GB1604450A - Derivatives of cyclopropanecarboxylic acids - Google Patents
Derivatives of cyclopropanecarboxylic acids Download PDFInfo
- Publication number
- GB1604450A GB1604450A GB4845477A GB4845477A GB1604450A GB 1604450 A GB1604450 A GB 1604450A GB 4845477 A GB4845477 A GB 4845477A GB 4845477 A GB4845477 A GB 4845477A GB 1604450 A GB1604450 A GB 1604450A
- Authority
- GB
- United Kingdom
- Prior art keywords
- isomer
- acid
- trans
- tetrahydrophthalimidomethyl
- compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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- YMGUBTXCNDTFJI-UHFFFAOYSA-N cyclopropanecarboxylic acid Chemical class OC(=O)C1CC1 YMGUBTXCNDTFJI-UHFFFAOYSA-N 0.000 title description 5
- 150000001875 compounds Chemical class 0.000 claims description 31
- 238000000034 method Methods 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 10
- -1 Tetrahydrophthalimidomethyl alcohol Chemical compound 0.000 claims description 9
- ZCVAOQKBXKSDMS-PVAVHDDUSA-N (+)-trans-(S)-allethrin Chemical compound CC1(C)[C@H](C=C(C)C)[C@H]1C(=O)O[C@@H]1C(C)=C(CC=C)C(=O)C1 ZCVAOQKBXKSDMS-PVAVHDDUSA-N 0.000 claims description 8
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 claims description 8
- 238000003197 gene knockdown Methods 0.000 claims description 8
- 229910052736 halogen Inorganic materials 0.000 claims description 7
- 150000002367 halogens Chemical class 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 7
- 241000607479 Yersinia pestis Species 0.000 claims description 6
- 229960001901 bioallethrin Drugs 0.000 claims description 6
- 230000000694 effects Effects 0.000 claims description 6
- 206010061217 Infestation Diseases 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- HYJYGLGUBUDSLJ-UHFFFAOYSA-N pyrethrin Natural products CCC(=O)OC1CC(=C)C2CC3OC3(C)C2C2OC(=O)C(=C)C12 HYJYGLGUBUDSLJ-UHFFFAOYSA-N 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 230000000749 insecticidal effect Effects 0.000 claims description 4
- 239000003350 kerosene Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 4
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 3
- 241000257226 Muscidae Species 0.000 claims description 3
- VXSIXFKKSNGRRO-MXOVTSAMSA-N [(1s)-2-methyl-4-oxo-3-[(2z)-penta-2,4-dienyl]cyclopent-2-en-1-yl] (1r,3r)-2,2-dimethyl-3-(2-methylprop-1-enyl)cyclopropane-1-carboxylate;[(1s)-2-methyl-4-oxo-3-[(2z)-penta-2,4-dienyl]cyclopent-2-en-1-yl] (1r,3r)-3-[(e)-3-methoxy-2-methyl-3-oxoprop-1-enyl Chemical class CC1(C)[C@H](C=C(C)C)[C@H]1C(=O)O[C@@H]1C(C)=C(C\C=C/C=C)C(=O)C1.CC1(C)[C@H](/C=C(\C)C(=O)OC)[C@H]1C(=O)O[C@@H]1C(C)=C(C\C=C/C=C)C(=O)C1 VXSIXFKKSNGRRO-MXOVTSAMSA-N 0.000 claims description 3
- 239000003085 diluting agent Substances 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 239000011737 fluorine Substances 0.000 claims description 3
- 229940070846 pyrethrins Drugs 0.000 claims description 3
- 239000002728 pyrethroid Substances 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- RPAJSBKBKSSMLJ-DFWYDOINSA-N (2s)-2-aminopentanedioic acid;hydrochloride Chemical class Cl.OC(=O)[C@@H](N)CCC(O)=O RPAJSBKBKSSMLJ-DFWYDOINSA-N 0.000 claims description 2
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 claims description 2
- FNGLEHQBWQQRIT-UHFFFAOYSA-N 3-(2,2-difluoroethenyl)-2,2-dimethylcyclopropane-1-carbonyl chloride Chemical compound CC1(C)C(C=C(F)F)C1C(Cl)=O FNGLEHQBWQQRIT-UHFFFAOYSA-N 0.000 claims description 2
- 241000238658 Blattella Species 0.000 claims description 2
