JP3139802B2 - A novel cyclopropanecarboxylic acid ester derivative, and an insecticide and acaricide containing the same. - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel cyclopropanecarboxylic acid ester derivative, and an insecticide and a killer containing the same .
It is related to mites .

[0002]

BACKGROUND OF THE INVENTION Natural pyrethrins and synthetic pyrethroids of chrysanthemic acid are known to have insecticidal and acaricidal activity. However, the action of these compounds is not always satisfactory in certain fields. on the other hand,
The use of organochlorine pesticides such as BHC and DDT has been banned due to problems such as environmental pollution and chronic toxicity. There is a sign that it is getting serious, and against this background, there has been a long-awaited desire to create new and better insecticides, acaricides and repellents. In particular, some conventional chrysanthenic synthetic pyrethroids applied to clothing pests have disadvantages such as being chemically unstable and affected by metals, and decomposing or polymerizing easily. The development of alternatives is urgent.

[0003]

DISCLOSURE OF THE INVENTION The present invention solves the problems of conventional insecticides, has excellent insecticidal and acaricidal activity, and has chemical stability especially for controlling insect pests on clothing.
This was done to develop a highly safe pyrethroid.

[0004]

Means for Solving the Problems In order to achieve the above object, the present inventors have conducted intensive studies, and as a result, have found a novel cyclopropane carboxylate derivative shown in claim 1 and can put it to practical use. After confirming the above, the present invention was completed. The cyclopropanecarboxylic acid ester of claim 1 according to the present invention is a novel compound,
Representative examples are as follows. In addition, the ester shown in claim 1 has an optical isomer or a geometric isomer based on a steric structure in carboxylic acid and alcohol,
All of these esters are also included in the present invention. The novel cyclopropanecarboxylic acid ester of claim 1 has not only sufficient activity, but also low toxicity to humans and animals, and in addition, does not cause decomposition or polymerization even under the influence of metals. This is extremely advantageous over conventional pyrethroids. Next, synthesis examples of typical examples of the compound described in claim 1 will be described. The synthesis routes thereof are as follows.

Embedded image

Synthesis Example 1 1-vinyl-2-hexynyl 2 ', 2'-dimethyl-
1.93 g of 3 '-(2 "-methyl-1" -propenyl) cyclopropanecarboxylate 1-vinyl-2-hexyn-1-ol
(14 mM) and 1.5 g of triethylamine (15 mM)
Is dissolved in 30 ml of dichloromethane, and cooled under ice-cooling to give 2,2-
2.80 g of dimethyl-3- (2'-methyl-1'-propenyl) cyclopropanecarboxylic acid chloride
mM). The reaction solution was returned to room temperature and stirred for 5 hours, and then the reaction solution was washed with 30 ml of a 5% hydrochloric acid aqueous solution, and further washed with saturated saline solution (30 ml). After the organic layer was dried over magnesium sulfate, dichloromethane was concentrated under reduced pressure, and the resulting oil was purified by silica gel column chromatography (ethyl acetate: hexane = 1: 40) to give 1-vinyl-2 as a colorless oil. -Hexynyl
2 ', 2'-dimethyl-3'-(2 "-methyl-1"-
Propenyl) cyclopropanecarboxylate 3.2
3 g were obtained. (80% yield)

Synthesis Example 1 1-vinyl-2-pentynyl-2 ', 2'-dimethyl-
1.28 g of 3 '-(2 "-methyl-1" -propenyl) cyclopropanecarboxylate 1-vinyl-2-pentyn-1-ol
(10 mM) and 2,2-dimethyl-3- (2'-methyl-1'-propenyl) cyclopropanecarboxylic acid.
68 g (10 mM) was dissolved in dichloromethane (30 ml), N, N-dicyclohexylcarbodiimide (2.27 g, 11 mM) was added thereto at room temperature, and the mixture was stirred at room temperature for 15 hours. The reaction mixture was filtered and the filtrate was concentrated under reduced pressure. The resulting oil was purified by silica gel column chromatography (ethyl acetate: hexane = 1: 30) to give a colorless oil, 1-. Vinyl-2-pentynyl-
2 ', 2'-dimethyl-3'-(2 "-methyl-1"-
Propenyl) cyclopropanecarboxylate 2.2
5 g were obtained. (80% yield)

