US 2006/0135504 A1 · N-(substituted arylmethyl)-4-(disubstituted methyl) piperidines and pyridines

Abstract

It has now been found that certain novel N-(substituted aryl)-4(disubstituted methyl)piperidine and pyridine derivatives have provided unexpected insecticidal activity. These compounds are represented by formula (I): wherein m, n, q, r, and s are independently selected from 0 or 1; and p is 0, 1, 2, or 3; A is C or CH; and B, D, E, R, R1, R2, R3, R4, R5, R6, R7 and R8 are fully described herein. In addition, compositions comprising an insecticidally effective amount of at least one compound of formula I, and optionally, an effective amount of at least one of a second compound, with at least one insecticidally compatible carrier are also disclosed; along with methods of controlling insects comprising applying said compositions to a locus where insects are present or are expected to be present.

A compound of formula I

wherein;
m, n, q, r, and s are independently selected from 0 or 1;
and p is 0, 1, 2, or 3;
A is selected from C and CH, forming a six-membered azine ring selected from piperidine, 1,4-dihydropyridine, and 1,2,5,6-tetrahydropyridine;
R2, R3, R4, R5, and R6 are independently selected from hydrogen, halogen, alkyl, haloalkyl, hydroxyl, alkoxy, haloalkoxy, pentahalothio, alkylthio, cyano, nitro, alkylcarbonyl, alkoxycarbonyl, aryl, or aryloxy, provided that at least one of R2, R3, R4, R5, and R6 are other than hydrogen;
and either of R2 and R3, or R3 and R4 may be taken together with —OCF2O—, —OCF2CF2—, —C2F2CO—, or —CH═CHCH═CH—, forming a benzo-fused ring;
and when,
(a) m and n are 0;
a double bond between methyl carbon (a) and the 4-position of the six-membered azine ring is formed,
where
B is phenyl substituted with R9, R10, R11, R12, and R13,
where
R9, R10, R11, R12, and R13 are independently selected from hydrogen, halogen, alkyl, haloalkyl, hydroxyl, alkoxy, haloalkoxy, mercapto, and alkylthio, cyano, alkylcarbonyl, alkoxycarbonyl, or aryloxy;
and, wherein either of R9 and R10, or R10 and R11 may be taken together with —OCF2O—, —OCF2CF2—, or —CF2CF2O—, forming a benzo-fused ring, and;
and when
(b) m is 1, and n is 0;
a double bond between methyl carbon (a) and the 4-position of the six-membered azine ring is formed,
where
B is a bridging group from methyl carbon (a) to R;
where
B is selected from O, S, *CH2O, *OCH2, OC(═O)O, *OC(═O)NR15, *NR15C(═O)O, *OC(═S)NR 5, *NR15C(═S)O, *OCH2C(═O)NR , *NR15C(═O)CH2O, *CH2OC(═O)NR15, *NR15C(═O)OCH2, *NR15CH2, *CH2NR15, *NR15C(═O), *C(═O)NR15, *NR15SO2, *SO2NR15, *NR15NHSO2, *SO2NHNR15, *OC(═O)NR15SO2, *SO2NR15C(=O)O, *OC(═O)NR15CHR16, *CHR16NR15C(=O)O, *NR15C(═O)NR16;
1,4-dioxycyclohexyl, or 4-oxypiperidin-1-yl, where the asterisk denotes attachment to the methyl carbon (a);
where
R15 and R16 are independently selected from hydrogen, alkyl, alkylaminocarbonyl, and arylcarbonyl wherein the aryl is optionally substituted with halogen, alkyl, alkoxy, haloalkyl, haloalkoxy, or nitro;
where
R is alkyl, cycloalkyl, alkenyl, or alkoxycarbonyl;
or
R is phenyl substituted with R17, R18, R19, R20, and R21;
or,
R is pyrid-2-yl substituted with R18, R19, R20, and R21,
or
pyrid-3-yl substituted with R17, R19, R20, and R21,
