CA1141389A - Fluoroalkenyl-substituted cyclopropane- carboxylic acid esters and their use as insecticides - Google Patents
Fluoroalkenyl-substituted cyclopropane- carboxylic acid esters and their use as insecticidesInfo
- Publication number
- CA1141389A CA1141389A CA000336559A CA336559A CA1141389A CA 1141389 A CA1141389 A CA 1141389A CA 000336559 A CA000336559 A CA 000336559A CA 336559 A CA336559 A CA 336559A CA 1141389 A CA1141389 A CA 1141389A
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- dimethyl
- fluoro
- trichloro
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
- C07D209/44—Iso-indoles; Hydrogenated iso-indoles
- C07D209/48—Iso-indoles; Hydrogenated iso-indoles with oxygen atoms in positions 1 and 3, e.g. phthalimide
- C07D209/49—Iso-indoles; Hydrogenated iso-indoles with oxygen atoms in positions 1 and 3, e.g. phthalimide and having in the molecule an acyl radical containing a saturated three-membered ring, e.g. chrysanthemumic acid esters
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N53/00—Biocides, pest repellants or attractants, or plant growth regulators containing cyclopropane carboxylic acids or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/09—Preparation of carboxylic acids or their salts, halides or anhydrides from carboxylic acid esters or lactones
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/58—Preparation of carboxylic acid halides
- C07C51/60—Preparation of carboxylic acid halides by conversion of carboxylic acids or their anhydrides or esters, lactones, salts into halides with the same carboxylic acid part
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/40—Radicals substituted by oxygen atoms
- C07D307/42—Singly bound oxygen atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/58—One oxygen atom, e.g. butenolide
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
- C07D333/14—Radicals substituted by singly bound hetero atoms other than halogen
- C07D333/16—Radicals substituted by singly bound hetero atoms other than halogen by oxygen atoms
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Environmental Sciences (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Health & Medical Sciences (AREA)
- Plant Pathology (AREA)
- Pest Control & Pesticides (AREA)
- Agronomy & Crop Science (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Medicines Containing Material From Animals Or Micro-Organisms (AREA)
- Furan Compounds (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
- Indole Compounds (AREA)
- Heterocyclic Compounds Containing Sulfur Atoms (AREA)
- Catching Or Destruction (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
3-Fluoroalkenyl-2,2-dimetyl-cyclopropanecarboxylic acid esters of the formula in which R1 is H, chlorine, bromine, C1-4-alkyl or C1-4 halogenoalkyl, R2 is chlorine, bromine, C1-4-alkyl or C1-4-halogenoalkyl, R3 is halogen, CF3 or R1-?-R2, and R is the radical of an alcohol customary in the case of pyrethroids, which possess arthropodicidal properties. They may be produced sequentially by reacting a compound of the formula with an olefin of the formula to produce (Abstract of the Disclosure continued) which is dehydrohalogenated to
3-Fluoroalkenyl-2,2-dimetyl-cyclopropanecarboxylic acid esters of the formula in which R1 is H, chlorine, bromine, C1-4-alkyl or C1-4 halogenoalkyl, R2 is chlorine, bromine, C1-4-alkyl or C1-4-halogenoalkyl, R3 is halogen, CF3 or R1-?-R2, and R is the radical of an alcohol customary in the case of pyrethroids, which possess arthropodicidal properties. They may be produced sequentially by reacting a compound of the formula with an olefin of the formula to produce (Abstract of the Disclosure continued) which is dehydrohalogenated to
Description
11~13~9 - 1 - Type Ia The present invention relates to certain new fluoro-alkenyl-substituted cyclopropanecarboxylic acid esters, to a process for their preparation and to their use as arthropodicides, especially as insecticides and acaricides.
The invention also relates to new inter~.ediate products for the preparation of these active compounds.
Fluoroalkenyl-substituted cyclopropanecarboxylic acid esters are already known from German Offenlegung~-schrift (German Published Specification) 2,802,962. How-10 ever, the compounds known from this publicavion have the disadvantage of too low an activity. The action, period of action and action spectrum are unsatisfactory, especi~lly when low concentrations are used.
Moreover, the fluoroalkenyl-substituted cylopropane-15 carboxylic acid esters of this invention can be preparedmore cheaply ~ince the fluorine-containing starting sub-stances are more readily accessible.
1. The present invention now provides, as new compounds, the fluoroalkenyl-substituted cyclopropanecarboxylic acid 20 esters of the general formula R2 H ~ H3 R C ~ C02R (I) in which Rl represents hydrogen, chlorine, bromine, Cl_4-alkyl or Cl_4-halogenoalkyl, R represents chlorine, bromine, Cl_4-alkyl or Cl-4-halogenoalkyl~
R~ represents halogen (preferably Cl or Br), CF or Rl-CF-R2 and 3 R represents the radical of an alcohol customary in the case of pyrethroids.
Le A 19 140 . ~
il~l3~9
The invention also relates to new inter~.ediate products for the preparation of these active compounds.
Fluoroalkenyl-substituted cyclopropanecarboxylic acid esters are already known from German Offenlegung~-schrift (German Published Specification) 2,802,962. How-10 ever, the compounds known from this publicavion have the disadvantage of too low an activity. The action, period of action and action spectrum are unsatisfactory, especi~lly when low concentrations are used.
Moreover, the fluoroalkenyl-substituted cylopropane-15 carboxylic acid esters of this invention can be preparedmore cheaply ~ince the fluorine-containing starting sub-stances are more readily accessible.
1. The present invention now provides, as new compounds, the fluoroalkenyl-substituted cyclopropanecarboxylic acid 20 esters of the general formula R2 H ~ H3 R C ~ C02R (I) in which Rl represents hydrogen, chlorine, bromine, Cl_4-alkyl or Cl_4-halogenoalkyl, R represents chlorine, bromine, Cl_4-alkyl or Cl-4-halogenoalkyl~
R~ represents halogen (preferably Cl or Br), CF or Rl-CF-R2 and 3 R represents the radical of an alcohol customary in the case of pyrethroids.
Le A 19 140 . ~
il~l3~9
2. The invention also provides a process for the pre-paration of a fluoroalkenyl-substituted cyclopropane-carboxylic acid ester of the formula (I),in which an acid or reactive derivative thereof, of the general formula H3C ~ 3 _z1 (II), o in which Rl, R2 and R3 have the meanings stated under 1.
(above) and zl denotes halogen, preferably chlorine, or OH, is reacted with an alcohol or reactive derivative thereof, of the general formula R _ z2 (III), in which R has the meaning stated under 1. (above) and 15z2 denotes OH, Cl or Br, if appropriate in the presence of a solvent and/or an acid acceptor andJor a phase transfer catalyst.
(above) and zl denotes halogen, preferably chlorine, or OH, is reacted with an alcohol or reactive derivative thereof, of the general formula R _ z2 (III), in which R has the meaning stated under 1. (above) and 15z2 denotes OH, Cl or Br, if appropriate in the presence of a solvent and/or an acid acceptor andJor a phase transfer catalyst.
3. The new acids and the reactive derivatives thereof, of the general formula 20~ ~ C z1 (II), R O
in which Rl, R2, R3 and zl have the meanings stated under 2. (above), have also been found
in which Rl, R2, R3 and zl have the meanings stated under 2. (above), have also been found
4. It has also been found that an acid, or the reactive derivative thereof, of the formula (II) is obtained by a process in which a compound of the general formula Le A 19 140 :`
11~13~9 R2 H C ~ H3 (IV), R -CF
R~
in which R4 represents -COOCl 4-alkyl, CN or -COCH3 and R , R and R3 have the meanings stated in 1. (above), is (a) saponified, in the case where R4 represents COOCl_4-alkyl or CN, or (b) oxidised, in the case where R represents -COGH3, and, if appropriate, the acid, in which R denotes COOH, is reacted with a halogenating agent.
11~13~9 R2 H C ~ H3 (IV), R -CF
R~
in which R4 represents -COOCl 4-alkyl, CN or -COCH3 and R , R and R3 have the meanings stated in 1. (above), is (a) saponified, in the case where R4 represents COOCl_4-alkyl or CN, or (b) oxidised, in the case where R represents -COGH3, and, if appropriate, the acid, in which R denotes COOH, is reacted with a halogenating agent.
5. The new compounds of the general formula ~ ~ R4 )' in which Rl, R2 and R3 have the meanings stated under 1.
(above) and R4 represents CN, -COCH3 or -COOCl_4-alkyl, have also been found.
(above) and R4 represents CN, -COCH3 or -COOCl_4-alkyl, have also been found.
6. It has al~o been found that a compound of the formula (IV) is obtained by a process in which a compound of the general formula CH
R2 R3 Hall 2 -CF -C CH2-CH-C-CH2R4 (V), Hal CH3 in which Rl, R2, R3 and R4 have the meanings stated under 5. (above) and Hal represents halogen, preferably chlorine or bromine, and the Hal atoms can be identical or different, is dehydrohalogenated.
,, Le A 19 140 .
~138~
R2 R3 Hall 2 -CF -C CH2-CH-C-CH2R4 (V), Hal CH3 in which Rl, R2, R3 and R4 have the meanings stated under 5. (above) and Hal represents halogen, preferably chlorine or bromine, and the Hal atoms can be identical or different, is dehydrohalogenated.
,, Le A 19 140 .
~138~
7. The new compounds of the general formula R2 R3 llal CH3 R 1 CF - C -CH 2 -CH--C~H 2 R4 ( V ), Hal CH3 in which Rl, R2, R3 and R4 have the meanings indicated under 5. (above) and Hal has the meaning indicated under 6. (above), have also been found.
8. It has also been found that a compound of the formula (V) is obtained by a process in which a halogen compound of the general formula 1 ~ (YI), R
in which Hal represents halogen, preferably chlorine or bromine, the Hal atoms being identical or different, and Rl, R2 and R3 have the meanings stated under 1.
(above), is added onto an olefin of the general formula ~ N2R4 (VII), in which R has the meaning indicated under 5. (above), if appropriate in the presence of a catalyst.
The compounds of the ~ormula (I) in 1. (above) exhibit good insecticidal properties. Surprisingly, these new Le A 19 140 11~13~
active ccmpounds (I) acoording to the invention exhibit a oonsiderably higher activity than the ccmpounds k~ow.n from the state of the art. They also possess an acaricidal activity.
Preferred co~pounds of the formula (I) are those in which Rl and R2 each represent Cl, Br or CF3, R represents Cl or Br and R represents one of the following radicals -CH ~ X-R12 R O
N O
2 ~ Rll o -C~ ~ or -CH2-CH=~ 2 wherein Y represents O or S, X represents -CH2-, -O- or -S-, Rll represents hydrogen, CN, -C02CH3, -C02C2H5 or -C~CH, R represents aIkyl, aLkenyl, aIkynyl or an aryl or ~uryl gr~up, R represents hydrogen or methyl, R6 represents an organic radical with a C-C double bond or triple ~ond in the ~-position, 11~13~9 R7 and R8 each represent hydrogen or Cl-C4-alkyl, R9 represents hydrogen, halogen or CF3 and R represents -CH2C~CH, -CHF2, -CF3, -CH-CC12 or an optionally sub-stituted aryl radical (especially a phenyl radical).
Parti~llarly preferred oompounds of the formLla (I) are those in which R represents CH2 ~ CH2 -CH2 ~
o~3 CH2~CH
-CH ~ O
N _ O
N ~ CH ~ --CH2--O F F
-CH2N ~ -CH2 ~ F
O F F
-CH -CH ~ 2 ~ or -CH
R
wherein Rll represents H, CN, -C02CH3, -C02C2H5 or -C~CH, 11413~39 R represents hydrogen or halogen and R represents -CH2C_CH, -CHF2, -CF3, -C9=CC12 or an aryl radical (especially phenyl) which optionally carries one or m~re sub, stituents selected from halogen atoms, methyl groups and methoxy groups.
Very particularly preferred cc}Founds of the formula (I) are those in which R represents F F ORlO
-CH ~ F or -CH
wherein R represents H or CN, R represents hydrogen, or halogen (especially fluorine), and R10 represents an aryl rA~;cal (especially phenyl) which optionally carries one or m~re substituents selected from halogen atoms and methyl and methoxy grcups.
The following conpoundb of the formula (I) may be mentioned as specific examples: 5'-benzyl-3'-furylmethyl 2,2-dimethyl-3-(2',3',3'-trichloro-3'-fluoro-propenyl)-cyclopropanecarboxylate, 5'-phenoxy-3'-furylmethyl 2,2-dimet~yl-3-(2',3',3'-trichloro-3'-fluoro-propenyl)-cycloprqpanecarboxylate, 3',4',5',6'-tetrahydrophthalimidomethyl 2,2-dimethyl-3-(2',3',3'-trichloro-3'-fluoro~prcpenyl)-cyclopropanecarboxylate, pentafluorobenzyl 2,2-dimethyl-3-(2'-, 3',3'-trichloro-3'-fluoro-prcpenyl)-cyclopropanecarboxylate, 3'-phenoxybenzyl 2,2~dimethyl-3-(2',3',3'-trichloro-3'-fluoro-propenyl)-cyclcpropanecarboxylate, 11413E~9 3'-phenoxy-~'-cyanobenzyl 2,2-dimethyl-3-(2',3',3'-trichloro-3'-fluoro-propenyl)-cyclopropanec~rboxylate, 3'-phenoxy-'-ethynylbenzyl 2,2-dimethyl-3-(2',3',3'-trichloro-3'-fluoro-propenyl)-cyclopropanecarboxylate, 3'-phenoxy-4'-fluoro-a'-cyanobenzyl 2,2-dimethyl-3-(2',3',3'-trichloro-3'-fluoro-propenyl)-cycloprcpane-carboxylate, 3'-phenoxy-Y'-cyanobenzyl 2,2~dimethyl-3-(2'-chloro-3'-trifluoro-methyl-3',4',4',4'-tetrafluoro-but-1'-enyl)-cyclopropanecarboxylate, 3'-phenoxy-benzyl 2,2-dimethyl-3-(2'-chloro-3'-trifluoro-3',4',4',4'-tetrafluoro-but-1'-enyl)-cyclopropanecarboxylate and pentafluorobenzyl 2,2-dimethyl-3-(2'-chloro-3'-trifluoromethyl-3',4',4',4'-tetrafluoro-but-1'-enyl)-cyclopropanecarboxylate.
