JPS62149606A - Arthropodicidal composition - Google Patents

Abstract

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

Description

DETAILED DESCRIPTION OF THE INVENTION Technical Field of the Invention The present invention relates to an arthropodicide (particularly an insecticide and acaricide) composition containing a cyclopropanecarboxylic acid ester of a halogenated alcohol as an active ingredient. It is.

2. Prior Art It is already known that the ester of 2-methyl-3-(-monomethylbuten-/-yl)-cyclopropanecarboxylic acid and 1M hydrogenated benzyl alcohol has insecticidal activity (French Patent No. 2.27//5;
'6 Specification and Japanese Patent Publication No. 33, Showa JO
No. 70). However, these known substances cannot always be said to be excellent in terms of quick action, insecticidal power, and duration of efficacy.

Disadvantages of the Invention The present invention is directed to an arthropod killer composition characterized in that it contains as an active ingredient a cyclopropanecarboxylic acid ester of halodanated pennoralcohol of the following formula.

Surprisingly, it has been found that the composition according to the present invention has strong and fast-acting arthropod-killing activity, such as insecticidal and acaricidal activity. This composition therefore represents a significant contribution to the industry.

The above formula (
Compound Ia) is a known compound per se, but its arthropod-killing activity has been completely unknown until now.

The IR-data [(to) cis/trans] of the compound of formula (Ia) are as follows.

IR-Data (m″″1), 2093, /74tO, /Otsu10, /3.
20, /≠70°/'l-, 20. /390. /3
70. /320. /300°/dark, i, 2oo, 1i
So, 10 Otsu 0. RigO.

The compound of the formula (Ia) is a compound known per se as described above, but it can be produced by the following production method, namely: (,) The compound of the following formula (where R is halogen, OH or C1-4-alkoxy group) and a compound of the following formula at a temperature of 1.20 to 7.20°C in an inert diluent (this term also includes "solvent"). (b) where R has the meaning given above and M+ is an alkali metal cation, an alkaline earth metal cation of equivalent value, or .representing a secondary or tertiary ammonium ion) and a compound of the following formula in an citrus bath medium at a temperature of 20 to 700°C, or (c) a compound of the following formula and a compound of the formula: and a compound of the formula in the presence of copper or a copper compound at a temperature of 30 to 720<0>C.

The compound of formula (IIL) exists in several stereoisomers. The multiple substituents on cyclopronolyl 1 are mutually cis-
or may exist in a trans-positional relationship.

Carbon atoms C1 and C3 in each case are present in the R-configuration as well as in the Hs-configuration, and these isomers therefore include cis- and/trans-isomers in optically active or racemic form. It can be a body.

When no dimethyl-ri-dimethyl-vinylcyclopropanecarboxylic acid chloride is used as the compound of formula (IN), and pentafluoropendyl alcohol is used as the benzyl alcohol of formula (III), the production method ( The reaction process a) can be expressed by the following formula.

As a salt of formula (R/), 2. ．． When sodium 2--/methyl-3-dimethyl-vinylcyclopropane-/-carboxylate is used and pentafluorobenzyl chloride of formula (to) is used, the reaction process of manufacturing method (b) is expressed by the following formula. be able to.

Process (b) can be carried out in polar organic diluents, examples of such diluents include diketones (e.g. acetone), nitriles (e.g. acetonitrile),
Acid amides (eg DMF, hexamethylphosphoric acid triamide) and their mixtures with water. This manufacturing method is 20~
It can be carried out at a temperature of 700°C.

This process can be carried out in the presence or absence of a suitable catalyst. A suitable compound is a methylated polyamine (eg, tetramethyl-ethylenenoamine).

This reaction is, for example, "synthesis", /97! Year, 0 disciples! It can be carried out according to the method described on page.

When using 3-pentadiene to /,/-dimethyl-≠-methyl of formula (■) and using diazoacetic acid fluoropendyl ester of formula (■), manufacturing method (c)
can be expressed by the following formula.

