WO2001068589A1

WO2001068589A1 - Acrylonitrile compounds and pest controllers

Info

Publication number: WO2001068589A1
Application number: PCT/JP2001/002096
Authority: WO
Inventors: Tomio Yagihara; Yasushi Shibata; Tatsumi Suzuki; Shigemi Suga; Minoru Sakatani; Renpei Hatano; Takao Iwasa; Tomohiro Take; Yukuo Mukohara; Yoshinobu Fujii
Original assignee: Nippon Soda Co.,Ltd.
Priority date: 2000-03-17
Filing date: 2001-03-16
Publication date: 2001-09-20
Also published as: AU2001241170A1

Abstract

Acrylonitrile compounds of the general formula (1); a process for preparing the compounds; and pest controllers characterized by containing as the active ingredient one or more of the compounds wherein A is a group of the general formula A1, A2, A3, A4, A5, or A6 (wherein X1, X2, X3, X4, X5, X6, and X7 are each halogeno, C1-6 alkyl, or the like); B is phenyl which may be substituted with W2 or a heterocyclic group which may be substituted with W2; R is C1-12 alkyl, C1-6 haloalkyl, C1-6 alkoxy, or the like; Y1 is oxygen, sulfur, or the like; Y2 is oxygen or sulfur; and Z1 and Z2 are each independently hydrogen or C1-6 alkyl, or alternatively Z1 and Z2 together with the carbon atom to which they are bonded may form a 5- to 8-membered ring.

Description

Specification

Acrylonitrile compounds and pesticides

The present invention relates to a novel nitrile derivative of thiazolyl cinnamate and a pesticidal agent containing the derivative as an active ingredient.

Conventionally, a large number of pesticides such as insecticides and acaricides have been used, but their efficacy is insufficient, their use is limited due to drug resistance problems, and plant In many cases, it is difficult to say that it is a satisfactory control agent because it causes phytotoxicity and contamination, or is highly toxic to humans, livestock and fish. Therefore, there is a demand for the development of a drug that can be used safely with few such disadvantages.

Examples of the citrate nitrile derivatives similar to the compounds of the present invention include, for example, JP-A-53-92769, JP-A-55-154963, and EP189890. Publication No., WO 97/40 009 Publication, WO 98/33593 Publication 5, W098Z426 83 Publication, WO 98/449 93 Publication, WO 00/17 1993 Publication And WO0Z39106. DISCLOSURE OF THE INVENTION:

An object of the present invention is to provide a pesticidal agent comprising a ditolyl thiazolyl cinnamate derivative as an active ingredient, which is effective and can be used safely.

The present invention relates to the following (a) —general formula (1)

[Where A is the following formula: A 1 A 2 A 3 A4 A 5 and A 6

Α1 Α2 A3 Α4

A5 A6 (Wherein, it represents a halogen atom, an alkyl group, C i ₆ haloalkyl group, - 6 alkoxy group, an optionally substituted C ₃ _ ₆ cycloalkyl group, in optionally substituted pyridyl group, in substitution A phenyl group which may be substituted with a phenyl group or a phenyl group which may be substituted with

X ₂ is a hydrogen atom, a halogen atom, CI- e alkyl group, C i-6 haloalkyl group, C, _ ₆ alkoxy Cal Poni group, a C _{3 6} cycloalkyl group or an optionally substituted phenylene Le group Wi Represent

X ₃ and X ₄ are each independently a hydrogen atom, a halogen atom, an alkyl group,

C i—e represents an alkoxyl group;

X ₅ represents a hydrogen atom, a C ^ e alkyl group, a C i-6 cycloalkyl group, a Ci ₆ haloalkyl group, a C i ₆ alkoxy C ₆ alkyl group,

X ₆ is a hydrogen atom, a halogen atom, a C ₆ alkyl group, a C ₃ _ ₆ cycloalkyl group, a C ₆ haloalkyl group, a d ₆ alkoxy group, a C ₆ alkoxy C i ₆ alkyl group, a C ₆ alkoxycarbonyl. Represents a phenyl group which may be substituted with

X ₇ is substituted with a nitro group, a cyano group, a halogen atom, a C—e alkyl group, a C— ₆ cycloalkyl group, a —6 haloalkyl group, a —6 alkoxy group, a C i- ₆ haloalkoxy group, A phenyl group, a pyridyl group optionally substituted with, a phenyl group optionally substituted with, a pyridyloxy group optionally substituted with

n represents 0 or an integer of 1 to 5.

Represents a nitro group, a cyano group, a halogen atom, a C i -e alkyl group, a C i -e cycloalkyl group, a C i ₆ haloalkyl group, a C ₆ alkoxy group or a C i ₆ haloalkoxy group. ) Represents one type of group selected from the groups represented by. May be the same or different and may be substituted plurally.

B is, W ₂ is substituted with substituted also a good phenyl group or W ₂ represents a heterocyclic group which may,

W ₂ is Shiano group, a nitro group, a halogen atom, Ji ₆ alkyl group, flicking ₆ Haroaru kill group, C i ₆ alkoxy group, C ₆ haloalkoxy group, C _{3 8} cycloalkyl group, which may have a substituent It represents a good phenyl group or a phenoxy group which may have a substituent, and W ₂ may be the same or different and may be plurally substituted.

w The heterocyclic group which may be substituted with ₂ is triazolyl, thiazolyl, oxazolyl, isoxazolyl, isothiazolyl, pyrazolyl, imidazolyl, tetrazolyl, oxadiazolyl, thiadiazolyl, chenyl, furyl, pyrrolyl, pyridyl, pyrimidinyl, pyrimidinyl, pyrimidinyl, pyrimidinyl It is a kind of group selected from the group.

R is an alkyl group, a haloalkyl group, flicking ₆ alkoxy groups, ₆ § alkoxy C ₆ alkyl group, d ₆ alkylthio group, C] ₆ alkylthio C Al kill group, mono C i ₆ alkylamino group, current events〗 - ₆ alkyl amino group, an optionally substituted C ₃ _ ₆ consequent opening alkyl group, an optionally substituted phenyl C alkyl group, an optionally substituted phenoxy C i _ ₆ alkyl group, a substituted A phenylthio C i_ ₆ alkyl group which may have a group or a phenyl group which may have a substituent,

Is replaced by an oxygen atom, sulfur atom, hydrogen atom or Cie alkyl group Represents a nitrogen atom

Y ₂ represents an oxygen atom or a sulfur atom,

Oyobi ^ Also, each independently, a hydrogen atom, an alkyl group, C i_ ₆ Haroa alkyl group, C ₆ alkoxy C, ₆ alkyl group, C i_ ₆ alkylthio C i _e alkyl group, mono-C i-6 alkylamino Represents a C i_ ₆ alkyl group, a di, — ₆ alkylamino C ₆ alkyl group or a phenyl group which may have a substituent. Also, they may form a 5-8 membered ring with the carbon atom to which the Z i and Z ₂ are bonded.

An acrylonitrile compound represented by

(b) General formula (2)

(Wherein, A and B have the same meanings as in the claims), and a compound represented by the general formula (3) υ ²

入人 R

(3)

(Wherein, R, Υ ₁ ; Υ ₂ , Ζ ₁ ; 同じ₂ have the same meaning as in claim 1, and L is a halogen atom, ρ-toluenesulfonyloxy group, methanesulfonyloxy group or trifluoromethanesulfonyl group. A method for producing an acrylonitrile compound represented by the above general formula (1), and a compound represented by the following general formula (1):

(c) A pesticidal composition characterized by containing one or more of the acrylonitrile compounds as an active ingredient.

Further, the present invention is an industrially advantageous method for producing the compound represented by the general formula (2), which is an intermediate for producing the compound of the present invention.

A-CH ₂ -CN (4)

(Wherein A has the same meaning as described above) and a magnesium salt of a compound represented by the general formula (5):

0

(Five)

(Wherein, Q and B have the same meanings as described above). A method for producing a compound represented by the general formula (2), characterized by reacting with a compound represented by the following formula: Embodiment of the invention: In the general formula (1),

Are halogen atoms such as fluorine, chlorine, bromine and iodine, methyl, ethyl, butyl, isopropyl, butyl, sec-butyl, isoptyl, t-butyl, pentyl and its isomers, hexyl and its isomers Ci-e alkyl group of chloromethyl, fluoromethyl, bromomethyl, dichloromethyl, difluoromethyl, dibromomethyl, trichloromethyl, trifluoromethyl, tripromomethyl, 2,2,2-trichloroethyl, 2,2, 2-Ci-ehaloalkyl groups such as trifluoroethyl, pendufluorethyl, C-alkoxy groups such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, sec-butoxy, isobutoxy, and t-butoxy; Cyclopropyl, cyclopentyl, 1-methylpentyl, cyclo To key Sil, 1 - which may have a substituent such as cyclohexyl methylcyclohexyl C ₃ - ₆ Shikuroaruki group, (nitro group, halogen atoms such as fluorine and chlorine, methyl, C _i-6 alkyl group such as Echiru , main butoxy, ethoxy, C i _ ₆ alkoxy group as any) may have a substituent second isopropoxy - pyridyl, 3 - pyridyl, 4 - peak lysyl groups such as pyridyl, (nitro group, fluorine, A halogen atom such as chlorine, an alkyl group such as methyl and ethyl, a C- ₆ alkoxy group such as methoxy, ethoxy, and isopropoxy; a phenyl group such as 2-phenyl and 3-phenyl; ,

(Nitro group, halogen atoms such as fluorine and chlorine, methyl, C i ₆ AL kill groups such Echiru, main butoxy, ethoxy, such as C i-6 alkoxy groups such as isopropoxy) which may have a substituent It may have a phenyl group or a substituent (such as a nitro group, a halogen atom such as fluorine or chlorine, a Ci- ₆ alkyl group such as methyl or ethyl, or a _6- alkoxy group such as methoxy, ethoxy, or isopropoxy). Represents a good phenoxy group. Further, the pyridyl group, the phenyl group, the phenyl group and the phenoxy group may have the same or different plural substituents.

X ₂ is a hydrogen atom, a halogen atom such as fluorine, chlorine, bromine, or iodine, methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, isobutyl, t-butyl, pentyl and its isomers, hexyl and C alkyl groups such as isomers, chloromethyl, fluoromethyl, bromomethyl, dichloromethyl, difluoromethyl, dibromomethyl, trichloromethyl, trifluoromethyl, tripromomethyl, 2,2,2-trichloroethyl, 2,2, 2-triflate Ruo Roe chill, such as penta full O Roe Chi le C - ₆ eight-necked alkyl group, main Bok alkoxycarbonyl, ethoxycarbonyl, Provo alkoxycarbonyl, Isopurobokishi, butoxycarbonyl, t-butoxide deer Lupo alkenyl of any C i _ ₆ Alkoxycarbonyl group, cyclopropyl, Cyclopentyl, C ₃ _ _e cycloalkyl or (nitro group, such as key sill cyclohexane, halogen atoms such as fluorine and chlorine, methyl, C _ ₆ alkyl groups such as Echiru, main butoxy, ethoxy, C i such Isopuropoki Shi — Represents a phenyl group which may have a substituent (such as an e-alkoxy group).

X ₃ and X ₄ are a hydrogen atom, a halogen atom such as fluorine, chlorine, bromine, or iodine, methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, isobutyl, t-butyl, pentyl and isomers thereof. C- ₆ alkyl groups such as xyl and its isomers, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopoxy Represents an butoxide C i _ ₆ alkoxy force Lupo two Le group such as deer Lupo sulfonyl - Robokishi, butoxide deer Lupo sulfonyl, t.

X ₅ represents a hydrogen atom, a C- ₆ alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, isoptyl, t-butyl, pentyl and its isomers, hexyl and its isomers, cyclopropyl, It represents a ₆ alkoxy C i _ ₆ alkyl group - cyclopentyl, C ₃ _ ₆ cycloalkyl group such as cyclohexyl, main Tokishimechiru, main Tokishechiru, ethoxymethyl, Provo carboxymethyl, C i of butoxymethyl and the like.

X ₆ is a hydrogen atom, a halogen atom such as fluorine, chlorine, bromine, or iodine, methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, isobutyl, t-butyl, pentyl and its isomers, hexyl and the like. C i _ ₆ alkyl groups such as isomers, cyclo propyl, cyclopentyl, C _3, such as cyclohexyl - ₆ cycloalkyl group, click port Romechiru, Furuoromechiru, bromomethyl, dichloromethyl, Jifuruoromechiru, dibromomethyl, trichloromethyl, triflic C— ₆ haloalkyl groups such as chloromethyl, tripromoxymethyl, 2,2,2_trichloroethyl, 2,2,2-trifluoroethyl, pendufluorethyl, methoxy, ethoxy, propoxy, isopropoxy, Butoxy, sec — butoxy, isobutoxy, t — C—e alkoxy groups such as butoxy, C— ₆ alkoxy C—6 alkyl groups such as methoxymethyl, methoxyshetyl, ethoxymethyl, propoxymethyl, butoxymethyl, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxy, Represents a C-6 alkoxycarbonyl group such as butoxycarbonyl and t-butoxycarbonyl, and a phenyl group which may be substituted with W.

X ₇ is a halogen atom such as a cyano group, a nitro group, fluorine, chlorine, bromine, methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, isobutyl, t-butyl, pentyl and its isomers, hexyl and C i, such as their isomers - e alkyl group, cyclopropyl, cyclopentyl, C ₃ _ ₆ cycloalkyl group such as cyclohexyl, chloromethyl, Furuoromechiru, Promo methyl, dichloromethyl, Jifuruoromechiru, diblock乇, trichloromethyl, Ci- ₆ haloalkyl groups such as trifluoromethyl, tripromomethyl, 2,2,2-trichloroethyl, 2,2,2-trifluoroethyl and pentafluoroethyl, methoxy, ethoxy, Proboxy, isopropoxy, butoxy, sec—butoxy, isobutoxy, t - C i, such as butoxy - ₆ alkoxy group, chloromethane butoxy, Jikurorome butoxy, trichloroacetic main butoxy, Torifuruorome butoxy, 1-Furuoroetokishi, 1, 1 - difluoromethyl O b C _ ₆ eight Roarukoki sheet group such as ethoxy, in substituted A phenyl group, a pyridyl group optionally substituted with, a phenyl group optionally substituted with, and a pyridyloxy group optionally substituted with W よい. Further, the substituents W i may be the same or different, and may be substituted plurally.

When n is 2 or more, X ₇ may be the same or different.

Are halogen atoms such as cyano group, nitro group, fluorine, chlorine, and bromine; methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, isobutyl, t-butyl, pentyl and its isomers, hexyl and its isomers ₆ cycloalkyl group, - C such body, _ ₆ alkyl groups, cyclopropyl, cyclopentyl, C _3, such as cyclohexyl Chloromethyl, fluoromethyl, bromomethyl, dichloromethyl, difluoromethyl, dibromomethyl, trichloromethyl, trifluoromethyl, tripromethyl, 2,2,2-trichloroethyl, 2,2,2-trifluoroethyl, pen Ci— ₆ haloalkyl groups such as fluorethyl, methoxy, ethoxy, propoxy, isopropoxy, butoxy, sec—butoxy, isobutoxy, t-butoxy and other C— ₆ alkoxy groups, chloromethoxy, dichloromethoxy, trichloromethoxy, Represents a C j-6 haloalkoxy group such as trifluoromethoxy, 1-fluoroethoxy, and 1,1-difluoroethoxy.

W ₂ is a halogen atom such as a cyano group, a nitro group, fluorine, chlorine, and bromine; methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, isobutyl, t-butyl, pentyl and isomers thereof, hexyl and C alkyl group such as its isomer, chloromethyl, fluoromethyl, bromomethyl, dichloromethyl, difluoromethyl, dibromomethyl, trichloromethyl, trifluoromethyl, tripromomethyl, 2,2,2-trichloroethyl, 2,2, 2—C- ₆ haloalkyl groups such as trifluoroethyl and pentafluoroethyl, d- ₆ alkoxy groups such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, sec—butoxy, isobutoxy, t—butoxy , Chloromethoxy, dichloromethoxy, tric Lome butoxy, Torifuruorome butoxy, 1-Furuoroetokishi, 1, -1-difluoromethyl O b C Interview _ ₆ eight Roarukoki sheet group such as ethoxy, cyclopropyl, cyclopentyl, C _3, such as cyclohexyl - ₆ cycloalkyl group, (nitro _6, such as an alkoxy group) which may have a substituent phenyl group - ₆ alkyl group, main butoxy, ethoxy, C i, such as isopropoxy - group, halogen atoms such as fluorine and chlorine, methyl, C ₁ such Echiru Or a substituent (such as a nitro group, a halogen atom such as fluorine or chlorine, a C i- ₆ alkyl group such as methyl or ethyl, or a C i- ₆ alkoxy group such as methoxy, ethoxy, or isopropoxy). Represents a good phenoxy group. Further, the phenyl group and the phenoxy group may have the same or different plural substituents.

The heterocyclic group in the heterocyclic group which may be substituted by W ₂ includes 1,2,3-triazolyl, 1,2,4-triazolyl, thiazolyl, oxazolyl, isoxazolyl, isothiazolyl, virazolyl, imidazolyl, tetrazolyl, 2,3-oxadiazolyl, 1,2,4—oxadiazolyl, 1,3,4-oxadiazolyl, 1,2,3-thiadiazolyl, 1,2,4-thiadiazolyl, 1,3,4-thiadiazolyl, chenyl , .Furyl, pyrrolyl, pyridyl, pyridazinyl, pyrimidinyl, birazinyl.

