JPH0245618B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention is based on the general formula (In the formula, R ¹ is hydrogen, halogen, methyl, ethyl,
represents trifluoromethyl or nitro; R ² represents hydrogen, halogen, methyl or trifluoromethyl; R ³ represents hydrogen, halogen or methyl; R ⁴ represents hydrogen or methyl; R ⁵ represents hydrogen or C _{1 ~4} -alkyl, provided that ^R4 and ^R5 cannot both represent hydrogen at the same time, ^R6 represents _C1-4 -alkyl, X represents oxygen, methylene or carbonyl, and Y represents oxygen or sulfur). The compounds of the formula have a pesticidal action and are therefore suitable as active substances in pesticidal compositions.
Accordingly, the present invention also encompasses pest control compositions containing one or more compounds of formula, methods of making these compounds, and the use of such compounds or compositions in pest control. The term "halogen" includes fluorine, chlorine, bromine and iodine. " _C1-4 -alkyl" means methyl, ethyl, n-propyl, isopropyl, n
- straight-chain and branched alkyl groups such as butyl, isobutyl and tertiary-butyl. Since asymmetric carbon atoms may be present in the compounds of formula, optical antipodes may exist in such cases.
The formulas are therefore intended to encompass these possible isomeric forms as well as the racemates. When R ¹ or R ³ represents halogen, this is preferably fluorine, chlorine or bromine.
When R ² represents halogen, it is preferably fluorine or chlorine. When R ⁵ represents C _1-4 -alkyl, it is preferably methyl or ethyl. Preferably R ¹ is hydrogen, halogen, methyl or trifluoromethyl. R ₂ preferably represents hydrogen or halogen. R ³ preferably represents hydrogen. R ⁵ preferably represents hydrogen, methyl or ethyl. R ⁶ preferably represents methyl, ethyl, isopropyl or isobutyl. X preferably represents oxygen or methylene. Preferred compounds of the formula are: 1 Ethyl [2-(p-phenoxyphenoxy)
Ethyl]ethylcarbamate, 2 Ethyl {2-[p-(p-fluorophenoxy)phenoxy]ethyl}methylcarbamate, 3 Ethyl[2-(p-phenoxyphenoxy)
Ethyl] methyl carbamate, 4 Ethyl 2-(p-phenoxyphenoxy) propyl carbamate, 5 Ethyl [2-(p-phenoxy-m-tolyloxy) ethyl] methyl carbamate, 6 Methyl [2-(p-phenoxyphenoxy) propyl carbamate, Shifuenoxy)
ethyl] methyl carbamate, 7 isopropyl [2-(p-phenoxyphenoxy) ethyl] methyl carbamate, 8 ethyl {2-[p-(3,5-dichlorophenoxy) phenoxy] ethyl} methyl carbamate, 9 S-Ethyl[2-(p-phenoxyphenoxy)ethyl]methylthiocarbamate, 10 Ethyl{2-[p-(m-chlorophenoxy)phenoxy]ethyl}methylcarbamate, 11 Ethyl{2-[p-(m -bromophenoxy)phenoxy]ethyl}methylcarbamate, 12 ethyl 2-[p-(p-fluorophenoxy)phenoxy]propylcarbamate, 13 ethyl 2-(p-benzylphenoxy)propylcarbamate, 14 ethyl 2-[ p-(m-fluorophenoxy)] phenoxypropyl carbamate, and 15 ethyl {2-[p-(m-fluorophenoxy) phenoxy] ethyl} methyl carbamate. Compounds 2), 3), 8) and 12) are particularly preferred. The method for producing compounds of the general formula according to the present invention includes the following methods: a General formula (In the formula, R ¹ , R ² , R ³ and X have the above meanings) (In the formula, R ⁴ , R ⁵ , R ⁶ and Y have the above meanings,
Q is then reacted with a compound of a leaving group, in particular chlorine, bromine, iodine, methyloxy or tosyloxy. or b general formula (wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ and X have the above meanings), an amine of the general formula (wherein R ⁶ and Y have the above meanings). The reaction according to embodiment a) is conveniently carried out in the presence of an inert organic solvent and an acid binder. Suitable solvents include dimethylformamide, dioxane, hexamethylphosphoric triamide, tetrahydrofuran, dimethoxyethane, toluene and combinations of two or more of these solvents. Suitable acid binders are alkali metals, especially sodium and potassium, alkali metal hydrides, alkali metal amides, alkali metal hydroxides and alkali metal carbonates, especially potassium carbonate. In this case, the corresponding alkali metal phenolates are formed from the phenols of the formula. Alternatively, phenolates are formed from phenols by azeotropic removal of water formed in the presence of alkali metal hydroxides with toluene. Embodiment a) The temperature at which the process is carried out is not critical. Generally, the reaction is carried out at a temperature of -20°C to the boiling point of the reaction mixture, preferably room temperature to 100°C, especially 80°C.
It is carried out at a temperature of 100℃ to 100℃. The leaving group Q of the formula
When is bromine or iodine, the reaction temperature is preferably somewhat lower than when using compounds of the formula where the leaving group Q is chlorine, mesyloxy or tosyloxy. Isolation of the compound of the formula thus obtained is carried out in a conventional manner. The reaction according to embodiment b) is carried out in the presence of an inert organic solvent such as acetone or methylene chloride, preferably in the presence of an acid binder such as an alkali metal carbonate (preferably potassium carbonate). convenient. This reaction is preferably carried out at the reflux temperature of the reaction mixture. Generally, the reaction is complete within one day. Thereafter, any insoluble salts that may be present are conveniently removed from the reaction mixture, the liquid is evaporated under reduced pressure and the residue is purified, for example by column chromatography, distillation or crystallization. Unless the synthesis is designed for isolation of the pure isomer, the product is usually obtained as a mixture of two isomers. These isomers can be separated according to methods known per se. The starting compounds of the formula, and are known or can be prepared by methods known per se. The compounds of the formula are particularly useful for controlling insects, acarids and nematodes, especially the following pests: Lepidoptera, such as Adoxophyes spp., Tortrix viridana, Cheimatobia brumata, Lyonetia Clerkella, Operophtera brumata, Lithocolletis
blancardella) and other boring moths (boring moths)
moth): Laspeyresia spp.