or
pyrid-4-yl substituted with R17, R18, R20, and R21,
or
pyridazin-3-yl substituted with R19, R20 and R21,
where
R17, R18, R19, R20, and R21 are independently selected from hydrogen, halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, cyano, nitro, alkylcarbonyl, alkoxycarbonyl, alkoxycarbonylamino, aryl, aryloxy, and 2-alkyl-2H-tetrazole, and, wherein either of R17 and R18, or R18 and R19 may be taken together with —CH2CH═CHCH2—, —OCF2O—, —OCF2CF2—, or —CF2CF2O—, to form a benzo-fused ring;
and when
(c) m and n are 1;
a single bond between methyl carbon (a) and the 4-position of the six-membered azine ring is formed;
where
B is a bridging group from methyl carbon (a) to R;
where
B is selected from 0, S, *CH2O, *OCH2, OC(═O)O, *OC(═O)NR15, *NR15C(═O)O, *OC(═S)NR15, *NR15C(═S)O, *OCH2C(═O)NR15, *NR15C(═O)CH2O, *CH2OC(═O)NR15, *NR15C(═O)OCH2, *NR15CH2, *CH2NR15, *NR15C(═O), *C(═O)NR15, *NR15SO2, *SO2NR15, *NR15NHSO2, *SO2NHNR15, *OC(═O)NR15SO2, *SO2NR15C(═O)O, *OC(═O)NR15CHR16, *CHR16NR15C(═O)O, *NR15C(═O)NR16;
1,4-dioxycyclohexyl, or 4-oxypiperidin-1-yl, where the asterisk denotes attachment to the methyl carbon (a);
where R15 and R16 are described above;
and,
R is alkyl, cycloalkyl, alkenyl, or alkoxycarbonyl;
or
R is phenyl substituted with R17, R18, R19, R20, and R21;
pyrid-2-yl substituted with R18, R19, R20, and R21;
pyrid-3-yl substituted with R17, R19, R20, and R21;
pyrid4-yl substituted with R17, R18, R20, and R21;
or pyridazin-3-yl substituted with R19, R20 and R21;
where R17, R18, R19, R20, and R21 are described above;
R1 is selected from hydrogen, alkyl, alkoxyalkyl, or aryl;
when p is 1, 2, or 3;
D is —CH2—, and an azabicyclo derivative of the six-membered azine ring is formed;
when q is 0, and r is 1, an N-oxide derivative of the six-membered azine ring nitrogen is formed;
when q is 1 and r is 0 or 1;
R7 is selected from alkyl, haloalkyl, hydroxyalkyl, alkoxyalkyl, dialkylaminoalkyl, alkylaminocarbonyloxyalkyl, alkylthioalkyl, alkylsulfonylalkyl, alkylcarbonyloxyalkyl, alkoxycarbonylalkyl, carboxyalkyl, arylalkyl, arylcarbonyl, sulfonato, or sulfonatoalkyl, and may bear a negative charge resulting in an inner salt;
and a separate ion is chloride, bromide, iodide, or an alkyl or phenyl sulfate or sulfonate;
when s is 0 or 1;
R8 is selected from hydrogen, alkyl, cycloalkyl, cycloalkylalkyl, alkoxy, alkoxyalkyl, amino, morpholinyl, optionally substituted indolyl, piperidinyl, optionally substituted (pyridyl)alkenyl, optionally substituted 1,2,3,4-tetrahydronaphthylenyl, optionally substituted arylpyrazolyl, benzo[b]thiophenyl, 5-hydropyridino[1,2a]pyrimidinonyl, optionally substituted 4-hydro-1,3-thiazolino[3,2a]pyrimidinonyl, 1,2,3,4-tetrahydroquinolinyl, 2-thioxo-1,3-dihydroquinazolinonyl, 1,3-dihydroquinazolindionyl, or benzo[c]azolindionyl, wherein the optional substituent is selected from halogen, alkyl, alkoxy, and nitro;
or
R8 is phenyl substituted with R22, R23, R24, R25, and R26,
or
pyrid-2-yl substituted with R23, R24, R25, and R26,
or
pyrid-3-yl substituted with R22, R24, R25, and R26
or
pyrid4-yl substituted with R22, R23, R25, and R26,
where
