JPS63170330A - Fluoroalkane compound, production thereof, insecticide and acaricide comprising said compound as active ingredient - Google Patents

Abstract

NEW MATERIAL:A fluoroalkane compound shown by formula I (R1 and R2 are H, halogen, lower alkyl, lower alkoxy, lower haloalkyl, lower haloalkoxy or lower alkenyloxy or R1 and R2 are bonded methylenedioxy or trimethylene; R3 is H or F). EXAMPLE:2-(4-Chlorophenyl)-5-(3-phenoxyphenyl)-1,1,1-trifluorope-ntane. USE:Useful as an insecticide and acaricide having low fish toxicity, effective especially against insect pests such as leaf-hoppers, insects belonging to the family Deltocephalidae, Blattella nipposica Asahina, insects of the family Tetranychidae, etc. PREPARATION:A novel alkene compound shown by formula II (R1' and R2' are R1 and R2 except lower alkenyloxy) is reduced to give a corresponding compound shown by formula I. The compound shown by formula II is obtained from a compound shown by formula III and a compound shown by formula IV.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a novel fluoroalkane compound, a method for producing the same, and an insecticide and acaricide containing the same as an active ingredient.

<Prior Art> As an aromatic alkane compound having insecticidal effect, for example, the compound described in JP-A-58-201737 is known.

<Problems to be Solved by the Invention> However, these compounds cannot be said to be fully satisfactory in their insecticidal and acaricidal activities.

<Means for Solving the Problems> In view of the above situation, the present inventors conducted various studies to develop a compound with excellent insecticidal and acaricidal activity and low toxicity to fish, and as a result, -a Formula (1) [wherein R6 and R2 are the same or different and represent a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxyl group, a lower haloalkyl group, a lower haloalkoxyl group, or a lower alkenyloxy group; When bonded with R2, it represents a methylenedioxy group or a trimethylene group, and Rs represents a hydrogen atom or a fluorine atom. The present inventors have discovered that the novel fluoroalkane compound represented by (hereinafter referred to as the compound of the present invention) is an excellent insecticidal and acaricidal compound with few of the above-mentioned drawbacks, and has thus arrived at the present invention.

That is, the present invention provides a metal compound represented by the above general formula (1),
The present invention relates to a method for producing the same and insecticides and acaricides containing the same as an active ingredient.

Specific pests for which the compounds of the present invention are particularly effective include hemipterans such as planthoppers, leafhoppers, aphids, stink bugs, and whiteflies, diamondback moths, Japanese snail moths, brown borer moths, armyworms, leafhoppers, white beetles, burrs, Lepidoptera such as carp moths, Diptera such as Culex mosquitoes, Anopheles mosquitoes, Aedes mosquitoes, and house flies; Reciptera such as German cockroaches, black cockroaches, Japanese cockroaches, and American cockroaches; other Coleoptera, Hymenoptera, Hymenoptera, and Orthoptera. Examples of the orders and spider mites include false red spider mite, two-spotted spider mite, orange spider mite, and the like.

Examples of the compounds of the present invention include the following compounds.