- 241001674044 Blattodea Species 0.000 claims description 2
- FIPWRIJSWJWJAI-UHFFFAOYSA-N Butyl carbitol 6-propylpiperonyl ether Chemical compound C1=C(CCC)C(COCCOCCOCCCC)=CC2=C1OCO2 FIPWRIJSWJWJAI-UHFFFAOYSA-N 0.000 claims description 2
- 241000255925 Diptera Species 0.000 claims description 2
- 244000141359 Malus pumila Species 0.000 claims description 2
- VQXSOUPNOZTNAI-UHFFFAOYSA-N Pyrethrin I Natural products CC(=CC1CC1C(=O)OC2CC(=O)C(=C2C)CC=C/C=C)C VQXSOUPNOZTNAI-UHFFFAOYSA-N 0.000 claims description 2
- 230000000052 comparative effect Effects 0.000 claims description 2
- 238000007599 discharging Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 229960000490 permethrin Drugs 0.000 claims description 2
- RLLPVAHGXHCWKJ-UHFFFAOYSA-N permethrin Chemical compound CC1(C)C(C=C(Cl)Cl)C1C(=O)OCC1=CC=CC(OC=2C=CC=CC=2)=C1 RLLPVAHGXHCWKJ-UHFFFAOYSA-N 0.000 claims description 2
- 230000000361 pesticidal effect Effects 0.000 claims description 2
- 229960005235 piperonyl butoxide Drugs 0.000 claims description 2
- VJFUPGQZSXIULQ-XIGJTORUSA-N pyrethrin II Chemical compound CC1(C)[C@H](/C=C(\C)C(=O)OC)[C@H]1C(=O)O[C@@H]1C(C)=C(C\C=C/C=C)C(=O)C1 VJFUPGQZSXIULQ-XIGJTORUSA-N 0.000 claims description 2
- 229940048383 pyrethrum extract Drugs 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 239000000344 soap Substances 0.000 claims description 2
- 239000004094 surface-active agent Substances 0.000 claims description 2
- 231100000419 toxicity Toxicity 0.000 claims description 2
- 230000001988 toxicity Effects 0.000 claims description 2
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims 1
- QQHOVRKETYPQHY-UHFFFAOYSA-N 2-(hydroxymethyl)-4,5,6,7-tetrahydroisoindole-1,3-dione Chemical compound O=C1N(CO)C(=O)C2=C1CCCC2 QQHOVRKETYPQHY-UHFFFAOYSA-N 0.000 claims 1
- VEMKTZHHVJILDY-UXHICEINSA-N bioresmethrin Chemical compound CC1(C)[C@H](C=C(C)C)[C@H]1C(=O)OCC1=COC(CC=2C=CC=CC=2)=C1 VEMKTZHHVJILDY-UXHICEINSA-N 0.000 claims 1
- 239000003701 inert diluent Substances 0.000 claims 1
- 125000005208 trialkylammonium group Chemical group 0.000 claims 1
- 239000000460 chlorine Substances 0.000 description 6
- 241000238631 Hexapoda Species 0.000 description 4
- XLOPRKKSAJMMEW-SFYZADRCSA-N (+)-trans-chrysanthemic acid Chemical compound CC(C)=C[C@@H]1[C@@H](C(O)=O)C1(C)C XLOPRKKSAJMMEW-SFYZADRCSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- XLOPRKKSAJMMEW-YUMQZZPRSA-N (+)-cis-chrysanthemic acid Chemical compound CC(C)=C[C@H]1[C@@H](C(O)=O)C1(C)C XLOPRKKSAJMMEW-YUMQZZPRSA-N 0.000 description 1
- DYLIWHYUXAJDOJ-OWOJBTEDSA-N (e)-4-(6-aminopurin-9-yl)but-2-en-1-ol Chemical compound NC1=NC=NC2=C1N=CN2C\C=C\CO DYLIWHYUXAJDOJ-OWOJBTEDSA-N 0.000 description 1
- LLMLSUSAKZVFOA-UHFFFAOYSA-N 3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylic acid Chemical compound CC1(C)C(C=C(Cl)Cl)C1C(O)=O LLMLSUSAKZVFOA-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical class CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- XLOPRKKSAJMMEW-UHFFFAOYSA-N chrysanthemic acid Chemical compound CC(C)=CC1C(C(O)=O)C1(C)C XLOPRKKSAJMMEW-UHFFFAOYSA-N 0.000 description 1
- 239000004495 emulsifiable concentrate Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 231100000518 lethal Toxicity 0.000 description 1
- 230000001665 lethal effect Effects 0.000 description 1
- 238000005949 ozonolysis reaction Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
Classifications
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Indole Compounds (AREA)
