JPS6383071A - Insecticidal and tickicidal phenoxypyridinyl esters and intermediate products - Google Patents

Abstract

(57) [Abstract] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a phenoxypyridinyl ester insecticide (i
n5ect i ci des) and acaricides (ac
aricides), intermediate products for their production,
Agricultural compositions containing the insecticides and acaricides and their use for controlling pests.

U.S. Pat. No. 4,162,366 discloses the following alcohols for use in the production of insecticidal esters: German Patent No. 2,810,881 discloses compounds of the following formula as insecticides: :[wherein,
F or Br, n is Oll or 2, Y is 0 or S, R is H, C? j, or C═CH, and Z is C1, F or Br].

European Patent No. 145,661 discloses the following intermediates in the synthesis of pesticides: c where x and Y are H, Hatff, No2. C, NC4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy,
C2-C5 alkenyl, or C2-C5 alkynyl].

Australian patent 84/34,055 discloses the following compounds as insecticides: where W is halogen, X is H, CN, or C=CH, and Y is H ,C,N
C4 alkyl, C1-C4 alkoxy, 01-C4 alkylthio, C1-C4 alkylsulfonyl, CF3.3
．． 4-methylenedioxy, CI, F or Br, n is 1 or 2, and Z is H, CI or Br].

U.S. Pat. No. 4,221,799 discloses compounds of the following formula as insecticides:

n is 0.1 or 2.

X is independently 01-C4 alkyl, 01-C4 alkoxy, c, -Ca alkylthio.

c, -c4 alkylsulfinyl, C1-C4 alkylsulfonyl, CF3, NO2.

CN, C1,F, Br, or 3,4-methylenedioxy and R is H%CN, or cacH].

U.S. Pat. No. 4,332,815 discloses compounds of the following formula as insecticides: where one of Y and Z is c, -c4 perhaloalkyl and the other is H, haloalkyl. , lower alkyl, phenyl, phenylthio, or benzyl.

provided that Y and Z can also be taken together to form a perhalocyclopentylidene group, R is arethrolonyl, tetrahydrophthalimidomethyl, or 1lil, provided that R1 is phenoxybenzyl, α-cyanophenoxybenzyl, or α- Other than ethynylphenoxybenzyl.

R2 is H1 lower alkyl, ethynyl, CN, or trihalomethyl; R3 is divalent 0.2 S, or vinylidene;
and R4, R5 and R6 are independently H1 lower alkyl, halogen, lower alkenyl, phenyl, phenoxy, benzyl, phenylthio, or two are bonded together and 2
with the proviso that when R4, R5, or R6 contains a phenyl ring, it may be substituted with 1 to 3 substituents selected from halogen or lower alkyl. ].

European Patent Application No. 61.114 discloses esters of the formula that are useful as insecticides: [wherein R is round or R1 is H, CN, or optionally] optionally substituted c, -Ca alkyl, alkenyl or alkynyl; R2 is H or halogen; R3 is H or halogen; R4 is H, C1, Br, CN, or optionally substituted with halo; R5 is H, halogen,
or alkyl or alkoxy, optionally substituted with halo, R5 is isopropyl or cyclopropyl, and R7 is H, F, CF3, CHFC1, or CF2C
].

British Patent 2,108,123 discloses esters of the formula that are useful as insecticides: cx, X2x3 ArC0C(0)B [wherein Ar is an optionally substituted aromatic represents a group or a heteroaromatic group.

x, , X2 and x3 may be the same or different and each represents a hydrogen atom or a halogen atom, provided that at least one represents a halogen atom.

and B is an alkyl group having 1 to 18 carbon atoms or the formula %, except for compounds of the general formula in which X, X2 and x3 each represent fluorine]・Control (Recent Ad
vances In The Chemistry
Janes (ed.), Royal Society of Chemistry, Burlington House, 1985, 153.
Page represents the formula: c where R1 is H, CN, CH3, CH2CH3, ethynyl, ethynyl, CF3. or CH3Co2 and R2 is phenyl or phenoxy].

US Pat. No. 4,323,574 discloses compounds of the fertile type as insecticides: where Wt is O or S.

The present invention relates to phenoxypyridinyl ester compounds of formula I, suitable agricultural compositions containing them, and the use of said compounds as pesticides. , ester substituent (RC02CHCF3-) and ether substituent (-X
- 1.3 between (optionally substituted phenyl)
The present invention also encompasses all geometric and stereoisomeric forms of the compounds of formula I. The present invention also relates to certain alcohol and ketone intermediates and methods for making those intermediates. The intermediates also contain 1.3 between the alcohol/ketone and ether substituents on the pyridine ring.
- Characterized by relationships.

R is and X is 0 or S.

n is 1 to 3.

m is 0 or 1, R1 is H, C, -C4 alkyl, C2-C5 alkenyl, C2-C5 alkynyl, C1-C4 haloalkyl, C
1-C4 alkoxy, 01-C4 haloalkoxy, 01
~C4 alkylthio, 01-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C1-C4 haloalkylthio, 01-C4 haloalkylsulfonyl, F, C
1,Br, and when n=2, the R1 substituents may together be 3,4-methylenedioxy, and R2
is H, F, C1, Br, CH3, or CF3, R3 is F, CI, Br, Cz-Ca alkyl, 01-C
4-haloalkyl, CO2CH3, or CO2CH2
CH3, R4 is F, CI, Br, or CH3, and R5 is H, F, C1, CF3, or C, to C4 alkyl.

R6 is CI or Br, R7 is CI or Br, R8 is H, C, -C4 alkylhaloalkyl, 01-C4 alkoxy, 01-C4 alkylthio, cl Nc4 alkylsulfinyl, c. −
Ca alkylsulfonyl, C1-C4 haloalkylthio, C1-C4 haloalkylsulfinyl, Cl-C4 haloalkylsulfonyl, F, C1. Or Br.

R9 is H,F. C I, CH3 , OCH3 or R8 and R9 taken together may be 3,4-methylenedioxy, RIG, R11. RI2 and R13 are independently H, F, or Cl, and RI4 is H, F. CI, OCH3, OCH2CH3, or 01-C2 haloalkoxy].

Suitable compounds are of formula Ia in which the meanings of substituents are as defined above.

More preferred compounds are: X is 0, n is 1, m is 1, and R1 is H, CH3, CF3.0CH3, QC F2
') i, F, C 1. S CH3, S0
2 CH3, SCF2H, or so,CF2H, R2 is H, F, or CI, and R8 is H. F. CI, or C1-C2 alkoxy, R9 is H, and R14 is H, F, C1. OCH3, OCH2 CH3, or OCF2H.

It is of formula Ia.

The most preferred compounds are those in which R is selected from the group consisting of R-A, R-B, R-D and R-E, and the remaining substituents are as defined above with respect to the "more preferred" compounds. It is of formula Ia as shown below.

Preferred types in which R is R-A are: 3-(2-chloro-3.3.3-)refluoro-1-
propenyl)-2.2-dimethylcyclopropanecarboxylic acid [1-(6-phenoxy-2-pyridinyl)-2.
2.2-trifluoroethyl] ・cis-3-(2.2-dichloroethenyl)-2,2-
Dimethylcyclopropanecarboxylic acid [1-(6-phenoxy-2-pyridinyl)-2.

2,2-trifluoroethyl] ・trans-3-(2,2-dichloroethenyl)-2,
2-dimethylcyclopropanecarboxylic acid [1-(6-phenoxy-2-pyridinyl)-2,2,2-trifluoroethyl] ・C-3-(2,2-dibromoethynyl)-2,2
-Dimethylcyclopropanecarboxylic acid [1-(6-phenoxy-2-pyridinyl)-2゜2.2-trifluoroethyl] ・(IR)-X-3-(2,2-dibromoethynyl)
-2,2-dimethylcyclopropanecarboxylic acid [1-(
6-phenoxy-2-pyridinyl)-2,2,2-trifluoroethyl]-(IR)-cis-3-(2,2-dibromoethynyl)-2,2-dimethylcyclopropanecarboxylic acid [1-( 6-phenoxy-2-pyridinyl)-
(S)-2,2,2-trifluoroethyl] ・(-3-(2-chloro-3,3,3-)lifluoro-1-propenyl)-2,2-dimethylcyclopropanecarboxylic acid [ 1-(6-phenoxy-2-pyridinyl)-2,2,2-trifluoroethyl]-(Is)-, 2-3-(2-chloro-3,3゜3
-trifluoro-1-propenyl)-2,2-dimethylcyclopropanecarboxylic acid [1-(6-7 enoxy 2
-pyridinyl)-(R)-2,2,2-trifluoroethyl] and (IR)-'yZ-3-(2-ri*rho3,3.