2-(4-chlorophenyl)-5-(3-phenoxyphenyl)-1,1,1-)lifluoropencune 2-(4-chlorophenyl)-5-(4-fluoro-3
-phenoxyphenyl)-1,1,1-trifluoropenkune 2-(4-fluorophenyl)-5-(3-phenoxyphenyl)-1,1,14-trifluoropenkune 2-(4-fluorophenyl) -5-(4-fluoro-
3-phenoxyphenyl)-1,1,1-trifluoropentane 2-(4-ethylphenyl") -5-(4-fluoro-3-phenoxyphenyl")-1,1,1-trifluoropentane 2- (4-methoxyphenyl)-5-, (3-phenoxyphenyl)-1,1,1-1-lifluoropencune 2-(4-ethoxyphenyl)-5-(3-phenoxyphenyl)-1,1 , 1-trifluoropentane 2-(4-i-propoxyphenyl)-5-(3-phenoxyphenyl)-1,1,1-trifluoropentane 2(4-n-propoxyphenyl)-5-(3- phenoxyphenyl')-1,1,1-)trifluoropentane 2- (4-t-butylphenyl)-5-(3-phenoxyphenyl)-1,1,l-trifluoropentane 2(4-i -propylphenyl) -5-(3-phenoxyphenyl)-1,1,1-trifluoropentane 2-(4-ethylphenyl)-5-(3-phenoxyphenyl)-1,1,1-)trifluoro Benkun 2-(4-methylphenyl')-5-(3-phenoxyphenyl)-1,1,1-trifluoropentane 2-(4-)lifluoromethylphenyl)-5-(3-
phenoxyphenyl)-1,1,1-trifluoropentane 2-(4-pentafluoroethylphenyl)-5-(3
-phenoxyphenyl)-1,1,1-trifluoropentane2-(4-difluoromethoxyphenyl)-5-(3-
phenoxyphenyl)-1,1,1-trifluoropentane2-(4-)lifluoromethoxyphenyl)-5-(3
-phenoxyphenyl)-1,l,1-trifluoropentane2- (4-(2-7"ropenyloxy)phenyl)-
5-(3-phenoxyphenyl)-1,1゜1-trifluoropentane 2- (4-(3-butenyloxy)phenyl)-5-
(3-phenoxyphenyl)-1,1,1-trifluoropentane 2- (3,4-methylenedioxyphenyl)-5-(
3-phenoxyphenyl)-1,1,1-trifluoropentane 2-(5-indanyl)-5-(3-phenoxyphenyl)-1,1,1-trifluoropentane 2-phenyl-5-(3- phenoxyphenyl)-1,
1,1-)lifluoropentane 2-(3-1lifluoromethoxyphenyl)-5-(3-phenoxyphenyl)
-1,1,1-trifluoropentane 2-(3-chlorophenyl'I -5-(3-phenoxyphenyl)-1,1,1-)lifluoropentane 2-(3-fluorophenyl)-5- (3-phenoxyphenyl)-1,1,1-)lifluoropentane 2-(3-methylphenyl)-5-(3-phenoxyphenyl)-1,1,1-)lifluoropentane 2-(3- chloro-4-ethoxyphenyl) = 5-(3
-phenoxyphenyl'I-1,1,1-trifluoropentane 2- (3,4-dichlorophenyl)-5-(3-phenoxyphenyl)-1,1,1-trifluoropentane 2-(3-fluoro- 4-ethoxyphenyl)-5-(
3-phenoxyphenyl)-1,1,1-trifluoropentane 2-(3-difluoromethoxyphenyl)-5-(3-
phenoxyphenyl)-1,1,1-trifluoropentane 2-(4-ethoxyphenyl)-5-(4-fluoro-
3-phenoxyphenyl)-1,1,1=trifluoropentane 2-(4-i-propylphenyl)-5-(4-fluoro-3-phenoxyphenyl)-1,1゜1-trifluoropentane 2- (4-t-butylphenyl)-5-(4-fluoro-3-phenoxyphenyl)-1,1゜1-trifluoropentane2-(4-methoxyphenyl)-5-(4-fluoro-3-phenoxy phenyl)-1,1,1-trifluoropentane 2-(4-!-lifluoromethylphenyl)-5-(4
-fluoro-3-phenoxyphenyl)-1,1,1-
) Lifluoropentane 2-(4-pentafluoroethylphenyl)-5-(4
-fluoro-3-phenoxyphenyl)-1,1,1-
) Lifluoropenkun 2-(4-difluoromethoxyphenyl)-5-(4-
Fluoro-3-phenoxyphenyl)-1,1,l-)
Lifluoropentane 2-(4-trifluoromethoxyphenyl)-5-(4
-fluoro-3-phenoxyphenyl)-1,1,1-
Trifluoropentane 2-(4-(2-propenyloxy)phenyl)-5
-(4-fluoro-3-phenoxyphenyl)-1,1
, l-trifluoropentane 2-(3,4-methylenedioxyphenyl)-5-(4-fluoro-3-phenoxyphenyl)-1,1,1-)lifluorobencune 2-phenyl-5-( 2-(5-indanyl)-5-(4-fluoro-3-phenoxyphenyl)-1,1,1- ) Lifluoropenkun 2-(3-)Lifluoromethylphenyl)-5-(4-
Fluoro-3-phenoxyphenyl)-1,1,1-)
2-(3-fluorophenyl)-5-(4-fluoro-
3-phenoxyphenyl)-1,1,1-trifluoropentane 2=(3-chloro-4-ethoxyphenyl)-5-(4
-fluoro-3-phenoxyphenyl)-1,1,1-
) trifluoropentane 2-(3,4-dichlorophenyl)-5-(4-fluoro-3-phenoxyphenyl)-1,1゜1-trifluoropentane 2-(3-difluoromethoxyphenyl)-5-(4 −
Fluoro-3-phenoxyphenyl)-1,1,1-1
-Lifluorobencune The compound of the present invention can be produced, for example, by the following method. That is, (Production method A) General formula (ff) R' [In the formula, R'1 and R'z are the same or different, hydrogen atom, halogen atom, lower alkyl group, lower alkoxyl group, lower haloalkyl group or lower halo It represents an alkoxyl group, or a combination of R/1 and R' represents a methylenedioxy group or a trimethylene group. R1 represents a hydrogen atom or a fluorine atom. ] By reducing the alkene compound represented by the general formula (III) J [wherein R'1, R/, and R3 have the same meanings as above. ] A fluoroalkane compound represented by the following can be produced.

Standard examples include alcohol solvents such as ethanol and methanol, ether solvents such as 1,4-dioxane and tetrahydrofuran, lower fatty acid solvents such as acetic acid and formic acid, hydrocarbon solvents such as toluene, benzene, and xylene, and acetic acid. Presence of a metal catalyst such as a palladium catalyst, rhodium catalyst, ruthenium catalyst, nickel catalyst, or platinum catalyst in an ester solvent such as ethyl or methyl acetate, or an acid anhydride solvent such as acetic anhydride or propionic anhydride, or in the absence of a solvent. A fluoroalkane compound represented by the general formula (III) is produced by the so-called catalytic reduction method in which the alkene compound represented by the general formula (■) and hydrogen are reacted under water cooling to heating and normal pressure to increased pressure for 1 to 36 hours. can be manufactured. (The catalytic reduction method is described, for example, in "Jikken Chemistry Course Vol. 17 Reactions of Organic Compounds I (Part 2)," page 245, Maruzen.)
Production method B) General formula (TV) J [wherein n represents an integer of 1 or 2, R''1 represents a hydrogen atom, a halogen atom, a lower alkyl group or a lower haloalkyl group, and R3 represents a hydrogen atom or represents a fluorine atom and the compound represented by the general formula (V) R,X (V) [wherein R1
represents a lower alkyl group, a lower haloalkyl group or a lower alkenyl group, and X represents a halogen atom. ] By reacting the compound represented by the formula (VT) in the presence of a base, a compound represented by the general formula (VT) [wherein R'', R1, R3 and n represent the same meanings as above] is produced. Can be done.

