OA16402A - Pesticidal compositions and process related thereto. - Google Patents

Pesticidal compositions and process related thereto. Download PDF

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OA16402A
OA16402A OA1201300186 OA16402A OA 16402 A OA16402 A OA 16402A OA 1201300186 OA1201300186 OA 1201300186 OA 16402 A OA16402 A OA 16402A
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substituted
unsubstituted
alkyl
molécule
composition according
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OA1201300186
Inventor
Negar Garizi
Maurice C. H. Yap
Tony K. Trullinger
Casandra Lee Mcleod
Paul Renee Leplae
Timothy C. Johnson
Ricky Hunter
John F. Daeuble
Ann M. Buysse
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Dow Agrosciences Llc
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Abstract

This document discloses molecules having the following (formula one)

Description

PESTICIDAL COMPOSITIONS AND PROCESSES RELATED THERETO
CROSS REFERENCE TO RELATED APPLICATIONS
This application claims the benefit of U.S. Provisional Patent Application Serial No. 61/409,379 ftled November 3, 2010 the entire disclosure of which is hereby incorporated by reference.
FIELD OF THIS DISCLOSURE
This disclosure is related to the field of processes to produce molécules that are useful as pesticides (e.g., acaricides, insecticides, molluscicides, and nematicides), such molécules, and processes of using such molécules to control pests.
BACKGROUND
Pests cause millions of human deaths around the world each year. Furthermore, there are more than ten thousand species of pests that cause losses in agriculture. The world-wide agricultural losses amount to billions of U.S. dollars each year.
Termites cause damage to ail kinds of private and public structures. The world-wide termite damage losses amount to billions of U.S. dollars each year.
Stored food pests eat and adulterate stored food. The world-wide stored food losses amount to billions of U.S. dollars each year, but more importantly, deprive people of needed food.
There is an acute need for new pesticides. Certain pests are developing résistance to pesticides in current use. Hundreds of pest species are résistant to one or more pesticides. The development of résistance to some of the older pesticides, such as DDT, the carbamates, and the organophosphates, is well known. But résistance has even developed to some of the newer pesticides.
Therefore, for many reasons, including the above reasons, a need exists for new pesticides.
DEFINITIONS
The examples given in the définitions are generally non-exhaustive and must not be construed as limiting the invention disclosed in this document. It is understood that a substituent should comply with chemical bonding rules and steric compatibility constraints in relation to the particular molécule to which it is attached.
“Alkenyl means an acyclic, unsaturated (at least one carbon-carbon double bond), branched orunbranched, substituent consisting of carbon and hydrogen, for example, vinyl, allyl, butenyl, pentenyl, and hexenyl.
I “Alkenyloxy means an alkenyl further consisting of a carbon-oxygen single bond, for example, allyloxy, butenyloxy, pentenyloxy, hexenyloxy.
“Alkoxy means an alkyl further consisting of a carbon-oxygen single bond, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, and tert-butoxy.
“Alkyl means an acyclic, saturated, branched or unbranched, substituent consisting of carbon and hydrogen, for example, methyl, ethyl, (C3)alkyl which represents n-propyl and isopropyl), (C4)alkyl which represents n-butyl, sec-butyl, isobutyl, and fert-butyl.
“Alkynyl means an acyclic, unsaturated (at least one carbon-carbon triple bond), branched or unbranched, substituent consisting of carbon and hydrogen, for example, ethynyl, 10 propargyl, butynyl, and pentynyl,
Alkynyloxy means an alkynyl further consisting of a carbon-oxygen single bond, for example, pentynyloxy, hexynyloxy, heptynyloxy, and octynyloxy.
“Aryl means a cyclic, aromatic substituent consisting of hydrogen and carbon, for example, phenyl, naphthyl, and biphenyl,
I5 “(Cx-Cy) where the subscripts x and “y are integers such as 1,2, or 3, means the range of carbon atoms for a substituent - for example, (Ci-C4)alkyl means methyl, ethyl, npropyl, isopropyl, n-butyl, sec-butyl, isobutyl, and fert-butyl, each individually.
“Cycloalkenyl means a monocyclic or polycyclic, unsaturated (at least one carboncarbon double bond) substituent consisting of carbon and hydrogen, for example, cyclobutenyl, 20 cyclopentenyl, cyclohexenyl, norbornenyl, bicyclo[2,2.2]octenyl, tetrahydronaphthyl, hexahydronaphthyl, and octahydronaphthyl.
“Cycloalkenyloxy” means a cycloalkenyl further consisting of a carbon-oxygen single bond, for example, cyclobutenyloxy, cyclopentenyloxy, norbornenyloxy, and bîcyclo[2,2,2]octenyloxy, “Cycloalkyl” means a monocyclic or polycyclic, saturated substituent consisting of carbon and hydrogen, for example, cyclopropyl, cyclobutyl, cyclopentyl, norbornyl, bicyclo[2.2.2]octyl, and decahydronaphthyl.
“Cycloalkoxy means a cycloalkyl further consisting of a carbon-oxygen single bond, for example, cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, norbornyloxy, and bicyclo[2.2.2]octyloxy.
“Halo means fluoro, chloro, bromo, and iodo.
“Haloalkoxy means an alkoxy further consisting of, from one to the maximum possible number of identical or different, halos, for example, fluoromethoxy, trifluoromethoxy, 2,2difluoropropoxy, chloromethoxy, trichloromethoxy, 1,1,2,2-tetrafluoroethoxy, and pentafluoroethoxy.
I “Haloalkyl means an alkyl further consisting of, from one to the maximum possible number of, identical or different, halos, for example, fluoromethyl, trifluoromethyl, 2,2difluoropropyl, chloromethyl, trichloromethyl, and 1,1,2,2-tetrafluoroethyl.
Heterocyclyl means a cyclic substituent that may be fully saturated, partially unsaturated, or fully unsaturated, where the cyclic structure contains at least one carbon and at least one heteroatom, where said heteroatom is nitrogen, sulfur, or oxygen. In the case of sulfur, that atom can be in other oxidation states such as a sulfoxide and sulfone. Examples of aromatic heterocyclyls include, but are not limited to, benzofuranyl, benzoisothiazolyl, benzoisoxazolyl, benzoxazolyl, benzothienyl, benzothiazolyl, cinnolinyl, furanyl, imidazolyl, indazolyl, indolyl, isoindolyl, isoquinolinyl, isothiazolyl, isoxazolyl, oxadiazolyl, oxazolinyl, oxazolyl, phthalazinyl, pyrazinyl, pyrazolinyl, pyrazolyl, pyridazinyl, pyridyl, pyrimidinyl, pyrrolyl, quinazolinyl, quinolinyl, quinoxalinyl, tetrazolyl, thiazolinyl, thiazolyl, thienyl, triazinyl, and triazolyl. Examples of fully saturated heterocyclyls include, but are not limited to, piperazinyl, pïperidinyl, morpholinyl, pyrrolidinyl, oxetanyl, tetrahydrofuranyl, tetrahydrothienyl and tetrahydropyranyl. Examples of partially unsaturated heterocyclyls include, but are not limited to, 1,2,3,4-tetrahydroquinolinyl, 4,5-dihydro-oxazolyl, 4,5-dihydro-1H-pyrazolyl, 4,5-dihydroisoxazolyl, and Z.S-dihydro-fl.S^l-oxadiazolyl. Additional examples include the foliowing thietanyl
O thîetanyl-dioxide.
DETA1LED DESCRIPTION
This document discloses molécules having the foliowing formula (“Formula One):
R7 N
Formula One wherein (a) X is N or CR8;
i ι
(b) R1 is H, F, Cl, Br, I, CN, NO2, substituted or unsubstituted CrC6 alkyl, substituted or unsubstituted C2-C6 alkenyl, substituted or unsubstituted CrC0 alkoxy, substituted or unsubstituted C2-C6 alkenyloxy, substituted or unsubstituted C3-Cw cycloalkyl, substituted or unsubstituted C3-Cw cycloalkenyl, substituted or unsubstituted C6-C2o aryl, substituted or unsubstituted CrC20 heterocyclyl, OR9, C(=X1)R9, C(=X1)OR9, C(=X1)N(R9)2, N(R9)2, N(R9)C(=X1)R9, SR9, S(O)nOR9, or R9S(O)nR9, wherein each said R1, which is substituted, has one or more substituents selected from F, Cl, Br, I, CN, NO2, CrC6 alkyl, C2-C6 alkenyl, C^Cg haloalkyl, C2-C6 haloalkenyl, CrC6 haloalkyloxy, C2-Ce haloalkenyloxy, C3-Ci0 cycloalkyl, C3-C10 cycloalkenyl, C3-C10 halocycloalkyl, C3-Ci0 halocycloalkenyl, OR9, S(O)nOR9, C6-C20 aryl, or CrC2o heterocyclyl, (each of which that can be substituted, may optionally be substituted with R9);
(c) R2 is H, F, Cl, Br, I, CN, NO2, substituted or unsubstituted CrC6 alkyl, substituted or unsubstituted C2-C6 alkenyl, substituted or unsubstituted CrC6 alkoxy, substituted or unsubstituted C2-C6 alkenyloxy, substituted or unsubstituted C3-Ci0 cycloalkyl, substituted or unsubstituted C3-C10 cycloalkenyl, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted Ci-C20 heterocyclyl, OR9, C(=X1)R9, C(=X1)OR9, C(=X1)N(R9)2, N(R9)2, N(R9)C(=X1)R9, SR9, S(O)nOR9, or R9S(O)nR9, wherein each said R2, which is substituted, has one or more substituents selected from F, Cl, Br, I, CN, NO21 CrC6 alkyl, C2-C6 alkenyl, CrC6 haloalkyl, C2-C6 haloalkenyl, CrC6 haloalkyloxy, C2-C6 haloalkenyloxy, C3-C10 cycloalkyl, C3-C10 cycloalkenyl, C3-Cio halocycloalkyl, C3-Cio halocycloalkenyl, OR9, S(O)nOR9, Cg-C2o aryl, or Ci-C2o heterocyclyl, (each of which that can be substituted, may optionally be substituted with R9);
(d) R3 is H, F, Cl, Br, I, CN, NO2, substituted or unsubstituted CrC6 alkyl, substituted or unsubstituted C2-C6 alkenyl, substituted or unsubstituted CrC6 alkoxy, substituted or unsubstituted C2-C6 alkenyloxy, substituted or unsubstituted C3-Ci0 cycloalkyl, substituted or unsubstituted C3-C10 cycloalkenyl, substituted or unsubstituted C6-C2Q aryl, substituted or unsubstituted CrC2o heterocyclyl, OR9, C(=X1)R9, C(=X1)OR9, C(=X1)N(R9)2, N(R9)2, N(R9)C(=X1)R9, SR9, S(O)nOR9, or R9S(O)nR9, wherein each said R3, which is substituted, has one or more substituents selected from F, Cl, Br, I, CN, NO2, CrC6 alkyl, C2-C6 alkenyl, Ci-C6 haloalkyl. C2-C6 haloalkenyl, CrC6 haloalkyloxy, C2-C6 haloalkenyloxy, C3-C1D cycloalkyl, C3-C10 cycloalkenyl, C3-Ci0 halocycloalkyl, C3-C10 halocycloalkenyl, OR9, S(O)nOR9, C0-C2O aryl, or C^Cæ heterocyclyl, (each of which that can be substituted, may optionally be substituted with R9);
Λ t
(e) R4 is H, F, Cl, Br, I, CN, NO2, substituted or unsubstituted CrC6 alkyl, substituted or unsubstituted C2-C6 alkenyl, substituted or unsubstituted Ci-C6 alkoxy, substituted or unsubstituted C2-C6 alkenyloxy, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C3-C10 cycloalkenyl, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted Ci-Cæ heterocyclyl, OR9, C(=X1)R9, C(=X1)OR9, C(=X1)N(R9)2, N(R9)2, N(R9)C(=X1)R9, SR9, S(O)nOR9, or R9S(O)nR9, wherein each said R4, which is substituted, has one or more substituents selected from F, Cl, Br, I, CN, NO2, Ο,-Ο6 alkyl, C2-C6 alkenyl, CrC6 haloalkyl, C2-C6 haloalkenyl, Ci-C6 haloalkyloxy, C2-C6 haloalkenyloxy, C3-C10 cycloalkyl, C3-Cio cycloalkenyl, C3-C10 halocycloalkyl, C3-C10 halocycloalkenyl, OR9, S(O)n0R9, C6-C20 aryl, or CrC20 heterocyclyl, (each of which that can be substituted, may optionally be substituted with R9);
(f) R5 is H, substituted or unsubstituted C^Ce alkyl, substituted or unsubstituted C2C6 alkenyl, substituted or unsubstituted CrC6 alkoxy, substituted or unsubstituted C2-C6 alkenyloxy, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C3-C1Q cycloalkenyl, substituted or unsubstituted C6-C2Û aryl, substituted or unsubstituted CrC2o heterocyclyl, OR9, C(=X1)R9, C(=X1)OR9, C(=X1)N(R9)2, N(R9)2, N(R9)C(=X1)R9, SR9, S(O)nOR9, R9S(O)nR9, Ci-C6 alkyl C6-C20 aryl (wherein the alkyl and aryl can independently be substituted or unsubstituted), C(=X2)R9, C(=X1)X2R9, R9X2C(=X1 )R9, R9X2R9, C(=0)(CrC6 alkyl)S(O)n(CrC6 alkyl), C(=O)(CrC6 alkyl)C(=O)O(Ci-C6 alkyl), (CrC6 alkyl)OC(=O)(C6-C20 aryl), (Ci-Cg alkyl)OC(=O)(Ci-Cfj alkyl), Ci-Cg alkyl-(C3-Cio cyclohaloalkyl), or (Ci~C6 alkenyl)C(=O)O(C1-C6 alkyl), or R9X2C(=X1 )X2R9;
wherein each said R5, which is substituted, has one or more substituents selected from F, Cl, Br, I, CN, NO2, CrCe alkyl, C2-C6 alkenyl, CrC6 haloalkyl, C2-C6 haloalkenyl, Ci-C6 haloalkyloxy, C2-C6 haloalkenyloxy, C3-C10 cycloalkyl, C3-C10 cycloalkenyl, C3-C10 halocycloalkyl, C3-C10 halocycloalkenyl, OR9, S(O)nOR9, C6-C20 aryl, or 0,-0^ heterocyclyl, R9 aryl (each of which that can be substituted, may optionally be substituted with R9) optionally R5 and R7 can be connected in a cyclic arrangement, where optionally such arrangement can hâve one or more heteroatoms selected from O, S, or, N, in the cyclic structure connecting R5 and R7;
(g) R6 is O, S, NR9, or NOR9;
(h) R7 is substituted or unsubstituted C^Ce alkyl, substituted or unsubstituted C2-C6 alkenyl, substituted or unsubstituted Ci-C6 alkoxy, substituted or unsubstituted C2-C6
Λ
I alkenyloxy, substituted or unsubstituted C3-Cio cycloalkyl, substituted or unsubstituted C3-Cw cycloalkenyl, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted Ci-C2o heterocyclyl, OR9, OR9S(O)nR9, C(=X1)R9, C(=X1)OR9, R9C(=X1)OR9, R9X2C(=X1)R9X2R9, C(=X1)N(R9)2, N(R9)Z, N(R9)(R9S(O)nR9), N(R9)C(=X1)R9, SR9, S(O)nOR9, R9S(O)nR9, Ci-C0alkylOC(=O)C1-C6alkyl, 0CrC6 alkyl Ci-C20 heterocyclyl, Cr CealkylC,-C2o heterocyclyl, CrC6, alkylS^N-CNXCrCgalkyl), C1-C6alkylS(O)(=N-CN)(C1C6alkyl), Ci-CealkylS(0)n(Ci-C6alkylCi-C2oheterocyclyl), C1-CealkylS(O)(=N-CN)(C1-C6 alkyl-Cr C2oheterocyclyl), CrC6alkylNH(C(=O)OCi-C6 alkyl), Ci-Ce alkylC(=O)OCrC6 alkyl, Cr C6alkyl(C6-C20aryl)NH(C(=O)OC1-C6alkyl), Cf-CealkylfS-CrCg alkyl)NH(C(=O)OCrCealkyl), Cr C6alkyl(S-C1-C6alkyl-C6-CZ0aryl)NH(C(=O)OC1-C6alkyl), Ci-C6 aikyl(NHC(=O)OC1-CealkylC6-C20 aryl)NH(C(=O)OCi-C6alkyl), Ci-C0alkyl(OC1-C6alkylC6-Czoaryl)NH(C(=O)OC1-C6alkyl), Cr C6alkylN(Ci-C5alkyl)(C(=O)OCrC6alkyl), CrCealkylNHfCrCealkyl), Ce-CaoarylSCrCehaloalkyl, Ci-C0alkyl-N(Ci-C0 alkyl)(C(=O)Ci-C0alkylC0-C20aryl), Ci-C0alkylN(Ci-C0alkyl)(Ci-C0alkyl), C,CealkylNiCrCe alkylXSfOJnCrCe alkyl), CrC6 alkylN(CrCe alkyl)(S(O)nCrCe alkenylC6-CZ0aryl), Ci-C0 alkylNfC^Cg alkyl)(C(=O)Ci-C20 heterocyclyl), C1-C6alkylN(Cl-C6alkyl)(C(=O)OC1-C6 alkylC6O20aryl), ΝΗ(Ο,-ΟΘ alkylStO^CrCealkyl), NH(CrCe alkylS(O)nC6-C20aryl), Cr C0alkyl(S(O)nCrC0 alkyl)(C(=O)Cl-C6alkylS(O)fl(C1-C6 alkyl). or R9S(O)n(NZ)R9, wherein each said R7, which is substituted, has one or more substituents selected from F, Cl, Br, I, CN, NO2, CrCe alkyl, C2-C0 alkenyl, CrC0 haloalkyl, C2-C6 haloalkenyl, Ci-Ce haloalkyloxy, Cz-C6 haloalkenyloxy, C3-C10 cycloalkyl, C3-C10 cycloalkenyl, C3-C10 halocycloalkyl, C3-C10 halocycloalkenyl, OR9, S(O)nOR9, C6-C20 aryl, or CrC20 heterocyclyl, (each of which that can be substituted, may optionally be substituted with R9), C(=X1)R9, C(=X1)OR9, C(=X1)N(R9)Z, =X2, N(R9)2, S(=X2)nR9, R9S(O)nR9, S(O)nN(R9)z;
(i) R8 is H, F, Cl, Br, I, CN, NO2, substituted or unsubstituted CrC6 alkyl, substituted or unsubstituted C2-C6 alkenyl, substituted or unsubstituted CrC0 alkoxy, substituted or unsubstituted C2-Ce alkenyloxy, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C3-C10 cycloalkenyl, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted CrC20 heterocyclyl, OR9, C(=X1)R9, C(=X1)OR9, C(=X1)N(R9)Z, N(R9)2, N(R9)C(=X1)R9, SR9, S(O)nR9, S(O)nOR9, or R9S(O)nR9, wherein each said R8, which is substituted, has one or more substituents selected from F, Cl, Br, I, CN, NOZ, CrC0 alkyl, C2-C6 alkenyl, Ci-C0 haloalkyl, C2-C0 haloalkenyl, CrC6 haloalkyloxy, C2-C6 haloalkenyloxy, C3-Ci0 cycloalkyl, C3-C10 cycloalkenyl, C3-Cw halocycloalkyl, C3-C10 halocycloalkenyl, OR9, S(O)nOR9, C0-C2O aryl, or CrC20 heterocyclyl, (each of which that can be substituted, may optionally be substituted with R9);
G) R9 (each independently) is H, CN, substituted or unsubstituted CrC6 alkyl, substituted or unsubstituted C2-C6 alkenyl, substituted or unsubstituted Ο,-Ο6 alkoxy, substituted or unsubstituted C2-C6 alkenyloxy, substituted or unsubstituted C3-Ci0 cycloalkyl, substituted or unsubstituted C3-Ci0 cycloalkenyl, substituted or unsubstituted Ce-C20 aryl, substituted or unsubstituted Ο,-Ο® heterocyclyl, S(O)nCi-Ca alkyl,, NfCrCealkyl^, wherein each said R9, which is substituted, has one or more substituents selected from F, Cl, Br, I, CN, NO2, CrCa alkyl, C2-Ca alkenyl, CrC6 haloalkyl, C2-C6 haloaikenyl, Ci-Ca haloalkyloxy, C2-C6 haloalkenyloxy, C3-Ci0 cycloalkyl, C3-Cio cycloalkenyl, C3-C10 halocycloalkyl, C3-Cw halocycloalkenyl, OCrCe alkyl, OCi-Ca haloalkyl, S(O)nCrC6alkyl, S(O)nOCi-C6 alkyl, Ca-C20 aryl, or Ci-C20heterocyclyl;
(k) R10 is H, F, Cl, Br, I, CN, NO2, substituted or unsubstituted CrCa alkyl, substituted or unsubstituted C2-Ca alkenyl, substituted or unsubstituted CrCa alkoxy, substituted or unsubstituted C2-Ca alkenyloxy, substituted or unsubstituted C3-Cw cycloalkyl, substituted or unsubstituted C3-C10 cycloalkenyl, substituted or unsubstituted C6-C20 aryl, OR9, C(=X1)R9, C(=X1)OR9, C(=X1 )N(R9)2, N(R9)Z, N(R9)C(=X1)R9, SR9, S(O)nOR9, or R9S(O)nR9, wherein each said R10, which is substituted, has one or more substituents selected from F, Cl, Br, I, CN, NO21 Ci-C6 alkyl, C2-C6 alkenyl, CrC6 haloalkyl, C2-Ca haloaikenyl, Ci-C6 haloalkyloxy, C2-Ca haloalkenyloxy, C3-Ci0 cycloalkyl, C3-C10 cycloalkenyl, C3-Ci0 halocycloalkyl, C3-Ci0 halocycloalkenyl, OR9, S(O)nOR9, or Ca-C20 aryl, (each of which that can be substituted, may optionally be substituted with R9);
(l) n is (each independently) 0, 1, or 2;
(m) X1 is (each independently) O or S;
(η) X2 is (each independently) O, S, =NR9, or =NOR9; and (ο) Z is CN, NO2, C;-C6 alkyl(R9), C(=X1 )N(R9)Z.
Formula One and its subparts (a) through (o) are hereafter referred to as “Embodiment AT’.
In another embodiment of this molécule X is CR8.
In another embodiment of this molécule R1 is H.
In another embodiment of this molécule R2 is H.
J l
In another embodiment of this molécule R3 is H.
In another embodiment of this molécule R4 is halo or unsubstituted CrCe alkyl.
In another embodiment of this molécule R4 is F, Cl, or unsubstituted C1-C2 alkyl.
In another embodiment of this molécule R4 is Cl, or CH3.
In another embodiment of this molécule R5 is H, substituted or unsubstituted CrCg alkyl.
In another embodiment of this molécule R5 is a substituted C^Ce alkyl that is substituted with a C3-C10 cycloalkyl.
In another embodiment of this molécule R5 is H, CH31 CH2-cyclopropyl, or CH2CH3.
In another embodiment of this molécule R6 is O.
In another embodiment of this molécule R7 is substituted or unsubstituted CrC6 alkyl, OR9, or R9S(O)nR9.
In another embodiment of this molécule R7 is a substituted C;-C6 alkyl wherein said substituent is one or more halos.
In another embodiment of this molécule R7 is a substituted C;-C6 alkyl wherein said substituent is one or more F or Cl or a combination thereof.
In another embodiment of this molécule R7 is a substituted CrCe alkyl wherein said substituent is one or more F,
In another embodiment of this molécule R7 is CH2CF3.
In another embodiment of this molécule R7 is an unsubstituted C;-C6 alkyl.
In another embodiment of this molécule R7 is CH(CH3)2, CH3, C(CH3)3, or CH2CH2CH2CH3.
In another embodiment of this molécule R7 is OR9.
In another embodiment of this molécule R7 is O(unsubstituted C^Cs alkyl).
In another embodiment of this molécule R7 is OC(CH3)3.
In another embodiment of this molécule R7 is R9S(O)nR9.
In another embodiment of this molécule R7 is (unsubstituted CrC6 alkyl)S(unsubstituted C,-C6 alkyl).
In another embodiment of this molécule R7 is CH2CH(CH3)SCH3, CH2CH2SCH3, CH(CH3)2SCH31 or CH(CH3)CH2SCH3.
In another embodiment of this molécule R8 is H or halo.
In another embodiment of this molécule R8 is H, F, or Cl.
In another embodiment of this molécule R8 is H or F.
In another embodiment of this molécule R9 is an unsubstituted CrC6 alkyl.
In another embodiment of this molécule R10 is H or unsubstituted C-|-C6 alkyl.
In another embodiment of this molécule R10 is H or CH3.