In process (c), the olefin of formula (Vl) is generally used in an amount of at least twice the amount per week, preferably 70%
~ θ times excess amount is used. The reaction to obtain the compound of formula (Ia) according to the invention can in this case be carried out, for example, according to the following method. A compound of formula (■), which is advantageously used in the form of a mixture with an olefin of formula (■), is reacted with copper or its compound (or other heavy metal compound) at 50 to 750°C. ) into a suspension with an olefin. The start of the reaction can be detected by the loss of nitrogen. The product can be obtained by a separation operation by distillation. The surplus of the olefins used and the olefins produced during the distillation run can be recycled to the reaction zone during the continuous reaction operation, ie this olefin can be fed to the reaction zone together with the fresh soazo ester.

As mentioned above, the composition according to the present invention is characterized by having excellent insecticidal and acaricidal activity. Therefore, it exhibits strong insecticidal activity against plant pests, pests that damage health, and pests that damage stored products, and has excellent activity against, for example, sucking insects, biting insects, and mites. Insecticidal tortoise 1 is the main species, and citrus killing is low.

For this reason, the composition according to the invention has il =Ory
It can be used advantageously as agrochemicals ("2-suicides") in the field of protection, hygiene and protection of stored products.

This composition has a high plant tolerance (i.e. low phytotoxicity) and low toxicity in warm-blooded animals, so it can be advantageously used as a control agent against pests that are arthropods (especially insects, mites and arachnids). The analogy can be used advantageously for the control of pests found in the following areas: the agricultural sector;
Forestry sector, protection of stored products and materials, hygiene sector. The composition exhibits insecticidal activity against pests of non-resistant (of normal susceptibility) and resistant species at all (or some) growth stages. Examples of these pests include:

Isopods such as Oniscus asellua, Armadillidium vulgare
), Porcellio 5caber
): The diplopod analogy is Braniurus gutulatus (B
laniulua guttulatus) : Labiopods such as Daophylus carpophagus (Geoph
illus carpophagus), Scutigera 5pace; combinations such as Scutigerel immaculata (Scutigerel
la immaculata) ; Spots such as Lepfsma 5acchartna * Collembola such as Onychilaris armaras (0nyc
hiurus armatus ); orthoptera such as the Kopane cockroach IJ (Blattaorientall
g), American cockroach (Periplanetaam)
sricana), Liucophaea maderae (L.
eucophaea maderae), German cockroach (Blattella germanlcm)
), Acheta domesticus (Acheta dome)
aticua), mole (Gryllotalpag)
pp-), Locusta migr
atoriamigratorloides), Melanopulus deifalentiales
ua differentialis), Schistocerca ψ gregaria
garla): Earwigs (Forficula garla)
auricularig); termites are called Reticulitermes (Reticulitermes spp); lice are called grape aphids (Phylloxera vastatrix)
Pemphigus spp,
Kimono louse (Pediculushumanus c)
orporis), buffalo lice (Haemat
opinis spp, ), dog lice (Lino
Gnathus 8+)P-) ; Examples of nobles include Trichodeetetespp@, Damalina app, ) ; Examples of totals include Hercinothripg femoralis
), Thrips tabaci
) :! The flying insect analogy is the European stink bug (Eury).
gasterspp, ), Dys stink bug (Dys
dercus Intermedius), Pfe++maquadrata (Pfe++maquadrata), bedbug (Clmex 1ectularius),
Rhodnius prolix
lixua), Triatom
a spp, ): congeners such as Aleurodes brasaic
ae), Whitefly (Bemis i atab)
aci), ToIJAleurodes vaporarioru (Trialeurodes vaporarioru)
m), cotton aphid (Aphis gossypi)
i), radish aphid (Brevicoryne
brasslcae), Cryptomyzus-ribis (Cryptomyzus
(ribig), Dorali Fapae (Dorali)
s fabae), Doralis
pomi), Erios
oma lanigerum), Momofuki aphid (Hyalopterus arundinla)
, Maerosiphum a.
venae), Myzusspp-, Phorodon humuli,
Rhopalosiphum pa
di), Empoasca s
pp, ), Eu5cells bilob
atua ), Nephotett
ix cincticeps), Lecanium corni, Olive snail (5aissetia oleae)
, U, t te # 77 ri, x, - Striaters (
Laodelphax 5trlatellus),
Brown planthopper (Ni1aparvata lugen)
s), Aonidiall
aurantii), Aspidiotus hederae, Pseudococcus spp,
), P'5ylla spp, ); Lepidoptera such as Pectinophora spp.
agossypiella), Bupa 7. -Bupalus piniariua,
Cheimatobia e plumata (Cheimatobia b)
rumata), Lithocholetis brancarbra (L.
ithocolletis blancardella
), Hyponomeuta padell
a), diamondback moth (Plutella maculipe)
nnis), Obikareno 1 (Malacosoma
neustria), Dokuga (Euprocti,
5chrysorrhea), ? Imaiga (L)
ymantria app,), Usuma dalamgriga (
Bucculatrix thurberiella)
, Phyllocnistis ci
trella), Yaga (Agrotis spp.
), Mugyaga (Euxoa spp, ), Hiro/Monyaga (Feltia spp, ), Linga (Earia
sinsulana), Heliot
hia spp, ), Laph spp.
ygma exigua), Mamestra brassicae',
? Panolis flammea
, Prodenia 1itura
), Shironayaga (5podopteraspp-),
Trichoplusia 9 = (Trtchopluslanl)
), Carbocapsa φ Pomonella
pomonella), white butterfly (Pieris)
5pp-), = Chilo spp,
), Awanomei (Pyrausta nubila)
lis), Kishitapa (Ephestiakuehni)
ella), honey hemlock (Galleriame)
llonella), ha? Cacoecia
podana), Kusumonhamaki (Capua r.
eticulana), Choristoneura fumiferana
), Hosoha'7ki (C1ysia ambigue)
lla), Chatsubamaki (Homona magnan)
ima), Usamimekihamaki (Tortrix
viridana): Coleoptera analogy is Anovius.
Anobium punctatum
), Rhinoceros beetle (Rh1zopsrtha
dominica), ? Bruch
ldlus obtectu+s), Acanthoscelides obtectus
x-
Hylotrupes bajulus *Alder beetle (Agelastlca alni)
s Legutino p /l/ f φf Semlineata (Le
ptinotarsadecemlineata)
, /% insect (Phaedon cochlearia)
e), Diabrotica 5pp-
), Psylliodes chrysosephala (Psyllio)
des ahrysocephala), Epilachna varivestls
).

Kiioma #*Swim beetle (Atomaria 8ppm
), sawfly (0ryzaephilis)
gurinamensls).

Anthonomus spp,
Black elephant (5ttophilus app-), Otiorrhynchus (0tiorrhynchus)
5ulcatuj), Cosmopolitea 5ordidus,
'Ceuthorrhyth
nchusasaimilis), Hyperapostica (Hyperapostica), Darmestes 1il (p-).

