JPS5823646A - Improvement on insecticide - 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 an insecticide (-!Suchiciage), and more particularly to a novel insecticidal compound, its production, an insecticidal composition containing the same, and its insecticidal use. .

Since the structure of the naturally occurring Pyrethyl IJ insecticide was discovered in the 1940's, much research and development has been directed towards the production of its synthetic congeners. Naturally occurring insecticides are esters of cyclopropanecarboxylic acids. First of all,
Research was directed to the production of new esters of the same cyclopropane carbon content from which the naturally occurring products were obtained, but
Research has since turned to esters in which the 7-chloropronocarboxylic acid moiety of the molecule has been modified, and most recently non-esters of cyclopropanecarboxylic acid, but α-
It has now been discovered that valuable insecticidal compounds can be produced which are esters of substituted phenylacetic acids.

In developing new congeners of naturally occurring insecticides, repeated use of compounds that have improved insecticidal properties while exhibiting acceptable low levels of toxicity to mammals, fish, etc. Attention is being directed to the production of compounds which exhibit a sufficient level of physical stability so that they can be used in both industrial and domestic and horticultural applications without the need for oxidation.

It has now been found that a new structural type of compounds has a particularly valuable combination of biological and physical properties, making these compounds useful as insecticidal compounds.

Therefore, the present invention relates to the general formula [wherein Y is 10-1-S-1-CO-1-CH2-1]
-CH=CII- or; c=cHx, X represents hydrogen, halogen or an alkyl group, 2 represents -CH=C=
represents a CHY' group (where Y' represents hydrogen or an alkyl group) and R represents a residue of a carboxylic acid RCOOH,
The carboxylic acid is an acid that produces an insecticidal compound when esterified with alpha-cyano-3-phenoxyindyl alcohol.

Structurally, the compounds of the invention have the formula V It can be seen as a novel alcohol ester.

Furthermore, alcohols of formula V and their esterogenic derivatives also form part of the invention.

In compounds of formulas I and V, Y is 10-te, Y
is preferably hydrogen'. When Y is a CH═CHX group, X is preferably hydrogen. When Y' (or X) is alkyl, it is preferably an alkyl group having 1 to 4 carbon atoms, especially a methyl group. When y/ (or X) is a halogen, the halogen is preferably chlorine or bromine.

Furthermore, in the compounds of formulas I and V, the Ph-Y- group is preferably substituted at the 3-position of the benzyl ring.

In the compound of formula 1, R represents the residue of a carboxylic acid RCOOH, which is known to form an insecticidal compound when esterified with α-cyano-3-phenoxyban-Q alcohol. It is an acid produced by There are a number of carboxylic acids known to produce insecticidal compounds of this type, and these carboxylic acids mostly fall into two well-defined #s. The first group are the cyclopro/cyclocarboxylic acids, which are compounds in which R is a group of formula. In formula (1), R1 and R4 are generally alkyl groups, usually the same alkyl group having from 1 to 4 carbon atoms as is well known in the art, and dimethyl substitution will generally give higher activity.

Bl in formula IK is generally hydrogen or an alkyl group having 1 to 4 carbon atoms, where experience in the art indicates that R3 is usually hydrogen for maximum activity.

However, compounds in which R1 is an alkyl group and B2 is preferably an alkyl group also have high activity,
In this case Bl, Bl 2 , Hm and R4 are all preferably the same alkyl group, for example methyl.

In formula 1, 11 can be hydrogen or a substituted or unsubstituted acyclic or carbocyclic group. R
When 1 is an unsubstituted hyP-locarbyl group, it represents a straight-chain or branched saturated or unsaturated acyclic or carbocyclic group, such as an alkyl, alkenyl or alkagenyl group, cycloalkyl, cyclo It can be an alkylalkyl or cycloalkylalkenyl group. These human 90 carbyl groups preferably have up to 10, especially up to 6 carbon atoms.

If the group R1 is substituted, it is preferably a 1fa of the above hydrocarbyl group substituted by one or more halogen groups (which can be fluorine, chlorine or bromine) or by an alkoxy or oximino group. . If the substituent is two or more halogen substituents, these halogen substituents need not necessarily be the same halogen, and if alkoxy groups are present, these are preferably up to four. carbon atoms and will generally be a methoxy group.

One structure of particular value for the group R'K is.

Formula ■ [In the formula, R1 and R'' may be the same or different (, respectively, an alkyl group having 1 to 4 carbon atoms, a trifluoromethyl group, or may be the same or different and preferably fluorine, chlorine or bromine) one of R7 and Ha can also represent hydrogen or a phenyl or substituted phenyl group.