In another embodiment of this molécule n is 0.
Combinations of these embodiments are also envisioned.
The molécules of Formula One will generally hâve a molecular mass of about 100 Daltons to about 1200 Daltons. However, it is generally preferred if the molecular mass is from about 120 Daltons to about 900 Daltons, and it is even more generally preferred if the molecular mass is from about 140 Daltons to about 600 Daltons.
The following scheme illustrâtes an approach to generating 2-methyl imidazolylamines. In step a of Scheme I, treatment of compounds of Formula III with ethyl acetimidate hydrochlorides of Formula IV wherein R5 is as defined in Embodiment A1 and R4 is methyl affords the corresponding acetamidines of Formula V. In step b of Scheme I, a-bromoketones of Formula II, wherein R1, R2, R3, R10, and X are as defined in Embodiment A1, can be treated with acetamidines of Formula V in the presence of an organic base, such as triethylamine, in a polar protic solvent such as ethyl alcohol to furnish N-Boc-aminoimidazoles of Formula la. When R5 = H, carbamates of Formula la, wherein R1, R2, R3, R4, R10 and X are as defined in Embodiment A1, can be alkylated in the presence of a base such as sodium hydride and an alkyl halide such as iodomethane in an aprotic polar solvent such as N,Ndimethylformamide to yield compounds of Formula Ib, as shown in step e of Scheme I. Deprotection of carbamic acid ferf-butyl esters of Formula la can be performed as in step c of Scheme I with trifluoroacetic acid (TFA) in a polar aprotic solvent such as dichloromethane (DCM) to yield the aminoimidazoles of Formula Via, wherein R1, R2, R3, R4, R10, R5 and X are as defined in Embodiment A1. In step dof Scheme I, compounds of the Formula Via can be treated with an acid chloride of Formula VII, wherein R7 is as defined in Embodiment A1, in the presence of both an organic base, such as Λ/,/V-dimethylaminopyridine (DMAP), and an înorganic base, such as potassium carbonate, in a polar aprotic solvent such as 1,2dichloroethane (DCE) to afford compounds of Formula le.
Scheme I
c
+ CY’
Ο
VII
Another approach to generating imidazolylamines is illustrated in Scheme II. Diones of
Formula VIII, wherein R1, R2, R3, R10 and X are as defined in Embodiment A1, can be treated with an aldéhyde, such as acetaldehyde, a source of ammonia, such as ammonium acetate and a catalyst, such as indium(lll)chloride, in a protic solvent, such as methanol to give compounds of Formula IX. Compounds of Formula IX, wherein R1, R2, R3, R4, R10 and X are as defined in Embodiment A1, can be treated with a base such as sodium hydride in a solvent such as THF and addition of oxazîridines of Formula Xa to afford compounds of Formula Id, wherein R5 is H.
Scheme II
r2 O îVSîR|0 R}° r2 x4anh A À R,» R, N Rj
VIII IX
4* ό
Ri q V- r2 Xa
1 jl· N'N R, N R3 10 ο I
Id
Another approach to generating imidazolylamines is illustrated in Scheme III, Substituted 2-aminoimidazoles of Formula XI were prepared according to the general procedure found in Li and co-workers, J. Med. Chem., 2010, 53, 2409. Treatment of compounds of Formula XI, wherein R1, R2, R3, R10, and X are as defined in Embodiment A1, under Sandmeyer conditions leads to the formation of compounds of Formula XII, wherein R4 is halogen, as shown ïn step a of Scheme lll. Hydrazones of Formula XII can be transformed to the corresponding amines of Formula Vlb, wherein R5 is H when treated with hydrazine in a polar protic solvent such as 2-methoxyethanol, as shown in step b.
il
XI b
XII
Another approach to generating imidazolylamines is illustrated in Scheme IV. Imidazoles of Formula XIII, wherein R4 and R10 are as defined in Embodiment A1 and Q is halogen (for example, bromine), can be treated with a base such as sodium hydride in a polar, aprotic solvent such as tetrahydrofuran and an aminating reagent such as oxaziridine of Formula Xb to afford compounds of Formula XlVa, as shown in step a of Scheme IV. Carbamates of Formula XlVa, can be alkylated in the presence of a base such as sodium hydride and an alkyl halide such as iodoethane in a polar aprotic solvent such as Λ/,Ν-dimethylformamide to yield compounds of Formula XlVb, wherein R5 is alkyl, as shown in step b. Compounds of Formula XIVb, wherein R4, R5 and R10 are as defined in Embodiment A1, can be allowed to react under Suzuki coupling conditions with a boronic acid of Formula XV, wherein X, R1, R2 and R3 are as defined in Embodiment A1, to provide the heterocycle-coupled imidazole of Formula le, as shown in step c. When R4 = H, compounds of Formula le can be halogenated in the presence of a base such as n-butyllithium in a polar aprotic solvent such as tetrahydrofuran and an electrophilic source of halogen such as hexachloroethane to yield 2-haloimidazoles of Formula If, wherein R4 is halogen and R1, R2, R3, R5, R10 and X are as defined in Embodiment A1, as shown in step d.
XIII
N
N-NH
Rio
XlVa
R2 OH i 1 χΑγ-Β ΌΗ R.^N^R,
EXAMPLES
The examples are for illustration purposes and are not to be construed as limiting the invention disclosed in this document to only the embodiments disclosed in these examples.
Starting materials, reagents, and solvents that were obtained from commercial sources were used without further purification. Anhydrous solvents were purchased as Sure/Seal™ from Aldrich and were used as received. Melting points were obtained on a Thomas Hoover Unimelt 10 capîllary melting point apparatus or an OptiMelt Automated Melting Point System from Stanford Research Systems and are uncorrected. Molécules are given their known names, named according to naming programs within ISIS Draw, ChemDraw or ACD Name Pro. If such programs are unable to name a molécule, the molécule is named using conventional namîng rules. Ail NMR are in ppm (δ) and were recorded at 300, 400, or 600 MHz unless otherwise stated.
Example 1, Step 1: Préparation of N’-(1-lmino-ethyl)-N-methyl-hydrazinecarboxylic acid tert-butyl ester
A solution of tert-butyl 1-methylhydrazinecarboxylate (10.0 g, 68.4 mmol), ethyl acetimidate hydrochloride (42.1 g, 342 mmol), and potassium carbonate (94.4 g, 684 mmol) in DMF (150 mL) was heated at 105 °C for 5 hours. The contents were cooled to 0 °C before the precipitated material was collected by vacuum filtration and resuspended in H2O (100 mL). After 30 minutes of vigorous stirring, the remaining precipitate was collected and dried in a 45 °C vacuum oven overnight to yield the title compound as a white solid (7.56 g, 59.0%): mp 187-189°C; 1H NMR (400 MHz, DMSO-de) δ 6.28 (brs, 1H), 2.77 (s, 3H), 1.64 (s, 3H), 1.36 (s, 9H).
Example 1, Step 2: Préparation of Methyl-(2-methyl-4-pyridin-3-yl-imidazol-1-yl)-carbamic acid tert-butyl ester (Compound 3)
To a solution of A/'-(1-imino-ethyl)-N-methyl-hydrazinecaroboxylic acid tert-butyl ester (5.00 g,
26.7 mmol) and triethylamine (9.30 mL, 66.8 mmol) in EtOH (100 mL) was added 2-bromo-1pyridin-3-yl-ethanone hydrobromide (8.99 g, 32.0 mmol), portionwise. The contents were heated at 80 °C for 3 hours before the solvent was removed under reduced pressure and the residue was purified via silica gel chromatography (DCM:MeOH, 10:1) to afford the title compound as an orange oil (1.55 g, 20.1 %): ’H NMR (400 MHz, CDCI3) δ 8.92 (d, J = 2.4 Hz, 1 H), 8.43 (dd, J = 4.9, 1.4 Hz, 1 H), 8.03 (dt, J = 8.3, 1.6 Hz, 1 H), 7.28 (dd, J = 7.7, 4.8 Hz, 1 H), 7.21 (s, 1H), 3.38 (s, 3H), 2.36 (s, 3H), 1.43 (s, 9H); ESIMS m/z 289 [<M+H)f,
Example 1, Step 3: Préparation of Methyl-(2-methyl-4-pyridin-3-yl-imidazole-1-yl)-amine
4-(5-Fluoropyridin-3-yl)-N,2-dimethyl-1/7-imidazol-1-amine was prepared in accordance with the procedures disclosed in Example 1, Step 3, Method B: 1H NMR (300 MHz, CD3OD) δ 9.05 (s, 1H), 8.84 (s, 1 H), 8.47-8.44 (m, 2H), 2.97 (s, 3H), 2.74 (s, 3H); ESIMS m/z 207 [(M+H)J*.
N-Ethyl-4-(5-fluoropyridin-3-yl)-2-methyl-1H-imidazol-1-amine was prepared in accordance with the procedures disclosed in Example 1, Step 3, Method B: ’H NMR (300 MHz, CD3OD) δ 8.99 (s, 1H), 8.80 (s, 1H), 8.41-8.35 (m, 2H), 3.26 (q, J = 7.2 Hz. 2H), 2.74 (s, 3H), 1.19 (t, 3H, J =
7.2 Hz); ESIMS m/z 221 [(M+H)]+.
N-(Cyclopropylmethyl)-4-(5-fluoropyridin-3-yl)-2-methyl-1H-imidazol-1-amine was prepared in accordance with the procedures disclosed in Example 1, Step 3, Method B: 1H NMR (300 MHz, CD3OD) δ 8.965 (s, 1H), 8.746 (s. 1H), 8.39-8.30 (m, 2H), 3.08-3.05 (m, 2H), 2.77 (s, 3H), 1.08-0.95 (m, 1H), 0.56-0.56 (m, 2H), 0.19-0.15 (m, 2H); ESIMS m/z 247 [(M+H)]*.
Example 1, Step 4: Préparation of N-Methyl-N-fa-methyl^-pyridin-S-yl-imidazol-l-ylFSmethylsulfanyl-butramide (Compound 2)
A solution of methyl-(2-methyl-4-pyridin-3-yl-imidazole-1-yl)-amine (400 mg, 2.13 mmol), 3methylsulfanyl-butyryl chloride (649 mg, 4.25 mmol), DMAP (260 mg, 2.13 mmol), and potassium carbonate (881 mg, 6.38 mmol) in DCE (5 mL) was heated at 80 °C for 6 hours. The solvent was removed under reduced pressure and the residue was purified via reverse phase chromatography (0 to 100% acetonitrile/water) to furnish the title compound as a brown oil (290 mg, 44.8%): 1H NMR (400 MHz, CDCI3) δ 8.94 (br s. 1H), 8.47 (dd, J= 5.0, 1.4 Hz, 1H), 8.04 (dt, J= 8.2, 1.5 Hz, 1H), 7.36-7,27 (m, 2H), 3.39 (s, 3H), 3.25-3.18 (m, 1H), 2.38 (s, 3H), 2.272.19 (m, 2H), 2.02 (s, 3H), 1.24 (d, J = 6.2 Hz, 3H); ESIMS m/z 304 [(M+H)]+.
Compounds 1, 5 - 38 were made in accordance with the procedures disclosed in Example 1.
Example 2, Step 1: Préparation of 3-(2,5-Dimethyl-1H-imidazol-4-yl)pyridine
The compound was prepared following the general procedure found In: Sharma, S.D.; Hazarika, P.; Konwar, D. Tetrahedron Lett. 2008, 49, 2216. 1-Pyridin-3-yl-propane-1,2-dione (prepared as described in Knaus, E.E.; Avasthi, K.; Redda, K.; Benderly, A. Can. J. Chem. 1980, 58(2), 130; 0.50 g, 3.35 mmol), ammonium acetate (0.517 g, 6.71 mmol) and indium (III) chloride (0.074 g, 0.033 mmol) were weighed into a 50 mL round bottomed flask. Methanol (MeOH, 7 mL) and acetaldehyde (0.148 g, 0.190 mL, 3.35 mmol) were added via syringe and the cloudy mixture was stirred vigorously overnight. Analysis by TLC CH2CI2:MeOH /10:1 indicated that some startîng material remained. Additional ammonium acetate (0.517 g, 6.71 mmol), indium (III) chloride (0.074 g, 0.033 mmol) and acetaldehyde (0.148 g, 0.190 mL, 3.35 mmol) were added and again allowed to stir overnight. The mixture was filtered through paper with MeOH to remove sédiment and concentrated to low volume. The residue was purified via flash silica gel chromatography, CH2CI2:MeOH /10:1 to afford a low Rf-spot-compound. The material was dissolved in a minimum amount of CH2CI2 and treated with sat. NaHCO3. The resulting precipitate was collected by filtration and washed with water and CH2CI2and dried to give 0.105 g of a light yellow powder. The layers of the filtrate were separated and the aqueous phase was extracted repeatedly with CH2CI2 and ethyl acetate (EtOAc). The combined extracts were dried over Na2SO4, filtered and concentrated to give an additional 0.06 g of the title compound as a yellow orange solid (0,165 g, 28%): mp 179 - 181 °C; 1H NMR (300 MHz, CDCI3) δ 8.85 (bs, 1H), 8.46 (d, 7 = 4.1 Hz, 1H), 7.99 (bs, 1H), 7.31 (dd,7=7.7, 4.7 Hz, 1H),
2.44 (s, 6H); ESIMS m/z 174 [(M+H)]4 and 172 [(M-H)]'.
Example 2, Step 2: Préparation of (2,5-Dimethyl-4-pyridin-3-yl-imidazol-1-yl)-carbamic acid fert-butyl ester (Compound 4)
3-(2,5-Dimethyl-1H-imidazol-4-yl)-pyridine (0.035 g, 0.220 mmol) was weighed into an oven dried, nitrogen swept 10 mL round bottomed flask. Tetrahydrofuran (THF, 1 mL) was added via
Method A:
A solution of methyl-(2-methyl-4-pyridin-3-yl-imidazol-1-yl)-carbamic acid tert-butyl ester (1.50 g, 5.20 mmol) and trifluoroacetic acid (0.40 mL, 5.20 mmol) in DCM (5 mL) was stirred under ambient conditions for 3 hours. The solvent was removed under reduced pressure and the residue was resuspended in DCM (10 mL) before the addition of triethylamine (1.45 mL, 10.4 mmol). After stirring for 10 minutes the solvent was removed and the residue was purified via silica gel chromatography (DCM:MeOH, 10:1) to afford an inséparable mixture of the title compound and triethylammonium salts (822 mg). The mixture was used without further purification in the subséquent reactions.
Method B:
A solution of tert-butyl methyl(2-methyl-4-(pyridin-3-yl)-1H-imidazol-1-yl) carbamate (2.7 g, 9.4 mmol) in dichloromethane (50 mL) was treated with HCl in dioxane (4M, 20 mL). The mixture was stirred overnight at room température. The precipitate was filtered off to give the title compound as a brown solid (1.15 g, 54.5%): 1H NMR (300 MHz, DMSO-d6) δ 9.41-9.32 (m, 1H), 8.82-8.56 (m, 3H), 7.97-7.89 (m, 1H), 2.85 (s, 3H), 2.67 (d, J = 3.0 Hz, 3H); ESIMS m/z 189 [(M+H)]*.
N-Ethyl-2-methyl-4-(pyridin-3-yl)-1H-imidazol-1-amine was prepared in accordance with the procedures disclosed in Example 1, Step 3, Method B: 1H NMR (300 MHz, DMSO-d6) δ 9.32 (s, 1H), 8.76-8.69 (m, 2H), 8.57-8.46 (m, 1H), 7.81 (s, 1 H), 3.12-3.03 (m, 2H), 2.63 (s, 3H), 1.06 (t, 3H, J = 7.2 Hz); ESIMS m/z 203 [(M+H)]+.
A/-(Cyclopropylmethyl)-2-methyl-4-(pyridin-3-yl)-1H-îmidazol-1-amine was prepared in accordance with the procedures disclosed in Example 1, Step 3, Method B: ’H NMR (300 MHz, DMSO-d6) δ 9.26 (s, 1H), 8.74-8.72 (m, 1H), 8.67-8.59 (m, 1H), 8.51-8.46 (m, 1H), 7.81 (s, 1 H),
2.95 (d, 2H, J= 7.2 Hz), 2.66 (s, 3H), 0.93-0.86 (m, 1H), 0.46-0.43 (m, 2H), 0.07-0.06 (m, 2H);
ESIMS m/z 229 [(M+H)]*.
ι syringe and the resulting slurry cooled on an ice bath under nitrogen and treated with sodium hydride (0.0097 g, 0.242 mmol. 60% dispersion in oil) with stirring. After 10 minutes, 3-(4cyano-phenyl)-oxaziridine-2-carboxylic acid tert-butyl ester (0.052 g, 0.212 mmol) was added as a solid and the thick yellow slurry allowed to warm to room température and stir for 2 hours. The crude reaction mixture was loaded direclly onto a flash silica gel column and eluted with CH2CI2:MeOH /10:1 giving (2,5-dimethyl-4-pyridin-3-yl-imidazol-1-yl)-carbamic acid tert-butyl ester as a light yellow oil as a 5:1 mixture with its regioisomer (0.027 g, 46 %): IR (film) 3389,
2978, 2930, 1730, 1478, 1275, 1252, 1156, 1017, 951,711, 573 cm'1; 1H NMR (300 MHz. DMSO, Major isomer) δ 10.41 (s, 1H), 8.81 (s, 1H), 8.39 (s, 1H), 7.95 (d, J =8.0 Hz, 1H), 7.44 - 7.28 (m, 1H), 2.21 (s, 3H). 2.18 (s, 3H), 1.46 (s, 9H); ESIMS m/z 289 [(M+H)]+ and 287 [(ΜΗ)]'.
Example 3: Préparation of fert-Butyl (2-methyl-4-(pyridin-3-yl)-1H-imidazol-1-yl)carbamate
To a mixture of ethyl acetimidate hydrochloride (2.0 g, 16.20 mmol) and triethylamine (3.28 g,
32.4 mmol) in éthanol (40 mL) was added a solution of tert-butyl hydrazinecarboxylate (2.14 g, 16.20 mmol) in éthanol (10 mL) at room température. The resulting mixture was stirred at room température overnight. Then to the mixture was added a solution of 2-bromo-1-(pyridin-3yl)ethanone hydrobromide (5.0 g, 17.9 mmol) and triethylamine (4.9 g, 48.6 mmol) in éthanol (20 mL). The reaction mixture was stirred at room température for 5 hours then heated to reflux overnight. The solvent was removed under reduced pressure and the residue was purified via silica gel chromatography (dichloromethane: methanol, 10:1) to give the title compound as an orange oil (0.76 g, 17.3%): 'H NMR (300 MHz, CDCI3) δ 8.87 (s, 1H), 8.45 (d, 1H, J = 6.3 Hz), 8.43 (s, 1 H). 8.05 (d, 1H, J = 6.3 Hz), 7.33-7.25 (m, 2H), 2.37 (s, 3H). 1.51 (s, 9H); ESIMS m/z 275 [{M+H)]+.
Example 4: Préparation of tert-Butyl methyl(2-methyl-4-(pyridin-3-yl)-1H-imidazol-1-yl) carbamate (Compound 3) (another way of making Compound 3)
To a solution of tert-butyl 2-methyl-4-(pyridin-3-yl)-1H-imidazol-1-ylcarbamate (2.0 g, 7.3 mmol) in dry DMF (15 mL) at 0 °C was added sodium hydride (0.35 g, 8.7 mmol, 60% dispersion in oil). The reaction was stirred at 0 °C for 30 minutes and then methyl iodide (1.55 g, 10.9 mmol) was added portionwise. The reaction mixture was stirred at 0 °C for 3 hours before it was warmed to ambient température. The reaction was extracted with ethyl acetate (15 mL x 2). The organic layer was washed with brine (10 mL), dried over anhydrous sodium sulfate, filtered and concentrated to give the title compound (1.18 g, 56,2%) as an orange oil, which was used in the next step without further purification: 1H NMR (300 MHz, CDCI3): δ 8.96 (s, 1 H), 8.49 (s, 1 H), 8.16-8,13 (m, 1H), 7.38-7.36 (m, 2H). 3.36 (s, 3H), 2.35 (s, 3H), 1.44 (s, 9H); ESIMS m/z 289 [(M+H)]+.
fert-Butyl ethyl(2-methyl-4-(pyridin-3-yl)-1H-imidazol-1-yl)carbamate was prepared in accordance with the procedures disclosed in Example 4:1H NMR (300 MHz, CDCI3) δ 8.94 (s, 1H), 8.48-8.46 (m, 1H), 8.09-8.05 (m, 1H), 7.31-7.29 (m, 1H), 7.20 (s, 1H), 3.86-3.67 (m, 2H),
2.34 (s, 3H), 1.44 (s, 9H), 1.21 (t, 7=7.2 Hz, 3H); ESIMS m/z 303 [(M+H)]+.
ferf-Butyl (cyclopropylmethyl)(2-methyl-4-(pyridin-3-yl)-1 H-imidazol-1-yl)carbamate was prepared in accordance with the procedures disclosed in Example 4:1H NMR (300 MHz, CDCI3) δ 8.94 (s, 1H), 8.48-8.46 (m, 1H), 8.10-8.06 (m, 1H), 7.31-7.28 (m, 1H), 7.25 (s, 1H), 3.59-3.54 (m, 2H), 2.37 (s, 3H), 1.44 (s, 9H), 1.05-0.93 (m, 1H), 0.56-0.53 (m, 2H), 0.20-0.15 (m, 2H); ESIMS m/z 329 [(M+H)]+.
fert-Butyl (4-(5-fluoropyrîdin-3-yl)-2-methyl-1H-imidazol-1-yl)(methyl)carbamate was prepared in accordance with the procedures disclosed in Example 4:1H NMR (300 MHz, CDCI3) δ 8.72 (s, 1H), 8.31 (d, 7 = 2.7 Hz, 1H), 7.83-7.78 (m, 1H). 7.27 (s, 1H), 3.36 (s. 3H), 2.34 (s, 3H), 1.44 (s, 9H); ESIMS m/z 307 [(M+H)f.
ferf-Butyl ethyl(4-(5-fluoropyridin-3-yl)-2-methyl-1/-/-imidazol-1-yl)carbamate was prepared in accordance with the procedures disclosed in Example 4:1H NMR (300 MHz, CDCI3) δ 8.73 (s, 1H), 8.32-8.31 (m, 1H), 7.84-7.80 (m, 1H), 7.23 (s, 1H), 3.87-3.70 (m, 2H), 2.34 (s, 3H), 1.45 (s, 9H), 1.21 (t, 7= 7.2 Hz, 3H); ESIMS m/z 321 [(M+H)]*.
tert-Butyl (cyclopropylmethyl)(4-(5-fluoropyridin-3-yl)-2-methyl-1 H-imidazol-1 -yljcarbamate was prepared in accordance with the procedures dïsclosed in Example 4:1H NMR (300 MHz, CDCIg)
Ô 8.7s (s, 1 H), 8.30-8.29 (m, 1H), 7.85-7.80 (m, 1H). 7.27 (s, 1H), 3.57-3.54 (m, 2H), 2.37 (s, 3H), 1.44 (s. 9H), 1.02-0.93 (m, 1 H), 0.55-0.53 (m, 2H), 0.21-0.17 (m, 2H); ESIMSm/z347 [(M+H)]*.
Example 5, Step 1: Préparation of E-2-Chloro-N-(4-chlorobenzylidene)-4-(pyridin-3-yl)-1Himidazol-1-amine
To a solution of (E)-N1-(4-chlorobenzylidene)-4-(pyridin-3-yl)-1H-imidazole-1,2-diamine (5.3 g, 18 mmol) and CuCI (1.79 g, 18 mmol) in acetonitrile (100 mL) was added isopentyl nitrite (3.15 g, 27 mmol) at 0 °C. The reaction mixture was stirred for 1 hour at room température, and then heated to 70 °C for 3 hours. The solvent was removed in vacuum, the residue was purified by column chromatography (petroleum ether: ethyl acetate = 2:1) to give the title compound (258 mg, 4%) as a white solid: 1H NMR (300 MHz, CDCI3) δ 8.99 (s, 1 H), 8.55-8.54 (m, 1H), 8.42 (s, 1H), 8.17-8.13 (m, 1H), 7.86-7.83 (m, 3H), 7.50 (d, J = 8.4 Hz, 2H), 7.36-7.31 (m, 1 H); ESIMS m/z 317 [(M+H)]*.