Porthetria dispar, Orgyia spp., Choristoneura spp., Clysia ambiguella, Lobesia botrana, Agrotis segetum, Heliothis sp.
spp.), Spodoptera spp., Ostrinia nubilalis, Ephestia spp., Galleria mellonella, Plodia interpunctella. Homoptera, i.e. shield and soft lice, such as Aspidiotus spp., Saissetia spp.
spp.), Quadraspidiotus perniciosus, Aonidiella auranhii, Coccus spp., Unaspis spp.,
Lecania spp., Lepidosaphes spp., Planococcus spp., Pseudococcus spp., Ceroplastes spp., Icerya
purchasi), Chrysomphalus spp., Parlatoria spp., Rhizoecus spp.
spp.), as well as cicadas, such as Nephotettix spp., Laodelphax spp., Nilaparvata spp., and leaf flukes, such as Psillamari ( Psyllamali), Psylla piri, Psylla pirisuga, Psylla piricula, Trioza apicalis, aphids such as Aphis fabas, Myzus persicae), as well as white flies, such as Trialeurodes vaporariorum,
Aleurodes Proletera
proletella), Bemisia
tabaci). Diptera, such as Aedes aegypti, Culex pipiens, Aedes taeniorrhynchus, Anopheles stephensi, Calliphora spp. spp.), Musca domestica (Musca
domestica), Sciara spp., phorbia spp., mushroom flies. Coleoptera, such as Oryzaephilus surinamensis
surinamensis), Rhizopertha dominica, Sitophilus granarius, Sitophilus oryzae, Tenebrio molitor, Tribolium castaneum, Trogo Trogoderma granarium, Lasioderma
serriorne), Epilachna spp.,
Leptiotarsa spp. Otiorhyn chus sulcatus,
Diabrotica spp., and other soil coleopterans. Ortheptera, such as Blattella germanica, Leucophea
surinamensis), Nauphoeta cinerea, Blatta orientalis, periplaneta americana. Heteroptera, such as Dysdercus cingulatus, Rhodnius prolixus,
Oncopeltus
fasciatus), Piesma spp., Lygus spp. Isoptera (termite species). Hymenoptera, such as Solenopsis invicte, Monomorium pharaonis,
Atta spp., as well as true sawflies
sawflies), for example Athalia
rosae), Hoplocampa spp.,
Pristiphora spp. Acari (Acarina), such as Tetranychus urticae, Tetranychus urticae
cinnabarinus), Panonychus
ulmi) and other Tetranychides, as well as Eriophyides, such as Phyllocoptruta oleivora and more especially Chic. Nematodes, such as Ditylenchus dipsaci, Meliodogyen incognita, Pratylenchus
penetrans), Aphelenchoidesrizemabosi and Globodera rostochiensis. The compounds of the formula according to the invention act as contact or food poisons or even in the gas phase. Compared to most previously known pest control agents that act on the central systems of animals and kill, maim, or repel them,
The compounds of the formula according to the invention interfere with the hormonal system of the animal tract. In the case of insects, for example, it interferes with the metamorphosis into adults, the production of viable mature eggs, and the development of normal eggs produced. Furthermore,
Interferes with larval molting in various insects. The order of alternation of generations is disrupted and the animal is indirectly killed. The compounds of formula are substantially non-toxic to vertebrates. Toxicity is greater than 1000mg/Kg body weight. Furthermore, compounds of formula are easily decomposed. The risk of accumulation is thus eliminated. Therefore, the compounds of the formula can be used without hindrance in the control of pests on animals, plants, food stocks, and materials as well as in water. The pest control composition according to the invention is characterized in that it contains an effective amount of at least one compound of the formula as defined above as well as an inert carrier material. The active substances of the formula according to the invention can be put into the customary formulations, such as solutions, emulsions, suspensions, powders, pastes and granules. These can be carried out in known ways, for example by combining the active substances with bulking agents (i.e. liquid solvents, liquefied gases under pressure and/or solid carrier materials) and optionally with surfactants (i.e.
emulsifying agents, wetting agents and/or dispersing agents). When using water as extender, organic solvents can also be used as auxiliary solvents, for example. As liquid solvents, the following solvents can in principle be considered: aromatics such as toluene, xylene and alkylnaphthalenes; chlorinated aromatic and chlorinated aliphatic hydrocarbons such as chlorobenzene, chlorethylene and methylene chloride; aliphatic hydrocarbons such as cyclohexane and paraffins (e.g. petroleum distillates); alcohols and their ethers and esters such as butanol and glycols; ketones such as acetone, methyl ketone, methyl isobutyl ketone and cyclohexanone; and dimethylformamide, Strongly polar solvents such as N-methylpyrrolidone and methylsulfoxide and water. The term liquefied gaseous bulking agent or carrier material refers to liquids that are gaseous at normal temperature and pressure, such as halogenated hydrocarbons (e.g.
an aerosol carrier gas such as dichlorodifluoromethane). In principle, the following substances can be considered as solid carrier materials: kaolin, clay, talc, chiyolk,
Natural minerals such as quartz, attapulgite, montmorillonite and diatomaceous earth; and synthetic minerals such as highly dispersed silicic acid, aluminum oxide and silicates. The following substances can be considered as surfactants, in particular emulsifiers and wetting agents: such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, alkylaryls, polyglycol ethers, alkylsulfonates, alkylsulfates and arylsulfonates. Nonionic and anionic emulsifiers; and as dispersants, for example lignin, sulfite alkali and methylcellulose. Pest control compositions according to the invention generally contain as active substance a compound or compounds of the formula
It contains 0.0005 to 95% by weight, preferably 1 to 75% by weight. These can be provided in a form suitable for storage and transportation. In such forms (eg emulsifiable concentrates), the active substance concentration is usually in a range higher than the above concentration range. These forms of the composition can then be diluted with the same or a different carrier material to give a practical active substance concentration, which concentration is usually in the lower range of concentrations mentioned above. Emulsifiable concentrates generally contain from 5 to 95% by weight, preferably from 10 to 75% by weight of the compound(s) of formula. Application forms include, in particular, ready-to-use solutions, emulsions, suspensions, foams,
Available in powders, pastes, powder compositions and granules.