The preparation of the fluoroalkenyl-substituted cyclopropane-carboxylic acid esters acoording to the invention can be represented by the follcwing equation:
2 3 CH3 Acid R CF ~ acceptor 3 ~ c_zl + R-Z ~ (I) R
If, for example, 2,2-dimethyl-3-(2',3',3'-trichloro-3'-fluoropropenyl)-cyclopropanecarboxylic acid chloride and 3-phenoxybenzyl alcohol are used as starting materials in process 2. (above), the course of the reaction can be represented by the followlng equation:
il413~9 0~ Acid H3 ~ 3 + HO-CH2 ~ ~ / aeceptor >
Cl ~ CO-Cl FC12C ~ o~3 Cl C02CH2 ~
If, for example, 2,2-dimethyl-3-(2'-chloro-3'-trifluoromethyl-3',4',4', 4'-tetrafluoro-but-1-enyl)-eyelopropanecarboxylic acid and 5-phenoxy-3-bromc-methyl-furan are used as starting materials, the eourse of the reaetion ean be represented by the following equatiQn:
31 3 X 3 Br-CH Aeid CF ' ~ \ \2 acoe ptor F3C Cl ~ ~ o ~ -HBr CF3 H3 ~ 3 FC
~ ' ~o43 The eyelopropaneearboxylie aeids and reactive derivatives thereof, of the fonmula (II), to be used as starting materials are new. The acid chlorides are preferably employed as the reactive derivatives.
Specific examples of the compounds of the formula (II) to be used as starting materials are: 2,2-dimethyl-3-(2',3',3'-trichloro-3'-fluorDpropenyl)-cyclopropanecarbo~ylic acid (and chloride) and 2,2-dimethyl-3-(2'-chloro-3'-tri-fluoromethyl-3',4',4',4'-tetrafluoro-but-1-enyl)-cyclopropanecarbcxylic acid (and chloride).
The new compDunds of the formula (II) can be prepared by the process indicated under 4. (above) (see below for details).
The aloohols and reactive derivatives, of the formula (III), also to be used as starting materials are known, and they can be prepared by generally customary processes - 9a -ii~13~9 described in the literature (sèe, for example, DT-AS or DT-OS (German Published Specifications) 2,554,883, 1,926,433, 2,612,115,2,~15,435 2,436,178 and 2,436,462 and Monatshefte 67, page 35 (1936)).
Compounds of the formula (III) in which R has the pre-ferred or particularly preferred meaning indicated above in connection with formula (I) are preferred.
Specific examples of the compounds of the formula tIII) to be used as starting materials are: 5-benzyl-3-hydroxymethyl-furane, 5-benzyl-2-hydroxymethyl-furane, 5-benzyl-3-hydroxymethyl-thiophene, 5-phenoxy-5-hydroxy-methyl-furane, 3-hydroxy-4-methyl-5-allyl-cyclopent-4-en-1-one, N-hydroxymethyl-phthalimide, N-hydroxymethyl-3,-~,5,6-tetrahydrophthalimide, pentafluorobenzyl alcohol, 4-phenyl-3-chloro-2-buten-1-ol, 3-trifluoromethoxybenzyl alco~lol, 3-dichlorovinyloxybenzyl alcohol, 3-propargyloxybenzyl alcohol, 3-dichlorovinyloxy-a-cyano-benzyl alcohol, 3-phenoxy-benzyl alcohol, 3-phenyl-a-cyano-benzyl alcohol, 3-phenoxy--methoxycarbonyl-benzyl alcohol, 3-phenoxy-~-ethynyl-benzyl alcohol, 3-phenoxy-4-fluoro-benzyl alcohol, 3-phenoxy-4-chloro-benzyl alcohol, 3-phenoxy-4-fluoro-a-cyanv-benzyl alcohol, 3-(4'-fluorophenoxy)-benzyl alcohol, 3-(4'-chlorophenoxy)-benzyl alcohol, 3-(4'-bromophenoxy)-benzyl alcohol, 3-difluoromethoxy-benzyl chloride, 3-phenoxy-benzyl bromide and pentafluorobenzyl chloride.
Acid acceptors which can be used for the preparationof the compounds of the formula (I) according to the in-vention from carboxylic acids or carboxylic acid halides of the formula (II) and alcohols or chlorides or bromides of the formula (III) are any of the customary acid-binding agents.
Alkali metal hydroxides, carbonates and alcoholates, such as potassium hydroxide, sodium hydroxide, sodium methylate, potassium carbonate and sodium ethylate, and furthermore aliphatic, aromatic or heterocyclic amines, for Le A 19 140 1~13~9 example triethylamine, trimethyiamine, dimethylaniline, dimethylbenzylamine and pyridine, have proved particularly suitable.
m e reaction temperature can be varied within a sub-stantial range. In general, the reaction of the acidhalides with alcohols, is carried out at from 0 to 100C, preferably at from 15 to 40C, and the reaction of the carboxylic acids with the halides is carried out at from 50 to 150C, preferably at from 80C to 120C. In the latter case, the reaction is preferably carried out in the presence of a catalyst.
Possible catalysts are all the so-called phase transfer catalysts, for example crown ethers or quat~rnary ammonium or quaternary phosphonium salts. Quaternary ammonium salts, for example tetrabutylammonium chloride, tetrabutylammonium bromide, benzyltriethylammonium chloride or methyltrioctylammonium chloride, are preferred.
In general, the reaction is allGwed to proceed under normal pressure. The process for the preparation of the compounds according to the invention is preferably carried out also using a suitable solvent or diluent. Possible solvents and diluents are virtually any of the inert organic solvents. These include, as preferences, aliphatic and aromatic, optionally chlorinated hydrocarbons, such as benzene, toluene, xylene, benzine, methylene chloride, chloroform, dichloroethane, chlorobenzene and o-dichloro-benzene; ethers, for example diethyl ether, diisopropyl ether or dibutyl ether; and nitriles, such as acetonitrile and propionitrile.
The starting materials are preferably employed in equimolar amounts for carrying out the process. In general, the reactants are brought together in one of the solvents indicated, and, after adding the acid acceptor and, if appropriate, the catalyst, the mixture is stirred for one or more hours, usually at elevated temperature, to bring the Le A 19 140 ~i4~389 reaction to completion. The`reaction mixture is then poured into water and the organic phase is separated off and washed with water until neutral. After drying, the solvent is distilled off in vacuo. The new compounds are obtained in the form of oils, some of which cannot be dis-tilled without decomposition, but which can be freed from the last volatile constituents by so-called "incipient distillation", that is to say by prolonged heating to moderately elevated temperatures under reduced pressure, and can be purified in this manner. The refractive index is used for their characterisation.
The new acids and acid halides of the formula (II) can be prepared from the compounds Or the formula (IV) by the process indicated under 4. (above).
In variant 4(a), in the case where ~ represents -COOCl_4-alkyl, saponification is carried out under acid or alkaline conditions in a manner which is in its~lf customary. Alkaline saponification is preferred.
In the case where R represents GN, the nitrile group is converted into an ester group by dissolving the nitrile in the corresponding alcohol Cl_4-alkyl-OH and saturating the solution with hydrogen chloride, usually at from O to 20C. After standing for some time, the imide chloride, from which the ester is obtained with water, is thereby formed.
All the customary saponifying agents, for example sulphuric acid, acetic acid or alkali metal hydroxide solutions, can be used for the saponification. KOH in alcoholic solution, for example in methanol, is particularly preferred.
The saponirication can be carried out at elevated temperature, for example at from 20 to 100C; however, the saponification is prererably carried out at from 20 to 40C.
The acids are liberated by acidification with aqueous Le A 19 140 13~39 acids and are separated off from the salts by extraction, and if appropriate purified by distillation.
The acid halides can be prepared by the customary methods with the customary halogenating agents, for p OC12, COC12, PC13, PC15, oxalyl chloride, oxalyl bromide or PBr3.
In the case of variant 4(b), R represents -COCH3.
The acid is obtained by oxidation, preferably with hypo-chlorite (hypochlorite solution) or hypobromite. Examples of such haloform reagents are sodium hypochlorite, potassium hypochlorite, calcium hypochlorite, sodium hypo-bromite, potassium hypobromite and calcium hypobromite.
Furthermore, the reaction can also be carried out by passing a halogen into an aqueous alkali metal hydroxide solution containing the starting compound. In general, the reaction temperature is from -20 to +100C, pre-ferably 0 to 70C. Water is generally used as the solvent, but it is also possible to add one or more organic solvents as solubilising agents. Acceleration of the reaction can be achieved by adding a phase transfer catalyst, for example a quaternary ammonium salt. Possible quaternary ammonium salts are those mentioned above.
Specific examples of the new compounds of the formula (IV) are: 2,2-dimethyl-3-(2',3',3'-trichloro-3'-fluoro-propenyl)-cyclopropanecarboxylic acid methyl ester, 2,2-dimethyl-3-(2',3',3'-trichloro-3'-fluoro-propenyl)-cyclopropanecarboxylic acid ethyl ester, 2,2-dimethyl-3-(2',3',3'-trichloro-3'-fluoro-propenyl)-cyclopropane-carboxylic acid butyl ester, l-cyano-2,2-dimethyl-3-(2t,3',3'-trichloro-3'-fluoro-propenyl)-cyclopropane, 2,2-dimethyl-3-(2'-chloro-3'-trifluoromethyl-3',4',4',4'-tetrafluoro-but-l'enyl)-cyclopropanecarboxylic acid methyl ester or e~hyl ester, l-acetyl-2,2-dimethyl-3-(2',3',3'-trichloro-3'-fluoropropenyl)-cyclopropane and 1-acetyl-2,2-dimethyl-3-(2'-chloro-3'-trifluoromethyl-3',4',4',4'-tetrafluoro-but-l'-enyl)-cyclopropane.
Le A 19 140 13~9 The new compounds of the formula (IV) can be prepared from the com-pounds of the formula (V) by dehydrohalogenation by the prDcess indicated under 6. (above). This reaction can be represented by the follcwnng equation:
Rl-CF -C(Hal) -CH2-CH(Hal) C-CH2 12 13 /\
base -2HHal R -CF-C= ~ R4 The dehydrohalogenation is effected by a base in the presence of a diluent or solvent. Preferred bases here are NaOH, KOH, K2CO3 or alcoholates, such as scdium methylate, sodium isopropylate or potassium tert.-butylate. Pre-ferred solvents are aloohols, for example methanol, ethanol, n- or iso-propanol,butanol, tert.-butanol, glycol or glycol monomethyl ether, and also optionally chlorinated hydrocarb~ns or ethers, such as b~nzene, toluene, xylene, chloro-b~nzene, dichloroben2ene, methylene chloride, THF, dioxan or dimethoxyethane.
It is also possible to carYy out the reactiQn in a two-phase systen, for example toluene/water, especially when NaOH or KOH is used. A phase-trans-fer catalyst, for example a quaternary ammanium salt, can be added if appro-priate. This is not only appropriate if the reaction is c~rried out in a two~
phase system, but is also advantageous if the reaction is carried out under anhydrous conditions, for example if potassium carb~nate is used as the base.
The base, preferably NaOCH3 or NaOC2H5, is initially intrcduced in a solvant, and the co~pound of the formula (V) to be dehydrohalogenated is then added slowly, and in particular first at 0 to 30C and then at 40 to 100C, kS~
~`,i,:
11~1389 preferably at 50 to 80C, until the reaction has ended.
Examples which may be mentioned of campo mds of the formula (V) are:
3,3-dimethyl-4,6,6,7,7-pentachloro-7-fluoro-enanthic acid methyl ester, 3,3-dimethyl-4,6,6,7,7-pentachloro-7-fluoro_enanthic acid ethyl ester, 3,3-dimethyl-4,6,6,7,7-pentachloro-7-fluoro-enanthic acid butyl ester, 3,3-dimethyl-4,6,6,7,7-pentachloro-7-fluoro-enanthic acid nitrile, 3,3~dimethyl-4,6,6-tribrcmD-7,7,7-triflu~ro-enanthic acid methyl ester, 2,2-dimethyl-3,5,5,6,6-pentachloro-6-fluoro-hexyl methyl ketone, 3,3-dimethyl-4,6,6-trichloro-7-trifluoramethyl-7,8,8,8-tetrafluoro-octanoic acid methyl ester, 3,3-dimethyl-4,6,6-trichloro-7-trifluoromethyl-7,8,8,8-tetrafluoro-octanoic acid ethyl ester and 2,2-dimethyl-3,5,5-trichloro-6-trifluoromethyl-6,7,7,7-tetrafluoro-heptyl methyl ketone.
m e new compounds of the formula (V) are obtained from the co~pounds of the formula (VI) and (VII) by process 8. (above). m e ccmpounds of the formLla (VI) and (VII) are known.