R is methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, isobutyl, t-butyl, pentyl and its isomers, hexyl and its isomers, heptyl and its isomers, Noel and its isomers, A d- ₁₂ alkyl group such as dodecyl and its isomer, particularly a branched alkyl group, is preferred. Chloromethyl, fluoromethyl, bromomethyl, dichloromethyl, difluoromethyl, dibromomethyl, tricrim Ci— ₆ octaalkyl groups such as methyl methyl, trifluoromethyl, tribromomethyl, 2,2,2-trichloroethyl, 2,2,2-trifluoroethyl, pendufluorethyl, methoxy, ethoxy, Purobokishi, Isopurobokishi, butoxy, sec - butoxy, isobutoxy, C i ₆ alkoxy group such as a t one-butoxy, main Bok Kishimechiru, main Tokishechiru, Provo carboxymethyl, C ₆ alkoxy C _i-6 alkyl group such as butoxymethyl , methylthio, Echiruchio, propylthio, isopropylthio, Puchiruchi O, sec - Puchiruchio, Isopuchiruchio, C i _ ₆ alkylthio O groups, such as t one Puchiruchio, methylthiomethyl, Mechiruchioechiru, Echiruchioechiru, Echiruchiomechiru, propyl thio methyl, Petit Lucio methyl Such as Cie Archi Lucio C i _ ₆ alkyl group, Mechiruamino, Echiruamino, mono C i _ ₆ alkylamino group, such as Puropiruamino, Jimechiruamino, Jechiruamino, dipropylamino, Jibuchiruamino, di- C i such Echiruiso Puropiruamino - e alkylamino group, cyclopropyl, Cyclopentyl,

-1-methyl pentyl, cyclohexyl, 1-methylstyrene cycloheteroalkyl perforated and may be C _{3 6} cycloalkyl group substituents such as cyclohexyl, (halogen atom at any position of the benzene ring portion, a nitro group, full Tsu-containing, such as chlorine , methyl, C i _ ₆ alkyl groups such as Echiru, main butoxy, ethoxy, phenyl C i, such as C, such as alkoxy group) which may have a substituent benzyl, phenethyl, phenylpropyl, such as isopropoxy - e alkyl group, (in any position of benzene ring portion, a nitro group, halogen atoms such as fluorine and chlorine, methyl, C t ₆ alkyl group, such as e chill, main butoxy, ethoxy, C i, such as isopropoxy - e § alkoxy such group) which may have a substituent Fuenokishimechiru, phenoxy C i _ ₆ alkyl groups such as Fuenokishechiru, (benzene ring At any position, a nitro group, halogen atoms such as fluorine and chlorine, methyl, C such Echiru - ₆ alkyl group, main butoxy, ethoxy alkoxy, such as C i-6 alkoxy groups such as isopropoxy) a substituent Phenylthio C, ₆ alkyl groups such as phenylthiomethyl, phenylthiopropyl, phenylthiobutyl, and phenylthiobutyl which may be possessed (or halogen atoms such as nitro group, fluorine, chlorine, etc .; methyl, ethyl, etc.) C i _ ₆ alkyl group, main butoxy, represents ethoxy, the C ie such alkoxy group) which may have a substituent phenylene Le group such Isopurobo alkoxy. Further, these benzene rings may have the same or different plural substituents.

Represents an oxygen atom, a sulfur atom or a hydrogen atom or a nitrogen atom substituted by a Ci-6 alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, isobutyl, and t-butyl.

2 _{1 and} ₂ are each independently a hydrogen atom or a C ₆ alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, isoptyl, t-butyl, chloromethyl, fluoromethyl, bromomethyl, Cie octaalkyl such as dichloromethyl, difluoromethyl, dibromomethyl, trichloromethyl, trifluoromethyl, tribromomethyl, 2,2,2-trichloroethyl, 2,2,2-trifluoroethyl and pentafluoroethyl C- ₆ alkoxy C alkyl groups such as methoxymethyl, methoxethyl, propoxymethyl, and butoxymethyl; C- ₆ alkylthio C i such as methylthiomethyl, methylthioethyl, ethylthioethyl, ethylthiomethyl, propylthiomethyl, and butylthiomethyl ₆ a Alkyl group, methylamido Mono d- ₆ alkylamino Ci- ₆ alkyl group such as nomethyl, ethylaminomethyl, propylaminomethyl, 2-methylaminoethyl, 2-ethylaminoethyl, dimethylaminomethyl, getylaminomethyl, dipropylaminomethyl Dialkylamino C- ₆ alkyl groups such as, dibutylaminomethyl, ethylisopropylaminomethyl, 2-dimethylaminoethyl, 2-ethylaminoethyl, 3-dipropylaminopropyl, 2-ethylisopropylaminoethyl, and ( Nitro group, halogen atom such as fluorine or chlorine, C ^ ₆ alkyl group such as methyl or ethyl, C i-e alkoxy group such as methoxy, ethoxy, isopropoxy, etc. Represents a phenyl group which may have a group. Further, heptyl together with the carbon atom to which the Z i and Z ₂ are bonded to the cyclopropyl, cyclohexyl, the cycloalkyl heptyl, may form a 5- to 8-membered ring such as Shikurookuchiru.

In the compound of the present invention, when (al) A is A 1, B is a Yoifu Eniru group which may be substituted with W _2, even in phenyl group substituted with a halogen atom or a haloalkyl group as W ₂ A compound wherein (a2) A is a heterocyclic ring represented by A 2, A 3, A 4 or A 5, B is a pyrazolyl group optionally substituted by W ₂ , and (a3) A) When A is A6, a compound in which B is a phenyl group which may be substituted by W ₂ is particularly excellent as a pesticide.

The production method of the present invention is represented by the following reaction formula.

(In the formula, A, B, R, Y _{1 (} Y ₂ , Z j, Z ₂ and L represent the same meaning as described above.) That is, one mole of the compound represented by the formula (2) is The present invention compound represented by the general formula (1) can be obtained by reacting 0.5 to 2 mol of the compound represented by the formula (3) in the presence of an inert solvent.

Examples of the solvent used in this reaction include polar solvents such as N, N-dimethylformamide (DMF) and dimethyl sulfoxide (DMSO), ether solvents such as tetrahydrofuran (THF), ketone solvents such as acetone, Examples include nitrile solvents such as acetonitrile, chlorinated solvents such as dichloromethane, chloroform, carbon tetrachloride, hexamethyl phosphate amide (HMPA), benzene, and toluene.

Examples of bases that can be used include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, carbonates such as sodium carbonate and potassium carbonate, metal hydrides such as sodium hydride, n-butyllithium, lithium diisopropyl Examples include organic metals such as amides (LDA) and organic bases such as triethylamine, diisopropylethylamine and pyridine.

These bases are used in the best combination at the time of use by selecting a substrate, a solvent, and the like. Particularly when a carbonate is used, a compound in which L in the general formula (3) is chlorine or bromine It is effective to carry out the reaction in the presence of sodium iodide and potassium iodide in the presence of sodium iodide and usually in equimolar amounts with (3).

The reaction temperature is preferably from room temperature to the boiling point of the solvent used, and the reaction time is in the range of 1 hour to 48 hours.

After completion of the reaction, the desired product can be obtained by performing ordinary post-treatment.

The structure of the compound of the present invention was determined from IR, NMR and MS. The compound of the present invention represented by the general formula (1) has two types of stereoisomers, and depending on the reaction conditions and purification method, either one of the isomers may be obtained or the mixture of isomers may be used. May be obtained. All of these isomers are included in the scope of the present invention.

The method for producing the compound represented by the formula (2) as a production raw material is described in the above cited document. For example, in the general formula (I), the compound in which Α is AI can be obtained as follows.

(Wherein, beta, and X ₂ are as defined above, Q is a halogen atom, C i_ _e alkoxy group, phenoxy group, a leaving group such as I imidazolyl group or I pyrazolyl group.)

That is, by reacting 0.5 to 2 moles of a compound represented by the formula (5) in an inert solvent in the presence of a base with I moles of the compound represented by the formula (4-I), The compound represented by (2) can be obtained.

As the base used in this reaction, the cited documents 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 triethylamine. And organic bases such as diisopropylethylamine, pyridine, and the like. Production examples using sodium hydride are described, but they cannot be said to be industrially advantageous.

The present inventors have made the compound represented by the general formula (4) into a magnesium salt using a magnesium alkoxide or the like, and then reacted with the compound represented by the general formula (5), thereby mildly. It has been found that the desired product can be obtained in a high yield under suitable conditions.

As the solvent, an aromatic hydrocarbon solvent such as benzene and toluene can be used. The reaction temperature is preferably in the temperature range from room temperature to the boiling point of the solvent used. Representative examples of the compounds of the present invention that can be produced as described above are shown in Tables 2 to 6. The abbreviations in the table have the following meanings.

Me: methyl, Et: ethyl, Pr: propyl, Bu: butyl, Pen: pentyl, Hex: hexyl, Ph: phenyl, n: normal, i: iso, t: tasiri, neo : Neo, c: Cyclo

Table 1 shows specific examples of the partial structure G of the general formula (1).

Table 1

2 tables

1-28 Table 2 (continued)

Table 2 (continued)

Table 2 (continued)

1-112

Table 2 (continued)

LI

68S89 / T0 OAV 10JT / I3d Table 2 (continued)

1-196 Table 2 (continued)

Table 2 (continued)

〇N

Factory.

Table 2 (continued)

The following table for all the compounds represented by 1-296 from the above equation 1 1, ^8, another exemplary combination of ^chi 9 and G. Table 2 (continued)

Table 2 (continued)

Table 2 (continued) ο x _q G ”o X a G x ₈ o X o GX o X a G

OPh H r 6 F F r 3 1 F Me r 9 F Me r 4 1

OPh H r 3 8 F F r 3 2 F Me r 1 0 F Me r 4 2

F F r l F F r 3 3 F Me r 1 1 F Me r 4 3

F F r 2 F F r 3 4 F Me r 1 2 F Me r 4 4

F F r 3 F F r 3 5 F Me r 1 3 F Me r 4 5

F F r 4 F F r 3 6 F Me r 1 4 F Me r 4 6

F F r 5 F F r 3 7 F Me r 1 5 F Me r 4 7

F F r 6 F F r 3 8 F Me r 1 6 F Me r 4 8

F F r 7 F F r 3 9 F Me r 1 7 F Me r 49

F r 8 F F r 4 0 F Me r 1 8 F Me r 5 0 r 9 F F r 4 1 F Me r 1 9 F Me r 5 1 r l 0 F F r 4 2 F Me r 2 0 F Me r 5 2

F r l l F F r 4 3 F Me r 2 1 F Me r 5 3

F _r 1 2 F r 4 4 F Mer 2 2 F Mer 5 4 rl 3 r 4 5 F Mer 2 3 F CI r 1 rl 4 FF r 4 6 F Me r 2 4 F CI r 2 rl 5 F r 4 7 F Me r 2 5 F CI r 3

F r 1 6 F r 4 8 F Me r 2 6 F CI r 4

F r l 7 F F r 4 9 F Me r 2 7 F CI r 5

F r l 8 F r 5 0 F Me r 2 8 F CI r 6 r l 9 F F r 5 l F Me r 2 9 F CI r 7 r 2 0 F F r 52 F M r 3 0 F CI r 8

F r 2 1 F r 5 3 F Me r 3 1 F CI r 9

F F r 2 2 F F r 5 4 F Me r 3 2 F CI r 1 0

F F r 2 3 F Me r 1 F Me r 3 3 F CI r 1 1

F F r 2 4 F Me r 2 F Me r 3 4 F CI r 1 2

F F r 2 5 F Me r 3 F Me r 3 5 F CI r 1 3

F F r 2 6 F Me r 4 F Me r 3 6 F CI r 1 4

F F r 2 7 F Me r 5 F Me r 3 7 F CI r 15

F F r 2 8 F Me r 6 F Me r 3 8 F CI r 16

F F r 2 9 F Me r 7 F Me r 3 9 F CI r 17

FF r 3 0 F Me r 8 F Me r 4 0 F CI r 18 Table 2 (continued)

P

WO 01/68589

Table 3 (continued)

1/68589

Table 3 (continued)

Table 3 (continued)

The following table exemplifies combinations of X ₈ , X ₉ , Y ₃ and G of all the compounds represented by the above formulas 2-1 to 2-99. ' Table 3 _{_{_{(Continued) γ 3 x 8 g GY 3}}} x 8 X g GY 3 x 8 9 G

F CF ₃ H r 1 F CF ₃ H r 3 3 F Me H r 1 1

F CF ₃ Hr 2 F CF ₃ Hr 3 4 F Me Hr 1 2

F CF ₃ Hr 3 F CF ₃ Hr 3 5 F Me Hr 13

F CF ₃ Hr 4 F CF ₃ Hr 36 FMe Hr 14

F CF ₃ Hr 5 F CF ₃ Hr 3 7 F Me Hr 15

F CF ₃ Hr 6 F CF ₃ Hr 3 8 F Me Hr 16

F CF ₃ H r 7 F CF ₃ H r 3 9 F Me H r 17

F CF ₃ Hr 8 F CF ₃ Hr 4 0 F Me Hr 18

F CF ₃ H r 9 F CF ₃ H r 4 1 F Me H r 1 9

F CF ₃ Hr 1 0 F CF ₃ Hr 4 2 F Me Hr 20

F CF ₃ Hr 1 1 F CF ₃ Hr 4 3 F Me Hr 2 1

F CF ₃ Hr 1 2 F CF ₃ Hr 4 4 F Me Hr 2 2

F CF ₃ Hr 1 3 F CF ₃ Hr 45 5 F Me Hr 23

F CF ₃ Hr 1 4 F CF ₃ Hr 4 6 F Me Hr 24

F CF ₃ H r 15 F CF ₃ H r 47 F Me H r 25

F CF ₃ H r 16 F CFg H r 48 F Me H r 26

F CF ₃ H r 17 F CF ₃ H r 49 F Me H r 27

F CF ₃ Hr 18 FCF ₃ Hr 5 0 F Me Hr 28

F CF ₃ Hr 1 9 F CF ₃ Hr 5 1 F Me Hr 29

F CF ₃ Hr 20 FCF ₃ Hr 52 FMe Hr 30

F CF ₃ Hr 2 1 F CF ₃ Hr 53 3 F Me Hr 31

F CF ₃ Hr 2 2 F CF ₃ Hr 5 4 F Me Hr 3 2

F CF ₃ Hr 2 3 F Me H r 1 F Me H r 3 3

F CF ₃ Hr 2 4 F Me H r 2 F Me H r 3 4

F CF ₃ Hr 25 F Me H r 3 F Me H r 35

F CF ₃ Hr 26 FMe Hr 4 F Me Hr 36

F CF ₃ Hr 2 7 F Me Hr 5 F Me Hr 37

F CF ₃ Hr 28 FMe Hr 6 F Me Hr 38

F CFg H r 2 9 F Me H r 7 F Me H r 39

F CF ₃ Hr 3 0 F Me Hr 8 F Me Hr 40

F CF ₃ Hr 3 1 F Me Hr 9 F Me Hr 4 1

F CF ₃ Hr 3 2 F Me Hr 10 F Me Hr 4 2 Table 3 (continued) v CI rr

^Y 3 input 8 input 9 v ^Y 3 input 8 ^ 9 v ¹ 3 ^Λ 8 input 9

Q c Γ Me XI Γ 1 1 Γ 1 Γ 丄 1 Γ 7 丄 rl _r

T o pi

Γ Me χα r AA Γ Mr. 1 X _r r o Γ Mr. 1 l丄r

Γ Me jl 1 Γ? 1 1 Γ1 0 Γ Γ5Γ rl I 丄

y A a

Γ Me M Γ 1 1 Jl _r 0 AT ΓT ∑> T 丄 τ? 7

Γ Me M Γ Shi 丄 rl \ ώ Ό T Γ? Rr Γ1 Γ Γ Me H r y A Q

4 0 Γ 丄 xl xl r r D Γ ± r rl _r Λ τ T _r 9 7

Γ? Me rl / 1 Q Γ 丄 xl Γ rr XI I Or

_ Me h Γ 0 u π

丄 Shi XI r Q

0 Γ rr xl Γ Ό 9

Me Ji Γ iD 丄 _ Shi 1 ri r Q y Γ r> r rl Γ (t ~

Me H X Ό _ _ 丄 r Π

0 υ or Jl Γ o r ^ r

Me T o 丄 Γ d 丄 Γ r> r Jl

^ Λ *. Q o

F Me r 0 4 Γ 1 1 XI V Γ rr M Γ 丄 u

1

r し 1 Γ 丄 Γ 丄 XI T ΓT or rl Γ 丄丄

* · A

CI r Γ Shi 1 Jl Γ or H Γ 丄

*

F CI r 6 Γ 1 1 Γ r> r rl rir 4 _r a

F CI then 1 Γ r rl Γ 丄 ^:

π

r CI V O.