Example 5, Step 2: Préparation of 2-Chloro-4-(pyridin-3-yl)-1H-Îmidazol-1-amine
To a solution of E-2-Chloro-/V-(4-chlorobenzylidene)-4-(pyndin-3-y!)-1H-imidazol-1-amine (210 mg, 0.66 mmol) in 2-methoxyethanol (5 mL) was added 80% hydrazine hydrate (0.5 mL). The reaction mixture was heated to 130 °C for 1 hour and then the reaction mixture was concentrated. The residue was purified by column chromatography (petroleum ether: ethyl acetate = 1:1) to give the title compound (100 mg, 78%) as a yellow solid: 1H NMR (300 MHz,
CDCI3) δ 8.91 (s, 1H), 8.50-8.49 (m, 1H), 8.06-8.03 (m, 1H), 7.43 (s, 1H), 7.34-7.30 (m, 1H),
4.87 (br, 2H); ESIMS m/z 195 [(M+H)]*.
Example 5, Step 3: Préparation of A/-(2-Chloro-4-{pyridjn-3-yl)-1/-/-imidazol-1-yl)acetamide (Compound 39)
To a solution of 2-Chloro-4-(pyridin-3-yl)-1H-imidazol-1 -amine (30 mg, 0.15 mmol) and triethylamine (15 mg, 0.15 mmol) in dichloromethane (5 mL) was added acetyl chloride (12 mg, 0.15 mmol) at 0 °C. The reaction mixture was stirred for 30 minutes at 0 °C. The solvent was removed in vacuum and the residue was purified by prep-TLC (petroleum ether: ethyl acetate = 1:2) to give the title compound (10 mg, 27%) as a yellow solid: mp 129 - 131 °C; ’H NMR (300 MHz, CDCI3) δ 10.69 (br, 1H), 8.81-8.80 (m, 1H), 8.44-8.43 (m, 1H), 8.02-8.00 (m, 1H), 7.33 (br s, 2H), 2.20 (s, 3H); ESIMS m/z 237 [(M+H)]+.
Example 6, Step 1: Préparation of fert-Butyl (4-bromo-1H-imidazol-1-yl)carbamate
Br
4-Bromo-1H-imidazole(3.2 g, 21.8 mmol) was weighed into a 500 mL round bottomed flask equipped with a magnetic stir bar under a nitrogen atmosphère. Anhydrous N,Ndimethylformamide (DMF, 12 mL) was added and the mixture was placed on ice. After 10 minutes the mixture was treated with sodium hydride (0.840 g, 21.0 mmol. 60% dispersion in oil). After 5 minutes, the ice bath was removed and the reaction warmed to room température. After 15 minutes of vigorous stirring the ice bath was re-inserted and 3-(4-cyano-phenyl)oxaziridine-2-carboxylic acid tert-butyl ester (1.92 g, 7.80 mmol) was added. The reaction was vigorously stirred for 5 minutes and the ice bath was removed. After 5 minutes the mixture was diluted with saturated sodium bicarbonate and extracted with ethyl acetate. The organics were washed with dilute sodium carbonate, dried over sodium sulfate, and concentrated. The residue was purified using silica gel chromatography (0-5% methanol/dichloromethane) to afford the
I t
title compound (1.16 g, 4.43 mmol, 57 %) as a yellow oil: H NMR (400 MHz, CDCI3) δ 9.22 (s, 1H), 7.36 (d, J= 1.5 Hz, 1H), 6.97 (d, J= 1.5 Hz, 1H), 1.48 (s, 9H); ESIMS m/z 262 ([M]*). 260 ([M-2]).
Example 6, Step 2: Préparation of tert-Butyl (4-bromo-1H-imidazol-1-yl)(ethyl)carbamate
O
N=\ X
tert-Butyl (4-bromo-1H-imidazol-1-yl)carbamate (1.16 g, 4.43 mmol) was dissolved in N,Ndimethylformamide (DMF, 12 mL) and treated with sodium hydride (0.310 g, 7.75 mmol, 60% dispersion in oil). After 45 minutes, the mixture was cooled on an ice bath and was treated with iodoethane (0.828 g, 5.31 mmol). The ice bath was removed after five minutes of stirring and the reaction was stirred for an additional 90 minutes. The reaction mixture was diluted with aqueous potassium carbonate (50 mL, 5% w/w) and the product was extracted with ethyl acetate. The organics were washed with 5% aqueous potassium carbonate and brine and dried over sodium sulfate. The organic layer was concentrated and the residue was purified using silica gel chromatography (0-10% methanol/dichloromethane) to afford the title compound (1.023 g, 3.53 mmol, 80%) as a yellow oil: 1H NMR (400 MHz, CDCI3) δ 7.37 (d, J= 1.5 Hz, 1H),
6.93 (d, J= 1.5 Hz, 1H), 3.71 (q, J = 7.2 Hz, 2H), 1.44 (s, 9H), 1.16 (t, J = 7.2 Hz, 3H); ESIMS m/z 290 ([M+Hf).
Example 6, Step 3: Préparation of tert-Butyl ethyl(4-(pyridin-3-yl)-1 H-imidazol-1yl)carbamate (Compound 40)
tert-Butyl (4-bromo-1H-imidazol-1-yl)(ethyl)carbamate (253.7 mg, 0.874 mmol), pyridin-3ylboronic acid (113 mg, 0.918 mmol), potassium carbonate (329 mg, 2.39 mmol), water (0.870 mL), absolute éthanol (1.74 mL), and toluene (3.50 mL) were placed into a 10 mL round bottomed flask equipped with condenser and magnetic stirrer. The atmosphère was flushed with nïtrogen and tetrakis triphenylphosphine palladium (30.0 mg, 0.026 mmol) was added. The
mixture was heated to 110 °C and stirred for 16 hours. The reaction was cooled, the organic layer set aside, and the aqueous layer was extracted with ethyl acetate. Ail organics were combined, dried over sodium sulfate, and concentrated. The residue was purified using silica gel chromatography (0-25% methanol/dichloromethane) to afford the title compound (81 mg, 0.28 mmol, 32%) as a yellow oil:’H NMR (400 MHz, CD3CN) δ 9.00 (d, J = 2.5 Hz, 1H), 8.46 (d, J = 4.8 Hz, 1 H), 8.11 (m, 1 H), 7.67 (d, J = 1.3 Hz. 1 H), 7.61 (d, J = 1.2 Hz, 1 H), 7.36 (m, 1 H),
3.76 (q, J = 7.1 Hz, 2H), 1.45 (s, 9H), 1.17 (t, J = 7.2 Hz, 3H); ESIMS m/z 289 ([M+H]+).
Example 6, Step 4: Préparation of fert-Butyl (2-chloro-4-(pyridin-3-yl)-1H-imidazol-1yl)(ethyl)carbamate (Compound 41)
A vacuum dried 25 mL round bottomed flask equipped with a magnetic stir bar and containing tert-butyl ethyl(4-(pyridin-3-yl)-1H-imidazol-1-yl)carbamate (77 mg, 0.267 mmol) was charged with anhydrous tetrahydrofuran (THF, 3 mL) and cooled to -78 °C. N-butyllithium (0.25 mL 0,675 mmol, 2.5 M in hexanes) was added and the mixture was stirred for 15 minutes. Hexachloroethane ( 189 mg, 0.80 mmol) dissolved in anhydrous THF (1 mL) was added dropwise to the reaction mixture while maintaining a température of - 78 °C. After stirring for 1 hour, the reaction was allowed to warm to room température. The reaction mixture was loaded directly on a silica gel column and the THF was removed in a vacuum oven. The crude product was purified using silica gel chromatography (0-25% methanol/dichloromethane) to afford the title compound (3 mg, 0.009 mmol, 3.5%) as a yellow oil:. 1H NMR (600 MHz, CDCI3) δ 8.92 (d, J = 1.6 Hz, 1 H), 8.50 (dd, J = 4.8, 1.5 Hz, 1 H), 8.06 (dt, J = 7.9, 2.0 Hz, 1 H), 7.33 - 7.27 (m, 2H), 3.89 (dq, J = 14.5, 7.3 Hz, 1H), 3.68 (dq, J = 14.3, 7.2 Hz, 1H). 1.44 (s, 9H). 1.22 (t, J =
7.2 Hz, 3H); 13CNMR(151 MHz, CDCI3) δ 152.90, 148.47, 146.02, 136.07, 134.08, 131.81, 128.79, 123.36, 117.66, 83.23, 45.32, 28.04, 13.03; ESIMS m/z 323 ([M+H]*).
Example A: Bioassays on Green Peach Aphid (“GPA”) (Myzus persicae) (MYZUPE).
GPA is the most significant aphid pest of peach trees, causing decreased growth, shriveling of the leaves, and the death of various tissues. It is also hazardous because it acts as a vector for the transport of plant viruses, such as potato virus Y and potato leafroll virus to members of the nightshade/potato family Solanaceae, and various mosaic viruses to many other food crops. GPA attacks such plants as broccoli, burdock, cabbage, carrot, cauliflower, daikon, eggplant, green beans, lettuce, macadamia, papaya, peppers, sweet potatoes, tomatoes, watercress, and zucchini, among other plants. GPA also attacks many ornamental crops such as carnation, chrysanthemum, flowering white cabbage, poinsettia, and roses. GPA has developed résistance to many pesticides.
Certain molécules disclosed in this document were tested against GPA using procedures described in the following example. In the reporting of the results, the “Table 3: GPA (MYZUPE) and sweetpotato whitefly-crawler (BEMITA) Rating Table was used (See Table Section).
Cabbage seedlings grown in 3-inch pots, with 2-3 small (3-5 cm) true leaves, were used as test substrate. The seedlings were infested with 20-50 GPA (wingless adult and nymph stages) one day prior to chemical application. Four pots with individual seedlings were used for each treatment. Test compounds (2 mg) were dissolved in 2 mL of acetone/methanol (1:1) solvent, forming stock solutions of 1000 ppm test compound. The stock solutions were diluted 5X with 0.025% Tween 20 in H2O to obtain the solution at 200 ppm test compound. A handheld aspirator-type sprayer was used for spraying a solution to both sides of cabbage leaves until runoff. Référencé plants (solvent check) were sprayed with the diluent only containing 20% by volume of acetone/methanol (1:1) solvent. Treated plants were held in a holding room for three days at approximately 25 “C and ambient relative humidity (RH) prior to gradîng. Evaluation was conducted by counting the number of live aphids per plant under a microscope. Percent Control was measured by using Abbott's correction formula (W.S. Abbott, “A Method of Computing the Effectiveness of an Insecticide J. Econ. Entomol. 18 (1925), pp.265-267) as follows.
Corrected % Control = 100 * (X - Y) / X where
X = No. of live aphids on solvent check plants and
Y = No. of live aphids on treated plants
The results are indicated in the table entitled “Table 4. Biological Data for GPA (MYZUPE) and sweetpotato whitefly-crawler (BEMITA) (See Table Section).
Example B: Insecticidal test for sweetpotato whitefly-crawler (Bemisia tabaci) (BEMITA) in foliar spray assay
Cotton plants grown in 3-inch pots, with 1 small (3-5 cm) true leaf, were used as test substrate. The plants were placed in a room with whitefly adults. Adults were allowed to deposit eggs for 2-3 days. After a 2-3 day egg-laying period, plants were taken from the adult whitefly room. Adults were blown off leaves using a hand-held Devilbiss sprayer (23 psi). Plants with
egg infestation (100-300 eggs per plant) were placed in a holding room for 5-6 days at 82 °F and 50% RH for egg hatch and crawler stage to develop. Four cotton plants were used for each treatment. Compounds (2 mg) were dissolved in 1 mL of acetone solvent, forming stock solutions of 2000 ppm. The stock solutions were diluted 10X with 0.025% Tween 20 in H2O to obtain a test solution at 200 ppm. A hand-held Devilbiss sprayer was used for spraying a solution to both sides of cotton leaf until runoff. Reference plants (solvent check) were sprayed with the diluent only. Treated plants were held in a holding room for 8-9 days at approximately 82°F and 50% RH prior to grading. Evaluation was conducted by counting the number of live nymphs per plant under a microscope. Insecticidal activity was measured by using Abbott's correction formula and presented in “Table 4. Biological Data for GPA (MYZUPE) and sweetpotato whitefly-crawler (BEMITA) (see column “BEMITA):
Corrected % Control = 100 * (X - Y) / X where X = No. of live nymphs on solvent check plants Y = No. of live nymphs on treated plants
PESTICIDALLY ACCEPTABLE ACID ADDITION SALTS, SALT DERIVATIVES, SOLVATES, ESTER DERIVATIVES, POLYMORPHS, ISOTOPES AND RADIONUCLIDES
Molécules of Formula One may be formulated into pesticidally acceptable acid addition salts. By way of a non-limiting example, an amine function can form salts with hydrochloric, hydrobromic, sulfuric, phosphoric, acetic, benzoic, citric, malonic, salicylic, malic, fumaric, oxalic, succinic, tartane, lactic, gluconic, ascorbic, maleic, aspartic, benzenesulfonic, methanesulfonic, ethanesulfonic, hydroxymethanesulfonic, and hydroxyethanesulfonic acids. Additionally, by way of a non-limiting example, an acid function can form salts including those derived from alkali or alkaline earth metals and those derived from ammonia and amines. Examples of preferred cations include sodium, potassium, and magnésium.
Molécules of Formula One may be formulated into sait dérivatives. By way of a nonlimiting example, a sait dérivative can be prepared by contacting a free base with a sufficient amount of the desired acid to produce a sait. A free base may be regenerated by treating the sait with a suitable dilute aqueous base solution such as dilute aqueous sodium hydroxide (NaOH), potassium carbonate, ammonia, and sodium bicarbonate. As an example, in many cases, a pesticide, such as 2,4-D, is made more water-soluble by converting it to its dimethylamine sait..
Molécules of Formula One may be formulated into stable complexes with a solvent, such that the complex remains intact after the non-complexed solvent is removed. These complexes are often referred to as solvatés. However, it is particularly désirable to form stable hydrates with water as the solvent.
Molécules of Formula One may be made into ester dérivatives. These ester dérivatives can then be applied in the same manner as the invention disclosed in this document is applied.
Molécules of Formula One may be made as various crystal polymorphs. Polymorphism is important in the development of agrochemicals since different crystal polymorphs or structures of the same molécule can hâve vastly different physical properties and biological performances.
Molécules of Formula One may be made with different isotopes. Of particular importance are molécules having ZH (also known as deuterium) in place of 1H.
Molécules of Formula One may be made with different radionuclides. Of particular importance are molécules having 14C.
STEREOISOMERS
Molécules of Formula One may exist as one or more stereoisomers. Thus, certain molécules can be produced as racemic mixtures. It will be appreciated by those skilled in the art 15 that one stereoisomer may be more active than the other stereoisomers. Individual stereoisomers may be obtained by known sélective synthetic procedures, by conventional synthetic procedures using resolved starting materials, or by conventional resolution procedures. Certain molécules disclosed in this document can exist as two or more isomers. The various isomers include géométrie isomers, diastereomers, and enantiomers. Thus, the 20 molécules disclosed in this document include géométrie isomers, racemic mixtures, individual stereoisomers, and optically active mixtures. It will be appreciated by those skilled in the art that one isomer may be more active than the others. The structures disclosed in the présent disclosure are drawn in only one géométrie form for clarity, but are intended to represent ail géométrie forms of the molécule.
COMBINATIONS
Molécules of Formula One may also be used in combination (such as, in a compositional mixture, or a simultaneous or sequential application) with one or more compounds having acaricidal, algicîdal, avicidal, bactericidal, fungicidal, herbicidal, insecticidal, 30 molluscicidal, nematicidal, rodenticidal, or virucidal properties. Additionally, the molécules of Formula One may also be used in combination (such as, in a compositional mixture, or a simultaneous or sequential application) with compounds that are antifeedants, bird repellents, chemosterilants, herbicide safeners, însect attractants, insect repellents, mammal repellents, mating disrupters, plant actîvators, plant growth regulators, or synergists. Examples of such 35 compounds in the above groups that may be used with the Molécules of Formula One are - (3ethoxypropyl)mercury bromide, 1,2-dichioropropane, 1,3-dichloropropene, 126
B methylcyclopropene, 1-naphthol, 2-(octyithio)ethanol, 2,3,5-tri-iodobenzoic acid, 2,3,6-TBA,
2,3,6-TBA-dimethylammonium, 2,3,6-TBA-lithium, 2,3,6-TBA-potassium, 2,3,6-TBA-sodium,
2.4.5- T, 2,4,5-T-2-butoxypropyl, 2,4,5-T-2-ethylhexyl, 2,4,5-T-3-butoxypropyl, 2,4,5-TB, 2,4,5-Tbutometyl, 2,4,5-T-butotyl, 2,4,5-T-butyl, 2,4,5-T-isobutyl, 2,4,5-T-isoctyl, 2,4,5-T-isopropyl,
2.4.5- T-methyl, 2,4,5-T-pentyl, 2,4,5-T-sodium, 2,4,5-T-triethylammonium, 2,4,5-T-trolamine,
2.4- D, 2,4-D-2-butoxypropyl, 2,4-D-2-ethylhexyl, 2,4-D-3-butoxypropyl, 2,4-D-ammonium, 2,4DB, 2,4-DB-butyl, 2,4-DB-dimethylammonium, 2,4-DB-îsoctyl, 2,4-DB-potassium, 2,4-DBsodium, 2,4-D-butotyl, 2,4-D-butyl, 2,4-D-diethylammonium, 2,4-D-dimethylammonium, 2,4-Ddiolamine, 2,4-D-dodecylammonium, 2,4-DEB, 2,4-DEP, 2,4-D-ethyl, 2,4-D-heptylammonium,
2.4- D-isobutyl, 2,4-D-isoctyl, 2,4-D-isopropyl, 2,4-D-isopropylammonîum, 2,4-D-lithium, 2,4-Dmeptyl, 2,4-D-methyl, 2,4-D-octyl, 2,4-D-pentyl, 2,4-D-potassium, 2,4-D-propyl, 2,4-D-sodium,
2.4- D-tefuryl, 2,4-D-tetradecylammonium, 2,4-D-triethylammonium, 2,4-D-tris(2hydroxypropyl)ammonium, 2,4-D-trolamine, 2iP, 2-methoxyethylmercury chloride, 2phenylphenol, 3,4-DA, 3,4-DB, 3,4-DP, 4-aminopyridine, 4-CPA, 4-CPA-potassium, 4-CPAsodium, 4-CPB, 4-CPP, 4-hydroxyphenethyl alcohol, 8-hydroxyquinoline sulfate, 8phenylmercurioxyquinoline, abamectin, abscisic acid, ACC, acephate, acequinocyl, acetamiprid, acethion, acetochlor, acetophos, acetoprole, acibenzolar, acîbenzolar-S-methyl, acifluorfen, acifluorfen-methyl, acifluorfen-sodium, aclonifen, acrep, acrinathrin, acrolein, acrylonitrile, acypetacs, acypetacs-copper, acypetacs-zinc, alachlor, alanycarb, albendazole, aldicarb, aldimorph, aldoxycarb, aldrin, allethrin, allicin, allidochlor, allosamidin, alloxydim, alloxydimsodium, allyl alcohol, allyxycarb, alorac, a/pha-cypermethrin, a/pha-endosulfan, ametoctradin, ametridione, ametryn, amibuzin, amicarbazone, amicarthiazol, amîdithion, amidoflumet, amidosulfuron, aminocarb, aminocyclopyrachlor, aminocyclopyrachlor-methyl, aminocyclopyrachlor-potassium, aminopyralid, aminopyralid-potassium, aminopyralid-tris(2hydroxypropyl)ammonium, amîprofos-methyl, amiprophos, amisulbrom, amiton, amiton oxalate, amitraz, amitrole, ammonium sulfamate, ammonium α-naphthaleneacetate, amobam, ampropylfos, anabasine, ancymidol, anilazine, anilofos, anisuron, anthraquinone, antu, apholate, aramite, arsenous oxide, asomate, aspirin, asulam, asulam-potassium, asulamsodium, athidathion, atraton, atrazine, aureofungin, aviglycine, aviglycine hydrochloride, azaconazole, azadirachtin, azafenidin, azamethiphos, azimsulfuron, azinphos-ethyl, azinphosmethyl, aziprotryne, azithiram, azobenzene, azocyclotin, azothoate, azoxystrobin, bachmedesh, barban, barium hexafluorosilicate, barium polysulfide, barthrin, BCPC, beflubutamid, benalaxyl, benalaxyl-M, benazolin, benazolin-dimethylammonium, benazolin-ethyl, benazolin-potassium, bencarbazone, benclothiaz, bendiocarb, benfluralin, benfuracarb, benfuresate, benodanil, benomyl, benoxacor, benoxafos, benquinox, bensulfuron, bensulfuron-methyl, bensulide, bensultap, bentaluron, bentazone, bentazone-sodium, benthiavalicarb, benthiavalicarb-
I
I isopropyl, benthiazole, bentranil, benzadox, benzadox-ammonium, benzalkonium chloride, benzamacril, benzamacril-isobutyl, benzamorf, benzfendizone, benzipram, benzobicyclon, benzofenap, benzofluor, benzohydroxamic acid, benzoximate, benzoylprop, benzoylprop-ethyl, benzthiazuron, benzyl benzoate, benzyladenine, berberine, berberine chloride, befa-cyfluthrin, beta-cypermethrin, bethoxazin, bicyclopyrone, bifenazate, bifenox, bifenthrîn, bifujunzhi, bilanafos, bilanafos-sodîum, binapacryl, bingqingxiao, bioallethrin, bioethanomethrin, biopermethrin, bioresmethrin, biphenyl, bisazir, bismerthiazol, bispyribac, bispyribac-sodium, bistrifluron, bitertanol, bithionol, bixafen, blasticidin-S, borax, Bordeaux mixture, boric acid, boscalid, brassinolide, brassinolide-ethyl, brevicomin, brodifacoum, brofenvalerate, brofluthrinate, bromacil, bromaciî-lithium, bromacii-sodium, bromadiolone, bromethalin, bromethrin, bromfenvinfos, bromoacetamide, bromobonil, bromobutide, bromocyclen, bromoDDT, bromofenoxim, bromophos, bromophos-ethyl, bromopropylate, bromothalonil, bromoxynil, bromoxynil butyrate, bromoxynil heptanoate, bromoxynil octanoate, bromoxynil-potassium, brompyrazon, bromuconazole, bronopol, bucarpolate, bufencarb, buminafos, bupirimate, buprofezin, Burgundy mixture, busulfan, butacarb, butachlor, butafenacil, butamifos, butathiofos, butenachlor, butethrin, buthidazole, buthiobate, buthiuron, butocarboxim, butonate, butopyronoxyl, butoxycarboxim, butralin, butroxydim, buturon, butylamine, butylate, cacodylic acid, cadusafos, cafenstrole, calcium arsenate, calcium chlorate, calcium cyanamide, calcium polysulfide, calvinphos, cambendichlor, camphechlor, camphor, captafol, captan, carbamorph, carbanolate, carbaryl, carbasulam, carbendazim, carbendazim benzenesulfonate, carbendazim sulfite, carbetamide, carbofuran, carbon disulfide, carbon tetrachloride, carbophenothion, carbosulfan, carboxazole, carboxide, carboxin, carfentrazone, carfentrazone-ethyl, carpropamid, cartap, cartap hydrochloride, carvacrol, carvone, CDEA, cellocidin, CEPC, ceralure, Cheshunt mixture, chinomethionat, chitosan, chlobenthiazone, chlomethoxyfen, chloralose, chloramben, chloramben-ammonium, chloramben-diolamine, chloramben-methyl, chloramben-methylammonium, chloramben-sodium, chloramine phosphorus, chloramphenicol, chloranîformethan, chloranil, chloranocryl, chlorantraniliprole, chlorazifop, chlorazifop-propargyl, chlorazine, chlorbenside, chlorbenzuron, chlorbicyclen, chlorbromuron, chlorbufam, chlordane, chlordecone, chlordimeform, chlordimeform hydrochloride, chlorempenthrin, chlorethoxyfos, chloreturon, chlorfenac, chlorfenac-ammonium, chlorfenac-sodiurn, chlorfenapyr, chlorfenazole, chlorfenethol, chlorfenprop, chlorfenson, chlorfensulphide, chlorfenvinphos, chlorfluazuron, chlorflurazole, chlorfluren, chlorfluren-methyl, chlorflurenol, chlorflurenol-methyl, chloridazon, chlorimuron, chlorimuron-ethyl, chlormephos, chlormequat, chlormequat chloride, chlomidine, chlornitrofen, chlorobenzilate, chlorodinitronaphthalenes, chloroform, chloromebuform, chloromethiuron, chloroneb, chlorophacinone, chlorophacinone-sodtum, chloropicrin, chloropon, chloropropylate, chlorothalonil, chlorotoluron, chloroxuron, chloroxynil, chlorphonium,