The process is represented by the following equation:
+ R CF C(Hal)2 CH2R l2 R CF -C(Hal) CH2-CH(Hal)-C-CH2R4 If, for example, 3,3-dimethyl-4-pentenoic acid methyl ester and l-fluoro-1,1,2,2,2-pentachloroethane are used as starting materials, the course of the reaction can be represented by the follcwing equation:
11~13~99 CEC12~C13 +
CFC12CK12-CH2-CHCl~C~ 2C02CH3 m e following starting materials of the form~la (VI) may be mentioned as examples: pentachlorofluoropentane, pentabr~fluoropentane, l,l,l-trichloro-2,3,3,3-tetrafluoro-2-trifluorometbyl-propane, l,2~difluoro-tetrachloroethane, l-fluoro,1,2,2-trichloro-1,2-~;hrcmDethane, 1,1,2,2-tetrachloro-fluoro-ethane, fluoroheptachloropropane, l,2~difluoro,hexachloropropane, pentachloro-1,1,2-tri-fluorcprcpane, tetrachloro-1,1,1,2-tetrafluoropropane, 1,2-dibromo-3-chlorc-pentafluoropropane, 1,3_dibromo-2-chloro,p~ntafluoropropane, 1,2,3-tribromD-pentafluoropropane, 1,2,3-trichloro-pentafluoropropane, tetrabrcmD-1,1,1,2-tetrafluoropropane and 1,1,2-trichloro-1,2-difluoro-2-iodoethane.
The following starting materials of the formula (VII) may he mentioned as examples: 3,3~dimethyl-4-peintenoic acid methyl ester, 3,3~dimethyl-4-pentenoic acid ethyl ester, 3,3-d~methyl-4-pent~noic acid butyl ester, 3,3-dimethyl-4-pentenoic acid nitrile and 2,2-dimethyl-3-butenyl methyl ketone.
The process is preferably carried out under pressure, but if higher-boiling oompounds of the formLla (VI) are used, it can also be carried out under normal pressure.
The pressure range can vary within wide limits, for exa~ple between 1 and 30 bars, preferably between 3 and 15 bars. The ex oe ss pressure can be achieved by forcing in an inert gas, for example nitrogen.
~13W
The reaction temperature can be from 50 to 200C, but the reaction is preferably carried out at from 100C
to 150C. If appropriate, a diluent is added to the two starting substances.
Possible diluents are: aliphatic or aromatic hydro-carbons, such as benzine or toluene, alcohols, such as methanol, ethanol, propanol or tert.-butanol, nitriles, such as acetonitrile or propionitrile, or DMF. Alcohols, acetonitrile and DMF are preferred.
A catalyst is required for carrying out the reaction, and in particular either ~a) a catalyst which supplies free radicals, for example azobisisobutyronitrile, benzoyl peroxide or di-tert.-butyl peroxide, in which case the compound of the formula (VI) is employed in an equimolar amount or, preferably, in excess, or (b) a catalyst mix-ture which consists of a metal salt, an amine and, if appropriate, a little benzoin. m e metal salt can also be in the form of the hydrate and the amine can also be in the form of a salt, for example in the form of the hydrochloride.
Examples of metal salts are: copper(I) chloride, copper(II) chloride, iron(II) chloride, iron(III) chloride, copper(II) sulphate, cobalt chloride, zinc chloride, iron sulphate, iron acetate, copper acetylacetonate or iron acetylacetonate.
Examples of amines are: dimethylamine, diethylamine, trimethyla~ine, triethylamine, diisopropylamine, n-butyl-amine, benzylamine, ethanolamine, aniline and pyridine.
Dimethylamine and diethylamine (in the form of the hydro-chlorides) and n-butylamine are preferred.
At least 1.5 moles, preferably 2 - 10 moles, of organic amine are preferably employed per mole of metal salt. m e metal salt is employed in an amount of 0.01 to 15 mol %, preferably 0.05 to 10 mol %, relative to the compound of the formula (VII).
It is frequently advantageous to add an equimolar Le A 19 140 11~1389 amount of benzoin, relative to the metal salt. It must be described as exceptionally surprising that the products of the formula (VI) according to the invention, in particular pentachlorofluoroethane, can be added onto the olerins of the formula ~VII) so readily, and it was not to be expected by the expert since hexachloroethane cannot be added onto olefins.
The active compounds are well tolerated by plants, have a favourable level of toxicity to warm-blooded animals, and can be used for combating arthropod pest;s, especially insects and acarids,which are enco~lntered in agriculture, in forestry, in the protection of stored products and of materials, and in the hygiene field.
They are active against normally sen~itive and resistant species and against all or some stages of development.
' m e abovementioned pests include:
from the class of the Isopoda, for example Oniscus asellus, Armadillidium vulgare and Porcellio-scaber;
from the class of the Diplopoda, for example Blaniulus guttulatus;
from the class of the Chilopoda, for example Geophilus -ca~pophagus and Scutigera spec.;
from the class of the Symph;yla, for example Scuti-gerella immaculata;
from the order of the Thysanura, for example Lepisma saccharina;
from the order of the Collembola, for example Onychiurus armatus;
from the order of the O~thoptera, for example Blatta: orientalis~ ~ aneta americana, Leucophaea maderae, Blattella ~rmanica, cheta domesticus, Gryllo-talpa spp., ocusta ~ig~ato~ia ~ig~atorioides, Melanoplus differe~t'ialis and Schi'stoce~ca ~eg~ria;
from the order of the Der~aptera, for example Forficula auricula~ia;
Le A 19 140 .. .... ....
from the order of the~ ~soptera, for example Retic~litermes spp.;
from the order of the A~noplura, for example Ph211oxerà ~astàtrix, Pe~phigus spp., Pe~i'cuIus 'h'uma'n'us corporis, Hàematopinus spp. and Li~ognathus spp.;
from the order of the Mal'lophàga, for example Trichodectes spp. and Damalinea spp.;
from the order of the Thysanopt-era, for example Hercinothrips femoralis and Thrips tabaci, from the order of the Heteroptera, for example Eurygaster spp., Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodnius prolixus and Triatoma spp.;
from the order of the Homoptera, for example Aleurodes brassicae, Bemisià tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Doralis fabae, DoFalis pomi, Eric;soma lanigerum, Hyàlopterus arundinis, Macrosiphum avenae, Myzus spp., Phorodon humuli, Rho~alosiphum padi, Empoasca spp., Euscelis bilo~atus, Nephotettix cincticeps, Lecanium corni, Saissetia oleae, Laode ~hax striatellus, Nilaparvata lugens, Aonidiella aur~ntii, Aspidiotus hederae, Pseudococcus spp. and Psylla spp.;
from the order of the Lepid:optera, for example Pectinophora gossypiella, ~upalus piniarius, Cheimatobia ' brumata, Lithocolletis b'lan'c'ardella,' Xyponomeuta padella, Plutella maculipennis, Malacosoma neustria, Euproctis chrysorrhoea, Lymantria spp., Bucculatrix thurberiella, _hyllocnis-tis' ci't~el'la, A~rotis spp., Euxoa 8pp., Feltia spp., Earias insulana, Heliothis spp.~ Laphygma exigua ~Mamestra;brassicae, Panolis ~flammea, Prodenia litura, ~ Spodoptera 8pp., Trichopl~s~ia~ ni, CarpocaDsa~ po~onella, Pieris spp., Chilo spp., Py~a~sta n'ubilalis, Ephest~ia kuehniella,''B~l'l'e~ia' mellonella,'Cacoecia po'dana, Capua ~eticulana, Cho~is'tone'u'ra''fu'~ife'~ana,' ~ysia~ amb~ ueIla, ~_omona ma~nanima and' To'~t'~ix ~i~idana;
Le A 19 140 11~13~9 .. .... .... ..
from the order of the CoIeoptera? for example -~nobium~pu~ct~atum,~ Rhizope~tha~~do~i~n~ica,~Pr'uc'h'i'd'i'us obtectus~ Acan~th~osce~Iid~es o~b~t~ec~t~us~ HyIo~t~rupes ~b~ajulus .. .... . .
A~elastica alni, Leptinota~sa dece'm-Ii~eata,''Pha'e'~on .. .. ..
cochleariae, Diabrotica spp., Psylliodes chr'y'soce'phala, Epilachna-~ari-~estis, Ato~aria spp., Oryzaephilus surinamensis, Ant-honomus spp., Sitophilus spp., Otiorrhynchus sulcatus, Cosmopolites sordidus,''Ceut'horr-hynchus assimilis, HyEera postica, Dermestes spp., TFogo-derma spp., Anthrenus spp., Attagenus spp., Lyctus spp.,Meligethes aeneus, Ptinus spp., Niptus hololeucus, Gibbium psylloides~ Tribolium spp., Te-nebrio molitor, A~riotes spp., Conoderus spp., Melolontha melolontha"
Amphimallon solstitialis and Costelytra ~ealandica;
from the order of the Hymenopt-era, for example Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis and Vespa spp.;
from the order of the Diptera, for example Aedes spp., Anopheles 9pp., Culex spp., Drosophila melano~aster, Musca spp., Fannia spp., Calliphora erythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp., Gastrophilus spp., Hyppobosca spp., Stomoxys spp., Oestrus spp., Hypoderma spp., Tabanus spp., Tannia spp., Bibio hortulanus, Oscinella frit, Phorbia spp., Pegom~ia hyoscyami, Ceratitis capitata, Dacus oleae and Tipula paludosa;
from t'he order of the Siphonaptera, for example Xenopsylla cheopis and Ceratophyllus spp.;
from the class of the Arachnida, for example Scorpio maurus and Latrodectus mactans;
from the order of the Acarina, for example Acarus siro,-Argas spp., Ornithodo~os spp., Dermanyssus ~allinae, Eriophyes ribis, Phyllocopt~ta olei~ora, ~oophilus spp., ~hipicepha~us spp.~ A~blyomma spp., Hyalo~ma spp., Ixodes spp., Psoroptes spp.~ Cho~ioptes spp., Sarcoptes spp., Tarsonemus spp., ~ryobia p~àetiosa, Panonychus spp. and Tetranychus spp..
Le A 19 140 ~ 413W
The active compounds can be` converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusting agents, foams, pastes, soluble powders, granules, aerosols, sus-pension-emulsion concentrates, seed-treatment powders, natural anà synthetic materials impregnated with active compound, very fine capsules in polymeric substances, coating compositions for use on seed~ and formulations used with burning equipment, such as fumigating cartridges, fumigating cans and fumigating coils, as well as UI.V
cold mist and warm mist formulations.
These formulations may be produced in known m~mner, for example by mixing the active compounds with ex1;enders, that is to say liquid or liquefied gaseous or solid diluents or carriers, optionally with the use of surface-ac;ive agents, that is to say emulsifying agents and/or dispersing agents and/or foam-forming agents. In the case of the use of water as an extender, organic solvents can, for example, also be used as auxiliary solvents.
As liquid diluents or carriers, especially solvents, there are suitable in the main, aromatic hydrocarbons, such as xylene, toluene or alkyl naphthalenes, chlorinated aromatic or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic or alicyclic hydrocarbons, such as cyclohexane or paraffins, for example mineral oil fractions, alcohols, such as butanol or glycol as well as their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, or strongly polar solvents, such as dimethylformamide and dimethyl-sulphoxide, as well as water.
By liquefied gaseous diluents or carriers are meant liquid~ which would be gaseous at normal temperature and under normal pressure, for example aerosol propellants, such as halogenated hydrocarbons as well as butane,-propane, Le A l9 140 11413~9 .
nitrc~en and carbon dioxide. ~
As solid carriers there may be used grour.d natur21 m.inerals, such as kaolins, clays, talc, chalk, ~u2rtz, a ~2pulgi te, mor.tmorillonite or diatomaceous earth, and ground synthetic minerals, such as highly-dispersed s licic acid, alumina and silicates. As solid carriers for ~ranules there may be used crushed and fractionated natural rccks such as calcite, marble, pumice, sepiolite and dolomite, as well as syrthetic granules of inorganic and or~nic meals, and granules of organic material such as sawdust, coconut shells, maize cobs and tobacco stal~s.
As emulsifying and~or oam-forming agents there may be used non-ionic and anionic emulsifiers, such 2S polyoxy-ethylene-fatty acid esters, polyoxyethylene-fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkyl sulphonates, alkyl sulphates, aryl sulphonates as well as albumin hydrclysis products. Dispersing agents include, for e~ample, lignin sulphite waste liquors and methyl-cellulose.
Adhesives such as carboxymethylcellulose and natural ar.d syr.thetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, can be used in the formulations.
It is possible to use colorants such as inorganic pigments, for example iron oxide, titanium oxide and Prussian Blue, and organic dyestuffs, such as alizarin dyestuffs, azo dyestuffs or metal phthalocyanine dyestuffs, and trace nutrients, such as salts of iron, man~anese, boron, copper, cobalt, molybdenum and zinc.
The formulations in general contain from 0.1 to 95 per cent by weight of active compound, preferably from 0.5 to 90 per cent by weight.
The active compounds according to the invention may be used in the form of their formulations of the types that are commercially available or in the use orms prepared Le A 19 140 from these formulations.
The active compound content of the use forms pre-pared from the formulations of the types that are com-mercially available can vary within wide ranges. The active compound concentration of the use forms can be from 0.0000001 to 100% by weight of active compound, pre-ferably from 0.01 to 10% by weight.
The compounds may be employed in a customary manner appropriate for the particular use forms.
When used against pests harmful to health and pests of stored products, the active compounds ar-e distinguished by an excellent residual activity on wood and clay as well as a good stability to alkali on limed substrates.
In the veterinary field, the active compounds according to the invention may be used in a known manner, such as orally in the form of, for example, tablets, capsules, drenches and granules; dermally by means of, for example, dipping, spraying, pouring-on, spotting-on and powdering;
and parenterally, for example by means of injections.
The present invention also provides an arthropodicidal composition containing as active ingredient a compound of the present invention in admixture with a solid or liqueried gaseous diluent or carrier or in admixture with a liquid diluent or carrier containing a surface-active agent.