V Γ r> r rl Γ 丄 J3

F then 1 H r b し then 1 i T o T Γ? Rr rl 丄丄 Ό 丄 L r / r- Q Q

Γ Shi XI Γ 0 y T 7

Γ? Rr xl Γ 丄 / Γ I I Γ 0 Γ 丄 XI r A Π Γ rr xl Γ 丄 O I I 11 ry Γ 丄 Jl Γ t 丄 Γ r> r xl r 丄 y

1 1 1 丄丄 D Γ 丄丄 rl 1 o

Γ ± 5r Jtl Ύ ώ 9 Π \) i

1 l 丄丄丄 pi x tJl _r A

丄丄 ^ ± i Qj o TJ _r 1

F C1 H r 1 2 F C1 H r 44 F Br H r 22

F C1 H r 1 3 F C1 H r 45 F Br H r 23

F C1 H r 14 F C1 H r 46 F Br H r 24

F C1 H r 15 F C1 H r 47 F Br H r 25

F C1 H r 16 F C1 H r 48 F Br H r 26

F C1 H r 17 F C1 H r 49 F Br H r 27

F C1 H r 18 F C1 H r 50 F Br H r 28

F C1 H r 19 F C1 H r 51 FBr H r 29

F C1 H r 20 F C1 H r 52 FBr H r 30 Table 3 _{_{(Continued) γ 3 8 g GY 3 8}} GY 3 x 8 X g G

F Br H r 3 1 F F F r 11 1 F F F r 4 3

F Br H r 3 2 F F F r 1 2 F F F r 4 4

F Br H r 33 F F F r 13 F F F r 45

F Br H r 3 4 F F F r 1 4 F F F r r 6

F Br H r 35 F F F r 15 F F F r 47

F Br H r 36 F F F r 16 F F F r 48

F Br H r 3 7 F F F r 17 F F F r 49

F Br H r 3 8 F F F r 18 F F F r 50

F Br H r 3 9 F F F r 1 9 F F F r r 5 1

F Br H r 4 0 F F F r 2 0 F F F r 5 2

F Br H r 4 1 FFF r 2 1 C 1 CF ₃ H r 1

F Br H r 4 2 FFF r 2 2 C 1 CF ₃ H r 2

F Br H r 4 3 FFF r 23 C 1 CF ₃ H r 3

F Br H r4 4 FFF r 24 C 1 CF ₃ H r 4

F Br H r 45 FFF r 25 C 1 CF ₃ H r 5

F Br H r 46 FFF r 26 C 1 CF ₃ H r 6

F Br H r 47 FFF r 27 C 1 CF ₃ H r 7

F Br H r 48 FFF r 28 C 1 CF ₃ H r 8

F Br H r 49 FFF r 29 C 1 CF ₃ H r 9

F Br H r 5 0 FFF r 3 0 C 1 CF ₃ H r 10

F Br H r 5 1 FFF r 31 C 1 CF ₃ H r 11

F Br H r 52 FFF r 32 C 1 CF ₃ H r 1

FFF r 1 FFF r 3 3 C 1 CF ₃ Hr 13

FFF r 2 FFF r 3 4 C 1 CF ₃ Hr 1 4

FFF r 3 FFF r 35 C 1 CF ₃ H r 15

FFF r 4 FFF r 3 6 C 1 CF ₃ Hr 16

FFF r 5 FFF r 3 7 C 1 CF ₃ Hr 17

FFF r 6 FFF r 3 8 C 1 CF ₃ Hr 18

FFF r 7 FFF r 39 C 1 CF ₃ H r 19

FFF r 8 FFF r 4 0 C 1 CF ₃ Hr 20

FFF r 9 FFF r 4 1 C 1 CF ₃ Hr 2 1

FFF r 1 0 FFF r 4 2 C 1 CF ₃ H r 2 2 Table 3 (continued) γ ₃ x ₈ X g GY ₃ x ₈ X g GY ₃ x ₈ X g G

C 1 CF ₃ Hr 23 C 1 Me H r 1 C 1 Me H r 33

C 1 CFg H r2 4 C 1 Me H r 2 C 1 Me H r 3 4

C 1 CF ₃ Hr 25 C 1 Me H r 3 C 1 Me H r 35

C 1 CF ₃ Hr 26 C1 Me Hr 4 C 1 Me Hr 36

C 1 CF ₃ Hr 27 C 1 Me H r 5 C 1 Me H r 37

C 1 CF ₃ Hr 28 C1 Me Hr 6 C 1 Me Hr 38

C 1 CF ₃ Hr 29 C 1 Me H r 7 C 1 Me H r 39

C 1 CF ₃ Hr 30 C1 Me Hr 8 C 1 Me Hr 40

C 1 CF ₃ Hr 3 1 C 1 Me Hr 9 C 1 Me Hr 4 1

C 1 CF ₃ Hr 3 2 C 1 Me Hr 10 C1 Me Hr 4 2

C 1 CF ₃ Hr 33 C 1 Me H r 1 1 C 1 Me H r 43

C 1 CF ₃ Hr 3 4 C 1 Me H r 1 2 C 1 Me H r 4 4

C 1 CF ₃ Hr 35 C1 Me Hr 13 C1 Me Hr 45

C 1 CF ₃ Hr 36 C 1 Me H r 14 C 1 Me H r 46

C 1 CF ₃ Hr 37 C1 Me Hr 15 C1 Me Hr 47

C 1 CF ₃ Hr 38 C1 Me Hr 16 C1 Me Hr 48

C 1 CF ₃ Hr 39 C 1 Me H r 17 C 1 Me H r 49

C 1 CF ₃ Hr 40 C1 Me Hr 18 C1 Me Hr 50

C 1 CF ₃ Hr 4 1 C 1 Me Hr 19 C1 Me Hr 51

C 1 CF ₃ Hr 4 2 C 1 Me Hr 20 C1 Me Hr 52

C 1 CF ₃ Hr 4 3 C 1 Me H r 2 1 C 1 Me H r 5 3

C 1 CF ₃ Hr 4 4 C 1 Me Hr 2 2 C 1 Me Hr 5 4

C 1 CF ₃ Hr 45 C 1 Me H r 23 C 1 Me H r 55

C 1 CF ₃ Hr 46 C 1 Me H r 24 C 1 Me H r 56

C 1 CF ₃ Hr 47 C 1 Me H r 25 C 1 Me H r 57

C 1 CF ₃ H r 4 8 C 1 Me H r 2 6

C 1 CF ₃ Hr 4 9 C 1 Me Hr 2 7

C 1 CF ₃ Hr 5 0 C 1 Me Hr 2 8

C 1 CF ₃ Hr 5 1 C 1 Me Hr 2 9

C 1 CF ₃ Hr 5 2 C 1 Me Hr 30

C 1 CF ₃ Hr 5 3 C 1 Me Hr 3 1

C 1 CF ₃ Hr 5 4 C 1 Me Hr 3 2 Table 4

3-28

The following table illustrates all of X n and G combination of compounds represented by 3- 2 ₈ from the above equation 3-1. Table 4 (continued)

X n G Xn G Xn G

2-CF ₃ -3,4-F ₂ r 1 2-Me-4,6-F ₂ r 3 8 2-Cl-4,6-F ₂ r 6

2-CF ₃ -3,4-F ₂ r 6 2-Me-5'6-F ₂ r 1 2-Cl-4,6-F ₂ r 3 8

2-CF ₃ -3,4-F ₂ r 3 8 2-Me-5,6-F ₂ r 6 2-Cl-5, 6-F ₂ r 1

2-CF ₃ -3,5-F ₂ r 1 2-Me-5, 6-F ₂ r 3 8 2-Cl-5,6-F ₂ r 6

2-CF ₃ -3,5-F ₂ r 6 2,3,4-F ₃ r 1 2-Cl-5,6-F ₂ r 3 8

2-CF ₃ -3,5-F ₂ r 3 8 2,3,4-F ₃ r 6 2-CF ₃ -3,4,6-F ₃ r 1

2-CF ₃ -3,6-F ₂ r 1 2,3,4-F ₃ r 3 8 2-CF ₃ -3'5'6-F ₃ r 1

2-CF ₃ -3,6-F ₂ r 6 2,3,5-F ₃ r 1 2-CF3-4-CI-6-F r 1

2-CF ₃ -3,6-F ₂ r 3 8 2,3,5-F ₃ r 6 2-Me-3,4,6-F ₃ r 1

2-CF ₃ -4,5-F ₂ r 1 2,3,5-F ₃ r 3 8 2-Me-3,5,6-F ₃ r 1

2-CF ₃ -4,5-F ₂ r 6 2,3,6-F ₃ r 1 2,3,4'5,6-F ₅ r 1

2-CF ₃ -4,5-F ₂ r 3 8 2,3,6-F ₃ r 6 2-OMe-4,5-F ₂ r 1

2-CF ₃ -4,6-F ₂ r 1 2,3,6-F ₃ r 3 8 2-OMe-4,5-Cl ₂ r 1

2-CF ₃ -4,6-F ₂ r 6 2,4,5-F ₃ r 1

2-CF ₃ -4,6-F ₂ r 3 8 2,4,5-F ₃ r 6

2-CF ₃ -5,6-F ₂ r 1 2,4,5-F ₃ r 3 8

2-CF ₃ -5,6-F ₂ r 6 2,4,6-F ₃ r 1

2-CF ₃ -5,6-F ₂ r 3 8 2,4,6-F ₃ r 6

2-Me-3,4-F ₂ r 1 2,4,6-Fg r 3 8

2-Me-3,4-F ₂ r 6 2-Cl-3,4-F ₂ r 1

2-Me-3,4-F ₂ r 3 8 2-Cl-3,4-F ₂ r 6

2-Me -3,5-F ₂ r 1 2-Cl-3,4-F ₂ r 3 8

2-Me-3,5-F ₂ r 6 2-Cl-3,5-F ₂ r 1

2-Me-3,5-F ₂ r 3 8 2-Cl-3,5-F ₂ r 6

2-Me-3,6-F ₂ r 1 2-Cl-3,5-F ₂ r 3 8

2-Me-3,6-F ₂ r 6 2-Cl-3,6-F ₂ r 1

2-Me-3,6-F ₂ r 3 8 2-Cl-3,6-F ₂ r 6

2-Me-4,5-F ₂ r 1 2-Cl-3, 6-F ₂ r 3 8

2-Me-4,5-F ₂ r 6 2-Cl-4,5-F ₂ r 1

2-Me-4,5-F ₂ r 3 8 2-Cl-4,5-F ₂ r 6

2-Me-4,6-F ₂ r 1 2-Cl-4,5-F ₂ r 3 8

2-Me-4,6-F ₂ r 6 2-Cl-4,6-F ₂ r 1 Table 5

4-16 4-17 4-18

The following table illustrates the combination of the above formula 4 all Xi compounds represented by one to 4 one 18, X ₂ and G. t

〇 a

en

X

to

〇〇

X

O

X X X X

, 4: ph-.

2 2 OT: F: P11--

o

(^) Halla s

Z0 / T0df / X3d Table 6

Table 6 (continued)

Table 6 (continued)

The following table exemplifies combinations of B and G of all the compounds represented by the above formulas 5 to 5-75. Table 6 (continued)

B G B G B G B G B G

b 1 r 1 b 1 r 3 3 b 2 r 1 1 b 2 r 4 3 b 3 r 2 1 b 1 r 2 b 1 r 3 4 b 2 r 1 2 b 2 r 4 4 b 3 r 2 2 b 1 r 3 b 1 r 3 5 b 2 r 1 3 b 2 r 4 5 b 3 r 2 3 b 1 r 4 b 1 r 3 6 b 2 r 1 4 b 2 r 4 6 b 3 r 2 4 b 1 r 5 b 1 r 3 7 b 2 r 1 5 b 2 r 4 7 b 3 r 2 5 b 1 r 6 b 1 r 3 8 b 2 r 1 6 b 2 r 4 8 b 3 r 2 6 b 1 r 7 blr 3 9 b 2 r 1 7 b 2 r 4 9 b 3 r 2 7 b 1 r 8 b 1 r 4 0 b 2 r 1 8 b 2 r 5 0 b 3 r 2 8 b 1 r 9 1 r 4 1 b 2 r 1 9 b 2 r 5 1 b 3 r 2 9 b 1 rl 0 1 r 4 2 b 2 r 2 0 b 2 r 5 2 b 3 r 3 0 b 1 rlllr 4 3 b 2 r 2 1 b 2 r 5 3 b 3 r 3 1 b 1 rl 2 b 1 r 4 4 b 2 r 2 2 b 2 r 5 4 b 3 r 3 2 lr 1 3 lr 4 5 b 2 r 2 3 b 3 r 1 b 3 r 3 3 blrl 4 b 1 r 4 6 b 2 r 2 4 b 3 r 2 b 3 r 3 4 b 1 rl 5 b 1 r 4 7 b 2 r 2 5 b 3 r 3 b 3 r 3 5 b 1 r 1 6 b 1 r 4 8 b 2 r 26 b 3 r 4 b 3 r 36 b 1 r 17 lr 49 b 2 r 27 b 3 r 5 b 3 r 37 b 1 r 18 b 1 r 50 b 2 r 2 8 b 3 r 6 b 3 r 3 8 b 1 r 1 9 b 1 r 5 1 b 2 r 2 9 b 3 r 7 b 3 r 3 9 b 1 r 2 0 1 r 5 2 b 2 r 3 0 b 3 r 8 b 3 r 4 0 b 1 r 2 1 b 1 r 5 3 b 2 r 3 1 b 3 r 9 b 3 r 4 1 b 1 r 2 2 b 1 r 5 4 b 2 r 3 2 b 3 r 1 0 b 3 r 4 2 b 1 r 2 3 b 2 r 1 b 2 r 3 3 b 3 r 1 1 b 3 r 4 3 b 1 r 2 4 b 2 r 2 b 2 r 3 4 b 3 r 1 2 b 3 r 4 4 b 1 r 2 5 b 2 r 3 b 2 r 3 5 b 3 r 1 3 b 3 r 4 5 b 1 r 2 6 b 2 r 4 b 2 r 3 6 b 3 r 1 4 b 3 r 4 6 b 1 r 2 7 b 2 r 5 b 2 r 3 7 b 3 r 1 5 b 3 r 4 7 b 1 r 2 8 b 2 r 6 b 2 r 3 8 b 3 r 1 6 b 3 r 4 8 b 1 r 2 9 b 2 r 7 b 2 r 3 9 b 3 r 1 7 b 3 r 4 9 b 1 r 3 0 b 2 r 8 b 2 r 4 0 b 3 r 1 8 b 3 r 5 0 b 1 r 3 1 b 2 r 9 b 2 r 4 1 b 3 r 1 9 b 3 r 5 1 1 r 3 2 b 2 r 1 0 b 2 r 4 2 b 3 r 2 0 b 3 r 5 2 Table 6 (continued)

B G B G B G B G B G

b 3 r 5 3 b 4 r 3 1 b 5 r 9 b 5 r 4 1 b 6 r 1 9 b 3 r 5 4 b 4 r 3 2 b 5 r 1 0 b 5 r 4 2 b 6 r 2 0 b 4 r 1 b 4 r 3 3 b 5 r 1 1 b 5 r 4 3 b 6 r 2 1 b 4 r 2 b 4 r 3 4 b 5 r 1 2 b 5 r 4 4 b 6 r 2 2 b 4 r 3 b 4 r 3 5 b 5 r 1 3 b 5 r 4 5 b 6 r 2 3 b 4 r 4 b 4 r 3 6 b 5 r 1 4 b 5 r 4 6 b 6 r 2 4 b 4 r 5 b 4 r 3 7 b 5 r 1 5 b 5 r 4 7 b 6 r 2 5 b 4 r 6 b 4 r 3 8 b 5 r 1 6 b 5 r 4 8 b 6 r 2 6 b 4 r 7 b 4 r 3 9 b 5 r 1 7 b 5 r 4 9 b 6 r 2 7 b 4 r 8 b 4 r 4 0 b 5 r 1 8 b 5 r 5 0 b 6 r 2 8 b 4 r 9 b 4 r 4 lb 5 r 1 9 b 5 r 5 1 b 6 r 2 9 b 4 rl 0 b 4 r 4 2 b 5 r 2 0 b 5 r 5 2 b 6 r 3 0 b 4 rllb 4 r 4 3 b 5 r 2 1 b 5 r 5 3 b 6 r 3 1 b 4 rl 2 b 4 r 4 4 b 5 r 2 2 b 5 r 5 4 b 6 r 3 2 b 4 rl 3 b 4 r 4 5 b 5 r 2 3 b 6 r 1 b 6 r 3 3 b 4 rl 4 b 4 r 4 6 b 5 r 24 b 6 r 2 b 6 r 3 4 b 4 rl 5 b 4 r 4 7 b 5 r 2 5 b 6 r 3 b 6 r 3 5 b 4 rl 6 b 4 r 4 8 b 5 r 2 6 b 6 r 4 b 6 r 3 6 b 4 rl 7 b 4 r 4 9 b 5 r 2 7 b 6 r 5 b 6 r 3 7 b 4 rl 8 b 4 r 5 0 b 5 r 2 8 b 6 r 6 b 6 r 3 8 b 4 r 1 9 b 4 r 5 1 b 5 r 2 9 b 6 r 7 b 6 r 3 9 b 4 r 2 0 b 4 r 5 2 b 5 r 3 0 b 6 r 8 b 6 r 4 0 b 4 r 2 1 b 4 r 5 3 b 5 r 3 1 b 6 r 9 b 6 r 4 1 b 4 r 2 2 b 4 r 5 4 b 5 r 3 2 b 6 r 1 0 b 6 r 4 2 b 4 r 2 3 b 5 r 1 b 5 r 3 3 b 6 r 1 1 b 6 r 4 3 b 4 r 2 4 b 5 r 2 b 5 r 3 4 b 6 r 1 2 b 6 r 4 4 b 4 r 2 5 b 5 r 3 b 5 r 3 5 b 6 r 1 3 b 6 r 4 5 b 4 r 2 6 b 5 r 4 b 5 r 3 6 b 6 r 1 4 b 6 r 4 6 b 4 r 2 7 b 5 r 5 b 5 r 3 7 b 6 r 1 5 b 6 r 4 7 b 4 r 2 8 b 5 r 6 b 5 r 3 8 b 6 r 1 6 b 6 r 4 8 b 4 r 2 9 b 5 r 7 b 5 r 3 9 b 6 r 1 7 b 6 r 4 9 b 4 r 3 0 b 5 r 8 b 5 r 4 0 b 6 r 1 8 b 6 r 5 0 Table 6 (continued)

