JPS598273B2 - Novel benzoyl ureido-diphenyl ether - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides certain novel benzoyl ureide
-NH-Co [wherein, R is hydrogen or chlorine, R' is chlorine or hydrogen,
represents cyano or nitro, provided that R relates to water*phenyl ether.

For example, N-(2.6-dichlorobenzoyl)-N-(
It is already known that certain benzoyl ureas, such as 4-cyclolephenyl and 3.4-cyclo5-lephenyl monourea, have insecticidal properties [German published specifications,
Book No. 2123236].

The present invention provides novel compounds with the general formula I□o□R" (I ClR', when R' is chlorine and R" is cyano, and when R is chlorine, R' is hydrogen and W ' is nitro] benzoylureido diphenyl ether.

It has been found that compounds of formula () have strong insecticidal properties. The present invention also provides the following features: (a) General formula [wherein R. R'' and w have the abovementioned meanings] with 2-chlorobenzoyl isocyanate of the formula, optionally in the presence of a solvent, or (b
) General formula [wherein, R. R'' and K have the above meanings]
There is also provided a method for producing benzoyl ureido diphenyl ether of formula (1), characterized in that isocyanato diphenyl ether is reacted with 2-chlorobenzamide of formula in the presence of a suitable solvent.

Surprisingly, the benzoyl ureido diphenyl ether according to the present invention is superior to the closest compounds already known in the art with similar preparation and the same type of activity.
It has substantially good insecticidal activity. The compounds according to the invention therefore represent a real benefit to the industry.
Using method a), 3,5-dichloro-
When using 4-(4'-nitrophenoxy)aniline and 2-chlorobenzoyl isocyanate and using method (5), 3-chloro-4-
When using (3'-chloro-4'-cyanophenoxy)-phenyl isocyanate and 2-chlorobenzamide, the reaction process is represented by the following formula: 2-chlorobenzoyl used as starting material. Isocyanates () are known from the literature and can be prepared according to general universal methods [see, A. J. Spezial (Sp
eziale) et al., J. Org. Chem. 3O(12
), pp. 4306-4307 (1957)], similarly 2-
Chlorbenzamide (V) can also be produced [see Beilstein's Handbook of Organic Chemistry].
insHandbuchderOrganischen
Chemie)” vol. 9, p. 336].

Phenoxyaniline () can be prepared from an alkali metal aminophenolate and an aromatic ditrohalogen compound in a solvent such as, for example, dimethyl sulfoxide, according to generally customary methods, and can likewise be prepared from an aminophenoxybenzo compound. Nitriles can also be produced [see Jürgen Schramm (
Jirgen Schranlm) et al., JuStu
SLiebigsAnnalenderChemie)
, 197017401169-179] o The amino group is =
It can be converted into isocyanate groups according to general universal methods, for example by reaction with phosgene. Examples of phenoxyaniline () and 4-isocyanatodiphenyl ether () and related compounds thereof used as starting materials include: 3-chloro-4-(3'-chloro-4 '-Nitro- or trichloro-4'
monocyanophenoxy)-aniline, 3,5-dichloro-
4-(4-nitro- or l-cyanophenoxy)-aniline, and 2,6-dichloro-4-isocyanato-4
/-Nitrodiphenyl ether, 2,6-dichloro-
4-isocyanato-4'-cyanodiphenyl ether, 2-chloro-4-isocyanato-3'-chloro-41
-Nitrodiphenyl ether and 2-chloro-4-isocyanato-3'-chloro-4/-cyanodiphenyl ether.

Each process for preparing compounds according to the invention is preferably carried out in the presence of suitable solvents and diluents. Virtually all inert solvents are suitable for this purpose, especially aliphatic and aromatic optionally chlorinated hydrocarbons, such as benzene,
Toluene, xylene, benzine, methylene chloride, chloroform, carbon tetrachloride and chlorobenzene ethers,
For example diethyl ether, dibutyl ether and dioxane; ketones such as acetone, methyl ethyl ketone, methyl isopropyl ketone and methyl isobutyl ketone; nitriles such as acetonitrile and propionitrile can be used. The reaction temperature can be varied within a fairly wide range.