The present invention also provides a method of com-bating arthropods tespecially insects or acarids) which comprises applying to the arthropods , or to a habitat thereof, a compound of the present invention alone or in the form of a composition containing as active ingredient a compound of the present invention in admixture with a diluent or carrier.
The present invention also provides a method of freeing or protecting domesticated animals from parasitical 3~ insects or acarids which comprises applying to said animals Le A 19 140 ll~tl3~9 a compound according to the present invention, in admixture with a diluent or carrier.
The present invention further provides crops protected from damage by arthropods by being grown in areas in which immediately prior to and/or during the time of the growing a compound of the present invention was applied alone or in admixture with a diluent or carrier.
It will be seen that the usual methocs of providing a harvested crop may be improved by the present invention.
The present invention further provid~s domesticated animals whenever freed or protected from parasitical insects or acarids by the application to said animals of a compound according to the present invention, in admixture wit;h a diluent or carrier.
The insecticidal and acaricidal activity of the compounds of this invention is illustratec by the following biotest Examples.
In these Examples, the compounds according to the present invention are each identified by the number (given in brackets) of the corresponding preparative Example, which will be found later in this specification.
Example A
Phaedon larvae test Solvent: 3 parts by weight of dimethylformamide 5 Emulsifier: 1 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, 1 part by weight of the active compound was mixed with the stated amount of solvent containing the stated amount of emulsifier and the concentrate was diluted with water to the desired concentration.
Cabbage leaves (Bras's'ica oleracea) were treated by being dipped into the preparation of the active compound of the desired concentration and were infested with mustard beetle larvae (Pha n cochleariae), as long as the leaves were still wet.
Le A 19 140 il413~39 After the specified periods of time, the degree of destruction was determined in %: 100% meant that all of the beetle larvae had been killed whereas 0% meant that none of the beetle larvae had been killed.
In this test, for example, the following compounds showed a superior activity compared with the prior art:
t2), (6) and (10).
Example B
Tetranychus test (resistant) Solvent: 3 parts by weight of dimethylformamide Emulsifier: 1 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, 1 part by weight of the active compound was mixed wish the stated amount of solvent and the stated amount of emulsifier and the concentrate was diluted with water to the desired concentration.
Bean plants (Phaseolus vulgaris) which were hea~ily infested with the two-spotted spider mite (Tetranychus urticae) in all stages of development were treated by being dipped into the preparation of the active compound of the desired concentration.
After the specified periods of time, the degree of destruction was determined as a percentage: 100%
meant that all of the spider mites were killed whereas 0% meant that none of the spider mites were killed.
In this test, for example, the following compounds showed a superior activity compared with the prior art:
(2) and (6~.
~x-ample C
Critical concentration test/soil insects Test insect: Tenebrio'm'ol'i't'or larvae in the soil Solvent: 3 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether Le A 19 140 1~13W
To produce a suitable preparation of active compound, 1 part by weight of active compound was mixed with the stated amount Or solvent, the stated amount of emulsifier was added and the concentrate was diluted with water to the desired concentration.
The preparation of active compound was intimately mixed with the soil. The concentration of the active compound in the preparation was practically immaterial, the only decisive factor being the amount by weight Or active compound per unit volume of soil, which is quoted hereinafter in ppm (~ mg/l). The treated soil was filled into pots and the pots were left to stand at room tempera-ture.
After 24 hours the test insects were introduced into the treated soil and after a further 2 to 7 days the degree of effectiveness of the active compound was de-termined in % by counting the dead and the live test insects.
The degree of effectiveness was 100% if all of the test insects had been killed and was 0% if exactly as many test insects were still alive as in the case of the untreated control.
In this test, for example, the following compounds showed a superior action compared with the prior art: (1) and (2).
25 Example D
DloO test Test animals: Blatta orientalis _ Number Or test animals: 10 Solvent: Acetone 3o The active compound was taken up in the solvent at a rate of 2 g per litre. The solution so obtained was diluted with further solvent to the desired concen-trations.
2.5 ml of the solution of the active compound were pipetted into a Petri dish. On the bottom of the Petri Le A 19 140 3~39 - dish there was a filter paper ~ith a diameter of about 9.5 cm. The Petri dish remained uncovered until the solvent had completely evaporated. The amount of active compound per square metre of filter paper varied with the concentration of the solution of active compound.
The stated number of test animals was then placed in the Petri dish and the dish was covered with a glass lid.
The condition of the test animals was observed 3 days after the commencement of the experiments. The destruction, in %, was determined. 100% denoted thc,t all of the test animals had been killed; 0% denoted that none of the test animals had been killed.
In this test, for example, the following compounds showed a superior action compared with the prior art:
(1), (2) and (6).
~ Example E
; LTloo test for Diptera Test animals: Aedes ae'gypti Number of test animals: 25 Solvent: Acetone The active compound was dissolved in the solvent at a rate of 2 g per litre. The solution so obtained was diluted with further solvent to the desired lower concentrations.
2.5 ml of the solution of active compound were pipetted into a Petri dish. On the bottom of the Petri dish there was a filter paper with a diameter of about
in which Hal represents halogen, preferably chlorine or bromine, the Hal atoms being identical or different, and Rl, R2 and R3 have the meanings stated under 1.
(above), is added onto an olefin of the general formula ~ N2R4 (VII), in which R has the meaning indicated under 5. (above), if appropriate in the presence of a catalyst.
The compounds of the ~ormula (I) in 1. (above) exhibit good insecticidal properties. Surprisingly, these new Le A 19 140 11~13~
active ccmpounds (I) acoording to the invention exhibit a oonsiderably higher activity than the ccmpounds k~ow.n from the state of the art. They also possess an acaricidal activity.
Preferred co~pounds of the formula (I) are those in which Rl and R2 each represent Cl, Br or CF3, R represents Cl or Br and R represents one of the following radicals -CH ~ X-R12 R O
N O
2 ~ Rll o -C~ ~ or -CH2-CH=~ 2 wherein Y represents O or S, X represents -CH2-, -O- or -S-, Rll represents hydrogen, CN, -C02CH3, -C02C2H5 or -C~CH, R represents aIkyl, aLkenyl, aIkynyl or an aryl or ~uryl gr~up, R represents hydrogen or methyl, R6 represents an organic radical with a C-C double bond or triple ~ond in the ~-position, 11~13~9 R7 and R8 each represent hydrogen or Cl-C4-alkyl, R9 represents hydrogen, halogen or CF3 and R represents -CH2C~CH, -CHF2, -CF3, -CH-CC12 or an optionally sub-stituted aryl radical (especially a phenyl radical).
Parti~llarly preferred oompounds of the formLla (I) are those in which R represents CH2 ~ CH2 -CH2 ~
o~3 CH2~CH
-CH ~ O
N _ O
N ~ CH ~ --CH2--O F F
-CH2N ~ -CH2 ~ F
O F F
-CH -CH ~ 2 ~ or -CH
R
wherein Rll represents H, CN, -C02CH3, -C02C2H5 or -C~CH, 11413~39 R represents hydrogen or halogen and R represents -CH2C_CH, -CHF2, -CF3, -C9=CC12 or an aryl radical (especially phenyl) which optionally carries one or m~re sub, stituents selected from halogen atoms, methyl groups and methoxy groups.
Very particularly preferred cc}Founds of the formula (I) are those in which R represents F F ORlO
-CH ~ F or -CH
wherein R represents H or CN, R represents hydrogen, or halogen (especially fluorine), and R10 represents an aryl rA~;cal (especially phenyl) which optionally carries one or m~re substituents selected from halogen atoms and methyl and methoxy grcups.
The following conpoundb of the formula (I) may be mentioned as specific examples: 5'-benzyl-3'-furylmethyl 2,2-dimethyl-3-(2',3',3'-trichloro-3'-fluoro-propenyl)-cyclopropanecarboxylate, 5'-phenoxy-3'-furylmethyl 2,2-dimet~yl-3-(2',3',3'-trichloro-3'-fluoro-propenyl)-cycloprqpanecarboxylate, 3',4',5',6'-tetrahydrophthalimidomethyl 2,2-dimethyl-3-(2',3',3'-trichloro-3'-fluoro~prcpenyl)-cyclopropanecarboxylate, pentafluorobenzyl 2,2-dimethyl-3-(2'-, 3',3'-trichloro-3'-fluoro-prcpenyl)-cyclopropanecarboxylate, 3'-phenoxybenzyl 2,2~dimethyl-3-(2',3',3'-trichloro-3'-fluoro-propenyl)-cyclcpropanecarboxylate, 11413E~9 3'-phenoxy-~'-cyanobenzyl 2,2-dimethyl-3-(2',3',3'-trichloro-3'-fluoro-propenyl)-cyclopropanec~rboxylate, 3'-phenoxy-'-ethynylbenzyl 2,2-dimethyl-3-(2',3',3'-trichloro-3'-fluoro-propenyl)-cyclopropanecarboxylate, 3'-phenoxy-4'-fluoro-a'-cyanobenzyl 2,2-dimethyl-3-(2',3',3'-trichloro-3'-fluoro-propenyl)-cycloprcpane-carboxylate, 3'-phenoxy-Y'-cyanobenzyl 2,2~dimethyl-3-(2'-chloro-3'-trifluoro-methyl-3',4',4',4'-tetrafluoro-but-1'-enyl)-cyclopropanecarboxylate, 3'-phenoxy-benzyl 2,2-dimethyl-3-(2'-chloro-3'-trifluoro-3',4',4',4'-tetrafluoro-but-1'-enyl)-cyclopropanecarboxylate and pentafluorobenzyl 2,2-dimethyl-3-(2'-chloro-3'-trifluoromethyl-3',4',4',4'-tetrafluoro-but-1'-enyl)-cyclopropanecarboxylate.
The preparation of the fluoroalkenyl-substituted cyclopropane-carboxylic acid esters acoording to the invention can be represented by the follcwing equation:
2 3 CH3 Acid R CF ~ acceptor 3 ~ c_zl + R-Z ~ (I) R
If, for example, 2,2-dimethyl-3-(2',3',3'-trichloro-3'-fluoropropenyl)-cyclopropanecarboxylic acid chloride and 3-phenoxybenzyl alcohol are used as starting materials in process 2. (above), the course of the reaction can be represented by the followlng equation:
il413~9 0~ Acid H3 ~ 3 + HO-CH2 ~ ~ / aeceptor >
Cl ~ CO-Cl FC12C ~ o~3 Cl C02CH2 ~
If, for example, 2,2-dimethyl-3-(2'-chloro-3'-trifluoromethyl-3',4',4', 4'-tetrafluoro-but-1-enyl)-eyelopropanecarboxylic acid and 5-phenoxy-3-bromc-methyl-furan are used as starting materials, the eourse of the reaetion ean be represented by the following equatiQn:
31 3 X 3 Br-CH Aeid CF ' ~ \ \2 acoe ptor F3C Cl ~ ~ o ~ -HBr CF3 H3 ~ 3 FC
~ ' ~o43 The eyelopropaneearboxylie aeids and reactive derivatives thereof, of the fonmula (II), to be used as starting materials are new. The acid chlorides are preferably employed as the reactive derivatives.
Specific examples of the compounds of the formula (II) to be used as starting materials are: 2,2-dimethyl-3-(2',3',3'-trichloro-3'-fluorDpropenyl)-cyclopropanecarbo~ylic acid (and chloride) and 2,2-dimethyl-3-(2'-chloro-3'-tri-fluoromethyl-3',4',4',4'-tetrafluoro-but-1-enyl)-cyclopropanecarbcxylic acid (and chloride).
The new compDunds of the formula (II) can be prepared by the process indicated under 4. (above) (see below for details).
The aloohols and reactive derivatives, of the formula (III), also to be used as starting materials are known, and they can be prepared by generally customary processes - 9a -ii~13~9 described in the literature (sèe, for example, DT-AS or DT-OS (German Published Specifications) 2,554,883, 1,926,433, 2,612,115,2,~15,435 2,436,178 and 2,436,462 and Monatshefte 67, page 35 (1936)).
Compounds of the formula (III) in which R has the pre-ferred or particularly preferred meaning indicated above in connection with formula (I) are preferred.
Specific examples of the compounds of the formula tIII) to be used as starting materials are: 5-benzyl-3-hydroxymethyl-furane, 5-benzyl-2-hydroxymethyl-furane, 5-benzyl-3-hydroxymethyl-thiophene, 5-phenoxy-5-hydroxy-methyl-furane, 3-hydroxy-4-methyl-5-allyl-cyclopent-4-en-1-one, N-hydroxymethyl-phthalimide, N-hydroxymethyl-3,-~,5,6-tetrahydrophthalimide, pentafluorobenzyl alcohol, 4-phenyl-3-chloro-2-buten-1-ol, 3-trifluoromethoxybenzyl alco~lol, 3-dichlorovinyloxybenzyl alcohol, 3-propargyloxybenzyl alcohol, 3-dichlorovinyloxy-a-cyano-benzyl alcohol, 3-phenoxy-benzyl alcohol, 3-phenyl-a-cyano-benzyl alcohol, 3-phenoxy--methoxycarbonyl-benzyl alcohol, 3-phenoxy-~-ethynyl-benzyl alcohol, 3-phenoxy-4-fluoro-benzyl alcohol, 3-phenoxy-4-chloro-benzyl alcohol, 3-phenoxy-4-fluoro-a-cyanv-benzyl alcohol, 3-(4'-fluorophenoxy)-benzyl alcohol, 3-(4'-chlorophenoxy)-benzyl alcohol, 3-(4'-bromophenoxy)-benzyl alcohol, 3-difluoromethoxy-benzyl chloride, 3-phenoxy-benzyl bromide and pentafluorobenzyl chloride.
