Thiazolylcinnamonitriles and pest controlling agents

Abstract

Compounds represented by the general formula (1); and pest controlling agents containing one or more of the compounds as the active ingredients, wherein A is substituted phenyl, C1-C6 alkly or the like; B is hydrogen, optionally substituted phenyl or the like; R is C1-C6 alkly, a group represented by the general formula: COR1 (wherein R1 is C1-C12 alkyl, C1-C6 alkoxy, C1-C6 haloalkyl or the like) or the like; X is halogeno, C1-C6 alkyl, C1-C6 haloalkyl or the like; and n is an integer of 1 to 5.

Description

FIELD OF INVENTION

The present invention relates to novel thiazolylcinnamonitriles and pest controlling agents containing the said compounds as active ingredients.

BACKGROUND ART

A large number of pest controlling agents, such as insecticides and acaricides, have been used so far. However, many of them are hardly satisfactory as controlling agents because of insufficient efficacy, restrictions on their use due to drug resistance problems, phytotoxicity or pollution on plants, or strong toxicity on humans, domestic animals and fish. Therefore, there has been a desire for the development of agents applicable safely and having less of the drawbacks mentioned above.

As for cinnamonitrile derivatives similar to the compounds of the present invention, for example, 3-hydroxy-2-(4-phenyl-2-thiazolyl)-cinnamonitriles are disclosed in Japanese Patent Laid-open No. Sho 53-92769, Japanese Patent Laid-open No. Sho 55-154963 and EP 189960, and their alkali metal and ammonium salts in Japanese Patent Laid-open No. Sho 55-154962. However, none of them has been put to practical use as insecticides because of insufficient efficacy and other problems.

Further, WO 95/29591 and Japanese Patent Laid-open No. Hei 10-158254 have disclosed cinnamonitrile derivatives, similar to the compounds of the present invention, that are useful as anti-fouling agents for aquatic adhesive organisms. There are, however, no descriptions on their insecticidal activities.

DISCLOSURE OF THE INVENTION

It is an object of the present invention to provide pest controlling agents containing thiazolylcinnamonitriles as active ingredients, that have sure efficacy and can be used safely.

The present invention is directed to compounds represented by Formula (1)

[wherein

A is halogen, C 1-6 alkyl, C 1-6 haloalkyl, C 1-6 alkoxy, optionally substituted C 3-6 cycloalkyl, optionally substituted pyridyl, optionally substituted thienyl, substituted phenyl or optionally substituted phenoxy;

B is hydrogen, halogen, C 1-6 alkoxycarbonyl, optionally substituted phenyl, C 1-6 alkyl, C 1-6 haloalkyl or C 3-6 cycloalkyl;

R is C 1-6 alkyl, a group of Formula COR 1 (wherein R 1 is C 1-12 alkyl, C 1-6 haloalkyl, optionally substituted C 3-6 cycloalkyl, C 1-6 alkoxy, C 1-6 alkoxy C 1-6 alkyl, C 1-6 alkylthio C 1-6 alkyl, mono-C 1-6 alkylamino, di-C 1-6 alkylamino, optionally substituted phenyl C 1-6 alkyl, optionally substituted phenoxy C 1-6 alkyl, optionally substituted phenylthio C 1-6 alkyl or optionally substituted phenyl), or a group of Formula SO 2 R 2 (wherein R 2 is C 1-6 alkyl or optionally substituted phenyl);

X is cyano, nitro, halogen, C 1-6 alkyl, C 1-6 haloalkyl, C 1-6 alkoxy, C 1-6 haloalkoxy, optionally substituted phenyl or optionally substituted phenoxy; and

n is an integer between 1 and 5], and pest controlling agents containing one or more of the said compounds as active ingredients.

In the above Formula (1),

A is halogen such as fluorine, chlorine, bromine and iodine;

C 1-6 alkyl such as methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, isobutyl, t-butyl, pentyl and its isomers, and hexyl and its isomers;

C 1-6 haloalkyl such as chloromethyl, fluoromethyl, bromomethyl, dichloromethyl, difluoromethyl, dibromomethyl, trichloromethyl, trifluoromethyl, tribromomethyl, trichloroethyl, trifluoroethyl and pentafluoroethyl;

C 1-6 alkoxy such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, sec-butoxy, isobutoxy and t-butoxy;

optionally substituted C 3-6 cycloalkyl such as cyclopropyl, cyclopentyl, 1-methylcyclopentyl, cyclohexyl and 1-methylcyclohexyl;

optionally substituted pyridyl, such as 2-pyridyl, 3-pyridyl and 4-pyridyl that may have substituents at arbitrary positions of the pyridine ring;

thienyl, such as 2-thienyl and 3-thienyl 1 that may have substituents at arbitrary positions of the thiophene ring;

phenyl having substituents at arbitrary positions of the benzene ring; or

phenoxy having optional substituents at arbitrary positions of the benzene ring.

Examples of substituents of the aforementioned pyridyl, thienyl, phenyl and phenoxy groups include halogens such as fluorine and chlorine; C 1-6 alkyl such as methyl and ethyl; C 1-6 alkoxy such as methoxy, ethoxy and isopropoxy; and nitro. These pyridyl, thienyl, phenyl and phenoxy groups may have two or more, same or different, substituents.

B is hydrogen;

halogen such as fluorine, chlorine, bromine and iodine;

C 1-6 alkoxycarbonyl such as methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl and t-butoxycarbonyl;

C 1-6 alkyl such as methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, isobutyl, t-butyl, pentyl and hexyl;

C 1-6 haloalkyl such as chloromethyl, fluoromethyl, bromomethyl, dichloromethyl, difluoromethyl, dibromomethyl, trichloromethyl, trifluoromethyl, tribromomethyl, trichloroethyl, trifluoroethyl and pentafluoroethyl; or

C 3-6 cycloalkyl such as cyclopropyl, cyclopentyl and cyclohexyl.

R is C 1-6 alkyl such as methyl, ethyl, propyl, isopropyl, butyl and t-butyl; or

a group represented by Formula COR 1 or SO 2 R 2 ,

wherein R 1 is C 1-12 alkyl such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, pentyl and its isomers, hexyl and its isomers, heptyl and its isomers, nonyl and its isomers and dodecyl, and branched alkyl groups are particularly preferred;

C 1-6 haloalkyl such as chloromethyl, fluoromethyl, bromomethyl, dichloromethyl, difluoromethyl, dibromomethyl, trichloromethyl, trifluoromethyl, tribromomethyl, trichloroethyl, trifluoroethyl and pentafluoroethyl;

optionally substituted C 3-6 cycloalkyl such as cyclopropyl, 1-methylcyclopropyl, cyclopentyl, 1-methylcyclopentyl, cyclohexyl and 1-methylcyclohexyl;

C 1-6 alkoxy C 1-6 alkyl such as methoxymethyl, methoxyethyl, ethoxymethyl, propoxymethyl and butoxymethyl;

C 1-6 alkylthio C 1-6 alkyl such as methylthiomethyl, methylthioethyl, ethylthioethyl, ethylthiomethyl, propylthiomethyl and butylthiomethyl;

mono- or di-C 1-6 alkylamino such as methylamino, ethylamino, propylamino, dimethylamino, diethylamino, dipropylamino, dibutylamino and ethylisopropylamino;

optionally substituted phenyl C 1-6 alkyl, such as benzyl, phenethyl and phenylpropyl that may have substituents at arbitrary positions of the benzene ring;

optionally substituted phenoxy C 1-6 alkyl, such as phenoxymethyl and phenoxyethyl that may have substituents at arbitrary positions of the benzene ring;

optionally substituted phenylthio C 1-6 alkyl, such as phenylthiomethyl, phenylthioethyl, phenylthiopropyl and phenylthiobutyl that may have substituents at arbitrary positions of the benzene ring; or

phenyl having optional substituents at arbitrary positions of the benzene ring.

R 2 is C 1-6 alkyl such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, pentyl and its isomers, and hexyl and its isomers, or phenyl having optional substituents at arbitrary positions of the benzene ring.

In these R 1 and R 2 , examples of benzene-ring substituents of the phenyl C 1-6 alkyl, phenylthio C 1-6 alkyl, phenoxy C 1-6 alkyl and phenyl groups include halogen such as fluorine and chlorine, C 1-6 alkyl such as methyl and ethyl, C 1-6 alkoxy such as methoxy, ethoxy and isopropoxy, and nitro. These benzene rings may have two or more, same or different, substituents.

X is cyano, nitro,

halogen such as chlorine, bromine and fluorine;

C 1-6 alkyl such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, pentyl and its isomers, and hexyl and its isomers;

C 1-6 haloalkyl such as chloromethyl, fluoromethyl, dichloromethyl, trichloromethyl, trifluoromethyl, 1-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl and pentafluoroethyl;

C 1-6 alkoxy such as methoxy, ethoxy, propoxy, isopropoxy and butoxy;

C 1-6 haloalkoxy such as chloromethoxy, dichloromethoxy, trichloromethoxy, trifluoromethoxy, 1-fluoroethoxy and 1,1-difluoroethoxy;

optionally substituted phenyl, or

optionally substituted phenoxy.

Examples of substituents of these phenyl and phenoxy groups include halogen such as fluorine and chlorine; C 1-6 alkyl such as methyl and ethyl; C 1-6 alkoxy such as methoxy, ethoxy and isopropoxy; and nitro. The said phenyl group may have two or more, same or different, substituents.

When n is 2 or larger, X's may be the same or different groups.

Compounds having particularly excellent pest controlling effects among the compounds of the present invention, compared to similar, known cinnamonitrile compounds, are those where, in the above Formula (1), A is C 1-6 alkyl, optionally substituted C 3-6 cycloalkyl, optionally substituted pyridyl, optionally substituted thienyl or substituted phenyl; B is hydrogen; R is COR 1 or SO 2 R 2 ; and X is halogen, C 1-6 alkyl, C 1-6 haloalkyl or C 1-6 alkoxy, and at least one of the substituents is at position 2.

FORMS TO IMPLEMENT THE INVENTION

The compounds of the present invention are prepared, for example, according to the following:

(wherein A, B, R, X and n are as defined above, and L 1 is a leaving group such as halogen, C 1-6 alkoxy, phenoxy, 1-imidazolyl, 1-pyrazolyl, p-toluenesulfonyloxy, methanesulfonyloxy or trifluoromethanesulfonyloxy).

That is, 1 mole of a compound of Formula (2) is reacted with 0.5 to 2 moles of a compound of Formula (3) in an inert solvent in the presence of a base, to give a compound of Formula (1).

Examples of bases used for this reaction include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; carbonates such as sodium carbonate and potassium carbonate; organic metals such as n-butyl lithium and lithium diisopropylamide (LDA); and organic bases such as triethylamine, diisopropylethylamine and pyridine.

Solvents able to be used include N,N-dimethylformamide (DMF), dimethylsulfoxide (DMSO), tetrahydrofuran (THF), acetonitrile, hexamethylphosphoramide (HMPT), benzene, toluene, dichloromethane, chloroform and carbon tetrachloride. Preferred reaction temperatures are from −78° C. to the boiling point of solvents used.

The compounds of Formula (1) of the present invention have 2 stereoisomers. One of the isomers or a mixture of the isomers may be produced, depending on reaction conditions and purification methods. These isomers are all covered by the present invention.

A compound of Formula (2) of a starting material can be prepared as follows:

(wherein A, B, X and n are as defined above, and L 2 is a leaving group such as halogen, C 1-6 alkoxy, phenoxy, 1-imidazolyl or 1-pyrazolyl).

That is, 1 mole of a compound of Formula (4) is reacted with 0.5 to 2 moles of a compound of Formula (5) in an inert solvent in the presence of a base, to give a compound of Formula (2).

Examples of bases used for this reaction include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; carbonates such as sodium carbonate and potassium carbonate; organic metals such as n-butyl lithium and LDA; and organic bases such as triethylamine, diisopropylethylamine and pyridine.

Solvents able to be used include DMF, DMSO, THF, acetonitrile, hexamethylphosphoramide (HMPT), benzene, toluene, dichloromethane, chloroform and carbon tetrachloride. Preferred reaction temperatures are from −78° C. to the boiling point of solvents used.

A target compound is obtained with usual post-treatments after the completion of the reaction.

The structures of the compounds of the present invention were determined by IR, MNR, MS and other means.

Representative examples of the compounds of the present invention, that can be prepared according to the above processes, are shown in Tables 1 to 4. The symbols used in the tables have the following meanings:

Me: methyl, Et: ethyl, Pr: propyl, Bu: butyl, Pen: pentyl, Hex: hexyl, Ph: phenyl, n: normal, i: iso, t: tertiary, neo: neo, and c: cyclo