3-trifluoro-1-propenyl)-2,2-dimethylcyclopropanecarboxylic acid [1-[6-phenoxy-
2-pyridinyl)-(S)-2,2,2-trifluoroethyl] ・(IR)-'y7. -3- (2-chloro-3,3゜3-trifluoro-1-propenyl)-2,2dimethylcyclopropanecarboxylic acid [1-(6-phenoxy-2
-pyridinyl) -(S) -2,2,2-trifluoroethyl] -2-3- (2,2-dichloroethenyl)-2,2
-dimethylcyclopropanecarboxylic acid [1-'(6-(
4-fluorophenoxy)-2-pyridinyl]-2,2
, 2-trifluoroethyl], and -(Is)-ヱ:z-3-(2,2-dichloroethenyl)-2,2-dimethylcyclopropanecarboxylic acid [1-
[6-(4-fluorophenoxy)-2-pyridinyl]
-(R)-2,2,2-trifluoroethyl] and (IR)-'y7゜-3-(2,2-dichloroethenyl)-2,2-dimethylcyclopropanecarboxylic acid [l-
[6-(4-fluorophenoxy)-2-pyridinyl]
-(S)-2,2,2-trifluoroethyl].

Preferred types in which R is R-B are: 2.2,3.3-tetramethylcyclopropanecarpon M[1-[6-phenoxy-2-pyridinyl]-2,
2,2-trifluoroethyl 1, and 2,2,3.3-tetramethylcyclopropanecarboxylic acid [1-[6-(4-fluorophenoxy)-2-pyridinyl]-2,2,2- trifluoroethyl].

A preferred species in which R is R-D is (IR)-'yX-2
．． 2-dimethyl-3-(1,2,2,2-tetrabromoethyl)-cyclopropanecarboxylic acid [1-[6-phenoxy-2-pyridinyl]-2,2,2-trifluoroethyl].

A preferred species in which R is R-E is 4-chloro-α-(l
-methylethyl)benzeneamE1-(6-phenoxy-2-pyridinyl)-2,2°2-trifluoroethyl].

Indication of suitable types of optical isomers is made in the same way as for other pyrethroids. Methods for making the compounds are described below.

Intermediates of the invention are compounds of formula II and formula (1): where R1, R2 and n are as defined above.

Suitable intermediates are those used to produce correspondingly suitable insecticidal and acaricidal compounds, and include: 1-(6-phenoxy-2 -pyridinyl)-2,2,
'2-)lifluoroethanol, -1-(6-phenoxy-2-pyridinyl)-(S)-2,2,2-)lifluoroethanol, and -1-(6-phenoxy-2-pyridinyl)- 2, 2,
2-) Lifluoroethanone.

The agricultural compositions of the present invention and their methods of use for controlling pests are described in further detail in the Uses, Formulation and Applications section of this disclosure.

The process of the invention comprises: (i) metallizing phenoxy or thiophenoxybi, wherein R1, R2, X and n are as defined above; (ii) step wi(i) The metallized product of N,N
-Production of novel ketone intermediates consisting of successive steps by reaction with dimethyltrifluoroacetamide (CF3CON(CH3)2) to form the corresponding phenoxypyridinyl tripleoethanone.

The alcohol intermediates listed are:

(iii) converting the ketone of step (ii), preferably using a hydride reducing agent, most preferably using NaBH4;
Produced by reduction.

Compounds of formula 1 are pyridine alcohols of formula 2 and formula ■
can be produced by reaction with any of the common pyrethroid acid chlorides. A typical reaction consists of combining equimolar amounts of 1 and 1 in the presence of an amine base such as triethylamine or pyridine at a temperature generally within the range of 0 DEG to 40 DEG C. For suitable solvents.

Included are ether, tetrahydrone, chloroform and benzene. Although only the 2,6-isomer of ■ is described for simplicity, it should be understood that the process is applicable to each of the disclosed pyridine isomers.

4 - Another method for preparing compounds of formula 1 which is preferred when the intermediate acid chloride of formula Ⅰ has low stability is formula Ⅰ.
The reaction of a pyrethroid acid with a pyridine of the formula (1) in which L represents a suitable free radical such as, for example, C1, Br, methanesulfonyloxy and p-)lylsulfonyloxy, is an alkali metal carbonate. Alternatively, equimolar amounts of V and 1 can be combined in a polar aprotic solvent such as dimethylformamide or dimethyl sulfoxide in the presence of an alkali metal bicarbonate to give esters of formula I. The reaction is about θ~80℃
Although temperatures within the range of 20 to 60°C are preferred.

Another method for preparing compounds of formula 1 is the reaction of an alcohol of formula V with an acid of formula V in the presence of a dehydrating agent such as dicyclohexylcarbodiimide (DCC).

The reaction is carried out in a solvent such as ether or methylene chloride, generally in the presence of an amine base such as pyridine.

It should be recognized that the compounds of Formula 1 encompass a large number of both geometric and optical isomers that may differ greatly in biological activity. In some cases, it is desirable to obtain compounds that are geometrically and/or optically pure or enriched in one or more of the possible isomers.

It is well recognized that compounds of the pyrethroid class require special spatial allocation for optimal activity levels. In general, most of the observed activity is due to a single enantiomer (e.g. RecenL Advances In Th
e Chemistry Of Ensect
Control), Janes (ed.), Royal Society Op Chemistry, Burlington.
House, 1985, p. 26).Based on the known spatial conditions, the compounds of the present invention exhibit the highest level of activity with respect to the compounds derived from the S-alcohols of 2. It was predicted.

The obligate reporter for the more active isomer of the acid moiety ('V) is determined by the specific acid used (where R is R-A-R-F
). However, optimal activity requires the same spatial arrangement for each of the acid groups.

As an example, an isomer mixture of formula I derived from racemic alcohol of 2) and racemic # of formula It has become. Diastereomeric mixtures can be separated by fractional recrystallization or chromatography. A pair of enantiomers containing the (IR)-Z-α-S enantiomer is predicted to exhibit relatively high levels of activity (designated (IR)->Z-α-
In 5, (IR)-1 refers to ciscyclopropane in which carbon number l is in the R configuration, and α-5 is the asymmetric center α and Sj! for the pyridine ring. 211).

Resolution of racemic alcohols can generally be carried out by any of a number of suitable methods known in the art for the resolution of alcohols. Such methods include reaction of the racemate (1) with an optically active resolving agent such as (R)-(+)-1-phenylethyl incyanate, chromatography of the diastereomeric carbamates (2). minutes, and finally includes the regeneration of the divided alcohol. Other suitable dispersants include (R)
-(-)-1-(naphthyl)-ethyl incyanate and (R)-(+)-1-α-methoxy-α-(trifluoromethyl)phenylacetic acid.

(R9S) and (R,R) (2) The novel intermediates of formula (2) can be prepared from the alcohols of (2) by any of the known methods for converting the hydroxy group to a suitable free radical.

For example, methanesulfonates of formula (L is 05o2C
H3) can be prepared by reaction of methanesulfonyl chloride with compounds of formula (1) in the presence of an amine base such as triethylamine. Chlorides of formula (1) (L is CI) can be prepared by reaction of (L is CI) with (2) and, for example, It can be produced by reaction with thionyl chloride. Variations on these reactions are well described in the chemical literature and will be known to those skilled in the art.

The pyridines in Part II are prepared by introducing (a) a trifluoroacetyl group into halopyridines (I) to produce II, and (b)
) n to the alcohol ■ in a two-step process: ■ (Y=Br
) with an alkyllithium such as n-butyllithium to effect a metal-halogen exchange, and then the pre-prepared pyridinyllithium tombs are treated with N,N-dimethyltrifluoroacetamide or an alkali metal salt of trifluoroacetic acid. to give novel trifluoroacetylpyridines of formula (1). Alternatively, the Grignard formation may be carried out by treatment of ① with magnesium at a temperature in the range of 60 to -80°C and in a solvent such as tetrahydrofuran or ether, followed by reaction with N,N-dimethyltrifluoroacetamide. , giving trifluoroacetylpyridines of formula (■). These are readily reduced to alcohols by any of a number of standard methods, such as with the hydride reducing agents lithium aluminum hydride and sodium borohydride.

Intermediate halopyridines (■) can be produced from 2,6-dihalopyridines and optionally substituted phenol or thiophenol. - By way of example, equimolar amounts of 2-halopyridinyl of the formula give ethers.

Compounds of formulas ■ and V are well known in the chemical literature. Those skilled in the art will know that these are the acid components of synthetic pyrethroid insecticides or are derived from them.Selected references regarding these are listed below: With respect to compounds in which
397: German Published Application No. 2,407,024 and U.S. Pat.
799: if R is R-C, see Japanese Patent Application J5 7,040,463; if R is R-D
In the case of German patents 2°742.546 and 2,7
42,547; when R is R-E, see U.S. Pat.
and US Pat. No. 4,360,690.

The following examples illustrate the invention.

To a solution of 6.5 g (0,135 mol) of 50% sodium hydride in 75 ml of dimethylformamide at 0 °C and under N2, 11.9 g (0,127 mol) of phenol in 75 ml of dimethylformamide medium solution was added. When the addition is complete, 30.0g (0,12
7 mol) of dibromopyridine was added portionwise and the mixture was heated to 60-65° C. for 18 hours. The mixture was then cooled and partitioned between ether and IN aqueous NaOH. The ether extracts were diluted with aqueous NaHCO3.
Washed twice, dried over MgSO4, filtered and concentrated in vacuo. The solid residue was stirred in hexane, filtered and dried to give 25.1 g (79%) of the title compound as a white powder: mp 83-86°C: 'HN
MR (CDC13) δ6.70 (d, IH), 7.0
-7.5 (m, 7H).