Description
(54) IMPROVEMENTS RELATING TO DERIVATIVES OF
CYCLOPROPANECARBOXYLIC ACIDS
(71) We, NATIONAL RESEARCH DEVELOPMENT CORPORATION, a British Corporation established by Statute of Kingsgate House, 66/74, Victoria
Street, London SW1, do hereby declare the invention for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:- This invention relates to new derivativcs of cyclopropanecarboxylic acids, particularly useful as insect knock-down agents, to processes for their preparation, to compositions containing them and to their use in controlling infestation by insects and other pests.
Our U.K. Patent No. 1,413,491 describes and claims compounds of the general formula:
in which R2 and R1 may represent, inter alia, halogen and R may represent, inter alia, a tetrahydrophthalimidomethyl group.
Compounds of formula I can exist in the form of geometrical isomers depending upon whether the hydrogen atoms carried at Cl and C3 of the cyclopropane ring are in the cis or trans relationship. Because of the unsymmetrical substitution at C1 and C, on the cyclopropane ring, each cis isomer can exist in one of two optically active forms and each trans isomer can exist in one of two optically active forms. When the absolute configuration at Cl of compounds of formula I is the same as that at C1 in (+)trans chrysanthemic acid, the absolute configuration of C1 in compound I is designated 1R.
The absolute configuration of C, in compounds of formula I cannot very independently of the C1 configuration in a compound having specified geometrical configuration and, for a compound having trans configuration and R configuration at Cl, strict application of the sequence rule (Cahn, R. S., Ingold C. and Prelog V. Angew. Chem. Int. Ed.
5,385 (1966)) requires the designation S to be applied at C3. However, application of the same sequence rule to the same C3 centre in (+)trans chrysanthemic acid requires that centre to be designated R, even though it is directly related in absolute configuration to the configuration designated S in compounds of formula I. This is because the nature of the substitution at C3 is different in ( T )-trans chrysanthemic acid from that of compounds of formula I. However, because the specification of the geometrical configuration and the absolute configuration at Cl fixes the C3 configuration absolutely, and to avoid possible confusion arising from the fact that different compounds of the same series may otherwise require sometimes R, sometimes S, designations of the configuration at C, we have proposed the nomenclature [lR,trans] for such compounds as this Drovides sufficient information to determine the absolute configuration of the whole molecule.
Similar considerations have resulted in our designating compounds having the same absolute configuration as (+ ) -cis chrysanthemic acid as [1R,cis] compounds.
In Example 18 of the Specification of our U.K. Patent No. 1,413,491, we describe a tetrahydrophthalimidomethyl ester of 3 - (2,2 - dichlorovinyl) - 2,2 - dimethylcyclopropane - carboxylic acid which is a racemic mixture of the two isomers having trans configuration of the hydrogens at C1 and C, on the cyclopropane ring.
We have now been able to prepare individual isomers of the tetrahvdronhthalimidomethyl esters which have surprisingly been found to have a particularly good knock-down effect towards houseflies as well as being lethal to the insects and other arthrapods.