I chlorphonium chloride, chlorphoxim, chlorprazophos, chlorprocarb, chlorpropham, chlorpyrifos, chlorpyrifos-methyl, chlorquinox, chlorsulfuron, chlorthal, chlorthal-dimethyl, chlorthalmonomethyl, chlorthiamid, chlorthiophos, chlozolinate, choline chloride, chromafenozide, cinerin I, cinerin II, cinerins, cinidon-ethyl, cinmethylin, cinosulfuron, ciobutîde, cisanilide, cismethrin, clethodim, climbazole, cliodinate, clodinafop, clodinafop-propargyl, cloethocarb, clofencet, clofencet-potassîum, clofentezine, clofibric acid, clofop, clofop-isobutyl, clomazone, clomeprop, cloprop, cloproxydim, clopyralid, clopyralid-methyl, clopyralid-olamine, clopyralid-potassium, clopyralid-tris(2-hydroxypropyl)ammonium, cloquintocet, cloquintocet-mexyl, cloransulam, cloransulam-methyl, closantel, clothianidin, clotrimazole, cloxyfonac, cloxyfonac-sodium, CMA, codlelure, colophonate, copper acetate, copper acetoarsenite, copper arsenate, copper carbonate, basïc, copper hydroxide, copper naphthenate, copper oleate, copper oxychloride, copper silicate, copper sulfate, copper zinc chromate, coumachlor, coumafuryl, coumaphos, cou ma tetra lyl, coumithoate, coumoxystrobin, CPMC, CPMF, CPPC, credazine, cresol, crlmidine, crotamiton, cratoxyphos, crufomate, cryolite, cue-lure, cufraneb, cumyluron, cuprobam, cuprous oxide, curcumenol, cyanamide, cyanatryn, cyanazine, cyanofenphos, cyanophos, cyanthoate, cyantraniliprole, cyazofamid, cybutryne, cyclafuramid, cyclanilide, cyclethrin, cycloate, cycloheximide, cycloprate, cycloprothrin, cyclosulfamuron, cycloxydim, cycluron, cyenopyrafen, cyflufenamid, cyflumetofen, cyfluthrin, cyhalofop, cyhalofop-butyl, cyhalothrin, cyhexatin, cymiazole, cymiazole hydrochloride, cymoxanil, cyometrinil, cypendazole, cypermethrin, cyperquat, cyperquat chloride, cyphenothrin, cyprazine, cyprazole, cyproconazole, cyprodinil, cyprofuram, cypromid, cyprosulfamide, cyromazine, cythioate, daimuron, dalapon, dalapon-calcium, dalapon-magnesium, dalapon-sodium, daminozide, dayoutong, dazomet, dazomet-sodium, DBCP, d-camphor, DCIP, DCPTA, DDT, debacarb, decafentin, decarbofuran, dehydroacetic acid, delachlor, deltamethrin, demephion, demephionO, demephion-S, demeton, demeton-methyl, demeton-O, demeton-O-methyl, demeton-S, demeton-S-methyl, demeton-S-methylsulphon, desmedipham, desmetryn, dfanshiluquebingjuzhi, diafenthiuron, dialifos, di-allate, diamidafos, diatomaceous earth, diazinon, dibutyl phthalate, dibutyl succinate, dicamba, dicamba-diglycolamine, dîcambadimethylammonium, dicamba-diolamine, dicamba-isopropylammonium, dicamba-methyl, dicamba-olamine, dicamba-potassium, dicamba-sodium, dicamba-trolamine, dicapthon, dichlobenil, dichlofenthion, dichlofluanid, dichlone, dichloralurea, dichlorbenzuron, dichlorflurenol, dichlorflurenol-methyl, dichlormate, dichlormid, dichlorophen, dichlorprop, dichlorprop-2-ethylhexyl, dichlorprop-butotyl, dichlorprop-dimethylammonium, dichlorpropethylammonium, dichlorprop-isoctyl, dichlorprop-methyl, dichlorprop-P, dichlorprop-P-2ethylhexyl, dichlorprop-P-dimethylammonium, dichlorprop-potassium, dichlorprop-sodium, dichlorvos, dichlozoline, diclobutrazol, diclocymet, diclofop, diclofop-methyl, diclomezine, t
diclomezine-sodium, dicloran, diclosulam, dicofol, dicoumarol, dicresyl, dicrotophos, dicyclanil, dicyclonon, dieldrin, dienochlor, diethamquat, diethamquat dichloride, diethatyl, diethatyl-ethyl, diethofencarb, dietholate, diethyl pyrocarbonate, diethyltoluamide, difenacoum, difenoconazole, difenopenten, difenopenten-ethyl, difenoxuron, difenzoquat, difenzoquat metilsulfate, difethialone, diflovidazin, diflubenzuron, diflufenican, diflufenzopyr, diflufenzopyr-sodium, diflumetorim, dikegulac, dikegulac-sodium, dilor, dimatif, dimefluthrin, dîmefox, dimefuron, dimepiperate, dimetachlone, dimetan, dimethacarb, dimethachlor, dimethametryn, dimethenamid, dimethenamid-P, dimethipin, dimethirimol, dimethoate, dimethomorph, dimethrin, dimethyl carbate, dimethyl phthalate, dîmethylvinphos, dimetilan, dimexano, dimidazon, dimoxystrobin, dinex, dinex-diclexine, dingjunezuo, diniconazole, diniconazole-M, dinitramine, dinobuton, dinocap, dinocap-4, dinocap-6, dinocton, dinofenate, dinopenton, dinoprop, dînosam, dinoseb, dinoseb acetate, dinoseb-ammonium, dinoseb-diolamine, dinosebsodium, dinoseb-trolamine, dinosulfon, dinotefuran, dînoterb, dinoterb acetate, dinoterbon, diofenolan, dîoxabenzofos, dioxacarb, dioxathion, diphacinone, diphacinone-sodium, diphenamid, diphenyl sulfone, diphenylamîne, dipropalin, dipropetryn, dipyrithione, diquat, diquat dibromide, disparlure, disul, disulfiram, disulfoton, disul-sodium, ditalimfos, dithianon, dithicrofos, dithioether, dithiopyr, diuron, d-limonene, DMPA, DNOC, DNOC-ammonium, DNOC-potassium, DNOC-sodium, dodemorph, dodemorph acetate, dodemorph benzoate, dodicin, dodicin hydrochloride, dodicin-sodium, dodine, dofenapyn. dominicalure, doramectin, drazoxolon, DSMA, dufulin, EBEP, EBP, ecdysterone, edifenphos, eglinazine, eglinazine-ethyl, emamectin, emamectin benzoate, EMPC, empenthrin, endosulfan, endothal, endothaldiammonium, endothal-dipotassium, endothal-dîsodium, endothion, endrin, enestroburin, EPN, epocholeone, epofenonane, epoxiconazole, eprinomectin, epronaz, EPTC, erbon, ergocalcîferol, erlujixiancaoan, esdépalléthrine, esfenvalerate, esprocarb, etacelasll, etaconazole, etaphos, etem, ethaboxam, ethachlor, ethalfluralin, ethametsulfuron, ethametsulfuron-methyl, ethaprochlor, ethephon, ethidimuron, ethiofencarb, ethiolate, ethion, ethiozin, ethiprole, ethirimol, ethoate-methyl, ethofumesate, ethohexadiol, ethoprophos, ethoxyfen, ethoxyfen-ethyl, ethoxyquîn, ethoxysulfuron, ethychlozate, ethyl formate, ethyl anaphthaleneacetate, ethyl-DDD, ethylene, ethylene dibromide, ethylene dichloride, ethylene oxide, ethylicin, ethylmercury 2,3-dihydroxypropyl mercaptide, ethylmercury acetate, ethylmercury bromide, ethylmercury chloride, ethylmercury phosphate, etinofen, etnipromid, etobenzanid, etofenprox, etoxazole, etridiazole, etrimfos, eugenol, EXD, famoxadone, famphur, fenamidone, fenaminosulf, fenamiphos, fenapanil, fenarimol, fenasulam, fenazaflor, fenazaquin, fenbuconazole, fenbutatin oxide, fenchlorazole, fenchlorazole-ethyl, fenchlorphos, fenclorim, fenethacarb, fenfluthrin, fenfuram, fenhexamid, fenitropan, fenitrothion, fenjuntong, fenobucarb, fenoprop, fenoprop-3-butoxypropyl, fenoprop-butometyl, fenoprop-butotyl, fenoprop-butyl, fenoprop-isoctyl, fenoprop-methyl, fenoprop-potassium, fenothiocarb, fenoxacrim, fenoxanil, fenoxaprop, fenoxaprop-ethyl, fenoxaprop-P, fenoxaprop-P-ethyl, fenoxasulfone, fenoxycarb, fenpiclonil, fenpirithrin, fenpropathrin, fenpropidin, fenpropimorph, fenpyrazamine, fenpyroximate, fenridazon, fenridazon-potassium, fenridazon-propyl, fenson, 5 fensulfothion, fenteracol, fenthiaprop, fenthiaprop-ethyl, fenthion, fenthion-ethyl, fentin, fentin acetate, fentin chloride, fentin hydroxide, fentrazamide, fentrifanil, fenuron, fenuron TCA, fenvalerate, ferbam, ferimzone, ferrous sulfate, fipronil, flamprop, flamprop-isopropyl, flampropM, flamprop-methyl, flamprop-M-isopropyl, flamprop-M-methyl, flazasulfuron, flocoumafen, flometoquin, flonîcamid, florasulam, fluacrypyrim, fluazifop, fluazifop-butyl, fluazifop-methyl, 10 fluazifop-P, fluazifop-P-butyl, fluazinam, fluazolate, fluazuron, flubendiamide, flubenzimine, flucarbazone, flucarbazone-sodlum, flucetosulfuron, fluchloralin, flucofuron, flucycloxuron, flucythrinate, fludioxonil, fluenetil, fluensulfone, flufenacet, flufenerîm, flufenican, flufenoxuron, flufenprox, flufenpyr, flufenpyr-ethyl, flufiprole, flumethrin, flumetover, flumetralin, flumetsulam, flumezin, flumiclorac, flumiclorac-pentyl, flumioxazin, flumipropyn, flumorph, fluometuron, 15 fluopicolide, fluopyram, fluorbenside, fluoridamid, fluoroacetamide, fluorodifen, fluoroglycofen, fluoroglycofen-ethyl, fluoroimide, fluoromidine, fluoronitrofen, fluothiuron, fluotrimazole, fluoxastrobin, flupoxam, flupropacil, flupropadine, flupropanate, flupropanate-sodium, flupyradifurone, flupyrsulfuron, flupyrsulfuron-methyl, flupyrsulfuron-methyl-sodium, fluquinconazole, flurazole, flurenol, flurenol-butyl, flurenol-methyl, fluridone, flurochlorîdone, 20 fluroxypyr, fluroxypyr-butometyl, fluroxypyr-meptyl, flurprimidol, flursulamid, flurtamone, flusilazole, flusulfamide, fluthiacet, fluthiacet-methyl, flutianil, flutolanil, flutriafol, fluvalinate, fluxapyroxad, fluxofenim, folpet, fomesafen, fomesafen-sodium, fonofos, foramsulfuron, forchlorfenuron, formaldéhyde, formetanate, formetanate hydrochloride, formothion, formparanate, formparanate hydrochloride, fosamine, fosamine-ammonium, fosetyl, fosetyl25 aluminium, fosmethilan, fospirate, fosthiazate, fosthietan, frontalin, fuberidazole, fucaojing, fucaomi, funaihecaoling, fuphenthiourea, furalane, furalaxyl, furamethrin, furametpyr, furathiocarb, furcarbanil, furconazole, furconazole-cis, furethrin, furfural, furilazole, furmecyclox, furophanate, furyloxyfen, gamma-cyhalothrin, gamma-HCH, genit, gibberellic acid, gibberellins, gliftor, glufosinate, glufosinate-ammonium, glufosinate-P, glufosinate-P-ammonium, glufosinate-P-sodium, glyodin, glyoxime, glyphosate, glyphosate-diammonium, glyphosatedimethylammonium, glyphosate-isopropylammonium, glyphosate-monoammonium, glyphosatepotassium, glyphosate-sesquisodium, glyphosate-trimesium, glyphosine, gossyplure, grandlure, griseofulvin, guazatine, guazatine acétates, halacrinate, halfenprox, halofenozide, halosafen, halosulfuron, halosulfuron-methyl, haloxydine, haloxyfop, haloxyfop-etotyl, haloxyfop-methyl, haloxyfop-P, haloxyfop-P-etotyl, haloxyfop-P-methyl, haloxyfop-sodium, HCH, hemel, hempa, HEOD, heptachlor, heptenophos, heptopargil, heterophos, hexachloroacetone,
I (
hexachlorobenzene, hexachlorobutadiene, hexachlorophene, hexaconazole, hexaflumuron, hexaflurate, hexalure, hexamide, hexazinone, hexylthiofos, hexythiazox, HHDN, holosulf, huancaiwo, huangcaoling, huanjunzuo, hydramethylnon, hydrargaphen, hydrated lime, hydrogen cyanide, hydroprene. hymexazol, hyquincarb, IAA, IBA, icaridin, imazalil, imazalil nitrate, imazalil sulfate, imazamethabenz, imazamethabenz-methyl, imazamox, imazamoxammonium, imazapic, imazapic-ammonium, imazapyr, imazapyr-isopropylammonium, imazaquin, imazaquin-ammonium, imazaquin-methyl, imazaquin-sodium, imazethapyr, imazethapyr-ammonium, imazosulfuron, imibenconazole, imicyafos, imidacloprid, imidaclothiz, iminoctadine, iminoctadine triacetate, iminoctadine trialbesilate, imiprothrin, inabenfide, indanofan, indazîflam, indoxacarb, inezin, iodobonil, iodocarb, iodomethane, iodosulfuron, iodosulfuron-methyl, iodosulfuron-methyl-sodium, iofensulfuron, iofensulfuron-sodium, ioxynil, ioxynil octanoate, ioxynil-lithium, ioxynil-sodium, ipazine, ipconazole, ipfencarbazone, iprobenfos, iprodione, iprovalicarb, iprymidam, ipsdienol, ipsenol, IPSP, isamïdofos, isazofos, isobenzan, isocarbamid, isocarbophos, isocil, isodrîn, isofenphos, isofenphos-methyl, isolan, isomethiozin, isonoruron, isopolinate, isoprocarb, isopropalin, isoprothiolane, isoproturon, isopyrazam, isopyrimol, isothioate, isotianil, isouron, isovaledione, isoxaben, isoxachlortole, isoxadifen, isoxadifen-ethyl, isoxaflutole, isoxapyrifop, isoxathion, ivermectin, izopamfos, japonilure, japothrins, jasmolin I, jasmolin II, jasmonic acid, jiahuangchongzong, jiajizengxiaoiin, jiaxiangjunzhi, jiecaowan, jiecaoxi, jodfenphos, juvénile hormone I, juvénile hormone II, juvénile hormone III, kadethrin, karbutilate, karetazan, karetazan-potassium, kasugamycin, kasugamycin hydrochloride, kejunlin, kelevan, ketospiradox, ketospiradox-potassium, kinetin, kinoprene, kresoxim-methyl, kuicaoxi, lactofen, lambda-cyhalothrin, latilure, lead arsenate, lenacil, lepimectin, leptophos, lindane, lineatin, linuron, lirimfos, litlure, looplure, lufenuron, Ivdingjunzhi, Ivxiancaolin, lythidathion, MAA, malathion, maleic hydrazide, malonoben, maltodextrin, ΜΑΜΑ, mancopper, mancozeb, mandipropamid, maneb, matrine, mazidox, MCPA, MCPA-2-ethylhexyl, MCPA-butotyl, MCPA-butyl, MCPA-dimethylammonium, MCPAdiolamine, MCPA-ethyl, MCPA-isobutyl, MCPA-isoctyl, MCPA-isopropyl, MCPA-methyl, MCPAolamine, MCPA-potassium, MCPA-sodium, MCPA-thioethyl, MCPA-trolamine, MCPB, MCPBethyl, MCPB-methyl, MCPB-sodium, mebenil, mecarbam, mecarbinzid, mecarphon, mecoprop, mecoprop-2-ethylhexyl, mecoprop-dimethylammonium, mecoprop-diolamine, mecopropethadyl, mecoprop-isoctyl, mecoprop-methyl, mecoprop-P, mecoprop-P-2-ethylhexyl, mecoprop-P-dimethylammonium, mecoprop-P-isobutyl, mecoprop-potassium, mecoprop-Ppotassium, mecoprop-sodium, mecoprop-trolamine, medimeform, medinoterb, medinoterb acetate, medlure, mefenacet, mefenpyr, mefenpyr-diethyl, mefluidide, mefluidide-diolamine, mefluidide-potassium, megatomoic acid, menazon, mepanipyrim, meperfluthrin, mephenate, mephosfolan, mepiquat, mepiquat chloride, mepiquat pentaborate, mepronil, meptyldinocap, mercuric chloride, mercuric oxide, mercurous chloride, merphos, mesoprazine, mesosulfuron, mesosulfuron-methyl, mesotrione, mesulfen, mesulfenfos, metaflumizone, metalaxyl, metalaxylM, metaldehyde, metam, metam-ammonium, metamifop, metamitron, metam-potassium, metam-sodium, metazachlor, metazosulfuron, metazoxolon, metconazole, metepa, metflurazon, methabenzthiazuron, methacrifos, methalpropalin, methamidophos, methasulfocarb, methazole, methfuroxam, methidathion, methiobencarb, methiocarb, methiopyrisulfuron, methiotepa, methiozolin, methiuron, methocrotophos, methometon, methomyl, methoprene, methoprotryne, methoquin-butyl, methothrin, methoxychlor, methoxyfenozide, methoxyphenone, methyl apholate, methyl bromide, methyl eugenol, methyl iodide, methyl isothiocyanate, methylacetophos, methylchloroform, methyldymron, methylene chloride, methylmercury benzoate, methylmercury dicyandiamide, methylmercury pentachlorophenoxide, methylneodecanamide, metiram, metobenzuron, metobromuron, metofluthrin, metolachlor, metolcarb, metominostrobin, metosulam, metoxadiazone, metoxuron, metrafenone, metribuzin, metsulfovax, metsulfuron, metsulfuron-methyl, mevinphos, mexacarbate, mieshuan, milbemectin, milbemycin oxime, milneb, mipafox, mirex, MNAF, moguchun, molinate, molosultap, monalide, monisouron, monochloroacetic acid, monocrotophos, monolinuron, monosulfuron, monosulfuron-ester, monuron, monuron TCA, morfamquat, morfamquat dichloride, moroxydine, moroxydine hydrochloride, morphothion, morzid, moxidectin, MSMA, muscalure, myclobutanil, myclozolin, N-(ethylmercury)-p20 toluenesulphonanilide, nabam, naftalofos, naled, naphthalene, naphthaleneacetamide, naphthalic anhydride, naphthoxyacetic acids, naproanilide, napropamide, naptalam, naptalamsodium, natamycin, neburon, niclosamide, niclosamide-olamine, nicosulfuron, nicotine, nifluridide, nipyraclofen, nitenpyram, nithiazine, nitralin, nitrapyrin, nitrilacarb, nitrofen, nitrofluorfen, nitrostyrene, nitrothal-isopropyl, norbormide, norflurazon, nornicotine, noruron, novaluron, noviflumuron, nuarimol, OCH, octachlorodipropyl ether, octhilinone, ofurace, omethoate, orbencarb, orfralure, ortho-dichlorobenzene, orthosulfamuron, oryctalure, orysastrobin, oryzalin, osthol, ostramone, oxabetrinil, oxadiargyl, oxadiazon, oxadixyl, oxamate, oxamyl, oxapyrazon, oxapyrazon-dimolamine, oxapyrazon-sodium, oxasulfuron, oxaziclomefone, oxine-copper, oxolinic acid, oxpoconazole, oxpoconazole fumarate, oxycarboxin, oxydemeton-methyl, oxydeprofos, oxydisulfoton, oxyfluorfen, oxymatrine, oxytetracycline, oxytetracycline hydrochloride, paclobutrazol, paichongding, paradichlorobenzene, parafluron, paraquat, paraquat dichloride, paraquat dimetilsulfate, parathion, parathion-methyl, parinol, pebulate, pefurazoate, pelargonic acid, penconazole, pencycuron, pendimethalin, penflufen, penfluron, penoxsulam, pentachlorophenol, pentanochlor, penthiopyrad, pentmethrin, pentoxazone, perfluidone, permethrin, pethoxamid, phenamacril, phenazine oxide, phenisopham, phenkapton, phenmedipham, phenmedipham-ethyl,
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« rimsulfuron, rotenone, ryania, saflufenacil, saijunmao, saisentong, salicylanilide, sanguinarine, santonin, schradan, scilliroside, sebuthylazine, secbumeton, sedaxane, selamectin, semiamitraz, semiamitraz chloride, sesamex, sesamolin, sethoxydim, shuangjtaancaolin, siduron, siglure, silafluofen, silatrane, silica gel, silthiofam, simazine, simeconazole, simeton, simetryn, sintofen, SMA, S-metolachlor, sodium arsenite, sodium azide, sodium chlorate, sodium fluoride, sodium fiuoroacetate, sodium hexafluorosilicate, sodium naphthenate, sodium orthophenylphenoxide, sodium pentachlorophenoxide, sodium polysulfide, sodium thiocyanate, sodium a-naphthaleneacetate, sophamide, spinetoram, spinosad, spirodiclofen, spiromesifen, spirotetramat, spiroxamine, streptomycin, streptomycin sesquisulfate, strychnine, sulcatol, sulcofuron, sulcofuron-sodium, sulcotrione, sulfallate, sulfentrazone, sulfiram, sulfluramid, sulfometuron, sulfometuron-methyl, sulfosulfuron, sulfotep, sulfoxaflor, sulfoxide, sulfoxime, sulfur, sulfuric acid, sulfuryl fluoride, sulglycapin, sulprofos, sultropen, swep, fau-fluvalinate, tavron, tazimcarb, TCA, TCA-ammonïum, TCA-calcium, TCA-ethadyl, TCA-magnesium, TCAsodium, TDE, tebuconazole, tebufenozide, tebufenpyrad, tebufloquin, tebupirimfos, tebutam, tebuthiuron, tecloftalam, tecnazene, tecoram, teflubenzuron, tefluthrin, tefuryltrione, tembotrione, temephos, tepa, TEPP, tepraloxydim, terallethrin, terbacil, terbucarb, terbuchlor, terbufos, terbumeton, terbuthylazine, terbutryn, tetcyclacis, tetrachloroethane, tetrachlorvinphos, tetraconazole, tetradifon, tetrafluron, tetramethrin, tetramethylfluthrin, tetramine, tetranactin, tetrasul, thallium sulfate, thenylchlor, theta-cypermethrin, thiabendazole, thiacloprid, thiadifluor, thiamethoxam, thiapronil, thiazafluron, thiazopyr, thicrofos, thicyofen, thidiazimin, thidiazuron, thiencarbazone, thiencarbazone-methyl, thifensulfuron, thifensulfuronmethyl, thifluzamide, thiobencarb, thiocarboxime, thiochlorfenphim, thiocyclam, thiocyclam hydrochloride, thiocyclam oxalate, thiodiazole-copper, thiodicarb, thiofanox, thiofluoximate, thiohempa, thiomersal, thiometon, thronazin, thiophanate, thiophanate-methyl, thioquinox, thiosemicarbazide, thiosultap, thiosultap-diammonium, thiosultap-disodium, thiosultapmonosodium, thiotepa, thiram, thuringiensin, tiadinil, tiaojiean, tiocarbazil, tioclorim, tioxymid, tirpate, tolclofos-methyl, tolfenpyrad, tolylfluanid, tolylmercury acetate, topramezone, tralkoxydîm, tralocythrin, tralomethrin, tralopyril, transfluthrin, transpermethrin, tretamine, triacontanol, triadimefon, triadimenol, triafamone, tri-allate, triamiphos, triapenthenol, triarathene, triarimol, triasulfuron, triazamate, triazbutil, triaziflam, triazophos, triazoxide, tribenuron, tribenuron-methyl, trîbufos, tributyltin oxide, tricamba, trichlamide, trichlorfon, trichlormetaphos-3, trichloronat, triclopyr, triclopyr-butotyl, triclopyr-ethyl, triclopyrtriethylammonium, tricyclazole, tridemorph, tridiphane, trietazine, trifenmorph, trifenofos, trifloxystrobin, trifloxysulfuron, trifloxysulfuron-sodium, triflumizole, triflumuron, trifluralin, triflusulfuron, triflusulfuron-methyl, trifop, trifop-methyl, trifopsime, triforine, trihydroxytriazine, trimedlure, trimethacarb, trimeturon, trinexapac, trinexapac-ethyl, triprene, tripropindan, triptolide, tritac, triticonazole, tritosulfuron, trunc-call, uniconazole, uniconazole-P, urbacide, uredepa, valerate, validamycin, valifenalate, valone, vamidothion, vangard, vaniliprole, vernolate, vinclozolin, warfarin, warfarin-potassium, warfarin-sodium, xiaochongliulin, xinjunan, xiwojunan, XMC, xylachlor, xylenols, xylylcarb, yishijing, zarilamid, zeatin, zengxiaoan, zeta5 cypermethrin, zinc naphthenate, zinc phosphide, zinc thiazole, zineb, ziram, zolaprofos, zoxamide, zuomihuanglong, α-chlorohydrin, a-ecdysone, a-multistriatin, and anaphthaleneacetic acid. For more information consult the “Compendium of Pesticide Common Names located at http://www.alanwood.net/pesticides/index.html· Also consult “The Pesticide Manual 14th Edition, edited by C D S Tomlin, copyright 2006 by British Crop Production
Council, or its prîor or more recent éditions.