Step B, 12.5 g of 2,2.2-trifluoro-1-(6-phenoxy-2-pyridinyl)-ethano (0,05
A solution of 2-bromo-6-fethoxyviridine of Step A (mol) in 100 ml of dry tetrahydrofuran was cooled to -70°C under N2. Add 20ml of this solution (0,0
2.6 M n-butyl-lithium in hexane (52 mol) was added at a rate such that the reaction temperature was kept below 160° C. The reaction was stirred for 5 minutes, then 2.6 M n-butyl-lithium in 15 ml of tetrahydrofuran was added at a rate such that the reaction temperature was kept below 160° C. 7-75 g (0°055 mol) of N,
Reaction of N-dimethyltrifluoroacetamide
Addition was made at a rate such that the temperature remained below 0°C. When the addition was complete, the -70°C bath was removed and the reaction was stirred for 1 hour with gradual warming. After this time 50 ml of 5
% aqueous NaHCO3 was added and the tetrahydrofuran was removed under vacuum. The aqueous residue was extracted twice with chloroform, and the chloroform extracts were then dried over MgSO4, filtered, and concentrated to yield 13.6 gH of an orange oil. Chromatography on silica gel gave 7.71 g (57%) of the title compound as a yellow oil =IHNMR and IR suggested that the title compound was present in hydrate form:'HNMRδ4 ．．
84 (S), 7.0-8.0 (m);
1588, 1735, 3400 cm-1° step C,6-phetoxyalpha-(trifluoromethyl)
-2-Pyridine-methanol 10.0 g (0,0375 mol) of Step B 2.2.
To a solution of 2-trifluoro-1-(6-phenoxy-2-pyridinyl)ethanone in 100 ml (F) ethanol at 0°C was added 1.5 g (0,0395 mol) of sodium borohydride in portions for 5-10 minutes. The reaction was then warmed to room temperature and stirred overnight. After this time the reaction was cooled with IN aqueous HC1 and aqueous NaH
Neutralized with CO3 and extracted with chloroform. The chloroform extracts were dried over NgSOa, filtered, and concentrated to give a yellow oil that solidified to a waxy solid on standing. Recrystallized from 4:1 hexane-ether to give 6.13 g (60%)
The title compound was obtained as a white powder, melting point 75-77°C.
:'HNMR (CDC13) δ4.67 (d,
IH), 4.92 (dq, IH), 6.9-7.5 (m
.

7H), 7.78 (t, 1B); IR (Nujoule) 1570.1600.3390 cm-'.

Step 0.3-(2,2-dichloroethenyl)-2,2-
Dimethylcyclopropanecarboxylic acid cis-[1-(6-
phenoxy-2-pyridinyl)-2,2,2-1 trifluoroethyl] 2.04 g (7,6 mmol) of the 6-7 enoxy α-(trifluoromethyl)-2-pyridine methanol of Step C and 1. 72 g (7.6 mmol) of 'yZ-3
To a solution of -(2,2-dichloroethenyl)-2,2-dimethylcyclopropanecarbonyl chloride in 30 ml of dry tetrahydrofuran was added 2.0 ml (14,2 mmol) of triethylamine.The reaction mixture was stirred for 72 hours. . The precipitated triethylamine salt e# salt was then filtered off and the filtrate was concentrated under vacuum. The residue was chromatographed through silica gel and then vacuum distilled (boiling point 155°C, 0.2 mm) to give 2.61 g
(74%) of the title compound as a clear colorless oil, which was obtained in the form of a mixture of diastereomers as shown by the IHNMR spectrum: 'HNMR (
CDC13) δ1.14.1.24.1.26.1.2
9 (4Xs, 6H), 2.0-2.2 (m, 2H),
6.0-6.2 (m, 2H), 6.90 (d, IH
), 7.1-7.5 (m, 6H), 7.75 (t
, IH); IR) 1742 cm-'.

Example 2 4-chloro-α-(1-methylethyl)benzene 11e
[1-(6-phenoxy-2-pyridinyl)2.2.2
-Trifluoroethyl The process of Example 1 was applied to give 0.20 g (51%) of the title compound as a clear colorless oil.

The IHNMR spectrum showed that the title compound was obtained as a mixture of diastereomerides: IHNMR
(CDC13) δ0.73 (d, 3H), 1.0
3 (2Xd, 3H)%2゜3 (m, IH), 3.
30 (2Xd, IH), 6.05 (triple line, IH)
, 6.8 (2Xd, IH), 7.0-7.7 (m, 7
H): IR (knee)) 1750 cm-'.

Wenshiga 1 3-(2-chloro-3,3,3-)lifluoro-1-propenyl)-2,2-dimethylcyclopropanecarboxylic acid [1-(6-phenoxy-2-pyridinyl')2, 2
．． 2-Trifluoroethyl] Applying the procedure of Example 1 gave 0.32 g (72%) of the title compound as a clear colorless oil.

The IHNMR spectrum showed that the product was obtained in the form of a mixture of isomers: 'HNMRδ1.1-1.3
(m, 6H), 1, 9-2, 5 (m, 2H), 6.
0-6.2 (m, 2H), 6.89 (d, IH), 7
．． 1-7.5 (m, 6H), :, 74 (t, to
); IR-t) 1750 cm-'.

Apex A Ga A 3-(2-chloro-3,3,3-)lifluoro-1-propenyl)-2,2-dimethylcyclopropanecarboxylic acid cis-[1-(6-phenoxy-2-pyridinyl)2
, 2.2-trifluoroethyl Example using 0.79 g of dex-3-(2-chloro-3,3,3-trifluoro-1-propenyl)-2,2-dimethylcyclopropanecarbonyl chloride Applying step 1 (step D).

This gave 1.0 g of the title compound as a clear colorless oil. '
The HNMR spectrum indicates that the compound is diastereomer 1:
It was shown that it was obtained in the form of a mixture: 'HNM
R (CD C13) 61.17.1.27% 1.
31.1.34 (4Xs, 6H), 2.1 (m, 2H
): 6.05.6.10 (2Xq, IH), 6.78.
6.82 (2Xd, IH), 6.87 (d, IH)
, 7.1-7.

9 (m, 7H); IR (knee)) 1748cm-'.

Example 5 3-(2-chloro-3,3,3-)lifluoro-1-propenyl)-2,2-dimethylcyclopropanecarboxylic acid cis-(1-(6-phenoxy-2-pyridinyl)2
, 2.2-trifluoroethyl] 8.4 g of the diastereomer mixture of Example 4 was subjected to chromatography (silica gel, 2% ethyl acetate/hexane) to yield 2.71 g of diastereomer A. (Rf
o, 45.5% ethyl acetate/hexane), melting point 100~
101°C, and diastereomer B (RfO,37,
5% ethyl acetate/hexane), mp 66-68°C. The relatively high Rf diastereomer (A) is (l
R)-α-R/(1 phantom-Z-α-S enantiomer pair, and the relatively low Rf diastereomer (B) is (IR)-?l-α- 5/ (IS
)-α-R enantiomer pair.

Diastereomeric mixture HNMR (CDC13) δ1.
26 (s, 3H), 1.34 (s, 3H), 2.13
(d, IH), 2.25 (t, 1H), 6.05
(q, IH), 6.75 (d, IH), 6.86
(d, IH), 7.1-7.5 (m, 6H), 7.
75 (t, IH); IR (nujour @) 1738cm
-'.

Diastereomer B: 'HNMR (CDC13)
61.17 (s, 3H), 1.31 (S,
3H), 2.15 (d, IH), 2.28 (t, IH)
, 6.02 (q, IH), 7.01 (d, IH
), 7.10 (d, IH), 7.2 (m, 4H), 7.
40 (t, 18), 7.74 (t, IH)
:IR (neat) 1735cm-'.

The configuration regarding diastereomer B is (IR)-'tZ-
The designation of the a-3/(Is)-'yZ-a-Rx nanthiomer pair is based on the observation that this diastereomer is considerably more active in biological tests. In the examples below, the diastereomers with the highest levels of activity are shown to contain the (IR)- and 2-α-S enantiomers and their optical isomers.

Example 6 3-(2-chloro-3,3,3-trifluoro-1-propenyl)-2,2-dimethylcyclopropanecarciponic acid trans-[1-(6-phenoxy-2-pyridinyl)2, 2.2-trifluoroethyl] 4.22 g of trans-3-(2-chloro-3,3,3
Example 1 using -)-lifluoro-1-propenyl)-2,2-dimethylcyclopropanecaronyl chloride
Applying the process (step D), l:・1 of the title compound
A mixture of diastereomers was obtained, the components of which were separated by chromatography (silica gel, 2% ethyl acetate/hexane) and vacuum distilled, yielding 2.96 g.
diastereomer A (Rfo, 45.5% ethyl acetate/hexane) and diastereomer B (Rfo, 3
9.5% ethyl acetate/hexane).