Acid acceptors which can be used for the preparationof the compounds of the formula (I) according to the in-vention from carboxylic acids or carboxylic acid halides of the formula (II) and alcohols or chlorides or bromides of the formula (III) are any of the customary acid-binding agents.
Alkali metal hydroxides, carbonates and alcoholates, such as potassium hydroxide, sodium hydroxide, sodium methylate, potassium carbonate and sodium ethylate, and furthermore aliphatic, aromatic or heterocyclic amines, for Le A 19 140 1~13~9 example triethylamine, trimethyiamine, dimethylaniline, dimethylbenzylamine and pyridine, have proved particularly suitable.
m e reaction temperature can be varied within a sub-stantial range. In general, the reaction of the acidhalides with alcohols, is carried out at from 0 to 100C, preferably at from 15 to 40C, and the reaction of the carboxylic acids with the halides is carried out at from 50 to 150C, preferably at from 80C to 120C. In the latter case, the reaction is preferably carried out in the presence of a catalyst.
Possible catalysts are all the so-called phase transfer catalysts, for example crown ethers or quat~rnary ammonium or quaternary phosphonium salts. Quaternary ammonium salts, for example tetrabutylammonium chloride, tetrabutylammonium bromide, benzyltriethylammonium chloride or methyltrioctylammonium chloride, are preferred.
In general, the reaction is allGwed to proceed under normal pressure. The process for the preparation of the compounds according to the invention is preferably carried out also using a suitable solvent or diluent. Possible solvents and diluents are virtually any of the inert organic solvents. These include, as preferences, aliphatic and aromatic, optionally chlorinated hydrocarbons, such as benzene, toluene, xylene, benzine, methylene chloride, chloroform, dichloroethane, chlorobenzene and o-dichloro-benzene; ethers, for example diethyl ether, diisopropyl ether or dibutyl ether; and nitriles, such as acetonitrile and propionitrile.
The starting materials are preferably employed in equimolar amounts for carrying out the process. In general, the reactants are brought together in one of the solvents indicated, and, after adding the acid acceptor and, if appropriate, the catalyst, the mixture is stirred for one or more hours, usually at elevated temperature, to bring the Le A 19 140 ~i4~389 reaction to completion. The`reaction mixture is then poured into water and the organic phase is separated off and washed with water until neutral. After drying, the solvent is distilled off in vacuo. The new compounds are obtained in the form of oils, some of which cannot be dis-tilled without decomposition, but which can be freed from the last volatile constituents by so-called "incipient distillation", that is to say by prolonged heating to moderately elevated temperatures under reduced pressure, and can be purified in this manner. The refractive index is used for their characterisation.
The new acids and acid halides of the formula (II) can be prepared from the compounds Or the formula (IV) by the process indicated under 4. (above).
In variant 4(a), in the case where ~ represents -COOCl_4-alkyl, saponification is carried out under acid or alkaline conditions in a manner which is in its~lf customary. Alkaline saponification is preferred.
In the case where R represents GN, the nitrile group is converted into an ester group by dissolving the nitrile in the corresponding alcohol Cl_4-alkyl-OH and saturating the solution with hydrogen chloride, usually at from O to 20C. After standing for some time, the imide chloride, from which the ester is obtained with water, is thereby formed.
All the customary saponifying agents, for example sulphuric acid, acetic acid or alkali metal hydroxide solutions, can be used for the saponification. KOH in alcoholic solution, for example in methanol, is particularly preferred.
The saponirication can be carried out at elevated temperature, for example at from 20 to 100C; however, the saponification is prererably carried out at from 20 to 40C.
The acids are liberated by acidification with aqueous Le A 19 140 13~39 acids and are separated off from the salts by extraction, and if appropriate purified by distillation.
The acid halides can be prepared by the customary methods with the customary halogenating agents, for p OC12, COC12, PC13, PC15, oxalyl chloride, oxalyl bromide or PBr3.
In the case of variant 4(b), R represents -COCH3.
The acid is obtained by oxidation, preferably with hypo-chlorite (hypochlorite solution) or hypobromite. Examples of such haloform reagents are sodium hypochlorite, potassium hypochlorite, calcium hypochlorite, sodium hypo-bromite, potassium hypobromite and calcium hypobromite.
Furthermore, the reaction can also be carried out by passing a halogen into an aqueous alkali metal hydroxide solution containing the starting compound. In general, the reaction temperature is from -20 to +100C, pre-ferably 0 to 70C. Water is generally used as the solvent, but it is also possible to add one or more organic solvents as solubilising agents. Acceleration of the reaction can be achieved by adding a phase transfer catalyst, for example a quaternary ammonium salt. Possible quaternary ammonium salts are those mentioned above.
Specific examples of the new compounds of the formula (IV) are: 2,2-dimethyl-3-(2',3',3'-trichloro-3'-fluoro-propenyl)-cyclopropanecarboxylic acid methyl ester, 2,2-dimethyl-3-(2',3',3'-trichloro-3'-fluoro-propenyl)-cyclopropanecarboxylic acid ethyl ester, 2,2-dimethyl-3-(2',3',3'-trichloro-3'-fluoro-propenyl)-cyclopropane-carboxylic acid butyl ester, l-cyano-2,2-dimethyl-3-(2t,3',3'-trichloro-3'-fluoro-propenyl)-cyclopropane, 2,2-dimethyl-3-(2'-chloro-3'-trifluoromethyl-3',4',4',4'-tetrafluoro-but-l'enyl)-cyclopropanecarboxylic acid methyl ester or e~hyl ester, l-acetyl-2,2-dimethyl-3-(2',3',3'-trichloro-3'-fluoropropenyl)-cyclopropane and 1-acetyl-2,2-dimethyl-3-(2'-chloro-3'-trifluoromethyl-3',4',4',4'-tetrafluoro-but-l'-enyl)-cyclopropane.
Le A 19 140 13~9 The new compounds of the formula (IV) can be prepared from the com-pounds of the formula (V) by dehydrohalogenation by the prDcess indicated under 6. (above). This reaction can be represented by the follcwnng equation:
Rl-CF -C(Hal) -CH2-CH(Hal) C-CH2 12 13 /\
base -2HHal R -CF-C= ~ R4 The dehydrohalogenation is effected by a base in the presence of a diluent or solvent. Preferred bases here are NaOH, KOH, K2CO3 or alcoholates, such as scdium methylate, sodium isopropylate or potassium tert.-butylate. Pre-ferred solvents are aloohols, for example methanol, ethanol, n- or iso-propanol,butanol, tert.-butanol, glycol or glycol monomethyl ether, and also optionally chlorinated hydrocarb~ns or ethers, such as b~nzene, toluene, xylene, chloro-b~nzene, dichloroben2ene, methylene chloride, THF, dioxan or dimethoxyethane.
It is also possible to carYy out the reactiQn in a two-phase systen, for example toluene/water, especially when NaOH or KOH is used. A phase-trans-fer catalyst, for example a quaternary ammanium salt, can be added if appro-priate. This is not only appropriate if the reaction is c~rried out in a two~
phase system, but is also advantageous if the reaction is carried out under anhydrous conditions, for example if potassium carb~nate is used as the base.
The base, preferably NaOCH3 or NaOC2H5, is initially intrcduced in a solvant, and the co~pound of the formula (V) to be dehydrohalogenated is then added slowly, and in particular first at 0 to 30C and then at 40 to 100C, kS~
~`,i,:
11~1389 preferably at 50 to 80C, until the reaction has ended.
Examples which may be mentioned of campo mds of the formula (V) are:
3,3-dimethyl-4,6,6,7,7-pentachloro-7-fluoro-enanthic acid methyl ester, 3,3-dimethyl-4,6,6,7,7-pentachloro-7-fluoro_enanthic acid ethyl ester, 3,3-dimethyl-4,6,6,7,7-pentachloro-7-fluoro-enanthic acid butyl ester, 3,3-dimethyl-4,6,6,7,7-pentachloro-7-fluoro-enanthic acid nitrile, 3,3~dimethyl-4,6,6-tribrcmD-7,7,7-triflu~ro-enanthic acid methyl ester, 2,2-dimethyl-3,5,5,6,6-pentachloro-6-fluoro-hexyl methyl ketone, 3,3-dimethyl-4,6,6-trichloro-7-trifluoramethyl-7,8,8,8-tetrafluoro-octanoic acid methyl ester, 3,3-dimethyl-4,6,6-trichloro-7-trifluoromethyl-7,8,8,8-tetrafluoro-octanoic acid ethyl ester and 2,2-dimethyl-3,5,5-trichloro-6-trifluoromethyl-6,7,7,7-tetrafluoro-heptyl methyl ketone.
m e new compounds of the formula (V) are obtained from the co~pounds of the formula (VI) and (VII) by process 8. (above). m e ccmpounds of the formLla (VI) and (VII) are known.
The process is represented by the following equation:
+ R CF C(Hal)2 CH2R l2 R CF -C(Hal) CH2-CH(Hal)-C-CH2R4 If, for example, 3,3-dimethyl-4-pentenoic acid methyl ester and l-fluoro-1,1,2,2,2-pentachloroethane are used as starting materials, the course of the reaction can be represented by the follcwing equation:
11~13~99 CEC12~C13 +
CFC12CK12-CH2-CHCl~C~ 2C02CH3 m e following starting materials of the form~la (VI) may be mentioned as examples: pentachlorofluoropentane, pentabr~fluoropentane, l,l,l-trichloro-2,3,3,3-tetrafluoro-2-trifluorometbyl-propane, l,2~difluoro-tetrachloroethane, l-fluoro,1,2,2-trichloro-1,2-~;hrcmDethane, 1,1,2,2-tetrachloro-fluoro-ethane, fluoroheptachloropropane, l,2~difluoro,hexachloropropane, pentachloro-1,1,2-tri-fluorcprcpane, tetrachloro-1,1,1,2-tetrafluoropropane, 1,2-dibromo-3-chlorc-pentafluoropropane, 1,3_dibromo-2-chloro,p~ntafluoropropane, 1,2,3-tribromD-pentafluoropropane, 1,2,3-trichloro-pentafluoropropane, tetrabrcmD-1,1,1,2-tetrafluoropropane and 1,1,2-trichloro-1,2-difluoro-2-iodoethane.
The following starting materials of the formula (VII) may he mentioned as examples: 3,3~dimethyl-4-peintenoic acid methyl ester, 3,3~dimethyl-4-pentenoic acid ethyl ester, 3,3-d~methyl-4-pent~noic acid butyl ester, 3,3-dimethyl-4-pentenoic acid nitrile and 2,2-dimethyl-3-butenyl methyl ketone.
The process is preferably carried out under pressure, but if higher-boiling oompounds of the formLla (VI) are used, it can also be carried out under normal pressure.
The pressure range can vary within wide limits, for exa~ple between 1 and 30 bars, preferably between 3 and 15 bars. The ex oe ss pressure can be achieved by forcing in an inert gas, for example nitrogen.
~13W
The reaction temperature can be from 50 to 200C, but the reaction is preferably carried out at from 100C
to 150C. If appropriate, a diluent is added to the two starting substances.
Possible diluents are: aliphatic or aromatic hydro-carbons, such as benzine or toluene, alcohols, such as methanol, ethanol, propanol or tert.-butanol, nitriles, such as acetonitrile or propionitrile, or DMF. Alcohols, acetonitrile and DMF are preferred.
A catalyst is required for carrying out the reaction, and in particular either ~a) a catalyst which supplies free radicals, for example azobisisobutyronitrile, benzoyl peroxide or di-tert.-butyl peroxide, in which case the compound of the formula (VI) is employed in an equimolar amount or, preferably, in excess, or (b) a catalyst mix-ture which consists of a metal salt, an amine and, if appropriate, a little benzoin. m e metal salt can also be in the form of the hydrate and the amine can also be in the form of a salt, for example in the form of the hydrochloride.
Examples of metal salts are: copper(I) chloride, copper(II) chloride, iron(II) chloride, iron(III) chloride, copper(II) sulphate, cobalt chloride, zinc chloride, iron sulphate, iron acetate, copper acetylacetonate or iron acetylacetonate.
Examples of amines are: dimethylamine, diethylamine, trimethyla~ine, triethylamine, diisopropylamine, n-butyl-amine, benzylamine, ethanolamine, aniline and pyridine.
Dimethylamine and diethylamine (in the form of the hydro-chlorides) and n-butylamine are preferred.
At least 1.5 moles, preferably 2 - 10 moles, of organic amine are preferably employed per mole of metal salt. m e metal salt is employed in an amount of 0.01 to 15 mol %, preferably 0.05 to 10 mol %, relative to the compound of the formula (VII).
It is frequently advantageous to add an equimolar Le A 19 140 11~1389 amount of benzoin, relative to the metal salt. It must be described as exceptionally surprising that the products of the formula (VI) according to the invention, in particular pentachlorofluoroethane, can be added onto the olerins of the formula ~VII) so readily, and it was not to be expected by the expert since hexachloroethane cannot be added onto olefins.
The active compounds are well tolerated by plants, have a favourable level of toxicity to warm-blooded animals, and can be used for combating arthropod pest;s, especially insects and acarids,which are enco~lntered in agriculture, in forestry, in the protection of stored products and of materials, and in the hygiene field.
They are active against normally sen~itive and resistant species and against all or some stages of development.