Standard solvents include aprotic polar solvents such as dimethylformamide, dimethylsulfoxide, dimethylacetamide, and 1,3-dimethyl-2-imidazolidinone, and ethers such as tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether, and diethylene glycol dimethyl ether. A solvent, a hydrocarbon solvent such as n-hexane, benzene, toluene, xylene, etc. or water is used as a reaction solvent, and a base (e.g., sodium hydride, potassium hydride, lithium hydride, potassium t-butoxy, potassium carbonate, sodium carbonate, sodium hydroxide,
potassium hydroxide, potassium fluoride, cesium fluoride, etc.)
A compound represented by the general formula (TV) and the general formula (
It can be produced by reacting the compound represented by V) with water cooling to heating for 1 to 72 hours. Also,
A phase transfer catalyst such as crown ethers, organic quaternary ammonium salts, phosphonium salts, etc. can also be used in the reaction, if necessary.

The compound of the present invention has optical isomers based on the asymmetric carbon of the benzyl moiety to which the trifluoromethyl group is bonded, and these optical isomers are also included in the present invention.

The compounds represented by general formulas (n) and (rV) used in production methods A and B are new substances, and can be produced, for example, as follows.

■ Production of a compound represented by general formula (II) [wherein R
'3, R'2, R1 and X have the same meanings as above. That is, a phenoxyphenylpropyl halide derivative and triphenylphosphine are typically mixed in an inert gas atmosphere in the presence of a solvent or in the absence of a solvent for 1 to 30 hours.
A phosphonium salt is produced by reacting at 20 to 200°C, and the liquid salt is reacted with a base (e.g., n-butyllithium, 5ec-butyllithium, phenyllithium, t-butoxypotassium, etc.) for 20 minutes to 6
A phosphorane derivative is obtained by reacting at -50°C to room temperature for an hour, and α, α, α-
Trifluoroacetophenone derivative for 1 to 72 hours, -
By reacting at 50°C to room temperature, general formula (n)
A compound represented by can be produced.

■ Production of a compound represented by the general formula (rV) [wherein R
1 and n have the same meanings as above. That is, the methyl ether derivative is typically mixed with boron tribromide in the presence of a halogenated solvent (e.g. dichloromethane, carbon tetrachloride, etc.) under an inert gas atmosphere. ~36 hours, -2
By reacting at 0°C to room temperature, the general formula (rV)
A compound represented by can be produced.

Hereinafter, the compounds of the present invention will be explained in more detail with reference to Examples and Table 1, but the compounds of the present invention are not limited to these examples.

Example 1 (Production of compound fi+ of the present invention by production method A) 0.50 g of 2-(4-chlorophenyl)-5-(3-phenoxyphenyl')-1,1,1-)lifluoro-2-pentene was added to ice. It was dissolved in 30 ml of acetic acid, 0.24 g of 10% palladium-carbon was added to form a suspension, and the mixture was shaken at room temperature under a hydrogen atmosphere for 10 hours. After the catalyst was filtered off and washed with toluene, the filtrate and washing liquid were combined, and the solvent was distilled off under reduced pressure. The residue was subjected to silica gel column chromatography, developing solvent: n-hexane:ethyl acetate-25:L), and the desired 2-(4-chlorophenyl)-5-(3-phenoxyphenyl)-1,1,1-
) 0.46 g of refluoropentane was obtained. n ” '
1.5380'H-NMR (deuterated chloroform solvent, TM
S internal standard) δ value (pp m) 1.10-2.15 (m, 4H
)2.55 (t, 2+ri 3.20(s, l11
) 6.60 to 7.45 (@, 13H) -9F-NMR (deuterochloroform solvent, trifluoroacetic acid external standard) δ value (P pm) +10.1 (d, J = 10H2
) Example 2 (Production of compound (2) of the present invention by production method A) 2-(4-chlorophenyl)-5-(4-fluoro-
Dissolve 1.80 g of 3-phenoxyphenyl)-1,1,1-trifluoro-2-pentene in 4 liters of glacial acetic acid,
0% palladium-carbon2. Og was added to form a suspension, and the mixture was shaken at room temperature for 3 hours under a hydrogen atmosphere. After separating the catalyst by filtration and washing with toluene, the filtrate and washing liquid were combined.
The solvent was distilled off under reduced pressure. The residue was subjected to silica gel column chromatography to obtain the desired 2-(4-chlorophenyl)-5-(4-fluoro-3-phenoxyphenyl)-1, 0.46 g of 1,1-trifluoropentane was obtained -n''1.5294'H-NMR (weight oo form solvent, TMS internal standard!
ri δ i direct (p p m) 1.12~2.2
0 (s, 4H) 2.53 (bt, 2) 1)
6.61-7.46 (m, 12H) 19F-NMR (
Deuterated chloroform solvent, trifluoroacetic acid external standard) δ value (ppm) +11.1 (d, 3F, J=10
Hz)-50,5(a+, IP) Example 3 (Production of the present compound (3) by production method A)
2-(4-chlorophenyl)- used in Example 1
5-(3-phenoxyphenyl)-1゜1.2-(4-fluorophenyl)-5-(3-phenoxyphenyl)-1,1, in place of 1-1-lifluoro-2-pentene
1-) The desired 2-(4
-fluorophenyl)-5-(3-phenoquinphenyl)-1.1.1-1-lifluoropencune 0.48 g was obtained.

no・'1.5350'H-NMR (deuterium chloroform as a medium, TMS internal standard) δ i (IP p m) 1.10~
2.20 (m, 4H) 2.55 (bt, 2H)
3.20 (w, IH) 6.70-7.45 (
m, 13H) 19F-NMR (deuterated chloroform solvent, trifluoroacetic acid external standard δ value (p p m) +10.5 (d, 3F, J-
10Hz) 50.5 (m, IF) Example 4 (Production of compound (5) of the present invention by a manufacturing corporation) 2-(4-chlorophenyl) used in Example 1
-5-(3-phenoxyphenyl)-1゜2-(4-trifluoromethylphenyl)-5-(3-phenoxyphenyl) in place of 1.1-trifluoro-2-pentene
-1,1,1-trifluoro-2-pentene 0.41
1.10% palladium-g and glacial acetic acid.
0.40 g of the target 2-(4-1-lifluoromethylphenyl-1-trifluoropentane) was obtained by the same operation as in Example 1 except that the amount of carbon used was changed to 0.20 g.