The present invention provides an individual isomer of the general formula:
wherein R2 and RS, which may be the same or different, are each halogen, in which the hydrogen atoms at C1 and C3 of the cyclopropane ring are substantially completely m the cis configuration or substantially completely in the trans configuration and in which
C1 of the cyclopropane ring is substantially completely in the absolute R configuration, the isomer being substantially free from isomers having other configurations.
In the isomers of the present invention, it is preferred that R2 and R3 both represent the same halogen and isomers wherein R2 and R3 both represent fluorine are preferred.
The individual isomers of the present invention may be prepared by esterifying tetrahydrophthalimidomethyl alcohol or an esterifiable derivative thereof with the selected isomer of 3 - (2,2 - dihalovinyl) - 2,2 - dimethylcyclopropane - carboxylic acid or an esterifiable derivative thereof. These esterification techniques are described more fully in the Specification of our U.K. Patent No. 1,413,491 and normally involve the esterification of the alcohol with an acid or acid chloride or reaction of a silver or triethylammonium salt of the carboxylic acid with a tetrahydrophthalimidomethyl halide, or by transesterification reacting a lower alkyl ester of the carboxylic acid with the alcohol.
The individual isomers of the cyclopropane-carboxylic acid or esterifiable derivative thereof can be prepared by the techniques described in the Specification of U.K.
Patent No. 1,413,491. Essentially, these involve converting the selected R isomer or isomer mixture of chrysanthemic acid by ozonolysis to form the corresponding isomer of caronaldehyde and reacting this aldehyde with the selected phosphorane of formula:
wherein R2 and R3 are as defined above and Ph represents phenyl.
The preparation of the [1R,cis] and [lR,trans] acid wherein R2 and R1 represent bromine, is described in Examples 27 and 28 respectively of the Specification of U.K.
Patent No. 1,413,491, while Examples 15 and 17 of the same Specification describe the preparation of the [1R,transj acid in which R2 and R3 each represent chlorine. The preparation of the [1R,cis] isomer of the acid in which R2 and R9 each represent chlorine is described in Example 3 of the Specification of U.K. Patent No. 1,448,228, while Example 2 of the same Specification describes the preparation of the [1R,cis] and [1R,trans} isomers of the acid in which R2 and R3 each represent fluorine.
One or more of the individual isomers of the present invention may be formulated with an inert carrier or diluent to give a composition which can be used to combat infestation by insects or other pests. The compositions may be prepared as dusts or granular solids, wettable powders, emulsions, emulsifiable concentrates, sprays, aerosols and other liquid preparations after the addition of appropriate solvents, diluents and surface active agents. The compositions may also contain other pesticidal compounds, for example to improve insecticidal activity.
The following Example is given to illustrate the invention. Tetrahydrophthalimidomethyl alcohol was esterified by the procedure described in Example 17 of the Specification of U.K. Patent No. 1,413,491 using the [1R,cis] or [1R,trans] isomer of 3 - (2,2 - difluorovinyl) - 2,2 - dimethylcyclopropane - carboxylic acid chloride prepared by reacting the acid (obtained as described in Example 2 of the Specification of Ú.K. Patent No. 1,448,228) with thionyl chloride. The resulting [1R,trans] and
[lR,cis] were designated DP870 and DP891 respectively. DP870 has nD20 1.5015
DP891 is a colourless crystalline solid mp 97--99"C. These esters were tested for their knock-down effect upon houseflies using a modified Kearns and March technique. The basic techniuqe (c.f. Soap, 19 page 101 and 128 (1943)) was modified by using a chamber having 2 sprayers at each end, each discharging 1 ml. of test solvent every 5 seconds. 0.1 ml of a known solution of test compound was introduced into each sprayer and 200 flies were introduced. The test compound was sprayed for 5 seconds and knock down counts taken at 1 minute intervals for 10 minutes. From these results KDao values were calculated. For comparative purposes, similar tests were carried out using natural pyrethrin (25% w/w pyrethrum extract) and bioallethrin when the following results were obtained:
% conc. giving KD,, of 4 mins.
