US 2013 OO19348A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2013/0019348 A1 Crouse et al. (43) Pub. Date: Jan. 17, 2013

(54) PESTICIDAL COMPOSITIONS AND AOIPI/00 (2006.01) PROCESSES RELATED THERETO AOIP3/00 (2006.01) AOIPI3/00 (2006.01) (75) Inventors: Gary D. Crouse, Noblesville, IN (US); AOIP 7/04 (2006.01) David A. Demeter, Fishers, IN (US); AOIP 9/00 (2006.01) Thomas C. Sparks, Greenfield, IN (US); AOIP5/00 (2006.01) Nick X. Wang, Westfield, IN (US); AOIP II/00 (2006.01) William H. Dent, III, Indianapolis, IN A6IP33/00 (2006.01) (US); Carl Deamicis, Indianapolis, IN A6IP33/14 (2006.01) (US); Noormohamed M. Niyaz, AOIN 43/78 (2006.01) Indianapolis, IN (US); Erich W. Baum, AOIN 25/32 (2006.01) Greenwood, IN (US); Lindsey G. AOIP 2L/00 (2006.01) Fischer, Indianapolis, IN (US); Natalie AOIP 9/00 (2006.01) C. Giampietro, Carmel, IN (US) AOIP 7/00 (2006.01) AOIN 25/00 (2006.01) (73) Assignee: DOWAGROSCIENCES LLC, AOIH 5/10 (2006.01) Indianapolis, IN (US) C07D 249/08 (2006.01) (52) U.S. Cl...... 800/298: 548/269.4: 514/383; (21) Appl. No.: 13/546,010 536/17.4: 514/24: 548/185: 514/369: 548/196: 514/371; 544/54: 514/227.2: 424/408; 424/451: (22) Filed: Jul. 11, 2012 504/272; 504/266; 504/221:504/103; 424/84 Related U.S. Application Data (57) ABSTRACT (60) Provisional application No. 61/506,743, filed on Jul. This document discloses molecules having the following for 12, 2011. mula (“Formula One') Publication Classification Formula One (51) Int. C. RI Q-R2 AOIN 43/653 (2006.01) / C7H 5/26 (2006.01) -Hen-N-M-R C07D 417/12 (2006.01) Air N-R AOIN 43/86 (2006.01) Q R3 AOIN 25/34 (2006.01) A6 IK9/48 (2006.01) A6 IK3I/496 (2006.01) The molecules disclosed in this document are related to the A6 IK3I/7056 (2006.01) field of processes to produce molecules that are useful as A6 IK3I/427 (2006.01) pesticides (e.g., acaricides, insecticides, molluscicides, and A6 IK3I/54 (2006.01) nematicides). Such molecules, and processes of using Such AOIP 7/02 (2006.01) molecules to control pests. US 2013/0019348 A1 Jan. 17, 2013

PESTICIDAL COMPOSITIONS AND Substituent consisting of carbon and hydrogen, for example, PROCESSES RELATED THERETO ethynyl, propargyl, butynyl, and pentynyl. CROSS REFERENCES TO RELATED 0014 Alkynyloxy' means an alkynyl further consisting APPLICATIONS of a carbon-oxygen single bond, for example, pentynyloxy, hexynyloxy, heptynyloxy, and octynyloxy. 0001. This application claims priority from U.S. provi sional application 61/506,743 filed on Jul. 12, 2011. The 00.15 "Aryl means a cyclic, aromatic substituent consist entire content of this provisional application is hereby incor ing of hydrogen and carbon, for example, phenyl, naphthyl, porated by reference into this application. and biphenyl. FIELD OF THE DISCLOSURE 0016 “Cycloalkenyl' means a monocyclic or polycyclic, unsaturated (at least one carbon-carbon double bond) sub 0002. The molecules disclosed in this document are stituent consisting of carbon and hydrogen, for example, related to the field of processes to produce molecules that are cyclobutenyl, cyclopentenyl, cyclohexenyl, norbornenyl, useful as pesticides (e.g., acaricides, insecticides, mollusci bicyclo2.2.2]octenyl, tetrahydronaphthyl, hexahydronaph cides, and nematicides). Such molecules, and processes of thyl, and octahydronaphthyl. using Such molecules to control pests. 0017 “Cycloalkenyloxy' means a cycloalkenyl further BACKGROUND OF THE DISCLOSURE consisting of a carbon-oxygen single bond, for example, 0003 Pests cause millions of human deaths around the cyclobutenyloxy, cyclopentenyloxy, norbornenyloxy, and world each year. Furthermore, there are more than ten thou bicyclo2.2.2]octenyloxy. sand species of pests that cause losses in agriculture. The 0018 “Cycloalkyl means a monocyclic or polycyclic, world-wide agricultural losses amount to billions of U.S. saturated Substituent consisting of carbon and hydrogen, for dollars each year. example, cyclopropyl, cyclobutyl, cyclopentyl, norbornyl, 0004 Termites cause damage to all kinds of private and bicyclo2.2.2]octyl, and decahydronaphthyl. public structures. The world-wide termite damage losses amount to billions of U.S. dollars each year. 0019. “Cycloalkoxy' means a cycloalkyl further consist 0005 Stored food pests eat and adulterate stored food. The ing of a carbon-oxygen single bond, for example, cyclopro world-wide stored food losses amount to billions of U.S. pyloxy, cyclobutyloxy, cyclopentyloxy, norbornyloxy, and dollars each year, but more importantly, deprive people of bicyclo[2.2.2]octyloxy. needed food. 0006. There is an acute need for new pesticides. Certain 0020 "Halo' means fluoro, chloro, bromo, and iodo. pests are developing resistance to pesticides in current use. 0021 “Haloalkoxy' means an alkoxy further consisting Hundreds of pest species are resistant to one or more pesti of from one to the maximum possible number of identical or cides. The development of resistance to some of the older different, halos, for example, fluoromethoxy, trifluo pesticides, such as DDT, the carbamates, and the organophos romethoxy, 2,2-difluoropropoxy, chloromethoxy, trichlo phates, is well known. But resistance has even developed to romethoxy, 1.1.2.2-tetrafluoroethoxy, and pentafluoroet Some of the newer pesticides. hoxy. 0007. Therefore, for many reasons, including the above reasons, a need exists for new pesticides. 0022 "Haloalkyl means an alkyl further consisting of, from one to the maximum possible number of identical or DEFINITIONS different, halos, for example, fluoromethyl, trifluoromethyl, 2,2-difluoropropyl, chloromethyl, trichloromethyl, and 1.1.2, 0008. The examples given in the definitions are generally 2-tetrafluoroethyl. non-exhaustive and must not be construed as limiting the molecules disclosed in this document. It is understood that a 0023 “Heterocyclyl means a cyclic substituent that may Substituent should comply with chemical bonding rules and be fully saturated, partially unsaturated, or fully unsaturated, steric compatibility constraints in relation to the particular where the cyclic structure contains at least one carbon and at molecule to which it is attached. least one heteroatom, where said heteroatom is nitrogen, Sul 0009 “Alkenyl' means an acyclic, unsaturated (at least fur, or oxygen. Examples of aromatic heterocyclyls include, one carbon-carbon double bond), branched or unbranched, but are not limited to, benzofuranyl, benzoisothiazolyl, ben Substituent consisting of carbon and hydrogen, for example, Zoisoxazolyl, benzoxazolyl, benzothienyl, benzothiazolyl, vinyl, allyl, butenyl, pentenyl, and hexenyl. cinnolinyl, furanyl, indazolyl, indolyl, imidazolyl, isoindolyl, 0010 Alkenyloxy' means an alkenyl further consisting isoquinolinyl, isothiazolyl, isoxazolyl, oxadiazolyl, oxazoli of a carbon-oxygen single bond, for example, allyloxy, bute nyl, oxazolyl, phthalazinyl, pyrazinyl, pyrazolinyl, pyrazolyl, nyloxy, pentenyloxy, hexenyloxy. pyridazinyl, pyridyl, pyrimidinyl, pyrrolyl, quinazolinyl, 0011 “Alkoxy' means an alkyl further consisting of a quinolinyl, quinoxalinyl, tetrazolyl, thiazolinyl, thiazolyl, carbon-oxygen single bond, for example, methoxy, ethoxy, thienyl, triazinyl, and triazolyl. Examples of fully saturated propoxy, isopropoxy, butoxy, isobutoxy, and tert-butoxy. heterocyclyls include, but are not limited to, piperazinyl, 0012 Alkyl means an acyclic, saturated, branched or piperidinyl, morpholinyl, pyrrolidinyl, tetrahydrofuranyl. unbranched, Substituent consisting of carbon and hydrogen, and tetrahydropyranyl. Examples of partially unsaturated het for example, methyl, ethyl, propyl, isopropyl, butyl, and tert erocyclyls include, but are not limited to, 1,2,3,4-tetrahydro butyl. quinolinyl, 4.5-dihydro-oxazolyl. 4,5-dihydro-1H-pyrazolyl, 0013 “Alkynyl' means an acyclic, unsaturated (at least 4,5-dihydro-isoxazolyl, and 2,3-dihydro-1,3,4-oxadiaz one carbon-carbon triple bond), branched or unbranched, olyl.

US 2013/0019348 A1 Jan. 17, 2013

which may contain one or more further heteroatoms selected C(=O)(C-C alkenyl), C(=O)C(C-C alkenyl), (C-C, from nitrogen, Sulfur, and oxygen, alkyl)O(C-C alkyl), (C-C alkyl)S(C-C alkyl), phenyl, 0041 wherein said hydrocarbyl cyclic group may option and phenoxy; and ally be substituted with R and R7, (M) n is each individually 0, 1, or 2. 0044) Many of the molecules of this invention may be I0042 wherein RandR are independently selected from depicted in two or more tautomeric forms such as when R', H. F. Cl, Br, I, CN, C-C alkyl, oxo, thioxo, C-Chaloalkyl, R, or R, is H (see for example, “Scheme TAU below). For C-C cycloalkyl, C-C halocycloalkyl, C-C cycloalkoxy, the sake of simplifying the schemes, all molecules have been C-C halocycloalkoxy, C-C alkoxy, C-C haloalkoxy, depicted as existing as a single tautomer. Any and all alterna C-C alkenyl, C-C cycloalkenyl, C-C alkynyl, C-C, tive tautomers are included within the scope of this invention, cycloalkynyl, S(=O), (C-C alkyl), S(=O), (C-C, and no inference should be made as to whether the molecule haloalkyl). OSO(C-C alkyl), OSO(C-C haloalkyl). exists as the tautomeric form in which it is drawn.

"Scheme TAU" O SH OH S

Arl Ar ls als ArlNH1NN Ar lsN ls NH NH1 SN N t H R3 R3 N / us-s-s-sO S R3

C(=O)(C-C alkyl), C(=O)C(C-C alkyl), C(=O)(C-C, 0045. In another embodiment Ar" is a substituted phenyl. haloalkyl), C(=O)C(C-C haloalkyl), C(=O)(C-C, 10046) In another embodiment Ar' is a substituted phenyl cycloalkyl), C(=O)C(C-C cycloalkyl), C(=O)(C-C alk that has one or more substituents selected from C-C, enyl), C(=O)C(C-C alkenyl), (C-C alkyl)O(C-C, haloalkyl and C-C haloalkoxy. alkyl), (C-C alkyl)S(C-C alkyl), C(=O)(C-C alkyl)C 10047. In another embodiment Ar' is a substituted phenyl (=O)C)(C-C alkyl), phenyl, Substituted phenyl, phenoxy, that has one or more substituents selected from CF. OCF, or (Het-1); and OCFs. 0048. In another embodiment Het is selected from benzo (L) (Het-1) is a 5- or 6-membered, saturated or unsaturated, furanyl, benzoisothiazolyl, benzoisoxazolyl, benzoxazolyl, heterocyclic ring, containing one or more heteroatoms inde benzothienyl, benzothiazolyl cinnolinyl, furanyl, indazolyl, pendently selected from nitrogen, Sulfur or oxygen, wherein indolyl, imidazolyl, isoindolyl, isoquinolinyl, isothiazolyl, said heterocyclic ring may also be substituted with one or isoxazolyl, oxadiazolyl, oxazolinyl, oxazolyl, phthalazinyl, more substituents independently selected from H. F. Cl, Br, I, pyrazinyl, pyrazolinyl, pyrazolyl pyridazinyl, pyridyl, pyri CN, NO, oxo, C-C alkyl, C-C haloalkyl, C-C, midinyl, pyrrolyl, quinazolinyl, quinolinyl, quinoxalinyl, tet cycloalkyl, C-C halocycloalkyl, C-C cycloalkoxy, C-C, razolyl, thiazolinyl, thiazolyl, thienyl, triazinyl, triazolyl, pip halocycloalkoxy, C-C alkoxy, C-Chaloalkoxy, C-C alk erazinyl, piperidinyl, morpholinyl, pyrrolidinyl, enyl, C-C alkynyl, S(=O), (C-C alkyl), S(=O), (C-C, tetrahydrofuranyl, tetrahydropyranyl, 1,2,3,4-tetrahydro haloalkyl). OSO(C-C alkyl). OSO(C-C haloalkyl). quinolinyl, 4.5-dihydro-oxazolyl. 4,5-dihydro-1H-pyrazolyl, C(=O)NR'R'', (C-C alkyl)NR'R'', C(=O)(C-C alkyl), 4,5-dihydro-isoxazolyl, and 2,3-dihydro-1,3,4-oxadiaz C(=O)C(C-C alkyl), C(=O)(C-C haloalkyl), C(=O)C) olyl. (C-C haloalkyl), C(=O)(C-C cycloalkyl), C(=O)C(C- 0049 In another embodiment Het is triazolyl. C. cycloalkyl), C(=O)(C-C alkenyl), C(=O)C(C-C alk 0050 In another embodiment Het is 1.2.4 triazolyl. enyl), (C-C alkyl)O(C-C alkyl), (C-C alkyl)S(C-C, 0051 In another embodiment Het is oxadiazolyl. alkyl), C(=O)(C-C alkyl)C(=O)C(C-C alkyl), phenyl, 0.052 In another embodiment Het is 1,3,4 oxadiazolyl. phenoxy, Substituted phenyl and Substituted phenoxy, 0053 In another embodiment Het is pyrazolyl. 0043 wherein such substituted phenyl and substituted 0054 In another embodiment Ari is phenyl. phenoxy have one or more Substituents independently I0055. In another embodiment Ar’ is a substituted phenyl. selected from H. F. Cl, Br, I, CN, NO, C-C alkyl, C-C, I0056. In another embodiment Ar is a substituted phenyl haloalkyl, C-C cycloalkyl, C-C halocycloalkyl, C-C, that has one or more Substituents selected from C-C alkyl. cycloalkoxy, C-C halocycloalkoxy, C-C alkoxy, C-C, I0057. In another embodiment Art is a substituted phenyl haloalkoxy, C-C alkenyl, C-C alkynyl, S(=O), (C-C, that has one or more substituents wherein said substituent is alkyl), S(=O), (C-Chaloalkyl), OSO(C-C alkyl), OSO CH. (C-C haloalkyl), C(=O)H, C(=O)NR'R'', (C-C alkyl) 0058. In another embodiment R' is H. NR'R''. C(=O)(C-C alkyl), C(=O)C(C-C alkyl), 0059. In another embodiment R is (K), H, C-C alkyl, C(=O)(C-C haloalkyl), C(=O)C(C-C haloalkyl). C-C alkyl-O C(=O)C-C alkyl, C-C alkyl-O C C(=O)(C-C cycloalkyl), C(=O)C(C-C cycloalkyl). (=O)N(R'R''), or (C-C alkyl)S-(Het-1). US 2013/0019348 A1 Jan. 17, 2013

I0060. In another embodiment R is (K), H, CH, C-C, described as follows. S R thiourea precursors (3) are pre alkyl, CHOC(=O)CH(CH), CHOC(=O)N(H)(C(=O) pared from the corresponding thiourea (1) by treatment with OCHPh), or CHS (3,4,5-trimethoxy-2-tetrahydropyran). R X, where X is a halogen or methanesulfonate or a similar 0061. In another embodiment R is substituted phenyl. displaceable group. These are usually isolated as their hydro I0062) In another embodiment R is substituted phenyl halide (methanesulfonate) salts. Subsequent treatment of the wherein said substituted phenyl has one or more substituents S R thiourea precursors (3) with either an isocyanate (4) selected from F, Cl, C-C alkyl, C-C cycloalkyl, C-C, (see, for example, Pandey, A. K.; et. al., IndJ. Chem. Sect. B: alkoxy, and phenyl. Org. Chem. Incl. Med. Chem. (1982), 21 B(2), 150-2) or with 0063. In another embodiment R is substituted phenyl a p-nitrophenyl carbamate, Such as (5), in the presence of a wherein said substituted phenyl has one or more substituents base. Such as triethylamine or potassium carbonate or cesium selected from F, CH, 2-CH(CH), CH(CH)(CH), OCH, and phenyl. carbonate, results in formation of an S-alkylthiobiuret (6). 0064. In another embodiment R is substituted phenyl wherein said substituted phenyl has more than one substituent and at least one pair of said Substituents are not ortho to each Scheme 1 other. R2 I0065. In another embodiment R is C-C alkylphenyl. S I 0066. In another embodiment R is (Het-1). S 0067. In another embodiment R is H. NH + R2-X --> 2 N. 0068. In another embodiment M is N. HN k R H-X 0069. In another embodiment M is CR wherein R is HN selected from H. CN, and C(=O)(C-C alkyl). 1 2 3 0070. In another embodiment Q is O. Arl Are (0071. In another embodiment Q is S. NH31NN.co 0072. In another embodiment Q is O. 4 0073. In another embodiment R and Rare (K) wherein 3 + O -e- RandR along with C(Q)(N), form a 4- to 7-membered O saturated or unsaturated, hydrocarbyl cyclic group. O 0074. In another embodiment R and Rare (K) wherein Arl Ar N R° and Ralong with C(Q)(N), form a 4- to 7-membered NH1 S-CH O \,, saturated or unsaturated, hydrocarbyl cyclic group, wherein said hydrocarbyl cyclic group is Substituted with oxo or 5 C-C alkyl. 0075. In another embodiment Rand Rare (K) wherein R° and Ralong with C(Q)(N), form a 4- to 7-membered R2 saturated or unsaturated, hydrocarbyl cyclic group, wherein O s1 the “link” between Q and N is CHC(=O), CHCH CHCHCH, or CHCH(CH). ArlNYN Ar l Nals NH 0076. The molecules of this invention will generally have H V a molecular mass of about 400 Daltons to about 1200 Daltons. R3 However, it is generally preferred if the molecular mass is 6 from about 300 Daltons to about 1000 Daltons, and it is even more generally preferred if the molecular mass is from about 400 Daltons to about 750 Daltons. 0079. When Ris-CHOC(O)alkyl, treatment with etha nolic HCl at temperatures from about 0°C. to about 50° C. Preparation of Triaryl-Intermediates results in removal of R and generation of the thiobiuret (7) 0077 Molecules of this invention can be prepared by mak (Scheme 2). Under more prolonged heating, for example, by ing a triary1 intermediate, Ar-Het-Ari, and then linking it to heating in ethanolic HCl to the reflux temperature for from a desired intermediate to form a desired compound. A wide about 1 to about 24 hours, the thiobiuret is converted into a variety of triaryl intermediates can be used to prepare mol biuret (8), with oxygen replacing the Sulfur atom. ecules of this invention, provided that such triary1 intermedi ates contain a suitable functional group on Ari to which the rest of the desired intermediate can be attached. Suitable Scheme 2 functional groups include an amino or isocyanate or a car boxyl group. These triaryl intermediates can be prepared by O methods previously described in the chemical literature, including Crouse, et al., PCT Int. Appl. Publ. WO2009/ O s1 No 102736A1 (the entire disclosure of which is hereby incorpo Air 2 EtOH rated by reference). S.-vi.NH1NN 1 N 1. NH HeHCl, H O-50° C. Preparation of Urea-Linked Compounds R3 0078. Thiobiurets (thio-bisureas) and biurets can be pre pared according to Scheme 1, Scheme 2, and Scheme 3, US 2013/0019348 A1 Jan. 17, 2013

-continued dihalides (for example, 1-bromo-2-chloroethane, to form O SH 2-imino-1,3-thiazolines (10a)), or with methyl bromoacetate (to form 2-limino 1,3-thiazolin-4-ones (10b)), or with C-halo us-sl-NH11NN 21als. SN ItBOH - ketones (to form 2-limino-1,3-thiazoles (10c)), as depicted in H | 20-70° C. Scheme 4. A base Such as potassium carbonate or Sodium R3 acetate, in a protic solvent or aprotic solvent, attemperatures 7 between about 0°C. and about 100° C. can be used. Using O OH conditions described above, it can be seen that other ring sizes ArlNH1NN Ar ls 21els NN and Substitutions can be envisioned as well; the correspond H ing six-membered ring analog (10d), for example, can be R3 prepared starting with a 1,3-dihalopropane precursor. 8

Scheme 4 0080. An alternative process to form thiobiurets has been O S described by Kaufmann, H. P. Luthje, K. (Archiv Pharm. and Ber. Deutschen Pharm. (1960), 293, 150-9) and Oertel, G., et ArlNYN1 Ar ls. NN1,NN 1. BrCHCHClV It? - al. (Farb. Bayer, DE 1443873 A 19681.031 (1972). A carbam H H V K2CO3, butanone oyl isothiocyanate (9) is treated with an equivalent of an R3 aniline to form (7) (Scheme 3). Yet another route to thiobi 7 urets involves treatment of an N-aryl urea with R. NCS (N. R6 O Siddiqui, et. al., Eur. J. Med. Chem., 46 (2011), 2236-2242). Br Another route to biurets (8) involves treatment of an N-aryl O S urea with R isocyanate (Briody, et al., J. Chem. Soc., Perk. OMe 2, 1977,934-939). ArlNH3. Y Ar NN l N2. N R - R 6 - H V NaOAc, EtOH R3 Scheme 3 10a O R6 Br O Arl Ar l NH2 NH NN NCS + -> O S ) ( H R3 Air He?? Ar2 N l N2. N O - R 6 R 7 - 9 H V NaOAc, EtOH O SH R3

ArlNH1NN Ar l Nals NH H R6 R3 O S 7 \ B R6 R7 C O Ar - Ar2 2 "N-XA-1 Het N N N R7 -e- Arl Ar l NCS V K2CO3, butanone NH NN NH + | -- R3 H R3 10c O SH

ArlNH1NN Ar ls Nals NH O 1/ H Arl Ar l als S. R 7 R3 NH1 SN 4. - 7 R3 O 10d Arl Ar l NCO NH NN NH + | -- H R3 O OH I0082 An alternative route to analogs of Formula (10b) is described in Scheme 5. Treatment of 2-imino-1,3-thiazolin ArlNH1NN Ar ls Nals NH 4-one (11) with an aryl isocyanate or with intermediate (5) H (Scheme 1), in the presence of an amine base Such as triethy R3 lamine, leads to the synthesis of (10b). Other routes to (10b) 8 include addition of carbonyldiimidazole to (11) to produce an intermediate (12a), or addition of 4-nitrophenyl chlorofor 0081. Thiobiurets (7) can be converted into a variety of mate to form (12b). Either (12a) or (12b) can then be made to cyclized analogs (10), by treatment with, for example, vicinal react with an aniline Ar"-Het-Ar NH, to generate (10b). US 2013/0019348 A1 Jan. 17, 2013

Scheme 5

S l Arl HN NHk

1 R6 BrCHCOMe NaOAc, EtOH

R6 lu-te-A-Nil, 6 COMe R NH O S R l Carbonyl- 7 N N2. N O diimidazole V (CDI) N - R3 R6 u 12a S p-nitrophenyl chloroformate R6 N O S R3 2 ON O N N O

12b

0083. Another route to 1-(3-aryl thiazolidin-2-ylidene)-3- in U.S. Pat. No. 4,867,780 and references contained therein. aryl ureas (10a) is shown in Scheme 6. Treatment of an aryl Subsequent treatment of (14) with carbonyldiimidazole (to cyanamide (12) with a thirane in the presence of a base Such form 15a) or 4-nitrophenyl chloroformate (to form 15b), fol as potassium carbonate yields the 2-imino-1,3-thiazoline lowed by addition of an aniline results in formation of (10a). (14). The synthesis and Subsequent acylation of 3-aryl-2- Alternatively, reaction of (14) with an aryl isocyanate or iminothiazolidines by this route is described by F.X. Woolard 4-nitrophenyl carbamate (5) also produces (10a).

t --CNBr. R3 NaOAc, EtOH

13 14

O CDI or p-nitrophenyl chloroformate Arl-Het-Ar-NCO US 2013/0019348 A1 Jan. 17, 2013

-continued R6 O S Arl Y Ar ArlNH11NN Ar ls N2. N NH31NNH, H V R3 --, 10a 15a, T = 1-imidazolyl 15b, T = 4-nitrophenoxy

0084. By using the protocols described in Schemes 4 I0085 Malonyl monothioamides ((25) and (26)) and malo nyl diamides (29) can be prepared as described in Scheme 8. through 6, it can be seen that other analogs containing 4-, 5-, Condensation of a B-ketoanilide or C-cyanoanilide (24) with and 6-membered rings, and containing a variety of Substitu R NCS results in formation of 2-acyl malono-monothioa tion patterns, can be produced. Other heterocyclic systems mide (25). When R is an acetyl group. deacylation occurs on containing an exo-imino group are known, including but not refluxing in EtOH to form the malono-monothioamide (26). Thioamides can be cyclized in a manner similar to that limited to, 2-imino thiadiazolinones (16) (see Scheme 7); or described in Schemes 5 and 6, to produce cyclic analogs (27). 2-imino oxadiazolinones (17) (Syn. Comm., 2002, 32(5), The diamide (29) can be prepared from the corresponding 803-812); or 2-imino oxazolinones (18); or 2-imino thiadia monocarboxylic acid (28), by means of dicyclohexyl carbo diimide-1-hydroxy 7-azabenzotriazole coupling conditions. Zoles (19). These can also be used to prepare molecules (20)- (for example, see Jones, J., in: The Chemical Synthesis of (23), by appropriate Substitution of precursors in the proce Peptides. Int. Ser. of Monographs on Chemistry, Oxford dures described in Scheme 5 and Scheme 6. Univ. (Oxford, 1994), 23).

Scheme 7 R6 R6 R6 Q-N S s (

HN 2. N >= O HN 2. N O HN 2. N N V 3 V 3 R R3 R 16, Q = S 18 19 17, Q = O sent 5 or 6

J R6 R6 N O O 4. s1 Y O S S. N N N O \,, O \,, O l \,, Y- R Y- R Y- R A2-NH A2-NH A2-NH Arl-Het Arl-Het Arl-Het 20, Q = S 22 23 21, Q = O US 2013/0019348 A1 Jan. 17, 2013

-continued Scheme 8 R2 O o1 O Arl Ar --- R5 NCS --K2CO3, DMF ArlNH1NN Air ls Nals N1 R4 NH11NN l, V V H R RI R3 24 O SH EtOH, reflux I0087 Analogs wherein R' is not H may also be prepared ArlNH1NN Ar afi (forfor RR3 = COCH3)COCH as in shown in Scheme 10. Alkylation of Ar"-Het-Ar° NH, H V and conversion into thiourea (31), can be accomplished by a R5 R3 variety of known methods. For example, reaction with form 25 aldehyde and benzotriazole, followed by reduction with sodium borohydride, generates the N-methyl analog (30). O SH Conversion to (31) can be accomplished by treatment with ArlN11 ArNN ---4N BrCH3COMeBrCH-COM thiophosgene and ammonia, or with benzoyl isothiocyanate H V followed by base-catalyzed cleavage of the benzoyl group. R3 Treatment of (31) with oxalyl chloride and triethylamine, 26 under conditions first described by J. Goerdeler and K. Jonas (Chem. Ber, 1966,99(11), p. 3572-3581), results in forma S tion of a 2-amino-1,3-thiazolin-4,5-dione (32). Pyrolysis of O O this intermediate in refluxingtoluene then generates an N-car bonyl isothiocyanate (33), which on treatment with an amine Ar2 Z N / "N R3 R NH, forms the thiobiuret (7b, R=CH). Thiobiurets Air NHet H where R' is not H can then be further elaborated using con 27 ditions described in Scheme 4, to form cyclic analogs such as O O 10e. ArlNH1NN Ar OH HOA H EDCI Scheme 10 R5 28 Arl Ar 1. benzotriazole. HCHO NH31NNH, s O OH 2. NaBH4 ArlNH11NN Ar 21SN ArlnS Ar 1. benzowlbenzoyl isothocyanateisothiocyanate H V 2. NaOH R5 R3 CH3 29 30 S I0086. Further modifications by alkylation of the NH group Arn-Air ls Oxalyl chloride ofanalogs such as (6), (10a), (10b), (10c), (20)-(23), and (27) Het NH2 HeEtN can be effected by treating the appropriate molecule with an CH alkylating agent, R. X., where X is a halogen or methane 31 Sulfonyl group, or other similar leaving group (Scheme 9). The reaction requires use of a strong base such as sodium O hydride (NaH) or potassium hexamethyldisilazane, in an S Toluene aprotic solvent such as tetrahydrofuran or N,N-dimethylfor O -e- mamide. v's N 100° C. Arl NHetASN \ CH Scheme 9 32 2 O o1 R O R-X Ar y-se ArlNH1NN Ar ls %els N1 R4 NaH, THF / N H V Air NHet V R3 CH3 6, 10a, 10b, 10c, 20-23, 27 33 US 2013/0019348 A1 Jan. 17, 2013

-continued O Scheme 12

Ar- X- NCS -R-NH2 is N Br or CI Catalyst, 2 ligand Ar’-N Het/ N\ - Hal -- f Ho CH3 Arl HN-N N Br or Cl 34 HS R6 (y- M N-N O 2 BrCHCOMe A ) N N -e-NaOAc Arl 35 N Ar / AP- R3 Ar"N-3 CH3 - Ar Catalyst (y-f 7b 35 + (RO)2B -- N-N R6

S O 2. O y 2 N I0090 We also disclosed novel 1-Ar"-3-bromo-1,2,4-tria N V 3 zoles, wherein Ar' is 4-(C1-Co-alkyl)phenyl, 4-(C-C-ha Ar2 N R loalkyl)phenyl, 4-(C-C alkoxy)phenyl, 4-(C-C-ha / \ loalkoxy)phenyl, 4-(C-C alkylthio)phenyl, or 4-(C-C- Al-Het CH3 haloalkylthio)phenyl, as useful intermediates for the 10e preparation of many of the molecules claimed in this inven tion (preparation is described in Scheme 12. 0088 An arylry isocyanate,y Ar-Het-Ar° NCO, can also be treated directly with an N-aryl thiourea in the presence of F a catalytic amount of base such as cesium carbonate or F N sodium hydride, resulting in the formation of a thiobiuret (7) O o (Scheme 11). YQ O- / F + HN Na2. DMSOCuI 80-120° C. Scheme 11 S

2O + H2N l NH SCSCO - Arl Ar 2 O NN2 R3 NaH O SH

Arl Art l als F YH1 SN N t F ?— N R3 F 2. 7 F O -O- Né Br I0089. A method to prepare 1-(Ar")-3-(Ar)-1,2,4-triaz oles (36), wherein Ar" is a 4-(haloalkoxy)phenyl or a 4-(ha EXAMPLES loalkyl)phenyl group, involves coupling of a 1-(4-ha 0091. The examples are for illustration purposes and are not to be construed as limiting the invention disclosed in this loalkoxy)phenyl-3-bromo-1,2,4-triazole or a 1-(4-haloalkyl) document to only the embodiments disclosed in these phenyl-3-bromo-1,2,4-triazole (35, Scheme 12) with an aryl examples. boronic acid or arylboronic ester, under Suzuki conditions. 0092 Starting materials, reagents, and solvents that were The intermediates (35) in turn can be prepared by reacting obtained from commercial sources were used without further 3-bromo-1H-1,2,4-triazole (Kroeger, C. F.; Miethchen, R., purification. Anhydrous solvents were purchased as Sure? Chemische Berichte (1967), 100(7), 2250) (however SealTM from Aldrich and were used as received. Melting 3-chloro-1H-1,2,4-triazole may be used) with a 4-ha points were obtained on an OptiMelt Automated Melting loalkoxy-1-halobenzene (where halo-independently I or Br Point System from Stanford Research Systems and are uncor rected. Molecules are given their known names, named or C1 or F), in the presence of a metal catalyst such as CuI or according to naming programs within MDL ISISTM/Draw Cu2O, and a base such as CsCO, K-PO, or KCO, with or 2.5, ChemBioDraw Ultra 12.0 or ACD Name Pro. If such without an added ligand such as quinolin-8-ol, or N,N'-dim programs are unable to name a molecule, the molecule is ethyl ethylenediamine or other 1,2-diamines, or glycine, in a named using conventional naming rules. "H NMR spectral polar aprotic solvent such as acetonitrile, DMF or DMSO at data are in ppm (ö) and were recorded at 400 MHz, unless temperatures between about 70 and 150° C. otherwise stated.