B G B G B G B G B G

b 6 r 5 1 b 7 r 2 9 b 8 r 7 b 8 r 3 9 b 9 r 17 b 6 r 5 2 b 7 r 30 b 8 r 8 b 8 r 40 b 9 r 18 b 6 r 5 3 b 7 r 3 1 b 8 r 9 b 8 r 4 1 b 9 r 1 9 b 6 r 5 4 b 7 r 3 2 b 8 r 1 0 b 8 r 4 2 b 9 r 2 0 b 7 r 1 b 7 r 3 3 b 8 r 1 1 b 8 r 4 3 b 9 r 2 1 b 7 r 2 b 7 r 3 4 b 8 r 1 2 b 8 r 4 4 b 9 r 2 2 b 7 r 3 b 7 r 3 5 b 8 r 1 3 b 8 r 4 5 b 9 r 2 3 b 7 r 4 b 7 r 3 6 b 8 r 1 4 b 8 r 4 6 b 9 r 2 4 b 7 r 5 b 7 r 3 7 b 8 r 1 5 b 8 r 4 7 b 9 r 2 5 b 7 r 6 b 7 r 3 8 b 8 r 1 6 b 8 r 4 8 b 9 r 2 6 b 7 r 7 b 7 r 3 9 b 8 r 17 b 8 r 49 b 9 r 27 b 7 r 8 b 7 r 40 b 8 r 18 b 8 r 50 b 9 r 28 b 7 r 9 b 7 r 41 b 8 r 1 9 b 8 r 5 1 b 9 r 2 9 b 7 r 1 0 b 7 r 4 2 b 8 r 2 0 b 8 r 5 2 b 9 r 3 0 b 7 r 1 1 b 7 r 4 3 b 8 r 2 1 b 8 r 5 3 b 9 r 3 1 b 7 r 1 2 b 7 r 4 4 b 8 r 2 2 b 8 r 5 4 b 9 r 3 2 b 7 r 1 3 b 7 r 4 5 b 8 r 2 3 b 9 r 1 b 9 r 3 3 b 7 r 1 4 b 7 r 4 6 b 8 r 2 4 b 9 r 2 b 9 r 3 4 b 7 r 1 5 b 7 r 4 7 b 8 r 2 5 b 9 r 3 b 9 r 3 5 b 7 r 1 6 b 7 r 4 8 b 8 r 2 6 b 9 r 4 b 9 r 3 6 b 7 r 1 7 b 7 r 4 9 b 8 r 2 7 b 9 r 5 b 9 r 3 7 b 7 r 1 8 b 7 r 5 0 b 8 r 2 8 b 9 r 6 b 9 r 3 8 b 7 r 1 9 b 7 r 5 1 b 8 r 2 9 b 9 r 7 b 9 r 3 9 b 7 r 2 0 b 7 r 5 2 b 8 r 3 0 b 9 r 8 b 9 r 4 0 b 7 r 2 1 b 7 r 5 3 b 8 r 3 1 b 9 r 9 b 9 r 4 1 b 7 r 2 2 b 7 r 5 4 b 8 r 3 2 b 9 r 1 0 b 9 r 4 2 b 7 r 2 3 b 8 r 1 b 8 r 3 3 b 9 r 1 1 b 9 r 4 3 b 7 r 2 4 b 8 r 2 b 8 r 3 4 b 9 r 1 2 b 9 r 4 4 b 7 r 2 5 b 8 r 3 b 8 r 3 5 b 9 r 1 3 b 9 r 4 5 b 7 r 26 b 8 r 4 b 8 r 36 b 9 r 14 b 9 r 46 b 7 r 27 b 8 r 5 b 8 r 37 b 9 r 15 b 9 r 47 b 7 r 2 8 b 8 r 6 b 8 r 3 8 b 9 r 16 b 9 r 4 8 Table 6 (continued)

B G B G B G B G B G

b 9 r 4 9 1 0 r 2 7 1 1 r 5 b 1 1 r 3 7 b 1 2 r 1 5 b 9 r 5 0 b 1 0 r 2 8 b 1 1 r 6 1 1 r 3 8 b 1 2 r 1 6 b 9 r 5 1 1 0 r 2 9 b 1 1 r 7 1 1 r 3 9 b 1 2 r 1 7 b 9 r 5 2 1 0 r 3 0 1 1 r 8 b 1 1 r 4 0 b 1 2 r 1 8 b 9 r 5 3 b 1 0 r 3 1 1 1 r 9 b 1 1 r 4 1 b 1 2 r 1 9 b 9 r 5 4 b 1 0 r 3 2 b 1 1 r 1 0 b 1 1 r 4 2 b 1 2 r 2 0 1 0 r 1 b 1 0 r 3 3 b 1 1 r 1 1 b 1 1 r 4 3 b 1 2 r 2 1 b 1 0 r 2 b 1 0 r 3 4 b 1 1 r 1 2 b 1 1 r 4 4 1 2 r 2 2

Four

b 1 0 r 3 b 1 0 r 3 5 1 1 r 71 3 b 1 1 r 4 5 b 1 2 r 2 3 b 1 0 r 4 b 1 0 r 3 6 1 1 r 1 4 b 1 1 r 4 6 b 1 2 r 2 4 l 0 r 5 1 0 r 3 7 1 1 r 1 5 1 1 r 4 7 b 1 2 r 2 5 1 0 r 6 b 1 0 r 3 8 1 1 r 1 6 1 1 r 4 8 1 2 r 2 6 b 1 0 r 7 b 1 0 r 3 9 b 1 1 r 1 7 b 1 1 r 4 9 b 1 2 r 2 7 b 1 0 r 8 b 1 0 r 4 0 1 1 r 1 8 1 1 r 5 0 1 2 r 2 8 b 1 0 r 9 b 1 0 r 4 1 b 1 1 r 1 9 1 1 r 5 1 b 1 2 r 2 9 b 1 0 rl 0 1 0 r 4 2 b 1 1 r 2 0 b 1 1 r 5 2 b 1 2 r 3 0 b 1 0 r 1 1 b 1 0 r 4 3 1 1 r 2 1 1 1 r 5 3 b 1 2 r 3 1 b 1 0 rl 2 1 0 r 4 4 b 1 1 r 2 2 b 1 1 r 5 4 b 1 2 r 3 2 b 1 0 rl 3 b 1 0 r 4 5 b 1 1 r 2 3 b 1 2 r 1 b 1 2 r 3 3 1 0 r 1 4 b 1 0 r 4 6 b 1 1 r 2 4 b 1 2 r 2 b 1 2 r 3 4 b 1 0 r 1 5 b 1 0 r 4 7 b 1 1 r 2 5 b 1 2 r 3 b 1 2 r 3 5 b 1 0 r 1 6 b 1 0 r 4 8 b 1 1 r 2 6 b 1 2 r 4 b 1 2 r 3 6 b 1 0 r 1 7 b 1 0 r 4 9 b 1 1 r 2 7 b 1 2 r 5 b 1 2 r 3 7 b 1 0 r 1 8 b 1 0 r 5 0 b 1 1 r 2 8 b 1 2 r 6 b 1 2 r 3 8 b 1 0 r 1 9 1 0 r 5 1 b 1 1 r 2 9 b 1 2 r 7 b 1 2 r 3 9 1 0 r 2 0 1 0 r 5 2 b 1 1 r 3 0 1 2 r 8 1 2 r 4 0 1 0 r 2 1 b 1 0 r 5 3 b 1 1 r 3 1 b 1 2 r 9 b 1 2 r 4 1 b 1 0 r 2 2 b 1 0 r 5 4 b 1 1 r 3 2 b 1 2 r 1 0 b 1 2 r 4 2 b 1 0 r 2 3 b 1 1 r 1 b 1 1 r 3 3 b 1 2 r 1 1 b 1 2 r 4 3 b 1 0 r 2 4 b 1 1 r 2 b 1 1 r 3 4 b 1 2 r 1 2 b 1 2 r 4 4 b 1 0 r 2 5 1 1 r 3 b 1 1 r 3 5 b 1 2 r 1 3 b 1 2 r 4 5 b 1 0 r 2 6 b 1 1 r 4 b 1 1 r 3 6 b 1 2 r 1 4 b 1 2 r 4 6 Table 6 (continued)

B G B G B G B G B G

bl 2 r 4 7 1 3 r 2 5 b 1 4 r 3 b 1 4 r 3 5 1 5 r 1 3 1 2 r 4 8 b 1 3 r 2 6 b 1 4 r 4 b 1 4 r 3 6 b 1 5 r 1 4 1 2 r 4 9 b 1 3 r 2 7 b 1 4 r 5 b 1 4 r 3 7 b 1 5 r 1 5 b 1 2 r 5 0 b 1 3 r 2 8 b 1 4 r 6 b 1 4 r 3 8 b 1 5 r 1 6 b 1 2 r 5 1 b 1 3 r 2 9 b 1 4 r 7 b 1 4 r 3 9 b 1 5 r 1 7 1 2 r 5 2 b 1 3 r 3 0 b 1 4 r 8 b 1 4 r 4 0 b 1 5 r 1 8 1 2 r 5 3 1 3 r 3 1 b 1 4 r 9 1 4 r 4 1 b 1 5 r 1 9 bl 2 r 5 4 1 3 r 3 2 b 1 4 r 1 0 b 1 4 r 4 2 1 5 r 2 0 l 3 rlb 1 3 r 3 3 b 1 4 r 1 1 1 4 r 4 3 b 1 5 r 2 1 l 3 r 2 1 3 r 3 4 b 1 4 r 1 2 1 4 r 4 4 1 5 r 2 2 b 1 3 r 3 b 1 3 r 3 5 b 1 4 r 1 3 1 4 r 4 5 b 1 5 r 2 3 b 1 3 r 4 b 1 3 r 3 6 1 4 r 1 4 b 1 4 r 4 6 b 1 5 r 2 4 l 3 r 5 b 1 3 r 3 7 b 1 4 r 1 5 1 4 r 4 7 1 5 r 2 5 bi 3 r 6 1 3 r 3 8 b 1 4 r 1 6 1 4 r 4 8 b 1 5 r 2 6 b 1 3 r 7 1 3 r 3 9 b 1 4 r 1 7 1 4 r 4 9 1 5 r 2 7 b 1 3 r 8 b 1 3 r 4 0 b 1 4 r 1 8 1 4 r 5 0 b 1 5 r 2 8 b 1 3 r 9 1 3 r 4 lb 1 4 r 1 9 b 1 4 r 5 1 1 5 r 2 9 l 3 rl 0 1 3 r 4 2 b 1 4 r 2 0 1 4 r 5 2 b 1 5 r 3 0 1 3 rllb 1 3 r 4 3 b 1 4 r 2 1 1 4 r 5 3 b 1 5 r 3 1 1 3 r 1 2 b 1 3 r 4 4 b 1 4 r 2 2 b 1 4 r 5 4 b 1 5 r 3 2 1 3 r 1 3 1 3 r 4 5 1 4 r 2 3 b 1 5 r 1 b 1 5 r 3 3 b 1 3 r 1 4 b 1 3 r 4 6 b 1 4 r 2 4 b 1 5 r 2 1 5 r 3 4 1 3 r 1 5 b 1 3 r 4 7 b 1 4 r 2 5 b 1 5 r 3 b 1 5 r 3 5 1 3 r 1 6 1 3 r 4 8 b 1 4 r 2 6 b 1 5 r 4 b 1 5 r 3 6 1 3 r 1 7 b 1 3 r 4 9 b 1 4 r 2 7 b 1 5 r 5 1 5 r 3 7 b 1 3 r 1 8 1 3 r 5 0 b 1 4 r 2 8 b 1 5 r 6 b 1 5 r 3 8 b 1 3 r 1 9 1 3 r 5 1 b 1 4 r 2 9 b 1 5 r 7 b 1 5 r 3 9 b 1 3 r 2 0 b 1 3 r 5 2 b 1 4 r 3 0 b 1 5 r 8 b 1 5 r 4 0 b 1 3 r 2 1 b 1 3 r 5 3 b 1 4 r 3 1 b 1 5 r 9 b 1 5 r 4 1 b 1 3 r 2 2 b 1 3 r 5 4 b 1 4 r 3 2 b 1 5 r 1 0 b 1 5 r 4 2 1 3 r 2 3 1 4 r 1 b 1 4 r 3 3 b 1 5 r 1 1 b 1 5 r 4 3 b 1 3 r 2 4 b 1 4 r 2 1 4 r 3 4 b 1 5 r 1 2 b 1 5 r 4 4 Table 6 (continued)

B G B G B G B G B G

1 5 r 4 5 b 1 6 r 2 3 b 1 7 r 1 b 1 7 r 3 3 b 1 8 r 1 1 1 5 r 4 6 1 6 r 2 4 b 1 7 r 2 b 1 7 r 3 4 b 1 8 r 1 2 b 1 5 r 4 7 b 1 6 r 2 5 b 1 7 r 3 b 1 7 r 3 5 1 8 r 1 3 1 5 r 4 8 b 1 6 r 2 6 b 1 7 r 4 b 1 7 r 3 6 b 1 8 r 1 4 1 5 r 4 9 1 6 r 2 7 1 7 r 5 b 1 7 r 3 7 b 1 8 r 1 5 b 1 5 r 5 0 b 1 6 r 2 8 b 1 7 r 6 1 7 r 3 8 b 1 8 r 1 6 b 1 5 r 5 1 b 1 6 r 2 9 1 7 r 7 b 1 7 r 3 9 b 1 8 r 1 7 b 1 5 r 5 2 b 1 6 r 3 0 b 1 7 r 8 b 1 7 r 4 0 b 1 8 r 1 8 1 5 r 5 3 1 6 r 3 1 1 7 r 9 b 1 7 r 4 1 b 1 8 r 1 9 b 1 5 r 5 4 b 1 6 r 3 2 b 1 7 r 1 0 1 7 r 4 2 b 1 8 r 2 0 1 6 rl 16 r 3 3 1 7 r 1 1 1 7 r 4 3 b 1 8 r 2 1 b 1 6 r 2 b 1 6 r 3 4 1 7 r 1 2 b 1 7 r 4 4 b 1 8 r 2 2 1 6 r 3 1 6 r 3 5 b 1 7 r 1 3 b 1 7 r 4 5 b 1 8 r 2 3 b 1 6 r 4 b 1 6 r 3 6 b 1 7 r 1 4 b 1 7 r 4 6 b 1 8 r 2 4 1 6 r 5 b 1 6 r 3 7 1 7 r 1 5 b 1 7 r 4 7 b 1 8 r 2 5 b 1 6 r 6 b 1 6 r 3 8 b 1 7 r 1 6 b 1 7 r 4 8 b 1 8 r 2 6 b 1 6 r 7 1 6 r 3 9 1 7 r 1 7 b 1 7 r 4 9 b 1 8 r 2 7 b 1 6 r 8 b 1 6 r 4 0 1 7 r 1 8 1 7 r 5 0 b 1 8 r 2 8 b 1 6 r 9 b 1 6 r 4 1 b 1 7 r 1 9 b 1 7 r 5 1 b 1 8 r 2 9 b 1 6 r 1 0 b 1 6 r 4 2 1 7 r 2 0 b 1 7 r 5 2 b 1 8 r 3 0 b 1 6 r 1 1 b 1 6 r 4 3 1 7 r 2 1 b 1 7 r 5 3 b 1 8 r 3 1 b 1 6 r 1 2 1 6 r 4 4 b 1 7 r 2 2 b 1 7 r 5 4 b 1 8 r 3 2 b 1 6 r 1 3 b 1 6 r 4 5 1 7 r 2 3 1 8 r 1 b 1 8 r 3 3 b 1 6 r 1 4 b 1 6 r 4 6 1 7 r 2 4 b 1 8 r 2 b 1 8 r 3 4 b 1 6 r 1 5 1 6 r 4 7 b 1 7 r 2 5 b 1 8 r 3 b 1 8 r 3 5 b 1 6 r 1 6 b 16 r 4 8 b 17 r 2 6 b 18 r 4 b 18 r 36 b 16 r 1 7 16 r 4 9 b 17 r 2 7 b 18 r 5 b 18 r 3 7 1 6 r 1 8 b 1 6 r 5 0 b 1 7 r 2 8 b 1 8 r 6 b 1 8 r 3 8 b 1 6 r 1 9 b 1 6 r 5 1 b 1 7 r 2 9 b 1 8 r 7 b 1 8 r 3 9 b 1 6 r 2 0 b 1 6 r 5 2 b 1 7 r 3 0 b 1 8 r 8 b 1 8 r 4 0 1 6 r 2 1 b 1 6 r 5 3 1 7 r 3 1 b 1 8 r 9 b 1 8 r 4 1 b 1 6 r 2 2 b 1 6 r 5 4 b 1 7 r 3 2 1 8 r 1 0 b 1 8 r 4 2 Table 6 (continued)