DP 870 0.04
DP 891 0.014
Pyrethrins 0.032
Bioallethrin 0.054
The knock-down effect against cockroaches was shown in the following tests. The compound under test was dissolved in odourless kerosene and sprayed on male
Blattella germanic at various concentrations. The KD-o at 5 minutes for the com- pounds were calculated to be as follows:
DP 870 .0057% w/v
Bioallethrin .064 % w/v
S-Bioallethrin .033 % w/v
Insecticidal properties of the compounds were shown in the following test. A mixed population of male and female M. domestica were sprayed in a Kearns and March chamber with a solution of a compound in odourless kerosene. The toxicity in terms of LD50 was calculated for the following compounds: LD.54 g/female .09
DP 870 .04 DP 870 + piperonyl butoxide .04
(1:5 w/w) .022 permethrin
WHAT WE CLAIM IS:
1. An isomer of the general formula:
wherein R2 and R3, which may be the same or different, are each halogen, in which the hydrogen atoms at C1 and C, of the cyclopropane ring are substantially completely in the cis configuration or substantially completely in the trans configuration and in which
**WARNING** end of DESC field may overlap start of CLMS **.
Claims (14)
1. An isomer of the general formula:
wherein R2 and R3, which may be the same or different, are each halogen, in which the hydrogen atoms at C1 and C, of the cyclopropane ring are substantially completely in the cis configuration or substantially completely in the trans configuration and in which
C1 of the cyclopropane ring is substantially completely in the absolute R configuration, the isomer being substantially free from isomers having other configurations.
2. An isomer according to Claim 1 wherein R2 and Rs each represent the same halogen.
3. An isomer according to Claim 1 or 2 wherein the halogen is fluorine.
4. 3,4,5,6 - Tetrahydrophthalimidomethyl [lR,cis] - 3 - (2,2 - difluorovinyl)2,2 - dimethyl cyclopropane carboxylate.
5. 3,4,5,6 - Tetrahydrophthalimidomethyl [lR,trans] - 3 - (2,2 - difluorovinyl)2,2 - dimethyl cyclopropane carboxylate.
6. A method of preparing an isomer according to any one of the preceding claims which comprises esterifying 3,4,5,6 - tetrahydrophthalimidomethyl alcohol or an esterifiable derivative thereof with the desired isomer of the 3 - (2,2 - dihalovinyl) - 2,2dimethylcyclopropane carboxylic acid or esterifiable derivative thereof.
7. A method according to Claim 6 wherein (a) the alcohol is reacted with the acid or acid chloride or (b) a 3,4,5,6 - tetrahydrophthalimidomethyl halide is reacted with a silver or trialkylammonium salt of the acid or (c) the alcohol is reacted with a C1-C4 alkyl ester of the acid.
8. A method according to claim 6 substantially as hereinbefore described with reference to the Example.
9. An isomer of formula II obtained by a method according to any one of Claims 6--8.
10. A composition for combatting pest infestation comprising an isomer as defined in any one of Claims 1-5 or 9 together with an inert diluent or carrier.
11. A composition according to Claim 10 including a further arthrapodicidal compound.
12. A composition according to Claim 10 or 11 including a compound which synergises the activity of pyrethrins or synthetic pyrethroids.