Alternatively, R and R can be taken together to form a substituted or unsubstituted saturated or unsaturated divalent hydrocarbon chain, which may contain one or more Further heteroatoms can be substituted, such as O, N or S, so that R7 and R1 together with the carbon atoms to which they are attached form a carbon at or heterocycle, which is preferably A cycloaliphatic product consisting of 5 to 7 ring atoms, optionally 1 or 2 carbon-carbon double bonds, and optionally 1 or more alkyl (at~C4) or halogen substituents. Have on top. Other compounds of interest are those in which R is a group of the structure or a radical such as chlorine.

Particular cyclopropane carboxylic acids from which Compound 1 of the present invention may be structurally derived include: chrysanthemum carboxylic acid;
Particularly including (IR)-tranNichiku carboxylic acid; pyrethric acid; dimethylcyclopronocarboxylic acid; trimethylcyclopropanecarboxylic acid; tetramethylcyclopropanecarboxylic acid; lydenmethyl)cyclopropanecarboxylic acid; z,z-:)methyl-3-(dibromvinyl)cyclopropanecarboxylic acid, especially its (IR)-:e1m isomer; 2,z-0methyl-3-(tchlorvinyl) Cyclopronocarboxylic acid, especially its (IR)ie1m isomer; 2,2-dimethyl-3-(1,2,2,2-tetrabromoethyl)cyclopropanecarboxylic acid; 2.2-:)methyl-3 -(1,2-dibromo-2,2-:)chloroethyl)cyclopropanecarboxylic acid; 2.2-:)methyl-3-(2-chloro-3,3゜3-
trifluoropronyl)cyclopropanecarboxylic acid; 2,2-dimethyl-3-(tetrahuman90-2-oxochen-3-ylidenemethyl)cyclopropanecarboxylic acid.

The second major class of carboxylic acids from which esters of formula I can be structurally derived are the alpha-substituted arylacetic acid esters. In these compounds, R in Formula 1 HC generally has the structural formula l R' -Ar-CH-1 l [wherein Ar represents an aryl group, and nm represents a saturated or unsaturated linear or branched acyclic group. or a cyclic hydrocarbon group, where R@ is hydrogen or one or more alkyl, alkoxy (e.g. 0CIPs and 0
(including substituted alkoxy such as CHF2) or a halogen substituent].

Mr is usually an aryl group based on a chain ring, but other aryl groups, such as polynuclear groups, are also of interest. R1 generally represents a saturated straight-chain or branched-chain hydrocarbon group%vr
- an alkyl group having up to s+m carbon atoms, which alkyl group has at least one second carbon atom, especially if the second carbon atom is directly bonded to the carbon atom directly bonded to the R6-substituted aryl group. It is often desirable to have one.

For example, R1 is preferably isopropyl or nibutyl. Furthermore, Ic, R'' may be a cycloaliphatic group, again preferably having a second carbon atom immediately adjacent to the carbon atom bearing the R6-substituted phenyl group, for example R'' is a cyclopropyl group or a cycloaliphatic group. It can be a substituted cyclopropyl group. Furthermore, 1m may be a cycloalkylalkyl group.

R6 preferably represents one or more halogen or halogen-containing substituents, such as F, CI.

Br is 0CHF2 or 0CFs, although if more than one halogen or halogen-containing substituent is present, they are generally the same halogen.

It doesn't necessarily have to be that way. If R6 is an alkyl or alkoxy group, these preferably have 41 carbon atoms; again, if two or more such groups are present, they are not necessarily the same group. There's no need. If only one substitution 4 R@ is present, this is preferably present in the p-position wtK. When two or more R6 substituents are present.

one or more 〇-positions and m-positions 1λ It is preferred that the p-position is substituted with.

Another class of carboxylic acids from which the esters of the present invention are structurally derived are the α-substituted arylaminoacetic acids of the formula: 11 , B@ and aryl are as defined above.

Particular α-substituted phenylacetic acids structurally derived from esters of formula ■ include: α-isofuropyru-P
-chlorophenylacetic acid; α-cyclopropyl-P-chlorophenylacetic acid; α-cyclopropyl-P-methylphenylacetic acid; α-isopropyl-p-(difluoromethoxy)-phenylacetic acid; α-isopropyl-(2-chloro- 4-trifluoromethylanilino)acetic acid.

Compounds of the invention may exhibit geometric and/or optical isomerism.