TABLE 1
X 1	X 2	R	X 1	X 2	R	X 1	X 2	R	X 1	X 2	R
CF 3	H	COtBu	CF 3	H	R21	Me	H	CO 2 CH 2 Ph	Me	H	R31
CF 3	H	COMe	CF 3	H	R22	Me	H	CONMe 2	Me	H	R32
CF 3	H	COEt	CF 3	H	R23	Me	H	R1	Me	H	R33
CF 3	H	COnPr	CF 3	H	R24	Me	H	R2	Me	H	R34
CF 3	H	COnBu	CF 3	H	R25	Me	H	R3	Me	H	R35
CF 3	H	COPh	CF 3	H	R26	Me	H	R4	Me	H	Me
CF 3	H	COCCl 3	CF 3	H	R27	Me	H	R5	Me	H	CH 3 Ph
CF 3	H	COCF 3	CF 3	H	R28	Me	H	R6	Me	H	SO 2 Me
CF 3	H	CO 2 Me	CF 3	H	R29	Me	H	R7	Me	H	SO 2 Et
CF 3	H	CO 2 nBu	CF 3	H	R30	Me	H	R8	Me	H	SO 2 nPr
CF 3	H	CO 2 CH 2 Ph	CF 3	H	R31	Me	H	R9	Me	H	SO 2 iPr
CF 3	H	CONMe 2	CF 3	H	R32	Me	H	R10	Me	H	R36
CF 3	H	R1	CF 3	H	R33	Me	H	R11	Cl	H	COtBu
CF 3	H	R2	CF 3	H	R34	Me	H	R12	Cl	H	COMe
CF 3	H	R3	CF 3	H	R35	Me	H	R13	Cl	H	COEt
CF 3	H	R4	CF 3	H	Me	Me	H	R14	Cl	H	COnPr
CF 3	H	R5	CF 3	H	CH 2 Ph	Me	H	R15	Cl	H	COnBu
CF 3	H	R6	CF 3	H	SO 2 Me	Me	H	R16	Cl	H	COPh
CF 3	H	R7	CF 3	H	SO 2 Et	Me	H	R17	Cl	H	COCCl 3
CF 3	H	R8	CF 3	H	SO 2 nPr	Me	H	R18	Cl	H	COCF 3
CF 3	H	R9	CF 3	H	SO 2 iPr	Me	H	R19	Cl	H	CO 2 Me
CF 3	H	R10	CF 3	H	R36	Me	H	R20	Cl	H	CO 2 nBu
CF 3	H	R11	Me	H	COtBu	Me	H	R21	Cl	H	CO 2 CH 2 Ph
CF 3	H	R12	Me	H	COMe	Me	H	R22	Cl	H	CONMe 2
CF 3	H	R13	Me	H	COEt	Me	H	R23	Cl	H	R1
CF 3	H	R14	Me	H	COnPr	Me	H	R24	Cl	H	R2
CF 3	H	R15	Me	H	COnBu	Me	H	R25	Cl	H	R3
CF 3	H	R16	Me	H	COPh	Me	H	R26	Cl	H	R4
CF 3	H	R17	Me	H	COCCl 4	Me	H	R27	Cl	H	R5
CF 3	H	R18	Me	H	COCF 4	Me	H	R28	Cl	H	R6
CF 3	H	R19	Me	H	CO 2 Me	Me	H	R29	Cl	H	R7
CF 3	H	R20	Me	H	CO 2 nBu	Me	H	R30	Cl	H	R8
Cl	H	R9	Cl	H	SO 2 iPr	Br	H	R19	I	H	COPh
Cl	H	R10	Cl	H	R36	Br	H	R20	CN	H	COtBu
Cl	H	R11	Br	H	COtBu	Br	H	R21	CN	H	COMe
Cl	H	R12	Br	H	COMe	Br	H	R22	CN	H	COPh
Cl	H	R13	Br	H	COEt	Br	H	R23	CO 2 Me	H	COtBu
Cl	H	R14	Br	H	COnPr	Br	H	R24	CO 2 Me	H	COMe
Cl	H	R15	Br	H	COnBu	Br	H	R25	CO 2 Me	H	COPh
Cl	H	R16	Br	H	COPh	Br	H	R26	CO 2 Et	H	COtBu
Cl	H	R17	Br	H	COCCl 3	Br	H	R27	CO 2 Et	H	COMe
Cl	H	R18	Br	H	COCF 4	Br	H	R28	CO 2 Et	H	COPh
Cl	H	R19	Br	H	CO 2 Me	Br	H	R29	Et	H	COtBu
Cl	H	R20	Br	H	CO 2 nBu	Br	H	R30	Et	H	COMe
Cl	H	R21	Br	H	CO 2 CH 2 Ph	Br	H	R31	Et	H	COPh
Cl	H	R22	Br	H	CONMe 2	Br	H	R32	iPr	H	COtBu
Cl	H	R23	Br	H	R1	Br	H	R33	iPr	H	COMe
Cl	H	R24	Br	H	R2	Br	H	R34	iPr	H	COPh
Cl	H	R25	Br	H	R3	Br	H	R35	CH 2 CF 3	H	COtBu
Cl	H	R26	Br	H	R4	Br	H	Me	CH 2 CF 3	H	COMe
Cl	H	R27	Br	H	R5	Br	H	CH 2 Ph	CH 2 CF 3	H	COPh
Cl	H	R28	Br	H	R6	Br	H	SO 2 Me	OMe	H	COtBu
Cl	H	R29	Br	H	R7	Br	H	SO 2 Et	OMe	H	COMe
Cl	H	R30	Br	H	R8	Br	H	SO 2 nPr	OMe	H	COPh
Cl	H	R31	Br	H	R9	Br	H	SO 2 iPr	OEt	H	COtBu
Cl	H	R32	Br	H	R10	Br	H	R36	OEt	H	COMe
Cl	H	R33	Br	H	R11	F	H	COtBu	OEt	H	COPh
Cl	H	R34	Br	H	R12	F	H	COMe	OiPr	H	COtBu
Cl	H	R35	Br	H	R13	F	H	COPh	OiPr	H	COMe
Cl	H	Me	Br	H	R14	F	H	R1	OiPr	H	COPh
Cl	H	CH 2 Ph	Br	H	R15	F	H	R2	OCF 3	H	COtBu
Cl	H	SO 2 Me	Br	H	R16	F	H	R25	OCF 3	H	COMe
Cl	H	SO 2 Et	Br	H	R17	I	H	COtBu	OCF 3	H	COPh
Cl	H	SO 2 nPr	Br	H	R18	I	H	COMe	OPh	H	COtBu
OPh	H	COMe	F	F	R19	F	Me	CO 2 Me	F	Me	R29
OPh	H	COPh	F	F	R20	F	Me	CO 2 nBu	F	Me	R30
F	F	COtBu	F	F	R21	F	Me	CO 2 CH 2 Ph	F	Me	R31
F	F	COMe	F	F	R22	F	Me	CONMe 2	F	Me	R32
F	F	COEt	F	F	R23	F	Me	R1	F	Me	R33
F	F	COnPr	F	F	R24	F	Me	R2	F	Me	R34
F	F	COnBu	F	F	R25	F	Me	R3	F	Me	R35
F	F	COPh	F	F	R26	F	Me	R4	F	Me	Me
F	F	COCCl 3	F	F	R27	F	Me	R5	F	Me	CH 2 Ph
F	F	COCF 3	F	F	R28	F	Me	R6	F	Me	SO 2 Me
F	F	CO 2 Me	F	F	R29	F	Me	R7	F	Me	SO 2 Et
F	F	CO 2 nBu	F	F	R30	F	Me	R8	F	Me	SO 2 nPr
F	F	CO 2 CH 2 Ph	F	F	R31	F	Me	R9	F	Me	SO 2 iPr
F	F	CONMe 2	F	F	R32	F	Me	R10	F	Me	R36
F	F	R1	F	F	R33	F	Me	R11	F	Cl	COtBu
F	F	R2	F	F	R34	F	Me	R12	F	Cl	COMe
F	F	R3	F	F	R35	F	Me	R13	F	Cl	COEt
F	F	R4	F	F	Me	F	Me	R14	F	Cl	COnPr
F	F	R5	F	F	CH 2 Ph	F	Me	R15	F	Cl	COnBu
F	F	R6	F	F	SO 2 Me	F	Me	R16	F	Cl	COPh
F	F	R7	F	F	SO 2 Et	F	Me	R17	F	Cl	COCCl 3
F	F	R8	F	F	SO 2 nPr	F	Me	R18	F	Cl	COCF 3
F	F	R9	F	F	SO 3 iPr	F	Me	R19	F	Cl	CO 2 Me
F	F	R10	F	F	R36	F	Me	R20	F	Cl	CO 2 nBu
F	F	R11	F	Me	COtBu	F	Me	R21	F	Cl	CO 2 CH 2 Ph
F	F	R12	F	Me	COMe	F	Me	R22	F	Cl	CONMe 2
F	F	R13	F	Me	COEt	F	Me	R23	F	Cl	R1
F	F	R14	F	Me	COnPr	F	Me	R24	F	Cl	R2
F	F	R15	F	Me	COnBu	F	Me	R25	F	Cl	R3
F	F	R16	F	Me	COPh	F	Me	R26	F	Cl	R4
F	F	R17	F	Me	COCCl 3	F	Me	R27	F	Cl	R5
F	F	R18	F	Me	COCF 3	F	Me	R28	F	Cl	R6
F	Cl	R7	F	Cl	SO 2 Et	CH 2 F	H	CO 2 CH 2 Ph	CH 2 F	H	R31
F	Cl	R8	F	Cl	SOnPr	CH 2 F	H	CONMe 2	CH 2 F	H	R32
F	Cl	R9	F	Cl	SO 2 iPr	CH 2 F	H	R1	CH 2 F	H	R33
F	Cl	R10	F	Cl	R36	CH 2 F	H	R2	CH 2 F	H	R34
F	Cl	R11	F	OMe	COtBu	CH 2 F	H	R3	CH 2 F	H	R35
F	Cl	R12	F	OMe	COMe	CH 2 F	H	R4	CH 2 F	H	Me
F	Cl	R13	F	OMe	COPh	CH 2 F	H	R5	CH 2 F	H	CH 2 Ph
F	Cl	R14	F	CF 3	COtBu	CH 2 F	H	R6	CH 2 F	H	SO 2 Me
F	Cl	R15	F	CF 3	COMe	CH 2 F	H	R7	CH 2 F	H	SO 2 Et
F	Cl	R16	F	CF 3	COPh	CH 2 F	H	R8	CH 2 F	H	SO 2 nPr
F	Cl	R17	Cl	Cl	COtBu	CH 2 F	H	R9	CH 2 F	H	SO 2 iPr
F	Cl	R18	Cl	Cl	COMe	CH 2 F	H	R10	CH 2 F	H	R36
F	Cl	R19	Cl	Cl	COPh	CH 2 F	H	R11
F	Cl	R20	Cl	Me	COtBu	CH 2 F	H	R12
F	Cl	R21	Cl	Me	COMe	CH 2 F	H	R13
F	Cl	R22	Cl	Me	COPh	CH 2 F	H	R14
F	Cl	R23	Me	Me	COtBu	CH 2 F	H	R15
F	Cl	R24	Me	Me	COMe	CH 2 F	H	R16
F	Cl	R25	Me	Me	COPh	CH 2 F	H	R17
F	Cl	R26	OMe	OMe	COtBu	CH 2 F	H	R18
F	Cl	R27	OMe	OMe	COMe	CH 2 F	H	R19
F	Cl	R28	OMe	OMe	COPh	CH 2 F	H	R20
F	Cl	R29	CH 2 F	H	COtBu	CH 2 F	H	R21
F	Cl	R30	CH 2 F	H	COMe	CH 2 F	H	R22
F	Cl	R31	CH 2 F	H	COEt	CH 2 F	H	R23
F	Cl	R32	CH 2 F	H	COnPr	CH 2 F	H	R24
F	Cl	R33	CH 2 F	H	COnBu	CH 2 F	H	R25
F	Cl	R34	CH 2 F	H	COPh	CH 2 F	H	R26
F	Cl	R35	CH 2 F	H	COCCl 3	CH 2 F	H	R27
F	Cl	Me	CH 2 F	H	COCF 3	CH 2 F	H	R28
F	Cl	CH 2 Ph	CH 2 F	H	CO 2 Me	CH 2 F	H	R29
F	Cl	SO 2 Me	CH 2 F	H	CO 2 nBu	CH 2 F	H	R30

