JPS59157077A - Insecticidal nitromethylene derivative - 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 The present invention relates to certain substitutions; i, 2-nitromethylene-
Tetrahydro-J H-/,3'-)riazine, a process for its preparation and its use as an insecticide, especially against insect pests.

U.S. Patent No.
．． The compound 3-trianone and its insecticidal properties are described. It has now been discovered that certain similar thianone derivatives containing ester or thioester groups also exhibit interesting insecticidal activity.

Accordingly, the present invention provides a purified non-nitromethylene-tetrahydro-jH-/3-thiazine represented by the following formula.

co-(co)m-x-g where n is 0 or p; m is 0 or /;
X is oxygen or sulfur; and R is 1 selected from a halodane atom and a hydroxy group, a thiol group, an acyloxy group, an acylthio group, an alkoxy group, an alkoxyalkoxy group, a haloalkoxy group, and an optionally substituted phenyl group. is an alkyl, alkenyl or alkynyl group optionally substituted by one or more of the same or different substituents.

Unless explicitly stated otherwise, throughout this specification each moiety of an alkyl, alkenyl or alkynyl group preferably has up to 6, in particular up to t, carbon atoms.

Preferred substituents that may be present on the optionally substituted phenyl moiety include halogen atoms and alkyl, haloalkyl, alkoxy, haloalkoxy, cyanogen, nitro, amino and hydroxy groups. Particularly preferred substituents are a halogen atom and a C(/-11-)alkyl group, especially a methyl group.

Preferred acyl groups are formyl and optionally substituted alkanoyl and benzoyl groups, wherein preferred substituents for the benzoyl group are those as indicated above for the phenyl group, and preferred substituents for the alkanoyl group. These are halogen atoms, alkoxy groups and phenyl groups.

The preferred structure R is a halogen atom and a hydroxy group, a formyloxy group, an alkanoyloxy group having /- carbon atoms in the alkyl moiety, an alkanoylthio group, an alkoxy group having /-≠ carbon atoms. , in particular up to 6, optionally substituted by 7 or more same or different substituents selected from alkoxyalkoxy groups having 7 or 2 carbon atoms in each alkoxy moiety and phenyl groups. Represents an alkyl group, an alkenyl group or an alkynyl group having up to ≠ carbon atoms.

Preferably X represents an acid group, preferably m is 0, preferably n is 0.

Thus, a typical compound of formula (III) is such that n is 0 and necessarily 9, and the group -(CO)mXR is optionally substituted by 3 chlorine atoms or phenyl groups at 1/-6 carbons. alkoxy radicals having atoms such as methoxy, ethoxy, imbutoxy, trichloroethoxy or pennoloxy, or alkoxycarbonyl or alkynyloxy radicals each having up to 6 carbon atoms, such as ethoxycarbonyl or propynyloxy A compound of formula I representing a group.

Another exemplary compound of formula I is where n is 0 and the group -(Co)XR is optionally substituted by a hydroxy group or an acyloxy group having up to 3 carbon atoms, Compounds of formula I which represent a substituted alkoxy radical having /-6 carbon atoms, such as a bromoethoxy radical, a hydroxyethoxy radical, a formyloxyethoxy radical or an acetoxyethoxy radical.

It will be appreciated that compounds of formula 1 can exist in various geometric isomeric forms. The present invention encompasses both individual isomers and mixtures of such isomers.

The present invention also provides R-X
-(Co)m-Co-Hal (III)
(wherein R, If desired, it also includes a process for the preparation of substituted non-nitromethylene-tetrahydro-,2H-/,3-thia-cines of formula I, which comprises liquefying this compound to the corresponding compound which is n2/. There is. The base is preferably an organic base such as a tertiary amine, such as a trialkylamine, with triethylamine being particularly preferred. The reaction is preferably carried out at a temperature of 0°C or lower, for example -60°C to 0°C, preferably -30°C to -70°C. The reaction is suitably carried out in an organic solvent, for example a chlorinated hydrocarbon such as dichloromethane or an amide such as trimethylformamide.

Compounds of formula I where n is / can be prepared by oxidizing the corresponding derivative where n is 0. This can be accomplished using conventional oxidizing agents such as peracids such as m-chloroperbenzoic acid or acidic potassium persulfate. The derivative to be oxidized is conveniently dissolved in a suitable agent, for example a chlorinated hydrocarbon solvent such as chloroform or dichloromethane or a liquid alkanol such as ethanol.