The compounds of the present invention exhibit optical isomerism in that the carbon atom having the substituent 2 can exist in the R or S configuration, and the present invention is characterized in that the carbon atom having substituent 2 can exist in the R or S configuration. It includes compounds that are S or mixtures thereof.

Compounds of the invention in which R represents a substituted cyclopropane group of the formula ■ can exist as both geometric and optical isomers. This is due to the asymmetric substitution at C1 and C3 of the cyclopropane ring. The compounds of the present invention are characterized in that the hydrogen atoms at 01 and C5 of the cyclopropane ring are almost completely in the cim configuration or almost completely in the tra configuration.
It includes isomers having the ns configuration or mixtures thereof. Additionally, the present invention includes compounds and mixtures thereof in which the configuration at C1 is almost entirely R or almost entirely S. In the compound of the present invention in which R represents a group of the formula [, the optical configuration at C1 and C5 is:
Cyclopronoq:/ cannot vary regardless of the geometric configuration of the hydrogen atoms at C1 and cH of the ring.

This effect is that by specifying the optical configuration in C1 and the geometrical configuration of hydrogen atoms in C1 and CS, the configuration of the cyclopro, C7 ring can be uniquely defined; The invention is (IR)-cisfJ
, (IR)-trams type, etc., and there is no need to specify the optical configuration at a fixed C3 once the other two factors are defined. The adoption of this nomenclature
This prevents confusion that would arise from having to assign either R or S to the same optical configuration in cB, depending on the nature of the substituents on the cyclopffzen ring and the substituents on the side chain.

R is a group of formula 2, R1 is a group of formula 2, and the substitution regarding the ethylenic bond is asymmetric, that is, R1
, the configuration of this part of the molecule is almost completely E
fJ, or almost entirely type 2, or a mixture thereof.

When R is a group of formula (1), the carbon atom to which R1 is attached may be present almost entirely in the S configuration or almost entirely in the R configuration, or be a mixture of these two types. You can also do it.

Compounds of the invention in which Y' represents alkyl or halogen, having regard to the asymmetric substitution on the carbon atom bound by an olefinic bond, can exist in the E or two isomers; Both the pure E isomer and the nearly pure 2 isomer.

and mixtures thereof.

Although the compounds of the invention exist as single isomers, the fact that these compounds have at least one asymmetric center, often H1iU or larger, generally makes the compounds of the invention more suitable for J! Although they may exist in the form of isomeric mixtures, these isomeric mixtures may be optically active and/or almost entirely of one chemical type.

The compound of the present invention comprises an alcohol (1) or a derivative thereof having an esterifiable formula, and a carporic acid or its esterifiable formula (RCOQC), in which R, Y and 2 are as defined above, and Q and Ql are It is a reactive group that reacts to form an ester bond.

Usually, in practical use, carboxylic acid salts such as silver are also used as L<G
! ) IJ ethyl ammonium salt sinapenzyl halide derivative i.e. 1-(3-7 dinoquitupenyl)but-
It is convenient to react with a 2,3-genyl halide, but it is also possible to react with an alcohol, for example in the presence of an acid or a suitable halide catalyst.

Alternatively, the ester of the present invention may be a C1-1C of a carboxylic acid.
It can be produced by transesterifying an alkyl ester by reacting it with benzyl alcohol of formula V in the presence of a basic transesterification catalyst. This method is usually not satisfactory when the molecule has other base-sensitive groups, for example when the carboxylic acid is pyrethric acid.

The esters of the present invention are α in the corresponding α-ethynylbenzyl carboxylate of formula
It can also be prepared by converting the -ethel group into an alkagenyl group by the synthesis described below.

Key to the synthesis of the insecticidal esters of the present invention is the novel alcohol. The synthesis of these new alcohols is
In a modification of the method described in Tetra-Shidoron, Letters (1980) p. 929, 1-(ft*phenyl)
This can be accomplished by reacting Furo/Q rugyl alcohol with an aldehyde in the presence of cuprous bromide and diisopropyl alcohol.

One or more insecticidal esters of formula X can be combined with an inert carrier or diluent to obtain insecticidal compositions, such compositions further forming an aspect of the invention. These compositions can be powders and granular solids, wettable powders, mosquito rolls and other solid preparations, or emulsions, emulsifiable concentrates, sprays and aerosols and suitable solvents, diluents and surfaces. Other liquid M controls after adding the activator are also possible.

The insecticidal composition of the present invention is usually 0.001 to 25 weight
However, these compositions contain a higher concentration of the active ingredient of formula I, for example at 95*t, and the compositions are sold as concentrates to be diluted before use by the end user. You can also do that.