nZ&・'1.5108'H-NMR (weight oo form solvent, TMS internal standard) δ value (ppm) 1.10-2.15 (m.4H
)2,55 (bt,2H) 3.20
((ltl)6, 65-7.60 (m, 138) "F-NMR (deuterochloroform solvent, trifluoroacetic acid external standard) δill (pp pm) +10.0 (d.3F,
J=1011z)+16.8 (s, 3F) Example 5 (Production of the present compound (7) by production method A)
2-(4-chlorophenyl)- used in Example 2
5-(4-fluoro-3-phenoxyphenyl)-1
．． 1.1-) 2-( instead of refluoro-2-pentene
4-ethoxyphenyl)-5-(3-phenoxyphenyl)-1.1.1-trifluoro-2-pentene2.
By the same operation as in Example 2 except that 19 g was used,
Target 2-(4-ethoxyphenyl)-5- (3
1.71 g of -)-1.1.1-)refluoropentane was obtained. rl t′” 1.54
01'H-NMR (deuterated chloroform solvent, TMS internal standard) δ value (p p m) 1.38 (t,3H)2,
51 (bt, 2H) 2.80~3.45 (m
, IH) 3, 82 (q, 2H) 6.6
1 to 7.40 (m.13H) 19F-NMR (deuterated chloroform solvent, trifluoroacetic acid external standard) δ value (pl) m) +11.3 (d, J = 10Hz)
Example 6 (Production of compound (8) of the present invention by production method A)
2-(4-chlorophenyl)- used in Example 2
5-(4-fluoro-3-phenoxyphenyl)-1
．． 1.1-) 2-( instead of refluoro-2-pentene
4-ethoxyphenyl)-5-(4-fluoro-3-phenoxyphenyl)=1,1.1-trifluoro-2-
The desired 2-(4-ethoxyphenyl)-
5-(4-fluoro-3-phenoxyphenyl)-1.

1.61 g of 1,1-trifluoropentane was obtained.

n'''1.5329'H-NMR (weight oo form solvent, TMS internal standard) δ value (ppm) 1.40 (t, 311) 2, 54
(bt, 2H) 3.86 (q, 2) 1) 6, 6
1-7.42 (s.12H) "F-NMR (deuterochloroform solvent, trifluoroacetic acid external standard) δ value (p p m) +10.8 (d,3F,J=
10Hz) 51,5 (s, IF) Example 7 (Production of Compound 0 of the Present Invention by Production Method A) 2-(4-chlorophenyl)-5 used in Example 1
- (3-phenoxyphenyl)-1.

2-(4
-methoxyphenyl)-5- (3-phenoquinphenyl)-1.1.1-4lifluoro-2-pentene 3.0
The desired 2-(4-methoxyphenyl) was prepared in the same manner as in Example 1, except that the amount of glacial acetic acid was changed to 501.10% palladium-carbon and 1.0 g.
2.9 g of -5-(3-phenoxyphenyl)-1,1,1-)lifluoropentane was obtained. n g"'t,
54ts'H-NMR (deuterated chloroform solvent, TMS internal standard) δ value CpI) m) 1.10 to 2.20 (m, 4
H) 2.55 (bt, 2H) 3.10 (m,
IH) 3.90 (s, 3N) 6.70
~7.50 (s, 13H) I9F-NMR (deuterochloroform solvent, trifluoroacetic acid external standard) δ value (p p m) +to, o (d, J-10H
z) Example 8 (Production of the compound of the present invention @ by a manufacturing corporation)
2-(4-chlorophenyl)- used in Example 1
2-(3,4-methylenedioxyphenyl)-5-(3-phenoxyphenyl) in place of 5-(3-phenoxyphenyl)-1゜1.1-)lifluoro-2-pentene
-1,1,1-trifluoro-2-pentene 0.50g
Example 1 except that the reaction time was changed to 2 hours.
By the same operation as above, 0.46 g of the target 2-(3,4-methylenedioxyphenyl)-5-(3-phenoxyphenyl)-1,1,1-trifluoropentane was obtained. n24・'1.5519'H-NMR (deuterated chloroform solvent, TMS internal standard) δ value (ppm) 1.10-2.10 (w, 48)2
．． 55 (bt, 2H) 3.15 (m
, IH) 5.80 (s, 2H) 6.60-7.
35 (s+, 1211)"F-NMR (, deuterated chloroform solvent, trifluoroacetic acid external standard) δ value (p p m) +10.6 (d, J = 10H
z) Example 9 (Production of the present compound 0η by a manufacturing corporation) 2-(4-chlorophenyl) used in Example 1
-5-(3-phenoxyphenyl)-1゜2-(4-methylphenyl") -5-(3-phenoxyphenyl)-1,1 in place of 1.1-trifluoro-2-pentene
, using 0.50 g of 1-trifluoro-2-pentene,
Also, add 20-1.10% palladium-carbon to 0.0% glacial acetic acid.
The desired 2-(4-methylphenyl)-5-(
0.49 g of 3-phenoxyphenyl)-1,1,1-trifluoropentane was obtained. n24・'1.5412'
H-NMR (deuterated chloroform solvent, TMS internal standard) δ value (p p m) 1.10-2.10 (a+,
4H) 2.25 (s, 3B) 2.50 (bt
, 2B) 3.10 (m, IH) 6.65-7.
35 (m, 13H)”F-NMR (deuterated chloroform solvent, trifluoroacetic acid external standard) δI (ppm) +10.0 (d, J = 10Hz
) Example 10 (Production of the present compound (II) by production method A) 2-(4-chlorophenyl)-5-(3-phenoxyphenyl)-1゜1.1-trifluoro-2 used in Example 1 -2-(indane-5 instead of pentene)
-yl)-5-(3-phenoxyphenyl)-1,1,
Using 0.15 g of l-trifluoro-2-pentene, 2 g of glacial acetic acid and 0.10 g of 110% palladium on carbon.
By the same operation as in Example 1 except that the amount used was changed,
0.13 g of the desired 2-(indan-5-yl)-5-(3-phenoxyphenyl)-1,1,1-trifluoropentane was obtained. nt3・'1.5520'H-N
MR (weight Rorojo) LL solvent, TMS internal standard) δ value (p p m) 1.10 to 3.55 (a+,
13H) 6.60-7.60 (fog, 12B) 1'F
-NMR (deuterated chloroform solvent, trifluoroacetic acid external standard t#) δ value (ppm) +12.0 (d, J=10Hz)
Example 11 (Production of G value of the compound of the present invention by production method A)
2-(4-chlorophenyl)- used in Example 1
5-(3-phenoxyphenyl)-1゜1.2-(3-)lifluoromethylphenyl)-5-(3-phenoxyphenyl) in place of 1-1-lifluoro-2-pentene
-1,1,1-trifluoro-2-pentene 0.70g
The desired 2-(3-trifluoromethylphenyl 1- 0.49 g of trifluoropentane was obtained.