Generally the reaction is carried out at 0-120<0>C, preferably 70-85<0>C. The reaction is generally carried out under normal pressure.

To carry out the process, the starting compounds are preferably used in equimolar amounts.

Excess of either reactant provides no substantial advantage. The 4-isocyanato diphenyl ether () used in solution b) can be used as such or without isolation of the intermediate product in the form of the reaction mixture obtained from the reaction of the amine with phosgene. You can also do that. The reaction mixture is treated with 2-chlorobenzamide in one of the solvents mentioned above. The reaction is carried out under the desired conditions and the separated product is isolated in the usual manner by filtration, washing and, if appropriate, recrystallization. As already mentioned,
The benzoylureido diphenyl ethers according to the invention are characterized by excellent insecticidal activity.

They are active not only against plant pests, but also in the field of veterinary medicine and against animal parasites (ectoparasites), such as, for example, parasitic fly larvae. For this reason, the compounds according to the invention can be successfully used in plant protection against pests and sucking insects and as insecticides in the veterinary medicine field.

Sap-sucking insects include especially aphid insects (Aphidae), such as the green peach aphid (My.
zuspersicae), Bean aphid (Bean
aphid) (DOralis fabae), Rhophyllus aphid (RhOpalOsiphumpadi)
, MacrOsiphu
nlpisi), potato aphide (POtatOaph)
id) (MacrOsiphumsOlanifOli
i), Currantgal Aphid
laphid) (CryptOnlyzuskOrsc
helti), ROsyap
pleaphid) (Sappaphismali),
Hyalopterusaru
ndinis) and Cheery black fly (Cher
ryblack-Fly) (MyzusCerasi)
;Other insects (COccina) such as scale insects and mealybugs (e.g. white scale insects)
AipidiOtushederae), Softscale (Lecaniumhesp)
eridurrl) and Grape Mealybug (Gr
apemealybug) (PseudOcOccus)
maritinlus); Thripsipidae (Thy
sanOptera), e.g. H.
ercinOthripsferOralis); Hemiptera insects such as Beetbug (Pi
esnlaquadrata), RedcOttOnbug (Dysdercusi)
ntermedius), bed bugs (Cimexl
ectularius), Assassin Bug (Assas)
sinbug) (RhOdniueprOlixus)
and Chagas'Bug (Tr
iatOmainfestans) and Cicadas, such as Euscellsbilobatus and NephOtettix
biPUnCtatllS).

Among the soft insects, especially the Coleoptera (Lepidoptera),
tera) insects, such as the diamondback moth (Plutellam)
acullpennis), gypsy moth (Lymani)
riadispar), browntail moss (BrOw
n-TailmOth) (EuprOctischry
sOrrhOes) and MalacOsO
maneustria);
labrassicae), CutwO
rm) (AgrOtissegetum), Large white butterfly (Largewhitebutterf)
ly) (Pierisbrassicae), Small winter moss (SmallwintermOth) (
Cheirnat Obiabrumata), Green Oak tortorix moss (GreenOaktOr
trixmOth) (TOrtrixviridana
), FallarnlywO
rm) (Laphygnla frugiperda),
Spodoptera (PrOdenialitura), ErminemOth (HypOnO lower Utapadella), MediterraneanflOurmOth (
Ephestia oil Hnietla), and honey hemlock (Galleriamello Onella).