' m e abovementioned pests include:
from the class of the Isopoda, for example Oniscus asellus, Armadillidium vulgare and Porcellio-scaber;
from the class of the Diplopoda, for example Blaniulus guttulatus;
from the class of the Chilopoda, for example Geophilus -ca~pophagus and Scutigera spec.;
from the class of the Symph;yla, for example Scuti-gerella immaculata;
from the order of the Thysanura, for example Lepisma saccharina;
from the order of the Collembola, for example Onychiurus armatus;
from the order of the O~thoptera, for example Blatta: orientalis~ ~ aneta americana, Leucophaea maderae, Blattella ~rmanica, cheta domesticus, Gryllo-talpa spp., ocusta ~ig~ato~ia ~ig~atorioides, Melanoplus differe~t'ialis and Schi'stoce~ca ~eg~ria;
from the order of the Der~aptera, for example Forficula auricula~ia;
Le A 19 140 .. .... ....
from the order of the~ ~soptera, for example Retic~litermes spp.;
from the order of the A~noplura, for example Ph211oxerà ~astàtrix, Pe~phigus spp., Pe~i'cuIus 'h'uma'n'us corporis, Hàematopinus spp. and Li~ognathus spp.;
from the order of the Mal'lophàga, for example Trichodectes spp. and Damalinea spp.;
from the order of the Thysanopt-era, for example Hercinothrips femoralis and Thrips tabaci, from the order of the Heteroptera, for example Eurygaster spp., Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodnius prolixus and Triatoma spp.;
from the order of the Homoptera, for example Aleurodes brassicae, Bemisià tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Doralis fabae, DoFalis pomi, Eric;soma lanigerum, Hyàlopterus arundinis, Macrosiphum avenae, Myzus spp., Phorodon humuli, Rho~alosiphum padi, Empoasca spp., Euscelis bilo~atus, Nephotettix cincticeps, Lecanium corni, Saissetia oleae, Laode ~hax striatellus, Nilaparvata lugens, Aonidiella aur~ntii, Aspidiotus hederae, Pseudococcus spp. and Psylla spp.;
from the order of the Lepid:optera, for example Pectinophora gossypiella, ~upalus piniarius, Cheimatobia ' brumata, Lithocolletis b'lan'c'ardella,' Xyponomeuta padella, Plutella maculipennis, Malacosoma neustria, Euproctis chrysorrhoea, Lymantria spp., Bucculatrix thurberiella, _hyllocnis-tis' ci't~el'la, A~rotis spp., Euxoa 8pp., Feltia spp., Earias insulana, Heliothis spp.~ Laphygma exigua ~Mamestra;brassicae, Panolis ~flammea, Prodenia litura, ~ Spodoptera 8pp., Trichopl~s~ia~ ni, CarpocaDsa~ po~onella, Pieris spp., Chilo spp., Py~a~sta n'ubilalis, Ephest~ia kuehniella,''B~l'l'e~ia' mellonella,'Cacoecia po'dana, Capua ~eticulana, Cho~is'tone'u'ra''fu'~ife'~ana,' ~ysia~ amb~ ueIla, ~_omona ma~nanima and' To'~t'~ix ~i~idana;
Le A 19 140 11~13~9 .. .... .... ..
from the order of the CoIeoptera? for example -~nobium~pu~ct~atum,~ Rhizope~tha~~do~i~n~ica,~Pr'uc'h'i'd'i'us obtectus~ Acan~th~osce~Iid~es o~b~t~ec~t~us~ HyIo~t~rupes ~b~ajulus .. .... . .
A~elastica alni, Leptinota~sa dece'm-Ii~eata,''Pha'e'~on .. .. ..
cochleariae, Diabrotica spp., Psylliodes chr'y'soce'phala, Epilachna-~ari-~estis, Ato~aria spp., Oryzaephilus surinamensis, Ant-honomus spp., Sitophilus spp., Otiorrhynchus sulcatus, Cosmopolites sordidus,''Ceut'horr-hynchus assimilis, HyEera postica, Dermestes spp., TFogo-derma spp., Anthrenus spp., Attagenus spp., Lyctus spp.,Meligethes aeneus, Ptinus spp., Niptus hololeucus, Gibbium psylloides~ Tribolium spp., Te-nebrio molitor, A~riotes spp., Conoderus spp., Melolontha melolontha"
Amphimallon solstitialis and Costelytra ~ealandica;
from the order of the Hymenopt-era, for example Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis and Vespa spp.;
from the order of the Diptera, for example Aedes spp., Anopheles 9pp., Culex spp., Drosophila melano~aster, Musca spp., Fannia spp., Calliphora erythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp., Gastrophilus spp., Hyppobosca spp., Stomoxys spp., Oestrus spp., Hypoderma spp., Tabanus spp., Tannia spp., Bibio hortulanus, Oscinella frit, Phorbia spp., Pegom~ia hyoscyami, Ceratitis capitata, Dacus oleae and Tipula paludosa;
from t'he order of the Siphonaptera, for example Xenopsylla cheopis and Ceratophyllus spp.;
from the class of the Arachnida, for example Scorpio maurus and Latrodectus mactans;
from the order of the Acarina, for example Acarus siro,-Argas spp., Ornithodo~os spp., Dermanyssus ~allinae, Eriophyes ribis, Phyllocopt~ta olei~ora, ~oophilus spp., ~hipicepha~us spp.~ A~blyomma spp., Hyalo~ma spp., Ixodes spp., Psoroptes spp.~ Cho~ioptes spp., Sarcoptes spp., Tarsonemus spp., ~ryobia p~àetiosa, Panonychus spp. and Tetranychus spp..
Le A 19 140 ~ 413W
The active compounds can be` converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusting agents, foams, pastes, soluble powders, granules, aerosols, sus-pension-emulsion concentrates, seed-treatment powders, natural anà synthetic materials impregnated with active compound, very fine capsules in polymeric substances, coating compositions for use on seed~ and formulations used with burning equipment, such as fumigating cartridges, fumigating cans and fumigating coils, as well as UI.V
cold mist and warm mist formulations.
These formulations may be produced in known m~mner, for example by mixing the active compounds with ex1;enders, that is to say liquid or liquefied gaseous or solid diluents or carriers, optionally with the use of surface-ac;ive agents, that is to say emulsifying agents and/or dispersing agents and/or foam-forming agents. In the case of the use of water as an extender, organic solvents can, for example, also be used as auxiliary solvents.
As liquid diluents or carriers, especially solvents, there are suitable in the main, aromatic hydrocarbons, such as xylene, toluene or alkyl naphthalenes, chlorinated aromatic or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic or alicyclic hydrocarbons, such as cyclohexane or paraffins, for example mineral oil fractions, alcohols, such as butanol or glycol as well as their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, or strongly polar solvents, such as dimethylformamide and dimethyl-sulphoxide, as well as water.
By liquefied gaseous diluents or carriers are meant liquid~ which would be gaseous at normal temperature and under normal pressure, for example aerosol propellants, such as halogenated hydrocarbons as well as butane,-propane, Le A l9 140 11413~9 .
nitrc~en and carbon dioxide. ~
As solid carriers there may be used grour.d natur21 m.inerals, such as kaolins, clays, talc, chalk, ~u2rtz, a ~2pulgi te, mor.tmorillonite or diatomaceous earth, and ground synthetic minerals, such as highly-dispersed s licic acid, alumina and silicates. As solid carriers for ~ranules there may be used crushed and fractionated natural rccks such as calcite, marble, pumice, sepiolite and dolomite, as well as syrthetic granules of inorganic and or~nic meals, and granules of organic material such as sawdust, coconut shells, maize cobs and tobacco stal~s.
As emulsifying and~or oam-forming agents there may be used non-ionic and anionic emulsifiers, such 2S polyoxy-ethylene-fatty acid esters, polyoxyethylene-fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkyl sulphonates, alkyl sulphates, aryl sulphonates as well as albumin hydrclysis products. Dispersing agents include, for e~ample, lignin sulphite waste liquors and methyl-cellulose.
Adhesives such as carboxymethylcellulose and natural ar.d syr.thetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, can be used in the formulations.
It is possible to use colorants such as inorganic pigments, for example iron oxide, titanium oxide and Prussian Blue, and organic dyestuffs, such as alizarin dyestuffs, azo dyestuffs or metal phthalocyanine dyestuffs, and trace nutrients, such as salts of iron, man~anese, boron, copper, cobalt, molybdenum and zinc.
The formulations in general contain from 0.1 to 95 per cent by weight of active compound, preferably from 0.5 to 90 per cent by weight.
The active compounds according to the invention may be used in the form of their formulations of the types that are commercially available or in the use orms prepared Le A 19 140 from these formulations.
The active compound content of the use forms pre-pared from the formulations of the types that are com-mercially available can vary within wide ranges. The active compound concentration of the use forms can be from 0.0000001 to 100% by weight of active compound, pre-ferably from 0.01 to 10% by weight.
The compounds may be employed in a customary manner appropriate for the particular use forms.
When used against pests harmful to health and pests of stored products, the active compounds ar-e distinguished by an excellent residual activity on wood and clay as well as a good stability to alkali on limed substrates.
In the veterinary field, the active compounds according to the invention may be used in a known manner, such as orally in the form of, for example, tablets, capsules, drenches and granules; dermally by means of, for example, dipping, spraying, pouring-on, spotting-on and powdering;
and parenterally, for example by means of injections.
The present invention also provides an arthropodicidal composition containing as active ingredient a compound of the present invention in admixture with a solid or liqueried gaseous diluent or carrier or in admixture with a liquid diluent or carrier containing a surface-active agent.
The present invention also provides a method of com-bating arthropods tespecially insects or acarids) which comprises applying to the arthropods , or to a habitat thereof, a compound of the present invention alone or in the form of a composition containing as active ingredient a compound of the present invention in admixture with a diluent or carrier.
The present invention also provides a method of freeing or protecting domesticated animals from parasitical 3~ insects or acarids which comprises applying to said animals Le A 19 140 ll~tl3~9 a compound according to the present invention, in admixture with a diluent or carrier.
The present invention further provides crops protected from damage by arthropods by being grown in areas in which immediately prior to and/or during the time of the growing a compound of the present invention was applied alone or in admixture with a diluent or carrier.
It will be seen that the usual methocs of providing a harvested crop may be improved by the present invention.
The present invention further provid~s domesticated animals whenever freed or protected from parasitical insects or acarids by the application to said animals of a compound according to the present invention, in admixture wit;h a diluent or carrier.
The insecticidal and acaricidal activity of the compounds of this invention is illustratec by the following biotest Examples.
In these Examples, the compounds according to the present invention are each identified by the number (given in brackets) of the corresponding preparative Example, which will be found later in this specification.
Example A
Phaedon larvae test Solvent: 3 parts by weight of dimethylformamide 5 Emulsifier: 1 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, 1 part by weight of the active compound was mixed with the stated amount of solvent containing the stated amount of emulsifier and the concentrate was diluted with water to the desired concentration.
Cabbage leaves (Bras's'ica oleracea) were treated by being dipped into the preparation of the active compound of the desired concentration and were infested with mustard beetle larvae (Pha n cochleariae), as long as the leaves were still wet.
Le A 19 140 il413~39 After the specified periods of time, the degree of destruction was determined in %: 100% meant that all of the beetle larvae had been killed whereas 0% meant that none of the beetle larvae had been killed.
In this test, for example, the following compounds showed a superior activity compared with the prior art:
t2), (6) and (10).
Example B
Tetranychus test (resistant) Solvent: 3 parts by weight of dimethylformamide Emulsifier: 1 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, 1 part by weight of the active compound was mixed wish the stated amount of solvent and the stated amount of emulsifier and the concentrate was diluted with water to the desired concentration.
Bean plants (Phaseolus vulgaris) which were hea~ily infested with the two-spotted spider mite (Tetranychus urticae) in all stages of development were treated by being dipped into the preparation of the active compound of the desired concentration.
After the specified periods of time, the degree of destruction was determined as a percentage: 100%
meant that all of the spider mites were killed whereas 0% meant that none of the spider mites were killed.
In this test, for example, the following compounds showed a superior activity compared with the prior art:
(2) and (6~.
~x-ample C
Critical concentration test/soil insects Test insect: Tenebrio'm'ol'i't'or larvae in the soil Solvent: 3 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether Le A 19 140 1~13W
To produce a suitable preparation of active compound, 1 part by weight of active compound was mixed with the stated amount Or solvent, the stated amount of emulsifier was added and the concentrate was diluted with water to the desired concentration.
The preparation of active compound was intimately mixed with the soil. The concentration of the active compound in the preparation was practically immaterial, the only decisive factor being the amount by weight Or active compound per unit volume of soil, which is quoted hereinafter in ppm (~ mg/l). The treated soil was filled into pots and the pots were left to stand at room tempera-ture.
After 24 hours the test insects were introduced into the treated soil and after a further 2 to 7 days the degree of effectiveness of the active compound was de-termined in % by counting the dead and the live test insects.
The degree of effectiveness was 100% if all of the test insects had been killed and was 0% if exactly as many test insects were still alive as in the case of the untreated control.
In this test, for example, the following compounds showed a superior action compared with the prior art: (1) and (2).
25 Example D
DloO test Test animals: Blatta orientalis _ Number Or test animals: 10 Solvent: Acetone 3o The active compound was taken up in the solvent at a rate of 2 g per litre. The solution so obtained was diluted with further solvent to the desired concen-trations.
2.5 ml of the solution of the active compound were pipetted into a Petri dish. On the bottom of the Petri Le A 19 140 3~39 - dish there was a filter paper ~ith a diameter of about 9.5 cm. The Petri dish remained uncovered until the solvent had completely evaporated. The amount of active compound per square metre of filter paper varied with the concentration of the solution of active compound.
The stated number of test animals was then placed in the Petri dish and the dish was covered with a glass lid.
The condition of the test animals was observed 3 days after the commencement of the experiments. The destruction, in %, was determined. 100% denoted thc,t all of the test animals had been killed; 0% denoted that none of the test animals had been killed.
In this test, for example, the following compounds showed a superior action compared with the prior art:
(1), (2) and (6).