Can be prepared in order by N-acylation of compounds 2〇,
Compounds of formula I -iH can also be prepared from compounds other than compounds of formula I. For example, compounds in which R contains a hydroxy group, a thiol (mercapto) group, an acyloxy group, or an acylthio group can be prepared by reaction with the corresponding acyloxy or acylthio salt and optionally hydrolyzed so that R is It can be produced from compounds containing atoms.

As mentioned above, the substituted nonitromethylene-tetrahydro-,2H-/,3-thianones of the present invention are of particular interest as insecticides against insect pests. These compounds are useful for insects such as Spodonotella (5podop.
tera) species and Heliosis (Hel 1othi)
s) exhibiting activity against pests such as larval or worm forms of seeds. They are particularly useful in combating all pests found in rice crops. For certain applications, the combined physical and biological properties of the compounds of the invention may be compared to the known insecticide, 3-acetyl-! -Nitromethylene-tetrahydro-2)I is more advantageous than that of -7,3-thiazine.

Accordingly, the present invention encompasses insecticide compositions comprising the substituted non-nitromethylene-tetrahydro-JH-/,3-thianone of the present invention together with a carrier.

Such compositions can contain a single compound of the invention or a mixture of several compounds. It is also anticipated that different isomers or mixtures of isomers will have different activity levels or spectra of activity, and that such compositions will include individual isomers or mixtures of isomers. The present invention further includes:
Also provided is a method of combating pests, particularly insect pests, at a location, which comprises applying to a location an insecticidal effective amount of a compound or composition of the invention. Particularly favorable locations are rice fields with rice crops.

The carrier in the composition of the invention may be, for example, a plant, seed or soil, to facilitate application to the area to be treated, to facilitate storage, transport or handling. The carrier is a solid or liquid material that is normally a gas except when compressed to form a liquid, and the insecticide composition is a material with which the active ingredient is formulated. Any carrier commonly used in formulations can be used. Preferably, the compositions of the invention contain 0.3-'; 3-% by weight of active ingredient.

Suitable solid carriers are natural and synthetic clays and silicates, such as natural silicas such as diatomaceous earth; magnesium silicates, such as talc; magnesium aluminum silicates, such as athanokurgite and... mica; calcium carbonate; calcium sulfate; ammonium sulfate; synthetic silicate hydrates and synthetic calcium or aluminum silicates; elements such as carbon and sulfur; natural and synthetic resins, such as coumaron resins,
Includes polyvinyl chloride and styrene polymers and copolymers; solid polychlorophenols, (8) olefins, waxes, waxes, and solid fertilizers such as superphosphates.

Suitable liquid carriers are water; alcohols such as inzolopanol and glycols; ketones such as acetone,
Methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ethers; aromatic or aromatic hydrocarbons such as benzene, toluene and cyclohexanone;
mixtures of different liquids are often suitable.

Agricultural composition! RI is often formulated and shipped in concentrated form, which is then diluted by the user before application. The presence of a small amount of surfactant carrier facilitates this dilution process. Thus, preferably at least seven carriers in the composition of the invention are surfactants. For example, the composition can include at least two carriers, at least/of which is a surfactant.

Surfactants are emulsifiers, dispersants or wetting agents, which may be nonionic or ionic.

Examples of suitable surfactants are sodium or calcium salts of polyacrylic acids and ligninsulfonic acids; fatty acids or aliphatic amines or amides containing at least 72 carbon atoms in the molecule and ethylene oxide and/or zolopyrene oxide. combinations of fatty acid esters of glycerol, nrubitan, saccharose or pentaerythritol; combinations of these esters with ethylene oxide and/or propylene oxide; fatty alcohols or alkylphenols such as p-octylphenol or p-octylcresol; condensation products with ethylene oxide and/or propylene oxide; sulphates or sulfonates of these condensation products; alkali or alkaline earth metal salts of sulphate or sulphonic acid esters containing at least 70 carbon atoms in the molecule, preferably ) sodium alkylaryl sulfonates such as sodium lauryl sulfate, sodium secondary alkyl sulfate, sodium salt of sulfonated castor oil, and dodecylbenzene sulfonate; and polymers of ethylene oxide and ethylene oxytodopropylene oxide. It includes copolymers with.