BIOPESTICIDES
Molécules of Formula One may also be used in combination (such as in a compositional mixture, or a simultaneous or sequentîal application) with one or more biopesticides. The term 15 “biopesticide” is used for microbial biological pest control agents that are applied in a similar manner to chemical pesticides. Commonly these are bacterial, but there are also examples of fungal control agents, including Trichoderma spp. and Ampelomyces quisqualis (a control agent for grape powdery mildew). Bacillus subtilis are used to control plant pathogens. Weeds and rodents hâve also been controlled with microbial agents. One well-known insecticide example is 20 Bacillus thuringiensis, a bacterial disease of Lepidoptera, Coleoptera, and Diptera. Because it has little effect on other organisms, it is considered more environmentally friendly than synthetic pesticides. Biological insecticides include products based on:
1.
2.
3.
entomopathogenîc fungi (e.g. Metarhizium anisopliae);
entomopathogenic nematodes (e.g. Steinernema feltiae); and entomopathogenîc viruses (e.g. Cydia pomonella granulovirus).
Other examples of entomopathogenic organisms include, but are not limited to, baculoviruses, bacteria and other prokaryotic organisms, fungi, protozoa and Microsproridia. Biologically derived insecticides include, but not limited to, rotenone, veratridine, as well as microbial toxins; insect tolérant or résistant plant varieties; and organisms modified by recombinant DNA technology to either produce insecticides or to convey an insect résistant property to the genetically modified organism. In one embodiment, the molécules of Formula One may be used with one or more biopesticides in the area of seed treatments and soit amendments. The Manual ofBiocontrol Agents gives a review of the available biological insecticide (and other biology-based control) products. Copping L.G. (ed.) (2004). The Manual of Biocontrol Agents (formerly the Biopesticide Manual) 3rd Edition. British Crop Production Council (BCPC), Farnham, Surrey UK.
OTHER ACTIVE COMPOUNDS
Molécules of Formula One may also be used in combination (such as in a compositional mixture, or a simultaneous or sequential application) with one or more of the following:
1. 3-(4-chloro-2,6-dimethylphenyl)-4-hydroxy-8-oxa-1 -azaspiro[4,5]dec-3-en-2-one;
2. 3-(4'-chloro-2,4-dimethyl[1,1'-biphenyl]-3-yl)-4-hydroxy-8-oxa-1-azaspiro[415]dec-3-en’2one;
3. 4-[[(6-chloro-3-pyridinyl)methyl]methylamino]-2(5/7)-furanone;
4. 4-[[(6-chloro-3-pyridinyl)methyl]cyclopropylamino]-2(5H)-furanone;
5. S-chloro-^-ftlSH-methyl^-imethylsulfonylJethylJ-A/l-^-methyl-^TV^^-tetrafluoro-
-(trifluo rom ethyl )ethyl] phe nyl]-1,2-benzenedicarboxamide;
6. 2-cyano-N-ethyl-4-fluoro-3-methoxy-benenesulfonamide;
7. 2-cyano-/V-ethyl-3-methoxy-benzenesulfonamide;
8. 2-cyano-3-difluoromethoxy-N-ethyl-4-fluoro-benzenesulfonamide;
9. 2-cyano-3-fluoromethoxy-/V-ethyl-benzenesulfonamide;
10. 2-cyano-6-fluoro-3-methoxy-N,A/-dimethyl-benzenesulfonamide;
11. 2-cyano-N-ethyl-6-fluoro-3-methoxy-N-methyl-benzenesulfonamide;
12. 2-cyano-3-difluoromethoxy-/V,A/-dimethylbenzenesulfon-amide;
13. 3-(difluoromethyl)-/V-[2-(3,3-dimethylbutyl)phenyl]-1-methyl-1H-pyrazole-4-carboxamide;
14. N-ethyl-2,2-dimethylpropionamide-2-(2(6-dichloro-a,a,a-trifluoro-p-tolyl) hydrazone;
15. A/-ethyl-2,2-dichloro-1-methylcyclopropane-carboxamide-2-(2,6-dichloro-a,a,a-trifluorop-tolyl) hydrazone nicotine;
16. 0-{(E-)-[2-(4-chloro-phenyl)-2-cyano-1 -(2-trifluoromethylphenyl)-vinyl]} S-methyl thiocarbonate;
17. (E)-N1-[(2-chloro-1,3-thiazol-5-ylmethyl)]-N2-cyano-N1-methylacetamidine;
18. 1 -(6-chloropyridin-3-ylmethyl)-7-methyl-8-nitro-1,2,3,5,6,7-hexahydro-imidazo[1,2a]pyridin-5-ol;
19. 4-[4-chlorophenyl-(2-butylidine-hydrazono)methyl)]phenyl mesylate; and
20. N-Ethyl“2,2-dichloro-1-methylcyclopropanecarboxamide“2-(2l6-dichloroa/p/7a,a/pha,a/pf?a-trifluoro-p-tolyl)hydrazone.
SYNERGISTIC MIXTURES
Molécules of Formula One may be used with certain active compounds to form synergistic mixtures where the mode of action of such compounds compared to the mode of action of the molécules of Formula One are the same, similar, or different. Examples of modes of action include, but are not limited to: acetylcholinesterase inhibitor; sodium channel modulator; chitin biosynthesis inhibitor; GABA and glutamate-gated chloride channel antagonist; GABA and glutamate-gated chloride channel agonist; acétylcholine receptor agonist; acétylcholine receptor antagonist; MET I inhibitor; Mg-stimulated ATPase inhibitor; nicotinic acétylcholine receptor; Midgut membrane disrupter; oxidative phosphorylation disrupter, and ryanodine receptor (RyRs). Generally, weight ratios of the molécules of Formula One in a synergistic mixture with another compound are from about 10:1 to about 1:10, in another embodiment from about 5:1 to about 1:5, and in another embodiment from about 3:1, and in another embodiment about 1:1.
FORMULATIONS
A pesticide is rarely suitable for application in its pure form. It is usually necessary to add other substances so that the pesticide can be used at the required concentration and in an appropriate form, permitting ease of application, handling, transportation, storage, and maximum pesticide activity. Thus, pesticides are formulated into, for example, baits, concentrated émulsions, dusts, emulsifiable concentrâtes, fumigants, gels, granules, microencapsulations, seed treatments, suspension concentrâtes, suspoemulsions, tablets, water soluble liquids, water dispersible granules or dry flowables, wettable powders, and ultra low volume solutions. For further information on formulation types see “Catalogue of Pesticide Formulation Types and International Coding System” Technical Monograph n°2, 5th Edition by CropLife International (2002).
Pesticides are applied most often as aqueous suspensions or émulsions prepared from concentrated formulations of such pesticides. Such water-soluble, water-suspendable, or emulsifiable formulations are either solids, usually known as wettable powders, or water dispersible granules, or liquids usually known as emulsifiable concentrâtes, or aqueous suspensions. Wettable powders, which may be compacted to form water dispersible granules, comprise an intimate mixture of the pesticide, a carrier, and surfactants. The concentration of the pesticide is usually from about 10% to about 90% by weight. The carrier is usually selected from among the attapulgite clays, the montmorillonite clays, the diatomaceous earths, or the purified silicates. Effective surfactants, comprising from about 0.5% to about 10% of the wettable powder, are found among sulfonated lignins, condensed naphthalenesulfonates, naphthalenesulfonates, alkylbenzenesulfonates, alkyl sulfates, and non-ionic surfactants such as ethylene oxide adducts of alkyl phénols.
Emulsifiable concentrâtes of pesticides comprise a convenient concentration of a pesticide, such as from about 50 to about 500 grams per liter of liquid dissolved in a carrier that is either a water miscible solvent or a mixture of water-immiscible organic solvent and emulsifiers. Useful organic solvents include aromatics, especially xylenes and petroleum fractions, especialiy the high-boiling naphthalenic and olefinic portions of petroleum such as heavy aromatic naphtha. Other organic solvents may also be used, such as the terpenic solvents including rosin dérivatives, aliphatic ketones such as cyclohexanone, and complex alcohols such as 2-ethoxyethanol. Suitable emulsifiers for emulsifiable concentrâtes are selected from conventional anionic and non-ionic surfactants.
Aqueous suspensions comprise suspensions of water-insoluble pesticides dispersed in an aqueous carrier at a concentration in the range from about 5% to about 50% by weight. Suspensions are prepared by finely grinding the pesticide and vigorously mixing it into a carrier comprised of water and surfactants. Ingrédients, such as inorganic salts and synthetic or natural gums may also be added, to increase the density and viscosity of the aqueous carrier. It is often most effective to grind and mix the pesticide at the same time by preparing the aqueous mixture and homogenizîng it in an implement such as a sand mill, bail mill, or piston-type homogenizer.
Pesticides may also be applied as granular compositions that are particularly useful for applications to the soil, Granular compositions usually contain from about 0.5% to about 10% by weight of the pesticide, dispersed in a carrier that comprises clay or a similar substance. Such compositions are usually prepared by dissolving the pesticide in a suitable solvent and applying it to a granular carrier which has been pre-formed to the appropriate particle size, in the range of from about 0.5 to about 3 mm. Such compositions may also be formulated by making a dough or paste of the carrier and compound and crushing and drying to obtain the desired granular particle size.
Dusts containing a pesticide are prepared by intimately mixing the pesticide 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 pesticide. They can be applied as a seed dressing or as a foliage application with a dust blower machine.
It is equally practical to apply a pesticide in the form of a solution in an appropriate organic solvent, usually petroleum oil, such as the spray oils, which are widely used in agricultural chemistry.
Pesticides can also be applied in the form of an aérosol composition. In such compositions the pesticide is dissolved or dispersed in a carrier, which is a pressure-generating propellant mixture. The aérosol composition is packaged in a container from which the mixture is dispensed through an atomizing valve.
Pesticide baits are formed when the pesticide is mixed with food or an attractant or both. When the pests eat the bait they also consume the pesticide. Baits may take the form of granules, gels, flowable powders, liquids, or solids. They can be used in pest harborages.
Fumîgants are pesticides that hâve a relatively high vapor pressure and hence can exist as a gas in sufficient concentrations to kill pests in soil or enclosed spaces. The toxicity of the fumigant is proportional to its concentration and the exposure time. They are characterized by a good capacity for diffusion and act by penetrating the pest's respiratory system or being absorbed through the pest’s cuticle. Fumîgants are applied to control stored product pests under gas proof sheets, in gas sealed rooms or buildings or in spécial chambers.
Pesticides can be microencapsulated by suspending the pesticide particles or droplets in plastic polymers of various types. By altering the chemistry of the polymer or by changing factors in the processing, microcapsules can be formed of various sizes, solubility, wall thicknesses, and degrees of penetrability. These factors govern the speed with which the active ingrédient within is released, which in turn, affects the residual performance, speed of action, and odor of the product.
Oil solution concentrâtes are made by dissolving pesticide in a solvent that will hold the pesticide in solution. Oil solutions of a pesticide usually provide faster knockdown and kill of pests than other formulations due to the solvents themselves having pesticidal action and the dissolution of the waxy covering of the integument increasing the speed of uptake of the pesticide. Other advantages of oil solutions include better storage stability, better pénétration of crevices, and better adhesion to greasy surfaces.
Another embodiment is an oil-in-water émulsion, wherein the émulsion comprises oily globules which are each provided with a lamellar liquid crystal coating and are dispersed in an aqueous phase, wherein each oily globule comprises at least one compound which is agrîculturally active, and is individually coated with a monolamellar or oligolamellar layer comprising: (1 ) at least one non-ionic lipophilie surface-active agent, (2) at least one non-ionic hydrophilic surface-active agent and (3) at least one ionic surface-active agent, wherein the globules having a mean particle diameter of less than 800 nanometers. Further information on the embodiment is disclosed in U.S. patent publication 20070027034 published February 1, 2007, having Patent Application serial number 11/495,228. For ease of use, this embodiment will be referred to as “OIWE.
For further information consult “Insect Pest Management 2nd Edition by D. Dent, copyright CAB International (2000). Additionally, for more detailed information consult “Handbook of Pest Control - The Behavior, Life History, and Control of Household Pests by Arnold Mallis, 9th Edition, copyright 2004 by GIE Media Inc.
OTHER FORMULATION COMPONENTS
Generally, when the molécules disclosed in Formula One are used in a formulation, such formulation can also contain other components. These components include, but are not «
t hmited to, (this is a non-exhaustive and non-mutually exclusive list) wetters, spreaders, stickers, pénétrants, buffers, sequestering agents, drift réduction agents, compatibility agents, anti-foam agents, cleaning agents, and emulsifiers. A few components are described forthwith.
A wetting agent is a substance that when added to a liquid increases the spreading or pénétration power of the liquid by reducing the interfacial tension between the liquid and the surface on which it is spreading. Wetting agents are used for two main functions in agrochemical formulations: during processing and manufacture to increase the rate of wetting of powders in water to make concentrâtes for soluble liquids or suspension concentrâtes; and during mixing of a product with water in a spray tank to reduce the wetting time of wettable powders and to improve the pénétration of water into water-dispersible granules. Examples of wetting agents used in wettable powder, suspension concentrate, and water-dispersible granule formulations are: sodium lauryl sulfate; sodium dioctyl sulfosuccinate; alkyl phénol ethoxylates; and aliphatic alcohol ethoxylates.
A dispersing agent is a substance which adsorbs onto the surface of particles and helps to preserve the state of dispersion of the particles and prevents them from reaggregating. Dispersing agents are added to agrochemical formulations to facilitate dispersion and suspension during manufacture, and to ensure the particles redisperse into water in a spray tank. They are widely used in wettable powders, suspension concentrâtes and water-dispersible granules. Surfactants that are used as dispersing agents hâve the ability to adsorb strongly onto a particle surface and provide a charged or steric barrier to reaggregation of particles. The most commonly used surfactants are anionic, non-ionic, or mixtures of the two types. For wettable powder formulations, the most common dispersing agents are sodium lignosulfonates. For suspension concentrâtes, very good adsorption and stabilization are obtained using polyelectrolytes, such as sodium naphthalene sulfonate formaldéhyde condensâtes.
Tristyrylphénol ethoxylate phosphate esters are also used. Non-ionics such as alkylarylethylene oxide condensâtes and EO-PO block copolymers are sometimes combined with anionics as dispersing agents for suspension concentrâtes. In recent years, new types of very high molecular weight polymeric surfactants hâve been developed as dispersing agents. These hâve very long hydrophobie ’backbones’ and a large number of ethylene oxide chains forming the 'teeth' of a ‘comb* surfactant. These high molecular weight polymers can give very good longterm stability to suspension concentrâtes because the hydrophobie backbones hâve many anchoring points onto the particle surfaces. Examples of dispersing agents used in agrochemical formulations are: sodium lignosulfonates: sodium naphthalene sulfonate formaldéhyde condensâtes; tristyrylphenol ethoxylate phosphate esters; aliphatic alcohol ethoxylates; alkyl ethoxylates; EO-PO block copolymers; and graft copolymers.
An emulsifying agent is a substance which stabilizes a suspension of droplets of one liquid phase in another liquid phase. Without the emulsifying agent the two liquids would separate into two immiscible liquid phases, The most commonly used emulsifier blends contain alkylphenol or aliphatic alcohol with twelve or more ethylene oxide units and the oii-soluble calcium sait of dodecylbenzenesulfonic acid. A range of hydrophile-lipophile balance (“HLB) values from 8 to 18 will normally provide good stable émulsions. Emulsion stability can sometimes be improved by the addition of a small amount of an EO-PO block copolymer surfactant.
A solubilizing agent is a surfactant which will form micelles in water at concentrations above the critical micelle concentration. The micelles are then able to dissolve or solubilize water-insoluble materials inside the hydrophobie part of the micelle. The types of surfactants usually used for solubilization are non-lonics, sorbitan monooleates, sorbitan monooleate ethoxylates, and methyl oleate esters.
Surfactants are sometimes used, either alone or with other additives such as minerai or vegetable oils as adjuvants to spray-tank mixes to improve the biological performance of the pesticide on the target. The types of surfactants used for bioenhancement dépend generally on the nature and mode of action of the pesticide. However, they are often non-ionics such as: alkyl ethoxylates; linear aliphatic alcohol ethoxylates; aliphatic amine ethoxylates.
A carrier or diluent in an agricultural formulation is a material added to the pesticide to give a product of the required strength. Carriers are usually materials with high absorptive capacities, while diluents are usually materials with low absorptive capacities. Carriers and diluents are used in the formulation of dusts, wettable powders, granules and water-dispersible granules.
Organic solvents are used mainly in the formulation of emulsifiable concentrâtes, oil-inwater émulsions, suspoemulsions, and ultra low volume formulations, and to a lesser extent, granular formulations. Sometimes mixtures of solvents are used. The first main groups of solvents are aliphatic paraffinic oils such as kerosene or refined parafons. The second main group (and the most common) comprises the aromatic solvents such as xylene and higher molecular weight fractions of C9 and C10 aromatic solvents. Chlorinated hydrocarbons are useful as cosolvents to prevent crystallization of pesticides when the formulation is emulsified into water. Alcohols are sometimes used as cosolvents to increase solvent power. Other solvents may include vegetable oils, seed oils, and esters of vegetable and seed oils.
Thickeners or gelling agents are used mainly in the formulation of suspension concentrâtes, émulsions and suspoemulsions to modify the rheology or flow properties of the liquid and to prevent séparation and settling of the dispersed particles or droplets. Thickening, gelling, and anti-settling agents generally fall into two categories, namely water-insoluble »
particulates and water-soluble polymers. It is possible to produce suspension concentrate formulations using clays and silicas. Examples of these types of materials, include, but are not limited to, montmorillonite, bentonite, magnésium aluminum silicate, and attapulgite. Watersoluble polysaccharides hâve been used as thickening-gelling agents for many years. The types of polysaccharides most commonly used are natural extracts of seeds and seaweeds or are synthetic dérivatives of cellulose. Examples of these types of materials include, but are not limited to, guar gum; locust bean gum; carrageenam; alginates; methyl cellulose; sodium carboxymethyl cellulose (SCMC); hydroxyethyl cellulose (HEC). Other types of anti-settling agents are based on modified starches, polyacrylates, polyvinyl alcohol and polyethylene oxide. Another good anti-settling agent is xanthan gum.
Microorganisms can cause spoilage of formulated products. Therefore préservation agents are used to eliminate or reduce their effect. Examples of such agents include, but are not limited to: propionic acid and its sodium sait; sorbic acid and its sodium or potassium salts; benzoic acid and its sodium sait; p-hydroxybenzoic acid sodium sait; methyl phydroxybenzoate; and 1,2-benzisothiazolin-3-one (BIT).
The presence of surfactants often causes water-based formulations to foam during mixing operations in production and in application through a spray tank. In order to reduce the tendency to foam, anti-foam agents are often added either during the production stage or before filling into bottles. Generally, there are two types of anti-foam agents, namely silicones and non-silicones. Silicones are usually aqueous émulsions of dimethyl polysiloxane, while the non-silicone anti-foam agents are water-insoluble oils, such as octanol and nonanol, or silica. In both cases, the function of the anti-foam agent is to displace the surfactant from the air-water interface.
“Green” agents (e.g., adjuvants, surfactants, solvents) can reduce the overall environmental footprint of crop protection formulations. Green agents are biodégradable and generally derived from natural and/or sustainable sources, e.g. plant and animal sources. Spécifie examples are: vegetable oils, seed oils, and esters thereof, also alkoxylated alkyl polyglucosides.
For further information, see “Chemistry and Technology of Agrochemical Formulations edited by D.A. Knowles, copyright 1998 by Kluwer Academie Publishers. Also see “Insecticides in Agriculture and Environment - Retrospects and Prospects by A.S. Perry, I. Yamamoto, I. Ishaaya, and R. Perry, copyright 1998 by Springer-Verlag.
PESTS
In general, the molécules of Formula One may be used to control pests e.g. beetles, earwigs, cockroaches, flies. aphids, scales, whiteflies, leafhoppers, ants, wasps, termites,
Λ
I moins, butterfhes, lice, grasshoppers, locusts, crickets, fleas, thrips, bristletails, mites, ticks, nematodes, and symphylans.
In another embodiment, the molécules of Formula One may be used to control pests in the Phyla Nematoda and/or Arthropoda.
In another embodiment, the molécules of Formula One may be used to control pests in the Subphyla Chelicerata, Myriapoda, and/or Hexapoda.
In another embodiment, the molécules of Formula One may be used to control pests in the Classes of Arachnida, Symphyla, and/or Insecta.
In another embodiment, the molécules of Formula One may be used to control pests of the Order Anoplura. A non-exhaustive list of particular généra includes, but is not limited to, Haematopinus spp„ Hoplopleura spp., Lïnognathus spp., Pediculus spp., and Polyplax spp, A non-exhaustive list of particular species includes, but is not limited to, Haematopinus asini, Haematopinus suis, Linognathus setosus, Lïnognathus ovillus, Pediculus humanus capitis, Pediculus humanus humanus, and Pthirus pubis.
In another embodiment, the molécules of Formula One may be used to control pests in the Order Coleoptera, A non-exhaustive list of particular généra includes, but is not limited to, Acanthoscelides spp., Agriotes spp., Anthonomus spp., Apion spp., Apogonia spp., Aulacophora spp., Bruchus spp., Cerostema spp., Cerotoma spp., Ceutorhynchus spp., Chaetocnema spp., Co/aspis spp., Ctenicera spp., Curculio spp., Cyclocephala spp., Diabrotica spp., Hypera spp., Ips spp., Lyctus spp., Megascelis spp., Meligethes spp., Otiorhynchus spp., Pantomorus spp., Phyllophaga spp., Phyllotreta spp., Rhizotrogus spp., Rhynchites spp., Rhynchophorus spp., Scolytus spp., Sphenophorus spp., Sitophilus spp., and Tribolium spp. A non-exhaustive list of particular species includes, but is not limited to, Acanthoscelides obtectus, Agrilus planipennis, Anoplophora glabripennis, Anthonomus grandis, Ataenius spretulus, Atomaria linearis, Bothynoderes punctiventris, Bruchus pisorum, Callosobruchus maculatus, Carpophilus hemipterus, Cassida vittata, Cerotoma trifurcata, Ceutorhynchus assimilis, Ceutorhynchus napi, Conoderus scalaris, Conoderus stigmosus, Conotrachelus nénuphar, Cotinis nitida, Crioceris asparagi, Cryptolestes ferrugineus, Cryptolestes pusillus, Cryptolestes turcicus, Cylindrocopturus adspersus, Deporaus marginatus, Dermestes lardarius, Dermestes maculatus, Epilachna varivestis, Faustinus cubae, Hylobius pales, Hypera postica, Hypothenemus hampei, Lasioderma serricorne, Leptinotarsa decemlineata, Liogenys fuscus, Liogenys suturalis, Lissorhoptrus oryzophîlus, Maecolaspis joliveti, Melanotus communis, Meligethes aeneus, Melolontha melolontha, Oberea brevis, Oberea linearis, Oryctes rhinocéros, Oryzaephilus mercator, Oryzaephilus surinamensis, Ouléma melanopus, Ouléma oryzae, Phyllophaga cuyabana, Popillia japonica, Prostephanus truncatus, Rhyzopertha dominica,, Sitona lineatus, Sitophilus granarius, Sitophilus oryzae, Sitophilus zeamais,
Stegobium paniceum, Tribolium castaneum, Tribolium confusum, Trogoderma variabile, and Zabrus tenebrioides.
In another embodiment, the molécules of Formula One may be used to control pests of the Order Dermaptera.
In another embodiment, the molécules of Formula One may be used to control pests of the Order Blattaria. A non-exhaustive list of particular species includes, but is not limited to, Blattella germanica, Blatta orientalis, Parcoblatta pennsylvanica, Periplaneta amerîcana, Periplaneta australasiae, Periplaneta brunnea, Periplaneta fuliginosa, Pycnoscelus surinamensis, and Supella longipalpa.