As an example of the compound used in the present invention,
It is as follows. Compound 1

Embedded image 1-vinyl-2-pentynyl 2 ', 2'-dimethyl-
3 '-(2 "-methyl-1" -propenyl) cyclopropanecarboxylate Compound 2

Embedded image 1-vinyl-2-hexynyl 2 ', 2'-dimethyl-
3 '-(2 "-methyl-1" -propenyl) cyclopropanecarboxylate Compound 3

Embedded image 1-vinyl-2-heptynyl 2 ', 2'-dimethyl-
3 '-(2 "-methyl-1" -propenyl) cyclopropanecarboxylate Compound 4

Embedded image 1-vinyl-2-octynyl 2 ', 2'-dimethyl-
3 '-(2 "-methyl-1" -propenyl) cyclopropanecarboxylate Compound 5

Embedded image 1-vinyl-2-noninyl 2 ', 2'-dimethyl-
3 '-(2 "-methyl-1" -propenyl) cyclopropanecarboxylate Compound 6

Embedded image 1-vinyl-6-chloro-2-hexynyl 2 ', 2'
-Dimethyl-3 '-(2 "-methyl-1" -propenyl) cyclopropanecarboxylate Compound 7

Embedded image Oct-2-en-5-in-4-yl 2 ', 2'-
Dimethyl-3 '-(2 "-methyl-1" -propenyl)
Cyclopropane carboxylate Compound 8

Embedded image 2-methylhept-1-en-4-yn-3-yl
2 ', 2'-dimethyl-3'-(2 "-methyl-1"-
Propenyl) cyclopropanecarboxylate Compound 9

Embedded image Non-2-en-5-yn-4-yl 2 ', 2'-dimethyl-3'-(2 "-methyl-1" -propenyl) cyclopropanecarboxylate Compound 10

Embedded image 2-methyloct-1-en-4-yn-3-yl
2 ', 2'-dimethyl-3'-(2 "-methyl-1"-
Propenyl) cyclopropane carboxylate Compound 11

Embedded image 10-fluorodec-2-en-5-yn-4-yl
2 ', 2'-dimethyl-3'-(2 "-methyl-1"-
Propenyl) cyclopropanecarboxylate Compound 12

Embedded image 2-methylnon-1-en-4-yn-3-yl
2 ', 2'-dimethyl-3'-(2 "-methyl-1"-
Propenyl) cyclopropanecarboxylate Compound 13

Embedded image Undec-2-en-5-yn-4-yl 2 ', 2'
-Dimethyl-3 '-(2 ", methyl-1" -propenyl) cyclopropanecarboxylate Compound 14

Embedded image 2-methyldec-1-en-4-yn-3-yl
2 ', 2'-dimethyl-3'-(2 "-methyl-1"-
Propenyl) cyclopropanecarboxylate Compound 15

Embedded image 1-vinyl-2-pentynyl 2,2,3,3-tetramethylcyclopropanecarboxylate Compound 16

Embedded image 1-vinyl-2-hexynyl 2,2,3,3-tetramethylcyclopropanecarboxylate Compound 17

Embedded image 1-vinyl-2-heptynyl 2,2,3,3-tetramethylcyclopropanecarboxylate Compound 18

Embedded image 1-vinyl-2-pentynyl 2 ', 2'-dimethyl-
3 '-(2 ", 2" -dichlorovinyl) cyclopropanecarboxylate Compound 19

Embedded image 1-vinyl-2-hexynyl 2 ', 2'-dimethyl-
3 '-(2 ", 2" -dichlorovinyl) cyclopropanecarboxylate Compound 20