These include conventional methods such as watering, spraying, smoke-
Screen method, scattering, scattering, digging, vaporization, injection,
Use in submergence or incrustating. The concentration of active substance in the ready-to-use preparations can be varied within a wide range. In spray liquids, they can be present, for example, in concentrations of 0.0005 to 20% by weight. In the Ultra-Low-Volume process,
Spray liquids can be formed with an active substance concentration of 0.5-20% by weight, whereas the spray liquids formed by the low-volume and high-volume methods are 0.02-1.0% by weight or 0.002% by weight, respectively.
With an active substance concentration of ~0.1% by weight. Granules used in particular for mosquito control preferably contain from 1 to 10% by weight of a compound of the formula as active substance. In addition to the active substances of the formula, the pest control compositions according to the invention can contain other active substances (eg, other pest control agents). Such combination preparations are suitable for enhancing the activity or broadening the spectrum of activity. In preparing the pest control composition according to the invention, the active substance of the formula is mixed with an inert carrier material. In the case of pulverulent compositions, the active substance is mixed with the carrier material (e.g. ground together)
Alternatively, an inert carrier material can be impregnated with a solution or suspension of the active substance and the solvent or suspending agent removed by evaporation, heating or vacuum suction. Such pulverulent compositions can be made readily wettable with water by the addition of wetting and/or dispersing agents, so that they can be converted into aqueous suspensions suitable, for example, as spray compositions. In order to produce emulsifiable concentrates which are particularly suitable for storage and transport, the active substance can be mixed with an emulsifier, for example, or can be dissolved in an inert solvent and then mixed with an emulsifier. By diluting such a concentrate with water, a ready-to-use emulsion is obtained. The method for controlling pests according to the invention is characterized in that the object to be protected or the pests themselves are treated with a compound according to the invention or a pest control composition according to the invention. This method of use can be carried out, depending on the type of pest to be controlled, by application to the soil or leaves, or by application to the animals, food or substances to be protected. Control is achieved, for example, by contact or feeding. The compounds of the formula, in addition to their insecticidal properties, also have special properties that result in improved silk quality in fomentation. Therefore, these compounds can be used in protein farming. For this purpose, the compounds of the formula are suitable as additives to silkworm feed. The following formula illustrates the invention: Example of Preparation of the Active Substance 1 18.6 g of p-phenoxyphenol are dissolved in 100 ml of dimethylformamide. 18.2 g of ethyl (2-chloroethyl) methyl carbamate and 27.6 g of potassium carbonate were added thereto, and the reaction mixture was heated to 80°C.
Heat for 15 hours while stirring. water the reaction mixture
Pour into 300ml and extract with diethyl ether.
The ether extract was washed with semi-saturated and saturated sodium chloride solutions, dried over sodium sulfate,
Then evaporate. Chromatography on silica gel with n-hexane/ethyl acetate (9:1) gives pure ethyl [2-(p-phenoxyphenoxy)ethyl]methyl carbamate; n ²⁰ _D =1.5503. The following compound is obtained in a similar manner to the above method: p
- Obtain ethyl {2-[p-(p-fluorophenoxy)phenoxy]ethyl}methylcarbamate from (p-fluorophenoxy)phenol and ethyl (2-chloroethyl)methylcarbamate; n ²⁰ _D = 1.5373 ; From p-benzylphenol and ethyl (2-chloroethyl) methyl carbamate, obtain ethyl [2- (p-benzylphenoxy) ethyl] methyl carbamate; n ²⁰ _D = 1.5495; p-phenoxyphenol and ethyl ( 2-
From chloroethyl)ethyl carbamate, ethyl [2-(p-phenoxyphenoxy)ethyl]ethyl carbamate is obtained; n ²⁰ _D = 1.5446; p-phenoxyphenol and ethyl (2-
From chloroethyl) isopropyl carbamate,
Ethyl [2-(p-phenoxyphenoxy)ethyl]isopropyl carbamate is obtained; n ²⁰ _D =
1.5415; p-phenoxyphenol and ethyl (2-
From chloroethyl)-n-butyl carbamate,
Ethyl [2-(p-phenoxyphenoxy)ethyl]-n-butyl carbamate is obtained; n ²⁰ _D =
1.5358; From p-(m-bromophenoxy)phenol and ethyl (2-chloroethyl)methylcarbamate, obtain ethyl {2-[p-(m-bromophenoxy)phenoxy]ethyl}methylcarbamate; n ²⁰ _D = 1.5672; p- Phenoxyphenol and ethyl 2-
Ethyl 2-(p-phenoxyphenoxy)propyl carbamate is obtained from (methylsulfonyloxy)propyl carbamate; mp=79-81
°C; Ethyl 2-[p-(m-bromophenoxy)phenoxy]propyl carbamate is obtained from p-(m-bromophenoxy)phenol and ethyl 2-(methylsulfonyloxy)propylcarbamate; n ²⁰ _D = 1.5660; p-( m-fluorophenoxy)phenol and ethyl (2-chloroethyl)methylcarbamate to obtain ethyl {2-[p-(m-fluorophenoxy)ethyl}methylcarbamate;
n ²⁰ _D = 1.5386; From p-(4-chloro-o-tolyloxy)phenol and ethyl (2-chloroethyl)methyl carbamate, ethyl {2-[p-(p-chloro-o-tolyloxy)phenoxy]ethyl}methyl Carbamate is obtained; n ²⁰ _D = 1.5537; from p-phenoxy-m-cresol and ethyl (2-chloroethyl) methyl carbamate,
Ethyl [2-(p-phenoxy-m-tolyloxy)ethyl]methyl carbamate is obtained; n ²⁰ _D =
1.546; p-phenoxyphenol and methyl (2-
From p-phenoxyphenol and isopropyl (2-chloroethyl) methyl carbamate, obtain methyl [2-(p-phenoxyphenoxy) ethyl] methyl carbamate; n ²⁰ _D = 1.5578; from p-phenoxyphenol and isopropyl (2-chloroethyl) methyl carbamate.