13. A composition according to any one of Claims 10--12 substantially as hereinbefore described.
14. A method of combatting pest infestation which comprises applying to the pest or to an environment susceptible to pest infestation an isomer according to any one of Claims 1-5 or 9 or a composition according to any one of Claims 10-13.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB4845477A GB1604450A (en) | 1977-11-21 | 1977-11-21 | Derivatives of cyclopropanecarboxylic acids |
| DE19782849942 DE2849942A1 (en) | 1977-11-21 | 1978-11-17 | CYCLOPROPANIC CARBONIC ACID DERIVATIVES, THE PROCESS FOR THEIR PRODUCTION AND THE REPRODUCTORS CONTAINING THESE |
| JP14240378A JPS5495560A (en) | 1977-11-21 | 1978-11-20 | Noxious biotic killing agent |
| FR7832650A FR2409261A1 (en) | 1977-11-21 | 1978-11-20 | PYRETHROID TYPE PESTICIDE COMPOUNDS AND THEIR PREPARATION PROCESS |
| US06/612,807 US4622337A (en) | 1972-05-25 | 1984-05-22 | 2,2-dimethyl-3-(2-halovinyl)cyclopropane carboxlic acid ester pesticides |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB4845477A GB1604450A (en) | 1977-11-21 | 1977-11-21 | Derivatives of cyclopropanecarboxylic acids |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| GB1604450A true GB1604450A (en) | 1981-12-09 |
Family
ID=10448660
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB4845477A Expired GB1604450A (en) | 1972-05-25 | 1977-11-21 | Derivatives of cyclopropanecarboxylic acids |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JPS5495560A (en) |
| DE (1) | DE2849942A1 (en) |
| FR (1) | FR2409261A1 (en) |
| GB (1) | GB1604450A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2678611B1 (en) * | 1991-07-04 | 1995-01-20 | Roussel Uclaf | NOVEL PYRETHRINOUID ESTERS OF ALCOHOL 1,3,4,5,6,7-HEXAHYDRO 1,3-DIOXO-2H-ISOINDOL-2-YL-METHYLIQUE, THEIR PREPARATION PROCESS AND THEIR APPLICATION AS PESTICIDES. |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2326077C2 (en) * | 1972-05-25 | 1985-12-12 | National Research Development Corp., London | Unsaturated cyclopropanecarboxylic acids and their derivatives, their preparation and insecticides containing them |
| GB1410080A (en) * | 1972-12-21 | 1975-10-15 | Nat Res Dev | Oxime derivatives of 2,2-dimethyl-3-formyl cyclopropane carboxylic acid and their use as insecticides |
| JPS5521010B2 (en) * | 1973-10-22 | 1980-06-06 | ||
| FR2290415A1 (en) * | 1974-11-06 | 1976-06-04 | Aries Robert | Insecticidal chrysanthemic acid analogues - viz. 2,2-dimethyl-3-(2,2-dichlorovinyl)-cyclopropanecarboxylate esters |
| FR2297834A1 (en) * | 1975-01-16 | 1976-08-13 | Aries Robert | Chlorine contg. chrysanthemic esters - esp. 3-(2-chloro 2-methyl vinyl) 2,2-dimethyl cyclopropane carboxylic ester used as insecticides |
| FR2355797A1 (en) * | 1975-09-05 | 1978-01-20 | Wellcome Found | PROCESS FOR THE PREPARATION OF SUBSTITUTE VINYLCYCLOPROPANES FOR USE IN THE PREPARATION OF INSECTICIDES |
| FR2398715A2 (en) * | 1977-07-25 | 1979-02-23 | Roussel Uclaf | Poly:haloethyl-cyclopropane-carboxylate ester(s) - useful as insecticides, acaricides, nematocides, fungicides (BE 20.3.78) |
-
1977
- 1977-11-21 GB GB4845477A patent/GB1604450A/en not_active Expired
-
1978
- 1978-11-17 DE DE19782849942 patent/DE2849942A1/en not_active Ceased
- 1978-11-20 FR FR7832650A patent/FR2409261A1/en active Granted
- 1978-11-20 JP JP14240378A patent/JPS5495560A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| DE2849942A1 (en) | 1979-05-23 |
| FR2409261A1 (en) | 1979-06-15 |
| JPS5495560A (en) | 1979-07-28 |
| FR2409261B1 (en) | 1983-07-01 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PS | Patent sealed | ||
| 732 | Registration of transactions, instruments or events in the register (sect. 32/1977) | ||
| PE20 | Patent expired after termination of 20 years |
Effective date: 19980530 |