The compositions of the invention can be formulated, for example, in the form of wettable powders, powders, granules, solutions, emulsifiable concentrates, emulsions, suspension concentrates and aerosols.

Wettable powders usually contain 2 to 70 parts by weight of active ingredient and, in addition to a solid inert carrier, usually 3 to 70 parts by weight of a dispersing agent and, if necessary, 0 to 70 parts by weight of a stable agent. and/or other additives such as penetrating or spreading agents.

Dusts are usually formulated in the form of dust concentrates with a similar composition to wettable powders but without dispersants, and are further diluted with solid carriers in the field, usually to a concentration of 0. j-70 by weight of the active ingredient. Granules are usually 10 to 10
OBS Metsuyu (/, Otsu 7 Otsu-0, / j 2 wn
) and can be manufactured by agglomeration or impregnation methods. Generally, granules are 0
．． It contains 3-75 parts by weight of active ingredient and o-1o-H parts by weight of additives such as stabilizers, surfactants, delayed release modifiers and binders. So-called "dry flowable powders" consist of a relatively low granulation force X containing a relatively high concentration of active ingredient.

Emulsifiable concentrates usually contain a solvent and, if necessary, a co-solvent, as well as 70-3;0 weight/volume of active ingredient, no 20 weight/volume of emulsifier and 0-20 weight/volume of active ingredient. Contains other additives like stabilizers, penetrants and anti-corrosion agents. Suspension concentrates are usually formulated to obtain stable, non-settling fluid products and usually contain 10-73 parts by weight active ingredient, 0.5 parts by weight dispersant, 0.7 parts by weight.
Suspending agents such as mining colloids and thixotropic agents by weight of 70, defoamers, anti-corrosion agents, stabilizers, penetrants and spreading agents by weight and water or organic substances in which the active ingredient is substantially insoluble. Other additives such as liquids may be included, and certain organic solids or inorganic salts may be present in the formulation in solution to help prevent settling or as antifreeze agents for water.

Also within the scope of the invention are aqueous dispersions and emulsions, such as compositions obtainable by diluting the wettable powders or concentrates according to the invention. The above emulsions can also be water-in-oil type.
Alternatively, it may be oil-in-water and have a "mayonnaise"-like consistency.

The compositions of the invention may also contain other ingredients, such as other compounds having insecticidal, herbicidal or fungicidal properties, or attractants, such as bait pheromones or food ingredients for use in bait and capture formulations. can include.

Thermal stability of the compounds and compositions of the invention is determined by the presence of stabilizing amounts of certain organic nitrogen compounds, such as urea, noalkylurea, thiourea or guanidine salts, usually 10-700 parts by weight, based on the compound; It has also been found that improvements can be made by the addition of alkali metal salts of weak acids such as bicarbonates, acetates or benzoates.

The invention is further illustrated by the following examples.

Non-nitromethylene in theazine chloromethane (Otsu 0ml)
A solution containing tetrahydro-,2H-7,3-thiazine (μI) and triethylamine (10,≠rnl) was added with dichloromethane (0ml) of methoxyrudenyl chloride (jnia) at -20°C under a nitrogen atmosphere. g) The solution was added in portions over 30 minutes. The reaction mixture was warmed to ambient temperature for 60 minutes and washed with to2'% hydrochloric acid. The organic phase was dried over magnesium sulfate).
, the solvent was removed under reduced pressure. The residue was triturated with ethyl acetate to give the desired product, mp 73-93°C.

Calculated value for analysis C7H1oO4N2S c3g, 3%
; HIA%; N/, 2. g % measured value C3f
,'lchi;1. Part 2: N/No, 100 grams of dichloromethane dissolved in a solution of 10 grams of free bromo ether chloroformate at -30°C under a nitrogen atmosphere! −
Nitromethylene-tetrahydro-2H-7,3-thiazine/2. fg1 triethylamine, 2/, m! and dichloromethane, added portionwise over 7 minutes. The reaction mixture was warmed to 0.degree. C. for 30 minutes with stirring and washed with aqueous hydrochloric acid.

The organic phase was separated and dried (over magnesium sulphate) and the solvent was evaporated. /99:/ mixture (volume/volume) of dichloromethane and methanol
, 272g) When purified on an FC silica gel column,
7 ter! A crystal with a melting point of i1'/°C/'l;'
, 7! j was obtained.