Obtain isopropyl [2-(p-phenoxyphenoxy)ethyl]methyl carbamate; n ²⁰ _D =
1.5388; p-phenoxyphenol and methyl 2-
From (methylsulfonyloxy)propyl carbamate, methyl 2-(p-phenoxyphenoxy)propyl carbamate is obtained; n ²⁰ _D =
1.5565; Isopropyl 2-(p-phenoxyphenoxy)propyl carbamate is obtained from p-phenoxyphenol and isopropyl 2-(methylsulfonyloxy)propyl carbamate; n ²⁰ _D
= 1.5422; From p-(3,5-dichlorophenoxy)phenol and ethyl(2-chloroethyl)methylcarbamate, ethyl {2-[p-(3,5-dichlorophenoxy)phenoxy]ethyl}methylcarbamate n ²⁰ _D = 1.5632; From p-(α,α,α-trifluoro-m-tolyloxy)phenol and isopropyl(2-chloroethyl)methylcarbamate, -Trifluoro-
From p-(m-tolyloxy)phenol and ethyl(2-chloroethyl)methylcarbamate, obtain ethyl{ _2- [p-(m ^- tolyloxy) Obtain phenoxy]ethyl}methyl carbamate;
n ²⁰ _D = 1.5485; From p-(nitrophenoxy)phenol and ethyl (2-chloroethyl) methyl carbamate, ethyl {2-[p-(p-nitrophenoxy) phenoxy] ethyl} methyl carbamate;
n ²⁰ _D = 1.5773; Obtain isopropyl [2-(p-benzoylphenoxy)ethyl] methyl carbamate from 4-hydroxy-benzophenone and isopropyl (2-chloroethyl) methyl carbamate;
n ²⁰ _D = 1.5608; From p-(p-fluorobenzoyl)phenol and ethyl 2-(methylsulfonyloxy)propyl carbamate, ethyl 2-[p-(p-
fluorobenzoyl)phenoxy]propylcarbamate; n ²⁰ _D = 1.5682; p-(m-bromophenoxy)phenol and isopropyl 2-(methylsulfonyloxy)
From propyl carbamate, isopropyl 2-
[p-(m-bromophenoxy)phenoxy]propyl carbamate is obtained; n ²⁰ _D = 1.5590; to obtain enoxyphenoxy)ethyl]methylthiocarbamate;
mp=28-32°C; Ethyl 2-[p-(m-chlorophenoxy)phenoxy]propylcarbamate is obtained from p-(m-chlorophenoxy)phenol and ethyl 2-(methylsulfonyloxy)propylcarbamate; n ²⁰ _D = 1.5578; P-(m-chlorophenoxy)phenol and ethyl (2-chloroethyl) methyl carbamate, etc., to obtain ethyl {2-[p-(m-chlorophenoxy) phenoxy] ethyl} methyl carbamate; n ²⁰ _D = 1.5570; p- Ethyl 2-[p-(m-nitrophenoxy)phenoxy]propyl carbamate is obtained from (m-nitrophenoxy)phenol and ethyl 2-(methylsulfonyloxy)propyl carbamate; n ²⁰ _D = 1.5640; p-(m-nitrophenoxy) From phenol and ethyl (2-chloroethyl) methyl carbamate, obtain ethyl {2-[p-(m-nitrophenoxy)phenoxy]ethyl}methylcarbamate; n ²⁰ _D = 1.5639; p-(p-fluorophenoxy)phenol and ethyl 2-[p-(p-
From p-(o-fluorophenoxy)phenol and ethyl(2-chloroethyl)methyl carbamate, obtain ethyl {2-[p-(o -Fluorophenoxy)phenoxy]ethyl}methylcarbamate; n ²⁰ _D = 1.5399; From p-benzylphenol and ethyl 2-(methylsulfonyloxy)propyl carbamate, ethyl 2-(p-benzylphenoxy)propyl is obtained. Carbamate is obtained; n ²⁰ _D = 1.5538; from 4-hydroxy-benzophenone and ethyl 2-(methylsulfonyloxy)propyl carbamate, ethyl 2-(p-benzoylphenoxy)propyl carbamate is obtained; n ²⁰ _D =
1.5820; from 4-hydroxy-benzophenone and ethyl (2-chloroethyl) methyl carbamate,
Ethyl [2-(p-benzoylphenoxy)ethyl]methyl carbamate is obtained; n ²⁰ _D = 1.5772; from p-(p-chlorobenzyl)phenol and ethyl (2-chloroethyl) methyl carbamate, ethyl {2-[ Obtain p-(p-chlorobenzyl)phenoxy]ethyl}methylcarbamate; mp=56-58°C; From p-(m-fluorophenoxy)phenol and ethyl 2-(methylsulfonyloxy)propylcarbamate, ethyl 2 -[p-(m-
Fluorophenoxy) phenoxy]propyl carbamate is obtained; n ²⁰ _D = 1.5382. Production example of raw material 2 2-(n-butylamino)ethanol 117.2g
into 300 ml of methylene chloride. Then, 54.3 g of ethyl chloroformate is added dropwise at 30-35° C. over 1 hour while cooling with ice. After stirring for a further 2 hours, the methylene chloride is evaporated and the residue is distilled. Pure ethyl (2-hydroxyethyl)-n
-Butyl carbamate is obtained; bp=112
°C/0.1 torr. Put 52 g of ethyl (2-hydroxyethyl)-n-butyl carbamate into 125 ml of methylene chloride,
It is treated by adding 41.6 g of thionyl chloride dropwise over a period of 45 minutes at 20-25°C. The mixture is then allowed to react for a further hour at room temperature. After removing the solvent, the residue is distilled. Obtain pure ethyl (2-chloroethyl)-n-butyl carbamate; bp=91
°C/0.07 torr. The following compound is obtained in a similar manner to that described in the example above: From 2-isopropylamino-ethanol and ethyl chloroformate, ethyl (2-hydroxyethyl) isopropyl carbamate is obtained; bp=
93°C/0.07 torr; from this using thionyl chloride, obtain ethyl (2-chloroethyl) isopropyl carbamate; bp = 84°C/0.1 torr; from 2-methylamino-ethanol and methyl chloroformate to bp 89-91°C/0.1 torr methyl (2-hydroxyethyl) methyl carbamate is then obtained using thionyl chloride to obtain methyl (2-chloroethyl) methyl carbamate; bp = 86-90°C/0.15 torr; 2-methylamino-ethanol and chlorgyl From the acid isopropyl, obtain isopropyl (2-hydroxyethyl) methyl carbamate of bp 100°C/0.15 torr; then from this using thionyl chloride, obtain isopropyl (2-chloroethyl) methyl carbamate; bp = 72°C/0.15 torr; 2 -Methylamino-ethanol and S-ethyl, chlorthioformate, bp110-115℃/0.2
S-ethyl (2-hydroxyethyl) methylthiocarbamate of toll is obtained; this is then used with thionyl chloride to obtain S-ethyl (2-chloroethyl) methylthiocarbamate; bp=70
~75℃/0.1 torr; Obtain isopropyl 2-hydroxypropyl carbamate from 1-amino-2-propanol and isopropyl chloroformate; bp105 ~
111℃/0.065 Torr. Example 3 32.3g of hydroquinone was added to dimethyl sulfoxide.