~ Example E
; LTloo test for Diptera Test animals: Aedes ae'gypti Number of test animals: 25 Solvent: Acetone The active compound was dissolved in the solvent at a rate of 2 g per litre. The solution so obtained was diluted with further solvent to the desired lower concentrations.
2.5 ml of the solution of active compound were pipetted into a Petri dish. On the bottom of the Petri dish there was a filter paper with a diameter of about
9.5 cm. The Petri dish remained uncovered until the solvent had completely evaporated. The amount of active compound per square metre of filter paper varied with the con-centration of the solution of active compound. The stated , number of test animals was then placed in the Petri dish ,' and the dish was covered with a glass lid.
The condition of the test animals was continuously observed. The time which was necessary for 100% "knock-down" was determined.
,t .
Le A 19 140 ~1413~9 - In this test, for example, the following compounds showed a superior action compared to the prior art: (1) (2) and (5).
Preparative EXamples Example 1 ; ~ 33 ~ (1) 5.88 g of 2,2-dimethyl-3-(2',3',3'-trichloro-3'-fluoropropenyl)-cyclopropanecarboxylic acid chloride were mixed with 100 ml of toluene and 4.0 g of 3-phenoxybenzyl alcohol. 1.8 g of pyridine in 50 ml of toluene were then added dropwise at room temperature, whilst stirring, and the mixture was subsequently stirred at room temperature for 4 hours. 150 ml of water were then added to the reaction - mixture and the organic phase was separated off and washed with 100 ml of water. m e organic phase was dried with sodium phosphate and filtered, the filtrate was concentrated in a rotary evaporator and the residue was subjected to incipient distillation at 60C under a high vacuum (~or about 1 hour). The residue weighed 8.o g and consisted of 20 2,2-dimethyl-3-(2',3',3'-trichloro-3'-fluoropropenyl)-cyclo-propanecarboxylic acid (3'-phenoxy)-benzyl ester.
Example 2 ~ 2 CN ~ ~ (2) 5.88 g of 2,2-dimethyl-3-(2',3',3'-trichloro-3'-fluoro-propenyl)-cyclopropanecarboxylic acid chloride were Le A 19 140 11413~39 mixed with 100 ml of toluene and 4~5 g of the cyanohydrin Or 3-phenoxybenzaldehyde. 1.8 g of pyridine in 50 ml Or toluene were then added dropwise at room temperature, whilst stirring, and the mixture was su~sequently stirred at room temperature for 4 hours. 150 ml of water were then added to the reaction mixture and the organic phase was separated off and washed with 100 ml of water. me organic phase was dried with sodium sulphate and filtered, the filtrate was concentrated in a rotary evaporator and the residue was sub-jected to incipient distillation at 60C under a highvacuum (for about 1 hour). m e residue weighed 9.1 g and consisted of 2,2-dimethyl-3-(2',3',3~-trichloro-3'-fluoro-propenyl)-cyclopropanecarboxylic acid(3'-phenoxy)-2-cyano-benzyl ester.
m e following compounds were prepared analogously to Examples 1 and 2:
Example Compound -3 C~2F~
H3C a:l3 \/ ~OCF3 4 C12FC~ X)2a;l2 Cl H3C~,~ p33 F~
S C12FC~ 2C4~P
C~ .
Le A 19 140 .
il~l3E~9 Examp le - Compound .
6 3 \,~3 0 , 2~C~-F
7 (CF3)2~C02CN2~C
Cl a (CF3)2CF~2~3 .
9 3)2 ~
(CF3)2Q~CN~--Cl 11 (CF3)2~ ~F
Le A 19 140 11413~9 Example Compound ~2 H3 ~ CH3 (CF3~2 ~ o2,~ ~
Preparation of the starting materials and vheir precursors.
Example 13 \
~
,a co Cl ,,; C~
20 g of 2,2-dimethyl-3-(2',3',3'-trichloro-3'-fluoropropenyl)-cyclopropanecarboxylic acid were dis~olved in 150 ml of methylene chloride, a few drops of dimethyl-formamide were added and phosgene was passed in at room temperature until the reaction had ended (monitoring by the infra-red spectrum). Excess phosgene and methylene chloride were then distilled off. Distillation of the - product gave 2,2-dimethyl-3-(2',3',3'-trichloro-3'-fluoro-propenyl)-cyclopropanecar~oxylic acid chloride of boiling point 82-86C/0.2 mm Hg.
Examele 14 H3C ~ 3 ~CF3)2C~ ~ C0-Cl C
20 g of 2,2-dimethyl-3-(2'-chloro-3'-trifluoro-methyl-3',4',4',4'-tetrafluoro-but-1-enyl)-cyclopropane-carboxylic acid were di~solved in 100 ml of thionyl chlorideand the solution was heated to the boil for one hour.
Le A 19 140 i~413~9 - ~2 -After distill:ing off excess thionyl chloride, the residue was distilled under a high vacuum. 2,2-Dimethyl-3-(2'-chloro-3'-trifluoromethyl-3',4',4',4'-tetrafluorobut-1-enyl)-cyclopropanecarboxylic acid chloride of boiling point 73-76~C/0.8 mm Hg was obtained.
Example 15 \/
C12FC ~ COOH
C
200 ml of 3 N methanolic KOH were added to 30.35 g of 2,2-dimethyl-3-(2',3',3'-trichloro-5'-fluoropropenyl)-cyclopropanecarboxylic acid ethyl ester and the mixtl~re was stirred at room temperature for 6 hours. 300 ml of ice-water were then added and the pH was adjusted to 1 w th concentrated HCl. Extraction with petroleum ether gave 23.5 g of the carboxylic acid, which only partly solidified (isomer mixture).
Example 16 ~3C~cH3 ICF3)2CF ~ -COOH
2,2-Dimethyl-3-(2'-chloro-3'-trifluoromethyl-3',4',4',4'-tetrafluoro-but~ enyl)-cyclopropanecarboxylic acid was obtained analogously to Example 15.
Example_17 ~
V
C12FC~C02C2H5 C
.
Le A 19 140 - 33 ~
120 g of 3,3-dimethyl-4,6,6,7,7-pentachloro-7-- fluoro-enanthic acid ethyl ester were added dropwise to a solution of 16.1 g of sodium in 800 ml of ethanol. The mixture was subsequently stirred at room temperature for 1 5 hour and then heated to 45-50C for 7 hours. After cooling, the sodium chloride which had separated out was filtered off, the filtrate was concentrated somewhat in vacuo, the concentrate was added to 500 ml of water and the mixture was rendered neutral. Extraction with methylene
The condition of the test animals was continuously observed. The time which was necessary for 100% "knock-down" was determined.
,t .
Le A 19 140 ~1413~9 - In this test, for example, the following compounds showed a superior action compared to the prior art: (1) (2) and (5).
Preparative EXamples Example 1 ; ~ 33 ~ (1) 5.88 g of 2,2-dimethyl-3-(2',3',3'-trichloro-3'-fluoropropenyl)-cyclopropanecarboxylic acid chloride were mixed with 100 ml of toluene and 4.0 g of 3-phenoxybenzyl alcohol. 1.8 g of pyridine in 50 ml of toluene were then added dropwise at room temperature, whilst stirring, and the mixture was subsequently stirred at room temperature for 4 hours. 150 ml of water were then added to the reaction - mixture and the organic phase was separated off and washed with 100 ml of water. m e organic phase was dried with sodium phosphate and filtered, the filtrate was concentrated in a rotary evaporator and the residue was subjected to incipient distillation at 60C under a high vacuum (~or about 1 hour). The residue weighed 8.o g and consisted of 20 2,2-dimethyl-3-(2',3',3'-trichloro-3'-fluoropropenyl)-cyclo-propanecarboxylic acid (3'-phenoxy)-benzyl ester.
Example 2 ~ 2 CN ~ ~ (2) 5.88 g of 2,2-dimethyl-3-(2',3',3'-trichloro-3'-fluoro-propenyl)-cyclopropanecarboxylic acid chloride were Le A 19 140 11413~39 mixed with 100 ml of toluene and 4~5 g of the cyanohydrin Or 3-phenoxybenzaldehyde. 1.8 g of pyridine in 50 ml Or toluene were then added dropwise at room temperature, whilst stirring, and the mixture was su~sequently stirred at room temperature for 4 hours. 150 ml of water were then added to the reaction mixture and the organic phase was separated off and washed with 100 ml of water. me organic phase was dried with sodium sulphate and filtered, the filtrate was concentrated in a rotary evaporator and the residue was sub-jected to incipient distillation at 60C under a highvacuum (for about 1 hour). m e residue weighed 9.1 g and consisted of 2,2-dimethyl-3-(2',3',3~-trichloro-3'-fluoro-propenyl)-cyclopropanecarboxylic acid(3'-phenoxy)-2-cyano-benzyl ester.
m e following compounds were prepared analogously to Examples 1 and 2:
Example Compound -3 C~2F~
H3C a:l3 \/ ~OCF3 4 C12FC~ X)2a;l2 Cl H3C~,~ p33 F~
S C12FC~ 2C4~P
C~ .
Le A 19 140 .
il~l3E~9 Examp le - Compound .
6 3 \,~3 0 , 2~C~-F
7 (CF3)2~C02CN2~C
Cl a (CF3)2CF~2~3 .
9 3)2 ~
(CF3)2Q~CN~--Cl 11 (CF3)2~ ~F
Le A 19 140 11413~9 Example Compound ~2 H3 ~ CH3 (CF3~2 ~ o2,~ ~
Preparation of the starting materials and vheir precursors.
Example 13 \
~
,a co Cl ,,; C~
20 g of 2,2-dimethyl-3-(2',3',3'-trichloro-3'-fluoropropenyl)-cyclopropanecarboxylic acid were dis~olved in 150 ml of methylene chloride, a few drops of dimethyl-formamide were added and phosgene was passed in at room temperature until the reaction had ended (monitoring by the infra-red spectrum). Excess phosgene and methylene chloride were then distilled off. Distillation of the - product gave 2,2-dimethyl-3-(2',3',3'-trichloro-3'-fluoro-propenyl)-cyclopropanecar~oxylic acid chloride of boiling point 82-86C/0.2 mm Hg.
Examele 14 H3C ~ 3 ~CF3)2C~ ~ C0-Cl C
20 g of 2,2-dimethyl-3-(2'-chloro-3'-trifluoro-methyl-3',4',4',4'-tetrafluoro-but-1-enyl)-cyclopropane-carboxylic acid were di~solved in 100 ml of thionyl chlorideand the solution was heated to the boil for one hour.
Le A 19 140 i~413~9 - ~2 -After distill:ing off excess thionyl chloride, the residue was distilled under a high vacuum. 2,2-Dimethyl-3-(2'-chloro-3'-trifluoromethyl-3',4',4',4'-tetrafluorobut-1-enyl)-cyclopropanecarboxylic acid chloride of boiling point 73-76~C/0.8 mm Hg was obtained.
Example 15 \/
C12FC ~ COOH
C
200 ml of 3 N methanolic KOH were added to 30.35 g of 2,2-dimethyl-3-(2',3',3'-trichloro-5'-fluoropropenyl)-cyclopropanecarboxylic acid ethyl ester and the mixtl~re was stirred at room temperature for 6 hours. 300 ml of ice-water were then added and the pH was adjusted to 1 w th concentrated HCl. Extraction with petroleum ether gave 23.5 g of the carboxylic acid, which only partly solidified (isomer mixture).
Example 16 ~3C~cH3 ICF3)2CF ~ -COOH
2,2-Dimethyl-3-(2'-chloro-3'-trifluoromethyl-3',4',4',4'-tetrafluoro-but~ enyl)-cyclopropanecarboxylic acid was obtained analogously to Example 15.
Example_17 ~
V
C12FC~C02C2H5 C
.
Le A 19 140 - 33 ~
120 g of 3,3-dimethyl-4,6,6,7,7-pentachloro-7-- fluoro-enanthic acid ethyl ester were added dropwise to a solution of 16.1 g of sodium in 800 ml of ethanol. The mixture was subsequently stirred at room temperature for 1 5 hour and then heated to 45-50C for 7 hours. After cooling, the sodium chloride which had separated out was filtered off, the filtrate was concentrated somewhat in vacuo, the concentrate was added to 500 ml of water and the mixture was rendered neutral. Extraction with methylene
10 chlorlde and fractional distillation gave &2 g of 2,2-dimethyl-3-(2~,3~,3~-trichloro-3~-fluoro-propenyl)-cyclopropanecarboxylic acid ethyl ester of boiling pcint 92-97C/0.3 mm Hg.
Example 18 FCl2c-ccl2-cH2-cHcl-c-cH2co2c2Hs 168 g of 3,3-dimethyl-4-pentenoic acid ethyl ester and 624 g of pentachlorofluoroethane were heated, together with 2.4 g of benzoyl peroxide, whilst stirring. At a bath temperature of 100C, the internal temperature rose 20 to 118C. The exothermic effect had ended after about 2.5 hours.
The excess pentachlorofluoroethane and the unreacted 3,3-dimethyl-4-pentenoic acid ethyl ester could easily be separated, by distillation, from the 3,3-dimethyl-25 4,6,6,7,7-pentachloro-7-fluoroenanthic acid ethyl ester formed (refractive index n20 = 1.487).
Example 19 N3C ,CH3 (CE3)2CF X
)=~co2c2H5 - Cl Le A 19 140 l~M~t 2,2-Dimethyl-3-(2~-chloro-3l-trifluoromethyl-3',4',4l,4'-tetrafluoro-but~ enyl)-cyclopropanecarboxylic acid ethyl ester Or boiling point 68-72C/0.3 mm Hg was obtained, analogously to Example 17, from 3,3-dimethyl-4,6~6-trichloro-7-trifluoromethyl-7~8,8~8-tetrafluoro-octanoic acid ethyl ester and sodium ethylate.