Trogoderma spp.
, ), Anthre
nus spp, ), Atta
genus spp, ), Lys spp.
ctus spp, ), Keshikisui (Mslige
thes aeneus), Hyouho/Mushi (Pt
1nus spp, ), Kabairo leopard beetle (
N1ptus hololeucus), Se? /
l/ Gibbium psyllo
ides), Tribolium
spp, ), White rice beetle (Te
nebrio molitor), Kometuki (Agr.
iotes8pp, ), Conoderu
s spp, ), Melontha m.
elolontba), Amphimallon solstitialis (Amphimallon golstiti)
Allg), Co5te
lytrazaalandica); Hymenoptera such as Dlprjon s
pp.), Hoplocampa/4
spp, ), Nasimi/Jchi (La5ius spp.
, ) Monomorium phala
aonig), Vespa (Vespa 5pp-):
Examples of Diptera include Anopheles spp, Culex spp, and Drosophila melanogaster.
), Musca spp*, Fannia spp, ), black fly (
Calliphoraerythrocephala
), golden fly (Lucllia 5pp-), Obi+
7 Hax (Chrysomyia!ipri-)
, Cuterebra spp, ), Gastrophilus spp-, Hypobosca 5pp-, Stomoxys 31 T)-), sheep fly (Oestruaspp-), cow fly (I(y Po
cterma Spp, ), Acausiab (Tab
anus spp, ), Tania (Tann1a!
11) p-)% Female Akakeba x (Bib1o hor
tulanus), Osinella fritto (0sci
nella frit), Phorbi
a spp, ), Begomiiya Hyoshami (Peg
omyia hyoscyami), Ceratitis capitata,
Dacus oleae, Tjpula paludosa;
is ), Ceratophyll
usspp・); Arachnids such as Scorpio maurus, Latrodectus mactan
s); The analogy for ticks is Acaru.
s 5iro), Arga 811 p.
p m ), Ornithodorus
ros spp, ), red mite (Dermanyssu)
sgallinae), Er1ophye
s ribls), Phyllocoptrutaolelvora
, Boophilus spp.
, Koitamada = (Ph1plcephalus !l
pp*), Amblyomma
spp, ), via o? (Hyalommasp
p-), tick (Ixodes 8TIP'@)s
Psoroptes spp, Chorloptes spp,
Spider mite (5arcoptes'pP"), Dust mite (Tarsonemus spp, ) 1 Clover spider mite (Bryolia praetiosa)
, /9nonychus (Panonychus spp,
), /%da= (Tetranychus11pp*
).

The compositions of the invention can be prepared in the form of conventional compositions, examples of such compositions include:
solutions, emulsions, wettable powders, suspensions, powders, dusts, foams, pastes, soluble powders,
Granules, aerosols, suspensions, emulsions, powders for yuzu treatment; fine capsules used with polymeric substances or seed coating compositions; formulations applied with combustion devices, e.g. for fumigation. Cartridges, fumigation cans, fumigation coils; cold mist and warm mist compositions used according to the ULV method (ultimate volume method).

These conventional compositions can be prepared according to known methods, for example by adding the active compound to a vehicle, i.e., liquid or solid.
! or by mixing with a liquefied gaseous diluent or carrier. In this case, if desired, surface-active agents, ie emulsifiers and/or dispersants and/or (
1 foaming agents
may be used. When using water as a vehicle,
For example, an organic solvent can be used as a supporting medium.

Examples Q of carriers (especially solvents) include aromatic hydrocarbons and evaxylene, toluene, benzene, alkyl-naphthalenes; salt-formed aromatics; or chlorinated aliphatic carbonized substances such as chlorobenzene, chloroethylene, methylene chloride; aliphatic and cycloaliphatic hydrocarbons such as cyclohexane, paraffins (such as mineral oil fractions); alcohols (such as butanol and glycols) and its ethers and esters; ketones such as acetone, methyl ethyl ketone, methyl imbutyl ketone, cyclohexanone; strong polar solvents such as trimethylformamide, dimethyl sulfoxide; water.

A liquefied gaseous diluent or carrier is a liquid that can become gaseous at normal temperature and pressure, and examples thereof include aerosol propellants such as dichlorodifluoromethane and trichlorofluoromethane.

Examples of preferred solid supports include: ground natural minerals such as kaolin, clay, talc, chalk, quartz, athanoglugite, montmorillonite, diatomaceous earth; ground synthetic materials such as highly dispersed minerals. Silicic acid, alumina, silicate.

Examples of preferred emulsifiers and foam formers include: nonionic and anionic emulsifiers, such as polyoxyethylene-fatty acid esters, polyoxyethylene-fatty alcohol ethers, such as alkylaryl polyglycol ethers, alkyl Sulfonates, alkyl sulfates, arylsulfonates, albumin hydrolysis products. Examples of preferred dispersants include lignin sulfide waste liquor and methyl cellulose.

Adhesives may also be included in the composition, examples of which include: carboxymethyl cellulose; natural and synthetic compounds in powdered, granular or latex form, such as gum arabic, polyvinyl alcohol, Polyvinyl acetate.