R22, R23, R24, R25, and R26 are independently selected from hydrogen, halogen, alkyl, hydroxy, alkoxy, alkoxyalkyl, dialkoxyalkyl, trialkoxyalkyl, alkoxyiminoalkyl, alkenyloxyiminoalkyl, alkynyloxyiminoalkyl, cycloalkylalkoxy, alkoxyalkoxy, alkylthio, dithioalkoxyalkyl, trithioalkoxyalkyl, alkylsulfonyl, alkylaminosulfonyl, dialkylaminosulfonyl, cycloalkylaminosulfonyl, alkenyloxy, alkynyloxy, haloalkenyloxy, alkylsulfonyloxy, optionally substituted arylalkoxy, cyano, nitro, amino, alkylamino, alkylcarbonylamino, alkoxycarbonylamino, alkenyloxycarbonylamino, alkynyloxycarbonylamino, haloalkylcarbonylamino, alkoxyalkoxycarbonylamino, (alkyl)(alkoxycarbonyl)amino, alkylsulfonylamino, optionally substituted (heteroaryl)(alkoxycarbonyl)amino, optionally substituted arylcarbonylamino, formyl, optionally substituted 1,3-dioxolan-2-yl, optionally substituted 1,3-dioxan-2-yl, optionally substituted 1,3-oxazolidin-2-yl, optionally substituted 1,3-oxazaperhydroin-2-yl, optionally substituted 1,3-dithiolan-2-yl, optionally substituted 1,3-dithian-2-yl, alkoxycarbonyl, alkylaminocarbonyloxy, alkylaminocarbonylamino, dialkylaminocarbonylamino, alkylamino(thiocarbonyl)amino, dialkylphosphoroureidyl, optionally substituted thienyl, optionally substituted 1,3-thiazolylalkoxy, optionally substituted aryl, optionally substituted aryloxy, optionally substituted aryloxyalkyl, optionally substituted arylaminocarbonyloxy, optionally substituted heteroaryl, optionally substituted heteroaryloxy, optionally substituted pyrrolyl, optionally substituted pyrazolyl, optionally substituted pyrazinyloxy. optionally substituted 1,3-oxazolinyl, optionally substituted 1,3-oxazolinyloxy, optionally substituted 1,3-oxazolinylamino, optionally substituted 1,2,4-triazolyl, optionally substituted 1,2,3-thiadiazolyl, optionally substituted 1,2,5-thiadiazolyl, optionally substituted 1,2,5-thiadiazolyloxy, optionally substituted 2H-tetrazolyl, optionally substituted pyridyl, optionally substituted pyridyloxy, optionally substituted pyridylamino, optionally substituted pyrimidinyl, optionally substituted pyrimidinyloxy, optionally substituted 3,4,5,6-tetrahydropyrimidinyloxy, optionally substituted pyridazinyloxy, or optionally substituted 1,2,3,4-tetrahydronaphthalenyl, wherein the optional substituent is selected from one or more of halogen, alkyl, haloalkyl, alkoxy, dialkoxyalkyl, dithioalkoxyalkyl, cyano, nitro, amino, or alkoxycarbonylamino, provided that at least one of R22, R23, R24, R25, and R26 is other than hydrogen;
when s is 1;
E is a bridging group selected from (CR27R28)x—(CR29R30)y—, (CR27R21)x—(CR29R30)yO*, C3H6, C4H8, , C(═O), C(═O)C2H*, C2H4C(═O)*, C3H6C(═O)*, C4H8NHC(═O)*, or C(═S)NH*, where the asterisk denotes attachment at R8,
where
x is 1;
y is 0, or 1;
and,
where R27, R28, R29, and R30 are independently selected from hydrogen, alkyl, and aryl optionally substituted with alkoxy;
N-oxides;
and
agriculturally-acceptable salts thereof.

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N-(substituted arylmethyl)-4-(disubstituted methyl) piperidines and pyridines

Life of this patent

N-(substituted arylmethyl)-4-(disubstituted methyl) piperidines and pyridines

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Abstract

Claims60