TABLE 2
	Y	X 1	X 2	R
	F	CF 3	H	COtBu
	F	CF 3	H	COMe
	F	CF 3	H	COEt
	F	CF 3	H	COnPr
	F	CF 3	H	COnBu
	F	CF 3	H	COPh
	F	CF 3	H	COCCl 3
	F	CF 3	H	COCF 3
	F	CF 3	H	CO 2 Me
	F	CF 3	H	CO 2 nBu
	F	CF 3	H	CO 2 CH 2 Ph
	F	CF 3	H	CONMe 2
	F	CF 3	H	R1
	F	CF 3	H	R2
	F	CF 3	H	R3
	F	CF 3	H	R4
	F	CF 3	H	R5
	F	CF 3	H	R6
	F	CF 3	H	R7
	F	CF 3	H	R8
	F	CF 3	H	R9
	F	CF 3	H	R10
	F	CF 3	H	R11
	F	CF 3	H	R12
	F	CF 3	H	R13
	F	CF 3	H	R14
	F	CF 3	H	R15
	F	CF 3	H	R16
	F	CF 3	H	R17
	F	CF 3	H	R18
	F	CF 3	H	R19
	F	CF 3	H	R20
	F	CF 3	H	R21
	F	CF 3	H	R22
	F	CF 3	H	R23
	F	CF 3	H	R24
	F	CF 3	H	R25
	F	CF 3	H	R26
	F	CF 3	H	R27
	F	CF 3	H	R28
	F	CF 3	H	R29
	F	CF 3	H	R30
	F	CF 3	H	R31
	F	CF 3	H	R32
	F	CF 3	H	R33
	F	CF 3	H	R34
	F	CF 3	H	R35
	F	CF 3	H	Me
	F	CF 3	H	CH 2 Ph
	F	CF 3	H	SO 2 Me
	F	CF 3	H	SO 2 Et
	F	CF 3	H	SO 2 nPr
	F	CF 3	H	SO 2 iPr
	F	CF 3	H	R36
	F	Me	H	COtBu
	F	Me	H	COMe
	F	Me	H	COEt
	F	Me	H	COnPr
	F	Me	H	COnBu
	F	Me	H	COPh
	F	Me	H	COCCl 3
	F	Me	H	COCF 3
	F	Me	H	CO 2 Me
	F	Me	H	CO 2 nBu
	F	Me	H	CO 2 CH 2 Ph
	F	Me	H	CONMe 2
	F	Me	H	R1
	F	Me	H	R2
	F	Me	H	R3
	F	Me	H	R4
	F	Me	H	R5
	F	Me	H	R6
	F	Me	H	R7
	F	Me	H	R8
	F	Me	H	R9
	F	Me	H	R10
	F	Me	H	R11
	F	Me	H	R12
	F	Me	H	R13
	F	Me	H	R14
	F	Me	H	R15
	F	Me	H	R16
	F	Me	H	R17
	F	Me	K	R18
	F	Me	H	R19
	F	Me	H	R20
	F	Me	H	R21
	F	Me	H	R22
	F	Me	H	R23
	F	Me	H	R24
	F	Me	H	R25
	F	Me	H	R26
	F	Me	H	R27
	F	Me	H	R28
	F	Me	H	R29
	F	Me	H	R30
	F	Me	H	R31
	F	Me	H	R32
	F	Me	H	R33
	F	Me	H	R34
	F	Me	H	R35
	F	Me	H	Me
	F	Me	H	CH 2 Ph
	F	Me	H	SO 2 Me
	F	Me	H	SO 2 Et
	F	Me	H	SO 2 nPr
	F	Me	H	SO 2 iPr
	F	Me	H	R36
	F	Cl	H	COtBu
	F	Cl	H	COMe
	F	Cl	H	COEt
	F	Cl	H	COnPr
	F	Cl	H	COnBu
	F	Cl	H	COPh
	F	Cl	H	COCCl 3
	F	Cl	H	COCF 3
	F	Cl	H	CO 2 Me
	F	Cl	H	CO 2 nBu
	F	Cl	H	CO 2 CH 2 Ph
	F	Cl	H	CONMe 2
	F	Cl	H	R1
	F	Cl	H	R2
	F	Cl	H	R3
	F	Cl	H	R4
	F	Cl	H	R5
	F	Cl	H	R6
	F	Cl	H	R7
	F	Cl	H	R8
	F	Cl	H	R9
	F	Cl	H	R10
	F	Cl	H	R11
	F	Cl	H	R12
	F	Cl	H	R13
	F	Cl	H	R14
	F	Cl	H	R15
	F	Cl	H	R16
	F	Cl	H	R17
	F	Cl	H	R18
	F	Cl	H	R19
	F	Cl	H	R20
	F	Cl	H	R21
	F	Cl	H	R22
	F	Cl	H	R23
	F	Cl	H	R24
	F	Cl	H	R25
	F	Cl	H	R26
	F	Cl	H	R27
	F	Cl	H	R28
	F	Cl	H	R29
	F	Cl	H	R30
	F	Cl	H	R31
	F	Cl	H	R32
	F	Cl	H	R33
	F	Cl	H	R34
	F	Cl	H	R35
	F	Cl	H	Me
	F	Cl	H	CH 2 Ph
	F	Cl	H	SO 2 Me
	F	Cl	H	SO 2 Et
	F	Cl	H	SO 2 nPr
	F	Cl	H	SO 2 iPr
	F	Cl	H	R36
	F	Br	H	COtBu
	F	Br	H	COMe
	F	Br	H	COEt
	F	Br	H	COnPr
	F	Br	H	COnBu
	F	Br	H	COPh
	F	Br	H	COCCl 3
	F	Br	H	COCF 3
	F	Br	H	CO 2 Me
	F	Br	H	CO 2 nBu
	F	Br	H	CO 2 CH 2 Ph
	F	Br	H	CONMe 2
	F	Br	H	R1
	F	Br	H	R2
	F	Br	H	R3
	F	Br	H	R4
	F	Br	H	R5
	F	Br	H	R6
	F	Br	H	R7
	F	Br	H	R8
	F	Br	H	R9
	F	Br	H	R10
	F	Br	H	R11
	F	Br	H	R12
	F	Br	H	R13
	F	Br	H	R14
	F	Br	H	R15
	F	Br	H	R16
	F	Br	H	R17
	F	Br	H	R18
	F	Br	H	R19
	F	Br	H	R20
	F	Br	H	R21
	F	Br	H	R22
	F	Br	H	R23
	F	Br	H	R24
	F	Br	H	R25
	F	Br	H	R26
	F	Br	H	R27
	F	Br	H	R28
	F	Br	H	R29
	P	Br	H	R30
	F	Br	H	R31
	F	Br	H	R32
	P	Br	H	R33
	F	Br	H	R34
	F	Br	H	R35
	F	Br	H	Me
	F	Br	H	CH 2 Ph
	F	Br	H	SO 2 Me
	F	Br	H	SO 2 Et
	F	Br	H	SO 2 nPr
	F	Br	H	SO 2 iPr
	F	Br	H	R36
	F	F	H	COtBu
	F	F	H	COMe
	F	F	H	COPh
	F	F	H	R1
	F	F	H	R2
	F	F	H	R25
	F	I	H	COtBu
	F	I	H	COMe
	F	I	H	COPh
	F	CN	H	COtBu
	F	CN	H	COMe
	F	CN	H	COPh
	F	CO 2 Me	H	COtBu
	F	CO 2 Me	H	COMe
	F	CO 2 Me	H	COPh
	F	CO 2 Et	H	COtBu
	F	CO 2 Et	H	COMe
	F	CO 2 Et	H	COPh
	F	Et	H	COtBu
	F	Et	H	COMe
	F	Et	H	COPh
	F	iPr	H	COtBu
	F	iPr	H	COMe
	F	iPr	H	COPh
	F	CH 2 CF 3	H	COtBu
	F	CH 2 CF 3	H	COMe
	F	CH 2 CF 3	H	COPh
	F	OMe	H	COtBu
	F	OMe	H	COMe
	F	OMe	H	COPh
	F	OEt	H	COtBu
	F	OEt	H	COMe
	F	OEt	H	COPh
	F	OiPr	H	COtBu
	F	OiPr	H	COMe
	F	OiPr	H	COPh
	F	OCF 3	H	COtBu
	F	OCF 3	H	COMe
	F	OCF 3	H	COPh
	F	OPh	H	COtBu
	F	OPh	H	COMe
	F	OPh	H	COPh
	F	F	F	COtBu
	F	F	F	COMe
	F	F	F	COEt
	F	F	F	COnPr
	F	F	F	COnBu
	F	F	F	COPh
	F	F	F	COCCl 3
	F	F	F	COCF 3
	F	F	F	CO 2 Me
	F	F	F	CO 2 Bu
	F	F	F	CO 2 CH 2 Ph
	F	F	F	CONMe 2
	F	F	F	R1
	F	F	F	R2
	F	F	F	R3
	F	F	F	R4
	F	F	F	R5
	F	F	F	R6
	F	F	F	R7
	F	F	F	R8
	F	F	F	R9
	F	F	F	R10
	F	F	F	R11
	F	F	F	R12
	F	F	F	R13
	F	F	F	R14
	F	F	F	R15
	F	F	F	R16
	F	F	F	R17
	F	F	F	R18
	F	F	F	R19
	F	F	F	R20
	F	F	F	R21
	F	F	F	R22
	F	F	F	R23
	F	F	F	R24
	P	F	F	R25
	P	F	F	R26
	F	F	F	R27
	F	F	F	R28
	F	F	F	R29
	F	F	F	R30
	F	F	F	R31
	F	F	F	R32
	F	F	F	R33
	F	F	F	R34
	F	F	F	R35
	F	F	F	Me
	F	F	F	CH 2 Ph
	F	F	F	SO 2 Me
	F	F	F	SO 2 Et
	F	F	F	SO 2 nPr
	F	F	F	SO 2 iPr
	F	F	F	R36
	F	F	Me	COtBu
	F	F	Me	COMe
	F	F	Me	COEt
	F	F	Me	COnPr
	F	F	Me	COnBu
	F	F	Me	COPh
	F	F	Me	COCCl 3
	F	F	Me	COCF 3
	F	F	Me	CO 2 Me
	F	F	Me	CO 2 nBu
	F	F	Me	CO 2 CH 2 Ph
	F	F	Me	CONMe 2
	F	F	Me	R1
	F	F	Me	R2
	F	F	Me	R3
	F	F	Me	R4
	F	F	Me	R5
	F	F	Me	R6
	F	F	Me	R7
	F	F	Me	R8
	F	F	Me	R9
	F	F	Me	R10
	F	F	Me	R11
	F	F	Me	R12
	F	F	Me	R13
	F	F	Me	R14
	F	F	Me	R15
	F	F	Me	R16
	F	F	Me	R17
	F	F	Me	R18
	F	F	Me	R19
	F	F	Me	R20
	F	F	Me	R21
	F	F	Me	R22
	F	F	Me	R23
	F	F	Me	R24
	F	F	Me	R25
	F	F	Me	R26
	F	F	Me	R27
	F	F	Me	R28
	F	F	Me	R29
	F	F	Me	R30
	F	F	Me	R31
	F	F	Me	R32
	F	F	Me	R33
	F	F	Me	R34
	F	F	Me	R35
	F	F	Me	Me
	F	F	Me	CH 2 Ph
	F	F	Me	SO 2 Me
	F	F	Me	SO 2 Et
	F	F	Me	SO 2 nPr
	F	F	Me	SO 2 iPr
	F	F	Me	R36
	F	F	Cl	COtBu
	F	F	Cl	COMe
	F	F	Cl	COEt
	F	F	Cl	COnPr
	F	F	Cl	COnBu
	F	F	Cl	COPh
	F	F	Cl	COCCl 3
	F	F	Cl	COCF 3
	F	F	Cl	CO 2 Me
	F	F	Cl	CO 2 nBu
	F	F	Cl	CO 2 CH 2 Ph
	F	F	Cl	CONMe 2
	F	F	Cl	R1
	F	F	Cl	R2
	F	F	Cl	R3
	F	F	Cl	R4
	F	F	Cl	R5
	F	F	Cl	R6
	F	F	Cl	R7
	F	F	Cl	R8
	F	F	Cl	R9
	F	F	Cl	R10
	F	F	Cl	R11
	F	F	Cl	R12
	F	F	Cl	R13
	F	F	Cl	R14
	F	F	Cl	R15
	F	F	Cl	R16
	F	F	Cl	R17
	F	F	Cl	R18
	F	F	Cl	R19
	F	F	Cl	R20
	F	F	Cl	R21
	F	F	Cl	R22
	F	F	Cl	R23
	F	F	Cl	R24
	F	F	Cl	R25
	F	F	Cl	R26
	F	F	Cl	R27
	F	F	Cl	R28
	F	F	Cl	R29
	F	F	Cl	R30
	F	F	Cl	R31
	F	F	Cl	R32
	F	F	Cl	R33
	F	F	Cl	R34
	F	F	Cl	R35
	F	F	Cl	Me
	F	F	Cl	CH 2 Ph
	F	F	Cl	SO 2 Me
	F	F	Cl	SO 2 Et
	F	F	Cl	SO 2 nPr
	F	F	Cl	SO 2 iPr
	F	F	Cl	R36
	F	F	OMe	COtBu
	F	F	OMe	COMe
	F	F	OMe	COPh
	F	F	CF 3	COtBu
	F	F	CF 3	COMe
	F	F	CF 3	COPh
	F	Cl	Cl	COtBu
	F	Cl	Cl	COMe
	F	Cl	Cl	COPh
	F	Cl	Me	COtBu
	F	Cl	Me	COMe
	F	Cl	Me	COPh
	F	Me	Me	COtBu
	F	Me	Me	COMe
	F	Me	Me	COPh
	F	OMe	OMe	COtBu
	F	OMe	OMe	COMe
	F	OMe	OMe	COPh
	Me	CF 3	H	COtBu
	Me	CF 3	H	COMe
	Me	CF 3	H	COEt
	Me	CF 3	H	COnPr
	Me	CF 3	H	COnBu
	Me	CF 3	H	COPh
	Me	CF 3	H	COCCl 3
	Me	CF 3	H	COCF 3
	Me	CF 3	H	CO 2 Me
	Me	CF 3	H	CO 2 nBu
	Me	CF 3	H	CO 2 CH 2 Ph
	Me	CF 3	H	CONMe 2
	Me	CF 3	H	R1
	Me	CF 3	H	R2
	Me	CF 3	H	R3
	Me	CF 3	H	R4
	Me	CF 3	H	R5
	Me	CF 3	H	R6
	Me	CF 3	H	R7
	Me	CF 3	H	R8
	Me	CF 3	H	R9
	Me	CF 3	H	R10
	Me	CF 3	H	R11
	Me	CF 3	H	R12
	Me	CF 3	H	R13
	Me	CF 3	H	R14
	Me	CF 3	H	R15
	Me	CF 3	H	R16
	Me	CF 3	H	R17
	Me	CF 3	H	R18
	Me	CF 3	H	R19
	Me	CF 3	H	R20
	Me	CF 3	H	R21
	Me	CF 3	H	R22
	Me	CF 3	H	R23
	Me	CF 3	H	R24
	Me	CF 3	H	R25
	Me	CF 3	H	R26
	Me	CF 3	H	R27
	Me	CF 3	H	R28
	Me	CF 3	H	R29
	Me	CF 3	H	R30
	Me	CF 3	H	R31
	Me	CF 3	H	R32
	Me	CF 3	H	R33
	Me	CF 3	H	R34
	Me	CF 3	H	R35
	Me	CF 3	H	Me
	Me	CF 3	H	CH 2 Ph
	Me	CF 3	H	SO 2 Me
	Me	CF 3	H	SO 2 Et
	Me	CF 3	H	SO 2 nPr
	Me	CF 3	H	SO 2 iPr
	Me	CF 3	H	R36
	Me	Me	H	COtBu
	Me	Me	H	COMe
	Me	Me	H	COEt
	Me	Me	H	COnPr
	Me	Me	H	COnBu
	Me	Me	H	COPh
	Me	Me	H	COCCl 3
	Me	Me	H	COCF 3
	Me	Me	H	CO 2 Me
	Me	Me	H	CO 2 tBu
	Me	Me	H	CO 2 CH 2 Ph
	Me	Me	H	CONMe 2
	Me	Me	H	R1
	Me	Me	H	R2
	Me	Me	H	R3
	Me	Me	H	R4
	Me	Me	H	R5
	Me	Me	H	R6
	Me	Me	H	R7
	Me	Me	H	R8
	Me	Me	H	R9
	Me	Me	H	R10
	Me	Me	H	R11
	Me	Me	H	R12
	Me	Me	H	R13
	Me	Me	H	R14
	Me	Me	H	R15
	Me	Me	H	R16
	Me	Me	H	R17
	Me	Me	H	R18
	Me	Me	H	R19
	Me	Me	H	R20
	Me	Me	H	R21
	Me	Me	H	R22
	Me	Me	H	R23
	Me	Me	H	R24
	Me	Me	H	R25
	Me	Me	H	R26
	Me	Me	H	R27
	Me	Me	H	R28
	Me	Me	H	R29
	Me	Me	H	R30
	Me	Me	H	R31
	Me	Me	H	R32
	Me	Me	H	R33
	Me	Me	H	R34
	Me	Me	H	R35
	Me	Me	H	Me
	Me	Me	H	CH 2 Ph
	Me	Me	H	SO 2 Me
	Me	Me	H	SO 2 Et
	Me	Me	H	SO 2 nPr
	Me	Me	H	SO 2 iPr
	Me	Me	H	R36
	Me	Cl	H	COtBu
	Me	Cl	H	COMe
	Me	Cl	H	COEt
	Me	Cl	H	COnPr
	Me	Cl	H	COnBu
	Me	Cl	H	COPh
	Me	Cl	H	COCCl 3
	Me	Cl	H	COCF 3
	Me	Cl	H	CO 2 Me
	Me	Cl	H	CO 2 nBu
	Me	Cl	H	CO 2 CH 2 Ph
	Me	Cl	H	CONMe 2
	Me	Cl	H	R1
	Me	Cl	H	R2
	Me	Cl	H	R3
	Me	Cl	H	R4
	Me	Cl	H	R5
	Me	Cl	H	R6
	Me	Cl	H	R7
	Me	Cl	H	R8
	Me	Cl	H	R9
	Me	Cl	H	R10
	Me	Cl	H	R11
	Me	Cl	H	R12
	Me	Cl	H	R13
	Me	Cl	H	R14
	Me	Cl	H	R15
	Me	Cl	H	R16
	Me	Cl	H	R17
	Me	Cl	H	R18
	Me	Cl	H	R19
	Me	Cl	H	R20
	Me	Cl	H	R21
	Me	Cl	H	R22
	Me	Cl	H	R23
	Me	Cl	H	R24
	Me	Cl	H	R25
	Me	Cl	H	R26
	Me	Cl	H	R27
	Me	Cl	H	R28
	Me	Cl	H	R29
	Me	Cl	H	R30
	Me	Cl	H	R31
	Me	Cl	H	R32
	Me	Cl	H	R33
	Me	Cl	H	R34
	Me	Cl	H	R35
	Me	Cl	H	Me
	Me	Cl	H	CH 2 Ph
	Me	Cl	H	SO 2 Me
	Me	Cl	H	SO 2 Et
	Me	Cl	H	SO 2 nPr
	Me	Cl	H	SO 2 iPr
	Me	Cl	H	R36
	Me	Br	H	COtBu
	Me	Br	H	COMe
	Me	Br	H	COtBu
	Me	F	H	COtBu
	Me	F	H	COMe
	Me	F	H	COtBu
	Me	I	H	COtBu
	Me	I	H	COMe
	Me	I	H	COPh
	Me	CN	H	COtBu
	Me	CN	H	COMe
	Me	CN	H	COPh
	Me	CO 2 Me	H	COtBu
	Me	CO 2 Me	H	COMe
	Me	CO 2 Me	H	COPh
	Me	CO 2 Et	H	COtBu
	Me	CO 2 Et	H	COMe
	Me	CO 2 Et	H	COPh
	Me	Et	H	COtBu
	Me	Et	H	COMe
	Me	Et	H	COPh
	Me	iPr	H	COtBu
	Me	iPr	H	COMe
	Me	iPr	H	COPh
	Me	CH 2 CF 3	H	COtBu
	Me	CH 2 CF 3	H	COMe
	Me	CH 2 CF 3	H	COPh
	Me	OMe	H	COtBu
	Me	OMe	H	COMe
	Me	OMe	H	COPh
	Me	OEt	H	COtBu
	Me	OEt	H	COMe
	Me	OEt	H	COPh
	Me	OiPr	H	COtBu
	Me	OiPr	H	COMe
	Me	OiPr	H	COPh
	Me	OCF 3	H	COtBu
	Me	OCF 3	H	COMe
	Me	OCF 3	H	COPh
	Me	OPh	H	COtBu
	Me	OPh	H	COMe
	Me	OPh	H	COPh
	Me	F	F	COtBu
	Me	F	F	COMe
	Me	F	F	COEt
	Me	F	F	COnPr
	Me	F	F	COnBu
	Me	F	F	COPh
	Me	F	F	COCCl 3
	Me	F	F	COCF 3
	Me	F	F	CO 2 Me
	Me	F	F	CO 2 nBu
	Me	F	F	CO 2 CH 2 Ph
	Me	F	F	CONMe 2
	Me	F	F	R1
	Me	F	F	R2
	Me	F	F	R3
	Me	F	F	R4
	Me	F	F	R5
	Me	F	F	R6
	Me	F	F	R7
	Me	F	F	R8
	Me	F	F	R9
	Me	F	F	R10
	Me	F	F	R11
	Me	F	F	R12
	Me	F	F	R13
	Me	F	F	R14
	Me	F	F	R15
	Me	F	F	R16
	Me	F	F	R17
	Me	F	F	R18
	Me	F	F	R19
	Me	F	F	R20
	Me	F	F	R21
	Me	F	F	R22
	Me	F	F	R23
	Me	F	F	R24
	Me	F	F	R25
	Me	F	F	R26
	Me	F	F	R27
	Me	F	F	R28
	Me	F	F	R29
	Me	F	F	R30
	Me	F	F	R31
	Me	F	F	R32
	Me	F	F	R33
	Me	F	F	R34
	Me	F	F	R35
	Me	F	F	Me
	Me	F	F	CH 2 Ph
	Me	F	F	SO 2 Me
	Me	F	F	SO 2 Et
	Me	F	F	SO 2 nPr
	Me	F	F	SO 2 iPr
	Me	F	F	R36
	Me	F	Me	COtBu
	Me	F	Me	COMe
	Me	F	Me	COEt
	Me	F	Me	COnPr
	Me	F	Me	COnBu
	Me	F	Me	COPh
	Me	F	Me	COCCl 3
	Me	F	Me	COCF 3
	Me	F	Me	CO 2 Me
	Me	F	Me	CO 2 nBu
	Me	F	Me	CO 2 CH 2 Ph
	Me	F	Me	CONMe 2
	Me	F	Me	R1
	Me	F	Me	R2
	Me	F	Me	R3
	Me	F	Me	R4
	Me	F	Me	R5
	Me	F	Me	R6
	Me	F	Me	R7
	Me	F	Me	R8
	Me	F	Me	R9
	Me	F	Me	R10
	Me	F	Me	R11
	Me	F	Me	R12
	Me	F	Me	R13
	Me	F	Me	R14
	Me	F	Me	R15
	Me	F	Me	R16
	Me	F	Me	R17
	Me	F	Me	R18
	Me	F	Me	R19
	Me	F	Me	R20
	Me	F	Me	R21
	Me	F	Me	R22
	Me	F	Me	R23
	Me	F	Me	R24
	Me	F	Me	R25
	Me	F	Me	R26
	Me	F	Me	R27
	Me	F	Me	R28
	Me	F	Me	R29
	Me	F	Me	R30
	Me	F	Me	R31
	Me	F	Me	R32
	Me	F	Me	R33
	Me	F	Me	R34
	Me	F	Me	R35
	Me	F	Me	Me
	Me	F	Me	CH 2 Ph
	Me	F	Me	SO 2 Me
	Me	F	Me	SO 2 Et
	Me	F	Me	SO 2 nPr
	Me	F	Me	SO 2 iPr
	Me	F	Me	R36
	Me	F	Cl	COtBu
	Me	F	Cl	COMe
	Me	F	Cl	COEt
	Me	F	Cl	COnPr
	Me	F	Cl	COnBu
	Me	F	Cl	COPh
	Me	F	Cl	COCCl 3
	Me	F	Cl	COCF 3
	Me	F	Cl	CO 2 Me
	Me	F	Cl	CO 2 nBu
	Me	F	Cl	CO 2 CH 2 Ph
	Me	F	Cl	CONMe 2
	Me	F	Cl	R1
	Me	F	Cl	R2
	Me	F	Cl	R3
	Me	F	Cl	R4
	Me	F	Cl	R5
	Me	F	Cl	R6
	Me	F	Cl	R7
	Me	F	Cl	R8
	Me	F	Cl	R9
	Me	F	Cl	R10
	Me	F	Cl	R11
	Me	F	Cl	R12
	Me	F	Cl	R13
	Me	F	Cl	R14
	Me	F	Cl	R15
	Me	F	Cl	R16
	Me	F	Cl	R17
	Me	F	Cl	R18
	Me	F	Cl	R19
	Me	F	Cl	R20
	Me	F	Cl	R21
	Me	F	Cl	R22
	Me	F	Cl	R23
	Me	F	Cl	R24
	Me	F	Cl	R25
	Me	F	Cl	R26
	Me	F	Cl	R27
	Me	F	Cl	R28
	Me	F	Cl	R29
	Me	F	Cl	R30
	Me	F	Cl	R31
	Me	F	Cl	R32
	Me	F	Cl	R33
	Me	F	Cl	R34
	Me	F	Cl	R35
	Me	F	Cl	Me
	Me	F	Cl	CH 2 Ph
	Me	F	Cl	SO 2 Me
	Me	F	Cl	SO 2 Et
	Me	F	Cl	SO 2 nPr
	Me	F	Cl	SO 2 iPr
	Me	F	Cl	R36
	Me	F	OMe	COtBu
	Me	F	OMe	COMe
	Me	F	OMe	COPh
	Me	F	CF 3	COtBu
	Me	F	CF 3	COMe
	Me	F	CF 3	COPh
	Me	Cl	Cl	COtBu
	Me	Cl	Cl	COMe
	Me	Cl	Cl	COPh
	Me	Cl	Me	COtBu
	Me	Cl	Me	COMe
	Me	Cl	Me	COPh
	Me	Me	Me	COtBu
	Me	Me	Me	COMe
	Me	Me	Me	COPh
	Me	OMe	OMe	COtBu
	Me	OMe	OMe	COMe
	Me	OMe	OMe	COPh
	Cl	CF 3	H	COtBu
	Cl	CF 3	H	COMe
	Cl	CF 3	H	COEt
	Cl	CF 3	H	COnPr
	Cl	CF 3	H	COnBu
	Cl	CF 3	H	COPh
	Cl	CF 3	H	COCCl 3
	Cl	CF 3	H	COCF 3
	Cl	CF 3	H	CO 2 Me
	Cl	CF 3	H	CO 2 nBu
	Cl	CF 3	H	CO 2 CH 2 Ph
	Cl	CF 3	H	CONMe 2
	Cl	CF 3	H	R1
	Cl	CF 3	H	R2
	Cl	CF 3	H	R3
	Cl	CF 3	H	R4
	Cl	CF 3	H	R5
	Cl	CF 3	H	R6
	Cl	CF 3	H	R7
	Cl	CF 3	H	R8
	Cl	CF 3	H	R9
	Cl	CF 3	H	R10
	Cl	CF 3	H	R11
	Cl	CF 3	H	R12
	Cl	CF 3	H	R13
	Cl	CF 3	H	R14
	Cl	CF 3	H	R15
	Cl	CF 3	H	R16
	Cl	CF 3	H	R17
	Cl	CF 3	H	R18
	Cl	CF 3	H	R19
	Cl	CF 3	H	R20
	Cl	CF 3	H	R21
	Cl	CF 3	H	R22
	Cl	CF 3	H	R23
	Cl	CF 3	H	R24
	Cl	CF 3	H	R25
	Cl	CF 3	H	R26
	Cl	CF 3	H	R27
	Cl	CF 3	H	R28
	Cl	CF 3	H	R29
	Cl	CF 3	H	R30
	Cl	CF 3	H	R31
	Cl	CF 3	H	R32
	Cl	CF 3	H	R33
	Cl	CF 3	H	R34
	Cl	CF 3	H	R35
	Cl	CF 3	H	Me
	Cl	CF 3	H	CH 2 Ph
	Cl	CF 3	H	SO 2 Me
	Cl	CF 3	H	SO 2 Et
	Cl	CF 3	H	SO 2 nPr
	Cl	CF 3	H	SO 2 iPr
	Cl	CF 3	H	R36
	Cl	Me	H	COtBu
	Cl	Me	H	COMe
	Cl	Me	H	COEt
	Cl	Me	H	COnPr
	Cl	Me	H	COnBu
	Cl	Me	H	COPh
	Cl	Me	H	COCCl 3
	Cl	Me	H	COCF 3
	Cl	Me	H	CO 2 Me
	Cl	Me	H	CO 2 nBu
	Cl	Me	H	CO 2 CH 2 Ph
	Cl	Me	H	CONMe 2
	Cl	Me	H	R1
	Cl	Me	H	R2
	Cl	Me	H	R3
	Cl	Me	H	R4
	Cl	Me	H	R5
	Cl	Me	H	R6
	Cl	Me	H	R7
	Cl	Me	H	R8
	Cl	Me	H	R9
	Cl	Me	H	R10
	Cl	Me	H	R11
	Cl	Me	H	R12
	Cl	Me	H	R13
	Cl	Me	H	R14
	Cl	Me	H	R15
	Cl	Me	H	R16
	Cl	Me	H	R17
	Cl	Me	H	R18
	Cl	Me	H	R19
	Cl	Me	H	R20
	Cl	Me	H	R21
	Cl	Me	H	R22
	Cl	Me	H	R23
	Cl	Me	H	R24
	Cl	Me	H	R25
	Cl	Me	H	R26
	Cl	Me	H	R27
	Cl	Me	H	R28
	Cl	Me	H	R29
	Cl	Me	H	R30
	Cl	Me	H	R31
	Cl	Me	H	R32
	Cl	Me	H	R33
	Cl	Me	H	R34
	Cl	Me	H	R35
	Cl	Me	H	Me
	Cl	Me	H	CH 2 Ph
	Cl	Me	H	SO 2 Me
	Cl	Me	H	SO 2 Et
	Cl	Me	H	SO 2 nPr
	Cl	Me	H	SO 2 iPr
	Cl	Me	H	R36
	Cl	Cl	H	COtBu
	Cl	Cl	H	COMe
	Cl	Cl	H	COEt
	Cl	Cl	H	COnPr
	Cl	Cl	H	COnBu
	Cl	Cl	H	COPh
	Cl	Cl	H	COCCl 3
	Cl	Cl	H	COCF 3
	Cl	Cl	H	CO 2 Me
	Cl	Cl	H	CO 2 nBu
	Cl	Cl	H	CO 2 CH 2 Ph
	Cl	Cl	H	CONMe 2
	Cl	Cl	H	R1
	Cl	Cl	H	R2
	Cl	Cl	H	R3
	Cl	Cl	H	R4
	Cl	Cl	H	R5
	Cl	Cl	H	R6
	Cl	Cl	H	R7
	Cl	Cl	H	R8
	Cl	Cl	H	R9
	Cl	Cl	H	R10
	Cl	Cl	H	R11
	Cl	Cl	H	R12
	Cl	Cl	H	R13
	Cl	Cl	H	R14
	Cl	Cl	H	R15
	Cl	Cl	H	R16
	Cl	Cl	H	R17
	Cl	Cl	H	R18
	Cl	Cl	H	R19
	Cl	Cl	H	R20
	Cl	Cl	H	R21
	Cl	Cl	H	R22
	Cl	Cl	H	R23
	Cl	Cl	H	R24
	Cl	Cl	H	R25
	Cl	Cl	H	R26
	Cl	Cl	H	R27
	Cl	Cl	H	R28
	Cl	Cl	H	R29
	Cl	Cl	H	R30
	Cl	Cl	H	R31
	Cl	Cl	H	R32
	Cl	Cl	H	R33
	Cl	Cl	H	R34
	Cl	Cl	H	R35
	Cl	Cl	H	Me
	Cl	Cl	H	CH 2 Ph
	Cl	Cl	H	SO 2 Me
	Cl	Cl	H	SO 2 Et
	Cl	Cl	H	SO 2 nPr
	Cl	Cl	H	SO 2 iPr
	Cl	Cl	H	R36
	Cl	Br	H	CO 2 tBu
	Cl	Br	H	COMe
	Cl	Br	H	COtBu
	Cl	F	H	COtBu
	Cl	F	H	COMe
	Cl	F	H	COtBu
	Cl	I	H	COtBu
	Cl	I	H	COMe
	Cl	I	H	COPh
	Cl	CN	H	COtBu
	Cl	CN	H	COMe
	Cl	CN	H	COPh
	Cl	CO 2 Me	H	COtBu
	Cl	CO 2 Me	H	COMe
	Cl	CO 2 Me	H	COPh
	Cl	CO 2 Et	H	COtBu
	Cl	CO 2 Et	H	COMe
	Cl	CO 2 Et	H	COPh
	Cl	Et	H	COtBu
	Cl	Et	H	COMe
	Cl	Et	H	COPh
	Cl	iPr	H	COtBu
	Cl	iPr	H	COMe
	Cl	iPr	H	COPh
	Cl	CH 2 CF 3	H	COtBu
	Cl	CH 2 CF 3	H	COMe
	Cl	CH 2 CF 3	H	COPh
	Cl	OMe	H	COtBu
	Cl	OMe	H	COMe
	Cl	OMe	H	COPh
	Cl	OEt	H	COtBu
	Cl	OEt	H	COMe
	Cl	OEt	H	COPh
	Cl	OiPr	H	COtBu
	Cl	OiPr	H	COMe
	Cl	OiPr	H	COPh
	Cl	OCF 3	H	COtBu
	Cl	OCF 3	H	COMe
	Cl	OCF 3	H	COPh
	Cl	OPh	H	COtBu
	Cl	OPh	H	COMe
	Cl	OPh	H	COPh
	Cl	F	F	COtBu
	Cl	F	F	COMe
	Cl	F	F	COEt
	Cl	F	F	COnPr
	Cl	F	F	COnBu
	Cl	F	F	COPh
	Cl	F	F	COCCl 3
	Cl	F	F	COCF 3
	Cl	F	F	CO 2 Me
	Cl	F	F	CO 2 nBu
	Cl	F	F	CO 2 CH 2 Ph
	Cl	F	F	CONMe 2
	Cl	F	F	R1
	Cl	F	F	R2
	Cl	F	F	R3
	Cl	F	F	R4
	Cl	F	F	R5
	Cl	F	F	R6
	Cl	F	F	R7
	Cl	F	F	R8
	Cl	F	F	R9
	Cl	F	F	R10
	Cl	F	F	R11
	Cl	F	F	R12
	Cl	F	F	R13
	Cl	F	F	R14
	Cl	F	F	R15
	Cl	F	F	R16
	Cl	F	F	R17
	Cl	F	F	R18
	Cl	F	F	R19
	Cl	F	F	R20
	Cl	F	F	R21
	Cl	F	F	R22
	Cl	F	F	R23
	Cl	F	F	R24
	Cl	F	F	R25
	Cl	F	F	R26
	Cl	F	F	R27
	Cl	F	F	R28
	Cl	F	F	R29
	Cl	F	F	R30
	Cl	F	F	R31
	Cl	F	F	R32
	Cl	F	F	R33
	Cl	F	F	R34
	Cl	F	F	R35
	Cl	F	F	Me
	Cl	F	F	CH 2 Ph
	Cl	F	F	SO 2 Me
	Cl	F	F	SO 2 Et
	Cl	F	F	SO 2 nPr
	Cl	F	F	SO 2 iPr
	Cl	F	F	R36
	Cl	F	Me	COtBu
	Cl	F	Me	COMe
	Cl	F	Me	COEt
	Cl	F	Me	COnPr
	Cl	F	Me	COnBu
	Cl	F	Me	COPh
	Cl	F	Me	COCCl 3
	Cl	F	Me	COCF 3
	Cl	F	Me	CO 2 Me
	Cl	F	Me	CO 2 nBu
	Cl	F	Me	CO 2 CH 2 Ph
	Cl	F	Me	CONMe 2
	Cl	F	Me	R1
	Cl	F	Me	R2
	Cl	F	Me	R3
	Cl	F	Me	R4
	Cl	F	Me	R5
	Cl	F	Me	R6
	Cl	F	Me	R7
	Cl	F	Me	R8
	Cl	F	Me	R9
	Cl	F	Me	R10
	Cl	F	Me	R11
	Cl	F	Me	R12
	Cl	F	Me	R13
	Cl	F	Me	R14
	Cl	F	Me	R15
	Cl	F	Me	R16
	Cl	F	Me	R17
	Cl	F	Me	R18
	Cl	F	Me	R19
	Cl	F	Me	R20
	Cl	F	Me	R21
	Cl	F	Me	R22
	Cl	F	Me	R23
	Cl	F	Me	R24
	Cl	F	Me	R25
	Cl	F	Me	R26
	Cl	F	Me	R27
	Cl	F	Me	R28
	Cl	F	Me	R29
	Cl	F	Me	R30
	Cl	F	Me	R31
	Cl	F	Me	R32
	Cl	F	Me	R33
	Cl	F	Me	R34
	Cl	F	Me	R35
	Cl	F	Me	Me
	Cl	F	Me	CH 2 Ph
	Cl	F	Me	SO 2 Me
	Cl	F	Me	SO 2 Et
	Cl	F	Me	SO 2 nPr
	Cl	F	Me	SO 2 iPr
	Cl	F	Me	R36
	Cl	F	Cl	COtBu
	Cl	F	Cl	COMe
	Cl	F	Cl	COEt
	Cl	F	Cl	COnPr
	Cl	F	Cl	COnBu
	Cl	F	Cl	COPh
	Cl	F	Cl	COCCl 3
	Cl	F	Cl	COCF 3
	Cl	F	Cl	CO 2 Me
	Cl	F	Cl	CO 2 nBu
	Cl	F	Cl	CO 2 CH 2 Ph
	Cl	F	Cl	CONMe 2
	Cl	F	Cl	R1
	Cl	F	Cl	R2
	Cl	F	Cl	R3
	Cl	F	Cl	R4
	Cl	F	Cl	R5
	Cl	F	Cl	R6
	Cl	F	Cl	R7
	Cl	F	Cl	R8
	Cl	F	Cl	R9
	Cl	F	Cl	R10
	Cl	F	Cl	R11
	Cl	F	Cl	R12
	Cl	F	Cl	R13
	Cl	F	Cl	R14
	Cl	F	Cl	R15
	Cl	F	Cl	R16
	Cl	F	Cl	R17
	Cl	F	Cl	R18
	Cl	F	Cl	R19
	Cl	F	Cl	R20
	Cl	F	Cl	R21
	Cl	F	Cl	R22
	Cl	F	Cl	R23
	Cl	F	Cl	R24
	Cl	F	Cl	R25
	Cl	F	Cl	R26
	Cl	F	Cl	R27
	Cl	F	Cl	R28
	Cl	F	Cl	R29
	Cl	F	Cl	R30
	Cl	F	Cl	R31
	Cl	F	Cl	R32
	Cl	F	Cl	R33
	Cl	F	Cl	R34
	Cl	F	Cl	R35
	Cl	F	Cl	Me
	Cl	F	Cl	CH 2 Ph
	Cl	F	Cl	SO 2 Me
	Cl	F	Cl	SO 2 Et
	Cl	F	Cl	SO 2 nPr
	Cl	F	Cl	SO 2 iPr
	Cl	F	Cl	R36
	Cl	F	OMe	COtBu
	Cl	F	OMe	COMe
	Cl	F	OMe	COPh
	Cl	F	CF 3	COtBu
	Cl	F	CF 3	COMe
	Cl	F	CF 3	COPh
	Cl	Cl	Cl	COtBu
	Cl	Cl	Cl	COMe
	Cl	Cl	Cl	COPh
	Cl	Cl	Me	COtBu
	Cl	Cl	Me	COMe
	Cl	Cl	Me	COPh
	Cl	Me	Me	COtBu
	Cl	Me	Me	COMe
	Cl	Me	Me	COPh
	Cl	OMe	OMe	COtBu
	Cl	OMe	OMe	COMe
	Cl	OMe	OMe	COPh
	Et	CF 3	H	COtBu
	Et	Me	H	COtBu
	Et	Cl	H	COtBu
	Et	F	F	COtBu
	Et	F	Me	COtBu
	Et	F	Cl	COtBu
	nPr	CF 3	H	COtBu
	nPr	Me	H	COtBu
	nPr	Cl	H	COtBu
	nPr	F	F	COtBu
	nPr	F	Me	COtBu
	nPr	F	Cl	COtBu
	iPr	CF 3	H	COtBu
	iPr	Me	H	COtBu
	iPr	Cl	H	COtBu
	iPr	F	F	COtBu
	iPr	F	Me	COtBu
	iPr	F	Cl	COtBu
	nBu	CF 3	H	COtBu
	nBu	Me	H	COtBu
	nBu	Cl	H	COtBu
	nBu	F	F	COtBu
	nBu	F	Me	COtBu
	nBu	F	Cl	COtBu
	tBu	CF 3	H	COtBu
	tBu	Me	H	COtBu
	tBu	Cl	H	COtBu
	tBu	F	F	COtBu
	tBu	F	Me	COtBu
	tBu	F	Cl	COtBu
	nHex	CF 3	H	COtBu
	nHex	Me	H	COtBu
	nHex	Cl	H	COtBu
	nHex	F	F	COtBu
	nHex	F	Me	COtBu
	nHex	F	Cl	COtBu
	cHex	CF 3	H	COtBu
	cHex	Me	H	COtBu
	cHex	Cl	H	COtBu
	cHex	F	F	COtBu
	cHex	F	Me	COtBu
	cHex	F	Cl	COtBu
	Ph	CF 3	H	COtBu
	Ph	Me	H	COtBu
	Ph	Cl	H	COtBu
	Ph	F	F	COtBu
	Ph	F	Me	COtBu
	Ph	F	Cl	COtBu
	CF 3	CF 3	H	COtBu
	CF 3	Me	H	COtBu
	CF 3	Cl	H	COtBu
	CF 3	F	F	COtBu
	CF 3	F	Me	COtBu
	CF 3	F	Cl	COtBu
	CH 2 CF 3	CF 3	H	COtBu
	CH 2 CF 3	Me	H	COtBu
	CH 2 CF 3	Cl	H	COtBu
	CH 2 CF 3	F	F	COtBu
	CH 2 CF 3	F	Me	COtBu
	CH 2 CF 3	F	Cl	COtBu
	OMe	CF 3	H	COtBu
	OMe	Me	H	COtBu
	OMe	Cl	H	COtBu
	OMe	F	F	COtBu
	OMe	F	Me	COtBu
	OMe	F	Cl	COtBu
	OEt	CF 3	H	COtBu
	OEt	Me	H	COtBu
	OEt	Cl	H	COtBu
	OEt	F	F	COtBu
	OEt	F	Me	COtBu
	OEt	F	Cl	COtBu
	OiPr	CF 3	H	COtBu
	OiPr	Me	H	COtBu
	OiPr	Cl	H	COtBu
	OiPr	F	F	COtBu
	OiPr	F	Me	COtBu
	OiPr	F	Cl	COtBu
	OtBu	CF 3	H	COtBu
	OtBu	Me	H	COtBu
	OtBu	Cl	H	COtBu
	OtBu	F	F	COtBu
	OtBu	F	Me	COtBu
	OtBu	F	Cl	COtBu
	OPh	CF 3	H	COtBu
	OPh	Me	H	COtBu
	OPh	Cl	H	COtBu
	OPh	F	F	COtBu
	OPh	F	Me	COtBu
	OPh	F	Cl	COtBu
	OCF 3	CF 3	H	COtBu
	OCF 3	Me	H	COtBu
	OCF 3	Cl	H	COtBu
	OCF 3	F	F	COtBu
	OCF 3	F	Me	COtBu
	OCF 3	F	Cl	COtBu
	CN	CF 3	H	COtBu
	CN	Me	H	COtBu
	CN	Cl	H	COtBu
	CN	F	F	COtBu
	CN	F	Me	COtBu
	CN	F	Cl	COtBu
	NO 2	CF 3	H	COtBu
	NO 2	Me	H	COtBu
	NO 2	Cl	H	COtBu
	NO 2	F	F	COtBu
	NO 2	F	Me	COtBu
	NO 2	F	Cl	COtBu
	F	CH 2 F	H	COtBu
	F	CH 2 F	H	COMe
	F	CH 2 F	H	COEt
	F	CH 2 F	H	COnPr
	F	CH 2 F	H	COCF 3
	F	CH 2 F	H	COPh
	F	CH 2 F	H	CO 2 Me
	F	CH 2 F	H	CO 2 nBu
	F	CH 2 F	H	R1
	F	CH 2 F	H	R2
	F	CH 2 F	H	R3
	F	CH 2 F	H	R13
	F	CH 2 F	H	R14
	F	CH 2 F	H	R19
	F	CH 2 F	H	R24
	F	CH 2 F	H	R25
	F	CH 2 F	H	R26
	F	CH 2 F	H	R27
	F	CH 2 F	H	R28
	F	CH 2 F	H	R29
	F	CH 2 F	H	R30
	F	CH 2 F	H	R31
	F	CH 2 F	H	R32
	F	CH 2 F	H	R35
	F	CH 2 F	H	Me
	F	CH 2 F	H	CH 2 Ph
	F	CH 2 F	H	SO 2 Me
	F	CH 2 F	H	SO 2 Et
	F	CH 2 F	H	SO 2 nPr
	F	CH 2 F	H	R36