Nine colors can also be used, examples of which include:
Rootless pigments such as iron oxide, titanium oxide, Prussian blue; organic dyes such as alizoline dyes, azo dyes, metal phthalocyanine dyes. Micronutrients such as iron, manganese, boron, copper, cobalt, molybdenum and zinc salts can also be included.

The compositions generally contain from 0.7% to 5% by weight of active compound, preferably from 0.5% to 5% by weight.

The compositions according to the invention may be of the same type as conventional commercially available compositions or may be used in the form of disseminated formulations prepared from the compositions described above.

The active compound content of the dispersible preparations prepared from the commercially available compositions mentioned above can vary within wide limits. The concentration of active compound in this spreading layer is 0.000.
0007 to 700% by weight, preferably 0.07 to 70% by weight (as active compound).

In the individual formulations for dissemination, the active compounds may be formulated according to the customary methods appropriate in the case.

When used against pests that damage health and storage products, this composition exhibits unique properties, namely it has an excellent residual effect on wood and clay. and has a lime-containing substrate (lime
It has good stability at d 5ubstrate+s ).

As can be easily understood, conventional crop growing and harvesting methods can be further improved by the present invention.

In order to specifically illustrate the insecticidal activity of the composition according to the present invention, biological test data is shown next.

Test / Test on larvae Test Insect: Aedes aegypti (larvae) Solvent: 77 parts by weight of acetone Emulsifier: Benzylhydroxydiphenyl polyglycol ether/parts by weight Into a km bottle of the appropriate active compound-containing preparation, add 2 ili portions of the active compound. 1000 parts of the above solvent containing the above amount of emulsifier were dissolved, and the solution thus prepared was diluted with water to the desired low density.

A desired volume of the active compound-containing preparation was placed in glass containers, and about 25 larvae were inhabited in each of 7 glass containers.

, the insecticidal rate was examined after 2≠ hours. A kill rate of 700% means that all larvae were killed, and 0% means that there were no dead larvae.

The results of this test are shown in the table below. As is clear from this table, the composition of the present invention exhibits an excellent insecticidal effect.

Margin test 2: LT of Diptera. . Test Insect: Musca domestica
a) Solvent: The acetone active compound double stop was placed in 1000 parts by volume of solvent and the resulting solution was further diluted with solvent until the desired low cloudiness was achieved.

The active compound solution, 24d, was pipetted into a Petri dish. The bottom of the Petri dish was about the diameter of VC, and a 5α paper was placed in it. The petri dish was not capped until the solvent had completely evaporated. P paper/rr? The amount of active compound in this υ is
It was varied by varying the concentration of active compound in the solution.

Then, a predetermined number of test insects were placed in the IJ dish and covered with a glass lid.

The condition of the test insects was constantly observed, and the insects were
The time required to achieve % knockdown was measured.

The results of this test are shown in the table below. As shown in this table, the composition of the present invention is far more effective than the comparative sample known insecticide.

Margin test 3: Yoto test Solvent: 3M parts of acetone Emulsifier: Alkylaryl polyglycol ether/parts by weight For the preparation of suitable active compound-containing preparations, the active compound/part by weight, the above amount of solvent and the above of emulsifier and the concentrate thus obtained was diluted with water to the desired concentration.

The leaves of cabbage (Braastca olaracea) are sprayed with a preparation containing the desired concentration of active compound until drippings, and then the leaves of armyworm (Laph
ygma frugiperda) larvae (caterpillars) were allowed to live there.

After a predetermined period of time, the insect killing rate (a) was examined. 700% means all larvae were killed, 0% means no larvae were killed.

The active compound, active compound concentration, observation period and test results are shown in the table below. In this test, it was confirmed that the compositions of the present invention shown in the following table exhibited excellent insecticidal effects against the above-mentioned pests, similar to known insecticides.

Claims (2)

[Claims] (1) An arthropod killing composition characterized by containing a cyclopropanecarboxylic acid ester of halogenated benzyl alcohol as an active ingredient, represented by the following formula ▲ Numerical formula, chemical formula, table, etc. ▼ (Ia). (2) The composition according to claim 1, which contains 0.1 to 95% by weight of the active compound.