Embedded image 1-vinyl-2-heptynyl 2 ', 2'-dimethyl-
3 '-(2 ", 2" -dichlorovinyl) cyclopropanecarboxylate Compound 21

Embedded image 1,1,1,3-tetrafluoronon-2-ene-5
In-4-yl 2 ', 2'-dimethyl-3'-(2 "
-Methyl-1 ″ -propenyl) cyclopropanecarboxylate Compound 22

Embedded image 1- (2,2, -difluorovinyl) -2-hexynyl 2 ', 2'-dimethyl-3'-(2 "-methyl-1"
-Propenyl) cyclopropanecarboxylate Compound 23

Embedded image 1- (2,2, -dichlorovinyl) -2-hexynyl
2 ', 2'-dimethyl-3'-(2 "-methyl-1"-
Propenyl) cyclopropanecarboxylate Compound 24

Embedded image 1-vinyl-2-hexynyl 2 ', 2'-dimethylcyclopropanecarboxylate Compound 25

Embedded image 1-vinyl-2-heptynyl 2 ', 2'-dimethyl-
3 '-(1 "-3" -butadienyl) cyclopropanecarboxylate Compound 26

Embedded image Oct-2-en-5-in-4-yl 2 ', 2'-
Dimethyl-3 '-(1 "-propenyl) cyclopropanecarboxylate Compound 27

Embedded image 5,5,5-trifluoro-1-vinyl-pentynyl
2 ', 2'-dimethyl-3'-(2 "-chloro-2"-
Trifluoromethylvinyl) cyclopropanecarboxylate Compound 28

Embedded image 1-vinyl-2-hexynyl 2 ', 2'-dimethyl-
3 '-(2 ", 2" -dibromovinyl) cyclopropanecarboxylate Compound 29

Embedded image 1,1-difluorooct-1-en-4-yne-3-
Yl 2 ', 2'-dimethyl-3'-(2 ", 2" -difluorovinyl) cyclopropanecarboxylate Compound 30

Embedded image 6-methoxyhex-1-en-4-yn-3-yl
2 ', 2'-dimethyl-3'-(2 "-methoxycarbonyl-1" -propenyl) cyclopropanecarboxylate Compound 31

Embedded image 6-ethoxyhex-1-en-4-yn-3-yl
2 ', 2'-dimethyl-3'-(2 "-methyl-1"-
Propenyl) cyclopropanecarboxylate

The compounds used in the present invention include agricultural pests such as flies, mosquitoes, cockroaches, etc. as well as planthoppers, leafhoppers, armyworms, moths, oysters, aphids, may insects, spider mites and the like. It is very effective for controlling pests such as insect pests, acarid mites, prickles, and elephants, as well as clothing pests such as iga, koiga, himemarukabuushimushi and himekatuobushimushi, and animal parasitic lice and ticks. Since the compound of the present invention not only knocks down pests and causes death, but also has repellency and also has an action of repelling pests from hosts, it can be put to practical use in various dosage forms.

[0009] The insecticide and acaricide of the present invention include N-octylbicycloheptenecarboximide (trade name: MG).
K-264), a mixture of N-octylbicycloheptenecarboximide and an aryl sulfonate (trade name M
GK-5026), synepiline 500, octachlorodipropyl ether, piperonyl butoxide and the like can further enhance the insecticidal effect. The compound of the present invention is excellent in chemical stability to metals, but is characterized by 2,6-di-tert-butyl-4-methylphenol (BHT), Yoshinox 425, 2,6
- adding a phenolic or antioxidant amine such as di-tert-butylphenol are useful in increasing the stability over time of the compound of the present invention. Also, other insecticides such as organophosphorus agents such as fenitrothion, DDVP, diazinon, NAC, MTMC, BPMC, P
By mixing a carbamate agent such as HC, pyrethrin, allethrin, phthalthrine, phenothrin, permethrin, empentrin and other conventional pyrethroid-based insecticides or fragrances, deodorants, bactericides, etc., a multipurpose composition having excellent efficacy can be obtained. Therefore, labor saving and synergistic effect between drugs can be expected.