Diastereomer A: 'HNMR (CDC13)
61.28 (s, 3H), 1.32 (3, 3H)
, 1.92 (d, IH), 2.4 (m, IH), 6
．． 1 (m, 2H), 6.85 (d, IH),
7.1-7.5 (m, 6H), 7.75 (t,
IH) ; NEET to IR) 1638cm''''
1° diastereomer B: 'HNMR (CDC1
3) 81.23 (s, 3H), 1.25 (s, 3H)
), 1.94 (d, IH), 2.44 (m, IH), 6
．． O6 (q, IH), 6.17 (d, IH), 6.
88 (d, IH), 7.1-7.5 (m, 6H),
7.74 (t, IH); IR-)) 163
6cm-'.

Example 7 Step A, l-Fecoluethylcarbamic acid [R-(R
book, R1)]- and [5-(R1,S associate)]-rl-
(6-phenoxy-2-pyridinyl)-2,2,2-trifluoroethyl] 2.40 g (8,91 mmol) of α-trifluoromethyl-6-phenoxy-2-pyridinemethanol, 1.
38 g (9,36 mmol) of (R)-(+)-1-
phenylethyl isocyanate and 22 mg (0,1
A stirred solution of 8 mmol) of 4-dimethylaminopyridine in 9 ml of benzene was heated to 50 °C for 17 h under a nitrogen atmosphere. The reaction mixture was then diluted with 150 ml of ether and treated with 25 ml of IN aqueous HCI, 25 ml saturated aqueous NaHCO3 and 25 ml saturated aqueous Na
Washed with C1. The organic layer was dried (Mg5O4) and concentrated under reduced pressure. The residue was repeatedly chromatographed on silica gel with benzene, first with 1
．． 77 g (48%) of [R-(R book, R book)] diastereomer: Rf = 0.10 (SiOz, benzene): I
HNMR (CDCa) δ1.52 (d, 6.
8Hz, 3H), 4.83 (quintet, 7.1Hz, I
H), 6.01 (q, 6.1Hz, IH), 6°83
(d, 8.2Hz, IH), 7.11-7°37 (wide m, 12H) and 7.68 (t.

7.8Hz, IH) and then 1.77g (48
%) of [5-(R units, 3 units)] diastereomer:
Rf=0.09 (S ich, benzene):'H
NMR (CDC13) 61.47 (d.

6.8Hz, 3H), 4.80 (quintet, 7.0Hz
, IH), 5.98 (q, 6.9Hz, IH), 6
．． 86 (d, 8.3Hz, IH), 7°13-7.42
(wide m, 12H) and 7.72 (t, 7.8
Hz, IH).

Step B, (S-
(R bottles, 3 bottles)] Carbamate, 0.52 ml
A stirred solution of (380 mg, 3.7 mmol) triethylamine, and 0.34 ml (460 mg, 3.4 mmol) trichlorosilane in 12 ml toluene was heated to 60 °C for 2 h under a nitrogen atmosphere. The reaction mixture was then diluted with 50 ml of saturated aqueous NHaCl,
It was then extracted with ether (3 x 25 ml). Drying (
After MgSOa), the combined organic extracts were concentrated under reduced pressure and the residue was chromatographed on 20 g of silica gel with 1:15 ethyl acetate/hexane to yield 667 mg (81%). The compound is 51.5-
Obtained as a white solid that melts at 53.5°C: [α]
' 2 = +2, 0'' (CHC13゜dan 1.0
0) and [α]365+4.8@(CHC13, 1.00)', the spectral and chromatographic properties of this material were identical to those of the racemic material prepared in Example 1 (Step C). Ta.

Step C, (IR)-1-(2-chloro-3,3,3-
Trifluoro-1-propenyl)-2,2-dimethylcyclopropanecarboxylic acid (S)-[1-(6-phenoxy-2-pyridinyl)-2,2,2-trifluoroethyl] (enantiomer B) 0°C 612 being cooled to
mg (2,52 mmol) of and 1-(2-chloro-3,
3,3-)lifluoro-1-propenyl)-2,2-dimethylcyclopropanecarboxylic acid, 647 mg (2.

40 mmol) of (S)-(+)-6-phenoxy-α-trifluoromethyl-2-pyridinemethanol from step B and 37 mg (0,30 mmol) of 4-dimethylaminopyridine in 6.0 ml of CH2Cl2 To the medium solution was added 620 mg (3,00 mmol) of 1,3-dicyclohexylcarbodiimide under a nitrogen atmosphere. After 2 hours at 0°C the reaction mixture was diluted with 50ml hexane and filtered. The filtrate was concentrated under reduced pressure and the residue was chromatographed on 100 g of silica gel using l:60 ether/hexane to initially yield 608 mg (51%) of (IS)-cis-α-
A colorless oil was obtained in which enantiomer A was shown to be in the 5-configuration = [α]” = -14,5@ (CHC
13, Danl.

20) Oyohi [a] M i s = −104
, 7° (CHC13, Dan 1.20).

When further dissolved, 573 mg (48%) of (IR)
Enantiomer B, designated as -'yZ-α-5 configuration, was given as a colorless oil: [α]′2=+48.
4° (CHC13, 1°og) and [α]215=
+183.8° (CHC13, 1.08°) was given.

The spectral and chromatographic properties of this material were identical to those of the racemic material prepared in Example 5.
2-dimethylcyclopropane-carboxylic acid (1-(6-
Example 1 (step Applying step D),
This gave 1.78 g (48%) of the title compound as a viscous yellow oil. IH NMR showed the product to be a 1:1 mixture of diastereomers. IHNMR
(CDC13) δ1.20.1.21.1.24.
1.28 (4Xs, 6H), 1=8 (m.

IH), 2.3 (m, IH), 5.64.5.66 (
2Xd, IH), 6.1 (m, IH), 6°88 (d
, IH), 7.1-7.8 (m, 7H).

IR) 1750cm-'.

Example 9 t, -3-(2,2-dichloroethenyl)-2゜2
-dimethylcyclopropane-carboxylic acid [1-[6-(
4-fluorophenoxy)-2-pyridinyl]-2,2
, 2-trifluoroethyl] 12 g of 6-(4-fluorophenoxy)-α-trifluoromethyl-2-pyridinemethanol and 9.7 g of cis-3-(2,2-dichloroethenyl)-2,2- 100 ml of dry THF stock solution of dimethylcyclopropanecarbonyl chloride was cooled to 10-15° C. under an elementary atmosphere and treated with 6.5 ml of triethylamine added dropwise. The reaction mixture was stirred at room temperature for about 14 hours. and then filtered. The filtrate was concentrated under vacuum to give 20.8 g of a pale orange semi-solid, which was analyzed by TLC (silica gel: 10%
(ethyl acetate/hexane) showed that it was composed of two types of components. Purification by flash chromatography gave the title compound as a mixture of diastereomers. Melting point 69-72℃: NMR (200MH2
,, CDC13) 61.14 (1°2H,s), 1
．． 24 (1,8H,s), 1.27 (1,2H,s)
, 1.30 (1,8H, s).

2.0-2.2 (2H, m), 5.95-8.2 (2
H, m), 6.89 (IH, d, J=8Hz), 7.
05-7.2 (5H, m), 7.75 (IH, t, J
=8H2).

Back Example A Cis-3-(2,2-dichloroethenyl)-2゜2-dimethylcyclopropanecarpon 5rt-[6-(4-fluorophenoxy)-2-pyridinyl]-2,2,2-
2 g of the above sample was subjected to chromatographic purification. 5
800 mg when eluted with % ethyl acetate/hexanes
Diastereomer (A) with a relatively high Rf of (Rfo,
57.10% ethyl acetate/hexane) was given as a white solid, mp 97-99"
MHz, CDC13) δ1.24 (3H, s)
, 1.30 (3B, s), 2.01 (IH, d, J=
8Hz), 2.12 (IH,t, J=8Hz), 6.
05 (IH, q, J=7Hz), 8, O8 (1B,
d, J=8Hz), 6.89 (IH, d, J=8H
z), 7°05-7.2 (5H, m), 7.75 (IH
, t, J=8 Hz), relatively low Rf diastereomer (B) (RfO, 50, 10% ethyl acetate/hexane) was obtained as a white solid (700 mg), melting point 78
．． 5-81℃: NMR (200MHz, CDC13)
61.14 (3H, s), 1.27 (3H, s),
2.01 (IH, d, J=8Hz), 2-14 (IH
, t, J=8Hz), 6.0 (IH,q, J=7Hz
), 6.15 (IH, d, J=8Hz), 6.89
(IH, d, J=8Hz), 7.05-7.2 (5H
, m), 7.75 (IH, t, J = 8 Hz).

Diastereomer A is (,IR)-E2-α-3/(I
s)-cis α-8 configuration, and diastereomer B is (IR)-'yZ-α-5/(Is)-
It is displayed as having an l-α-R configuration.