In another embodiment, the molécules of Formula One may be used to control pests of the Order Diptera. A non-exhaustive list of particular généra includes, but is not limited to, Aedes spp., Agromyza spp., Anastrepha spp., Anopheles spp., Bactrocera spp., Ceratitis spp., Chrysops spp., Cochliomyia spp., Contarinia spp., Culex spp., Dasineura spp., Délia spp., Drosophila spp., Fannia spp., Hylemyia spp., Liriomyza spp., Musca spp., Phorbia spp.,
Tabanus spp., and Tipula spp. A non-exhaustive list of particular species includes, but is not limited to, Agromyza frontella, Anastrepha suspensa, Anastrepha ludens, Anastrepha obliqa, Bactrocera cucurbitae, Bactrocera dorsalis, Bactrocera invadens, Bactrocera zonata, Ceratitis capitata, Dasineura brassicae, Délia piatura, Fannia canicularis, Fannia scalaris, Gasterophilus intestinalis, Gracillia perseae, Haematobia irritans, Hypoderma lineatum, Liriomyza brassicae,
Melophagus ovinus, Musca autumnalis, Musca domestica, Oestrus ovis, Oscinella frit, Pegomya betae, Psila rosae, Rhagoletis cerasi, Rhagoletis pomonella, Rhagoletis mendax, Sitodiplosis mosellana, and Stomoxys calcitrans.
In another embodiment, the molécules of Formula One may be used to control pests of the Order Hemiptera. A non-exhaustive list of particular généra includes, but is not limited to,
Adelges spp., Aulacaspis spp., Aphrophora spp., Aphis spp., Bemisia spp., Ceroplastes spp., Chionaspis spp., Chrysomphalus spp., Coccus spp., Empoasca spp., Lepidosaphes spp., Lagynotomus spp., Lygus spp., Macrosiphum spp., Nephotettix spp., Nezara spp., Philaenus spp., Phytocoris spp., Piezodorus spp., Planococcus spp., Pseudococcus spp., Rhopalosiphum spp., Saissetia spp., Therioaphis spp., Toumeyella spp., Toxoptera spp., Trialeurodes spp.,
Triatoma spp. and Unaspis spp. A non-exhaustive list of particular species includes, but is not limited to, Acrosternum hilare, Acyrthosiphon pisum, Aleyrodes proletelta, Aleurodicus dispersus, Aleurothrixus floccosus, Amrasca biguttula biguttula, Aonidiella aurantii, Aphis gossypii, Aphis glycines, Aphis pomi, Aulacorthum solani, Bemisia argentifolü, Bemisia tabaci, Blissus leucopterus, Brachycorynella asparagi, Brevennia rehi, Brevicoryne brassicae,
Caiocoris norvegicus, Ceroplastes rubens, Cimex hemipterus, Cimex lectularius, Dagbertus fasciatus, Dichelops furcatus, Diuraphis noxia, Diaphorina citri, Dysaphis plantaginea, i
Dysdercus suturellus, Edessa meditabunda, Eriosoma lanigerum, Eurygaster maura, Euschistus héros, Euschistus servus, Helopeltis antonii, Helopeltis theivora, Icerya purchasi, Idioscopus nitidulus, Laodelphax striatellus, Leptocorisa oratorius, Leptocorisa varîcornis, Lygus hesperus, Maconellicoccus hirsutus, Macrosiphum euphorbiae, Macrosiphum granarium, Macrosiphum rosae, Macrosteles quadrilineatus, Mahanarva frimbiolata, Metopolophium dirhodum, Midis longicornis, Myzus persicae, Nephotettix cindipes, Neurocolpus longirostris, Nezara viridula, Nilaparvata lugens, Parlatoria pergandii, Parlatoria ziziphï, Peregrinus maidis, Phylloxéra vitifoliae, Physokermes piceae,, Phytocoris californicus, Phytocoris relativus, Piezodorus guildinii, Poecilocapsus lineatus, Psallus vaccinicola, Pseudacysta perseae, Pseudococcus brevipes, Quadraspidiotus perniciosus, Rhopalosiphum maidis, Rhopalosiphum padi, Saissetia oleae, Scaptocoris castanea, Schizaphis graminum, Sitobion avenae, Sogatella furcifera, Trialeurodes vaporariorum, Trialeurodes abutiloneus, Unaspis yanonensis, and Zulia entrerriana.
In another embodiment, the molécules of Formula One may be used to control pests of the Order Hymenoptera. A non-exhaustive list of particular généra includes, but is not limited to, Acromyrmex spp., Atta spp., Camponotus spp., Diprion spp., Formica spp., Monomorium spp., Neodiprion spp., Pogonomyrmex spp., Polistes spp., Solenopsis spp., Vespula spp., and Xylocopa spp. A non-exhaustive list of particular species includes, but is not limited to, Athalia rosae, Atta texana, Iridomyrmex humilis, Monomorium minimum, Monomorium pharaonis, Solenopsis invicta, Solenopsis geminata, Solenopsis molesta, Solenopsis richtery, Solenopsis xyloni, and Tapinoma sessile.
In another embodiment, the molécules of Formula One may be used to control pests of the Order Isoptera. A non-exhaustive list of particular généra includes, but is not limited to, Coptotermes spp., Cornitermes spp., Cryptotermes spp., Heterotermes spp., Kalotermes spp., Incisitermes spp., Macrotermes spp., Marg initerme s spp., Microcerotermes spp., Procornitermes spp., Reticulitermes spp., Schedorhinotermes spp., and Zootermopsis spp. A non-exhaustive list of particular species includes, but is not limited to, Coptotermes curvignathus, Coptotermes frenchi, Coptotermes formosanus, Heterotermes aureus, Microtermes obesi, Reticulitermes banyulensis, Reticulitermes grassei, Reticulitermes flavipes, Reticulitermes hageni, Reticulitermes hesperus, Reticulitermes santonensis, Reticulitermes speratus, Reticulitermes tibialis, and Reticulitermes virginicus.
In another embodiment, the molécules of Formula One may be used to control pests of the Order Lepidoptera. A non-exhaustive list of particular généra includes, but is not limited to, Adoxophyes spp., Agrotis spp., Argyrotaenia spp., Cacoecia spp., Caloptilia spp., Chilo spp., Chrysodeixis spp., Colias spp., Crambus spp., Diaphania spp., Diatraea spp., Earias spp., Ephestia spp., Epimecis spp., Feltia spp., Gortyna spp., Helicoverpa spp., Heliothîs spp.,
Indarbela spp., Lithocolletis spp., Loxagrotis spp., Malacosoma spp., Peridroma spp., Phyllonorycter spp., Pseudaletia spp., Sesamia spp., Spodoptera spp., Synanthedon spp., and Yponomeuta spp. A non-exhaustive list of particular species includes, but is not limited to, Achaea janata, Adoxophyes orana, Agrotis ipsilon, Alabama argillacea, Amorbia cuneana,
Amyelois transitella, Anacamptodes defectaria, Anarsia lineatella, Anomis sabulifera, Anticarsia gemmatalis, Archips argyrospila, Archips rosana, Argyrotaenia citrana, Autographa gamma, Bonagota cranaodes, Borbo cinnara, Bucculatrix thurberiella, Capua reticulana, Carposîna niponensis, Chlumetia transversa, Choristoneura rosaceana, Cnaphalocrocis medinalis, Conopomorpha cramerella, Cossus cossus, Cydia caryana, Cydia funebrana, Cydia molesta,
Cydia nigricana, Cydia pomonella, Darna diducta, Diatraea saccharalis, Diatraea grandiosella, Earias insulana, Earias vittella, Ecdytolopha aurantianum, Elasmopalpus lignosellus, Ephestia cautella, Ephestia elutella, Ephestia kuehniella, Epinotia aporema, Epiphyas postvittana, Erionota thrax, Eupoecilia ambiguella, Euxoa auxiliaris, Grapholita molesta, Hedylepta Indicata, Helicoverpa armigera, Helicoverpa zea, Heliothis virescens, Hellula undalis, Keiferia lycopersicella, Leucinodes orbonalis, Leucoptera coffeella, Leucoptera malifoliella, Lobesia botrana, Loxagrotis albicosta, Lymantria dispar, Lyonetia clerkella, Mahasena corbetti, Mamestra brassicae, Maruca testulalis, Metisa plana, Mythimna unipuncta, Neoleucinodes elegantalis, Nymphula depunctalis, Operophtera brumata, Ostrinia nubilalis, Oxydia vesulia, Pandemis cerasana, Pandemis heparana, Papilio demodocus, Pectinophora gossypiella,
Peridroma saucia, Perileucoptera coffeella, Phthorimaea operculella, Phyllocnistis citrella, Pieris rapae, Plathypena scabra, Plodia interpunctella, Plutella xylostella, Polychrosis viteana, Prays endocarpa, Prays oleae, Pseudaletia unipuncta, Pseudoplusia includens, Rachiplusia nu, Scirpophaga incertulas, Sesamia inferens, Sesamia nonagrioides, Setora nitens, Sitotroga cerealella, Sparganothis pilleriana, Spodoptera exigua, Spodoptera frugiperda, Spodoptera eridania, Thecla basilides, Tineola bisselliella, Trîchoplusia ni, Tuta absoluta, Zeuzera coffeae, and Zeuzera pyrina.
In another embodiment, the molécules of Formula One may be used to control pests of the Order Mallophaga. A non-exhaustive list of particular généra includes, but is not limited to, Anaticola spp., Bovicola spp., Chelopistes spp., Goniodes spp., Menacanthus spp., and
Trichodectes spp. A non-exhaustive list of particular species includes, but is not limited to, Bovicola bovis, Bovicola caprae, Bovicola ovis, Chelopistes meleagridis, Goniodes dissimilis, Goniodes gigas, Menacanthus stramineus, Menopon gallinae, and Trichodectes canis.
In another embodiment, the molécules of Formula One may be used to control pests of the Order Orthoptera. A non-exhaustive list of particular généra includes, but is not limited to, 35 Melanoplus spp., and Pterophylla spp. A non-exhaustive list of particular species includes, but is not limited to, Anabrus simplex, Gryllotalpa africana, Gryllotalpa australis, Gryllotalpa brachyptera, Gryllotalpa hexadactyla, Locusta migratoria, Microcentrum retinerve, Schistocerca gregaria, and Scudderia furcata.
In another embodiment, the molécules of Formula One may be used to control pests of the Order Siphonaptera. A non-exhaustive list of particular species includes, but is not limited 5 to, Ceratophyllus gallinae, Ceratophyllus niger, Ctenocephalides canis, Ctenocephalides felis, and Pulex irritans.
In another embodiment, the molécules of Formula One may be used to control pests of the Order Thysanoptera. A non-exhaustive list of particular généra includes, but is not limited to, Caliothrips spp., Frankliniella spp., Scirtothrips spp., and Thrips spp. A non-exhaustive list of tO particular sp. includes, but is not limited to, Frankliniella fusca, Frankliniella occidentalis, Frankliniella schultzel, Frankliniella williamsi, Heliothrips haemorrhoidalis, Rhipiphorothrips cruentatus, Scirtothrips cîtri, Scirtothrips dorsalis, and Taeniothrips rhopalantennalis, Thrips hawaiiens!s, Thrips nigropilosus, Thrips orientalis, Thrips tabaci.
In another embodiment, the molécules of Formula One may be used to control pests of 15 the Order Thysanura. A non-exhaustive list of particular généra includes, but is not limited to, Lepisma spp. and Thermobia spp.
In another embodiment, the molécules of Formula One may be used to control pests of the Order Acarina. A non-exhaustive list of particular généra includes, but is not limited to, Acarus spp., Aculops spp., Boophilus spp., Demodex spp., Dermacentor spp., Epitrimerus spp., 20 Eriophyes spp., Ixodes spp., Oligonychus spp., Panonychus spp., Rhizoglyphus spp., and Tetranychus spp. A non-exhaustive list of particular species includes, but is not limited to, Acarapis woodi, Acarus siro, Aceria mangiferae, Aculops lycopersici, Aculus pelekassi, Aculus schlechtendali, Amblyomma americanum, Brevipalpus obovatus, Brevipalpus phoenicis, Dermacentor variabilis, Dermatophagoides pteronyssinus, Eotetranychus carpini, Notoedres cati, Oligonychus coffeae, Oligonychus ilicis, Panonychus citri, Panonychus ulml, Phyllocoptruta oleivora, Polyphagotarsonemus latus, Rhipicephalus sanguineus, Sarcoptes scabiei, Tegolophus perseaflorae, Tetranychus urticae, and Varroa destructor.
In another embodiment, the molécules of Formula One may be used to control pest of the Order Symphyla. A non-exhaustive list of particular sp. includes, but is not limited to,
Scutigerella immaculata,
In another embodiment, the molécules of Formula One may be used to control pests of the Phylum Nematoda. A non-exhaustive list of particular généra includes, but is not limited to, Aphelenchoidesspp., Belonolaimus spp., Criconemella spp., Ditylenchus spp., Heterodera spp., Hirschmanniella spp., Hoplolaimus spp., Meloidogyne spp., Pratylenchus spp., and
Radopholus spp. A non-exhaustive list of particular sp. includes, but is not limited to, Dirofilaria immitis, Heterodera zeae, Meloidogyne incognita, Meloidogyne javanica, Onchocerca volvulus, Radopholus similis, and Rotylenchulus reniformis.
For additional information consult Handbook of Pest Control-The Behavior, Life History, and Control of Household Pests by Arnold Mallis, 9th Edition, copyright 2004 by 5 GIE Media Inc.
APPLICATIONS
Molécules of Formula One are generally used in amounts from about 0.01 grams per hectare to about 5000 grams per hectare to provide control. Amounts from about 0.1 grams per 10 hectare to about 500 grams per hectare are generally preferred, and amounts from about 1 gram per hectare to about 50 grams per hectare are generally more preferred.
The area to which a molécule of Formula One is applied can be any area inhabited (or maybe inhabited, or traversed by) a pest, for example: where crops, trees, fruits, cereals, fodder species, vines, turf and ornamental plants, are growing; where domesticated animais are 15 residing; the interior or exterior surfaces of buildings (such as places where grains are stored), the materials of construction used in building (such as impregnated wood), and the soil around buildings. Particular crop areas to use a molécule of Formula One include areas where apples, corn, sunflowers, cotton, soybeans, canola, wheat, rice, sorghum, barley, oats, potatoes, oranges, alfalfa, lettuce, strawberries, tomatoes, peppers, crucifers, pears, tobacco, almonds, 20 sugar beets, beans and other valuable crops are growing or the seeds thereof are going to be planted. It is also advantageous to use ammonium sulfate with a molécule of Formula One when growing various plants.
Controlling pests generally means that pest populations, pest activity, or both, are reduced in an area. This can corne about when: pest populations are repulsed from an area;
when pests are incapacitated in or around an area; or pests are exterminated, in whole, or in part, in or around an area. Of course, a combination of these results can occur. Generally, pest populations, activity, or both are desirably reduced more than fifty percent, preferably more than 90 percent. Generally, the area is not in or on a human; consequently, the locus is generally a non-human area.
The molécules of Formula One may be used in mixtures, applied simultaneously or sequentially, alone or with other compounds to enhance plant vigor (e.g. to grow a better root System, to better withstand stressful growing conditions). Such other compounds are, for example, compounds that modulate plant ethylene receptors, most notably 1methylcyclopropene (also known as 1-MCP). Furthermore, such molécules may be used during times when pest activity is low, such as before the plants that are growing begin to produce
V valuable agricultural commodities. Such times include the early planting season when pest pressure is usually low.
The molécules of Formula One can be applied to the foliar and fruiting portions of plants to control pests. The molécules will either corne in direct contact with the pest, or the pest will consume the pesticide when eating leaf, fruit mass, or extracting sap, that contains the pesticide. The molécules of Formula One can also be applied to the soil, and when applied in this manner, root and stem feeding pests can be controlled. The roots can absorb a molécule taking it up into the foliar portions of the plant to control above ground chewing and sap feeding pests.
Generally, with baits, the baits are placed in the ground where, for example, termites can corne into contact with, and/or be attracted to, the bait. Baits can also be applied to a surface of a building, (horizontal, vertical, or slant surface) where, for example, ants, termites, cockroaches, and flies, can corne into contact with, and/or be attracted to, the bait. Baits can comprise a molécule of Formula One.
The molécules of Formula One can be encapsulated inside, or placed on the surface of a capsule. The size of the capsules can range from nanometer size (about 100-900 nanometers in diameter) to micrometer size (about 10-900 microns in diameter).
Because of the unique ability of the eggs of some pests to resist certain pesticides, repeated applications of the molécules of Formula One may be désirable to control newly emerged larvae.
Systemic movement of pesticides in plants may be utilized to control pests on one portion of the plant by applying (for example by spraying an area) the molécules of Formula One to a different portion of the plant. For example, control of foliar-feeding insects can be achieved by drip irrigation or furrow application, by treating the soil with for example pre- or post-planting soil drench, or by treating the seeds of a plant before planting.
Seed treatment can be applied to ail types of seeds, including those from which plants genetically modified to express specialized traits will germinate. Représentative examples include those expressing proteins toxic to invertebrate pests, such as Bacillus thuringiensis or other insecticidal toxins, those expressing herbicide résistance, such as “Roundup Ready” seed, or those with “stacked” foreign genes expressing insecticidal toxins, herbicide résistance, nutrition-enhancement, drought résrstance, or any other bénéficiai traits. Furthermore, such seed treatments with the molécules of Formula One may further enhance the ability of a plant to better withstand stressful growing conditions. This results in a healthier, more vigorous plant, which can lead to higher yields at harvest time. Generally, about 1 gram of the molécules of Formula One to about 500 grams per 100,000 seeds is expected to provide good benefits, amounts from about 10 grams to about 100 grams per 100,000 seeds is expected to provide better benefits, and amounts from about 25 grams to about 75 grams per 100,000 seeds is expected to provide even better benefits.
It should be readily apparent that the molécules of Formula One may be used on, in, or around plants genetically modified to express specialized traits, such as Bacillus thuringiensis or other insecticidal toxins, or those expressing herbicide résistance, or those with “stacked foreign genes expressing insecticidal toxins, herbicide résistance, nutrition-enhancement, or any other bénéficiai traits.
The molécules of Formula One may be used for controliing endoparasites and ectoparasites in the veterinary medicine sector or in the fleld of non-human animal keeping. The molécules of Formula One are applied, such as by oral administration in the form of, for example, tablets, capsules, drinks, granules, by dermal application in the form of, for example, dipping, spraying, pouring on, spotting on, and dusting, and by parentéral administration in the form of, for example, an injection.
The molécules of Formula One may also be employed advantageously in livestock keeping, for example, cattle, sheep, pigs, chickens, and geese. They may also be employed advantageously in pets such as, horses, dogs, and cats. Particular pests to control would be fleas and ticks that are bothersome to such animais. Suitable formulations are administered orally to the animais with the drinking water or feed. The dosages and formulations that are suitable dépend on the species.
The molécules of Formula One may also be used for controliing parasitic worms, especially of the intestine, in the animais listed above.
The molécules of Formula One may also be employed in therapeutic methods for human health care. Such methods include, but are limited to, oral administration in the form of, for example, tablets, capsules, drinks, granules, and by dermal application.
Pests around the world hâve been migrating to new environments (for such pest) and thereafter becoming a new invasive species in such new environment. The molécules of Formula One may also be used on such new invasive species to control them in such new environment.
The molécules of Formula One may also be used in an area where plants, such as crops, are growing (e.g. pre-planting, planting, pre-harvesting) and where there are low levels (even no actual presence) of pests that can commercially damage such plants. The use of such molécules in such area is to benefit the plants being grown in the area. Such benefits, may include, but are not limited to, improving the health of a plant, improving the yield of a plant (e.g. increased biomass and/or increased content of valuable ingrédients), improving the vigor of a plant (e.g. improved plant growth and/or greener leaves), improving the quality of a plant (e.g.
improved content or composition of certain ingrédients), and improving the tolérance to abiotic and/or biotic stress of the plant.
Before a pesticide can be used or sold commercially, such pesticide undergoes lengthy évaluation processes by various governmental authorities (local, régional, state, national, and international). Voluminous data requirements are specified by regulatory authorities and must be addressed through data génération and submission by the product registrant or by a third party on the product registrant's behalf, often using a computer with a connection to the World Wide Web. These governmental authorities then review such data and if a détermination of safety is concluded, provide the potential user or seller with product registration approval. Thereafter, in that locality where the product registration is granted and supported, such user or seller may use or sell such pesticide.
A molécule according to Formula One can be tested to détermine its efficacy against pests. Furthermore, mode of action studies can be conducted to détermine if said molécule has a different mode of action than other pesticides. Thereafter, such acquired data can be disseminated, such as by the internet, to third parties.
The headings in this document are for convenience only and must not be used to interpret any portion hereof.
TABLE SECTION
Table 1. Compound Number and Structure
Compound No. Appearance Structure
1 4‘Wh’
2 x ch, fj p CH,
3 Orange Oil P H, O Η-Λν? /—CH, r y
4 0 CH, U )LC’K, H,C
5 Semi-solid CH,° Γ\_ΛσΗ3
6 Yellow Oil CH,° nX /-ch, q^-Λ.. N
7 Yellow Oil L/-<rch, ^tr
8 Yellow Solid F F J'/'-·... N
9 Yellow Oil -
10 Yellow Oil CH, q CHj
11 Yellow Oil
12 Yellow Oil CHj 0 FF
13 Yellow Solid PH1O ch nF AF H’c
14 Yellow Solid CHj O AF H’c
15 Yellow Oil
16 Yellow Oil _ZHjWh’ c,,‘ V
17 Yellow Oil ryM CH1 < HjC N
18 Yellow Oil
19 Yellow Oil cÆT
20 Yellow Oil P1’0, cil Νχ O111 en? ~
21 Yellow Oil
22 Yellow Oil X”W'
23 Yellow Oil A y ch,
24 Yellow Oil AH’ CH> M ic
25 White Oil ΧΆ
26 Yellow Oil
27 White Oil CH „ /«> O*
28 Yellow Oil z^A/-n\ ch> < ch,
29 Yellow Oil rr
30 Yellow Oil rCW’ 0¾
31 Yellow Oil C1O VX /—CH, Ci ~N> v
32 Yellow Oil C J ch’
33 White Oil ch30 /-ch 3 σ4?
34 White Oil
35 Yellow Oil vJÎK. ΎΎ CK) CH,
36 Yellow Oil rCW''’ Fy^Y/ 'c,l> IL HjC N
37 White Oil ’yY ) f CH, LL Λ h,c
38 Yellow Oil /W-
39 Brown Solid 7C‘ °\ c/
40 Yellow Oil (/χ
41 Yellow Oil h: kx N
Table 2. Analytical Data
Compound No. MP (°C) IR (cm' 1) Mass HNMR CNMR
1 122- 125 ESIMS m/z 259 (M+1) 1H NMR (400 MHz, DMSO-dg) δ 8.97 (br s, 1H), 8.42 (dd, 7 = 4.8, 1.5 Hz, 1H). 8.12-8.01 (m, 2H), 7.41-7.38 (m, 1H), 3.27 (s, 3H), 2.24 (s, 3H), 2.19-2.09 (m, 1H), 0.98 (d, 7 = 7.2 Hz, 6H).
2 1682 ESIMS m/z 304 (M+1) 1H NMR (400 MHz, CDCI3) C 8.94 (br s, 1 H). 8.47 (dd, 7 = 5.0, 1.4 Hz, 1H), 8.04 (dt, 7 = 8.2, 1.5 Hz, 1H). 7.36-7.27 (m, 2H), 3.39 (s, 3H), 3.25-3.18 (m, 1H), 2.38 (s, 3H), 2.27-2.19 (m, 2H), 2.02 (s, 3H), 1.24 (d, 7 = 6.2 Hz, 3H).
3 1717 ESIMS m/z 289 (M+1) 1H NMR (400 MHz, CDCI3) 5 8.92 (d, J = 2.4 Hz, 1H), 8.43 (dd, 7 = 4.9,1.4 Hz, 1H), 8.03 (dt, 7 = 8.3, 1.6 Hz, 1H), 7.28 (dd, 7= 7.7, 4.8 Hz, 1H), 7.21 (s, 1H), 3.38 (s, 3H), 2.36 (s, 3H), 1.43 (s, 9H).
4 3389, 2978, 2930, 1730, 1478, 1275, 1252, 1156, 1017, 951, 711, 573 ESIMS m/z 289 (M+1), 287 (M-1) ’H NMR (300 MHz, DMSO, Major isomer) Ô 10.41 (s, 1H), 8.81 (s, 1H), 8.39 (s, 1H), 7.95 (d, 7 = 8.0 Hz, 1H), 7.44 - 7.28 (m, 1H), 2.21 (s, 3H), 2.18 (s, 3H), 1.46 (s, 9H).