Calculated value for analysis C3H11N204SBr C30,9
%; H3J%; N5', 0'g measurement value C30,7qb
;H3,,! Section; N, Section 7 Compound of Example No. (g
&)'e33; ml of hexamethylphosphoramide (H
MPA) and added to a solution of sodium formate in MPA≠jml at θ° C. under a nitrogen atmosphere.

The mixture was stirred at 20° C. for 3 hours, then poured into diethyl ether and washed with brine and back with diethyl ether. The combined organic phases were dried and evaporated to yield an oil (IOI), which was purified by column chromatography on silica to give the title compound in the form of an entirely yellow crystalline solid (3,fg). The starting material (0,7,?) was recovered at the same time as the melting point Otsu Otsu - Otsuri °C Calculated value for analysis C7H,,,2N206S C39,1
%;[444”16;N10./%1jllll constant value C39,,2%; H41-,,2%;N10.0
% hydro-2H-7,3-thiazine at a flow rate of about 33 ml per minute using a dichloromethane/methanol mixture (9 min/3. vol/vol) as eluent. Neutral alumina (200
g) column. The eluted material was concentrated and purified by column chromatography on silica to yield the title compound (/, 7 g) and the starting material (
ooog) '1 recovered. The melting point of the product is j7-6/
It was ℃.

Calculated values for analysis C3H12N205S C3f, 7chi;
HIAg section', N//, 3 section analysis value C39, 0 section; H
EXAMPLE 10.5 - 2f Further compounds were prepared using a procedure similar to that of the previous example. These compounds had melting points and analyzes as shown in Table A. ° is identified.

Example 27 Preparation of S-oxide of the compound shown in the example. The compound shown in the example (,
2.0 g) Add 75 g of ffi to the dissolved solution while stirring.
m-Chloroperbenzoic acid (,2,0y) dissolved in nochloromethane (100 ml) was added portionwise over 30 minutes at 0.degree. C. The mixture was warmed to room temperature and then 2.
Stir for hours. Sodium carbonate (2 g) was added and the mixture was stirred for an additional 7 hours, filtered, and the solvent was removed under reduced pressure. The residue was purified by column chromatography on silica to yield the desired product in the form of ONk oil.

Calculated value for elemental analysis C7H12N03Br C2'7%
;H3,! f; %: Ng, / % measured value C2, ≠; H3, ≠; Nff, ≠; activity was evaluated.

Aphis fabae:r, (Aphis fabae
) (A, f,) The test method used for each type is shown below. For each test, unless otherwise stated, o, o Il's Torida (Trit.
on) Contains X-100 (Trade Name)/B, 7 A solution or suspension containing all of the test compounds of Section 0.2 in an aqueous solution of thiacetone was sprayed onto all test species, and the same proportion of water, A control solution of acetone and Tricon X-700 (trademark 315) was sprayed onto all controls. All tests were conducted under normal insect farm conditions of 23°C (with varying light and humidity).

(1) Subodoptera littoralis (S, 1.) second instar larvae were used in the test. Each test and control solution was sprayed onto a separate feed containing nutritious food on which Subodozotella littoralis larvae were being maintained.

When the spray deposit dried, 70 second instar larvae were placed on each side. Seven days after spraying and 7 days later, all deaths were counted and the mortality percentage was calculated.

(11) Early fourth instar larvae of Aedes aegypti (A. a. a.) were used in the test. 0.0≠ Triton x-ioo
The test solution was prepared to contain 3 ppm of active ingredient in water.

Acetone was initially present to aid dissolution, but this was later removed by evaporation.

Seventy early fourth instar larvae were placed in 700 ml of the test solution. Larval mortality (expressed as a percentage) was recorded after ≠ hours.

The surviving larvae are then fed a small amount of animal food pellets;
Then all the larvae turn into spiders and turn into adults'l)
The final mortality percentage of adults and axes was assessed at h, or when they died.

011) House flies (M, d,) Seventy adult female house flies, 1, 2-3 days old and fed with milk, anesthetized using carbon dioxide, were placed in Petri dishes lined with Gucci K, F paper. placed on top. The test formulation vI:J was sprayed onto the dishes using a spray machine operating on the logarithmic dilution principle. The flies were then kept in a Petri dish and given a thin milk solution that was dripped onto the side of the Petri dish and absorbed onto the paper. Mortality was assessed after 241 hours.

