4) branched alkyl, phenyl, (C1-C4) alkoxy, or thienyl;
(d) a group of formula (5) or (6) (5) (6) where R15 is as defined in paragraph (b), J is N or CH, and G is O, NR17, or S, provided that if J is not N then G is NR, where R17 is H, (C1-C4) alkyl, (C1-C4) alkanoyl, phenylsulfonyl, or substituted phenylsulfonyl;
(e) a group selected from optionally substituted naphthyl, dihydronaphthyl, tetrahydronaphthyl, and decahydronaphthyl;
optionally substituted indolyl;
1,3-benzodioxolyl;
2,6-dimethyl-4-morpholinyl; and (f) a group of the formula wherein m is 4; each R20 is independendy H, halo, lower alkyl, lower alkoxy, haloalkyl, haloalkoxy, NO2, CN, lower alkyl carbonyl, S(O)R14, SO2R14, or OSO2R14, phenoxy, or substituted phenoxy, where R14 is (C1-C10) alkyl, phenyl, or substituted phenyl; provided that at least two of R20 are selected from H and F; and Het is pyridinyl, pyrazinyl, pyrimidinyl, or pyridazinyl, optionally substituted with one or more groups selected from halo, lower alkyl, lower alkoxy, haloalkyl, haloalkoxy, NO2, CN, and lower alkyl carbonyl;
(g) a group of the formula wherein one of X2 and X3 is N and the other is CR23;

R21 is -T-R22, phenyl, substituted phenyl, (C1-C10) alkyl, halo, or halo (C1-C8)alkyl, where T is O or S, and R22 is (C1-C4) alkyl, (C3-C7) branched alkyl, halo (C1-C7) alkyl, halo (C3-C7) branched alkyl, (C1-C4) alkoxy (C1-C4) alkyl, or naphthyl or phenyl, either of which may be optionally substituted with up to three groups selected from halo, (C1-C10) alkyl, branched (C3-C7) alkyl, halo (C1-C7) alkyl, hydroxy (C1-C7) alkyl, (C1-C4) alkoxy, halo (C1-C4) alkoxy, phenoxy, substituted phenoxy, phenyl, substituted phenyl, CN, NO2, OH, (C1-C4) alkanoyloxy, or benzyloxy;
R23 is:
H, halo, (C3-C8) cycloalkyl, (C3-C8) cycloalkenyl, phenoxy, substituted phenoxy, phenylthio, substituted phenylthio, phenyl, substituted phenyl, NO2, O
¦¦
--C-R8, where R8 is (C1-C7) alkyl, halo (C1-C7) alkyl, (C3-C7) branched alkyl, halo (C3-C7) branched alkyl, (C3-C7) cycloalkyl, halo (C3-C7) cycloalkyl, (C1-C7) alkoxy, phenyl, substituted phenyl, or hydroxy, acetoxy, OH, CN, SiR9R10R11 or OSiR9R10R11, where R9,R10 and R11 are independently (C1-C4) alkyl, (C3-C4) branched alkyl, phenyl, or substituted phenyl, NR12R13, where R12 and R13 are independently H, (C1-C4) alkyl, or (??-C4) alkanoyl, S(O)R14, or SO2R14, where R14 is (C1-C10)alkyl, phenyl, or substituted phenyl;
a (C1-C12) saturated or unsaturated hydrocarbon chain, straight chain or branched optionally including a hetero atom selected from O, S, SO, SO2, NR5, orSiR6R7, where R5, R6 and R7 are as defined above, and optionally substituted with halo, halo (C1-C4) alkoxy, hydroxy, (C3-C8) cycloalkyl or cycloalkenyl, (C1-C4) alkanoyl, phenoxy, substituted phenoxy, phenyl, substituted phenyl, phenylthio, substituted phenylthio, or cyano;
(C1-C7) alkoxy optionally substituted with halo, phenyl, substituted phenyl, (C3-C8) cycloalkyl or cycloalkenyl, phenoxy, or substituted phenoxy; or (C1-C7) alkylthio optionally substituted with halo, phenyl, substituted phenyl, (C3-C8) cycloalkyl or cycloalkenyl, phenoxy or substituted phenoxy;
or Y-Z together form a (C2-C11) saturated or unsaturated hydrocarbon chain, straight chain or branched;
W is O, S(O)y, wherein y is an integer from 0 to 2, or NR24, where R24 is H, OH,(C1-C4) alkyl, (C1-C4) alkoxy, aryl, (C1-C4) alkanoyl, NR25R26, benzyl, or benzyl optionally substituted with (C1-C4) alkyl, (C1-C4) alkoxy, halo, halo (C1-C4) alkyl, and R25 and R26 are independently H, (C1-C4) alkyl, aryl, alkanoyl, or together form with nitrogen a saturated (C3-C7) ring such as morpholino, piperidinyl, pyrrolidinyl;
G is (C1-C4) alkyl, aryl, (C1-C4) alkanoyl, NR25R26, deuterio (C1-C4) alkyl, halo (C1-C4) alkyl, benzyl, or benzyl optionally substituted with (C1-C4) alkyl, (C1-C4) alkoxy, halo, or halo (C1-C4) alkyl, where R25 and R26 are as defined above; or W-G together are halo, SH, or NR25R26 where R25 and R26 are as defined above;
provided that the following compound is excluded:
(1) the compound of formula 1 wherein R1 and R2 are H, and Y-Z together form t-butyl.

2. A compound of claim 1 wherein Y is -CH2-.

3. A compound of claim 1 wherein Z is aryl.

4. A compound of claim 3 wherein Z is substituted phenyl.

5. A compound of claim 4 wherein Z is phenyl substituted with a halo(C1-C4)alkoxy group.

6. A compound of claim 4 wherein Z is phenyl substituted with a phenoxy or substituted phenoxy group.

7. A compound of claim 4 wherein the phenyl group is substituted in the 4-position.

8. A compound of claim 4 having the formula (1A) (1A) where R1 is alkyl; and R29 is an electron withdrawing group selected from the group consisting of halo, halo(C1-C4)alkyl, (C1-C4) alkanoyl, CN, and NO2.

9. A compound of claim 8 wherein R1 is ethyl and R29 is CF3, CN, or Cl.

10. A pesiticidal composition which comprises a compound of claim 1 in combination with a phytologically acceptable carrier.

11. A method of inhibiting a nematode population which comprises applying to the locus of a nematode, a nematode inactivating amount of a compound of claim 1.

12. A method of inhihiting an insect or mite population which comprises applying to the locus of the insect or arachnid an effective insect or mite inactivating amount of a compound of claim 1.

13. A method of inhibiting plant pathogens which comprises applying an effective amount of a compound of claim 1 to a locus of the pathogen.