Next, examples and test results of the effects are shown to clarify that the compounds used in the present invention are excellent.

[0011]

Example 1 White kerosene was added to 0.3 part of the compound (1) of the present invention to obtain a 0.3% oil solution with the whole being 100 parts.

[0012]

EXAMPLE 2 White kerosene was added to 0.2 part of the compound (2) of the present invention and 0.8 part of piperonyl butoxide to give a total of 10 parts.
An oil solution was obtained as 0 parts.

[0013]

Example 3 To 20 parts of the compound (3) of the present invention, 10 parts of Solpol SM-200 (trade name of Toho Kagaku) and 70 parts of xylol were added and mixed with stirring to obtain a 20% emulsion.

[0014]

Example 4 0.4 part of the compound (4) of the present invention, 0.1 part of resmethrin, 1.5 parts of octachlorodipropyl ether
The resulting solution was dissolved in 28 parts of refined kerosene, filled in an aerosol container, and a valve portion was attached. Then, 70 parts of a propellant (liquefied petroleum gas) was charged under pressure through the valve portion to obtain an aerosol.

[0015]

Example 5 Compound (5) of the present invention (0.5 g), BHT0.
5 g was uniformly mixed with 99.0 g of a mosquito coil base material such as pyrethrum extract meal powder, wood flour, and starch powder, and a mosquito coil was obtained by a known method.

[0016]

Example 6 0.03 g of the compound (11) of the present invention, 0.15 g of sinepiline 500 and 0.01 g of dibutyl hydroquinone (DBHQ) were impregnated into a cardboard sheet having a thickness of 2 mm, a length of 35 mm and a width of 22 mm to be used for clothing. An insect repellent mat was obtained.

[0017]

Effect Example 1 (70 cm) About 50 adult Culex pipiens were released into a ^three glass chamber, and the compounds of the present invention (1), (3), (4), (6) and (1) obtained in Example 4 were released.
0), (14), (17), (22), (25), (2)
Spraying the aerosols of 8) and (31) allowed more than 80% of the mosquitoes to fall and turn within 10 minutes, and more than 80% were killed the next day.

[0018]

[Effect Example 2] (70 cm) Approximately 50 adult Culex pipiens are released into a ^three glass chamber, and a small battery-powered fan (feather diameter: 13 cm) is set in a box and rotated. Thereupon, the compound of the present invention (2) obtained in Example 5,
(5), (8), (12), (16), (21), (2
5), (29), When ignited at both ends of 0.1 g of mosquito coil, more than 80% of Culex pipiens can fall within 30 minutes, and the next day, more than 80% Was killed.

[0019]

Effect Example 3 1 ml of an acetone solution containing a predetermined amount of a test compound was dropped on a 9 cm-diameter and 2.1 cm-height petri dish, and acetone was air-dried to form a dry film. Similarly, 10 moth larvae were released on a petri dish having a diameter of 9 cm and a height of 2.1 cm, and a 16-mesh wire net was placed on the soil surface, and then the petri dish was treated with the bottom face of the chemical-treated petri dish upward. That is, the knot moths were left for 24 hours so as to be exposed only to the drug paper, and the knockdown status of the test insects was observed. Further, after the exposure was completed, the test insects were transferred to another container, and the mortality after 24 hours was examined.

[0020]

[Table 1] In the above Table 1, the control compound pyrethroid A is represented by the following formula (A)

Embedded image It is a commercially available pyrethroid having normal temperature volatility represented by

[0021]

Effect Example 4 The insect repellent mat for clothing prepared in Example 6 was housed in a plastic case, and suspended in a 600-liter closet. Immediately after the start of the test and 6 months later, a glass ring of 4 cm in diameter and 2 cm in width (covered on both sides with a wool cloth) in which 20 first instar larvae of Iga were released was left in a closet, and after 1 day, 2 days, and 3 days Table 2 shows the observed mortality.