Dissolve in 250ml. 100 ml of toluene and 30 g of 86% potassium hydroxide are added successively, with stirring and with constant introduction of nitrogen. Then, the bath temperature
Adjust the temperature to 160℃ and completely remove water using a water separator. Thereafter, the bath temperature is further increased and toluene is distilled off until the internal temperature reaches 155°C. next,
40 g of 3-bromo-fluorobenzene are introduced and the mixture is kept at this temperature for 20 hours. The dimethyl sulfoxide is then distilled off under water jet vacuum. The cooled residue is poured into ice water, neutralized with hydrochloric acid and then extracted three times with ethyl acetate. The extract is washed twice with water and once with saturated sodium chloride solution, dried over sodium sulfate and evaporated. By chromatography on silica gel with n-hexane/ethyl acetate (9:1), p
-obtain (m-bromophenoxy)phenol;
^n20D ₌ 1.6018. The following compound is obtained in a similar manner to that described above:
From hydroquinone and 3-trifluoromethyl-chlorobenzene, with the addition of a catalytic amount of copper powder, p
-(α,α,α-trifluoro-m-tolyloxy)phenol is obtained, which is heated in a spherical tube at 140℃/
Distill at 0.05 torr; n ²⁰ _D = 1.5370. Example 4 Ethyl 2-hydroxypropyl carbamate
Dissolve 29.4g in 27g of triethylamine, then
22.9 g of methanesulfonyl chloride are added dropwise within 1 hour with stirring at 15-20°C. The concentrated reaction mixture is stirred for 2.5 hours and then poured into ice water. The mixture is acidified with 2N hydrochloric acid and extracted three times with methylene chloride. Wash the extract with water to neutralize it,
Dry over sodium sulfate. After evaporating the solvent, ethyl 2-(methylsulfonyloxy)
Propyl carbamate is obtained (n ²⁰ _D =1.4577). This product can be used without further purification. The following compound is obtained in a similar manner to that described above: From methyl 2-hydroxypropyl carbamate and methanesulfonyl chloride, methyl 2-
(Methylsulfonyloxy)propyl carbamate (mp 37-40 °C) is obtained; the product can be used without further purification; obtain. Example 5 21.8 g of sodium hydride (55% in oil) are placed in 100 ml of anhydrous pyridine and treated by adding 54.1 g of m-cresol in 200 ml of pyridine dropwise over the course of 1 hour. After the reaction is complete, add 1.2 g of cupric chloride,
93.5 g of 4-bromoanisole are then added dropwise over the course of 1 hour at reflux temperature. After refluxing for 4 hours, the pyridine is distilled off and the mixture is
Heat to 170°C (internal temperature). 2 hours later
350 ml of water is added dropwise while cooling with ice, followed by 500 ml of diethyl ether and then 150 ml of water.
The mixture is filtered with suction over Celite and the phases are separated. The organic phase is washed successively once with 200 ml of 2N hydrochloric acid, three times with 100 ml each time of 2N sodium hydroxide, 200 ml of water and then with 200 ml of saturated sodium chloride solution. After drying over sodium sulfate and evaporation, a brown-red oil is obtained. The product is first filtered over 5 times the amount of silica gel using n-hexane/diethyl ether and then distilled. Pure p-(m-
tolyloxy)anisole is obtained; bp106
_~ 108°C/0.04 Torr; ^n20D = 1.5738. 77 g of p-(m-tolyloxy)anisole are dissolved in 360 ml of acetic acid and then treated with 300 ml of 48% hydrobromic acid. The mixture is then allowed to react for 5 hours at reflux temperature. The cooled reaction solution is poured into 1.5 liters of ice water and extracted three times with 150 ml of methylene chloride each time. The organic solution is washed three times with 150 ml each time of water, then with 150 ml of saturated sodium bicarbonate, dried over sodium sulfate and then evaporated. Distillation of the crude product yields pure p-(m-tolyloxy)phenol; bd 88-89°C/0.04 torr. The following compound is obtained in a similar manner to that of the above example: from 4-chloro-o-cresol and 4-bromoanisole bp 112-116°C/p of 0.04 Torr.
-(p-chloro-o-tolyloxy)anisole is obtained; from this using hydrobromic acid/acetic acid, p-
-(p-chloro-o-tolyloxy)phenol is obtained; mp 83-85°C; from m-nitrophenol and 4-bromoanisole, p-(m-nitrophenoxy)anisole with mp 69-71°C is obtained; Using hydrohydric acid/acetic acid, p-(m-nitrophenoxy)phenol is obtained, the product is collected in a spherical tube from 95 to
Distill at 97°C/0.04 torr; from 4-methoxy-o-cresol and bromobenzene to bp 102-104°C/0.035 torr and
Obtain 5-methoxy-2-phenoxytoluene with mp 39-42°C, then use hydrobromic acid/acetic acid from this to obtain p-phenoxy-m-cresol; mp 96-99°C; m-fluorophenol and 4-bromoanisole to p-(m
-fluorophenoxy)anisole, which is then converted to p-(m
-fluorophenoxy) phenol; m.