B G B G B G B G B G

1 8 r 4 3 1 9 r 2 1 1 9 r 5 3 b 2 0 r 3 1 b 2 1 r 9 b 1 8 r 4 4 1 9 r 2 2 b 1 9 r 5 4 b 2 0 r 3 2 b 2 1 r 1 0 1 8 r 4 5 b 1 9 r 2 3 b 2 0 r 1 b 2 0 r 3 3 b 2 1 r 1 1 1 8 r 4 6 b 1 9 r 2 4 b 2 0 r 2 b 2 0 r 3 4 b 2 1 r 1 2 1 8 r 4 7 b 1 9 r 2 5 b 2 0 r 3 b 2 0 r 3 5 b 2 1 r 1 3 1 8 r 4 8 1 9 r 2 6 b 2 0 r 4 b 2 0 r 3 6 b 2 1 r 1 4 b 1 8 r 4 9 1 9 r 2 7 b 2 0 r 5 b 2 0 r 3 7 b 2 1 r 1 5 b 1 8 r 5 0 1 9 r 2 8 b 2 0 r 6 b 2 0 r 3 8 b 2 1 r 16 l 8 r 5 l 1 9 r 2 9 b 2 0 r 7 b 2 0 r 3 9 b 2 1 r 1 7 b 1 8 r 5 2 b 1 9 r 3 0 b 2 0 r 8 b 2 0 r 4 0 b 2 1 r 1 8 l 8 r 5 3 b 1 9 r 3 1 b 2 0 r 9 b 2 0 r 4 1 b 2 1 r 1 9 b 1 8 r 5 4 1 9 r 3 2 b 2 0 r 1 0 b 2 0 r 4 2 b 2 1 r 2 0 b 1 9 rlb 1 9 r 3 3 b 2 0 r 1 1 b 2 0 r 4 3 b 2 1 r 2 1 b 1 9 _r 2 b 1 9 r 3 4 b 2 0 r 1 2 b 2 0 r 4 4 b 2 1 r 2 2 b 1 9 r 3 1 9 r 3 5 b 2 0 r 1 3 b 2 0 r 4 5 b 2 1 r 2 3 1 9 r 4 b 1 9 r 3 6 b 2 0 r 1 4 b 2 0 r 4 6 b 2 1 r 2 4 b 1 9 r 5 b 1 9 r 3 7 b 2 0 r 1 5 b 2 0 r 4 7 b 2 1 r 2 5 1 9 r 6 b 1 9 r 3 8 b 2 0 r 1 6 b 2 0 r 4 8 b 2 1 r 2 6 b 1 9 r 7 1 9 r 3 9 b 2 0 r 1 7 b 2 0 r 4 9 b 2 1 r 2 7 1 9 r 8 b 1 9 r 4 0 b 2 0 r 1 8 b 2 0 r 5 0 b 2 1 r 2 8 1 9 r 9 b 1 9 r 4 1 b 2 0 r 1 9 b 2 0 r 5 1 b 2 1 r 2 9 b 1 9 r 1 0 b 1 9 r 4 2 b 2 0 r 2 0 b 2 0 r 5 2 b 2 1 r 3 0 b 1 9 r 1 1 b 1 9 r 4 3 b 2 0 r 2 1 b 2 0 r 5 3 b 2 1 r 3 1 b 1 9 r 1 2 b 1 9 r 4 4 b 2 0 r 2 2 b 2 0 r 5 4 b 2 1 r 3 2 1 9 r 1 3 b 1 9 r 4 5 b 2 0 r 2 3 b 2 1 r 1 b 2 1 r 3 3 b 1 9 r 1 4 b 1 9 r 4 6 b 2 0 r 2 4 b 2 1 r 2 b 2 1 r 3 4 b 1 9 r 1 5 b 1 9 r 4 7 b 2 0 r 2 5 b 2 1 r 3 b 2 1 r 3 5 1 9 r 1 6 1 9 r 4 8 b 2 0 r 2 6 b 2 1 r 4 b 2 1 r 3 6 1 9 r 1 7 b 1 9 r 4 9 b 2 0 r 2 7 b 2 1 r 5 b 2 1 r 3 7 1 9 r 1 8 b 1 9 r 5 0 b 2 0 r 2 8 b 2 1 r 6 b 2 1 r 3 8 b 1 9 r 1 9 b 1 9 r 5 1 b 2 0 r 2 9 b 2 1 r 7 b 2 1 r 3 9 b 1 9 r 2 0 1 9 r 5 2 b 2 0 r 3 0 b 2 1 r 8 b 2 1 r 4 0 Table 6 (continued)

B G B G B G B G B G

b 2 1 r 4 1 b 2 2 r 1 9 b 2 2 r 5 1 b 2 3 r 2 9 b 2 4 r 7 b 2 1 r 4 2 b 2 2 r 2 0 b 2 2 r 5 2 b 2 3 r 3 0 b 2 4 r 8 b 2 1 r 4 3 b 2 2 r 2 1 b 2 2 r 5 3 b 2 3 r 3 1 b 2 4 r 9 b 2 1 r 4 4 b 2 2 r 2 2 b 2 2 r 5 4 b 2 3 r 3 2 b 2 4 r 1 0 b 2 1 r 4 5 b 2 2 r 2 3 b 2 3 r 1 b 2 3 r 3 3 b 2 4 r 1 1 b 2 1 r 4 6 b 2 2 r 2 4 b 2 3 r 2 b 2 3 r 3 4 b 2 4 r 1 2 b 2 1 r 4 7 b 2 2 r 2 5 b 2 3 r 3 b 2 3 r 3 5 b 2 4 r 1 3 b 2 1 _r 4 8 b 2 2 r 2 6 b 2 3 r 4 b 2 3 r 3 6 b 2 4 r 1 4 b 2 1 _r 4 9 b 2 2 _r 2 7 b 2 3 r 5 b 2 3 r 3 7 b 2 4 r 1 5 b 2 1 _r 5 0 b 2 2 r 2 8 b 2 3 r 6 b 2 3 r 3 8 b 2 4 r 1 6 b 2 1 _r 5 1 b 2 2 r 2 9 b 2 3 r 7 b 2 3 r 3 9 b 2 4 r 1 7 b 2 1 _r 5 2 2 2 _r 3 0 b 2 3 r 8 b 2 3 r 4 0 b 2 4 r 1 8 b 2 1 _r 5 3 b 2 2 _r 3 1 b 2 3 r 9 b 2 3 r 4 1 b 2 4 r 1 9 h 2 1 _r 5 4 b 2 2 _r 3 2 b 2 3 rl 0 b 2 3 r 4 2 b 2 4 r 2 0 b 2 2 _r ib 2 2 _r 3 3 b 2 3 rllb 2 3 r 4 3 b 2 4 r 2 1 b 2 2 _r 2 b 2 2 r 3 4 b 2 3 rl 2 b 2 3 r 4 4 b 2 4 r 2 2 b 2 2 _r 3 b 2 2 r 3 5 b 2 3 r 1 3 b 2 3 r 4 5 b 2 4 r 2 3 b 2 2 r 4 b 2 2 r 3 6 b 2 3 r 1 4 b 2 3 r 4 6 b 2 4 r 2 4 2 2 r 5 b 2 2 r 3 7 b 2 3 r 1 5 b 2 3 r 4 7 b 2 4 r 2 5 b 2 2 r 6 b 2 2 r 3 8 b 2 3 r 1 6 b 2 3 r 4 8 b 2 4 r 2 6 b 2 2 r 7 b 2 2 r 3 9 b 2 3 r 1 7 b 2 3 r 4 9 b 2 4 r 2 7 b 2 2 r 8 b 2 2 r 4 0 b 2 3 r 1 8 b 2 3 r 5 0 b 2 4 r 2 8 b 2 2 r 9 b 2 2 r 4 1 b 2 3 r 1 9 b 2 3 r 5 1 b 2 4 r 2 9 b 2 2 r 1 0 b 2 2 r 4 2 b 2 3 r 2 0 b 2 3 r 5 2 b 2 4 r 3 0 b 2 2 r 1 1 b 2 2 r 4 3 b 2 3 r 2 1 b 2 3 r 5 3 b 2 4 r 3 1 b 2 2 r 1 2 b 2 2 r 4 4 b 2 3 r 2 2 b 2 3 r 5 4 b 2 4 r 3 2 b 2 2 r 1 3 b 2 2 r 4 5 b 2 3 r 2 3 b 2 4 r 1 b 2 4 r 3 3 b 2 2 r 1 4 b 2 2 r 4 6 b 2 3 r 2 4 b 2 4 r 2 b 2 4 r 3 4 b 2 2 r 1 5 b 2 2 r 4 7 b 2 3 r 2 5 b 2 4 r 3 b 2 4 r 3 5 b 2 2 r 1 6 b 2 2 r 4 8 b 2 3 r 2 6 b 2 4 r 4 b 2 4 r 3 6 b 2 2 r 1 7 b 2 2 r 4 9 b 2 3 r 2 7 b 2 4 r 5 b 2 4 r 3 7 b 2 2 r 1 8 b 2 2 r 5 0 b 2 3 r 2 8 b 2 4 r 6 b 2 4 r 3 8 Table 6 (continued)

Table 6 (continued)

B G B G B G B G B G

b 2 7 r 3 7 b 2 8 r 1 5 b 2 8 r 4 7 b 2 9 r 2 5 b 3 0 r 3 b 2 7 r 3 8 b 2 8 r 1 6 b 2 8 r 4 8 b 2 9 r 2 6 b 3 0 r 4 b 2 7 r 3 9 b 2 8 r 1 7 b 2 8 r 4 9 b 2 9 r 2 7 b 3 0 r 5 b 2 7 r 4 0 b 2 8 r 1 8 b 2 8 r 5 0 b 2 9 r 2 8 b 3 0 r 6 b 2 7 r 4 1 b 2 8 r 1 9 b 2 8 r 5 1 b 2 9 r 2 9 b 3 0 r 7 b 2 7 r 4 2 b 2 8 r 2 0 b 2 8 r 5 2 b 2 9 r 3 0 b 3 0 r 8 b 2 7 r 4 3 b 2 8 r 2 1 b 2 8 r 5 3 b 2 9 r 3 1 b 3 0 r 9 b 2 7 r 4 4 b 2 8 r 2 2 b 2 8 r 5 4 b 2 9 r 3 2 b 3 0 r 1 0 b 2 7 r 4 5 b 2 8 r 2 3 b 2 9 r 1 b 2 9 r 3 3 b 3 0 r 1 1 b 2 7 r 4 6 b 2 8 r 2 4 b 2 9 r 2 b 2 9 r 3 4 b 3 0 r 1 2 b 2 7 r 4 7 b 2 8 r 2 5 b 2 9 r 3 b 2 9 r 3 5 b 3 0 r 1 3 b 2 7 r 4 8 b 2 8 r 2 6 b 2 9 r 4 b 2 9 r 3 6 b 3 0 r 1 4 b 2 7 r 4 9 b 2 8 r 2 7 b 2 9 r 5 b 2 9 r 3 7 b 3 0 r 1 5 b 2 7 r 5 0 b 2 8 r 2 8 b 2 9 r 6 b 2 9 r 3 8 b 3 0 r 1 6 b 2 7 r 5 1 b 2 8 r 2 9 b 2 9 r 7 b 2 9 r 3 9 b 3 0 r 17 b 2 7 r 5 2 b 2 8 r 3 0 b 2 9 r 8 b 2 9 r 4 0 b 3 0 r 1 8 b 2 7 r 5 3 b 2 8 r 3 1 b 2 9 r 9 b 2 9 r 4 1 b 3 0 r 1 9 b 2 7 r 5 4 b 2 8 r 3 2 b 2 9 r 1 0 b 2 9 r 4 2 b 3 0 r 2 0 b 2 8 r 1 b 2 8 r 3 3 b 2 9 r 1 1 b 2 9 r 4 3 b 3 0 r 2 1 b 2 8 r 2 b 2 8 r 3 4 b 2 9 r 1 2 b 2 9 r 4 4 b 3 0 r 2 2 b 2 8 r 3 b 2 8 r 3 5 b 2 9 r 1 3 b 2 9 r 4 5 b 3 0 r 2 3 b 2 8 r 4 b 2 8 r 3 6 b 2 9 r 1 4 b 2 9 r 4 6 b 3 0 r 2 4 b 2 8 r 5 b 2 8 r 3 7 b 2 9 r 1 5 b 2 9 r 4 7 b 3 0 r 2 5 b 2 8 r 6 b 2 8 r 3 8 b 2 9 r 16 b 2 9 r 4 8 b 3 0 r 26 b 2 8 r 7 b 2 8 r 3 9 b 2 9 r 1 7 b 2 9 r 4 9 b 3 0 r 2 7 b 2 8 r 8 b 2 8 r 4 0 b 2 9 r 1 8 b 2 9 r 5 0 b 3 0 r 2 8 b 2 8 r 9 b 2 8 r 4 1 b 2 9 r 1 9 b 2 9 r 5 1 b 3 0 r 2 9 b 2 8 r 1 0 b 2 8 r 4 2 b 2 9 r 2 0 b 2 9 r 5 2 b 3 0 r 3 0 b 2 8 r 1 1 b 2 8 r 4 3 b 2 9 r 2 1 b 2 9 r 5 3 b 3 0 r 3 1 b 2 8 r 1 2 b 2 8 r 4 4 b 2 9 r 2 2 b 2 9 r 5 4 b 3 0 r 3 2 b 2 8 r 1 3 b 2 8 r 4 5 b 2 9 r 2 3 b 3 0 r 1 b 3 0 r 3 3 b 2 8 r 1 4 b 2 8 r 4 6 b 2 9 r 2 4 b 3 0 r 2 b 3 0 r 3 4 Z £ ^ e sq S ■! 2 ε q 22 -1 2 ε qj ΐ ε q 2 Τ -ΐ I ε qi ε -t ε εα ε s J 2 ε q Τ 2 -i 2 ε q ζ -ί τ ε q ΐ Τ -ΐ I ε qo ε -i ε ε q Z ^ 2 ε q 0 Ζ J 2 ε q Ζ J τ ε ε q 0 Τ J ΐ ε q

6 z ^ ε ε q I Sew 2 ε q 6 s s ε q I J I ε q 6 J τ ε q

82 -t e sq 0 S J 2 ε q 8 key 2 ε q 0 -i τ ε q 8 key τ ε q

Z 2 -i ε ε q 6 ^ 2 ε q L I J 2 ε q 6 ε J I ε q q τ ε q

9 S -i ε ε q 8 J 2 ε q 9 I J s ε q 8 ε Τ 2Ά 9 τ ε q

S 2 J ε ε q LV ^ ε ε q 9 Τ -ts ε q ε ε J ι ε qg τ ε ε q ΐ '2 -i ε ε q 9 J 2 ε qs ε q 9 ε J τ ε q q ι ι ε q ε s ”ε ε QSW ζ ε q q ε τ J s ε qs ε ュ τ ε q ε τ ε q ε ε q · Ι 2 ε q ζ \ s ε q ε J τ ε q ζ ι ι ε q

T Z -i ε ε q ε J s ε q τ τ -ι 2 ε q ε ε J τ ε q I u τ ε q

02 -1 e sq 2 J 2 ε q ο τ s s ε q 2 ε J τ ε q ο ε q

6 I J ε ε q I 2 ε q 6 z z ε q I ε J τ ε q ε s J ο ε q

8 ε ε εα 0 ue sq 8 J 2 ε qo ε J τ ε q Z 9 J ο ε q

Z T -i ε ε q 6 ε ^ 2 ε q s s ε q 62 J τ ε q I 9 -t ο ε q

9 τ ε ε q 82 -t s ε q 9 '' s ε q 82 -1 τ ε q 09 -1 ο ε q

S ε ε ε q ζ ε J 2 ε q 2 ε q ZZJ τ ε q 6 · ο ο ε q τ · ΐ ε ε α 9 ε J ε ε q s ε ε q 92 J τ ε q 8 u ο ε q ε τ -ι ε ε qs ε -ι 2 ε q ε s s ε q 92 -1 τ ε q L ^ ο ε q

2 τ -ι ε ε q ε · ι 2 ε q ζ 2 ε q S J τ ε q 9 u ο ε q

I Τ -ΐ ε ε q ε ε J ζ ε q τ J s ε q ε 2 j τ ε q S ^ J ο ε q

0 I J ε ε q ζ ε J 2 ε q I ε q 22 J ε ε q Jt ο ε q

6 J ε ε q τ ε -ι 2 ε q ε s s T T ε q I 2 J τ ε q ε J ο ε q

8 -i ε ε q ο ε -ι s ε q 2 g -i T ε Q 02 J ι ε q S ·! ο ε q

Z J e sq 6 ζ -ΐ ζ ε q I S J T ε q 6 T J τ ε q 1 -i ο ε q

9 J ε ε q 82 -1 s ε q 09 -t T ε q 8 T -t τ ε q O ο ε q

5 J ε ε q Ζ 2 -ΐ ζ ε α T ε q ZI τ τ ε q 6 ε J ο ε q J ε ε q 92 -t 2 ε q 8 W τ ε q 9 TJ τ ε q 8 ε oo ε q ε -ie sq S 2 J 2 ε q Z ΐ '-i τ ε q STJ τ ε q ε ü ο ε q

Z J ε ε q ^ 2 ΐ2 ε q9 J τ ε q I -t τ ε q9 ε J ο ε q

T J e sq ε Ζ -ΐ 2 ε q 9 ^ -1 I ε q ε ΐ J τ ε q s ε -t ο ε q

0 a 0 a 0 a 0 a 0 a

(^ PC) Halla 9

Z0 / T0df / X3d Table 6 (continued)