X twist 11 3-(2,2-dibromoethynyl)-2,2-dimethylcyclopropanecarboxylic acid 1-R-zZ-[1-(6-
phenoxy-2-pyridinyl)2゜2.2-trifluoroethyl] 4.5 g of 1-R-pyridinyl7. Application of the process of Example 1 (Step D) using -3- (2,2-dibromoethynyl)-2,2-dimethylcyclopropanecarbonyl chloride gave 3.59 g of the title compound as a yellow oil. . IHNMR showed that the product consisted of a 1=1 mixture of diastereomers. ' HNMR (CDC
13) δ1.15.1.25.1.27.1.29 (
4XS, 6H), 2.02 (m, 2H), 6.03 (m
, IH), 6.65' (m, IH), 6.85 (d,
IH), 7.1-7.5 (m, 6H), 7.78 (
m, IH); IR (knee)) 1745 cm-'.

Example 12 2.2-dimethyl-3-(1,2,2,2-tetrabromoethyl)-cyclopropanecarbon #1-R-KiX-
[1-(6-phenoxy-2-pyridinyl)2,2.2
-trifluoroethyl] 1.76 g (3.2 mmol)
A solution of the ester of Example 11 in 10 ml of carbon tetracarbon was cooled to 0° C. under N2. Add 0.2 ml (
3.9 mmol) of bromine was added and the reaction was then warmed to room temperature. After 5 days the solvent and excess bromine were removed in vacuo to give the title compound as a sticky oil. IHN
MR analysis showed the product to be a four-component mixture of diastereomers. lHNMR (CDCI3)
81.1-1゜5 (m, 68), 1.9-2.1 (m
, 2H), 4.9'-5,4(m, IH), 6.1 (
m, IH), 6.9 (m, IH), 7.1-7.9 (m
,7H); IR(=-))1730cm-'
.

XA Pigmaster 1 1.2,3.3-Tetramethylcyclopropanecarboxylic acid [1-(6-phenoxy-2-pyridinyl)2,2.
2-trifluoroethyl] 1.0 g of 2.2,3.3-
Applying the process of Example 1 (Step D) using tetramethylcyclopropane carbonyl chloride gave 1.0 g of the title compound as a yellow oil. IHNMR (CDC
13) 61.16 (s, 3H), 1.21 (s, 3
H), 1.23 (s, 6H), 1.38 (s, H), 6
．． 06 (q, IH), 6.86 (d, IH), 7.1
-7.5 (m, 6H); IR to) 1750c
m-'.

Example 14 Cis-3-(2-chloro-3,3,3-trifluoro-
1-propenyl)-2,2-dimethylcyclopropanecarboxylic acid [1-(5-phenoxy-3-pyridinyl)2
. -dimethylcyclopropanecarboxylic acid, 265 mg (0,984 mmol) of 5
-Phenoxy-α-trifluoromethyl-3-pyridinemethanol.

and 15 mg (0,12 mmol) of 4-dimethylamino-pyridine (DMA P) (7) 3 ,0 m
1 of a stirred solution in CH2C1z under a nitrogen atmosphere.
54 mg (1,23 mmol) of 1,3-dicyclohexylcarbodiimide (DCC) were added. After 1 hour at 0°C the mixture was diluted with 20ml hexane and
And filtered. The filtrate was concentrated under reduced pressure and the residue was chromatographed on 50 g of silica gel with 1=20 ethyl acetate/hexane, initially giving 227 mg (4
7%) of (IR)-'yZ-a-R/ (Is)-'y
Diastereomer A designated as Z-a-5 configuration
gave: Rf=0.10 (Sift, 1:20 ethyl acetate/hexane); I HNMR (CDC13)
δ1.29 (s, 3H), 1.36 (s, 3H),
2.11 (d, 8.2Hz, IH), 2.25 (t,
8.6Hz, IH), 6.17(q, 6.2Hz, IH
), 6-76 (d, 9°3Hz, IH), 7.04 (d
, 8.6Hz, 2H), 7.21 (m, IH), 7
．． 40 (t.

8.0Hz, 2H), 7.40(s, IH) and 8.
43(s, 2H).

Further elution then resulted in 206 mg (42%) of (I
gave the diastereomer B in which R)- is shown to be -α-5/(IS)-2-α-R configuration: Rf=0
．． 06 (Si02.1:20 ethyl acetate/hexane);' HNMR (CDC13) 61.17 (s,
3H), 1.32 (s, 3H), 2.13 (d, 8.
2Hz, IH), 2.28 (t, 8.'6Hz, IH
), 6°10 (q, 6.9Hz, IH), 6.78 (d
.

9.0Hz, IH), 7.05 (d, 8.3Hz, 2
H), 7.21 (m, IH), 7.37 (s, IH
), 7.41 (t, 8.0Hz, 2H) and 8.4
3(s, 2H).

Example 15 Beg 7. -3-(2-chloro-3,3,3-trifluna
-1-propenyl)-2,2-dimethylcyclopropanecarboxylic acid [1-(2-phenoxy-4-pyridinyl)
2,2,2-trifluoroethyl] 215 in 2,4 ml of CH2Cl2 cooled to 0 °C
mg (0-0886 mmol) of carboxylic acid, 215
mg (0,799 mmol) of 2-phenoxy-α-
Trifluoromethyl-4-pyridinemethanol, 12m
g (0,098 mmol) of DMAP and 206 mg
Example 8 (0,998 mmol) of DCC was used (
Applying the process in step C), after treatment and σ chromatography, initially 184 mg (47%) of (IR) −'
yx -a -R/ (IS) -'y7. -a
-Sfi! , giving diastereomer A shown as: Rf=0.12 (Si02, l:20
ethyl acetate/hexane); 'HNMR (CDC1
3) 61.32 (S, 3H), 1.38 (s, 3H),
2.17 (d, 8.1Hz, IH), 2.28 (t,
8.6Hz, IH), 6.14(q, 6°6Hz, IH
), 6.77 (d, 9.0Hz.

IH), 7.03 (s, IH), 7.06 (d
.

5.0Hz, IH), 7.15(d, 7.31(z, 2
H), 7.23 (m, IH), 7.43 (t, 8.
0Hz, 2H) and 8.23(d.

5.0Hz, IH) and then 171mg (43%)
(7) (I R) -'yZ-a-S/ (I S
) -'yZ-α-R stirrup gave diastereomer B, which is reported to be: Rf=0.08 (SiO2
, 1:20 ethyl acetate/hexane), IHNMR (C
DC13) δ1.・'21 (s, 3H).

1.36 (s, 3B), 2.18 (d, 8.1Hz
, IH), 2.32 (t, 8.6Hz, IH).

6.07 (q, 6.7Hz, IH), 6.80 (d,
'lOH2, IH), 7.00 (s, IH), 7.0
5 (d, 5.0Hz, 1B), 7°15 (d, 8.
6Hz, 2H), 7.24 (m.

IH), 7.43 (t, 7.8Hz, 2H) and 8
．． 24 (d, 5.0Hz, IH).

Yuyu Tsuse 1 Cis-3-(2,2-dichloroethenyl)-2゜2-dimethylcyclopropanecarpon #[1-(4-phenoxy-2-pyridinyl)-2,2゜2-trifluoroethyl ] 280 mg (1,04 mmol) of 4-phenoxy-α-trifluoromethyl-2-pyridinemethanol and 0.29 mg (210 mg, 2
．． 08 mmol) 2.6 ml of notriethylamine C
To a stirred solution in H2Cl2, under a nitrogen atmosphere, 2 g 4 m
'y of g (i, 25 mmol); l-3-(2,2
-dichloroethenyl)-2,2-dimethylcyclopropanecarbonyl chloride was added. After 1 hour at 0°C, the reaction mixture was allowed to warm to room temperature over 15 hours. The mixture was then diluted with 60 ml saturated aqueous NaHCO
3 and extracted with CH2C12 (2X25ml). The extracts combined with dry mCMg5Oa)* were chromatographed under reduced pressure on 50 g of silica gel using 1=15 ethyl acetate/hexane, initially containing 215 mg (45%) of (I
gave diastereomer A, designated as R)-'yZ-a-R/(Is)-2-α-5 configuration:
Rf=0.12 (Si02.1:15 ethyl acetate/hexane');' HNMR (CDC13) δ1°26 (s, 3H), 1.30 (s, 3H), 2°03 (d, 8. 0Hz, IH), 2.13(t.

8.0Hz, IH), 6.11 (d, 8-IHz, I
H), 6.17 (q', 6.6Hz, IH), 6.82
(dd, 2.4Hz, 6.0Hz, IH), 7.08
(wide s, IH), 7.11 (d, 8.1Hz, 2
H), 7.29 (m, IH).

7.46 (t, 7.7Hz, 2H) and 8.4
7 (d, 6.0)1z, IH).

Further elution then resulted in 185 mg (39%) of (I
R)- gave diastereomer B designated as -α-5/(Is)-21α-Rfflfi: R
f=0.08 (Si02, l:15 ethyl acetate/hexane); 'HNMR (CDCI3) δ1.14
(s, 3H), 1°26 (s, 3B), 2.03
(d, 8.0Hz.