p.53-55℃. Formulation Examples Example 6 Emulsified concentrate (particularly suitable for liquid active substances of the formula) g/active substance of the formula 250 N-methyl-2-pyrrolidone 300 alkylphenol-ethylene oxide adduct
35 Calcium salt of dodecylbenzenesulfonic acid 15 Cycloalkyl epoxy stearate 25 Aromatic solvents (mixtures of C ₁₀ -alkylbenzenes)
Volume to bring the total volume to 1000 ml The active substance is dissolved in N-methyl-2-pyrrolidone, then the remaining ingredients are added, dissolved and the mixture is quantified with an aromatic solvent. To prepare a ready-to-use spray solution, this product is added to water, thus immediately obtaining a time-stable emulsion (O/W). Example 7 Powder for spraying Weight % Active substance of the formula 25 Silicic acid, hydrate (approximately 87% SiO ₂ ) 30 Sodium lauryl sulfate 2 Sodium lignosulfonate 4 Kaolin, mainly AAl ₂ [Si ₂ O ₅ ] (OH) ₄ 39 100 Mix the active substance homogeneously with the remaining ingredients in suitable equipment. The resulting powder is then milled using a suitable grinding device (for example, a disc mill with pins, a hammer mill,
Finely milled in a ball mill or air jet mill to the particle size required for optimal biological activity and then mixed again. This sprayable powder immediately wets with water to give a ready-to-use spray liquid that is well suspended. Example 8 Granules Weight % Active substance of the formula 5 Ethylenediaminotetraacetic acid tetrasodium salt (Na ₄ - EDTA) 1 Pumice granules, 0.6-1.0 mm 94 100 Place the pumice granules in a suitable mixing mill and add Na ₄ -
Spray an aqueous solution of EDTA onto it with constant stirring. The mixture is dried at 110° C. and then the active substance dissolved in a suitable solvent (for example methylene chloride) is sprayed onto the dry mixture. The solvent is evaporated by heating. Granules are obtained which have good shakenability and can be applied to soil or water by hand, with a suitable granule spreader or even by aircraft. The porous structure of pumice often provides the desired delayed release of active substances over extended periods of time. Evaluation of pest control activity The compounds according to the present invention represented by the following compounds A to K were tested for their activity against pests: Test 1: Activity against orthoptera, Blattella ermanica (Japanese cockroach) (first method) The bottom of a glass Petri dish (φ48 mm x 18.1 cm ² ) is treated with an acetone solution of a test compound at a known concentration.
Place 10 newly hatched, first instar larvae into each dish, then cover with a small plastic cup. Feed the larvae with dog biscuits and water;
℃ and maintained at 60% relative humidity. As a control, use untreated and larvae on glass Petri dishes treated with acetone solution. After a test duration of 14 days, the percentage reduction in larval survival compared to the control was evaluated. Untreated controls showed a 3% mortality rate. Test 2: Homoptera, Aphis
Activity against the black bean aphid (black bean aphid) Young bean plants in the field are sprayed with an acetone solution of the test compound at a known concentration. Two hours after treatment, plants are infected with 5 female wingless adults (p generation) and incubated at 21° C. and 60% relative humidity. Two days later, the adults are removed and the expression of the F ₁ -generation is followed. On day 8 post-infection, F ₁ -animals and
F ₂ - Record the number of animals. Adults on untreated and acetone-treated plants are used as targets. The results are shown in the table below as a comparison against the control.
Expressed as a percentage reduction in the number of F. fae (F ₂ -animals). Test 3: Homoptera Trialeurodes vaporariorum (greenhouse white fly)
Activity against 30-50 newly laid eggs (0-15 hours old)
Spray an acetone solution of the test compound at a known concentration onto a bean leaf disk (φ25 mm). The test disk was placed on damp foam rubber at 25°C.
and maintained under 60% relative humidity. On day 9 after treatment, the percentage reduction in survival of F ₁ -generation animals was evaluated compared to controls. Untreated controls showed 3% mortality (first method) Test 4: Diptera, Musca domestica
Activity against the domestic fly 0.5 ml of an acetone solution of the test compound of known concentration is mixed with 50 g of dirt (“Dielsdorfer Landerde”). On the first day after treatment, 10 final instar larvae are added and maintained at 25°C and 60% relative humidity until adults emerge. As a control, larvae in untreated soil and acetone treated soil are used. On day 9 after treatment, the percentage reduction in the number of normal adult worms compared to the control was assessed. Untreated controls showed a 4% mortality rate. Test 5: Mobile stage mite, Tetranychus urticae (two-spotted spider mite)
Activity against Bean leaf discs (3.8 cm ² ), each infected with 10 adult female two-spotted spider mites, are sprayed with an acetone solution of the test compound at a known concentration. The sprayed infected discs are placed on moist foam rubber and maintained at 25°C and 60% relative humidity. As a control, discs of untreated and acetone-treated bean leaves are used which are also infected with two-spotted spider mites. The test duration is 3 days. On the third day after treatment, the percent reduction in survival of adult female two-spotted spider mites treated with the test compound compared to the control was evaluated. Controls showed a 2% mortality rate. Test 6: Activity against eggs of the mite Tetranychus urticae (two-spotted spider mite) Bean leaf disks (3.8 cm ² ) are infected with 8 to 10 adult female two-spotted spider mites per disk.
After one day, remove the female two-spotted spider mite and remove disk 1.
Leaf discs containing approximately 80 eggs each are sprayed with a solution of the test compound in acetone at a known concentration. The sprayed infected discs are placed on moist foam rubber and maintained at 25°C and 60% relative humidity.
As controls, discs of untreated and acetone-treated bean leaves infected with one-day-old eggs of the two-spotted spider mite are used. The test duration is 7 days. The percentage reduction in the hatching rate of _L2 larvae of eggs treated with the test compound compared to the control was evaluated 7 days after treatment. The control showed a mortality rate of 6%. Test 7: Activity against the lepidopteran, Adoxophyes orana (summerfruit tortrix moth) Ten final instar larvae were placed in small larvae whose base had been treated with an acetone solution of the test compound at a known concentration. Place in a petri dish. The larvae are fed artificial food and maintained at 25°C and 60% relative humidity until they develop into adults. As controls, untreated and acetone-treated dishes are used that also contain larvae. The study duration is 15-20 days. 15-20 days after treatment, the percentage reduction in the number of normal adults from larvae treated with the test compound compared to the control was evaluated. Controls showed 4% or 5% mortality. Test 8: Activity against the Coleoptera, Leptinotarsa decemlineate (Colorado Potato Beetle) (Method 1) 1 ml each of the acetone solution of the test compound is mixed with 50 cm ³ of a clay pot (“Dielsdorfer Landerde”). On the first day after treatment, 10 final instar larvae are added and maintained at 25°C and 60% relative humidity until adults emerge. As a control, larvae were also infected with
Use untreated and acetone treated clay jars. The test duration is 9 days. On day 9 after treatment, the percentage reduction in the number of normal adults from larvae treated with the test compound compared to the control was evaluated. Controls showed a 4% mortality rate. Test 9: Diptera, Aedes
aegypti) (yellow fever pathogenic mosquito) 20μ of an acetone solution of the test compound of known concentration is mixed with 2ml of water (tap water: distilled water = 1:1).