US 2013/0019348 A1 Jan. 17, 2013

0122) To a solution of Molecule A3 (125 mg, 0.203 mmol) the title compound, mp 190-196° C. "H NMR (CDC1) & 8.54 in 5 mL of MeOH was added 0.5 mL of 7 N NH in MeOH. (s, 1H), 8.12 (d. J=8.7 Hz, 2H), 7.79 (d. J=9.1 Hz, 2H), 7.62 The resulting Solution was allowed to stiratambient tempera (d. J=8.8 Hz, 2H), 7.44-7.29 (m, 4H), 7.22 (d. J–7.5 Hz, 2H), ture for 16 h. The solution was concentrated and chromato 4.01 (s. 2H), 2.17 (s, 6H); ESIMS m/z 567 (M+H"). graphed (0-100% EtOAc-hexanes) to give 28 mg (27%) of the (O127 Compounds A35-A37, A65, A66, A69, A74-A77, thiobiuretas a white solid, mp.204-212° C. "HNMR (DMSO A85-A88, A92-A95, A103-A105, A108-A111, A115, A117, d) & 11.30 (s, 1H), 10.20 (s, 1H), 9.52 (s, 1H), 9.51 (s, 1H), A120-A121, and A125 in Table 1 were made in accordance 8.19 (d. J=8.4 Hz, 2H), 8.11 (d. J=8.7 Hz, 2H), 7.99 (d. J=8.6 with the procedures disclosed in Example 14. Hz, 2H), 7.62 (d. J=8.8 Hz, 2H), 720-7.09 (m, 3H), 2.20 (s, 6H), ESIMS m/z 511 (M+H"). Example 15 Example 13 Preparation of (Z)-2-(2,6-dimethylphenyl)imino)-N- (4-(1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol Preparation of 1-(2-isopropylphenyl)-3-4-1-4- 3-yl)phenyl)thiazolidine-3-carboxamide (Molecule (trifluoromethoxy)phenyl-1,2,4-triazol-3-yl)phenyl A15) carbamoylurea (Molecule A13) 0128 (0123

f=N O S -O N. 2 O -->

(0.124 Molecule A5 (500 mg. 0.78 mmol) was added to 10 I0129. To a solution of Molecule A11 (350 mg, 0.665 mL of THF and 2 mL of 1 NHCl and the solution was stirred mmol) in 7 mL of acetone was added potassium carbonate for 24 h. The solution was then partitioned between EtOAc (200 mg, 1.44 mmol) and 1-chloro-2-bromoethane (0.20 g, (30 mL) and saturated NaHCO, solution (15 mL). Separation 1.40 mmol), and the solution was heated at 50° C. for 5h. The and drying of the organic layer followed by removal of the cooled solution was adsorbed onto Silica gel and chromato Solvent gave a crude Solid which was chromatographed on graphed (0-80% EtOAc-hexanes) to give 99 mg (26%) of silica gel to furnish 160 mg (38%) of the title compound as a Molecule A15: mp 145-150° C. "H NMR (CDC1) & 8.51 (s, white solid; mp300° C. (dec); H NMR (DMSO-d) 89.86 (s, 1H), 8.07 (d. J=7.9 Hz, 2H), 7.81-7.74 (m, 2H), 7.59 (d. J=6.8 1H), 9.57 (s, 1H), 9.37 (d. J=13.8 Hz, 2H), 8.15-7.98 (m, 4H), Hz, 2H), 7.36 (d. J=8.3 Hz, 2H), 7.19 (m, 3H), 7.12 (s, 1H), 7.74 (dd, J=7.9, 1.5 Hz, 1H), 7.67-7.53 (m, 4H), 7.33 (dd, 3.81 (t, J=7.7 Hz, 2H), 3.37 (t, J=7.6 Hz, 2H), 2.23 (s, 6H): J=7.5, 1.8 Hz, 1H), 7.24-7.06 (m, 2H), 3.20-2.99 (m, 1H), ESIMS m/z 553 (M+H"). 1.22 (d. J=6.8 Hz, 6H). ESIMS m/z 525 (IM+H"). Example 16 Example 14 Preparation of (Z)-2-(2,6-dimethylphenyl)imino)-N- Preparation of (Z)-1-(3-(2,6-dimethylphenyl)-4- (4-(1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol oxothiazolidin-2-ylidene)-3-(4-(1-(4-(trifluo 3-yl)phenyl)-1,3-thiazinane-3-carboxamide (Mol romethoxy)phenyl)-1H-1,2,4-triazol-3-yl)phenyl) ecule A16) urea (Molecule A14) O130 0125

f=N O S ?Na O O ...OrN 2 O --> ...Or Oll,

I0131 To a solution of Molecule A11 (150 mg 0.28 mmol) 0126 To a suspension of Molecule A11 (200 mg, 0.38 in 5 mL of acetone was added potassium carbonate (150 mg. mmol) in 5 mL of EtOH was added sodium acetate (200 mg. 1.08 mmol) and 1-chloro-3-bromopropane (0.16 g, 1.00 2.43 mmol) and methyl bromoacetate (0.14 g. 0.91 mmol), mmol), and the solution was heated at 50° C. for 5 h. The and the solution was heated at 60° C. for 3 h. The cooled cooled solution was adsorbed onto Silica gel and chromato solution was then diluted with 2 mL of water and the resulting graphed (0-70% EtOAc-hexanes) to give 22 mg (12%) of the white solid was filtered and air-dried to give 142 mg (64%) of thiazinane: mp 121-125° C. "H NMR (CDC1) & 12.81 (s,

US 2013/0019348 A1 Jan. 17, 2013 20 was stirred at room temperature overnight. The Solution was 7.50-7.10 (m,3H), 6.84 (d.J=2.8 Hz, 1H), 6.72 (dd, J=8.7, 2.9 diluted with water and extracted with EtOAc. The organic HZ, 1H), 4.02 (s.3H), 3.80 (s. 2H), 3.08 (dt, J=13.6, 6.8 Hz, solution was washed with water (5x) and brine. The solution 1H), 1.20 (d. J=6.9 Hz, 6H). 'C NMR (101 MHz, CDC1) & was then dried over MgSO filtered and concentrated. The 166.81, 166.13, 162.98, 158.40, 144.30, 141.54, 139.02, 135. residue was purified via radial chromatography using a 97.5: 54, 127.30, 127.05, 126.87, 126.52, 126.30, 122.36, 121.13, 2.5 ratio of CHCl/MeOH as the eluent (R-0.2). The fraction 120.10, 111.97, 110.85, 56.04, 55.36, 44.26, 28.37, 23.06. containing the product was contaminated with the dimethyl ESIMS m/z 553 (M+H") amide of the starting carboxylic acid. This mixture was puri fied via reverse phase chromatography using CHCN/HO Example 35 gradient to give the pure desired diamide (9 mg, 12%). (0172 H NMR (CDC1: mixture of resonance forms, Preparation of 4-fluoro-2-nitro-1-(prop-1-en-2-yl) major reported) & 10.53 (s, 1H), 9.71 (s, 1H), 8.55 (s, 1H), benzene (B14) 8.13 (m, 3H), 7.79 (d. J=9.1 Hz, 2H), 7.71 (d. J=8.7 Hz, 1H), 7.65 (d. J=8.7 Hz, 1H), 7.37 (d. J=8.3 Hz, 2H), 7.12 (m, 1H), 0.177 3.49 (s. 2H), 3.12 (s, 3H), 3.04 (s, 3H). ESIMS m/z 509 (M+H") Example 33 Preparation of (Z)-3-hydroxy-3-(4-methoxy-2-meth ylphenylamino)-N-(4-(1-(4-(trifluoromethoxy)phe nyl)-1H-1,2,4-triazol-3-yl)phenyl)acrylamide (Mol ecule A33) 0173 (0178. To 1-chloro-4-fluoro-2-nitrobenzene (1.03 g, 5.87 mmol) in a 100 mL round-bottomed flask equipped with a stir bar and nitrogen was added sodium carbonate (0.746g, 7.04 HO f= N O H mmol), dioxane (23.47 ml) and water (5.87 ml). To this was N. % Z N added 4.4.5.5-tetramethyl-2-(prop-1-en-2-yl)-1,3,2-diox FCO N aborolane (1.323 ml, 7.04 mmol) followed by bis(triph H enylphosphine)palladium(II) chloride (0.329 g, 0.469 mmol). OMe The reaction mixture was evacuated and backfilled with nitro gen (3x). The reaction was heated to 80° C. overnight. The reaction was determined to be complete by TLC (10% 0.174. Using Step 3 of the above procedure, and replacing EtOAc/Hex). The reaction was cooled, filtered through 2,6-dimethylaniline with 2-methyl-4-methoxyaniline, there Celite, washed with EtOAc and concentrated. The residue was obtained 83 mg (56%) of the diamide as a tan solid, mp was taken up in dichloromethane, poured through a phase 168-171° C. "H NMR (DMSO-d) & 10.39 (s, 1H), 9.48 (s, separator and concentrated. Purification by flash column 1H), 9.38 (s, 1H), 8.07 (d. J=8.9 Hz, 4H), 7.77 (d. J=8.8 Hz, chromatography provided the title compound 4-fluoro-2-ni 2H), 7.62 (d. J=8.3 Hz, 2H), 7.28 (d. J–8.7 Hz, 1H), 6.81 (d. tro-1-(prop-1-en-2-yl)benzene (0.837g, 75%) as a yellow oil: J=2.8 Hz, 1H), 6.74 (dd, J=8.7, 2.9 Hz, 1H), 3.73 (s.3H), 3.51 IR (thin film) 3091 (w), 2979 (w), 2918 (w), 1642 (w), 1530 (s. 2H), 2.21 (s.3H). EIMS 525 (M). (s), 1350 (s) cm': "H NMR (400 MHz, CDC1,) & 7.60 (dd. J=8.2, 2.5 Hz, 1H), 7.37-7.21 (m, 2H), 5.19 (p, J=1.5 Hz, 1H), Example 34 4.97-489 (m. 1H), 2.11-2.04 (m, 3H); 'C NMR (101 MHz, Preparation of (Z)-3-hydroxy-3-(2-isopropyl-4-meth CDC1) & 160.96 (d. J–250.8 Hz), 148.46, 141.88, 135.18 oxyphenylamino)-N-(4-(1-(4-(trifluoromethoxy) (d. J. 4.1 Hz), 132.09 (d. J–7.8 Hz), 119.98 (d. J–20.9 phenyl)-1H-1,2,4-triazol-3-yl)phenyl)acrylamide Hz), 115.99, 111.63 (d. J–26.4 Hz), 23.35. (0179 The following molecules (B15 and B16) were made (Molecule A34) in accordance with the procedures disclosed in Example 35. 0175 0180 1-Fluoro-3-nitro-2-(prop-1-en-2-yl)benzene (B15)

f=N o "R. H N FCO N H

OMe

0176). Using Step 3 of the above procedure, and replacing 0181 IR (thin film) 3091 (w), 2978 (w), 2922 (w), 1645 2,6-dimethylaniline with 2-isopropyl-4-methoxyaniline, (w), 1528 (s), 1355 (s) cm; H NMR (400 MHz, CDC1) & there was obtained 38 mg (36%) of the diamide. "H NMR 7.64 (dt, J=8.1, 1.2 Hz, 1H), 7.39 (td, J=8.2, 5.4 Hz, 1H), 7.31 (CDC1) 89.81 (s, 1H), 8.92 (s, 1H), 8.58 (s, 1H), 8.12 (d. (td, J=8.5, 1.2 Hz, 1H), 5.28 (p, J–1.5 Hz, 1H), 4.91 (p, J=1.0 J=8.6 Hz, 2H), 7.79 (d. J=9.0 Hz, 2H), 7.69 (d.J=8.7 Hz, 2H), HZ, 1H), 2.16 (t, J=1.3 Hz,3H); 'CNMR (101 MHz, CDC1)

US 2013/0019348 A1 Jan. 17, 2013

0230 "H NMR (400 MHz, DMSO-d) 89.35 (s, 1H), 8.07 A118 and A119 in Table 1 were made either in accordance (s, 1H), 7.41 (d.J=1.9Hz, 1H), 7.10 (s, 1H), 6.07 (d. J=1.9Hz, with the procedures disclosed in Example 39 or by the pro 1H), 4.36 (hept, J=6.6 Hz, 1H), 1.33 (d. J=6.6 Hz, 6H); 'C cedure described in Example 53. NMR (101 MHz, DMSO-d) & 183.02, 137.47, 135.00, 102. 00, 48.12, 22.27; ESIMS m/z 185 (IM+H"). Example 41 1-(3-Isopropylphenyl)thiourea (B39) Preparation of N-(2-methyl-4-methoxyphenyl) 0231 aminoloxomethyl-N'-(4-(1-(4-(trifluoromethyl)phe nyl)-1H-1,2,4-triazol-3-yl)phenyl urea (Molecule A53) S 0236 N l NH H 2

0232 'H NMR (400 MHz, CDC1,) & 7.99 (s, 1H), 7.36 (t, J=7.8 Hz, 1H), 7.20 (dt, J=7.8, 1.4 Hz, 1H), 7.12-7.02 (m, 2H), 6.11 (s. 2H), 2.92 (hept, J=6.9 HZ, 1H), 1.25 (d. J–7.0 Hz, 6H); 'C NMR (101 MHz, CDC1) & 181.65, 151.61, 136.18, 130.11, 126.13, 123.17, 122.40, 33.98, 23.83; ESIMS m/z 195 (IM+H"). Example 39 Preparation of N-(2-isopropylphenyl)aminothiox omethyl-N'-(4-(1-(4-(trifluoromethyl)phenyl)-1H-1, 0237. In a 100 mL round-bottomed flask were added 1-(4- 2,4-triazol-3-yl)phenyl urea. (Molecule A48) (1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)phe nyl)urea (200 mg, 0.551 mmol) and 1-isocyanato-4-meth 0233 oxy-2-methylbenzene (135 mg. 0.826 mmol) in dioxane (10 mL). The vessel was heated at 100° C. for 2 hours before the contents were cooled and the solvent removed under reduced a N pressure. The residue was suspended in DCM and purified via CX- )-NH N normal phase chromatography (silica gel; hexanes/EtOAc) to afford the title product as a white solid (30 mg): mp 213-233° y C O y C.; H NMR (400 MHz, DMSO-d) & 10.71 (s, 1H), 10.34 (s, O 1H), 10.13 (s, 1H), 9.39 (s, 1H), 8.08 (m, 4H), 7.70-7.57 (m, F 4H), 7.26 (d. J=8.7 Hz, 1H), 6.87 (d. J=2.9 HZ, 1H), 6.81 (dd. J=8.7, 2.9 Hz, 1H), 3.75 (s.3H), 2.20 (s.3H); EIMS m/z 527 (IM+H"). 0234. To a round bottom flask was added 4-(1-(4-(trifluo romethoxy)phenyl)-1H-1,2,4-triazol-3-yl)benzoyl azide Example 42 (300 mg. 0.802 mmol). The flask was evacuated/backfilled with N, then toluene (20.0 mL) was added, followed by 1-(2-isopropylphenyl)thiourea (30 mg, 0.154 mmol). The Preparation of (E)-methyl 4-(3-(dimethylamino) reaction mixture was heated to 100° C. for 1 h. the reaction acryloyl)benzoate (B40) was then cooled to 50° C. and stirred for an additional 1 h. The reaction mixture was then cooled to 35°C. THF (1 mL) was 0238 added, followed by sodium hydride (32.1 mg, 0.802 mmol) in one portion. Vigorous bubbling occurred, and the reaction mixture turned yellow. The reaction mixture was stirred at 35° O C. for an additional 15 min. The reaction mixture was cooled N Y to room temperature, poured over ice water, extracted with EtO, dried, and concentrated onto silica. The crude residue was purified via flash chromatography (silica/EtOAc/hex anes) to yield the title compound as a white solid (57 mg, O 0.104 mmol, 13%); mp 201-203° C.; H NMR (400 MHz, N CDC1) & 8.57 (s, 1H), 8.16 (m. 2H), 7.80 (m, 3H), 7.56 (d. O J=8.3 Hz, 2H), 7.40 (ddt, J=8.0, 6.7, 1.7 Hz, 2H), 7.28 (dt, J=6.8, 1.8 Hz, 2H), 7.23 (m, 2H), 3.16 (dp, J=16.4, 6.9 Hz, 3H), 1.22 (d. J=6.9 Hz, 6H); 'F NMR (37.6 MHz, CDC1) & 0239. A mixture of methyl 4-acetylbenzoate (5.00g, 28.1 -58.02: EIMS m/z 542 (M+2). mmol) in DMF-DMA (38 mL, 284 mmol) was heated at 105° 0235 Molecules A46, A63, A64, A67. A68, A70-A73, C. for 20 hours. The reaction was cooled, concentrated, and A78-A84, A89, A97-A101, A106, A107, A112, A113, A116, used crude in the next reaction. US 2013/0019348 A1 Jan. 17, 2013 26

Example 43 phy (0-10% MeOH/dichloromethane) gave 44144-(trifluo romethoxy)phenyl)-1H-pyrazol-3-yl)benzoic acid as a Preparation of methyl 4-(1H-pyrazol-3-yl)benzoate brown solid (580 mg, 16%); H NMR (400 MHz, CDC1) & (B41) 8.19 (d. J=7.7 Hz, 2H), 8.03 (d. J=7.7 Hz, 2H), 7.98 (d. J=2.5 HZ, 1H), 7.85-7.79 (m, 2H), 7.35 (d. J=8.4 Hz, 2H), 6.88 (d. 0240 J–2.5 Hz, 1H); F NMR (376 MHz, CDC1) & -58.05; ESIMS m/z 349 (IM+H"). Example 45 Preparation of 4-(1-(4-(trifluoromethoxy)phenyl)- 1H-pyrazol-3-yl)benzoyl azide (B43) 0244 O N

0241. To a solution of crude (E)-methyl 4-(3-(dimethy lamino)acryloyl)benzoate (28.1 mmol) in EtOH (100 mL) was added hydrazine monohydrate (1.50 mL, 30.9 mmol) and the reaction was heated at 50° C. for 24 hours. The reaction temperature was then increased to 60° C. for 24 hours. Addi tional hydrazine monohydrate (1.5 mL) was added, and the reaction was heated at 60° C. for an additional 6 hours. The reaction was cooled, concentrated, and dried in a vacuum N oven at 45° C. overnight to yield methyl 4-(1H-pyrazol-3-yl) benzoate as an orange solid (8.15g, quantitative): mp 106°C. (dec); H NMR (400 MHz, CDC1) & 8.15-8.05 (m, 2H), 0245. To 4-(1-(4-(trifluoromethoxy)phenyl)-1H-pyrazol 7.91-7.83 (m, 2H), 7.65 (d. J=2.4 Hz, 1H), 6.71 (d. J=2.3 Hz, 3-yl)benzoic acid (0.58 g, 1.67 mmol) in isopropanol (10.7 1H), 3.94 (s, 3H); C NMR (101 MHz, CDC1) & 166.91, mL) was added triethylamine (0.30 mL, 2.17 mmol) and 136.89, 131.83, 130.13, 129.37, 125.50, 103.35, 52.14, diphenylphosphoryl azide (0.47 mL, 2.17 mmol) and the 22.46; EIMS m/z. 202. reaction was stirred at room temperature for 16 hours. The orange precipitate that had formed was filtered through a Example 44 fritted glass funnel, rinsed with isopropanol, and dried in a vacuum oven to provide 4-(1-(4-(trifluoromethoxy)phenyl)- Preparation of 4-(1-(4-(trifluoromethoxy)phenyl)- 1H-pyrazol-3-yl)benzoyl azide as an orange solid (188 mg, 1H-pyrazol-3-yl)benzoic acid (B42) 30%): 'H NMR (400 MHz, DMSO-d) & 8.69 (d. J–2.6 Hz, 1H), 8.17-8.11 (m, 2H), 8.09-8.04 (m, 4H), 7.57 (d. J=8.4 Hz, 0242 2H), 7.24 (d. J=2.6 Hz, 1H); 'F NMR (376 MHz, DMSO-d) & -56.97: ESIMS m/z. 374 (IM+H"). Example 46 Preparation of N-(2-isopropylphenyl)aminothiox omethyl-N'-((4-(1-(4-(trifluoromethoxy)phenyl)- 1H-pyrazol-3-yl)phenyl))urea (Molecule A114) 0246

HO

0243 Methyl 4-(1H-pyrazol-3-yl)benzoate (2.00 g, 9.89 mmol), 1-bromo-4-(trifluoromethoxy)benzene (2.38 g. 9.88 mmol), copper (I) iodide (0.28 g, 1.47 mmol), 8-hydrox yduinoline (0.21 g, 1.45 mmol), and cesium carbonate (6.47 0247 A solution of 4-(1-(4-(trifluoromethoxy)phenyl)- g, 19.86 mmol) in DMF/water (11:1) was heated at 120° C. 1H-pyrazol-3-yl)benzoyl azide (186 mg 0.50 mmol) in DCE for 20 hours. The reaction was cooled, diluted with water and (2.5 mL) was heated at 80°C. for 2 hours. The reaction was EtOAc, and decanted from the copper solids. The mixture was cooled to room temperature and 1-(2-isopropylphenyl)thio extracted three times with EtOAc (3x150 mL) and the com urea (97 mg, 0.50 mmol) and cesium carbonate (170 mg. 0.52 bined organic layers washed with water. The organic layers mmol) were added. The mixture was stirred at room tempera were dried over anhydrous sodium sulfate, filtered, and ture for 3 days. The reaction was diluted with EtOAc and adsorbed onto silica gel. Purification by flash chromatogra transferred to a separatory funnel containing water. The aque US 2013/0019348 A1 Jan. 17, 2013 27 ous layer was extracted twice with EtOAc. The organic layers Example 48 were dried over anhydrous sodium sulfate, filtered, and adsorbed onto silica gel. Purification by flash chromatogra Preparation of 4-(perfluoroethoxy)benzohydrazide phy (0-20% EtOAc/B, where B=1:1 dichloromethane/hex anes) provided a yellow solid that contained a 10% impurity (B45) by LC/MS. Reverse-phase flash chromatography (0-100% 0250 acetonitrile/water) provided the title compound as a white solid (36.5 mg, 13%): mp 131° C. (dec); H NMR (400 MHz, CDC1) & 11.98 (s, 1H), 10.56 (s, 1H), 8.16 (s, 1H), 7.93 (d. NH J=2.5 Hz, 1H), 7.86 (d. J=8.5 Hz, 2H), 7.83-7.76 (m, 2H), N1" 7.47 (d. J=7.9 Hz, 2H), 7.43-7.35 (m,3H), 7.35-7.27 (m,3H), F 6.76 (d. J=2.5 Hz, 1H), 3.15 (dt, J=13.7, 6.8 Hz, 1H), 1.26 (d. F F O J=6.5 Hz, 6H); F NMR (376 MHz, CDC1) & -58.06; F ESIMS m/z 540 (IM+H"). F O Example 47 0251 To a solution of ethyl 4-(perfluoroethoxy)benzoate (4.58 g. 16.1 mmol) in EtOH (16 mL) was added hydrazine Preparation of ethyl 4-(perfluoroethoxy)benzoate monohydrate (1.96 mL, 40.3 mmol) and the reaction was (B44) heated at 85°C. for 36 hours. The reaction was cooled and poured into ice water (100 mL). A white gel-solid formed and 0248 was filtered through a Bichner funnel under vacuum. The solid was dried in a vacuum oven at 45° C. overnight to provide 4-(perfluoroethoxy)benzohydrazide as an off-white solid (3.177 g, 73%); mp 117-119.5° C.; H NMR (400 MHz, CDC1,) & 7.83-7.76 (m, 2H), 7.36 (s, 1H), 7.31 (d. J=8.8 Hz, - 2H), 4.13 (s. 2H); 'F NMR (376 MHz, CDC1) 8 -86.01, F -87.83; ESIMS m/z 269 (M-HI). F F O

F Example 49 F O Preparation of 2-(4-(perfluoroethoxy)phenyl)-1,3,4-oxadiazole 0249. To an oven-dried 500-mL round bottom flask (B46) equipped with a stirring bar was added 1-bromo-4-(perfluo roethoxy)benzene (9.35 g, 32.1 mmol) and anhydrous THF 0252) (200 mL). The flask was placed under nitrogen and cooled in an ice bath for 10 min A solution of 1.3 M isopropylmagne sium chloride-lithium chloride complex (30 mL, 38.6 mmol) N-NN was added over 15 min. The ice bath was removed after 1 F ) hour, and the reaction was warmed to room temperature and F F O stirred overnight. GC/MS showed the presence of starting material. The reaction was cooled in an ice bath and 1.3 M DyF O O's isopropylmagnesium chloride-lithium chloride complex (5 mL) was added. The ice bath was removed after 20 min and 0253) A mixture of 4-(perfluoroethoxy)benzohydrazide stirred at room temperature for 9 hours. Ethyl chloroformate (3.17 g, 11.7 mmol) in trimethyl orthoformate (11.6 mL, 106 (3.4 mL, 35.3 mmol) was added in a slow, steady stream. The mmol) and acetic acid (0.13 mL, 2.35 mmol) was heated at reaction was warmed slightly during the addition and was 120° C. for 5 hours. The reaction was diluted with MeOH (15 stirred at room temperature overnight. The reaction was mL) and poured into a beaker containing ice water (150 mL). diluted with EtOAc and washed with saturated aqueous The white precipitate was vacuum filtered and dried in a ammonium chloride. The aqueous layer was extracted three vacuum oven to provide 166 mg of 2-(4-(perfluoroethoxy) times with EtOAc. The organic layers were dried over anhy phenyl)-1,3,4-oxadiazole as an off-white Solid. An orange drous sodium sulfate, filtered, and concentrated to give a precipitate had formed in the aqueous filtrate and was col yellow liquid, which was purified by flash chromatography lected by vacuum filtration and adsorbed onto silica gel. Puri fication by flash chromatography (0-40% EtOAc/hexanes) (0–0, 0–4. 4-10% EtOAc/hexanes) to provide ethyl 4-(perfluo provided 2.02 g of 2-(4-(perfluoroethoxy)phenyl)-1,3,4-oxa roethoxy)benzoate as a yellow liquid (4.58g, 50%): "H NMR diazole as an off-white solid giving a combined yield of 2.186 (400 MHz, CDC1) & 8.10 (d. J=8.8 Hz, 2H), 7.28 (d. J=8.7 g (67%); mp 87-89° C.; H NMR (400 MHz, CDC1) & 8.49 Hz, 2H), 4.39 (q, J=7.1 Hz, 2H), 1.40 (t, J=7.1 Hz, 3H); 'F (s, 1H), 8.28-8.05 (m, 2H), 7.40 (d. J=8.9 Hz, 2H); 'F NMR NMR (376 MHz, CDC1) 8 -86.05, -87.84: ESIMS m/z 284 (376 MHz, CDC1) 8 -85.98, -87.82: ESIMS m/z 280 (M+ (M+H"). HI). US 2013/0019348 A1 Jan. 17, 2013 28

Example 50 J=8.6 Hz, 2H), 7.68 (d. J=8.8 Hz, 2H), 'F NMR (376 MHz, DMSO-d) 8 -85.25, -86.89; ESIMS m/z 401 (IM+H"). Preparation of methyl 4-(5-(4-(perfluoroethoxy)phe nyl)-1,3,4-oxadiazol-2-yl)benzoate (B47) Example 52 Preparation of 4-(5-(4-(perfluoroethoxy)phenyl)-1,3, 0254 4-oxadiazol-2-yl)benzoyl azide (B49) 0258 N N1 N F O -N F F O N \ F O F O-N- F O F NSN - F O NSN 0255. A mixture of 2-(4-(perfluoroethoxy)phenyl)-1,3,4- oxadiazole (2.186 g, 7.80 mmol), methyl 4-iodobenzoate 0259. To a solution of 4-(5-(4-(perfluoroethoxy)phenyl)- (3.07 g., 11.70 mmol), copper(I) iodide (0.28 g, 1.47 mmol), 1,3,4-oxadiazol-2-yl)benzoic acid (217 mg, 0.54 mmol) in 1,10-phenanthroline (0.30g, 1.67 mmol), and cesium carbon isopropanol (5.4 mL) was added triethylamine (0.09 mL, 0.65 ate (2.54 g, 7.80 mmol) in anhydrous DMSO (20 mL) was mmol) and diphenyl phosphorazidate (0.13 mL, 0.60 mmol) heated at 100° C. for 18 hours. The reaction was cooled, and the reaction was stirred at room temperature for 16 hours. diluted with water, and extracted three times with EtOAc. The The white precipitate that had formed was filtered and dried in organic layers were dried over anhydrous sodium Sulfate, a vacuum oven to provide 4-(5-(4-(perfluoroethoxy)phenyl)- filtered, and adsorbed onto silica gel. Purification by flash 1,3,4-oxadiazol-2-yl)benzoyl azide as a white solid (145 mg. chromatography (0-50% EtOAc/hexanes) provided methyl 63%): mp 140° C. (dec); H NMR (400 MHz, DMSO-d) & 4-(5-(4-(perfluoroethoxy)phenyl)-1,3,4-oxadiazol-2-yl)ben 8.32 (m, 4H), 8.24-8.17 (m, 2H), 7.68 (d. J=8.9 Hz, 2H); 'F zoate as a white solid (1.08 g., 33%); mp 185-191° C.; H NMR (37.6 MHz, DMSO-d) 8 -85.25, -86.89; ESIMS m/z NMR (400 MHz, CDC1) & 8.25-8.19 (m, 6H), 7.41 (t, J=9.4 Hz, 2H), 3.98 (s.3H); 'FNMR (376MHz, CDC1)8-85.96, 426 (M+H"). -85.98, -87.79; ESIMS m/z 415 (IM+H"). Example 53 Preparation of N-(2-isopropylphenyl)aminothiox Example 51 omethyl-N'-((4-(5-(4-(perfluoroethoxy)phenyl)-1,3, 4-oxadiazol-2-yl)phenyl))urea (Molecule A96) Preparation of 4-(5-(4-(perfluoroethoxy)phenyl)-1,3, 4-oxadiazol-2-yl)benzoic acid (B48) 0260 0256 F. F N-N HS F O F ( \ e N N O- C y --N F Y O F F O

F OH 0261) A solution of 4-(5-(4-(perfluoroethoxy)phenyl)-1, F O 3,4-oxadiazol-2-yl)benzoyl azide (278 mg, 0.65 mmol) in DCE (3.3 mL) was heated at 80° C. for 3 hrs. The reaction was cooled to room temperature and 1-(2-isopropylphenyl)thio 0257 To methyl 4-(5-(4-(perfluoroethoxy)phenyl)-1,3,4- urea (131 mg, 0.67 mmol) followed by cesium carbonate (243 oxadiazol-2-yl)benzoate (1.07 g. 2.58 mmol) was added mg, 0.75 mmol) were added. The reaction mixture was stirred MeOH (26 mL) (starting material remained partially at room temperature for 18 hours. The reaction was diluted insoluble). A solution of 2 N. NaOH (5.2 mL, 10.33 mmol) with EtOAc and transferred to a separatory funnel containing was added, and the reaction was stirred at room temperature aqueous Sodium bicarbonate. The aqueous layer was for 18 h. Stirring had become hindered overnight due to the extracted twice with EtOAc. The organic layers were dried formation of solid. LC/MS showed 25% conversion to prod over anhydrous sodium sulfate, filtered, and adsorbed onto uct. The reaction mixture was diluted with MeOH and addi silica gel. Purification by flash chromatography (0-20% tional 2 N NaOH (20 mL) was added and the reaction was EtOAc/B, where B=1:1 dichloromethane/hexanes) provided heated to 45° C. for 24 h. The reaction was cooled and neu the title compound as a white powder (43 mg, 11%): mp 219 tralized with 2 N HCl (20 mL). Some of the MeOH was C. (dec); H NMR (400 MHz, DMSO-d) & 11.61 (s, 1H), concentrated offin vacuo, causing the product to precipitate. 10.25 (s, 1H), 9.71 (s, 1H), 8.30-8.22 (m, 2H), 8.14 (d. J=8.8 The white precipitate was vacuum filtered and dried in a Hz, 2H), 7.71 (d. J=8.8 Hz, 2H), 7.66 (d. J=8.7 Hz, 2H), 7.39 vacuum oven at 45° C. to provide 4-(5-(4-(perfluoroethoxy) (dd, J=10.3, 3.9 Hz, 2H), 7.27 (ddd, J=13.5, 10.6, 6.1 Hz, 2H), phenyl)-1,3,4-oxadiazol-2-yl)benzoic acid as a white Solid 3.07 (heptet, J=6.8 Hz, 1H), 1.20 (d. J=6.9 Hz,6H); 'F NMR (760 mg, 90% purity, 66%); mp301-307 C.; H NMR (400 (376 MHz, DMSO-d) 8 -85.25, -86.89; ESIMS m/z 590 MHz, DMSO-d) & 13.40 (s, 1H), 8.34-8.26 (m, 4H), 8.18 (d. (IM-HI).

US 2013/0019348 A1 Jan. 17, 2013 31

Example 56 Example 58 Preparation of (Z)-1-(3-mesityl-4-methylthiazol-2 Preparation of 4-(1-(4-(perfluoropropyl)phenyl)-1H (3H)-ylidene)-3-(4-(1-(4-(trifluoromethoxy)phenyl)- 1,2,4-triazol-3-yl)benzoic acid (B59) 1H-1,2,4-triazol-3-yl)phenyl)urea (Molecule A43) 0283 0287

? O -O-O-,Ya -(alS OH

0284. A solution of the tolyl triazole (1.0g, 2.48 mmol) in 6 mL of AcOH was heated to 60° C., and ceric ammonium nitrate (4.50 g, 8.21 mmol) in 3 mL of water was added over 10 minutes. Heating was continued for 1 hr., then the solution (0288 To free thiobiuret (100 mg, 0.185 mmol) in 3 mL of was cooled and diluted with 30 mL of water. The liquid was butanone was added triethylamine (0.052 mL, 0.370 mmol) decanted from a light yellow gummy solid which formed over followed by chloroacetone (0.021 mL, 0.259 mmol). The 30 min. This residue was then combined with 10 mL of solution was heated at reflux for 20 hrs, then it was cooled, dioxane and 3 mL of 50% aqueous KOH, and heated at 75-80° diluted with 20 mL of CHCl, washed with water (10 ml), C. for 2 hrs. The solution was cooled and diluted with 20 mL dried and concentrated in vacuo. Chromatography (silica, of water. The resulting solid was filtered and then re-dissolved 0-100% EtOAc-hexanes) furnished the desired product as a in 15 mL of acetonitrile, and sodium bromate (1.12 g, 7.44 viscous yellow oil (0.92 g, 84%); H NMR (400 MHz, mmol) and sodium bisulfite (0.298g, 2.48 mmol) were added. CDC1,) & 8.55 (s, 1H), 8.17 (d. J=8.7 Hz, 2H), 7.85-7.68 (m, The solution was heated at reflux for 2 hr., then cooled and 5H), 7.37 (d. J=8.3 Hz, 2H), 7.02 (s. 2H), 6.35 (d. J=0.9 Hz, diluted with 10 mL of water. A white precipitate formed, 1H), 2.43 (s, 3H), 2.34 (s, 3H), 2.17 (s, 6H); 'F NMR (376 which was filtered and air-dried to give 4-(1-(4-(perfluoro MHz, CDC1) & -58.01 (s): ESIMS m/z 579 (M+H"). propyl)phenyl)-1H-1,2,4-triazol-3-yl)benzoic acid as a white 0289 Molecule A42 in Table 1 was made in accordance powder (472 mg, 41%): mp 225° C.; H NMR (400 MHz, with the procedures disclosed in Example 58. DMSO-d) & 9.60 (s, 1H), 8.29-8.20 (m, 4H), 8.13-8.06 (m, 2H), 7.96 (d. J=8.7 Hz, 2H); ESIMS m/z 434 (M+H"). Example 59 Example 57 Preparation of 3-bromo-1-(4-(trifluoromethoxy)phe nyl)-1H-1,2,4-triazole (B61) Preparation of 4-(1-(4-(perfluoropropyl)phenyl)-1H 0290 1,2,4-triazol-3-yl)benzoyl azide (B60) 0285

0291 To a 250 mL reaction flask was added 3-bromo-1H 1,2,4-triazole (5 g, 33.8 mmol), copper(I) iodide (0.644 g, 3.38 mmol) and cesium carbonate (11.01 g, 33.8 mmol). The flask was evacuated/backfilled with N, then DMSO (33.8 ml) and 1-iodo-4-(trifluoromethoxy)benzene (4.87 g. 16.90 0286 4-(1-(4-(Perfluoropropyl)phenyl)-1H-1,2,4-tria mmol) were added. The reaction mixture was heated to 100° Zol-3-yl)benzoic acid (400 mg. 0.92 mmol) was dissolved in C. for 20 h. The reaction was cooled to room temperature, 7 mL of isopropanol and treated with diphenylphosphoryl diluted with EtOAc and filtered through a plug of Celite. The azide (0.300 g, 1.09 mmol) and triethylamine (0.200 g, 2.0 Celite was further washed with EtOAc. Water was added to mmol). The solution was allowed to stir for 6 h, then it was the combined organics, and the layers were separated. The cooled to 0°C. and the resulting solid was filtered, washed aqueous phase was neutralized to pH7, and further extracted with a minimum amount of PrOH, and dried under high with EtOAc. The combined organics were concentrated in vacuum to give the azideas an off-white solid (0.120g, 30%). vacuo. Purification via flash chromatography (silica/EtOAc/ This solid was not further characterized, but used directly in Hex) yielded 3-bromo-1-(4-(trifluoromethoxy)phenyl)-1H the Subsequent Curtius rearrangement to prepare molecule 1,2,4-triazole as an off white solid (3.78 g. 12.27 mmol. A113, using conditions described in Example 39. 72.6%); mp 69-70° C.; H NMR (400 MHz, CDC1) & 8.44 (s, US 2013/0019348 A1 Jan. 17, 2013 32

1H), 7.70 (d. J=8.9 Hz, 2H), 7.38 (d. J–8.5 Hz, 2H); 'F NMR 2H), 8.03-7.89 (m, 3H), 7.61 (d. J=8.7 Hz, 2H), 2.60 (s.3H): (376 MHz, CDC1) & -58.04; EIMS m/z 307. 'F NMR (376 MHz, DMSO-d) & -56.95: ESIMS m/z. 364 (IM+H"). Example 60 Example 62 Preparation of methyl 2-methyl-4-(1-(4-(trifluo romethoxy)phenyl)-1H-1,2,4-triazol-3-yl)benzoate Preparation of 2-methyl-4-(1-(4-(trifluoromethoxy) (B62) phenyl)-1H-1,2,4-triazol-3-yl)benzoyl azide (B64) 0292 0297

N N F F F F N 2 F >Q N2 O O YQO O YN O -- O-N NSNS

0293 To 3-bromo-1-(4-(trifluoromethoxy)phenyl)-1H-1, 0298 To 2-methyl-4-(1-(4-(trifluoromethoxy)phenyl)- 2,4-triazole (0.496 g, 1.609 mmol), methyl 2-methyl-4-(4.4, 1H-1,2,4-triazol-3-yl)benzoic acid (0.412 g, 1.134 mmol) in 5.5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzoate (0.466 g. a 100 mL round-bottomed flask equipped with a stir bar under 1.689 mmol), sodium bicarbonate (0.405 g, 4.83 mmol) and N was added isopropyl alcohol (11 mL), triethylamine tetrakis(triphenylphosphine)palladium (0.186 g., 0.161 (0.205 ml, 1.474 mmol) and diphenylphosphorazidate (0.319 mmol) in a 2.0 mL microwave vial was added dioxane (6 mL) ml. 1.474 mmol). The reaction was stirred at room tempera and water (1.5 mL). ture overnight. The resultant solid was filtered, washed with 0294 The reaction was capped and placed on a Biotage(R) isopropyl alcohol followed by hexanes and dried under Initiator microwave reactor for 30 minat 140°C. The reaction vacuum providing the title compound as a white solid (0.294 mixture was then diluted with EtOAc and washed with water. g, 0.757 mmol, 67%): 'H NMR (300 MHz, CDC1) & 8.60 (s, The aqueous layer was extracted with EtOAc. The combined 1H), 8.13 (s, 1H), 8.11-8.02 (m, 2H), 7.84-7.77 (m, 2H), 7.40 organic layers were dried over MgSO, filtered and concen (d. J=8.6 Hz, 2H), 2.74 (s.3H); 'F NMR (376 MHz, CDC1) trated. Purification by flash column chromatography pro & -58.02; ESIMS m/z 389 (IM+H"). vided the title compound as a white solid (0.376 g. 0.997 mmol, 62%); H NMR (400 MHz, CDC1) & 8.59 (s, 1H), Example 63 8.10 (dt, J=1.6,0.7 Hz, 1H), 8.09-8.00 (m, 2H), 7.84-7.78 (m, Preparation of N-(2-isopropylphenyl)aminothiox 2H), 7.44-7.37 (m, 2H), 3.93 (s.3H), 2.70 (s.3H); F NMR omethyl-N'-(2-methyl(4-(1-(4-(trifluoromethoxy) (376 MHz, CDC1) & -58.02; ESIMS m/z. 378 (M+H"). phenyl)-1H-1,2,4-triazol-3-yl)phenyl))urea (Mol Example 61 ecule A122) 0299 Preparation of 2-methyl-4-(1-(4-(trifluoromethoxy) phenyl)-1H-1,2,4-triazol-3-yl)benzoic acid (B63)

0295) HS N 2 & - > O YN a YN y N(N H N

0300. To 2-methyl-4-(1-(4-(trifluoromethoxy)phenyl)- OH 1H-1,2,4-triazol-3-yl)benzoyl azide (0.294g, 0.757 mmol) in a 25 mL vial equipped with a stir bar and a Vigreux column was added 1,2-dichloroethane (4 ml). The reaction was 0296 To two batches of methyl 2-methyl-4-(1-(4-(trifluo heated to 80°C. Following isocyanate formation the reaction romethoxy)phenyl)-1H-1,2,4-triazol-3-yl)benzoate (0.452 g, was cooled to room temperature. To the reaction was added 1.198 mmol) in a 250 mL round-bottomed flask equipped 1-(2-isopropylphenyl)thiourea (0.162 g, 0.833 mmol) and with a stir bar was added MeOH (12 ml), THF (12 ml) and 2N cesium carbonate (0.271 g, 0.833 mmol). The reaction was sodium hydroxide (5.99 ml, 11.98 mmol). The reaction was stirred overnight. The reaction mixture was diluted with stirred overnight. The reaction mixture was diluted with water EtOAc and washed with saturated sodium bicarbonate. The and acidified with 1N HC1. The solid was extracted with aqueous layer was extracted with EtOAc. The combined EtOAc (3x). The organic layer was dried over MgSO, fil organic layers were dried over MgSO4, filtered and concen tered and concentrated providing the title compound as a trated. Purification by flash column chromatography pro yellow solid (0.412 g, 1.134 mmol, 95%): "H NMR (300 vided the title compound as a white solid (0.243 g, 0.438 MHz, DMSO-d) & 12.94 (s, 1H), 9.43 (s, 1H), 8.14-8.03 (m, mmol, 58%): 'H NMR (400 MHz, DMSO-d) & 11.74 (s,

US 2013/0019348 A1 Jan. 17, 2013 35

TABLE 1

Structures for Compounds

No. Structure

A1 O N s1 No N| N N2 lyO N >SN FC N

O

A2 / N S / O > F N YN2 X SN F N F O

A3 O

A4 O

AS O US 2013/0019348 A1 Jan. 17, 2013 36

TABLE 1-continued

Structures for Compounds

No. Structure

A6 O

A7 O

A8 O US 2013/0019348 A1 Jan. 17, 2013 37

TABLE 1-continued

Structures for Compounds

No. Structure

A11

A12 F Né?—N yO HS - F N F

A13 HO F F N?=N 2 O ZNN2 > O -O YN N X

A14 F O Dr H F N-N N N

U.)SN Ory

A15 US 2013/0019348 A1 Jan. 17, 2013 38

TABLE 1-continued Structures for Compounds

No. Structure

A16 S H F >{ O N1 NN Ny-- N O F F O

A17 H S O N F N N F N >{F O- S-O- y-O ( Pl

A18 H S O N F N N={ F ( N1 N Y N O

A19 H S O N F N N

F XF N1\ o S-O- yO -Cl O

A21

A22 US 2013/0019348 A1 Jan. 17, 2013 39

TABLE 1-continued

Structures for Compounds

No. Structure

A23

A24 ry O N?=N 2 y - NH FCO

A25

A26 HS

A27 HS O

A28 HS US 2013/0019348 A1 Jan. 17, 2013 40

TABLE 1-continued

Structures for Compounds

No. Structure

A3O HS F

A31 O ?=SN O ry Né Z N FCO N H CN

A32

A33 N 7 O NN % Z NH FCO N

OMe

A34 N HO I O NN % Z NH FCO N

OMe US 2013/0019348 A1 Jan. 17, 2013 41

TABLE 1-continued

Structures for Compounds

No. Structure

A36

A37 ?=N O -O-O--N2 S

A38

A39 ... O ?=N O'O US 2013/0019348 A1 Jan. 17, 2013 42

TABLE 1-continued

Structures for Compounds

No. Structure A40 -O O'o

A41 ?=N O Né S

Or O' N

A42 ... O ?=N C-calO

A43 ... O ?=N C-calO

US 2013/0019348 A1 Jan. 17, 2013 44

TABLE 1-continued Structures for Compounds

No. Structure

A52

AS4 O F O ) ( > O N-N N

ASS O FCO ) ( O N-N N

A56 O F O ) ( F> O N-N N US 2013/0019348 A1 Jan. 17, 2013 45

TABLE 1-continued

Structures for Compounds

No. Structure

A57 O F O ) ( > O N-N N

AS8 O F O ) ( F> O N-N N

C

AS9 O F O ) ( F> O N-N N

A60 O F O ) ( > O N-N N US 2013/0019348 A1 Jan. 17, 2013 46

TABLE 1-continued

Structures for Compounds

No. Structure

A61 O F O ) ( > O N-N N

A62 O FCO ) ( O

N-N N

A63 ?=N O NNYN 2 A. SH FCO N NF(

A65 F f=N US 2013/0019348 A1 Jan. 17, 2013 47

TABLE 1-continued

Structures for Compounds

No. Structure

A66 O F O S

F Dr Ol N-N y Ny-N

A68 / N O NN 2 FCO Ors’ O’.N N =

A69 CH

C

A71 ?=N O NNé A SH FCO N N=( US 2013/0019348 A1 Jan. 17, 2013 48

TABLE 1-continued

Structures for Compounds

No. Structure

A72 / N O NNé A SH FCO N N=(

A74 O F O ^- C F O N F N- N y-N NH

A75 O F O CH3 F O N F N N CH N- 3

A76 O F O ^- CH3 F O N F N-N )-

A77 O F O S ^- C F O N F N-N )- NH

US 2013/0019348 A1 Jan. 17, 2013 50

TABLE 1-continued

Structures for Compounds

No. Structure

A84 CH3

A85 N S F f= O O CH

A86 F f= N O )- O CH

A87 N S F ?— O O CH

CH

A89 CH3 US 2013/0019348 A1 Jan. 17, 2013 51

TABLE 1-continued

Structures for Compounds

No. Structure

A92 O F O S ^- C F O / N F N-N y N

C

A93 O F O S ^- CH F O / N F N-N y N F

N

A94 O S F O M N F N-N N

U.)S. NH N

A95 O Pro y- C

F F N-N O HS

F O N H O O- 2-C N X- 2 H H3C CH3

A97 HC

N YQO O S. C. N y-?’ N H CH3 US 2013/0019348 A1 Jan. 17, 2013

TABLE 1-continued

Structures for Compounds

No. Structure

A98 O-CH

HS

O )-NH CH N y-N

A99 C

N HS F. F ? O Z YQ YN 2 N NH O O H NCH,

A100 CH3

N HS F. F ? O Z CH YQ YN2 N NH 3 O N H

A101 F FN O HS O ?NN

A1 O2 O S CH3 US 2013/0019348 A1 Jan. 17, 2013 53

TABLE 1-continued

Structures for Compounds

No. Structure

A103 O S O / N CH3 r)

A104 Sy– ^-

M NH CH3

A105 O y S - O

A106

/ N HS CH F F N O Z 3 YQ YN 2 N NH O N CH H HC

A107

HS

A108 F / N O )- O CH3 US 2013/0019348 A1 Jan. 17, 2013 54

TABLE 1-continued

Structures for Compounds

No. Structure

A109 S N

F. F ? O ch 3 ?NN N YQO O Né NX CH 3 H

A110 ry O -N

F NN, > O-CH F O A111 YO

NS F N > C F O

A112 F F N HS F f= O 2 F N n 2 2 N F N N H O N H HC CH

A113

CH

A114

F. F O 2 YQ NNYN 2 N ?NNH O N H HC CH

US 2013/0019348 A1 Jan. 17, 2013 peas, peppers, potatoes, pumpkin, Snap beans, spinach, 0323 Cabbage seedlings grown in 3-inch pots, with 2-3 squash, Sweet potatoes, and watermelon, among other plants. small (3-5 cm) true leaves, were used as test substrate. The CEW is also known to be resistant to certain insecticides. seedlings were infested with 20-50 GPA (wingless adult and Consequently, because of the above factors control of these nymph stages) one day prior to chemical application. Four pests is important. Furthermore, molecules that control these pots with individual seedlings were used for each treatment. pests (BAW and CEW), which are known as chewing pests, Test compounds (2 mg) were dissolved in 2 mL of acetone/ are useful in controlling other pests that chew on plants. MeOH (1:1) solvent, forming stock solutions of 1000 ppm 0318 Certain molecules disclosed in this document were test compound. The stock solutions were diluted 5x with tested against BAW and CEW using procedures described in 0.025% Tween 20 in HO to obtain the solution at 200 ppm the following examples. In the reporting of the results, the test compound. A hand-held aspirator-type sprayer was used “BAW & CEW Rating Table” was used (See Table Section). for spraying a solution to both sides of cabbage leaves until Bioassays on BAW (Spodoptera exigua) runoff. Reference plants (solvent check) were sprayed with 0319 Bioassays on BAW were conducted using a 128 the diluent only containing 20% by volume of acetone/MeCH well diet tray assay, one to five second instar BAW larvae (1:1) solvent. Treated plants were held in a holding room for were placed in each well (3 mL) of the diet tray that had been three days at approximately 25° C. and ambient relative previously filled with 1 mL of artificial diet to which 50 humidity (RH) prior to grading. Evaluation was conducted by ug/cm of the test compound (dissolved in 50 uL of 90:10 counting the number of live aphids per plant under a micro acetone-water mixture) had been applied (to each of eight scope. Percent Control was measured by using Abbott’s cor wells) and then allowed to dry. Trays were covered with a rection formula (W. S. Abbott, “A Method of Computing the clear self-adhesive cover and held at 25°C., 14:10 light-dark Effectiveness of an Insecticide” J. Econ. Entomol. 18 (1925), for five to seven days. Percent mortality was recorded for the pp. 265-267) as follows. larvae in each well; activity in the eight wells was then aver Corrected 96 Control=100*(X-Y)/X aged. The results are indicated in the table entitled “Table ABC: Biological Results” (See Table Section). 0324 where Bioassays on CEW (Helicoverpa zea) 0325 X=No. of live aphids on solvent check plants and 0320 Bioassays on CEW were conducted using a 128 0326 Y=No. of live aphids on treated plants well diet tray assay, one to five second instar CEW larvae 0327. The results are indicated in the table entitled “Table were placed in each well (3 mL) of the diet tray that had been ABC: Biological Results” (See Table Section). previously filled with 1 mL of artificial diet to which 50 ug/cm of the test compound (dissolved in 50 uL of 90:10 Example C acetone-water mixture) had been applied (to each of eight wells) and then allowed to dry. Trays were covered with a Bioassays on Yellow Fever Mosquito “YFM” (Aedes clear self-adhesive cover and held at 25°C., 14:10 light-dark aegypti) for five to seven days. Percent mortality was recorded for the larvae in each well; activity in the eight wells was then aver 0328 YFM prefers to feed on humans during the daytime aged. The results are indicated in the table entitled “Table and is most frequently found in or near human habitations. ABC: Biological Results” (See Table Section). YFM is a vector for transmitting several diseases. It is a mosquito that can spread the dengue fever and yellow fever Example B viruses. Yellow fever is the second most dangerous mosquito borne disease after malaria. Yellow fever is an acute viral Bioassays on Green Peach Aphid (“GPA) (Myzus hemorrhagic disease and up to 50% of severely affected per persicae) sons without treatment will die from yellow fever. There are 0321 GPA is the most significant aphid pest of peach an estimated 200,000 cases of yellow fever, causing 30,000 trees, causing decreased growth, shriveling of the leaves, and deaths, worldwide each year. Dengue fever is a nasty, Viral the death of various tissues. It is also hazardous because it acts disease; it is sometimes called “breakbone fever” or “break as a vector for the transport of plant viruses, such as potato heart fever because of the intense pain it can produce. Den virus Y and potato leafroll virus to members of the night gue fever kills about 20,000 people annually. Consequently, shade/potato family Solanaceae, and various mosaic viruses because of the above factors control of this pest is important. to many other food crops. GPA attacks such plants as broc Furthermore, molecules that control this pest (YFM), which coli, burdock, cabbage, carrot, cauliflower, daikon, eggplant, is known as a sucking pest, are useful in controlling other green beans, lettuce, macadamia, papaya, peppers, Sweet pests that cause human and animal Suffering. potatoes, tomatoes, watercress, and Zucchini, among other 0329. Certain molecules disclosed in this document were plants. GPA also attacks many ornamental crops such as tested againstYFM using procedures described in the follow carnation, chrysanthemum, flowering white cabbage, poin ing paragraph. In the reporting of the results, the “YFM settia, and roses. GPA has developed resistance to many pes Rating Table' was used (See Table Section). ticides. Consequently, because of the above factors control of 0330 Master plates containing 400 ug of a molecule dis this pest is important. Furthermore, molecules that control solved in 100 uL of dimethyl sulfoxide (DMSO) (equivalent this pest (GPA), which is known as a Sucking pest, are useful to a 4000 ppm solution) are used. A master plate of assembled in controlling other pests that Suck on plants. molecules contains 15 uL per well. To this plate, 135 uL of a 0322 Certain molecules disclosed in this document were 90:10 water:acetone mixture is added to each well. A robot tested against GPA using procedures described in the follow (BiomekRNXP Laboratory Automation Workstation) is pro ing example. In the reporting of the results, the “GPA Rating grammed to dispense 15uL aspirations from the masterplate Table' was used (See Table Section). into an empty 96-well shallow plate (“daughter plate). There US 2013/0019348 A1 Jan. 17, 2013 74 are 6 reps (“daughter plates) created per master. The created Stereoisomers daughter plates are then immediately infested with YFM lar Wa. 0340 Molecules of Formula One may exist as one or more 0331. The day before plates are to be treated, mosquito Stereoisomers. Thus, certain molecules can be produced as eggs are placed in Millipore water containing liverpowder to racemic mixtures. It will be appreciated by those skilled in the begin hatching (4 g. into 400 ml). After the daughter plates are art that one stereoisomer may be more active than the other created using the robot, they are infested with 220 uL of the stereoisomers. Individual stereoisomers may be obtained by liver powder/larval mosquito mixture (about 1 day-old lar known selective synthetic procedures, by conventional Syn vae). After plates are infested with mosquito larvae, a non thetic procedures using resolved starting materials, or by evaporative lid is used to cover the plate to reduce drying. conventional resolution procedures. Certain molecules dis Plates are held at room temperature for 3 days prior to grad closed in this document can exist as two or more isomers. The ing. After 3 days, each well is observed and scored based on various isomers include geometric isomers, diastereomers, mortality. and enantiomers. Thus, the molecules disclosed in this docu ment include geometric isomers, racemic mixtures, indi 0332 The results are indicated in the table entitled “Table vidual stereoisomers, and optically active mixtures. It will be ABC: Biological Results” (See Table Section). appreciated by those skilled in the art that one isomer may be Pesticidally Acceptable Acid Addition Salts, Salt Derivatives, more active than the others. The structures disclosed in the Solvates, Ester Derivatives, Polymorphs, Isotopes and present disclosure are drawn in only one geometric form for Radionuclides clarity, but are intended to representall geometric forms of the molecule. 0333 Molecules of Formula One may be formulated into pesticidally acceptable acid addition salts. By way of a non Combinations limiting example, an amine function can form salts with hydrochloric, hydrobromic, Sulfuric, phosphoric, acetic, ben 0341 Molecules of Formula One may also be used in Zoic, citric, malonic, Salicylic, malic, fumaric, oxalic, suc combination (such as, in a compositional mixture, or a simul cinic, tartaric, lactic, gluconic, ascorbic, maleic, aspartic, taneous or sequential application) with one or more com benzenesulfonic, methanesulfonic, ethanesulfonic, pounds having acaricidal, algicidal, avicidal, bactericidal, hydroxymethanesulfonic, and hydroxyethanesulfonic acids. fungicidal, herbicidal, insecticidal, molluscicidal, nemati Additionally, by way of a non-limiting example, an acid cidal, rodenticidal, or virucidal properties. Additionally, the function can form salts including those derived from alkali or molecules of Formula One may also be used in combination alkaline earth metals and those derived from ammonia and (such as, in a compositional mixture, or a simultaneous or amines. Examples of preferred cations include Sodium, potas sequential application) with compounds that are antifeedants, sium, and magnesium. bird repellents, chemosterilants, herbicide safeners, insect 0334 Molecules of Formula One may be formulated into attractants, insect repellents, mammal repellents, mating dis salt derivatives. By way of a non-limiting example, a salt rupters, plant activators, plant growth regulators, or syner derivative can be prepared by contacting a free base with a gists. Examples of such compounds in the above groups that sufficient amount of the desired acid to produce a salt. A free may be used with the Molecules of Formula One are—(3- base may be regenerated by treating the salt with a suitable ethoxypropyl)mercury bromide, 1,2-dichloropropane, 1.3- dilute aqueous base solution Such as dilute aqueous sodium dichloropropene, 1-methylcyclopropene, 1-naphthol. 2-(oc hydroxide (NaOH), potassium carbonate, ammonia, and tylthio)ethanol, 2,3,5-tri-iodobenzoic acid, 2.3.6-TBA, 2.3.6- Sodium bicarbonate. As an example, in many cases, a pesti TBA-dimethylammonium, 2.3,6-TBA-lithium, 2.3.6-TBA cide, such as 2,4-D, is made more water-soluble by convert potassium, 2.3.6-TBA-sodium, 2,4,5-T 2,4,5-T-2- ing it to its dimethylamine salt. butoxypropyl. 2,4,5-T-2-ethylhexyl, 2,4,5-T-3- butoxypropyl. 2,4,5-TEB, 2,4,5-T-butomethyl, 2,4,5-T- 0335 Molecules of Formula One may be formulated into butotyl, 2,4,5-T-butyl, 2,4,5-T-isobutyl, 2,4,5-T-isoctyl, 2.4. stable complexes with a solvent, such that the complex 5-T-isopropyl. 2,4,5-T-methyl, 2,4,5-T-penty1, 2,4,5-T- remains intact after the non-complexed solvent is removed. Sodium, 2.4.5-T-triethylammonium, 2,4,5-T-trolamine, 2,4- These complexes are often referred to as “solvates. However, D, 2,4-D-2-butoxypropyl. 2,4-D-2-ethylhexyl, 2,4-D-3- it is particularly desirable to form stable hydrates with water butoxypropyl. 2,4-D-ammonium, 2,4-DB, 2,4-DB-butyl, as the solvent. 2,4-DB-dimethylammonium, 2,4-DB-isoctyl, 2,4-DB-potas 0336 Molecules of Formula One may be made into ester sium, 2,4-DB-sodium, 2,4-D-butotyl, 2,4-D-butyl, 2,4-D-di derivatives. These ester derivatives can then be applied in the ethylammonium, 2,4-D-dimethylammonium, 2,4-D-diola same manner as the molecules disclosed in this document is mine, 2,4-D-dodecylammonium, 2,4-DEB, 2,4-DEP, 2,4-D- applied. ethyl, 2,4-D-heptylammonium, 2,4-D-isobutyl, 2,4-D- 0337 Molecules of Formula One may be made as various isoctyl, 2,4-D-isopropyl. 2,4-D-isopropylammonium, 2,4-D- crystal polymorphs. Polymorphism is important in the devel lithium, 2,4-D-mepty1, 2,4-D-methyl, 2,4-D-octyl, 2,4-D- opment of agrochemicals since different crystal polymorphs pentyl, 2,4-D-potassium, 2,4-D-propyl. 2,4-D-Sodium, 2.4- or structures of the same molecule can have vastly different D-tefuryl, 2,4-D-tetradecylammonium, 2,4-D- physical properties and biological performances. triethylammonium, 2,4-D-tris(2-hydroxypropyl)ammonium, 0338 Molecules of Formula One may be made with dif 2,4-D-trolamine, 21P 2-methoxyethylmercury chloride, ferent isotopes. Of particular importance are molecules hav 2-phenylphenol, 3,4-DA, 3,4-DB, 3,4-DP, 4-aminopyridine, ing H (also known as deuterium) in place of H. 4-CPA, 4-CPA-potassium, 4-CPA-sodium, 4-CPB, 4-CPP. 0339 Molecules of Formula One may be made with dif 4-hydroxyphenethyl alcohol, 8-hydroxyquinoline Sulfate, ferent radionuclides. Of particular importance are molecules 8-phenylmercurioxyquinoline, abamectin, abscisic acid, having C. ACC, acephate, acequinocyl, acetamiprid, acethion, US 2013/0019348 A1 Jan. 17, 2013

acetochlor, acetophos, acetoprole, acibenzolar, acilbenzolar furan, carbon disulfide, carbon tetrachloride, carbophe 5-methyl, acifluorfen, acifluorfen-methyl, acifluorfen-so nothion, carbosulfan, carboxazole, carboxide, carboxin, dium, aclonifen, acrep, acrinathrin, acrolein, acrylonitrile, carfentraZone, carfentraZone-ethyl, carpropamid, cartap, car acypetacs, acypetacs-copper, acypetacs-Zinc, alachlor, alany tap hydrochloride, carvacrol, carvone, CDEA, cellocidin, carb, albendazole, aldicarb, aldimorph, aldoxycarb, aldrin, CEPC, ceralure, Cheshunt mixture, chinomethionat, chito allethrin, allicin, allidochlor, allosamidin, alloxydim, alloxy san, chlobenthiaZone, chlomethoxyfen, chloralose, chloram dim-Sodium, allyl alcohol, allyxycarb, alorac, alpha-cyper ben, chloramben-ammonium, chloramben-diolamine, methrin, alpha-endosulfan, ametoctradin, ametridione, chloramben-methyl, chloramben-methylammonium, ametryn, amibuzin, amicarbazone, amicarthiazol, chloramben-sodium, chloramine phosphorus, chlorampheni amidithion, amidoflumet, amidosulfuron, aminocarb, ami col, chloraniformethan, chloranil, chloranocryl, chlorantra nocyclopyrachlor, aminocyclopyrachlor-methyl, aminocy niliprole, chlorazifop, chlorazifop-propargyl, chlorazine, clopyrachlor-potassium, aminopyralid, aminopyralid-potas chlorbenside, chlorbenzuron, chlorbicyclen, chlorbromuron, sium, aminopyralid-tris(2-hydroxypropyl)ammonium, chlorbufam, chlordane, chlordecone, chlordimeform, chlo amiprofoS-methyl, amiprophos, amisulbrom, amiton, amiton rdimeform hydrochloride, chlorempenthrin, chlorethoxyfos, oxalate, amitraz, amitrole, ammonium sulfamate, ammonium chloreturon, chlorfenac, chlorfenac-ammonium, chlorfenac C.-naphthaleneacetate, amobam, ampropylfos, anabasine, sodium, chlorfenapyr, chlorfenazole, chlorfenethol, chlor ancymidol, anilazine, anilofos, anisuron, anthraquinone, fenprop, chlorfenson, chlorfensulphide, chlorfenvinphos, antu, apholate, aramite, arsenous oxide, asomate, aspirin, chlorfluaZuron, chlorflurazole, chlorfluren, chlorfluren-me asulam, asulam-potassium, asulam-Sodium, athidathion, thyl, chlorflurenol, chlorflurenol-methyl, chloridazon, chlo atraton, atrazine, aureofungin, aviglycine, aviglycine hydro rimuron, chlorimuron-ethyl, chlormephos, chlormeduat, chloride, azaconazole, azadirachtin, azafenidin, azame chlormeduat chloride, chlomidine, chlornitrofen, chloroben thiphos, azim Sulfuron, azinphos-ethyl, azinphos-methyl, Zilate, chlorodinitronaphthalenes, chloroform, chloromebu aZiprotryne, azithiram, azobenzene, azocyclotin, azothoate, form, chloromethiuron, chloroneb, chlorophacinone, chlo azoxystrobin, bachmedesh, barban, barium hexafluorosili rophacinone-sodium, chloropicrin, chloropon, cate, barium polysulfide, barthrin, BCPC, beflubutamid, chloropropylate, chlorothalonil, chlorotoluron, chloroXuron, benalaxyl, benalaxyl-M, benazolin, benazolin-dimethylam chloroxynil, chlorphonium, chlorphonium chloride, chlor monium, benazolin-ethyl, benazolin-potassium, bencarba phoxim, chlorpraZophos, chlorprocarb, chlorpropham, chlo Zone, benclothiaz, bendiocarb, benfluralin, benfuracarb, ben rpyrifos, chlorpyrifos-methyl, chlorquinox, chlorSulfuron, furesate, benodanil, benomyl, benoxacor, benoxafos, chlorthal, chlorthal-dimethyl, chlorthal-monomethyl, chlor benquinox, benSulfuron, benSulfuron-methyl, benSulide, thiamid, chlorthiophos, chlozolinate, choline chloride, chro bensultap, bentaluron, bentaZone, bentazone-sodium, mafenozide, cinerin I, cinerin II, cinerins, cinidon-ethyl, cin benthiavalicarb, benthiavalicarb-isopropyl, benthiazole, ben methylin, cinosulfuron, ciobutide, cisanilide, cismethrin, tranil, benzadox, benzadox-ammonium, benzalkonium chlo clethodim, climbazole, cliodinate, clodinafop, clodinafop ride, benzamacril, benzamacril-isobutyl, benzamorf, ben propargyl, cloethocarb, clofencet, clofencet-potassium, Zfendizone, benzipram, benzobicyclon, benzofenap, clofentezine, clofibric acid, clofop, clofop-isobutyl, cloma benZofluor, benzohydroxamic acid, benzoximate, benzoyl Zone, clomeprop, cloprop, cloproxydim, clopyralid, clopy prop, benzoylprop-ethyl, benzthiazuron, benzyl benzoate, ralid-methyl, clopyralid-olamine, clopyralid-potassium, clo benzyladenine, berberine, berberine chloride, beta-cy pyralid-tris(2-hydroxypropyl)ammonium, cloquintocet, fluthrin, beta-cypermethrin, bethoxazin, bicyclopyrone, cloquintocet-mexyl, cloranSulam, cloranSulam-methyl, clos bifenazate, bifenox, bifenthrin, bifujunzhi, bilanafos, antel, clothianidin, clotrimazole, cloxyfonac, cloxyfonac-so bilanafos-Sodium, binapacryl, bingqingxiao, bioallethrin, dium, CMA, codlelure, colophonate, copper acetate, copper bioethanomethrin, biopermethrin, bioresmethrin, biphenyl, acetoarsenite, copper arsenate, copper carbonate, basic, cop bisazir, bismerthiazol, bispyribac, bispyribac-sodium, bistri per hydroxide, copper naphthenate, copper oleate, copper fluoron, bitertanol, bithionol, bixafen, blasticidin-S, borax, oxychloride, copper silicate, copper Sulfate, copper Zinc chro Bordeaux mixture, boric acid, boscalid, brassinolide, brassi mate, coumachlor, coumafuryl, coumaphos, coumatetralyl, nolide-ethyl, brevicomin, brodifacoum, brofenvalerate, brof coumithoate, coumoxystrobin, CPMC, CPMF, CPPC, cre luthrinate, bromacil, bromacil-lithium, bromacil-sodium, dazine, cresol, crimidine, crotamiton, crotoxyphos, crufo bromadiolone, bromethalin, bromethrin, bromfenvinfos, bro mate, cryolite, cue-lure, cufraneb, cumyluron, cuprobam, moacetamide, bromobonil, bromobutide, bromocyclen, cuprous oxide, curcumenol, cyanamide, cyanatryn, cyana bromo-DDT, bromofenoxim, bromophos, bromophos-ethyl, Zine, cyanofenphos, cyanophos, cyanthoate, cyantraniliprole, bromopropylate, bromothalonil, bromoxynil, bromoxynil cyaZofamid, cybutryne, cyclafuramid, cyclanilide, butyrate, bromoxynil heptanoate, bromoxynil octanoate, bro cyclethrin, cycloate, cycloheximide, cycloprate, cyclopro moxynil-potassium, brompyrazon, bromuconazole, bro thrin, cyclosulfamuron, cycloxydim, cycluron, cyenopy nopol, bucarpolate, bufencarb, buminafos, bupirimate, rafen, cyflufenamid, cyflumetofen, cyfluthrin, cyhalofop, buprofezin, Burgundy mixture, busulfan, butacarb, butachlor, cyhalofop-butyl, cyhalothrin, cyhexatin, cymiazole, cymiaZ butafenacil, butamifos, butathiofos, butenachlor, butethrin, ole hydrochloride, cymoxanil, cyometrinil, cypendazole, buthidazole, buthiobate, buthiuron, butocarboxim, butonate, cypermethrin, cyperquat, cyperquat chloride, cyphenothrin, butopyronoxyl, butoxycarboxim, butralin, butroxydim, butu cyprazine, cyprazole, cyproconazole, cyprodinil, cypro ron, butylamine, butylate, cacodylic acid, cadusafos, cafens furam, cypromid, cyprosulfamide, cyromazine, cythioate, trole, calcium arsenate, calcium chlorate, calcium cyana daimuron, dalapon, dalapon-calcium, dalapon-magnesium, mide, calcium polysulfide, calvinphos, cambendichlor, dalapon-Sodium, daminozide, dayoutong, dazomet, camphechlor, camphor, captafol, captan, carbamorph, car dazomet-sodium, DBCP, d-camphor, DCIP, DCPTA, DDT, banolate, carbaryl, carbasulam, carbendazim, carbendazim debacarb, decafentin, decarbofuran, dehydroacetic acid, benzenesulfonate, carbendazim Sulfite, carbetamide, carbo delachlor, deltamethrin, demephion, demephion-O, deme US 2013/0019348 A1 Jan. 17, 2013 76 phion-S, demeton, demeton-methyl, demeton-O, demeton mide, ethylene dichloride, ethylene oxide, ethylicin, ethylm O-methyl, demeton-S, demeton-S-methyl, demeton-S-meth ercury 2,3-dihydroxypropyl mercaptide, ethylmercury ylsulphon, desmedipham, desmetryn, acetate, ethylmercury bromide, ethylmercury chloride, eth d-fanshiluquebinguzhi, diafenthiuron, dialifos, di-allate, ylmercury phosphate, etinofen, etnipromid, etobenzanid, diamidafos, diatomaceous earth, diazinon, dibutyl phthalate, etofemproX, etoxazole, etridiazole, etrimfos, eugenol, EXD, dibutyl Succinate, dicamba, dicamba-diglycolamine, famoxadone, famphur, fenamidone, fenaminosulf, fenami dicamba-dimethylammonium, dicamba-diolamine, phos, fenapanil, fenarimol, fenasulam, fenaZaflor, fenaza dicamba-isopropylammonium, dicamba-methyl, dicamba quin, fenbuconazole, fenbutatin oxide, fenchlorazole, olamine, dicamba-potassium, dicamba-Sodium, dicamba fenchlorazole-ethyl, fenchlorphos, fenclorim, fenethacarb, trolamine, dicapthon, dichlobenil, dichlofenthion, dichloflu fenfluthrin, fenfuram, fenhexamid, fenitropan, fenitrothion, anid, dichlone, dichloralurea, dichlorbenzuron, fenjuntong, fenobucarb, fenoprop, fenoprop-3-butoxypro dichlorflurenol, dichlorflurenol-methyl, dichlormate, dichlo pyl, fenoprop-butomethyl, fenoprop-butotyl, fenoprop-butyl, rmid, dichlorophen, dichlorprop, dichlorprop-2-ethylhexyl, fenoprop-isoctyl, fenoprop-methyl, fenoprop-potassium, dichlorprop-butotyl, dichlorprop-dimethylammonium, fenothiocarb, fenoxacrim, fenoxanil, fenoxaprop, fenox dichlorprop-ethylammonium, dichlorprop-isoctyl, dichlor aprop-ethyl, fenoxaprop-P, fenoxaprop-P-ethyl, fenoxasul prop-methyl, dichlorprop-P, dichlorprop-P-2-ethylhexyl, fone, fenoxycarb, fenpiclonil, fempirithrin, fenpropathrin, dichlorprop-P-dimethylammonium, dichlorprop-potassium, fenpropidin, fenpropimorph, fenpyraZamine, fenpyroximate, dichlorprop-sodium, dichlorvos, dichlozoline, diclobutrazol, fenridazon, fenridazon-potassium, fenridazon-propyl, fen diclocymet, diclofop, diclofop-methyl, diclomeZine, diclom son, fensulfothion, fenteracol, fenthiaprop, fenthiaprop eZine-Sodium, dicloran, dicloSulam, dicofol, dicoumarol, ethyl, fenthion, fenthion-ethyl, fentin, fentin acetate, fentin dicresyl, dicrotophos, dicyclanil, dicyclonon, dieldrin, chloride, fentin hydroxide, fentraZamide, fentrifanil, fenuron, dienochlor, diethamquat, diethamquat dichloride, diethatyl, fenuron TCA, fenvalerate, ferbam, ferimzone, ferrous sulfate, diethatyl-ethyl, diethofencarb, dietholate, diethyl pyrocar fipronil, flamprop, flamprop-isopropyl, flamprop-M, flam bonate, diethyltoluamide, difenacoum, difenoconazole, prop-methyl, flamprop-M-isopropyl, flamprop-M-methyl, difenopenten, difenopenten-ethyl, difenoXuron, difenZoquat, flaZaSulfuron, flocoumafen, flonicamid, florasulam, fluacry difenzoquat metilsulfate, difethialone, diflovidazin, difluben pyrim, fluazifop, fluazifop-butyl, fluazifop-methyl, fluazi Zuron, diflufenican, diflufenZopyr, diflufenZopyr-sodium, fop-P, fluazifop-P-butyl, fluazinam, fluazolate, fluaZuron, diflumetorim, dikegulac, dikegulac-Sodium, dilor, dimatif, flubendiamide, flubenzimine, flucarbazone, flucarbazone-so dimefluthrin, dimefox, dimefuron, dimepiperate, dium, flucetosulfuron, fluchloralin, flucofuron, flucycloxu dimetachlone, dimetan, dimethacarb, dimethachlor, ron, flucythrinate, fludioxonil, fluenetil, fluensulfone, flufen dimethametryn, dimethenamid, dimethenamid-P, dime acet, flufenerim, flufenican, flufenoxuron, flufenprox. thipin, dimethirimol, dimethoate, dimethomorph, dimethrin, flufenpyr, flufenpyr-ethyl, flufiprole, flumethrin, flumetover, dimethyl carbate, dimethyl phthalate, dimethylvinphos, flumetralin, flumetSulam, flumezin, flumiclorac, flumiclorac dimetilan, dimexano, dimidazon, dimoxystrobin, dinex, pentyl, flumioxazin, flumipropyn, flumorph, fluometuron, dinex-diclexine, dingjuneZuo, diniconazole, diniconazole fluopicolide, fluopyram, fluorbenside, fluoridamid, fluoroac M. dinitramine, dinobuton, dinocap, dinocap-4, dinocap-6, etamide, fluorodifen, fluoroglycofen, fluoroglycofen-ethyl, dinocton, dinofenate, dinopenton, dinoprop, dinosam, fluoroimide, fluoromidine, fluoronitrofen, fluothiuron, fluot dinoseb, dinoseb acetate, dinoseb-ammonium, dinoseb-di rimazole, fluoxastrobin, flupoxam, flupropacil, flupropadine, olamine, dinoseb-sodium, dinoseb-trolamine, dinosulfon, flupropanate, flupropanate-sodium, flupyrsulfuron, flupyr dinotefuran, dinoterb, dinoterbacetate, dinoterbon, diofeno Sulfuron-methyl, flupyrsulfuron-methyl-Sodium, fluguin lan, dioxabenzofos, dioxacarb, dioxathion, diphacinone, conazole, flurazole, flurenol, flurenol-butyl, flurenol-methyl, diphacinone-sodium, diphenamid, diphenyl Sulfone, diphe fluridone, fluorochloridone, fluoroxypyr, fluoroxypyr-bu nylamine, dipropalin, dipropetryn, dipyrithione, diguat, tomethyl, fluoroxypyr-meptyl, flurprimidol, flursulamid, diquat dibromide, disparlure, disul, disulfuram, disulfoton, flurtamone, flusilazole, flusulfamide, fluthiacet, fluthiacet disul-sodium, ditalimfos, dithianon, dithicrofos, dithioether, methyl, flutianil, flutolanil, flutriafol, fluvalinate, fluxapy dithiopyr, diuron, d-limonene, DMPA, DNOC, DNOC-am roXad, fluxofenim, folpet, fomesafen, fomesafen-Sodium, monium, DNOC-potassium, DNOC-sodium, dodemorph, fonofos, foramsulfuron, forchlorfenuron, formaldehyde, dodemorph acetate, dodemorph benzoate, dodicin, dodicin formetanate, formetanate hydrochloride, formothion, form hydrochloride, dodicin-sodium, dodine, dofenapyn, domini paranate, formparanate hydrochloride, fosamine, fosamine calure, doramectin, drazoxolon, DSMA, dufulin, EBEP, EBP. ammonium, fosetyl, fosetyl-aluminium, foSmethilan, fospi ecdysterone, edifenphos, eglinazine, eglinazine-ethyl, ema rate, fosthiazate, fosthietan, frontalin, fuberidazole, mectin, emamectin benzoate, EMPC, empenthrin, endosul fucaojing, fucaomi, funaihecaoling, fuphenthiourea, fan, endothal, endothal-diammonium, endothal-dipotassium, furalane, furalaxyl, furamethrin, furametpyr, furathiocarb, endothal-disodium, endothion, endrin, enestroburin, EPN, furcarbanil, furconazole, furconazole-cis, furethrin, furfural, epocholeone, epolfenonane, epoxiconazole, eprinomectin, furilazole, furmecyclox, furophanate, furyloxyfen, gamma epronaz, EPTC, erbon, ergocalciferol, erluixiancaoan, esde cyhalothrin, gamma-HCH, genit, gibberellic acid, gibberel pallethrine, esfenvalerate, esprocarb, etacelasil, etaconazole, lins, gliftor, glufosinate, glufosinate-ammonium, glufosi etaphos, etem, ethaboxam, ethachlor, ethalfluralin, ethamet nate-P. glufosinate-P-ammonium, glufosinate-P-Sodium, Sulfuron, ethametSulfuron-methyl, ethaprochlor, ethephon, glyodin, glyoxime, glyphosate, glyphosate-diammonium, ethidimuron, ethiofencarb, ethiolate, ethion, ethiozin, glyphosate-dimethylammonium, glyphosate-isopropylam ethiprole, ethirimol, ethoate-methyl, ethofumesate, etho monium, glyphosate-monoammonium, glyphosate-potas hexadiol, ethoprophos, ethoxyfen, ethoxyfen-ethyl, ethox sium, glyphosate-sesquisodium, glyphosate-trimesium, gly ycuin, ethoxysulfuron, ethychloZate, ethyl formate, ethyl phosine, gossyplure, grandlure, griseofulvin, guaZatine, C.-naphthaleneacetate, ethyl-DDD, ethylene, ethylene dibro guazatline acetates, halacrinate, halfenproX, halofenozide, US 2013/0019348 A1 Jan. 17, 2013 77 halosafen, halosulfuron, halosulfuron-methyl, haloxydine, one, mesulfen, mesulfenfos, metaflumizone, metalaxyl, haloxyflop, haloxyfop-etotyl, haloxyfop-methyl, haloxyfop metalaxyl-M, metaldehyde, metam, metam-ammonium, P. haloxyfop-P-etotyl, haloxyfop-P-methyl, haloxyfop-so metamifop, metamitron, metam-potassium, metam-Sodium, dium, HCH, hemel, hempa, HEOD, heptachlor, heptenophos, metaZachlor, metazosulfuron, metaZOXolon, metconazole, heptopargil, heterophos, hexachloroacetone, hexachloroben metepa, metflurazon, methabenzthiaZuron, methacrifos, Zene, hexachlorobutadiene, hexachlorophene, hexaconazole, methalpropalin, methamidophos, methasulfocarb, meth hexaflumuron, hexaflurate, hexylure, hexamide, hexaZinone, azole, methfuroxam, methidathion, methiobencarb, methio hexylthiofos, hexythiazox, HHDN, holosulf, huancaiwo, carb, methiopyrisulfuron, methiotepa, methioZolin, methi huangcaoling, huanjunZuo, hydramethylnon, hydrargaphen, uron, methocrotophos, methometon, methomyl, methoprene, hydrated lime, hydrogen cyanide, hydroprene, hymexaZol. methoprotryne, methoduin-butyl, methothrin, methoxychlor, hyduincarb, IAA, IBA, icaridin, imazalil, imazalil nitrate, methoxyfenozide, methoxyphenone, methyl apholate, imazalil Sulfate, imazamethabenZ, imazamethabenZ-methyl, methyl bromide, methyl eugenol, methyl iodide, methyl imaZamox, imaZamox-ammonium, imaZapic, imaZapic-am isothiocyanate, methylacetophos, methylchloroform, meth monium, imazapyr, imazapyr-isopropylammonium, imaza yldymron, methylene chloride, methylmercury benzoate, quin, imaZaquin-ammonium, imaZaquin-methyl, imaZaquin methylmercury dicyandiamide, methylmercury pentachlo Sodium, imazethapyr, imazethapyr-ammonium, rophenoxide, methylneodecanamide, metiram, metobenzu imaZoSulfuron, imibenconazole, imicyafos, imidacloprid, ron, metobromuron, metofluthrin, metolachlor, metolcarb, imidaclothiz, iminoctadine, iminoctadine triacetate, iminoc metominostrobin, metoSulam, metoxadiaZone, metoXuron, tadine trial besilate, imiprothrin, inabenfide, indanofan, metrafenone, metribuzin, metSulfovax, metSulfuron, metSul indaziflam, indoxacarb, inezin, iodobonil, iodocarb, furon-methyl, mevinphos, mexacarbate, mieshuan, milbe iodomethane, iodosulfuron, iodosulfuron-methyl, iodosulfu mectin, milbemycin oxime, milineb, mipafox, mirex, MNAF, ron-methyl-Sodium, ioxynil, ioxynil octanoate, ioxynil moguchun, molinate, moloSultap, monalide, monisouron, lithium, ioxynil-sodium, ipazine, ipconazole, ipfencarba monochloroacetic acid, monocrotophos, monolinuron, Zone, iprobenfos, iprodione, iprovalicarb, iprymidam, monosulfuron, monosulfuron-ester, monuron, monuron ipsodienol, ipsenol, IPSP, isamidofos, isazofos, isobenzan, TCA, morfamquat, morfamquat dichloride, moroxydine, isocarbamid, isocarbophos, isocil, isodrin, isofenphos, moroxydine hydrochloride, morphothion, morzid, moxidec isofenphos-methyl, isolan, isomethiozin, isonoruron, isopo tin, MSMA, muscalure, myclobutanil, myclozolin, N-(eth linate, isoprocarb, isopropalin, isoprothiolane, isoproturon, ylmercury)-p-toluenesulphonanilide, nabam, naftalofos, isopyrazam, isopyrimol, isothioate, isotianil, isouron, isov naled, naphthalene, naphthaleneacetamide, naphthalic anhy aledione, isoxaben, isoxachlortole, isoxadifen, isoxadifen dride, naphthoxyacetic acids, naproanilide, napropamide, ethyl, isoxaflutole, isoxapyrifop, isoxathion, ivermectin, izo naptalam, naptalam-Sodium, natamycin, neburon, niclosa pamfos, japonilure, japothrins, jasmolin I, jasmolin II, mide, niclosamide-olamine, nicosulfuron, nicotine, niflurid jasmonic acid, jiahuangchongzong, jiajizengxiaolin, jiax ide, nipyraclofen, nitenpyram, nithiazine, nitralin, nitrapyrin, iangjunzhi, jiecaowan, jiecaoxi, jodfenphos, juvenile hor nitrilacarb, nitrofen, nitrofluorfen, nitrostyrene, nitrothal-iso mone I, juvenile hormone II, juvenile hormone III, kadethrin, propyl, norbormide, norflurazon, nornicotine, noruron, nov karbutilate, karetazan, karetazan-potassium, kasugamycin, aluron, noviflumuron, nuarimol, OCH, octachlorodipropyl kasugamycin hydrochloride, kejunlin, kelevan, ketospiradox, ether, octhillinone, ofurace, omethoate, orbencarb, orfralure, ketospiradox-potassium, kinetin, kinoprene, kresoxim-me ortho-dichlorobenzene, orthosulfamuron, oryctalure, orysas thyl, kuicaoxi, lactofen, lambda-cyhalothrin, latilure, lead trobin, oryzalin, osthol, ostramone, Oxabetrinil, oxadiargyl. arsenate, lenacil, lepimectin, leptophos, lindane, lineatin, oxadiazon, oxadixyl, oXamate, oxamyl, oxapyrazon, oxapy linuron, lirimfos, litlure, loopilure, lufenuron, lvdingjunzhi, razon-dimolamine, Oxapyrazon-sodium, oxasulfuron, oxazi lvXiancaolin, lythidathion, MAA, malathion, maleic clomefone, oxine-copper, OXolinic acid, Oxpoconazole, hydrazide, malonoben, maltodextrin, MAMA, mancopper, Oxpoconazole fumarate, oxycarboxin, oxydemeton-methyl, mancoZeb, mandipropamid, maneb, matrine, mazidox, Oxydeprofos, oxydisulfoton, oxyfluorfen, oxymatrine, MCPA, MCPA-2-ethylhexyl, MCPA-butotyl, MCPA-butyl, oxytetracycline, Oxytetracycline hydrochloride, paclobutra MCPA-dimethylammonium, MCPA-diolamine, MCPA Zol, paichongding, para-dichlorobenzene, parafluoron, ethyl, MCPA-isobutyl, MCPA-isoctyl, MCPA-isopropyl, paraquat, paraquat dichloride, paraquat dimetilsulfate, par MCPA-methyl, MCPA-olamine, MCPA-potassium, MCPA athion, parathion-methyl, parinol, pebulate, pefurazoate, pel sodium, MCPA-thioethyl, MCPA-trolamine, MCPB, MCPB argonic acid, penconazole, pencycuron, pendimethalin, pen ethyl, MCPB-methyl, MCPB-sodium, mebenil, mecarbam, flufen, penfluoron, penoXSulam, pentachlorophenol, mecarbinzid, mecarphon, mecoprop, mecoprop-2-ethyl pentanochlor, penthiopyriad, pentmethrin, pentoxazone, per hexyl, mecoprop-dimethylammonium, mecoprop-diola fluidone, permethrin, pethoxamid, phenamacril, phenazine mine, mecoprop-ethadyl, mecoprop-isoctyl, mecoprop-me oxide, phenisopham, phenkapton, phenmedipham, phenme thyl, mecoprop-P, mecoprop-P-2-ethylhexyl, mecoprop-P- dipham-ethyl, phenobenzuron, phenothrin, phenproxide, dimethylammonium, mecoprop-P-isobutyl, mecoprop phenthoate, phenylmercuriurea, phenylmercury acetate, phe potassium, mecoprop-P-potassium, mecoprop-sodium, nylmercury chloride, phenylmercury derivative of pyrocat mecoprop-trolamine, medimeform, medinoterb, medinoterb echol, phenylmercury nitrate, phenylmercury salicylate, acetate, medlure, mefenacet, mefenpyr, mefenpyr-diethyl, phorate, phosacetim, phosalone, phosdiphen, phosfolan, mefluidide, mefluidide-diolamine, mefluidide-potassium, phosfolan-methyl, phosglycin, phosmet, phosnichlor, phos megatomoic acid, menazon, mepanipyrim, meperfluthrin, phamidon, phosphine, phosphocarb, phosphorus, phostin, mephenate, mephosfolan, mepiquat, mepiduat chloride, phoxim, phoxim-methyl, phthalide, picloram, picloram-2- mepiduat pentaborate, mepronil, meptylidinocap, mercuric ethylhexyl, picloram-isoctyl, picloram-methyl, picloram chloride, mercuric oxide, mercurous chloride, merphos, olamine, picloram-potassium, picloram-triethylammonium, mesoprazine, mesosulfuron, mesosulfuron-methyl, mesotri picloram-tris(2-hydroxypropyl)ammonium, picolinafen, US 2013/0019348 A1 Jan. 17, 2013

picoxystrobin, pindone, pindone-sodium, pinoxaden, pipera Sultropen, Swep, tau-fluvalinate, tavron, tazimcarb, TCA, lin, piperonyl butoxide, piperonyl cyclonene, piperophos, TCA-ammonium, TCA-calcium, TCA-ethadyl, TCA-mag piproctanyl, piproctanyl bromide, piprotal, pirimetaphos, pir nesium, TCA-sodium, TDE, tebuconazole, tebufenozide, imicarb, pirimioxyphos, pirimiphos-ethyl, pirimiphos-me tebufenpyrad, tebufloquin, tebupirimfos, tebutam, tebuthi thyl, plifenate, polycarbamate, polyoxins, polyoxorim, poly uron, tecloftalam, tecnaZene, tecoram, teflubenZuron, oXorim-zinc, polythialan, potassium arsenite, potassium tefluthrin, tefuryltrione, tembotrione, temephos, tepa, TEPP. azide, potassium cyanate, potassium gibberellate, potassium tepraloxydim, terallethrin, terbacil, terbucarb, terbuchlor, ter naphthenate, potassium polysulfide, potassium thiocyanate, bufos, terbumeton, terbuthylazine, terbutryn, tetcyclacis, tet potassium C.-naphthaleneacetate, pp'-DDT, prallethrin, pre rachloroethane, tetrachlorvinphos, tetraconazole, tetradifon, cocene I, precocene II, precocene III, pretilachlor, primi tetrafluoron, tetramethrin, tetramethylfluthrin, tetramine, tet dophos, primisulfuron, primisulfuron-methyl, probenazole, ranactin, tetraSul, thallium sulfate, thenylchlor, theta-cyper methrin, thiabendazole, thiacloprid, thiadifluor, thia prochloraz, prochloraZ-manganese, proclonol, procyazine, methoxam, thiapronil, thiazafluoron, thiazopyr, thicrofos, procymidone, prodiamine, profenofos, profluaZol, proflura thicyofen, thidiazimin, thidiaZuron, thiencarbazone, thien lin, profluthrin, profoxydim, proglinazine, proglinazine carbazone-methyl, thifensulfuron, thifensulfuron-methyl, ethyl, prohexadione, prohexadione-calcium, prohydrolas thifluzamide, thiobencarb, thiocarboxime, thiochlorfenphim, mon, promacyl, promecarb, prometon, prometryn, promurit, thiocyclam, thiocyclam hydrochloride, thiocyclam oxalate, propachlor, propamidine, propamidine dihydrochloride, pro thiodiazole-copper, thiodicarb, thiofanox, thiofluoximate, pamocarb, propamocarb hydrochloride, propanil, propaphos, thiohempa, thiomersal, thiometon, thionazin, thiophanate, propaquizafop, propargite, proparthrin, propazine, pro thiophanate-methyl, thioquinox, thiosemicarbazide, thiosul petamphos, propham, propiconazole, propineb, propisochlor, tap, thiosultap-diammonium, thiosultap-disodium, thiosul propoXur, propoxycarbazone, propoxycarbazone-sodium, tap-monosodium, thiotepa, thiram, thuringiensin, tiadinil, propyl isome, propyrisulfuron, propyZamide, produinazid, tiaojiean, tiocarbazil, tioclorim, tioxymid, tirpate, tolclofos proSuler, prosulfalin, prosulfocarb, prosulfuron, prothi methyl, tolfenpyrad, tolylfluanid, tolylmercury acetate, dathion, prothiocarb, prothiocarb hydrochloride, prothio toprameZone, tralkoxydim, tralocythrin, tralomethrin, tral conazole, prothiofos, prothoate, protrifenbute, proxan, opyril, transfluthrin, transpermethrin, tretamine, triacontanol, proXan-sodium, prynachlor, pydanon, pymetrozine, pyracar triadimefon, triadimenol, triafamone, tri-allate, triamiphos, bolid, pyraclofos, pyraclonil, pyraclostrobin, pyraflufen, triapenthenol, triarathene, triarimol, triasulfuron, triazamate, pyraflufen-ethyl, pyrafluprole, pyramat, pyrametostrobin, triazbutil, triaziflam, triazophos, triazoxide, tribenuron, tribe pyraoxystrobin, pyrasulfotole, pyrazolynate, pyrazophos, nuron-methyl, tribufos, tributyltin oxide, tricamba, trichla pyrazosulfuron, pyrazosulfuron-ethyl, pyrazothion, pyra mide, trichlorfon, trichlorimetaphos-3, trichloronat, triclopyr. ZOxyfen, pyresmethrin, pyrethrin I, pyrethrin II, pyrethrins, triclopyr-butotyl, triclopyr-ethyl, triclopyr-triethylammo pyribambenz-isopropyl, pyribambenZ-propyl, pyribencarb, nium, tricyclazole, tridemorph, tridiphane, trietazine, trifen pyribenZoxim, pyributicarb, pyriclor, pyridaben, pyridafol. morph, trifenofos, trifloxystrobin, trifloxysulfuron, triflox pyridalyl pyridaphenthion, pyridate, pyridinitril, pyrifenox, ysulfuron-sodium, triflumizole, triflumuron, trifluralin, pyrifluquinazon, pyriftalid, pyrimethanil, pyrimidifen, triflusulfuron, triflusulfuron-methyl, trifop, trifop-methyl, pyriminobac, pyriminobac-methyl, pyrimisulfan, pyrimitate, trifopsime, triforine, trihydroxytriazine, trimedlure, tri pyrinuron, pyriofenone, pyriprole, pyripropanol, pyriproxy methacarb, trimeturon, trinexapac, trinexapac-ethyl, triprene, fen, pyrithiobac, pyrithiobac-Sodium, pyrolan, pyroquilon, tripropindan, triptolide, tritac, triticonazole, tritosulfuron, pyroxasulfone, pyroxSulam, pyroxychlor, pyroxyfur, quassia, trunc-call, uniconazole, uniconazole-P. urbacide, uredepa, quinacetol, quinacetol Sulfate, quinalphos, quinalphos-me Valerate, validamycin, Valifenalate, valone, Vamidothion, thyl, quinaZamid, quinclorac, quinconazole, quinmerac, Vangard, Vaniliprole, Vernolate, VincloZolin, warfarin, war quinoclamine, quinonamid, quinothion, quinoxyfen, quintio farin-potassium, warfarin-Sodium, Xiaochongliulin, Xin fos, quintoZene, quizalofop, quizalofop-ethyl, quizalofop-P, junan, Xiwojunan, XMC, Xylachlor, Xylenols, Xylylcarb, quizalofop-P-ethyl, quizalofop-P-tefuryl, quwenzhi, quy yishijing, Zarilamid, Zeatin, Zengxiaoan, Zeta-cypermethrin, ingding, rabenzazole, rafoxanide, rebemide, resmethrin, rho Zinc naphthenate, Zinc phosphide, Zinc thiazole, Zineb, Ziram, dethanil, rhodojaponin-III, ribavirin, rimsulfuron, rotenone, Zolaprofos, Zoxamide, Zuomihuanglong, C-chlorohydrin, ryania, Saflufenacil, saijunmao, Saisentong, salicylanilide, C-ecdysone, C.-multistriatin, and C-naphthaleneacetic acid. sanguinarine, Santonin, Schradan, Scilliroside, Sebuthylazine, For more information consult the “COMPENDIUM OF PESTICIDE secbumeton, sedaxane, Selamectin, semiamitraz, semiami COMMON NAMEs' located at http://www.alanwood.net/pesti traZ chloride, Sesamex, Sesamolin, Sethoxydim, Shuangjiaan cides/index.html. Also consult “THE PESTICIDE MANUAL 14th caolin, Siduron, siglure, Silafluofen, silatrane, silica gel, silth Edition, edited by CD S Tomlin, copyright 2006 by British iofam, Simazine, Simeconazole, simeton, simetryn, sintofen, SMA, S-metolachlor, Sodium arsenite, Sodium azide, sodium Crop Production Council, or its prior or more recent editions. chlorate, Sodium fluoride, Sodium fluoroacetate, sodium Biopesticides hexafluorosilicate, Sodium naphthenate, Sodium orthophe nylphenoxide, Sodium pentachlorophenoxide, sodium 0342 Molecules of Formula One may also be used in polysulfide, Sodium thiocyanate, sodium C.-naphthaleneac combination (such as in a compositional mixture, or a simul etate, Sophamide, spinetoram, spinosad, spirodiclofen, taneous or sequential application) with one or more biopes spiromesifen, Spirotetramat, spiroxamine, Streptomycin, ticides. The term “biopesticide' is used for microbial biologi streptomycin sesquisulfate, Strychnine, Sulcatol, Sulcofuron, cal pest control agents that are applied in a similar manner to Sulcofuron-Sodium, Sulcotrione, Sulfallate, SulfentraZone, chemical pesticides. Commonly these are bacterial, but there Sulfuram, Sulfluramid, Sulfometuron, Sulfometuron-methyl, are also examples of fungal control agents, including Tricho sulfosulfuron, sulfotep, sulfoxaflor, sulfoxide, sulfoxime, derma spp. and Ampelomyces quisqualis (a control agent for Sulfur, Sulfuric acid, Sulfuryl fluoride, Sulglycapin, Sulprofos, grape powdery mildew). Bacillus subtilis are used to control US 2013/0019348 A1 Jan. 17, 2013 79 plant pathogens. Weeds and rodents have also been controlled 0361) 14. N-ethyl-2,2-dimethylpropionamide-2-(2,6- with microbial agents. One well-known insecticide example dichloro-C.C.C.-trifluoro-p-tolyl)hydrazone; is Bacillus thuringiensis, a bacterial disease of Lepidoptera, 0362. 15. N-ethyl-2,2-dichloro-1-methylcyclopropane Coleoptera, and Diptera. Because it has little effect on other carboxamide-2-(2,6-dichloro-C.C.C.-trifluoro-p-tolyl)hy organisms, it is considered more environmentally friendly draZone nicotine; than synthetic pesticides. Biological insecticides include 0363 16. O-(E-)-2-(4-chloro-phenyl)-2-cyano-1-(2-tri products based on: fluoromethylphenyl)-vinylS-methylthiocarbonate; 0343 1. entomopathogenic fungi (e.g. Metarhizium 0364 17. (E)-N1-(2-chloro-1,3-thiazol-5-ylmethyl)- anisopliae): N2-cyano-N1-methylacetamidine: 0344 2. entomopathogenic nematodes (e.g. Steinemena 0365. 18. 1-(6-chloropyridin-3-ylmethyl)-7-methyl-8-ni feltiae); and tro-1,2,3,5,6,7-hexahydro-imidazo 1,2-alpyridin-5-ol; 0345 3.entomopathogenic viruses (e.g. Cydia pomonella 0366 19. 4-4-chlorophenyl-(2-butylidine-hydrazono) granulovirus). methyl)phenyl mesylate; and 0346. Other examples of entomopathogenic organisms 0367. 20. N-Ethyl-2,2-dichloro-1-methylcyclopropan include, but are not limited to, baculoviruses, bacteria and ecarboxamide-2-(2,6-dichloro-alpha,alpha,alpha-trif other prokaryotic organisms, fungi, protozoa and MicroSpro luoro-p-tolyl)hydraZone. ridia. Biologically derived insecticides include, but not lim ited to, rotenone, Veratridine, as well as microbial toxins: Synergistic Mixtures insect tolerant or resistant plant varieties; and organisms modified by recombinant DNA technology to either produce 0368 Molecules of Formula One may be used with certain insecticides or to convey an insect resistant property to the active compounds to form synergistic mixtures where the genetically modified organism. In one embodiment, the mol mode of action of such compounds compared to the mode of ecules of Formula One may be used with one or more biope action of the molecules of Formula One are the same, similar, sticides in the area of seed treatments and soil amendments. or different. Examples of modes of action include, but are not The Manual of Biocontrol Agents gives a review of the avail limited to: acetylcholinesterase inhibitor; sodium channel able biological insecticide (and other biology-based control) modulator; chitin biosynthesis inhibitor; GABA and products. Copping L. G. (ed.) (2004). The Manual of Biocon glutamate-gated chloride channel antagonist; GABA and trol Agents (formerly the Biopesticide Manual) 3rd Edition. glutamate-gated chloride channel agonist; acetylcholine British Crop Production Council (BCPC), Farnham, Surrey receptor agonist; acetylcholine receptor antagonist; MET I UK. inhibitor; Mg-stimulated ATPase inhibitor; nicotinic acetyl choline receptor; Midgut membrane disrupter; oxidative Other Active Compounds phosphorylation disrupter, and ryanodine receptor (RyRs). Generally, weight ratios of the molecules of Formula One in 0347 Molecules of Formula One may also be used in a synergistic mixture with another compound are from about combination (Such as in a compositional mixture, or a simul 10:1 to about 1:10, in another embodiment from about 5:1 to taneous or sequential application) with one or more of the about 1:5, and in another embodiment from about 3:1, and in following: another embodiment about 1:1. 0348 1. 3-(4-chloro-2,6-dimethylphenyl)-4-hydroxy-8- Oxa-1-azaspiro4.5 dec-3-en-2-one; Formulations 0349 2. 3-(4-chloro-2,4-dimethyl 1, 1'-biphenyl-3-yl)- 4-hydroxy-8-Oxa-1-azaspiro4.5dec-3-en-2-one; 0369 A pesticide is rarely suitable for application in its 0350 3.4-(6-chloro-3-pyridinyl)methylmethylamino pure form. It is usually necessary to add other Substances so 2(5H)-furanone; that the pesticide can be used at the required concentration 0351. 4. 4-(6-chloro-3-pyridinyl)methylcyclopropy and in an appropriate form, permitting ease of application, lamino-2(5H)-furanone; handling, transportation, storage, and maximum pesticide 0352 5. 3-chloro-N2-(1S)-1-methyl-2-(methylsulfonyl) activity. Thus, pesticides are formulated into, for example, ethyl)-N1-(2-methyl-4-1.2.2.2-tetrafluoro-1-(trifluorom baits, concentrated emulsions, dusts, emulsifiable concen ethyl)ethylphenyl-1,2-benzenedicarboxamide: trates, fumigants, gels, granules, microencapsulations, seed treatments, Suspension concentrates, Suspoemulsions, tab 0353 6. 2-cyano-N-ethyl-4-fluoro-3-methoxy-benene lets, water Soluble liquids, water dispersible granules or dry Sulfonamide; flowables, wettable powders, and ultra low volume solutions. 0354 7. 2-cyano-N-ethyl-3-methoxy-benzenesulfona For further information on formulation types see “Catalogue mide; of Pesticide Formulation Types and International Coding 0355 8. 2-cyano-3-difluoromethoxy-N-ethyl-4-fluoro System’Technical Monograph no 2, 5th Edition by CropLife benzenesulfonamide; International (2002). 0356 9. 2-cyano-3-fluoromethoxy-N-ethyl-benzene 0370 Pesticides are applied most often as aqueous sus Sulfonamide; pensions or emulsions prepared from concentrated formula 0357 10. 2-cyano-6-fluoro-3-methoxy-N,N-dimethyl tions of such pesticides. Such water-soluble, water-Suspend benzenesulfonamide; able, or emulsifiable formulations are either solids, usually 0358 11. 2-cyano-N-ethyl-6-fluoro-3-methoxy-N-me known as wettable powders, or water dispersible granules, or thyl-benzenesulfonamide: liquids usually known as emulsifiable concentrates, or aque 0359 12. 2-cyano-3-difluoromethoxy-N,N-dimethylben ous Suspensions. Wettable powders, which may be com Zenesulfon-amide; pacted to form water dispersible granules, comprise an inti 0360 13. 3-(difluoromethyl)-N-2-(3,3-dimethylbutyl) mate mixture of the pesticide, a carrier, and Surfactants. The phenyl-1-methyl-1H-pyrazole-4-carboxamide; concentration of the pesticide is usually from about 10% to US 2013/0019348 A1 Jan. 17, 2013 about 90% by weight. The carrier is usually selected from the bait they also consume the pesticide. Baits may take the among the attapulgite clays, the montmorillonite clays, the form of granules, gels, flowable powders, liquids, or solids. diatomaceous earths, or the purified silicates. Effective sur They can be used in pest harborages. factants, comprising from about 0.5% to about 10% of the 0378 Fumigants are pesticides that have a relatively high wettable powder, are found among Sulfonated lignins, con vapor pressure and hence can exist as a gas in Sufficient densed naphthalenesulfonates, naphthalenesulfonates, alkyl concentrations to kill pests in Soil or enclosed spaces. The benzenesulfonates, alkyl Sulfates, and non-ionic Surfactants toxicity of the fumigant is proportional to its concentration Such as ethylene oxide adducts of alkyl phenols. and the exposure time. They are characterized by a good 0371 Emulsifiable concentrates of pesticides comprise a capacity for diffusion and act by penetrating the pest's respi convenient concentration of a pesticide. Such as from about ratory system or being absorbed through the pest’s cuticle. 50 to about 500 grams per liter of liquid dissolved in a carrier Fumigants are applied to control stored product pests under that is either a water miscible solvent or a mixture of water gas proofsheets, in gas sealed rooms or buildings or in special immiscible organic solvent and emulsifiers. Useful organic chambers. Solvents include aromatics, especially Xylenes and petroleum 0379 Pesticides can be microencapsulated by suspending fractions, especially the high-boiling naphthalenic and ole the pesticide particles or droplets in plastic polymers of vari finic portions of petroleum Such as heavy aromatic naphtha. ous types. By altering the chemistry of the polymer or by Other organic Solvents may also be used. Such as the terpenic changing factors in the processing, microcapsules can be Solvents including rosin derivatives, aliphatic ketones Such as formed of various sizes, solubility, wall thicknesses, and cyclohexanone, and complex alcohols such as 2-ethoxyetha degrees of penetrability. These factors govern the speed with nol. Suitable emulsifiers for emulsifiable concentrates are which the active ingredient within is released, which in turn, selected from conventional anionic and non-ionic Surfactants. affects the residual performance, speed of action, and odor of 0372 Aqueous Suspensions comprise Suspensions of the product. water-insoluble pesticides dispersed in an aqueous carrier at a 0380 Oil solution concentrates are made by dissolving concentration in the range from about 5% to about 50% by pesticide in a solvent that will hold the pesticide in solution. weight. Suspensions are prepared by finely grinding the pes Oil solutions of a pesticide usually provide faster knockdown ticide and vigorously mixing it into a carrier comprised of and kill of pests than other formulations due to the solvents water and Surfactants. Ingredients, such as inorganic salts and themselves having pesticidal action and the dissolution of the synthetic or natural gums may also be added, to increase the waxy covering of the integument increasing the speed of density and viscosity of the aqueous carrier. It is often most uptake of the pesticide. Other advantages of oil solutions effective to grind and mix the pesticide at the same time by include better storage stability, better penetration of crevices, preparing the aqueous mixture and homogenizing it in an and better adhesion to greasy Surfaces. implement Such as a sand mill, ball mill, or piston-type 0381 Another embodiment is an oil-in-water emulsion, homogenizer. wherein the emulsion comprises oily globules which are each 0373 Pesticides may also be applied as granular compo provided with a lamellar liquid crystal coating and are dis sitions that are particularly useful for applications to the soil. persed in an aqueous phase, wherein each oily globule com Granular compositions usually contain from about 0.5% to prises at least one compound which is agriculturally active, about 10% by weight of the pesticide, dispersed in a carrier and is individually coated with a monolamellar or oligola that comprises clay or a similar substance. Such compositions mellar layer comprising: (1) at least one non-ionic lipophilic are usually prepared by dissolving the pesticide in a Suitable Surface-active agent, (2) at least one non-ionic hydrophilic Solvent and applying it to a granular carrier which has been Surface-active agent and (3) at least one ionic Surface-active pre-formed to the appropriate particle size, in the range of agent, wherein the globules having a mean particle diameter from about 0.5 to about 3 mm. Such compositions may also be of less than 800 nanometers. Further information on the formulated by making a dough or paste of the carrier and embodiment is disclosed in U.S. patent publication compound and crushing and drying to obtain the desired 20070027034 published Feb. 1, 2007, having patent applica granular particle size. tion Ser. No. 1 1/495,228. For ease of use, this embodiment 0374 Dusts containing a pesticide are prepared by inti will be referred to as “OIWE. mately mixing the pesticide in powdered form with a suitable 0382 For further information consult “Insect Pest Man dusty agricultural carrier, such as kaolin clay, ground Volca agement” 2nd Edition by D. Dent, copyright CAB Interna nic rock, and the like. Dusts can Suitably contain from about tional (2000). Additionally, for more detailed information 1% to about 10% of the pesticide. They can be applied as a consult"Handbook of Pest Control The Behavior, Life His seed dressing or as a foliage application with a dust blower tory, and Control of Household Pests” by Arnold Mallis, 9th machine. Edition, copyright 2004 by GIE Media Inc. 0375. It is equally practical to apply a pesticide in the form of a solution in an appropriate organic solvent, usually petro Other Formulation Components leum oil. Such as the spray oils, which are widely used in 0383 Generally, when the molecules disclosed in For agricultural chemistry. mula One are used in a formulation, such formulation can also 0376 Pesticides can also be applied in the form of an contain other components. These components include, but aerosol composition. In such compositions the pesticide is are not limited to, (this is a non-exhaustive and non-mutually dissolved or dispersed in a carrier, which is a pressure-gen exclusive list) wetters, spreaders, Stickers, penetrants, buff erating propellant mixture. The aerosol composition is pack ers, sequestering agents, drift reduction agents, compatibility aged in a container from which the mixture is dispensed agents, anti-foam agents, cleaning agents, and emulsifiers. A through an atomizing valve. few components are described forthwith. 0377 Pesticide baits are formed when the pesticide is 0384. A wetting agent is a substance that when added to a mixed with food or an attractant or both. When the pests eat liquid increases the spreading or penetration power of the US 2013/0019348 A1 Jan. 17, 2013

liquid by reducing the interfacial tension between the liquid bilization are non-ionics, Sorbitan monooleates, Sorbitan and the Surface on which it is spreading. Wetting agents are monooleate ethoxylates, and methyl oleate esters. used for two main functions in agrochemical formulations: 0388 Surfactants are sometimes used, either alone or with during processing and manufacture to increase the rate of other additives Such as mineral or vegetable oils as adjuvants wetting of powders in water to make concentrates for soluble to spray-tank mixes to improve the biological performance of liquids or Suspension concentrates; and during mixing of a the pesticide on the target. The types of Surfactants used for product with water in a spray tank to reduce the wetting time bioenhancement depend generally on the nature and mode of of wettable powders and to improve the penetration of water action of the pesticide. However, they are often non-ionics into water-dispersible granules. Examples of wetting agents Such as: alkyl ethoxylates; linear aliphatic alcohol ethoxy used in wettable powder, Suspension concentrate, and water lates; aliphatic amine ethoxylates. dispersible granule formulations are: sodium lauryl Sulfate; 0389. A carrier or diluent in an agricultural formulation is Sodium dioctyl sulfoSuccinate; alkyl phenol ethoxylates; and a material added to the pesticide to give a product of the aliphatic alcohol ethoxylates. required strength. Carriers are usually materials with high 0385) A dispersing agent is a substance which adsorbs absorptive capacities, while diluents are usually materials onto the surface of particles and helps to preserve the state of with low absorptive capacities. Carriers and diluents are used dispersion of the particles and prevents them from reaggre in the formulation of dusts, wettable powders, granules and gating. Dispersing agents are added to agrochemical formu water-dispersible granules. lations to facilitate dispersion and Suspension during manu 0390 Organic solvents are used mainly in the formulation facture, and to ensure the particles redisperse into water in a of emulsifiable concentrates, oil-in-water emulsions, Suspo spray tank. They are widely used in wettable powders, Sus emulsions, and ultra low Volume formulations, and to a lesser pension concentrates and water-dispersible granules. Surfac extent, granular formulations. Sometimes mixtures of Sol tants that are used as dispersing agents have the ability to vents are used. The first main groups of solvents are aliphatic adsorb strongly onto a particle Surface and provide a charged paraffinic oils such as kerosene or refined paraffins. The sec or steric barrier to reaggregation of particles. The most com ond main group (and the most common) comprises the aro monly used Surfactants are anionic, non-ionic, or mixtures of matic solvents such as Xylene and higher molecular weight the two types. For wettable powder formulations, the most fractions of C9 and C10 aromatic solvents. Chlorinated common dispersing agents are sodium lignoSulfonates. For hydrocarbons are useful as cosolvents to prevent crystalliza Suspension concentrates, very good adsorption and stabiliza tion of pesticides when the formulation is emulsified into tion are obtained using polyelectrolytes, such as sodium water. Alcohols are sometimes used as cosolvents to increase naphthalene Sulfonate formaldehyde condensates. solvent power. Other solvents may include vegetable oils, Tristyrylphenol ethoxylate phosphate esters are also used. seed oils, and esters of vegetable and seed oils. Non-ionics Such as alkylarylethylene oxide condensates and 0391 Thickeners or gelling agents are used mainly in the EO-PO block copolymers are sometimes combined with formulation of Suspension concentrates, emulsions and Sus anionics as dispersing agents for Suspension concentrates. In poemulsions to modify the rheology or flow properties of the recent years, new types of very high molecular weight poly liquid and to prevent separation and settling of the dispersed meric Surfactants have been developed as dispersing agents. particles or droplets. Thickening, gelling, and anti-settling These have very long hydrophobic backbones and a large agents generally fall into two categories, namely water-in number of ethylene oxide chains forming the teeth of a soluble particulates and water-soluble polymers. It is possible comb surfactant. These high molecular weight polymers to produce Suspension concentrate formulations using clays can give very good long-term stability to Suspension concen and silicas. Examples of these types of materials, include, but trates because the hydrophobic backbones have many anchor are not limited to, montmorillonite, bentonite, magnesium ing points onto the particle Surfaces. Examples of dispersing aluminum silicate, and attapulgite. Water-soluble polysac agents used in agrochemical formulations are: Sodium ligno charides have been used as thickening-gelling agents for Sulfonates; sodium naphthalene Sulfonate formaldehyde con many years. The types of polysaccharides most commonly densates; tristyrylphenol ethoxylate phosphate esters; ali used are natural extracts of seeds and seaweeds or are syn phatic alcohol ethoxylates; alkyl ethoxylates; EO-PO block thetic derivatives of cellulose. Examples of these types of copolymers; and graft copolymers. materials include, but are not limited to, guar gum, locust 0386. An emulsifying agent is a substance which stabi bean gum, carrageenam; alginates; methyl cellulose; sodium lizes a Suspension of droplets of one liquid phase in another carboxymethyl cellulose (SCMC); hydroxyethyl cellulose liquid phase. Without the emulsifying agent the two liquids (HEC). Other types of anti-settling agents are based on modi would separate into two immiscible liquid phases. The most fied Starches, polyacrylates, polyvinyl alcohol and polyethyl commonly used emulsifier blends contain alkylphenol or ali ene oxide. Another good anti-settling agent is Xanthan gum. phatic alcohol with twelve or more ethylene oxide units and 0392 Microorganisms can cause spoilage of formulated the oil-soluble calcium salt of dodecylbenzenesulfonic acid. products. Therefore preservation agents are used to eliminate A range of hydrophile-lipophile balance (“HLB) values or reduce their effect. Examples of such agents include, but from 8 to 18 will normally provide good stable emulsions. are not limited to: propionic acid and its sodium salt; Sorbic Emulsion stability can sometimes be improved by the addi acid and its sodium or potassium salts; benzoic acid and its tion of a small amount of an EO-PO block copolymer surfac Sodium salt; p-hydroxybenzoic acid sodium salt; methyl tant. p-hydroxybenzoate; and 1,2-benzisothiazolin-3-one (BIT). 0387. A solubilizing agent is a surfactant which will form 0393. The presence of surfactants often causes water micelles in water at concentrations above the critical micelle based formulations to foam during mixing operations in pro concentration. The micelles are then able to dissolve or solu duction and in application through a spray tank. In order to bilize water-insoluble materials inside the hydrophobic part reduce the tendency to foam, anti-foam agents are often of the micelle. The types of surfactants usually used for solu added either during the production stage or before filling into US 2013/0019348 A1 Jan. 17, 2013 bottles. Generally, there are two types of anti-foam agents, scalaris, Conoderus Stigmosus, Conotrachelus menuphar, namely silicones and non-silicones. Silicones are usually Cotinis initida, Crioceris asparagi, Cryptolestes ferrugineus, aqueous emulsions of dimethyl polysiloxane, while the non Cryptolestes pusillus, Cryptolestes turcicus, Cylindrocoptu silicone anti-foam agents are water-insoluble oils, such as rus adspersus, Deporaus marginiatus, Dermestes lardarius, octanol and nonanol, or silica. In both cases, the function of Dermestes maculatus, Epilachna varivestis, Faustinus the anti-foam agent is to displace the Surfactant from the cubae, Hylobius pales, Hypera postica, Hypothenemus air-water interface. hampei, Lasioderma serricorne, Leptinotarsa decemlineata, 0394 “Green’ agents (e.g., adjuvants, surfactants, sol Liogeny's fiscus, Liogenys suturalis, Lissorhoptrus Oryzophi vents) can reduce the overall environmental footprint of crop lus, Maecolaspis joliveti, Melanotus communis, Melligethes protection formulations. Green agents are biodegradable and aeneus, Melolontha melolontha, Oberea brevis, Oberea lin generally derived from natural and/or Sustainable sources, earis, Oryctes rhinoceros, Oryzaephilus mercator; Oryza e.g. plant and animal sources. Specific examples are: Veg ephilus surinamensis, Oulema melanopus, Oulema Oryzae, etable oils, seed oils, and esters thereof, also alkoxylated alkyl Phyllophaga cuyabana, Popillia japonica, Prostephanus polyglucosides. truncatus, Rhyzopertha dominica, Sitona lineatus, Sitophilus 0395. For further information, see “Chemistry and Tech granarius, Sitophilus Oryzae, Sitophilus zeanais, Stegobium nology of Agrochemical Formulations' edited by D. A. paniceum, Tribolium castaneum, Tribolium confusum, Tro Knowles, copyright 1998 by Kluwer Academic Publishers. goderma variabile, and Zabrus tenebrioides. Also see “Insecticides in Agriculture and Environment Ret 0402. In another embodiment, the molecules of Formula rospects and Prospects” by A. S. Perry, I. Yamamoto, I. One may be used to control pests of the Order Dermaptera. Ishaaya, and R. Perry, copyright 1998 by Springer-Verlag. 0403. In another embodiment, the molecules of Formula One may be used to control pests of the Order Blattaria. A Pests non-exhaustive list of particular species includes, but is not 0396. In general, the molecules of Formula One may be limited to, Blattella germanica, Blatta orientalis, Parcoblatta used to control pests e.g. beetles, earwigs, cockroaches, flies. pennsylvanica, Periplaneta americana, Periplaneta aus aphids, scales, whiteflies, leafhoppers, ants, wasps, termites, tralasiae, Periplaneta brunnea, Periplaneta fuliginosa, Pyc moths, butterflies, lice, grasshoppers, locusts, crickets, fleas, noscelus surinamensis, and Supella longipalpa. thrips, bristletails, mites, ticks, nematodes, and Symphylans. 0404 In another embodiment, the molecules of Formula 0397. In another embodiment, the molecules of Formula One may be used to control pests of the Order Diptera. A One may be used to control pests in the Phyla Nematoda non-exhaustive list of particular genera includes, but is not and/or Arthropoda. limited to, Aedes spp., Agromyza spp., Anastrepha spp., 0398. In another embodiment, the molecules of Formula Anopheles spp., Bactrocera spp., Ceratitis spp., Chrysops One may be used to control pests in the Subphyla Chelicerata, spp., Cochliomyia spp., Contarinia spp., Culex spp., Myriapoda, and/or Hexapoda. Dasineura spp., Delia spp., Drosophila spp., Fannia spp., 0399. In another embodiment, the molecules of Formula Hvlemyia spp., Liriomyza spp., Musca spp., Phorbia spp., One may be used to control pests in the Classes of Arachnida, Tabanus spp., and Tipula spp. A non-exhaustive list of par Symphyla, and/or Insecta. ticular species includes, but is not limited to, Agromyza fron 0400. In another embodiment, the molecules of Formula tella, Anastrepha suspensa, Anastrepha ludens, Anastrepha One may be used to control pests of the Order Anoplura. A obliga, Bactrocera cucurbitae, Bactrocera dorsalis, Bactro non-exhaustive list of particular genera includes, but is not cera invadens, Bactrocera zonata, Ceratitis capitata, limited to, Haematopinus spp., Hoplopleura spp., Linog Dasineura brassicae, Delia platura, Fannia canicularis, Fan nathus spp., Pediculus spp., and Polyplax spp. A non-exhaus nia scalaris, Gasterophilus intestinalis, Gracilia perseae, tive list of particular species includes, but is not limited to, Haematobia irritans, Hypoderma lineatum, Liriomyza bras Haematopinus asini, Haematopinus suis, Linognathus Seto sicae, Mellophagus Ovinus, Musca autumnalis, Musca domes sus, Linognathus Ovillus, Pediculus humanus capitis, Pedicu tica, Oestrus ovis, Oscinella frit, Pegomya betae, Psila rosae, lus humanus humanus, and Pthirus pubis. Rhagoletis cerasi, Rhagoletis pomonella, Rhagoletis 04.01. In another embodiment, the molecules of Formula mendax, Sitodiplosis mosellana, and Stomoxys calcitrans. One may be used to control pests in the Order Coleoptera. A 0405. In another embodiment, the molecules of Formula non-exhaustive list of particular genera includes, but is not One may be used to control pests of the Order Hemiptera. A limited to, Acanthoscelides spp., Agriotes spp., Anthononus non-exhaustive list of particular genera includes, but is not spp., Apion spp., Apogonia spp., Aulacophora spp., Bruchus limited to, Adelges spp., Aulacaspis spp., Aphrophora spp., spp., Cerosterna spp., Cerotoma spp., Ceutorhynchus spp., Aphis spp., Bemisia spp., Ceroplastes spp., Chionaspis spp., Chaetocnema spp., Colaspis spp., Ctenicera spp., Curculio Chrysomphalus spp., Coccus spp., Empoasca spp., Lepi spp., Cyclocephala spp., Diabrotica spp., Hypera spp., Ips dosaphes spp., Lagynotomus spp., Lygus spp., Macrosiphum spp., Lyctus spp., Megascelis spp., Melligethes spp., Otiorhyn spp., Nephotettix spp., Nezara spp., Philaenus spp., Phyto chus spp., Pantomorus spp., Phyllophaga spp., Phyllotreta coris spp., Piezodorus spp., Planococcus spp., Pseudococcus spp., Rhizotrogus spp., Rhynchites spp., Rhynchophorus spp., spp., Rhopalosiphum spp., Saissetia spp., Therioaphis spp., Scolytus spp., Sphenophorus spp., Sitophilus spp., and Tribo Toumeyella spp., Toxoptera spp., Trialeurodes spp., Triatoma lium spp. A non-exhaustive list of particular species includes, spp. and Unaspis spp. A non-exhaustive list of particular but is not limited to, Acanthoscelides Obtectus, Agrilus pla species includes, but is not limited to, Acrosternum hilare, nipennis, Anoplophora glabripennis, Anthonomus grandis, Acyrthosiphon pisum, Aleyrodes proletella, Aleurodicus dis Ataenius spretulus, Atomaria linearis, Bothynoderes punc persus, Aleurothrixus floccosus, Amrasca biguttula biguttula, tiventris, Bruchus pisorum, Callosobruchus maculatus, Car Aonidiella aurantii, Aphis gossypii, Aphis glycines, Aphis pophilus hemipterus, Cassida vittata, Cerotoma trifurcata, pomi, Aulacorthum Solani, Bemisia argentifolii, Bemisia Ceutorhynchus assimilis, Ceutorhynchus mapi, Conoderus tabaci, Blissus leucopterus, Brachycorynella asparagi, US 2013/0019348 A1 Jan. 17, 2013

Brevennia rehi, Brevicoryne brassicae, Calocoris norvegi Orana, Agrotis ipsilon, Alabama argillacea, Amorbia cus, Ceroplastes rubens, Cimex hemipterus, Cimex lectu cuneana, Amyelois transitella, Anacamptodes defectaria, larius, Dagbertus fasciatus, Dichelops fircatus, Diuraphis Anarsia lineatella, Anomis Sabulifera, Anticarsia gemmata noxia, Diaphorina citri, Dysaphis plantaginea, Dysdercus lis, Archips argyrospilla, Archips rosana, Argyrotaenia cit suturellus, Edessa meditabunda, Eriosoma lanigerum, Eury rana, Autographa gamma, Bonagota Cranaodes, Borbo cin gaster maura, Euschistus heros, Euschistus servus, Helopel nara, Bucculatrix thurberiella, Capua reticulana, Carposina tis antonii, Helopeltis theivora, Icerva purchasi, Idioscopus niponensis, Chlumetia transversa, Choristoneura rosaceana, initidulus, Laodelphax striatellus, Leptocorisa Oratorius, Cnaphalocrocis medinalis, Conopomorpha cramerella, Cos Leptocorisa varicornis, Lygus hesperus, Maconellicoccus sus Cossus, Cydia caryana, Cydia funebrana, Cydia molesta, hirsutus, Macrosiphum euphorbiae, Macrosiphum grana Cydia nigricana, Cydia pomonella, Darna diducta, Diatraea rium, Macrosiphum rosae, Macrosteles quadrilineatus, saccharalis, Diatraea grandiosella, Earias insulana, Earias Mahanarva frimbiolata, Metopolophium dirhodium, Mictis vittella, Ecdytolopha aurantianum, Elasmopalpus lignosel longicornis, Myzus persicae, Nephotettix cinctipes, Neuro lus, Ephestia cautella, Ephestia elutella, Ephestia kuehniella, colpus longirostris, Nezara viridula, Nilaparvata lugens, Epinotia aporema, Epiphyas postvittana, Erionota thrax, Parlatoria pergandii, Parlatoria Ziziphi, Peregrinus maidis, Eupoecilia ambiguella, Euxoa auxiliaris, Grapholita Phylloxera vitifoliae, Physokermes piceae, Phytocoris cali molesta, Hedylepta indicata, Helicoverpa armigera, Heli fornicus, Phytocoris relativus, Piezodorus guildinii, Poecilo coverpa zea, Heliothis virescens, Hellula undalis, Keiferia capsus lineatus, Psallus vaccinicola, Pseudacy.sta perseae, lycopersicella, Leucinodes Orbonalis, Leucoptera coffeella, Pseudococcus brevipes, Ouadraspidiotus peniciosus, Rho Leucoptera malifoliella, Lobesia botrana, Loxagrotis albi palosiphum maidis, Rhopalosiphum padi, Saissetia oleae, costa, Lymantria dispar, Lyonetia clerkella, Mahasena cor Scaptocoris castanea, Schizaphis graminum, Sitobion ave betti, Mamestra brassicae, Maruca testulalis, Metisa plana, nae, Sogatella furcifera, Trialeurodes vaporariorum, Trialeu Mythinna unipuncta, Neoleucinodes elegantalis, Nymphula rodes abutiloneus, Unaspis yanonensis, and Zulia entrerri depunctalis, Operophtera brumata, Ostrinia nubilalis, Oxy CF2C dia vesulia, Pandemis cerasana, Pandemis heparana, Papilio 0406. In another embodiment, the molecules of Formula demodocus, Pectinophora gossypiella, Peridroma Saucia, One may be used to control pests of the Order Hymenoptera. Perileucoptera coffeella, Phthorimaea operculella, Phylloc A non-exhaustive list of particular genera includes, but is not mistis citrella, Pieris rapae, Plathypena scabra, Plodia inter limited to, Acromyrmex spp., Atta spp., Camponotus spp., punctella, Plutella xylostella, Polychrosis viteana, Prays Diprion spp., Formica spp., Monomorium spp., Neodiprion endocarpa, Prays oleae, Pseudaletia unipuncta, Pseudoplu spp., Pogonomyrmex spp., Polistes spp., Solenopsis spp., sia includens, Rachiplusia nu, Scirpophaga incertulas, Sesa Vespula spp., and Xvlocopa spp. A non-exhaustive list of mia inferens, Sesamia nonagrioides, Setora initens, Sitotroga particular species includes, but is not limited to, Athalia cerealella, Sparganothis pilleriana, Spodoptera exigua, rosae, Atta texana, Iridomyrmex humilis, Monomorium mini Spodoptera frugiperda, Spodoptera eridania, Thecla basil mum, Monomorium pharaonis, Solenopsis invicta, Solenop ides, Tineola bisselliella, Trichoplusiani, Tuta absoluta, Zeu sis geminata, Solenopsis molesta, Solenopsis richtery, Sole zera coffeae, and Zeuzera pyrina. nopsis xyloni, and Tapinoma sessile. 04.09. In another embodiment, the molecules of Formula 0407. In another embodiment, the molecules of Formula One may be used to control pests of the Order Mallophaga. A One may be used to control pests of the Order Isoptera. A non-exhaustive list of particular genera includes, but is not non-exhaustive list of particular genera includes, but is not limited to, Anaticola spp., Bovicola spp., Chelopistes spp., limited to, Coptotermes spp., Cornitermes spp., Cryptoter Goniodes spp., Menacanthus spp., and Trichodectes spp. A mes spp., Heterotermes spp., Kalotermes spp., Incisitermes non-exhaustive list of particular species includes, but is not spp., Macrotermes spp., Marginitermes spp., Microceroter limited to, Bovicola bovis, Bovicola caprae, Bovicola ovis, mes spp., Procorinitermes spp., Reticulitermes spp., Sche Chelopistes meleagridis, Goniodes dissimilis, Goniodes dorhinotermes spp., and Zootermopsis spp. A non-exhaustive gigas, Menacanthus stramineus, Menopon gallinae, and Tri list of particular species includes, but is not limited to, Cop chodectes canis. totermes curvignathus, Coptotermes frenchi, Coptotermes 0410. In another embodiment, the molecules of Formula formosanus, Heterotermes aureus, Microtermes Obesi, Reti One may be used to control pests of the Order Orthoptera. A culitermes banyulensis, Reticulitermes grassei, Reticuliter non-exhaustive list of particular genera includes, but is not mes flavipes, Reticulitermes hageni, Reticulitermes hesperus, limited to, Melanoplus spp., and Pterophylla spp. A non Reticulitermes Santonensis, Reticulitermes speratus, Reticu exhaustive list of particular species includes, but is not limited litermes tibialis, and Reticulitermes virginicus. to, Anabrus simplex, Gryllotalpa africana, Gryllotalpa aus 0408. In another embodiment, the molecules of Formula tralis, Gryllotalpa brachyptera, Gryllotalpa hexadactyla, One may be used to control pests of the Order Lepidoptera. A Locusta migratoria, Microcentrum retinerve, Schistocerca non-exhaustive list of particular genera includes, but is not gregaria, and Scudderia furcata. limited to, Adoxophyes spp., Agrotis spp., Argyrotaenia spp., 0411. In another embodiment, the molecules of Formula Cacoecia spp., Caloptilia spp., Chilo spp., Chrysodeixis spp., One may be used to control pests of the Order Siphonaptera. Colias spp., Crambus spp., Diaphania spp., Diatraea spp., A non-exhaustive list of particular species includes, but is not Earias spp., Ephestia spp., Epimecis spp., Feltia spp., Gor limited to, Ceratophyllus gallinae, Ceratophyllus niger, tyna spp., Helicoverpa spp., Heliothis spp., Indarbela spp., Ctenocephalides canis, Ctenocephalides felis, and Pulex irri Lithocolletis spp., Loxagrotis spp., Malacosoma spp., tan.S. Peridroma spp., Phyllonorycter spp., Pseudaletia spp., Sesa 0412. In another embodiment, the molecules of Formula mia spp., Spodoptera spp., Synanthedon spp., and One may be used to control pests of the Order Thysanoptera. Yponomeuta spp. A non-exhaustive list of particular species A non-exhaustive list of particular genera includes, but is not includes, but is not limited to, Achaea janata, Adoxophyes limited to, Calliothrips spp., Frankliniella spp., Scirtothrips US 2013/0019348 A1 Jan. 17, 2013

spp., and Thrips spp. A non-exhaustive list of particular sp. include areas where apples, corn, Sunflowers, cotton, Soy includes, but is not limited to, Frankliniella fisca, Franklin beans, canola, wheat, rice, Sorghum, barley, oats, potatoes, iella Occidentalis, Frankliniella Schultzei, Frankliniella will oranges, alfalfa, lettuce, Strawberries, tomatoes, peppers, cru iamsi, Heliothrips haemorrhoidalis, Rhipiphorothrips cruen cifers, pears, tobacco, almonds, Sugar beets, beans and other tatus, Scirtothrips citri, Scirtothrips dorsalis, and valuable crops are growing or the seeds thereofare going to be Taeniothrips rhopalantennalis, Thrips hawaiiensis, Thrips planted. It is also advantageous to use ammonium sulfate with nigropilosus, Thrips Orientalis, Thrips tabaci. a molecule of Formula One when growing various plants. 0413. In another embodiment, the molecules of Formula 0420 Controlling pests generally means that pest popula One may be used to control pests of the Order Thysanura. A tions, pest activity, or both, are reduced in an area. This can non-exhaustive list of particular genera includes, but is not come about when: pest populations are repulsed from an area; limited to, Lepisma spp. and Thermobia spp. when pests are incapacitated in or around an area; or pests are 0414. In another embodiment, the molecules of Formula exterminated, in whole, or in part, in or around an area. Of One may be used to control pests of the Order Acarina. A course, a combination of these results can occur. Generally, non-exhaustive list of particular genera includes, but is not pest populations, activity, or both are desirably reduced more limited to, Acarus spp., Aculops spp., Boophilus spp., Demo than fifty percent, preferably more than 90 percent. Generally, dex spp., Dermacentor spp., Epitrimerus spp., Eriophyes the area is not in or on a human; consequently, the locus is spp., Ixodes spp., Oligonychus spp., Panonychus spp., generally a non-human area. Rhizoglyphus spp., and Tetranychus spp. A non-exhaustive 0421. The molecules of Formula One may be used in list of particular species includes, but is not limited to, Acara mixtures, applied simultaneously or sequentially, alone or pis woodi, Acarus siro, Aceria mangiferae, Aculops lycoper with other compounds to enhance plant vigor (e.g. to grow a Sici, Aculus pelekassi, Aculus Schlechtendali, Amblyomma better root system, to better withstand stressful growing con americanum, Brevipalpus Obovatus, Brevipalpus phoenicis, ditions). Such other compounds are, for example, compounds Dermacentor variabilis, Dermatophagoides pteronyssinus, that modulate plant ethylene receptors, most notably 1-me Eotetranychus carpini, Notoedres cati, Oligonychus coffeae, thylcyclopropene (also known as 1-MCP). Furthermore, such Oligonychus ilicis, Panonychus citri, Panonychus ulmi, Phyl molecules may be used during times when pest activity is low, locoptruta oleivora, Polyphagotarisonemus latus, Rhipiceph Such as before the plants that are growing begin to produce alus sanguineus, Sarcoptes scabiei, Tegolophus perseaflorae, valuable agricultural commodities. Such times include the Tetranychus urticae, and Varroa destructor: early planting season when pest pressure is usually low. 0415. In another embodiment, the molecules of Formula 0422 The molecules of Formula One can be applied to the One may be used to control pest of the Order Symphyla. A foliar and fruiting portions of plants to control pests. The non-exhaustive list of particular sp. includes, but is not lim molecules will either come in direct contact with the pest, or ited to, Scutigerella immaculata. the pest will consume the pesticide when eating leaf fruit 0416. In another embodiment, the molecules of Formula mass, or extracting sap, that contains the pesticide. The mol One may be used to control pests of the Phylum Nematoda. A ecules of Formula One can also be applied to the soil, and non-exhaustive list of particular genera includes, but is not when applied in this manner, root and stem feeding pests can limited to, Aphelenchoides spp., Belonolaimus spp., Cricone be controlled. The roots can absorb a molecule taking it up mella spp., Dity lenchus spp., Heterodera spp., Hirschman into the foliar portions of the plant to control above ground niella spp., Hoplolaimus spp., Meloidogyne spp., Pratylen chewing and sap feeding pests. chus spp., and Radopholus spp. A non-exhaustive list of 0423 Generally, with baits, the baits are placed in the particular sp. includes, but is not limited to, Dirofilaria immi ground where, for example, termites can come into contact tis, Heterodera zeae, Meloidogyne incognita, Meloidogyne with, and/or be attracted to, the bait. Baits can also be applied javanica, Onchocerca volvulus, Radopholus similis, and to a Surface of a building, (horizontal, Vertical, or slant Sur Rotylenchulus reniformis. face) where, for example, ants, termites, cockroaches, and 0417 For additional information consult “HANDBOOK OF flies, can come into contact with, and/or be attracted to, the PEST CONTROL THE BEHAVIOR, LIFE HISTORY, AND CONTROL OF bait. Baits can comprise a molecule of Formula One. HoUSEHOLD PESTs' by Arnold Mallis, 9th Edition, copyright 0424 The molecules of Formula One can be encapsulated 2004 by GIE Media Inc. inside, or placed on the Surface of a capsule. The size of the capsules can range from nanometer size (about 100-900 Applications nanometers in diameter) to micrometer size (about 10-900 0418 Molecules of Formula One are generally used in microns in diameter). amounts from about 0.01 grams per hectare to about 5000 0425 Because of the unique ability of the eggs of some grams per hectare to provide control. Amounts from about 0.1 pests to resist certain pesticides, repeated applications of the grams per hectare to about 500 grams per hectare are gener molecules of Formula One may be desirable to control newly ally preferred, and amounts from about 1 gram per hectare to emerged larvae. about 50 grams per hectare are generally more preferred. 0426 Systemic movement of pesticides in plants may be 0419. The area to which a molecule of Formula One is utilized to control pests on one portion of the plant by apply applied can be any area inhabited (or maybe inhabited, or ing (for example by spraying an area) the molecules of For traversed by) a pest, for example: where crops, trees, fruits, mula One to a different portion of the plant. For example, cereals, fodder species, vines, turf and ornamental plants, are control of foliar-feeding insects can be achieved by drip irri growing; where domesticated animals are residing; the inte gation or furrow application, by treating the Soil with for rior or exterior Surfaces of buildings (such as places where example pre- or post-planting soil drench, or by treating the grains are stored), the materials of construction used in build seeds of a plant before planting. ing (Such as impregnated wood), and the soil around build 0427 Seed treatment can be applied to all types of seeds, ings. Particular crop areas to use a molecule of Formula One including those from which plants genetically modified to US 2013/0019348 A1 Jan. 17, 2013

express specialized traits will germinate. Representative biomass and/or increased content of valuable ingredients), examples include those expressing proteins toxic to inverte improving the vigor of a plant (e.g. improved plant growth brate pests, such as Bacillus thuringiensis or other insecti and/or greener leaves), improving the quality of a plant (e.g. cidal toxins, those expressing herbicide resistance, Such as improved content or composition of certainingredients), and “Roundup Ready’ seed, or those with “stacked' foreign improving the tolerance to abiotic and/or biotic stress of the genes expressing insecticidal toxins, herbicide resistance, plant. nutrition-enhancement, drought resistance, or any other ben 0435. Before apesticide can be used or sold commercially, eficial traits. Furthermore, such seed treatments with the mol Such pesticide undergoes lengthy evaluation processes by ecules of Formula One may further enhance the ability of a various governmental authorities (local, regional, state, plant to better withstand stressful growing conditions. This national, and international). Voluminous data requirements results in a healthier, more vigorous plant, which can lead to are specified by regulatory authorities and must be addressed higher yields at harvest time. Generally, about 1 gram of the through data generation and Submission by the product reg molecules of Formula One to about 500 grams per 100,000 istrant or by a third party on the product registrants behalf, seeds is expected to provide good benefits, amounts from often using a computer with a connection to the World Wide about 10 grams to about 100 grams per 100,000 seeds is Web. These governmental authorities then review such data expected to provide better benefits, and amounts from about and if a determination of safety is concluded, provide the 25 grams to about 75 grams per 100,000 seeds is expected to potential user or seller with product registration approval. provide even better benefits. Thereafter, in that locality where the product registration is 0428. It should be readily apparent that the molecules of granted and Supported. Such user or seller may use or sell Such Formula One may be used on, in, or around plants genetically pesticide. modified to express specialized traits. Such as Bacillus thur 0436. A molecule according to Formula One can be tested ingiensis or other insecticidal toxins, or those expressing to determine its efficacy against pests. Furthermore, mode of herbicide resistance, or those with “stacked foreign genes action studies can be conducted to determine if said molecule expressing insecticidal toxins, herbicide resistance, nutrition has a different mode of action than other pesticides. Thereaf enhancement, or any other beneficial traits. ter, Such acquired data can be disseminated, such as by the 0429. The molecules of Formula One may be used for controlling endoparasites and ectoparasites in the Veterinary internet, to third parties. medicine sector or in the field of non-human animal keeping. 0437. The headings in this document are for convenience The molecules of Formula One are applied, such as by oral only and must not be used to interpret any portion hereof. 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 TABLE SECTION dusting, and by parenteral administration in the form of for example, an injection. % Control (or Mortality) Rating 0430. The molecules of Formula One may also be BAW & CEW Rating Table employed advantageously in livestock keeping, for example, cattle, sheep, pigs, chickens, and geese. They may also be SO-100 A. More than O-Less than 50 B employed advantageously in pets such as, horses, dogs, and Not Tested C cats. Particular pests to control would be fleas and ticks that No activity noticed in this bioassay D are bothersome to such animals. Suitable formulations are GPA Rating Table administered orally to the animals with the drinking water or 80-100 A. feed. The dosages and formulations that are Suitable depend More than O-Less than 80 B on the species. Not Tested C 0431. The molecules of Formula One may also be used for No activity noticed in this bioassay D controlling parasitic worms, especially of the intestine, in the YFM Rating Table animals listed above. 80-100 A. 0432. The molecules of Formula One may also be More than O-Less than 80 B employed in therapeutic methods for human healthcare. Such Not Tested C methods include, but are limited to, oral administration in the No activity noticed in this bioassay D form of for example, tablets, capsules, drinks, granules, and by dermal application. 0433 Pests around the world have been migrating to new TABLE ABC environments (for Such pest) and thereafter becoming a new invasive species in Such new environment. The molecules of Biological Results Formula One may also be used on Such new invasive species Rating Rating Rating Rating to control them in Such new environment. Molecule # YFM CEW BAW GPA 0434. The molecules of Formula One may also be used in A1 an area where plants, such as crops, are growing (e.g. pre A2 planting, planting, pre-harvesting) and where there are low A3 A4 levels (even no actual presence) of pests that can commer AS cially damage Such plants. The use of Such molecules in Such A6 area is to benefit the plants being grown in the area. Such A7 benefits, may include, but are not limited to, improving the A8 health of a plant, improving the yield of a plant (e.g. increased

US 2013/0019348 A1 Jan. 17, 2013 89

group, which may contain one or more further heteroa azolyl, benzoxazolyl, benzothienyl, benzothiazolyl cinnoli toms selected from nitrogen, Sulfur, and oxygen, nyl, furanyl, indazolyl, indolyl, imidazolyl, isoindolyl, iso wherein said hydrocarbyl cyclic group may optionally quinolinyl, isothiazolyl, isoxazolyl, oxadiazolyl, oxazolinyl, be substituted with Rand R', oxazolyl, phthalazinyl, pyrazinyl, pyrazolinyl, pyrazolyl, wherein RandR are independently selected from H. F. pyridazinyl, pyridyl, pyrimidinyl, pyrrolyl, quinazolinyl, Cl, Br, I, CN, C-C alkyl, oxo, thioxo, C-C, quinolinyl, quinoxalinyl, tetrazolyl, thiazolinyl, thiazolyl, haloalkyl, C-C cycloalkyl, C-C halocycloalkyl, thienyl, triazinyl, triazolyl, piperazinyl, piperidinyl, mor C-C cycloalkoxy, C-C halocycloalkoxy, C-C, pholinyl, pyrrolidinyl, tetrahydrofuranyl, tetrahydropyranyl. alkoxy, C-C haloalkoxy, C-C alkenyl, C-C, 1,2,3,4-tetrahydro-quinolinyl. 4,5-dihydro-oxazolyl. 4.5-di cycloalkenyl, C-C alkynyl, C-C cycloalkynyl, hydro-1H-pyrazolyl. 4,5-dihydro-isoxazolyl, and 2,3-dihy S(=O)(C-C alkyl), S(=O), (C-C haloalkyl). dro-1,3,4-oxadiazolyl. OSO(C-C alkyl). OSO(C-Chaloalkyl), C(=O) 6. A composition according to claim 1 wherein Het is (C-C alkyl), C(=O)C(C-C alkyl), C(=O)(C-C, triazolyl. haloalkyl), C(=O)C(C-C haloalkyl), C(=O)(C- 7. A composition according to claim 1 wherein Het is 1.2.4 C. cycloalkyl), C(=O)C(C-C cycloalkyl), C(=O) triazolyl. (C-C alkenyl), C(=O)C(C-C alkenyl), (C-C, 8. A composition according to claim 1 wherein Ar is alkyl)O(C-C alkyl), (C-C alkyl)S(C-C alkyl). phenyl. C(=O)(C-C alkyl)C(=O)C(C-C alkyl), phenyl, 9. A composition according to claim 1 wherein R' is H. substituted phenyl, phenoxy, or (Het-1); 10. A composition according to claim 1 wherein R is (K), (L) (Het-1) is a 5- or 6-membered, saturated or unsaturated, H. C-C alkyl, C-C alkyl-O-C(=O)C-C alkyl, C-C, heterocyclic ring, containing one or more heteroatoms alkyl-O C(=O)N(R'R''), or (C-C alkyl)S-(Het-1). independently selected from nitrogen, Sulfur or oxygen, 11. A composition according to claim 1 wherein is (K), H. wherein said heterocyclic ring may also be substituted CH, C-C alkyl, CHC(=O)CH(CH), CHC(=O)N(H) with one or more substituents independently selected (C(=O)CCHPh), or CHS (3,4,5-trimethoxy-2-tetrahydro from H. F. Cl, Br, I, CN, NO, oxo, C-C alkyl, C-C, pyran). haloalkyl, C-C cycloalkyl, C-C halocycloalkyl, 12. A composition according to claim 1 wherein R is C-C cycloalkoxy, C-C halocycloalkoxy, C-C, substituted phenyl. alkoxy, C-C haloalkoxy, C-C alkenyl, C-C alky 13. A composition according to claim 1 wherein R is nyl, S(=O), (C-C alkyl), S(=O), (C-C haloalkyl). substituted phenyl wherein said substituted phenyl has one or OSO(C-C alkyl). OSO(C-C haloalkyl), C(=O) more substituents selected from F, C-C alkyl, C-C alkoxy, NR'R'', (C-C alkyl)NR'R''. C(=O)(C-C alkyl), and phenyl. C(=O)C(C-C alkyl), C(=O)(C-C haloalkyl). 14. A composition according to claim 1 wherein R is C(=O)C(C-Chaloalkyl), C(=O)(C-C cycloalkyl). substituted phenyl wherein said substituted phenyl has one or C(=O)C(C-C cycloalkyl), C(=O)(C-C alkenyl), more substituents selected from F, CH, 2-CH(CH), C(=O)C(C-C alkenyl), (C-C alkyl)O(C-C alkyl). CH(CH)(CH), OCH, and phenyl. (C-C alkyl)S(C-C alkyl), C(=O)(C-C alkyl)C 15. A composition according to claim 1 wherein R is (=O)C(C-C alkyl), phenyl, phenoxy, substituted phe substituted phenyl wherein said substituted phenyl has more nyl and Substituted phenoxy, than one Substituent and at least one pair of said Substituents wherein such substituted phenyl and substituted phenoxy are not ortho to each other. have one or more Substituents independently selected 16. A composition according to claim 1 wherein R is H. from H. F. Cl, Br, I, CN, NO, C-C alkyl, C-C, 17. A composition according to claim 1 wherein M is N. haloalkyl, C-C cycloalkyl, C-C halocycloalkyl, 18. A composition according to claim 1 wherein Mis CR C-C cycloalkoxy, C-C halocycloalkoxy, C-C, wherein R is selected from H. CN, and C(=O)(C-C alkyl). alkoxy, C-C haloalkoxy, C-C alkenyl, C-C alky 19. A composition according to claim 1 wherein Q' is O. nyl, S(=O), (C-C alkyl), S(=O), (C-C haloalkyl). 20. A composition according to claim 1 wherein Q is S. OSO(C-C alkyl). OSO(C-Chaloalkyl), C(=O)H, 21. A composition according to claim 1 wherein RandR C(=O)NR'R'', (C-C alkyl)NR'R'', C(=O)(C-C, are (K) wherein RandR along with C(Q)(N), form a 4 alkyl), C(=O)C(C-C alkyl), C(=O)(C-C, to 7-membered saturated or unsaturated, hydrocarbyl cyclic haloalkyl), C(=O)C(C-C haloalkyl), C(=O)(C-C, group. cycloalkyl), C(=O)C(C-C cycloalkyl), C(=O)(C- 22. A composition according to claim 1 wherein R and R' Calkenyl), C(=O)C(C-C alkenyl), (C-C alkyl)O are (K) wherein RandR along with C(Q)(N), form a 4 (C-C alkyl), (C-C alkyl)S(C-C alkyl), phenyl, and to 7-membered saturated or unsaturated, hydrocarbyl cyclic phenoxy; and group, wherein said hydrocarbyl cyclic group is Substituted (M) n is each individually 0, 1, or 2. with oxo or C-C alkyl. 2. A composition according to claim 1 wherein Ar' is a 23. A composition according to claim 1 wherein R and R' substituted phenyl. are (K) wherein RandR along with C(Q)(N), form a 4 3. A composition according to claim 1 wherein Ar' is a to 7-membered saturated or unsaturated, hydrocarbyl cyclic substituted phenyl that has one or more substituents selected group, wherein the link between Q and N is CHC(=O), from C-C haloalkyl and C-C haloalkoxy. CHCH, CHCHCH, or CHCH(CH). 4. A composition according to claim 1 wherein Ar' is a 24. A composition according to claim 1 wherein at least substituted phenyl that has one or more substituents selected one of R', R, or R, is Hand said molecule exists as one or from CF. OCF, and OCFs. more tautomerS. 5. A composition according to claim 1 wherein Het is 25. A composition according to claim 1 wherein said mol selected from benzofuranyl, benzoisothiazolyl, benzoisox ecule is Molecule HA63. US 2013/0019348 A1 Jan. 17, 2013 90

26. A composition according to claim 1 wherein said mol 58. A composition according to claim 1 wherein said mol ecule is Molecule HA64. ecule is Molecule HA105. 27. A composition according to claim 1 wherein said mol 59. A composition according to claim 1 wherein said mol ecule is Molecule HA65. ecule is Molecule HA106. 28. A composition according to claim 1 wherein said mol 60. A composition according to claim 1 wherein said mol ecule is Molecule HA67. ecule is Molecule HA107. 29. A composition according to claim 1 wherein said mol 61. A composition according to claim 1 wherein said mol ecule is Molecule HA68. ecule is Molecule HA108. 30. A composition according to claim 1 wherein said mol 62. A composition according to claim 1 wherein said mol ecule is Molecule HA69. ecule is Molecule HA109. 31. A composition according to claim 1 wherein said mol 63. A composition according to claim 1 wherein said mol ecule is Molecule HA70. ecule is Molecule HA110. 32. A composition according to claim 1 wherein said mol 64. A composition according to claim 1 wherein said mol ecule is Molecule HA72. ecule is Molecule #A111. 33. A composition according to claim 1 wherein said mol 65. A composition according to claim 1 wherein said mol ecule is Molecule HA73. ecule is Molecule #A114. 34. A composition according to claim 1 wherein said mol 66. A composition according to claim 1 wherein said mol ecule is Molecule #A74. ecule is Molecule HA115. 35. A composition according to claim 1 wherein said mol 67. A composition according to claim 1 wherein said mol ecule is Molecule HA75. ecule is Molecule #A116. 36. A composition according to claim 1 wherein said mol 68. A composition according to claim 1 wherein said mol ecule is Molecule HA76. ecule is Molecule HA117. 37. A composition according to claim 1 wherein said mol 69. A composition according to claim 1 wherein said mol ecule is Molecule HA77. ecule is Molecule #A121. 38. A composition according to claim 1 wherein said mol 70. A composition according to claim 1 wherein said mol ecule is Molecule HA79. ecule is Molecule #A122. 39. A composition according to claim 1 wherein said mol 71. A composition according to claim 1 wherein said mol ecule is Molecule #A82. ecule is Molecule #A123. 40. A composition according to claim 1 wherein said mol 72. A composition according to claim 1 wherein said mol ecule is Molecule #A84. ecule is in the form of a pesticidally acceptable acid addition 41. A composition according to claim 1 wherein said mol salt. ecule is Molecule HA85. 73. A composition according to claim 1 wherein said mol 42. A composition according to claim 1 wherein said mol ecule is in the form of a salt derivative. ecule is Molecule #A86. 74. A composition according to claim 1 wherein said mol 43. A composition according to claim 1 wherein said mol ecule is in the form of solvate. ecule is Molecule HA87. 75. A composition according to claim 1 wherein said mol 44. A composition according to claim 1 wherein said mol ecule is in the form of an ester derivative. ecule is Molecule HA88. 76. A composition according to claim 1 wherein said mol 45. A composition according to claim 1 wherein said mol ecule is in the form of a polymorph. ecule is Molecule HA89. 77. A composition according to claim 1 wherein said mol 46. A composition according to claim 1 wherein said mol ecule has a H. ecule is Molecule #A92. 78. A composition according to claim 1 wherein said mol 47. A composition according to claim 1 wherein said mol ecule has a ''C. ecule is Molecule #A93. 79. A composition according to claim 1 wherein said mol 48. A composition according to claim 1 wherein said mol ecule has one or more stereoisomers. ecule is Molecule #A94. 80. A composition according to claim 1 further comprising 49. A composition according to claim 1 wherein said mol one or more compounds having acaricidal, algicidal, avicidal, ecule is Molecule #A95. bactericidal, fungicidal, herbicidal, insecticidal, mollusci 50. A composition according to claim 1 wherein said mol cidal, nematicidal, rodenticidal, or virucidal properties. ecule is Molecule #A94. 81. A composition according to claim 1 further comprising 51. A composition according to claim 1 wherein said mol one or more compounds that are antifeedants, bird repellents, ecule is Molecule #A97. chemosterilants, herbicide Safeners, insect attractants, insect 52. A composition according to claim 1 wherein said mol repellents, mammal repellents, mating disrupters, plant acti ecule is Molecule #A98. vators, plant growth regulators, or synergists. 53. A composition according to claim 1 wherein said mol 82. A composition according to claim 1 further comprising ecule is Molecule HA100. one or more of the following (3-ethoxypropyl)mercury bro 54. A composition according to claim 1 wherein said mol mide, 1,2-dichloropropane, 1,3-dichloropropene, 1-methyl ecule is Molecule HA101. cyclopropene, 1-naphthol, 2-(octylthio)ethanol. 2,3,5-tri-io 55. A composition according to claim 1 wherein said mol dobenzoic acid, 2,3,6-TBA, 2,3,6-TBA ecule is Molecule HA102. dimethylammonium, 2.3.6-TBA-lithium, 2.3.6-TBA 56. A composition according to claim 1 wherein said mol potassium, 2.3.6-TBA-sodium, 2,4,5-T 2,4,5-T-2- ecule is Molecule HA103. butoxypropyl. 2,4,5-T-2-ethylhexyl, 2,4,5-T-3- 57. A composition according to claim 1 wherein said mol butoxypropyl. 2,4,5-TEB, 2,4,5-T-butomethyl, 2,4,5-T- ecule is Molecule #A104. butotyl, 2,4,5-T-butyl, 2,4,5-T-isobutyl, 2,4,5-T-isoctyl, 2.4. US 2013/0019348 A1 Jan. 17, 2013

5-T-isopropyl. 2,4,5-T-methyl, 2,4,5-T-penty1, 2,4,5-T-so nolide-ethyl, brevicomin, brodifacoum, brofenvalerate, brof dium, 2.4.5-T-triethylammonium, 2.4.5-T-trolamine, 2,4-D, luthrinate, bromacil, bromacil-lithium, bromacil-sodium, 2,4-D-2-butoxypropyl. 2,4-D-2-ethylhexyl, 2,4-D-3-butox bromadiolone, bromethalin, bromethrin, brom fenvinfos, bro ypropyl. 2,4-D-ammonium, 2,4-DB, 2,4-DB-butyl, 2,4-DB moacetamide, bromobonil, bromobutide, bromocyclen, dimethylammonium, 2,4-DB-isoctyl, 2,4-DB-potassium, bromo-DDT, bromofenoxim, bromophos, bromophos-ethyl, 2,4-DB-sodium, 2,4-D-butotyl, 2,4-D-butyl, 2,4-D-diethy bromopropylate, bromothalonil, bromoxynil, bromoxynil lammonium, 2,4-D-dimethylammonium, 2,4-D-diolamine, butyrate, bromoxynil heptanoate, bromoxynil octanoate, bro 2,4-D-dodecylammonium, 2,4-DEB, 2,4-DEP, 2,4-D-ethyl, moxynil-potassium, brompyrazon, bromuconazole, bro 2,4-D-heptylammonium, 2,4-D-isobutyl, 2,4-D-isoctyl, 2,4- nopol, bucarpolate, bufencarb, buminafos, bupirimate, D-isopropyl. 2,4-D-isopropylammonium, 2,4-D-lithium, buprofezin, Burgundy mixture, busulfan, butacarb, butachlor, 2,4-D-meptyl, 2,4-D-methyl, 2,4-D-octyl, 2,4-D-penty1, 2,4- butafenacil, butamifos, butathiofos, butenachlor, butethrin, D-potassium, 2,4-D-propyl. 2,4-D-Sodium, 2,4-D-tefuryl, buthidazole, buthiobate, buthiuron, butocarboxim, butonate, 2,4-D-tetradecylammonium, 2,4-D-triethylammonium, 2.4- butopyronoxyl, butoxycarboxim, butralin, butroxydim, butu D-tris(2-hydroxypropyl)ammonium, 2,4-D-trolamine, 21 P. ron, butylamine, butylate, cacodylic acid, cadusafos, cafens 2-methoxyethylmercury chloride, 2-phenylphenol, 3,4-DA, trole, calcium arsenate, calcium chlorate, calcium cyana 3,4-DB,3,4-DP, 4-aminopyridine, 4-CPA, 4-CPA-potassium, mide, calcium polysulfide, calvinphos, cambendichlor, 4-CPA-sodium, 4-CPB, 4-CPP 4-hydroxyphenethyl alcohol, camphechlor, camphor, captafol, captan, carbamorph, car 8-hydroxyquinoline Sulfate, 8-phenylmercurioxyquinoline, banolate, carbaryl, carbasulam, carbendazim, carbendazim abamectin, abscisic acid, ACC, acephate, acequinocyl. benzenesulfonate, carbendazim Sulfite, carbetamide, carbo acetamiprid, acethion, acetochlor, acetophos, acetoprole, furan, carbon disulfide, carbon tetrachloride, carbophe acilbenzolar, acilbenzolar-5-methyl, acifluorfen, acifluorfen nothion, carbosulfan, carboxazole, carboxide, carboxin, methyl, acifluorfen-Sodium, aclonifen, acrep, acrinathrin, carfentraZone, carfentraZone-ethyl, carpropamid, cartap, car acrolein, acrylonitrile, acy petacs, acy petacs-copper, acy tap hydrochloride, carvacrol, carvone, CDEA, cellocidin, petacs-zinc, alachlor, alanycarb, albendazole, aldicarb, CEPC, ceralure, Cheshunt mixture, chinomethionat, chito aldimorph, aldoxycarb, aldrin, allethrin, allicin, allidochlor, san, chlobenthiaZone, chlomethoxyfen, chloralose, chloram allosamidin, alloxydim, alloxydim-Sodium, allyl alcohol, ben, chloramben-ammonium, chloramben-diolamine, allyxycarb, alorac, alpha-cypermethrin, alpha-endosulfan, chloramben-methyl, chloramben-methylammonium, ametoctradin, ametridione, ametryn, amibuzin, amicarba chloramben-sodium, chloramine phosphorus, chlorampheni Zone, amicarthiazol, amidithion, amidoflumet, amidosulfu col, chloraniformethan, chloranil, chloranocryl, chlorantra ron, aminocarb, aminocyclopyrachlor, aminocyclopyrachlor niliprole, chlorazifop, chlorazifop-propargyl, chlorazine, methyl, aminocyclopyrachlor-potassium, aminopyralid, chlorbenside, chlorbenzuron, chlorbicyclen, chlorbromuron, aminopyralid-potassium, aminopyralid-tris(2-hydroxypro chlorbufam, chlordane, chlordecone, chlordimeform, chlo pyl)ammonium, amiprofoS-methyl, amiprophos, amisul rdimeform hydrochloride, chlorempenthrin, chlorethoxyfos, brom, amiton, amiton oxalate, amitraz, amitrole, ammonium chloreturon, chlorfenac, chlorfenac-ammonium, chlorfenac Sulfamate, ammonium C.-naphthaleneacetate, amobam, sodium, chlorfenapyr, chlorfenazole, chlorfenethol, chlor ampropylfos, anabasine, ancymidol, anilazine, anilofoS, ani fenprop, chlorfenson, chlorfensulphide, chlorfenvinphos, Suron, anthraquinone, antu, apholate, aramite, arsenous chlorfluaZuron, chlorflurazole, chlorfluren, chlorfluren-me oxide, asomate, aspirin, asulam, asulam-potassium, asulam thyl, chlorflurenol, chlorflurenol-methyl, chloridazon, chlo Sodium, athidathion, atraton, atrazine, aureofungin, avigly rimuron, chlorimuron-ethyl, chlormephos, chlormeduat, cine, aviglycine hydrochloride, azaconazole, azadirachtin, chlormeduat chloride, chlomidine, chlornitrofen, chloroben aZafenidin, azamethiphos, azim Sulfuron, azinphos-ethyl, Zilate, chlorodinitronaphthalenes, chloroform, chloromebu azinphos-methyl, aziprotryne, azithiram, azobenzene, azocy form, chloromethiuron, chloroneb, chlorophacinone, chlo clotin, azothoate, azoxystrobin, bachmedesh, barban, barium rophacinone-sodium, chloropicrin, chloropon, hexafluorosilicate, barium polysulfide, barthrin, BCPC, chloropropylate, chlorothalonil, chlorotoluron, chloroXuron, beflubutamid, benalaxyl, benalaxyl-M, benazolin, benazolin chloroxynil, chlorphonium, chlorphonium chloride, chlor dimethylammonium, benazolin-ethyl, benazolin-potassium, phoxim, chlorpraZophos, chlorprocarb, chlorpropham, chlo bencarbazone, benclothiaz, bendiocarb, benfluralin, benfura rpyrifos, chlorpyrifos-methyl, chlorquinox, chlorSulfuron, carb, benfuresate, benodanil, benomyl, benoxacor, benox chlorthal, chlorthal-dimethyl, chlorthal-monomethyl, chlor afos, benquinox, benSulfuron, benSulfuron-methyl, ben thiamid, chlorthiophos, chlozolinate, choline chloride, chro Sulide, benSultap, bentaluron, bentaZone, bentaZone-sodium, mafenozide, cinerin I, cinerin II, cinerins, cinidon-ethyl, cin benthiavalicarb, benthiavalicarb-isopropyl, benthiazole, ben methylin, cinosulfuron, ciobutide, cisanilide, cismethrin, tranil, benzadox, benzadox-ammonium, benzalkonium chlo clethodim, climbazole, cliodinate, clodinafop, clodinafop ride, benzamacril, benzamacril-isobutyl, benzamorf, ben propargyl, cloethocarb, clofencet, clofencet-potassium, Zfendizone, benzipram, benzobicyclon, benzofenap, clofentezine, clofibric acid, clofop, clofop-isobutyl, cloma benZofluor, benzohydroxamic acid, benzoximate, benzoyl Zone, clomeprop, cloprop, cloproxydim, clopyralid, clopy prop, benzoylprop-ethyl, benzthiazuron, benzyl benzoate, ralid-methyl, clopyralid-olamine, clopyralid-potassium, clo benzyladenine, berberine, berberine chloride, beta-cy pyralid-tris(2-hydroxypropyl)ammonium, cloquintocet, fluthrin, beta-cypermethrin, bethoxazin, bicyclopyrone, cloquintocet-mexyl, cloranSulam, cloranSulam-methyl, clos bifenazate, bifenox, bifenthrin, bifujunzhi, bilanafos, antel, clothianidin, clotrimazole, cloxyfonac, cloxyfonac-so bilanafos-Sodium, binapacryl, bingqingxiao, bioallethrin, dium, CMA, codlelure, colophonate, copper acetate, copper bioethanomethrin, biopermethrin, bioresmethrin, biphenyl, acetoarsenite, copper arsenate, copper carbonate, basic, cop bisazir, bismerthiazol, bispyribac, bispyribac-sodium, bistri per hydroxide, copper naphthenate, copper oleate, copper fluoron, bitertanol, bithionol, bixafen, blasticidin-S, borax, oxychloride, copper silicate, copper Sulfate, copper Zinc chro Bordeaux mixture, boric acid, boscalid, brassinolide, brassi mate, coumachlor, coumafuryl, coumaphos, coumatetralyl, US 2013/0019348 A1 Jan. 17, 2013 92 coumithoate, coumoxystrobin, CPMC, CPMF, CPPC, cre dithiopyr, diuron, d-limonene, DMPA, DNOC, DNOC-am dazine, cresol, crimidine, crotamiton, crotoxyphos, crufo monium, DNOC-potassium, DNOC-sodium, dodemorph, mate, cryolite, cue-lure, cufraneb, cumyluron, cuprobam, dodemorph acetate, dodemorph benzoate, dodicin, dodicin cuprous oxide, curcumenol, cyanamide, cyanatryn, cyana hydrochloride, dodicin-sodium, dodine, dofenapyn, domini Zine, cyanofenphos, cyanophos, cyanthoate, cyantraniliprole, calure, doramectin, drazoxolon, DSMA, dufulin, EBEP, EBP. cyaZofamid, cybutryne, cyclafuramid, cyclanilide, ecdysterone, edifenphos, eglinazine, eglinazine-ethyl, ema cyclethrin, cycloate, cycloheximide, cycloprate, cyclopro mectin, emamectin benzoate, EMPC, empenthrin, endosul thrin, cyclosulfamuron, cycloxydim, cycluron, cyenopy fan, endothal, endothal-diammonium, endothal-dipotassium, rafen, cyflufenamid, cyflumetofen, cyfluthrin, cyhalofop, endothal-disodium, endothion, endrin, enestroburin, EPN, cyhalofop-butyl, cyhalothrin, cyhexatin, cymiazole, cymiaZ epocholeone, epolfenonane, epoxiconazole, eprinomectin, ole hydrochloride, cymoxanil, cyometrinil, cypendazole, epronaz, EPTC, erbon, ergocalciferol, erluixiancaoan, esde cypermethrin, cyperquat, cyperquat chloride, cyphenothrin, pallethrine, esfenvalerate, esprocarb, etacelasil, etaconazole, cyprazine, cyprazole, cyproconazole, cyprodinil, cypro etaphos, etem, ethaboxam, ethachlor, ethalfluralin, ethamet furam, cypromid, cyprosulfamide, cyromazine, cythioate, Sulfuron, ethametSulfuron-methyl, ethaprochlor, ethephon, daimuron, dalapon, dalapon-calcium, dalapon-magnesium, ethidimuron, ethiofencarb, ethiolate, ethion, ethiozin, dalapon-Sodium, daminozide, dayoutong, dazomet, ethiprole, ethirimol, ethoate-methyl, ethofumesate, etho dazomet-sodium, DBCP, d-camphor, DCIP, DCPTA, DDT, hexadiol, ethoprophos, ethoxyfen, ethoxyfen-ethyl, ethox debacarb, decafentin, decarbofuran, dehydroacetic acid, ycuin, ethoxysulfuron, ethychloZate, ethyl formate, ethyl delachlor, deltamethrin, demephion, demephion-O, deme C.-naphthaleneacetate, ethyl-DDD, ethylene, ethylene dibro phion-S, demeton, demeton-methyl, demeton-O, demeton mide, ethylene dichloride, ethylene oxide, ethylicin, ethylm O-methyl, demeton-S, demeton-S-methyl, demeton-S-meth ercury 2,3-dihydroxypropyl mercaptide, ethylmercury ylsulphon, desmedipham, desmetryn, acetate, ethylmercury bromide, ethylmercury chloride, eth d-fanshiluquebinguzhi, diafenthiuron, dialifos, di-allate, ylmercury phosphate, etinofen, etnipromid, etobenzanid, diamidafos, diatomaceous earth, diazinon, dibutyl phthalate, etofemproX, etoxazole, etridiazole, etrimfos, eugenol, EXD, dibutyl Succinate, dicamba, dicamba-diglycolamine, famoxadone, famphur, fenamidone, fenaminosulf, fenami dicamba-dimethylammonium, dicamba-diolamine, phos, fenapanil, fenarimol, fenasulam, fenaZaflor, fenaza dicamba-isopropylammonium, dicamba-methyl, dicamba quin, fenbuconazole, fenbutatin oxide, fenchlorazole, olamine, dicamba-potassium, dicamba-Sodium, dicamba fenchlorazole-ethyl, fenchlorphos, fenclorim, fenethacarb, trolamine, dicapthon, dichlobenil, dichlofenthion, dichloflu fenfluthrin, fenfuram, fenhexamid, fenitropan, fenitrothion, anid, dichlone, dichloralurea, dichlorbenzuron, fenjuntong, fenobucarb, fenoprop, fenoprop-3-butoxypro dichlorflurenol, dichlorflurenol-methyl, dichlormate, dichlo pyl, fenoprop-butomethyl, fenoprop-butotyl, fenoprop-butyl, rmid, dichlorophen, dichlorprop, dichlorprop-2-ethylhexyl, fenoprop-isoctyl, fenoprop-methyl, fenoprop-potassium, dichlorprop-butotyl, dichlorprop-dimethylammonium, fenothiocarb, fenoxacrim, fenoxanil, fenoxaprop, fenox dichlorprop-ethylammonium, dichlorprop-isoctyl, dichlor aprop-ethyl, fenoxaprop-P, fenoxaprop-P-ethyl, fenoxasul prop-methyl, dichlorprop-P, dichlorprop-P-2-ethylhexyl, fone, fenoxycarb, fenpiclonil, fempirithrin, fenpropathrin, dichlorprop-P-dimethylammonium, dichlorprop-potassium, fenpropidin, fenpropimorph, fenpyraZamine, fenpyroximate, dichlorprop-sodium, dichlorvos, dichlozoline, diclobutrazol, fenridazon, fenridazon-potassium, fenridazon-propyl, fen diclocymet, diclofop, diclofop-methyl, diclomeZine, diclom son, fensulfothion, fenteracol, fenthiaprop, fenthiaprop eZine-Sodium, dicloran, dicloSulam, dicofol, dicoumarol, ethyl, fenthion, fenthion-ethyl, fentin, fentin acetate, fentin dicresyl, dicrotophos, dicyclanil, dicyclonon, dieldrin, chloride, fentin hydroxide, fentraZamide, fentrifanil, fenuron, dienochlor, diethamquat, diethamquat dichloride, diethatyl, fenuron TCA, fenvalerate, ferbam, ferimzone, ferrous sulfate, diethatyl-ethyl, diethofencarb, dietholate, diethyl pyrocar fipronil, flamprop, flamprop-isopropyl, flamprop-M, flam bonate, diethyltoluamide, difenacoum, difenoconazole, prop-methyl, flamprop-M-isopropyl, flamprop-M-methyl, difenopenten, difenopenten-ethyl, difenoXuron, difenZoquat, flaZaSulfuron, flocoumafen, flonicamid, florasulam, fluacry difenzoquat metilsulfate, difethialone, diflovidazin, difluben pyrim, fluazifop, fluazifop-butyl, fluazifop-methyl, fluazi Zuron, diflufenican, diflufenZopyr, diflufenZopyr-sodium, fop-P, fluazifop-P-butyl, fluazinam, fluazolate, fluaZuron, diflumetorim, dikegulac, dikegulac-Sodium, dilor, dimatif, flubendiamide, flubenzimine, flucarbazone, flucarbazone-so dimefluthrin, dimefox, dimefuron, dimepiperate, dium, flucetosulfuron, fluchloralin, flucofuron, flucycloxu dimetachlone, dimetan, dimethacarb, dimethachlor, ron, flucythrinate, fludioxonil, fluenetil, fluensulfone, flufen dimethametryn, dimethenamid, dimethenamid-P, dime acet, flufenerim, flufenican, flufenoxuron, flufenprox. thipin, dimethirimol, dimethoate, dimethomorph, dimethrin, flufenpyr, flufenpyr-ethyl, flufiprole, flumethrin, flumetover, dimethyl carbate, dimethyl phthalate, dimethylvinphos, flumetralin, flumetSulam, flumezin, flumiclorac, flumiclorac dimetilan, dimexano, dimidazon, dimoxystrobin, dinex, pentyl, flumioxazin, flumipropyn, flumorph, fluometuron, dinex-diclexine, dingjuneZuo, diniconazole, diniconazole fluopicolide, fluopyram, fluorbenside, fluoridamid, fluoroac M. dinitramine, dinobuton, dinocap, dinocap-4, dinocap-6, etamide, fluorodifen, fluoroglycofen, fluoroglycofen-ethyl, dinocton, dinofenate, dinopenton, dinoprop, dinosam, fluoroimide, fluoromidine, fluoronitrofen, fluothiuron, fluot dinoseb, dinoseb acetate, dinoseb-ammonium, dinoseb-di rimazole, fluoxastrobin, flupoxam, flupropacil, flupropadine, olamine, dinoseb-sodium, dinoseb-trolamine, dinosulfon, flupropanate, flupropanate-sodium, flupyrsulfuron, flupyr dinotefuran, dinoterb, dinoterbacetate, dinoterbon, diofeno Sulfuron-methyl, flupyrsulfuron-methyl-Sodium, fluguin lan, dioxabenzofos, dioxacarb, dioxathion, diphacinone, conazole, flurazole, flurenol, flurenol-butyl, flurenol-methyl, diphacinone-sodium, diphenamid, diphenyl Sulfone, diphe fluridone, fluorochloridone, fluoroxypyr, fluoroxypyr-bu nylamine, dipropalin, dipropetryn, dipyrithione, diguat, tomethyl, fluoroxypyr-meptyl, flurprimidol, flursulamid, diquat dibromide, disparlure, disul, disulfuram, disulfoton, flurtamone, flusilazole, flusulfamide, fluthiacet, fluthiacet disul-sodium, ditalimfos, dithianon, dithicrofos, dithioether, methyl, flutianil, flutolanil, flutriafol, fluvalinate, fluxapy US 2013/0019348 A1 Jan. 17, 2013

roXad, fluxofenim, folpet, fomesafen, fomesafen-Sodium, MCPA-dimethylammonium, MCPA-diolamine, MCPA fonofos, foramsulfuron, forchlorfenuron, formaldehyde, ethyl, MCPA-isobutyl, MCPA-isoctyl, MCPA-isopropyl, formetanate, formetanate hydrochloride, formothion, form MCPA-methyl, MCPA-olamine, MCPA-potassium, MCPA paranate, formparanate hydrochloride, fosamine, fosamine sodium, MCPA-thioethyl, MCPA-trolamine, MCPB, MCPB ammonium, fosetyl, fosetyl-aluminium, foSmethilan, fospi ethyl, MCPB-methyl, MCPB-sodium, mebenil, mecarbam, rate, fosthiazate, fosthietan, frontalin, fuberidazole, mecarbinzid, mecarphon, mecoprop, mecoprop-2-ethyl fucaojing, fucaomi, funaihecaoling, fuphenthiourea, hexyl, mecoprop-dimethylammonium, mecoprop-diola furalane, furalaxyl, furamethrin, furametpyr, furathiocarb, mine, mecoprop-ethadyl, mecoprop-isoctyl, mecoprop-me furcarbanil, furconazole, furconazole-cis, furethrin, furfural, thyl, mecoprop-P, mecoprop-P-2-ethylhexyl, mecoprop-P- furilazole, furmecyclox, furophanate, furyloxyfen, gamma dimethylammonium, mecoprop-P-isobutyl, mecoprop cyhalothrin, gamma-HCH, genit, gibberellic acid, gibberel potassium, mecoprop-P-potassium, mecoprop-sodium, lins, gliftor, glufosinate, glufosinate-ammonium, glufosi mecoprop-trolamine, medimeform, medinoterb, medinoterb nate-P. glufosinate-P-ammonium, glufosinate-P-Sodium, acetate, medlure, mefenacet, mefenpyr, mefenpyr-diethyl, glyodin, glyoxime, glyphosate, glyphosate-diammonium, mefluidide, mefluidide-diolamine, mefluidide-potassium, glyphosate-dimethylammonium, glyphosate-isopropylam megatomoic acid, menazon, mepanipyrim, meperfluthrin, monium, glyphosate-monoammonium, glyphosate-potas mephenate, mephosfolan, mepiquat, mepiduat chloride, sium, glyphosate-sesquisodium, glyphosate-trimesium, gly mepiduat pentaborate, mepronil, meptylidinocap, mercuric phosine, gossyplure, grandlure, griseofulvin, guazatline, chloride, mercuric oxide, mercurous chloride, merphos, guaZatine acetates, halacrinate, halfenproX, halofenozide, mesoprazine, mesosulfuron, mesosulfuron-methyl, mesotri halosafen, halosulfuron, halosulfuron-methyl, haloxydine, one, mesulfen, mesulfenfos, metaflumizone, metalaxyl, haloxyflop, haloxyfop-etotyl, haloxyfop-methyl, haloxyfop metalaxyl-M, metaldehyde, metam, metam-ammonium, P. haloxyfop-P-etotyl, haloxyfop-P-methyl, haloxyfop-so metamifop, metamitron, metam-potassium, metam-Sodium, dium, HCH, hemel, hempa, HEOD, heptachlor, heptenophos, metaZachlor, metazosulfuron, metaZOXolon, metconazole, heptopargil, heterophos, hexachloroacetone, hexachloroben metepa, metflurazon, methabenzthiaZuron, methacrifos, Zene, hexachlorobutadiene, hexachlorophene, hexaconazole, methalpropalin, methamidophos, methasulfocarb, meth hexaflumuron, hexaflurate, hexylure, hexamide, hexaZinone, azole, methfuroxam, methidathion, methiobencarb, methio hexylthiofos, hexythiazox, HHDN, holosulf, huancaiwo, carb, methiopyrisulfuron, methiotepa, methioZolin, methi huangcaoling, huanjunZuo, hydramethylnon, hydrargaphen, uron, methocrotophos, methometon, methomyl, methoprene, hydrated lime, hydrogen cyanide, hydroprene, hymexazol, methoprotryne, methoduin-butyl, methothrin, methoxychlor, hyduincarb, IAA, IBA, icaridin, imazalil, imazalil nitrate, methoxyfenozide, methoxyphenone, methyl apholate, imazalil Sulfate, imazamethabenZ, imazamethabenZ-methyl, methyl bromide, methyl eugenol, methyl iodide, methyl imaZamox, imaZamox-ammonium, imaZapic, imaZapic-am isothiocyanate, methylacetophos, methylchloroform, meth monium, imazapyr, imazapyr-isopropylammonium, imaza yldymron, methylene chloride, methylmercury benzoate, quin, imaZaquin-ammonium, imaZaquin-methyl, imaZaquin methylmercury dicyandiamide, methylmercury pentachlo Sodium, imazethapyr, imazethapyr-ammonium, rophenoxide, methylneodecanamide, metiram, metobenzu imaZoSulfuron, imibenconazole, imicyafos, imidacloprid, ron, metobromuron, metofluthrin, metolachlor, metolcarb, imidaclothiz, iminoctadine, iminoctadine triacetate, iminoc metominostrobin, metoSulam, metoxadiaZone, metoXuron, tadine trial besilate, imiprothrin, inabenfide, indanofan, metrafenone, metribuzin, metSulfovax, metSulfuron, metSul indaziflam, indoxacarb, inezin, iodobonil, iodocarb, furon-methyl, mevinphos, mexacarbate, mieshuan, milbe iodomethane, iodosulfuron, iodosulfuron-methyl, iodosulfu mectin, milbemycin oxime, milineb, mipafox, mirex, MNAF, ron-methyl-Sodium, ioxynil, ioxynil octanoate, ioxynil moguchun, molinate, moloSultap, monalide, monisouron, lithium, ioxynil-sodium, ipazine, ipconazole, ipfencarba monochloroacetic acid, monocrotophos, monolinuron, Zone, iprobenfos, iprodione, iprovalicarb, iprymidam, monosulfuron, monosulfuron-ester, monuron, monuron ipsodienol, ipsenol, IPSP, isamidofos, isazofos, isobenzan, TCA, morfamquat, morfamquat dichloride, moroxydine, isocarbamid, isocarbophos, isocil, isodrin, isofenphos, moroxydine hydrochloride, morphothion, morzid, moxidec isofenphos-methyl, isolan, isomethiozin, isonoruron, isopo tin, MSMA, muscalure, myclobutanil, myclozolin, N-(eth linate, isoprocarb, isopropalin, isoprothiolane, isoproturon, ylmercury)-p-toluenesulphonanilide, nabam, naftalofos, isopyrazam, isopyrimol, isothioate, isotianil, isouron, isov naled, naphthalene, naphthaleneacetamide, naphthalic anhy aledione, isoxaben, isoxachlortole, isoxadifen, isoxadifen dride, naphthoxyacetic acids, naproanilide, napropamide, ethyl, isoxaflutole, isoxapyrifop, isoxathion, ivermectin, izo naptalam, naptalam-Sodium, natamycin, neburon, niclosa pamfos, japonilure, japothrins, jasmolin I, jasmolin II, mide, niclosamide-olamine, nicosulfuron, nicotine, niflurid jasmonic acid, jiahuangchongzong, jiajizengxiaolin, jiax ide, nipyraclofen, nitenpyram, nithiazine, nitralin, nitrapyrin, iangjunzhi, jiecaowan, jiecaoxi, jodfenphos, juvenile hor nitrilacarb, nitrofen, nitrofluorfen, nitrostyrene, nitrothal-iso mone I, juvenile hormone II, juvenile hormone III, kadethrin, propyl, norbormide, norflurazon, nornicotine, noruron, nov karbutilate, karetazan, karetazan-potassium, kasugamycin, aluron, noviflumuron, nuarimol, OCH, octachlorodipropyl kasugamycin hydrochloride, kejunlin, kelevan, ketospiradox, ether, octhillinone, ofurace, omethoate, orbencarb, orfralure, ketospiradox-potassium, kinetin, kinoprene, kresoxim-me ortho-dichlorobenzene, orthosulfamuron, oryctalure, orysas thyl, kuicaoxi, lactofen, lambda-cyhalothrin, latilure, lead trobin, oryzalin, osthol, ostramone, Oxabetrinil, oxadiargyl. arsenate, lenacil, lepimectin, leptophos, lindane, lineatin, oxadiazon, oxadixyl, oXamate, oxamyl, oxapyrazon, oxapy linuron, lirimfos, litlure, loopilure, lufenuron, lvdingjunzhi, razon-dimolamine, Oxapyrazon-sodium, oxasulfuron, oxazi lvXiancaolin, lythidathion, MAA, malathion, maleic clomefone, oxine-copper, OXolinic acid, Oxpoconazole, hydrazide, malonoben, maltodextrin, MAMA, mancopper, Oxpoconazole fumarate, oxycarboxin, oxydemeton-methyl, mancoZeb, mandipropamid, maneb, matrine, mazidox, Oxydeprofos, oxydisulfoton, oxyfluorfen, oxymatrine, MCPA, MCPA-2-ethylhexyl, MCPA-butotyl, MCPA-butyl, oxytetracycline, Oxytetracycline hydrochloride, paclobutra US 2013/0019348 A1 Jan. 17, 2013 94

Zol, paichongding, para-dichlorobenzene, parafluoron, dethanil, rhodojaponin-III, ribavirin, rimsulfuron, rotenone, paraquat, paraquat dichloride, paraquat dimetilsulfate, par ryania, saflufenacil, saijunmao, Saisentong, Salicylanilide, athion, parathion-methyl, parinol, pebulate, pefurazoate, pel sanguinarine, Santonin, Schradan, Scilliroside, Sebuthylazine, argonic acid, penconazole, pencycuron, pendimethalin, pen secbumeton, sedaxane, Selamectin, semiamitraz, semiami flufen, penfluoron, penOXSulam, pentachlorophenol, traZ chloride, Sesamex, Sesamolin, Sethoxydim, Shuangjiaan pentanochlor, penthiopyriad, pentmethrin, pentoxazone, per caolin, siduron, siglure, Silafluofen, silatrane, silica gel, silth fluidone, permethrin, pethoxamid, phenamacril, phenazine iofam, simazine, Simeconazole, simeton, simetryn, sintofen, oxide, phenisopham, phenkapton, phenmedipham, phenme SMA, S-metolachlor, Sodium arsenite, Sodium azide, sodium dipham-ethyl, phenobenzuron, phenothrin, phenproxide, chlorate, Sodium fluoride, sodium fluoroacetate, sodium phenthoate, phenylmercuriurea, phenylmercury acetate, phe hexafluorosilicate, Sodium naphthenate, Sodium orthophe nylmercury chloride, phenylmercury derivative of pyrocat nylphenoxide, Sodium pentachlorophenoxide, Sodium echol, phenylmercury nitrate, phenylmercury salicylate, polysulfide, Sodium thiocyanate, Sodium C.-naphthaleneac phorate, phosacetim, phosalone, phosdiphen, phosfolan, etate, Sophamide, spinetoram, spinosad, spirodiclofen, phosfolan-methyl, phosglycin, phosmet, phosnichlor, phos spiromesifen, Spirotetramat, spiroxamine, Streptomycin, phamidon, phosphine, phosphocarb, phosphorus, phostin, streptomycin sesquisulfate, Strychnine, Sulcatol, Sulcofuron, phoxim, phoxim-methyl, phthalide, picloram, picloram-2- Sulcofuron-sodium, Sulcotrione, Sulfallate, SulfentraZone, ethylhexyl, picloram-isoctyl, picloram-methyl, picloram Sulfuram, Sulfluramid, Sulfometuron, Sulfometuron-methyl, olamine, picloram-potassium, picloram-triethylammonium, sulfosulfuron, sulfotep, sulfoxaflor, sulfoxide, sulfoxime, picloram-tris(2-hydroxypropyl)ammonium, picolinafen, Sulfur, Sulfuric acid, Sulfuryl fluoride, Sulglycapin, Sulprofos, picoxystrobin, pindone, pindone-sodium, pinoxaden, pipera Sultropen, Swep, tau-fluvalinate, tavron, tazimcarb, TCA, lin, piperonyl butoxide, piperonyl cyclonene, piperophos, TCA-ammonium, TCA-calcium, TCA-ethadyl, TCA-mag piproctanyl, piproctanyl bromide, piprotal, pirimetaphos, pir nesium, TCA-sodium, TDE, tebuconazole, tebufenozide, imicarb, pirimioxyphos, pirimiphos-ethyl, pirimiphos-me tebufenpyrad, tebufloquin, tebupirimfos, tebutam, tebuthi thyl, plifenate, polycarbamate, polyoxins, polyoxorim, poly uron, tecloftalam, tecnaZene, tecoram, teflubenZuron, oXorim-zinc, polythialan, potassium arsenite, potassium tefluthrin, tefuryltrione, tembotrione, temephos, tepa, TEPP. azide, potassium cyanate, potassium gibberellate, potassium tepraloxydim, terallethrin, terbacil, terbucarb, terbuchlor, ter naphthenate, potassium polysulfide, potassium thiocyanate, bufos, terbumeton, terbuthylazine, terbutryn, tetcyclacis, tet potassium C.-naphthaleneacetate, pp'-DDT, prallethrin, pre rachloroethane, tetrachlorvinphos, tetraconazole, tetradifon, cocene I, precocene II, precocene III, pretilachlor, primi tetrafluoron, tetramethrin, tetramethylfluthrin, tetramine, tet dophos, primisulfuron, primisulfuron-methyl, probenazole, ranactin, tetraSul, thallium sulfate, thenylchlor, theta-cyper prochloraz, prochloraZ-manganese, proclonol, procyazine, methrin, thiabendazole, thiacloprid, thiadifluor, thia procymidone, prodiamine, profenofos, profluaZol, proflura methoxam, thiapronil, thiazafluoron, thiazopyr, thicrofos, lin, profluthrin, profoxydim, proglinazine, proglinazine thicyofen, thidiazimin, thidiaZuron, thiencarbazone, thien ethyl, prohexadione, prohexadione-calcium, prohydrolas carbazone-methyl, thifensulfuron, thifensulfuron-methyl, mon, promacyl, promecarb, prometon, prometryn, promurit, thifluzamide, thiobencarb, thiocarboxime, thiochlorfenphim, propachlor, propamidine, propamidine dihydrochloride, pro thiocyclam, thiocyclam hydrochloride, thiocyclam oxalate, pamocarb, propamocarb hydrochloride, propanil, propaphos, thiodiazole-copper, thiodicarb, thiofanox, thiofluoximate, propaquizafop, propargite, proparthrin, propazine, pro thiohempa, thiomersal, thiometon, thionazin, thiophanate, petamphos, propham, propiconazole, propineb, propisochlor, thiophanate-methyl, thioquinox, thiosemicarbazide, thiosul propoXur, propoxycarbazone, propoxycarbazone-sodium, tap, thiosultap-diammonium, thiosultap-disodium, thiosul propyl isome, propyrisulfuron, propyZamide, produinazid, tap-monosodium, thiotepa, thiram, thuringiensin, tiadinil, proSuler, prosulfalin, prosulfocarb, prosulfuron, prothi tiaojiean, tiocarbazil, tioclorim, tioxymid, tirpate, tolclofos dathion, prothiocarb, prothiocarb hydrochloride, prothio methyl, tolfenpyrad, tolylfluanid, tolylmercury acetate, conazole, prothiofos, prothoate, protrifenbute, proxan, toprameZone, tralkoxydim, tralocythrin, tralomethrin, tral proXan-sodium, prynachlor, pydanon, pymetrozine, pyracar opyril, transfluthrin, transpermethrin, tretamine, triacontanol, bolid, pyraclofos, pyraclonil, pyraclostrobin, pyraflufen, triadimefon, triadimenol, triafamone, tri-allate, triamiphos, pyraflufen-ethyl, pyrafluprole, pyramat, pyrametostrobin, triapenthenol, triarathene, triarimol, triasulfuron, triazamate, pyraoxystrobin, pyrasulfotole, pyrazolynate, pyrazophos, triazbutil, triaziflam, triazophos, triazoxide, tribenuron, tribe pyrazosulfuron, pyrazosulfuron-ethyl, pyrazothion, pyra nuron-methyl, tribufos, tributyltin oxide, tricamba, trichla ZOxyfen, pyresmethrin, pyrethrin I, pyrethrin II, pyrethrins, mide, trichlorfon, trichlorimetaphos-3, trichloronat, triclopyr. pyribambenz-isopropyl, pyribambenZ-propyl, pyribencarb, triclopyr-butotyl, triclopyr-ethyl, triclopyr-triethylammo pyribenZoxim, pyributicarb, pyriclor, pyridaben, pyridafol. nium, tricyclazole, tridemorph, tridiphane, trietazine, trifen pyridalyl pyridaphenthion, pyridate, pyridinitril, pyrifenox, morph, trifenofos, trifloxystrobin, trifloxysulfuron, triflox pyrifluquinazon, pyriftalid, pyrimethanil, pyrimidifen, ysulfuron-sodium, triflumizole, triflumuron, trifluralin, pyriminobac, pyriminobac-methyl, pyrimisulfan, pyrimitate, triflusulfuron, triflusulfuron-methyl, trifop, trifop-methyl, pyrinuron, pyriofenone, pyriprole, pyripropanol, pyriproxy trifopsime, triforine, trihydroxytriazine, trimedlure, tri fen, pyrithiobac, pyrithiobac-Sodium, pyrolan, pyroquilon, methacarb, trimeturon, trinexapac, trinexapac-ethyl, triprene, pyroxasulfone, pyroxSulam, pyroxychlor, pyroxyfur, quassia, tripropindan, triptolide, tritac, triticonazole, tritosulfuron, quinacetol, quinacetol Sulfate, quinalphos, quinalphos-me trunc-call, uniconazole, uniconazole-P. urbacide, uredepa, thyl, quinaZamid, quinclorac, quinconazole, quinmerac, Valerate, validamycin, Valifenalate, valone, Vamidothion, quinoclamine, quinonamid, quinothion, quinoxyfen, quintio Vangard, Vaniliprole, Vernolate, VincloZolin, warfarin, war fos, quintoZene, quizalofop, quizalofop-ethyl, quizalofop-P, farin-potassium, warfarin-Sodium, Xiaochongliulin, Xin quizalofop-P-ethyl, quizalofop-P-tefuryl, quwenzhi, quy junan, Xiwojunan, XMC, Xylachlor, Xylenols, Xylylcarb, ingding, rabenzazole, rafoxanide, rebemide, resmethrin, rho yishijing, Zarilamid, Zeatin, Zengxiaoan, Zeta-cypermethrin, US 2013/0019348 A1 Jan. 17, 2013

Zinc naphthenate, Zinc phosphide, Zinc thiazole, Zineb, Ziram, chloropyridin-3-ylmethyl)-7-methyl-8-nitro-1,2,3,5,6,7- Zolaprofos, Zoxamide, Zuomihuanglong, C-chlorohydrin, hexahydro-imidazol-2-alpyridin-5-ol: 4-4-chlorophenyl C-ecdysone, C.-multistriatin, and C-naphthaleneacetic acid. (2-butylidine-hydrazono)methyl)phenyl mesylate; and 83. A composition according to claim 1 further comprising N-Ethyl-2,2-dichloro-1-methylcyclopropanecarboxamide one or more of the following 1,3-dichloropropene, 1-methyl 2-(2,6-dichloro-alpha,alpha,alpha-trifluoro-p-tolyl)hydra cyclopropene, 2,4-D, 2,4-D-2-butoxypropyl. 2,4-D-2-ethyl ZO. hexyl, 2,4-D-3-butoxypropyl. 2,4-D-ammonium, acetochlor, 86. A composition according to claim 1 further comprising aminopyralid, aminopyralid-potassium, aminopyralid-tris(2- one or more compounds having one of the following modes of hydroxypropyl)ammonium, atrazine, bromoxynil, bromoxy action: acetylcholinesterase inhibitor, sodium channel modu nil butyrate, bromoxynil heptanoate, bromoxynil octanoate, lator; chitin biosynthesis inhibitor; GABA and glutamate bromoxynil-potassium, chloropicrin, chlorpyrifos, chlorpy gated chloride channel antagonist; GABA and glutamate rifos-methyl, clopyralid, clopyralid-methyl, clopyralid-ola gated chloride channel agonist; acetylcholine receptor mine, clopyralid-potassium, clopyralid-tris(2-hydroxypro agonist; acetylcholine receptor antagonist, METI inhibitor; pyl)ammonium, cloquintocet, cloquintocet-mexyl, Mg-stimulated ATPase inhibitor; nicotinic acetylcholine cloranSulam, cloranSulam-methyl, cyhalofop, cyhalofop-bu receptor, Midgut membrane disrupter, oxidative phosphory tyl, diclosulam, ethalfluralin, fenbuconazole, florasulam, flu lation disrupter, and ryanodine receptor (RyRs). metSulam, fluoroxypyr, fluoroxypyr-butomethyl, fluoroxy 87. A composition according to claim 1 further comprising pyr-meptyl, gamma-cyhalothrin, glyphosate, glyphosate a seed. diammonium, glyphosate-dimethylammonium, glyphosate 88. A composition according to claim 1 further comprising isopropylammonium, glyphosate-monoammonium, a seed that has been genetically modified to express one or glyphosate-potassium, glyphosate-sesquisodium, glypho more traits. sate-trimesium, isoxaben, lambda-cyhalothrin, mancoZeb, 89. A composition according to claim 1 wherein said com MCPA, MCPA-2-ethylhexyl, MCPA-butotyl, MCPA-butyl, position is encapsulated inside, or placed on the Surface of, or MCPA-dimethylammonium, MCPA-diolamine, MCPA both, a capsule. ethyl, MCPA-isobutyl, MCPA-isoctyl, MCPA-isopropyl, 90. A composition according to claim 1 wherein said com MCPA-methyl, MCPA-olamine, MCPA-potassium, MCPA position is encapsulated inside, or placed on the Surface of, or sodium, MCPA-thioethyl, MCPA-trolamine, MCPB, MCPB both, a capsule, wherein said capsule has a diameter of about ethyl, MCPB-methyl, MCPB-sodium, methoxyfenozide, 100-900 nanometers or about 100-900 microns. myclobutanil, nitrapyrin, oxyfluorfen, penoxSulam, piclo 91. A process comprising applying a composition accord ram, picloram-2-ethylhexyl, picloram-isoctyl, picloram-me ing to claim 1, to an area to control a pest, in an amount thyl, picloram-olamine, picloram-potassium, picloram-tri Sufficient to control Such pest. ethylammonium, picloram-tris(2-hydroxypropyl) 92. A process according to claim 91 wherein said pest is ammonium, propiconazole, propyZamide, pyroxSulam, selected from beetles, earwigs, cockroaches, flies. aphids, quinoxyfen, spinetoram, spinosad, SulfentraZone, tebuthi scales, whiteflies, leafhoppers, ants, wasps, termites, moths, uron, triclopyr, triclopyr-butotyl, triclopyr-ethyl, triclopyr butterflies, lice, grasshoppers, locusts, crickets, fleas, thrips, triethylammonium, and trifluralin. bristletails, mites, ticks, nematodes, and Symphylans. 84. A composition according to claim 1 further comprising 93. A process according to claim 91 wherein said pest is one or more biopesticides. from the Phyla Nematoda or Arthropoda. 85. A composition according to claim 1 further comprising 94. A process according to claim 91 wherein said pest is one or more of the following 3-(4-chloro-2,6-dimethylphe from the Subphyla Chelicerata, Myriapoda, or Hexapoda. nyl)-4-hydroxy-8-Oxa-1-azaspiro4.5 dec-3-en-2-one; 3-(4- 95. A process according to claim 91 wherein said pest is chloro-2,4-dimethyl 1, 1'-biphenyl-3-yl)-4-hydroxy-8-oxa from the Class of Arachnida, Symphyla, or Insecta. 1-azaspiro4.5 dec-3-en-2-one: 4-(6-chloro-3-pyridinyl) 96. A process according to claim 91 wherein said pest is methylmethylamino-2(5H)-furanone; 4-(6-chloro-3- from the Order Anoplura, Order Coleoptera, Order Der pyridinyl)methylcyclopropylamino-2(5H)-furanone; maptera, Order Blattaria, Order Diptera, Order Hemiptera, 3-chloro-N2-(1S)-1-methyl-2-(methylsulfonyl)ethyl)-N1 Order Hymenoptera, Order Isoptera, Order Lepidoptera, 2-methyl-4-1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl Order Mallophaga, Order Orthoptera, Order Siphonaptera, phenyl-1,2-benzenedicarboxamide; 2-cyano-N-ethyl-4- Order Thysanoptera, Order Thysanura, Order Acarina, or fluoro-3-methoxy-benenesulfonamide: 2-cyano-N-ethyl-3- Order Symphyla. methoxy-benzenesulfonamide: 2-cyano-3-difluoromethoxy 97. A process according to claim 91 wherein said pest is N-ethyl-4-fluoro-benzenesulfonamide: 2-cyano-3- BAW, CEW, YFM, or GPA. fluoromethoxy-N-ethyl-benzenesulfonamide: 2-cyano-6- 98. A process according to claim 91 wherein said amount is fluoro-3-methoxy-N,N-dimethyl-benzenesulfonamide: from about 0.01 grams per hectare to about 5000 grams per 2-cyano-N-ethyl-6-fluoro-3-methoxy-N-methyl-benzene hectare. sulfonamide: 2-cyano-3-difluoromethoxy-N,N-dimethyl 99. A process according to claim 91 wherein said amount is benzenesulfon-amide: 3-(difluoromethyl)-N-2-(3.3-dim from about 0.1 grams per hectare to about 500 grams per ethylbutyl)phenyl-1-methyl-1H-pyrazole-4-carboxamide: hectare. N-ethyl-2,2-dimethylpropionamide-2-(2,6-dichloro-C.C.C.- 100. A process according to claim 91 wherein said amount trifluoro-p-tolyl)hydrazone; N-ethyl-2,2-dichloro-1-methyl is from about 1 gram per hectare to about 50 grams per cyclopropane-carboxamide-2-(2,6-dichloro-C.C.C.-trif hectare. luoro-p-tolyl)hydrazone nicotine; O-(E-)-2-(4-chloro 101. A process according to claim 91 wherein said area is phenyl)-2-cyano-1-(2-trifluoromethylphenyl)-vinyl S an area where apples, corn, cotton, Soybeans, canola, wheat, methyl thiocarbonate; (E)-N1-(2-chloro-1,3-thiazol-5- rice, Sorghum, barley, oats, potatoes, oranges, alfalfa, lettuce, ylmethyl)-N2-cyano-N1-methylacetamidine: 1-(6- Strawberries, tomatoes, peppers, crucifers, pears, tobacco, US 2013/0019348 A1 Jan. 17, 2013 96 almonds, Sugar beets, or beans, are growing, or the seeds 108. A molecule according to claim 106 wherein said mol thereof are going to be planted. ecule is 102. A process according to claim 91 further comprising applying said composition to a genetically modified plant that F has been genetically modified to express one or more traits. F F N 103. A process according to claim 91 where said compo sition further comprises ammonium Sulfate. F N 2 104. A process comprising: orally administering; or topi O cally applying; a composition according to claim 1, to a non-human animal, to control endoparasites, ectoparasites, or both. 109. A process comprising reacting (a) one or more of 105. A process comprising applying a composition accord (1) 4-(C-C alkyl)-1-halobenzene, ing to claim 1 to a plant to enhance the plants health, yield, (2) 4-(C-C haloalkyl)-1-halobenzene, vigor, quality, or tolerance, at a time when pest activity is low. (3) 4-(C-C alkoxy)-1-halobenzene, 106. A molecule having the following formula (4) 4-(C-C haloalkoxy)-1-halobenzene, (5) 4-(C-C alkylthio)-1-halobenzene, and (6) 4-(C-C haloalkylthio)-1-halobenzene, Arx N-N (hereafter symbolized as “Arx') with

wherein Arx is 4-(C-C alkyl)phenyl, 4-(C-Chaloalkyl) phenyl, 4-(C-C alkoxy)phenyl, 4-(C-C haloalkoxy) phenyl, 4-(C-C alkylthio)phenyl, or 4-(C-C, H haloalkylthio)phenyl. 107. A molecule according to claim 106 wherein said mol (b) 3-(bromo or chloro)-1H-1,2,4-triazole, ecule is to produce