4V) Aphis fapae (A, f,) adult black bean
Tests were conducted on Aphis fabs. A pair of broad bean leaves on a paper in a Petri dish were sprayed in parallel with numerous aphids in a small gauze-covered container. After being sprayed, the aphids were attached to the leaves and the petri dish was covered with a lid. , mortality was assessed after 241 hours.

The results of these tests are shown in Table B, in which the test glazes are identified by the initials above, and the activity of each compound is expressed by percentage mortality.

Showing the mortality rate of A-line o-1oo, B indicates a mortality rate of 0%, C indicates the mortality rate of θ-17-Oqb.

Example 3 / Determination of Toxicity Index Corn airworm larvae of a compound according to the invention compared with the standard insecticide parathion by spraying broad bean plants with a dilute aqueous solution of the test compound in acetone containing an emulsifier. He1iothis zea
) was tested for toxicity. Immediately after spraying, five larvae were transferred to the plants, and the number of dead larvae and larvae that died and ceased to be active during the holding period was counted.

Tests were carried out using several different application rates for each test compound. In each case, the toxicity of the compound of the invention was compared to that of the standard insecticide, parathion, and then
The relative toxicity was expressed by the relationship between the amount of the compound of the invention and the standard insecticide required to produce =% mortality. Standard insecticides are given an arbitrary toxicity index of 100. Therefore, a test compound with a toxicity index of 200 will have twice the activity of a standard insecticide. The measured toxicity index is shown in Table 6.

Table C Example number ・Survivability index of compound with parent thione 'r100/
Otsu3g 2 / 000 3 2000 ≠ 3000 evening /4#3; ta /f3ioio ioo.

// 1000 /-21000 Agent's name: Kawahara 1) - Ho

Claims (9)

[Claims] (1) Substituted ! expressed by the following formula! -nitromethylene-tetrahydro-2H-/, 3-thianone, where n is 0 or /; m is 0 or /;
XI′i is oxygen or sulfur; and R is a halogen atom and a hydroxy group, a thiol group, an acyloxy group, an acylthio group, an alkoxy group, an alkoxyalkoxy group, a haloalkoxy group, and an optionally substituted phenyl group. It is an alkyl group, alkenyl group or alkynyl group optionally substituted with 7 or more selected substituents of the same or different. (2) R is a halogen atom and a hydroxy group, a polmyloxy group, an alkanoyloxy group or an alkanoylthio group having /-≠ carbon atoms in the alkyl moiety, /-
7 or 2 selected from alkoxy groups having ≠ carbon atoms, alkoxyalkoxy groups having 7 or 1 carbon atoms in each alkoxy moiety, and phenyl groups.
Compounds according to claim 1 representing an alkyl, alkenyl or alkynyl group having up to 6 carbon atoms, optionally substituted by one or more of the same or different substituents. (3) The compound according to claim (1) or (2), wherein X is acid purple. (4) The compound according to any one of claims (1) to (3), wherein m is 0. (5) The compound according to any one of claims (1) to (4), wherein n is 0. (6) n is 0 and the group -(CO)mXR is optionally substituted by up to 3 chlorine atoms or phenyl groups/-alkoxy groups having up to 6 carbon atoms, or up to 6 each Alkoxylic with carbon atoms of ?
Compound 0 according to claim (1), in which all 7 nyl groups or alkynyloxy groups are present (7) n is 0 and the group -(CO)mXR is substituted by a bromine atom or a hydroxy group or an acyloxy group having up to 3 carbon atoms/-6 carbons represents an alkoxy group having an atom,
A compound according to claim (1). (8) In the presence of a base, a compound represented by the following formula is reacted with a halo compound represented by the following formula to obtain R-X
-(CO)m-CO-Hal (m)
(wherein R, , and, if desired, oxidizing this compound to the corresponding compound in which n is /. (9) An insecticide composition containing the compound described in any one of claims (1) to (7) together with a carrier. (1,0 The composition according to claim (9), comprising at least two carriers, at least seven of which are surfactants. 0]) Claim (1) Compounds described in any one of paragraphs to (7) are included in the scope of claims (
9) A method for exterminating pests at a certain place by applying the composition according to any one of item 10 to the place.