TABLE 3
	Xn	R	Xn	R
	2-CF 3 -3,4-F 2	COtBu	2,3,5-F 3	COtBu
	2-CF 3 -3,4-F 2	R1	2,3,5-F 3	R1
	2-CF 3 -3,4-F 2	R2	2,3,5-F 3	R2
	2-CF 3 -3,5-F 2	COtBu	2,3,6-F 3	COtBu
	2-CF 3 -3,5-F 2	R1	2,3,6-F 3	R1
	2-CF 3 -3,5-F 2	R2	2,3,6-F 3	R2
	2-CF 3 -3,6-F 2	COtBu	2,4,5-F 3	COtBu
	2-CF 3 -3,6-F 2	R1	2,4,5-F 3	R1
	2-CF 3 -3,6-F 2	R2	2,4,5-F 3	R2
	2-CF 3 -4,5-F 2	COtBu	2,4,6-F 3	COtBu
	2-CF 3 -4,5-F 2	R1	2,4,6-F 3	R1
	2-CF 3 -4,5-F 2	R2	2,4,6-F 3	R2
	2-CF 3 -4,6-F 2	COtBu	2-Cl-3,4-F 2	COtBu
	2-CF 3 -4,6-F 2	R1	2-Cl-3,4-F 2	R1
	2-CF 3 -4,6-F 2	R2	2-Cl-3,4-F 2	R2
	2-CF 3 -5,6-F 2	COtBu	2-Cl-3,5-F 2	COtBu
	2-CF 3 -5,6-F 2	R1	2-Cl-3,5-F 2	R1
	2-CF 3 -5,6-F 2	R2	2-Cl-3,5-F 2	R2
	2-Me-3,4-F 2	COtBu	2-Cl-3,6-F 2	COtBu
	2-Me-3,4-F 2	R1	2-Cl-3,6-F 2	R1
	2-Me-3,4-F 2	R2	2-Cl-3,6-F 2	R2
	2-Me-3,5-F 2	COtBu	2-Cl-4,5-F 2	COtBu
	2-Me-3,5-F 2	R1	2-Cl-4,5-F 2	R1
	2-Me-3,5-F 2	R2	2-Cl-4,5-F 2	R2
	2-Me-3,6-F 2	COtBu	2-Cl-4,6-F 2	COtBu
	2-Me-3,6-F 2	R1	2-Cl-4,6-F 2	R1
	2-Me-3,6-F 2	R2	2-Cl-4,6-F 2	R2
	2-Me-4,5-F 2	COtBu	2-Cl-5,6-F 2	COtBu
	2-Me-4,5-F 2	R1	2-Cl-5,6-F 2	R1
	2-Me-4,5-F 2	R2	2-Cl-5,6-F 2	R2
	2-Me-4,6-F 2	COtBu	2-CF 3 -3,4,6-F 3	COtBu
	2-Me-4,6-F 2	R1	2-CF 3 -3,5,6-F 3	COtBu
	2-Me-4,6-F 2	R2	2-CF 3 -4-Cl-6-F	COtBu
	2-Me-5,6-F 2	COtBu	2-Me-3,4,6-F 3	COtBu
	2-Me-5,6-F 2	R1	2-Me-3,5,6-F 3	COtBu
	2-Me-5,6-F 2	R2	2,3,4,5,6-F 3	COtBu
	2,3,4-F 3	COtBu	2-OMe-4,5-F 2	COtBu
	2,3,4-F 3	R1	2-OMe-4,5-Cl 2	COtBu
	2,3,4-F 3	R2