B G B G B G B G B G

b 3 3 r 3 3 b 3 4 r 1 1 b 3 4 r 4 3 b 3 5 r 2 1 b 3 5 r 5 3 b 3 3 r 3 4 b 3 4 r 1 2 b 3 4 r 4 4 b 3 5 r 2 2 b 3 5 r 5 4 b 3 6 r 3 5 b 3 4 r 1 3 b 3 4 r 4 5 b 3 5 r 2 3 b 3 6 r 1 b 3 6 r 3 6 b 3 4 r 1 4 b 3 4 r 4 6 b 3 5 r 2 4 b 3 6 r 2 b 3 3 r 3 7 b 3 4 r 1 5 b 3 4 r 4 7 b 3 5 r 2 5 b 3 6 r 3 b 3 3 r 3 8 b 3 4 r 1 6 b 3 4 r 4 8 b 3 5 r 2 6 b 3 6 r 4 b 3 3 r 3 9 b 3 4 r 1 7 b 3 4 r 4 9 b 3 5 r 2 7 b 3 6 r 5 b 3 3 r 4 0 b 3 4 r 1 8 b 3 4 r 5 0 b 3 5 r 2 8 b 3 6 r 6 b 3 3 r 4 1 b 3 4 r 1 9 b 3 4 r 5 1 b 3 5 r 2 9 b 3 6 r 7 b 3 3 r 4 2 b 3 4 r 2 0 b 3 4 r 5 2 b 3 5 r 3 0 b 3 6 r 8 b 3 3 r 4 3 b 3 4 r 2 1 b 3 4 r 5 3 b 3 5 r 3 1 b 3 6 r 9 b 3 3 r 4 4 b 3 4 r 2 2 b 3 4 r 5 4 b 3 5 r 3 2 b 3 6 r 1 0 b 3 3 r 4 5 b 3 4 r 2 3 b 3 5 r 1 b 3 5 r 3 3 b 3 6 r 1 1 b 3 3 r 4 6 b 3 4 r 2 4 b 3 5 r 2 b 3 5 r 3 4 b 3 6 r 1 2 b 3 3 r 4 7 b 3 4 r 2 5 b 3 5 r 3 b 3 5 r 3 5 b 3 6 r 1 3 b 3 3 r 4 8 b 3 4 r 2 6 b 3 5 r 4 b 3 5 r 3 6 b 3 6 r 1 4 b 3 3 r 4 9 b 3 4 r 2 7 b 3 5 r 5 b 3 5 r 3 7 b 3 6 r 1 5 b 3 3 r 5 0 b 3 4 r 2 8 b 3 5 r 6 b 3 5 r 3 8 b 3 6 r 16 b 3 3 r 5 1 b 3 4 r 2 9 b 3 5 r 7 b 3 5 r 3 9 b 3 6 r 1 7 b 3 3 r 5 2 b 3 4 r 3 0 b 3 5 r 8 b 3 5 r 4 0 b 3 6 r 18 b 3 3 r 5 3 b 3 4 r 3 1 b 3 5 r 9 b 3 5 r 4 1 b 3 6 r 1 9 b 3 3 r 5 4 b 3 4 r 3 2 b 3 5 r 1 0 b 3 5 r 4 2 b 3 6 r 2 0 b 3 4 r 1 b 3 4 r 3 3 b 3 5 r 1 1 b 3 5 r 4 3 b 3 6 r 2 1 b 3 4 r 2 b 3 4 r 3 4 b 3 5 r 1 2 b 3 5 r 4 4 b 3 6 r 2 2 b 3 4 r 3 b 3 4 r 3 5 b 3 5 r 1 3 b 3 5 r 4 5 b 3 6 r 2 3 b 3 4 r 4 b 3 4 r 3 6 b 3 5 r 1 4 b 3 5 r 4 6 b 3 6 r 2 4 b 3 4 r 5 b 3 4 r 3 7 b 3 5 r 1 5 b 3 5 r 4 7 b 3 6 r 2 5 b 3 4 r 6 b 3 4 r 3 8 b 3 5 r 1 6 b 3 5 r 4 8 b 3 6 r 2 6 b 3 4 r 7 b 3 4 r 3 9 b 3 5 r 17 b 3 5 r 4 9 b 3 6 r 2 7 b 3 4 r 8 b 3 4 r 4 0 b 3 5 r 1 8 b 3 5 r 5 0 b 3 6 r 2 8 b 3 4 r 9 b 3 4 r 4 1 b 3 5 r 1 9 b 3 5 r 5 1 b 3 6 r 2 9 b 3 4 r 1 0 b 3 4 r 4 2 b 3 5 r 2 0 b 3 5 r 5 2 b 3 6 r 3 0 Table 6 (continued)

B G B G B G B G B G

b 3 6 r 3 1 b 3 7 r 9 b 3 7 r 4 1 b 3 8 r 1 9 b 3 8 r 5 1 b 3 6 r 3 2 b 3 7 r 1 0 b 3 7 r 4 2 b 3 8 r 2 0 b 3 8 r 5 2 b 3 6 r 3 3 b 3 7 r 1 1 b 3 7 r 4 3 b 3 8 r 2 1 b 3 8 r 5 3 b 3 6 r 3 4 b 3 7 r 1 2 b 3 7 r 4 4 b 3 8 r 2 2 b 3 8 r 5 4 b 3 6 r 3 5 b 3 7 r 1 3 b 3 7 r 4 5 b 3 8 r 2 3 b 3 9 r 1 b 3 6 r 3 6 b 3 7 r 1 4 b 3 7 r 4 6 b 3 8 r 2 4 b 3 9 r 2 b 3 6 r 3 7 b 3 7 r 1 5 b 3 7 r 4 7 b 3 8 r 2 5 b 3 9 r 3 b 3 6 r 3 8 b 3 7 r 1 6 b 3 7 r 4 8 b 3 8 r 2 6 b 3 9 r 4 b 3 6 r 3 9 b 3 7 r 1 7 b 3 7 r 4 9 b 3 8 r 2 7 b 3 9 r 5 b 3 6 r 4 0 b 3 7 r 1 8 b 3 7 r 5 0 b 3 8 r 2 8 b 3 9 r 6 b 3 6 r 4 1 b 3 7 r 1 9 b 3 7 r 5 1 b 3 8 r 2 9 b 3 9 r 7 b 3 6 r 4 2 b 3 7 r 2 0 b 3 7 r 5 2 b 3 8 r 3 0 b 3 9 r 8 b 3 6 r 4 3 b 3 7 r 2 1 b 3 7 r 5 3 b 3 8 r 3 1 b 3 9 r 9 .b 3 6 r 4 4 b 3 7 r 2 2 b 3 7 r 5 4 b 3 8 r 3 2 b 3 9 r 1 0 b 3 6 r 4 5 b 3 7 r 2 3 b 3 8 r 1 b 3 8 r 3 3 b 3 9 r 1 1 b 3 6 r 4 6 b 3 7 r 2 4 b 3 8 r 2 b 3 8 r 3 4 b 3 9 r 1 2 b 3 6 r 4 7 b 3 7 r 2 5 b 3 8 r 3 b 3 8 r 3 5 b 3 9 r 1 3 b 3 6 r 4 8 b 3 7 r 2 6 b 3 8 r 4 b 3 8 r 3 6 b 3 9 r 1 4 b 3 6 r 4 9 b 3 7 r 2 7 b 3 8 r 5 b 3 8 r 3 7 b 3 9 r 1 5 b 3 6 r 5 0 b 3 7 r 2 8 b 3 8 r 6 b 3 8 r 3 8 b 3 9 r 1 6 b 3 6 r 5 1 b 3 7 r 2 9 b 3 8 r 7 b 3 8 r 3 9 b 3 9 r 1 7 b 3 6 r 5 2 b 3 7 r 3 0 b 3 8 r 8 b 3 8 r 4 0 b 3 9 r 1 8 b 3 6 r 5 3 b 3 7 r 3 1 b 3 8 r 9 b 3 8 r 4 1 b 3 9 r 1 9 b 3 6 r 5 4 b 3 7 r 3 2 b 3 8 r 1 0 b 3 8 r 4 2 b 3 9 r 2 0 b 3 7 r 1 b 3 7 r 3 3 b 3 8 r 1 1 b 3 8 r 4 3 b 3 9 r 2 1 b 3 7 r 2 b 3 7 r 3 4 b 3 8 r 1 2 b 3 8 r 4 4 b 3 9 r 2 2 b 3 7 r 3 b 3 7 r 3 5 b 3 8 r 1 3 b 3 8 r 4 5 b 3 9 r 2 3 b 3 7 r 4 b 3 7 r 3 6 b 3 8 r 1 4 b 3 8 r 4 6 b 3 9 r 2 4 b 3 7 r 5 b 3 7 r 3 7 b 3 8 r 1 5 b 3 8 r 4 7 b 3 9 r 2 5 b 3 7 r 6 b 3 7 r 3 8 b 3 8 r 1 6 b 3 8 r 4 8 b 3 9 r 2 6 b 3 7 r 7 b 3 7 r 3 9 b 3 8 r 1 7 b 3 8 r 4 9 b 3 9 r 2 7 b 3 7 r 8 b 3 7 r 4 0 b 3 8 r 18 b 3 8 r 5 0 b 3 9 r 2 8 Table 6 (continued)

B G B G B G B G B G

b 3 9 r 2 9 b 4 0 r 7 b 4 0 r 3 9 b 4 1 r 17 b 4 1 r 4 9 b 3 9 r 3 0 b 4 0 r 8 b 4 0 r 4 0 b 4 1 r 1 8 b 4 1 r 5 0 b 3 9 r 3 1 b 4 0 r 9 b 4 0 r 4 1 b 4 1 r 1 9 b 4 1 r 5 1 b 3 9 r 3 2 b 4 0 r 1 0 b 4 0 r 4 2 b 4 1 r 2 0 b 4 1 r 5 2 b 3 9 r 3 3 b 4 0 r 1 1 b 4 0 r 4 3 b 4 1 r 2 1 b 4 1 r 5 3 b 3 9 r 3 4 b 4 0 r 1 2 b 4 0 r 4 4 b 4 1 r 2 2 b 4 1 r 5 4 b 3 9 r 3 5 b 4 0 r 1 3 b 4 0 r 4 5 b 4 1 r 2 3 b 4 2 r 1 b 3 9 r 3 6 b 4 0 r 1 4 b 4 0 r 4 6 b 4 1 r 2 4 b 4 2 r 2 b 3 9 r 3 7 b 4 0 r 1 5 b 4 0 r 4 7 b 4 1 r 2 5 b 4 2 r 3 b 3 9 r 3 8 b 4 0 r 16 b 4 0 r 4 8 b 4 1 r 2 6 b 4 2 r 4 b 3 9 r 3 9 b 4 0 r 1 7 b 4 0 r 4 9 b 4 1 r 2 7 b 4 2 r 5 b 3 9 r 4 0 b 4 0 r 18 b 4 0 r 5 0 b 4 1 r 2 8 b 4 2 r 6 b 3 9 r 4 1 b 4 0 r 1 9 b 4 0 r 5 1 b 4 1 r 2 9 b 4 2 r 7 b 3 9 r 4 2 b 4 0 r 2 0 b 4 0 r 5 2 b 4 1 r 3 0 b 4 2 r 8 b 3 9 r 4 3 b 4 0 r 2 1 b 4 0 r 5 3 b 4 1 r 3 1 b 4 2 r 9 b 3 9 r 4 4 b 4 0 r 2 2 b 4 0 r 5 4 b 4 1 r 3 2 b 4 2 r 1 0 b 3 9 r 4 5 b 4 0 r 2 3 b 4 1 r 1 b 4 1 r 3 3 b 4 2 r 1 1 b 3 9 r 4 6 b 4 0 r 2 4 b 4 1 r 2 b 4 1 r 3 4 b 4 2 r 1 2 b 3 9 r 4 7 b 4 0 r 2 5 b 4 1 r 3 b 4 1 r 3 5 b 4 2 r 1 3 b 3 9 r 4 8 b 4 0 r 2 6 b 4 1 r 4 b 4 1 r 3 6 b 4 2 r 1 4 b 3 9 r 4 9 b 4 0 r 2 7 b 4 1 r 5 b 4 1 r 3 7 b 4 2 r 1 5 b 3 9 r 5 0 b 4 0 r 2 8 b 4 1 r 6 b 4 1 r 3 8 b 4 2 r 1 6 b 3 9 r 5 1 b 4 0 r 2 9 b 4 1 r 7 b 4 1 r 3 9 b 4 2 r 1 7 b 3 9 r 5 2 b 4 0 r 3 0 b 4 1 r 8 b 4 1 r 4 0 b 4 2 r 1 8 b 3 9 r 5 3 b 4 0 r 3 1 b 4 1 r 9 b 4 1 r 4 1 b 4 2 r 1 9 b 3 9 r 5 4 b 4 0 r 3 2 b 4 1 r 1 0 b 4 1 r 4 2 b 4 2 r 2 0 b 4 0 r 1 b 4 0 r 3 3 b 4 1 r 1 1 b 4 1 r 4 3 b 4 2 r 2 1 b 4 0 r 2 b 4 0 r 3 4 b 4 1 r 1 2b 4 1 r 4 4 b 4 2 r 2 2 b 4 0 r 3 b 4 0 r 3 5 b 4 1 r 1 3 b 4 1 r 4 5 b 4 2 r 2 3 b 4 0 r 4 b 4 0 r 3 6 b 4 1 r 1 4 b 4 1 r 4 6 b 4 2 r 2 4 b 4 0 r 5 b 4 0 r 3 7 b 4 1 r 1 5 b 4 1 r 4 7 b 4 2 r 2 5 b 4 0 r 6 b 4 0 r 3 8 b 4 1 r 1 6 b 4 1 r 4 8 b 4 2 r 2 6 Table 6 (continued)

B G B G B G B G B G

b 4 2 r 2 7 b 6 r 5 7 b 3 8 r 5 7 b 5 r 6 2 b 2 4 r 5 8 b 4 2 r 2 8 b 7 r 5 7 b 3 9 r 5 7 b 5 r 6 3 b 2 4 r 5 9 b 4 2 r 2 9 b 8 r 5 7 b 4 0 r 5 7 b 6 r 5 8 b 2 4 r 6 0 b 4 2 r 3 0 b 9 r 5 7 b 4 2 r 5 7 b 6 r 5 9 b 2 4 r 6 1 b 4 2 r 3 1 1 0 r 5 7 b 1 r 5 8 b 6 r 6 0 b 2 4 r 6 2 b 4 2 r 3 2 b 1 1 r 5 7 b 1 r 5 9 b 6 r 6 1 b 2 4 r 6 3 b 4 2 r 3 3 b 1 2 r 5 7 b 1 r 6 0 b 6 r 6 2 b 3 0 r 5 8 b 4 2 r 3 4 b 1 3 r 5 7 b 1 r 6 1 b 6 r 6 3 b 3 0 r 5 9 b 4 2 r 3 5 b 1 4 r 5 7 b 1 r 6 2 b 1 3 r 5 8 b 3 0 r 6 0 b 4 2 r 3 6 1 5 r 5 7 1 r 6 3 b 1 3 r 5 9 b 3 0 r 6 1 b 4 2 r 3 7 b 1 6 r 5 7 b 2 r 5 8 b 1 3 r 6 0 b 3 0 r 6 2 b 4 2 r 3 8 b 1 7 r 5 7 b 2 r 5 9 1 3 r 6 1 b 3 0 r 6 3 b 4 2 r 3 9 1 8 r 5 7 b 2 r 6 0 1 3 r 6 2 b 3 2 r 5 8 b 4 2 r 4 0 b 1 9 r 5 7 b 2 r 6 1 b 1 3 r 6 3 b 3 2 r 5 9 b 4 2 r 4 1 b 2 0 r 5 7 b 2 r 6 2 b 2 1 r 5 8 b 3 2 r 6 0 b 4 2 r 4 2 b 2 1 r 5 7 b 2 r 6 3 b 2 1 r 5 9 b 3 2 r 6 1 b 4 2 r 4 3 b 2 2 r 5 7 b 3 r 5 8 b 2 1 r 6 0 b 3 2 r 6 2 b 4 2 r 4 4 b 2 3 r 5 7 b 3 r 5 9 b 2 1 r6 1 b 3 2 r 6 3 b 4 2 r 4 5 b 2 4 r 5 7 b 3 r 6 0 b 2 1 r 6 2 b 3 6 r 5 8 b 4 2 r 4 6 b 2 5 r 5 7 b 3 r 6 1 b 2 1 r 6 3 b 3 6 r 5 9 b 4 2 r 4 7 b 2 6 r 5 7 b 3 r 6 2 b 2 2 r 5 8 b 3 6 r 6 0 b 4 2 r 4 8 b 2 7 r 5 7 b 3 r 6 3 b 2 2 r 5 9 b 3 6 r 6 1 b 4 2 r 5 0 b 2 8 r 5 7 b 4 r 5 8 b 2 2 r 6 0 b 3 6 r 6 2 b 4 2 r 5 1 b 2 9 r 5 7 b 4 r 5 9 b 2 2 r 6 1 b 3 6 r 6 3 b 4 2 r 5 2 b 3 0 r 5 7 b 4 r 6 0 b 2 2 r 6 2 b 3 7 r 5 8 b 4 2 r 5 3 b 3 1 r 5 7 b 4 r 6 1 b 2 2 r 6 3 b 3 7 r 5 9 b 4 0 r 5 4 b 3 2 r 5 7 b 4 r 6 2 b 2 3 r 5 8 b 3 7 r 6 0 b 1 r 5 7 b 3 3 r 5 7 b 4 r 6 3 b 2 3 r 5 9 b 3 7 r 6 1 b 2 r 5 7 b 3 4 r 5 7 b 5 r 5 8 b 2 3 r 6 0 b 3 7 r 6 2 b 3 r 5 7 b 3 5 r 5 7 b 5 r 5 9 b 2 3 r 6 1 b 3 7 r 6 3 b 4 r 5 7 b 3 6 r 5 7 b 5 r 6 0 b 2 3 r 6 2

b 5 r 5 7 b 3 7 r 5 7 b 5 r 6 1 b 2 3 r 6 3 The symbols b1 to b42 used in the above represent the following chemical structures.