Also, those classified as insects include Coleoptera (CO).
leOpiera), e.g. Granary Weevil (G
ranaryweevil) (SitOphitusg
ranariut: Calandragranaria
), Colorado Beetle
)(LeptinOtarsadecemlineat
a), DOckbeetle (Ga
strOphysaviridula), Mustardbeetle (PhaedO
ncOckleariae), Brasssum Beetle (B
lOssOmbeetle) (Meligethesa
eneus), Raspberry Beetle (Raspber)
rybeetle) (ByturstOmentOs
us), bean weevil (Bruchidius
:Li:AcanthOscellaesObject
s), Filicopsis (4) Ermestesf
rischi)) Khaprabe
etle) (TrOgOdermagranari2l
), Tribium oliurncasl (TribOliurncasl)
aneum), Calanara or Sit
Ophiluszeamais), StegObiunlPaniCellnl, StegObiunlPaniCellnl, TenebriOmOll
tOr), and saw-whet beetle (Oryzaeph
i1ussurinamensis); as well as species of insects that live in the soil, such as the wireworm (Wireworm);
-WOrm) (AgriOtOs material), and COckchafer (MelOlOnth)
amelOlOntha); insects of the Order Cockroaches, such as the Blatellager
manica), American cockroach (Periplane)
taamericana), Madeira Kotsukurochi (
MadeiracOckrOach) (LeucOph
aea or Rhypar Obiamadeirae),
Oriental Cot Cloche (0rienta1c0ck
r0ach) (Blatta Orientalis),
GiarltcOcla'
0ach) (Blaberus gigantsus) and Blackgi
antcOckrOach) (Blaberusfus
cus); and HenschOutedeniaflexivitt
a); Furthermore, Orthoptera (0rtheptera),
For example, house cricket
(GryllusdOmesticus); Insects of the order Termite, such as Eastern subterranean termite (GryllusdOmesticus);
ite) (Reticulitermesflevip
es); and Hymenoptera
For example, Gardenant (Las
Includes ant species such as iusniger).

Insects of the order Diptera are mainly flies, such as DrOsOphilam.
eian Ogaster), Mediterranean fruit fly (Mediterranean fruit fly)
) (Ceratitiscapitata), Muscad Omestica, Muscad Omestica, F.
anIllacanicularis), PhOrmiaaegina, Bluebottlefly (CallphO
raerythrOcepkala) and stable fly (S
tOmOxyscalcitrans); and Gnat species, such as Aedesa aegypti
ewpti)・Northern House Mosquito (NOrth)
ernhOusemOsquitO) (Culexpi
piens) and malaria mosquitoes (Malaria
mOsquite) (AnOphelessstephe
Includes powers such as nsi).

The active compounds according to the invention can be converted into the customary compositions, such as solutions, emulsions, suspensions, powders, coatings and granules.

These can be carried out in known manner, for example by mixing the active compound with extenders, i.e. liquid or solid or liquefied gaseous diluents or carriers, optionally using surfactants, i.e. emulsifiers and/or dispersants and/or blowing agents. It can be prepared by When using water as an extender, for example, an organic solvent can be used as an auxiliary solvent. Preferred liquid diluents or carriers are aromatic hydrocarbons such as xylene, toluene, benzene or alkylnaphthalenes, chlorinated aromatic or aliphatic hydrocarbons such as chlorobenzene, chlorethylene or methylene chloride, aliphatic hydrocarbons. , for example cyclohexane or paraffins such as mineral oil fractions, alcohols such as butanol or glycols and their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, or strong polar solvents such as dimethylformamide, dimethyl sulfoxide or acetonitrile, and water. used.

By liquefied gaseous diluent or carrier is meant a liquid that is a gas at ambient temperature and pressure, for example an aerosol propellant such as a halogenated hydrocarbon (eg Freon).

As solid diluents or carriers, preference is given to ground natural ores such as kaolin, clay, talc, silicic acid, quartz, attabalite, montmorillonite or diatomaceous earth, or ground synthetic ores such as highly dispersed silicic acid, Use alumina or silicate.