[0022]

[Table 2] In the table, pyrethroid A is a commercially available pyrethroid represented by the above formula (A).

As a result of the test, the compound of the present invention showed an insecticidal effect on the harmful insect pests of Iga, which is superior to that of the control compound, pyrethroid A, and its volatility and efficacy were excellent as an insecticide for clothing. It was confirmed. It was similarly effective against other clothing pests, such as the burrowing beetle, the beetle beetle, the carp, and the jutanga.

[0024]

Test Example 1 Stability test on metal A few drops of a reagent were dropped on the center of a copper plate measuring 2 cm × 5 cm, and the copper plate was placed in a glass pot.
It was left in a constant temperature room at 0 ° C. Three days later, the surface of each copper plate was observed.

[0025]

[Table 3]

As a result of the test, the compound of the present invention, unlike the control pyrethroid A, does not undergo deterioration due to the action of metal, and is used not only in a closet but also in various applications such as machinery and exhibition rooms. It was confirmed that it could be used without problems. Therefore, when combined with the insecticidal efficacy test, the compound of the present invention is more practical than commercial pyrethroid A in both efficacy and metal stability.

[0027]

Industrial Applicability The novel cyclopropanecarboxylic acid ester derivative of the formula I of the present invention has low toxicity to warm-blooded animals, but also has high insecticidal and acaricidal properties against various pests, especially clothing pests. It shows activity and is also excellent in chemical stability (including being less affected by metals).

──────────────────────────────────────────────────続 き Continuation of front page (56) References JP-A-2-22248 (JP, A) JP-A-63-280044 (JP, A) JP-A-61-249952 (JP, A) JP-A-61-24995 280453 (JP, A) JP-A-49-132230 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C07C 69/74-69/747 A01N 53/02 CA (STN) REGISTRY (STN)

Claims (2)

(57) [Claims] (1) The following formula I: (Wherein, R ₁ represents a hydrogen atom or a methyl group.
₂ represents a hydrogen atom, a methyl group, a 2-methyl-1-propenyl group, a 1-propenyl group, a 1,3-butadienyl group, a 2,2-dichlorovinyl group, a 2-methyl group when R ₁ represents a hydrogen atom; Methoxycarbonyl-1-propenyl group, 2-
A chloro-2-trifluoromethylvinyl group, a 2,2-dibromovinyl group, or a 2,2-difluorovinyl group; and when R ₁ represents a methyl group, R ₂ represents
Represents a methyl group. R ₃ represents a lower alkyl group having 2 to 6 carbon atoms, a lower haloalkyl group having 1 to 4 carbon atoms or alkoxyalkyl. R ₄ , R ₅ ,
R ₆ represents a hydrogen atom, a halogen atom or a methyl group. A cyclopropanecarboxylic acid ester derivative represented by the formula: 2. The following formula I (Wherein, R1 represents a hydrogen atom or a methyl group. R2
When R1 represents a hydrogen atom, a hydrogen atom, a methyl group, a 2-methyl-1-propenyl group, a 1-propenyl group, a 1,3-butadienyl group, a 2,2-dichlorovinyl group, a 2-methoxycarbonyl -1-propenyl group, 2-
A chloro-2-trifluoromethylvinyl group, a 2,2-dibromovinyl group or a 2,2-difluorovinyl group; and when R1 represents a methyl group, R2 represents
Represents a methyl group. R3 represents a lower alkyl group having 2 to 6 carbon atoms, a lower haloalkyl group having 1 to 4 carbon atoms or an alkoxyalkyl group. R4, R
5, R6 represents a hydrogen atom, a halogen atom or a methyl group. Insecticides and miticides containing the cyclopropanecarboxylic acid ester derivative represented by the formula (1).