TABLE 4
	A	B	R
	2-CF 3 -3-F—Ph	H	COtBu
	2-CF 3 -4-F—Ph	H	COtBu
	2-CF 3 -5-F—Ph	H	COtBu
	2-F-3-Me—Ph	H	COtBu
	2-F-4-Me—Ph	H	COtBu
	2-F-5-Me—Ph	H	COtBu
	2-F-3-Cl—Ph	H	COtBu
	2-F-4-Cl—Ph	H	COtBu
	2-F-5-Cl—Ph	H	COtBu
	2-Br-3-F—Ph	H	COtBu
	2-Br-4-F—Ph	H	COtBu
	2-Br-5-F—Ph	H	COtBu
	2-OMe-3-F—Ph	H	COtBu
	2-OMe-4-F—Ph	H	COtBu
	2-OMe-5-F—Ph	H	COtBu
	2-OMe-3-Cl—Ph	H	COtBu
	2-OMe-4-Cl—Ph	H	COtBu
	2-OMe-5-Cl—Ph	H	COtBu
	2-CF 3 -3,4-F 2 —Ph	H	COtBu
	2-CF 3 -3,5-F 2 —Ph	H	COtBu
	2-CF 3 -3,6-F 2 —Ph	H	COtBu
	2-CF 3 -4,5-F 2 —Ph	H	COtBu
	2-CF 3 -4,6-F 2 —Ph	H	COtBu
	2-CF 3 -5,6-F 2 —Ph	H	COtBu
	2-Me-3,4-F 2 —Ph	H	COtBu
	2-Me-3,5-F 2 —Ph	H	COtBu
	2-Me-3,6-F 2 —Ph	H	COtBu
	2-Me-4,5-F 2 —Ph	H	COtBu
	2-Me-4,6-F 2 —Ph	H	COtBu
	2-Me-5,6-F 2 —Ph	H	COtBu
	2-Cl-3,4-F 2 —Ph	H	COtBu
	2-Cl-3,5-F 2 —Ph	H	COtBu
	2-Cl-3,6-F 2 —Ph	H	COtBu
	2-Cl-4,5-F 2 —Ph	H	COtBu
	2-Cl-4,6-F 2 —Ph	H	COtBu
	2-Cl-5,6-F 2 —Ph	H	COtBu
	2-CF 3 -3,4,6-F 3 —Ph	H	COtBu
	2-CF 3 -3,5,6-F 3 —Ph	H	COtBu
	2-CF 3 -4-Cl-6-F—Ph	H	COtBu
	2-Me-3,4,6-F 3 —Ph	H	COtBu
	2-Me-3,5,6-F 3 —Ph	H	COtBu
	2-OMe-4,5-F 2 —Ph	H	COtBu
	2-OMe-4,5-Cl 3 —Ph	H	COtBu
	2-Me-cHex	H	COtBu
	2-Me-cHex	H	R1
	2-Me-cHex	H	R2
	Me	H	COtBu
	Me	H	R1
	Me	H	R2
	Et	H	COtBu
	Et	H	R1
	Et	H	R2
	iPr	H	COtBu
	Pr	H	R1
	Pr	H	R2
	nPr	H	COtBu
	nPr	H	R1
	nPr	H	R2
	nBu	H	COtBu
	nBu	H	R1
	nBu	H	R2
	nPen	H	COtBu
	nPen	H	R1
	nPen	H	R2
	nHex	H	COtBu
	nHex	H	R1
	nHex	H	R2
	CF 1	H	COtBu
	CF 2	H	R1
	CF 3	H	R2
	F	H	COtBu
	F	H	R1
	F	H	R2
	F	Cl	COtBu
	Cl	H	COtBu
	Cl	H	R1
	Cl	H	R2
	Cl	H	COtBu
	Cl	Cl	COtBu
	OMe	H	COtBu
	OiPr	H	COtBu
	OtBu	H	COtBu
	OPh	H	COtBu
	OCF 3	H	COtBu
	2-pyridyl	H	COtBu
	2-pyridyl	H	R1
	2-pyridyl	H	R2
	3-pyridyl	H	COtBu
	3-pyridyl	H	R1
	3-pyridyl	H	R2
	4-pyridyl	H	COtBu
	4-pyridyl	H	R1
	4-pyridyl	H	R2
	2-thienyl	H	COtBu
	2-thienyl	H	R1
	2-thienyl	H	R2
	2-Me—Ph	Me	COtBu
	2,6-F 2 —Ph	Me	COtBu
	2-F-6-CF 1 —Ph	Me	COtBu
	2-F-6-Me—Ph	Me	COtBu
	2-Cl-6-F—Ph	Me	COtBu
	tBu	Me	COtBu
	2-Me—Ph	Et	COtBu
	2,6-F 2 —Ph	Et	COtBu
	2-F-6-CF 4 —Ph	Et	COtBu
	2-F-6-Me—Ph	Et	COtBu
	2-Cl-6-F—Ph	Et	COtBu
	tBu	Et	COtBu
	2-Me—Ph	iPr	COtBu
	2,6-F 2 —Ph	iPr	COtBu
	2-F-6-CF 3 —Ph	iPr	COtBu
	2-F-6-Me—Ph	iPr	COtBu
	2-Cl-6-F—Ph	iPr	COtBu
	tBu	iPr	COtBu
	2-Me—Ph	Ph	COtBu
	2,6-F 2 —Ph	Ph	COtBu
	2-F-6-CF 3 —Ph	Ph	COtBu
	2-F-6-Me—Ph	Ph	COtBu
	2-Cl-6-F—Ph	Ph	COtBu
	tBu	Ph	COtBu
	2-Me—Ph	CF 3	COtBu
	2,6-F 2 —Ph	CF 3	COtBu
	2-F-6-CF 3 —Ph	CF 3	COtBu
	2-F-6-Me—Ph	CF 3	COtBu
	2-Cl-6-F—Ph	CF 3	COtBu
	tBu	CF 3	COtBu
	2-Me—Ph	cPr	COtBu
	2,6-F 2 —Ph	cPr	COtBu
	2-F-6-CF 1 —Ph	cPr	COtBu
	2-F-6-Me—Ph	cPr	COtBu
	2-Cl-6-F—Ph	cPr	COtBu
	tBu	cPr	COtBu
	2-Me—Ph	cHex	COtBu
	2,6-F 2 —Ph	cHex	COtBu
	2-F-6-CF 3 —Ph	cHex	COtBu
	2-F-6-Me—Ph	cHex	COtBu
	2-Cl-6-F—Ph	cHex	COtBu
	tBu	cHex	COtBu
	2-Me—Ph	F	COtBu
	2,6-F 2 —Ph	F	COtBu
	2-F-6-CF 3 —Ph	F	COtBu
	2-F-6-Me—Ph	F	COtBu
	2-Cl-6-F—Ph	F	COtBu
	tBu	F	COtBu
	2-Me—Ph	Cl	COtBu
	2,6-F 2 —Ph	Cl	COtBu
	2-F-6-CF 3 —Ph	Cl	COtBu
	2-F-6-Me—Ph	Cl	COtBu
	2-Cl-6-F—Ph	Cl	COtBu
	tBu	Cl	COtBu
	2-Me—Ph	CO 2 Me	COtBu
	2,6-F 2 —Ph	CO 2 Me	COtBu
	2-F-6-CF 3 —Ph	CO 2 Me	COtBu
	2-F-6-Me—Ph	CO 2 Me	COtBu
	2-Cl-6-F—Ph	CO 2 Me	COtBu
	tBu	CO 2 Me	COtBu
	2-Me—Ph	CO 3 Et	COtBu
	2,6-F 2 —Ph	CO 3 Et	COtBu
	2-F-6-CF 3 —Ph	CO 3 Et	COtBu
	2-F-6-Me—Ph	CO 3 Et	COtBu
	2-Cl-6-F—Ph	CO 3 Et	COtBu
	tBu	CO 3 Et	COtBu
	2-Me—Ph	CO 3 tBu	COtBu
	2,6-F 2 —Ph	CO 3 tBu	COtBu
	2-F-6-CF 3 —Ph	CO 3 tBu	COtBu
	2-F-6-Me—Ph	CO 3 tBu	COtBu
	2-Cl-6-F—Ph	CO 3 tBu	COtBu
	tBu	CO 3 tBu	COtBu