Suitable examples of emulsifiers and blowing agents include nonionic and anionic emulsifiers, such as polyoxyethylene monofatty acid esters, polyoxyethylene fatty alcohol ethers, such as alkylaryl polyglycol ethers,
Included are alkyl sulfonates, alkyl sulfates and aryl sulfonates, and albumin hydrolysis products; suitable examples of dispersants include lignin, sulfite waste and methyl cellulose.

The active compounds according to the invention can be present in compositions mixed with other active compounds.

Generally the above compositions have a
Contains ~90% by weight of active compound. The active compound can be used as it is or in prepared solutions, concentrated emulsions, emulsions, foams,
It can be used in compositions such as suspensions, atomized powders, coatings, wettable powders, dusts and granules, or application forms made from the compositions. The application can be carried out by the customary methods, such as spraying, liquid atomization, atomization, dusting, granulating, fumigation, evaporation, liquid spreading, smearing or adhesive application. The concentration of active compound in the prepared preparations can be varied within a fairly wide range.

Generally this concentration is between 0.0001 and 10% by weight, preferably between 0.01 and 1% by weight. The active compounds can also be used with good results using the ultra concentrated low volume method (ULV), in which case it is also possible to use compositions with up to 95% active compound or only the active compound. .

Insecticidal compositions are thus obtained by incorporating the compound as active ingredient in a mixture with a solid or liquefied gaseous diluent or carrier or a liquid diluent or carrier containing a surfactant.

Insects can also be exterminated by applying the compound alone or a composition containing the compound of the present invention mixed as an active ingredient with a diluent or carrier to pests or their habitats.

Furthermore, the compounds, alone or in mixtures with diluents or carriers, can be applied to the crop field immediately before and/or during the growing season to protect the crop from damage by insects. The insecticidal activity of the compounds of the present invention will be illustrated by the following biological experimental examples.

Experimental Example A Plutella Test Solvent: 3 parts by weight dimethylformamide Emulsifier: 1 part by weight alkylaryl polyglyconoleether To prepare a suitable formulation of the active compound,
One part by weight of active compound is mixed with the above amount of solvent containing the above amount of emulsifier, and the concentrate is diluted with water to the desired concentration.

The cabbage leaves (Brassica Oleracea) are sprayed with the active compound preparation until dripping wet and then the diamondback moth (Plutella maculip
Ennis) caterpillars were infected.

The degree of mortality (%) was measured after a certain period of time. 100% means that all caterpillars are killed, and 0% means that no caterpillars are killed.

The active compound, the concentration of the active compound, the evaluation time and the results are shown in the table below.

Experimental Example B Testing with parasitic fly larvae Solvent: 35 parts by weight of ethylene polyglycol monomethylene ether Emulsifier: 35 parts by weight of nonylphenol polyglycol ether An appropriate formulation of the active compound is prepared. For this purpose, 30 parts by weight of the active substance of the invention are mixed with the above amount of solvent containing the emulsifier in the above proportion and the concentrate thus obtained is diluted with water to obtain the desired concentration. I made it.

Approximately 20 fly larvae (Lucilia cuprina)
) was added to a test tube containing approximately 2 cd of horsemeat.

0.5 ml of the active compound formulation was applied to this horsemeat. The degree of mortality (%) was measured after 24 hours.

100% means all larvae are killed and 0% means no deaths.

The active compounds tested, the concentrations of active compounds used and the results obtained are shown in the table below.

Fly larva (Lucillacua) resistance) The method of the present invention will be illustrated by the following production examples.

Preparation Example A solution of 15.5y (0.03 mol) of 2-chlorobenzoyl isocyanate in 50 ml of toluene is prepared at 80°C from a solution of 9y (0 ml) in 150 ml of toluene.
．． 03 mol) of 3,5-dichloro-4-(4'-nitroxy)-aniline.