IH), 2.14 (t, 8.0Hz, IH), 6.1
0 (q, 7.3Hz, IH), 6.19 (d, 8.0
Hz, IH), 6.82 (cld.

2.3Hz, 5.3Hz, IH), 7.03 (wide s
, IH), 7.10 (d, 8.6Hz, 2H), 7.2
9 (m, IH), 7.46 (t.

8.2Hz, 2H) and g, 48 (d, 5.2H
z, IH).

By the general process described above, the compounds in Tables 1 to 9 (insecticides and acaricides) and Tables 10 and 11 (intermediate products) could be produced.

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Applications The compounds of the invention exhibit activity against a wide range of foliar and soil-dwelling insects and mites.

Some of the compounds of the invention surprisingly retain activity in soil. Those skilled in the art recognize that not all compounds are equally effective against all insects or mites, but the compounds of the present invention are particularly effective against all insects or mites.
tera), control many economically important pest species of insects of the order Hosoptera and Coleoptera, as well as important mite species of the order Acar, i. Will,
Individual types of control examples are listed below: fall armyworm, Spodoptera frgi
perda); Paul Rybill (ball we)
eviυ, Anthonomus Grunges
mus grandis); European corn barer
, Ostrinia nubilalis (O5trinia nu
bilalis): Southern e-corn rootworm (
southern c.

rn rootworm), Diabrotica undesinpunctata howardi (Diabrotica un
decimpunctata howardi); aster fist leaf hopper
er), Macrosteres fasciphrons (Macro
black bean aphid
, Aphis fabae
; and two-spotted spider mite (Tetranychus u
rticae)*L However, the control of pests by the compounds of the present invention is not limited to these types.

The compounds of the present invention are useful formulations of compounds of formula 1, generally used in formulations with liquid or solid diluents or with organic solvent carriers. can be manufactured using standard methods. They include powders, tablets, solutions, suspensions, emulsions, wettable powders, concentrated emulsions, dry flow agents, and the like.

Many of these can be applied directly. Spray formulations can be bulked up in a suitable medium and used in spray volumes ranging from 1 liter to several hundred liters per hectare. High strength compositions are primarily used as intermediates for subsequent formulations. According to JK, the formulation contains about 1 to 99 active ingredients.
% by weight and a) about 0.1-20% surfactant and b
) Contains about 5-99% of at least one solid or liquid diluent. More particularly, the formulation will contain these ingredients in approximately the following proportions.

Weight % Active ingredient Diluent Human blood shield hydrating agent 25-90 0-74 1-1
0 oil suspension, 5-50 40-95 0-
15 Emulsion, liquid (including concentrated emulsion) Powder 1-25 70-99 0-5
Granules and tablets 1-95 5,913 0-1
5 High strength composition 90-99 0-10 0-
2 Of course, lower or higher amounts of active ingredients than listed may also be present depending on the intended use and physical properties of the compound.
A high proportion of surface-active to active ingredients is sometimes desirable and is achieved by incorporation into the formulation or by mixing in a tank.

A typical solid diluent is Watkins
Other authors, “Handbook of In5ecti
cide Dust Diluents and
"Carriers", 2nd edition, Dorland Books.

Caldwell, N. J.). Further absorbent diluents are preferred for wettable powders and concentrated emulsions. Representative liquid diluents and solvents are described by Marsden, "S.

1vents guide'', 2nd edition, Interscience, N.

Y.), 1950. A solubility of 0.1% or less is suitable for concentrated suspensions, which are preferably stable to phase separation at 0°C. “McCutc
heon's detergents and
Emulsifiers Annual”, Arua L
/-/Allured Publ, Cor
p,,N,J,), as well as Sisely and Wo.

d), “Encyclopedia of 5u”
rface Active Agents''.

Chemical Publisher.

Corp., N. Y.), 1964, displays surface activity and its recommended uses. All formulations may contain small amounts of additives to reduce foaming, caking, corrosion, microbial growth, etc.

Preferably, each ingredient should be approved by the US Environmental Protection Agency for its intended use.

Methods for producing such compositions are well known.

Solutions are prepared by simply mixing the components.

Finely divided solid compositions are produced by mixing and generally grinding using a hammer mill or fluid energy mill. Suspensions are manufactured by wet milling (see Littler (7) U.S. Pat. No. 3,060,084). Granules and tablets are
They can be prepared by spraying the active substance onto preformed particulate carriers or by agglomeration methods. References J.E. Browning, “Agglomer
ation”, Chemical Engineer
ing, December 4 issue, p. 147 (1967), and Ferry's Chemical Eng.
iners Handbook, 4th edition, MeGraw-Hill, N, Y
), 1963, pp. 8-59 et seq.

Examples of useful formulations of the compounds of this invention are described below, Example 17 Concentrated Emulsion 3-(2,2-dichloroethenyl)-2,2-dimethylcyclopropanecarboxylic acid cis-[1-(6- phenoxy-2-pyridinyl)-2,2,2-trifluoroethyl] 30% blend of oil-soluble sulfonates and polyoxyethylene ethers 4% xylene 66% Combine the above ingredients and gently stir to promote dissolution Stir while warming. A fine screen filter was used in the packaging operation to ensure that there was no excess undissolved material in the product.

3-(2-chloro-3,3,3-)lifluoro-1-propenyl)-2,2-dimethylcyclopropanecarboxylic acid [1-(6-phenoxy-2-pyridinyl)] -2,2,2-trifluoroethyl] 30% Sodium alkylnaphthalene sulfonate 2% Sodium lignin sulfonate 2% Synthetic amorphous silica 3% Kaolinite
In a 63% mixer, the active ingredient was sprayed onto the inert material while it was being warmed up to reduce the viscosity. After milling in the hammer mill, the material was remixed and passed through a 50 mesh screen.

Example 19 Granule Wettable powder of Example 18 10% pyrophyllite (powder) 90% Wettable powder and pyrophyllite diluent were thoroughly mixed and first packaged. The product was suitable for use as a powder.

Example 20 Granules 4-chloro-α-(-methylethyl) Benzene acetic acid [1-(6-7 enoxy 2-pyridinyl)-2,2,2-trifluoroethyl] 10% attapulgide particles (low volatile material , 0.7110.30 mm; US Standard Sieve No. 25-50) The active ingredient was warmed in a double cone mixer to reduce the viscosity and sprayed onto the dedusted and prewarmed attapul guide particles. The particles were placed in stirrups, cooled, and packaged.

Example 21 Wettable powder of Example 18 15% dibutham
69% potassium sulfate
16% The above ingredients were mixed in a rotary mixer and granulated by spraying with water. Most substances have the desired dimensions 0
, 1~0, 42mm (US standard sieve 18~40
When the particle size reached 1), one particle was taken out and dried.

The 8 size large sieved material was ground to produce the desired range of additional material. These particles contained 4.5% active ingredient.

Example 22 Solution 3-(2,2-dichloroethenyl)-2,2-dimethylcyclopropanecarboxylic acid cis-[1-(6-phenoxy-2-pyridinyl)-2,2,2-trifluoroethyl] 50 % Infron 50% The above ingredients were combined and stirred to produce a solution suitable for low volume direct application.

Mixing compounds of formula 1 with one or more insecticides, fungicides, nematicides, bactericides, acaricides or other biologically active compounds Multi-component pesticides can also be produced which provide a wider range of effective agricultural protection. It is particularly advantageous to combine the compounds of formula 1 with substances having synergistic or enhancing activity. Representative substances are the pyrethrin synergists exemplified below: (2-(2 −
butoxyethoxy)-ethoxy]-4,5-methylenedioxy-2-propyltoluene (leheronyl butoxide), 3-hexyl-5-(3,4-methylenedioxyphenyl)-2-cyclohexanone (pipero nylcyclonene), 2-(3,4-methylene-dioxyphenoxy)
-3,6,9-trioxaundecane, 1,2-(methylenedioxy)-4-[2-(octylsulfinyl)
Propyltorunzene, dipropyly-5,6,7゜8-tetrahydro-7-methylnaphtho-[2,3-dl-3-
Dioxo-5,6-dicarboxylate and propynyl ethers and propynyl oximes 0 Examples of other agricultural protection agents that can be mixed or formulated with the compounds of the invention are listed below: Insecticides: 3 -Hydroxy-N-methylcrotonamide (dimethylphosphoric acid) ester (monocrotophos) ester of methylcarbamic acid with 2,3-dihydro-2,2-dimethyl-7-benzofuranol (carbofuran) 0-[2,4, 5-Trichloro-α-(chloromethyl)
benzyl] Phosphorus @ O', O'-dimethyl ester (tetrachlorvinfos) 2-mercaptosuccinic acid diethyl ester, S-ester with thionophosphoric acid, dimethyl ester (malathion) phosphorothionate 01 O-dimethyl, 0-p- Nitrophenyl ester (methylparathion) Ester of methylcarbamic acid with α-naphthol (carbaryl) 0-(Methylcarbamoyl)thiol Methyl acetohydroxamate (methomyl) N”-(4-chloro-p-tolyl)-N,N-dimethyl Formamidine (chloromethyl) 0.0-diethyl-
〇-(2-isopropyl-4-methyl-6-pyrimidylphosphorothioate (diazinon) octachlorocamphene (toxaphene) 〇-ethyl 0-p-nitrophenylphenylphosphonothionate (E
P N) (S)-α-cyano-m-phenoxybenzyl (IR,
3R)-3-(2,2-dibromo-vinyl)-2,2-
Dimethylcyclopropanecarboxylate (deltamethrin)'N',N''-dimethyl-N-[(methylcarbamoyl)
Methyl oxy]-1-thioxamimidate (oxamyl) Cyan(3-phenoxyphenyl)-methyl-4-chloro-α-(1-methylethyl)benzene acetate (fenvalerate) (3-phenoxyphenyl) ) Methyl (±)-female, trans-3-(2,2-dichloro-ethynyl)-2,-dimethylcyclopropanecarboxylate (bermethrin) 3-(2,2-dichlorovinyl)-2,2-dimethylcyclo Propanecarboxylic acid α-cyano-3-phenoxybenzyl (dibermethrin)〇-ethyl-S-(p-chlorophenyl)ethylphosphonodithioate (prophenophos)phosphorothiolothionate, 0-ethyl-〇-
[4-(Methylthio)-phenyl]-5-n-propyl ester (sulprofos).