(Pest control agent)

The composition containing the compound of the present invention obtained in this way is useful, for example, as an insecticide, a pesticide, a sanitary pest control agent, or an antifouling agent for water-borne organisms. The composition containing the compound of the present invention can be particularly preferably applied as an insecticide or acaricide.

When the compound of the present invention is actually applied as an insecticide or acaricide, it can be used in a pure form without adding other components, and can be in the form of a general pesticide for use as a pesticide, for example, It can also be used in the form of wettable powders, granules, powders, emulsions, aqueous solvents, suspensions, flowables, wettable powders and the like.

For the purpose of solidification, additives and carriers include soybean grains, vegetable powders such as flour, diatomaceous earth, apatite, gypsum, talc, bentonite, pyrophyllite, clay and other mineral powders. Organic and inorganic compounds such as sodium benzoate, urea, and sodium sulfate can be used. When a liquid dosage form is intended, kerosene, xylene and petroleum aromatic hydrocarbons, cyclohexane, cyclohexanone, DMF, DMSO, alcohol, acetone, trichloroethylene, methyl are used as additives and carriers. Isobutyl ketone, mineral oil, vegetable oil, water, etc. can be used as the solvent.

In order to obtain a uniform and stable form in these preparations, a surfactant may be further added, if desired. The surfactant is not particularly limited. For example, alkyl phenyl ether to which polyoxyethylene is added, alkyl ether to which polyoxyethylene is added, higher fatty acid ester to which polyoxyethylene is added, sorbitan to which polyoxyethylene is added Nonionic surfactants such as higher fatty acid esters, tristyryl ether to which polyoxyethylene has been added, sulfates of alkylphenyl ethers to which polyoxyethylene has been added, alkylbenzene sulfonates, sulfuric acid of higher alcohols Examples thereof include ester salts, alkyl naphthalene sulfonates, polycarboxylic acid salts, lignin sulfonates, formaldehyde condensates of alkyl naphthylene sulfonates, and copolymers of isobutylene monomaleic anhydride.

The amount of the active ingredient (compound of the present invention) in the preparation is preferably about 0.01 to 90% by weight, more preferably about 0.05 to 85% by weight.

The obtained wettable powder, emulsion, suspension, flowable, aqueous solvent, and granular wettable powder are diluted with water to a specified concentration to obtain a solution, suspension, or emulsion, which is used as a powder, granule, etc. The agent is used by spraying it on plants or soil as it is.

The formulated pesticidal composition of the present invention is applied to a plant, a seed, a water surface or soil as it is or after being diluted with water or the like. The application rate varies depending on the weather conditions, formulation, application magnetism, application method, application site, target disease, target crop, etc., but usually 1 to 1 to 1,000 g in terms of the amount of active compound per quartal. And preferably 100 to 100 g.

When water-dispersible powders, emulsions, flowables, suspensions, aqueous solvents, water-dispersible granules, etc. are diluted with water and applied, the application concentration is 1 to 100 ppm, preferably 100 to 2 ppm. 50 ppm. In the case of granules and powders, apply directly without dilution.

It goes without saying that the compound of the present invention alone is sufficiently effective, but it can also be used in combination with one or more of various fungicides, insecticides and acaricides, or synergists. Representative examples of fungicides, insecticides, acaricides, and plant growth regulators that can be used by mixing with the compound of the present invention are shown below. Fungicide:

Kyabtan, Forpet, Thiuram, Ziram, Zineb, Maneb. Mancozeb, Provineb, Polycarbamate, Chlorothalonil, Quintzenzen, Captafor, Iprodione, Procymidone, Vinclozolin, Fluoroimid, Thimoxanil, Mepronil, Cycloproxy, Flutronil, Cycloproxy , Josetyl aluminum, Propamocab, Triadimefon, Triadimenol, Propiconazole, Diclobutrazole, Vitertanol, Hexaconazole, Microbutynyl, Flusilazole, Ethaconazole, Fluotrimazole, Flutriafen, Benconazole, Diniconazole, cyproconazoles, fenarimol, triflumizole, puchloraz, imazalil, zef Zoet, Tridemorph, Fenpropimorph, Triforin, Petiobate, Pyrifenox, Anilazine, Polyoxin, Metalaxyl, Oxazixyl, Flaralxil, Isoprothiolane, Probenazole, Pyrrolnitrin, Blascymycin s, Kasugamycin Dihydrostreptomycin sulfate, benomyl, carbendazim, thiophanate methyl, himexazole, basic copper chloride, basic copper sulfate, fentin acetate, triphenyltin hydroxide, dietofencalp, metasulfocalc, quinomethionate, pinapacryl, lecithin , Baking soda, dithianon, dinocap, phenaminosulf, diclomedine, guazatine, dozine, IBP, edifenphos, mepanipyrim, Lumsone, Trichloramide, Metasulfocarb, Fluazinam, Ethoquinolac, Dimethomorph, Pyrokirone, Teclofuram, Fusalide, Fenatazine Oxide, Thiabendazole, Tricyclazol, Vinclozolin, Simoxanil, Cyclobutynil, Guazatine, Propaginil Mocarb hydrochloride, oxolinic acid, insecticide and acaricide:

Organophosphorus and power bamate insecticides:

Phenthion, phennitrothion, diazinon, chlorpyrifos, ESP, bamidothion, fentoate, dimethate, formotione, marathon, trichlorfon, thiomethone, phosmet, dichlorvos, acephate, EPBP, methyl parathion, thioxion, thioxion, thioxion, thioxion, thioxion, thioxion, thioxion, thioxion, thioxion, thioxion, thioxion, thioxion, thioxion, thioxion, thioxion, methyloxy. , Isoxathion, pyridafenthion, phosalon, metidathion, sulprophos, chlorphenvinphos, tetrachlorvinphos, dimethylvinphos, propaphos, isofenfos, ethylthiomethone, profenophos, pyraclophos, monocrotophos, azinfomethyl, aldicarbime, aldicarbime Carbofuran, Carbosulfuan, Benfracalp, Fratikar , Purobokisuru, B P M C, M T M C, M l P C, force Rubariru, Pirimika one blanking, E Chio Fen Culp, Fuenokishikarupu like, Piresuroi de insecticides:

Permethrin, cypermethrin, deltamethrin, fenvalerate, fenpro Patrin, pyrethrin, allethrin, tetramethrin, resmethrin, dimethrin, propasulin, phenothrin, prothrin, fluvalinate, cyfluthrin, cyhalothrin, flucitrinate, etofenprox, cycloprotrin, trolametrin, silafluofen, aclinatrin, etc.

Benzoylurea and other insecticides:

Difluvenzuron, chlorfluazuron, hexaflumuron, triflumuron, tetrabenzuron, flufenoxuron, flucycloxuron, buprofezin, pyriproxyfen, methoprene, benzepin, diafentiuron, acetamiprid, imidacloprid Denitanilam, fipronil, cartap, thiocyclam, bensultap, chlorfenavir, emamectin benzoate, tebufenozide, nicotine sulfate, rotenone, metaaldehyde, machine oil, microbial nematicides such as BT and insect pathogenic viruses:

Fenamiphos, phosthiazate, etc.

Acaricide:

Chlorbenzylate, fenisobromolate, dichophor, amitraz, BPPS, benzomate, hexthiazox, fenbutin oxide, polynactin, quinomethionate, CPCBS, tetradihon, avermectin, milbemectin, clofentezine, cihexatin, pyridaben , Fenpyroximate, tebufenvirad, pyrimidifen, phenothocalp, dienochlor, ethoxazole, halfenprox, etc.

Plant growth regulator:

Gibberellins (eg, gibberellin A 3, gibberellin A 4, gibberellin A 7), IA A, N A A and the like. The compound of the present invention can be used for controlling agricultural pests, sanitary pests, storage pests, clothing pests, house pests, and the like, and has an insecticidal, nymphalidal, larvicidal, and ovicidal action. The following are typical examples.

Lepidopteran insect pests, for example, Spodoptera litura, Ganoderma elegans, Managana evening, Aomushi, Managinaba, Konaga, Chiyanokomakumaki, Chiyamahamaki, Momomoshiniga, Pear Himeshingui, Mikanhamogorigami, Chinomonogoshiga, Chinomonogiga Kamiga, Kobu nomeiga, Yochi bitten bean corn poler, American white cockroach, Suzima larva, Heliotis genus, Helicoverpa genus, Agrotis genus, Iga, Kodolinga, ヮカ

Hemiptera pests, for example, peach aphid, mosquito aphid, red radish aphid, wheat viper aphid, scorpion beetle, scorpion beetle, ssamoptera serrata, skull stag beetle, sssssssssssssssssssssssssss. Pear beetle, flying beetle force, dark beetle force, shiro-louka, tsumaguro leafhopper, etc.

Coleoptera pests, for example, Lepidoptera, Beetle, Colorado potato beetle, rice Dipter beetles, stag beetles, azuki beetles, mamekogane, himekogane, diablotica, tobacco beetle, platypus beetle, pine beetle longhorn beetle, sesame beak beetle, genus agliotis, swelling insects, etc. House flies, oak blow flies, Sentinic flies, Periform flies, Mycophores flies, Tane flies, rice hammogli flies, key flies, Drosophila melanogaster, sand flies, Koga squid moss force, Nesuna esima power, Shinahamadara power, etc.

Thrips pests, for example, Thrips palmi Karny, Thrips palmi, etc., Hymenoptera, pests, for example, Diplomatidae, Rhododendron, Dermatophagoides, Orthoptera, pests, for example, Tonosamabatu, etc.

Reticulate pests, for example, Japanese cockroaches, cockroaches, black cockroaches, etc., Isoptera pests, for example, house termites, japonicus, etc.

Lepidoptera, for example, human flea, lice, for example, Lice, for example, human lice, ticks, for example, Namihadani, Kansahadahada2, Citrus spider mite, Apple spider mite, Mikansapidanii, Apple sabida2, Tyanohocolidina, Brevipalpas, Jeoptera nicas , Robin's mite, Dermatophagoides farinae, Dermatophagoides farinae, Dermatophagoides farinae, Dermatophagoides farinae,

Plant-parasitic nematodes, for example, sweet potato nematode, negusarecentiyu, soybean cyst centiyu, rice singarecentiyu, matsunoza centiyu, etc. Many insect pests such as aphids and aphids have developed resistance to organophosphorus agents, carbamates and acaricides, and have caused problems with the lack of efficacy of these agents. Effective drugs are needed. The compound of the present invention is an agent having an excellent insecticidal and acaricidal effect against not only susceptible strains but also pests of an organophosphate, carbamate or pyrethroid-resistant strain and mites of acaricide-resistant strains.

In addition, the compound of the present invention is a highly safe drug with little phytotoxicity, low toxicity to fish and warm-blooded animals. BEST MODE FOR CARRYING OUT THE INVENTION:

Next, the present invention will be described more specifically with reference to Examples and Reference Examples. Example 1

Preparation of 2- [4- (2,6-difluorophenyl) -2- (thiazolyl) -13-bivaloyloxymethyleneoxy-2'-trifluoromethyl-nitrile cinnamate (Compound No. 7-1)

2-[4-(2, 6-Difluorophenyl) 1-2-thiazolyl] 13-Hydroxy-1 2 '-trifluoromethyl-nitrile cinnamate lg (2.45 mmo 1) to DMF After adding sodium hydride (oil-based 60%) 0.1 lg (2.70 mmo 1) under ice-cooling, the mixture was returned to room temperature and stirred for 1 hour. Again, the reaction solution was ice-cooled, 0.4 g (2.70 mmo 1) of chloromethyl vivalate was added, and the mixture was heated at 100 for 4 hours. After cooling, the reaction solution was poured into ice water, extracted with ethyl acetate, and the organic layer was washed with water (twice) and concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (eluent: ethyl ethyl acetate / hexane = 1/1/10) to give 0.69 g of the desired compound. Yield 5 4% Melting point 16 0-16 2 ° C Example 2

Preparation of 2— [4- (2,6-difluorophenyl) —2-thiazolyl] —3 _ (petit mouth xymethoxy) —2′—trifluoromethyl—cinnamic ditril (Compound No. 7—7)

2- [4-2,6-difluorophenyl) -1-2-thiazolyl] —3-hydroxy2, — trifluoromethyl-cinnamic nitrile 68.5 g (0.167 mol) of acetonitrile 6 In a solution dissolved in 0 0 m 1, 27.8 g (0.201 mol) of potassium carbonate 20.3 g (0.201 mol) of sodium iodide, chloromethyl butyrate 27, 5 g (0.228 mo 1) was added, and the mixture was heated under reflux for 2.5 hours. The reaction mixture was filtered, and acetonitrile was distilled off under reduced pressure. The remaining crude product was dissolved in ethyl acetate and washed with water and saturated saline. After liquid separation, the ethyl acetate layer was dried over anhydrous magnesium sulfate. Ethyl acetate was distilled off under reduced pressure to obtain crystals, which were washed with ether to obtain 60.7 g of the desired product. Yield 71.0% Melting point 1 13 3 1 1 4 ° C Example 3

2— [4— (2,6-difluorophenyl) -2-thiazolyl)] — 3— [1— (pivaloyloxypropyl) oxy-1 2′—trifluoromethyl—cinnamic ditril (Compound No. 7_32) Manufacturing

2— [4— (2,6-difluorophenyl) —2-thiazolyl] —3-hydroxy-1 2'-trifluoromethyl-cinnamic nitrile 0.61 g (1.5 mm o 1) of acetone Dissolved in 10 ml of tril, 0.41 g (1.8 mmol) of potassium carbonate, 0.45 g (1.8 mmo1) of sodium iodide and 0.53 g of trichloropropyl vivalate (1.8 mmo 1), stirred for 9 hours at room temperature, filtered the reaction solution, concentrated under reduced pressure, added ethyl acetate to the obtained residue, washed with water, and dehydrated with anhydrous magnesium sulfate. The residue obtained by concentration under reduced pressure was purified by silica gel column chromatography (developing solvent: n-hexane / ethyl acetate = 41) to obtain 0.41 g of the desired product. Yield 49.7% Melting point 144-144 ° C Example 4

2- [4- (2,6-difluorophenyl) -l-thiazolyl]-(l-acetoxy-2-methylpropyl) oxy-l 2'-trifluoromethyl-cinnamic ditril (Compound No. 7-5 5) manufacture

2— [4 -— (2,6-difluorophenyl) -1-2-thiazolyl] —3-hydroxy 2′—trifluoromethyl monocinnamic nitrile 1.02 g (2.5 mm o 1) of acetonitrile Dissolve in 20 ml, and add 0.69 g (5.0 mmol) of potassium carbonate, 0.75 g of sodium iodide (5.0 mmo1) and 0.75 g of propyl acetate (5.Ommo 1) was added, and the mixture was stirred at room temperature for 16 hours.The reaction solution was filtered, and the residue obtained by concentration under reduced pressure was added with ethyl acetate, washed with water, and dried over anhydrous magnesium sulfate. The residue obtained by concentration under reduced pressure was purified by silica gel column chromatography (eluent: n-hexaneethyl acetate = 41) to give 0.23 g of the desired product. Yield 17.6% Melting point 15 5—15 7 ° C Example 5

2-[4--(2, 6-difluorophenyl)-2-thiazolyl)]-3-(1-pentanolyloxetyl) oxy-1 2 '-trifluoromethyl-cinnamic nitrile (Compound No. 7-2 9) Manufacturing

2— [4 -— (2,6-difluorophenyl) -1-2-thiazolyl] —3-hydroxy 2 '— Dissolve 4.2 g (10.0 mm o 1) of trifluoromethyl monocinnamic nitrile in 30 ml of dimethylformamide, and add sodium hydride (oil-based 60%) under ice-cooling. Add 48 g (12.Ommol), stir for 20 minutes at room temperature, add 1-chlorethyl valerate under ice-cooling and add 4.92 g (30.Ommol) for 16 hours 50 After stirring at ~ 60, the mixture was cooled, poured into 250 ml of ice water, the reaction solution was filtered with ethyl acetate, and the residue obtained by concentration under reduced pressure was added with ethyl acetate, washed with water and dried. After dehydration with magnesium sulfate, the residue obtained by concentration under reduced pressure was purified by silica gel column chromatography (developing solvent: n-hexane / ethyl acetate = 4Z1) to obtain the target compound 1.7. g was obtained. Yield '31 .0% Melting point 1 30-13 2 ° C Example 6

2— [4— (2,6-difluorophenyl) -1-2-thiazolyl] —3 — {[1- (ethoxycarponyloxy) ethyl] oxy}-2'-trifluoromethyl-cinnamic nitrile ( Preparation of Compound No. 7-19)