Approximately 10 newly hatched first instar larvae were added to the treated water and incubated in test tubes at 25°C (compound E) or 20°C.
(Compounds F and H) and maintained at 60% relative humidity. The test tubes are filled with pieces of fish food (compound E) or hampster food (compounds F and H) as nutrients. As controls, untreated and acetone-treated larvae in water are used. On the fourth day after treatment, the percentage reduction in larval survival compared to the control was assessed. Untreated controls showed 6% or 7% mortality. Test 10: Activity against the Diptera, Culex pipiens (boreal mosquito) 1 ml of an acetone solution of the test compound of known concentration is mixed with 100 ml of tap water. Ten final instar larvae are then added to the treated water and maintained at 25° C. and 60% relative humidity until the adults emerge. Feed small pieces of dog biscuits. As controls, untreated and acetone-treated larvae in water are used. Seven days after treatment, the percentage reduction in the number of adult adults was evaluated compared to the control. Untreated controls showed 6% or 2% mortality. Test 11: Diptera Musca domestica
Activity against domestica domestica (house fly) (second method) A set of Petri dishes (φ9 cm) is sprayed with an acetone solution of the test compound at a known concentration. Two to three hours after spraying, ten 4-5 day old flies are placed in each Petri dish and maintained at 25°C and 60% relative humidity. As controls, untreated and acetone-treated dishes are used that also contain larvae. The test duration is 1 day. At 24 hours after treatment, the reduction in survival of flies treated with the test compound compared to controls is assessed. Controls showed a 2% mortality rate. Test 12: Orthoptera, Blattella germanica (Japanese cockroach)
Activity against (second method) A filter paper disk (10 cm ² ) is moistened with an acetone solution of the test compound at a known concentration. The treatment disk is then folded into a tunnel and placed into a small plastic cup along with the early final instar larvae. For three weeks, the insects are fed dog biscuits and water and maintained at 25°C and 60% relative humidity. Untreated and acetone-treated larvae are used as controls. After a test period of 3 weeks, the percentage reduction in the number of normal larvae from larvae treated with the test compound compared to the control was evaluated. Controls showed 4% or 1% mortality. Test 13: Activity against the Diptera Tribolium castaneum (Red Frauer Beetle) 10 g each of flour is moistened with an acetone solution of the test compound of known concentration. Each of the treated flour
Place the 20 final instar larvae in one of a set of small glass tubes at 29°C and 75°C until the adults emerge.
Maintain at ~80% relative humidity. As a control, untreated and acetone-treated flour is used, also with larvae, in glass tubes. The test duration is 2 days. After 2 days, the percentage reduction in the number of normal adults from larvae treated with the test compound compared to the control was evaluated. Controls exhibited a 4% mortality rate. Test 14: Activity against the Diptera Rhyzopertha dominica (Meal beetle) A quantity of 20 g each of flour is moistened with an acetone solution of the test compound of known concentration. 20 wheat grains for each treatment
They were placed in a set of small glass tubes along with a few adult white-bellied beetles and incubated for 20 minutes until _F1 generations emerged.
Maintain at 75-80% relative humidity. As a control, untreated and acetone-treated wheat grains placed with adult mealybugs in glass tubes are used. The trial duration is approximately 60 days. After approximately 60 days, the percentage reduction in F ₁ -generation from adult mealybugs treated with the test compound compared to the control was evaluated. Controls showed a 4% mortality rate. Test 15: Activity against the dipteran Sitophilus granarius (cereal weevil) Wheat kernels in quantities of 20 g each are moistened with an acetone solution of the test compound of known concentration. Each amount of grain processed
Place in a set of glass tubes with 20 adult elephants and maintain at 29 °C and 75-80% relative humidity. Ten
After a day, the parental food was removed and the tubes and contents were kept at the above temperature and humidity until the F ₁ -generation emerged.
Retain for an additional period of time. For comparison,
Untreated and acetone-treated kernels are used with adult elephant insects in glass tubes. The trial duration is approximately 50 days. After approximately 50 days, the percentage reduction in F ₁ A-development from adult elephant insects treated with the test compound compared to the control was evaluated. Controls showed a 4% mortality rate. Test 16: Diptera Musca domestica
Activity against Domestica domestica (house fly) (third method) 10 g of medium are mixed with a solution of the test compound of known concentration in acetone. Ten 2-day-old larvae were placed in this treated medium and kept for 25 days until adults emerged.