(Insecticides and Acaricides)

Compositions containing the compounds of the present invention obtained in such ways as those mentioned above are useful, for example, as agricultural and horticultural insecticides, acaricides, sanitary insect pest controlling agents and anti-fouling agents for aqueous adhesive organisms. It is particularly preferable to apply compositions containing the compounds of the present invention as agricultural and horticultural insecticides and acaricides.

The compounds of the present invention can be used in the pure form without adding other ingredients, when they are actually applied as agricultural and horticultural insecticides or acaricides. When applied as agrochemicals, they may be used in forms that general agrochemicals can take, such as wettable powders, granules, dusts, emulsifiable concentrates, water soluble powders, flowable concentrates and flowables.

In order to make solid formulations, vegetable powders such as soybean flour and wheat flour; fine mineral powders such as diatomaceous earth, apatite, gypsum, talc, bentonite, pyrophylite and clay; and organic and inorganic compounds such as sodium benzoate, urea and Glauber's salt can be used as additives and carriers. When the purpose is to prepare liquid formulations, as additives and carriers, petroleum fractions such as kerosene, xylene and solvent naphtha, cyclohexane, cyclohexanone, DMF, DMSO, alcohol, acetone, trichloroethylene, methyl isobutyl ketone, mineral oils, vegetable oils, water and the like can be used as solvents.

It is possible to further add surfactant, if required, to make these formulations homogeneous and stable forms. There are no particular restrictions on surfactant used. Their examples include nonionic surfactant such as polyoxyethylene-added alkylphenyl ethers, polyoxyethylene-added alkyl ethers, polyoxyethylene-added higher fatty acid esters, polyoxyethylene-added sorbitan higher fatty acid esters and polyoxyethylene-added tristylylphenyl ethers; polyoxyethylene-added alkylphenyl ether sulfates, alkylbenzenesulfonates, higher alcohol sulfates, alkylnaphthalene sulfonates, polycarboxylic acid salts, lignin sulfonates, condensation products of alkylnaphthalene sulfonates with formaldehyde, and copolymers of isobutylene and maleic anhydride.

An amount of the active ingredient (a compound of the present invention) in a formulation is preferably 0.01 to 90% by weight, more preferably about 0.05 to 85% by weight. The obtained wettable powders, emulsifiable concentrates, flowable concentrates and flowables are diluted with water to specified concentrations to use as suspensions or emulsions. The dusts and granules are used as they are to directly spray on plants or soil.

It goes without saying that the compounds of the present invention are sufficiently effective by themselves. They can be used, however, by mixing with one or more of various fungicides, insecticides, acaricides or synergists.

Representative examples of fungicides, insecticides, acaricides and plant growth regulators that can be used to mix with the compounds of the present invention are shown in the following:

Fungicides

Captan, Forpet, Thiuram, Ziram, Zineb, Maneb, Mancozeb, Propineb, Polycarbamate, Chlorotalonyl, Quintozene, Captafol, Iprodione, Prothimidon, Vinclosolin, Fluorimide, Cymoxanil, Mepronyl, Flutoranyl, Penthichlon, Oxycarboxin, Phosethyl-aluminum, Propamocarb, Triazimefon, Triazimenol, Propiconazole, Dichloptrazole, Bitertanol, Hexaconazole, Microbutanil, Flusilazole, Ethaconazole, Fluotrimazole, Flutriafen, Penconazole, Diniconazole, Cyproconazole, Phenalimol, Triflumizole, Prochloraz, Imazaryl, Pefurazoate, Tridemorph, Fenpropymorph, Triforin, Buthiobate, Pryfenox, Anilazine, Polyoxin, Metharaxyl, Oxadixyl, Flaraxyl, Isoprothiorane, Probenazole, Pyrolnitrin, Blasticidin S, Kasugamycin, Validamycin, Sulfric acid dihydrostreptomycin, Benomil, Carbendazim, Thiophanate-methyl, Hymexazole, Basic copper chloride, Basic copper sulfate, Triphenyl tin acetate, Triphenyl tin hydroxide, Diethofencarb, Methasulfocarb, Quinomethionate, Binapacryl, Lecithin, Sodium carbonate, Dithianon, Dinocap, Phenaminosulf, Dichlomezine, Guazatine, Dozin, IBP, Edifenphos, Mepanipyrim, Ferimzone, Trichlamide, Methasulfocarb, Fluazinam, Etokinorakku (oxolinic acid), Dimethomorph, Pyroquiron, Tecrofutaram, Futharide, Phenazinoxyde, Thiabendazole, Tricyclazole, Vinclozolin, Cymoxanil, Cyclobutanyl, Guazatine, Propamocarb-hydrochloride, Oxolinic acid and the like.