Other insecticides are listed below by their common names: nitriflumuron, diflubenzuron, methoprene, buprofezin, thiodicarb, acephate, azinph, os-methyl, chlorpyrifos, dimethoate, phonophos, infenfos, methidathion, metamidiphos, monochrome. Fosmet, Fosfumitone, Fosalon, Pirimicarb, Fuorate, Profenofos, Terbufos, Trichlorfon, Methoxychlor, Bifenthrin, Biphenate, Cyfluthrin, Fenpropathrin, Fluvalinate, Flucythrinate, Tralomethrin, Metaldehyde and Rotinone.

2-benzimidazole methyl carbamate (carpendazim) tetramethylthiuram disulfide, (thiuram) vinegar fin-
Dodecylguanidine (Dodine) Manganese ethylenebisdithiocarbamate (Maneb) 1,4-Dichloro-2,5-dimethoxybenzene (Chloroneb) l-(Butylcarbamoyl)-2-benzimidazole Methylcarbamate (Benomyl) 1- [2- (2,4
-dichlorophenyl)-4-propyl-1,3-dioxolan-2-ylmethyl]-1H-1,2,4-)riazole (propiconazole) 2-cyano-N-ethylcarbamoyl-2-methoxyiminoacetamide (symoxanil) ) l-(4-chlorophenoxy)-3,3-dimethyl-1-(IH-1,2,
4-) Riazol-1-yl)-2-butanone (triadimetuone) N-(trichloromethylthio)tetrahydrophthalimide (cabutane) N-(trichloromethylthio)phthalimide ()milpet) 1-[[[bis(4-fluorophenyl) )] [methyl]
silyl]methyl]-1H-1,2,4-)riazole.

Nematicides: 1-(dimethylcarbamoyl)-N-(methylcarbamoyloxy)-thioformimidate S-methyl 1-carbamoyl-N-(methylcarbamoyloxy)
-Thioformimidic acid S-methyl N-isopropylphosphoramidic acid, 0-ethyl 0'-(4-(methylthio)-m-tolyl) diester (Zenamitsuos).

Stomach fungus: tribasic copper sulfate Streptomycin sulfate.

Acaricides: Esters of senecioic acid with 2-sec-butyl-4゜6-sinitrophenol (binapacryl) 6-methyl-1,3-dithiolo[4,5-β]quinoxalin-2-one (oxythio Quinox) 4.4'-Ethyl dichlorobenzilate (chlorohendylate) 1.1-Bis(P-chlorophenyl)-2,2°2-trichloroethanol (dicofol) Bis(pentachloro-2,4-cyclopentadiene) -1-yl) (genochlor) tricyclohexyltin hydroxide (cyhexatin) trans-5-(4-chlorophenyl)-N-cyclohexyl-
4-Methyl-2-oxo-thiazolidine-3-carboxamide (hexythiazox) Amitrazpropargitefenbutatin-oxide bischlorentedine Bacillus thuringiensis
ringiensis) avermectin B.

Insects and mites are controlled by applying an effective amount of one or more compounds of formula 1 of the invention to the infected area, the area to be protected or directly to the pests to be controlled. And agricultural crops will be protected. A preferred method of application is a spraying method using a spray device to distribute the compound on the leaves, in the soil or on the parts of the plant that are infected or need to be protected. Alternatively, granular formulations of these compounds are applied to the soil or to the leaves. or optionally added to the soil. Either aerial or ground applications can be used.

Although the phenoxypyridinyl compound(s) of the present invention can be applied in their pure state, they are often incorporated into one or more compounds of the present invention in an agriculturally suitable carrier or diluent. The most preferred method of application, which will be applied in the form of a containing formulation, is spraying of an aqueous dispersion or refined oil solution of the compounds.

The rate of application of the compounds of formula 1 depends on the type of insect or mite to be controlled, the growth stage of the pest, its size, its location, the parasitic crop, the year and time of application, the surrounding humidity and temperature conditions, etc. Depends on factors. Generally, an application rate of 0.05 to 2 kg of active ingredient per hectare is sufficient to provide effective control in large field operations under normal circumstances, but depending on the factors listed above. 0
．． As low as 0.01 kg/ha may be sufficient, or as high as 8 kg/ha may be required.

The following examples demonstrate the control effectiveness of Formula 1 against individual insect and acarid pests.

Compounds 1-14 are therefore the compounds of Examples 1-14 and the remaining compounds are those identified in Table 12.

00000 00 00W TA 0OOOO Clear Contains M. Maint Memical Example 23 Fall Army Warm A test device consisting of 8 -ounce plastic plastic kotsup, which contains one -layer wheat feed of about 0.5 cm thick, respectively. did. Fall Armyworm (S
A tertiary larva of P. podoptera frugiperda was placed in each pot. Solutions of the following test compounds (acetone/distilled water 75/25 solvent) were sprayed onto the tips at a rate of one solution per tip. 0.5 bond per knee car (approximately 0.55 kg/
Spraying was carried out by passing directly under a flat fan hydraulic nozzle discharging a spray solution with a proportion of active ingredient of 0.0 °C and a relative humidity of 50%. The cells were kept for 72 hours, and the mortality rate was read after that time. The results are shown in the table below.

36A 8736B
10037A
7 Example 24 Tobacco, Budworm The test process of Example 23 was performed on Tobacco, Budworm ()I.
The effect on tertiary larvae of E. eliothis virescen+ was repeated. The results are shown in the table below.

%Cei Rorororororototorororo dai c Rororotoroto 00 Rorororo C Rorororo C Roto t + - machine Roro no Ro QOe
Φ Roro CΦ Rororo 0 Rororo o c', Φ-Roku mouth > O: l O' + Low C'J So dimension inner dimension to ω roll inner dimension C Low - to ~ to N ~ ~ ~ ~ ~ Hesokan ~ Sosonai Kanso 37A 337B
100418
100' Example 25 A test apparatus was constructed consisting of 8 ounce plastic scoops in which each European corn pollel contained 1 square inch of wheat sprout/soybean flour feed. European corn pollel (
A tertiary larva of Ostrinia nubilalig was placed in each pot. The test apparatus was sprayed with individual solutions of the following compounds as described in Example 23, then capped and heated at 27°C and 50%
The relative humidity was maintained for 72 hours and mortality was read after that time. The results are shown in the table below.

37A 7 Example 26 14F each! A test device was constructed consisting of an 8 oz. plastic scoop containing germinated corn seeds. The test apparatus was sprayed with individual solutions of the following compounds as described in Example 23. After the spray on the tip dries, five southern corn rootworms (Diabrotica undecimpu)
A tertiary larva of C. nctata howardi was placed in each pot. A moist dental wick was inserted into each tip to prevent desiccation and the tips were capped.The tips were then kept at 27°C and 50% relative humidity for 48 hours, after which time mortality was determined. I read it. The results are shown in the table below.

36B ] OU
37A-41β
100 Example 27 Paul Rybill 5 Paul Rybills (Anthonomus g.
randiS) into a series of 9 oz scoops.

The test procedure used was otherwise the same as Example 23. Mortality rates measured 48 hours after treatment are shown in the table below.

6A 476B
1 007B
100a
io.

3:) -3
6A 7 3:i
6 B 1 003
7A 041F
3 100 Example 28 5-10 Black Bean Fist Aphis
A null test specimen was prepared from a single nasturtium (Tropaeolum sp.) (1) leaf infected with Tropaeolum sp. The sweets were cut and kept individually in l-dram glass bottles filled with 10% sugar solution before and after spraying. During spraying, the infected leaves were turned over to expose the aphids and the leaves, which were then clipped in place, were sprayed with individual solutions of the following compounds according to the spraying process of Example 23. The sprayed leaves were returned to individual vials, capped with clear 1 oz. scoops, and kept at 27° C. and 50% relative humidity for 48 hours, after which time mortality was read. The results are shown in the table below.