The following compounds were obtained analogously to Example 18.
Example Compound Bgiling point ( C/mm ~g) CH
CFcl2ccl2cH2cHcl-c-cN2co2c~ t22-130/'0,3 21 CFcl2ccl2cH2cHcl-c-cH2co-cH3 103-107/0,25 Example 22 (cF3)2cFccl2cH2cHcl-c-cH2co2c2~5 c~3 78 g Or 3,3-dLmethyl-4-pentenoic acid ethyl ester, 287.5 g Or 1,1,1-trichloro-2,3,3,3-tetrafluoro-2-trifluoro-methylpropane, 50 g of acetonitrile, 0.65 g of FeC13.6H20, 0.51 g of benzoin and 0.4 g of dimethylamine hydrochloride were heated to 100-120C in a VA autoclave under 6 bars of nitrogen for 7 hours, and, after cooling and letting down, the product was distilled over a Vigreux column. 3,3-Dimethyl-4,6,6-trichloro-7,8,8,8-tetrafluoro-7-trifluoro-methyloctanoic acid ethyl ester of boiling point 115-118C/0.25 mm Hg was obtained.
Le A 19 140
Example 18 FCl2c-ccl2-cH2-cHcl-c-cH2co2c2Hs 168 g of 3,3-dimethyl-4-pentenoic acid ethyl ester and 624 g of pentachlorofluoroethane were heated, together with 2.4 g of benzoyl peroxide, whilst stirring. At a bath temperature of 100C, the internal temperature rose 20 to 118C. The exothermic effect had ended after about 2.5 hours.
The excess pentachlorofluoroethane and the unreacted 3,3-dimethyl-4-pentenoic acid ethyl ester could easily be separated, by distillation, from the 3,3-dimethyl-25 4,6,6,7,7-pentachloro-7-fluoroenanthic acid ethyl ester formed (refractive index n20 = 1.487).
Example 19 N3C ,CH3 (CE3)2CF X
)=~co2c2H5 - Cl Le A 19 140 l~M~t 2,2-Dimethyl-3-(2~-chloro-3l-trifluoromethyl-3',4',4l,4'-tetrafluoro-but~ enyl)-cyclopropanecarboxylic acid ethyl ester Or boiling point 68-72C/0.3 mm Hg was obtained, analogously to Example 17, from 3,3-dimethyl-4,6~6-trichloro-7-trifluoromethyl-7~8,8~8-tetrafluoro-octanoic acid ethyl ester and sodium ethylate.
The following compounds were obtained analogously to Example 18.
Example Compound Bgiling point ( C/mm ~g) CH
CFcl2ccl2cH2cHcl-c-cN2co2c~ t22-130/'0,3 21 CFcl2ccl2cH2cHcl-c-cH2co-cH3 103-107/0,25 Example 22 (cF3)2cFccl2cH2cHcl-c-cH2co2c2~5 c~3 78 g Or 3,3-dLmethyl-4-pentenoic acid ethyl ester, 287.5 g Or 1,1,1-trichloro-2,3,3,3-tetrafluoro-2-trifluoro-methylpropane, 50 g of acetonitrile, 0.65 g of FeC13.6H20, 0.51 g of benzoin and 0.4 g of dimethylamine hydrochloride were heated to 100-120C in a VA autoclave under 6 bars of nitrogen for 7 hours, and, after cooling and letting down, the product was distilled over a Vigreux column. 3,3-Dimethyl-4,6,6-trichloro-7,8,8,8-tetrafluoro-7-trifluoro-methyloctanoic acid ethyl ester of boiling point 115-118C/0.25 mm Hg was obtained.
Le A 19 140
Claims (17)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A 3-fluoroalkenyl-2,2-dimethyl-cyclopropanecarboxylic acid ester of the formula in which R1 is H, chlorine, bromine, C1-4-alkyl or C1-4-halogenoalkyl, R2 is chlorine, bromine, C1-4-alkyl or C1-4-halogenoalkyl, R3 is halogen, CF3 or R1-?-R2, and R is wherein Y is O or S, X is -CH2-, -O- or S, R11 is hydrogen, CN, -CO2CH3, -CO2C2H5 or -C?CH, R12 is alkyl, alkenyl, alkynyl or an aryl or furyl group, R5 is hydrogen or methyl, R6 is an organic radical with a C-C double bond or triple bond in the .alpha.-position, R7 and R8 each independently is hydrogen or C1-4-alkyl, R9 is hydrogen, halogen or CF3, and R10 is -CH2C?CH, -CHF2, -CF3, -CH?CCl2 or an aryl radical optionally substituted by halogen, methyl or methoxy.
2. A compound according to claim 1, in which R1 and R2 each independently is Cl, Br or CF3, and R3 is Cl or Br.
3. A compound according to claim 2, in which R is or R11 is H, CN, -CO2CH3, -CO2C2H5 or C?CH, R9 is hydrogen or halogen and R10 is -CH2C?CH, CHF2, CF3, -CH=CCl2, aryl or aryl substituted by halogen, methyl and/or methoxy.
4. A compound according to claim 3 wherein R10, where present, is -CH2C?CH, -CHF2, -CF3, -CH?CCl2 or phenyl.
5. 2,2-Dimethyl-3-(2',3',3'-trichloro-3'-fluoro-propenyl)-cyclopropane-carboxylic acid (3'-phenoxy)-.alpha.-cyano-benzyl ester of the formula
6. 2,2-Dimethyl-3-(2',3',3'-trichloro-3'-fluoro-propenyl)-cyclopropane-carboxylic acid pentafluorobenzyl ester of the formula
7. 2,2-Dimethyl-3-(2',3',3'-trichloro-3'-fluoro-propenyl)-cyclopropane-carboxylic acid (4'-fluoro-3'-phenoxy)-.alpha.-cyano-benzyl ester of the formula
8. A method of combating arthropods which comprises applying to the arthropods, or to a habitat thereof, an arthropodically effective amount of a compound according to claim 1.
9. A method according to claim 8 wherein the compound is applied in the form of a composition containing said compound as active ingredient in admixture with a suitable carrier or diluent.
10. A method according to claim 9 in which a composition is used containing from 0.0000001 to 95% of said compound, by weight.
11. A method according to claim 9 in which a composition is used containing from 0.01 to 10% of said compound, by weight.
12. A method according to claim 8, 9 or 11 in which the arthropods are insects or acarids.
13. A method according to claim 8, 9 or 11, in which said compound is 2,2-dimethyl-3-(2',3',3'-trichloro-3-fluoro-propenyl)-cyclopropanecarboxylic acid (3'-phenoxy)-.alpha.-cyano-benzyl ester.
14. A method according to claim 8, 9 or 11, in which said conpound is 2,2-dimethyl-3-(2',3',3'-trichloro-3'-fluoro-propenyl)-cyclopropanecarboxylic acid pentafluorobenzyl ester.
15. A method according to claim 8, 9 or 11, in which said compound is 2,2-dimethyl-3-(2',3',3'-trichloro-3'-fluoro-propenyl)-cyclopropanecarboxylic acid (4'-fluoro-3'-phenoxy)-.alpha.-cyano-benzyl ester.
16. A method of combating parasitical insects and acarids of domestic animals which comprises applying to said insects or acarids, or to the habitat thereof, an insecticidally or acaricidally effective amount of a compound according to claim 2, 3 or 4.
17. A process for the preparation of an ester according to claim 1, comprising reacting a compound of the formula in which Hal is halogen, with an olefin of the formula in which or thereby to produce a compound of the formula , dehydrohalogenating said compound to produce a cyclopropane compound of the formula converting R4 of said cyclopropane compound to -COHal or COOH, and reacting the compound so produced with a compound of the formula in which Z2 is OH, Cl or Br.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP2842541.4 | 1978-09-29 | ||
| DE19782842541 DE2842541A1 (en) | 1978-09-29 | 1978-09-29 | FLUORALKENYL-SUBSTITUTED CYCLOPROPANCARBONIC ACID ESTERS AND THEIR USE AS INSECTICIDES |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1141389A true CA1141389A (en) | 1983-02-15 |
Family
ID=6050908
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000336559A Expired CA1141389A (en) | 1978-09-29 | 1979-09-28 | Fluoroalkenyl-substituted cyclopropane- carboxylic acid esters and their use as insecticides |
Country Status (21)
| Country | Link |
|---|---|
| EP (1) | EP0009709B1 (en) |
| JP (1) | JPS5549341A (en) |
| AT (1) | ATE6249T1 (en) |
| AU (1) | AU531782B2 (en) |
| BG (1) | BG30623A3 (en) |
| BR (1) | BR7906171A (en) |
| CA (1) | CA1141389A (en) |
| CS (1) | CS209935B2 (en) |
| DD (1) | DD147907A5 (en) |
| DE (2) | DE2842541A1 (en) |
| DK (1) | DK409179A (en) |
| EG (1) | EG13891A (en) |
| ES (1) | ES484574A1 (en) |
| GR (1) | GR70672B (en) |
| IL (1) | IL58332A0 (en) |
| PL (1) | PL218599A1 (en) |
| PT (1) | PT70222A (en) |
| RO (1) | RO78868A (en) |
| SU (1) | SU1071196A3 (en) |
| TR (1) | TR20542A (en) |
| ZA (1) | ZA795166B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3364135D1 (en) * | 1982-04-05 | 1986-07-24 | Ici Plc | Method for combating insect pests, and novel cyclopropane carboxylates useful as active ingredients therein |
| DE3312543A1 (en) * | 1983-04-07 | 1984-10-11 | Bayer Ag, 5090 Leverkusen | 2,2-DIMETHYL-3- (2-HALOGEN-VINYL) -CYCLOPROPANCARBONIC ACID ESTER, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS A PEST CONTROL |
| FR2687152A1 (en) * | 1992-02-07 | 1993-08-13 | Roussel Uclaf | NOVEL PYRETHRINOUID ESTERS DERIVED FROM FURANIC OR THIOPHENIC ALCOHOL, PROCESS FOR THEIR PREPARATION AND THEIR USE AS PESTICIDES |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5813522B2 (en) * | 1974-10-24 | 1983-03-14 | 住友化学工業株式会社 | Insecticide and acaricide containing new cyclopropane carboxylic acid ester |
| US4183948A (en) * | 1977-01-24 | 1980-01-15 | Imperial Chemical Industries Limited | Halogenated esters |
| GB2000764B (en) * | 1977-03-23 | 1982-04-28 | Ici Ltd | Halogenated esters |
| IN150399B (en) * | 1978-01-20 | 1982-09-25 | Fmc Corp |
-
1978
- 1978-09-29 DE DE19782842541 patent/DE2842541A1/en not_active Withdrawn
-
1979
- 1979-09-17 AT AT79103488T patent/ATE6249T1/en not_active IP Right Cessation
- 1979-09-17 DE DE7979103488T patent/DE2966668D1/en not_active Expired
- 1979-09-17 EP EP79103488A patent/EP0009709B1/en not_active Expired
- 1979-09-21 CS CS796378A patent/CS209935B2/en unknown
- 1979-09-24 BG BG7944933A patent/BG30623A3/en unknown
- 1979-09-25 PT PT70222A patent/PT70222A/en unknown
- 1979-09-26 SU SU792815597A patent/SU1071196A3/en active
- 1979-09-26 IL IL58332A patent/IL58332A0/en unknown
- 1979-09-26 BR BR7906171A patent/BR7906171A/en unknown
- 1979-09-27 GR GR60132A patent/GR70672B/el unknown
- 1979-09-27 TR TR20542A patent/TR20542A/en unknown
- 1979-09-28 JP JP12427579A patent/JPS5549341A/en active Pending
- 1979-09-28 ZA ZA00795166A patent/ZA795166B/en unknown
- 1979-09-28 ES ES484574A patent/ES484574A1/en not_active Expired
- 1979-09-28 DK DK409179A patent/DK409179A/en not_active Application Discontinuation
- 1979-09-28 CA CA000336559A patent/CA1141389A/en not_active Expired
- 1979-09-28 AU AU51311/79A patent/AU531782B2/en not_active Ceased
- 1979-09-28 PL PL21859979A patent/PL218599A1/xx unknown
- 1979-09-28 DD DD79215891A patent/DD147907A5/en unknown
- 1979-09-29 RO RO7998813A patent/RO78868A/en unknown
- 1979-09-29 EG EG573/79A patent/EG13891A/en active
Also Published As
| Publication number | Publication date |
|---|---|
| RO78868B (en) | 1983-07-30 |
| DE2842541A1 (en) | 1980-05-22 |
| EP0009709A1 (en) | 1980-04-16 |
| EG13891A (en) | 1982-09-30 |
| RO78868A (en) | 1983-08-03 |
| AU531782B2 (en) | 1983-09-08 |
| DK409179A (en) | 1980-03-30 |
| IL58332A0 (en) | 1979-12-30 |
| ZA795166B (en) | 1980-10-29 |
| CS209935B2 (en) | 1981-12-31 |
| ATE6249T1 (en) | 1984-03-15 |
| TR20542A (en) | 1981-10-21 |
| PT70222A (en) | 1979-10-01 |
| SU1071196A3 (en) | 1984-01-30 |
| BR7906171A (en) | 1980-05-27 |
| PL218599A1 (en) | 1980-06-16 |
| JPS5549341A (en) | 1980-04-09 |
| AU5131179A (en) | 1980-04-03 |
| GR70672B (en) | 1982-12-06 |
| DE2966668D1 (en) | 1984-03-22 |
| BG30623A3 (en) | 1981-07-15 |
| ES484574A1 (en) | 1980-06-16 |
| DD147907A5 (en) | 1981-04-29 |
| EP0009709B1 (en) | 1984-02-15 |
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| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |