WO1999031072A1

WO1999031072A1 - Cyclohexylamine arthropodicides and fungicides

Info

Publication number: WO1999031072A1
Application number: PCT/US1998/026013
Authority: WO
Inventors: Kevin Chun Lee
Original assignee: E.I. Du Pont De Nemours And Company
Priority date: 1997-12-18
Filing date: 1998-12-08
Publication date: 1999-06-24
Also published as: AU1631699A

Abstract

Compounds of Formula (I), and their agriculturally suitable salts, are disclosed which are useful as arthropodicides and fungicides wherein G is selected from the group consisting of (G-1) and (G-2); Y is a direct bond or C1-C4 alkylene optionally substituted with C1-C4 alkyl; X is O, NR7 or S(O)¿p?; each Z is independently selected from N and CR?3¿; each Z1 is independently selected from O, S and NR?8; and R1-R8¿, m and p are as defined in the disclosure. Also disclosed are compositions containing the compounds of Formula (I) and a method for controlling arthropods which involves contacting the arthropods or their environment with an effective amount of a compound of Formula (I). Also disclosed are compositions containing the compounds of Formula (I) and a method for controlling plant diseases caused by fungal plant pathogens which involves applying an effective amount of a compound of Formula (I).

Description

TITLE

CYCLOHEXYLAMINE ARTHROPODICIDES AND FUNGICIDES

BACKGROUND OF THE INVENTION

This invention relates to certain cyclohexylamine arthropodicides and fungicides, agriculturally suitable salts and compositions, and methods of their use as arthropodicides and fungicides.

The control of arthropod pests is extremely important in achieving high crop efficiency. Arthropod damage to growing and stored agronomic crops can cause significant reduction in productivity and thereby result in increased costs to the consumer. The control of arthropod pests in forestry, greenhouse crops, ornamentals, nursery crops, stored food and fiber products, livestock, household, and public and animal health is also important. The control of plant diseases caused by fungal plant pathogens is also extremely important in achieving high crop efficiency. Plant disease damage to ornamental, vegetable, field, cereal, and fruit crops can cause significant reduction in productivity and thereby result in increased costs to the consumers. Many products are commercially available for these purposes, but the need continues for new compounds which are more effective, less costly, less toxic, environmentally safer or have different modes of action.

WO 96/06086 discloses compounds of Formula i and their composition and method of use as pest control agents

wherein Q is

Qa, Qb or Qc;

R¹ is halogen, C₂-C₅ acyloxy, OH, C_j-C-_j alkoxy or C₁-C4 alkylthio; and

R² is Ci-Cg alkyl, phenyl, pyrimidinylamino, Cj-Cg alkoxy, COOR³, amino or

NHCOR⁴. The cyclohexylamines of the present invention are not disclosed in this publication. SUMMARY OF THE INVENTION This invention is directed to compounds of Formula I including all geometric and stereoisomers, agriculturally suitable salts thereof, agricultural compositions containing them and their use as arthropodicides and fungicides,

I wherein:

G is selected from the group consisting of

G-l G-2

Y is a direct bond or C1 -C4 alkylene optionally substituted with Cj-C4 alkyl;

X is O, NR⁷ or S(O)_p; each Z is independently selected from N and CR³; each Z¹ is independently selected from O, S and NR⁸; each R¹ is independently selected from the group consisting of H, halogen, C1-C4 alkyl, C1 -C4 haloalkyl, C -Cg cycloalkyi, C3-C.5 halocycloalkyl, C1-C4 alkoxy, C_rC₄ haloalkoxy and R⁹S(O)_p; each R² is independently selected from the group consisting of H, CF₃, C_j alkyl optionally substituted with one or two R¹⁰ substituents, C2-C4 alkyl, R¹0CH₂CH₂-, (RlO)2CHCH2^:» R¹⁰CH₂CH(Rl°)-, CH₃C(R¹⁰)₂-, C3-C4 haloalkyl, C₂-C₄ alkenyl, C2-C4 haloalkenyl, C2-C4 alkynyl, C2-C4 haloalkynyl, C1-C4 alkoxy, C\-C^ haloalkoxy, halogen, hydroxy, C2-C4 alkylcarbonyl, C2-C4 haloalkylcarbonyl, C_β-Cg cycloalkyi, C3-C6 halocycloalkyl, cyano, nitro, thiocyanato, C2-C4 alkoxycarbonyl, C2-C4 haloalkoxycarbonyl, C1-C4 alkylamino, C2-C4 dialkylamino and R^{1 1}S(O)_p; each R³ is independently selected from the group consisting of H, C1-C4 alkyl optionally substituted with one or two R¹⁰, CF₃, C2-C4 alkenyl, C2-C4 haloalkenyl, C2-C4 alkynyl, C2-C4 haloalkynyl, C C4 alkoxy, C1-C4 haloalkoxy, halogen, hydroxy, C2-C4 alkylcarbonyl, C2-C4 haloalkylcarbonyl, C3-C6 cycloalkyi, C3-C6 halocycloalkyl, cyano, nitro, thiocyanato, C2-C4 alkoxycarbonyl, C2-C₄ haloalkoxycarbonyl, C1-C4 alkylamino, C₂-C₄ dialkylamino and R^{1 1}S(O)_p; or R² and R³ with the carbon atoms to which they are attached are taken together to form a: (1) 5- or 6-membered unsaturated carbocyclic ring optionally substituted with

R¹²; or (2) 5- or 6-membered unsaturated heterocyclic ring optionally substituted with R¹² containing at least one of the atoms selected from O, N and S in the ring; or R² and R³ with the carbon atoms to which they are attached are taken together to form a: (1) 5-, 6- or 7-membered saturated carbocyclic ring optionally substituted with a

Cj-C4 alkyl group; or (2) 5-, 6- or 7-membered saturated heterocyclic ring optionally substituted with a C1-C4 alkyl group containing one or two O and/or S(O)_p atoms in the ring; each R⁴ is independently selected from the group consisting of C₁-C4 alkyl and

C₁-C₄ alkoxy; R⁵ is H, C_rC₆ alkyl optionally substituted with R¹³, C_rC₆ haloalkyl, C₃-C₆ cycloalkyi, C3-C6 halocycloalkyl, C3-C6 alkenyl, C3-C6 haloalkenyl, C₃-Cg alkynyl, C3-C6 haloalkynyl, C Cg alkoxy, Cj-Cg haloalkoxy, C3-C6 alkynyloxy,

C₃-Cg haloalkenyloxy, Q-t-Cg cycloalkylalkoxy, C2-C6-cyanoalkoxy, phenylmethoxy, C₂-C6 alkylcarbonyl, C3-C6 cycloalkylcarbonyl, phenylmethoxycarbonyl, formyl, C2-Cg haloalkylcarbonyl, C2-C.5 alkoxycarbonyl, C₂-C6 haloalkoxycarbonyl, C₂-C6 alkylaminocarbonyl, C₃-C₈ dialkylaminocarbonyl, hydroxy, R¹⁴S(O)_p, (R¹⁵)^¹⁶)P(O), phenyl or benzoyl each optionally substituted with one, two or three R¹⁷ substituents, naphthalenyl or a 5- or 6-membered unsaturated heterocyclic ring optionally substituted with one or two R¹⁷ substituents; R⁶ is G, H, C-I -CG alkyl, C*(-C₆ haloalkyl, C₂-C₆ alkylcarbonyl, C₂-C₆ alkoxycarbonyl, C2-C6 alkylaminocarbonyl, C3-Cg dialkylaminocarbonyl, R¹⁴S(O)_p,

(R¹⁵)(R¹⁶)P(O), phenyl optionally substituted with one, two or three R¹⁷ substituents, naphthalenyl or a 5- or 6-membered unsaturated heterocyclic ring optionally substituted with one or two R¹⁷ substituents; or R⁵ and R⁶ with the nitrogen atom to which they are attached are taken together to form a:

(1) 5- or 6-membered unsaturated heterocyclic ring optionally containing an additional heteroatom selected from N, O and S in the ring and optionally containing one or two ring members C(=O), the ring optionally substituted with one or two R¹⁸ substituents;

(2) 5-, 6- or 7-membered saturated heterocyclic ring optionally containing an additional heteroatom selected from N, O and S(O)_p in the ring and optionally containing one or two ring members C(=O), the ring optionally substituted with one or two R¹⁸ substituents; or

(3) 9-, 10- or 11-membered fused bicyclic ring system optionally containing an additional heteroatom selected from N, O and S(O)_p in the ring and optionally containing one or two ring members C(=O), the ring optionally substituted with one or two R¹⁸ substituents;

R⁷ is H, C_rC₄ alkyl, C₂-C₄ alkenyl, C₂-C₄ alkynyl, C₂-C₄ alkylcarbonyl, C₂-C₄ alkoxycarbonyl, C2-C4 alkylaminocarbonyl or C₃-Cg dialkylaminocarbonyl; each R⁸ is independently selected from the group H, C**-C4 alkyl and C3-C6 cycloalkyi; each R⁹ is independently selected from the group C1-C₄ alkyl and C_j-C4 haloalkyl; each R¹⁰ is independently selected from the group consisting of halogen, C1-C4 alkoxy,

C C₄ haloalkoxy, C2-Cg alkylcarbonyl, C2-Cg alkoxycarbonyl, hydroxy, cyano, nitro, thiocyanato and R⁹S(O)_p; each R¹¹ is independently selected from the group C1-C₄ alkyl and C₁-C4 haloalkyl; each R¹² is independently selected from the group consisting of halogen, cyano, nitro, hydroxy, C1-C4 alkyl, C1-C4 haloalkyl, C C4 alkoxy, C_j-C₄ haloalkoxy, C₁-C₄ alkylthio, C₁-C₄ alkylsulfinyl and C**-C₄ alkylsulfonyl; each R¹³ is independently selected from the group consisting of halogen, hydroxy, cyano, nitro, C3-C.5 cycloalkyi, C1-C4 alkoxy, C₁-C4 haloalkoxy, phenylmethoxy, C2-C6 alkylcarbonyl, C₂-Cg haloalkylcarbonyl, C2-C alkoxycarbonyl, C2-Cg haloalkoxycarbonyl, C-*-C₄ alkylthio, C1-C4 alkylsulfinyl,

C1-C4 alkylsulfonyl, C1-C4 haloalkylsulfonyl, aminocarbonyl, C2-Cg alkylaminocarbonyl, C3-Cg dialkylaminocarbonyl, R⁹S(O)_p and phenyl optionally substituted with one, two or three R¹⁷ substituents; each R¹⁴ is independently selected from the group consisting of C1-C4 alkyl, C₁-C4 haloalkyl and phenyl optionally substituted with one, two or three R¹⁷ substituents; each R¹⁵ and each R¹⁶ are independently selected from the group consisting of C1-C₄ alkyl, C_j-C4 haloalkyl, C1-C4 alkoxy and C_j^ haloalkoxy; each R¹⁷ is independently selected from the group consisting of halogen, cyano, nitro, hydroxy, C1-C₄ alkyl, C1-C₄ haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C*₍-C4 alkylthio, C1-C4 alkylsulfinyl and C1-C₄ alkylsulfonyl; each R¹⁸ is independently selected from the group consisting of halogen, cyano, nitro, hydroxy, C1-C₄ alkyl, C1-C4 haloalkyl, C₁-C₄ alkoxy, C₁-C₄ haloalkoxy, R¹⁴S(O)_p, C₂-C₆ alkylcarbonyl, C₂-C₆ alkoxycarbonyl, C₂-C₆ alkylaminocarbonyl, C3~Cg dialkylaminocarbonyl and phenyl, phenylmethyl or pyridinyl each optionally substituted with one, two or three R¹⁷ substituents; m is 0, 1 or 2; and each p is independently selected from 0, 1 and 2.

In the above recitations, the term "alkyl", used either alone or in compound words such as "haloalkyl" includes straight-chain or branched alkyl, such as, methyl, ethyl, «-propyl, /-propyl, or the different butyl, pentyl or hexyl isomers. "Alkenyl" includes straight-chain or branched alkenes such as ethenyl, 1-propenyl, 2-propenyl, and the different butenyl, pentenyl or hexenyl isomers. "Alkenyl" also includes polyenes such as 1 ,2-propadienyl and

2,4-hexadienyl. "Alkynyl" includes straight-chain or branched alkynes such as ethynyl, 1-propynyl, 2-propynyl and the different butynyl, pentynyl or hexynyl isomers. "Alkynyl" can also include moieties comprised of multiple triple bonds such as 2,5-hexadiynyl. "Alkylene" denotes a straight-chain or branched alkanediyl. Examples of "alkylene" include CH₂, CH₂CH₂, CH(CH₃), CH₂CH₂CH₂, CH₂CH(CH₃) and the different butylene isomers. "Alkoxy" includes, for example, methoxy, ethoxy, -propyloxy, isopropyloxy and the different butoxy, pentoxy or hexyloxy isomers. "Alkynyloxy" includes straight-chain or branched alkynyloxy moieties. Examples of "alkynyloxy" include HC≡CCH₂O, CH₃C≡CCH₂O and CH₃C≡CCH₂CH₂O. "Cyanoalkoxy" denotes cyano substitution on alkoxy. Examples of "cyanoalkoxy" include NCCH₂O and NCCH₂CH₂O.

"Alkylamino" denotes an amino group substituted with one alkyl group. Examples of "alkylamino" include CH₃NH, CH₃CH₂NH, CH₃CH₂CH₂NH, (CH₃)₂CHNH and the different butylamino isomers. "Dialkylamino", and the like, are defined analogously to the above examples. Examples of "dialkylamino" include (CH₃)₂N and (CH₃)(CH₃CH₂)N. "Dialkylaminocarbonyl" denotes dialkylamino substitution on carbonyl. Examples of "dialkylaminocarbonyl" include (CH₃)₂NC(=O), (CH₃CH₂)2NC(=O) and (CH₃)(CH₂CH₂)NC(*=O). "Alkylaminocarbonyl", "aminocarbonyl" and the like, are defined analogously to the above examples. "Phenylmethoxycarbonyl" denotes phenylmethoxy substitution on carbonyl [i.e., C6H5CH₂OC(=O)]. "Phenylcarbonyl" is defined analogously to the above examples.

"Cycloalkyi" includes, for example, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl. "Cycloalkylalkoxy" denotes cycloalkyi substitution on alkoxy. Examples of "cycloalkylalkoxy" include cyclopropyl-CH₂O and cyclohexyl-C^O. "Cycloalkylcarbonyl" denotes cycloalkyi substitution on carbonyl. Examples of "cycloalkylcarbonyl" include cyclopropyl-C(=O) and cyclohexyl-C(=O).

Examples of G-l heterocycles include optionally substituted 4-pyrimidinyl; 5,6,7,8- tetrahydro-4-quinazolinyl; 4-quinazolinyl; thieno[3,2-d]pyrimidin-4-yl; and thieno[2,3- d]pyrimidin-4-yl. Examples of G-2 heterocycles include optionally substituted 5- isothiazolyl; l,2,4-thiadiazol-5-yl; 5-isoxazolyl; lH-pyrazol-5-yl; l,2,4-oxadiazol-5-yl; and lH-l,2,4-triazol-5-yl.

The term "unsaturated carbocyclic ring" includes fully aromatic carbocycles (where aromatic indicates that the Ηϋckel rule is satisfied). The term "saturated carbocyclic ring" denotes fully saturated carbocycles. The term "unsaturated heterocyclic ring" includes fully aromatic heterocycles (where aromatic indicates that the Ηϋckel rule is satisfied). The term "saturated heterocyclic ring" denotes fully saturated heterocycles.

Examples of R⁵ and/or R⁶ as a "5- or 6-membered unsaturated heterocyclic ring" include optionally substituted 2-pyridinyl, 3-pyridinyl, 4-pyridinyl and 2-thienyl. An example of "R⁵ and R⁶ with the nitrogen atom at which they are attached taken together to for a 5- or 6-membered unsaturated heterocyclic ring optionally containing an additional heteroatom selected from N, O and S in the ring and optionally containing one or two ring members C(=O)" includes optionally substituted 2,5-dihydro-2,5-dioxo-lH- pyrrol-1-yl. Examples of "R⁵ and R⁶ with the nitrogen atom at which they are attached taken together to for a 5-, 6- or 7-membered saturated heterocyclic ring(s) optionally containing an additional heteroatom selected from N, O and S(O)_p in the ring and optionally containing one or two ring members C(=O)" include optionally substituted 1 -piperidinyl, 4-morpholinyl, 1-piperazinyl and 2,5-dioxo-l-pyrrolidinyl. Examples of "R⁵ and R⁶ with the nitrogen atom at which they are attached taken together to for a 9-, 10- or 11 -membered fused bicyclic ring system optionally containing an additional heteroatom selected from N, O and S(O)_p in the ring and optionally containing one or two ring members C(=O)" include optionally substituted l,3-dihydro-l,3-dioxo-2H- isoindol-2-yl and octahydro-l,3-dioxo-2H-isoindol-2-yl. The term "halogen", either alone or in compound words such as "haloalkyl", includes fluorine, chlorine, bromine or iodine. Further, when used in compound words such as "haloalkyl", said alkyl may be partially or fully substituted with halogen atoms which may be the same or different. Examples of "haloalkyl" include F₃C, C1CΗ₂, CF₃CH₂ and CF₃CC1₂. The terms "haloalkenyl", "haloalkynyl", "haloalkoxy", "halocycloalkyl", "haloalkylcarbonyl" "haloalkoxycarbonyl" and the like, are defined analogously to the term "haloalkyl".

Examples of "haloalkenyl" include (C1)₂C=CHCH₂ and CF₃CH=CHCH₂. Examples of "haloalkynyl" include HC≡CCHCl, CF₃C≡C, CC1₃C≡C and FCH₂C≡CCH₂. Examples of "haloalkoxy" include CF₃O, CCl₃CH₂O, HCF₂CH₂CH₂O and CF₃CH₂O. Examples of "halocycloalkyl" include 2-chlorocyclopropyl and 2-fluorocyclohexyl. Examples of "haloalkylcarbonyl" include CF₃C(=O), CCl₃CH₂C(=O) and HCF₂CH₂CH₂C(*=O). Examples of "haloalkoxycarbonyl" include CF₃OC(=O), CCl₃CH₂OC(=O) and HCF2CH₂CH₂OC(=O). "Haloalkenyloxy" denotes haloalkenyl substitution on alkoxy. Examples of "haloalkenyloxy" include CF₂=CF(CH₂)₂O and CF₂=CFCH₂O. "Alkylthio" includes branched or straight-chain alkylthio moieties such as methylthio, ethylthio, and the different propylthio and butylthio isomers. "Alkylsulfinyl" includes both enantiomers of an alkylsulfinyl group. Examples of "alkylsulfinyl" include CH₃S(O), CH₃CH₂S(O), CH₃CH₂CH₂S(O), (CH₃)₂CHS(O) and the different butylsulfinyl isomers. Examples of "alkylsulfonyl" include CH₃S(O)₂, CH₃CH₂S(O)₂, CH₃CH₂CH2S(O)₂, (CH₃)₂CHS(O)₂ and the different butylsulfonyl isomers.

The total number of carbon atoms in a substituent group is indicated by the "Cj-C;" prefix where i and j are numbers from 1 to 8. For example, C₂ alkylcarbonyl designates C(O)CH₃ and C₄ alkylcarbonyl designates C(O)CH₂CH₂CH₃ and C(O)CH(CH₃)₂. Examples of "alkoxycarbonyl" include CH₃OC(=O), CH₃CH₂OC(=O),

CH₃CH₂CH₂OC(=O), (CH₃)₂CHOC(=O) and the different butoxy-, pentoxycarbonyl, etc. isomers.

When a group contains a substituent which can be hydrogen, for example R² or R⁷, then, when this substituent is taken as hydrogen, it is recognized that this is equivalent to said group being unsubstituted. When a group is optionally substituted with a substituent, for example with R¹⁷, then, when the group is not substituted with that substituent, it is recognized that this is equivalent to said group having a hydrogen substituent.

Compounds of this invention can exist as one or more stereoisomers. The various stereoisomers include enantiomers, diastereomers, atropisomers and geometric isomers (e.g., cis and trans cyclohexane isomers). For 1 ,4-disubstituted cyclohexanes, the cis isomer is preferred. One skilled in the art will appreciate that one stereoisomer may be more active and/or may exhibit beneficial effects when enriched relative to the other stereoisomer(s) or when separated from the other stereoisomer(s). Additionally, the skilled artisan knows how to separate, enrich, and/or to selectively prepare said stereoisomers. Accordingly, the present invention comprises compounds selected from Formula I and agriculturally suitable salts thereof. The compounds of the invention may be present as a mixture of stereoisomers, individual stereoisomers, or as an optically active form.

The salts of the compounds of the invention include acid-addition salts with inorganic or organic acids such as hydrobromic, hydrochloric, nitric, phosphoric, sulfuric, acetic, butyric, fumaric, lactic, maleic, malonic, oxalic, propionic, salicylic, tartaric,

4-toluenesulfonic or valeric acids. The salts of the compounds of the invention also include quaternary salts formed with alkyl halides (e.g., iodomethane, iodoethane or 1-chlorododecane). The salts of the compounds of the invention also include those formed with organic bases (e.g., pyridine, ammonia or triethylamine) or inorganic bases (e.g., hydrides, hydroxides or carbonates of sodium, potassium, lithium, calcium, magnesium or barium) when the compound contains an acidic group such as a carboxylic acid or phenol. Preferred compounds for reasons of better activity and/or ease of synthesis are: Preferred 1. Compounds of Formula I above, and agriculturally suitable salts thereof, wherein G is G-1;

Y is a direct bond; X is NR⁷;

RUs H or -C4 alkyl;

R² is C_rC₄ alkyl, CF₃, C₃-C₆ cycloalkyi, Rl°CH₂CH₂-, (R^lO)₂CHCH₂-,

R¹⁰CH₂CH(R¹⁰)-, CH₃C(R¹⁰)₂-, or C, alkyl optionally substituted with C1-C4 alkoxy; R³ is C₁-C4 alkyl, CF₃, C_j alkyl optionally substituted with C C₄ alkoxy,

C₂-C₄ alkenyl, C₂-C4 alkynyl, C_J-C4 alkoxy, C1-C4 haloalkoxy, halogen, hydroxy, cyano, nitro, thiocyanato or R¹¹S(O)_p; and m is 0. Preferred 2. Compounds of Preferred 1 above, and agriculturally suitable salts thereof, wherein

R⁵ is H, C_rC₆ alkyl optionally substituted with R¹³, C_rC₆ haloalkyl, C₃-C₆ cycloalkyi, C₃-C₆ alkenyl, C₃-C₆ haloalkenyl, C₃-Cg alkynyl, C_j-Cg alkoxy, Cj-Cg haloalkoxy, C3-C6 alkynyloxy, C₃-Cg haloalkenyloxy, C₄-C cycloalkylalkoxy, C₂-Cg-cyanoalkoxy, phenylmethoxy, C -Cg alkylcarbonyl, C₃-Cg cycloalkylcarbonyl, phenylmethoxycarbonyl, formyl, C₂-Cg haloalkylcarbonyl, C -Cg alkoxycarbonyl, C₂-C₆ haloalkoxycarbonyl, C₂-C6 alkylaminocarbonyl, C₃-C₈ dialkylaminocarbonyl, hydroxy, R¹⁴S(O)_p, or (R¹⁵)(R¹⁶)P(O); R⁶ is G, H, C_rC₆ alkyl, C_rC₆ haloalkyl, C₂-C₆ alkylcarbonyl, C₂-C₆ alkoxycarbonyl, C₂-C6 alkylaminocarbonyl, C -Cg dialkylaminocarbonyl, R¹⁴S(O)_p, (R¹⁵)(R¹⁶)P(O), phenyl optionally substituted with one, two or three R¹⁷ substituents, naphthalenyl or a 5- or 6-membered unsaturated heterocyclic ring optionally substituted with one or two R¹⁷ substituents; or R⁵ and R⁶ with the nitrogen atom to which they are attached are taken together to form a 1-piperazinyl; 2,5-dioxo-l-pyrrolidinyl; 2,5-dihydro- 2,5-dioxo-lH-pyrrol-l-yl; or 1,3-dihydro-l ,3-dioxo-2H-isoindol-2-yl; ring each optionally substituted with R¹⁸. Preferred 3. Compounds of Preferred 2 above, and agriculturally suitable salts thereof, wherein

R⁵ is Η, C_rC₆ alkyl optionally substituted with R¹³, C_rC₆ haloalkyl, C₃-C₆ cycloalkyi, C₃-C₆ alkenyl, C3-C6 haloalkenyl, C3-C6 alkynyl, C_j-Cg alkoxy, C_j-Cg haloalkoxy, C3-C₆ alkynyloxy, C3-C6 haloalkenyloxy, C4-C6 cycloalkylalkoxy, C -C-5-cyanoalkoxy, phenylmethoxy, C₂-Cg alkylcarbonyl, C₃-Cg cycloalkylcarbonyl, phenylmethoxycarbonyl, formyl, C₂-C6 haloalkylcarbonyl, C₂-Cg alkoxycarbonyl, C₂-C6 haloalkoxycarbonyl, C₂-C6 alkylaminocarbonyl, C₃-Cg dialkylaminocarbonyl, hydroxy, R¹⁴S(O)_p, or (R¹⁵)(R¹⁶)P(O);

R⁶ is G, H, C_rC₆ alkyl, C_rC₆ haloalkyl, C₂-C₆ alkylcarbonyl, C₂-C₆ alkoxycarbonyl, C2-Cg alkylaminocarbonyl, C₃-Cg dialkylaminocarbonyl, phenyl optionally substituted with one, two or three R¹⁷ substituents, or pyridinyl optionally substituted with one or two R¹⁷ substituents; or

R⁵ and R⁶ with the nitrogen atom to which they are attached are taken together to form a 1-piperazinyl; 2,5-dioxo-l-pyrrolidinyl; 2,5-dihydro- 2,5-dioxo-lH-pyrrol-l-yl; or l,3-dihydro-l,3-dioxo-2H-isoindol-2-yl; ring each optionally substituted with R¹⁸. Preferred 4. Compounds of Preferred 2 above, and agriculturally suitable salts thereof, wherein

R⁵ is Η, C_rC₆ alkyl optionally substituted with R¹³, C_rC₆ haloalkyl, C₃-C₆ cycloalkyi, C3-C6 alkenyl, C₃-Cg haloalkenyl, C3-C6 alkynyl, Cj-Cg alkoxy, C_j-Cg haloalkoxy, C₃-Cg alkynyloxy, C3-C6 haloalkenyloxy, C4-C6 cycloalkylalkoxy, C₂-C6-cyanoalkoxy, phenylmethoxy, C₂-C₆ alkylcarbonyl, C3-C6 cycloalkylcarbonyl, phenylmethoxycarbonyl, formyl, C2-Cg haloalkylcarbonyl, C₂-C₆ alkoxycarbonyl, C2-Cg haloalkoxycarbonyl, C2-Cg alkylaminocarbonyl, C3-Cg dialkylaminocarbonyl, hydroxy, R¹⁴S(O)_p, or (R¹⁵)(R¹⁶)P(O); R6 is Η, C_rC₆ alkyl, C_rC₆ haloalkyl, C₂-C₆ alkylcarbonyl, C₂-C₆ alkoxycarbonyl, C2-Cg alkylaminocarbonyl, C₃-Cg dialkylaminocarbonyl, phenyl optionally substituted with one, two or three R¹⁷ substituents, or pyridinyl optionally substituted with one or two R¹⁷ substituents; or R⁵ and R⁶ with the nitrogen atom to which they are attached are taken together to form a 1-piperazinyl; 2,5-dioxo-l-pyrrolidinyl; 2,5-dihydro- 2,5-dioxo- lH-pyrrol- 1 -yl; or 1 ,3-dihydro- 1 ,3-dioxo-2H-isoindol-2-yl; ring each optionally substituted with R¹⁸. Prefened 5. Compounds of Formula I above, and agriculturally suitable salts thereof, wherein

G is G-2;

Y is a direct bond;

X is NR⁷; Z¹ is S;

R² is C1-C4 alkyl, C_j-Q^ haloalkoxy, C3-C₆ cycloalkyi or C_j alkyl optionally substituted with C₁-C4 alkoxy; R³ is C1-C4 alkyl, CF₃, C-* alkyl optionally substituted with C*₍-C4 alkoxy, 2-C4 alkenyl, C2-C4 alkynyl, C1-C₄ alkoxy, C₁-C₄ haloalkoxy, halogen, hydroxy, cyano, nitro, thiocyanato or R^πS(O)_p; and m is 0. This invention also relates to arthropodicidal compositions comprising arthropodicidally effective amounts of the compounds of the invention and at least one of a surfactant, a solid diluent or a liquid diluent. The preferred compositions of the present invention are those which comprise the above preferred compounds.

This invention also relates to a method for controlling arthropods comprising contacting the arthropods or their environment with an arthropodicidally effective amount of the compounds of the invention (e.g., as a composition described herein). The preferred methods of use are those involving the above preferred compounds.

This invention also relates to fungicidal compositions comprising fungicidally effective amounts of the compounds of the invention and at least one of a surfactant, a solid diluent or a liquid diluent. The preferred compositions of the present invention are those which comprise the above preferred compounds. This invention also relates to a method for controlling plant diseases caused by fungal plant pathogens comprising applying to the plant or portion thereof, or to the plant seed or seedling, a fungicidally effective amount of the compounds of the invention (e.g., as a composition described herein). The preferred methods of use are those involving the above preferred compounds. DETAILS OF THE INVENTION

The compounds of Formula I can be prepared by one or more of the following methods and variations as described in Schemes 1-17. The definitions of G, G-1, G-2, Y, X, Z, Z¹, m, p and R---R²² in the compounds of Formulae I and 1-23 below are as defined above (including the Summary of the Invention) or below (including the Schemes). Compounds of Formulae la-lb are various subsets of the compounds of Formula I, and all substituents for Formulae la-lb are as defined above for Formula I.

Compounds of Formula I can be prepared by reaction of a heterocycle of Formula 1 with a compound of Formula 2 in the presence of an acid acceptor or a base. Typical bases can be triethylamine, pyridine, sodium hydride or potassium carbonate. The reaction can be carried out in the presence of a solvent such as toluene, tetrahydrofuran, acetonitrile,

N,N-dimethylformamide or isopropanol. The reaction can be conducted in the temperature range of 0 °C to the reflux temperature of the solvent. Scheme 1 depicts this transformation. Scheme 1

X = NR⁷, O, S

E = F, Cl, Br, I, S0₂Me, S0₂Ar,

OS0₂Me, OS0₂CF₃, OS0₂Ar (e.g., OS0₂(4-CH₃-Ph))

Alternatively, compounds of Formula I can be prepared by reaction of a heterocycle of Formula 3 with a compound of Formula 4 in the presence of a base. Typical bases can include sodium hydride, potassium tert-butoxide or potassium carbonate. Typical solvents for the reaction include ether, tetrahydrofuran, acetonitrile or NN-dimethylformamide. The reaction can be conducted in the temperature range of 0 °C to the reflux temperature of the particular solvent. Scheme 2 depicts this transformation.

Scheme 2

L = F, Cl, Br, I, OS0₂Me,

X -^ NR', 0, S OS0₂CF₃, OS0₂Ar

Alternatively, compounds of Formula I can be prepared by reaction of a heterocycle of Formula 3 (X = NR⁷) with a ketone of Formula 5 in the presence of a reducing agent. One skilled in the art will recognize said transformations as reductive aminations. A typical example of a reductive amination is described by Bagley et al. (J. Med. Chem. 1989, 32, 663-671). The desired reductions can be performed with hydride agents such as sodium borohydride, sodium cyanoborohydride or sodium triacetoxyborohydride, or by catalytic hydrogenation (Hudlicky, M., Reductions in Organic Chemistry; Academic: New York, 1984). The reaction is typically conducted in methanol, ethanol, ether, tetrahydrofuran, dichloromethane, 1 ,2-dichloroethane or toluene in the presence of an additive such as hydrochloric or acetic acid. Scheme 3 depicts this transformation. Scheme 3

5

Alternatively, compounds of Formula I can be prepared by reaction of a heterocycle of

Formula 3 with an alcohol of Formula 2 (X = O) in the presence of a phosphine and an azodicarboxylate. One skilled in the art will recognize said reactions as Mitsunobu reactions

(Hughes, D. L. Org. Prep. Proc. Int. 1996, 28, 127-164). Typical phosphines can include triphenylphosphine, tributylphosphine or trimethylphosphite. Typical azodicarboxylates can include diethyl azodicarboxylate (DEAD) or diisopropyl azodicarboxylate (DIAD). The reaction is typically conducted in ether, tetrahydrofuran, benzene or toluene. Scheme 4 depicts this transformation.

Scheme 4

3 ( X = NR⁷, 0, S ) + 2 ( X = 0 ) *- I ( X = NR⁷, 0, S )

Alternatively, compounds of Formula I can be prepared by reaction of an amine of Formula 6 with a compound of Formula 7 in the presence of a base. Typical bases can be triethylamine, pyridine, potassium carbonate or sodium bicarbonate. This reaction can be repeated with compounds of Formula 8 in the presence of another base to provide compounds of Formula I (R⁶ is other than H). Typical bases for the second reaction can include triethylamine, potassium carbonate, sodium hydride or potassium tert-butoxide. Typical solvents for these reactions can be dichloromethane, ether, tetrahydrofuran, toluene, acetonitrile or N,N-dimethylformamide. The reaction can be conducted in the temperature range of 0 °C to the reflux temperature of the solvent. When R⁶ is a phenyl group, the reaction can be carried out in the presence of either a palladium or a copper catalyst. Such reactions are well known to one skilled in the art. For example, conversion of aryl bromides into arylamines in the presence of a palladium catalyst is described by Buchwald et al.

(Angew. Chem. Int. Ed. Engl. 1995, 34, 1348-1350). Compounds of Formulae 7 and 8 can be obtained from commercial sources or prepared by conventional methods well known to one skilled in the art. Scheme 5 depicts this transformation. Scheme 5

I ( R° is other than H )

L = F, O, Br, I, OSθ2Me, OSO2CF3, OSθ2Ar

Alternatively, compounds of Formula I can be prepared by reductive amination of an amine of Formula 6 with a carbonyl compound of Formula 9. The reaction can be carried out in a manner analogous to Scheme 3 reactions to provide compounds of Formula I (R⁶ is H). The carbonyl compounds of Formula 9 can be obtained from commercial sources or prepared by conventional methods well known to one skilled in the art. Scheme 6 depicts this transformation.

Scheme 6

R¹⁹ = H, Me, Et R²⁰ = H, Me, Et, Ph

Alternatively, compounds of Formula I can be prepared by reductive amination of a ketone of Formula 10 with an amine of Formula 11. The reaction can be carried out in a manner analogous to Scheme 3 reactions. The reaction also can be carried out in a stepwise manner. Such alternative procedures are well known to one skilled in the art. The amines of Formula 11 can be obtained from commercial sources or prepared by conventional methods well known to one skilled in the art. Scheme 7 depicts this transformation.

Scheme 7

10 11 amine

Alternatively, compounds of Formula I can be prepared by displacement of a leaving group in a compound of Formula 12 by an amine of Formula 11 in the presence of a base. The reaction can be carried out in a manner analogous to Scheme 5 reactions. Scheme 8 depicts this transformation.

Scheme 8

12 11

L = F, Cl, Br, I, OS0₂Me, amine

OS0₂CF₃, OS0₂Ar

Alternatively, compounds of Formula I can be prepared by reaction of an alcohol of Formula 13 with an activated amide of Formula 14 under Mitsunobu conditions. Mitsunobu reactions were already described in detail in Scheme 4. The amides of Formula 14 can be obtained from commercial sources or prepared by conventional methods well known to one skilled in the art. Scheme 9 depicts this transformation.

Scheme 9

13 14 amide

Alternatively, compounds of Formula Ia can be prepared by reaction of a heterocycle of Formula 1 with a diaminocyclohexane of Formula 15 in the presence of an acid acceptor or a base. The reaction is generally carried out with two or more equivalents of a heterocycle of Formula 1 in the presence of an excess amount of a base. Typical bases can be triethylamine, N,N-diisopropylethylamine, pyridine or potassium carbonate. The reaction can be carried out in the presence of a solvent such as toluene, tetrahydrofuran, acetonitrile, N,N-dimethylformamide or isopropanol. Typical reaction temperature can range from 0 °C to the reflux temperature of the particular solvent. The product can be derivatized further by reaction with compounds of Formula 7 in the presence of a base to provide compounds of Formula Ib (R⁵ is other than H). Typical bases for this can include sodium hydride, N,N-diisopropylethylamine, potassium tert-butoxide or potassium carbonate. Typical solvents can be ether, tetrahydrofuran, toluene, acetonitrile or NN-dimethylformamide. The reaction can be conducted in the temperature range of 0 °C to the reflux temperature of the solvent. The diaminocyclohexanes of Formula 15 can be obtained from commercial sources or prepared by conventional methods well known to one skilled in the art. An example of such preparation of diaminocyclohexanes is described by Johnston et al. (J Med. Chem. 1977, 20, 279-290). Scheme 10 depicts this transformation.

Scheme 10

15 Ia ( RZs H )

Ib ( R³ is other than H )

Heterocycles of Formulae 1 and 3 can be prepared by a variety of literature methods or can be obtained from commercial sources. For example, pyrimidines of Formulae 1 and 3 can be prepared by procedures taught in U.S. Patent 4,977,264 and Foster et al. (Org. Synth. 1955, 35, 80-82), respectively. One skilled in the art will recognize that heterocycles of Formulae 1 and 3 can be interconverted by well-known chemistry. For example, heterocycles of Formula 1 (E = Cl, Br) can be converted into heterocycles of Formula 3 (X = O) by hydrolysis. Conversely, heterocycles of Formula 3 (X = NH) can be converted into heterocycles of Formula 1 (E = Cl, Br) by a Sandmeyer reaction (March, J. Advanced Organic Chemistry; 3rd ed.; John Wiley & Sons: New York, 1985; pp 647-648).

Compounds of Formula 2 can be prepared by reductive amination of a ketone of Formula 5 with an amine of Formula 16. The reaction can be carried out in a manner analogous to Scheme 3 reactions. Scheme 11 depicts this transformation.

Scheme 11

H₂NR^; 2 ( X-Y = NR⁷ )

16

Alternatively, compounds of Formula 2 (X = NR⁷) can be prepared by reaction of a compound of Formula 4 with an amine of Formula 16 in the presence of a base. The reaction can be carried out in a manner analogous to Scheme 5 reactions. Compounds of Formula 2 (X = S) can be prepared by reaction of a compound of Formula 4 with a sulfur nucleophile of Formula 17 in the presence of a base. A typical sulfur nucleophile of Formula 17 can be thiourea, sodium hydrosulfide, sodium sulfide, potassium thioacetate, potassium thiocyanate, sodium thiophosphate or potassium O-ethyl xanthate. The utility of these reagents is well known in literature. For example, the use of sodium thiophosphate is described by Bieniarz et al. (Tetrahedron Lett. 1993, 34, 939-942). The reaction of a compound of Formula 4 with sulfur nucleophile of Formula 17 may subsequently require a hydrolysis step in preparing compounds of Formula 2 (X = S). Scheme 12 depicts this transformation.

Scheme 12

H₂NR⁷

16

4 + base *- 2 ( X = NR⁷, S ) or

H₂NC(S)NH₂, NaSH, Na₂S, AcSK KSCN, Na₃P(S)0₃, KSC(S)OEt

17 Alternatively, compounds of Formula 2 can be prepared from ketones of Formula 5 by a sequence of homologation reactions that are well known to one skilled in the art. For example, a ketone of Formula 5 is first converted into unsaturated ester of Formula 19 with a phosphonate of Formula 18 under Horner-Emmons olefmation conditions (March, J. Advanced Organic Chemistry; 3rd Ed.; John Wiley & Sons; New York, (1985); p 848). Compounds of Formula 19 then can be converted into compounds of Formula 2

(X-Y = OCH₂CHR²¹) via catalytic hydrogenation followed by reduction. Phosphonates of Formula 18 can be obtained from commercial sources. Scheme 13 depicts this transformation.

Scheme 13

18

19

R²¹ = H, Me

R²² = Me, Et

(i) catalytic hydrogenation

2 ( X- -Y= OC H2CHR²¹ )

(ii) reduction Alternatively, compounds of Formula 2 can be prepared from aminocyclohexanols of Formula 20 by a sequence of reactions with compounds of Formulae 7 and 8 in the presence of a base. The reaction can be carried out in a manner analogous to Scheme 5 reactions. Compounds of Formula 2 can be also prepared from cyclohexanediols of Formula 21 by Mitsunobu reaction with activated amide of Formula 14 in the presence of a phosphine and an azodicarboxylate. The reaction can be carried out in a manner analogous to Scheme 9 reactions. Compounds of Formulae 20 and 21 can be obtained from commercial sources or prepared by conventional methods well known to one skilled in the art. Scheme 14 depicts this transformation.

Scheme 14

20 14 21 amide

L = F, Cl, Br, I, OSθ2Me, OSO2CF3, OSθ2Ar Compounds of Formula 4 can be prepared from alcohols of Formula 2 (X = O) by a variety of literature methods. Such conversions of alcohols are well known to one skilled in the art (Carey, F. A.; Sundberg, R. J. Advanced Organic Chemistry; 2nd ed.; Plenum: New York, 1983; Part B, pp 95-101).

Compounds of Formula 5 can be prepared by oxidation of alcohols of Formula 2 (X-Y = O). One skilled in the art will recognize that ketones of Formula 5 and alcohols of Formula 2 (X-Y = O) can be interconverted by a variety of reduction and oxidation methods (March, J. Advanced Organic Chemistry; 3rd ed.; John Wiley & Sons: New York, 1985; pp 809-814, 1057-1060).

Compounds of Formula 6 can be prepared by reductive amination of compounds of Formula 10 with ammonia in the presence of a reducing agent. The reaction can be carried out in a manner analogous to Scheme 7 reactions.

Alternatively, compounds of Formula 6 can be prepared by reaction of one or less equivalent of a heterocycle of Formula 1 with diaminocyclohexane of Formula 15 with or without a base. The reaction can be carried out in a manner analogous to Scheme 10 reactions. Scheme 15 depicts this transformation.

Scheme 15

neat

15

Compounds of Formula 10 can be prepared by oxidation of alcohols of Formula 13. One skilled in the art will recognize that ketones of Formula 10 and alcohols of Formula 13 can be interconverted by a variety of reduction and oxidation methods (March, J. Advanced Organic Chemistry; 3rd ed.; John Wiley & Sons: New York, 1985; pp 809-814, 1057-1060). Compounds of Formula 12 can be prepared from alcohols of Formula 13 by a variety of literature methods. Such conversions of alcohols are well known to one skilled in the art (Carey, F. A.; Sundberg, R. J. Advanced Organic Chemistry; 2nd ed.; Plenum: New York, 1983; Part B, pp 95-101).

Compounds of Formula 13 can be prepared by reaction of a heterocycle of Formula 1 with a compound of Formula 22 in the presence of a base. The reaction can be carried out in a manner analogous to Scheme 1 reactions. Scheme 16 depicts this transformation.

Scheme 16

22

X = NR⁷, O, S

Compounds of Formula 22 can be obtained from commercial sources or prepared by conventional methods well known to one skilled in the art. For example, compounds of Formula 22 (X-Y = OCH₂CHR²¹) can be prepared from cyclohexanediols of Formula 21 by oxidation followed by a sequence of reactions described in detail in Scheme 13. Scheme 17 depicts this transformation.

Scheme 17

21 23

Compounds of Formula I (G = G-2) can be prepared in a manner exactly analogous to reactions described in Schemes 1-17 for Formula I (G = G-1) compounds. It is recognized that some reagents and reaction conditions described above for preparing compounds of Formula I may not be compatible with certain functionalities present in the intermediates. In these instances, the incorporation of protection and deprotection sequences or functional group interconversions into the synthesis will aid in obtaining the desired products. The use and choice of the protecting groups will be apparent to one skilled in chemical synthesis (see, for example, Greene, T. W. Protective Groups in Organic

Synthesis; John Wiley & Sons: New York, 1981). One skilled in the art will recognize that, in some cases, after the introduction of a given reagent as it is depicted in any individual scheme, it can be necessary to perform additional routine synthetic steps not described in detail to complete the synthesis of compounds of Formula I. One skilled in the art will also recognize that it can be necessary to perform a combination of the steps illustrated in the above schemes in an order other than that implied by the particular sequence presented to prepare the compounds of Formula I. One skilled in the art will also recognize that compounds of Formula I and the intermediates described herein can be subjected to various electrophilic, nucleophilic, radical, organometallic, oxidation, and reduction reactions to add substituents or modify existing substituents.

Without further elaboration, it is believed that one skilled in the art using the preceding description can utilize the present invention to its fullest extent. The following Examples are, therefore, to be construed as merely illustrative, and not limiting of the disclosure in any way whatsoever. The title compound in each example is indicated by the abbreviation "Ex." followed by a number showing in which example the compound is prepared. Percentages are by weight except for chromatographic solvent mixtures or where otherwise indicated. Parts and percentages for chromatographic solvent mixtures are by volume unless otherwise indicated. -Η NMR spectra are reported in ppm downfield from tetramethylsilane; s = singlet, d = doublet, t = triplet, q = quartet, m = multiplet, dd = doublet of doublets, ddd = doublet of doublet of doublets, tt = triplet of triplets, br s = broad singlet, br d = broad doublet. The following examples illustrate the invention:

EXAMPLE 1 c/.s-NN'-Bis(5-chloro-6-ethyl-4-pyrimidinyl)-1.4-cvclohexanediamine

To a magnetically-stirred solution of 0.50 g (4.38 mmol) of 1 ,4-cyclohexanediamine (ca. cis/trans = 80/20) in 30 mL of acetonitrile were sequentially added 1.8 mL (13.14 mmol) of triethylamine and a solution of 1.63 g (9.20 mmol) of 4,5-dichloro-6-ethylpyrimidine in 10 mL of acetonitrile dropwise under nitrogen. The resultant clear solution was heated at reflux for 72 h. The mixture was cooled and diluted with ethyl acetate and water. The layers were separated and the aqueous layer was extracted with ethyl acetate (2x). The combined organic layers were washed with brine, dried over anhydrous magnesium sulfate, filtered, and concentrated at reduced pressure. The residue was purified by silica gel flash column chromatography eluting with 10%, 40%, then 60% ethyl acetate/hexane to afford 1.10 g (64%) of the title compound (Ex. 1) as a white solid, melting at 119-121 °C. Η ΝMR (CDC1₃): δ 8.43 (s, 2H), 5.43 (d, 2H), 4.22 (m, 2H), 2.80 (q, 4H), 1.96 (m, 4H), 1.76 (m, 4H), 1.27 (t, 6H). EXAMPLE 2 (a) c/ '-N-(5-Chloro-6-ethyl-4-pyrimidinyl)-N-(5-chloro-6-ethyl-4-pyrimidinyl)-N-methyl- 1 ,4-cyclohexanediamine, (b) ct -N V^,-bis(5-chloro-6-ethyl-4-pyrimidinyl)-N-N-dimethyl- 1 ,4-cyclohexanediamine and (c) -N-(5-chloro-6-ethyl-4-pyrimidinyl)-N-[5-chloro-6-(l- methylethyl -pyrimidinyll-N-N -dimethyl- 1 ,4-cyclohexanediamine

To a magnetically-stirred suspension of 0.28 g (7.06 mmol) of sodium hydride (60 wt% dispersion in mineral oil) in 20 mL of N-N-dimethylformamide was added a solution of 0.93 g (2.35 mmol) of 5-N-N-bis(5-chloro-6-ethyl-4-pyrimidinyl)-l,4-cyclohexanediamine in 10 mL of N-N-dimethylformamide dropwise under nitrogen. The resultant mixture was heated and stirred at 85-90 °C for 40 min and a solution of 0.44 mL (7.06 mmol) of iodomethane in 10 mL of N-N-dimethylformamide was added dropwise. The resultant clear yellow solution was stirred at the same temperature overnight. The mixture was cooled and poured onto a diethyl ether-water solution. The layers were separated and the aqueous layer was extracted with diethyl ether (2x). The combined organic layers were washed with water and brine, dried over anhydrous magnesium sulfate, filtered, and concentrated at reduced pressure. The residue was purified by silica gel flash column chromatography eluting with 20%, 30%, 40%, 50%, then 100% ethyl acetate/hexane to afford 0.07 g (6%) of cis-N-(5- chloro-6-ethyl-4-pyrimidinyl)-N-[5-chloro-6-(l-methylethyl)-4-pyrimidinyl]-N^V-dimethyl- 1,4-cyclohexanediamine (Ex. 2c) as a white solid, melting at 95-97 °C, ^JH ΝMR (CDC1₃): δ 8.57 (s, IH), 8.52 (s, IH), 4.07 (m, 2H), 3.54 (m, IH), 2.96 (s, 3H), 2.94 (s, 3H), 2.88 (q, 2H), 2.06 (m, 4H), 1.61 (m, 4H), 1.30 (t, 3H), 1.26 (d, 6H), 0.21 g (21%) of cw-N-N-bis(5- cWoro-6-ethyl-4-pyrimidinyl)-N-N-dimethyl-l,4-cyclohexanediamine (Ex. 2b) as a white solid, melting at 86-87 °C, *H ΝMR (CDC1₃): δ 8.53 (s, 2H), 4.07 (m, 2H), 2.96 (s, 6H), 2.89 (q, 4H), 2.05 (m, 4H), 1.61 (m, 4H), 1.30 (t, 6H), and 0.16 g (16%) of -N-(5-chloro- 6-ethyl-4-pyrimidinyl)-N-(5-chloro-6-ethyl-4-pyrimidinyl)-N-methyl- 1 ,4- cyclohexanediamine (Ex. 2a) as a white solid, melting at 68-70 °C, Η ΝMR (CDC1₃): δ 8.45 (s, IH), 8.43 (s, IH), 5.58 (br d, IH), 4.33 (m, IH), 4.18 (m, IH), 3.03 (s, 3H), 2.86 (q, 2H), 2.81 (q, 2H), 2.10 (m, 2H), 1.81 (m, 6H), 1.29 (t, 3H), 1.28 (t, 3H).

EXAMPLE 3 c/s-N-N-Bis(5-chloro-6-ethyl-4-pyrimidinyl - 1 ,4-cyclohexanediamine dihydrochloride

To a magnetically-stirred solution of 0.72 g (1.82 mmol) of ct5^,-N V-bis(5-chloro-6- ethyl-4-pyrimidinyl)-l,4-cyclohexanediamine in 20 mL of dichloromethane was added 5 mL of 1 HO solution in methanol. The resultant mixture was stirred at room temperature overnight and concentrated at reduced pressure. The solid residue was washed with dichloromethane and diethyl ether, and dried to afford 0.51 g (60%) of the title compound (Ex. 3) as a white solid, melting at 239-242 °C, ^lH ΝMR (DMSO-e?₆): δ 8.67 (s, 2H), 7.73 (br s, 2H), 4.27 (m, 2H), 2.82 (q, 4H), 1.95 (m, 4H), 1.71 (m, 4H), 1.22 (t, 6H). EXAMPLE 4 ct5^,-N-(5-Chloro-6-ethyl-4-pyrimidinyl)-N-(4-quinazolinyl)-1.4-cvclohexanediamine

To a magnetically-stirred solution of 0.50 g (4.38 mmol) of 1 ,4-cyclohexanediamine (ca. cis/trans = 80/20) in 30 mL of acetonitrile were sequentially added 1.8 mL (13.14 mmol) of triethylamine and a solution of 0.78 g (4.38 mmol) of 4,5-dichloro-6-ethylpyrimidine in 10 mL of acetonitrile dropwise under nitrogen. The clear solution was heated at reflux for 1 h. The resultant mixture was cooled to 40 °C and a slurry of 0.72 g (4.38 mmol) of 4-chloroquinazoline in 10 mL of acetonitrile was added. The resultant mixture was heated at reflux overnight. The mixture was cooled and diluted with ethyl acetate and water. The layers were separated and the aqueous layer was saturated with sodium chloride and extracted with ethyl acetate (2x). The combined organic layers were washed with brine, dried over anhydrous magnesium sulfate, filtered, and concentrated at reduced pressure. The solid residue was purified by silica gel flash column chromatography eluting with ethyl acetate to afford 0.24 g (14%) of the title compound (Ex. 4) as a white solid, melting at 188-191 °C. ^!H ΝMR (CDC1₃): δ 8.68 (s, IH), 8.44 (s, IH), 7.86 (d, IH), 7.75 (m, 2H), 7.49(ddd, IH), 5.69 (br d, IH), 5.46 (br d, IH), 4.47 (m, IH), 4.28 (m, IH), 2.80 (q, 2H), 2.05 (m, 4H), 1.84 (m, 4H), 1.28 (t, 3H).

EXAMPLE 5 Step A: trα/j -4-|^"(5-chloro-6-ethyl-4-pyrimidinyl)amino1cyclohexanol To a magnetically-stirred solution of 1.00 g (8.68 mmol) of trαMs-4-aminocyclohexanol in 40 mL of acetonitrile were sequentially added 1.8 mL (13.02 mmol) of triethylamine and a solution of 1.69 g (9.55 mmol) of 4,5-dichloro-6-ethylpyrimidine in 10 mL of acetonitrile dropwise under nitrogen. The pale yellow solution was heated at reflux overnight. The resultant clear orange mixture was cooled and diluted with ethyl acetate and water. The layers were separated and the aqueous layer was saturated with ΝaCl and extracted with ethyl acetate (2x). The combined organic layers were washed with brine, dried over anhydrous magnesium sulfate, filtered, and concentrated at reduced pressure. The residue was purified by silica gel flash column chromatography eluting with 50%, then 100% ethyl acetate/hexane to afford 1.87 g (84%) of trα«s-4-[(5-chloro-6-ethyl-4-pyrimidinyl)amino]cyclohexanol as a white solid, melting at 138-139 °C, --H ΝMR (CDC1₃): δ 8.41 (s, IH), 5.16 (br d, IH), 3.99 (m, IH), 3.69 (m, IH), 2.78 (q, 2H), 2.15 (m, 2H), 2.04 (m, 2H), 1.50 (m, 2H), 1.48 (d, IH), 1.32 (m, 2H), 1.26 (t, 3H). Step B: 4-r(5-chloro-6-ethyl-4-pyrimidinyl)amino^"|cyclohexanone

To a magnetically-stirred solution of 2.00 g

4-pyrimidinyl)amino]cyclohexanol in 60 mL of dichloromethane was added 2.02 g

(9.38 mmol) of pyridinium chlorochromate in one portion. The resultant black mixture was stirred at room temperature overnight. The mixture was diluted with ethyl acetate and filtered through a short pad of silica gel. The black solid that remained behind was dissolved in 1 N aqueous ΝaOH solution and extracted with ethyl acetate (3x). The combined organic layers were washed with brine, dried over anhydrous magnesium sulfate, filtered, and concentrated at reduced pressure. The residue was purified by silica gel flash column chromatography eluting with ethyl acetate to afford 1.58 g (80%) of 4-[(5-chloro-6-ethyl-4- pyrimidinyl)amino]cyclohexanone as a white solid, melting at 115-116 °C, ^}H ΝMR

(CDC1₃): δ 8.45 (s, IH), 5.29 (d, IH), 4.49 (m, IH), 2.80 (q, 2H), 2.63-2.34 (m, 6H), 1.81 (m, 2H), 1.27 (t, 3H).

Step C: (a) c/^-N-(5-Chloro-6-ethyl-4-pyrimidinyl)-N -phenyl- 1 ,4-cyclohexanediamine and (b) tra«s-N-(5-chloro-6-ethyl-4-pyrimidinyl -N -phenyl- 1,4- cyclohexanediamine

To a magnetically-stirred solution of 1.00 g (3.94 mmol) of 4-[(5-chloro-6-ethyl-4- pyrimidinyl)amino]cyclohexanone in 50 mL of 1 ,2-dichloroethane were sequentially added 0.37 g (3.94 mmol) of aniline, 1.67 g (7.88 mmol) of sodium triacetoxyborohydride and 0.24 g (3.94 mmol) of glacial acetic acid under nitrogen. The resultant cloudy white mixture was stirred at room temperature overnight. The mixture was diluted with diethyl ether and washed with 1 N aqueous ΝaOH solution. The aqueous wash was extracted with diethyl ether (2x). The combined organic layers were washed with brine, dried over anhydrous magnesium sulfate, filtered, and concentrated at reduced pressure. The residue was purified by silica gel flash column chromatography eluting with 20%, then 50% ethyl acetate/hexane to afford 0.60 g (46%) of c/s-N-(5-chloro-6-ethyl-4-pyrimidinyl)-N-phenyl- 1 ,4- cyclohexanediamine (Ex. 5a) as a white solid, melting at 88-93 °C, ^!H ΝMR (CDC1₃): δ 8.42 (s, IH), 7.18 (dd, 2H), 6.69 (t, IH), 6.62 (d, 2H), 5.40 (br d, IH), 4.19 (m, IH), 3.71 (br s, IH), 3.54 (m, IH), 2.79 (q, 2H), 1.89 (m, 4H), 1.73 (m, 4H), 1.27 (t, 3H) and 0.57 g (44%) of tra«5-N-(5-chloro-6-ethyl-4-pyrimidinyl)-N -phenyl- 1 ,4-cyclohexanediamine (Ex. 5b) as a white solid, melting at 137-139 °C, --H ΝMR (CDC1₃): δ 8.42 (s, IH), 7.17 (dd, 2H), 6.68 (t, IH), 6.60 (d, 2H), 5.21 (d, IH), 4.03 (m, IH), 3.51 (s, IH), 3.31 (m, IH), 2.79 (q, 2H), 2.21 (m, 4H), 1.37 (m, 4H), 1.26 (t, 3H).

EXAMPLE 6 ct -N-(5-Chloro-6-ethyl-4-pyrimidinyl -N-phenyl-N-2-propynyl-l,4-cvclohexanediamine To a magnetically-stirred solution of 0.40 g ( 1.21 mmol) of c/5-N-(5-chloro-6-ethyl-4- pyrimidinyl)-N -phenyl- 1 ,4-cyclohexanediamine in 10 mL of toluene were sequentially added 0.31 mL (1.81 mmol) of N-N-diisopropylethylamine and 0.13 mL (1.45 mmol) of 80 wt% propargyl bromide solution in toluene dropwise under nitrogen. The clear red solution was heated at reflux overnight. The resultant mixture was cooled and concentrated at reduced pressure. The residue was purified by silica gel flash column chromatography eluting with 8%, then 100% acetone/dichloromethane to afford 0.32 g (72%) of the title compound (Ex. 6) as an orange viscous oil, iH ΝMR (CDC1₃): δ 8.42 (s, IH), 7.28 (m, 2H), 6.99 (m, 2H), 6.86 (t, IH), 5.57 (d, IH), 4.31 (m, IH), 3.99 (d, 2H), 3.70 (m, IH), 2.80 (q, 2H), 2.22 (t, IH), 2.04 (m, 2H), 1.94-1.68 (m, 6H), 1.27 (t, 3H).

EXAMPLE 7 (a) et -N-(5-Chloro-6-ethyl-4-pyrimidinyl)-N V-dimethyl-l,4-cyclohexanediamine and (b trα« -N-(5-chloro-6-ethyl-4-pyrimidinyl)-N-N-dimethyl-l,4-cyclohexanediamine

To a magnetically-stirred solution of 3.00 g (11.82 mmol) of 4-[(5-chloro-6-ethyl-4- pyrimidinyl)amino]cyclohexanone in 120 mL of toluene were sequentially added 0.11 g (0.59 mmol) of -toluenesulfonic acid monohydrate and 5 mL of water containing 0.96 g (11.82 mmol) of dimethylamine hydrochloride. The clear mixture was stirred at reflux for 4 h with the water removed azeotropically through a Dean-Stark trap. The mixture was cooled to room temperature and to this were sequentially added 3.76 g (23.64 mmol) of sodium triacetoxyborohydride and 0.68 mL (11.82 mmol) of glacial acetic acid. The resultant cloudy white mixture was stirred at room temperature overnight. The mixture was quenched with 6 mL of 1 M aqueous ΝaHC03 solution and concentrated at reduced pressure. The residue was purified by silica gel flash column chromatography eluting with 10%, 12%, then 15%) methanol/dichloromethane to afford 0.58 g (17%) of c/s-N-(5-chloro-6-ethyl-4- pyrimidinyl)-N-N-dimethyl-l,4-cyclohexanediamine (Ex. 7a) as a yellow solid, melting at 62-66 °C, IH ΝMR (CDC1₃): δ 8.40 (s, IH), 5.48 (d, IH), 4.22 (m, IH), 2.78 (q, 2H), 2.32 (s, 6H), 2.16 (m, IH), 1.95-1.60 (m, 8H), 1.26 (t, 3H) and 0.87 g (26%) of trans-N¹ -(5- chloro-6-ethyl-4-pyrimidinyl)-N-N-dimethyl-l ,4-cyclohexanediamine (Ex. 7b) as a yellow viscous oil, ⁱH ΝMR (CDC1₃): δ 8.40 (s, IH), 5.19 (d, IH), 3.94 (m, IH), 2.78 (q, 2H), 2.38 (m, IH), 2.36 (s, 6H), 2.21 (m, 2H), 2.01 (m, 2H), 1.47 (m, 2H), 1.28 (m, 2H), 1.26 (t, 3H).

EXAMPLE 8 c/ -4-r(5-Chloro-6-ethyl-4-pyrimidinyπamino]-N V^τ-N-trimethylcyclohexanaminium iodide To a magnetically-stirred solution of 0.30 g (1.06 mmol) of c/,s-N'-(5-chloro-6-ethyl-4- pyrimidinyl)-N-N-dimethyl-l,4-cyclohexanediamine in 10 mL of dichloromethane was added 0.72 mL (11.6 mmol) of iodomethane dropwise under nitrogen. The clear tan solution was stirred at room temperature overnight and concentrated at reduced pressure. The solid residue was oven-dried to afford 0.45 g (100%) of the title compound (Ex. 8) as a white solid, melting at 217-221 °C, iH ΝMR (DMSO-^₆): δ 8.38 (s, IH), 6.44 (d, IH), 4.21 (m, IH), 3.35 (m, IH), 3.03 (s, 3H), 2.72 (q, 2H), 2.13 (m, 2H), 1.98 (m, 2H), 1.78 (m, 2H), 1.67 (m, 2H), 1.18 (t, 3H).

EXAMPLE 9 Step A: cts-N-(5-Chloro-6-ethvI-4-pyrimidinyl)- 1.4-cyclohexanediamine To a magnetically-stirred solution of 6.45 g (56.5 mmol) of 1 ,4-cyclohexanediamine

(ca. cis/trans - 90/10) in 80 mL of acetonitrile was added a solution of 2.00 g (11.3 mmol) of 4,5-dichloro-6-ethylpyrimidine in 20 mL of acetonitrile dropwise under nitrogen. The resultant mixture was stirred at room temperature for 72 h. The cloudy white mixture was concentrated to a volume of approximately 20 mL and diluted with diethyl ether and water. The layers were saturated with NaCl and were separated, and the aqueous layer was extracted with diethyl ether (2x). The combined organic layers were washed with brine, dried over anhydrous sodium sulfate, filtered, and concentrated at reduced pressure. The oil residue was oven-dried to afford 2.94 g (100%) of c/.s-N-(5-chloro-6-ethyl-4-pyrimidinyl)-l ,4- cyclohexanediamine as a tan solid, melting at 76-79 °C, --H ΝMR (CDC1₃): δ 8.41 (s, IH), 5.46 (d, IH), 4.19 (m, IH), 2.98 (m, IH), 2.78 (q, 2H), 1.92-1.68 (m, 6H), 1.45 (m, 2H), 1.27 (m, 2H), 1.26 (t, 3H). Azeotropic distillation of the aqueous layer in toluene gave 3.11 g (61%) recovery) of 1 ,4-cyclohexanediamine as an orange oil. Step B: ct ^,-N-(5-Chloro-6-ethyl-4-pyrimidinyl)-N- 5-methoxy-6-(methoxymethyl)-4- pyrimidinyl]- 1 ,4-cyclohexanediamine To a magnetically-stirred solution of 0.30 g (1.18 mmol) of c/s-N-(5-chloro-6-ethyl-4- pyrimidinyl)-l,4-cyclohexanediamine in 10 mL of toluene were sequentially added 0.31 mL (1.77 mmol) of N-N-diisopropylethylamine and 0.24 g (1.30 mmol) of 4-chloro-5-methoxy-6- (methoxymethyl)pyrimidine under nitrogen. The clear solution was heated at reflux overnight. The resultant mixture was cooled and concentrated at reduced pressure. The residue was purified by silica gel flash column chromatography eluting with 50%, 100% ethyl acetate/hexane, then 5% methanol/dichloromethane to afford 0.11 g (23%) of the title compound (Ex. 9) as a tan solid, which starts to melt at 104 °C, --H ΝMR (CDC1₃): δ 8.42 (s, IH), 8.38 (s, IH), 5.41 (d, IH), 5.31 (d, IH), 4.47 (s, 2H), 4.20 (m, 2H), 3.83 (s, 3H), 3.49 (s, 3H), 2.80 (q, 2H), 1.95 (m, 4H), 1.75 (m, 4H), 1.27 (t, 3H).

EXAMPLE 10 -2-r4-r(5-Chloro-6-ethyl-4-pyrimidinyl)aminolcvclohexyll-lH-isoindole-l,3(2H)dione To a magnetically-stirred solution of 0.60 g (2.36 mmol) of cz^'s-N-(5-chloro-6-ethyl-4- pyrimidinyl)- 1,4-cyclohexanediamine in 20 mL of tetrahydrofuran was added a solution of 0.35 g (2.36 mmol) of phthalic anhydride in 10 mL of tetrahydrofuran dropwise under nitrogen. The clear yellow solution was heated at reflux for 2 h. The resultant mixture was cooled and concentrated. The solid residue was dissolved in 5 mL of N,N- dimethylformamide and approximately 1 g of polyphosphoric acid was added. The resultant mixture was heated at 80 °C for 2 h and poured onto a mixture of diethyl ether and 1 M aqueous ΝaΗCO₃ solution. The layers were separated and the aqueous layer was extracted with diethyl ether (2x). The combined organic layers were washed with water and brine, dried over anhydrous magnesium sulfate, filtered, and concentrated at reduced pressure. The residue was purified by silica gel flash column chromatography eluting with 40%, 70%, then 100% ethyl acetate/hexane to afford 0.20 g (22%) of the title compound (Ex. 10) as a white solid, melting at 157-160 °C, *H NMR (CDC1₃): δ 8.43 (s, IH), 7.84 (m, 2H), 7.72 (m, 2H), 5.88 (d, IH), 4.47 (m, IH), 4.25 (tt, IH), 2.82 (q, 2H), 2.47 (m, 2H), 2.09 (m, 2H), 1.83-1.66 (m, 4H), 1.29 (t, 3H). EXAMPLE 11 Step A: 4-r(5-Chloro-6-ethyl-4-pyrimidinyl)amino]cvclohexanone O-methyloxime

To a magnetically-stirred solution of 1.00 g (3.94 mmol) of 4-[(5-chloro-6-ethyl-4- pyrimidinyl)amino]cyclohexanone in 10 mL of pyridine was added 0.40 g (4.73 mmol) of methoxyamine hydrochloride in one portion. The clear yellow mixture was stirred at room temperature overnight. The resultant mixture was diluted with dichloromethane and washed with water. The aqueous wash was extracted with dichloromethane (2x). The combined organic layers were washed with brine, dried over anhydrous sodium sulfate, filtered, and concentrated at reduced pressure. The residue was purified by silica gel flash column chromatography eluting with 50% ethyl acetate/hexane to afford 0.99 g (89%>) of 4-[(5- chloro-6-ethyl-4-pyrimidinyl)amino]cyclohexanone O-methyloxime as a white solid, melting at 105-106 °C, --H NMR (CDC1₃): δ 8.42 (s, IH), 5.25 (d, IH), 4.24 (m, IH), 3.84 (s, 3H), 3.18 (m, IH), 2.79 (q, 2H), 2.47 (m, IH), 2.36-2.00 (m, 4H), 1.51 (m, 2H), 1.26 (t, 3H). Step B: (a) e/ -N-(5-Chloro-6-ethyl-4-pyrimidinylVN-methoxy-l ,4- cyclohexanediamine and (b) tra«,s-N-(5-chloro-6-ethyl-4-pyrimidinyl)-N- methoxy- 1 ,4-cyclohexanediamine To a cooled (0 °C), magnetically-stirred solution of 0.28 g (1.06 mmol) of 4-[(5- chloro-6-ethyl-4-pyrimidinyl)amino]cyclohexanone O-methyloxime in 5 mL of ethanol were sequentially added dropwise 0.44 mL (3.53 mmol) of borane-pyridine complex and 4 mL of 10% aqueous HCl solution. The clear mixture was allowed to warm to room temperature and stirred for 10 min. The resultant mixture was quenched with 1 M aqueous ΝaHCO₃ solution and diluted with ethyl acetate. The layers were separated and the aqueous layer was extracted with ethyl acetate (2x). The combined organic layers were washed with brine, dried over anhydrous magnesium sulfate, filtered, and concentrated at reduced pressure. The residue was purified by silica gel flash column chromatography eluting with 55%, 70%, then 100% ethyl acetate/hexane to afford 0.11 g (36%) of c/s-N-(5-chloro-6-ethyl-4-pyrimidinyl)- N-methoxy-l,4-cyclohexanediamine (Ex. 1 la) as a clear oil, *H ΝMR (CDC1₃): δ 8.41 (s, IH), 5.47 (br s, IH), 5.42 (br d, IH), 4.18 (m, IH), 3.58 (s, 3H), 3.07 (m, IH), 2.78 (q, 2H), 1.87-1.55 (m, 8H), 1.26 (t, 3H) and 0.15 g (50%) of tra«s-N-(5-chloro-6-ethyl-4- pyrimidinyl)-N-methoxy-l,4-cyclohexanediamine (Ex. 1 lb) as a white solid, melting at 87- 88 °C, !H ΝMR (CDCI3): δ 8.41 (s, IH), 5.43 (br s, IH), 5.18 (br d, IH), 3.98 (m, IH), 3.55 (s, 3H), 2.90 (m, IH), 2.78 (q, 2H), 2.18 (m, 2H), 2.00 (m, 2H), 1.31 (m, 4H), 1.26 (t, 3H).

EXAMPLE 12 c 5^ι-N-r4-r(5-Chloro-6-ethyl-4-pyrimidinyl)amino1cvclohexyll-N-methoxyacetamide To a magnetically-stirred solution of 0.50 g ( 1.75 mmol) of cts-N-(5-chloro-6-ethyl-4- pyrimidinyl)-N'-methoxy-l,4-cyclohexanediamine in 20 mL of dichloromethane were sequentially added 0.17 mL (1.75 mmol) of acetic anhydride, 0.21 g (1.75 mmol) of 4-(dimethylamino)pyridine and 0.24 mL (1.75 mmol) of triethylamine under nitrogen. The clear mixture was stirred at room temperature for 72 h. The resultant mixture was diluted with diethyl ether and water. The layers were separated and the aqueous layer was extracted with diethyl ether (2x). The combined organic layers were washed with brine, dried over anhydrous magnesium sulfate, filtered, and concentrated at reduced pressure. The residue was purified by silica gel flash column chromatography eluting with 15%, 17.5%, then 20% acetone/hexane to afford 0.45 g (79%) of the title compound (Ex. 12) as a clear viscous oil,

!H NMR (CDC1₃): δ 8.42 (s, IH), 5.61 (d, IH), 4.33 (m, IH), 4.28 (m, IH), 3.79 (s, 3H),

2.80 (q, 2H), 2.16 (s, 3H), 2.06 (m, 2H), 1.97-1.68 (m, 6H), 1.27 (t, 3H).

By the procedures described herein together with methods known in the art, the following compounds of Tables 1 to 26 can be prepared. The following abbreviations are used in the Tables which follow: t = tertiary, s = secondary, n = normal, i = iso, c = cyclo,

Me = methyl, Et = ethyl, Pr = propyl, Bu = butyl, Pen = pentyl, /-Am = 1,1-dimethylpropyl,

Hex = hexyl, Ph = phenyl, Bn = phenylmethyl, OMe = methoxy, OEt = ethoxy, CN = cyano,

SMe = methylthio,

2-Pyr = 3-Pyr = 4-Pyr = 2-Th =

Piper = Morph = Phth = Hphth =

0-9 = Q-10 = Q-l l Q-12

Q-13 = Q-14 - Q-15 = Q-16 =

Key for Tables 1 -26

Tables 1 to 3 Table 4 Tables 5 to 8

Tables 9 to 16 Tables 17 and 18 Table 19

Table 22

Table 23 Tables 24 to 26

TABLE 1

COLUMN

G = Q- R⁶ = Me; R5 = G = Q- R⁶ = Me; R5 = G = Q- R⁶ = Me; R5 = G = Q- R⁶ = Me; R5 = G = Q- R⁶ = Me; R5 = G = Q- R⁶ = Me; R5 = G = Q- R⁶ = Me; R5 = G = Q- R⁶ = Me; R5 = G = Q- R⁶ = Me; R5 = G = Q- R⁶ = Me; R5 = G = Q- R⁶ = Me; R5 = G = Q- R⁶ = Me; R5 = G = Q- R⁶ = Me; R5 = G = Q- R⁶ = Me; R5 = G = Q- R⁶ = Me; R5 = G = Q- R⁶ = Me; R5 = G = Q- R⁶ = Ph R5 = G = Q- R⁶ = Ph R5 = G = Q- R⁶ = Ph R5 =

TABLE 2

COLUMN

1 2 3

G = Q-l;R⁶ = COMe R5 = Et /-Pr c-Pr

G*****Q-l;R⁶ = COMe R5 = c-Hex Bn CH₂C≡CH

G-****Q-l;R⁶ = COMe R5 = CH₂CN CH₂CONMe₂ CH₂OMe

G*****Q-l;R⁶ = COMe R5 = CH₂SMe CH₂S0₂Me (CH₂)₂CF=CF₂

G = Q-l;R⁶ = COMe R5 = OH OMe OBn

G = Q-l;R⁶ = COMe R5 = OCH₂CN 0(CH₂)₂CF=CF₂ CH₂C0₂Me

G****-Q-l;R⁶ = CO-t-Bu; R5 = Me Et t-Pr

G = Q-l;R⁶ = CO-t-Bu; R5 = c-Pr n-Bu c-Hex

G = Q-l;R⁶ = CO-t-Bu; R5 = Bn Ph CH₂C≡CH

G = Q-l;R⁶ = CO-t-Bu; R5 = CH₂CN CH₂CONMe₂ CH₂OMe

G = Q-l;R⁶ = CO-t-Bu; R5 = CH₂SMe CH₂S0₂Me (CH₂)₂CF=CF₂

G = Q-l;R⁶ = CO-t-Bu; R5 = OH OMe OBn

G = Q-l;R⁶ = CO-t-Bu; R5 = OCH₂CN 0(CH₂)₂CF=CF₂ CH₂C0₂Me

G = Q-l;R⁶ = C0₂Me; R5 = Et /-Pr c-Pr

G = Q-l;R⁶ = C0₂Me; R5 = c-Hex Bn CH₂C≡CH

G-*=Q-l;R⁶ = C0₂Me; R5 = CH₂CN CH₂CONMe₂ CH₂OMe

G = Q-l;R⁶ = C0₂Me; R5 = CH₂SMe CH₂S0₂Me (CH₂)₂CF=CF₂

G = Q-l;R⁶ = C0₂Me; R5 = OH OMe OBn

G = Q-l;R⁶ = C0₂Me; R5 = OCH₂CN 0(CH₂)₂CF=CF₂ CH₂C0₂Me

G = Q-l;R⁶ = C0₂-t-Bu; R5 = Me Et /-Pr

G = Q-l;R⁶ = C0₂-t-Bu; R5 = c-Pr n-Bu c-Hex

G = Q-l;R⁶ = C0₂-t-Bu; R5 = Bn Ph CH₂C≡CH

G = Q-l;R⁶ = C0₂-t-Bu; R5 = CH₂CN CH₂CONMe₂ CH₂OMe

G = Q-l;R⁶ = C0₂-t-Bu; R5 = CH₂SMe CH₂S0₂Me (CH₂)₂CF=CF₂

G = Q-l;R⁶ = C0₂-t-Bu; R5 = OH OMe OBn

G=*-Q-l;R⁶ = C0₂-t-Bu; R5 = OCH₂CN 0(CH₂)₂CF=CF₂ CH₂C0₂Me

G = Q-l;R⁶ = CONMe₂; R5 = Me Et /-Pr

G = Q-l;R⁶ = CONMe₂; R5 = c-Pr n-Bu c-Hex

G = Q-l;R⁶*=CONMe₂; R5 = Bn Ph CH₂C≡CH

G = Q-l;R⁶ = CONMe₂; R5 = CH₂CN CH₂CONMe₂ CH₂OMe .

G = Q-l;R⁶ = CONMe₂; R5 = CH₂SMe CH₂S0₂Me (CH₂)2CF*=CF₂

G = Q-l;R⁶ = CONMe₂; R5 = OH OMe OBn

G = Q-l;R⁶ = CONMe₂; R5 = OCH₂CN 0(CH₂)₂CF=CF₂ CH₂C0₂Me

G = Q-l;R⁶ = S0₂Me; R5 = Me Et t-Pr

G = Q-l;R⁶ = S0₂Me; R5 = c-Pr n-Bu c-Hex

G = Q-l;R⁶ = S0₂Me; R5 = Bn Ph CH₂C≡CH

G = Q-l;R⁶ = S0₂Me R5 = CH₂CN CH₂CONMe₂ CH₂OMe 1 G

G

78 G = Q-2 R⁶ = C0₂Me; R5 = CH₂SMe CH₂S0₂Me (CH₂)₂CF=CF₂

79 G = Q-2 R⁶ = C0₂Me; R5 = OH OMe OBn

80 G = Q-2 R⁶ = C0₂Me; R5 = OCH₂CN 0(CH₂)₂CF=CF₂ CH₂C0₂Me

81 G = Q-2 R6 = C0₂-t-Bu; R5 = Me Et /-Pr

82 G = Q-2 R6 = cθ₂-t-Bu; R5 = c-Pr n-Bu c-Hex

83 G = Q-2 R6 = cθ₂-t-Bu; R5 = Bn Ph CH₂C≡CH

84 G = Q-2 R6 = C0₂-t-Bu; R5 = CH₂CN CH₂CONMe₂ CH₂OMe

85 G = Q-2 R6 = cθ₂-t-Bu; R5 = CH₂SMe CH₂S0₂Me (CH₂)₂CF=CF₂

86 G = Q-2 R6 = cθ₂-t-Bu; R5 = OH OMe OBn

87 G = Q-2 R6 = cθ₂-t-Bu; R5 = OCH₂CN 0(CH₂)₂CF=CF₂ CH₂C0₂Me

88 G = Q-2 R⁶ = CONMe₂; R5 = Me Et /-Pr

89 G = Q-2 R⁶ = CONMe₂; R5 = c-Pr n-Bu c-Hex

90 G = Q-2 R⁶ = CONMe₂; R5 = Bn Ph CH₂C≡CH

91 G = Q-2 R⁶ = CONMe₂; R5 = CH₂CN CH₂CONMe₂ CH₂OMe

92 G = Q-2 R⁶ = CONMe₂; R5 = CH₂SMe CH₂S0₂Me (CH₂)2CF*=CF₂

93 G = Q-2 R⁶ = CONMe₂; R5 = OH OMe OBn

94 G = Q-2 R⁶ = CONMe₂; R5 = OCH₂CN 0(CH₂)₂CF=CF₂ CH₂C0₂Me

95 G = Q-2 R⁶ = S0₂Me; R5 = Me Et /-Pr

96 G = Q-2 R⁶ = S0₂Me; R5 = c-Pr n-Bu c-Hex

97 G = Q-2 R⁶ = S0₂Me; R5 = Bn Ph CH₂C≡CH

98 G = Q-2 R⁶ = S0₂Me; R5 = CH₂CN CH₂CONMe₂ CH₂OMe

99 G = Q-2 R⁶ = S0₂Me; R5 = CH₂SMe CH₂S0₂Me (CH₂)2CF=CF₂

100 G = Q-2 R⁶ = S0₂Me; R5 = OH OMe OBn

101 G = Q-2 R⁶ = S0₂Me; R5 = OCH₂CN 0(CH₂)₂CF=CF₂ CH₂C0₂Me

102 G = Q-2 R⁶ = S0₂CF₃; R5 = Me Et /-Pr

103 G = Q-2 R⁶ = S0₂CF₃; R5 = c-Pr n-Bu c-Hex

104 G = Q-2 R⁶ = S0₂CF₃; R5 = Bn Ph CH₂C≡CH

105 G = Q-2 R⁶ = S0₂CF₃; R5 = CH₂CN CH₂CONMe₂ CH₂OMe

106 G = Q-2 R⁶ = S0₂CF₃; R5 = CH₂SMe CH₂S0₂Me (CH₂)₂CF=CF₂

107 G = Q-2 R⁶ = S0₂CF₃; R5 = OH OMe OBn

108 G = Q-2 R⁶ = S0₂CF₃; R5 = OCH₂CN 0(CH₂)₂CF=CF₂ CH₂C0₂Me

109 G = Q-2 R⁶ = P(0)(OMe)₂; R5 = Me Et /-Pr

110 G = Q-2 R⁶ = P(0)(OMe)₂; R5 = c-Pr n-Bu c-Hex

111 G = Q-2 R⁶ = P(0)(OMe)₂; R5 = Bn Ph CH₂C≡CH

112 G = Q-2 R⁶ = P(0)(0Me)₂; R5 = CH₂CN CH₂CONMe₂ CH₂OMe

113 G = Q-2 R⁶ = P(OXOMe)₂; R5 = CH₂SMe CH₂S0₂Me (CH₂)₂CF=CF₂

114 G = Q-2 R⁶ = P(0)(OMe)₂; R5 = OH OMe OBn

115 G = Q-2 R⁶ = P(0)(OMe)₂; R5 = OCH₂CN 0(CH₂)₂CF=CF₂ CH₂C0₂Me

116 G = Q-2 R⁶ = P(0)(OMe)Me; R5 = Me Et /-Pr

117 G = Q-2 R⁶ = P(0)(OMe)Me; R5 = c-Pr n-Bu c-Hex 118 G CH₂C≡CH

119 G CH₂OMe

120 G (CH₂)₂CF=CF₂

121 G OBn

122 G CH₂C0₂Me

123 G c-Pr

124 G CH₂C≡CH

125 G CH₂OMe

126 G (CH₂)₂CF-CF₂

127 G OBn

128 G CH₂C0₂Me

129 G /-Pr

130 G c-Hex

131 G CH₂C≡CH

132 G CH₂OMe

133 G (CH₂)₂CF=CF₂

134 G OBn

135 G CH₂C0₂Me

136 G c-Pr

137 G CH₂C≡CH

138 G CH₂OMe

139 G (CH₂)₂CF=CF₂

140 G OBn

141 G CH₂C0₂Me

142 G /-Pr

143 G c-Hex

144 G CH₂C≡CH

145 G CH₂OMe

146 G (CH₂)₂CF-CF₂

147 G OBn

148 G CH₂C0₂Me

149 G /-Pr

150 G c-Hex

151 G CH₂C≡CH

152 G CH₂OMe

153 G (CH₂)₂CF=CF₂

154 G OBn

155 G CH₂C0₂Me

156 G

/-Pr 157 G = Q-3; R⁶ = = S0₂Me; R5

158 G = Q-3; R⁶ = = S0₂Me; R5

159 G = Q-3; R⁶ = = S0₂Me; R5

160 G = Q-3; R⁶ = = S0₂Me; R5

161 G = Q-3; R⁶ = = S0₂Me; R5

162 G = Q-3; R⁶ = = S0₂Me; R5

163 G = Q-3; R⁶ = = S0₂CF₃; R5

164 G = Q-3; R⁶ = = S0₂CF₃; R5

165 G = Q-3; R⁶ = = S0₂CF₃; R5

166 G = Q-3; R⁶ = ■** S0₂CF₃; R5

167 G = Q-3; R⁶ = = S0₂CF₃; R5

168 G = Q-3; R⁶ = = S0₂CF₃; R5

169 G = Q-3; R⁶ = = S0₂CF₃; R5

170 G = Q-3; R⁶ = = P(0)(OMe)₂; R5

171 G = Q-3; R⁶ = = P(0)(OMe)₂; R5

172 G = Q-3; R⁶ -- = P(0)(OMe)₂; R5

173 G = Q-3; R⁶ = = P(0)(OMe)₂; R5

174 G = Q-3; R⁶ = *- P(0)(OMe)₂; R5

175 G = Q-3; R⁶ = = P(0)(OMe)₂; R5

176 G = Q-3; R⁶ = = P(0)(O e)₂; R5

177 G = Q-3; R⁶ - - -- P(0)(OMe)Me; R5

178 G = Q-3; R⁶ = = P(0)(OMe)Me; R5

179 G = Q-3; R⁶ = = P(0)(OMe)Me; R5

180 G = Q-3; R⁶ = = P(0)(OMe)Me; R5

181 G = Q-3; R⁶ = = P(0)(OMe)Me; R5

182 G = Q-3; R⁶ = = P(0)(OMe)Me; R5

183 G = Q-3; R⁶ = = P(0)(OMe)Me; R5

TABLE 3

COLUMN

1 G = Q-1 R6 = ₂-_Pyr; R5 =

2 G = Q-1 R6 = ₂-_Pyr; R5 =

3 G = Q-1 R6 ₂.p_yr; R5 =

G = Q-1 R6 = ₂-_Pyr; R5 =

5 G = Q-1 R6 = -p_yr; R5 =

6 G = Q-1 R6 _{= 2}-_Pyr; R5 =

G = Q-1 R6 = ₂-py_r; R5 =

8 G = Q-1 R6 -- ₂.py_r; R5 =

G = Q-1 R6 -- ₂-_Pyr; R5 =

o

•

00

>*, . >s >*. >s S*^***. *, > . > , >> , >. >**> *, fe fe fes P >L,> fe J > fe -F* fe >^*Λ p.-,, >*. * fe fe fe fe fe fe fe fe fe fe fe fe fe fe fe fe £ fe fe fe fe fN CN CN CN CN CN CN CN CN CN r r ro ro c^ rO ro ro ro r ro ro ro co ro ro ro ^**^*J-

II II II II II II II II II II II II II II II II II II II II II II II II vo f**- Pi Pi Pi Pi Pi Pi Pi Pi Pi pi Pi pi Pi Pi Pi Pi Pi Pi pi pi Pi Pi Pi pi Pi Pi Pi Pi Pi Pi Pi Pi Pi Pi Pi Pi pi o erf as p^/ p p^, c^χ o^/ P' c^y p' θ^/ p^/ P' θ o^/ P' P' P' c^y o o c>' P' c^y p^/ p^/ o

Os II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II

O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O

O —i CN ro 0 —' CN ro -^* m vo t^ oo σs O *-< eN ι- *^- ιn vo ι oo σv O —^■ CN ro f^»- 00 cN cN CN CN CN eN CN rN CN CN ro ro ro r ro ro ro ro ro ro ^*^* *^- *^- *^-

o

^% ^^ ^*» ^*_* ^^> fe fe fe fefe fe fe fe fe fe fe fe fe fe fe fe fe fe fe fe fe fe *^*o ro ro ro ro r c^*o *^**fr ^*i*t ^**^*t ^***t ** II II II II II II II II II II II II II II II II II II II II II Pi Pi Pi Pi Pi Pi Pi pi Pi Pi Pi Prf Pi Pi pi Pi Pi Pi Pi Pi Pi ^* CN^* CN^* CN^* CN^* CN^* CN^* CN^* CN^* CN^* CN^* CN^* CN^* CN^* CN^* CN^* CN^* CN" CN" CN^* CN" CN"

II II II II II II II II II II II II II II II II II II II II II

O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O o — i cN ro ^****f- ιn vo t-- oo o -ι cN ro

Os Os Os Os

i i— ; i — I

ζj

00 Os

fe fe fe fe xT -c^* -3 X -3 J-l x! X XI Xl Λ XI S XI Xi Xl XI -3 -3 **. ^ >^ ?^***> **, *-. ₁ >*-. >

(C p., P_H ( H H H H H H H H H H H H H H H H H H H fe fe fe fe fe fe fe fe fe fe fe fe fe f£? fe

II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II vo vo vo vo vo vo v vo vo vo vo vo vo vo o vo vo vo vo vo vo vo o v o v vo vo vo vo vo v vo o o r^*- o crf pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi crf pi pi pi pi pi erf erf pi pi erf erf erf pi pi oi pi pi

CN^* N^* CN^* cN^* CN" CN" CN^* CN^* CN" N^* cN^* CN^* CN" CN" CN" CN" CN" CN" CN" CN" CN" CN" CN" CO" ro" co" co^" (X co" co" c^" co^* ro" ro^* ro^* co^* co" co^" ro^"

OS Os ό ό ό ό ό ό ό ό ό ό ό ό ό ό ό ό ό

II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II

O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O o *- cN ro *^ ιn vo r-~ co <^ o *— ' CN ro *^ ιo vo t--- oo ov θ *- eN ro *^ tn vo r-*- oo σv o *-ι CN CO *^***|- ιn vo f- 00 ro ro rθ f r c^ r ro rθ f *^ *f *ι^ * *^ *^ *^ *<t *^ *^ *n * n " ι *n ^*n " ιn vo vo vo v vo vo vo vo vo

(*> ^■r-j oo

*. fe fe fe fe

TiTi"^* Till ll II ll

VO VO VO o m m m Λ

O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O oo

CN

G = Q-3; R⁶ ■ ^■■ 2-Th: R5 =

G = Q-3; R⁶ - ^■■ 2-Th R5 =

G = Q-3; R⁶ = ^■■ 2-Th: R5 =

G - Q-3; R⁶ - ^■■ 2-Th: R5 =

G = Q-3; R⁶ = 2-Th; R5 =

G = Q-3; R⁶ = ^■■ 2-Th: R5 =

G - Q-3; R⁶ = 2-Th R5 =

G = Q-3; R⁶ = 2-Th R5 =

G - Q-3; R⁶ = 2-Th R5 =

G ^ ^■ Q-3; R⁶ - 2-Th R5 =

G ^ ^■ Q-3; R⁶ - 2-Th: R5 =

G ^: • Q-3; R⁶ = 2-Th: R5 =

G * ^■ Q-3; R⁶ = 2-Th R$ = G ^ • Q-3; R⁶ = 2-Th: R5 = G ^ ^■ Q-3; R⁶ = 2-Th R$ = G ^: ^■ Q-3; R⁶ = 2-Th R5 = G ^■ Q-3; R⁶ = 2-Th R5 =

G ^: • Q-3; R⁶ = 2-Th: R5 =

TABLE 4

COLUMN

G = Q-1 R⁵ = Me; R17 __

G = Q-1 R⁵ = Me; R17 =

G = Q-1 R⁵ = Me; R17 ₌

G = Q-1 R⁵ = Me; R17 =

G = Q-1 R⁵ = (CH₂)₂CF=CF₂; R17 ₌

G = Q-1 R⁵ = (CH₂)₂CF=CF₂; R17 -.

G = Q-1 R⁵ = (CH₂)₂CF=CF₂; R17 ₌

G = Q-1 R⁵ = (CH₂)₂CF=CF₂; R17 =

G = Q-1 R⁵ = (CH₂)₂CF=CF₂; R17 ₌

G = Q-1 R⁵ = (CH₂)₂CF*=CF₂; R17 ₌

ro o vo

pi Pi erf erf erf Pi ei Pi Pi Pi Pi Pi Pi Pi Pi Pi Pi Pi Pi Pi erf erf Pi Pi Pi Pi Pi Pi i-rf Pi Pi Pi Pi Pi Pi Pi Pi Pi Pi

fe fe fe fe fe fe fe fe fe fe fe fe fe o o o u u u

II u

II II II II II II o U u o

II II II II u u

II II fe fe fe fe fe fe fe fe fe fe fe fe fe u u u <υ ω ω α ω ω <υ α> u u U υ o u o o o υ α> <u <υ o

2 2 2 2 2 2 2 2 2 2 — . 2 2 2 2 2 2

PC PC PC P o P P P P P P P o DC DD X DD X DD DC DD DD DD ^s u—- u u o u u o o u o u u u 2 2 2 2 2 2 2 2 2 2 u u o o u u υ U o o P P P P P P υ o o u u o

II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II

I ^■n ^*n ^*n ^*n ^*n ^{* *}n ^*n n ιn *n ^*n n ι ιn ιn «n " ιn n ιn ιn ^*n ιn "n ιo ^*n ^*n ^* ιn ^*n ιn ιn ιn t-

O erf erf e prfi pi Pi Pi erf Pi Pi Pi Pi erf Pi Pi Pi Pi Pi Pi Pi Pi erf erf Pi Pi Pi Pi Pi Pi Pi Pi Pi Pi Pi Pi Pi Pi Pi Pi crf fe^" fe" fe" fe" fe^" fe" fe" fe" fe^" fe" fe" fe" fe^" ^^" ff CN^" CN^" CN^" CN" CN" CN^" CN^" CN" CN" N^* CN^* CN" N" CN^" N^" CN" CN" CN" N^" CN" CN" CN" CN^" CN^"

Os Os ό ό ό ό ό o II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II

O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O o σv o CN Tf tn vo r- oo CTv o CN m Tiin O r- oo C7v o CN m Tf in VO r- oo OS O CN ro rt tn O

CN CN CN fN CN CN CN CN fN CN CO m ro m ro m m Ti- t Tt Tt Tt Tt Tt Tt Tt Tt in in tn in m in in

G = Q-2 R5 = C0₂Me; Rl7: G = Q-2 R5 = C0₂Me; _R17_: G = Q-2 R5 = C0₂Me; R17_: G - Q-3 R5 ^ e; Rl7: G = Q-3 R5 ^Me; Rl7: G = Q-3 R5 Me; Rl7: G = Q-3 R5 ^Me; Rl7: G = Q-3 RZ ^Me; Rl7: G = Q-3 RS: ^Me; Rl7: G = Q-3 R5: ^Me; _R17: G = Q-3 R5 ^;Me; Rl7: G = Q-3 R5 ^Me; Rl7: G = Q-3 RS ^Me; R17_: G = Q-3 R5 = (CH₂)₂CF_: =CF₂; Rl7: G = Q-3. RZ ■ (CH₂)₂CF =CF₂; Rl7: G = Q-3. R5 = (CH₂)₂CF CF₂; Rl7: G = Q-3 R5 = (CH₂)₂CF: ^:CF₂; Rl7: G = Q-3 R5 ^: (CH₂)₂CF =CF₂; Rl7 G = Q-3 RZ = (CH₂)₂CP =CF₂; Rl7: G = Q-3 R5_: = (CH₂)₂CF =CF₂; Rl7: G = Q-3 R5 = = (CH₂)₂CP ^:CF₂; Rl7: G = Q-3 R5: = (CH₂)₂CF -CF₂; R17_: G = Q-3 R5 = = (CH₂)₂CF ^:CF₂; Rl7: G = Q-3 R5_: ^■■ C0₂Me; Rl7: G = Q-3 R5_: ^■■ C0₂Me; Rl7: G = Q-3 R5 ^■■ C0₂Me; Rl7: G = Q-3 R5 ^■■ C0₂Me; Rl7: G = Q-3 R5: C0₂Me; R17 = G = Q-3 R5 C0₂Me; Rl7: G = Q-3 R5_: C0₂Me; Rl7: G = Q-3 R5_: C0₂Me; Rl7 G = Q-3 R5: C0₂Me; Rl7: G = Q-3 R5 C0₂Me; Rl7:

TABLE 5

(R² = Et) COLUMN

R³ = Br; R⁶ = Me; R^{5 ■}■ R³ = Br; R⁶ = Me; R^{5 ■}■ R³ = Br; R⁶ = Me; R⁵ >

e

^•τ ιn vo ι^**- oo

o o

•-1 CN CO ro co m ro ro co ro

R³ = SMe R⁶ = Me; R5 = R³ = SMe R⁶ = Me; RZ R³ = SMe R⁶ = Me; R5 R³ = SMe R⁶ = Ph: R5: R³ = SMe R⁶ = Ph R5: R³ = SMe R⁶ = Ph R5: R³ = SMe R⁶ = Ph: R5: R³ = SMe R⁶ = Ph R5: R³ = SMe R⁶ = Ph R5: R³ = SMe R⁶ = Ph R5 R³ = SMe R⁶ = Ph RZ R³ = CN R⁶ = Me; RZ R³ = CN R⁶ = Me; R5_: R³ = CN; R⁶ = Me; R5: R³ = CN R⁶ = Me; RZ R³ = CN R⁶ = Me; R5- R³ = CN R⁶ = Me; R5_: R³ = CN R⁶ = Me; R5 R³ = CN R⁶ *= Me; R5 R³ = CN R⁶ = Ph RZ R³ = CN R⁶ = Ph R5 R³ = CN R⁶ = Ph R5: R³ = CN: R⁶ = Ph R5 R³ = CN R⁶ = Ph R5: R³ = CN R⁶ = Ph R5 = R³ = CN: R⁶ = Ph R5: R³ = CN R⁶ = Ph R5_:

TABLE 7

(R² = Me) COLUMN

R³ - Cl R⁶ = Me; R5: R³ = C1 R⁶ = Me; R5 R³ = C1 R⁶ = Me; R5 R³ = C1 R⁶ = Me; R5 R³ = C1 R⁶ = Me; R5 R³ = C1 R⁶ = Me; R5_: R³ = C1 R⁶ = Ph R5 R³ = C1 R⁶ = Ph: R5 R³=C1 R⁶ = Ph: RZ

R³ = Cl; R⁶ = Ph R5: R³ = Cl; R⁶ = Ph R5 R³ = Cl; R⁶ = Ph R5: R³ = Br; R⁶ = Me; R5: R³ = Br; R⁶ = Me; R5: R³ = Br; R⁶ = Me; R5: R³ = Br; R⁶ = Me; R5: R³ = Br; R⁶ = Me; R5: R³ = Br; R⁶ = Me; R5 R³ = Br; R⁶ = Ph R5 R³ = Br; R⁶ = Ph R5: R³ = Br; R⁶ = Ph RZ R³ = Br; R⁶ = Ph R5 R³ = Br; R⁶ = Ph RZ R³ = Br; R⁶ = Ph R5: R³ = Me; R⁶ = Me; R5 R³ = Me; R⁶ = Me; R5: R³ = Me; R⁶ = Me; R5 R³ = Me; R⁶ = Me; R5_: R³ = Me; R⁶ = Me; RZ R³ = Me; R⁶ = Me; R5: R³ = Me; R⁶ = Ph R5 = R³ = Me; R⁶ = Ph: R5: R³ = Me; R⁶ = Ph RZ R³ = Me; R⁶ = Ph RZ R³ = Me; R⁶ = Ph: R5 R³ = Me; R⁶ = Ph R5

R³ = OMe R⁶ = Me; R5: R³ = OMe R⁶ = Me; R5 R³ = OMe R⁶ = Me; R5 R³ = OMe R⁶ = Me; R5 = R³ = OMe R⁶ = Me; R5_: R³ = OMe R⁶ = Me; R5 R³ = OMe R⁶ = Ph R5_: R³ = OMe R⁶ = Ph R5 R³ = OMe R⁶ = Ph R5 R³ = OMe R⁶ = Ph R5_: R³ = OMe R⁶ = Ph R5_: R³ = OMe R⁶ = Ph R5 =

TABLE 8

(R2 = _c._Pr) COLUMN

R³ = C1 R⁶ = Me ; R =

R³ = C1 R⁶ = Me ; R5 =

R³ = C1 R⁶ = Ph, R5 =

R³ *= C1 R⁶ = Ph; R5 =

R³ = C1 R⁶ = Ph; R5 =

R³ = Br R⁶ = Me ; R⁵ =

R³ = Br R⁶ = Me ; R5 =

R³ -= Br R⁶ = Me ; R5 =

R³ = Br R⁶ = Me ; R⁵ =

R³ = Br R⁶ = Me ; R5 =

R³ = Br R⁶ = Me ; R⁵ =

R³ = Br R⁶ = Ph; R5 =

R³ = Me; R⁶ = M e; R⁵ =

R³ *= Me; R⁶ = M Ϊ; R⁵ =

R³ = Me; R⁶ = Ph ; R5 =

R³ = Me ; R⁶ = Ph ; R5 =

NJ NJ NJ NJ NJ ω NJ H- 4-- 4-. 4-. 4^*-. 4^*>. 4^***. 4^ 4^*- 4-. ) (-0 c-

4^*. NJ H- O 00 -J σ coi 4^*- ) NJ O VO 00 -J

O O O O O O O O O O O O O O O O O O O O O O O O p pϋ p p 'T '^t F 'T pi pi pi pi

II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II P P P P P /P P /P P II II P P P P P P P P P P P P P

Pi Pi Pi Pi Pi Pi Pi 3 pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi 2 CD 2o o 2 2o 2o 2o 2o o 2 2o 2o 2o o 2 σv OS σv Os Os Os σv Os Os σv σv σv σv σv σv σv σv σv σv σv σv

II II II II II II II I III IIII II II II II II II II II II II II pi *?i pi pi pi pi pi pi pi pi pi pi

Os Os Os Os Os Os Os Os Os Os Os Os

T> TJ TJ T) T

3- Cr cr crJ TJ

Cr Cr 2 2 22 22 2 2 2 TJ TJ J J TJ J cr cr cr cr cr cr 2 2 2 2 II II II II II II II II II II II II o ^■U '. TI 'fl '. 'β ? ? ? ? ? ? crr. cr. r3i- rcir £yi rcri ofe ofe ofe ofe fe o fe o

pi pi pi pi pi pii pi pi 'pi pi pi pi *i ps 'ύ *pϋ j^*d pi pi d pi

II II II II II II II II II II II II II II II II II II II II II II II II II II II II II

G = Q-3; R⁶ = Me y, R5

G = Q-3; R⁶ = Me ;; R⁵

G = Q-3; R⁶ = Me ^y, R5

G = Q-3; R⁶ = Me :; R⁵

G = Q-3; R⁶ = Ph R5

G = Q-4; R⁶ = Me ; R⁵

G = Q-4; R⁶ = Ph R5

TABLE 10

COLUMN

(X = S)

G = Q-1 R⁶ = Me ; R⁵

G = Q-1 R⁶ = Me -; R⁵

G = Q-1 R⁶ = Me ; R⁵

G = Q-1 R⁶ = Ph R5

G = Q-2; R⁶ = Me ^y, R =

G = Q-2; R⁶ = Me y, R⁵ =

G = Q-2; R⁶ = Me v, R5 =

G = Q-2; R⁶ = Me :; R⁵ =

G = Q-2; R⁶ = Me ^y, R5 =

G = Q-2; R⁶ = Ph R⁵ =

G = Q-2; R⁶ = Ph R5 =

G = Q-2; R⁶ = Ph ; R⁵ =

G = Q-2; R⁶ = Ph R⁵ =

G = Q-3; R⁶ = Me ;; R⁵ =

G = Q-3; R⁶ = Me :; R⁵ =

G = Q-3; R⁶ = Me :; R⁵ *****

G = Q-3; R⁶ = Me :; R⁵ =

G = Q-3; R⁶ = Me :; R⁵ ****-

G = Q-3; R⁶ = Me :; R⁵ =

G = Q-3; R⁶ = Ph R5 =

G = Q-4; R⁶ = Me ; R⁵ =

G = Q-4; R⁶ = Me ; R5 =

G = Q-4; R⁶ = Me ; R⁵ =

G = Q-4; R⁶ = Ph R5 =

G = Q-4; R⁶ = Ph, R5 =

O O O O O O O O O O O O O O O O O O O O O O Ω O O O O O O O

G Q-7; R⁶

G Q-8; R⁶

G Q-9; R⁶

vo vo vo oo oo oo

U) NJ *— σv cn 4-. o oo 4^**. > o oo o o o o o o o o o o o o o o o o o X o o o o o

II II II II II II II II II II II II II II II II II II II II II II II /P /P P P /P O /P o O a © <=> © - pi pi pi pi pi

II II II II II II II II II II II II II II II II II Os Os Os Os s

II II II II II J TJ TJ J TJ cr cr sr cr cr

pi Pi Pi Pi pi pi pi pi *ϋ pi Pi pi pi pi pi $ϋ pi ιoι pi pi i pi pi pi pi pi pi pi i i pi pi pi pi pi p pi

II II II II II II II II II II II II II II II II II II II II II II II II II

10^*1 4^**. 4- 4- 4-. 4» 4"*. 4- O LO

-o σv u, 4- L © vo oo -o, σv έ 4- . 4-. (_*) L L ⁾ NJ H- oo σv 4-. © vo --) σv o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o

II II II II II II II II II II II II II II II II II II II II II II II II II O iO O / O O O O O G O O O i O O O O

^*o vo vo vo vo vo vo vo vo oo cβ oo oo (» oo oo oo cβ oo oo oo *-j *-j -j -j pi pi pi pi i pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi po

Os Os Os Os Os Os Os Os Os Os Os Os Os Os Os Os Os Os Os Os Os Os Os Os

II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II

T crJ SJ TJ TJ TJ TJ TJ TJ -?¹ cr cr cr cr cr 2 2 2 2 _.c tr 3- cr _.cr cr fe

Pi Pi P LiΛ Pi i Pi Pi Pi Pi Pi Pi Pi Pi P cioPi i Pi P i cioPi P Pi Pi Pi Pi Pi pi Pi Pi P ui, Pi Pi P ui, Pi Pi Pi Pi Pi pi i P cio¬

II II II II II II II II II II II II II ll II II II ll II II II II II II II II II II II II II II II II II II II II II ll o O o ri o O o

PC ri ri o P PC o O o P DC o o ri o DC ri o ri ri P PD r P PC o ri P DC o i X P o o DC o i o

DD O ri P

2 DC o o r PC o o o o

2 PC o P i

2 r P r

2 DC O PC o DD o o DD i o 7 7^* o o to X i

7 o 2 PC o 7 2 9 o 2 r o ro o P o r P dd O o o dd

8 o o o o O o o

8 z 2 z o o o o o

2 z z 2 z o 8 z 2 z o 8 z o ω

2 S 8 z o dd

2 z 8 z 2 z o Os o o o o o o o o o o o o o

?5 o o o o o ri CΛ o PC ri CΛ

DC o PC o i PD o CΛ

PC r PC P ri PC o o CΛ

PC o X ri PC ri DC o CΛ

DC

P P tfl o P P o O PC

NJ' P o o P P O P P i o D o DD ri PD P Tϊ O' P W P NJ' ir O C O DC J P

PC P r P W w

2 Tj 2 C o Tj Tj ri Tj o T ri o DC P

Tj o

LO II 2 2 o o Tj II 2 2 o o Tj II 2 o 2 II i 2 ro o II 2 2 o II 2 o ri o ri ri

TJ

G = Q-9; R⁶ = Ph; R5

G = Q-10 R⁶ = Me; R5

G = Q-10 R⁶ = Ph; R5

TABLE 13

(X = S) COLUMN

G = Q-5; R⁶ = Me; R5

G = Q-5; R⁶ = Ph; R5

G = Q-6; R⁶ = Me; R5

G = Q-6; R⁶ = Ph; R5

σv σv -fc*. 4^*-. 4^*. 4-. 4^*-. 4=*. 4"^*-

*-) σv σv 4^*- LO NO ^■— © oo oo σv 4^**.

O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O Ω O O O O

II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O

H- vo vo vo vo vo vo vo vo vo vo vo vo c» oo oo oo cx oo oo oo oo oo oo oo **o *-ι *-j *-ι *-) *-α *-ι *-ι ~o -α *-ι *-ι σv σv σv

"X pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi i pi pi pi i pi pi pi pi pi pi pi i pi pi pi i

P Os O Os Os Os Os Os Os Os Os Os O Os Os Os Os Os OS Os Os Os Os O Os Os Os O Os Os OS Os Os Os Os Os Os Os Os Os f II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II fe ^ r3:* ^****r *^**r cr cr cr fe fe fe ^ fe fe !^**r cr cr cr !'^*r cr fe fe fe fe fe fe C'r' 3' cr c fe fe o r: r: r: ri r: o o o o o ri ri n ri n n o o o o o o n π n nr πcr πcr o o feo feo feo fe n!^**r ncr rcir

pi pi pi pi pi pi

Uι Uι Ul Uι

Ul Ul

II II II II II II II II II II II II II II II II II II II II II II

to LO to H- -o σv σv σv σv σv σv σv σv

4^*- © © oo σv 4-.

O O O O O O O O O O O O O O O O O O O O O O O O O o o o o o o o o o o o

II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II

O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O

LO NO NJ NJ NJ NJ NJ NJ NJ NO NJ NJ pi pi pi pi pi pi pi pi pi

Os Os Os OS Os Os Os Os Os

II II II II II II II II II g J T TJ TJ TJ TJ g *' fe o π^***r π^***r n***r ncr π ncr fe fe o

pϋ pϋ pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi TJ pi TJ pi pi pi

Uι Ui U> U> Uι Uι Ui Ui Ui Ui Ui Ul Ul Ul Ui Ui Ui Ui Ui Ui Ui Ui Ui Ui Ui Ui Ui Ui Ui Ui Ui Ui Ui Ui Ul Ul

G

LO K) i— oo oo 00 oo 00 -J --1 *-) *-. o σv σv σv

LO > 4-. LO NJ H- o VO oo σv 4- © *-) σv

O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O

II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II

O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O to to to t to O O Os Os Os O Os pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi

Os Os Os O Os Os Os Os Os Os Os Os OS Os Os Os O Os Os Os Os Os Os Os Os Os Os Os Os Os Os Os Os Os Os Os II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II

G = Q-12 R⁶ = Me y, R5 = CONMe₂ S0₂CF₃ P(0)(OMe)Me

G = Q-12 R⁶ = Ph ; R5 = Me Et c-Pr

G = Q-12 R⁶ = Ph R⁵ = CH₂CN CH₂OMe (CH₂)₂CF=CF₂

G = Q-12 R⁶ = Ph R⁵ = CH₂C0₂Me OH OMe

G = Q-12 R⁶ = Ph R5 = OCH₂CN 0(CH₂)₂CF=CF COMe

G = Q-12 R⁶ = Ph R5 = CO-t-Bu C0₂Me C0₂-t-Bu

G = Q-12 R⁶ = Ph R5 = CONMe₂ S0₂CF₃ P(0)(OMe)Me

G = Q-13 R⁶ = Mc y, R5 = Me t-Pr c-Pr

G = Q-13 R⁶ = Mt ^■; R5 = CH₂CN CH₂OMe (CH₂)₂CF=CF₂

G = Q-13 R⁶ = Me ^y, R⁵ = CH₂C0₂Me OH OMe

G = Q-13 R⁶ = M« :; R⁵ = OCH₂CN 0(CH₂)₂CF=CF₂ COMe

G = Q-13 R⁶ = Me :; R⁵ = CO-t-Bu C0₂Me C0₂-t-Bu

G = Q-13 R⁶ = Me :; R⁵ = CONMe₂ S0₂CF₃ P(0)(OMe)Me

G = Q-13 R⁶ = Ph R5 = Me Et c-Pr

G = Q-13 R⁶ = Ph R5 - CH₂CN CH₂OMe (CH₂)₂CF=CF₂

G = Q-13 R⁶ = Ph R5 ₌ CH₂C0₂Me OH OMe

G = Q-13 R⁶ = Ph R5 - OCH₂CN 0(CH₂)₂CF=CF₂ COMe

G = Q-13 R⁶ = Ph R5 = CO-t-Bu C0₂Me C0₂-t-Bu

G = Q-13 R⁶ = Ph R5 = CONMe₂ S0₂CF₃ P(0)(OMe)Me

G = Q-14 R⁶ = Me ; R⁵ = Me t-Pr c-Pr

G = Q-14 R⁶ = Me ; R5 = CH₂CN CH₂OMe (CH₂)₂CF=CF₂

G = Q-14 R⁶ = Me ; R⁵ = CH₂C0₂Me OH OMe

G = Q-14 R⁶ = Me ; R5 = OCH₂CN 0(CH₂)₂CF=CF₂ COMe

G = Q-14 R⁶ = Me ; R5 = CO-t-Bu C0₂Me C0₂-t-Bu

G = Q-14 R⁶ = Me ; R⁵ = CONMe₂ S0₂CF₃ P(0)(OMe)Me

G = Q-14 R⁶ = Ph R5 = Me Et c-Pr

G = Q-14 R⁶ = Ph R5 = CH₂CN CH₂OMe (CH₂)₂CF=CF₂

G = Q-14 R⁶ = Ph R5 = CH₂C0₂Me OH OMe

G = Q-14 R⁶ = Ph R5 = OCH₂CN 0(CH₂)₂CF=CF₂ COMe

G = Q-14 R⁶ = Ph R5 = CO-t-Bu C0₂Me C0₂-t-Bu

G = Q-14 R⁶ = Ph R5 = CONMe₂ S0₂CF₃ P(0)(OMe)Me

G = Q-15 R⁶ = Me ; R⁵ = Me t-Pr c-Pr

G = Q-15 R⁶ = Me ; R⁵ = CH₂CN CH₂OMe (CH₂)₂CF=CF₂

G = Q-15 R⁶ = Me ; R⁵ = CH₂C0₂Me OH OMe

G = Q-15 R⁶ = Me ; R⁵ = OCH₂CN 0(CH₂)₂CF=CF₂ COMe

G = Q-15 R⁶ = Me ; R5 = CO-t-Bu C0₂Me C0 -t-Bu

G = Q-15 R⁶ = Me ; R⁵ = CONMe₂ S0₂CF₃ P(0)(OMe)Me

G = Q-15 R⁶ = Ph _R5 = Me Et c-Pr

G = Q-15 R⁶ = Ph R5 = CH₂CN CH₂OMe (CH₂)₂CF=CF₂

G = Q-15 R⁶ = Ph R5 = CH₂C0₂Me OH OMe

II II II II II II II II II II II II I III II II II II II II II II 11 II II II II II II II II II II II II II II

TJ TJ T) TJ J TJ J π 5 n5 n5 2 o 2 o 2 o 2 o 2 o 2 o cr εr cr .t. .tr ft rn ft ft ft ft .!"". .Ϊ-- ,!~- . .►^■- '-' — o — — o — - o - cr cr 3^*

TJ TJ pi pi pi pi pi pi pi pi pi pi pi pi _fϋ pi pi pi pi pi pc* pi pi pi pi pi pi pi pi pi pi pi Pi Pi i P

Ul Ul Uι Ul Ui Ul Ul Ul Ui Ui Ul Ul Ul Ui Ul Ui Ul Ul Ul Ul Ui Ui Ui Ui Ui Ui Uι Ul Ul Ul Ux Ui Ui Ui Ui Ui

II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II

fe fe fe fe fe fe fe fe fe o *-) Os Ui fe O oo fe © vo σ\ o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o

II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi

Os Os Ox Ox Os Ox Os Os Os Os Os Os Os Os Os Os Os Os Os Os Os Ox Os Os Os Os Os Os Os Os Os Os Os Os Os Os Os Os Os Os

II II II II II II II II II II II II II II II I III IIII IIII IIII II II II II II II II II II II

TI TJ TJ TJ TJ TJ ^ I^ tξ' g' g' ^' TJ TJ TJ TJ J TJ Tf cr cr cr cr cr cr fe fe fe fe fe fe cr cr tr cr n 5 n5 o2 2 o 2 o 2 o 2 o 2 o 3^* cr cr cr cr cr 2 o 2 o 2 o 2 o 2 o 2 o cr cr r

Pi Pi Pi Pi i pi Pi i Pi Pi Pi Pi i Pi Pi pa Pi pa i Pi Pi Pi Pi Pi Pi Pi Pi i Pi Pi Pi Pi i Pi Pi Pi Pi Pi Pi Pi

II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II

^_^^ __^^

TJ ri TJ ri TJ o TJ ri o TJ ri TJ

O ri DC O ri DC O DC ri PC ri DC ri DC o p ri P p ri P O ri P o ri O o ri P o ri P o o

^'o o No' P O NO' riι TJ ^'o o NO' ^■p o to' ri C> o NO' ^■p o to' p d ^'o

"I 2 2 2 τι 2 7 2 2 τ "I τι d 2 7^* r r o 2 2 i τι 2 7 τι ω 2 7 2 2 o 2 2 i 2 7 2 2 ri Tl 2 —_*. ω o ω o 2

II II o dd o II II o ω o II o ω o II o ω o

2 8 ri r 8 r o τι 2 8 i τι i Tl 2 8 ri τι 2 8 ri i 8 o 2 o o o Tl 2 8 r o τι 2 o

G = Q- 5; R⁶ = Me; G = Q- R⁶ = Me; G = Q- R⁶ = Me; G = Q- R⁶ = Me; G = Q- R⁶ = Me; G = Q- R⁶ = Ph; G = Q- R⁶ = Ph: G = Q- R⁶ = Ph: G = Q- R⁶ = Ph G = Q- R⁶ = Ph G = Q- R⁶ = Ph G = Q- R⁶ = Me; G = Q- R⁶ = Me; G = Q- R⁶ = Me; G = Q- R⁶ = Me; G = Q- R⁶ = Me; G = Q- R⁶ = Me; G = Q- R⁶ = Ph G = Q- R⁶ = Ph: G = Q- R⁶ = Ph: G = Q- R⁶ = Ph G = Q- R⁶ = Ph G = Q- R⁶ = Ph: G = Q- R⁶ = Me; G = Q- R⁶ = Me; G = Q- R⁶ = Me; G = Q- R⁶ = Me; G = Q- R⁶ = Me; G = Q- R⁶ = Me; G = Q- R⁶ = Ph: G = Q- R⁶ = Ph G = Q- R⁶ = Ph G = Q- R⁶ = Ph G = Q- R⁶ = Ph: G = Q- R⁶ = Ph

*-) σv fe vo σv fe

O O O O O O O O O O O O O O O O O O O O O Ω O O O O O O O O O Ω Ω O O Ω O II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o

pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi Pi pi i pi i pi pi pi pi pi pi pi pi pi pi pi pi pi pi Pi Pi

Ul Uι Ui Uι Ul Ul Ui Ui Ul Ui Ui Ui Ul Ul Ux Ux Pi

Ux

G = Q-3

G - Q-3

G = Q-3

G = Q-4

G = Q-4,

G = Q-4;

fe σv fe © LO NJ H-

Ω Ω O O Ω Ω Ω O O Ω Ω Ω Ω O O Ω Ω Ω Ω O O Ω Ω Ω O O O O Ω Ω Ω Ω Ω Ω Ω Ω Ω

pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi Pi pi pi pi pi pi

Os Ux

Ω O O O O O O Ω Ω O Ω Ω Ω Ω Ω Ω O Ω Ω Ω O Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω

O O O O O O o o o o o o o o o o o o o o o o o o o o o o o o o o o o o pi pi pi pi pi pi pi

Os Os Os Os Os Os Os II II II II II II II

O O O O O O O

pi pi Pi i Pi Pi Pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi TJ pi pi pi

Ui Ux Ux Ui Ul Uι Ui Ui Ui Uι Ui Ui Ui Ui Ui Ui U

G

oo oo -o -o σs σv σv σv σv σ σv σs σv σv fe fe σv fe © σv fe © vo -o. σv fe o vo oo σv fe oo

O O Ω Ω Ω O Ω Ω O O Ω Ω Ω Ω Ω Ω Ω O O Ω Ω Ω Ω Ω Ω Ω Ω Ω O O O O Ω Ω Ω Ω Ω Ω Ω Ω II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II ll ll II II II o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o

NJ NO JO JO JO NJ JO JO JO JO NJ JO JO JO JO NJ JO NO JO JO JO J-O JO J-O JO JO JO JO JO NO NO NO O H- H H- H H- H- H- pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi

Os Os Os Os Os Os Os O Ox Os Os Os Os Os O Ox Ox Ox Os Os Os Os Os Os Ox Os Os O OS Os Os Os Os Ox Os O Os Os Ox Os

II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o

-^{• » ■ »•} -^• -^• -^• -^■ ~j -j - . -o σv σv σv

pi Pi pi Pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi po pi pi pi pi pi pi pi

Uix Ui Ul Ui Ui Uι Ui Ui Ui Ui Ui

II II II II II II II II II II II II II II II II II II II II

o P o ri ri ri ri CΛ ri CΛ o CΛ n i i CΛ ri o PC PC O ri PC r ri PC ri C o CΛ r

P P DC NJ ui P ri P

O P P P DC DC o Ul Ui 2 2 P to O P P tn o O P Ul

2 o o ri 2 O 2 o ri o 2 o ri 2 P 2 ri to P P to' P ri PD P 2 ri ι o 2 P 2 ri 2

2 τ 2 TJ ri DC o 2 J' o i τι o o r ri PC P ri o 2 τι 2 o o TJ 2 Tt 2 o Tl o 2 2 τι

II 2 II o II 2 o 2 τι 2 ri ri τι ri ⁱ-n τι

vo vo vo oo oo oo -o --) •-) -o σv fe vo oo -o σv Ul fe fe —-

O

II o

LO x

Ui Ui Ul pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi Pi

Os Os Ox II II II II II II II II II II II II II II II II II II II II II II

II II II

υ fe

43 43 43 43 43 43 43 43 43 43 43 43 43 43 43 43 43 43 43 43 43 43 43 Xi 43 43 43 43 43 43 43 43 43 fe fe fe fe fe fe fe fe fe fe fe fe fe fe fe fe fe fe fe fe fe fe fe fe fe fe fe fe fe fe fe fe fe

43 43 -8 43 43 43 43 43 43 43 43 43 43 43 43 43 43 43 43 43 43 43 43 .8 43 43 43 43 43 43 43 43 43

B - B^* B- B- B^* B* B"

-^H fN

4-. 4-ι fe fe LO L L L L L LO L L L N NO NO NO NJ NJ NO NO NO NJ H- H-i HH H- H- . σv ui fe Lo to H- o vo oo *— i σv ui fe Lo i-O H- o vo oo — ^* σv uι LO to

Pi Pi Pi pi Pi J* Pi > i Pi *J i * Pi i Pi *J i Pi !*> Pi *J pi Pi i IΛ Pi Pi *J Pi *J Pi Pi *J pa i

00 oo oo 00 oo oo 00 00 00 oo 00 00 oo oo 00 oo oo 00 00 oo oo 00 oo 00 00 00 oo oo 00 oo oo 00 oo oo 00 00 oo 00 00 oo

P P P P O P P O O P P

PC PD DC DC PC C DC P PC PC DC DC PC DC DC DD P P DC g o ^HD 2o '^ 2o ^ 2o ^ o2 ^ 2o ^ o2 ^ o2 ^ 2o '^ 2o '^:c^ o

2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 | 2 CgΛ 2 g 2 C2Λ 2 CgΛ 2 2 2 CgΛ 2 | 2 CgΛ 2 CgΛ 2 CgΛ O O 0 O O 0 O O 0 O 0 O O ^ O « O ^ « £* 0 fr θ £* S?' « 0 fc?^ι O t?^ι

J Ti TJ TJ TJ TJ TJ TJ J TJ TJ TJ TJ TJ TJ J TJ TJ J TJ J TJ TJ TJ TJ J TJ TJ TJ id J cr cr cr cr cr cr cr cr cr cr cr cr cr cr cr -r cr cr cr r TJ cr d cr cr cr TJ

•-I cr TJ cr TJ cr Tl cr TJ cr TS cr

_{v f ^} ^ _{s r} _{/ s ^} ^^ ^-_{^ v} ^ _{r ^} —. , ^^ ^ ^*— . ^^ _{f ^} , _{v r ^ ι r s} , _{^ κ r s} , _s ^-_^ ^

NO o NO NJ NJ NJ NJ NJ NJ NO NO NJ t NJ NO to NJ NJ NJ NJ NJ NO NJ NO NJ NO NO NO NO NO σv σv σv o σv σs σv σv σv σs σv σv σv σ- σv O σv σv σs σs σs σs σv σv σs σv σv σs σv σs fe c fe ei. fe fe ca- fe fe fe a. ei. o- fe fe a. a. fe D. U fe U fe U fe u fe u fe U fe u fe u fe u α. u &.

T| Tj T| T| T| τι Tj T| Ti T| Tj Tj Tl T| PC * -_^ T-^| TΪ T| T| T| τι PC

-- T Ui --*| T| PC Tj PC Tl i τι PC T| DC T| T| Ui T| PC

*-- Tl^'

TJ TJ TJ J TJ TJ TJ TJ J TJ TJ J TJ TJ TJ TJ TJ TJ TJ TJ TJ TJ TJ TJ TJ TJ TJ TJ T) TJ cr cr cr cr cr cr cr cr cr cr cr cr cr cr cr ~r cr cr cr cr cr cr cr cr cr cr cr cr cr cr

G = Q-9; X = S; _R18

G = Q-10;X = S _R18

G = Q-15;X = S, _R18

G = Q-16;X = S; _R18

G = Q-17;X = S; _R18

TABLE 22

COLUMN

G = Q-1 ,X = NH _R18

G = Q-1 X = NH _R18

G = Q-2 X = NH _R18

G = Q-3 X = NH _R18

G = Q-4 X = NH _R18

G = Q-4 X = NH, _R18

G = Q-5 X = NH, _R18

G = Q-5 X = NH; _R18

G = Q-6 X = NH; _R18

G = Q-7 X = NH; _R18

G = Q-9 X = J H; _R18

G = Q-9 X = NH; _R18

G = Q-10;X = NF I; Rl8

G = Q-10;X = NF 1; Rl8

G = Q-15;X = NF I; Rl8

G = Q-15;X = NF 1; Rl

G = Q-15;X = NF 1; Rl8

G = Q-1( >;X = NF [; Rl

fl

VO

43 43 43 43 43 43 43 43 43 43 43 43 43 43 43 43 43 43 43 43 43 -3 43 43 43 43 fe ef fe fe fe fe fe fe fe fe fe fe fe fe fe fe fe fe fe fe fe fe fe fe fe fe 3 3 e fe fe fe fe fe fe fe fe fe fe fe fe fe fe fe fe fe fe fe fe fe fe fe fe fe 3 « 3 m υ H fe f

^•Ό fe K -o -a -α -o Ό -α -o -α -α -α ^•o -α -3 -o -o Ό J -o -α ^•α -α -o -o Ό m fe 43 m

T 43 rΛ vo fe fN CN CN CN o fe

P u P υ P u u

3 3

2 -8 3 43 -8 43 43 43 43 43 43 43 43 43 43 43 43 43 fe 2 2 4 ef fe fe fe fe fe fe fe fe fe fe fe fe fe fe fe fe fe fe fe fe fe fe fe fe

T *^r T T T T T T T T ιn m —i CN fl in vo

fe fe fe fe fe fe fe fe > σv fe σv fe oo σv fe LO NJ i--

Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω

Pi Pi Pi i Pi Pi pa pa r0 Pi Pi pa pa pa Pi pa Pi pa Pi pa pa pa pa pa pa pa Pi Pi Pi Pi Pi pa Pi i Pi pa pa pa pa pa

00 00 00 00 00 oo oo 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 oo oo 00 00 00 00 00 00 00 00 00 00 oo 00 00 00

ri ri ri ri ri ri CΛ ri ΓΛ ri CΛ n ΓΛ O ΓΛ ri ΓΛ ri CΛ O CΛ ri CΛ ri

O o — . O «-. O ~. O ~. U O ~. υ O ~. υ O ~. o O ~. U O —. U ~. U O ~. υ O ~. O O ~. O P

7 TJ 7^* J TJ *-_* TJ Tl TJ TJ TJ TJ m m ι-1 m ffl m ^' T3 T)

2 ^'ύ 2 ι-1 ^'ύ 2 ^'ύ 2 -I ^' TJ

2 H 2 ^' 2 a TJ

2 •- o to o to o to o o o o to ^'ύ TJ

2 o ^'

8 8 8 8 8 to o 2 o

ri ri ri ri ri ri ri n ri ri ri ri ri ri ri

P P o o P O ri P ri O ri P o P ri P ri P n O ri P ri P ri

TJ TJ TJ TJ O T cr a Tl cr § TJ cr § cr 3 TJ cr § r § P Tl cr j-a P TJ O cr § o T3 P cr § 7 cr X TJ P J 9 cr § 9 TJ O J cr X TJ cr § 7 cr § 7 cr

7 • ** 7 ro 7 ω ro »-_*. ro ro 7 « ro ro 7 W ro

8 ro 8 ro 8 ro 8 w 8 ω ω 8

8 ω 8 c ro 8

8 8 ro 8

8 ω 8 ro 8

8 ω 3 ro 8 or 8

8 8 ro 8

8 8

O Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω

II II

O O

X X

II II

CΛ CΛ

pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pj pi pi pi pi pl pi

00 oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo 00 oo oo oo

II II II II II II II II II II II II II II II II II II II II II II II II

O O Ω Ω Ω Ω O Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω X II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o II -^• -^• Ux © -^■ *-) σs l 4- LO to H- o ^**^• pi pi pi pi pi pi ''X "χ pi pi pi pi pi pi pi pi ''X 'X ''X ''X ''X ''X ''X ''χ pi pi pi pi pi pa pa pi pi pi pi pi pi

Ox Os Os Ox Os Os pa pa Os Os Ox Os Os Os Ox Os pi pi pi pi pi pi pi pi Os Os Os Os Os Os Ox Os Os Os Os Os Ox PC

II II II II II II f ¹ II II II II II II II II f* " ¹ f f¹ f f " II II II II II II II II II II II II II NJ NJ tO NJ NO No " " d ⁱ-d TJ TJ TJ TJ TJ Tj " " " " " " " ^ll 5' -?' l?' t?' l?' -?' -?' !?' 5^,' S?' 5ⁱ' t' - II

>-i *~i *~i *~i <-- "0 Λ >^ n n n n n n n π fe fe fe fe fe fe fe fe o o o o o o o o o o o o ^>< ^{, v}< -- ι--^ι ι-- j-; j-; o o o o o o o o *** -* *'* *'* -* *'* "'* *'* *'* -* -* ''* -*

pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi ^ϋ pi pi pi pi pi pi pi pi pi pi pi pi

Ui Ul Ul Ui Ul Ui Ui Ui Ui Ui Ul Ul Ul Ul Ui Ul II II II II II II II II II II II II II II II II II II II II II II II II II II II II II

TJ TJ pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi

Ui Ui Uι Ui II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II

PC DC PC PC PC C fe fe H fe fe H C fe H fe fe H fe fe PC fe HH fe fe fe fe fe fe PC fe fe fe HH P fe

00 NO

2 a 2 *π 2 2 2o 2* 2*n> 2o 2<i> 2'n> 2*rD 2_'n> 2o 2o 2 2*n> 2 2 2fD 2_'rD 2*-ri. 2O 2_'fl> 2o 2 2 2 2 2 2 2 2 2 2 2 2 2 2

m rn m tn tn tn m in tn m tn tn m hi tn m tn m rn m m rn in hi m tn hi m i hi tn hi hi hi hi hi hi tn

a a 3 a a 3 a 3 3 3 3 3 3 3 a 3 3 3 3 3 a 3 J TJ TJ TJ -d TJ TJ TJ TJ Tl TJ TJ TJ J TJ TJ J TJ J TJ TJ TJ J TJ J TJ TJ TJ TJ TJ TJ TJ J TJ J TJ TJ TJ

3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 J Tl Tl TJ D oC o DC P oC ώ o D oC P oD oC P oC o PC o DC D oC P oC P oC P oC o PC P oC P oC PC D oC P oC P oC PC P oC D oC o PC P oD D oC o PC o PC P oC P oC P oC P oC P oC

X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X n rs

TJ TJ TJ TJ ro ω ro ω ω ro » ω ω W ω ro W

3 3 3 3 3 3 3 3 ω 3 » 3 ro W

3 3 3 ω 3 ro 3 3 3 ω ro 3 ro 3 3 ω 3 ω ro 3 ω 3 ro 3 ro 3 3 ω ω 3 ro a

3 3 ω 3 ro

3 3 3 3

pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi TJ TJ TJ pi pi Pi

II II II II II II II II II II II II II II II II II II II II II

fe NO NO to

pi pi pi pi pi po pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi pi

Ux Ux Ux Ux Ux Ux Ux Ux Ui Ui Ui Ui Ui Ui Ui Ui Ui p Uax Ul Ux Ux Ux Ux Ux Ux Ux Ui Ui

II II II II II II II II II II II II II II II II II II II II II II

PC PC PD DC PC PC C PC - PC PC C PC PD PC PD PC PC PC PC C DC C PC PC X PC PC DC PC DC DC PC r 00 w -fe

2 2 2 2 NO o o 2 o o 2 o o o 2 2 o σv 2 o 2 o 2 o 2 o 2 o 2 o 2 o 2 o 2 o 2 o o 2 2 o 2 o o 2 2 o 2 o o 2 2 o 2 o 2 o 2 o 2 o 2 o 2 o

hi h tn W ffl hi hi hi tn in tn hi i tn hi W hi hi hi tn hi tn hi hi tn hi hi hi W m W

3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 f TJ TJ TJ TJ TJ TJ TJ fe TJ TJ TJ TJ TJ TJ ) TJ TJ T* TJ TJ TJ J TJ TJ TJ TJ TJ TJ TJ TJ TJ

"1 n - •-I

3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3

PC PC PC PC C PC PC PC PC PC PC PC PC PC PC PC DC PC PC DC PC DC DD PC PC PC DD DC DC PC PC o o o o o o o o o o o o o o o o o o o O O o o X o o o o o o o X X X S X X X X X X X X X X X X X X X X X X X 8 X X X X X X X ω ro ro w ω ro W ω σs ω ro ro ω ω ω ro ro r ro ro ro ro ω ro ro ω ro ω ω ro ro

3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 « 3 3 w o

3 3 3 3 3 3 3 3 3 3 3 3 3 3 3

9 G = Q-10; R⁶ = Me; R⁵

10 G = Q-15; R⁶ = Me; R⁵

11 G = Q-l; R⁶ = Ph R5

12 G = Q-2; R⁶ = Ph R5

13 G = Q-3; R⁶ = Ph R5

14 G = Q-4; R⁶ = Ph R5

15 G = Q-5; R⁶ = Ph R5

16 G = Q-6; R⁶ = Ph R5

17 G = Q-7; R⁶ = Ph R5

18 G = Q-9; R⁶ = Ph R5

19 G = Q-10; R⁶ = PJ ; R⁵

20 G = Q-15; R⁶ = P1 I; R⁵

(X = S; Hal = Br)

21 G = Q-l; R⁶ = Me ; R⁵

22 G = Q-2; R⁶ = Me ; R⁵

23 G = Q-3; R⁶ = Me ; R⁵

24 G = Q-4; R⁶ = Me ; R⁵

25 G = Q-5; R⁶ = Me ; R⁵

26 G = Q-6; R⁶ = Me ; R⁵

27 G = Q-7; R⁶ = Me ; R⁵

28 G = Q-9; R⁶ = Me ; R⁵

29 G = Q-10; R⁶ = M e; R⁵

30 G = Q-15; R⁶ = M e; R⁵

(X = S; Hal = Cl)

31 G = Q-l; R⁶ = Me; R5 =

32 G = Q-2; R⁶ = Me; R5 =

33 G = Q-3; R⁶ = Me; R5 =

34 G = Q-4; R⁶ = Me; R5 =

35 G = Q-5; R⁶ = Me; R5 =

36 G = Q-6; R⁶ = Me; R5 =

37 G = Q-7; R⁶ = Me; R5 =

38 G = Q-9; R⁶ = Me; R5 =

39 G = Q-10; R⁶ = Me; R5 =

40 G = Q-15; R⁶ = Me; R5 =

Formulation/Utility

Compounds of this invention will generally be used as a formulation or composition with an agriculturally suitable carrier comprising at least one of a liquid diluent, a solid diluent or a surfactant. The formulation or composition ingredients are selected to be consistent with the physical properties of the active ingredient, mode of application and environmental factors such as soil type, moisture and temperature. Useful formulations include liquids such as solutions (including emulsifiable concentrates), suspensions, emulsions (including microemulsions and/or suspoemulsions) and the like which optionally can be thickened into gels. Useful formulations further include solids such as dusts, powders, granules, pellets, tablets, films, and the like which can be water-dispersible ("wettable") or water-soluble. Active ingredient can be (micro)encapsulated and further formed into a suspension or solid formulation; alternatively the entire formulation of active ingredient can be encapsulated (or "overcoated"). Encapsulation can control or delay release of the active ingredient. Sprayable formulations can be extended in suitable media and used at spray volumes from about one to several hundred liters per hectare. High-strength compositions are primarily used as intermediates for further formulation.

The formulations will typically contain effective amounts of active ingredient, diluent and surfactant within the following approximate ranges which add up to 100 percent by weight.

Weight Percent

Active Ingredient Diluent Surfactant

Water-Dispersible and Water-soluble 5-90 0-94 1-15 Granules, Tablets and Powders.

Suspensions, Emulsions, Solutions 5-50 40-95 0-15 (including Emulsifiable Concentrates)

Dusts 1-25 70-99 0-5

Granules and Pellets 0.01-99 5-99.99 0-15

High Strength Compositions 90-99 0-10 0-2

Typical solid diluents are described in Watkins, et al., Handbook of Insecticide Dust Diluents and Carriers, 2nd Ed., Dorland Books, Caldwell, New Jersey. Typical liquid diluents are described in Marsden, Solvents Guide, 2nd Ed., Interscience, New York, 1950. McCutcheon 's Detergents and Emulsifiers Annual, Allured Publ. Corp., Ridgewood, New Jersey, as well as Sisely and Wood, Encyclopedia of Surface Active Agents, Chemical Publ. Co., Inc., New York, 1964, list surfactants and recommended uses. All formulations can contain minor amounts of additives to reduce foam, caking, corrosion, microbiological growth and the like, or thickeners to increase viscosity.

Surfactants include, for example, polyethoxylated alcohols, polyethoxylated alkylphenols, polyethoxylated sorbitan fatty acid esters, dialkyl sulfosuccinates, alkyl sulfates, alkylbenzene sulfonates, organosilicones, N,N-dialkyltaurates, lignin sulfonates, naphthalene sulfonate formaldehyde condensates, polycarboxylates, and polyoxyethylene/polyoxypropylene block copolymers. Solid diluents include, for example, clays such as bentonite, montmorillonite, attapulgite and kaolin, starch, sugar, silica, talc, diatomaceous earth, urea, calcium carbonate, sodium carbonate and bicarbonate, and sodium sulfate. Liquid diluents include, for example, water, N-N-dimethylformamide, dimethyl sulfoxide, N-alkylpyrrolidone, ethylene glycol, polypropylene glycol, paraffins, alkylbenzenes, alkylnaphthalenes, oils of olive, castor, linseed, tung, sesame, corn, peanut, cotton-seed, soybean, rape-seed and coconut, fatty acid esters, ketones such as cyclohexanone, 2-heptanone, isophorone and 4-hydroxy-4-methyl-2-pentanone, and alcohols such as methanol, cyclohexanol, decanol and tetrahydrofurfuryl alcohol.

Solutions, including emulsifiable concentrates, can be prepared by simply mixing the ingredients. Dusts and powders can be prepared by blending and, usually, grinding as in a hammer mill or fluid-energy mill. Suspensions are usually prepared by wet-milling; see, for example, U.S. 3,060,084. Granules and pellets can be prepared by spraying the active material upon preformed granular carriers or by agglomeration techniques. See Browning, "Agglomeration", Chemical Engineering, December 4, 1967, pp 147-48, Perry 's Chemical Engineer 's Handbook, 4th Ed., McGraw-Hill, New York, 1963, pages 8-57 and following, and WO 91/13546. Pellets can be prepared as described in U.S. 4,172,714. Water-dispersible and water-soluble granules can be prepared as taught in U.S. 4,144,050, U.S. 3,920,442 and DE 3,246,493. Tablets can be prepared as taught in U.S. 5,180,587, U.S. 5,232,701 and U.S. 5,208,030. Films can be prepared as taught in GB 2,095,558 and U.S. 3,299,566.

For further information regarding the art of formulation, see U.S. 3,235,361, Col. 6, line 16 through Col. 7, line 19 and Examples 10-41; U.S. 3,309,192, Col. 5, line 43 through Col. 7, line 62 and Examples 8, 12, 15, 39, 41, 52, 53, 58, 132, 138-140, 162-164, 166, 167 and 169-182; U.S. 2,891,855, Col. 3, line 66 through Col. 5, line 17 and Examples 1-4; Klingman, Weed Control as a Science, John Wiley and Sons, Inc., New York, 1961, pp 81-96; and Hance et al., Weed Control Handbook, 8th Ed., Blackwell Scientific Publications, Oxford, 1989.

In the following Examples, all percentages are by weight and all formulations are prepared in conventional ways. Compound numbers refer to compounds in Index Tables A-B.

Example A Wettable Powder

Compound 2 65.0% dodecylphenol polyethylene glycol ether 2.0% sodium ligninsulfonate 4.0% sodium silicoaluminate 6.0% montmorillonite (calcined) 23.0%. Example B

Granule

Compound 4 10.0% attapulgite granules (low volatile matter,

0.71/0.30 mm; U.S.S. No. 25-50 sieves) 90.0%

Example C

Extruded Pellet

Compound 2 25.0% anhydrous sodium sulfate 10.0% crude calcium ligninsulfonate 5.0% sodium alkylnaphthalenesulfonate 1.0% calcium magnesium bentonite 59.0%.

Example D

Emulsifiable Concentrate Compound 4 20.0% blend of oil soluble sulfonates and polyoxyethylene ethers 10.0% isophorone 70.0%.

The compounds of this invention exhibit activity against a wide spectrum of foliar-feeding, fruit-feeding, stem or root feeding, seed-feeding, aquatic and soil-inhabiting arthropods (term "arthropods" includes insects, mites and nematodes) which are pests of growing and stored agronomic crops, forestry, greenhouse crops, ornamentals, nursery crops, stored food and fiber products, livestock, household, and public and animal health. Those skilled in the art will appreciate that not all compounds are equally effective against all growth stages of all pests. Nevertheless, all of the compounds of this invention display activity against pests that include: eggs, larvae and adults of the Order Lepidoptera; eggs, foliar-feeding, fruit-feeding, root-feeding, seed-feeding larvae and adults of the Order Coleoptera; eggs, immatures and adults of the Orders Hemiptera and Homoptera; eggs, larvae, nymphs and adults of the Order Acari; eggs, immatures and adults of the Orders Thysanoptera, Orthoptera and Dermaptera; eggs, immatures and adults of the Order Diptera; and eggs, juveniles and adults of the Phylum Nematoda. The compounds of this invention are also active against pests of the Orders Hymenoptera, Isoptera, Siphonaptera, Blattaria, Thysanura and Psocoptera; pests belonging to the Class Arachnida and Phylum Platyhelminthes. Specifically, the compounds are active against southern corn rootworm (Diabrotica undecimpunctata howardi), aster leafhopper (Mascrosteles fascifrons), boll weevil (Anthonomus grandis), two-spotted spider mite (Tetranychus urticae), fall armyworm (Spodoptera frugiperda), black bean aphid (Aphis fabae), green peach aphid (Myzus persica), cotton aphid (Aphis gossypii), Russian wheat aphid (Diuraphis noxia), English grain aphid (Sitobion avenae), tobacco budworm (Heliothis virescens), rice water weevil (Lissorhoptrus oryzophilus), rice leaf beetle (Oulema oryzae), whitebacked planthopper (Sogatella furcifera), green leafhopper (Nephotettix cincticeps), brown planthopper (Nilaparvata lugens), small brown planthopper (Laodelphax striatellus), rice stem borer (Chilo suppressalis), rice leafroller (Cnaphalocrocis medinalis), black rice stink bug (Scotinophara lurida), rice stink bug (Oebalus pugnax), rice bug (Leptocorisa chinensis), slender rice bug (Cletus puntiger), and southern green stink bug (Nezara viridula). The compounds are active on mites, demonstrating ovicidal, larvicidal and chemosterilant activity against such families as Tetranychidae including Tetranychus urticae, Tetranychus cinnabarinus, Tetranychus mcdanieli, Tetranychus paciβcus, Tetranychus turkestani, Byrobia rubrioculus, Panonychus ulmi, Panonychus citri, Eotetranychus carpini borealis, Eotetranychus, hicoriae, Eotetranychus sexmaculatus, Eotetranychus yumensis, Eotetranychus banksi and Oligonychus pratensis; Tenuipalpidae including Brevipalpus lewisi, Brevipalpus phoenicis, Brevipalpus californicus and Brevipalpus obovatus; Eriophyidae including Phyllocoptruta oleivora, Eriophyes sheldoni, Aculus cornutus, Epitrimerus pyri and Eriophyes mangiferae. See WO 90/10623 and WO 92/00673 for more detailed pest descriptions.

The compounds of this invention are also useful as plant disease control agents. The present invention therefore further comprises a method for controlling plant diseases caused by fungal plant pathogens comprising applying to the plant or portion thereof to be protected, or to the plant seed or seedling to be protected, an effective amount of a compound of the invention or a fungicidal composition containing said compound. The compounds and compositions of this invention provide control of diseases caused by a broad spectrum of fungal plant pathogens in the Basidiomycete, Ascomycete, Oomycete and Deuteromycete classes. They are effective in controlling a broad spectrum of plant diseases, particularly foliar pathogens of ornamental, vegetable, field, cereal, and fruit crops. These pathogens include Plasmopara viticola, Phytophthora infestans, Peronospora tabacina, Pseudoperonospora cubensis, Pythium aphanidermatum, Alternaria brassicae, Septoria nodorum, Septoria tritici, Cercosporidium personatum, Cercospora arachidicola, Pseudocercosporella herpotrichoides, Cercospora beticola, Botrytis cinerea, Monilinia fructicola, Pyricularia oryzae, Podosphaera leucotricha, Venturia inaequalis, Erysiphe graminis, Uncinula necatur, Puccinia recondita, Puccinia graminis, Hemileia vastatrix, Puccinia striiformis, Puccinia arachidis, Rhizoctonia solani, Sphaerotheca fuliginea, Fusarium oxysporum, Verticillium dahliae, Pythium aphanidermatum, Phytophthora megasperma, Sclerotinia sclerotiorum, Sclerotium rolfsii, Erysiphe polygoni, Pyrenophora teres, Gaeumannomyces graminis, Rynchosporium secalis, Fusarium roseum, Bremia lactucae and other generea and species closely related to these pathogens.

Compounds of this invention can also be mixed with one or more other insecticides, fungicides, nematocides, bactericides, acaricides, growth regulators, chemosterilants, semiochemicals, repellents, attractants, pheromones, feeding stimulants or other biologically active compounds to form a multi-component pesticide giving an even broader spectrum of agricultural protection. Examples of such agricultural protectants with which compounds of this invention can be formulated are: insecticides such as abamectin, acephate, azinphos-methyl, bifenthrin, buprofezin, carbofuran, chlorfenapyr, chlorpyrifos, chlorpyrifos-methyl, cyfluthrin, beta-cyfluthrin, cyhalothrin, lambda-cyhalothrin, deltamethrin, diafenthiuron, diazinon, diflubenzuron, dimethoate, esfenvalerate, fenoxycarb, fenpropathrin, fenvalerate, fipronil, flucythrinate, tau-fluvalinate, fonophos, imidacloprid, isofenphos, malathion, metaldehyde, methamidophos, methidathion, methomyl, methoprene, methoxychlor, methyl 7-chloro-2,5-dihydro-2-[[N-(methoxycarbonyl)-N-[4-

(trifluoromethoxy)phenyl] amino] carbonyl] indeno [ 1 ,2-e] [ 1 ,3 ,4] oxadiazine-4a(3H)- carboxylate (DPX-JW062), monocrotophos, oxamyl, parathion, parathion-methyl, permethrin, phorate, phosalone, phosmet, phosphamidon, pirimicarb, profenofos, rotenone, sulprofos, tebufenozide, tefluthrin, terbufos, tetrachlorvinphos, thiodicarb, tralomethrin, trichlorfon and triflumuron; fungicides such as azoxystrobin, benomyl, blasticidin-S,

Bordeaux mixture (tribasic copper sulfate), bromuconazole, captafol, captan, carbendazim, chloroneb, chlorothalonil, copper oxychloride, copper salts, cymoxanil, cyproconazole, cyprodinil (CGA 219417), diclomezine, dicloran, difenoconazole, dimethomorph, diniconazole, diniconazole-M, dodine, edifenphos, epoxiconazole (BAS 480F), famoxadone, fenarimol, fenbuconazole, fenpiclonil, fenpropidin, fenpropimorph, fluazinam, fluquinconazole, flusilazole, flutolanil, flutriafol, folpet, fosetyl-aluminum, furalaxyl, hexaconazole, ipconazole, iprobenfos, iprodione, isoprothiolane, kasugamycin, kresoxim-methyl, mancozeb, maneb, mepronil, metalaxyl, metconazole, S-methyl 7-benzothiazolecarbothioate (CGA 245704), myclobutanil, neo-asozin (ferric methanearsonate), oxadixyl, penconazole, pencycuron, probenazole, prochloraz, propiconazole, pyrifenox, pyroquilon, quinoxyfen, spiroxamine (KWG4168), sulfur, tebuconazole, tetraconazole, thiabendazole, thiophanate-methyl, thiram, triadimefon, triadimenol, tricyclazole, triticonazole, validamycin and vinclozolin; nematocides such as aldoxycarb and fenamiphos; bactericides such as streptomycin; acaricides such as amitraz, chinomethionat, chlorobenzilate, cyhexatin, dicofol, dienochlor, etoxazole, fenazaquin, fenbutatin oxide, fenpropathrin, fenpyroximate, hexythiazox, propargite, pyridaben and tebufenpyrad; and biological agents such as Bacillus thuringiensis, Bacillus thuringiensis delta endotoxin, baculovirus, and entomopathogenic bacteria, virus and fungi.

In certain instances, combinations with other fungicides or arthropodicides having a similar spectrum of control but a different mode of action will be particularly advantageous for resistance management.

Preferred for better control of pests (use rate or spectrum) or resistance management are mixtures of a compound of this invention with an arthropodicide selected from the group: acephate, buprofezin, carbofuran, 2,5-dihydro-2-[[N-(methoxycarbonyl)-N-[4- (trifluoromethoxy)phenyl] amino] carbonyl] indeno [ 1 ,2 -e] [ 1 ,3 ,4] oxadiazine-4a(3H)- carboxylate (DPX-JW062), dimethoate, esfenvalerate, fipronil, imidacloprid, methomyl, monocrotophos, phorate, and phosphamidon. Arthropod pests are controlled and protection of agronomic, horticultural and specialty crops, animal and human health is achieved by applying one or more of the compounds of this invention, in an effective amount, to the environment of the pests including the agronomic and/or nonagronomic locus of infestation, to the area to be protected, or directly on the pests to be controlled. Thus, the present invention further comprises a method for the control of foliar and soil inhabiting arthropods and nematode pests and protection of agronomic and/or nonagronomic crops, comprising applying one or more of the compounds of the invention, or compositions containing at least one such compound, in an effective amount, to the environment of the pests including the agronomic and/or nonagronomic locus of infestation, to the area to be protected, or directly on the pests to be controlled. A preferred method of application is by spraying. Altematively, granular formulations of these compounds can be applied to the plant foliage or the soil. Other methods of application include direct and residual sprays, aerial sprays, seed coats, microencapsulations, systemic uptake, baits, eartags, boluses, foggers, fumigants, aerosols, dusts and many others. The compounds can be incorporated into baits that are consumed by the arthropods or in devices such as traps and the like.

For the control arthropod pests, the compounds of this invention can be applied in their pure state, but most often application will be of a formulation comprising one or more compounds with suitable carriers, diluents, and surfactants and possibly in combination with a food depending on the contemplated end use. A preferred method of application involves spraying a water dispersion or refined oil solution of the compounds. Combinations with spray oils, spray oil concentrations, spreader stickers, adjuvants, other solvents, and synergists such as piperonyl butoxide often enhance compound efficacy.

The rate of application required for effective control will depend on such factors as the species of arthropod to be controlled, the pest's life cycle, life stage, its size, location, time of year, host crop or animal, feeding behavior, mating behavior, ambient moisture, temperature, and the like. Under normal circumstances, application rates of about 0.01 to 2 kg of active ingredient per hectare are sufficient to control pests in agronomic ecosystems, but as little as 0.001 kg/hectare may be sufficient or as much as 8 kg/hectare may be required. For nonagronomic applications, effective use rates will range from about 1.0 to 50 mg/square meter but as little as 0.1 mg/square meter may be sufficient or as much as 150 mg/square meter may be required.

Plant disease control is ordinarily accomplished by applying an effective amount of a compound of this invention either pre- or post-infection, to the portion of the plant to be protected such as the roots, stems, foliage, fruit, seeds, tubers or bulbs, or to the media (soil or sand) in which the plants to be protected are growing. The compounds can also be applied to the seed to protect the seed and seedling.

For plant disease control, rates of application for these compounds can be influenced by many factors of the environment and should be determined under actual use conditions. Foliage can normally be protected when treated at a rate of from less than 1 g/ha to 5,000 g/ha of active ingredient. Seed and seedlings can normally be protected when seed is treated at a rate of from 0.1 to 10 g per kilogram of seed.

The following tests demonstrate the control efficacy of compounds of this invention on specific arthropod and pathogen pests. For the tests on arthropod pests, "control efficacy" represents inhibition of arthropod development (including mortality) that causes significantly reduced feeding. The arthropod and pathogen pest control protection afforded by the compounds is not limited, however, to these species. See Index Tables A-D for compound descriptions. The abbreviation "Ex." stands for "Example" and is followed by a number indicating in which example the compound is prepared. Isomer indicates cis or trans with respect to the cyclohexane ring.

INDEX TABLE A

Cmpd No. Isomer EZ R5 mp CO

(Ex. No.)

1 (Ex. 1) cis H H 6-Et-5-Cl-4- 119-121 pyrimidinyl

2 trans H H 6-Et-5-Cl-4- > 255 ^α pyrimidinyl

3 cis: trans = 7.5:1 H H 4-quinazolinyl solid ^a

4 trans H H 4-quinazolinyl > 260 ^α

5 cis H H 6-MeOCH₂-5- 109-111 MeO-4- pyrimidinyl

6 cis: trans = 18: 1 H H 6-MeOCH₂-4- solid ^a pyrimidinyl

7 cis H H 5,6,7,8- solid ^a tetrahydro-4- quinazolinyl

CIS H H 6-Et-4- 123-124 pyrimidinyl Cmod No. Isomer R⁷ R G mo (°C)

(Ex. No.)

9 cis H H 3-t-Bu- 1,2,4- 175-180 thiadiazol-5-yl

10 (Ex. 2a) cis H Me 6-Et-5-Cl-4- 68-70 pyrimidinyl

11 cis H Et 6-Et-5-Cl-4- oil ^α pyrimidinyl

12 cis H n-Pr 6-Et-5-Cl-4- 81-83 pyrimidinyl

13 cis H n-Bu 6-Et-5-Cl-4- oil " pyrimidinyl

14 cis H CH₂CH=CH₂ 6-Et-5-Cl-4- oil " pyrimidinyl

15 (Ex. 2b) cis Me Me 6-Et-5-Cl-4- 86-87 pyrimidinyl

16 cis Et Et 6-Et-5-Cl-4- 99-100 pyrimidinyl

17 cis CH₂CH=CH₂ CH₂CH=CH₂ 6-Et-5-Cl-4- oil ^Ω pyrimidinyl

18 (Ex. 3) cis H-HC1 H'HCl 6-Et-5-Cl-4- 239-242 pyrimidinyl

" See Index Table D for --H NMR data.

INDEX TABLE B

Cmpd No. Isomer RZ si x mp (°C)

19 cis H COMe H 158-159

20 cis Me COMe H 126-133 "

21 cis H C0₂- -Bu H 152-154

22 cis Me C0₂-/-Bu H 121-127

23 cis Et C0₂-t-Bu H oil "

24 cis CH₂C ≡CH C0 -t-Bu H solid " Cmpd No. Isomer sZ si si mt> (°C)

25 cis H C0₂Bn H oil"

26 (Ex. Ila) cis H OMe H oil"

27 (Ex. lib) trans H OMe H 87-88

28 cis Me OMe H oil"

29 cis: trans = 7:1 H OBn H oil"

30 trans H OBn H 116-121

31 (Ex.7a) cis H Me Me 62-66

32 (Ex. 7b) trans H Me Me oil"

33 cis H n-Bu Me oil"

34 trans H n-Bu Me 47-48

35 cis Me C0₂Et Me oil"

36 cis H OMe Me oil"

37 (Ex. 5a) cis H H Ph 88-93

38 (Ex. 5b) trans H H Ph 137-139

39 cis H Me Ph oil" 0 trans:cis = 8:1 H Me Ph 83-84 " 1 trans:cis = H Et Ph oil" 1.3:1 2 cis:trans = 2:\ H Bn Ph oil" 3 trans H Bn Ph oil" 4 cis:trans = H CH₂CH=CH₂ Ph oil" 1.5:1 5 trans:cis = 6: 1 H CH₂CH=CH₂ Ph oil" 6 (Ex. 6) cis H CH₂C≡CH Ph oil" 7 cis H CH₂CN Ph 79-80 8 cis H (CH₂)2θH Ph 111-115 9 trans H (CH₂)₂OH Ph solid " 0 cis H CH₂C0₂-.-Bu Ph solid " 1 cis H COMe Ph 125-127 2 cis H COEt Ph 86-90 3 cis H COCF₃ Ph 99-101 4 cis H CO-c-Pr Ph oil" 5 cis H CO-Z-Bu Ph 80-81 6 cis H COPh Ph 134-136 7 cis H C0₂Me Ph 95 8 cis H C0₂Et Ph oil" 9 trans H C0₂Et Ph 137-140 0 cis H C0₂-.-Pr Ph 72-75 1 cis H C0₂--Bu Ph oil" 2 cis H C0₂Bn Ph 88-89 3 cis H CONMe₂ Ph oil" 4 cis H S0₂CF₃ Ph 93-94 5 cis H S0₂Ph Ph solid " Cmpd No. Isomer R^ si si mp (°C)

66 (Ex. 12) cis H OMe COMe oil "

67 cis H OBn COMe 132-134

68 cis H H 2,6-diCl-4-CF₃-Ph 71-72

69 cis H H 3-CI-5-CF3-2- 91-92 pyridinyl

70 (Ex. 2c) cis Me Me 5-Cl-6---Pr-4- 95-97 pyrimidinyl

71 (Ex. 9) cis H H 6-MeOCH₂-5-MeO- > 104 " 4-pyrimidinyl

72 (Ex. 4) cis H H 4-quinazolinyl 188-191

73 cis H H 3-t-Bu- 1,2,4- solid " thiadiazol-5-yl

" See Index Table D for ^lH NMR data.

INDEX TABLE C

Cmpd No. Isomer RZ NR⁵ R⁶ mp (°C)

74 cis:trans = 1.4:1 H 1-piperidinyl solid «

75 cis H 1-pyrrolidinyl 95-97

76 trans H 1-pyrrolidinyl 59-62

77 cis H 4-morpholinyl 145-146

78 trans H 4-morpholinyl 141-146

79 cis H 4-Me- 1 -piperazinyl oil "

80 trans H 4-Me- 1 -piperazinyl 85-89

81 cis H 4-Et- 1 -piperazinyl oil "

82 trans H 4-Et-l -piperazinyl 91-96

83 cis H 4-(C₆H₅CH )- 1 -piperazinyl oil "

84 trans H 4-(C₆H₅CH₂)- 1 -piperazinyl 88-89

85 cis H -(C^H_ζ)- 1 -piperazinyl 105-108

86 trans H 4-(C₍,H_ζ)- 1 -piperazinyl 115-120

87 cis H 4-(4-F-CgH5)- 1 -piperazinyl 93-94

88 trans H 4-(4-F-C₆H₅)- 1-piperazinyl 70-72

89 cis F I 4-(2 -pyridinyl)- 1 -piperazinyl 130-137 " Cmpd No. Isomer RZ NR⁵ R⁶ mp (°C)

94 trans H

" See Index Table D for *H NMR data.

INDEX TABLE D

Cmpd Isomer ^l NMR Data ^b No. δ (CF₃C0₂D) 8.57 (s, 2H), 4.36 (m, 2H), 2.99 (q, 4H), 2.26 (m, 4H), 1.71 (m, 4H),

1.36 (t, 6H). cis δ (DMSO-ci₆) 8.50 (s, 2H), 8.43 (dd, 2H), 7.81 (d, 2H), 7.77 (ddd, 2H), 7.68 (dd, 2H),

7.52 (ddd, 2H), 4.32 (m, 2H), 2.09 (m, 4H), 1.80 (m, 4H). trans δ (CF₃C0₂D) 8.92 (s, 2H), 8.35 (d, 2H), 8.15 (t, 2H), 7.91 (m, 4H), 4.70 (m, 2H),

2.47 (m, 4H), 1.98 (m, 4H). cis δ 8.48 (s, 2H), 6.47 (s, 2H), 5.04 (br s, 2H), 4.40 (s, 4H), 3.92 (br s, 2H), 3.49 (s, 6H),

1.92 (m, 4H), 1.72 (m, 4H). cis δ 8.42 (s, 2H), 4.50 (d, 2H), 4.25 (m, 2H), 2.71 (t, 4H), 2.33 (t, 4H), 2.06-1.62 (m,

16H). Cmpd Isomer --H NMR Data ^b

No. 11 cis δ 8.48 (s, IH), 8.43 (s, IH), 5.63 (d, IH), 4.34 (m, IH), 4.03 (m, IH), 3.55 (q, 2H),

2.87 (q, 2H), 2.81 (q, 2H), 2.13-1.65 (m, 8H), 1.29 (t, 3H), 1.28 (t, 3H), 1.16 (t, 3H).

13 cis δ 8.48 (s,lH), 8.43 (s, IH), 5.61 (d, IH), 4.33 (m, IH), 3.98 (m, IH), 3.45 (m, 2H),

2.87 (q, 2H), 2.81 (q, 2H), 2.14-1.64 (m, 8H), 1.50 (m, 2H), 1.32 (m, 2H), 1.29 (t, 3H), 1.28 (t, 3H), 0.91 (t, 3H).

14 cis δ 8.49 (s, IH), 8.42 (s, IH), 5.92 (ddt, IH), 5.64 (d, IH), 5.21 (dq, IH), 5.12 (dq, IH),

4.35 (m, IH), 4.15 (dt, 2H), 4.00 (m, IH), 2.87 (q, 2H), 2.81 (q, 2H), 2.04 (m, 4H),

1.85-1.63 (m, 4H), 1.29 (t, 3H), 1.28 (t, 3H). 17 cis δ 8.56 (s, 2H), 5.79 (m, 2H), 5.13 (m, 2H), 5.06 (m, 2H), 4.08 (m, 6H), 2.89 (q, 4H),

2.01 (m, 4H), 1.56 (m, 4H), 1.30 (t, 6H). 20 cis δ 8.44 (s, IH), 5.68 (br d, IH), 4.12 (m, 2H), 3.01 (s, 3H), 2.85 (q, 2H), 2.04 (s, 3H),

1.96 (m, 2H), 1.73 (m, 6H), 1.28 (t, 3H).

23 cis δ 8.46 (s, IH), 4.78 (br s, IH), 4.02 (m, IH), 3.82 (m, IH), 3.54 (q, 2H), 2.86 (q, 2H),

1.97-1.53 (m, 8H), 1.47 (s, 9H), 1.28 (t, 3H), 1.12 (t, 3H).

24 cis δ 8.56 (s, IH), 4.72 (br s, IH), 4.24 (d, 2H), 4.15 (m, IH), 3.80 (m, IH), 2.89 (q, 2H),

2.19 (t, IH), 1.98-1.56 (m, 8H), 1.47 (s, 9H), 1.29 (t, 3H).

25 cis δ 8.40 (s, IH), 7.35 (m, 5H), 5.34 (d, IH), 5.10 (s, 2H), 4.98 (br s , IH), 4.13 (m, lH),

3.78 (m, IH), 2.77 (q, 2H), 1.84 (m, 4H), 1.68 (m, 4H), 1.25 (t, 3H).

26 cis δ 8.41 (s, IH), 5.47 (br s, IH), 5.42 (br d, IH), 4.18 (m, IH), 3.58 (s, 3H), 3.07 (m,

IH), 2.78 (q, 2H), 1.87-1.55 (m, 8H), 1.26 (t, 3H).

28 cis δ 8.43 (s, IH), 5.43 (br s, IH), 4.15 (d, IH), 3.59 (s, 3H), 3.17 (m, IH), 3.00 (s, 3H),

2.85 (q, 2H), 2.06-1.87 (m, 4H), 1.61 (m, 4H), 1.28 (t, 3H).

29 cis δ 8.40 (s, IH), 7.39-7.23 (m, 5H), 5.46 (br s, IH), 5.40 (d, IH), 4.73 (s, 2H), 4.17 (m,

IH), 3.12 (m, IH), 2.78 (q, 2H), 1.82-1.57 (m, 8H), 1.26 (t, 3H).

32 trans δ 8.40 (s, IH), 5.19 (d, IH), 3.94 (m, IH), 2.78 (q, 2H), 2.36 (s, 6H), 2.38 (m, IH),

2.21 (m, 2H), 2.01 (m, 2H), 1.47 (m, 2H), 1.28 (m, 2H), 1.26 (t, 3H).

33 cis δ 8.41 (s, IH), 5.53 (d, IH), 4.27 (m, IH), 2.79 (q, 2H), 2.64 (m, 3H), 2.42 (s, 3H),

2.12-1.47 (m, 10H), 1.34 (m, 2H), 1.26 (t, 3H), 0.95 (t, 3H).

35 cis δ 8.58 (s, IH), 4.13 (q, 2H), 4.06 (m, IH), 3.95 (m, IH), 2.91 (s, 3H), 2.90 (q, 2H),

2.84 (s, 3H), 2.15 (m, 2H), 1.83-1.44 (m, 6H), 1.31 (t, 3H), 1.26 (t, 3H).

36 cis δ 8.41 (s, IH), 5.46 (d, IH), 4.22 (m, IH), 3.55 (s, 3H), 2.78 (q, 2H), 2.59 (s, 3H), 2.51

(m, IH), 1.93-1.60 (m, 8H), 1.26 (t, 3H).

39 cis δ 8.43 (s, IH), 7.24 (m, 2H), 6.82 (d, 2H), 6.74 (t, IH), 5.58 (br d, IH), 4.33 (m, IH),

3.67 (m, IH), 2.82 (s, 3H), 2.81 (q, 2H), 2.10 (m, 2H), 1.74 (m, 6H), 1.28 (t, 3H).

40 trans S 8.42 (s, IH), 7.23 (m, 2H), 6.79 (d, 2H), 6.71 (t, IH), 5.20 (d, IH), 3.99 (m, IH), 3.66

(tt, IH), 2.79 (s, 3H), 2.78 (q, 2H), 2.23 (d, 2H), 1.94-1.66 (m, 4H), 1.41 (m, 2H), 1.26 (t, 3H). Cmpd Isomer *H NMR Data ^b

No.

41 cis δ 8.43 (s, IH), 7.24 (m, 2H), 6.79 (d, 2H), 6.71 (t, IH), 5.58 (d, IH), 4.34 (m, IH), 3.63

(m, IH), 3.30 (q, 2H), 2.82 (q, 2H), 2.08 (br d, 2H), 1.88-1.63 (m, 6H), 1.28 (t, 3H), 1.17 (t, 3H).

41 trans δ 8.42 (s, IH), 7.21 (m, 2H), 6.74 (d, 2H), 6.68 (t, IH), 5.21 (d, IH), 4.01 (m, IH), 3.63

(m, IH), 3.29 (q, 2H), 2.78 (q, 2H), 2.23 (br d, 2H), 1.96 (br d, 2H), 1.65 (m, 2H), 1.40 (m, 2H), 1.27 (t, 3H), 1.17 (t, 3H).

42 cis δ 8.41 (s, IH), 7.38-7.11 (m, 7H), 6.72 (m, 3H), 5.51 (br d, IH), 4.50 (s, 2H), 4.32 (m,

IH), 3.88 (m, IH), 2.78 (q, 2H), 2.08 (br d, 2H), 1.93-1.57 (m, 6H), 1.26 (t, 3H).

43 trans δ 8.38 (s, IH), 7.34-7.11 (m, 7H), 6.70 (m, 3H), 5.19 (d, IH), 4.48 (s, 2H), 3.97 (m,

IH), 3.86 (m, IH), 2.77 (q, 2H), 2.21 (br d, 2H), 2.00 (br d, 2H), 1.66 (m, 2H), 1.41 (m, 2H), 1.25 (t, 3H).

44 cis δ 8.43 (s, IH), 7.22 (m, 2H), 6.76 (m, 3H), 5.91 (m, IH), 5.57 (d, IH), 5.21 (m, 3H),

4.33 (m, IH), 3.87 (m, 2H), 3.73 (m, IH), 2.80 (q, 2H), 2.09 (br d, 2H), 1.92-1.59 (m, 6H), 1.28 (t, 3H).

45 trans δ 8.41 (s, IH), 7.21 (dd, 2H), 6.72 (m, 3H), 5.89 (m, IH), 5.19 (m, 3H), 4.20 (m, IH),

3.86 (m, 2H), 3.73 (m, IH), 2.79 (q, 2H), 2.23 (br d, 2H), 1.97 (br d, 2H), 1.67 (m, 2H), 1.41 (m, 2H), 1.26 (t, 3H).

46 cis δ 8.42 (s, IH), 7.28 (m, 2H), 6.99 (m, 2H), 6.86 (t, IH), 5.57 (d, IH), 4.31 (m, IH),

3.99 (d, 2H), 3.70 (m, IH), 2.80 (q, 2H), 2.22 (t, IH), 2.04 (m, 2H), 1.94-1.68 (m, 6H), 1.27 (t, 3H).

49 trans δ 8.40 (s, IH), 7.25 (dd, 2H), 6.90 (d, 2H), 6.83 (t, IH), 5.20 (d, IH), 3.97 (m, IH),

3.67 (t, 2H), 3.53 (m, IH), 3.37 (t, 2H), 2.78 (q, 2H), 2.23 (br d, 2H), 1.94 (br d, 2H), 1.87-1.58 (m, 3H), 1.38 (m, 2H), 1.26 (t, 3H).

50 cis δ 8.43 (s, IH), 7.24 (m, 2H), 6.73 (m, 3H), 5.57 (d, IH), 4.34 (m, IH), 3.90 (s, 2H),

3.77 (m, IH), 2.80 (q, 2H), 2.08 (m, 2H), 1.98-1.50 (m, 6H), 1.45 (s, 9H), 1.28 (t,

3H). 54 cis δ 8.36 (s, IH), 7.44 (m, 3H), 7.22 (m, 2H), 5.27 (d, IH), 4.67 (tt, IH), 4.26 (m, IH),

2.73 (q, 2H), 1.97 (br d, 2H), 1.78 (m, 4H), 1.34 (m, 2H), 1.23 (t, 3H), 1.12 (m, IH),

0.98 (m, 2H), 0.57 (m, 2H). 58 cis δ 8.37 (s, IH), 7.43-7.27 (m, 3H), 7.12 (m, 2H), 5.32 (d, IH), 4.34-4.06 (m, 4H), 2.74

(q, 2H), 1.99 (br d, 2H), 1.85 (br d, 2H), 1.73 (m, 2H), 1.47 (m, 2H), 1.23 (t, 3H),

1.16 (t, 3H). 61 cis δ 8.37 (s, IH), 7.41-7.25 (m, 3H), 7.09 (m, 2H), 5.31 (d, IH), 4.31-4.11 (m, 2H), 2.73

(q, 2H), 2.04-1.65 (m, 6H), 1.42 (m, 2H), 1.37 (s, 9H), 1.23 (t, 3H). 63 cis δ 8.38 (s, IH), 7.34 (m, 2H), 7.19 (m, IH), 7.06 (m, 2H), 5.53 (d, IH), 4.31 (m, IH),

3.99 (m, IH), 2.75 (q, 2H), 2.62 (s, 6H), 1.97 (br d, 2H), 1.89-1.61 (m, 6H), 1.24 (t,

3H). Cmpd Isomer ^H NMR Data ^b

No.

65 cis δ 8.35 (s, IH), 7.73 (m, 2H), 7.58-7.29 (m, 6H), 7.05 (m, 2H), 5.12 (d, IH), 4.28 (tt,

IH), 4.22 (m, IH), 2.70 (q, 2H), 2.01-1.67 (m, 6H), 1.33 (m, 2H), 1.20 (t, 3H).

66 cis δ 8.42 (s, IH), 5.61 (d, IH), 4.33 (m, IH), 4.28 (m, IH), 3.79 (s, 3H), 2.80 (q, 2H),

2.16 (s, 3H), 2.06 (m, 2H), 1.97-1.68 (m, 6H), 1.27 (t, 3H). 71 cis δ 8.42 (s, IH), 8.38 (s, IH), 5.41 (d, IH), 5.31 (d, IH), 4.47 (s, 2H), 4.20 (m, 2H), 3.83

(s, 3H), 3.49 (s, 3H), 2.80 (q, 2H), 1.95 (m, 4H), 1.75 (m, 4H), 1.27 (t, 3H).

73 cis δ 8.41 (s, IH), 5.88 (d, IH), 5.31 (d, IH), 4.17 (m, IH), 3.49 (m, IH), 2.79 (q, 2H),

1.92 (m, 6H), 1.68 (m, 2H), 1.36 (s, 9H), 1.27 (t, 3H).

74 cis δ 8.41 (s, IH), 5.54 (d, IH), 4.30 (m, IH), 2.79 (m, 7H), 2.17-1.42 (m, 14H), 1.26 (t,

3H). 74 trans δ 8.40 (s, IH), 5.17 (d, IH), 3.96 (m, IH), 2.94-2.61 (m, 7H), 2.32-1.28 (m, 14H), 1.25

(t, 3H). 79 cis δ 8.41 (s, IH), 5.48 (d, IH), 4.24 (m, IH), 2.78 (q, 2H), 2.71-2.34 (m, 8H), 2.30 (s,

3H), 2.23 (m, IH), 1.97-1.53 (m, 8H), 1.26 (t, 3H). 81 cis δ 8.40 (s, IH), 5.49 (d, IH), 4.24 (m, IH), 2.78 (q, 2H), 2.75-2.33 (m, 8H), 2.42 (q,

2H), 2.23 (m, IH), 1.97-1.52 (m, 8H), 1.26 (t, 3H), 1.10 (t, 3H). 83 cis δ 8.40 (s, IH), 7.34-7.20 (m, 5H), 5.48 (d, IH), 4.23 (m, IH), 3.52 (s, 2H), 2.77 (q,

2H), 2.54 (m, 8H), 2.22 (m, IH), 1.97-1.52 (m, 8H), 1.26 (t, 3H).

89 cis δ 8.41 (s, IH), 8.20 (ddd, IH), 7.48 (ddd, IH), 6.66 (d, IH), 6.62 (dd, IH), 5.49 (d,

IH), 4.25 (m, IH), 3.56 (m, 4H), 2.78 (q, 2H), 2.67 (m, 4H), 2.29 (m, IH), 2.01-1.59 (m, 8H), 1.26 (t, 3H).

90 trans δ 8.41 (s, IH), 8.20 (m, IH), 7.47 (m, IH), 6.63 (m, 2H), 5.19 (d, IH), 3.96 (m, IH),

3.55 (m, 4H), 2.78 (q, 2H), 2.70 (m, 4H), 2.41 (t, IH), 2.22 (d, 2H), 2.01 (d, 2H), 1.51 (q, 2H), 1.28 (m, 2H), 1.26 (t, 3H).

91 cis δ 8.41 (s, IH), 6.66 (s, 2H), 5.79 (d, IH), 4.42 (m, IH), 4.04 (tt, IH), 2.81 (q, 2H), 2.32

(m, 2H), 2.07 (br d, 2H), 1.67 (m, 4H), 1.28 (t, 3H). ^{b J}H NMR spectra are recorded in CDCI3 unless otherwise indicated. *^**H NMR spectra are reported in ppm downfield from tetramethylsilane; s = singlet, d = doublet, t = triplet, q = quartet, m = multiplet, dd = doublet of doublets, dt = doublet of triplets, dq = doublet of quartets, ddd = doublet of doublet of doublets, ddt = double of doublet of triplets, tt = triplet of triplets, br s = broad singlet and br d = broad doublet.

BIOLOGICAL EXAMPLES OF THE INVENTION TEST A Fall Armyworm

Test units, each consisting of a H.I. S. (high impact styrene) tray with 16 cells were prepared. Wet filter paper and approximately 8 cm² of lima bean leaf was placed into twelve of the cells. A 0.5-cm layer of wheat germ diet was placed into the four remaining cells. Fifteen to twenty third-instar larvae of fall armyworm (Spodoptera frugiperda) were placed into a 230-mL (8-ounce) plastic cup. Solutions of each of the test compounds in 75:25 acetone-distilled water solvent were sprayed into the tray and cup. Spraying was accomplished by passing the tray and cup on a conveyer belt directly beneath a flat fan hydraulic nozzle which discharged the spray at a rate of 0.138 kilograms of active ingredient per hectare (about 0.13 pounds per acre) at 207 kPa (30 p.s.i.). The insects were transferred from the 230-mL cup to the H.I.S. tray (one insect per cell). The trays were covered and held at 27°C and 50% relative humidity for 48 hours, after which time readings were taken on the twelve cells with lima bean leaves. The four remaining cells were read at 6-8 days for delayed toxicity. Of the compounds tested, the following gave control efficacy levels of 80% or greater: 1, 5, 10, 15, 18, 26, 71, 72 and 92.

TEST B Tobacco Budworm

The test procedure of TEST A was repeated for determining efficacy against third-instar larvae of the tobacco budworm (Heliothis virescens) except that three 230-mL (8-ounce) plastic cups with wheat germ diet were used in place of the H.I.S. tray, with each cup pre-infested with five third-instar larvae. Of the compounds tested, the following gave mortality levels of 80% or higher: 1, 10, 18, 46, 71 and 92.

TEST C Southern Corn Rootworm Test units, each consisting of a 230-mL (8-ounce) plastic cup containing a 6.5-cm²

(1 -square-inch) plug of a wheatgerm diet, were prepared. The test units were sprayed as described in TEST A with individual solutions of the test compounds. After the spray on the cups had dried, five second-instar larvae of the southern corn rootworm (Diabrotica undecimpunctata howardi) were placed into each cup. The cups were held at 27°C and 50%) relative humidity for 48 hours, after which time mortality readings were taken. The same units were read again at 6-8 days for delayed toxicity. Of the compounds tested, the following gave control efficacy levels of 80% or greater: 1, 10, 15, 18, 19, 20, 21, 24, 26, 27, 31, 33, 37, 39, 40, 41, 42, 46, 47, 48, 51, 53, 58, 63, 69, 71, 72, 73, 75, 77 and 92.

TEST D Two-Spotted Spider Mite

Pieces of kidney bean leaves, each approximately 6.5 cm² (1 square inch) in area, that had been infested on the undersides with 25 to 30 adult mites (Tetranychus urticae), were sprayed with their undersides facing up on a hydraulic sprayer with a solution of the test compound in 75:25 acetone-distilled water solvent. Spraying was accomplished by passing the leaves, on a conveyor belt, directly beneath a flat fan hydraulic nozzle which discharged the spray at a rate of 0.138 kilograms of active ingredient per hectare (about 0.13 pounds per acre) at 207 kPa (30 p.s.i.). The leaf squares were then placed underside-up on a square of wet cotton in a petri dish and the perimeter of the leaf square was tamped down onto the cotton with forceps so that the mites could not escape onto the untreated leaf surface. The test units were held at 27°C and 50% relative humidity for 48 hours, after which time mortality readings were taken. Of the compounds tested, the following gave mortality levels of 80% or higher: 1, 5, 6, 10, 15, 18, 19, 21, 22, 23, 24, 25, 26, 27, 33, 37, 39, 40, 41, 42, 44, 45, 46, 47, 48, 50, 51, 52, 53, 57, 58, 60, 61, 62, 63, 68, 69, 70, 71, 72, 73, 74, 77 and 92.

TEST E Corn Planthopper Test

Test Unit: The test unit consists of a plastic cup containing 126 +/- 4 grams of sterilized, non-fertilized sassafras (sandy loam) soil. One pre-germinated Pioneer variety 3394 corn seed is placed in a 1 inch depression in the soil and covered. The test unit is watered with 15 mL of distilled water and placed in a closed Plexiglas box inside a greenhouse operating at 24 degrees centigrade and 36% relative humidity for 4 days at which time it is ready for test. A snug fitting test unit lid with a small opening at the top is placed on all test units prior to test. Compound Application: Test compounds are formulated at 200 ppm in 20% acetone:

80% water containing 500 ppm Ortho X-77 surfactant. Compounds are applied through the opening in the test unit lid with an atomizer sprayer fitted with a Model 17690- 1/8 JJAU nozzle and a spray set-up consisting of a J2850 Fluid Cap and J70 Air Cap (Spray Systems, Inc.). The sprayer was operated at 12-13 psi. For each compound, 2 test units are sprayed with a total of 2 mL each of test solution. After spraying, test units are placed in a ventilated enclosure for 10-15 minutes to dry.

Insect Infesting/Evaluation: After drying, a thin layer of white quartz sand is poured onto the soil of each test unit to aid in the evaluation of live and dead insects at the conclusion of the test. Each unit is infested with a minimum of 15 nymphs of the corn planthopper (Peregrinus maidis) which are approximately 21 days old. Infested test units are held in a growth chamber operating at 22 degrees centigrade and 50% relative humidity with a 16:8 ligh dark photoperiod. Insect mortality is evaluated at 6 days post-infestation. Moribund insects are counted as dead. Of the compounds tested, the following gave mortality of 80% or greater: 1, 5, 10, 15, 18, 19, 21, 22, 24, 26, 37, 39, 46, 47, 50, 58, 60, 70, 71, 72 and 92.

TEST F Green Peach Aphid Test

A turnip plant infested with Green Peach Aphid (Myzus persicae) serves as a test unit for this bioassay. All plants have between 15 and 25 aphids (all life stages) on them. The turnip plants are sprayed with a single rate of 0.25 lb. AI/A of each compound at 30 p.s.i. on a moving belt sprayer. All test compounds are formulated using 75/25 acetone/distilled water solvent. All treatments are replicated once. A soil drench of the compound is also applied to each test unit. The drench consists of 2 mL the compound at 0.25 lb. AI/A. Mortality is assessed at 7 days post compound application by counting live and dead insects under a microscope. Of the compounds tested, the following gave mortality of 80 % or greater: 1, 10, 18, 26, 70 and 71.

Test compounds in Tests G-K were first dissolved in acetone in an amount equal to 3% of the final volume and then suspended at a concentration of 200 ppm in purified water containing 250 ppm of the surfactant Trem® 014 (polyhydric alcohol esters). The resulting test suspensions were then used in Tests G-K. Spraying these 200 ppm test suspensions to the point of run-off on the test plants is the equivalent of a rate of 500 g/ha.

TEST G The test suspension was sprayed to the point of run-off on wheat seedlings. The following day the seedlings were inoculated with a spore dust of Erysiphe graminis f sp. tritici, (the causal agent of wheat powdery mildew) and incubated in a growth chamber at 20°C for 7 days, after which disease ratings were made.

TEST H The test suspension was sprayed to the point of run-off on wheat seedlings. The following day the seedlings were inoculated with a spore suspension of Puccinia recondita (the causal agent of wheat leaf rust) and incubated in a saturated atmosphere at 20°C for 24 h, and then moved to a growth chamber at 20°C for 6 days, after which disease ratings were made. TEST I

The test suspension was sprayed to the point of run-off on rice seedlings. The following day the seedlings were inoculated with a spore suspension of Pyricularia oryzae (the causal agent of rice blast) and incubated in a saturated atmosphere at 27°C for 24 h, and then moved to a growth chamber at 30°C for 5 days, after which disease ratings were made. TEST J

The test suspension was sprayed to the point of run-off on tomato seedlings. The following day the seedlings were inoculated with a spore suspension of Phytophthora infestans (the causal agent of potato and tomato late blight) and incubated in a saturated atmosphere at 20°C for 24 h, and then moved to a growth chamber at 20°C for 5 days, after which disease ratings were made.

TEST K The test suspension was sprayed to the point of run-off on cucumber seedlings. The following day the seedlings were inoculated with a spore suspension of Botrytis cinerea (the causal agent of gray mold on many crops) and incubated in a saturated atmosphere at 20°C for 48 h, and moved to a growth chamber at 20°C for 5 days, after which disease ratings were made.

Results for Tests G-K are given in Table A. In the table, a rating of 100 indicates 100% disease control and a rating of 0 indicates no disease control (relative to the controls). A dash (— ) indicates no test results. ND indicates disease control not determined due to phytotoxicity.

TABLE A

Cmpd No. TestG TestH Test I Test J TestK

1 99 100 86 99 -

2 32 86 0 0 -

3 0 0 0 0 -

4 0 0 0 5 -

5 0 0 0 21 0

6 0 0 0 0 0

7 0 0 0 63 0

8 0 0 0 85 0

9 0 25 0 76 8

10 100 100 86 ND 43

15 100 100 86 - 0

18 99 100 0 75 0

19 0 99 0 ND 69

20 39 0 0 61 19

21 95 100 0 - 0

22 86 0 0 47 65

23 61 0 0 26 0

24 0 0 0 0 0

25 97 99 0 86 0

26 99 100 0 93 0

27 98 99 0 47 0

31 77 85 0 62 8

32 0 0 0 23 8

33 62 97 0 86 8

34 0 25 0 23 47

37 99 100 53 100 47

38 98 0 0 21 0

39 20 100 0 100 48

40 80 97 0 84 0

41 80 94 0 92 0

42 88 86 0 74 94

43 93 0 0 59 83

44 80 86 0 99 0

45 46 68 0 92 0

46 97 100 0 95 0

47 99 100 53 ND 0 Cmpd No. TestG TestH Test I TestJ TestK

48 97 97 0 99 0

49 96 0 0 74 0

50 86 — 0 ND 0

51 97 99 53 0 83

52 73 85 0 45 0

53 90 0 0 23 94

54 87 28 0 0 0

55 0 0 0 0 96

56 55 27 0 23 0

57 90 97 0 0 0

58 99 99 0 0 0

59 88 0 0 16 0

60 95 0 0 ND 0

61 0 0 0 0 0

62 90 85 0 0 94

63 0 0 0 26 65

64 0 0 0 0 0

65 0 0 0 0 88

68 95 99 86 ND 8

69 86 93 53 0 8

70 61 0 0 26 39

71 55 100 53 97 0

72 94 99 0 ND 0

73 0 66 0 ND 8

74 63 68 0 21 0

75 62 85 0 86 8

76 0 0 0 45 47

77 0 97 0 100 8

78 0 0 0 45 8

91 0 85 0 ND 69

92 95 100 74 26 0

93 0 0 0 60 0

94 0 0 0 85 0

Claims

CLAIMSWhat is claimed is:

1. A compound selected from Formula I, and agriculturally suitable salts thereof,

I wherein:

G is selected from the group consisting of

G-1 Q-2

Y is a direct bond or C1-C4 alkylene optionally substituted with C C₄ alkyl;

X is O, NR⁷ or S(O)_p; each Z is independently selected from N and CR³; each Z¹ is independently selected from O, S and NR⁸; each R¹ is independently selected from the group consisting of H, halogen, C1-C4 alkyl, C_j-Q^ haloalkyl, C3-C6 cycloalkyi, C3-C6 halocycloalkyl, C₁-C4 alkoxy, C_rC₄ haloalkoxy and R⁹S(O)_p; each R² is independently selected from the group consisting of H, CF₃, Cj alkyl optionally substituted with one or two R¹⁰ substituents, C -C₄ alkyl, RⁱOOL-CH^ (R¹⁰)₂CHCH₂-, R¹⁰CH₂CH(RlO)-, CH₃C(R-^*┬░)₂-_> C₃-C₄ haloalkyl, C2-C4 alkenyl, C₂-C4 haloalkenyl, C₂-C4 alkynyl, C -C₄ haloalkynyl, C*₍-C4 alkoxy, C₁-C4 haloalkoxy, halogen, hydroxy, C -C4 alkylcarbonyl, C₂-C4 haloalkylcarbonyl, C3-C6 cycloalkyi, C3-C6 halocycloalkyl, cyano, nitro, thiocyanato, C₂-C4 alkoxycarbonyl, C₂-C4 haloalkoxycarbonyl, C1-C4 alkylamino, C₂-C4 dialkylamino and R-* *-S(O)p; each R³ is independently selected from the group consisting of H, C1-C4 alkyl optionally substituted with one or two R¹⁰, CF₃, C₂-C4 alkenyl, C₂-C4 haloalkenyl, C₂-C4 alkynyl, C₂-C4 haloalkynyl, C1-C4 alkoxy, C1-C4 haloalkoxy, halogen, hydroxy, C₂-C alkylcarbonyl, C₂-C₄ haloalkylcarbonyl, C3-C6 cycloalkyi, C3-C halocycloalkyl, cyano, nitro, thiocyanato, C₂-C4 alkoxycarbonyl, C2-C4 haloalkoxycarbonyl, C₁-C₄ alkylamino, C₂-C₄ dialkylamino and R¹ -*S(O)_p; or R² and R³ with the carbon atoms to which they are attached are taken together to form a: (1) 5- or 6-membered unsaturated carbocyclic ring optionally substituted with

C_j-C alkyl group; or (2) 5-, 6- or 7-membered saturated heterocyclic ring optionally substituted with a C₁-C₄ alkyl group containing one or two O and/or S(O)_p atoms in the ring; each R⁴ is independently selected from the group consisting of C_J-C4 alkyl and

C1-C4 alkoxy; R⁵ is H, C_rC₆ alkyl optionally substituted with R¹³, C_rC₆ haloalkyl, C₃-C₆ cycloalkyi, C3-C₆ halocycloalkyl, C3-C.5 alkenyl, C₃-Cg haloalkenyl, C₃-Cg alkynyl, C3-C6 haloalkynyl, C_j-Cg alkoxy, C-i-Cg haloalkoxy, C3-C6 alkynyloxy,

C₃-C₆ haloalkenyloxy, C4-C6 cycloalkylalkoxy, C2-C6-cyanoalkoxy, phenylmethoxy, C₂-C6 alkylcarbonyl, C3-C6 cycloalkylcarbonyl, phenylmethoxycarbonyl, formyl, C₂-Cg haloalkylcarbonyl, C₂-Cg alkoxycarbonyl, C₂-C6 haloalkoxycarbonyl, C₂-Cg alkylaminocarbonyl, C3-Cg dialkylaminocarbonyl, hydroxy, R¹⁴S(O)_p, (R¹⁵)(R¹⁶)P(O), phenyl or benzoyl each optionally substituted with one, two or three R¹⁷ substituents, naphthalenyl or a 5- or 6-membered unsaturated heterocyclic ring optionally substituted with one or two R¹⁷ substituents; R⁶ is G, H, Cj-Cg alkyl, C_rC₆ haloalkyl, C -C₆ alkylcarbonyl, C₂-C₆ alkoxycarbonyl, C₂-Cg alkylaminocarbonyl, C3-C8 dialkylaminocarbonyl, R¹⁴S(O)_p,

R⁷ is H, C_rC₄ alkyl, C₂-C₄ alkenyl, C₂-C₄ alkynyl, C₂-C₄ alkylcarbonyl, C₂-C₄ alkoxycarbonyl, C₂-C alkylaminocarbonyl or C3-C8 dialkylaminocarbonyl; each R⁸ is independently selected from the group H, C_j-Qi alkyl and C₃-Cg cycloalkyi; each R9 is independently selected from the group C1-C₄ alkyl and C1-C4 haloalkyl; each R¹⁰ is independently selected from the group consisting of halogen, C_J-C4 alkoxy,

C₁-C4 haloalkoxy, C₂-C₆ alkylcarbonyl, C₂-Cg alkoxycarbonyl, hydroxy, cyano, nitro, thiocyanato and R⁹S(O)_p; each R¹¹ is independently selected from the group C₁-C4 alkyl and C1-C4 haloalkyl; each R¹² is independently selected from the group consisting of halogen, cyano, nitro, hydroxy, C_j-C-i alkyl, C₁-C4 haloalkyl, C-*-C alkoxy, C**-C₄ haloalkoxy, C C4 alkylthio, C_j*-C alkylsulfinyl and 0*^4 alkylsulfonyl; each R¹³ is independently selected from the group consisting of halogen, hydroxy, cyano, nitro, C3-C6 cycloalkyi, C_j-C₄ alkoxy, CJ-C4 haloalkoxy, phenylmethoxy, C₂-C6 alkylcarbonyl, C₂-C₆ haloalkylcarbonyl, C₂-C6 alkoxycarbonyl, C₂-Cg haloalkoxycarbonyl, -C4 alkylthio, C1-C₄ alkylsulfinyl,

C-.-C₄ alkylsulfonyl, C1-C4 haloalkylsulfonyl, aminocarbonyl, C₂-C6 alkylaminocarbonyl, C3-C8 dialkylaminocarbonyl, R⁹S(O)_p and phenyl optionally substituted with one, two or three R¹⁷ substituents; each R¹⁴ is independently selected from the group consisting of C-1-C4 alkyl, C_]-C₄ haloalkyl and phenyl optionally substituted with one, two or three R¹⁷ substituents; each R¹⁵ and each R¹⁶ are independently selected from the group consisting of C1-C₄ alkyl, C₁-C4 haloalkyl, C-₁-C₄ alkoxy and C-1-C4 haloalkoxy; each R¹⁷ is independently selected from the group consisting of halogen, cyano, nitro, hydroxy, C1-C4 alkyl, C_]-C haloalkyl, C_rC alkoxy, C_rC₄ haloalkoxy, C_rC₄ alkylthio, C₁-C4 alkylsulfinyl and C₁-C alkylsulfonyl; each R¹⁸ is independently selected from the group consisting of halogen, cyano, nitro, hydroxy, C₁-C₄ alkyl, C1-C4 haloalkyl, C₁-C₄ alkoxy, C-.-C₄ haloalkoxy, R¹⁴S(O)_p, C₂-C₆ alkylcarbonyl, C₂-C₆ alkoxycarbonyl, C₂-C₆ alkylaminocarbonyl, C3-C8 dialkylaminocarbonyl and phenyl, phenylmethyl or pyridinyl each optionally substituted with one, two or three R¹⁷ substituents; m is 0, 1 or 2; and each p is independently selected from 0, 1 and 2.

2. A compound of Claim 1 wherein

G is G-1;

Y is a direct bond; X is NR⁷; RUs H or C_rC₄ alkyl;

R² is C_rC₄ alkyl, CF₃, C₃-C₆ cycloalkyi, R¹⁰CH₂CH₂-, (R¹⁰)₂CHCH₂-,

R¹⁰CH₂CH(R¹⁰)-, CH₃C(R¹⁰)₂-, or C_{ alkyl optionally substituted with

C_j-C₄ alkoxy; R³ is C1-C₄ alkyl, CF₃, C_j alkyl optionally substituted with C_j-C₄ alkoxy, C-2-C4 alkenyl, C₂-C₄ alkynyl, C-₁-C₄ alkoxy, C₁-C4 haloalkoxy, halogen, hydroxy, cyano, nitro, thiocyanato or R^{1 1}S(O)_p; and m is 0.

3. A compound of Claim 2 wherein

R⁵ is H, C_rC₆ alkyl optionally substituted with R¹³, C_rC₆ haloalkyl, C₃-C₆ cycloalkyi, C₃-C₆ alkenyl, C₃-C₆ haloalkenyl, C₃-C₆ alkynyl, C_rC₆ alkoxy, Cj-Cg haloalkoxy, C3-C5 alkynyloxy, C3-C6 haloalkenyloxy, C4-C6 cycloalkylalkoxy, C₂-Cg-cyanoalkoxy, phenylmethoxy, C -C6 alkylcarbonyl, C3-C.5 cycloalkylcarbonyl, phenylmethoxycarbonyl, formyl, C₂-C6 haloalkylcarbonyl, C₂-C6 alkoxycarbonyl, C₂-C₆ haloalkoxycarbonyl, C -C alkylaminocarbonyl, C3-C8 dialkylaminocarbonyl, hydroxy, R¹⁴S(O)_p, or (R¹⁵)(R¹⁶)P(O); R⁶ is G, H, C_rC₆ alkyl, C_rC₆ haloalkyl, C₂-C₆ alkylcarbonyl, C₂-C₆ alkoxycarbonyl, C -Cg alkylaminocarbonyl, C3-C8 dialkylaminocarbonyl, R¹⁴S(O)_p, (R¹⁵)(R¹⁶)P(O), phenyl optionally substituted with one, two or three R¹⁷ substituents, naphthalenyl or a 5- or 6-membered unsaturated heterocyclic ring optionally substituted with one or two R¹⁷ substituents; or R⁵ and R⁶ with the nitrogen atom to which they are attached are taken together to form a 1 -piperazinyl; 2,5-dioxo-l-pyrrolidinyl; 2,5-dihydro- 2,5-dioxo-lH-pyrrol-l-yl; or l,3-dihydro-l,3-dioxo-2H-isoindol-2-yl; ring each optionally substituted with R¹⁸.

4. A compound of Claim 3 wherein

R⁵ is H, C_rC₆ alkyl optionally substituted with R¹³, C_rC₆ haloalkyl, C₃-C₆ cycloalkyi, C3-C.5 alkenyl, C3-C.5 haloalkenyl, C3-C6 alkynyl, C Cg alkoxy, C Cg haloalkoxy, C3-C6 alkynyloxy, C3-C.5 haloalkenyloxy, C₄-C₆ cycloalkylalkoxy, C₂-C6-cyanoalkoxy, phenylmethoxy, C₂-C₆ alkylcarbonyl, C3-C6 cycloalkylcarbonyl, phenylmethoxycarbonyl, formyl, C₂-Cg haloalkylcarbonyl, C -Cg alkoxycarbonyl, C₂-C₆ haloalkoxycarbonyl, C₂-Cg alkylaminocarbonyl, C3-C8 dialkylaminocarbonyl, hydroxy, R¹ S(O)_p, or (R¹⁵)(R¹⁶)P(O); R⁶ is G, H, C _j -C₆ alkyl, C_rC₆ haloalkyl, C₂-C₆ alkylcarbonyl, C₂-C₆ alkoxycarbonyl, C₂-Cg alkylaminocarbonyl, C3-C8 dialkylaminocarbonyl, phenyl optionally substituted with one, two or three R¹⁷ substituents, or pyridinyl optionally substituted with one or two R¹⁷ substituents; or R⁵ and R⁶ with the nitrogen atom to which they are attached are taken together to form a 1 -piperazinyl; 2,5-dioxo-l-pyrrolidinyl; 2,5-dihydro- 2,5-dioxo-lH-pyrrol-l-yl; or l,3-dihydro-l,3-dioxo-2H-isoindol-2-yl; ring each optionally substituted with R¹⁸.

5. A compound of Claim 3 wherein R⁵ is ╬ù, C_rC₆ alkyl optionally substituted with R¹³, C_rC₆ haloalkyl, C₃-C₆ cycloalkyi, C3-C6 alkenyl, C3-C6 haloalkenyl, C3-C6 alkynyl, C_]-C₆ alkoxy, C C6 haloalkoxy, C3-C₆ alkynyloxy, C3-C.5 haloalkenyloxy, C4-C₆ cycloalkylalkoxy, C₂-C6-cyanoalkoxy, phenylmethoxy, C -C₆ alkylcarbonyl, C3-C.5 cycloalkylcarbonyl, phenylmethoxycarbonyl, formyl, C₂-C,5 haloalkylcarbonyl, C₂-Cg alkoxycarbonyl, C₂-Cg haloalkoxycarbonyl, C -Cg alkylaminocarbonyl, C3-C8 dialkylaminocarbonyl, hydroxy, R¹⁴S(O)_p, or (R¹⁵)(R¹⁶)P(O); R⁶ is ╬ù, C_rC₆ alkyl, C_rC₆ haloalkyl, C₂-C₆ alkylcarbonyl, C₂-C₆ alkoxycarbonyl, C -C₆ alkylaminocarbonyl, C3-C8 dialkylaminocarbonyl, phenyl optionally substituted with one, two or three R¹⁷ substituents, or pyridinyl optionally substituted with one or two R¹⁷ substituents; or R⁵ and R⁶ with the nitrogen atom to which they are attached are taken together to form a 1 -piperazinyl; 2,5-dioxo-l-pyrrolidinyl; 2,5-dihydro- 2,5-dioxo-lH-pyrrol-l-yl; or l,3-dihydro-l,3-dioxo-2H-isoindol-2-yl; ring each optionally substituted with R¹⁸.

6. A compound of Claim 1 wherein

G is G-2; Y is a direct bond; X is NR⁷; Z¹ is S;

R² is C1-C₄ alkyl, C₁-C4 haloalkoxy, C3-C6 cycloalkyi or Cj alkyl optionally substituted with C1-C4 alkoxy;

R³ is C₁-C4 alkyl, CF3, C_j alkyl optionally substituted with C_J-C4 alkoxy, C -C₄ alkenyl, C₂-C alkynyl, C_j-C₄ alkoxy, C1-C4 haloalkoxy, halogen, hydroxy, cyano, nitro, thiocyanato or R^{1 1}S(O)_p; and m is 0.

7. An arthropodicidal composition comprising an arthropodicidally effective amount of a compound of Claim 1 and at least one of a surfactant, a solid diluent or a liquid diluent.

8. A method for controlling arthropods comprising contacting the arthropods or their environment with an arthropodicidally effective amount of a compound of Claim 1.

9. A fungicidal composition comprising a fungicidally effective amount of a compound of Claim 1 and at least one of a surfactant, a solid diluent or a liquid diluent.

10. A method for controlling plant diseases caused by fungal plant pathogens comprising applying to the plant or portion thereof, or to the plant seed or seedling, a fungicidally effective amount of a compound of Claim 1.