The compositions of the invention may include, for example, hydrocarbon oils (e.g. xylene or other petroleum distillates), water, anionic, cationic or nonionic surfactants, antioxidants and other stabilizers, and fragrances and colorants. may include fees. These inert ingredients can be of a type and proportion as conventionally used in insecticidal compositions containing pyrethroid-like compounds.

Besides these inactive ingredients, the compositions of the invention contain other insecticidal compounds of the pyrethroid type or of other types.
The composition may further contain 11i or more active ingredients, and the composition may further contain natural pyrethrins and ah synergists known to synergize the activity of pyrethroid-like insecticides. Synergists of this type include piperonyl butoxide, Tropital and Sesamex.

The compounds can be used to control pest infections in the domestic, horticultural or agricultural or medical fields, including the veterinary field. Use the compounds or compositions of the present invention to treat pests or surfaces or environments susceptible to pest infection in effective amounts! Pest infections can be eradicated by treatment with a composition containing the active compound T.

For example, they can be used in the domestic environment as a room spray to eradicate infestations by house flies or other insects, and they can be used to treat stored dry crops or grains to prevent insects or other insects. They can be used to eradicate infections caused by pests, and they can also be used to spray growing crops, such as cotton or rice, to eradicate infections caused by common pests, and finally in these medical or veterinary fields, such as cattle. It can be used as a spray to prevent or treat infections caused by insects or pests.

The present invention will be explained below using examples containing F%. Temperature is in °C.

Example l Stel (a) 1-(3-phenoxyphenyl)pro/Qrugyl alcohol (2,24,9,10 mmol), cuprous bromide (0,48,9) and/ormaldehyde (
A mixture of 0,3,9), di-isopropylamine (1,1#) and dioxane (10m/) was refluxed for 30 minutes, cooled, poured into 2M hydrochloric acid (15011/) and dichloromethane (15011/X3). Extracted with.

The extracts were combined, washed thoroughly with 2M hydrochloric acid, water and saturated chloride, dried and the solvent was evaporated. The residue was chromatographed on a silica gel thin layer chromatography plate, eluting with 40% diethyl ether/hexane. 1-(3-phenoquinphenyl)buta-
Yield of 2,3-dienol: l 11 (42,7%
) n91°6008, (b) Dry $1 Benzene (
Al from the above (at) in 5v): l-A/(0,27
1,0,84? '1aL) and Pirijiy (0,07,9,
IR, trans chrysanthenic acid chloride (0.1519, 0.79 mmol) was added to a stirred solution with IR, trans-chrysanthenic acid chloride (0.1519, 0.79 mmol). After 4 hours, the mixture was passed through an alumina column (
59) and bathed in benzene. The eluate was evaporated to give the title product (compound-1). Yield: 0.25Ji' (76%) n"1.3568
゜aim) -3-(2,2-dibromvinyl)-2,2
-dimethylcyclopropanecarboxylic acid chloride by repeating the procedure described in Example 1 (IRlCl.
1-(3-phenoxyphenyl)-but-2,3-genyl)-3-(2,2-dibromvinyl)-2°2-dimethylcycloprono-q'onecarboxylic acid was obtained. n!
01°5912 (Compound 2) The insecticidal activity of the ester of formula I of the present invention was evaluated against house fly and mustard beetle using the following technique: House fly (musca domestica) Insecticide dissolved in acetone 1μ! The female fly was treated on its thorax with one drop of . Two replicates of 15 flies were used at each dose rate, and 6 dose rates were used for each test compound. After treatment, the flies were maintained at a temperature of 20°C±f, and the insecticidal effect was evaluated by counting the number of dead insects 24 and 48 hours after treatment. L.D.
5. The value was calculated as (sg of insecticide per fly) and the specific toxicity was calculated from the inverse ratio of the LD50 value.

(qawickiet ml, Bull*tln of
the World Health Organilt
ion, 3°5,893. (1966) and 8a
v1ek1 @tml, Entomologim
and Exp-Appl · 10,253. (19
67)).

-rXl-do b) A/ Pha@tLon co
A solution of the test compound in acetone was applied to 11 portions of adult mustard beetles using a microdroplet abicide.

Treated insects were kept for 48 hours and then membraned and evaluated. Two replicates of 40-50 mustard beetles were used at each dose level, and five dose levels were used for each compound. In this case as well, LD
5. Calculate the value of LDs.

Specific toxicity was calculated for the inverse ratio of (Elliatt e
tml, J Fist Sei, Food Agrie,
20, 561 (1969)).