5 ESIMS m/z 217 [(M+H)]+. ’H NMR (300 MHz, CDCI3) δ 10.87 (s, 1H), 8.76 (s, 1H), 8.36 (brs, 1H), 7.96 (d, J=7.7, 1H), 7.31-7.20 (m,2H), 2.25 (s, 3H), 2.13 (s, 3H). 13C NMR (76 MHz, CDCI3) δ 169.11, 147.16, 146.66, 145.81, 135.00, 132.92, 124.15, 116.96, 30.11, 21.26, 12.22.
6 ESIMS m/z 231 ([M+Hf). 1H NMR (300 MHz, CDCI3) δ 8.98-8.87(m, 1H), 8.50 (s, 1H), 8.07 (dd, J = 7.6, 2.0 Hz, 1H). 7.36-7.31 (m, 1H), 7.30-7.28 (m, 1H), 3.35 (s, 3H), 2.38 (d, J= 1.3 Hz. 3H), 1.84 (s, 3H). 13C NMR (76 MHz, CDCh) δ 171.74, 148.65, 146.34, 145.35, 137.32, 132.34, 129.32, 123.94, 114.61, 36.83, 20.20,12.15.
7 ESIMS m/z 273 ([M+Hf). 1H NMR (300 MHz, CDCI3) δ 8.93 (s, 1H), 8.47 (s, 1H), 8.11-8.02 (m, 1H), 7.30 (d, J =1.4 Hz, 2H), 3.31 (d, J = 2.1 Hz, 3H), 2.37 (d, J = 2.1 Hz, 3H), 1.13 (d, J= 2.1 Hz, 9H). ,3C NMR (76 MHz, CDCI3) δ 153.30, 148.16, 146.33, 136.37, 132.44, 123.63, 116.04, 40.57, 28.44, 27.49, 16.33, 12.63, 12.61.
8 130.9 131.5 ESIMS m/z 299 ([M+Hf). 1H NMR (300 MHz, CDCI3) δ 8.96 (s, 1H), 8.54 (d, J4.3 Hz, 1H), 8.08 (d. J 7.9 Hz, 1H), 7.39-7.31 (m, 1 H), 7.30 (s. 1H), 3.43 (s, 3H), 3.05-2.78 (m, 2H), 2.41 (s, 3H).
6I
9 ESIMS m/z 273 ([M+Hf). 1H NMR (300 MHz. CDCI3) Ô 8.95 (s, 1 H), 8.51 (s, 1H), 8.08 (d, J =7.9 Hz, 1H), 7.33 (dd, J= 7.6, 5.0 Hz, 1H), 7.26 (s, 1H), 3.38 (s, 3H), 2.37 (s, 3H), 2.12 -1.92(m, 2H), 1.60 (dt, J = 14.8, 7.3 Hz, 2H), 1.351.20 (m, 2H), 0.86 (t, J = 7.2 Hz, 3H). 13C NMR (76 MHz, CDCI3) δ 174.17, 147.97, 146.43, 145.42, 136.73, 132.21, 123.65, 114.79, 37.11, 31.51, 30.09, 26.99, 22.56, 14.33, 12.43.
10 ESIMS m/z 291 ([M+Hf). 1H NMR (300 MHz, CDCI3) 6 8.97-8.89 (d, J = 2.4 Hz, 1H), 8.54-8.44 (m, 1H), 8.11 -7.98 (m, 1H), 7.35 - 7.28 (m, 2H), 3.42 - 3.38 (s, 3H), 2.85-2.66 (t, J = 6.9 Hz, 2H), 2.42- 2.38 (S, 3H), 2.37-2.16 (m, 2H). 2.09-2.00 (s. 3H). 13C NMR (76 MHz, CDCI3) δ 172.34, 148.63, 146.47, 145.34, 137.05, 132.21, 128.84, 123.56, 114.79, 37.14, 31.46,29.22, 16.10, 12.38.
11 ESIMS m/z 313 ([M+Hf). ’H NMR (300 MHz, CDCI3) δ 8.92 (s, 1H), 8.47 (s, 1H), 8.08 (d, J =7.8 Hz, 1H), 7.38-7.23 (m, 2H), 3.81 (dd, J= 14.1, 7.1 Hz, 1H), 3.30 (dd, J= 14.2, 7.1 Hz, 1H), 2.39 (s, 3H), 1.21 (s, 3H), 1.12 (s, 9H), 0.96 -0.80(m, 1H), 0.54-0.43 (m. 2H), 0.08 (d. J = 4.7 Hz, 2H). 13C NMR (76 MHz, CDCI3) δ 177.72, 148.07. 147.05, 146.11, 135.23, 132.08, 129.62, 123.72, 117.42, 56.21, 40.51,29.96, 28.76, 27.70,12.70, 8.86, 4.34, 3.33.
12 ESIMS m/z 339 ([M+Hf). 1H NMR (300 MHz, CDCI3) 6 8.96 (s, 1H), 8.52 (s, 1H), 8.10 (dd, 7 = 8.0, 1.9 Hz, 1H), 7.36 (dd, 7 = 8.4, 5.2 Hz, 1H), 7.31 (s, 1H), 3.86-3.71 (m, 1H), 3.663.52 (m, 1H), 3.05-2.79 (m, 2H), 2.43 (s, 3H), 0.89 (ddd, 7=7.6, 4.9, 2.7 Hz, 1H), 0.63-0.52 (m, 2H), 0.22 (t, 7=3.8 Hz, 2H). 13C NMR (76 MHz, CDCh) 6 164.22, 148.46, 146.04, 137.03, 132.33, 129.01, 125.67, 123.65, 122.27, 115.77, 53.92, 37.26, 36.87, 36.47, 36.07, 12.21,8.56, 4.20, 3.44.
13 ESIMS m/z 287 ([M+Hf). 1H NMR (300 MHz, CDCI3) 6 8.95 (s, 1H), 8.51 (s, 1H), 8.09 (dt,7 = 8.0, 1.8 Hz, 1H), 7.32 (m, 1H), 7.27 (s, 1H), 4.14 (dq, 7 =14.3, 7.2 Hz, 1H), 3.40 (dq, 7 = 14.1,7.1 Hz, 1H), 2.39 (s, 3H), 1.26-1.17 (m, 3H), 1.14 (s, 9H). 13C NMR (76 MHz, CDCh) 6 177.89, 148.35, 146.90, 135.90, 132.36, 129.57, 123.88, 117.53, 47.56, 40.55, 29.93, 28.66, 27.64, 12.88.
14 ESIMS m/z 313 ([M+Hf). 1H NMR (300 MHz, CDCI3) 6 8.98 (d, 7 = 2.2 Hz, 1H), 8.52 (s, 1H>, 8.17-7.99 (m, 1H), 7.43-7.29 (m, 1H), 4.13 (dq, 7= 14.4, 7.3 Hz, 1H), 3.68 (dq, 7 = 14.2, 7.1 Hz, 1H), 2.85 (dt, 7= 17.6, 8.2 Hz. 2H), 2.40 (s, 3H), 1.20 (t, 7 = 7,2 Hz, 3H). 13C NMR (76 MHz, CDCI3) 6 148.88, 146.66, 146.01, 132.54, 129.05, 125.45, 123.94, 121.78, 115.69, 44.82, 37.08, 36.61, 29.96, 12.59, 12.19.
15 ESIMS m/z 313 ([M+H]4). ’H NMR (300 MHz. CDCI3) 6 8.95 (s, 1H), 8.50 (d, J = 4.8 Hz. 1H). 8.09 (d, J = 7.9 Hz. 1H). 7.33 (dd, J = 8.0, 4.9 Hz. 1H), 7.277.26 (m, 2H), 3.82-3.65 (m, 1H), 3.65-3.51 (m, 1H), 2.40 (s, 3H), 2.081.92 (m, 2H), 1.59 (p, J = 7.4 Hz, 2H), 1.34-1.15 (m, 4H), 1.01 -0.91 (m, 1H), 0.85 (t, J = 7.3 Hz, 3H), 0.54 (d, J = 8.0 Hz, 2H), 0.18 (t, J = 4.6 Hz, 2H). 13C NMR (76 MHz, CDCI3) 6 154.33, 153.77, 148.52, 146.65, 132.25, 123.85, 115.84, 53.59, 31.69, 29.94, 26.85, 24.05, 22.55, 14.06, 12.42, 9.17, 4.24, 3.70.
16 ESIMS m/z 319 ([M+H]4). 1H NMR (301 MHz, CDCI3) 6 8.98 (s, 1H), 8.51 (s, 1H), 8.21 (d, J= 7.6 Hz, 1H), 7.51 -7.34 (m, 2H), 3.36 (s, 3H), 2.84 (d, J = 12.7 Hz. 1H), 2.69-2.58 (m, 1H), 2.45 (s, 3H), 2.15 (s, 3H), 1.24 (s, 3H), 1.15 (d, J = 8.7 Hz, 3H). 13C NMR (76 MHz, CDCI3) 6 176.05, 146.89, 146.39, 144.66, 135.66, 133.74, 124,44, 116.68, 47.84, 46.51, 40.76, 30.03, 26.48, 25.90, 18.35, 12.69.
17 ESIMS m/z 273 ([M+H]4). 1H NMR (300 MHz. CDCI3) 6 8.93 (s, 1H), 8.48 (s, 1H), 8.06 (d, J = 7.9 Hz, 1H), 7.30 (dd, J= 7.6, 4.8 Hz, 1H), 7.22 (s, 1H), 4.03 (dt, J= 14.3, 7.1 Hz, 1H), 3.61 (dq, J= 14.1, 7.1 Hz, 1H). 2.35 (s, 3H). 2.21 (s, 1H), 1.20- 1.15(m, 3H), 1.08 (d, J = 6.4 Hz. 6H). 13C NMR (76 MHz, CDCI3) 6 148.36, 146.47, 146.18, 136.36, 132.27, 123.80, 116.23, 44.53, 30.11,20.70, 19.54, 12.97, 12.45.
18 ESIMS m/z 305 ([M+Hf). 1H NMR (301 MHz, CDCI3) δ 8.92 (s, 1H), 8.47 (s, 1H), 8.06 (d, 7=7.9 Hz, 1H), 7.31 (dd,7=7.4, 4.1 Hz, 1H), 7.26-7.23 (m, 1H), 4.06 (dq, 7=14.4, 7.1 Hz, 1H), 3.64 (dq, 7 = 14.3, 7.2 Hz, 1H), 2.75 (t, 7 = 6.7 Hz, 2H), 2.38 (s, 3H), 2.26 (dd, 7= 13.5, 6.7 Hz, 2H), 2.01 (s, 3H), 1.19 (t, 7 = 7.5 Hz, 3H). 13C NMR (76 MHz, CDCI3) δ 171.98, 148.24, 146.28, 146.10, 136.77, 132.45, 129.43, 123.89, 116.06, 44.51, 32.22,29.39, 16.31, 12.90, 12.49.
19 ESIMS m/z 287 ([M+Hf). 1H NMR (300 MHz, CDCI3) 6 8.95 (s, 1H), 8.50 (s, 1H), 8.08 (d,7 = 7.8 Hz. 1H), 7.32 (t, 7 = 6.0 Hz, 1H), 7.21 (s, 1H), 4.05 (dd, 7= 13.9, 7.0 Hz, 1H), 3.65 (dd, 7= 14.0, 7.0 Hz, 1H), 2.37 (s, 3H), 1.96 (s, 2H), 1.59 (t, 7= 7.3 Hz. 2H). 1.25-1.16 (m, 5H), 0.85 (t, 7 = 7.2 Hz, 3H). 13C NMR (76 MHz, CDCI3) δ 148.26, 146.37, 146.12, 132.35, 123.88, 115.97, 44.36, 31.88, 30.03, 26.93, 22.64, 14.16, 12.98, 12.48.
20 ESIMS m/z 299 ([M+Hf). 'H NMR (300 MHz, CDCI3) δ 8.92 (s, 1H), 8.47 (s, 1H), 8.05 (d. 7 = 7.4 Hz, 1H), 7.26 (s, 2H), 3.793.61 (m. 1H), 3.55 (dd, 7 = 14.1,7.2 Hz, 1H), 2.37 (s, 3H), 2.25 (s, 1H), 1.08 (d, 7 = 5.9 Hz, 6H), 0.92 (s, 1H), 0.51 (d, 7 = 7.5 Hz, 2H), 0.14 (d, 7= 3.9 Hz. 2H). 13C NMR (76 MHz, CDCh) δ 148.32, 146.47, 136.48, 132.20, 129.47, 123.78, 116.11, 53.77, 30.00, 20.76, 19.52. 12.49, 9.25, 4.38, 3.73.
21 ESIMS m/z 331 ([M+H]*). ’H NMR (300 MHz, CDCI3) 5 8.95 (s, 1H), 8.50 (s, 1H), 8.09 (d, J =7.9 Hz, 1H), 7.30 (s, 2H), 3.823.67 (m, 1H), 3.67-3.53 (m, 1H), 2.78 (t, 7 = 6.9 Hz, 2H), 2.42 (s, 3H), 2.31 (t, 7 = 6.8 Hz, 2H), 2.04 (s, 3H), 0.95 (dd, J = 9.8, 5.2 Hz, 1H), 0.55 (d, 7 = 7.8 Hz, 2H), 0.19 (t, 7=3.9 Hz, 2H). ’3C NMR (76 MHz, CDCI3) δ 172.12, 148.48, 146.53, 146.29, 136.78, 132.21, 129.33, 123.67,115.82, . 53.83, 32.19, 29.41, 16.32, 12.56, 9.23, 4.44, 3.89.
22 ESIMS m/z 277 ([M+H]*). ’H NMR (300 MHz, CDCI3) δ 8.73 (s, 1H), 8.34 (d, J = 2.3 Hz. 1H), 7.82 (ddd, J = 9.6, 2.7, 1.7 Hz, 1H), 7.30 (s, 1H), 3.38 (S, 3H), 2.37 (s, 3H), 2.17-1.94 (m, 1H), 1.10 (d, J = 6.5 Hz, 6H). 13C NMR (76 MHz, CDCI3) δ 146.17, 142.30, 136.75, 136.43, 119.19, 118.93, 115.93, 37.40, 29.77, 29.60, 20.49, 19.41, 12.06.
23 ESIMS m/z 309 ([M+H]*). ’H NMR (300 MHz, CDCI3) δ 8.74 (s, 1 H), 8.35 (s, 1H), 7.81 (d, 7 = 9.3 Hz, 1H), 7.32 (s, 1H), 3.39 (s. 3H), 2.77 (t, 7 = 6.8 Hz, 2H), 2.39 (s, 3H), 2.30 (dt, 7= 13.9, 6.8 Hz, 2H), 2.03 (s, 3H). 13C NMR (76 MHz, CDCI3) δ 161.87, 158.47, 145.96, 142.37, 136.90, 136.58, 119.19, 118.94, 115.66, 37.25, 31.88, 29.30, 16.21, 12.13.
24 ESIMS m/z 291 ([M+Hf). ’H NMR (300 MHz, CDCI3) δ 8.75 (s, 1H), 8.36 (s, 1H), 7.83 (d, J = 9.3 Hz, 1H), 7.26 (s, 1H), 4.06 (dq, J = 14.1, 7.1 Hz, 2H), 3.63 (dq, J = 14.2, 7.2 Hz, 2H), 2.37 (s, 3H), 2.29-2.14 (m, 1H), 1.20 (t, J = 7.2 Hz, 3H), 1.10 (d, J = 6.4 Hz, 6H). 13C NMR (76 MHz, CDCIs) δ 177.82, 146.53, 142.21, 136.64, 136.33, 119.24, 118.98, 117.05,44.55, 30.24, 30.10, 20.76, 19.60, 13.08, 12.50
25 ESIMS m/z 323 ([M+Hf). 1H NMR (300 MHz, CDCI3) δ 8.73 (s, 1H), 8.35 (s, 1H), 7.82 (d, J = 9.6 Hz, 1H), 7.29 (s, 1H), 4.08 (dq. J = 14.0, 7.0 Hz, 1H), 3.66 (dq, J = 14.1,7.1 Hz, 1H), 2.76 (t, J = 6.9 Hz, 2H), 2.39 (s, 3H), 2.26 (br s, 2H), 2.03 (s, 3H), 1.20 (t, J = 7.2 Hz, 3H). 13C NMR (76 MHz, CDCI3) δ 171.95, 146.41, 142.25, 136.65, 136.45, 119.12, 118.91, 116.81,44.54, 32.20, 29.46, 16.31, 13.00, 12.58, 7.71.
26 ESIMS m/z 317 ([M+Hf). ’H NMR (300 MHz, CDCI3) δ 8.74 (s, 1H), 8.34 (s, 1H), 7.83 (d, J = 9.4 Hz, 1H), 7.32 (s, 1H), 3.823.66 (m, 1H), 3.64-3.48 (m, 1H), 2.39 (s, 3H), 2.26 (br s, 1H), 1.10 (d, J = 6.4 Hz, 6H), 0.92 (tt, J =13.1, 6.3 Hz, 1H), 0.53 (d, J = 7.7 Hz, 2H), 0.16 (t, J = 4.1 Hz, 2H). ,3C NMR (76 MHz, CDCI3) δ 170.65, 154.09, 146.75, 142.12, 136.49, 136.20, 135.22, 131.18,119.25, 118.99, 116.98, 29.99, 20.83, 19.60, 12.54, 9.34, 4.49, 3.81.
27 ESIMS m/z 349 ([M+H]+). 1H NMR (300 MHz, CDCI3) 5 8.74 (s, 1H), 8.36 (d, 7 = 2.6 Hz, 1H), 7.84 (dt, 7 = 9.6, 2.4 Hz, 1H), 7.34 (s, 1H), 3.76 (dd, J= 14.4, 7.4 Hz, 1H), 3.65-3.53 (m, 1H), 2.78 (t, 7 = 6.9 Hz, 2H), 2.42 (s, 3H), 2.372.23 (m, 2H), 2.05 (s, 3H), 1.03-0.88 (m, 1H), 0.55 (d, J = 7.4 Hz, 2H), 0.18 (t, J = 3.9 Hz, 2H). ’3C NMR (76 MHz. CDCI3) δ 171.95, 161.77, 158.29, 146.73, 142.14, 136.60, 136,30, 131.17, 119.27, 119.01, 116.71, 53.82, 32.28, 30.11, 29.47, 16.44, 12.58, 9.29, 4.53, 3.89.
28 ESIMS m/z 305 ([M+H]+). 1H NMR (300 MHz, CDCI3) δ 8.97 (s, 1H), 8.52 (s, 1H), 8.11 (t, J = 7.1 Hz, 1H), 7.48 (s, 0.5H), 7.36 (s, 1H), 7.29 (s, 0.5H), 3.42 (s, 3H), 2.95-2.80 (m, 1H), 2.54-2.43 (m, 2H), 2.41 (s, 3H), 2.00 (d, 7= 13.3 Hz, 3H), 1.16 (t, J = 7.2 Hz, 3H). 13C NMR (76 MHz, CDCI3) δ 176.76, 148.16, 146.21, 132.54, 116.13, 115.28, 39.07, 38.18, 37.55, 36.55, 35.41, 19.62, 18.68, 16.90, 12.32.
29 ESIMS m/z 319 ([M+Hf). 1H NMR (300 MHz, CDCI3) 5 8.91 (s, 1H), 8.45 (d. 7 = 4.5 Hz, 1H), 8.12-7.99 (m, 1H), 7.42 (s, 0.5H), 7.30 (d, 7= 5.6 Hz, 1H), 7.26 (s, 0.5H), 4.11 (dd, 7 = 13.8, 6.9 Hz, 1H), 3.57 (dq, 7= 13.8, 6.9 Hz, 1H), 2.95-2.73 (m, 1H), 2.552.42 (m. 2H), 2.36 (s, 3H), 1.95 (d, J= 14.8 Hz, 3H), 1.30-1.01 (m, 6H). 13C NMR (76 MHz, CDCI3) δ 176.42, 148.08, 146.08, 132.32, 123.96, 117.37, 116.50, 44.77, 40.20, 39.12, 38.11,35.56, 18.63, 16.84, 12.95, 12.45.
30 ESIMS m/z 333 ([M+Hf). 1H NMR (301 MHz, COCI3) 6 8.92 (s, 1H), 8.46 (d, J = 4.1 Hz, 1H), 8.05 (d, J = 7.9 Hz, 1H), 7.37 (s, 1H), 7.32-7.27 (m, 1H), 4.13 (dq, J - 14.3, 7.2 Hz, 1H), 3.39 (dq, J= 14.1, 7.1 Hz, 1H), 2.81 (d, J= 12.6 Hz, 1H), 2.58 (d, J =12.6 Hz, 1H), 2.42 (s, 3H), 2.12 (s, 3H), 1.17 (t, J = 7.2 Hz, 3H), 1.09 (d, J = 6.8 Hz, 6H). 13C NMR (76 MHz, CDCI3) 6 175.70, 148.33, 146.93, 146.46, 136.00, 132.29, 123.83, 117.50, 48.08, 47.85, 46.66, 30.08, 26.45, 25.95, 18.42, 13.04, 12.70.
31 ESIMS m/z 245 ([M+Hf). 1H NMR (300 MHz, CDCI3) 6 8.98 (s, 1H), 8.52 (s, 1H), 8.11 (d, J = 7.3 Hz, 1H), 7.33 (d, J =7.7 Hz, 1H), 7.30 (s, 1H), 4.04 (t, J = 6.5 Hz, 1H), 3.68 (dd, J = 13.5, 6.6 Hz, 1H), 2,40 (s, 3H), 1.87 (s, 3H), 1.23 (d, J = 6.2 Hz, 3H). 13C NMR (76 MHz, CDCI3) 6 172.33, 171.04, 148.26, 146.35, 145.86, 132.37, 123.82, 115.86, 44.22, 20.66, 12.96, 12.46, 7.78.
32 ESIMS m/z 359 ([M+H]4). 1H NMR (301 MHz, CDCI3) 0 8.91 (s, 1H), 8.44 (s, 1H), 8.05 (dt, 7 = 7.9, 1.8 Hz, 1H), 7.41 (s. 1H), 7.32 -7.24(m, 1H), 3.84 (dd, 7 = 14.1, 7.2 Hz, 1H), 3.33 (dd, 7= 14.1, 7.2 Hz, 1H), 2.81 (d, 7= 12.7 Hz, 1H), 2.57 (d, 7=12.6 Hz, 1H), 2.43 (s, 3H), 2.11 (s, 3H), 1.10 (d, 7 = 8.5 Hz, 6H), 0.89 (dtd, 7= 12.1, 7.4, 2.6 Hz, 1H). 0.48 (ddd, 7 = 7.7, 4.1,2.6 Hz, 2H), 0.10 (dt, 7 = 6.5, 3.1 Hz, 2H). 13C NMR (76 MHz, CDCI3) 5 175.95, 172.32, 148.33, 147.19, 146.48, 135.89, 132.21, 123.82, 117.54, 56.75, 48.14, 46.84, 26.53, 25.98, 18.43, 13.15, 8.98, 4.64, 3.78.
33 ESIMS m/z 271 ([M+H]4). 1H NMR (300 MHz, CDCI3) 5 8.97 (s, 1H), 8.52 (s, 1H), 8.10 (d, 7= 7.9 Hz, 1H), 7.34-7.32 (m, 1H), 7.31 (s, 1H), 3.85-3.67 (m, 1H), 3.67-3.54 (m, 1H), 2.43 (s, 3H), 1.89 (s, 3H), 0.96 (ddd, 7= 12.4, 7.7, 4.8 Hz, 1H), 0.56 (d, 7 = 7.8 Hz, 2H), 0.20 (t, 7 = 4.6 Hz, 2H). 13C NMR (76 MHz, CDCI3) 5 171.14, 148.35, 146.48, 146.24, 136.66, 132.28, 123.77, 115.45, 53.57, 20.63, 12.57, 9.77, 9.33, 4.45, 3.94.
34 ESIMS m/z 323 ([M+H]+). 1H NMR (300 MHz, CDCI3) 5 8.75 (s. 1 H), 8.37 (s, 1H), 7.91 -7.75 (m, 1H), 7.52 (s, 0.5H), 7.32 (s, 0.5H), 3.42 (s, 3H), 2.99 2.79 (m, 1H), 2.55-2.44 (m, 2H), 2.42 (s, 3H), 2.02 (d, J= 12.8 Hz, 3H), 1.17 (t, 7 = 6.7 Hz, 3H). 13C NMR (76 MHz, CDCI3) 5 176.70, 145.86, 142.09, 136.74, 119.18, 116.83, 115.94, 39.07, 38.17,37.62, 36.60, 35.47, 32.32, 23.11, 18.71, 16.87, 12.27.