Insecticides and Acaricides

Organophosphorus and Carbamate Insecticides

Fenthion, Fenitrothion, Diazinon, Chlorpyrifos, ESP, Vamidothion, Fenthoate, Dimethoate, Formothion, Malathon, Trichlorfon, Thiomethon, Phosmet, Dichlorvos, Acephate, EPBP, Methylparathion, Oxydimethonmethyl, Ethion, Salithion, Cyanophos, Isoxathion, Pyridafenthion, Phosalon, Methidathion, Sulprofos, Chlorfenvinphos, Tetrachlorvinphos, Dimethylvinphos, Propaphos, isofenphos, Ethylthiomethon, Profenofos, Pyrachlofos, Monoclotophos, Adinphosmethyl, Aldicarb, Methomyl, Thiodicarb, Carbofuran, Carbosulfan, Benfuracarb, Furathiocarb, Propoxur, BPMC, MTMC, MIPC, Carbaryl, Pyrimicarb, Ethiofencarb, Fenoxycarb and the like.

Pyrethroid Type Insecticides

Permethrin, Cypermethrin, Deltamethrin, Fenvalerate, Fenpropathrin, Pyrethrin, Allethrin, Tetramethrin, Resmethrin, Dimethrin, Propathrin, Phenothrin, Prothrin, Fulvalinate, Cyfluthrin, Cyhalothrin, Flucythrinate, Ethofenprox, Cycloprothrin, Tralomethrin, Silafluofen, Profenprox, Acrynathrin and the like.

Benzoyl Urea and other Insecticides

Diflubenzuron, Chlorfluazuron, Hexaflumron, Triflumron, Tetrabenzuron, Flufenoxuron, Flucycloxuron, Buprofezin, Pyriproxyfen, Methoprene, Benzoepin (endosulfan), Diafenthiuron, Acetamiprid, Imidacloprid, Nitenpyram, Fipronyl, Caltop, Thiocyclam, Bensultap, Chlorphenapyr, Emanectin-benzoate, Tebufenozide, Nicotine sulfate, Rotenone, Metaldehyde, machine oils, BT, agrochemicals for microbial organisms such as insect disease viruses, and the like.

Nematicides

Phenamiphos, Fosthiazate and the like.

Acaricides

Chlorbenzylate, Phenisobromolate, Dicofol, Amitraz, BPPS, Benzomate, Hexythiazox, Fenbutatin oxide, Polynactins, Quinomethionate, CPCBS, Tetradifon, Abermectin, Milbemectin, Clofentezin, Cyhexatin, Pyridaben, Fenpyroximate, Tebufenpyrad, Pyrimidifen, Phenothiocarb, Dienochlor, Etoxazole, Halfenprox and the like.

Plant Growth Regulators

Gibberellins (for example, gibberellin A3, gibberellin A4 and gibberellin A7), IAA, NAA and the like.

The compound of the present invention can be used to control agricultural pests, sanitary insect pests, stored grain insect pests, cloth insect pests, house insect pests and the like, and have activities of killing adults, nymphs, larvae and eggs. Their representative examples are shown in the following:

Examples of Lepidopterous pest insects include cotton leafworm, cabbage armyworm, black cutworm, common cabbegeworm, cabbage looper, diamond-back, smaller tea tortrix, tea leaf roller, peach fruit moth, oriental fruit moth, citrus leaf miner, tea leaf roller, apple leaf miner, gypsy moth, tea tussock moth, rice stem borer, grass leaf roller, European corn borer, fall webworm, almond moth, Heliothis sp., Helicoverpa sp., Agrotis sp., casemaking clothes moth, codling moth and cotton bollworm.

Examples of Hemipterous pest insects include green peach aphid, cotton aphid, turnip aphid, grain aphid, bean bug, common green stink bug, arrowhead scale, mulberry mealy scale, greenhouse whitefly, tabacco whitefly, pear psylla, Japanese pear lace bug, brown planthopper, small brown planthopper, white-backed planthopper and green rice leafhopper.

Examples of Coleopterous pest insects include striped flea beetle, cucurbit leaf beetle, Colorado potato beetle, rice water weevil, rice weevil, adzuki bean weevil, Japanese beetle, soybean beetle, Diabrotica sp., cigarette beetle, powder post beetle, pine sawyer, white-spotted longicorn beetle, Agriotis sp., 28-spotted ladybeetle, rust-red flour beetle and cotton boll weevil.

Examples of Dipterous pest insects include housefly, Calliphora lata, Boettcherisca peregrina, cucurbit fruit fly, citrus fruit fly, seed maggot, rice leaf miner, yellow drosophila, Stomoxys calcitrans, Culex tritaeniarhynchus, Aedes aegypti and Anlopheles hyrcanus.

Examples of Thysanopterous pest insects include Thrips palmi and tea thrips.

Examples of Hymenopterous pest insects include Monomorium pharaonis, yellow harnet and cabbage sawfly.

Examples of Orthopterous pest insects include grasshopper.

Examples of Dictyopterous pest insects include German cockroach, American cockroach and Japanese cockroach.

Examples of Isopterous pest insects include Formosan subterranean termite and Reticulitermes speratus Kolbe.

Examples of Aphanipterous pest insects include human flea.

Examples of Anoplurous pest insects include human louse.

Examples of mites include two-spotted spider mite, Kanzawa spider mite, citrus red mite, European red mite, citrus rust mite, apple rust mite, Tarsonemus sp., Brevipalpus sp., Eotetranychus sp., Robin bulb mite, common grain mite, Desmatophagoides farinae, Boophilus microplus and Haemaphysallis bispinosa.

Examples of plant-parasitic nematodes include southern root-knot nematode, root lesion nematode, soybean cyst nematode, rice white-tip nematode and pine wood nematode.

Many pests such as diamond-back, planthoppers, leafhoppers and aphids, and phytophagous mites have developed resistance against organophosphorus pesticides, carbamate insecticides and acaricides. Therefore, the chemicals have had the problem of lack of efficacy. There has been a desire for chemicals effective on pests and mites of resistant strains. The compounds of the present invention are chemicals having excellent insecticidal and acaricidal effects on pests resistant to organophosphorus pesticides, carbamate insecticides or pyrethroid type agents and mites resistant to acaricides, as well as those of sensitive strains.

The compounds of the present invention induce very slight chemical injuries, have low toxicity on fish and warm-blood animals, and are highly safe.

BEST FORMS TO IMPLEMENT THE INVENTION

The present invention is further described in detail in reference to a Reference Example and Examples.

Reference Example 1

Preparation of 2-[4-(2,6-difluorophenyl)-2-thiazolyl]-3-hydroxy-2′-trifluoromethy-cinnamonitrile

To a solution of 0.8 g (4.2 mmol) of 2-trifluoromethylbenzoic acid in 10 ml of THF was added 0.69 g (4.2 mmol) of carbonylbisimidazole, followed by stirring at room temperature for an hour. To the mixture was added 1.0 g(4.2 mmol) of 2-cyanomethyl-4-(2,6-difluorophenyl)thiazole, and then, 0.17 g (4.2 mmol) of sodium hydride (60% in oil) in an ice-bath. After stirring at room temperature for an hour, another equivalent of sodium hydride (0.17 g, 4.2 mmol: 60% in oil) was added, followed by stirring at room temperature overnight. The reaction mixture was poured into ice-water, acidified with dilute hydrochloric acid, and then, extracted with ethyl acetate. The organic layer was concentrated under diminished pressure, followed by chromatography on silica-gel column (ethyl acetate/n-hexane=1/1, as an eluent) to give 1.1 g(64%) of the title compound. Melting point: 170-172° C.

EXAMPLE 1

Preparation of 2-[4-(2,6-difluorophenyl)-2-thiazolyl]-3-pivaloyloxy-2′-trifluormethyl-cinnamonitrile (Compound No. 3-1)

To a solution of 0.6 g (1.5 mmol) of 2-[4-(2,6-difluorophenyl)-2-thiazolyl]-3-hydroxy-2′-trifluoromethylcinnamonitrile in 5 ml of THF were added 0.16 g (1.6 mmol) of triethylamine and 0.2 g (1.6 mmol) of pivaloyl chloride in an ice-bath, respectively, and then, the mixture was stirred at room temperature for 2 hours. After the precipitate was filtered, the filtrate was concentrated under diminished pressure, followed by chromatography on silica-gel column (ethyl acetate/n-hexane=1/4, as an eluent) to give 0.28 g (39%). Melting point: 163-165° C.

Representative examples of the compounds of the present invention that were prepared in such ways as described above are shown in Table 5. The NMR data of oily substances and others are in Table 6.

The symbols used in the tables have the same meanings as those for Tables 1 to 4.

TABLE 5
Compound					Physical
No.	A	B	R	Xn	constant*
5-1	2,6-F 2 —Ph	H	COtBu	2-CF 3	[163-165] a
5-2	2,6-F 2 —Ph	H	COMe	2-CF 3	[165-167] a
5-3	2,6-F 2 —Ph	H	COPh	2-CF 3	[135-136]
5-4	2,6-F 2 —Ph	H	COtBu	2-Me	[111-121]
5-5	2,6-F 2 —Ph	H	COMe	2-Me	[120-128]
5-6	2,6-F 2 —Ph	H	COPh	2-Me	[182-183.5] a
5-7	2,6-F 2 —Ph	H	R35	2-Me	Viscous oil
5-8	2,6-F 2 —Ph	H	COtBu	2-Cl	[143-146]
5-9	2,6-F 2 —Ph	H	COtBu	2,6-F	[141-143.5]
5-10	2,6-F 2 —Ph	H	COtBu	2-Cl-6-F	n D 20.4 1.5726
5-11	2,6-F 2 —Ph	H	COtBu	2-F-6-CF 3	Viscous oil
5-12	2,6-F 2 —Ph	H	COtBu	2-Br	[119-122]
5-13	2,6-F 2 —Ph	H	COtBu	2-OMe	[72-74]
5-14	2,6-F 2 —Ph	H	COtBu	2,3-F 2 —6-CF 3	[142-144]
5-15	2-F—Ph	H	COtBu	2-CF 3	Viscous oil
5-16	3-F—Ph	H	COtBu	2-CF 3	Viscous oil
5-17	4-F—Ph	H	COtBu	2-CF 3	Viscous oil
5-18	2-Cl—Ph	H	COtBu	2-CF 3	Viscous oil
5-19	3-Cl—Ph	H	COtBu	2-CF 3	Viscous oil
5-20	tBu	H	COtBu	2-CF 3	n D 20.9 1.5193
5-21	tBu	H	COtBu	2,6-F 2	Viscous oil
5-22	tBu	H	COtBu	2,3-F 2 -6-CF 3	[181-183]
5-23	cHex	H	R34	2-Me	[128-129.5]
5-24	2,6-F 2 —Ph	H	COcPr	2-Me	[146-148]
5-25	2,6-F 2 —Ph	H	COiPr	2-Me	[137-139]
5-26	2,6-F 2 —Ph	H	R1	2-Me	[120-122]
5-27	2,6-F 2 —Ph	H	CO 2 nPr	2-Me	Viscous oil
5-28	2,6-F 2 —Ph	H	CO 2 CH 2 Ph	2-Me	Viscous oil
5-29	2,6-F 2 —Ph	H	SO 2 nPr	2-CF 3	[115-119]
5-30	2,6-F 2 —Ph	H	SO 2 Me	2-Me	[163-165]
5-31	2,6-F 2 —Ph	H	SO 2 nPr	2-Me	Viscous oil
5-32	2,6-F 2 —Ph	H	COtBu	2-Et	[98.5-99.5]
5-33	2,6-F 2 —Ph	H	COtBu	2-F	[153-155]
5-34	2,6-F 2 —Ph	H	COtBu	2-NO 2	Viscous oil
5-35	2,6-F 2 —Ph	H	COtBu	2-OCF 3	[114-117]
5-36	2,6-F 2 —Ph	H	COtBu	2-CO 2 Et	[127-130]
5-37	2,6-F 2 —Ph	H	COtBu	2,6-Cl 2	[154-159]
5-38	2,6-F 2 —Ph	H	COtBu	2-Me-3-F	[131-135]
5-39	2,6-F 2 —Ph	H	COtBu	2-Me-4-F	[131-143]
5-40	2,6-F 2 —Ph	H	COtBu	2-Me-5-F	[108-109]
5-41	2,6-F 2 —Ph	H	COtBu	2-Me-6-F	[103-104]
5-42	2,6-F 2 —Ph	Me	COtBu	2-Me	[140-141]
5-43	2,6-F 2 —Ph	Me	COMe	2-Me	Viscous oil
5-44	2-Cl—Ph	H	COtBu	2-Me	[123-125]
5-45	2-Cl—Ph	H	COtBu	2-Cl	[106-107]
5-46	2-Cl—Ph	H	COtBu	2,6-F 2	[144-147]
5-47	4-Cl—Ph	H	COtBu	2-CF 3	Viscous oil
5-48	2-CF 3 —Ph	H	COtBu	2-CF 3	[146-147]
5-49	2-CF 3 —Ph	H	COtBu	2-Me	[131-132]
5-50	2-CF 3 —Ph	H	COtBu	2,6-F 2	[86-87]
5-51	2-CF 3 —Ph	H	COtBu	2-Cl	[140-141]
5-52	2-F—Ph	H	COtBu	2-Me	[144-145]
5-53	2-F—Ph	H	COMe	2-Me	[127-129]
5-54	2-F—Ph	H	COPh	2-Me	[140-143]
5-55	2-F—Ph	H	COtBu	2-Cl	[143-145]
5-56	3-F—Ph	H	COtBu	2-Me	[129-130]
5-57	3-F—Ph	H	COMe	2-Me	[119-120]
5-58	3-F—Ph	H	COPh	2-Me	[148-149]
5-59	3-F—Ph	H	COtBu	2-Cl	[150-151]
5-60	2-Me—Ph	H	COtBu	2-CF 3	Viscous oil
5-61	2-Me—Ph	H	R31	2-Me	[161-164]
5-62	2-Me—Ph	H	COtBu	2-Me	[118-119]
5-63	2-Me—Ph	H	COtBu	2-F	[123-125]
5-64	2-Me—Ph	H	COtBu	2-Cl	n D 20.2 1.5808
5-65	2-Me—Ph	H	COtBu	2-Br	[99-103]
5-66	2-Me—Ph	H	COtBu	2,6-F 2	[133-135]
5-67	2-Me—Ph	H	COtBu	2-Cl-6-F	[124-126]
5-68	2-Me—Ph	H	COtBu	2-Me-6-F	[125-129]
5-69	3-Me—Ph	H	COtBu	2-CF 3	Viscous oil
5-70	3-Me—Ph	H	R31	2-Me	[130—131]
5-71	3-Me—Ph	H	COtBu	2-Me	Viscous oil
5-72	3-Me—Ph	H	COtBu	2,6-F 2	[103-105]
5-73	2,3-F 2 —Ph	H	COtBu	2-CF 3	[134-136]
5-74	2,3-F 2 —Ph	H	COtBu	2-Me	[101-102]
5-75	2,5-F 2 —Ph	H	COtBu	2-CF 3	[134-136]
5-76	2,5-F 2 —Ph	H	COtBu	2-Me	[126-128]
5-77	3,5-F 2 —Ph	H	COtBu	2-Me	[114-116]
5-78	2,3,6-F 2 —Ph	H	COtBu	2-Me	[105-107]
5-79	2-Cl-6-F—Ph	H	COtBu	2-CF 3	[150-163]
5-80	2-Cl-6-F—Ph	H	COtBu	2-Me	[121-122]
5-81	2-Cl-6-F—Ph	H	COtBu	2-Cl	[123-126]
5-82	2-Cl-6-F—Ph	H	COtBu	2,6-F 2	[136-138]
5-83	2-Me-3-F—Ph	H	COtBu	2-Me	[99-104]
5-84	2-Me-4-F—Ph	H	COtBu	2-Me	[139-144]
5-85	2-Me-5-F—Ph	H	COtBu	2-Me	[146-149]
5-86	2-Me-5-F—Ph	H	COtBu	2-Me	[111-116] b
5-87	2-Me-6-F—Ph	H	COtBu	2-CF 3	[98-101]
5-88	2-Me-6-F—Ph	H	COtBu	2-Me	[109-111]
5-89	2-OMe-5-F—Ph	H	COtBu	2-Me	[148-153]
5-90	2-OMe-5-Cl—Ph	H	COtBu	2-Me	[144-156]
5-91	2-OMe-3,5-F 2 —Ph	H	COtBu	2-Me	[134-136]
5-92	4-OCF 3 —Ph	H	COtBu	2-CF 3	Viscous oil
5-93	4-OCF 3 —Ph	H	COtBu	2-Me	[123-124]
5-94	4-OCF 3 —Ph	H	COtBu	2-Cl	[119-120]
5-95	Me	H	COtBu	2-Me	Viscous oil
5-96	tBu	H	COtBu	2-Me	[112-113]
5-97	tBu	H	COMe	2-Me	n D 21.5 1.5800
5-98	tBu	H	R31	2-Me	[125-126]
5-99	2-pyridyl	H	COtBu	2-Me	[153-157]
5-100	2-thienyl	H	COtBu	2-Me	[134-138]
5-101	2,6-F 2 —Ph	H	COtBu	2-Cl-4-F	[155-157]
5-102	2,6-F 2 —Ph	H	COtBu	2-F-6-OMe	[153-155]
5-103	1-Me-cHex	H	COtBu	2-Me	[96-98]
5-104	1-Me-cHex	H	COtBu	2-CF 3	[92-93]
5-105	2-Me-cHex	H	COtBu	2-Me	[92-94]
5-106	2-Me-cHex	H	COtBu	2-CF 3	[82-85]
5-107	2,6-F 2 —Ph	H	R2	2-Me	[96-98]
5-108	2,6-F 2 —Ph	H	R1	2-CF 3	[156-158]
5-109	2,6-F 2 —Ph	H	R2	2-CF 3	[101-103]
5-110	cHex	H	COtBu	2-Me	Viscous oil
*[ ]: Melting point ° C., and n D : refractive index. These are the same for the following tables.
a: One of isomers. Others are a mixture of isomers.
b: Isomer of Compound No. 5-85.