2-[4-(2, 6-difluorophenyl)-2-thiazolyl]-3-hydroxy-2 '-trifluoromethyl-cinnamate nitrile 1. O g (2.4 mmol), carbon dioxide rim 0.4 g (2.9 mmol), 0.4 g (2.9 mmol) sodium iodide, 13 ml of acetonitrile 1-chloroethylethyl carbonate 0.45 g (2.9 mmo 1) was added at Ot. After reacting for 6 hours under reflux, the reaction solution was poured into ice water and extracted with ethyl acetate. After the extract was washed with water and dried over magnesium sulfate, the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography (eluent: n-hexane / ethyl acetate = 41) to give 1.1 g of the desired product. Yield 85.7% Melting point 156--15 8 ° C Example 7

2- [4- (2,6-Difluorophenyl) -1-2-thiazolyl] —3 _ {[1-N, N-Jetylcarbamoyloxy) ethyl] oxy}-2'-Trifluoromethyl-cinnamon Production of tolyl (Compound No. 7-26)

2- [4- (2,6-difluorophenyl) —2—thiazolyl] —3-hydroxy2, —trifluoromethyl—cinnamic nitrile 0.4 g (1.0 mmol), carbonated lithium 0.16 g (1.1 mm o 1), sodium iodide 0.17 g (1.1 mm o 1) Acetonitrile In a mixture of 5 m 1, N, N-Jetylcarbamide 1-chloroethyl 0.21 g (1.1 mmol) was added at Ot. After reacting at room temperature for 5 hours, the reaction solution was poured into ice water and extracted with ethyl acetate. After the extract was washed with water and dried over magnesium sulfate, the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography (developing solvent: n-hexane / ethyl acetate = 4/1) to obtain 0.41 g of the desired product. Yield 75.9% Melting point 1 110--113 ° C Example 8

3-(4-1-Methoxycarbo 2-1-2-[4- (2, 6-difluorophenyl)-2-thiazolyl] 1-trifluoromethyl-cinnamate nitrile (Compound No. 7-6 1 ) Manufacturing of

2— [4— (2,6-Difluorophenyl) -1-2-thiazolyl] —3-hydroxy 2′-trifluoromethyl—cinnamic nitrile 0.69 g (1.7 mm o 1), carbon dioxide 0.57 g (3.4 mm o 1), sodium iodide 0.5 1 g (3.4 mm o 1), sodium acetate 10 ml 0.8 g (3.4 mmo 1) of mouth-2-benzyl methyl was added at 0 ° C. After reacting under reflux for 3 hours, the reaction solution was poured into ice water and extracted with ethyl acetate. After the extract was washed with water and dried over magnesium sulfate, the solvent was distilled off under reduced pressure. The obtained residue was washed with getyl ether to obtain 0.75 g of the desired product. Yield 72.7% Melting point 1 36 -1 40 ° C Example 9 Preparation of 2- [4-(2,6-difluorophenyl)-2-thiazolyl] 3-hydroxy- 1 2 '-trifluoromethyl-nitrile cinnamate

6-1.7 g of 2-cyanomethyl-1- (2,6-difluorophenyl) thiazole was dissolved in a mixed solvent of 480 ml of benzene and 120 ml of THF, and 59.8 g of magnesium ethoxide was further dissolved. Was added. After heating this solution at 60 ° C for 2 hours, 60 g of 2-trifluoromethylbenzoyl chloride was gradually added at room temperature, and the mixture was stirred as it was for 2 hours. The reaction mixture was poured into ice water (600 ml), and the precipitated crystals were dissolved in ethyl acetate (300 ml). The crystals were washed with saturated saline and dried over anhydrous magnesium sulfate. Ethyl acetate was distilled off under reduced pressure, and the obtained crystals were washed with n-hexane to obtain 98.4 g of the desired product. Yield 92.2% Melting point: 170-172

Dissolve 0.8 g (4.2 mm o 1) of 2-trifluoromethylbenzoic acid in THF 10 ml and add 0.69 g (4.2 mm o 1) of carbonylbisimidazole. At room temperature

Stir for 1 hour. Next, 1.0 g (4.2 mmo 1) of 2-cyanomethyl-1- (2,6-difluorophenyl) thiazole was added to this solution, and then sodium hydride (60% oil-based) was added under ice-cooling. ) 0.17 g (4.2 mm 01) was added, and the mixture was stirred at room temperature. One hour later, 0.17 g (4.2 mmo 1) of sodium hydride (oil-based 60%) was further added under ice-cooling, followed by stirring at room temperature. The reaction solution was poured into ice water, acidified with dilute hydrochloric acid, extracted with ethyl acetate, and the organic layer was concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (developing solvent: ethyl acetate / n-hexane = 1 1) to obtain 1.1 g of the desired compound. Yield 64% Melting point 170-172 ° C Representative examples of the compound of the present invention produced as described above are shown in Tables 7 and 8 (where the abbreviations in the table are It has the same meaning as in Tables 1 to 6. L— L: (TB)

° ¾

：: ^a u¾ ^ ¾¾ ϋ: [] *

960Z0 / T0df / X3d

Me

N-N

8-8 2, 6-F ₂ -Ph nPr H [88-89] (a2)

Me

N-N

8-9 b2 nPr H [115-116] (a)

Me

8-13 bl nPr H [100-102] (a3)

Me

8-14 bl3 nPr H

Me _ς

8-15 Me Me [146-148] (a)

(a 3) 8-12 isomer.

(a) Indicates that either isomer is I.X. (A 2) 8-7 isomers. Others are mixtures of isomers. Next, some examples of the composition of the present invention will be described. However, the additives and the addition ratio should not be limited to these examples, but can be changed in a wide range. The parts in the preparation examples are parts by weight. Example 10 wettable powder

Compound of the present invention 40 parts

Clay 4 8 parts

Dioctyl sulfosuccinate sodium salt 4 parts

Lignin sulfonic acid sodium salt 8 parts

By uniformly mixing the above and finely pulverizing, a wettable powder of 40% of active ingredient is obtained, Example 11 Emulsion

Compound of the present invention 10 parts

Solbesso 2 0 0 5 3 parts

Cyclohexanone 2 6 parts

Lucium salt 1 part

Lil ether 10 parts

By mixing and dissolving the above, an emulsion containing 10% of the active ingredient is obtained. Example 1 2 Dust

Compound of the present invention 10 parts

Clay 90 parts

By uniformly mixing the above and finely pulverizing, a powder of 10% of active ingredient is obtained, Example 13 3 granules

5 parts of the compound of the present invention

Clay 7 3 parts Bentonite 20 parts

Dioctyl sulfosuccinate sodium salt 1 part

Potassium phosphate 1 part

The above ingredients are well ground and mixed, water is added, the mixture is kneaded well, and the mixture is granulated and dried to obtain granules with an active ingredient of 5%. Example 14 Suspension

Compound of the present invention 10 parts

Polyoxyethylene alkylaryl ether 4 parts

Polypyrroleic acid sodium salt 2 parts

Glycerin 10 parts

Xanthan gum 0.2 parts

73.8 parts of water

The above ingredients are mixed and wet-pulverized until the particle size becomes 3 cron or less to obtain a 10% active ingredient suspending agent. Example 15 5 Granule wettable powder

Compound of the present invention 40 parts

Clay 3 6 parts

Lithium chloride 10 parts

Alkylbenzenesulfonic acid sodium salt 1 part

Lignin sulfonic acid sodium salt 8 parts

Alkylbenzenesulfonic acid sodium salt

5 parts formaldehyde condensate

After mixing the above uniformly and finely pulverizing, add an appropriate amount of water and knead to make a clay. If the clay is granulated and dried, a wettable powder with an active ingredient of 40% is obtained. Industrial applicability:

Test examples in which the preparation containing the compound of the present invention obtained as described above was applied as an insecticide and acaricide are shown below. Test Example 1 Efficacy against tabular beetle

The seeds germinated 10 days after sowing in a three-dimensional bowl were inoculated with an adult of Aphid aphid <1 day after the inoculation, the adults were removed, and the cucumber parasitized by the nymphs produced was shown in Example 11 of the drug. According to the formulation of the emulsion, the drug diluted with water was sprayed so that the compound concentration was 125 ppm. They were placed in a constant temperature room at a temperature of 25 ° C and a humidity of 65%, and after 5 days, they were examined for viability and the insecticidal rate was determined. The test was performed in duplicate.

Table 9 shows the results. Test example 2 Efficacy against aphalt According to the formulation of the wettable powder described in Example 10 of the above-mentioned drug, it was diluted with water so that the compound concentration became 125 ppm. Corn leaves were immersed in the chemical solution for 30 seconds, air-dried, placed in a petri dish covered with filter paper, and inoculated with 5 larvae of 2nd instar larvae. They were covered with a glass lid and placed in a thermostatic chamber at a temperature of 25 and a humidity of 65%, and after 5 days, they were examined for viability and the insecticidal rate was determined. The test is in duplicate. Table 9 shows the results.

The insecticidal rates of the following known compounds used as controls were all 0%.

Control compound (A) A compound described in JP-A-53-92769.

Control compound (B) The compound described in JP-A No. 555-154963.

Control compound (C) The compound described in EP18989.

Control Compound (D) The compound described in JP-A-55-154629.

Control compound (E) The compound described in JP-A-10-298169, WO95 / 29591. Test Example 3 Efficacy against Citrus red mites

Eight adult female susceptible tangerine spider mites were inoculated to the tangerine leaves placed in a petri dish. According to the formulation of the emulsion shown in Example 11 of the above-mentioned drug, a certain amount of a drug solution diluted to a compound concentration of 125 ppm was sprayed by a rotary spray tower. The plants were kept in a constant temperature room at a temperature of 25 ° C and a humidity of 65%. Three days after spraying, they were examined for viability and the insecticidal rate was determined. The test is in duplicate. The results are summarized in Table 9. Test Example 4 Efficacy against Namihadaji

After 15 to 10 days after germination of the wings inoculated in a three-size bowl, 15 adult females of Nami-nada mosquito resistant to organophosphorus acid were inoculated, and the results are shown in Example 10 of the drug. In accordance with the formulation of the wettable powder, a chemical solution diluted with water was applied so that the compound concentration became 125 ppm. They were placed in a thermostatic chamber at a temperature of 25 ° C and a humidity of 65%, and after 3 days, they were examined for viability and the insecticidal rate was determined. The test is in duplicate.

Table 9 summarizes the results. Table 9 Concentrations of two compounds

/, Insect rate after 5 days Insect rate after 5 days Insect rate after 3 days Insecticide rate after 3 days Number (ppm)

(%) (%) (%) (%)

7-1 125 100 100 100

7-2 125 100 100

7-3 125 100 100

7-4 125 100 100

7-5 125 100 100

7-6 125 100 100

7-7 125 100 100

7-8 125 100 100 100 100

7-9 125 100 100

7-10 125 100 100 100 100

7-11 125 100 100

7-12 125 100 100

7-13 125 100 100 100

7-14 125 100 100

7-15 125 100 100

7-16 125 100 100

7-17 125 100 100

7-18 125 100 100 100

7-19 125 100 100 100

7-20 125 100 100 100 100

7-21 125 100 100 100

7-22 125 100 100 100

7-23 125 100 100 100

7-24 125 100 100 100

7-25 125 100 100

7-26 125 100

7-27 125 100 100

7-28 125 100 100

7-29 125 100 100 100

7-30 125 100 100

7-31 125 100 100 100 100

7-32 125 100

7-33 125 100 100 100

7-34 125 100 100

7-35 125 100 100

7-36 125 100 100

7-38 125 100 100

7-39 125 100 100

7-40 125 100 100 100 100 Le A! At present, there is no red mite, Namihadani.

Insect rate after 5 days Insect rate after 5 days Insect rate after 3 days Insect rate after 3 days Number \ V \) \ n)

(%) (%) (%) (%)

7-41 125 100 100

7-42 125 100 100

7-43 125 100 100 100

7-44 125 100 100

7-45 125 100 100 100

7-46 125 100 100 100

7-47 125 100 100 100

7-48 125 100 100 100

7-49 125 100 100 100 100

7-50 125 100 100

7-51 125 100 100

7-52 125 .100

7-53 125 100 100 100

7-54 125 100 100

7-55 125 100 100 100

7-57 125 100 100 100

7-58 125 100

7-59 125 100 100 100

7-60 125 100 100

8-1 125 100 100

8-2 125 100 100

8-3 125 100 100

8-4 125 100 100

8-5 125 100 100 100 100

8-6 125 100 100 100 100

8-7 125 100

8-8 125 100

8-9 125 100 100 100

8-10 125 100 100 100

8-11 125 100 100 100 100

8-12 125 100 100

8-13 125 100 100 100

8-14 125 100 100 100 100

8-15 125 100 100

A 125 9

B 125 40 13 13

A: Target compound Pirimicarb

B: Target compound chlordimeform

Claims

The scope of the claims

1. General formula (1)

(1)

[Where A is the following formula A A2, A3 A4, A5 and A6

A1 A2 A3 A4

A5 A6

(Wherein the halogen atom, C _i-6 alkyl group, - 6 haloalkyl group, C -! ₆ alkoxy group, an optionally substituted C _{3 6} cycloalkyl group, in optionally substituted pyridyl Represents a group, a phenyl group optionally substituted with W ニル, a phenyl group optionally substituted with or a phenoxy group optionally substituted with

X ₂ is a hydrogen atom, a halogen atom, —6 alkyl group, —6 haloalkyl group, C i

Represents _ ₆ alkoxy Cal Poni group, C _{3 6} cycloalkyl group, or an optionally substituted phenylene group,

X ₃ and X ₄ each independently represent a hydrogen atom, a halogen atom, a Ci-e alkyl group, a Cie alkoxy group,

X ₅ represents a hydrogen atom, a C ₆ alkyl group, a C ₆ cycloalkyl group, a haloalkyl group, a C alkoxy C ぃ₆ alkyl group,

X ₆ is a hydrogen atom, a halogen atom, _alkyl group, C ₃ - ₆ cycloalkyl group, C - 6 alkyl group, C i ₆ alkoxy groups, C i ₆ alkoxy C i-6 alkyl group, C i - ₆ alkoxy A carbonyl group, represents a phenyl group which may be substituted with

X ₇ is a phenyl group which may be substituted with a nitro group, a cyano group, a halogen atom, a Cie alkyl group, a —6 cycloalkyl group, a Ci ₆ haloalkyl group, a C ₆ alkoxy group, a C! -6 haloalkoxy group. Represents a group, a pyridyl group optionally substituted with, a phenyl group optionally substituted with, a pyridyloxy group optionally substituted with W, n represents 0 or an integer of 1 to 5.

Is nitro group, Shiano group, a halogen atom, C _i-6 alkyl groups, C _i-6 Shikuroa alkyl group, - it represents a 6 haloalkyl groups, C physician ₆ alkoxy or C i-6 haloalkoxy group. ) Represents one type of group selected from the groups represented by. May be the same or different and may be substituted plurally.

W ₂ is Shiano group, a nitro group, a halogen atom, C _i-6 alkyl group, one ₆ Haroaru kill group, - 6 alkoxy groups, C haloalkoxy groups, C ₃ - ₈ cycloalkyl group, substituted Represents a phenyl group or a phenoxy group which may have a substituent, and w ₂ may be the same or different and may be substituted by plural.

R is, C _{i-1 2} alkyl group, - 6 haloalkyl group, - ₆ alkoxy groups, Ji ₆ § alkoxy C _i-6 alkyl group, C _i-6 alkylthio group, C alkylthio C - ₆ Al Kill group, mono C i_ ₆ alkylamino group, di 〇 _i-6 alkylamino group, an optionally substituted C ₃ _ ₆ consequent opening alkyl group, phenyl which may have a substituent C i - ₆ alkyl group, a substituted group which may phenoxy C _i-6 alkyl group having a represents an phenylene Le group optionally having a good phenyl Chio C i_ ₆ alkyl group or a substituted group may have a substituent,

Represents an oxygen atom, a sulfur atom, a hydrogen atom or a nitrogen atom substituted by a C i-6 alkyl group,

Y ₂ represents an oxygen atom or a sulfur atom,

And Zeta ₂ are each independently a hydrogen atom, - 6 alkyl group, CL- ₆ haloalkyl group, C alkoxy C - ₆ alkyl group, C _i-6 alkylthio C Al kill group, mono CL - 6 alkylamino C — ₆ alkyl group, di i — ₆ alkylamino C i — ₆ alkyl group or a phenyl group which may have a substituent. Moreover, the may form a 5-8 membered ring together with the carbon atom to which Z ₂ and is attached. An acrylonitrile compound represented by the formula:

2. — General formula (2)

(Wherein A and B have the same meanings as in claim 1) and a compound represented by the general formula (3):

(Wherein, R, Yj, Y ₂ , Z _1; Z ₂ have the same meaning as in claim _1; L is a halogen atom, p-toluenesulfonyloxy group, methanesulfonyloxy group or trifluoromethanesulfonyl group And a compound represented by the following general formula (1):

(Wherein, A, B, R, Y ₁ ; Y ₂₎ Z t and Z ₂ have the same meanings as described above. A method for producing an acrylonitrile compound represented by the formula:

3. —General formula (1)

(Wherein A, B, R, Y _{1 ¾Y} ₂ , and Z ₂ have the same meanings as in claim 1), and contain one or more acrylonitrile compounds as active ingredients A pesticidal agent characterized by that:

4. General formula (4)

A-CH ₉ -CN (4)

(Where A represents the same meaning as described above) and a compound represented by the general formula (5):

0

( Five)

(Wherein Q and B have the same meanings as described above), and reacted with a magnesium alkoxide as a base in an inert solvent in a general formula (2)

(Wherein, A and B represent. The same meaning as in claim 1) Process _c of the compound represented by