35 ESIMS m/z 337 «Μ+ΗΓ). 1H NMR (301 MHz, CDCI3) 5 8.74 (s, 1H), 8.35 (d, J = 2.1 Hz, 1H), 7.83 (dt, 7 = 9.6, 2.2 Hz, 1H). 7.45 (s, 1H), 3.36 (s, 3H), 2.832.77 (m, 1H), 2.69-2.60 (m, 1H), 2.46 (s, 3H), 2.16 (s, 3H), 1.16 (d, 7 = 7.4 Hz, 6H). 13C NMR (76 MHz, CDCI3) 5 176.01, 146.99, 142.17, 136.61, 136.30, 119.27, 119.01, 116.89, 47.91, 46.59, 45.63, 40.80, 30.10,26.52,25.98, 25.23, 18.42, 12.73.
36 ESIMS m/z 337 ([M+H]*). 1H NMR (300 MHz, CDCI3) 5 8.74 (s, 1H), 8.33 (s, 1H), 7.80 (d, 7 = 8.5 Hz, 1H), 7.47 (s, 0.5H), 7.28 (s. 0.5H), 4.21 -3.98(m, 1H), 3.57 (dd, 7= 13.3, 6.7 Hz, 1H), 2.85 (dq, J = 23.7, 13.2, 11.6 Hz, 1H), 2.47-2.43 (m, 2H), 2.37 (s, 3H), 1.96 (d, 7= 14.0 Hz, 3H), 1.24-1.01 (m, 6H). 13C NMR (76 MHz, CDCI3) 5 176.30, 146.93, 146.29, 141.89, 136.15, 135.01, 118.99, 118.14, 117.23, 44.78, 39.11, 38.08, 36.83, 35.63, 18.66, 16.84, 12.84, 12.40.
7l
37 ESIMS m/z 351 <[M+H]+). 1H NMR (300 MHz, CDCI3) 6 8.77 (s, 1H), 8.36 (s, 1H), 7.85 (d, 7=9.5 Hz, 1H), 7.43 (s, 1H), 4.16 (dq, 7 = 14.3, 7.2 Hz, 1H), 3.44 (dq. 7= 14.1, 7.1 Hz. 1H), 2.83 (d,7= 12.7 Hz, 1H), 2.62 (d,7= 12.7 Hz, 1H), 2.45 (s, 3H), 2.16 (s, 3H), 1.20 (t, 7=7.2 Hz, 3H), 1,14 (d, 7 = 2.7 Hz, 6H). 13C NMR (76 MHz, CDCI3) 6 175.61, 147.23, 142.17, 136.65, 136.23, 134.79,119.21, 118.84, 118.27, 48.07, 47.85, 46.68, 26.41, 26.06, 18.44, 13.01, 12.73.
38 ESIMS m/z 377 ([M+Hf). 1H NMR (300 MHz, CDCI3) 6 8.77 (s, 1H), 8.36 (s, 1H), 7.91 -7.74(m, 1H), 7.49 (s, 1H), 3.89 (dd, 7 = 14.1, 7.2 Hz, 1H), 3.38 (dd, 7= 14.2, 7.2 Hz, 1H), 2.90-2.80 (m, 1H), 2.68- 2.58 (m, 1H), 2.47 (s, 3H), 2.16 (s, 3H), 1.15 (d, 7 = 4.7 Hz, 6H), 0.93 (tdd, 7 = 12.2, 6.1,2.6 Hz, 1H), 0.53 (dd, 7 = 7.8, 3.5 Hz, 2H), 0.14 (dd, 7= 7.9, 3.7 Hz, 2H). ’3C NMR (76 MHz, CDCI3) 6 175.83, 147.51, 142.19, 136.50, 136.19, 134.60, 119.13, 118.94, 118.23, 56.80, 48.07, 46.86, 26.50, 26.06, 18.45, 13.11, 8.98, 4.65, 3.78.
39 129- 131 ESIMS m/z 237 ([M+Hf). ’H NMR (300 MHz, CDCI3) 6 10.68 (s, 1H), 8.80 (s, 1H), 8.43 (s, 1H), 8.01 (d, 7 =7.5 Hz, 1H), 7.33 (s, 2H), 2.20 (S, 3H).
40 ESIMS m/z 289 ([M+H]*). 1H NMR (400 MHz, CD3CN) δ 9.00 (d, J = 2.5 Hz, 1H), 8.46 (d, J =4.8 Hz, 1H), 8.11 (m, 1H), 7.67 (d, J= 1.3 Hz, 1H), 7.61 (d, J =1.2 Hz, 1H), 7.36 (m, 1H), 3.76 (q, J =7.1 Hz, 2H), 1.45 (s, 9H), 1.17 (t, J = 7.2 Hz, 3H).
41 ESIMS m/z 323 ([M+H]*). 1H NMR (600 MHz, CDCI3) δ 8.92 (d, J =1.6 Hz, 1H), 8.50 (dd, J = 4.8, 1.5 Hz, 1H), 8.06 (dt, J = 7.9, 2.0 Hz, 1H), 7.33-7.27 (m, 2H), 3.89 (dq, J= 14.5, 7.3 Hz, 1H), 3.68 (dq. J = 14.3, 7.2 Hz, 1H), 1.44 (s, 9H), 1.22 (t, J = 7.2 Hz, 3H). 13CNMR(151 MHz, CDCI3) δ 152.90, 148.47, 146.02, 136.07, 134.08, 131.81, 128.79, 123.36, 117.66, 83.23, 45.32, 28.04, 13.03.
Table 3: MYZUPE and BEMITA Rating Table
GPA and BEMITA Rating Table
% Control (or Mortality) Rating
80-100 A
More than 0 - Less than 80 B
Not Tested C
No activity noticed in this bioassay D
Table 4. Biological Data for MYZUPE and BEMITA
Compound No. MYZUPE BEMITA
% Ctrl @ 200 ppm % Ctrl @ 200 ppm
1 B B
2 B D
3 B B
4 D B
5 A A
6 B A
7 B A
8 B A
9 B A
10 B A
11 B A
12 D A
13 D B
14 D D
15 B A
16 D D
17 B B
18 A A
19 B A
20 B D
21 B A
22 B A
23 A A
24 B B
25 B A
26 B B
27 B A
28 C C
29 C C
30 C C
31 C C
32 C C
33 C C
34 C C
35 C C
36 C C
37 C c
38 C c
39 C c
40 C c
41 B A
WE CLAIM

Claims (33)

  1. WE CLAIM
    1. A composition comprising a molécule according to Formula One:
    R7 wherein (a) X is N or CR8;
    (b) R1 is H, F, Cl, Br, I, CN, NO2, substituted or unsubstituted C,-C6 alkyl, substituted or unsubstituted C2-C6 alkenyl, substituted or unsubstituted Ci-Ce alkoxy,
    10 substituted or unsubstituted C2-C6 alkenyloxy, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C3-C10 cycloalkenyl, substituted or unsubstituted Ce-C2o aryl, substituted or unsubstituted Ci-C20 heterocyclyl, OR9, C(=X1)R9, C(=X1)OR9, C(=X1 )N(R9)2, N(R9)2> N(R9)C(=X1 )R9, SR9, S(O)nOR9, or R9S(O)nR9, wherein each said R1, which is substituted, has one or more substituents
    15 selected from F, Cl, Br, I, CN, NO2, C,-Ce alkyl, C2-C8 alkenyl, C,-C6 haloalkyl, C2-Ce haloalkenyl, C,-Ce haloalkyloxy, C2-C6 haloalkenyloxy, C3-C10 cycloalkyl, C3-C10 cycloalkenyl, C3-Cw halocycloalkyl, C3-C10 halocycloalkenyl, OR9, S(O)nOR9, C6-C20 aryl, or C,-C20 heterocyclyl, (each of which that can be substituted, may optionally be substituted with R9);
    20 (c) R2 is H, F, Cl, Br, I, CN, NO2, substituted or unsubstituted C,-C6 alkyl, substituted or unsubstituted C2-C6 alkenyl, substituted or unsubstituted 0,-06 alkoxy, substituted or unsubstituted C2-C6 alkenyloxy, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C3-C10 cycloalkenyl, substituted or unsubstituted C6-C2o aryl, substituted or unsubstituted Ci-C20 heterocyclyl, 0R9, C(=X1 )R9, C(=X1 )0R9, C(=X1 )N(R9)2, 25 N(R9)Z, N(R9)C(=X1 )R9, SR9, S(O)nOR9, or R9S(O)nR9, wherein each said R2, which is substituted, has one or more substituents selected from F, Cl, Br, I, CN, N02, CrC6 alkyl, C2-C6 alkenyl, C,-C6 haloalkyl, C2-C6 haloalkenyl, Ci-C6 haloalkyloxy, C2-C6 haloalkenyloxy, C3-C10 cycloalkyl, C3-C10 cycloalkenyl, C3-C10 halocycloalkyl, C3-C10 halocycloalkenyl, 0R9, S(O)nOR9, C6-C20 aryl, or C,-C20
    30 heterocyclyl, (each of which that can be substituted, may optionally be substituted with R9);
    (d) R3 is H, F, Cl, Br, I, CN, NO2, substituted or unsubstituted Ci-C6 alkyl, substituted or unsubstituted C2-C6 alkenyl, substituted or unsubstituted CrC0 alkoxy, substituted or unsubstituted C2-C6 alkenyloxy, substituted or unsubstituted C3-Cto cycloalkyl, substituted or unsubstituted C3-C1() cycloalkenyl, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted Ci-C2o heterocyclyl, OR9, C(=X1)R9, C(=X1)OR9, C(=X1)N(R9)2, N(R9)z, N(R9)C(=X1)R9, SR9, S(O)nOR9, or R9S(O)nR9, wherein each said R3, which is substituted, has one or more substituents selected from F, Cl, Br, I, CN, NO21 ϋ,-ϋβ alkyl, C2-C6 alkenyl, Ci-C6 haloalkyl, C2-C6 haloalkenyl, Ci-Ce haloalkyloxy, C2-Ca haloalkenyloxy, C3-C10 cycloalkyl, C3-C10 cycloalkenyl, C3-C10 halocycloalkyl, C3-C10 halocycloalkenyl, OR9, S(O)nOR9, Ce-C20 aryl, or CrC20 heterocyclyl, (each of which that can be substituted, may optionally be substituted with R9);
    (e) R4 is H, F, Cl, Br, I, CN, NO2, substituted or unsubstituted CrCg alkyl, substituted or unsubstituted C2-C6 alkenyl, substituted or unsubstituted CrCe alkoxy, substituted or unsubstituted C2-C6 alkenyloxy, substituted or unsubstituted C3-Cw cycloalkyl, substituted or unsubstituted C3-Ci0 cycloalkenyl, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted Ci-C20 heterocyclyl, OR9, C(=X1)R9, C(=X1)OR9, C(=X1)N(R9)2, N(R9)2, N(R9)C(=X1 )R9, SR9, S(O)nOR9, or R9S(O)nR9, wherein each said R4, which is substituted, has one or more substituents selected from F, Cl, Br, I, CN, NO2, C^Ce alkyl, C2-C6 alkenyl, Ci-C6 haloalkyl, C2-C0 haloalkenyl, CrC6 haloalkyloxy, C2-Ce haloalkenyloxy, C3-C10 cycloalkyl, C3-C10 cycloalkenyl, C3-C10 halocycloalkyl, C3-Ci0 halocycloalkenyl, OR9, S(O)nOR9, C6-C20 aryl, or Ci-C20 heterocyclyl, (each of which that can be substituted, may optionally be substituted with R9);
    (f) R5 is H, substituted or unsubstituted C^Ce alkyl, substituted or unsubstituted C2C6 alkenyl, substituted or unsubstituted alkoxy, substituted or unsubstituted C2-C6 alkenyloxy, substituted or unsubstituted C3-Cw cycloalkyl, substituted or unsubstituted C3-C10 cycloalkenyl, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted Ci-C20 heterocyclyl, OR9, C(=X1)R9, C(=X1)OR9, C(=X1 )N(R9)2, N(R9)Z, N(R9)C(=X1)R9, SR9, S(O)nOR9, R9S(O)nR9, CrC6 alkyl C6-C2o aryl (wherein the alkyl and aryl can independently be substituted or unsubstituted), C(=X2)R9, C(=X1)X2R9, R9X2C(=X1)R9, R9X2R9, C(=O)(CrCe alkyOSfOWCrCe alkyl), C(=O)(CrC6 alkyl)C(=O)O(C1-C6 alkyl), (CrCe alkyl)OC(=O)(C6-C20 aryl), (CrC6 alkyl)OC(=O)(CrC6 alkyl), CrC6 alkyl-(C3-C10 cyclohaloalkyl), or (Ci-Ce alkenyl)C(=O)O(C1-C6 alkyl), or R9X2C(=X1 )X2R9;
    wherein each said R5, which is substituted, has one or more substituents selected from F, Cl, Br, I, CN, NO2, Ci-Cg alkyl, Cz-C6 alkenyl, Ci~C0 haloalkyl, C2-Ce haloalkenyl, Ci-C6 haloalkyloxy, C2-C6 haloalkenyloxy, C3-Ci0 cycloalkyl, C3-C10 cycloalkenyl, C3-C10 halocycloalkyl, C3-Cw halocycloalkenyl, OR9, S(O)nOR9, C6-C20 aryl, or Ci-C20 heterocyclyl, R9 aryl (each of which that can be substituted, may optionally be substituted with R9) optionally R5 and R7 can be connected in a cyclic arrangement, where optionally such arrangement can hâve one or more heteroatoms selected from O, S, or, N, in the cyclic structure connecting R5 and R7;
    (g) R6 is O, S, NR9, or NOR9;
    (h) R7 is substituted or unsubstituted CrC6 alkyl, substituted or unsubstituted C2-C6 alkenyl, substituted or unsubstituted Ci-C6 alkoxy, substituted or unsubstituted C2-C6 alkenyloxy, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C3-C10 cycloalkenyl, substituted or unsubstituted C6-C2o aryl, substituted or unsubstituted CrC20 heterocyclyl, OR9, OR9S(O)nR9, C(=X1)R9, C(=X1)OR9, R9C(=X1)OR9, R9X2C(=X1)R9X2R9, C(=X1)N(R9)2, N(R9)2, N(R9)(R9S(O)nR9), N(R9)C(=X1 )R9, SR9, S(O)nOR9, R9S(O)nR9, Ci-CgalkylOC(=O)CiCealkyl, OCi-Ce alkyl Ci-C2q heterocyclyl, CfC6alkylCrC20 heterocyclyl, Ci-C6,alkylS(=N’CN)(C1-C6alkyl), C1-C6alkylS(O)(=N-CN)(C1C6alkyl), CrCgalkylSiOUCi-CealkylCrC^heterocyclyl), CrCealkylStOX^N-CNXCrCg alkyl-C;C20heterocyclyl), CrCealkylNHCC^OJOCrCg alkyl), Ci-C6 alkylC^OJOCrCe alkyl, CiC6alkyl(C6-C20aryl)NH(C(=O)OC1-C6alkyl), CrCealkyKS-CrCe alkyl)NH(C(=O)OCrC6alkyl), Cr C6alkyl(S-Cl-C6alkyl·C6-C20aΓyl)NH(C(=O)OC1-C6alkyl), CrC6 alkyl(NHC(=O)OCi-C6alkylC6-C20 aryl)NH(C(=O)OC1-C6alkyl), C;-C6alkyl(OCi-CgalkylC6-C2Qaryl)NH(C(=O)OCi-Cealkyl), C,C6al kyl Ν(Ο3-Ο63 Ikyl )(C(=OJOCi-Cgalkyl), Ci-CgalkylNH(Ci-C6alkyl), C(j-C2oarylSCi-C6haloalkyl, CrCealkyl-NiCrCe alkyl)(C(=O)CrC6alkylC6-C20aryl), Ci-C6alkylN(CrC6alkyl)(CrC6alkyl), Cr CealkylNiC-i-CG alkyl)(S(O)r,Ci-C6 alkyl), CpCe alkylN(Ci-Cg alkyl)(S(O)nCi-C6 alkenylCg-C^aryl), Ci-C6 alkylN(Ci-Ce alkyl)(C(=O)CrC20 heterocyclyl), C1-C6alkylN(Cl-C6alkyl)(C(=O)OC1-C6 alkylC6-C20aryl), NH(CrC6 alkylSÎOJnCrCgalkyl), NH(C,-C6 alkylS(O)nC6-C20aryl), Cr C6alkyl(S(O)nCi-Ce alkyl)(C(=O)CrC6alkylS(O)n(CrC6 alkyl), or R9S(O)n(NZ)R9, wherein each said R7, which is substituted, has one or more substituents selected from F, Cl, Br, I, CN, NO2, C^Cg alkyl, C2-C6 alkenyl, CpCg haloalkyl, C2-Ce haloalkenyl, haloalkyloxy, C2-C6 haloalkenyloxy, C3-Ci0 cycloalkyl, C3-C10 cycloalkenyl, C3-Ci0 halocycloalkyl, C3-C10 halocycloalkenyl, OR9, S(O)nOR9, C6-C20 aryl, or CrC20 heterocyclyl, (each of which that can be substituted, may optionally be substituted with R9), C(=X1)R9, C(=X1)OR9, C(=X1 )N(R9)2, =X2, N(R9)2, S(=X2)nR9, R9S(O)nR9, S(O)nN(R9)2;
    (i) R8 is H, F, Cl, Br, I, CN, NO21 substituted or unsubstituted Ci-Cfl alkyl, substituted or unsubstituted C2-Ce alkenyl, substituted or unsubstituted Ci-C5 alkoxy, substituted or unsubstituted C2-C6 alkenyloxy, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C3-C10 cycloalkenyl, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted CrC20 heterocyclyl, OR9, C(=X1)R9, C(=X1)0R9, C(=X1 )N(R9)2, N(R9)2, N(R9)C(=X1 )R9, SR9, S(O)nR9, S(O)nOR9, or R9S(O)nR9, wherein each said R8, which is substituted, has one or more substituents selected from F, Cl, Br, I, CN, NO2, C-|-C6 alkyl, C2-C6 alkenyl, CrC6 haloalkyl, C2-Ce haloalkenyl, CrCe haloalkyloxy, C2-C6 haloalkenyloxy, C3-C10 cycloalkyl, C3-C10 cycloalkenyl, C3-C10 halocycloalkyl, C3-C10 halocycloalkenyl, OR9, S(O)nOR9, Ce-C20 aryl, or CrC20 heterocyclyl, (each of which that can be substituted, may optionally be substituted with R9);
    G*) R9 (each independently) is H, CN, substituted or unsubstituted Ci-CB alkyl, substituted or unsubstituted C2-C6 alkenyl, substituted or unsubstituted CrCe alkoxy, substituted or unsubstituted C2-CB alkenyloxy, substituted or unsubstituted C3-Ci0 cycloalkyl, substituted or unsubstituted C3-Ci0 cycloalkenyl, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted Ci-C20 heterocyclyl, SiOJnCpCe alkyl, , NiCrCealkyl)^ wherein each said R9, which is substituted, has one or more substituents selected from F, Cl, Br, I, CN, NO2, Ci-C6 alkyl, C2-C6 alkenyl, CrC6 haloalkyl, C2-CB haloalkenyl, CrC6 haloalkyloxy, C2-C6 haloalkenyloxy, C3-C10 cycloalkyl, C3-C1Q cycloalkenyl, C3-Cio halocycloalkyl, C3-C10 halocycloalkenyl, OCi-C6 alkyl, 0CrCe haloalkyl, S(O)nC1-C6alkyl, S(O)nOCrC6 alkyl, C6-C20 aryl, or C^C^ heterocyclyl;
    (k) R10 is H, F, Cl, Br, I, CN, NO2, substituted or unsubstituted CrCB alkyl, substituted or unsubstituted C2-C6 alkenyl, substituted or unsubstituted CrC6 alkoxy, substituted or unsubstituted C2-C6 alkenyloxy, substituted or unsubstituted C3-Ci0 cycloalkyl, substituted or unsubstituted C3-C10 cycloalkenyl, substituted or unsubstituted C6-C20 aryl, OR9, C(=X1)R9, C(=X1)OR9, C(=X1)N(R9)2, N(R9)2, N(R9)C(=X1 )R9, SR9, S(O)nOR9, or R9S(O)nR9, wherein each said R10, which is substituted, has one or more substituents selected from F, Cl, Br, I, CN, NO2, CrC0 alkyl, C2-C6 alkenyl, CrCB haloalkyl, C2-C6 haloalkenyl, Ci-C6 haloalkyloxy, C2-CB haloalkenyloxy, C3-C10 cycloalkyl, C3-Cw cycloalkenyl, C3-Cw halocycloalkyl, C3-C10 halocycloalkenyl, OR9, S(O)nOR9, or C6-C2o aryl, (each of which that can be substituted, may optionally be substituted with R9);
    (l) n is (each independently) 0, 1, or 2;
    (m) X1 is (each independently) O or S;
    (η) X2 is (each independently) O, S, =NR9, or =NOR9; and (ο) Z is CN, NOZ, Ci-C6 alkyl(R9), C(=X1 )N(R9)2.
  2. 2. A composition according to claim 1 wherein said molécule said X is CR8.
  3. 3. A composition according to claim 1 wherein said molécule said R1 isH.
  4. 4. A composition according to claim 1 wherein said molécule said R2 isH.
  5. 5. A composition according to claim 1 wherein said molécule said R3 isH.
  6. 6. A composition according to claim 1 wherein said molécule said R4 is halo or unsubstituted CrC6 alkyl.
  7. 7. A composition according to claim 1 wherein said molécule said R4 is F, Cl, or unsubstituted CrC2 alkyl.
  8. 8. A composition according to claim 1 wherein said molécule said R4 is Cl, or CH3.
  9. 9. A composition according to claim 1 wherein said molécule said R5 is H, substituted or unsubstituted C^Ce alkyl.
  10. 10. A composition according to claim 1 wherein said molécule said R5 is a substituted Ci-C6 alkyl which is substituted with a C3-Ci0 cycloalkyl.
  11. 11. A composition according to claim 1 wherein said molécule said R5 is H, CH3r CH2cyclopropyl, or CHZCH3.
  12. 12. A composition according to claim 1 wherein said molécule said R6 is O.
  13. 13. A composition according to claim 1 wherein said molécule said R7 is substituted or unsubstituted Ci-C6 alkyl, 0R9, or R9S(O)nR9.
  14. 14. A composition according to claim 1 wherein said molécule said R7 is a substituted Ci-Ce 5 alkyl wherein said substituent is one or more halos.
  15. 15. A composition according to claim 1 wherein said molécule said R7 is a substituted Ci-C6 alkyl wherein said substituent is one or more F or Cl or a combination thereof.
    10
  16. 16. A composition according to claim 1 wherein said molécule said R7 is a substituted CrC6 alkyl wherein said substituent is one or more F.
  17. 17. A composition according to claim 1 wherein said molécule said R7 is CH2CF3.
    15
  18. 18. A composition according to claim 1 wherein said molécule said R7 is a unsubstituted Cr
    C0 alkyl.
  19. 19. A composition according to claim 1 wherein said molécule said R7 is CH(CH3)2, CH3, C(CH3)3, or CH2CH2CH2CH3.
  20. 20. A composition according to claim 1 wherein said molécule said R7 is OR9.
  21. 21. A composition according to claim 1 wherein said molécule said R7 is O(unsubstituted CrCe alkyl).
  22. 22. A composition according to claim 1 wherein said molécule said R7 is OC(CH3)3.
  23. 23. A composition according to claim 1 wherein said molécule said R7 ts R9S(O)nR9.
    30
  24. 24, A composition according to claim 1 wherein said molécule said R7 is (unsubstituted C-iCe alkyl)S(unsubstituted CrC6 alkyl).
  25. 25. A composition according to claim 1 wherein said molécule said R7 is CH2CH(CH3)SCH3, CH2CH2SCH3, CH(CH3)2SCH3, or CH(CH3)CH2SCH3.
  26. 26. A composition according to claim 1 wherein said molécule said R8 is H or halo.
    l
  27. 27. A composition according to claim 1 wherein said molécule said R8 is H, F, or Cl.
  28. 28. A composition according to claim 1 wherein said molécule said R8 is H or F.
  29. 29. A composition according to claim 1 wherein said molécule said R9 is an unsubstituted CrC6 alkyl.
  30. 30. A composition according to claim 1 wherein said molécule said R10 is H or
    10 unsubstituted CrC6 alkyl.
  31. 31. A composition according to claim 1 wherein said molécule said R10 is H or CH3.
  32. 32. A composition according to claim 1 wherein said molécule said n is 0.
  33. 33. A composition according to claim 1 wherein said molécule is selected from
OA1201300186 2010-11-03 2011-10-31 Pesticidal compositions and process related thereto. OA16402A (en)

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