TABLE 6
NMR Data
Compound
No    1                                                                    H—NMR (CDCl                                                                        3                                                                    , δppm)
5-7   1.68 and 1.70(total 6H, 2s), 2.06 and 2.30
      (total 3H, 2s), 6.90-7.05(2H, m), 7.10-7.49(m)
      and 7.59(s) (total 10H)
5-11  1.27 and 1.33(total 9H, 2s), 6.83-7.08(2H, m),
      7.20-7.70(m) and 7.76(s) (total 5H)
5-15  1.29 and 1.32(total 9H, 2s), 6.95-7.12(1H, m),
      7.29-7.51(2H, m), 7.63-7.90(6H, m)
5-16  1.29 and 1.32(total 9H, 2s), 7.03-7.40(3H, m),
      7.62-8.00(m) and 8.33-8.41(m) (total 6H)
5-17  1.28 and 1.30(total 9H, 2s), 7.00-7.19(2H, m),
      7.60(1H, s), 7.61-7.90(4H, m), 7.93-8.00(2H, m)
5-18  1.29 and 1.30(total 9H, 2s), 7.25-7.51(4H, m),
      7.61-7.90(4H, m), 8.09 and 8.12(total 1H, 2s)
5-19  1.28 and 1.31(total 9H, 2s), 7.30-7.41(2H, m),
      7.62-7.90(6H, m), 7.97(1H, bs)
5-21  1.10, 1.32, 1.33 and 1.36(total 18H, 4s), 6.89-
      7.12(total 3H, m), 7.39-7.54(1H, m)
5-27  1.92 and 1.96(total 3H, 2s), 1.61-1.79(2H, m),
      2.34 and 2.53(total 3H, 2s), 4.17 and 4.18(total
      2H, 2t), 6.91-7.00(2H, m), 7.28-7.72(6H, m)
5-28  2.48 and 2.49(total 3H, 2s), 5.19 and 5.21(total
      2H, 2s), 6.92-7.70(13H, m)
5-31  1.96(3H, t), 1.81-1.98(2H, m), 2.53(3H, s), 2.99
      (2H, dd), 6.97-7.08(2H, m), 7.28-7.62(5H, m),
      7.76(1H, bs)
5-34  1.23 and 1.29(total 9H, 2s), 6.90 and 7.01(total
      total 2H, 2t), 7.20-7.40(1H, m), 7.51-7.95(4H,
      m), 8.20-8.28(1H, m)
5-43  2.19, 2.28, 2.33, 2.35, 2.44 and 2.50(total 9H,
      6s), 6.92-7.12(2H, m), 7.27-7.58(5H, m)
5-47  1.30 and 1.34(total 9H, 2s), 7.15-7.46 and 7.59-
      7.96(total 9H, 2m)
5-60  1.29 and 1.32(total 9H, 2s), 2.32 and 2.50(total
      3H, 2s), 7.15-7.33(4H, m), 7.48-7.91(5H, m)
5-69  1.30 and 1.33(total 9H, 2s), 2.37 and 2.42(total
      3H, 2s), 7.18-7.38(2H, m), 7.63-7.90(7H, m)
5-71  1.32 and 1.33(total 9H, 2s), 2.31, 2.39, 2.42 and
      2.59(total 6H, 4s), 7.12-7.87(9H, m)
5-92  1.30 and 1.33(9H, 2s), 7.14-7.40, 7.66-7.90 and
      7.98-8.04(total 9H, 3m)
5-95  1.32(9H, s), 2.52(3H, s), 2.56(3H, s), 7.04(1H,
      bs), 7.23-7.48(4H, m)
5-110 1.20-1.57(5H, m), 1.35(9H, s), 1.73-1.91(3H,
      m), 2.11-2.20(2H, m), 2.59(3H, s), 2.82-2.95
      (1H, m), 7.03(1H, s), 7.28-7.50(4H, m)

A few examples of compositions of the present invention are described below. Additives and addition ratios are not limited to those in the examples, and can be changed in a wide range. The “parts” used in the formulation examples are parts by weight.

EXAMPLE 2

Wettable Powder

	A compound of the present invention	40	parts
	Diatomaceous earth	53	parts
	Higher alcohol sulfate	4	parts
	Alkylnaphthalene sulfonate	3	parts

The above compounds were mixed uniformly and pulverized finely to give a wettable powder containing 40% of the active ingredient.

EXAMPLE 3

Emulsifiable Concentrate

	A compound of the present invention	30	parts
	Xylene	33	parts
	Dimethylformamide	30	parts
	Polyoxyethylene alkylallyl ether	7	parts

The above compounds were mixed and solved to give an emulsifiable concentrate containing 30% of the active ingredient.

EXAMPLE 4

Dust

	A compound of the present invention	10	parts
	Talc	89	parts
	Polyoxyethylene alkylallyl ether	1	part

The above compounds were mixed uniformly and pulverized finely to give a dust containing 10% of the active ingredient.

EXAMPLE 5

Granules

	A compound of the present invention	5	parts
	Clay	73	parts
	Bentonite	20	parts
	Sodium dioctylsulfosuccinate	1	part
	Sodium phosphate	1	part

The above compounds were sufficiently pulverized and mixed. Water was added to it to knead well, followed by granulation and drying to give granules containing 5% of the active ingredient.

EXAMPLE 6

Flowable Concentrate

	A compound of the present invention	10	parts
	Sodium lignin sulfonate	4	parts
	Sodium dodecylbenzenesulfonate	1	part
	Xanthane gum	0.2	parts
	Water	84.8	parts

The above compounds were mixed and wet pulverized until the granule size became smaller than 1 μ, to give a flowable concentrate containing 10% of the active ingredient.

Availability in Industry

Examples are shown below that formulations containing compounds of the present invention, which were prepared according to such ways as described above, were applied as agricultural and horticultural insecticides and acaricides.

Test Example 1

Effects on Pseudaletia separata Walker

According to the instructions of the wettable powder described in the above Example 2, a wettable powder was diluted with water to make the compound concentration 125 ppm. Corn leaves were immersed in the solution for 30 seconds, air-dried and placed in a Petri dish containing 5 third instar larvae of Pseudaletia separata Walker. The dish was covered with a glass lid and placed in a thermostatic chamber of temperature of 25° C. and relative humidity of 65%. Mortality was assessed 6 days after treatment. Each test was replicated twice.

The results show that the following compounds had mortality of 100%.

5-1, 5-2, 5-3, 5-4, 5-5, 5-6, 5-7, 5-8, 5-9, 5-10, 5-11, 5-12, 5-13, 5-15, 5-16, 5-17, 5-18, 5-20, 5-21, 5-22, 5-23, 5-24, 5-25, 5-26, 5-27, 5-28, 5-30, 5-31, 5-33, 5-34, 5-38, 5-39, 5-40, 5-41, 5-48, 5-49, 5-50, 5-51, 5-54, 5-56, 5-57, 5-58, 5-59, 5-60, 5-61, 5-62, 5-63, 5-64, 5-65, 5-66, 5-67, 5-68, 5-69, 5-74, 5-78, 5-80, 5-83, 5-84, 5-85, 5-86, 5-87, 5-88, 5-96, 5-97, 5-99, 5-100, 5-101, 5-102, 5-103, 5-104, 5-105, 5-106, 5-107, 5-108, 5-109 and 5-110.

Chlordimeform used as a control killed 40% of the larvae.

Test Example 2

Effects on Aphis gossypii Glover

Adults of Aphis gossypii Glover were inoculated on cucumber seedlings planted in a 10-cm (diameter) pot and 10 days old after the germination. On the following day the adult aphids were removed, According to the instructions of the emulsifiable concentrate described in the above Example 3, an emulsifiable concentrate was diluted with water to make a compound concentration 8 ppm. The diluted formulation was sprayed over the cucumber seedlings infested with hatched nymphs. The seedlings were placed in a thermostatic chamber of temperature of 25° C. and relative humidity of 65%. Mortality was assessed 6 days after treatment. Each test was replicated twice.

The results show that the following compounds had mortality of 100 %.

5-1, 5-3, 5-4, 5-5, 5-6, 5-7, 5-8, 5-10, 5-12, 5-13, 5-15, 5-16, 5-20, 5-24, 5-25, 5-26, 5-27, 5-28, 5-30, 5-31, 5-33, 5-38, 5-39, 5-40, 5-41, 5-44, 5-45, 5-49, 5-51, 5-52, 5-54, 5-55, 5-56, 5-57,5-58, 5-60, 5-61, 5-62, 5-63, 5-64, 5-65, 5-68, 5-69, 5-71, 5-74, 5-76, 5-77, 5-78, 5-79, 5-80, 5-83, 5-84, 5-85, 5-86, 5-87, 5-88, 5-89, 5-90, 5-91, 5-96, 5-99, 5-100, 5-101, 5-102, 5-103, 5-104, 5-105, 5-106, 5-107, 5-108, 5-109 and 5-110.

The known compounds shown in the following and used as controls killed none of the nymphs.

Control Compound A

A compound disclosed in Japanese Patent Laid-open No. Sho 53-92769

Control Compound B

A compound disclosed in Japanese Patent Laid-open No. Sho 55-154963

Control Compound C

A compound disclosed in EP 189960

Control Compound D

A compound disclosed in Japanese Patent Laid-open No. Sho 55-154962

Control Compound E

A compound disclosed in Japanese Patent Laid-open No. Hei 10-298169 and WO 95/29591

Claims

1. A compound represented by the formula (1) whereinA is C1-6 alkyl, C3-6 cycloalkyl optionally substituted by halogen, C1-6 alkyl, C1-6 alkoxy or nitro, pyridyl optionally substituted by halogen, C1-6 alkyl, C1-6 alkoxy or nitro, thienyl optionally substituted by halogen, C1-6 alkyl, C1-6 alkoxy or nitro, or 2,6 di-substituted phenyl by halogen, C1-6 alkyl, C1-6 alkoxy or nitro; B is hydrogen; R is a group of Formula COR1 (wherein R1 is C1-12 alkyl, C1-6 haloalkyl, optionally substituted C3-6 cycloalkyl, C1-6 alkoxy, C1-6 alkoxy C1-6 alkyl, C1-6 alkylthio C1-6 alkyl, mono-C1-6 alkylamino, di-C1-6 alkylamino, optionally substituted phenyl C1-6 alkyl, optionally substituted phenoxy C1-6 alkyl, optionally substituted phenylthio C1-6 alkyl or optionally substituted phenyl, or a group of Formula SO2R2 (wherein R2 is C1-6 alkyl or optionally substituted phenyl); X is halogen, C1-6 alkyl, C1-6 haloalkyl, or C1-6 alkoxy and at least one of the substituents is at position 2; and n is an integer between 1 and 5.

2. A pest controlling agent containing one or more compounds of Formula (1) (wherein A, B, R, X and n are as defined above) as active ingredients.