n Z 3・'1.5139'H-NMR (deuterated chloroform solvent, TMS internal standard) δ value (1) pm) 1.15-2.30 (m,
4H) 2,54 (bt, 2H) 3.25 (m
, IH) 6,70-7.70 (m, 13H) 1qF-NMR (deuterochloroform solvent, trifluoroacetic acid external standard) δ value Cppm) +10.8 (d, 3F) +17.
6 (s, 3F) Example 12 (Production of the present compound on according to the production method)
Under a nitrogen atmosphere, 43 mg of sodium hydride (60% oil dispersion, hereinafter) was suspended in dry tetrahydrofuran 5-1, and 2-(4-hydroxyphenyl)-5-(3-phenoxyphenyl) was added to the suspension. )-1
．． 1.1-1-Lifluorobencune 0.40 g and allylpromide 0.40 g were dried in tetrahydrofuran 1
The solution dissolved in 0 ml was added dropwise while cooling with water. 2 at room temperature
After further stirring at 40°C for 48 hours, the reaction solution was poured into dilute hydrochloric acid-ice water and extracted twice with diethyl ether. The ether layers were combined, washed with saturated brine, dried over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure, and the residue was subjected to silica gel column chromatography using the developing solvent Hn.
-hexane:ethyl acetate-20:l), the desired 2-
(4-allyloxyphenyl)-5-(3-phenoxyphenyl)-1.1.1-trifluoropentane0.
39g was obtained. n! 4・'1.5369'H
-NMR (deuterated chloroform solvent, TMS internal standard) δ value (ppm) 1.10-2.10 (m, 4H)2
, 50 (bt, 28) 3.10 (禦, IH)
4, 40-4.50 (w, 2H) 5.10-5.
45 (m, 2H) 6,00 (w.LH)
6.65~7.40 (m, 13H)”F-NM
R (deuterated chloroform solvent, trifluoroacetic acid external standard) δ value (ppm) +10.5 (d, J = lOHz)
Example 13 (Production of compound α of the present invention by production method B)
Under a nitrogen atmosphere, 31-g of sodium hydride was suspended in 10 pieces of dry tetrahydrofuran, and 2=(4-
A solution prepared by dissolving 0.30 g of (hydroxyphenyl)-5-(3-phenoxyphenyl)-1.1.1-)lifluoropentane and 0.50 g of isopropylioside in 101 ml of dry tetrahydrofuran was added dropwise under water cooling. After stirring at room temperature for 2 hours and at 50°C for 4 days, the reaction solution was poured into dilute hydrochloric acid-ice water and extracted twice with diethyl ether. The ether layers were combined, washed with saturated brine, dried over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure, and the residue was subjected to silica gel column chromatography (developing solvent: n-hexane: ethyl acetate = 20:1). The desired 2-(4-isopropyloxyphenyl)-5-(
3-phenoxyphenyl)-1. 1. 0.39 g of 1-drifluorobentane was obtained.

n 2 4°'1.5360'H-NMR (deuterated chloroform solvent, TMS internal standard) δ (direct (pp m) 1.10-2.10
(m.4H) 1, 26 (s, 31) 1.3
6 (s, 3H) 2, 55 (bt, 2H) 3.1
5 axes. IH) 4,50 (dt.IH) 6.65
~7.50 (m, 1311)"F-NMR (deuterated chloroform solvent, trifluoroacetic acid external standard) δ value (ppm) + 8.8 (d, J = 10Hz)
Example 14 (Production of compound α of the present invention by production method B) 2-(4-hydroxyphenyl)-5-(3-phenoxyphenyl)-1.1.1-1-'J fluorobencune 0.50 g was dissolved in 8+el of 1,4-dioxane, and 81 g of a 45% aqueous sodium hydroxide solution and 0.06 g of benzyltriethylammonium chloride were added.