Specificity is (IR)-trans-ri Q Santen #5-
Calculated by comparison with benzyl-3-furylmethyl (bioresmeth 1 non);
Its toxicity to house flies is approximately 24 times that of Ares.
1 Allethrin's 65 against Mustard Pitre
It's double.

Specific toxicity is shown below.

The compounds of formula 1 can be incorporated as active compounds and as one of the active compounds in insecticidal compositions, which are described in the following formulations.

Formulation l Oil-based liquid spray active compound against household insect control g, o1s* w/Ma25
% Piresulum Extract 0.25 x Piperonyl Butoxide 0.5X Antioxidants 0. IX Made up to 100 volumes using an odorless light oil solvent such as xylene.

Formulation 2 Active compound 0.25XW/mapiperonyl butoxide 1. O% Non-ionic emulsifier 0.25% Antioxidant
Make up to 100 volumes with 0.1% water.

This concentrate should be mixed with water at a ratio of e.g. 1:80 before spraying.
It should be diluted to M/M.

Formulation 3 Aerosol active compound 0.05% 25% Viresulum extract 0.8X piperonyl butoxide
1.5x Muoku petroleum distillate (boiling point 200-2
65°) 17.338% Propellant For example: Equal mixture of trichloromonofluoromethane and dichlorodifluoromethane 80.0% Fragrance 0.2% Antioxidant 0.1 Ci Formula 4 Mosquito Encircle Active Compound 0. 25 x Tab powder (also known as Presulum pith and 30.0%) Fillers such as wood flour, powdered shizai or Natsutu 7el 68.75%
Brilliant green (coloring agent) 05X,
p-Nitrophenol 0.5
x formulation 5 emulsifying concentrate active compound 1.5 x w/w
Nonionic emulsifier 25. O% xylene 73.4% antioxidant
This concentrate can then be diluted with 0.1% water to 4.51% water.

Powdered active compound of formulation 6 0.05j% v/
w Trobital (piperonyl bis-2-(2-n-butoxyquiethoxy)ethyl acetal synergist) 0.25% Antioxidants, such as butylated hydroxytoluene or butylated hydroxyquanisole 0.03%
Filler 99.67% Continued from page 1 101102 6956-4H149
/36 7162-4H @ Inventor: Norman Frank Janes, Marston Gardens, Luton, Betfordshire, United Kingdom 82 0 Inventor: Bhupinder Paul Sink Cambay, Middlesex, United Kingdom, Harrow Weald, Warham, United Kingdom road 85

Claims (9)

[Claims] (1) General formula [In the formula, Y is 10-1-s-1-00-1-CH2-1
-CH=CH- or /C=CH is carbon! This carboxylic acid is α-
A compound which produces an insecticidal compound when esterified with cyano-3-phenoxybenzyl alcohol. (2) R is 1 [In the formula, R1 represents hydrogen or an I11-substituted or unsubstituted acyclic or carbocyclic group, R2 represents hydrogen or an alkyl group, and R3 and R4 each represent an alkyl group. ] The compound according to claim 1, which is a group of (3) R is attached carbon L! ! or 3 (2,2-:
2. A compound according to claim 2, characterized in that it is a residue from methylcyclopropanecarboxylic acid (bromvinyl)-2,2-:). (4) The compound according to claim 3, wherein the acid has an IR, e1s arrangement. (5) R is the formula % [In the formula, Ar represents an aryl group, R1 represents a saturated or unsaturated linear or branched acyclic or cyclic hydrocarbon group, and R@ represents hydrogen or one or more alkyl, alkoxylic acids (e.g. 0CF5 and OC
2. A compound according to claim 1, characterized in that it represents a group of ) or a halogen substituent. (6) R has the meaning described in formula range item 5] Claim #! Compound according to item 1. (7) The compound according to any one of claims 1 to 6, wherein Y represents 0 and Y' represents H. (8) Carboxylic acid or its esterification formula RCO
A derivative of Q can be converted into an alcohol or an ester thereof [in the above two formulas, R, Y and 2 have the meanings described in claim 1, and Q and Ql react with each other to form an ester. A method for producing a compound of formula I according to claim 1, characterized in that the compound is reacted with a derivative represented by the following formula: (9) An insecticidal composition containing an active compound and an inert diluent or carrier, characterized in that the active compound is as described in any one of claims 811 to 7. a [As an insecticide. Use of a compound according to any of claims 1111 to 7. (b) General formula [wherein Y and 2, Claim I! ! 1. A compound having the meaning given in item 1. (The compound according to claim 11, wherein 13Y represents 0 and Y' represents H.