The batch was stirred for 1 hour at 80° C. and after cooling the precipitated product was filtered off and washed first with toluene and then with petroleum ether. After drying, I
OV (69% of theory) of analytically pure 4-nitro-
Z・6'-dichloro-4'-[N-(Π-(o
-chlorobenzoyl))-ureido]-diphenyl ether (melting point 184°C) was obtained. Preparation Example 2 A solution of 7.3y (0.04 mol) of 2-chlorobenzoyl isocyanate in 50 ml of toluene was added to 10.2y (0.04 mol) of 3-chloro-4 at 80°C.
A solution of -(3'-chloro-4'-cyanophenoxy)-aniline in 100 ml of toluene was added.

The batch was stirred at 80° C. for 1 hour, and after cooling the reaction mixture to 20° C., the precipitated material was separated and washed with toluene and petroleum ether. 12 after drying
y (65% of theoretical value) of 3-*chloro-4-cyano-z△chloro-4'-[N-(R-(o-chlorobenzoyl))-ureido]-diphenyl ether (melting point 209°C) was gotten. The above compound was obtained from the corresponding 4-isocyanato diphenyl ether by reaction with 2-chlorobenzamide.

Matters related to the present invention are described below.

1. Benzoyl ureido diphenyl ethers of the general formula: wherein R and R' are different from each other and are each hydrogen or chlorine, and W' is nitro or cyano.

2. formula compound.

3. formula compound.

4(a) Phenoxyaniline of the general formula, in which R and k are different from each other and each is hydrogen or chlorine, and k is nitro or cyano, is substituted with 2-chloro (b) general formula [wherein R, R' and W' have the above meanings]
4-isocyanatodiphenyl ether of formula 2-
The general formula [wherein R, R'1!1. A method for producing benzoyl ureido diphenyl ether.

5. 4. above, wherein phenoxyaniline () is as described in the specification. Method according to (a).

6. The method for use in 4(b) above, wherein the 4-isocyanato diphenyl ether () is as described in the specification.

7. 4 above, wherein the reaction is carried out in the presence of a diluent or solvent.
, 5 or 6.

8. A method according to any one of 4 to 7 above, wherein the reaction is carried out at a temperature between 0°C and 120°C.

9. A method according to 8 above, wherein the reaction is carried out at 70°C to 80°C.

110. A method according to any of 4 to 9 above, in which the reactants are used in equimolar amounts. 11
．． 1 above, substantially as described in Preparation Example 1 or 2.
A method for producing a compound according to.

12. Produced by the method according to any of the above 4 to 11 1
A compound according to 1 above, which has been prepared.

13. As active ingredient, a compound according to any of 1 to 3 and 12 above, mixed with a solid or liquefied gaseous diluent or carrier, or with a liquid diluent or carrier containing a surfactant. An insecticide composition comprising:

14. Compositions according to 12 above, containing from 0.1 to 95% by weight of active compound.

15. Composition according to 13 above, containing from 0.5 to 90% by weight of active compound.

16. Insects or their habitats, 1 to 3 and 12 above.
alone or in the form of a composition containing as active ingredient a compound according to any of the above 1 to 3 and 12 in admixture with a diluent or carrier. How to get rid of insects.

17. A method according to 16 above, using a composition containing from 0.0001 to 10% by weight of active compound.

18. Process according to 17 above, using a composition containing from 0.01 to 1% by weight of active compound.

19. 19. A method according to any of 16 to 18 above, wherein the active compound is any of those listed in Example A or B.

20. Immediately before and/or during the growing season, the above 1.
Crops protected from damage by insects by application of a compound according to any of ~3 and 12, alone or mixed with a diluent or carrier, and growing in situ.

Claims (1)

[Claims] 1 General formula ▲ Numerical formula, chemical formula, table, etc. ▼ [In the formula, R is hydrogen or chlorine, R' is chlorine or hydrogen, R''
represents cyano or nitro, provided that when R is hydrogen, R' is chlorine and R'' is cyano, and when R is chlorine, R' is hydrogen and R'' is nitro]. diphenyl ether.