Chlorodifluoromethane gas was passed through the reaction solution, and the mixture was stirred at 50°C for 1 hour. The reaction solution was poured into ice water and extracted twice with diethyl ether. The ether layers were combined, washed with saturated brine, dried over anhydrous magnesium sulfate, and then the solvent was distilled off under reduced pressure. The residue was subjected to silica gel column chromatography, and the developing solvent was Hn-hexane:ethyl acetate-20:
1), the target 2-(4-difluoromethoxyphenyl)-5-(3-phenoxyphenyl)-1,1,1-
0.33 g of trifluoropentane was obtained. n”'1.
5237'H-NMR (deuterated chloroform solvent, T
MS internal standard) - δ (direct (f) p m) 1.25-2.20
(m, 4) 1) 2.53 (bt, 2H) 3.2
0 (+w, LH) 6.38 (t, IH)
6.60~7.40 (-,13H)”F-NM
R (deuterated chloroform solvent, trifluoroacetic acid external standard) δ value (pi)m) +9.8 (d, 3F, J-10H
z)-18,0 (d, 2F, J-75Hz) Example 15
(Production of compound (21) of the present invention according to the production method) 2-(3-chloro-4-hydroxyphenyl) in a nitrogen atmosphere
-5-(4-fluoro-3-phenoxyphenyl)-1
, 1.2 g of 1,1-trifluoropentane was dissolved in dry dimethylformamide, and 1.2 g of sodium hydride was dissolved under water cooling.
09g seaweed was added little by little. The mixture was stirred at room temperature for 30 minutes, and a solution of 470a+g of ethyl iosite dissolved in 3 ml of dry dimethylformamide was added dropwise while cooling with water. 2 at room temperature
After stirring for 2 hours, the reaction solution was poured into dilute hydrochloric acid-ice water and extracted twice with diethyl ether. The ether layers were combined, washed with saturated brine, dried over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure, and the residue was subjected to silica gel column chromatography (developing solvent: n-hexane:ethyl acetate-30:1). Target 2-(3-chloro-4-ethoxyphenyl)-5-(4-fluoro-3-phenoxyphenyl)-1゜1.1-)lifluoropencune 0.9
8 g was obtained.

n'''1.5411'H-NMR (deuterated chloroform solvent, TMS internal standard) δ value (p p m) 1.45 (t, 3H) 2.5
5 (bt, 28) 4.05 (q, 2H)6.
6'? "7.50 (s, IIH)" F-NMR (deuterochloroform solvent, trifluoroacetic acid external standard) δ value (+) pm) +11.0 (d, 3F, J-10
Hz) -52,7(++, IF) Reference Example 1 Production of (3-(3-phenoxyphenyl)propyl)triphenylphosphonium bromide 3-(3-phenoxyphenyl)propyl bromide 15
．． Mix 0g and 14.86g of triphenylphosphine,
The reactant was kept at 170-180°C for 3 hours, cooled to room temperature, and then ground. The white solid obtained was washed with diethyl ether and dried to obtain the desired (3-(3-phenoxyphenyl)propyl) trifluoride. Phenylphosphonium bromide 25
J1g was obtained. Melting point: 194°C Reference example 22-(4-chlorophenyl)-5-(3-phenoxyphenyl)-1,1
, Production of 1-trifluoro-2-pentene Under a nitrogen atmosphere, 3.4 g of 3-(3-phenoxyphenyl)propyltriphenylphosphonium bromide was suspended in dry tetrahydrofuran 20s+1, and an n-butyllithium hexane solution (1,51 MtIF liquid) 3.5ml
was added dropwise at -50°C. 5 hours after the addition, stirring was continued for 30 minutes, and stirring was further continued at -15°C for 15 minutes, then -70°C.
At ℃, a solution of 1.0 g of 4-chloro-α,α,α-trifluoroacetophenone dissolved in 10-1 dry tetrahydrofuran was added dropwise, and the temperature was raised to room temperature over 5 hours after the dropwise addition. 6. N-hexane was added to the reaction solution. was added, the precipitate was filtered off, and the precipitate was washed with n-hexane. The filtrate and washing liquid were combined and the solvent was distilled off under reduced pressure, and the residue was subjected to silica gel column chromatography to obtain the target 2-(4-chlorophenyl)-
0.15 g of 5-(3-phenoxyphenyl)-1,1,1-trifluoro-2-pentene was obtained.

n! 3・'1.5630 Kaso H-NMR (deuterated chloroform solvent, TMS internal standard) δ value (p p m) 2.10 to 2.80 (+w,
4H) 5.70-7.45 (■, 14H)”F-N
MR (deuterated chloroform solvent, trifluoroacetic acid external standard) δ value (1) I) m) +14.0 (s) +22
．． 2 (s) Reference Example 32-(4-hydroxyphenyl)-5=(3-
phenoxyphenyl)-1,1゜l-trifluoro-2
-Production of pentane 2-(4-methoxyphenyl')-5
2.60 g of -(3-phenoxyphenyl)-1,1,1-)lifluoro-2-pentane was dissolved in dry dichloromethane 80-1, and 3.25 g of boron tribromide was added dropwise while cooling with water. Stir at room temperature for 1 hour, then stir at 10°C for 2 hours.
After continuing to stir for an hour, the reaction solution was poured into ice water, the dichloromethane layer was separated, and the aqueous layer was further extracted with dichloromethane. The dichloromethane layers were combined, washed with saturated brine, dried over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure, and the residue was subjected to silica gel column chromatography to obtain the desired amount. 2-(4-hydroxyphenyl')-5-(3-
phenoxyphenyl)-1,1,1-trifluoro-2
- 1.80 g of pentane were obtained. n■・'1.5552'H-NMR (weight oo form solvent, TMS internal standard) δ value (+) pm) 1.15-2.20 (+*,
4H) 2.52 (t, 21) 3.10 (m, I
H) 5.31 (s, IH) 6.60-7.42
(m, 13H)”F-NMR (deuterated chloroform solvent, trifluoroacetic acid external standard) δ value (pl) m) +10.8 (d, J=10tlz
) Reference Example 4 Production of 4-ethoxy-α,α,α-trifluoroacetophenone J, Agr, Food Ches, Vol. 22.1
), 926 (1974), using 4-ethoxybromobenzene as a starting material, 4-ethoxy-α,α, α-Trifluoroacetophenone was produced. b, p, 116-117℃ (12
wa+Hg)'H-NMR (deuterated chloroform solvent, TM
S internal standard) δ value (p p m) 1.47 (t, 3o) 4.1
5 (q, 2H) 7.00 (d, 2) 1) 8.0
7 (bd, 28) Reference Example 5 Production of 4-chloro-α,α,α-trifluoroacetophenone Under a nitrogen atmosphere, 70 g of p-bromobenzene was suspended in dry tetrahydrofuran 4001, and n-butyllithium hexane solution (1,5 M Solution) 245 ml was added dropwise at -60°C. After the addition, it was stirred at -60°C for 1 hour, and then -
After continuing stirring at 50°C for 2 hours, a solution of 62.3 g of ethyl trifluoroacetate dissolved in dry tetrahydrofuran 601 was added dropwise at -60°C, and after the dropwise addition, the mixture was stirred at the same temperature for 1 hour, and then the temperature was raised to 0°C. .