℃ and maintained at 60% relative humidity. As a control, larvae in untreated and acetone-treated medium are used. After a test period of 10 days, the percentage reduction in the number of normal adults compared to the control was evaluated. Untreated controls showed 8% mortality. Test 17: Activity against the Diptera, Leptinotarsa decemlineata (Colorado Potato Beetle) (Second Method) Approximately 30 newly laid eggs of Leptinotarsa decemlineata were sprayed with an acetone solution of a known concentration of the test compound and 25 Incubate at °C and 60% humidity. Feed newly hatched larvae with fresh leaves. Untreated and acetone treated are used as controls. On the 6th day after treatment, the percentage reduction in first instar larval survival compared to the control was assessed. Controls showed a 1% mortality rate. The results of the above tests are shown in the table below:

【table】

【table】

【table】

Claims (1)

[Claims] 1. General formula (In the formula, R ¹ is hydrogen, halogen, methyl, ethyl,
represents trifluoromethyl or nitro; R ² represents hydrogen, halogen, methyl or trifluoromethyl; R ³ represents hydrogen, halogen or methyl; R ⁴ represents hydrogen or methyl; R ⁵ represents hydrogen or C _{1 ~4} - Represents alkyl, provided that R ⁴ and R ⁵ cannot both represent hydrogen at the same time. R ⁶ represents C _1-4 alkyl, X represents oxygen, methylene or carbonyl, and Y represents oxygen or sulfur). 2. A compound according to claim 1, wherein R ¹ represents hydrogen, fluorine, chlorine, bromine, methyl or trifluoromethyl. 3. A compound according to claim 1 or 2, wherein R ² represents hydrogen, fluorine or chlorine. 4 Claims 1 to 4 in which R ³ represents hydrogen
A compound according to any one of clauses 3. 5. A compound according to any one of claims 1 to 4, wherein ^R5 represents hydrogen, methyl or ethyl. 6 Claims 1 to 5 in which R ⁶ represents methyl, ethyl, isopropyl or isobutyl
A compound according to any one of paragraphs. 7. A compound according to any one of claims 1 to 6, wherein X represents oxygen or methylene. 8. The compound according to claim 1, which is ethyl {2-[p-(p-fluorophenoxy)phenoxy]ethyl}methylcarbamate. 9 Ethyl [2-(p-phenoxyphenoxy)
The compound according to claim 1, which is ethyl]methyl carbamate. 10. The compound according to claim 1, which is ethyl {2-[p-(3,5-dichlorophenoxy)phenoxy]ethyl}methylcarbamate. 11. The compound according to claim 1, which is ethyl 2-[p-(p-fluorophenoxy)phenoxy]propyl carbamate. 12 Ethyl [2-(p-benzylphenoxy)
Ethyl] methyl carbamate, Ethyl [2-(p-phenoxyphenoxy) ethyl] ethyl carbamate, Ethyl [2-(p-phenoxyphenoxy) ethyl] isopropyl carbamate, Ethyl [2-(p-phenoxyphenoxy) ethyl] cyphenoxy) ethyl]-n-butyl carbamate, ethyl {2-[p-(m-bromophenoxy)
phenoxy]ethyl}methyl carbamate, ethyl 2-(p-phenoxyphenoxy)propyl carbamate, and ethyl 2-[p-(m-bromophenoxy)phenoxy]propyl carbamate. Compound. 13 Ethyl {2-[p-(m-fluorophenoxy)phenoxy]ethyl}methylcarbamate, Ethyl {2-[p-(p-chloro-o-tolyloxy)phenoxy]ethyl}methylcarbamate, Ethyl[2- (p-phenoxy-m-tolyloxy)ethyl] methyl carbamate, methyl [2-(p-phenoxyphenoxy) ethyl] methyl carbamate, isopropyl [2-(p-phenoxyphenoxy) ethyl] methyl carbamate, Methyl 2-(p-phenoxyphenoxy)propylcarbamate, Isopropyl 2-(p-phenoxyphenoxy)propylcarbamate, Isopropyl {2-[p-(α,α,α-trifluoro-m-tolyloxy) )-phenoxy]ethyl}methylcarbamate, ethyl {2-[p-(m-tolyloxy)phenoxy]ethyl}methylcarbamate, ethyl{2-[p-(p-nitrophenoxy)
Phenoxy]ethyl}methylcarbamate, isopropyl[2-(p-benzoylphenoxy)ethyl]methylcarbamate, ethyl 2-[p-(p-fluorobenzoyl)
Phenoxy]propyl carbamate, isopropyl 2-[p-(m-bromophenoxy)phenoxy]propyl carbamate, S-ethyl[2-(p-phenoxyphenoxy)ethyl]methylthiocarbamate, ethyl 2-[p-(m- Chlorphenoxy) Phenoxy] Propyl carbamate, Ethyl {2-[p-(m-Chlorphenoxy)
Phenoxy]ethyl}methylcarbamate, ethyl 2-[p-(m-nitrophenoxy)phenoxy]propylcarbamate, ethyl{2-[p-(m-nitrophenoxy)
Phenoxy]ethyl}methylcarbamate, Ethyl{2-[p-(o-fluorophenoxy)phenoxy]ethyl}methylcarbamate, Ethyl 2-(p-benzylphenoxy)propylcarbamate, Ethyl 2-(p-benzoyl phenoxy)propyl carbamate, ethyl [2-(p-benzoylphenoxy)ethyl]methylcarbamate, ethyl {2-[p-(p-chlorobenzyl)phenoxy]ethyl}methylcarbamate, and ethyl 2-[p -(m-fluorophenoxy)
Phenoxy]propyl carbamate, a compound according to claim 1 selected from: 14 At least one general formula (In the formula, R ¹ is hydrogen, halogen, methyl, ethyl,
represents trifluoromethyl or nitro, R ² represents hydrogen, halogen, methyl or trifluoromethyl, R ³ represents hydrogen, halogen or methyl, R ⁴ represents hydrogen or methyl, R ⁵ represents hydrogen or C _{1 ~4} - Represents alkyl, provided that R ⁴ and R ⁵ cannot both represent hydrogen at the same time. R ⁶ represents C _1-4 -alkyl, X represents oxygen, methylene or carbonyl, and Y represents oxygen or sulfur) and an inert carrier material. thing. 15. The composition of claim 14 containing an effective amount of ethyl {2-[p-(p-fluorophenoxy)phenoxy]ethyl}methylcarbamate. 16. The composition of claim 14 containing an effective amount of ethyl [2-(p-phenoxyphenoxy)ethyl]methyl carbamate. 17. The composition of claim 14 containing an effective amount of ethyl {2-[p-(3,5-dichlorophenoxy)phenoxy]ethyl}methylcarbamate. 18. The composition of claim 14 containing an effective amount of ethyl 2-[p-(p-fluorophenoxy)phenoxy]propyl carbamate. 19 General formula (In the formula, R ¹ is hydrogen, halogen, methyl, ethyl,
represents trifluoromethyl or nitro, R ² represents hydrogen, halogen, methyl or trifluoromethyl, R ³ represents hydrogen, halogen or methyl, R ⁴ represents hydrogen or methyl, R ⁵ represents hydrogen or C _{1 ~4} - Represents alkyl, provided that R ⁴ and R ⁵ cannot both represent hydrogen at the same time. R ⁶ represents C _1-4 -alkyl, X represents oxygen, methylene or carbonyl, and Y represents oxygen or sulfur), comprising: (wherein R ¹ , R ² , R ³ and X have the above meanings), the phenol of the general formula A process characterized in that it is reacted with a compound of the formula (R ⁴ , R ⁵ , R ⁶ and Y have the meanings given above and Q represents a leaving group).