Example 29 Each oat (
Test devices were constructed from a series of 12-ounce scoops containing seedlings of Avena 5ative. The test apparatus was sprayed with individual solutions of the following compounds as described in Example 23. After the oats have dried from the spray, 10 to 15 mature aster leafhoppers (Mascrosteles fascifron)
s) was injected into each of the capped cups.

Cops were kept at 27° C. and 50% relative humidity for 48 hours, after which time mortality was read. The results are shown in the table below.

5A 1 005B
1006A
1006B
1 007B 1
0010A 521
0B 1 0036A
1003 G B
1 0 (137A
173 7B
1 0041B
IQQ Example 30 200g each of moist sassafras loam soil and 2
Grain decalping Tl 100) Containing corn 3
A test bag consisting of an inch cylindrical pot was manufactured. 0.25 bond per knee car (approx. 0.275 kg/
Spraying was carried out by passing directly under a flat fan hydraulic nozzle discharging a spray liquid with a proportion of active ingredient of 100 kg. After spraying the test equipment, the corn seeds were covered with soil and 10 southern hoon rootworms (Diabrotica undecimp) were added.
A tertiary larva of C. unctata howardi was placed in each pot. The test apparatus was kept at 24°C, 70% relative humidity and under a light cycle of 16 hours light and 78 hours dark for 7 days, after which time control was measured - control was determined by a root damage rating of 1 to 5. The percentage of corn seedlings that germinated was also used to determine the control rate, where 1 was no damage and 5 was complete destruction of the root system.・No damage to plants was observed.

The results are shown in the table below.

Root M1 Kizoku Climbing Pond - Yoshi Tribute Value ---- % Vinegar Germination Village 4
1.0 1005B
1.0 1
006＾ 3.3
386B 1.1
to.

8 1.3
889 1.5
8810B 1.4
10011
2.1 7512
2.6 3813
1.3 8818
2.8
5019 3.5
1320 3.5
021
1.6 10022
2, ] 7523
1.9 1002
4 2.3
7525 1.6
81 (261,3100 301,975 381,3100 41B 1.5 100Example 31) Twenty to thirty adult two-spotted spider mites (Tet
ranychus urtica) and sprayed with individual solutions of the following compounds as described in Example 23. The sprayed leaf sections were then placed on top of a moist layer of cotton in a Petri dish and 27
℃ and 50% relative humidity for 48 hours, after which time mortality was read. The results are shown in the table below.

Compound A B A B B 0A 0B 6A 6B 7A 7B % mortality rate

Claims (1)

[Claims] 1. A formula characterized by a 1,3-relationship between an ester substituent and an ether substituent on the pyridine ring ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R is ▲There are mathematical formulas, chemical formulas, tables, etc.▼￥R-A￥, ▲There are mathematical formulas, chemical formulas, tables, etc.▼￥R-B￥, ▲There are mathematical formulas, chemical formulas, tables, etc.▼￥R-C￥, ▲Mathematical formulas , there are chemical formulas, tables, etc. ▼￥R-D￥, ▲ there are mathematical formulas, chemical formulas, tables, etc. ▼￥R-E￥, ▲ there are mathematical formulas, chemical formulas, tables, etc. ▼￥R-F￥, and is O or S, n is 1 to 3, m is 0 or 1, R_1 is H, C_1 to C_4 alkyl, C_2 to C_5
Alkenyl, C_2-C_5 alkynyl, C_1-C_
4 haloalkyl, C_1~C_4 alkoxy, C_1~
C_4 haloalkoxy, C_1-C_4 alkylthio,
C_1-C_4 alkylsulfinyl, C_1-C_4
Alkylsulfonyl, C_1-C_4 haloalkylthio, C_1-C_4 haloalkylsulfonyl, F, Cl,
Br, and when n=2, the R_1 substituents may together be 3,4-methylenedioxy, and R_2
is H, F, Cl, Br, CH_3, or CF_3, and R_3 is F, Cl, Br, C_1-C_4 alkyl, C
_1-C_4 haloalkyl, CO_2CH_3, or CO_2CH_2CH_3; R_4 is F, Cl, Br, or CH_3; R_5 is H, F, Cl, CF_3, or C_1-C_
4 alkyl, R_6 is Cl or Br, R_7 is Cl or Br, R_8 is H, C_1-C_4 alkyl, C_1-C_4
Haloalkyl, C_1-C_4 alkoxy, C_1-C
_4 alkylthio, C_1-C_4 alkylsulfinyl, C_1-C_4 alkylsulfonyl, C_1-C_
4 haloalkylthio, C_1-C_4 haloalkylsulfinyl, C_1-C_4 haloalkylsulfonyl, F
, Cl, or Br, and R_9 is H, F, Cl, CH_3, OCH_3, or R_8 and R_9 together may be 3,4-methylenedioxy, R_1_0, R_1_
1, R_1_2 and R_1_3 are independently H, F, or Cl, and R_1_4 is H, F, Cl, OCH_3, OCH_2CH_3, or C_1-C_2 haloalkoxy]. 2. The ester substituent and ether substituent have the formula ▲ mathematical formula,
There are chemical formulas, tables, etc. ▼ A compound according to claim 1, which has a 1,3-relationship represented by ▼. 3, X is 0, n is 1, m is 1, R_1 is H, CH_3, CF_3, OCH_3, OCF
_2H, F, Cl, SCH_3, SO_2CH_3, S
CF_2H, or SO_2CF_2H, and R_2
is H, F, or Cl, R_8 is H, F, Cl, or C_1-C_2 alkoxy, R_9 is H, and R_1_4 is H, F, Cl, OCH_3, OCH_2CH_3, or OCF_2H, A compound according to claim 2. 4. The compound according to claim 3, wherein R is selected from the group consisting of RA, RB, RD and RE. 5. The compound according to claim 4, wherein R is RA. 6, \cis\-3-(2,2-dichloroethenyl)-2
,2-dimethyl-cyclopropanecarboxylic acid [1-(5
-fluoro-6-phenoxy-2-pyridinyl)-2,
6. The compound according to claim 5, which is a 2,2-trifluoroethyl] ester. 7. The compound according to claim 4, wherein R is R-B. 8. Formulas ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R_1 is H, C_1 to C_4 alkyl, C_2 to C_5
Alkenyl, C_2-C_5 alkynyl, C_1-C_
4 haloalkyl, C_1~C_4 alkoxy, C_1~
C_4 haloalkoxy, C_1-C_4 alkylthio,
C_1-C_4 alkylsulfinyl, C_1-C_4
Alkylsulfonyl, C_1-C_4 haloalkylthio, C_1-C_4 haloalkylsulfonyl, F, Cl,
Br, and when n=2, the R_1 substituents may together be 3,4-methylenedioxy, and R_2
is H, F, Cl, Br, CH_3, or CF_3, and n is 1-3. 9. Formulas ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R_1 is H, C_1 to C_4 alkyl, C_2 to C_5
Alkenyl, C_2-C_5 alkynyl, C_1-C_
4 haloalkyl, C_1~C_4 alkoxy, C_1~
C_4 haloalkoxy, C_1-C_4 alkylthio,
C_1-C_4 alkylsulfinyl, C_1-C_4
Alkylsulfonyl, C_1-C_4 haloalkylthio, C_1-C_4 haloalkylsulfonyl, F, Cl,
Br, and when n=2, the R_1 substituents may together be 3,4-methylenedioxy, and R_2
is H, F, Cl, Br, CH_3, or CF_3 and -n is 1 to 3]. 10. Formulas ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, X is O or S, R_1 is H, C_1 to C_4 alkyl, C_2 to C_5
Alkenyl, C_2-C_5 alkynyl, C_1-C_
4 haloalkyl, C_1~C_4 alkoxy, C_1~
C_4 haloalkoxy, C_1-C_4 alkylthio,
C_1-C_4 alkylsulfinyl, C_1-C_4
Alkylsulfonyl, C_1-C_4 haloalkylthio, C_1-C_4 haloalkylsulfonyl, F, Cl,
Br, and when n=2, the R_1 substituents may together be 3,4-methylenedioxy, and R_2
is H, F, Cl, Br, CH_3, or CF_3, and n is 1 to 3] (i) the following phenoxy or thiophenoxypyridinyl halide Cl or ▲ formula , chemical formulas, tables, etc. ▼ where R_1, R_2, X and n are as defined above] and (ii) metallizing the metallized product of step (i) A method consisting of reacting with N,N-dimethyltrifluoroacetamide (CF_3CON(CH_3)_2). 11. The method of claim 10, comprising an additional step of reducing the ketone of step (ii). 12. An agricultural composition comprising a compound according to claim 1 and a diluent or carrier suitable for agricultural use. 13. consisting of applying an effective amount of the compound according to claim 1 to the pest or the environment of the pest,
Pest control methods.