The reaction solution was poured into dilute hydrochloric acid-ice water, and diluted with diethyl ether.
After extraction, the ether layer was washed with saturated brine, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure.
Chloro-α,α,α-trifluoroacetophenone 47
．． 5g was obtained.

b, p, 80-b When the compound of the present invention is used as an active ingredient of an insecticide or acaricide, it may be used as it is without adding any other ingredients, but it is usually a solid carrier, a liquid carrier, It can be mixed with gaseous carriers, surfactants, other formulation auxiliaries, baits, etc., or impregnated into the base material of incense sticks or mats to produce emulsions, wettable powders, powders, granules, oils, aerosols, and mosquito repellents. It is used in formulations as heating fumigants for incense sticks, electric mosquito repellents, etc., fogging agents for fogging, non-heating fumigants, poison baits, etc.

In these preparations, the content of the compound of the present invention as an active ingredient is 0.01 to 95% by weight. Solid carriers include fine powders or granules such as kaolin clay, attapulgite clay, bentonite, acid clay, pyrophyllite, talc, diatomaceous earth, calcite, corn cob powder, walnut shell powder, urea, ammonium sulfate, and synthetic hydrous silicon oxide. Liquid carriers include kerosene, aliphatic hydrocarbons such as kerosene, benzene, toluene, xylene,
Aromatic hydrocarbons such as methylnaphthalene, halogenated hydrocarbons such as dichloroethane, trichloroethylene, carbon tetrachloride, alcohols such as ethylene glycol and cellosolve, acetone, methyl ethyl ketone, cyclohexanone,
Ketones such as isophorone, ethers such as diethyl ether, dioxane, and tetrahydrofuran, esters such as ethyl acetate, nitrites such as acetonitrile and isobutyronitrile, acid amides such as dimethylformamide and dimethylacetamide, dimethyl sulfoxide, soybean oil, cottonseed oil, etc. Examples include vegetable oil. Examples of the gaseous carrier include chlorofluorocarbon gas, LPG (liquefied petroleum gas), dimethyl ether, and the like. Surfactants used for emulsification, dispersion, wet layer, etc. include alkyl sulfate ester salts, alkyl (aryl) sulfonates, dialkyl sulfosuccinates, polyoxoethylene alkylaryl ethers,
Phosphate ester salts, anionic surfactants such as naphthalene sulfonic acid formalin condensates, polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene block copolymer, sorbitan 11 fatty acid esters,
Examples include nonionic surfactants such as polyoxyethylene sorbitan fatty acid ester. Formulation aids such as fixing agents and dispersants include lignin sulfonate, alginate, polyvinyl alcohol, gum arabic, molasses, casein, gelatin, CMC (carboxymethylcellulose), pine oil, agar, etc., and are stable. As an agent, PA
P (isopropyl acid phosphate), alkyl phosphates such as TCP (tricresyl phosphate), vegetable oils, epoxidized oils, the above-mentioned surfactants, antioxidants such as BHT and BHA, fatty acids such as sodium oleate and calcium stearate. Examples include salts, fatty acid esters such as methyl oleate and methyl stearate.

Examples of formulations are shown below. Parts are parts by weight. In addition, the compounds of the present invention are indicated by compound numbers in Table 1.

Formulation Example 1 0.2 parts of each of the compounds (1) to (37) of the present invention, 2 parts of xylene and 97.8 parts of white kerosene were mixed to obtain an oil solution! - Formulation Example 2 10 parts each of the compounds (1) to (37) of the present invention, 14 parts of polyoxyethylene styrylphenyl ether, 6 parts of calcium dodecylbenzenesulfonate, and 70 parts of xylene
Mix well to obtain an emulsion.

Formulation Example 3 20 parts of the present compound (1), 10 parts of fenitrothion,
3 parts of calcium lignin sulfonate, 2 parts of sodium lauryl sulfate, and 65 parts of synthetic hydrous silicon oxide are thoroughly ground and mixed to obtain a wettable powder.

Formulation Example 4 1 part of the compound (8) of the present invention, 2 parts of carbaryl, 87 parts of kaolin clay and 10 parts of talc are thoroughly ground and mixed to obtain a powder.

Formulation Example 5 5 parts of the compound of the present invention (5), 1 part of synthetic hydrous silicon oxide, 2 parts of calcium lignosulfonate, 30 parts of bentonite, and 62 parts of kaolin clay were thoroughly ground and mixed, water was added, and the mixture was thoroughly kneaded. The granules are dried to obtain granules.

Formulation Example 6 0.05 parts of the compound of the present invention (7), 0.05 parts of tetramethrin.
2 parts of resmethrin, 0.05 parts of xylene, and 32.7 parts of deodorized kerosene are mixed and dissolved, and the mixture is filled into an aerosol container.
After installing the valve part, 60 parts of propellant (liquefied petroleum gas) is pressurized and filled through the valve part to obtain an aerosol.

Formulation Example 7 Add 0.3 g of the d-) lance isomer of allethrin to 0.3 g of the compound (3) of the present invention, dissolve in 20 ml of methanol,
After stirring and mixing uniformly with 99.4 g of carrier for mosquito coil (Tab powder: lees powder: wood flour mixed at a ratio of 3:5:1), methanol was evaporated, water 1501 was added, and the mixture was thoroughly kneaded. If you mold something and dry it, you can get mosquito coils.

These preparations can be used as they are or diluted with water. In addition, other insecticides, acaricides, nematicides, fungicides,
It can also be used in combination with herbicides, plant growth regulators, fertilizers, soil conditioners, etc.

When the compound of the present invention is used as an insecticide or acaricide, the application amount is usually 5 g to 500 g per 10 ares, and when the emulsion, wettable powder, etc. is diluted with water and applied, the application concentration is 1 Q ppm. ~1000 pp+m, and powders, granules, oils, aerosols, etc. are applied as they are without any dilution.

Next, a test example is shown. The compounds of the present invention are indicated by the compound numbers in Table 1, and the compounds used for comparison are indicated by the compound symbols in Table 2.

Table 2 Test Example 1 An emulsion of the following invention compound obtained according to Formulation Example 2 was mixed with water for 3. It was diluted to sppm. Diluted liquid 100m
1 was placed in a 180 ml polycup, and 20 final instar Culex Culex larvae were released. The survival and death of the animals was investigated on the day after release.

After that, food was added to each plot, and when all the untreated plots had emerged, the inhibition rate of emergence was investigated.

The mortality rate and emergence inhibition rate were each divided into the following three levels and displayed.

The results are shown in Table 3.

Table 3 Test Example 2 A 200-fold diluted solution (equivalent to 500 ppm) of an emulsion of the compound of the present invention below with water obtained according to Formulation Example 2 was added to 13
Soaked in artificial feed for Spodoptera g, diameter 11
It was placed in a sterile polyethylene cup. Ten 4th instar Spodoptera larvae were released into the larvae, and after 6 days, the survival rate was determined by examining whether they were alive or dead (2 repetitions).

The results are shown in Table 4.

Table 4 Test Example 3 A 667-fold dilution with water of an emulsion of the following invention compound and control compound obtained according to Formulation Example 2 (150ppa
Rice stems (approximately 12 cm long) were soaked in the same solution for 1 minute.

After air-drying, the rice stems were placed in test tubes, 10 adult leafhoppers of a resistant strain were released, and one day later, the survival rate was determined by examining whether they were alive or dead (two repetitions).

The results are shown in Table 5.

Table 5 Test Example 4 A 2000-fold dilution with water of an emulsion of the following inventive compound and control compound obtained according to Formulation Example 2 (50PP-
(equivalent) 1-1 was soaked into 5 g of artificial feed for snails prepared in a polyethylene cup with a diameter of 5.5 cm. They released 10 10-day-old nymph moth larvae into it.
After 8 days, the animals were examined for survival and the survival rate was determined (2 repetitions).

The results are shown in Table 6.

Table 6 Test Example 5 Seven days after sowing, potted green beans (first leaf stage) were given -
10 adult female spider mites per leaf, 2
It was stored in a constant temperature room at 5°C.

After 6 days, the emulsion of the compound of the present invention and the control compound obtained according to Formulation Example 2 was diluted with water so that the active ingredient was 500 pp-, and 10 μl per pot was sprayed on a turntable. -1 was irrigated into the soil. Eight days later, the degree of damage caused by spider mites to the green beans was investigated.

The degree of damage was divided into the following three levels.

-No damage is detected in case 2. +: Slight damage is observed.

++: Damage similar to non-processing is observed.

The results are shown in Table 7.

Table 7

Claims (4)

[Claims] (1) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ [In the formula, R_1 and R_2 are the same or different, hydrogen atom, halogen atom, lower alkyl group, lower alkoxyl group, lower haloalkyl group, lower haloalkoxyl group, or It represents a lower alkenyloxy group, and R_1 and R_2 combine to represent a methylenedioxy group or a trimethylene group. R_3 represents a hydrogen atom or a fluorine atom. ] A fluoroalkane compound represented by (2) General formula ▲ Numerical formulas, chemical formulas, tables, etc. Represents a haloalkoxyl group. Further, R'_1 and R'_2 combine to represent a methylenedioxy group or a trimethylene group. R_3 represents a hydrogen atom or a fluorine atom. ] There are general formulas ▲ mathematical formulas, chemical formulas, tables, etc. that are characterized by reducing the alkene compound represented by ▼ [In the formula, R′_1, R′_2, and R_3 represent the same meanings as above. ] A method for producing a fluoroalkane compound shown by. (3) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. represents a hydrogen atom or a fluorine atom.] Compounds represented by the general formula R_5X [wherein R_5 represents a lower alkyl group, lower haloalkyl group, or lower alkenyl group, and X represents a halogen atom] There are general formulas ▲ mathematical formulas, chemical formulas, tables, etc., characterized by reacting with and in the presence of a base ▼ [In the formula, R″_1, R_3, R_5 and n represent the same meanings as above. ] A method for producing a fluoroalkane compound shown by. (4) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. Represents a lower alkenyloxy group. Further, R_1 and R_2 combine to represent a methylenedioxy group or a trimethylene group. R_3 represents a hydrogen atom or a fluorine atom. ] An insecticide and acaricide characterized by containing a fluoroalkane compound represented by the following as an active ingredient.